Preparation method and application of nonionic fluorinated surfactant

Abstract

The invention discloses a preparation method and application of a nonionic fluorinated surfactant, and the preparation method includes: S100: mixing non-fluorinated component material with water, and then stirring at a speed of 500r / min-800r / min for 15min-40min to obtain a first mixed material; S200: dripping an organic alkali material at a speed of 5mL / min-8mL / min into the first mixed material, and continuously stirring the first mixed material at a speed of 300r / min-400r / min to obtain a second mixed material; S300: mixing the fluorinated component material with the second mixed material, and then stirring at a speed of 2000r / min-2500r / min for 30min-50min to obtain a nonionic fluorinated surfactant. The nonionic fluorinated surfactant prepared by the method has lower surface tension and smaller contact angle, and will not pull the photoresist pattern to cause the collapse of the group when rinsing, thereby effectively ensuring the quality of photolithography.

Description

Technical Field

[0001] The present invention relates to the technical field of surfactants, and in particular to a preparation method and application of a nonionic fluorine-containing surfactant. Background Art

[0002] In the photolithography process, a series of processes such as coating, exposure, development, and etching are required. Among them, the coating step is applied by spin coating, and the thickness of the coating is adjusted by the rotation speed of the spin coating. After the coating is completed, a pre-baking step will be performed. The pre-baking volatilizes the organic solvent in the photoresist through temperature to solidify the glue on the surface of the wafer. Then the exposure step is performed. The exposure is completed by exposing the mask and the exposure system, such as the step-and-step mask alignment or contact exposure system within the respective spectral working range, or direct laser maskless exposure. After exposure, the development step is performed. During the development process, the formation of the positive photoresist film structure is by dissolving the exposed area, while the negative photoresist development removes the unexposed area. Common development methods include: immersion, spray, and stirring. After the development is completed, the substrate should be immediately rinsed with deionized water (corresponding to the water-soluble alkaline developer). For photoresists using organic solvents as developers, the corresponding fixing solution is usually selected to rinse the residual developer clean to prevent the residual developer from continuing to corrode the photoresist. After development, a very thin layer of colloid usually remains on the surface of the wafer. This residual glue phenomenon is particularly obvious when the depth-to-width ratio of the exposed pattern is high, because the pattern is very deep and it is not easy for the developer to fully develop the bottom of the pattern. Although this layer of residual glue is only a few nanometers thick, it has a great impact on the subsequent pattern transfer, so it is necessary to remove the residual glue. After that, the pattern transfer is carried out. The purpose of photolithography is to obtain the pattern. After that, it is necessary to transfer the pattern to the substrate through some processes. The photoresist itself only plays the role of a mask, that is, to protect the wafer so that only the exposed part after development can be further processed. There are many ways to transfer the pattern, such as dry etching, wet etching, lift-off, injection, LIGA, etc. After the pattern is transferred, the photoresist is no longer needed, so it needs to be removed cleanly. There are usually two methods for removing the glue: wet and dry. The wet method is to use an organic solvent or a solution that has a corrosive effect on the photoresist to dissolve or corrode the photoresist, so as to achieve the purpose of removing the glue. The dry method of removing the glue is to use oxygen plasma to ashed the photoresist, so as to achieve the purpose of removing the glue.

[0003] With the development of technology, people have lower and lower requirements for etching width, so the width of development is required to shrink. However, due to the need to protect 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 cleaning liquid deionized water. Therefore, in order to achieve the reduction of feature size and prevent pattern collapse, a surfactant with a smaller surface tension and a smaller contact angle for the developer cleaning liquid is urgently needed. Summary of the invention

[0004] 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, and will not pull the photoresist pattern to cause the group to collapse during washing, thereby effectively ensuring the quality of photolithography.

[0005] The technical solution adopted by the present invention to solve the above technical problems is: a method for preparing a non-ionic fluorinated surfactant, comprising:

[0006] S100: mixing the non-fluorine component material with water, and then stirring at a speed of 500 r / min-800 r / min for 15 min-40 min to obtain a first mixed material;

[0007] S200: adding an organic alkali material dropwise to the first mixed material at a rate of 5 mL / min-8 mL / min, and continuously stirring the first mixed material at a rate of 300 r / min-400 r / min to obtain a second mixed material;

[0008] S300: mixing the fluorine-containing component material with the second mixed material, and then stirring at a speed of 2000r / min-2500r / min for 30min-50min to obtain a non-ionic fluorine-containing surfactant.

[0009] 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 S300 is controlled at 45°C-50°C.

[0010] Furthermore, the non-fluorine component is selected from at least one of small molecule hyaluronic acid, sodium dodecylbenzene sulfonate, sodium tetradecyl sulfate, sodium dibutylnaphthalene sulfonate, sodium dialkyl succinate sulfonate, castor oil polyoxyethylene ether, and alkylphenol polyoxyethylene ether sodium sulfate.

[0011] Furthermore, 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).

[0012] Furthermore, in S100, the non-fluorine component material is mixed with water in a mass ratio of (0.1-0.13):(45-55).

[0013] Furthermore, the fluorine-containing component is selected from at least one of perfluorobutylsulfonamide, perfluorohexylsulfonamide, perfluorooctanesulfonamide, perfluorooctylquaternary ammonium iodide, perfluoro(2-methyl-3-oxahexanoic acid)ammonium, perfluoro(2-methyl-3-oxahexanoic acid)ammonium, N-ethylperfluorooctanesulfonamideacetic acid, N-methylperfluorooctanesulfonamideacetic acid, N-ethylperfluorooctanesulfonamideethanol, and perfluorobutylsulfonamideethanol.

[0014] Furthermore, the fluorine-containing component material includes perfluorooctane sulfonamide, perfluorooctyl quaternary ammonium iodide, and N-ethylperfluorooctane sulfonamide ethanol in a mass ratio of (1-1.5): (0.5-0.8): (0.1-0.3).

[0015] Furthermore, the mass ratio of the fluorine-containing component to the non-fluorine component is (1.5-3):1.

[0016] Furthermore, the organic alkali material is selected from at least one of 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, and N,N-diisopropylethylamine.

[0017] Furthermore, the mass ratio of the organic alkali material to the non-fluorine component material is (4-7):1.

[0018] 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.

[0019] Compared with the prior art, the advantages of the present invention are:

[0020] (1) In the present invention, the non-fluorine component and water are first mixed, and then the organic base is added, and then the fluorine-containing component is added. This can effectively promote the uniform mixing of the various components. At the same time, the fluorine-containing component and the second mixed material are mixed and stirred at a high speed, which can promote the uniform dispersion of the various components and avoid the occurrence of uneven components and agglomeration. The uniform dispersion can also effectively reduce the residue of the components. In the present invention, the mixing temperature is also controlled, which can effectively promote the dispersion of the components and avoid the problem of component agglomeration caused by the addition of hyaluronic acid.

[0021] (2) The non-fluorine components of the present invention are selected from small molecule hyaluronic acid and sodium dodecylbenzene sulfonate. The addition of a small amount of small molecule hyaluronic acid can effectively adjust the tension in the surfactant, and hyaluronic acid can also reduce the residual surfactant components;

[0022] (3) The fluorine-containing components in the present invention are selected from perfluorooctane sulfonamide, perfluorooctane quaternary ammonium iodide, and N-ethylperfluorooctane sulfonamide ethanol. This ratio can effectively reduce the tension and contact angle of the cleaning agent. At the same time, the overall content is relatively balanced and will not damage the structure of the photoresist. DETAILED DESCRIPTION

[0023] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, specific embodiments of the present invention are described in detail below.

[0024] Embodiment 1:

[0025] This embodiment provides a method for preparing a nonionic fluorinated surfactant, comprising:

[0026] S100: small molecule hyaluronic acid and sodium dodecylbenzene sulfonate in a mass ratio of 0.2:35 are mixed to obtain a non-fluorine component material, and then the non-fluorine component material in a mass ratio of 0.11:50 is mixed with water, and then stirred at a speed of 650 r / min for 25 minutes at 45° C. to obtain a first mixed material;

[0027] S200: N-ethylpiperidine is added dropwise to the first mixture at a rate of 5.5 mL / min at a temperature of 40° C., and the first mixture is continuously stirred at a rate of 320 r / min, and the mass ratio of the first mixture to N-ethylpiperidine is controlled to be 50.11:0.55, to obtain a second mixture;

[0028] S300: Mixing a fluorine-containing component material with a mass ratio of 0.28:50.66 with a second mixed material, wherein the fluorine-containing component material contains perfluorooctane sulfonamide, perfluorooctyl quaternary ammonium iodide, and N-ethylperfluorooctane sulfonamide ethanol with a mass ratio of 1.4:0.6:0.24, and then stirring at a speed of 2300 r / min for 40 minutes at a temperature of 48°C to obtain a non-ionic fluorine-containing surfactant.

[0029] Embodiment 2:

[0030] This embodiment provides a method for preparing a nonionic fluorinated surfactant, comprising:

[0031] S100: mixing sodium dodecylbenzene sulfonate and water in a mass ratio of 0.11:50, and stirring at a speed of 650 r / min for 25 min at 45° C. to obtain a first mixture;

[0032] S200: N-ethylpiperidine is added dropwise to the first mixture at a rate of 5.5 mL / min at a temperature of 40° C., and the first mixture is continuously stirred at a rate of 320 r / min, and the mass ratio of the first mixture to N-ethylpiperidine is controlled to be 50.11:0.55, to obtain a second mixture;

[0033] S300: Mixing a fluorine-containing component material with a mass ratio of 0.28:50.66 with a second mixed material, wherein the fluorine-containing component material contains perfluorooctane sulfonamide, perfluorooctyl quaternary ammonium iodide, and N-ethylperfluorooctane sulfonamide ethanol with a mass ratio of 1.4:0.6:0.24, and then stirring at a speed of 2300 r / min for 40 minutes at a temperature of 48°C to obtain a non-ionic fluorine-containing surfactant.

[0034] Embodiment three:

[0035] This embodiment provides a method for preparing a nonionic fluorinated surfactant, comprising:

[0036] S100: sodium dialkyl succinate sulfonate and sodium dodecylbenzene sulfonate in a mass ratio of 0.2:35 are mixed to obtain a non-fluorine component material, and then the non-fluorine component material in a mass ratio of 0.11:50 is mixed with water, and then stirred at a speed of 650 r / min for 25 minutes at 45° C. to obtain a first mixed material;

[0037] S200: N-ethylpiperidine is added dropwise to the first mixture at a rate of 5.5 mL / min at a temperature of 40° C., and the first mixture is continuously stirred at a rate of 320 r / min, and the mass ratio of the first mixture to N-ethylpiperidine is controlled to be 50.11:0.55, to obtain a second mixture;

[0038] S300: Mixing a fluorine-containing component material with a mass ratio of 0.28:50.66 with a second mixed material, wherein the fluorine-containing component material contains perfluorooctane sulfonamide, perfluorooctyl quaternary ammonium iodide, and N-ethylperfluorooctane sulfonamide ethanol with a mass ratio of 1.4:0.6:0.24, and then stirring at a speed of 2300 r / min for 40 minutes at a temperature of 48°C to obtain a non-ionic fluorine-containing surfactant.

[0039] Embodiment 4:

[0040] This embodiment provides a method for preparing a nonionic fluorinated surfactant, comprising:

[0041] S100: small molecule hyaluronic acid and sodium dodecylbenzene sulfonate in a mass ratio of 0.2:35 are mixed to obtain a non-fluorine component material, and then the non-fluorine component material in a mass ratio of 0.11:50 is mixed with water, and then stirred at a speed of 650 r / min for 25 minutes at 45° C. to obtain a first mixed material;

[0042] S200: adding 1,8-diazabicyclo[5.4.0]undec-7-ene to the first mixture at a rate of 5.5 mL / min at a temperature of 40° C., and continuously stirring the first mixture at a rate of 320 r / min, and controlling the mass ratio of the first mixture to 1,8-diazabicyclo[5.4.0]undec-7-ene to be 50.11:0.55, to obtain a second mixture;

[0043] S300: Mixing a fluorine-containing component material with a mass ratio of 0.28:50.66 with a second mixed material, wherein the fluorine-containing component material contains perfluorooctane sulfonamide, perfluorooctyl quaternary ammonium iodide, and N-ethylperfluorooctane sulfonamide ethanol with a mass ratio of 1.4:0.6:0.24, and then stirring at a speed of 2300 r / min for 40 minutes at a temperature of 48°C to obtain a non-ionic fluorine-containing surfactant.

[0044] Embodiment five:

[0045] This embodiment provides a method for preparing a nonionic fluorinated surfactant, comprising:

[0046] S100: small molecule hyaluronic acid and sodium dodecylbenzene sulfonate in a mass ratio of 0.2:35 are mixed to obtain a non-fluorine component material, and then the non-fluorine component material in a mass ratio of 0.11:50 is mixed with water, and then stirred at a speed of 650 r / min for 25 minutes at 45° C. to obtain a first mixed material;

[0047] S200: N,N-diisopropylethylamine is added dropwise to the first mixture at a rate of 5.5 mL / min at a temperature of 40° C., and the first mixture is continuously stirred at a rate of 320 r / min, and the mass ratio of the first mixture to N,N-diisopropylethylamine is controlled to be 50.11:0.55, to obtain a second mixture;

[0048] S300: Mixing a fluorine-containing component material with a mass ratio of 0.28:50.66 with a second mixed material, wherein the fluorine-containing component material contains perfluorooctane sulfonamide, perfluorooctyl quaternary ammonium iodide, and N-ethylperfluorooctane sulfonamide ethanol with a mass ratio of 1.4:0.6:0.24, and then stirring at a speed of 2300 r / min for 40 minutes at a temperature of 48°C to obtain a non-ionic fluorine-containing surfactant.

[0049] Embodiment six:

[0050] This embodiment provides a method for preparing a nonionic fluorinated surfactant, comprising:

[0051] S100: small molecule hyaluronic acid and sodium dodecylbenzene sulfonate in a mass ratio of 0.2:35 are mixed to obtain a non-fluorine component material, and then the non-fluorine component material in a mass ratio of 0.11:50 is mixed with water, and then stirred at a speed of 650 r / min for 25 minutes at 45° C. to obtain a first mixed material;

[0052] S200: N-ethylpiperidine is added dropwise to the first mixture at a rate of 5.5 mL / min at a temperature of 40° C., and the first mixture is continuously stirred at a rate of 320 r / min, and the mass ratio of the first mixture to N-ethylpiperidine is controlled to be 50.11:0.55, to obtain a second mixture;

[0053] S300: Perfluorooctane sulfonamide and the second mixed material in a mass ratio of 0.28:50.66 are mixed, and then stirred at a speed of 2300 r / min for 40 minutes at a temperature of 48° C. to obtain a non-ionic fluorine-containing surfactant.

[0054] Embodiment seven:

[0055] This embodiment provides a method for preparing a nonionic fluorinated surfactant, comprising:

[0056] S100: small molecule hyaluronic acid and sodium dodecylbenzene sulfonate in a mass ratio of 0.2:35 are mixed to obtain a non-fluorine component material, and then the non-fluorine component material in a mass ratio of 0.11:50 is mixed with water, and then stirred at a speed of 650 r / min for 25 minutes at 45° C. to obtain a first mixed material;

[0057] S200: N-ethylpiperidine is added dropwise to the first mixture at a rate of 5.5 mL / min at a temperature of 40° C., and the first mixture is continuously stirred at a rate of 320 r / min, and the mass ratio of the first mixture to N-ethylpiperidine is controlled to be 50.11:0.55, to obtain a second mixture;

[0058] S300: Perfluorooctyl quaternary ammonium iodide and the second mixed material in a mass ratio of 0.28:50.66 are mixed, and then stirred at a speed of 2300 r / min for 40 minutes at a temperature of 48° C. to obtain a non-ionic fluorine-containing surfactant.

[0059] Embodiment eight:

[0060] This embodiment provides a method for preparing a nonionic fluorinated surfactant, comprising:

[0061] S100: small molecule hyaluronic acid and sodium dodecylbenzene sulfonate in a mass ratio of 0.2:35 are mixed to obtain a non-fluorine component material, and then the non-fluorine component material in a mass ratio of 0.11:50 is mixed with water, and then stirred at a speed of 650 r / min for 25 minutes at 45° C. to obtain a first mixed material;

[0062] S200: N-ethylpiperidine is added dropwise to the first mixture at a rate of 5.5 mL / min at a temperature of 40° C., and the first mixture is continuously stirred at a rate of 320 r / min, and the mass ratio of the first mixture to N-ethylpiperidine is controlled to be 50.11:0.55, to obtain a second mixture;

[0063] S300: N-ethyl perfluorooctane sulfonamide ethanol is mixed with the second mixed material in a mass ratio of 0.28:50.66, and then stirred at a speed of 2300 r / min for 40 minutes at a temperature of 48° C. to obtain a non-ionic fluorine-containing surfactant.

[0064] Embodiment nine:

[0065] This embodiment provides a method for preparing a nonionic fluorinated surfactant, comprising:

[0066] S100: small molecule hyaluronic acid and sodium dodecylbenzene sulfonate in a mass ratio of 0.2:35 are mixed to obtain a non-fluorine component material, and then the non-fluorine component material in a mass ratio of 0.11:50 is mixed with water, and then stirred at a speed of 650 r / min for 25 minutes at 45° C. to obtain a first mixed material;

[0067] S200: N-ethylpiperidine is added dropwise to the first mixture at a rate of 5.5 mL / min at a temperature of 40° C., and the first mixture is continuously stirred at a rate of 320 r / min, and the mass ratio of the first mixture to N-ethylpiperidine is controlled to be 50.11:0.55, to obtain a second mixture;

[0068] S300: Perfluoro(2-methyl-3-oxahexanoic acid)ammonium is mixed with the second mixed material in a mass ratio of 0.28:50.66, and then stirred at a speed of 2300 r / min for 40 minutes at a temperature of 48° C. to obtain a non-ionic fluorine-containing surfactant.

[0069] Performance Testing

[0070] The nonionic fluorinated surfactant prepared in Examples 1 to 9 was mixed with deionized water, and the mass ratio of the nonionic fluorinated surfactant to the deionized water was controlled to be 1:4 to obtain a cleaning agent. The cleaning agent was then used to clean the substrate after photolithography development, the collapse of the pattern was observed, and the tension and contact angle of the pattern to the cleaning agent were tested. The test results are shown in Table 1.

[0071] Table 1 Test results of patterns

[0072]

[0073] It can be seen from the test results in Table 1 that the surfactant prepared by the formula of Example 1 can better avoid the collapse of the pattern during the cleaning process.

[0074] 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 shall be subject to the scope defined by the claims.

Claims

1. A method for preparing a nonionic fluorinated surfactant, characterized in that: include: S100: mixing the non-fluorine component material with water, and then stirring at a speed of 500 r / min-800 r / min for 15 min-40 min to obtain a first mixed material; S200: adding an organic alkali material dropwise to the first mixture at a rate of 5 mL / min-8 mL / min, and continuously stirring the first mixture at a rate of 300 r / min-400 r / min to obtain a second mixture; S300: mixing the fluorine-containing component material with the second mixed material, and then stirring at a speed of 2000r / min-2500r / min for 30min-50min to obtain the non-ionic fluorine-containing surfactant; The non-fluorine component is selected from at least one of small molecule hyaluronic acid, sodium dodecylbenzene sulfonate, sodium tetradecyl sulfate, sodium dibutylnaphthalene sulfonate, sodium dialkyl succinate sulfonate, castor oil polyoxyethylene ether, and alkylphenol polyoxyethylene ether sodium sulfate; The fluorine-containing component is selected from at least one of perfluorobutylsulfonamide, perfluorohexylsulfonamide, perfluorooctylsulfonamide, perfluorooctylquaternary ammonium iodide, perfluoro(2-methyl-3-oxahexanoic acid)ammonium, perfluoro(2-methyl-3-oxahexanoic acid)ammonium, N-ethylperfluorooctanesulfonamideacetic acid, N-methylperfluorooctanesulfonamideacetic acid, N-ethylperfluorooctanesulfonamideethanol, and perfluorobutylsulfonamideethanol; The organic alkali is selected from at least one of 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, and N,N-diisopropylethylamine; 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 S300 is controlled at 45°C-50°C.

2. The preparation method according to claim 1, characterized in that 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).

3. The preparation method according to claim 1, characterized in that: In the S100, the non-fluorine component material is mixed with water in a mass ratio of (0.1-0.13):(45-55).

4. The preparation method according to claim 1, characterized in that: The fluorine-containing component material includes perfluorooctane sulfonamide, perfluorooctyl quaternary ammonium iodide, and N-ethyl perfluorooctane sulfonamide ethanol in a mass ratio of (1-1.5): (0.5-0.8): (0.1-0.3).

5. The preparation method according to claim 1, characterized in that: The mass ratio of the fluorine-containing component to the non-fluorine component is (1.5-3):

1.

6. The preparation method according to claim 1, characterized in that: The mass ratio of the organic alkali material to the non-fluorine component material is (4-7):

1.

7. An application of a nonionic fluorinated surfactant, characterized in that: The nonionic fluorine-containing surfactant prepared by the preparation method according to any one of claims 1 to 6 is applied to a cleaning agent after photolithography development.

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