CN113698329B - 193nm immersion lithography photoacid generator and intermediate thereof - Google Patents
193nm immersion lithography photoacid generator and intermediate thereof Download PDFInfo
- Publication number
- CN113698329B CN113698329B CN202110979288.1A CN202110979288A CN113698329B CN 113698329 B CN113698329 B CN 113698329B CN 202110979288 A CN202110979288 A CN 202110979288A CN 113698329 B CN113698329 B CN 113698329B
- Authority
- CN
- China
- Prior art keywords
- compound
- formula
- photoresist composition
- reaction
- photoacid generator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/12—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing esterified hydroxy groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The invention discloses a 193nm immersion lithography photoacid generator and an intermediate thereof. The photoacid generator is shown in the formula I. The photoresist containing the photoacid generator has the advantages of high resolution, high sensitivity and low line width roughness, and has good application prospect.
Description
Technical Field
The invention relates to a photoacid generator for 193nm immersion lithography and an intermediate thereof.
Background
The photolithography technique refers to a pattern micromachining technique for transferring a pattern designed on a mask plate onto a substrate through exposure, development, etching and other technological processes by utilizing chemical sensitivity of a photolithography material (particularly photoresist) under the actions of visible light, ultraviolet rays, electron beams and the like. Photolithography materials (particularly photoresists), also known as photoresists, are the most critical functional chemical materials involved in photolithography, the main components of which are resins, photoacid generators (Photo Acid Generator, PAG), and corresponding additives and solvents. The photoacid generator is a photosensitive compound which is decomposed under illumination to generate acid, and the generated acid can lead acid-sensitive resin to generate decomposition or crosslinking reaction, so that the dissolution contrast of an illumination part and a non-illumination part in a developing solution is increased, and the photoacid generator can be used in the technical field of pattern micromachining.
Three important parameters of photoresist include resolution, sensitivity, line width roughness, which determine the process window of the photoresist at the time of chip fabrication. With the continuous improvement of the performance of semiconductor chips, the integration level of integrated circuits increases exponentially, and the patterns in the integrated circuits continue to shrink. In order to make smaller sized patterns, the performance index of the above three photoresists must be improved. The use of a short wavelength light source in the photolithography process may increase the resolution of the photoresist according to the rayleigh equation. The light source wavelength of the photolithography process has evolved from 365nm (I-line) to 248nm (KrF), 193nm (ArF), 13nm (EUV). In order to improve the sensitivity of the photoresist, the currently mainstream KrF, arF, EUV photoresist adopts a chemically amplified photosensitive resin. Thus, photosensitizers (photoacid generators) compatible with chemically amplified photosensitive resins are widely used in high-end photoresists.
With the gradual development of the photoetching process, the immersion process of 193nm is adopted, the process complexity is increased, and the requirements on the photoacid generator are increased. Development of a photoacid generator capable of improving resolution, sensitivity and line width roughness of photoresist becomes a problem to be solved urgently in the industry.
Disclosure of Invention
The invention aims to overcome the defect of few types of photoacid generators matched with chemical amplification type photosensitive resin in the prior art, and provides a photoacid generator for 193nm immersion lithography and an intermediate thereof so as to improve performances of photoresist in various aspects such as resolution, sensitivity, line width roughness and the like.
The invention solves the technical problems through the following technical proposal.
The invention provides a compound as shown in formula I:
a is I or S;
n is 2 or 3;
r is H, halogen,C 1-6 Alkyl or C 1-6 One or more of alkoxy, R has a substituent number of 1-5 on the benzene ring;
y is
Quilt Y 1 Substituted->
Or by Y 2 Substituted->
Wherein Y is 1 And Y 2 Independently 1, 2, 3 or 4; m is m 1 、m 2 、n 1 And n 2 Independently 0, 1, 2 or 3; y is Y 1 And Y 2 Independently amino, C 1-6 Alkylamino, carboxyl, C 1-6 Alkylcarboxyl or C 1-6 An alkyl group.
In some embodiments, R is F, cl, br, or I.
In some embodiments, R is said C 1-6 Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
In some embodiments, R is said C 1-6 Alkoxy is methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy.
In some embodiments, Y 1 In (C) 1-6 Alkyl, said C 1-6 Alkylamino and said C 1-6 C in alkylcarboxyl 1-6 Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
In some embodiments, Y 2 In (C) 1-6 Alkyl, said C 1-6 Alkylamino and said C 1-6 C in alkylcarboxyl 1-6 Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
In some embodiments, Y 1 And Y 2 And independently 1 or 2.
In some embodiments, m 1 、m 2 、n 1 And n 2 And independently 0 or 1.
In some embodiments, R is H.
In some embodiments, n is 3.
In some embodiments, a is S.
In some embodiments, Y 1 And Y 2 Independently amino, carboxyl or C 1-6 An alkyl group.
In some embodiments, R is H;
a is S;
n is 3;
y is
Quilt Y 1 Substituted->
Or by Y 2 Substituted->
Y 1 And Y 2 1 or 2 independently;
m 1 、m 2 、n 1 and n 2 Independently 0 or 1;
Y 1 and Y 2 Independently an amino group, a carboxyl group or a methyl group.
In some of the embodiments of the present invention,
is->
In some embodiments, Y is
In some embodiments, the compound of formula I is any one of the following:
the invention also provides a preparation method of the compound shown in the formula I, which comprises the following steps:
in a solvent, carrying out salt forming reaction of a compound II and a compound III as shown below to obtain a compound shown in the formula I;
wherein, the definition of A, R, Y, N is as above, X is halogen, N is alkali metal.
In X, the halogen is preferably F, cl, br or I, such as Cl.
In N, the alkali metal is preferably Li, na or K, for example Na.
The salt-forming reaction may be a conventional reaction of the type in the art, and the present invention particularly preferably employs the following conditions and operations:
in the salt forming reaction, the solvent can be an alcohol solvent and water. The alcohol solvent can be methanol, ethanol, n-propanol or isopropanol, and can further be methanol. The volume ratio of the alcohol solvent to the water is 0.8:1 to 1.5:1, for example 1.0:1. The amount of the alcohol solvent is 60-80ml, for example 70ml.
In the salt-forming reaction, the molar ratio of the compound III to the compound II may be 1.5:1 to 2.5:1, for example 2.0:1.
In the salt formation reaction, the compound III is preferably added to the solution containing the compound II in the form of an aqueous solution.
The salification reaction can be carried out under the condition of avoiding light.
The temperature of the salt formation reaction may be 5-40 ℃, for example room temperature.
The progress of the salt formation reaction can be monitored by methods conventional in the art (e.g., TLC) with the compound III no longer reacting as an endpoint of the reaction. The salt formation reaction may take from 8 to 24 hours, for example 16 hours.
The post-treatment step of the salt formation reaction may be a conventional post-treatment step of such salt formation reaction in the art, preferably extraction. The solvent for extraction may be a halogenated hydrocarbon solvent (e.g., chloroform). The number of extractions may be 2-3, for example 3.
The preparation method of the compound shown in the formula I can further comprise the following steps:
step 1, in the presence of an alkaline reagent, reacting a compound V with a compound IV in a solvent to obtain a mixture;
step 2, in the presence of hydrogen peroxide, reacting the mixture obtained in the step 1 in water to obtain the compound II;
in step 1, the alkaline agent may be an alkaline agent conventional in the art, preferably an alkali metal carbonate and/or alkali metal bicarbonate (e.g., sodium bicarbonate).
In step 1, the molar ratio of the basic reagent to the compound V may be a molar ratio conventional in the art, preferably 1.5:1 to 4.0:1, for example 3.0:1.
In step 1, the molar ratio of said compound IV to said compound V may be a molar ratio conventional in the art, preferably 1.5:1 to 2.5:1, for example 2.0:1.
In step 1, the solvent may be a solvent conventional in such reactions in the art, preferably a nitrile solvent (e.g., acetonitrile) and water. The volume ratio of the nitrile solvent to the water is 0.8:1 to 1.2:1, e.g., 1.0:1. The nitrile solvent is used in an amount of 70-90ml, for example 80ml.
In step 1, the temperature of the reaction may be 50-90 ℃, for example 70 ℃.
In step 1, the reaction time may be 8 to 24 hours, for example 16 hours.
In step 2, the molar ratio of the compound hydrogen peroxide to the compound V may be a molar ratio conventional in the art, preferably 1.5:1 to 3.0:1, for example 2.0:1.
In step 2, the temperature of the oxidation reaction may be 5-40 ℃, for example, room temperature.
In step 2, the time of the oxidation reaction may be 8 to 24 hours, for example, 16 hours.
The preparation method of the compound shown in the formula I can further comprise the following steps: in the presence of p-toluenesulfonic acid, carrying out esterification reaction of a compound VII and a compound VI in a solvent to obtain a compound V;
the esterification reaction may be conventional in the art, and the present invention particularly preferably employs the following conditions and operations:
in the esterification reaction, the molar ratio of the p-toluenesulfonic acid to the compound VI may be in the range of 0.1:1 to 0.3:1, for example 0.22:1.
In the esterification reaction, the molar ratio of the compound VI to the compound VII may be 2.0:1 to 4.0:1, for example 3.0:1.
In the esterification reaction, the solvent may be an aromatic solvent (e.g., toluene). The aromatic solvent is used in an amount of 70 to 90ml, for example 80ml.
The temperature of the esterification reaction may be 110-130 ℃, for example 120 ℃.
The progress of the esterification reaction can be monitored by methods conventional in the art (e.g., TLC) with the compound VI no longer reacting as an endpoint of the reaction. The time of the esterification reaction may be 5 to 10 hours, for example 8 hours.
The post-treatment step of the esterification reaction may be a post-treatment step conventional in the art for such esterification reaction, preferably alkali washing (e.g., 3 times), saturated saline washing (e.g., 1 time), and drying (e.g., anhydrous sodium sulfate drying).
The invention also provides a compound II:
wherein Y and N are as defined above.
The compound II is any one of the following compounds:
the invention also provides application of the compound shown in the formula I in photoresist as a photoacid generator.
The invention also provides a photoresist composition, which comprises the following raw materials: the compound, the resin, the alkaline additive and the solvent are as shown in the formula I;
the resin is
In the photoresist composition, the parts by weight of the compound of formula I are preferably 2 to 10 parts, for example 4 parts.
In the photoresist composition, the resin is preferably 20 to 120 parts by weight, for example, 100 parts by weight.
In the photoresist composition, the alkali additive is preferably present in an amount of 0.1 to 1 parts by weight, for example, 0.5 parts by weight.
In the photoresist composition, the alkaline additive is preferably C 1-4 Alkyl quaternary ammonium bases such as tetramethyl ammonium hydroxide.
In the photoresist composition, the solvent is preferably 500 to 2000 parts by weight, for example, 1000 parts by weight.
In the photoresist composition, the solvent is preferably an ester solvent such as propylene glycol methyl ether acetate.
The photoresist composition comprises the following raw materials in parts by weight: 4 parts of the above-described compound of formula I, 100 parts of a resin, 0.5 part of an alkaline additive and 1000 parts of a solvent.
The photoresist composition consists of the following raw materials: the compound shown as the formula I, the resin, the alkaline additive and the solvent.
The invention also provides a preparation method of the photoresist composition, which comprises the following steps: mixing the above materials uniformly.
In the preparation method, the mixing mode can be a mixing mode conventional in the field, and vibration is preferred.
In the preparation method, the mixing step preferably further comprises filtration with a filter membrane, for example, a 0.2 μm filter membrane.
The invention also provides application of the photoresist composition in a photoetching process.
Wherein, the photoetching process preferably comprises the following steps: the photoresist composition is applied to a pretreated substrate, dried (e.g., at 110 ℃ for 90 seconds), exposed to light, and developed (e.g., using a developer solution that is an aqueous solution of tetramethylammonium hydroxide).
The above preferred conditions can be arbitrarily combined on the basis of not deviating from the common knowledge in the art, and thus, each preferred embodiment of the present invention can be obtained.
The reagents and part of raw materials used in the invention are commercially available, and part of raw materials are self-made.
The invention has the positive progress effects that: the photoresist composition prepared by adopting the photoacid generator has the advantages of high resolution, high sensitivity and low line width roughness, and compared with the comparative photoresist composition, the photoresist composition has the advantages of 25-49% improvement of the sensitivity, 4-44% improvement of the resolution and 40-74% reduction of the line width roughness.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Preparation of the resin
In the examples or comparative examples of the present invention, the resin was prepared as follows:
3-bicyclo [2.2.1] hept-5-en-2-yl-3-hydroxypropionate (hereinafter referred to as BHP), 1-methyladamantane acrylate and gamma-butyrolactone acrylate were added in a molar ratio of 1:1:1. 1, 4-dioxane was added in an amount of 300 parts by weight with respect to 100 parts by weight of the total amount of the reaction monomers as a polymerization solvent, azobisisobutyronitrile was added in an amount of 4 parts by mole with respect to 100 parts by weight of the total amount of the reaction monomers as an initiator, and the mixture was reacted at 65℃for 16 hours.
After the reaction, the reaction solution was precipitated with n-hexane, and the precipitate was removed and dried in vacuo. Thereby, a product is obtained
The weight average molecular weight thereof was about 8500g/mol.
Example 1
Step 1: synthesis of Compound V-1
A250 mL glass bottle equipped with an oil-water separator and a condenser was charged with 2-bromo-2, 2-difluoroethanol (76.94 g,0.48mol,3.0 eq), compound VII-1 (38 g,0.16mol,1.0 eq), p-toluenesulfonic acid (5.53 g,0.03mol,0.22 eq) and 80mL toluene, and the mixture was heated under reflux with stirring for 8h. After completion of the reaction, the reaction mixture was cooled, washed 3 times with 50mL of an aqueous sodium carbonate solution, 1 time with 50mL of a saturated brine, and the organic phase was dried over anhydrous sodium sulfate and concentrated to give 55.0g of an intermediate in total, the yield was 66.0%.
1 HNMR(300MHz,DMSO)：δppm：8.52,2H；1.50,2H；2.01,4H；1.67,2H；2.15,2H；1.79,4H；4.90,4H.
Step 2: synthesis of Compound II-1
In a 500mL round bottom flask, compound V-1 (78.0 g,0.15mol,1.0 eq) and 80mL acetonitrile were added and dissolved with stirring. Under the protection of nitrogen, 80mL of an aqueous solution containing sodium dithionite (51.98 g,0.30mol,2.0 eq) and sodium bicarbonate (37.56 g,0.45mol,3.0 eq) was added dropwise, and after the addition was completed, the reaction solution was heated and stirred at 70℃for 16 hours. After the reaction was completed, it was cooled and a proper amount of sodium chloride solid was added until the solution was saturated. The reaction was separated and the aqueous phase was extracted 2 times with 30mL of acetonitrile. The organic phases were combined and transferred to a 500mL round bottom flask, and 100mL of pure water was added. The mixture was added dropwise with 30% hydrogen peroxide (10.1 g,0.30mol,2.0 eq) under nitrogen, followed by stirring at room temperature for 16h. After the completion of the reaction, the mixture was separated into layers, the aqueous phase was extracted 2 times with 50mL of acetonitrile, the organic phase was dried over anhydrous sodium sulfate, and the mixture was concentrated to give 47.36g of Compound II-1, with a yield of 55.8%.
1 HNMR(300MHz,DMSO)：δppm：8.52,2H；1.50,2H；2.01,4H；1.67,2H；2.15,2H；1.79,4H；4.96,2H；4.4,2H.
Step 3: synthesis of Compound I-1
Triphenylsulfonium chloride synthesis
Diphenylsulfoxide (7.56 g,0.037mol,1.0 eq) and 60mL of anhydrous methylene chloride were added dropwise to a 250mL three-necked flask at a temperature below 0deg.C under nitrogen blanket, and trimethylchlorosilane (12.18 g,0.112mol,3.0 eq) was added dropwise. After the dripping is finished, the temperature is slowly raised to the room temperature, and stirring is continued for 1h. Then, the reaction mixture was cooled to 0℃or lower again, and at this temperature, a tetrahydrofuran solution (45 ml/2M,0.113mol,3.01 eq) of phenylmagnesium chloride was added dropwise. After the dripping is finished, the temperature is slowly raised to the room temperature, and stirring is continued for 2 hours. The reaction mixture was quenched with a small amount of water, and 75mL of a 0.2N aqueous hydrochloric acid solution was added. After the mixed solution is washed twice with 30mL of diethyl ether, the water phase is the aqueous solution of triphenylsulfonium chloride salt, and the aqueous solution is placed in a dark place for standby.
Synthesis of Compound I-1
A250 mL round bottom flask was charged with Compound II-1 (13.1 g,0.023mol,1.0 eq) and 70mL methanol, and dissolved with stirring. Then, an aqueous solution (0.045 mmol,2.0 eq) of a previously prepared triphenylsulfonium chloride salt was added dropwise under light-protected conditions. After the dripping is finished, stirring for 16 hours in a dark place is continued. After the completion of the extraction, 30mL of chloroform was used for 3 times, and the organic phases were combined and washed with 30mL of pure water 2 times. The aqueous phase was removed by separation and the organic phase was concentrated to give compound I-1.55 g in 43.6% yield.
1 HNMR(300MHz,DMSO)：δppm：8.52,2H；7.33,12H；7.35,12H；7.36,6H；1.50，2H；2.01，4H；1.67，2H；2.15，2H；1.79，4H；4.96，2H；4.4，2H.
Examples 2 to 6
Examples 2-6 were prepared as described in reference to example 1. The starting materials, intermediate compounds II and compounds I used are shown in tables 1 and 2, respectively.
TABLE 1
TABLE 2
EXAMPLE 7 preparation of Photoresist composition
The photoresist composition of the present invention and the comparative photoresist composition were prepared as follows:
100 parts by weight of the resin prepared as above, 4 parts by weight of the photoacid generator prepared as above, and 0.5 parts by weight of tetramethylammonium hydroxide (as an alkaline additive) were dissolved in 1000 parts by weight of propylene glycol methyl ether acetate, and then the solution was filtered through a 0.2- μm membrane filter, thereby preparing a photoresist composition. Among them, photoacid generators in the photoresist compositions of examples 1 to 7 and comparative example 1 are shown in table 3.
TABLE 3 Table 3
| Photoresist composition numbering | Photoacid generator species |
| Photoresist composition 1 | Compound I-1 |
| Photoresist composition 2 | Compound I-2 |
| Photoresist composition 3 | Compound I-3 |
| Photoresist composition 4 | Compound I-4 |
| Photoresist composition 5 | Compound I-5 |
| Photoresist composition 6 | Compound I-6 |
| Comparative example 1 Photoresist composition | Comparative Compound 1 |
| Comparative example 2 Photoresist composition | Comparative Compound 2 |
| Comparative example 3 Photoresist composition | Comparative Compound 3 |
| Comparative example 4 Photoresist composition | Comparative Compound 4 |
| Comparative example 5 Photoresist composition | Comparative Compound 5 |
| Comparative example 6 Photoresist composition | Comparative Compound 6 |
| Comparative example 7 Photoresist composition | Comparative Compound 7 |
| Comparative example 8 Photoresist composition | Comparative Compound 8 |
| Comparative example 9 Photoresist composition | Comparative Compound 9 |
| Comparative example 10 Photoresist composition | Comparative Compound 10 |
| Comparative example 11 Photoresist composition | Comparative Compound 11 |
Comparative example Compound 1 bis-triphenylsulfonium salt bis (2-sulfonic acid-2, 2-difluoroethoxy) succinate
The preparation of bis (triphenylsulfonium salt) bis (2-sulfonic acid-2, 2-difluoroethoxy) succinate was carried out in the same manner as in example 1.
1 HNMR(300MHz,DMSO)：δppm:2.73,4H；4.96,2H；4.4,2H；7.33,12H；7.35,12H；7.36,6H；
Comparative Compounds 2-11
Comparative compounds 2-9 were prepared according to step 2 and step 3 of example 1.
Comparative compounds 10-11 were prepared as in example 1.
Effect examples and comparative effect examples
An anti-reflective coating ARC-29 (Nissan Chemical Industries, ltd.) was coated on a silicon wafer (12 inches) using a spin coater, then baked at 205 ℃ for 60 seconds to form an organic anti-reflective coating layer 70nm thick, then the prepared photoresist composition was coated, and dried at 110 ℃ for 90 seconds to form a film having a thickness of 0.20 μm. The resulting structure was exposed to light using an immersion exposure apparatus (1700 i, manufactured by ASML co.) and baked at 105 ℃ for 60 seconds. Thereafter, the film was developed with 2.38 wt% aqueous tetramethylammonium hydroxide solution for 40 seconds, and washed and dried. Thereby forming a photoresist pattern using ultrapure water as an immersion medium.
The exposure amount used when forming a line-and-space (L/S) pattern of 0.10 μm at a line width of 1:1 after development was designated as the optimum exposure amount, and the optimum exposure amount was designated as the sensitivity (unit: mJ/cm) 2 ). The minimum pattern size resolved at this time is designated as resolution (unit: nm).
Further, in the case of Line Edge Roughness (LER), pattern roughness in a line pitch (L/S) pattern of 0.10 μm formed after development was observed, and LER (smaller value indicates better LER) (unit: nm) was measured.
The effects of the photoresist compositions of examples 1 to 6 and comparative examples 1 to 11 are shown in Table 4.
TABLE 4 Table 4
Therefore, the photoresist composition prepared by the photoacid generator has the advantages of high resolution, high sensitivity and low line width roughness, and compared with the photoresist composition of the comparative example, the photoresist composition has the advantages of 25-49% improvement of the sensitivity, 4-44% improvement of the resolution and 40-74% reduction of the line width roughness.
Claims (9)
1. A compound according to formula I:
wherein A is I or S;
n is 2 or 3;
r is H, halogen or C 1-6 Alkyl or C 1-6 One or more of alkoxy groups, R has a substituent number of 1 to 5 on the benzene ring；
Y is
2. The compound of formula I according to claim 1, wherein the compound of formula I satisfies one or more of the following conditions:
(1) in R, halogen is F, cl, br or I;
(2) r is the same as the C 1-6 Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl;
(3) r is the same as the C 1-6 Alkoxy is methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy.
3. The compound of formula I according to claim 1, wherein the compound of formula I satisfies one or more of the following conditions:
(1) r is H;
(2) a is S;
(3) n is 3.
4. The compound of formula I according to claim 1, wherein R is H;
a is S;
n is 3.
5. The compound of formula I according to claim 1, wherein the compound of formula I satisfies the following conditions:
6. The compound of formula I according to claim 1, wherein the compound of formula I is any one of the following:
7. a compound II:
wherein Y is as defined in any one of claims 1 to 5; n is an alkali metal.
8. The compound II according to claim 7, wherein in N, the alkali metal is Li, na or K.
9. The compound II of claim 7, wherein said compound II is any one of the following:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110979288.1A CN113698329B (en) | 2021-08-25 | 2021-08-25 | 193nm immersion lithography photoacid generator and intermediate thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110979288.1A CN113698329B (en) | 2021-08-25 | 2021-08-25 | 193nm immersion lithography photoacid generator and intermediate thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113698329A CN113698329A (en) | 2021-11-26 |
| CN113698329B true CN113698329B (en) | 2023-07-04 |
Family
ID=78654544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110979288.1A Active CN113698329B (en) | 2021-08-25 | 2021-08-25 | 193nm immersion lithography photoacid generator and intermediate thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113698329B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149349A (en) * | 2021-12-21 | 2022-03-08 | 江苏汉拓光学材料有限公司 | Preparation method of photoacid generator, photoacid generator and intermediate thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6002430B2 (en) * | 2012-05-08 | 2016-10-05 | 東京応化工業株式会社 | Resist composition, resist pattern forming method, compound |
| JP6076029B2 (en) * | 2012-10-19 | 2017-02-08 | 東京応化工業株式会社 | Resist composition and resist pattern forming method |
| JP6206311B2 (en) * | 2014-04-22 | 2017-10-04 | 信越化学工業株式会社 | Photoacid generator, chemically amplified resist material, and pattern forming method |
| JP6974981B2 (en) * | 2016-09-06 | 2021-12-01 | 住友化学株式会社 | Method for producing salt, resist composition and resist pattern |
| JP6974982B2 (en) * | 2016-09-06 | 2021-12-01 | 住友化学株式会社 | Method for producing salt, resist composition and resist pattern |
| JP6761384B2 (en) * | 2016-09-29 | 2020-09-23 | 信越化学工業株式会社 | Adhesive composition, bioelectrode, and method for manufacturing bioelectrode |
| JP7099030B2 (en) * | 2017-06-20 | 2022-07-12 | 住友化学株式会社 | Method for manufacturing resist composition and resist pattern |
| JP7151245B2 (en) * | 2017-08-09 | 2022-10-12 | 住友化学株式会社 | Salt, acid generator, resist composition and method for producing resist pattern |
| JP7245580B2 (en) * | 2017-09-15 | 2023-03-24 | 住友化学株式会社 | Salt, acid generator, resist composition and method for producing resist pattern |
| CN109796382A (en) * | 2019-02-27 | 2019-05-24 | 江苏南大光电材料股份有限公司 | The salty photo-acid generator of long flexible chain, preparation method and photoetching compositions |
-
2021
- 2021-08-25 CN CN202110979288.1A patent/CN113698329B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113698329A (en) | 2021-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101430941B1 (en) | Calixarene compound and photoresist composition comprising same | |
| JPWO2008153154A1 (en) | Cyclic compound, photoresist base material, and photoresist composition | |
| KR20130032854A (en) | Calixarene and photoresist composition comprising same | |
| CN113698329B (en) | 193nm immersion lithography photoacid generator and intermediate thereof | |
| CA2263254A1 (en) | Alkysulfonyloximes for high-resolution i-line photoresists of high sensitivity | |
| US20090181319A1 (en) | Aromatic fluorine-free photoacid generators and photoresist compositions containing the same | |
| CN113703285B (en) | 193nm immersion type photoacid generator for lithography and photoresist composition | |
| CN113698330B (en) | Preparation method of 193nm immersion type photoacid generator for lithography | |
| JP2007293249A (en) | Positive resist composition and pattern forming method using it | |
| US8663901B2 (en) | Fluorine-free fused ring heteroaromatic photoacid generators and resist compositions containing the same | |
| CN113754573B (en) | Photoacid generator for immersion ArF lithography and intermediate thereof | |
| CN113801048B (en) | Preparation method of photo-acid generator for immersion ArF lithography | |
| CN113820918B (en) | Photoacid generator for immersion ArF lithography and photoresist composition | |
| KR101274399B1 (en) | Fluorine-free heteraromatic photoacid generators and photoresist compositions containing the same | |
| CN113820919B (en) | Application of multi-onium salt type photoacid generator for ArF light source dry lithography | |
| CN113816885B (en) | Preparation method of multi-onium salt type photoacid generator for dry-process ArF light source photoetching | |
| CN113801042B (en) | Multi-onium salt type photoacid generator for dry-process photoetching of ArF light source | |
| CN112142769B (en) | Silicon-containing polyphenyl monomolecular resin and photoresist composition thereof | |
| CN108314785B (en) | Octaphenyl substituted cage-like silsesquioxane derivative molecular glass and application thereof | |
| KR20240051205A (en) | Polyionium salt-type photoacid generator for ArF light source dry photolithography, manufacturing method and use thereof | |
| TWI434863B (en) | Copolymer, method for producing the same, and resist composition containing the same | |
| JP5681339B2 (en) | Method for producing compound | |
| KR100465448B1 (en) | Photoresist composition | |
| JPH0768238B2 (en) | Novel Meldrum's acid derivative | |
| TW202405559A (en) | Photosensitive radiation or radiation sensitive resin composition, photosensitive radiation or radiation sensitive film, pattern forming method and manufacturing method of electronic device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |