Preparation method of model

Abstract

The invention provides a preparation method of a model, which comprises the following steps: chemically modifying a silicon-based substrate by using a siloxane compound containing double bonds to obtain a chemically modified silicon-based substrate; fixing the chemically modified silicon-based substrate on a metal platform, performing 3D printing according to a pre-constructed model, and forming a model on the chemically modified silicon-based substrate; and separating the silicon-based substrate on which the model is formed from a metal platform of the 3D printer. The silicon-based substrate is chemically modified by adopting the siloxane compound containing the double bonds, so that the adhesive force between the model and the silicon-based substrate is improved, and a tiny model with the size as small as 10 microns can be printed on the flat and smooth silicon-based substrate. Moreover, the model is directly prepared on the silicon-based substrate, so that a silicon-based chip or a micro-fluidic chip can be directly obtained. And on the other hand, the model can be separated from the silicon-based substrate by adopting acid liquor treatment, and the model, especially a tiny model, cannot be damaged.

Description

Technical Field

[0001] The present invention relates to the technical field of 3D printing, and in particular to a method for preparing a model. Background Art

[0002] 3D printing technology, also known as additive manufacturing technology, is a type of rapid prototyping technology. It is based on digital model files and constructs three-dimensional objects by printing point by point or layer by layer. Compared with traditional manufacturing, 3D printing technology does not require mold manufacturing or mechanical processing, avoiding the waste of materials and energy in traditional subtractive manufacturing processes. 3D printing based on induced curing occupies an absolute dominant position in new 3D printing methods, and has unique advantages in the preparation of high-precision structures. Using a curable liquid as ink to trigger its curing can make the structure to be printed grow out of the liquid material, thereby opening up new sensor technology, new drug delivery technology, and new chip laboratory applications.

[0003] Stereolithography is a 3D printing technology based on light-induced curing. A computer controls the laser beam, uses ultraviolet light to cure liquid photocurable resin layer by layer through the design data provided by the computer-aided design (CAD) system, and combines the planar movement of the light source with the vertical movement of the platform to create three-dimensional objects. Stereolithography has the advantages of high precision, less time consumption, no tools required in the molding process, no need for human intervention, and highly integrated design and manufacturing.

[0004] Existing stereolithography 3D printing is usually performed on a metal platform. In order to ensure that the printed model adheres to the platform and does not fall off, the platform usually needs to have a certain degree of roughness to increase the contact area between the light-curing resin and the platform, thereby improving the adhesion between the two. After printing is completed, the model usually needs to be removed with a tool such as a blade. This process may cause damage to the model, and the damage to the tiny model is even more serious. Summary of the invention

[0005] In view of this, the present invention provides a method for preparing a model. The method provided in the present application does not require the use of tools such as blades to remove the model, and will not cause damage to the model, especially the tiny model.

[0006] In the existing stereolithography 3D printing technology, in order to ensure the close integration of the model and the platform, it is usually necessary to carry out the work on a platform with a certain degree of roughness. If stereolithography 3D printing is carried out on a flat and smooth silicon-based substrate, the van der Waals force between the non-polar silicon-based substrate and the polar resin is weak, and the contact area between the resin and the substrate is small on the smooth surface, resulting in poor adhesion between the model formed by the resin and the substrate, especially small-sized models are easily fallen off during printing or cleaning.

[0007] Based on this, the present application provides a method for preparing a model, comprising the following steps: a) chemically modifying a silicon-based substrate using a siloxane compound containing a double bond to obtain a chemically modified silicon-based substrate; b) fixing the chemically modified silicon-based substrate on a metal platform of a 3D printer, performing 3D printing according to a pre-constructed model, and forming a model on the chemically modified silicon-based substrate; c) Separating the silicon-based substrate with the pattern formed thereon from the metal platform of the 3D printer.

[0008] The present application uses a siloxane compound containing a double bond to chemically modify the silicon-based substrate, thereby improving the adhesion between the model and the silicon-based substrate, so that a micro-model as small as 10 μm can be printed on a flat and smooth silicon-based substrate. Moreover, the present application directly prepares the model on the silicon-based substrate, and a silicon-based chip or a microfluidic chip can be directly obtained. On the other hand, the present application can use acid treatment to separate the model from the silicon-based substrate without causing damage to the model, especially the micro-model.

[0009] The present application adopts a stereolithography 3D printer to prepare the model, for example, it can be a MMF Precision S230 Micro Stereolithography Precision Printing System, etc. The present application has no special restrictions on the photocurable resin used in the 3D printing, and resins containing unsaturated double bonds such as polyurethane acrylate, epoxy acrylate resin and polyester acrylate resin can be used, preferably polyurethane acrylate. The present application has no special restrictions on the metal platform used in the 3D printing, and the metal platform supporting the printer can be used.

[0010] The present application uses a chemically modified silicon-based substrate as a carrier to print the model. Specifically, the present application first cuts the silicon-based substrate into appropriate sizes. The minimum required size is enough for the laser to measure distance at four corners, such as covering the four laser ranging points of the metal platform of the stereolithography 3D printer to ensure smooth leveling of the silicon-based substrate surface. The maximum size is approximately equal to the size of the metal platform. For example, when using the Mofang Precision S230 Micro Stereolithography Precision Printing System, the minimum size of the silicon-based substrate is about 1*1cm and the maximum size is about 6*6cm. In some specific implementations, the silicon-based substrate is a substrate containing silicon or silicon compounds as the main component, including but not limited to quartz, glass, silicon wafers or silicon dioxide ceramics, etc., preferably quartz, glass or silicon wafers.

[0011] After obtaining a silicon-based substrate of suitable size, it is chemically modified. Specifically, the silicon-based substrate can be chemically modified according to the following method: a1) pre-treating the silicon-based substrate; a2) After the pre-treated silicon-based substrate is subjected to plasma treatment, chemical modification is performed using a siloxane compound containing double bonds to obtain a chemically modified silicon-based substrate.

[0012] The present application first pre-treats the silicon-based substrate to improve the bonding ability of the siloxane compound containing double bonds with the silicon-based substrate. Specifically, the pre-treatment includes the following steps: The silicon-based substrate is cleaned in acetone, anhydrous ethanol and water respectively, and then treated in a cleaning solution, and then washed with water to obtain a pretreated silicon-based substrate; The cleaning solution includes concentrated sulfuric acid, hydrogen peroxide and water.

[0013] The present application cleans the silicon-based substrate in acetone, anhydrous ethanol and water respectively, preferably ultrasonic cleaning, the cleaning time is preferably 3min~10min, the water is preferably deionized water, and then the surface is preferably fully cleaned with deionized water, and then the treatment is continued in the cleaning solution. In some specific implementations, the cleaning solution includes concentrated sulfuric acid, hydrogen peroxide and water. In some specific implementations, the cleaning solution includes concentrated sulfuric acid and hydrogen peroxide solution in a volume ratio of 50~70:30~50, preferably 70:30; the concentration of the concentrated sulfuric acid is more than 90%, preferably 98%; the concentration of the hydrogen peroxide solution is 20wt%~40wt%, preferably 30%. The treatment temperature is preferably 100℃~150℃, more preferably 120℃~140℃, and the time is preferably 1h~2h, more preferably 1.5h. After the treatment in the cleaning solution, it is washed, preferably with deionized water until there is no acid residue.

[0014] Since the upper surface of the silicon-based substrate needs to be determined as the initial plane for printing during the 3D printing process, and the upper surface of the transparent substrate (such as quartz, glass) cannot be accurately focused, it is necessary to construct an opaque area on its surface to facilitate focusing. The present application uses a vacuum evaporation method to deposit a 10nm~20nm metal chromium layer on a corner of the surface of the cleaned transparent silicon-based substrate. In some specific implementations, the area of ​​the metal chromium layer is approximately 3*3mm.

[0015] After the silicon-based substrate is pretreated, it is treated in plasma, preferably in oxygen plasma, so that functional groups such as hydroxyl groups are generated on the surface of the silicon-based substrate. In some specific implementations, the treatment time is preferably 3min~8min, more preferably 5min, and then chemically modified with a siloxane compound containing a double bond. Specifically, the silicon-based substrate after plasma treatment can be immersed in a solution of a siloxane compound containing a double bond for treatment. The chemical formula of the siloxane compound containing a double bond can be Y-Si(OR)3, wherein Y is an organic functional group containing a double bond, R is an alkyl group, etc., and the silaneoxy group is reactive to inorganic substances, and the organic functional group is reactive or compatible with organic substances. Therefore, the siloxane compound containing a double bond can form a bonding layer of an organic matrix-silane coupling agent-inorganic matrix between the inorganic and organic interfaces. In some specific implementations, the siloxane compound containing double bonds includes, but is not limited to, one or more of γ-methacryloxypropyltrimethoxysilane (silane coupling agent KH-570, chemical formula CH2=C(CH3)COO(CH2)3Si(OCH3)3), vinyltrimethoxysilane (A-171, chemical formula CH2=CHSi(OCH3)3), vinyltri(β-methoxyethoxy)silane (A-172, chemical formula CH2=CHSi(OCH2CH2OCH3)3) or vinyltriethoxysilane (A-151, chemical formula CH2=CHSi(OC2H5)3), preferably silane coupling agent KH-570. The present application has no special restrictions on the solvent of the solution of the siloxane compound containing double bonds, and any solvent that can dissolve the siloxane compound containing double bonds to form a solution, such as toluene, is sufficient. The present application has no special limitation on the immersion temperature, which can be room temperature. The present application has no special limitation on the immersion time, which is preferably 10 h to 20 h, and more preferably 12 h.

[0016] Taking silane coupling agent KH570 as an example, the principle of chemical modification of silicon-based substrates is as follows: Figure 1 As shown, Figure 1 Schematic diagram of the principle of chemical modification of silicon-based substrate for this application: There are a large number of -OH (hydroxyl) groups on the surface of the silicon-based substrate treated with oxygen plasma, in which the O (oxygen) atoms perform nucleophilic substitution on the Si (silicon) atoms in the coupling agent, ultimately forming SiO2 (Si)-O-Si bonds, thereby modifying the carbon-carbon double bonds on the substrate surface.

[0017] After completing the modification of the silicon-based substrate, fix it on the metal platform of the 3D printer. The present application preferably uses a photocurable resin to fix the silicon-based substrate on the metal platform. Specifically, for a transparent silicon-based substrate, first drip a photocurable resin on the metal platform, then cover the silicon-based substrate on the photocurable resin so that the photocurable resin is fully filled into the gap between the silicon-based substrate and the metal platform, and then use an ultraviolet flashlight to irradiate for about 5 seconds to cure the photocurable resin in the gap to fix the silicon-based substrate. For an opaque silicon-based substrate, first place the silicon-based substrate on the metal platform, then drip the photocurable resin evenly along the edge of the silicon-based substrate, and then irradiate with an ultraviolet flashlight for about 5 minutes.

[0018] After the modified silicon-based substrate is fixed on the metal platform, the four corners of the silicon-based substrate are preferably laser-measured and leveled, and the upper surface of the silicon-based substrate is determined to be the initial plane for printing by focusing with ultraviolet light, and then 3D printing is performed. As mentioned above, the present application has no special restrictions on the parameters of the 3D printing, and they can be adjusted according to the model to be printed.

[0019] The photocurable resin used in 3D printing contains photoinitiators, resin monomers / oligomers, adhesives, etc. The photoinitiator can absorb light of a specific wavelength and generate active free radicals. The active free radicals can combine with the monomers / oligomers and activate them, and cross-link and cure with other monomers / oligomers to change from liquid to solid. In stereolithography 3D printing, the binding force between the model and the substrate is mainly a weak intermolecular force, and a stronger chemical bond can enhance its binding force. Photocurable resin monomers usually contain unsaturated double bonds. Under the action of active free radicals, the double bonds will be activated and react with the double bonds of other resin monomers. The present application modifies the carbon-carbon double bonds on the surface of the silicon-based substrate. When the photocurable resin is irradiated with ultraviolet light on the surface of the substrate, the double bonds on the surface of the substrate participate in the reaction and couple with the double bonds in the resin monomer. Therefore, the binding force between the model and the substrate changes from a weak intermolecular force to a strong chemical bond, achieving the effect of enhancing the adhesion between the model and the substrate. Taking polyurethane acrylate resin as an example, the schematic diagram of the coupling mechanism of the photocurable resin and quartz during the photocuring process is shown in the figure. Figure 2 As shown, Figure 2The schematic diagram of the coupling mechanism of photocurable resin and quartz. When the photoinitiator R in the photocurable resin is irradiated by a light source of a certain wavelength, it will absorb energy and undergo a photolysis reaction to generate free radicals. The reaction process is shown in formula (1). The free radicals can activate the polyurethane acrylate monomers and oligomers (in the subsequent steps, the monomers are replaced by the letter M), activate and initiate the polymerization of the active monomers and oligomers, as shown in formula (2). The active monomers and oligomers will couple with the carbon-carbon double bonds on the surface of the substrate, and crosslink and cure with other monomers and oligomers to form a polymer with a photoinitiator and one end coupled to the surface of the substrate, as shown in formula (3). When encountering another polymer with a photoinitiator, the polymerization reaction is terminated to form a high molecular polymer coupled to the substrate, as shown in formula (4).

[0020] After printing is completed, the obtained model is attached to the silicon-based substrate. The silicon-based substrate is separated from the metal platform to obtain a silicon-based substrate with an integrated model, which can be directly used as a silicon-based chip. In some specific implementations, a blade can be used to separate the silicon-based substrate from the metal platform without damaging the model. After separating the silicon-based substrate, it is preferred to rinse the silicon-based substrate with ethanol, then rinse it in DMF (N-N'dimethylformamide) for 3 to 5 seconds to remove the residual uncured resin, and finally rinse it with ethanol and blow dry.

[0021] The present application may also adopt the method of soaking the silicon-based substrate integrated with the model in an acid solution to non-destructively separate the model from the silicon-based substrate. Specifically, the present application may soak the silicon-based substrate integrated with the model in a hydrofluoric acid solution to separate the model from the silicon-based substrate. In some specific implementations, the concentration of the hydrofluoric acid is preferably 5% to 15%, more preferably 10%. In some specific implementations, the soaking is preferably carried out under ultrasound, the power of the ultrasound is preferably 10W to 50W, more preferably 10W to 30W, most preferably 10W to 20W, and the soaking time is preferably 20s to 90s, more preferably 30s to 60s. After soaking, filter with a stainless steel mesh and wash to obtain a model.

[0022] The method provided in the present application can prepare a model or a microfluidic chip by a 3D printing method, and there is no special restriction on the size of the model, which can be as low as 10 μm, for example, 10 μm to 100 μm.

[0023] This application couples the printed model with a smooth silicon-based substrate through a siloxane compound containing double bonds, so that the binding force between the model and the substrate changes from a weak physical adsorption force to a strong chemical bond, and realizes 3D printing of a micro-model on a smooth silicon-based substrate, which can realize the direct integration of micro-components. Compared with an unmodified silicon-based substrate, the method provided by this application can reduce the model size to 20μm ~30μm, or even 10μm ~20μm, which is smaller than the size of the model directly printed on the metal platform of the printer. Moreover, this application uses acid immersion to separate the model from the silicon-based substrate, without the use of tools such as blades, and will not cause damage to the model. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a schematic diagram of the principle of chemically modifying a silicon-based substrate in this application; Figure 2 Schematic diagram of the coupling mechanism between photocurable resin and quartz; Figure 3 A photo of the printed silicon wafer provided in Example 1; Figure 4 A microscope image of the micro-model on the silicon wafer after printing provided in Example 1; Figure 5 A microscope photo of the printed quartz plate provided in Example 2; Figure 6 A microscopic photograph of the model after shedding provided in Example 2; Figure 7 A microscope photo of the printed silicon wafer provided in Example 3; Figure 8 A microscope photo of the printed quartz plate provided in Example 4; Fig. 9 A microscope photo of the metal platform after printing provided for Comparative Example 1; Fig.10 A microscope photo of the printed silicon wafer provided for Comparative Example 2; Fig.11 This is a microscope photo of the printed quartz plate provided for Comparative Example 3. DETAILED DESCRIPTION

[0025] It should be understood that the expression "one or more of..." includes each of the items recited after the expression individually and in various different combinations of two or more of the recited items, unless otherwise understood from the context and usage. The expression "and / or" in combination with three or more recited items should be understood to have the same meaning, unless otherwise understood from the context.

[0026] The use of the terms "comprising", "having" or "containing", including their grammatical synonyms, should generally be understood as open and non-restrictive, for example not excluding other unrecited elements or steps, unless otherwise specifically stated or otherwise understood from the context.

[0027] It should be understood that the order of steps or the order in which certain actions are performed is not important as long as the present invention remains operable. In addition, two or more steps or actions may be performed simultaneously.

[0028] The use of any and all examples or exemplary language, such as "for example" or "including", herein is intended only to better illustrate the invention and does not limit the scope of the invention unless otherwise claimed. No language in this specification should be construed as indicating that any non-claimed element is essential to the practice of the invention.

[0029] In addition, the numerical ranges and parameters used to define the present invention are approximate values, and the relevant values ​​in the specific embodiments have been presented as accurately as possible. However, any numerical value inherently inevitably contains standard deviations due to individual test methods. Therefore, unless otherwise expressly stated, it should be understood that all ranges, quantities, values ​​and percentages used in this disclosure are modified by "about". Here, "about" generally means that the actual value is within plus or minus 10%, 5%, 1% or 0.5% of a specific value or range.

[0030] The present application provides a method for preparing a model, comprising the following steps: a) chemically modifying a silicon-based substrate using a siloxane compound containing a double bond to obtain a chemically modified silicon-based substrate; b) fixing the chemically modified silicon-based substrate on a metal platform of a 3D printer, performing 3D printing according to a pre-constructed model, and forming a model on the chemically modified silicon-based substrate; c) Separating the silicon-based substrate with the pattern formed thereon from the metal platform of the 3D printer.

[0031] The present application uses a siloxane compound containing a double bond to chemically modify the silicon-based substrate, thereby improving the adhesion between the model and the silicon-based substrate, so that a micro-model as small as 10 μm can be printed on a flat and smooth silicon-based substrate. Moreover, the present application directly prepares the model on the silicon-based substrate, and a silicon-based chip or a microfluidic chip can be directly obtained. On the other hand, the present application can use acid treatment to separate the model from the silicon-based substrate without causing damage to the model, especially the micro-model.

[0032] The present invention is further described below in conjunction with the following examples. The protection scope of the present invention is not limited by the following examples.

[0033] In the following embodiments, the photocurable resin is HTL resin produced by Shenzhen Mofang Material Technology Co., Ltd., and its main components are polyurethane acrylate, 2-methyl-1,8-neodiol diacrylate, (2,4,6-trimethylbenzoyl) diphenylphosphine oxide, 4-acryloylmorpholine and tris(2-acryloyloxyethyl) isocyanurate.

[0034] Example 1 The silicon wafer was cut into pieces of about 3*4cm in size and ultrasonically treated with acetone, anhydrous ethanol and deionized water for 5min respectively. Then the surface of the silicon wafer was thoroughly cleaned with deionized water. The silicon wafer was then placed in a cleaning solution (a mixed solution of 98% concentrated sulfuric acid and 30% hydrogen peroxide with a volume ratio of 7:3) and heated at 140℃ for 1h. Then the silicon wafer was cleaned with deionized water until no acid residue remained.

[0035] Use a pipette to take 500 μL of silane coupling agent KH-570 and add it to 100 mL of toluene to prepare a coupling agent solution. Treat the cleaned silicon wafer with oxygen plasma for 5 minutes, then soak it in the coupling agent solution for 12 hours to obtain a modified silicon wafer, which is then rinsed with ethanol and blown dry.

[0036] Place the modified silicon wafer on the printing platform, use a dropper to absorb some photocurable resin and then drip it along the edge of the silicon wafer, irradiate it evenly with a UV flashlight with a wavelength of 405nm for about 5 minutes to fix the silicon wafer on the platform, import the STL file of the concentric ring model with a line diameter of 20μm pre-built in Solidworks, and then use the MMF Precision S230 micro-stereolithography precision printing system to perform normal 3D printing operations.

[0037] After printing, the model adheres to the silicon wafer. Remove the silicon wafer with a blade, rinse it with ethanol, and then rinse it in DMF for 5 seconds to remove the residual resin, and obtain a silicon wafer with a 20μm diameter concentric ring model attached. Figure 3 and Figure 4 , Figure 3 This is a photo of the printed silicon wafer provided in Example 1. Figure 4 The microscopic picture of the micro-model on the silicon wafer after printing provided in Example 1 is provided by Figure 3 and Figure 4 It can be seen that the method provided in the present application can prepare a concentric ring model with a wire diameter of 20 μm without any damage.

[0038] Example 2 The quartz slice was cut into pieces of about 3*3cm in size, and ultrasonically treated with acetone, anhydrous ethanol, and deionized water for 5 minutes respectively. The surface of the quartz slice was then thoroughly cleaned with deionized water. The quartz slice was then placed in a cleaning solution (a mixed solution of 98% concentrated sulfuric acid and 30% hydrogen peroxide, with a volume ratio of 7:3) and heated at 140°C for 1 hour. The quartz slice was then cleaned with deionized water until no acid remained. A layer of chromium with a thickness of 10-20nm was then deposited on a portion about 3mm wide on one side of the quartz slice using a vacuum evaporator for focusing.

[0039] Use a pipette to take 500 μL of silane coupling agent KH-570 and add it to 100 mL of toluene to prepare a coupling agent solution. Treat the treated quartz plate with oxygen plasma for 5 minutes, then soak it in the coupling agent solution for 12 hours to obtain a modified quartz plate, rinse the modified quartz plate with ethanol and blow dry.

[0040] Add a few drops of photocurable resin on the printing platform, cover the quartz plate on the resin, and evenly fill the resin into the interlayer gap between the quartz plate and the platform. Use a 405nm UV flashlight to evenly irradiate the quartz plate for 3-5 seconds to fix the quartz plate on the platform. Import the STL file of the 70μm wide five-pointed star-shaped model array pre-built with Solidworks, and then use the Mofang Precision S230 Micro-stereolithography Precision Printing System to perform normal 3D printing operations. After printing, the model adheres to the quartz plate. Remove the quartz plate with a blade, rinse it with ethanol, and then rinse it in DMF solution for 3 seconds to remove residual resin.

[0041] The quartz plate was placed in a 10% hydrofluoric acid solution and ultrasonicated at 50W power for 1 min, and the model fell off without damage. The obtained model was filtered through a stainless steel mesh and dispersed in ethanol. After standing, the solution was separated to obtain the model.

[0042] See also Figure 5 and Figure 6 , Figure 5 This is a microscope photo of the printed quartz plate provided in Example 2. Figure 6 The microscopic photograph of the model after the fall-off provided in Example 2 is shown by Figure 5 and Figure 6 It can be seen that the method provided in the present application can prepare a 70 μm wide five-pointed star-shaped model, and when it is removed from the substrate using hydrofluoric acid, there is no damage.

[0043] Example 3 The difference from Example 1 is that an STL file of a square model array pre-built with Solidworks is imported, wherein in the square model array, the square models in the same column have the same size, and the side lengths of the square models in the same row decrease by 5 μm column by column, namely 50 μm, 45 μm, 40 μm…15 μm, 10 μm.

[0044] Results Figure 7 , Figure 7 The microscopic photo of the printed silicon wafer provided in Example 3 is shown in FIG. Figure 7 It can be seen that the minimum model size that can be printed on silicon wafers treated with silane coupling agents is about 10~20μm.

[0045] Example 4 The difference from Example 2 is that an STL file of a square model array pre-built with Solidworks is imported, wherein in the square model array, the square models in the same column have the same size, and the side lengths of the square models in the same row decrease by 10 μm column by column, namely 100 μm, 90 μm, 80 μm…20 μm, 10 μm.

[0046] Results Figure 8 , Figure 8 The microscopic photograph of the printed quartz sheet provided in Example 4 is shown in FIG. Figure 8 It can be seen that the minimum model size that can be printed on silicon wafers treated with silane coupling agents is about 20~30μm.

[0047] Comparative Example 1 The difference from Example 4 is that 3D printing is performed directly on the metal platform.

[0048] Results Fig. 9 , Fig. 9 Microscope photo of the printed metal platform provided for Comparative Example 1, by + Fig. 9 It can be seen that the minimum model size that can be printed on the metal platform is about 30~40μm.

[0049] Comparative Example 2 The difference from Example 4 is that the step of treating the silicon wafer with a coupling agent solution is omitted.

[0050] Results Fig.10 , Fig.10 Microscope photo of the printed silicon wafer provided for Comparative Example 2, Fig.10 It can be seen that the minimum model size that can be printed on unprocessed silicon wafers is about 60~70μm.

[0051] Comparative Example 3 The difference from Example 4 is that the step of treating the quartz plate with a coupling agent solution is omitted.

[0052] Results Fig.11 , Fig.11 This is a microscope photo of the printed quartz plate provided for Comparative Example 3, with no model attached to the quartz plate.

[0053] It can be seen that the method provided by the present application improves the adhesion between the model and the substrate and reduces the size of the printable model, even if the minimum printable model size is smaller than the minimum model size of the matching metal platform.

[0054] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A method for preparing a model, characterized in that: The following steps are involved: a) chemically modifying a silicon-based substrate using a siloxane compound containing a double bond to obtain a chemically modified silicon-based substrate; b) fixing the chemically modified silicon-based substrate on a metal platform of a 3D printer, performing 3D printing according to a pre-constructed model, and forming a model on the chemically modified silicon-based substrate; c) Separating the silicon-based substrate with the pattern formed thereon from the metal platform of the 3D printer.

2. The preparation method according to claim 1, characterized in that: Also includes: d) treating the silicon-based substrate on which the model is formed in an acid solution to separate the silicon-based substrate from the model to obtain the model.

3. The preparation method according to claim 2, characterized in that: In the step d), the acid solution is hydrofluoric acid.

4. The preparation method according to any one of claims 1 to 3, characterized in that The step a) specifically includes: a1) pre-treating the silicon-based substrate; a2) After the pre-treated silicon-based substrate is subjected to plasma treatment, chemical modification is performed using a siloxane compound containing double bonds to obtain a chemically modified silicon-based substrate.

5. The preparation method according to claim 4, characterized in that: The siloxane compound containing double bonds includes one or more of γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane or vinyltriethoxysilane; The silicon-based substrate is selected from quartz, glass, silicon wafer or silicon dioxide ceramic.

6. The preparation method according to claim 4, characterized in that: The step a1) specifically includes: The silicon-based substrate is cleaned in acetone, anhydrous ethanol and water respectively, and then treated in a cleaning solution, and then washed with water to obtain a pretreated silicon-based substrate; The cleaning solution includes concentrated sulfuric acid, hydrogen peroxide and water.

7. The preparation method according to claim 6, characterized in that: The cleaning solution comprises concentrated sulfuric acid and hydrogen peroxide solution in a volume ratio of 50-70:30-50; The concentration of the concentrated sulfuric acid is above 90%; The concentration of the hydrogen peroxide solution is 20wt%-40wt%.

8. The preparation method according to any one of claims 1 to 3, characterized in that In the step b), the light-curable resin used in the 3D printing includes one or more of polyurethane acrylate, epoxy acrylate resin and polyester acrylate resin.

9. The preparation method according to any one of claims 1 to 3, characterized in that: In the step b), the chemically modified silicon-based substrate is fixed on a metal platform of a 3D printer using a photocurable resin; In the step c), a cutter is used to separate the silicon-based substrate on which the model is formed from the metal platform of the 3D printer.

10. The preparation method according to any one of claims 1 to 3, characterized in that: In the step b), the size of the model is 10 μm to 100 μm.

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