Super-amphiphobic / super-amphiphilic surface patterned chip, preparation method and liquid drop control method

Abstract

The invention discloses a super-amphiphobic / super-amphiphilic surface patterned chip, a preparation method thereof and a liquid drop control method, and the method comprises the steps: 1) pretreating the surface of an aluminum sheet, and then carrying out ultrasonic cleaning and nitrogen blow-drying; (2) an HCl / HF solution is used for etching the aluminum sheet, ultrasonic cleaning is carried out, and nitrogen blow-drying is carried out; 3) placing the etched aluminum sheet in a silane solution for modification, and taking out the aluminum sheet for vacuum drying; and (4) carrying out patterning treatment on the super-amphiphobic aluminum sheet, destroying a surface hydrophobic layer, forming super-hydrophilicity, and further forming a super-hydrophilic / super-oleophylic dot matrix in a treatment region, thereby obtaining the super-amphiphobic / super-amphiphilic patterned chip. The interior of the prepared patterned chip dot matrix has a super-amphiphilic property, the exterior of the dot matrix has a super-amphiphobic property, the pattern surface can control liquid drops in an amphiphilic patterned area due to the amphiphilic and amphiphobic difference inside and outside the dot matrix, diffusion of the liquid drops to the surrounding amphiphobic area is limited, liquid flowing and diffusion are effectively inhibited, accurate control over the liquid drops is achieved, and the accuracy of the liquid drops is improved. And cross contamination is avoided.

Description

Technical Field

[0001] The present invention belongs to the technical field of chip preparation, and in particular, relates to a super-amphiphobic / super-amphiphilic surface patterned chip, a preparation method thereof, and a droplet control method. Background Art

[0002] With the rapid development of life sciences, DNA synthesis has important value in many fields such as medical health, biopharmaceuticals, agricultural production, and information storage. Rapid, accurate, and efficient synthesis of DNA is of great significance. The development of DNA synthesis has gone through the first generation of column synthesis, the second generation of chip synthesis, and the third generation of enzymatic synthesis. Among them, the chip synthesis technology is relatively mature, with high synthesis flux, low reagent consumption, and low synthesis cost. It is more suitable for large-scale DNA synthesis and assembly, and is an important way to synthesize DNA. However, this method still has problems such as low reagent utilization, easy cross-contamination of reagents at adjacent sites, complex synthesis process, and high cost.

[0003] In view of the above problems, patent CN115323019A proposes a hydrophilic and hydrophobic grid chip and its preparation method, which first etches the grid chip drawn by CAD, and then coats it with liquid monohydroxysilane or gas phase mixed silane, so as to achieve hydrophilic inside the grid and hydrophobic outside the grid. However, the coating process of this method is time-consuming, the hydrophilic and hydrophobic difference of the grid chip provided is not obvious, and it is impossible to control oil droplets. Summary of the invention

[0004] The present invention aims to provide a super-amphiphobic / super-amphiphobic surface patterned chip, a preparation method thereof and a droplet control method. The chip has a super-amphiphobic / super-amphiphobic surface structure, which can effectively inhibit the flow and diffusion of liquid, thereby achieving the effect of improving the synthesis accuracy.

[0005] Specifically, the technical solution of the present invention is as follows:

[0006] According to the present invention, a method for preparing a super-amphiphobic / super-amphiphilic surface patterned chip is provided, comprising the following steps:

[0007] 1) Pre-treating the surface of the aluminum sheet, including grinding, polishing, ultrasonic cleaning, and nitrogen drying;

[0008] 2) etching the aluminum sheet using HCl / HF solution, then taking out the aluminum sheet, ultrasonically cleaning it, and drying it with nitrogen;

[0009] 3) The etched aluminum sheet is placed in a silane solution for modification, and then taken out and vacuum dried, and the modified aluminum sheet exhibits super hydrophobicity, super oleophobicity and super amphiphobicity;

[0010] 4) The super-amphiphobic aluminum sheet is further patterned to destroy the surface hydrophobic layer, form super-hydrophilic properties, and then form super-hydrophilic / super-oleophilic lattices in the treated area, thereby obtaining a super-amphiphobic / super-amphiphobic patterned chip.

[0011] The present invention adopts raw aluminum sheet as the chip substrate. The aluminum sheet is low in price and has excellent electrical conductivity, thermal conductivity and corrosion resistance. It is a metal material with excellent comprehensive performance.

[0012] In one embodiment of the present invention, the composition of the HCl / HF solution in step 2) includes 60-78% HCl, 2-10% HF, and 20-30% deionized water, calculated by volume percentage, and the sum of the components is 100%.

[0013] Exemplarily, the composition of the HCl / HF solution is 73% HCl, 5% HF and 22% double distilled water, by volume percentage.

[0014] In one embodiment of the present invention, the etching time of the HCl / HF solution is 10-30 seconds, until the surface presents a uniform gray-black color, and a special micro-nano structure is formed on the surface of the aluminum sheet.

[0015] Exemplarily, the etching time of the HCl / HF solution is 10s, 12s, 15s, 18s, 20s, 22s, 25s, 28s, or 30s.

[0016] In one embodiment of the present invention, the silane solution is a low surface energy solution, and the silane solution is selected from one or more of perfluorodecyltrimethoxysilane, perfluorodecyltriethoxysilane, perfluorooctyltrimethoxysilane, perfluorooctyltriethoxysilane, perfluorooctyltrichlorosilane, perfluorooctyldimethylchlorosilane and n-decyltriethoxysilane solution.

[0017] In one embodiment of the present invention, the concentration of the silane solution is 0.1 wt % to 1 wt %.

[0018] Exemplarily, the silane solution is a toluene solution of perfluorodecyltrimethoxysilane with a concentration of 0.1 wt %.

[0019] In one embodiment of the present invention, the modification with silane solution in step 3) is carried out for 6 to 60 minutes, preferably 8 to 30 minutes.

[0020] Exemplarily, 5min, 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 30min.

[0021] In one embodiment of the present invention, in step 3), after the aluminum sheet is modified in the silane solution, it is taken out and placed in a vacuum drying oven at 90 to 110° C. for 0.5 to 1.5 hours.

[0022] In one embodiment of the present invention, in step 4), the super-amphiphobic aluminum sheet is patterned by laser, and the laser parameters are adjusted to have a wavelength of 800 nm, a frequency of 1-10 kHz, and a pulse width of 1-150 fs.

[0023] The present invention uses laser etching technology to pattern the super-amphiphobic aluminum sheet. Laser etching has the advantages of high precision, high efficiency and low cost. By adjusting the laser parameter wave, a low-power laser beam with high beam quality is focused into an extremely small spot, and a very high power density is formed at the focus, so that the material is melted and vaporized to form holes, seams, grooves, etc., thereby constructing a microstructure on the substrate surface.

[0024] In one embodiment of the present invention, in step 1), acetone, anhydrous ethanol and deionized water are used for ultrasonic cleaning in sequence.

[0025] In one embodiment of the present invention, in step 2), anhydrous ethanol and deionized water are used for ultrasonic cleaning in sequence.

[0026] The present invention also provides a super-amphiphobic / super-amphiphobic surface patterned chip, which is prepared by using the method of the super-amphiphobic / super-amphiphobic surface patterned chip.

[0027] In one embodiment of the present invention, the contact angle of the amphiphilic region is 152° to 158°, and the contact angle of the amphiphilic region is <5°. In one embodiment of the present invention, the pattern includes a lattice, the lattice has super-amphiphobic properties, and the lattice has super-amphiphobic properties.

[0028] Specifically, due to the difference in the amphiphilic and amphiphobic properties inside and outside the lattice, the patterned surface can control the droplets in the amphiphilic patterned area and restrict their diffusion to the surrounding amphiphilic areas, thereby achieving precise control of the droplets and avoiding cross contamination.

[0029] The present invention also provides a droplet control method, wherein the above-mentioned super-amphiphobic / super-amphiphilic surface patterned chip is used to realize the control of droplets, such as water and oil.

[0030] In one embodiment of the present invention, the chip is used to precisely control the droplets within the lattice without spreading outward, thereby forming a variety of micro-droplet arrays, including but not limited to water micro-droplet arrays, oil micro-droplet arrays, etc.

[0031] Specifically, the method can effectively inhibit the flow and diffusion of liquid.

[0032] The present invention has the following beneficial effects:

[0033] The present invention provides a super-amphiphobic / super-amphiphobic patterned chip and a preparation method thereof, wherein the patterned chip has a super-amphiphobic property in a lattice and a super-amphiphobic property outside the lattice, and the pattern surface can control the droplets in the amphiphilic patterned area due to the amphiphilic and amphiphilic differences in the lattice outside the lattice, and limit their diffusion to the surrounding amphiphilic areas, thereby achieving accurate control of the droplets and avoiding cross contamination. For example, the patterned chip prepared by the present invention can accurately control water and oil, accurately control the droplets in the lattice, and do not diffuse outward, and can form a variety of micro-droplet arrays, including but not limited to water micro-droplet arrays, oil micro-droplet arrays, etc., effectively inhibiting the flow and diffusion of liquids. In addition, the preparation method of the present invention is simple and fast, and improves the chip preparation efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 Schematic diagram of the microstructure of the super-amphiphobic / super-amphiphilic surface patterned chip prepared by the present invention.

[0035] Figure 2 It is the contact angle of the super-amphiphobic / super-amphiphobic surface patterned chip before and after laser treatment of the present invention. DETAILED DESCRIPTION

[0036] In order to make the purpose, technical scheme and advantages of the present invention more clearly understood, the present invention is 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 used to better illustrate the present invention, are some embodiments of the present invention, not all embodiments, and 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.

[0037] Example 1

[0038] The preparation of a super-amphiphobic / super-amphiphilic patterned chip comprises the following steps:

[0039] 1) Use sandpaper to grind the surface of 1060 aluminum sheet, and polish it with a polisher until there is no obvious scratch. Use acetone, anhydrous ethanol, and deionized water to ultrasonically clean for 1 minute, and blow dry with nitrogen for later use.

[0040] 2) Prepare a HCl / HF etching solution with a volume fraction of 73% HCl, 5% HF, and 22% double distilled water, and place the aluminum sheet in the prepared HCl / HF etching solution and etch for 10 seconds until the surface is uniformly gray-black and a special micro-nano structure is formed on the surface of the aluminum sheet. Take out the aluminum sheet, rinse it with deionized water, and blow dry it with nitrogen.

[0041] 3) The etched aluminum sheet was placed in a perfluorodecyltrimethoxysilane solution with a mass concentration of 0.1% for modification for 10 minutes, and then taken out and placed in a vacuum drying oven at 100° C. for drying for 60 minutes.

[0042] 4) The super-amphiphobic aluminum sheet is patterned by laser in a dot matrix mode. The laser has a wavelength of 800 nm, a pulse width of 10 fs, and a frequency of 30 kHz, which destroys the hydrophobic layer on the surface and forms a super-hydrophilic property, thereby forming a super-hydrophilic / super-oleophilic dot matrix in the treated area to obtain a super-amphiphobic / super-amphiphobic patterned chip.

[0043] Figure 1 This is a microstructure diagram of the patterned chip prepared in Example 1. It can be seen that the surface has a relatively uniform nanostructure.

[0044] The patterned chip prepared in Example 1 was subjected to multiple droplet contact angle tests (including water droplets and oil droplets) using a contact angle measuring instrument. Figure 2 As shown, the contact angle of the amphiphilic region is 156°, and the contact angle of the amphiphilic region is <5°, indicating that the target effect has been achieved.

[0045] The patterned chip prepared in Example 1 was tested for water contact angle multiple times. Figure 2 As shown in the figure, the contact angle of the amphiphilic region is 156°, and the contact angle of the amphiphilic region is <5°. It can be seen that after the modification, the contact angle of the amphiphilic surface reaches >150°, and the droplets in this area are very easy to roll off; the contact angle of the amphiphilic surface after laser treatment is close to 0°, and it can be completely wetted, indicating that the lattice has super-amphiphobic properties, and the lattice has super-amphiphobic properties, which can be used as a liquid storage area to achieve the target effect.

[0046] Example 2

[0047] 1) Use sandpaper to grind the surface of 1060 aluminum sheet, and polish it with a polisher until there is no obvious scratch. Use acetone, anhydrous ethanol, and deionized water to ultrasonically clean for 10 minutes, and blow dry with nitrogen for later use.

[0048] 2) Prepare an HCl / HF etching solution with a volume fraction of 70% HCl, 10% HF, and 20% double distilled water, and place the aluminum sheet in the prepared etching solution (Baker solution) for 15 seconds until the surface is uniformly gray-black and a special micro-nano structure is formed on the surface of the aluminum sheet. Take out the aluminum sheet, rinse it with deionized water, and blow it dry with nitrogen.

[0049] 3) The etched aluminum sheet was placed in a perfluorodecyltrimethoxysilane solution with a mass concentration of 0.1 wt % for modification for 10 min, and then taken out and placed in a vacuum drying oven at 110° C. for drying for 90 min.

[0050] 4) The super-amphiphobic aluminum sheet was patterned by laser in a dot matrix mode, with a wavelength of 800 nm, a pulse width of 10 fs, and a frequency of 30 kHz, to destroy the hydrophobic layer on the surface and form a super-hydrophilic property, thereby forming a super-hydrophilic / super-oleophilic dot matrix in the treated area to obtain a super-amphiphobic / super-amphiphobic patterned chip.

[0051] The patterned chip prepared in Example 2 was subjected to multiple water contact angle tests, and the contact angle of the amphiphobic region was 158°, and the contact angle of the amphiphilic region was <5°.

[0052] It can be seen that after the modification treatment, the contact angle of the amphiphilic surface reaches >150°, and the droplets can easily roll off in this area; the contact angle of the amphiphilic surface after laser treatment is close to 0°, and it can be completely wetted, indicating that the lattice has super-amphiphobic properties, and the lattice has super-amphiphobic properties, which can be used as a liquid storage area to achieve the target effect.

[0053] Example 3

[0054] 1) Use sandpaper to polish the surface of 1060 aluminum sheet, and polish it with a polisher until there is no obvious wear mark. Then use acetone, anhydrous ethanol, and deionized water to ultrasonically clean for 10 minutes in sequence, and blow dry with nitrogen for later use.

[0055] 2) Prepare a HCl / HF etching solution with a volume ratio of 78% HCl, 2% HF and 20% double distilled water, place the aluminum sheet in the prepared HCl / HF etching solution and etch for 15 seconds until the surface is uniformly gray-black and a special micro-nano structure is formed on the surface of the aluminum sheet. Take out the aluminum sheet, rinse it with deionized water, and blow dry it with nitrogen.

[0056] 3) The etched aluminum sheet was placed in a perfluorooctyltriethoxysilane solution with a mass concentration of 0.2% for modification for 20 minutes, and then taken out and placed in a vacuum drying oven at 90° C. for drying for 30 minutes.

[0057] 4) The super-amphiphobic aluminum sheet was patterned by laser in a dot matrix mode with a wavelength of 800 nm, a pulse width of 10 fs, and a frequency of 20 kHz to destroy the hydrophobic layer on the surface and form a super-hydrophilic property, thereby forming a super-hydrophilic / super-oleophilic dot matrix in the treated area to obtain a super-amphiphobic / super-amphiphobic patterned chip.

[0058] The prepared patterned chip was tested for water contact angles multiple times. The contact angle of the amphiphilic area was 152°, and the contact angle of the amphiphilic area was <5°, achieving the target effect. After the modification, the contact angle of the amphiphilic surface reached >150°, and the droplets in this area rolled off easily; the contact angle of the amphiphilic surface after laser treatment was close to 0°, and it could be completely wetted, indicating that the lattice had super-amphiphobic properties, and the lattice had super-amphiphobic properties, which could be used as a liquid storage area to achieve the target effect.

[0059] Example 4

[0060] The preparation method is the same as that of Example 1, except that the composition of the HCl / HF solution in step 2) includes 50% HCl, 10% HF, and 40% double distilled water by volume, and the etching time is 25 s.

[0061] The prepared patterned chip was subjected to multiple droplet contact angle tests. The contact angle of the amphiphilic area was 140°, and the contact angle of the amphiphilic area was 8°. The super-amphiphobic properties within the lattice of the prepared patterned chip and the super-amphiphobic properties outside the lattice were inferior to those of the chips prepared in Examples 1-3.

[0062] In summary, the patterned chip prepared by the method of the present invention has super-amphiphobic properties inside the lattice, with a water contact angle of ≥150°, and super-amphiphobic properties outside the lattice, with a water contact angle of ≤5°, showing obvious effects compared with untreated aluminum sheets.

[0063] It can be seen that the super-amphiphobic / super-amphiphilic surface patterned chip prepared by the present invention can accurately control water and oil. Through the performance difference between the substrate and the patterned area, the flow and diffusion of the liquid can be effectively inhibited, and the droplets can be effectively confined to the patterned area. A variety of micro-droplet arrays can be formed, including but not limited to water micro-droplet arrays, oil micro-droplet arrays, etc.

[0064] The above is only a preferred application implementation of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the technical principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a super-amphiphobic / super-amphiphilic surface patterned chip, characterized in that: The following steps are involved: 1) Pre-treating the surface of the aluminum sheet, including grinding, polishing, ultrasonic cleaning, and nitrogen drying; 2) etching the aluminum sheet using HCl / HF solution, then taking out the aluminum sheet, ultrasonically cleaning it, and drying it with nitrogen; 3) The etched aluminum sheet is placed in a silane solution for modification, and then taken out and vacuum dried, and the modified aluminum sheet exhibits super hydrophobicity, super oleophobicity and super amphiphobicity; 4) The super-amphiphobic aluminum sheet is further patterned to destroy the surface hydrophobic layer, form super-hydrophilic properties, and then form super-hydrophilic / super-oleophilic lattices in the treated area, thereby obtaining a super-amphiphobic / super-amphiphobic patterned chip.

2. The preparation method according to claim 1, characterized in that: In terms of volume percentage, the composition of the HCl / HF solution in step 2) includes 60-78% HCl, 2-10% HF, and 20-30% deionized water, and the sum of the components is 100%. Preferably, the HCl / HF solution comprises 73% HCl, 5% HF and 22% double distilled water in volume percentage.

3. The preparation method according to claim 1, characterized in that: The HCl / HF solution etching time is 10-30 seconds, until the surface presents a uniform gray-black color, and a micro-nano structure is formed on the surface of the aluminum sheet. For example, the etching time is 10s, 12s, 15s, 18s, 20s, 22s, 25s, 28s, and 30s.

4. The preparation method according to claim 1, characterized in that: The silane solution is selected from one or more of perfluorodecyltrimethoxysilane, perfluorodecyltriethoxysilane, perfluorooctyltrimethoxysilane, perfluorooctyltriethoxysilane, perfluorooctyltrichlorosilane, perfluorooctyldimethylchlorosilane and n-decyltriethoxysilane solutions.

5. The preparation method according to any one of claims 1 to 4, characterized in that: The concentration of the silane solution is 0.1 wt % to 1 wt %. For example, the silane solution is a toluene solution of perfluorodecyltrimethoxysilane with a concentration of 0.1 wt %.

6. The preparation method according to claim 5, characterized in that: In step 3), the silane solution is used for modification for 6 to 60 minutes, preferably 8 to 30 minutes.

7. The preparation method according to any one of claims 1 to 4, characterized in that In the step 3), after the aluminum sheet is modified in the silane solution, it is taken out and placed in a vacuum drying oven at 90 to 110° C. for 0.5 to 1.5 hours; Preferably, in step 4), the super-amphiphobic aluminum sheet is patterned by laser, and the laser parameters are adjusted to have a wavelength of 800 nm, a frequency of 1-10 kHz, and a pulse width of 1-150 fs, preferably 30-80 fs; Preferably, in step 1), acetone, anhydrous ethanol and deionized water are used for ultrasonic cleaning in sequence; Preferably, in step 2), anhydrous ethanol and deionized water are used for ultrasonic cleaning in sequence.

8. A super-amphiphobic / super-amphiphilic surface patterned chip, characterized in that: The super-amphiphobic / super-amphiphilic surface patterned chip is prepared by the method of any one of claims 1 to 7.

9. The super-amphiphobic / super-amphiphilic surface patterned chip according to claim 8, characterized in that: The patterned chip includes a dot matrix, which has super-amphiphobic properties inside the dot matrix and super-amphiphobic properties outside the dot matrix. Due to the difference between the amphiphilicity and amphiphilicity inside and outside the dot matrix, the pattern surface can control droplets in the amphiphilic patterned area and restrict their diffusion to the surrounding amphiphilic areas, thereby achieving precise control of droplets and avoiding cross contamination. Preferably, the contact angle of the amphiphilic region is 152° to 158°, and the contact angle of the amphiphilic region is <5°.

10. A droplet control method, characterized in that: The droplets are controlled by using the super-amphiphobic / super-amphiphobic surface patterned chip described in claim 8 or 9, and the droplets are precisely controlled within the lattice and do not diffuse outward, thereby forming a micro-droplet array; For example, water or oil droplets are precisely controlled within the dot matrix and do not spread outward, forming a water or oil micro-droplet array.

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