Dustproof, anti-pollution and anti-fingerprint functional chip and preparation method thereof

Abstract

The invention discloses a dustproof, anti-pollution and anti-fingerprint functional chip and a preparation method thereof. The preparation method comprises the following steps: 1) preparing a fluorosilicone polymer from perfluoropolyether alcohol and a silane monomer; 2) preparing a diluent from a fluorosilicone polymer, and soaking a carrier to be etched in the diluent to obtain a fluorosilicone modified low surface energy carrier; 3) etching a nano structure on the low surface energy carrier to obtain a functionalized chip; the structural formula of the perfluoropolyether alcohol is as follows: # imgabs0 # n = 10-20; the silane monomer is isocyanate alkyl trialkoxy silane, the structural formula is OCN (CH2) mSi (OR) 3, m is equal to 1-5, and R is selected from at least one of methyl, ethyl and propyl. The fluorosilicone polymer film is constructed on the chip substrate, so that the purposes of inhibiting microparticle adsorption and aggregation, resisting pollution and fingerprints and being easy to clean are achieved, the hydrophobic, oleophobic, dustproof and anti-pollution effects are achieved, the chip can be effectively prevented from being polluted, and the reliability and stability of the chip are ensured.

Description

Technical Field

[0001] The present invention belongs to the technical field of chip preparation, and more particularly, relates to a functionalized chip with dust and stain resistance, fingerprint resistance and a preparation method thereof. Background Art

[0002] Biochip technology integrates discontinuous analysis processes in the field of life sciences on the chip surface according to the principle of specific intermolecular interactions through microscale technology, and can be used in many fields such as disease diagnosis and treatment, drug research and development, forensic identification, food safety, and health supervision to achieve accurate, rapid, and large-information detection. However, due to the large number of microparticles and organic solvent vapors present in the air, they will naturally settle and adhere to the surfaces of various objects, causing harm to production work such as fine processing, food and pharmaceutical manufacturing. To ensure the reliability and stability of the chip, chip production often needs to be carried out in a clean room, which brings many inconveniences to the production process. Currently, the construction of dust and stain resistant surfaces has been developed in many fields such as dust-proof glass, architectural coatings, and instrument surface cleaning. Therefore, how to prepare a chip with dust and stain resistance, fingerprint resistance, reliability, and stability has become an urgent problem to be solved. Summary of the Invention

[0003] To solve the above problems, the present invention provides a functionalized chip with dust and stain resistance, fingerprint resistance and a preparation method thereof. By constructing a fluorosilicon polymer film on the chip substrate, the purposes of inhibiting microparticle adsorption, aggregation, stain and fingerprint resistance, and easy cleaning are achieved, and the functions of hydrophobicity, oleophobicity, dust and stain resistance are played, which can effectively prevent the chip from being contaminated, thereby ensuring the reliability and stability of the chip.

[0004] To achieve the above object, according to one aspect of the present invention, there is provided a preparation method of a functionalized chip with dust and stain resistance, fingerprint resistance, including the following steps:

[0005] 1) Prepare a fluorosilicon polymer using perfluoropolyether alcohol and a silane monomer;

[0006] 2) Prepare the fluorosilicon polymer into a dilution, and soak the carrier to be etched in the dilution to obtain a fluorosilicon-modified low surface energy carrier;

[0007] 3) Etch and modify nanostructures on the low surface energy carrier to obtain a functionalized chip with dust and stain resistance, fingerprint resistance;

[0008] Among them, the structural formula of the perfluoropolyether alcohol is as follows,

[0009] n = 10 - 20;

[0010] Preferably, the silane monomer is alkyl isocyanate trialkoxysilane, and the structural formula is OCN(CH2) mSi(OR)3, where m = 1 - 5 and R is selected from at least one of methyl, ethyl, and propyl.

[0011] In one embodiment of the present invention, the step of preparing the fluorosilicon polymer in step 1) includes:

[0012] Under the protection of nitrogen environment, dissolve the perfluoropolyether alcohol in a perfluorinated solvent, add the silane monomer and the initiator, heat and stir. After the reaction is completed, remove the solvent by vacuum distillation to obtain a concentrated solution, and dry it under vacuum at room temperature to obtain the fluorosilicon polymer.

[0013] In one embodiment of the present invention, the molar ratio of the perfluoropolyether alcohol to the silane monomer is 1:(1 - 5).

[0014] Preferably, the mass ratio of the perfluorinated solvent to the perfluoropolyether alcohol is (0.5 - 3):1, preferably (1 - 2):1.

[0015] In one embodiment of the present invention, the amount of the initiator used is 0.5 - 2.0% of the molar amount of the perfluoropolyether alcohol. For example, 0.5%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%.

[0016] In one embodiment of the present invention, the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, and diisopropyl peroxydicarbonate; more preferably azobisisobutyronitrile accounting for 1% of the molar amount of the perfluoropolyether alcohol.

[0017] Preferably, the perfluorinated solvent is selected from one or more of perfluorohexane, perfluorocyclohexane, perfluoroalkyl methyl ether, and perfluoroalkyl ethyl ether.

[0018] In one embodiment of the present invention, heat and stir at 60 - 80 °C for 5 - 15 hours for the reaction; wash the concentrated solution with hexane and dry it under vacuum at room temperature for 10 - 24 h;

[0019] In one embodiment of the present invention, the fluorosilicon polymer in step 2) is diluted with a perfluorinated solvent to a solution with a mass fraction of 0.1 - 1%.

[0020] In one embodiment of the present invention, the carrier is a glass slide or a silicon wafer; before immersing the carrier to be etched in the diluted solution in step 2), it further includes a step of pretreating it to remove surface oil stains;

[0021] Preferably, the pretreatment step includes immersing the carrier in a piranha solution, then ultrasonically cleaning it with anhydrous ethanol and deionized water, and drying it with nitrogen;

[0022] In one embodiment of the present invention, in step 3), a nanostructure is modified on the surface of the glass sheet by laser etching, and the laser parameters are adjusted to a wavelength of 800 nm, a frequency of 1-20 kHz, and a pulse width of 1-200 fs;

[0023] For example, the laser wavelength is 800 nm, the pulse width is 15 fs, and the frequency is 20 kHz.

[0024] In one embodiment of the present invention, the carrier modified with the nanostructure is immersed in an alcoholic solution of silane for 2-4 h, ultrasonically cleaned with absolute ethanol and deionized water, and then placed in an oven for heating and drying;

[0025] In one embodiment of the present invention, the silane is selected from one or more of N-(3-triethoxysilylpropyl)-4-hydroxybutyramide silane, 3-aminopropyltrimethoxysilane, (3-aminopropyl)triethoxysilane, and 2-(3,4

[0026] -epoxycyclohexyl)ethyltrimethoxysilane;

[0027] In one embodiment of the present invention, the volume ratio of the silane to the alcohol solvent is 1:(30-60);

[0028] In one embodiment of the present invention, it is placed in an oven at 100-120 °C for heating and drying.

[0029] According to another aspect of the present invention, there is also provided a functionalized chip with dust-proof, anti-fouling, and fingerprint-proof functions, which is prepared by the method of the above-mentioned functionalized chip with dust-proof, anti-fouling, and fingerprint-proof functions.

[0030] Advantages of the present invention:

[0031] 1) The present invention uses perfluoropolyether alcohol and silane monomers to prepare a fluorosilicon polymer. The carrier to be etched is immersed in a dilution of the fluorosilicon polymer, so that the fluorosilicon polymer is coated on the surface of the carrier, forming a low surface energy substrate surface, and obtaining a low surface energy carrier modified with fluorosilicon. This provides an extremely low surface tension for the treated surface and is a good method for constructing a dust-proof surface. After subsequent etching, a functionalized chip with dust-proof, anti-fouling, and fingerprint-proof functions is obtained.

[0032] 2) The present invention utilizes the extremely low surface energy and good hydrophobic and oleophobic properties of organofluorine, introduces a fluorine-containing compound into an organosilicon material, and the obtained fluorosilicon compound has characteristics such as low surface energy, high and low temperature resistance, oil resistance, solvent resistance, and corrosion resistance, and can be used for the preparation of superhydrophobic and oleophobic surfaces. By constructing a fluorosilicon polymer film on the chip substrate, the purposes of inhibiting the adsorption and aggregation of microparticles, anti-fouling and fingerprint-proof, and easy cleaning are achieved, playing the roles of hydrophobic and oleophobic, dust-proof and anti-fouling, and can effectively prevent the chip from being contaminated, thereby ensuring the reliability and stability of the chip. Description of the Drawings

[0033] Figure 1 It is a schematic diagram for comparing the anti-dust accumulation effect in Example 1.

[0034] Figure 2 It is a schematic diagram for comparing the anti-oil stain effect in Example 1. Detailed implementation manners

[0035] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be emphasized that the specific embodiments described herein are only for better explaining the present invention, which are partial embodiments of the present invention, rather than all embodiments, so they are not used to limit the present invention. In addition, the technical features involved in the embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0036] Example 1

[0037] Under nitrogen protection, 10 g of perfluoropolyether alcohol (n = 10) was added to a 50 mL three-necked flask and dissolved in 20 mL of perfluorohexane.

[0038] 1 equivalent of silane monomer alkyltrialkoxysilane isocyanate, with the structural formula OCN(CH2) m Si(OR)3 (R = Me, m = 2), 1% azobisisobutyronitrile as an initiator (molar ratio relative to perfluoropolyether alcohol is 1%), and the reaction was carried out under heating and stirring at 70 °C for 5 h. After the reaction, the solvent was removed by distillation under reduced pressure to obtain a concentrated solution, which was washed with hexane and then vacuum dried at room temperature for 12 h to obtain fluorosilicon polymer I. The fluorosilicon polymer I was diluted with perfluorohexane to a 0.5% dilution.

[0039] The glass slides were soaked in piranha solution for 20 min, ultrasonically cleaned with absolute ethanol 3 times, 1 min each time, then rinsed with deionized water and dried with nitrogen. The slides were soaked in the prepared fluorosilicon polymer dilution for 5 min, taken out and air-dried naturally to obtain fluorosilicon-modified low surface energy slides. The surface of the modified slides was laser-etched to obtain a nanostructure with a wavelength of 800 nm, a pulse width of 15 fs, and a frequency of 20 kHz.

[0040] The etched fluorosilicon-modified low surface energy slides were soaked in an ethanol solution (1:50) of N-(3-triethoxysilylpropyl)-4-hydroxybutyramide silane for 2 h, and ultrasonically cleaned with absolute ethanol and deionized water 3 times, 1 min each time. The slides were placed in an oven at 110 °C and heated and dried for 2 h to obtain a stain- and fingerprint-resistant substrate, and the substrate surface had a functionalized pattern.

[0041] Fingerprints are stained on the surface of the glass slide. After gently wiping with a lint-free cloth, all the stains are removed. The water contact angle of the glass slide is tested using a contact angle measuring instrument, and the hydrophobic effect is 131°.

[0042] The glass slides before and after treatment are taken and placed in the natural environment for 30 minutes, and then observed under a microscope. The results are compared as Figure 1 shown. It can be seen that the treated glass slide surface has a good effect of inhibiting dust accumulation.

[0043] Figure 2 It is a schematic diagram for comparing the anti-oil pollution effect. The glass slides before and after treatment are taken, and commercial ink pens are used to draw lines on the surface. After treatment, the ink on the glass slide surface shrinks into dots. It can be seen that compared with before treatment, it has a good anti-oil pollution effect.

[0044] Example 2

[0045] Under nitrogen protection, 10 g of perfluoropolyether alcohol (n = 15) is added to a 50 mL three-necked flask and dissolved in 20 mL of perfluoroalkyl methyl ether. 1 equivalent of silane monomer alkyl isocyanatotrialkoxysilane with the structural formula OCN(CH2) m Si(OR)3 (R = Me, m = 2) and 1% azobisisobutyronitrile as an initiator (molar ratio relative to perfluoropolyether alcohol is 1%) are added, and the reaction is carried out under heating and stirring at 80 °C for 5 h. After the reaction is completed, the solvent is removed by distillation under reduced pressure. The concentrated solution is washed with hexane, and then vacuum dried at room temperature for 12 h to obtain fluorosilicon polymer II. The polymer II is diluted with perfluoroalkyl methyl ether to a 0.1% dilution.

[0046] The glass slide is immersed in piranha solution for 20 minutes, ultrasonically cleaned with absolute ethanol for 1 min * 3 times, then rinsed thoroughly with deionized water, and dried with nitrogen. The glass slide is immersed in the fluorosilicon polymer dilution for 5 minutes and dried naturally. A fluorosilicon-modified low surface energy glass slide is obtained. The surface of the laser-etched modified glass slide is nanostructured with a wavelength of 800 nm, a pulse width of 200 fs, and a frequency of 20 kHz.

[0047] The etched fluorosilicon-modified low surface energy glass slide is immersed in an ethanol solution (1:50) of N-(3-triethoxysilylpropyl-4-hydroxybutyramide) for 2 h, and ultrasonically cleaned with absolute ethanol and deionized water for 1 min * 3 times. The glass slide is placed in an oven at 110 °C and heated and dried for 2 h to obtain a glass slide with an anti-fouling and anti-fingerprint substrate and a functionalized pattern on the substrate surface.

[0048] The obtained glass slide is tested. Commercial ink pens are used to draw lines on the surface, and the ink shrinks into dots. Fingerprints are stained on the surface of the glass slide. After gently wiping with a lint-free cloth, all the stains are removed. The water contact angle of the glass slide is tested using a contact angle measuring instrument, and the hydrophobic effect is 136°.

[0049] Example 3

[0050] Under nitrogen protection, 10 g of perfluoropolyether alcohol (n = 15) was added to a 50 mL three-necked flask and dissolved in 20 mL of perfluoroalkyl methyl ether. 2 equivalents of silane monomer OCN(CH2) m Si(OR)3 (R = Et, m = 2) and 1% azobisisobutyronitrile as an initiator (molar ratio relative to perfluoropolyether alcohol is 1%) were added, and the reaction was carried out under heating and stirring at 60 °C for 15 h. After the reaction, the solvent was removed by distillation under reduced pressure, the concentrated solution was washed with hexane, and then vacuum dried at room temperature for 12 h to obtain fluorosilicon polymer II. The fluorosilicon polymer II was diluted with perfluoroalkyl methyl ether to a 1.0% dilution.

[0051] The glass slide was immersed in piranha solution for 20 min, ultrasonically cleaned with absolute ethanol for 1 min * 3 times, then rinsed with deionized water and dried with nitrogen. The slide was immersed in the fluorosilicon polymer dilution for 5 min and air-dried naturally to obtain a fluorosilicon-modified low-surface-energy slide.

[0052] The surface of the modified slide was laser-etched to obtain nanostructures with a wavelength of 800 nm, a pulse width of 15 fs, and a frequency of 30 kHz.

[0053] The etched fluorosilicon-modified low-surface-energy slide was immersed in an ethanol solution (1:40) of (3-aminopropyl)triethoxysilane for 2 h, ultrasonically cleaned with absolute ethanol and deionized water for 1 min * 3 times. The slide was placed in an oven at 110 °C and heated and dried for 2 h to obtain a stain- and fingerprint-resistant substrate with a functionalized pattern on the substrate surface.

[0054] The obtained slide was tested. A commercially available ink pen was used to draw lines on the surface, and the ink shrank into dots. Fingerprints were stained on the slide surface, and all the stains were removed after gently wiping with a dust-free cloth. The water contact angle of the slide was measured with a contact angle measuring instrument, and a hydrophobic effect of 140° was obtained.

[0055] The above is only the preferred application implementation mode of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the technical principle of the present invention, several improvements and retouches can be made, and these improvements and retouches should also be regarded as the protection scope of the present invention.

Claims

1. A preparation method of a functionalized chip with dust-proof, anti-fouling and fingerprint-proof functions, characterized in that, It includes the following steps: 1) Prepare a fluorosilicon polymer using perfluoropolyether alcohol and a silane monomer; 2) Formulate the fluorosilicon polymer into a dilution solution, and soak the carrier to be etched in the dilution solution to obtain a low surface energy carrier modified with fluorosilicon; 3) Etch and modify nanostructures on the low surface energy carrier to obtain a functionalized chip with dust-proof, anti-fouling, and fingerprint-proof functions; Among them, the structural formula of the perfluoropolyether alcohol is as follows, Preferably, the silane monomer is an alkyl isocyanate trialkoxysilane with the structural formula OCN(CH2)mSi(OR)3, where m = 1 - 5, and R is selected from at least one of methyl, ethyl, and propyl.

2. The preparation method according to claim 1, wherein, The steps for preparing the fluorosilicon polymer in step 1) include: Under the protection of nitrogen environment, dissolve the perfluoropolyether alcohol in a perfluorinated solvent, add the silane monomer and an initiator, heat and stir. After the reaction ends, distill off the solvent under reduced pressure to obtain a concentrated solution, and dry it under vacuum at room temperature to obtain the fluorosilicon polymer.

3. The preparation method according to claim 2, wherein The molar ratio of the perfluoropolyether alcohol to the silane monomer is 1:(1 - 5); Preferably, the mass ratio of the perfluorinated solvent to the perfluoropolyether alcohol is (0.5 - 3):1, preferably (1 - 2):

1.

4. The preparation method according to claim 2, wherein The dosage of the initiator is 0.5 - 2% of the molar amount of the perfluoropolyether alcohol; Preferably, the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, and diisopropyl peroxydicarbonate; more preferably, azobisisobutyronitrile accounting for 1% of the molar amount of the perfluoropolyether alcohol. Preferably, the perfluorinated solvent is selected from one or more of perfluorohexane, perfluorocyclohexane, perfluoroalkyl methyl ether, and perfluoroalkyl ethyl ether.

5. The preparation method according to claim 2, characterized in that, Heat and stir at 60 - 80 °C for 5 - 15 hours for the reaction; wash the concentrated solution with hexane and dry it under vacuum at room temperature for 10 - 24 h.

6. The preparation method according to any one of claims 1 to 5, characterized in that, In step 2), dilute the fluorosilicon polymer with a perfluorinated solvent into a solution with a mass fraction of 0.1 - 1%.

7. The preparation method according to any one of claims 1 to 6, characterized in that, The carrier is a glass sheet or a silicon wafer; Before soaking the carrier to be etched in the dilution solution in step 2), it also includes a step of pre-treating it to remove surface oil stains; Preferably, the pre-treatment step includes soaking the carrier in a piranha solution, then ultrasonically cleaning it with anhydrous ethanol and deionized water, and drying it with nitrogen.

8. The preparation method according to any one of claims 1 to 7, characterized in that, In step 3), use laser etching to modify nanostructures on the surface of the glass sheet, and adjust the laser parameters: wavelength 800 nm, frequency 1 - 20 kHz, pulse width 1 - 200 fs.

9. The preparation method according to claim 1, wherein Soak the carrier modified with nanostructures in an alcohol solution of silane for 2 - 4 h, ultrasonically clean it with anhydrous ethanol and deionized water, and heat and dry it in an oven; The silane is selected from one or more of N-(3-triethoxysilylpropyl)-4-hydroxybutyramide silane, 3-aminopropyltrimethoxysilane, (3-aminopropyl)triethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; Preferably, the volume ratio of the silane to the alcohol solvent is 1:(30 - 60); Preferably, heat and dry it in an oven at 100 - 120 °C.

10. A functional chip with dust-proof, anti-fouling, and fingerprint-proof functions, characterized in that, It is obtained by using the preparation method of the functionalized chip with dust-proof, anti-fouling, and fingerprint-proof functions according to any one of claims 1 to 9.

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