CN113372237B - Fluorine-containing surfactant for immersion photoresist and preparation method thereof - Google Patents
Fluorine-containing surfactant for immersion photoresist and preparation method thereof Download PDFInfo
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- CN113372237B CN113372237B CN202110488255.7A CN202110488255A CN113372237B CN 113372237 B CN113372237 B CN 113372237B CN 202110488255 A CN202110488255 A CN 202110488255A CN 113372237 B CN113372237 B CN 113372237B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
- C07C233/77—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/78—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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Abstract
The invention discloses a fluorine-containing surfactant for an immersion photoresist, which is characterized by comprising the following components in percentage by weight: r is straight-chain alkane with 2 to 9 carbon atoms
The preparation method comprises the following steps: 2) Filling nitrogen into the first three-neck flask, and arranging a constant-pressure dropping funnel and a reflux condenser pipe; 3) Putting triethylamine, N-dimethylethylenediamine and dichloromethane into a first three-neck flask; 4) Dropwise adding isophthaloyl dichloride into the first three-neck flask at the temperature of 0-10 ℃, wherein the dropwise adding is finished within one hour; 5) Removing the second dichloromethane solvent and recrystallizing the intermediate B; 6) Putting the intermediate into a second three-neck flask, arranging a constant-pressure dropping funnel and a reflux condenser tube, dropwise adding a dichloromethane solution of perfluoroiodobutane at room temperature, completing dropwise adding for 1 hour, and heating to 40 ℃ for reacting for 12 hours; after the reaction is finished, performing rotary evaporation, dissolving the crude product in ethanol, adding petroleum ether until a precipitate is separated out, standing, filtering the precipitate, and recrystallizing with ethanol to obtain a yellow solid; 8) The yellow solid was removed and dried in vacuo.
Description
Technical Field
The invention relates to a fluorine-containing surfactant for an immersion photoresist and a preparation method thereof.
Background
ArF photoresist is one of the key materials in the field of integrated circuit manufacturing, wherein the immersion photoresist is a main product used in the current technology node below 40nm, the immersion photoresist is in contact with the lens of the lithography machine during the use process, and in order to avoid the contamination of the lens of the lithography machine by the impurities generated by the photoresist in water, a hydrophobic additive is usually added into the immersion photoresist to prevent the contamination of the lens of the lithography machine by the impurities generated by the photoresist entering water. The hydrophobic additive is generally a surfactant containing fluorine, a hydrophobic layer is formed on the surface of the photoresist, the photoresist is isolated from a water layer, the isolation effects of different hydrophobic layers are different, and the hydrophobic additive with good isolation effect needs to be developed in order to further reduce the precipitation of the photoresist in water.
Disclosure of Invention
The invention aims to solve the technical problem of providing a fluorine-containing surfactant for an immersion photoresist, the fluorine-containing additive prepared by the invention has simple preparation process, and the precipitation amount of the photoresist in pure water can be reduced when the fluorine-containing surfactant is used in the immersion photoresist, so that a lens of a photoetching machine is protected, and pollution is avoided.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
the invention provides a fluorine-containing surfactant for an immersion photoresist, which comprises the following substances with the structural formula:
wherein R is a linear alkane of 2 to 9 carbon atoms.
As a further improvement of the invention: is synthesized by the following process route:
the invention also provides a preparation method of the fluorine-containing surfactant for the immersion photoresist, which has good product performance and comprises the following steps:
1) Cleaning the first three-neck flask with pure water, and blowing the first three-neck flask with nitrogen for later use;
2) Filling nitrogen into the first three-neck flask, and arranging a constant-pressure dropping funnel and a reflux condenser pipe;
3) Putting triethylamine, N-dimethyl ethylenediamine and dichloromethane into a first three-neck flask for later use;
4) Under ice bath magnetic stirring, dropwise adding isophthaloyl dichloride into the first three-neck flask, keeping the temperature at 0-10 ℃, continuously reacting for 12 hours or more after dropwise adding is finished within one hour;
5) Removing a dichloromethane solvent in the first three-neck flask and recrystallizing to obtain an intermediate B;
6) Putting the intermediate into a second three-neck flask, arranging a constant-pressure dropping funnel and a reflux condenser tube, dropwise adding a dichloromethane solution of perfluoroiodobutane at room temperature by magnetic stirring, completing dropwise adding for 1 hour, and heating to 40 ℃ for reaction for 12 hours;
7) After the reaction is finished, removing the solvent by rotary evaporation, dissolving the crude product in ethanol, adding petroleum ether until a precipitate is separated out, standing for a period of time, filtering the precipitate, and recrystallizing with ethanol to obtain a yellow solid product;
8) And (4) leading out a yellow solid product of the solid precipitate in the reaction kettle, and drying in vacuum to obtain a resin product.
As a further improvement of the invention: the triethylamine, the N, N-dimethylethylenediamine and the dichloromethane are all in AR analytical purity levels.
As a further improvement of the invention: the volume of the first three-neck flask is larger than that of the second three-neck flask.
The fluorine-containing additive preparation method prepared by the invention has good product performance and simple process, and can reduce the precipitation amount of the photoresist in pure water when used in the immersion photoresist, thereby protecting the lens of a photoetching machine and avoiding pollution.
Drawings
FIG. 1 is a process diagram of a synthetic route.
Detailed Description
The fluorine-containing surfactant for immersion photoresist and the preparation method thereof provided by the invention are further explained in more detail by the following specific examples:
example 1
Adding 1mol of N, N-dimethylethylenediamine and 1mol of triethylamine and 300mL of dichloromethane into a 1000mL three-neck flask provided with a constant-pressure dropping funnel and a reflux condenser tube, slowly dropwise adding 50mL of dichloromethane solution containing 0.5mol of terephthaloyl chloride under ice-bath magnetic stirring, controlling the dropwise adding for 1 hour, then raising the temperature to 45 ℃, finishing the reaction after reacting for a period of time, and recrystallizing by dichloromethane to obtain a white solid.
A certain amount of perfluoroiodobutane is added into a 500mL three-neck flask provided with a constant-pressure dropping funnel and a reflux condenser tube, a dichloromethane solution of the perfluoroiodobutane is slowly dropped under magnetic stirring, and the mixture is stirred in a shading way and refluxed for reaction for a certain time. And after the reaction is finished, removing the solvent and unreacted raw materials by rotary evaporation, dissolving the crude product in a proper amount of ethanol, adding petroleum ether until a precipitate is separated out, standing for a period of time, filtering the precipitate, and recrystallizing with ethanol to obtain a yellow solid product.
Example 2
Adding 1mol of N, N-dimethyl dibutylamine, 1mol of triethylamine and 300mL of dichloromethane into a 1000mL three-neck flask provided with a constant-pressure dropping funnel and a reflux condenser tube, slowly dropwise adding 50mL of dichloromethane solution containing 0.5mol of terephthaloyl chloride under ice-bath magnetic stirring, controlling the dropwise adding for 1 hour, then raising the temperature to 45 ℃, finishing the reaction after reacting for a period of time, and recrystallizing by dichloromethane to obtain a white solid.
A certain amount of perfluoroiodobutane is added into a 500mL three-neck flask provided with a constant-pressure dropping funnel and a reflux condenser tube, a dichloromethane solution of the perfluoroiodobutane is slowly dropped under magnetic stirring, and the mixture is stirred in a shading way and refluxed for reaction for a certain time. And after the reaction is finished, removing the solvent and unreacted raw materials by rotary evaporation, dissolving the crude product in a proper amount of ethanol, adding petroleum ether until a precipitate is separated out, standing for a period of time, filtering the precipitate, and recrystallizing with ethanol to obtain a yellow solid product.
Example 3
Adding 1mol of N, N-dimethyldihexylamine and 1mol of triethylamine and 300mL of dichloromethane into a 1000mL three-neck flask provided with a constant-pressure dropping funnel and a reflux condenser tube, slowly dropwise adding 50mL of dichloromethane solution containing 0.5mol of terephthaloyl chloride under ice-bath magnetic stirring, controlling the dropwise adding for 1 hour, then raising the temperature to 45 ℃, finishing the reaction after reacting for a period of time, and recrystallizing by dichloromethane to obtain a white solid.
A certain amount of perfluoroiodobutane is added into a 500mL three-neck flask provided with a constant-pressure dropping funnel and a reflux condenser tube, a dichloromethane solution of the perfluoroiodobutane is slowly dropped under magnetic stirring, and the mixture is stirred in a shading way and refluxed for reaction for a certain time. And after the reaction is finished, removing the solvent and unreacted raw materials by rotary evaporation, dissolving the crude product in a proper amount of ethanol, adding petroleum ether until a precipitate is separated out, standing for a period of time, filtering the precipitate, and recrystallizing with ethanol to obtain a yellow solid product.
Experimental part: adding the synthesized fluorine-containing surfactant (0.03 wt%) into a formula of an immersion photoresist, coating a layer of film with the thickness of 1 micrometer on the surface of a silicon wafer by using the photoresist, dropwise adding 5 milliliters of water on the surface, and testing the precipitation amount of impurities in the water after 10 minutes, wherein the results are as follows:
note: the preparation method of the fluorine-containing additive has good product performance and simple process, and can reduce the precipitation amount of the photoresist in pure water when the fluorine-containing additive is used in the immersed photoresist, thereby protecting the lens of a photoetching machine and avoiding pollution.
It will be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should also be understood that various alterations, modifications and/or variations can be made to the present invention by those skilled in the art after reading the technical content of the present invention, and all such equivalents fall within the protective scope defined by the claims of the present application.
It will be appreciated by those skilled in the art that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The embodiments disclosed above are therefore to be considered in all respects as illustrative and not restrictive. All changes which come within the scope of or equivalence to the invention are intended to be embraced therein.
Claims (2)
1. The preparation method of the fluorine-containing surfactant for the immersion photoresist is characterized by comprising the following steps: the method comprises the following steps:
1) Cleaning the first three-neck flask with pure water, and blowing the first three-neck flask with nitrogen for later use;
2) Filling nitrogen into the first three-neck flask, and arranging a constant-pressure dropping funnel and a reflux condenser pipe;
3) Putting triethylamine, N-dimethyl ethylenediamine and dichloromethane into a first three-neck flask for later use;
4) Under ice bath magnetic stirring, dropwise adding terephthaloyl chloride into the first three-neck flask, keeping the temperature at 0-10 ℃, continuously reacting for 12 hours or more after dropwise adding is finished within one hour;
5) Removing a dichloromethane solvent in the first three-neck flask and recrystallizing to obtain an intermediate;
6) Putting the intermediate into a second three-neck flask, arranging a constant-pressure dropping funnel and a reflux condenser tube, dropwise adding a dichloromethane solution of perfluoroiodobutane at room temperature by magnetic stirring, completing dropwise adding for 1 hour, and heating to 40 ℃ for reaction for 12 hours;
7) After the reaction is finished, removing the solvent by rotary evaporation, dissolving the crude product in ethanol, adding petroleum ether until a precipitate is separated out, standing for a period of time, filtering the precipitate, and recrystallizing with ethanol to obtain a yellow solid product;
8) Leading out a yellow solid product of the solid precipitate in the reaction kettle, and drying in vacuum to obtain a resin product; the structure of the resin product is:
2. The method of claim 1, wherein the fluorosurfactant is selected from the group consisting of: the volume of the first three-neck flask is larger than that of the second three-neck flask.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5345683A (en) * | 1976-10-07 | 1978-04-24 | Asahi Glass Co Ltd | Fluoroalkyl-containing amphoteric surfactant and preparation thereof |
| CN102188928A (en) * | 2010-03-08 | 2011-09-21 | 中国科学院成都有机化学有限公司 | Fluorocarbon cationic gemini and hybridized gemini surfactants and synthesis method thereof |
| CN102652910A (en) * | 2011-09-05 | 2012-09-05 | 京东方科技集团股份有限公司 | Non-ionic surface active agent, and preparation method and use thereof, as well as photoresist developing solution |
| CN103831057B (en) * | 2014-03-19 | 2016-01-20 | 中国科学院上海有机化学研究所 | Fluorocarbon surfactant and preparation method thereof |
| CN106823987B (en) * | 2017-01-16 | 2019-08-20 | 广州理文科技有限公司 | A kind of hydrofluorocarbons carboxylic acid type surfactant and preparation method thereof |
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