A cross-scale extreme precision manufacturing technology method and application thereof

Abstract

The application belongs to the field of surface processing, and particularly relates to a cross-scale limit precision manufacturing technology method and application thereof. The method comprises the following steps: respectively prefabricating an imprinting template with a nano-array structure, a micro-array structure and a millimeter-array structure on a processing surface, sequentially performing nano-imprinting, micro-imprinting and millimeter-imprinting on a carrier with a work hardening effect, and controlling the structure scale of the processing surface of the imprinting template used in the subsequent imprinting process to be larger than the structure scale of the processing surface of the imprinting template used in the previous imprinting process. The application can functionalize and beautify the surface of any material with work hardening characteristics through multi-stage imprinting cooperation, and the process is simple and efficient, suitable for batch production and preparation, has strong industrial value, and the carrier after the imprinting processing is convenient for additive shape manufacturing, can realize more diversified application, and can easily manufacture a material with multi-stage micro-nano structure in more materials.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of surface processing, and particularly relates to a cross-scale limit precision manufacturing technology method and application thereof. BACKGROUND

[0002] Cross-scale multi-level structures have important research value and broad application prospects in pressure sensing, photothermal management, photoelectrocatalysis, hydrophilic and hydrophobic, and Raman enhancement. For example, the combination of nano and micro structures has a better cooling effect in the field of thermal management; the pressure sensing layer combined with nano, micro and millimeter structures has higher sensitivity and linearity. High precision (especially accurate control of nano structures), low cost, high throughput and multi-material preparation of cross-scale multi-level structures have become key technical problems to be solved at present. At present, there are many technical methods for preparing cross-scale multi-level structures, including 3D printing, laser direct writing technology, electron beam lithography, etc. However, these methods have many shortcomings, such as poor precision and low processing efficiency of 3D printing and laser direct writing technology, high processing cost and limited materials of electron beam lithography technology. In addition, the current preparation methods are mainly based on micro-nano scale structures, and have the disadvantages of simple patterning and small cross-scale range, which cannot meet the requirements of related materials and devices for multi-scale structures.

[0003] Nanoimprint technology is a new material patterning technology. This technology is a technology for transferring structures on a template to a material to be processed, which can achieve ultra-high resolution (up to 2 nm), become an important processing means in the field of microelectronics and materials, and is considered as one of the most potential technologies for the next generation of low-cost, large-scale manufacturing of nanostructures. At present, according to the process and the used materials, it can be divided into thermal curing nanoimprint, ultraviolet curing nanoimprint and mechanical imprint. However, the current nanoimprint technology mainly stays in the nanoscale range, and the cross-scale range formed is extremely limited. In addition, thermal curing nanoimprint and ultraviolet curing nanoimprint technology are mainly used for high polymer materials, and the involved materials are relatively single. Through the intrinsic work hardening characteristics of aluminum metal (one of the work hardening materials), multi-level imprinting is realized, and anodic oxidation means is combined to accurately control nano structures, so as to prepare a cross-scale porous anodic aluminum oxide template, which can realize the replication of multi-material cross-scale multi-level structures by taking the template as a substrate. This method solves the shortcomings of the existing technology, such as small cross-scale range, difficulty in accurate control of micro-nano structures, and narrow range of materials involved. SUMMARY

[0004] In order to solve the characteristics of the existing micro-nano processing method, such as small cross-scale range of the prepared structure, difficulty in accurate control, difficulty in low-cost high-throughput manufacturing, and single material system of the constructed structure, the present application provides a cross-scale limit precision manufacturing technology method and application thereof.

[0005] The present application aims at:

[0006] One, can effectively form multi-level, cross-scale structure;

[0007] Two, controllable precision is high;

[0008] Three, the method is simple and efficient, and can realize low-cost high-throughput manufacturing;

[0009] Four, has good practicability and applicability, and can be effectively used for structured preparation of various materials.

[0010] To achieve the above object, the present application adopts the following technical scheme.

[0011] A cross-scale limit precision manufacturing technical method,

[0012] The method comprises:

[0013] The pre-processed processing surface of the imprinting template contains nano array structure, micro array structure and millimeter array structure, the carrier with work hardening effect is sequentially subjected to nano imprinting, micro imprinting and millimeter imprinting, and the structure size of the processing surface of the imprinting template used in the subsequent imprinting process is controlled to be larger than that of the imprinting template used in the previous imprinting process.

[0014] As shown in Figure 1 The previous imprinting process first forms a nano-micro array structure with smaller size, and then Figure 2 As shown, the structure size of the processing surface of the imprinting template is increased to form a millimeter array structure, and several times of imprinting are performed, so that the preparation of cross-scale array structure can be realized.

[0015] As a preferred,

[0016] The strength and hardness of the imprinting template material are greater than those of the carrier material.

[0017] The specific strength and hardness are hardness and Young's modulus, and at least the hardness performance should be ensured to be greater than that of the carrier material.

[0018] As a preferred,

[0019] The carrier adopts a material with work hardening effect.

[0020] The technical scheme of the present application is based on the work hardening effect of the carrier material, if the work hardening effect is not possessed, the structure produced by the previous imprinting will be seriously damaged when multiple imprinting is performed, which leads to the fact that the technical scheme of the present application cannot be implemented.

[0021] As a preferred,

[0022] The carrier adopts an aluminum carrier, compared with other work-hardened materials, has a wider application field and the largest commercial value.

[0023] The embossing template adopts a nickel embossing template.

[0024] Generally, nickel has high strength and hardness, can effectively emboss the carrier material, and the nickel surface itself is more convenient to form diversified and stable micro-nano structures through deposition or electrochemistry, and is more adjustable, controllable and operable. Therefore, compared with other materials, it has a more optimal actual use effect.

[0025] Preferably,

[0026] The pretreatment includes cleaning, polishing and drying.

[0027] The cleaning of the carrier surface through the pretreatment can guarantee the optimal embossing effect.

[0028] Preferably,

[0029] When the processing surface of the embossing template is a nano-scale structure:

[0030] The embossing treatment controls the pressure of 15-20 MPa.

[0031] When the processing surface of the embossing template is a micro-scale structure:

[0032] The embossing treatment controls the pressure of 3-5 MPa.

[0033] When the processing surface of the embossing template is a millimeter-scale structure:

[0034] The embossing treatment controls the pressure of 1-2 MPa.

[0035] Preferably,

[0036] The structure of the processing surface of the embossing template is an arbitrary customized design structure or pattern, including columnar or hemispherical or table-shaped or conical or hole-shaped structure.

[0037] The above structure can successively prepare a porous array structure, a bowl-shaped array structure, a table-shaped hole array structure, a conical hole array structure and various column / table / cone array structures on the carrier surface. The formed microstructure has strong controllability.

[0038] An application of a cross-scale limit precision manufacturing technology method,

[0039] The method is used for high-precision processing of a material surface micro-nano structure.

[0040] The beneficial effects of the present application are:

[0041] 1) can effectively form multi-level, cross-scale structures;

[0042] 2) high controllable precision;

[0043] 3) simple and efficient method, can realize low-cost high-throughput manufacturing;

[0044] 4) good practicability and applicability, can be effectively used for the structured preparation of various materials;

[0045] 5) the carrier after the imprinting processing is convenient for additive manufacturing, which can realize more diversified applications, so that it can be manufactured with more materials to have multi-level micro-nano structures. BRIEF DESCRIPTION OF DRAWINGS

[0046] Figure 1 Process diagram for sequentially forming a nano array and a micro array on a carrier;

[0047] Figure 2 Schematic diagram for further performing millimeter imprinting on the basis of the nano array and the micro array;

[0048] Figure 3 Characterization diagram of the periodic cross-scale multi-level structure on the surface of the sample obtained in step 4) of Example 1;

[0049] Figure 4 Structural color schematic diagram of the product obtained in step 4) of Example 1;

[0050] Figure 5 Characterization diagram of the regular periodic nano and micro composite structure formed in step 3) of Example 2;

[0051] Figure 6 Characterization diagram of the regular periodic nano and micro composite structure formed in step 3) of Example 3. DETAILED DESCRIPTION

[0052] The present application will be further described and illustrated in detail in the following in combination with specific embodiments and the accompanying drawings. Those skilled in the art will be able to implement the present application based on these descriptions. In addition, the embodiments of the present application involved in the following description are generally only a part of the embodiments of the present application, not all the embodiments. Therefore, based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor shall fall within the scope of protection of the present application.

[0053] Unless otherwise specified, the raw materials used in the embodiments of the present application are commercially available or can be obtained by those skilled in the art; unless otherwise specified, the methods used in the embodiments of the present application are methods mastered by those skilled in the art.

[0054] Example 1

[0055] A cross-scale multi-level carbon structure manufacturing technology method, which specifically comprises:

[0056] 1) Cleaning and polishing of ultra-high purity aluminum sheet: cut 2 cm x 2 cm 99.999% ultra-high purity aluminum sheet with a thickness of 250 μm, ultrasonic cleaning with acetone, isopropyl alcohol and ultrapure water for 10 min respectively, and then electrochemical polishing. The polishing solution is a mixed solution of perchloric acid and ethanol with a volume ratio of 1:9, the polishing voltage is 20 V, the polishing time is 3 min, and after deionized water washing, dry with nitrogen gun.

[0057] 2) Nanostructure imprinting: select a nickel film with a period of 400 nm square array arranged nanorod structure, place the nickel film with the structure on the top of the aluminum sheet treated in step 1), and apply a pressure of 20 MPa for 3 min. After imprinting, regular periodic nanostructures will be obtained on the aluminum sheet.

[0058] 3) Microstructure imprinting: select a nickel film with a period of 20 μm square arranged pyramid microstructure, place the structure on the top of the nanostructure obtained in step 2), and apply a pressure of 5 MPa for 3 min. After imprinting, regular periodic nano and micro composite structures will be obtained on the aluminum sheet.

[0059] 4) Millimeter structure imprinting: replace the 20 μm period pyramid structure nickel template in step 3) with a 0.6 mm period millimeter hemisphere nickel template, and then imprint on the sample after step 3), with a pressure of 2 Mpa and an imprinting time of 3 min. After imprinting, regular periodic cross-scale multi-level structures will be obtained on the aluminum sheet.

[0060] 5) Anodizing process: place the sample after step 4) in a 0.3 M phosphoric acid solution, anodize at 160 V for 20 min, and place the oxidized sample in a 5 wt% phosphoric acid solution, and heat in a 30℃ oven for 30 min.

[0061] 6) Cross-scale multi-level carbon structure replication: place the sample obtained in step 5) in a CVD tube furnace to grow carbon nanotubes, with a gas flow of argon:acetylene:hydrogen = 150:10:15, a temperature of 625℃, a holding time of 1 h, and a heating rate of 20℃ / min. After CVD, spin-coat PDMS (dimethylsiloxane: tetraethyl orthosilicate = 10:1) on the surface of the sample, and cure it in an 80℃ oven for 3 h. After cooling to room temperature, remove the aluminum with a CuCl2 / HCl mixed solution, and then place it in concentrated phosphoric acid to remove the aluminum oxide, and a cross-scale multi-level carbon structure is obtained.

[0062] The periodic cross-scale multi-level structure obtained in step 4) is characterized, as shown in FIG. 4, achieving rapid formation and construction of an ordered and complete cross-scale multi-level array structure. As shown in FIG. 5, after processing by the method of the present application, the aluminum sheet surface forms a structural color, and the micron and macro structures formed can be finely regulated by controlling the embossed array structure, period, and scale. In addition, the nanostructure can be accurately controlled in combination with an anodization process, including parameters such as pore diameter, length, and spacing. Figure 3 Figure 4

[0063] On the other hand, as described in steps 5) and 6) above, the carrier after embossing treatment by the technical solution of the present application can be directly used for additive manufacturing simply and efficiently. Since the technical solution of the present application is limited by the properties of the carrier material and the relative strength and hardness of the carrier material and the embossing template, it is difficult to directly and effectively achieve the preparation of partial material cross-scale multi-level structures, such as common organic film materials, which generally do not have work hardening effect, and some organic materials even have obvious brittleness, such as elemental carbon or materials with brittleness or excessive hardness, thus limiting direct embossing. After adjusting the constructed cross-scale multi-level structure for additive manufacturing, an organic film material and / or a super-hard material film with a cross-scale multi-level array structure can be adaptively manufactured, greatly improving its functionality, aesthetics, and applicability.

[0064] Example 2

[0065] A cross-scale multi-level semiconductor structure manufacturing technology method, the method specifically comprises:

[0066] 1) Cleaning and polishing of ultra-high purity aluminum sheet: cut 2 cm x 2 cm 99.999% ultra-high purity aluminum sheet with a thickness of 250 μm, and ultrasonically clean with acetone, isopropanol and ultrapure water for 10 min, then electrochemically polish. The polishing solution is a mixed solution of perchloric acid and ethanol with a volume ratio of 1:9, the polishing voltage is 20 V, the polishing time is 3 min, and after deionized water washing, dry with a nitrogen gun.

[0067] 2) Nanostructure embossing: select a nickel film with a square arranged nanorod array structure with a period of 400 nm, place the nickel film with the structure facing upwards directly above the aluminum sheet treated in step 1), and apply a pressure of 20 MPa for 3 min. After embossing, regular periodic nanostructures will be obtained on the aluminum sheet.

[0068] ​​3) Microstructure imprinting: A 20 μm square arranged pyramid microstructure nickel film was selected, and the structured side was placed directly above the nanostructure obtained in step 2), and a pressure of 5 MPa was applied for 3 min. After imprinting, a regular periodic nano and micro composite structure was obtained on the aluminum sheet. The obtained sample was characterized, and the results are shown in FIG. 3. Figure 5 As can be clearly seen from Figure 5 The present application further obtains a periodic microstructure on the basis of the original periodic nanostructure, effectively maintains the integrity of the original periodic nanostructure, and realizes the manufacture of a cross-scale multi-level structure.

[0069] 4) Millimeter structure imprinting: The 20 μm period pyramid structure nickel template in step 3) was replaced with a 0.6 mm period millimeter hemispherical nickel template, and then the sample after step 3) was imprinted, with a pressure of 2 Mpa and an imprinting time of 3 min. After imprinting, a regular periodic cross-scale multi-level structure was obtained on the aluminum sheet.

[0070] 5) Anodic oxidation process: The sample after three-dimensional imprinting in step 4) was placed in a 0.3 M phosphoric acid solution for anodic oxidation at 160 V for 20 minutes, and the oxidized sample was placed in a 5 wt% phosphoric acid solution and expanded in a 30 ℃ oven for 30 min.

[0071] 6) Cross-scale multi-level titanium dioxide structure replication: The surface of the sample treated in step 5) was grown with 50 nm titanium dioxide by ALD, and then PMMA solution was spin-coated on the surface and naturally cured. Then, Al was removed using a CuCl2 / HCl mixed solution, and it was placed in 0.5M NaOH at room temperature for 2.5 h to obtain a cross-scale multi-level titanium dioxide structure.

[0072] The obtained cross-scale multi-level titanium dioxide structure not only has a nanotube array structure, but also forms a pyramid array structure at the microscale and a hemispherical array structure at the millimeter scale, and the specific surface area is further significantly increased compared to conventional titanium dioxide nanorod arrays, with a larger active area. Moreover, the preparation process is more simple and efficient, enabling rapid imprinting and replication preparation, significantly improving the preparation efficiency, and significantly reducing the energy consumption compared to the solvothermal method or chemical vapor deposition method, and the structural precision and quality stability of the obtained product are very excellent.

[0073] The obtained titanium dioxide-PMMA film with cross-scale multi-level structure can obtain larger surface area when used for manufacturing oxygen evolution electrode, especially the combination of microscale and millimeter scale structure can enhance its hydrophobicity, so that the subsequent loading of metal oxyacid salt and / or transition metal oxide and other oxygen evolution catalysts in acidic solution has stability, or produces other additional technical effects.

[0074] Example 3

[0075] A cross-scale multi-level PDMS structure manufacturing technology method, the method specifically comprises:

[0076] 1) Cleaning and polishing ultra-high purity aluminum sheet: cut 4 cm x 4 cm 99.999% ultra-high purity aluminum sheet with a thickness of 250 μm, and clean it with acetone, isopropanol and ultrapure water for 10 min, and then electrochemically polish it. Among them, the polishing solution is a mixed solution of perchloric acid and ethanol with a volume ratio of 1:9, the polishing voltage is 20 V, the polishing time is 3 min, and after washing with deionized water, dry it with a nitrogen gun.

[0077] 2) Nanostructure imprinting: select a conical nickel film with a period of 100 nm arranged in a hexagonal pattern, place its structured side directly above the aluminum sheet treated in step 1), and apply a pressure of 20 MPa for 3 min. After imprinting, the aluminum sheet will have regular periodic nanostructures.

[0078] 3) Microstructure imprinting: select a hemispherical nickel film with a period of 5 μm arranged in a hexagonal pattern, place its structured side directly above the nanostructure obtained in step 2), and apply a pressure of 5 MPa for 3 min. After imprinting, the aluminum sheet will have regular periodic nano and micro composite structures. The obtained sample is characterized, and the characterization results are shown in Figure 6 The microscale bowl array formed on the basis of the nanometer conical hole array retains the structural characteristics and high integrity of the nanoarray, and realizes effective cross-scale multi-level structure cooperation.

[0079] 4) Multiscale hierarchical PDMS structure: PDMS solution (dimethylsiloxane: tetraethyl orthosilicate = 10:1) and toluene reagent were mixed in a mass ratio of 3:2, and after stirring, the mixture was placed in a vacuum drying box to remove bubbles. The diluted PDMS solution was dropped onto the surface of the aluminum sheet processed by step 3) and spin-coated at 1000 rpm for 30 s. The spin-coated sample was placed in a vacuum drying box and vacuumized, and after standing for half an hour, it was cured at 90°C for 2 hours. Subsequently, a multiscale hierarchical PDMS structure antireflection film was obtained by a direct peeling method. The PDMS film has a higher antireflection effect, which is at least 6% higher than that of a flat PDMS film. At the same time, it has a strong wide-angle antireflection effect for incident light at angles of -45° to 45°.

Claims

1. A cross-scale extreme precision manufacturing technology method, characterized in that, The method includes: Imprint templates with nano-array, micro-array, and millimeter-array structures on their processing surfaces are prefabricated. Nano-imprinting, micro-imprinting, and millimeter-imprinting are performed sequentially on a carrier with a work-hardening effect. The processing surface structure of the imprint template used in the later imprinting process is controlled to be larger than that of the imprint template used in the earlier imprinting process. The strength and hardness of the embossing template material are greater than those of the carrier material; The carrier is made of a material with a work hardening effect; The imprinted carrier is used for additive composite manufacturing.

2. The method for cross-scale extreme precision manufacturing technology according to claim 1, characterized in that, The carrier is made of aluminum.

3. The method for cross-scale extreme precision manufacturing technology according to claim 1, characterized in that, When the processing surface of the imprint template has a nanoscale structure: The pressure during the imprinting process is controlled at 15–20 MPa; When the processing surface of the imprint template has a micron-level structure: The pressure for the imprinting process is controlled at 3–5 MPa. When the processing surface of the embossing template has a millimeter-level structure: The pressure for the imprinting process is controlled at 0.1–2 MPa.

4. The cross-scale extreme precision manufacturing technology method according to claim 1, characterized in that, The surface structure of the embossing template can be arbitrarily customized.

5. The method for cross-scale extreme precision manufacturing technology according to claim 4, characterized in that, The structure includes columnar, hemispherical, frustum-shaped, conical, or porous structures.

6. A cross-scale extreme precision manufacturing technology method, characterized in that, The method includes: 1) Cleaning and polishing ultra-high purity aluminum sheets: Cut 2 cm × 2 cm sheets of 99.999% ultra-high purity aluminum with a thickness of 250 μm. Clean them ultrasonically with acetone, isopropanol and ultrapure water for 10 min respectively. Then perform electrochemical polishing. The polishing solution is a mixed solution of perchloric acid and ethanol with a volume ratio of 1:

9. The polishing voltage is 20 V and the polishing time is 3 min. After washing with deionized water, dry with a nitrogen gun. 2) Nanostructure Imprinting: Select a nickel film with a period of 400 nm and arrange nanorods in a square array. Place the nickel film with the structure facing up directly above the aluminum sheet treated in step 1), and apply a pressure of 20 MPa for 3 min. After imprinting, a regular periodic nanostructure is obtained on the aluminum sheet. 3) Micron structure imprinting: Select a nickel film with a period of 20 μm square pyramid micron structure, place the structured side of the film directly above the nanostructure obtained in step 2), apply a pressure of 5 MPa, and imprint for 3 min. After imprinting, a regular periodic composite structure of nano and micro will be obtained on the aluminum sheet. 4) Millimeter structure imprinting: Replace the 20 μm periodic pyramid structure nickel template in step 3) with a 0.6 mm periodic millimeter hemispherical nickel template, and then imprint it on the sample after imprinting in step 3). The pressure is 2 MPa and the imprinting time is 3 min. After imprinting, a regular periodic multi-scale structure will be obtained on the aluminum sheet. 5) Anodizing process: The sample after imprinting in step 4) is placed in a 0.3 M phosphoric acid solution and anodized at 160 V for 20 min. The oxidized sample is then placed in a 5 wt% phosphoric acid solution and dried in a 30℃ oven for 30 min to expand the pores. 6) Multiscale carbon structure reconstruction: The sample obtained in step 5) is placed in a CVD tube furnace to grow carbon nanotubes. The gas flow is argon:acetylene:hydrogen = 150:10:15, the temperature is 625℃, the holding time is 1 h, and the heating rate is 20℃ / min. After CVD, PDMS of dimethylsiloxane and tetraethyl orthosilicate = 10:1 is spin-coated onto the surface of the sample and cured in an oven at 80℃ for 3 h. After cooling to room temperature, the aluminum in the sample is removed by CuCl2 / HCl mixed solution, and then the sample is placed in concentrated phosphoric acid to remove alumina, thus obtaining the multiscale carbon structure.

7. A cross-scale extreme precision manufacturing technology method, characterized in that, The method includes: 1) Cleaning and polishing ultra-high purity aluminum sheets: Cut 2 cm × 2 cm sheets of 99.999% ultra-high purity aluminum with a thickness of 250 μm. Clean them ultrasonically with acetone, isopropanol and ultrapure water for 10 min respectively. Then perform electrochemical polishing. The polishing solution is a mixed solution of perchloric acid and ethanol with a volume ratio of 1:

9. The polishing voltage is 20 V and the polishing time is 3 min. After washing with deionized water, dry with a nitrogen gun. 2) Nanostructure Imprinting: Select a nickel film with a period of 400 nm square nanorod array structure, place the structured side of the nickel film directly above the aluminum sheet after step 1), apply a pressure of 20 MPa, and imprint for 3 min. After imprinting, a regular periodic nanostructure will be obtained on the aluminum sheet. 3) Micron structure imprinting: Select a pyramid micron structure nickel film with a period of 20 μm and place it directly above the nanostructure obtained in step 2) with the structured side facing it, and apply a pressure of 5 MPa for 3 min. After imprinting, a regular periodic composite structure of nano and micro will be obtained on the aluminum sheet. 4) Millimeter structure imprinting: Replace the 20 μm periodic pyramid structure nickel template in step 3) with a 0.6 mm periodic millimeter hemispherical nickel template, and then imprint it on the sample after imprinting in step 3). The pressure is 2 MPa and the imprinting time is 3 min. After imprinting, a regular periodic multi-scale structure will be obtained on the aluminum sheet. 5) Anodizing process: Place the sample obtained after three-dimensional imprinting in step 4) into a 0.3 M phosphoric acid solution for anodizing at 160 V for 20 minutes. Place the oxidized sample into a 5 wt% phosphoric acid solution and bake in a 30 ℃ oven for 30 min to expand the pores. 6) Multiscale multilevel titanium dioxide structure reconstruction: 50 nm titanium dioxide was grown on the surface of the sample treated in step 5) using ALD, and then PMMA solution was spin-coated on the surface and allowed to cure naturally. Then, Al was removed using CuCl2 / HCl mixed solution, and the sample was placed in 0.5M NaOH at room temperature for 2.5 h to obtain a multiscale multilevel titanium dioxide structure.

8. An application of the method according to any one of claims 1 to 7, characterized in that, The method is used for the processing of multi-scale micro / nano structures on material surfaces.

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