Liquid diffusion regulation and control method based on wettability guidance and substrate

Abstract

The invention relates to the technical field of semiconductor manufacturing, in particular to a liquid diffusion regulation and control method based on wettability guidance and a substrate, the regulation and control method comprises the steps that a homogeneous liquid film layer or a porous structure film layer is arranged on the surface of the substrate, and the homogeneous liquid film layer is prepared from homogeneous liquid; the homogeneous liquid has a chemical structure which is the same as or similar to that of the liquid to be diffused, and the porous structure membrane layer is prepared from a porous material. The solid-liquid friction resistance can be reduced after the substrate is treated by the homogeneous liquid film layer, the contact area and the capillary acting force can be increased after the substrate is treated by the porous structure film layer, and when liquid to be diffused has good wettability on the surface of the substrate, the diffusivity of the liquid can be remarkably improved by arranging the homogeneous liquid film layer or the porous structure film layer; the spreading performance is obviously improved.

Description

Technical Field

[0001] The present invention relates to the field of semiconductor manufacturing technology, and in particular to a liquid diffusion control method based on wettability guidance and a substrate. Background Art

[0002] In the semiconductor integrated circuit manufacturing process, many key process steps involve controlling the diffusion of liquids onto the solid surface of the substrate, such as mask etching, immersion lithography, and photoresist coating, to achieve patterning of the substrate surface. Poorly controlled liquid diffusion on the substrate can lead to defects (streaks, spots, residues, undercuts), critical dimension variations, and the inability to achieve high-precision patterning, severely compromising device performance and manufacturing yield. Therefore, controlling the diffusion of liquids onto the solid surface is a key factor influencing process precision, device performance, and yield.

[0003] To address the above-mentioned problems, existing methods for improving the diffusion of liquids on solid surfaces include liquid modification and solid surface modification. Liquid modification involves adding additives such as surfactants, wetting agents, co-solvents, viscosity modifiers, etc. to liquids (such as developers, etching solutions, cleaning solutions, and photoresist solvents) to reduce the surface tension of the liquid and improve its compatibility with specific surfaces, thereby reducing the contact angle and promoting the spreading and penetration of additives. However, this may introduce the risk of impurity contamination and may change the core chemical properties of the liquid (such as etching / reaction rates); it may generate foam or affect waste liquid treatment; and the formula optimization process is complex, requiring repeated experiments for different surfaces.

[0004] Solid surface modification uses methods such as plasma treatment and surface chemical modification to alter the chemical composition or physical morphology of the solid surface, increasing its hydrophilicity (reducing the contact angle) to promote spreading, or enhancing its hydrophobicity (increasing the contact angle) to restrict spreading or prevent wetting. When the liquid to be spread is an immersion liquid or a curing adhesive, the liquid already exhibits good wettability on the substrate surface, with a very small contact angle (e.g., less than 10°). At this point, the liquid spreads easily and spontaneously on the substrate surface, exhibiting good spreading properties. However, when higher liquid wetting requirements are required, existing solid surface modification methods are unable to further reduce the contact angle with the substrate, and thus fail to further improve the liquid's spreading properties on the substrate.

[0005] Therefore, it is urgent to develop a control method for optimizing the diffusivity of liquid when the liquid to be diffused has good wettability on the substrate surface, so as to meet higher wetting requirements. Summary of the Invention

[0006] The purpose of the present invention is to solve the problem that when the liquid to be diffused has good wettability on the substrate surface, the existing solid surface modification method cannot further improve the spreading performance of the liquid on the substrate, and to provide a liquid diffusion control method and substrate based on wettability guidance.

[0007] In a first aspect, the present invention provides a liquid diffusion control method based on wettability guidance, the control method comprising setting a homogeneous liquid film layer or a porous structure membrane layer on the surface of the substrate, wherein the homogeneous liquid film layer is prepared using a homogeneous liquid, the homogeneous liquid has a chemical structure that is the same or similar to that of the liquid to be diffused, and the porous structure membrane layer is prepared using a porous material.

[0008] As a preferred embodiment of the present invention, before providing the homogeneous liquid membrane layer or the porous structure membrane layer on the substrate, the substrate is pretreated, including at least cleaning and drying.

[0009] As a preferred embodiment of the present invention, the thickness of the homogeneous liquid film layer is 5-100 nm.

[0010] As a preferred embodiment of the present invention, the thickness of the porous structure membrane layer is 5-100 nm.

[0011] As a preferred embodiment of the present invention, the homogeneous liquid film layer is prepared on the surface of the substrate by spin coating, dip coating or spray coating.

[0012] As a preferred embodiment of the present invention, the porous structure membrane layer is prepared on the surface of the substrate by spin coating, dip coating or spray coating.

[0013] As a preferred embodiment of the present invention, the substrate comprises one of a silicon wafer, a silicon / silicon dioxide wafer, a silicon / diamond-like carbon wafer and a silicon / metal wafer.

[0014] As a more preferred embodiment of the present invention, when the liquid to be diffused is an alkane-aromatic hydrocarbon mixed immersion liquid, the homogeneous liquid is one of an alkane organic liquid, an aromatic hydrocarbon organic liquid, and an alkane-aromatic hydrocarbon mixed organic liquid; When the liquid to be diffused is an acrylate curing adhesive, the homogeneous liquid is at least one of epoxy acrylate, polyurethane acrylate, polyether acrylate and polyester acrylate.

[0015] As a preferred embodiment of the present invention, the porous material includes at least one of a metal organic framework porous material and a covalent organic framework porous material.

[0016] As a more preferred embodiment of the present invention, the porous material is zeolite imidazolate skeleton-8, and the pore size of the zeolite imidazolate skeleton-8 is 0.34~1.16nm; the concentration of the zeolite imidazolate skeleton-8 in the porous material solution prepared using the zeolite imidazolate skeleton-8 is greater than or equal to 0.2mg / mL.

[0017] In a second aspect, a method for segmented liquid diffusion control based on wettability guidance is characterized by comprising the following steps: S1. Testing the initial contact angle between the liquid to be diffused and the substrate surface; S2. When the initial contact angle is ≤10°, a homogeneous liquid film layer or a porous structure film layer is provided on the surface of the substrate, wherein the homogeneous liquid film layer is prepared using a homogeneous liquid having a chemical structure identical or similar to that of the liquid to be diffused, and the porous structure film layer is prepared using a porous material; When the initial contact angle is greater than 10°, the surface of the substrate is chemically modified.

[0018] In a third aspect, the present invention provides a substrate, which is obtained by processing using one of the above-mentioned methods for controlling liquid diffusion based on wettability guidance or one of the above-mentioned methods for controlling liquid diffusion in a segmented manner based on wettability guidance.

[0019] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention provides a liquid diffusion control method based on wettability guidance, in which a homogeneous liquid film layer is pre-laid on a substrate or a porous structure film layer is arranged on the substrate; the homogeneous liquid film layer is prepared by using a homogeneous liquid with the same or similar chemical structure as the liquid to be diffused, which can reduce the solid-liquid friction resistance, and the porous structure film layer is prepared by using a porous material. After the substrate is treated with the porous structure film layer, the contact area and capillary force can be increased, especially when the liquid to be diffused has shown good wettability on the substrate surface, arranging a homogeneous liquid film layer or a porous structure film layer on the substrate surface can significantly improve the diffusivity of the liquid, and the spreading performance is significantly improved.

[0020] 2. The present invention provides a method for regulating the diffusion of liquid on the solid surface of a substrate. Experimental verification shows that when the liquid to be diffused has already shown good wettability on the substrate surface, the spreading diameter of the pre-laid homogeneous liquid film layer on the substrate is expanded by 1.396 times, and the spreading diameter of the porous structure film layer provided on the substrate is expanded by 1.604 times, both of which can significantly improve the diffusivity of the liquid. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a test diagram of the spreading diameter of the liquid on the Si wafer and Si-YPM wafer in Example 1; Figure 2 This is a test diagram of the spreading diameter of the liquid on the Si wafer and Si-0.2ZIF wafer in Example 2; Figure 3 The contact angle test diagram of the substrate in Example 3-5; Figure 4 This is a test diagram of the spread diameter of the substrate of Example 3-5; Figure 5 This is the contact angle test diagram of the substrates with different modification treatments in Test Example 2; Figure 6 This is a test diagram of the spreading diameter of substrates with different modification treatments in Test Example 2; Figure 7 The spreading diameter test diagram of the liquid in Test Example 4 on the surfaces of (a) Si wafer (b) Si-0.05ZIF wafer (c) Si-0.1ZIF wafer (d) Si-0.2ZIF wafer (e) Si-0.3ZIF wafer (f) Si-0.8ZIF wafer; Figure 8 This is a bar graph of the spreading diameter of the liquid on different substrate surfaces in Test Example 4. DETAILED DESCRIPTION

[0022] The present invention will be further described in detail below with reference to specific embodiments. However, this should not be construed as limiting the scope of the present invention to the following embodiments, as all technologies implemented based on the present invention fall within the scope of the present invention.

[0023] In the semiconductor integrated circuit manufacturing process, existing methods for improving the diffusion of liquids on solid surfaces include liquid modification and solid surface modification. Solid surface modification uses plasma treatment, surface chemical modification, and other means to change the chemical composition or physical morphology of the solid surface. When the liquid to be diffused is an immersion liquid or a curing glue, the liquid to be diffused already exhibits good wettability on the substrate surface, and the contact angle between the liquid and the substrate is very small, such as a contact angle of less than 10°. At this time, the liquid can easily spread spontaneously on the substrate surface and exhibit good expansion performance. However, when higher liquid infiltration requirements need to be met, the existing solid surface modification methods cannot further reduce the contact angle between the liquid and the substrate, and cannot further improve the spreading performance of the liquid on the substrate.

[0024] The present disclosure provides a liquid diffusion control method based on wettability guidance, which includes setting a homogeneous liquid film layer or a porous structure film layer on the surface of a substrate, wherein the homogeneous liquid film layer is prepared using a homogeneous liquid, and the homogeneous liquid has a chemical structure that is the same or similar to that of the liquid to be diffused, and the porous structure film layer is prepared using a porous material.

[0025] In the above technical solution, the liquid diffusion control method pre-lays a homogeneous liquid film layer on the substrate or sets a porous structure film layer on the substrate; the homogeneous liquid film layer is prepared using a homogeneous liquid with the same or similar chemical structure as the liquid to be diffused, which can reduce the solid-liquid friction resistance, and the porous structure film layer is prepared using a porous material, which can increase the contact area and capillary force after treatment.

[0026] After extensive research and experiments, the inventors found that when the liquid has good wettability on the solid surface, surface chemical modification has no obvious effect on improving the diffusivity of the liquid. The present invention adopts the method of setting a homogeneous liquid film layer or a porous structure film layer on the substrate surface. When the liquid to be diffused already shows good wettability on the substrate surface, setting a homogeneous liquid film layer or a porous structure film layer can further enhance the diffusivity of the liquid, and the spreading performance is significantly improved.

[0027] In some embodiments, before applying a homogeneous liquid film layer or a porous structure film layer to a substrate, the substrate undergoes pretreatment. This pretreatment includes cleaning to remove surface particles, impurities such as metal impurities, impurity oxides, and organic contaminants. Specific cleaning methods include ultrasonic cleaning with solutions such as ethanol, acetone, and distilled water for 10-80 minutes, or soaking in a piranha solution (concentrated sulfuric acid + hydrogen peroxide), SC-1 (ammonia + hydrogen peroxide + water), or SC-2 (hydrochloric acid + hydrogen peroxide + water) for 30-60 minutes, followed by a deionized water rinse. Cleaning methods vary for different substrate materials; the primary purpose of cleaning is to remove surface particles, impurities such as metal impurities, impurity oxides, and organic contaminants.

[0028] In some embodiments, the substrate may include one of a silicon (Si) wafer, a silicon / silicon dioxide (Si / SiO2) wafer, a silicon / diamond-like carbon (Si / DLC) wafer, and a silicon / metal wafer. The Si / SiO2 wafer is a Si wafer having a SiO2 film layer provided on the surface, the Si / DLC wafer is a Si wafer having a diamond-like carbon (DLC) film layer provided on the surface, and the silicon / metal wafer is a Si wafer having a metal film layer, such as metal Ag, platinum, etc., provided on the surface.

[0029] In some embodiments, a homogenous liquid film layer is formed on a substrate surface by spin coating, dip coating, or spray coating. The method for forming a homogenous liquid film on a substrate surface by spin coating is to dilute a homogenous liquid with a solvent or directly spin coat the homogenous liquid onto the substrate surface. During the spin coating process, the thickness of the liquid film is adjusted by controlling parameters such as spin speed, time, and solution viscosity.

[0030] The dip coating method for preparing a homogenous liquid film involves slowly immersing a substrate vertically into a homogenous liquid at a constant speed, sufficient to fully cover the substrate surface. After immersion for a specified period, the substrate is then removed from the solution at the same or varying speeds. The film thickness is influenced by controlling the removal speed during the dip coating process; slower removal speeds result in thicker films.

[0031] Spray coating creates a homogenous liquid film by using compressed air or other gases to atomize a homogenous liquid into tiny droplets from a spray gun nozzle. The spray gun is then moved to deposit these droplets evenly onto the substrate surface. During the spraying process, parameters such as pressure, flow rate, movement speed, and the distance between the nozzle and the substrate are controlled to achieve uniform film thickness and excellent film formation.

[0032] When the viscosity of the homogeneous liquid is relatively high and it is not suitable for spin coating, dip coating or spray coating, the homogeneous liquid is prepared into a solution of appropriate concentration using an organic solvent according to the film-forming material and process requirements to facilitate the preparation of a homogeneous liquid film layer.

[0033] In some embodiments, when the liquid to be diffused is an alkane-aromatic hydrocarbon mixed immersion liquid, the homogeneous liquid is selected from an alkane organic liquid, an aromatic hydrocarbon organic liquid, or an alkane-aromatic hydrocarbon mixed organic liquid. The alkane-aromatic hydrocarbon mixed immersion liquid is a liquid prepared by mixing an alkane and an aromatic hydrocarbon solvent in a specific ratio, and is used to completely immerse the object in the liquid for treatment.

[0034] In some embodiments, when the liquid to be diffused is an acrylate-based curing glue, the homogeneous liquid is at least one of epoxy acrylate, polyurethane acrylate, polyether acrylate, and polyester acrylate. In the above technical solution, a homogeneous liquid with the same or similar chemical structure is selected to prepare a homogeneous liquid film layer. By preparing a homogeneous liquid film layer on a substrate in advance, the homogeneous liquid film layer can form good adhesion with the substrate. More importantly, the homogeneous liquid film layer can reduce the solid-liquid friction resistance and significantly improve the diffusivity of the liquid. When it is necessary to remove the homogeneous liquid film layer, the substrate is immersed in a suitable organic solvent, and the pre-laid homogeneous liquid film will be dissolved and detached from the substrate surface. This flushable property allows the homogeneous liquid film layer to be easily processed according to actual process requirements.

[0035] In some embodiments, the thickness of the homogenous liquid film layer is 5-100 nm. More preferably, the thickness of the homogenous liquid film layer is 10-30 nm.

[0036] In some embodiments, a porous structure membrane layer is prepared on the surface of a substrate by spin coating, dip coating or spray coating. The method of setting a porous structure membrane layer on the surface of a substrate by spin coating is as follows: dissolve the porous material in a solvent, stir evenly to obtain a porous material solution; spin coat the porous material solution onto the surface of the substrate, and bake it at 80-150°C for 5-15 minutes. During the spin coating process, the thickness of the porous structure membrane layer is adjusted by controlling parameters such as the rotation speed, time and solution viscosity, and the thickness of the porous structure membrane layer is controlled within the nanometer range. The preparation of a porous structure membrane layer by dip coating is similar to the preparation of a homogeneous liquid membrane layer by dip coating, and the preparation of a porous structure membrane layer by spray coating is similar to the preparation of a homogeneous liquid membrane layer by spray coating. The solution dipped or sprayed in the preparation of the porous structure membrane layer is a porous material solution.

[0037] In some embodiments, the porous material may include at least one of a Metal-Organic Framework (MOF) porous material and a Covalent Organic Framework (COF) porous material. MOF porous material is a material with a highly ordered porous structure formed by self-assembly of metal ions or metal clusters and organic ligands. Its structure is like a three-dimensional framework built by metal nodes (metal ions or clusters) and organic linkers (organic ligands). COF porous material is an organic porous polymer completely connected by covalent bonds. Its structure is a two-dimensional or three-dimensional porous network composed of light elements (such as boron, carbon, nitrogen, oxygen, etc.). The porous material is arranged on the surface of the substrate. The porous material has a fine pore structure, which can increase the contact area and capillary force, increase wettability, and achieve better wettability of the solid surface.

[0038] In some embodiments, the porous material can be zeolitic imidazolate framework-8 (ZIF-8), and the pore size of ZIF-8 is 0.34-1.16 nm. ZIF-8 is composed of zinc ions (Zn 2+ ) and 2-methylimidazole (2-MIM) to form a porous metal-organic framework material through self-assembly.

[0039] In some embodiments, when the porous material is ZIF-8, the concentration of ZIF-8 in the prepared porous material solution is greater than or equal to 0.2 mg / mL, more preferably, the concentration of ZIF-8 is 0.2-0.8 mg / mL.

[0040] In some embodiments, the thickness of the porous structure membrane layer is 5-100 nm, more preferably, the thickness of the porous structure membrane layer is 10-50 nm.

[0041] The present disclosure also provides a method for segmented liquid diffusion control based on wettability guidance, comprising the following steps: S1. Testing the initial contact angle between the liquid to be diffused and the substrate surface; S2. When the initial contact angle is ≤10°, a homogeneous liquid film layer or a porous structure film layer is provided on the substrate surface, wherein the homogeneous liquid film layer is prepared using a homogeneous liquid having the same or similar chemical structure as the liquid to be diffused, and the porous structure film layer is prepared using a porous material; When the initial contact angle is >10°, the substrate surface is chemically modified.

[0042] In the above technical solution, for the liquid whose diffusion is to be optimized, an initial contact angle of 10° is used as a threshold to determine whether the initial contact angle is greater than 10°. Different control methods are then used in stages to improve the diffusion performance of the liquid on the substrate surface. When the liquid wets the solid substrate surface well and the contact angle is ≤10°, a homogeneous liquid film layer is pre-laid on the substrate or a porous structure film layer is provided on the substrate. The homogeneous liquid film layer can reduce the solid-liquid friction resistance, and the porous structure film layer can increase the contact area and capillary force after treatment. Both the homogeneous liquid film layer and the porous structure film layer provided on the substrate surface can significantly improve the diffusivity of the liquid. When the liquid wets the solid surface poorly and the contact angle is greater than 10°, the substrate surface is chemically modified to improve the wettability and significantly improve the spreading performance. The use of a single method of solid surface modification or liquid modification to treat the substrate to achieve optimized diffusion does not take into account the difference in the initial contact angle (wettability) between the liquid and the solid, and ignores the threshold effect of the contact angle. The above scheme first tests the initial contact angle between the liquid and the substrate surface, considers the threshold effect of the contact angle, and uses different methods to treat the substrate surface based on the initial contact angle, which has a significant effect on the diffusion regulation of the liquid.

[0043] In some embodiments, the method for chemically modifying the substrate can be: dissolving ACL (3-methoxysilane acrylate) in an alcohol solvent to obtain an ACL solution, wherein the mass concentration of ACL is 2-8%, and the ACL solution is spin-coated onto the substrate surface at a speed of 1500-2500 rpm for 20-40 seconds, and then baked at 80-140° C. for 6-15 minutes, and then cooled to room temperature.

[0044] The present disclosure also provides a substrate, which is obtained by processing using the above-mentioned liquid diffusion control method based on wettability guidance or the above-mentioned liquid diffusion segmented control method based on wettability guidance.

[0045] The present disclosure is further described below through specific embodiments. The following examples specifically illustrate the above-mentioned methods for controlling the liquid diffusion of the immersion liquid and curing adhesive. However, the following examples are merely illustrative of the present disclosure and are not intended to limit the scope of the present disclosure.

[0046] Example 1: This embodiment provides a liquid diffusion control method based on wettability guidance. The control method is to set a homogeneous liquid film layer or a porous structure film layer on the surface of the substrate. The homogeneous liquid film layer is prepared using a homogeneous liquid. The homogeneous liquid has the same or similar chemical structure as the liquid to be diffused. The porous structure film layer is prepared using a porous material.

[0047] In this embodiment, the substrate is a Si wafer, and the liquid to be diffused is an immersion liquid, specifically an alkane-aromatic hydrocarbon mixed immersion liquid. The contact angle between the test liquid and the substrate surface is 5.53°. A homogeneous liquid film layer is provided on the substrate surface to improve the diffusion performance of the immersion liquid on the Si wafer. The homogeneous liquid film layer is prepared using the immersion liquid to be diffused. The method for preparing the homogeneous liquid film layer on the substrate surface by spin coating is as follows: (1) Clean the Si wafer by ultrasonic cleaning with ethanol, acetone, and distilled water for 10 to 80 minutes to remove surface particles, impurity metals, impurity oxides, organic pollutants and other impurities; (2) The immersion liquid was spin-coated onto the surface of the Si wafer to prepare a Si-YPM wafer, and the thickness of the homogeneous liquid film layer was about 30 nm.

[0048] The contact angle of the liquid on the substrate surface was measured using a contact angle measuring instrument. 0.5 μL of immersion liquid was dropped onto the surface of the Si wafer and Si-YPM wafer, and the spreading diameter of the liquid was observed under a microscope for 60 seconds. Figure 1 The results are shown in Table 1. The expansion factor is the ratio of the liquid spreading diameter on the Si wafer surface to the liquid spreading diameter on the Si-YPM wafer surface.

[0049] Table 1 Contact angle, spreading diameter and surface energy of Si sheet and Si-YPM sheet in Example 1

[0050] From the data in Table 1, it can be seen that when the liquid has good wettability on the solid surface (contact angle ≤ 10°), by setting a homogeneous liquid film layer on the substrate, the spreading diameter of the immersion liquid on the Si-YPM sheet surface is greatly increased. Compared with the spreading diameter on the Si sheet surface, the expansion factor is more than 1.3 times, which significantly improves the diffusivity of the liquid. This can be attributed to the fact that setting a homogeneous liquid film layer on the substrate can effectively reduce the solid-liquid friction resistance.

[0051] Example 2: This embodiment adopts the control method of Example 1. In this embodiment, the substrate is a Si wafer, the liquid to be diffused is an immersion liquid, specifically an alkane-aromatic hydrocarbon mixed immersion liquid, the contact angle between the test liquid and the substrate surface is 5.53°, and the contact angle is judged to be ≤10°. A porous structure membrane layer is provided on the substrate surface, and the porous structure membrane layer is prepared using ZIF-8. The method for preparing the porous structure membrane layer on the substrate surface by spin coating is as follows: (1) Clean the Si wafer by ultrasonic cleaning with ethanol, acetone, and distilled water for 10 to 80 minutes to remove surface particles, impurity metals, impurity oxides, organic pollutants and other impurities; (2) Ultrasonic dispersion of ZIF-8 with a pore size of 0.34-1.16 nm in ethanol to obtain a 0.2 mg / mL ZIF-8 solution; (3) 0.2 mg / mL ZIF-8 solution was spin-coated onto the surface of the Si wafer and baked at 100 °C for 10 min to prepare a Si-0.2ZIF sheet with a porous structure membrane layer thickness of approximately 40 nm.

[0052] The contact angle of the liquid on the substrate surface was measured using a contact angle measuring instrument. 0.5 μL of immersion liquid was dropped onto the surface of the Si wafer and Si-0.2ZIF wafer. The spreading diameter of the liquid was observed under a microscope after 60 seconds. Figure 2 The results are shown in Table 2. The expansion factor is the ratio of the liquid spreading diameter on the Si wafer surface to the liquid spreading diameter on the Si-0.2ZIF wafer surface.

[0053] Table 2 Contact angle, spreading diameter and surface energy of Si sheet and Si-0.2ZIF sheet in Example 2

[0054] From the data in Table 2, it can be seen that when the liquid has good wettability on the solid surface (contact angle ≤ 10°), by setting a porous structure membrane layer on the substrate, the Si wafer can increase the contact area and capillary force after being treated with porous materials, and the spreading effect is significantly improved. The spreading diameter of the immersion liquid on the surface of the Si-0.2ZIF wafer is greatly increased. Compared with the spreading diameter on the Si wafer surface, the expansion ratio reaches more than 1.6 times, which significantly improves the diffusibility of the liquid.

[0055] Example 3: This embodiment provides a method for controlling liquid diffusion in sections based on wettability guidance, comprising the following steps: S1. Testing the initial contact angle between the liquid to be diffused and the substrate surface; S2. When the initial contact angle is ≤10°, a homogeneous liquid film layer or a porous structure film layer is set on the surface of the substrate, wherein the homogeneous liquid film layer is prepared by homogeneous liquid, the homogeneous liquid has the same or similar chemical structure as the liquid to be diffused, and the porous structure film layer is prepared by porous material; when the initial contact angle is >10°, the substrate surface is chemically modified.

[0056] In this embodiment, the substrate is a Si wafer, the liquid to be diffused is a curing adhesive solution, the initial contact angle between the test liquid and the substrate surface is 33.8°, and it is judged that the initial contact angle is greater than 10°. The substrate is chemically modified by the following method: (1) Clean the Si wafer by ultrasonic cleaning with ethanol, acetone, and distilled water for 10 to 80 minutes to remove surface particles, impurity metals, impurity oxides, organic pollutants and other impurities; (2) Dissolving ACL in an alcohol solvent to obtain an ACL solution with a mass concentration of 3%; (3) The ACL solution was spin-coated onto the surface of the Si wafer at a speed of 2000 rpm for 30 s, baked at 100 °C for 10 min, and then cooled to room temperature to obtain a chemically modified Si-ACL wafer.

[0057] Example 4: This embodiment adopts the segmented control method of Example 3. In this embodiment, the substrate is a Si-10nm SiO2 sheet. The Si-10nm SiO2 sheet is prepared by depositing a 10nm SiO2 thin film on the Si sheet using chemical vapor deposition or physical vapor deposition. The liquid to be diffused is the curing glue solution used in Example 3. The initial contact angle between the test liquid and the substrate surface is 30.29°. It is determined that the initial contact angle is greater than 10°. The substrate is chemically modified to obtain a Si-10nm SiO2-ACL sheet using the ACL chemical modification method of Example 3.

[0058] Example 5: This example uses the control method of Example 3. In this example, the substrate is a Si-30 nm SiO2 sheet. The Si-30 nm SiO2 sheet is prepared by depositing a 30 nm SiO2 thin film on the Si sheet using chemical vapor deposition or physical vapor deposition. The liquid to be diffused is the curing adhesive solution used in Example 3. The initial contact angle between the liquid and the substrate surface is tested to be 29.21°, and the initial contact angle is determined to be greater than 10°. The substrate is chemically modified to obtain a Si-30 nm SiO2-ACL sheet using the ACL chemical modification method of Example 3.

[0059] The contact angle of the liquid on the substrate surface is measured using a contact angle measuring instrument, such as Figure 3As shown, 0.5 μL of the curing glue solution was dropped onto the substrate surface of Example 3-Example 5, and the spreading diameter of the liquid was observed under a microscope after 60 seconds. Figure 4 The results are shown in Table 3, and the data in the table are average values.

[0060] Table 3 Contact angle, spreading diameter and surface energy of the substrates of Examples 3-5

[0061] The data in Table 3 shows that when the liquid has poor wettability on the solid surface (contact angle > 10°), the spreading diameter of the cured adhesive solution on the Si-ACL, Si-10nmSiO2-ACL, and Si-30nmSiO2-ACL surfaces increases by 1.643, 1.236, and 1.14 times, respectively, compared to substrates without surface chemical modification, improving the liquid's diffusivity. This demonstrates that chemical modification of ACL can enhance the liquid's wettability on the substrate, significantly improving its spreading properties.

[0062] Test Example 1: This test example is used to test the spreadability of the same liquid on different substrate surfaces. The liquid is a perfluoropolyether solution. The substrate of Test Example 1-1 is a Si wafer, and the substrate of Test Example 1-2 is a Si-50PFPE wafer. The preparation method of the Si-50PFPE wafer is as follows: spin-coating the silane-modified perfluoropolyether solution onto the Si wafer, baking it at 120°C for 10 minutes, and chemically modifying the surface of the Si wafer using the silane-modified perfluoropolyether solution. The thickness of the perfluoropolyether on the silicon wafer is about 10 nm.

[0063] The contact angle of the liquid on the substrate surface was measured using a contact angle measuring instrument. 0.5 μL of perfluoropolyether solution was dropped onto the substrate surfaces of Test Example 1-1 and Test Example 1-2, and the spreading diameter of the liquid was observed under a microscope for 60 seconds. The results are shown in Table 4.

[0064] Table 4 Spreading diameter and surface energy of different treated surfaces in Test Example 1

[0065] From the data in Table 3, it can be seen that the substrate of Test Example 1-2 is modified with perfluoropolyether, and there is no obvious change in the spreading diameter of the perfluoropolyether solution on the substrate surface before and after the chemical treatment. Combined with the contact angle, it can be seen that when the liquid has good wettability on the solid surface, the chemical treatment of the solid surface has basically no effect on the spreading improvement of the liquid.

[0066] Test Example 2: This test example is used to test the spreadability of the same liquid on different surfaces. The liquid is an alkane-aromatic hydrocarbon mixed immersion liquid. The substrate of Test Example 2-1 is a Si substrate, the substrate of Test Example 2-2 is a Si-ACL substrate, the substrate of Test Example 2-3 is a Si-hexyl substrate, the substrate of Test Example 2-4 is a Si-dodecyl substrate, and the substrate of Test Example 2-5 is a Si-phenyl substrate.

[0067] The Si-ACL sheet was prepared by dissolving ACL in an alcohol solvent to obtain an ACL solution with a mass concentration of 3%. The ACL solution was spin-coated onto the surface of a Si sheet at a speed of 2000 rpm for 30 seconds, baked at 100°C for 10 minutes, and then cooled to room temperature to obtain a chemically modified Si-ACL sheet.

[0068] The preparation method of the Si-hexyl wafer is as follows: hexyltrimethoxysilane is diluted with ethanol to a solution with a mass concentration of 3%, the prepared solution is spin-coated on the Si wafer at a speed of 2000 rpm for 30 seconds, and the wafer is baked at 100°C for 10 minutes, and then cooled to room temperature to obtain a Si-hexyl wafer with the Si wafer surface chemically modified with hexyltrimethoxysilane.

[0069] The preparation method of Si-dodecyl sheet is as follows: spin-coating a 3% mass concentration of dodecyltrimethoxysilane solution onto a Si sheet at a rotation speed of 2000 rpm for 30 seconds, baking at 100°C for 10 minutes, and cooling to room temperature to obtain a Si-dodecyl sheet whose surface is chemically modified with dodecyltrimethoxysilane.

[0070] The preparation method of Si-phenyl sheet is as follows: spin-coating a 3% mass concentration phenyltrimethoxysilane solution onto a Si sheet at a rotation speed of 2000 rpm for 30 seconds, baking at 100°C for 10 minutes, and then cooling to room temperature to obtain a Si-phenyl sheet whose surface is chemically modified with phenyltrimethoxysilane.

[0071] The contact angle of the liquid on the substrate surface was measured using a contact angle measuring instrument. 0.5 μL of alkane and aromatic hydrocarbon immersion liquid was dropped onto the substrate surfaces of Test Examples 2-1 to 2-5. Figure 5 As shown in the figure, the spreading diameter of the liquid at 60s is observed under a microscope, as shown in the figure. Figure 6 The results are shown in Table 5, and the data in the table are average values.

[0072] Table 5 Contact angle, diffusion diameter and surface energy of test example 2 on substrate surfaces with different treatments

[0073] From the data in Table 5, it can be seen that when the liquid has good wettability on the solid surface (contact angle ≤ 10°), surface chemical modification has no obvious effect on improving the diffusivity of the liquid.

[0074] Test Example 3: This test example is used to test the spreading properties of different liquids on the same solid surface. The substrate is a Si wafer, the solution of Test Example 3-1 is a perfluoropolyether solution, and the solution of Test Example 3-2 is an alkane-aromatic hydrocarbon mixed immersion liquid. 0.5 μL of the perfluoropolyether solution of Test Example 3-1 and the immersion liquid of Test Example 3-2 are respectively dropped onto the substrate surface. A contact angle measuring instrument is used to measure the contact angle between the liquid and the substrate surface. The spreading diameter of the liquid is observed under a microscope for 60 seconds. The test data are shown in Table 6.

[0075] Table 6 Test data of test case 3

[0076] From the data in Table 6, it can be seen that the perfluoropolyether solutions in Test Examples 3-1 and 3-2 have smaller contact angles and larger spreading diameters on the Si wafer surface, and the contact angles of the solutions on the Si wafer surface are all ≤10°. This indicates that under the condition of good wettability (contact angle ≤10°), the driving force for liquid diffusion is determined by the properties of the liquid itself.

[0077] Test Example 4: This test example is used to test the spreading of porous materials based on capillary force. The liquid is an alkane-aromatic hydrocarbon mixed immersion liquid. The substrate of test example 4-1 is a Si wafer, the substrate of test example 4-2 is a Si-0.05ZIF wafer, the substrate of test example 4-3 is a Si-0.1ZIF wafer, the substrate of test example 4-4 is a Si-0.2ZIF wafer, the substrate of test example 4-5 is a Si-0.3ZIF wafer, and the substrate of test example 4-6 is a Si-0.8ZIF wafer.

[0078] The Si-0.05ZIF sheet is a sheet of Si with a porous material layer arranged on it. The preparation method of the Si-0.05ZIF sheet is as follows: the porous material is ZIF-8 with a pore size of 0.34-1.16 nm. ZIF-8 is dissolved in ethanol to obtain a 0.05 mg / mL ZIF-8 solution. The 0.05 mg / mL ZIF-8 solution is then spin-coated onto the Si sheet, baked at 100°C for 10 minutes, and then cooled to room temperature to obtain the Si-0.05ZIF sheet.

[0079] The preparation method of Si-0.1ZIF sheet is as follows: prepare 0.1mg / mL ZIF-8 solution, then spin-coat the 0.1mg / mL ZIF-8 solution onto Si sheet, bake at 100℃ for 10min, and then cool to room temperature to obtain Si-0.1ZIF sheet.

[0080] The preparation method of Si-0.2ZIF sheet is as follows: prepare 0.2mg / mL ZIF-8 solution, then spin-coat the 0.2mg / mL ZIF-8 solution onto Si sheet, bake at 100℃ for 10min, and then cool to room temperature to obtain Si-0.2ZIF sheet.

[0081] The preparation method of Si-0.3ZIF sheet is as follows: prepare 0.3mg / mL ZIF-8 solution, then spin-coat the 0.3mg / mL ZIF-8 solution onto Si sheet, bake at 100℃ for 10min, and then cool to room temperature to obtain Si-0.3ZIF sheet.

[0082] The preparation method of Si-0.8ZIF sheet is as follows: prepare 0.8mg / mL ZIF-8 solution, then spin-coat the 0.8mg / mL ZIF-8 solution onto Si sheet, bake at 100℃ for 10min, and then cool to room temperature to obtain Si-0.8ZIF sheet.

[0083] 0.5 μL of alkane-aromatic hydrocarbon mixed immersion liquid was dropped onto the substrate surface of Test Examples 4-1 to 4-6, and the spreading diameter of the liquid was observed under a microscope at 60s and 120s. Figure 7 The average result statistics are shown in Table 7, where the expansion factor 1 is the ratio of the spreading diameters of test cases 4-2 to 4-6 to the spreading diameter of test case 4-1 under 60s, and the expansion factor 2 is the ratio of the spreading diameters of test cases 4-2 to 4-6 to the spreading diameter of test case 4-1 under 120s.

[0084] Table 7 Spreading diameter of Test Example 4 on different treated surfaces

[0085] From the data in Table 7, we can see that the spreading diameter of the immersion solution on the porous structure membrane layer with different concentrations first increases and then decreases as the ZIF concentration increases from 0.05 mg / mL to 0.8 mg / mL. Figure 8 As shown in the figure, when the ZIF concentration is ≥0.2 mg / mL, the spreading diameter of the liquid increases significantly, and the spreading diffusion speed increases with time from 60s to 120s, until the spreading rate decreases at the ZIF concentration of 0.8 mg / mL. After treatment with a certain concentration of porous material, the contact area and capillary force can be increased, and the spreading effect is significantly improved. When the porous material concentration is too low, due to insufficient capillary force, it has little effect on liquid spreading. Therefore, when preparing porous structure membrane layers, the concentration of porous material is greater than or equal to 0.2 mg / mL.

[0086] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A liquid diffusion control method based on wettability guidance, characterized in that: The control method includes setting a homogeneous liquid film layer or a porous structure film layer on the surface of the substrate, wherein the homogeneous liquid film layer is prepared using a homogeneous liquid, the homogeneous liquid has the same or similar chemical structure as the liquid to be diffused, and the porous structure film layer is prepared using a porous material.

2. The method for controlling liquid diffusion based on wettability guidance according to claim 1, characterized in that: Before providing the substrate with a homogeneous liquid membrane layer or a porous structure membrane layer, the substrate is pretreated, and the pretreatment at least includes cleaning and drying.

3. The method for controlling liquid diffusion based on wettability guidance according to claim 1, characterized in that: The homogeneous liquid film layer is prepared on the surface of the substrate by spin coating, dip coating or spray coating, and the porous structure film layer is prepared on the surface of the substrate by spin coating, dip coating or spray coating.

4. The method for controlling liquid diffusion based on wettability guidance according to claim 1, characterized in that: The thickness of the homogeneous liquid membrane layer is 5-100 nm, and the thickness of the porous structure membrane layer is 5-100 nm.

5. The method for controlling liquid diffusion based on wettability guidance according to any one of claims 1 to 4, characterized in that: The substrate comprises one of a silicon wafer, a silicon / silicon dioxide wafer, a silicon / diamond-like carbon wafer and a silicon / metal wafer.

6. The method for controlling liquid diffusion based on wettability guidance according to claim 5, characterized in that: When the liquid to be diffused is an alkane-aromatic hydrocarbon mixed immersion liquid, the homogeneous liquid is one of an alkane organic liquid, an aromatic hydrocarbon organic liquid, and an alkane-aromatic hydrocarbon mixed organic liquid; When the liquid to be diffused is an acrylate curing adhesive, the homogeneous liquid is at least one of epoxy acrylate, polyurethane acrylate, polyether acrylate and polyester acrylate.

7. The method for controlling liquid diffusion based on wettability guidance according to claim 6, characterized in that: The porous material includes at least one of a metal organic framework porous material and a covalent organic framework porous material.

8. The method for controlling liquid diffusion based on wettability guidance according to claim 7, characterized in that: The porous material is zeolite imidazolate skeleton-8, and the pore diameter of the zeolite imidazolate skeleton-8 is 0.34~1.16nm; the concentration of the zeolite imidazolate skeleton-8 in the porous material solution prepared using the zeolite imidazolate skeleton-8 is greater than or equal to 0.2mg / mL.

9. A liquid diffusion segmented control method based on wettability guidance, characterized in that: The following steps are involved: S1. Testing the initial contact angle between the liquid to be diffused and the substrate surface; S2. When the initial contact angle is ≤10°, a homogeneous liquid film layer or a porous structure film layer is provided on the surface of the substrate, wherein the homogeneous liquid film layer is prepared using a homogeneous liquid having a chemical structure identical or similar to that of the liquid to be diffused, and the porous structure film layer is prepared using a porous material; When the initial contact angle is greater than 10°, the surface of the substrate is chemically modified.

10. A substrate, characterized in that: The substrate is obtained by processing the liquid diffusion control method based on wettability guidance according to any one of claims 1 to 8 or the liquid diffusion segmented control method based on wettability guidance according to claim 9.

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