CN117757488A - Preparation method and application of nonionic fluorine-containing surfactant - Google Patents

Abstract

The invention discloses a preparation method and application of a nonionic fluorine-containing surfactant, wherein the preparation method comprises the following steps: s100: mixing the non-fluorine component material with water, and stirring at a speed of 500-800 r/min for 15-40 min to obtain a first mixture; s200: dropwise adding an organic alkali material into the first mixture at a speed of 5-8 mL/min, and continuously stirring the first mixture at a speed of 300-400 r/min to obtain a second mixture; s300: and mixing the fluorine-containing component material with the second mixture, and stirring at a speed of 2000r/min-2500r/min for 30min-50min to obtain the nonionic fluorine-containing surfactant. The nonionic fluorine-containing surfactant prepared by the method has lower surface tension and smaller contact angle, and can not pull the photoresist pattern to cause the collapse of the group during flushing, thereby effectively guaranteeing the photoetching quality.

Description

Preparation method and application of non-ionic fluorine-containing surfactant

Technical field

The present invention relates to the technical field of surfactants, and specifically to a preparation method and application of a nonionic fluorine-containing surfactant.

Background technique

In the photolithography process, a series of processes such as glue coating, exposure, development, and etching are required. Among them, the glue coating step is carried out by spin coating, and the thickness of the glue is adjusted by the rotation speed of the spin coating. After the glue coating is completed, a pre-baking step is performed. The pre-baking step uses the temperature to remove the organic solvent in the photoresist. Evaporate away and solidify the glue on the wafer surface. Then the exposure step is carried out. The exposure is completed through an exposure mask and an exposure system, such as a step mask alignment or contact exposure system, which exposes within the respective spectral working range. Direct laser exposure without a mask can also be used. After exposure, the development step is performed. During the development process, the positive film structure is formed by dissolving the exposed area, while the negative film development removes the unexposed area. Common development methods include: immersion, spray and stirring. . After development is completed, the substrate should be rinsed immediately with deionized water (corresponding to a water-soluble alkaline developer). For photoresists that use organic solvents as developers, the corresponding fixer is usually selected to rinse the remaining developer. To prevent residual developer from continuing to corrode the photoresist. After development, a very thin glue layer usually remains on the wafer surface. This glue residue phenomenon is especially obvious when the aspect ratio of the exposed pattern is high. Because the pattern is very deep, it is difficult for the developer to fully penetrate the bottom of the pattern. development. Although this layer of residual glue is only a few nanometers thick, it has a great impact on subsequent pattern transfer, so the residual glue needs to be removed. Then the pattern transfer is performed. The purpose of photolithography is to obtain the pattern. Then the pattern needs to be transferred to the substrate through some processes. The photoresist itself only acts as a mask, that is, it protects the wafer so that it can only be exposed after development. Only the parts can be further processed. There are many ways to transfer patterns, such as dry etching, wet etching, lift-off, implantation, L IGA, etc. After the pattern is transferred, the photoresist is no longer needed, so it needs to be removed cleanly. There are usually two methods of removing the resist: wet and dry. The wet method uses organic solvents or solutions that are corrosive to the photoresist to dissolve or corrode the photoresist to achieve the purpose of removing the glue. The dry method uses oxygen plasma to ashes the photoresist, thereby removing the photoresist. Achieve the purpose of removing glue.

With the development of technology, people's requirements for the etching width are getting smaller and smaller, so the width of the development is also required to shrink. However, due to the need to protect the etching, the thickness of the photoresist cannot be reduced accordingly. Therefore, as the aspect ratio increases, the photoresist pattern will have a greater risk of collapse during the development process and the cleaning process after development. Among them, the collapse during the cleaning process after development is mainly caused by the high surface tension of the deionized water in the cleaning solution. Therefore, in order to achieve reduction in feature size and prevent pattern collapse, a surfactant for developing cleaning solutions with smaller surface tension and smaller contact angle is urgently needed.

Contents of the invention

The invention provides a method for preparing a nonionic fluorine-containing surfactant. The nonionic fluorine-containing surfactant prepared by the method has lower surface tension and smaller contact angle. It will not pull the photoresist pattern and cause the group to collapse, thus effectively ensuring the quality of photolithography.

The technical solution adopted by the present invention to solve the above technical problems is: a preparation method of non-ionic fluorine-containing surfactant, including:

S100: Mix the non-fluorine ingredients with water, and then stir at a speed of 500r/min-800r/min for 15min-40min to obtain the first mixture;

S200: Add organic alkali material dropwise to the first mixture at a speed of 5mL/min-8mL/min, and continuously stir the first mixture at a speed of 300r/min-400r/min to obtain a second mixture;

S300: Mix the fluorine-containing component material with the second mixture, and then stir it at a speed of 2000r/min-2500r/min for 30min-50min to obtain a non-ionic fluorine-containing surfactant.

Further, the stirring temperature in S100 is controlled at 40°C-55°C, the dropping temperature in S200 is controlled at 35°C-45°C, and the stirring temperature in S500 is controlled at 45°C-50°C.

Further, the non-fluorine ingredients are selected from the group consisting of small molecule hyaluronic acid, sodium dodecyl benzene sulfonate, sodium tetradecyl sulfate, sodium dibutyl naphthalene sulfonate, sodium dialkyl succinate sulfonate, At least one of castor oil polyoxyethylene ether and alkylphenol polyoxyethylene ether sodium sulfate.

Further, the non-fluorine component material includes small molecule hyaluronic acid and sodium dodecylbenzene sulfonate in a mass ratio of (0.1-0.5): (30-40).

Further, in S100, the non-fluorine component material is mixed with water in a mass ratio of (0.1-0.13): (45-55).

Further, the fluorine-containing component material is selected from perfluorobutanesulfonamide, perfluorohexanesulfonamide, perfluorooctanesulfonamide, perfluorooctyl quaternary ammonium iodide, perfluoro(2-methyl-3-oxa) Ammonium hexanoate, ammonium perfluoro(2-methyl-3-oxahexanoate), N-ethyl perfluorooctane sulfonamide acetic acid, N-methyl perfluorooctane sulfonamide acetic acid, N-ethyl At least one of perfluorooctane sulfonamide ethanol and perfluorobutane sulfonamide ethanol.

Further, the fluorine-containing component material includes perfluorooctane sulfonamide, perfluorooctyl quaternary ammonium iodide, N- Ethyl perfluorooctane sulfonamide ethanol.

Further, the mass ratio of the fluorine-containing component material and the non-fluorine component material is (1.5-3):1.

Further, the organic base material is selected from triethylamine, triethylenediamine, tetramethylethylenediamine, pyridine, 4-N,N-dimethylpyridine, N-ethylpiperidine, tetramethylguanidine, 1 ,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, N,N-diisopropylethyl At least one of the amines.

Further, the mass ratio of the organic alkali material and the non-fluorine component material is (4-7):1.

The present application also provides an application of a nonionic fluorine-containing surfactant, and the nonionic fluorine-containing surfactant prepared by the above method is applied to a cleaning agent after photolithography development.

Compared with the prior art, the advantages of the present invention are:

(1) In the present invention, the non-fluorine component and water are first mixed, then the organic base is added, and then the fluorine-containing component is added, which can effectively promote the uniform mixing of each component, and at the same time, the fluorine-containing component and the second mixing After the materials are mixed, high-speed stirring can promote the uniform dispersion of each component, avoid the occurrence of uneven components and agglomeration, and effectively reduce the residue of components through uniform dispersion; in the present invention, the mixing temperature is also controlled. It can effectively promote the dispersion of ingredients and avoid problems such as agglomeration of ingredients caused by the addition of hyaluronic acid;

(2) Small molecule hyaluronic acid and sodium dodecyl benzene sulfonate are selected as the non-fluorine components in the present invention. By adding a small amount of small molecule hyaluronic acid, the tension in the surfactant can be effectively adjusted. At the same time, hyaluronic acid It can also reduce the residue of surfactant ingredients;

(3) The fluorine-containing components in the present invention are perfluorooctane sulfonamide, perfluorooctyl quaternary ammonium iodide, and N-ethyl perfluorooctane sulfonamide ethanol. This ratio can effectively reduce cleaning costs. The effect of agent tension and contact angle, while the overall content is relatively balanced, will not damage the structure of the photoresist.

Detailed ways

In order to make the above objects, features and advantages of the present invention more obvious and understandable, specific embodiments of the present invention are described in detail below.

Example 1:

This embodiment provides a method for preparing a nonionic fluorine-containing surfactant, including:

S100: Mix small molecule hyaluronic acid and sodium dodecylbenzene sulfonate in a mass ratio of 0.2:35 to obtain a non-fluorine component, and then mix the non-fluorine component in a mass ratio of 0.11:50 with Mix with water, and then stir at 650r/min for 25min at 45°C to obtain the first mixture;

S200: Add N-ethylpiperidine dropwise to the first mixture at a speed of 5.5mL/min at a temperature of 40°C, and continuously stir the first mixture at a speed of 320r/min to control the first mixture. The mass ratio of N-ethylpiperidine and N-ethylpiperidine is 50.11:0.55, and a second mixture is obtained;

S300: Mix a fluorine-containing component with a mass ratio of 0.28:50.66 and the second mixture. The fluorine-containing component contains perfluorooctane sulfonamide and perfluorooctane in a mass ratio of 1.4:0.6:0.24. quaternary ammonium iodide and N-ethyl perfluorooctane sulfonamide ethanol, and then stirred at a speed of 2300 r/min for 40 minutes at a temperature of 48°C to obtain a nonionic fluorine-containing surfactant.

Example 2:

This embodiment provides a method for preparing a nonionic fluorine-containing surfactant, including:

S100: Mix sodium dodecylbenzene sulfonate and water in a mass ratio of 0.11:50, and then stir at a speed of 650r/min for 25min at 45°C to obtain the first mixture;

S200: Add N-ethylpiperidine dropwise to the first mixture at a speed of 5.5mL/min at a temperature of 40°C, and continuously stir the first mixture at a speed of 320r/min to control the first mixture. The mass ratio of N-ethylpiperidine and N-ethylpiperidine is 50.11:0.55, and a second mixture is obtained;

S300: Mix a fluorine-containing component with a mass ratio of 0.28:50.66 and the second mixture. The fluorine-containing component contains perfluorooctane sulfonamide and perfluorooctane in a mass ratio of 1.4:0.6:0.24. quaternary ammonium iodide and N-ethyl perfluorooctane sulfonamide ethanol, and then stirred at a speed of 2300 r/min for 40 minutes at a temperature of 48°C to obtain a nonionic fluorine-containing surfactant.

Embodiment three:

This embodiment provides a method for preparing a nonionic fluorine-containing surfactant, including:

S100: Mix sodium dialkyl succinate sulfonate and sodium dodecyl benzene sulfonate in a mass ratio of 0.2:35 to obtain a non-fluorine component material, and then mix Mix the non-fluorine component with water, and then stir at 650r/min for 25 minutes at 45°C to obtain the first mixture;

S200: Add N-ethylpiperidine dropwise to the first mixture at a speed of 5.5mL/min at a temperature of 40°C, and continuously stir the first mixture at a speed of 320r/min to control the first mixture. The mass ratio of N-ethylpiperidine and N-ethylpiperidine is 50.11:0.55, and a second mixture is obtained;

S300: Mix a fluorine-containing component with a mass ratio of 0.28:50.66 and the second mixture. The fluorine-containing component contains perfluorooctane sulfonamide and perfluorooctane in a mass ratio of 1.4:0.6:0.24. quaternary ammonium iodide and N-ethyl perfluorooctane sulfonamide ethanol, and then stirred at a speed of 2300 r/min for 40 minutes at a temperature of 48°C to obtain a nonionic fluorine-containing surfactant.

Embodiment 4:

This embodiment provides a method for preparing a nonionic fluorine-containing surfactant, including:

S100: Mix small molecule hyaluronic acid and sodium dodecylbenzene sulfonate in a mass ratio of 0.2:35 to obtain a non-fluorine component, and then mix the non-fluorine component in a mass ratio of 0.11:50 with Mix with water, and then stir at 650r/min for 25min at 45°C to obtain the first mixture;

S200: 1,8-diazabicyclo[5.4.0]undec-7-ene was added dropwise to the first mixture at a speed of 5.5mL/min at a temperature of 40°C, and the speed was 320r/min. The first mixture is continuously stirred at a speed, and the mass ratio of the first mixture and 1,8-diazabicyclo[5.4.0]undec-7-ene is controlled to 50.11:0.55 to obtain the second mixture. ;

S300: Mix a fluorine-containing component with a mass ratio of 0.28:50.66 and the second mixture. The fluorine-containing component contains perfluorooctane sulfonamide and perfluorooctane in a mass ratio of 1.4:0.6:0.24. quaternary ammonium iodide and N-ethyl perfluorooctane sulfonamide ethanol, and then stirred at a speed of 2300 r/min for 40 minutes at a temperature of 48°C to obtain a nonionic fluorine-containing surfactant.

Embodiment five:

This embodiment provides a method for preparing a nonionic fluorine-containing surfactant, including:

S100: Mix small molecule hyaluronic acid and sodium dodecylbenzene sulfonate in a mass ratio of 0.2:35 to obtain a non-fluorine component, and then mix the non-fluorine component in a mass ratio of 0.11:50 with Mix with water, and then stir at 650r/min for 25min at 45°C to obtain the first mixture;

S200: Add N,N-diisopropylethylamine dropwise to the first mixture at a speed of 5.5mL/min at a temperature of 40°C, and continuously stir the first mixture at a speed of 320r/min. Control The mass ratio of the first mixture and N,N-diisopropylethylamine is 50.11:0.55, and the second mixture is obtained;

S300: Mix a fluorine-containing component with a mass ratio of 0.28:50.66 and the second mixture. The fluorine-containing component contains perfluorooctane sulfonamide and perfluorooctane in a mass ratio of 1.4:0.6:0.24. quaternary ammonium iodide and N-ethyl perfluorooctane sulfonamide ethanol, and then stirred at a speed of 2300 r/min for 40 minutes at a temperature of 48°C to obtain a nonionic fluorine-containing surfactant.

Embodiment 6:

This embodiment provides a method for preparing a nonionic fluorine-containing surfactant, including:

S100: Mix small molecule hyaluronic acid and sodium dodecylbenzene sulfonate in a mass ratio of 0.2:35 to obtain a non-fluorine component, and then mix the non-fluorine component in a mass ratio of 0.11:50 with Mix with water, and then stir at 650r/min for 25min at 45°C to obtain the first mixture;

S200: Add N-ethylpiperidine dropwise to the first mixture at a speed of 5.5mL/min at a temperature of 40°C, and continuously stir the first mixture at a speed of 320r/min to control the first mixture. The mass ratio of N-ethylpiperidine and N-ethylpiperidine is 50.11:0.55, and a second mixture is obtained;

S300: Mix perfluorooctane sulfonamide with a mass ratio of 0.28:50.66 and the second mixture, and then stir at a speed of 2300 r/min for 40 minutes at a temperature of 48°C to obtain non-ionic fluorinated surface activity. agent.

Embodiment 7:

This embodiment provides a method for preparing a nonionic fluorine-containing surfactant, including:

S100: Mix small molecule hyaluronic acid and sodium dodecylbenzene sulfonate in a mass ratio of 0.2:35 to obtain a non-fluorine component, and then mix the non-fluorine component in a mass ratio of 0.11:50 with Mix with water, and then stir at 650r/min for 25min at 45°C to obtain the first mixture;

S200: Add N-ethylpiperidine dropwise to the first mixture at a speed of 5.5mL/min at a temperature of 40°C, and continuously stir the first mixture at a speed of 320r/min to control the first mixture. The mass ratio of N-ethylpiperidine and N-ethylpiperidine is 50.11:0.55, and a second mixture is obtained;

S300: Mix perfluorooctyl quaternary ammonium iodide with a mass ratio of 0.28:50.66 and the second mixture, and then stir at a speed of 2300 r/min for 40 minutes at a temperature of 48°C to obtain non-ionic fluorine-containing Surfactant.

Embodiment 8:

This embodiment provides a method for preparing a nonionic fluorine-containing surfactant, including:

S100: Mix small molecule hyaluronic acid and sodium dodecylbenzene sulfonate in a mass ratio of 0.2:35 to obtain a non-fluorine component, and then mix the non-fluorine component in a mass ratio of 0.11:50 with Mix with water, and then stir at 650r/min for 25min at 45°C to obtain the first mixture;

S200: Add N-ethylpiperidine dropwise to the first mixture at a speed of 5.5mL/min at a temperature of 40°C, and continuously stir the first mixture at a speed of 320r/min to control the first mixture. The mass ratio of N-ethylpiperidine and N-ethylpiperidine is 50.11:0.55, and a second mixture is obtained;

S300: Mix N-ethyl perfluorooctane sulfonamide ethanol with a mass ratio of 0.28:50.66 and the second mixture, and then stir at a speed of 2300 r/min for 40 minutes at a temperature of 48°C to obtain a non-ionic Fluorinated surfactants.

Embodiment nine:

This embodiment provides a method for preparing a nonionic fluorine-containing surfactant, including:

S100: Mix small molecule hyaluronic acid and sodium dodecylbenzene sulfonate in a mass ratio of 0.2:35 to obtain a non-fluorine component, and then mix the non-fluorine component in a mass ratio of 0.11:50 with Mix with water, and then stir at 650r/min for 25min at 45°C to obtain the first mixture;

S200: Add N-ethylpiperidine dropwise to the first mixture at a speed of 5.5mL/min at a temperature of 40°C, and continuously stir the first mixture at a speed of 320r/min to control the first mixture. The mass ratio of N-ethylpiperidine and N-ethylpiperidine is 50.11:0.55, and a second mixture is obtained;

S300: Mix ammonium perfluoro(2-methyl-3-oxacaproate) with a mass ratio of 0.28:50.66 and the second mixture, and then stir at a speed of 2300r/min for 40min at a temperature of 48°C. , obtaining nonionic fluorine-containing surfactants.

Performance Testing

Mix the nonionic fluorinated surfactant prepared in Examples 1 to 9 with deionized water, and control the mass ratio of the nonionic fluorinated surfactant to deionized water to 1:4 to obtain detergent. Then use a cleaning agent to clean the substrate after photolithography development, observe the collapse of the pattern, and detect the tension and contact angle of the pattern to the cleaning agent. The test results are shown in Table 1.

Table 1 Pattern test results

It can be seen from the test results in Table 1 that the surfactant prepared through the formula of Example 1 can better prevent the collapse of the pattern during the cleaning process.

Although the present invention is disclosed as above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be subject to the scope defined by the claims.

Claims (10)

1. A method for preparing a non-ionic fluorine-containing surfactant, which is characterized by comprising: S100: Mix the non-fluorine ingredients with water, and then stir at a speed of 500r/min-800r/min for 15min-40min to obtain the first mixture; S200: Add organic alkali material dropwise to the first mixture at a speed of 5mL/min-8mL/min, and continuously stir the first mixture at a speed of 300r/min-400r/min to obtain a second mixture. material; S300: Mix the fluorine-containing component material with the second mixture, and then stir at a speed of 2000r/min-2500r/min for 30min-50min to obtain the non-ionic fluorine-containing surfactant. 2. The preparation method according to claim 1, wherein the non-fluorine component is selected from the group consisting of small molecule hyaluronic acid, sodium dodecylbenzene sulfonate, sodium tetradecyl sulfate, and dibutylnaphthalene. At least one of sodium sulfonate, sodium dialkyl succinate sulfonate, castor oil polyoxyethylene ether, and sodium alkylphenol polyoxyethylene ether sulfate. 3. The preparation method according to claim 2, wherein the non-fluorine component material includes small molecule hyaluronic acid and dodecyl in a mass ratio of (0.1-0.5): (30-40) Sodium benzenesulfonate. 4. The preparation method according to claim 3, characterized in that, in S100, the non-fluorine component material is mixed with water in a mass ratio of (0.1-0.13): (45-55). 5. The preparation method according to claim 1, wherein the fluorine-containing component material is selected from the group consisting of perfluorobutanesulfonamide, perfluorohexanesulfonamide, perfluorooctanesulfonamide, and perfluorooctyl quaternary ammonium. Iodide, ammonium perfluoro(2-methyl-3-oxahexanoate), ammonium perfluoro(2-methyl-3-oxahexanoate), N-ethyl perfluorooctane sulfonamide acetic acid, N -At least one of methyl perfluorooctane sulfonamide acetic acid, N-ethyl perfluorooctane sulfonamide ethanol, and perfluorobutane sulfonamide ethanol. 6. The preparation method according to claim 5, wherein the fluorine-containing component material includes perfluorooctine in a mass ratio of (1-1.5): (0.5-0.8): (0.1-0.3) Sulfonamide, perfluorooctyl quaternary ammonium iodide, N-ethyl perfluorooctane sulfonamide ethanol. 7. The preparation method according to claim 6, characterized in that the mass ratio of the fluorine-containing component material and the non-fluorine component material is (1.5-3):1. 8. The preparation method as claimed in claim 1, characterized in that the organic alkali material is selected from the group consisting of triethylamine, triethylenediamine, tetramethylethylenediamine, pyridine, 4-N,N-dimethyl Pyridine, N-ethylpiperidine, tetramethylguanidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazabicyclo[4.4.0] At least one of dec-5-ene and N,N-diisopropylethylamine. 9. The preparation method according to claim 8, characterized in that the mass ratio of the organic alkali material and the non-fluorine component material is (4-7):1. 10. The application of a non-ionic fluorine-containing surfactant, characterized in that the non-ionic fluorine-containing surfactant prepared by the preparation method according to any one of claims 1-9 is used in photolithography in the cleaning solution after development.