High-precision cross-scale 3D structure manufacturing method and application thereof

Abstract

A high-precision, multi-scale 3D structure manufacturing method and its application are disclosed. The method includes: performing multi-stage imprinting on a substrate using an imprinting mold, with each imprinting process forming one or more imprinted patterns composed of the target 3D structure; the hardness of the imprinting mold is greater than the hardness of the surface to be processed; during multiple imprinting processes, the target 3D structure is formed sequentially from smallest to largest scale; during multiple imprinting processes, bidirectional calculations are performed based on the morphological requirements of the target 3D structure and / or the mechanical properties of the formed imprinted patterns and the operating parameters of the imprinting operation. This method enables the simple and efficient processing and manufacturing of high-precision, multi-scale 3D structures. Furthermore, through process improvements, the overall solution is applicable to almost all materials, and key parameters are set to significantly improve industrial operability and production efficiency.

Description

High-precision cross-scale 3D structure manufacturing method and application thereof TECHNICAL FIELD

[0001] The application belongs to the field of micro-nano manufacturing technology, and particularly relates to a high-precision cross-scale 3D structure manufacturing method and application thereof. BACKGROUND

[0002] Cross-scale multi-level 3D structures have important research value and broad application prospects in photothermal management, electromagnetic wave regulation, flexible sensing, hydrophilic and hydrophobic, and biochips. For example, a hierarchical porous coating based on expandable phase change has obtained better high-efficiency passive daytime radiative cooling effect (Science 362, 315-319 (2018)). In flexible sensing, cross-scale structures manufactured by high-resolution 3D printing are applied to flexible pressure sensors to obtain high sensitivity and ultrafast response characteristics (Adv. Mater. 2023, 35, 2304070). In the field of superhydrophobicity, Deng Xu of the University of Electronic Science and Technology combined hydrophobic nanoparticles and micrometer structures with high mechanical robustness to obtain a mechanically tough superhydrophobic surface, which can still maintain high-efficiency self-cleaning and antifouling ability in harsh operating environments (Nature 582, 55-59 (2020).). Therefore, high precision (especially accurate control of nanostructures), low cost, high throughput, and multi-material preparation of cross-scale multi-level 3D structures have become key technical problems that need to be solved at present.

[0003] [According to Rule 26 Corrected 27.08.2024] Currently, the fabrication of multi-scale 3D structures mainly includes three different strategies: "top-down", "bottom-up" and "hybrid". In the top-down strategy, the currently studied techniques include electron beam lithography-electroforming, gray-tone lithography, three-beam direct writing technology (electron beam, focused ion beam and laser beam), nanoimprint and 3D printing, etc. Electron beam lithography-electroforming technology needs to combine multi-layer photoresist process, reactive ion beam etching and electroforming to realize the fabrication of multi-scale 3D structures (Acta Physica Sinica, 2013(15):6.). However, its processing technology is complex, the processing equipment is expensive and it cannot realize large-area preparation. Gray-tone lithography uses a mask or direct writing method to obtain different exposure doses at different positions on the same photoresist film, and then completely or partially develops in the developer to obtain 3D micron structures (International Journal of Extreme Manufacturing, 2020, 2(2): 022004.). However, the 3D profile of gray-tone lithography is not an arbitrary curved surface and this technology is limited to micron scale. Three-beam direct writing technology belongs to point-by-point processing technology, which has low processing efficiency, poor nanoscale resolution and high cost, and is not suitable for batch processing (CN201810288939.0). Although most of the "top-down" strategies can well realize the controlled fabrication of 2D planar micron and nanometer structures, the accurate control and fabrication on the cross-scale 3D curved surface are still very challenging.

[0004] In recent years, nanoimprint has made great progress in the preparation of 3D micro-nano structures. For example, in 2015, Professor Choi of Seoul University in South Korea and Professor Saifullah of National University of Singapore based on oxygen inhibition effect and sacrificial layer creep assisted mechanism, obtained polymer film with multi-level 3D micro-nano structure by combining nanoimprint and micro-lithography / imprint (Nat. Commun. 6, 8484 (2015).). In 2019, Professor Shao Jinyou of Xi'an Jiaotong University used the suspended and discrete 3D imprinting technology of superimposed micro-pattern and nano-pattern to obtain good nanoimprint patterns on micro-curved surface and steps. But the current imprinting technology is only suitable for a few specific polymer film materials and the cross-scale range is limited (ACS Nano 2019, 13, 9, 10333-10342). For example, in 2011, Professor Chu Jin-kui of Dalian University of Technology published a patent CN201110043750.3 based on one-dimensional soft template nanoimprint to make three-dimensional nano-grid structure, which uses soft template imprinting, reactive ion etching and dry etching combined with multiple processing to form three-dimensional nano-network structure. Although it can realize the preparation of cross-scale three-dimensional micro-nano structure, the scale span is small, and it is very limited by material and etching process, with low manufacturing efficiency and high cost, and the etching process will also generally bring pollution. In 2008, Professor Liu Hongzhong of Xi'an Jiaotong University published a patent CN200810018360.9 full band three-dimensional photonic crystal imprint forming method and full band three-dimensional photonic crystal structure, which uses imprinting to realize the construction of specific structure, but the imprinting operation used is only used for specific materials to obtain specific products, with poor universality and difficult to effectively realize cross-scale imprinting manufacturing, and also difficult to precisely manufacture new designed micro-nano cross-scale structure.

[0005] Before this, our party has carried out partial research on the embossing technology, which uses nano embossing, micro embossing and macro (millimeter level) embossing processing in turn to realize cross-scale precision embossing manufacturing. However, the previous research still has certain applicability defects. Firstly, the universality defect, that is, when the work hardening material is implemented, the previous research mainly takes the applied pressure as the main control parameter, but the technical effect of different pressures is completely different for different materials. Secondly, the previous research takes the pressure as the direct single control parameter, which may cause the mechanical properties of the processed substrate to fluctuate due to the difference between materials and even the difference between batches of materials in the industrial operation process, and the fluctuation is amplified in the embossing process, so that the same different batches of materials may form good and bad processing effects. For example, different batches of the same aluminum material may have similar basic mechanical properties, but due to other intrinsic reasons, the work hardening degree is different, so that when the same operation parameters are used for processing or the embossing process is carried out within the same pressure range, the target 3D structure formed by embossing is not clear, not complete or the embossed pattern is not clear, not complete. Thirdly, due to the poor operability and poor manufacturing stability, the actual industrialization and industrialization are difficult.

[0006] SUMMARY

[0007] The existing cross-scale multi-level structure processing and manufacturing technology has certain defects, and the previous micro-nano embossing technology solves some problems of traditional processing and manufacturing technology, but still has problems such as difficult industrialization, and the present application provides a method for realizing high-precision cross-scale 3D structure manufacturing with more effective parameter control and the application of the method.

[0008] The main purpose of the present application is to:

[0009] I. can realize cross-scale (span size reaches 10 8 and above), high-precision (5 nanometers and above) structure manufacturing more quickly and effectively through parameter optimization;

[0010] II. The method is simple and efficient, and improves the reliability and effectiveness of the method;

[0011] III. can be effectively applied to industrialization improvement.

[0012] In order to achieve the above purpose, the present application adopts the following technical scheme.

[0013] A high-precision cross-scale 3D structure manufacturing method,

[0014] The method comprises:

[0015] selecting a processing substrate, and performing multiple imprinting processes on the processing substrate;

[0016] The imprinting process uses an imprinting mold, which is aligned with the surface to be processed of the processing substrate, fixes the processing substrate and applies pressure to the imprinting mold towards the surface to be processed, so that the imprinting mold performs imprinting process on the processing substrate. After each imprinting process, a single or multiple imprinting patterns composed of the target 3D structure are formed;

[0017] The hardness of the imprinting mold is greater than the hardness of the surface to be processed;

[0018] And during the multiple imprinting processes, the mold hardness used in each imprinting process must be greater than the hardness of the surface to be processed after the previous processing, so as to ensure that the imprinting process can be effectively carried out, not just greater than the hardness of the original processing substrate surface; During the multiple imprinting processes, the target 3D structure is formed from small to large in size;

[0019] During the multiple imprinting processes, the target 3D structure is formed from small to large in size;

[0020] After the multiple imprinting processes, the target material can be deposited according to the requirements of the target material using physical and / or chemical methods to form the required secondary 3D structure.

[0021] As a preferred,

[0022] The processing substrate is a material with ductility;

[0023] The material with ductility includes carbon and / or semiconductor and / or metal and / or alloy and / or metal compound and / or organic material and / or ceramic.

[0024] As a preferred,

[0025] If the target 3D structure is a structure protruding from the surface before the imprinting process, an imprinting mold with a groove structure is used for the imprinting process;

[0026] If the target 3D structure is a structure recessed from the surface before the imprinting process, an imprinting mold with a protruding structure is used for the imprinting process.

[0027] As a preferred,

[0028] The mechanical property is the hardness of the surface to be processed;

[0029] The operating parameter of the imprinting work is the pressure;

[0030] From the second imprinting process, the hardness of the surface to be processed before each imprinting process is H0, and the conversion hardness H of the pressure used in the imprinting process is ensured by the conversion of the hardness by pressure F satisfies H F ≤ H0, and the hardness of the surface to be processed after the processing is H0+△H, and the maximum conversion hardness H of the surface to be processed after the processing is H0+△H, which is estimated to be the maximum conversion hardness of the surface to be processed after the processing F-max , and the maximum conversion hardness H F-max The upper limit value F of the pressure in the next imprinting process is calculated by the conversion of the hardness by pressure max ; when the conversion hardness H F does not satisfy H F ≤ H0, it is determined that the result of the imprinting process is unqualified, and the pressure used in the imprinting process is reduced to the conversion hardness H F satisfies H F ≤ H0, the surface to be processed is resampled and processed, and if the reduced pressure cannot be used for the imprinting process so that the complete target 3D structure or the imprinting pattern formed by the target 3D structure cannot be obtained, the surface to be processed is chemically and / or physically processed to improve the surface hardness of the surface to be processed to a degree that satisfies the imprinting process.

[0031] As preferred,

[0032] The target material constituting the secondary 3D structure is carbon and / or semiconductor and / or metal and / or alloy and / or metal compound and / or organic material and / or ceramic.

[0033] An application of the manufacturing method for manufacturing semiconductor and / or flexible electronic material and / or catalytic material and / or optical material, or for coloring treatment.

[0034] As preferred,

[0035] The manufacturing method is also used for manufacturing a material mold for manufacturing nanostructures and / or microstructures and / or macrostructures with specific topographic characteristics.

[0036] The technical scheme of the present application is mainly used to realize the preparation of nano to millimeter cross-scale structure imprinting as shown in Figure 1. Specifically, as shown in Figures 2, 3 and 4. First, as shown in Figure 2, the minimum scale template (only the size of the array structure on it is used to determine the scale size, and if both are nano-scale structures, they are determined as the same scale, and 20 nm structure imprinting can be performed first, and then 10 nm structure imprinting) has an array structure on its surface to form an imprinting processing pattern. After aligning the template with the processing substrate, pressure is applied to the processing substrate, so that the array structure on the template is processed by imprinting replication on the processing substrate to form a first imprinting pattern (replicated array). Then, as shown in Figure 3, a template with the same scale or larger scale array structure is used to continue the imprinting processing on the previously formed imprinting pattern to realize cross-scale micro-nano structure processing. As shown in Figure 3, a larger scale micron-level imprinting pattern can be further formed to form a nano-micron composite array. The difference between the present application and the prior art is that the present application can almost retain the previously formed imprinting pattern. Finally, as shown in Figure 4, macro (millimeter level) imprinting processing is performed, which can quickly and effectively form multi-level cross-scale (nano-micron-millimeter level) micro-nano precision imprinting manufacturing. For the present application, unlike the previous application technical scheme, a more effective processing determination condition is adopted to realize more material processing applicability and operability, greatly improving the effectiveness of imprinting and the stability and yield of the target 3D structure. In previous studies, the processing control condition used by the research group was 15-20 MPa for nano-imprinting, 3-5 MPa for micron-imprinting, and 1-2 MPa for macro (millimeter level) imprinting. However, in actual production and processing, due to the differences in the physical properties of materials, some materials with high strength cannot be processed as expected, or some materials with low strength are over-processed.

[0037] For example, materials such as nickel or alloy or single crystal silicon have higher mechanical strength (surface hardness). In the nano-imprinting process, 15-20 MPa cannot effectively form the target 3D structure imprinting, or after forming a certain imprinting pattern, effective work hardening cannot be formed, or for example, low hardness materials such as organic semiconductor sheets or films, the pressure is too large, which will cause damage to the previously formed target 3D structure and / or imprinting pattern.

[0038] In the present application, specific effective parameters are selected to determine the effectiveness of processing and the stability of the target 3D structure and / or imprinting pattern formed. That is, the hardness of the target 3D structure and / or imprinting pattern formed by imprinting.

[0039] Hardness is a very important mechanical property for the technical solution of the present application, which can be simply converted by equipment pressure, imprint depth, etc. during the imprinting process, and also can be converted by the limit pressure that can be applied by the hardness in reverse, so as to avoid the damage of the target 3D structure and / or the imprint pattern formed in advance caused by excessive pressure. In addition, it is necessary to pay attention to the conversion hardness H F It also needs to be always greater than the surface hardness of the original machining substrate to be machined, because in the imprinting process, the present application is to carry out the imprinting process from small to large, so a large part of the imprinting process carried out later is still acting on the non-deformation area of the original machining substrate to be machined. Of course, in the imprinting process with similar scales, it is best to meet the minimum surface hardness formed after the imprinting with similar scales.

[0040] For example, 1 μm scale imprinting, 3 μm scale imprinting, 15 μm scale imprinting and 50 μm scale imprinting are carried out in turn, and the surface hardness formed after the imprinting is marked as H x , the conversion hardness of the pressure used in the imprinting process is H Fx , where x corresponds to 1 μm, 3 μm, 15 μm and 50 μm, then the optimal H F3μm ≤H 1μm , H F5μm ≤{H 1μm ,H 3μm} min , H F15μm ≤{H 1μm ,H 3μm ,H 5μm} min , H F50μm ≤{H 1μm ,H 3μm ,H 5μm ,H 15μm} min , so as to guarantee the integrity and clarity of the target 3D structure and / or the imprint pattern formed in advance with similar scales.

[0041] Therefore, it can be seen that the present application actually proposes a completely different parameter control system from the conventional one, so that the rapid cross-scale imprinting technology has higher effectiveness and stability when used for complex imprint pattern formation. Specifically, the pressure hardness conversion can be converted through a general technical reference table, or a certain imprint processing depth is taken as an operating quantity, and the synchronous measurement is realized during the processing through the uniaxial stress (processing axis uniaxial stress feedback data) and strain (which can be calculated by the original material size specification and the target operating quantity), or other existing pressure-hardness conversion methods, so as not to be described too much. Therefore, with the hardness, which is a parameter that can be measured synchronously during the processing, the effectiveness and reliability of the processing can be verified, and the integrity of the previously formed target 3D structure and / or imprint pattern can be indirectly verified. It is a very effective, highly versatile and almost irreplaceable important parameter feature.

[0042] Firstly, during the imprint processing of the present application, the target 3D structure and the imprint pattern formed by processing are given sufficient strength in the manner of work hardening, so that they can remain complete and effective during multiple imprint processing. After imprinting, the hardness of the material will show a trend of increasing hardness. Secondly, compared with other performance representations, the representation of hardness is convenient to sample, high in detection efficiency, and small in damage to the sample.

[0043] Through the selection of the above-mentioned indexes, the present application has completely left the experimental stage and entered the industrial implementation stage compared with the prior application, and its effective value is much higher than that of the prior application. This is the most obvious technical difference compared with the prior application.

[0044] The beneficial effects of the present application are:

[0045] The technical scheme of the present application can simply and efficiently realize the processing and manufacturing of high-precision, cross-scale 3D structures, and through process improvement, the overall scheme can be applied to almost all materials, and important parameters that cannot be replaced are set to greatly improve the industrial operability and production effectiveness. BRIEF DESCRIPTION OF DRAWINGS

[0046] Fig. 1 is a macro-micro scale schematic diagram of cross-scale processing;

[0047] Fig. 2 is a nano processing schematic diagram of the cross-scale processing of the present application;

[0048] Fig. 3 is a nano-micro processing schematic diagram of the cross-scale processing of the present application;

[0049] Fig. 4 is a nano-micro-millimeter processing schematic diagram of the cross-scale processing of the present application;

[0050] Fig. 5 is a characterization diagram of the target sample B obtained in step 2-3) of Example 1;

[0051] Figure 6 is an SEM characterization diagram of the sample after the constant-pressure embossing treatment in Example 3;

[0052] Figure 7 is an SEM characterization diagram of the sample after the embossing treatment in Example 3, in which the actual processing pressure is calculated according to the converted hardness;

[0053] Figure 8 is an SEM characterization diagram of the cross-scale nanometer grating structure prepared in Example 7. DETAILED DESCRIPTION

[0054] The present application will be further described in detail in the following with reference to specific embodiments and the accompanying drawings. A person of ordinary skill in the art can implement the present application based on these descriptions. In addition, the embodiments of the present application involved in the following descriptions are generally only a part of the embodiments of the present application, rather than all the embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making creative efforts shall fall within the protection scope of the present application.

[0055] Unless otherwise specified, the raw materials used in the embodiments of the present application are commercially available or can be obtained by a person of ordinary skill in the art. Unless otherwise specified, the methods used in the embodiments of the present application are the methods mastered by a person of ordinary skill in the art.

[0056] Unless otherwise specified, T1-TN (N is any positive integer greater than 1) in the embodiments of the present application represent the first processing to the Nth processing, arranged in order.

[0057] Example 1

[0058] A high-precision cross-scale 3D structure manufacturing method, the method comprising:

[0059] 1) Cleaning the aluminum sheet: cutting an aluminum sheet with a size of 2 cm x 2 cm and a thickness of 250 μm, and then ultrasonic cleaning with acetone, isopropyl alcohol and ultrapure water for 10 min, respectively, and then washing with deionized water and blowing dry with a nitrogen gun, so as to obtain a processing substrate. The surface hardness of the processing substrate is characterized, and HB = 15.6 MPa;

[0060] 2) Multiple embossing treatments are performed on multiple processing substrates, which are sequentially subjected to the following embossing treatments: 2-1) selecting a nickel film with a square array arrangement of nanorod structures with a period of 400 nm as an embossing mold, and the nanorod length is about 150 nm and the diameter is about 200 nm, and then the embossing mold is aligned with the processing surface of the processing substrate obtained in step 1) to be processed, and then the processing surface is subjected to embossing treatment, and then an intermediate sample A is obtained. According to the uniaxial stress feedback data of the embossing equipment and the hardness HB = 17.2 MPa of the embossed pattern calculated synchronously by strain, it is shown that work hardening is generated in the process;

[0061] 2-2) Based on the imprinting in step 2-1), further imprinting is performed. A nickel film with a period of 20 μm and a square array of micron-sized hemispheres is selected as the imprinting mold. The diameter of the micron-sized hemispheres is approximately 20 μm. The mold is aligned with the surface to be processed of the intermediate sample A, and the imprinting mold is aligned with the area covering the area to form the target imprinting pattern (hereinafter referred to as the overlapping area). At the same time, it covers the blank areas where the imprinting pattern was not formed in step 2-1). The imprinting process is then performed on these areas. The hardness H of the pressure used for imprinting is calculated. F =16.5MPa, satisfying 15.6MPa≤H F When the pressure is ≤H0 (H0=17.2MPa), the embossing depth is controlled to be 6μm. After embossing, intermediate sample B is obtained. Based on the uniaxial stress feedback data of the embossing equipment and the hardness of the embossed pattern formed by synchronous strain calculation, the hardness of the overlapping area is calculated to be HB=19.3MPa. The hardness of the overlapping area is greater than the hardness of the embossed pattern formed in step 2-1), indicating that a complete and effective target embossed pattern has been formed and the target embossed pattern formed in step 2-1) has been retained. The hardness of the blank area is calculated to be HB=18.2MPa. The hardness of the blank area is lower than the hardness of the overlapping area, and the hardness of the overlapping area is greater than the hardness of the embossed pattern formed in the previous processing. This also indicates that a significant work hardening effect has been produced. Moreover, due to the multiple embossing processes, the work hardening effect produced in the overlapping area is more obvious.

[0062] 2-3) Based on the imprinting in step 2-2), further imprinting is performed. A nickel film with a pyramid structure arranged in a square array with a period of 3 mm is selected as the imprinting mold. The bottom of the pyramid structure is a square with a side length of 1 mm and a height of 1 mm. The mold is aligned with the surface to be processed of the middle sample B, and imprinting is performed on it. The imprinting depth is controlled to be 300 μm. The hardness H of the pressure used for imprinting is calculated. F =19.5MPa, which does not satisfy 15.6MPa≤H F When the hardness is ≤H0 (H0=19.3MPa), target sample A is obtained after imprinting. Based on the uniaxial stress feedback data of the imprinting equipment and the hardness of the imprinted pattern formed by synchronous strain measurement, the hardness HB after processing five target samples A is calculated to be 19.1MPa. This result shows that the hardness has decreased. This may be due to damage to the target 3D structure or imprinted pattern caused by excessive imprinting, or even structural collapse. Therefore, this invention improves this step by anodizing the surface of the intermediate sample B where the imprinted pattern is formed, so that an aluminum oxide hardened layer with a thickness of about 3nm is grown on its surface, increasing the surface hardness HB from 19.3MPa to about 20.6MPa, satisfying 15.6MPa≤H0. FIn the case of < H0(H0=20.6 MPa), the target sample B is obtained after imprinting, and the hardness of the imprint pattern formed is calculated according to the uniaxial stress feedback data of the imprinting equipment and the strain synchronous measurement, and the hardness HB=25.1 MPa is calculated after the processing of five target samples B. The results show that effective work hardening is produced, and the hardness is further increased.

[0063] To verify the above rule, the microstructure of the intermediate sample A, the intermediate sample B, the target sample A and the target sample B is characterized, and the characterization results show that the imprint pattern of the intermediate sample A is clear, and the imprint pattern of the intermediate sample B and the target sample B, including the previously formed imprint pattern, is well preserved, the structure is complete and the boundary is clear. The characterization of the target sample B is shown in Figure 5. As can be seen from the results of Figure 5, the boundary of the pyramid structure formed is clear, the edge is clear, and the micrometer half-sphere groove array in the inverted pyramid-shaped groove is complete and clear, and the hole is not blocked and deformed. The characterization results of the target sample A show that the boundary of the previously formed part of the imprint pattern is blurred, and even part of the imprint pattern collapses seriously. Through the results, the significant effectiveness and convenience of the hardness parameter selected by the present application are also verified.

[0064] Example 2

[0065] Based on the results summarized in Example 1, further verification tests are carried out, and the same scale step-by-step imprinting is carried out. The hardness and morphology results (complete or blurred, etc.) after each step of imprinting are shown in Table 1 below.

[0066] Table 1: Verification test results of step-by-step imprinting.

[0067] Note: The processing templates in each imprinting process in the above table are the same, i.e. the same morphology and size, and the only difference is the imprinting depth, so different degrees of work hardening are produced. In addition to the converted hardness, the hardness in the table refers to the hardness of the surface to be processed.

[0068] From the characterization results of Table 1 above, it is verified that the core purpose of Example 1 and the present application is achieved, i.e. by controlling the pressure in the processing process in the form of pressure-hardness conversion, cross-scale multi-step imprinting can be effectively carried out. As can be seen from the comparison of the two experimental groups numbered Al-01 and Al-02, under the condition that the substrate type and the pre-processing pattern are completely the same except for the depth, after T3 processing, the surface hardness is different. When T4 processing is carried out, the same pressure is actually applied, the boundary of the processing pattern in the Al-01 experimental group appears blurred at the converted hardness of 21.5 MPa, while under the pressure condition of the converted hardness of 20.5 MPa, the actual pattern is still clear and effective.

[0069] It can be seen that the processing process is controlled by the converted hardness, which is more effective in practice. Moreover, the processing process is controlled by the converted hardness, which can effectively avoid material interference. As mentioned above, the hardness of copper is greater than that of aluminum, so the converted hardness of the initial imprint pressure is different. On the other hand, it can be clearly seen that the actual work hardening effect produced after the imprinting of different materials and different imprint depths also has significant differences. Therefore, for the cross-scale imprinting scheme, a certain pressure can be set as a control parameter for a specific material. In order to improve the universality and versatility of the industry, the pressure converted hardness used in the present application is obviously more effective as a parameter.

[0070] Example 3

[0071] Based on the technical scheme of the present application, the silver-based material is also subjected to imprinting treatment, and is compared with the same-scale fixed pressure (with a specified actual pressure, not a fixed pressure, referring to the previous research scheme, not like the present application which calculates by converting hardness, the same below) imprinting. Some process parameters and data are shown in Table 2 below.

[0072] Table 2: Comparison of multi-stage imprinting under different parameter conditions.

[0073] From the process parameters and data of Table 2 above, it can be clearly seen that the actual processing pressure calculated in terms of hardness is greatly different from the direct use of pressure in the previous research scheme. In the process of step-by-step imprinting in the technical scheme of the present application, the pressure remains relatively constant, while in the previous research scheme, the actual pressure change rate is very large. In the previous research process, it was found that under the condition of similar actual processing pressure, there was a probability that the first formed target 3D structure would collapse or the pattern would be blurred. In order to realize multi-stage imprinting and effectively protect the first formed target 3D structure, the pressure can only be continuously reduced to ensure that it does not affect the first formed target 3D structure and / or the imprinting pattern. However, as shown in Table 2, only by controlling the pressure, the Ag-02 experimental group silver substrate forms extremely strong work hardening too early, and the hardness reaches 35.1 MPa after the first (T1) processing, which is excellent for protecting the first formed target 3D structure and / or the imprinting pattern, but it also affects the subsequent imprinting process, making it difficult to effectively form the target 3D structure, as shown in Figure 6, resulting in incomplete or blurred target 3D structure, and the target 3D structure itself has a wide boundary and becomes blurred. At the same time, part of the structure formed earlier also becomes blurred. This blur is not that the structure formed earlier is destroyed, but that the subsequent structure cannot be clearly and effectively formed due to uneven deformation. This is more obvious for some high-hardness substrates. For the technical scheme of the present application, the degree of work hardening is more effectively controlled during processing, and the first formed target 3D structure and / or the imprinting pattern is effectively protected, so that the cross-scale target 3D structure and / or the imprinting pattern is more clear and complete, as shown in Figure 7, and the precision is higher.

[0074] As in the present embodiment, the Ag-01 experimental group and the Ag-02 experimental group carried out 150 nm scale-10 μm scale imprinting processing. At the nanoscale, the target 3D structure formed by the Ag-01 experimental group and the Ag-02 experimental group has a difference of ≤0.5% from the expected size. Further at the micrometer scale, the target 3D structure formed by the Ag-01 experimental group still maintains a size difference of ≤0.5% from the expected size, while the target 3D structure formed by the Ag-02 experimental group has a difference of about 1.3% from the expected size. Although it still has the characteristic of high precision, it is obvious that with the further deepening of the subsequent work hardening degree and the further reduction of the pressure, the Ag-02 experimental group scheme will produce increasingly larger processing errors, while the technical scheme of the present application can more effectively control the extremely small processing error and maintain extremely high processing precision.

[0075] Example 4

[0076] Further, based on the technical scheme of the present application, the same scale multiple imprinting processing is carried out, and the parameters and data are shown in Table 3.

[0077] Table 3: Comparison of approximate scale multi-stage imprinting processing.

[0078] From the results in Table 3, as described above, in the imprinting process of similar scales, the converted hardness preferably satisfies the minimum surface hardness formed after the imprinting of similar scales. In this example, 1 μm scale imprinting, 5 μm scale imprinting, and 15 μm scale imprinting are sequentially carried out, and the surface hardness formed after the imprinting is marked as H x , the converted hardness of the pressure used in the imprinting process is H Fx , where x corresponds to 1 μm, 5 μm, and 15 μm. In the Al-03 experimental group, H F5μm ≤ H 1μm , H F5μm ≤ {H 1μm , H 5μm} min , H F15μm ≤ {H 1μm , H 5μm , H 5μm} min , the processing effect formed is better than that of the Al-04 experimental group, and has higher processing precision. On this basis, orthogonal experiments are also carried out, and when the target 3D structure size of the sequential imprinting process is within 30 times, the converted hardness should preferably satisfy the minimum surface hardness formed after the imprinting of similar scales. This process can be represented by the following general formula.

[0079] H Fb ≤ {H a , H m , H b}, where a < m < b ≤ 30a, and a, m, and b all represent scales.

[0080] Example 5

[0081] Based on the technical scheme of Example 3, the present application also carries out imprinting processing for different substrates, and compares with the same scale and constant pressure imprinting. The total imprinting processing is carried out 5 times, the imprinting scale of T1 (the first time) is 8 nm, and the imprinting scale of T5 (the fifth time) is 8 mm. During this period, 300 nm, 10 μm, and 500 μm scale imprinting processing are sequentially carried out. After the imprinting processing, the sample is characterized by SEM, and the deviation value of the constructed target 3D structure size and the imprinting scale is detected.

[0082] The specific pressure parameters are shown in Table 4.

[0083] Table 4: T1-T5 cross-scale processing pressure parameters and hardness after each imprinting process.

[0084] From the above table of processing pressure and hardening trend after each processing, it can be seen that after the processing pressure is determined in the form of hardness-pressure conversion of the technical scheme of the application, the hardness of the material after step-by-step processing is slowly stepped up, while using the prior art to determine the pressure processing according to the processing scale, it is easy to cause the material to appear extremely obvious work hardening effect in the early stage, resulting in the hardness of the material to appear explosive rise in the early processing process, and then the rising speed decreases significantly. Further micro characterization of the sample obtained after the final T5 imprinting process and detection of the deviation value of the target 3D structure size formed by processing from the predetermined processing size are shown in the following table 5.

[0085] Table 5: Average value of size deviation of each level of imprinting after T5 imprinting process.

[0086] From the deviation value obtained by the above detection, it can be seen that the application can effectively ensure the processing precision, and the size error of the target 3D structure formed by processing is always maintained within 0.5%, while using the prior art of fixed pressure processing, it will cause the increase of processing deviation, especially for T1 imprinting structure and T4 imprinting structure, the relative processing deviation value is large. Among them, because the T1 imprinting structure is formed earliest, it is affected by subsequent imprinting multiple times, and it does not produce any other strengthening effect in the step-by-step processing process, and it is easy to produce deformation after extremely strong work hardening too early, and the T4 imprinting structure is difficult to effectively form the target 3D structure due to the small subsequent pressure, thereby producing size deviation. In theory, T5 will also have this problem, but due to its large actual scale, it can to some extent ignore the error of microns and nanometers. For the technical scheme of the application, the hardness is stepped up slowly during each imprinting process, which to some extent is to realize the secondary hardening and strengthening of the target 3D structure formed in the prior art, so as to ensure the stability of the structure, rather than reaching the almost upper limit at the beginning and being easily affected by the subsequent process.

[0087] Example 6

[0088] Based on the technical scheme of example 1, the application also tests the limit processing precision.

[0089] The pretreated Al substrate is respectively subjected to T1 imprinting process of 3nm, 5nm, 7nm, T1 imprinting process H F is 16.0MPa, and then T2 imprinting process is carried out, the imprinting scale of T2 imprinting process is 120nm, and T2 imprinting process H F is 16.5MPa.

[0090] The samples after the two imprinting processes were characterized by SEM and the size deviation was calculated, and the results are shown in Table 6 below.

[0091] Table 6: Limiting small-scale imprinting process size deviation.

[0092] From the results shown in Table 6 above, although the technical scheme of the present application can also achieve a certain degree of one-time processing of 3nm scale and approach the extremely small size deviation range of <0.5%, due to the extremely small size processing, the effect is not completely clear, which causes the T1 structure formed in the previous process to be greatly affected by the subsequent imprinting process in the cross-scale processing process, and the size deviation value rises sharply and cannot effectively maintain a low deviation state. Therefore, at present, the smallest limit scale that the technical scheme of the present application can be applied to is about 5nm. On the other hand, due to the large-scale imprinting processing of the substrate, the mechanical properties of the large-scale substrate plate itself may not be uniform or limited by the equipment. At present, only large-scale imprinting of more than 100 microns can be effectively realized while maintaining the imprinting precision, so that the deviation value is ≤200μm (significantly <0.5%). Therefore, according to the results of Example 5, the present application can completely realize the super-large cross-scale processing of 10 6 ~10 8 When the millimeter-level imprinting overcomes the existing defects, the cross-scale processing span can be completely expanded to 10 8 The above, and the scheme is widely applicable.

[0093] Example 7

[0094] Based on the technical scheme of the present application, a cross-scale construction of a nanometer grating and a microparticle array is carried out.

[0095] 1) Clean the aluminum sheet: cut 2cm x 2cm aluminum sheet with a thickness of 250μm, and ultrasonically clean with acetone, isopropanol and ultrapure water for 10min, and then wash with deionized water and dry with a nitrogen gun. The surface hardness of the processed substrate is characterized, and HB=15.6MPa;

[0096] 2) multiple imprinting processes are performed on the multiple processing substrates, which are sequentially performed as follows: 2-1): a nickel film with a parallel line-shaped nanostructure array with a period of 180 nm is selected as an imprinting mold, the line-shaped nanostructure has a width of 180 nm and a length of 2.5 cm, so that one-time imprinting can form a continuous groove line-shaped nano-grating structure on the surface of the processing substrate, the processing substrate obtained in step 1) is aligned with the processing surface to be processed, and the processing surface is subjected to an imprinting process, and an intermediate sample is obtained after imprinting, the hardness of the imprinting pattern formed according to the uniaxial stress feedback data of the imprinting equipment and the strain synchronous measurement is HB = 16.3 MPa, which indicates that work hardening is generated in the process;

[0097] 2-2) on the basis of the imprinting in step 2-1), further imprinting is performed, a nickel film with a face-centered hexagonal array of micro-bowl-shaped structures with a period of 1.75 μm is selected as an imprinting mold, the micro-hemisphere has a diameter of about 1.0 μm, the mold is aligned with the processing surface to be processed, and the imprinting mold is aligned to cover the area of the target imprinting pattern, and the processing surface is subjected to an imprinting process, the hardness H F = 16.0 MPa of the pressure used for imprinting satisfies the condition 15.6 MPa ≤ H F ≤ H0 (H0 = 16.3 MPa), the control imprinting processing depth is 1.0 μm, and the target sample is obtained after imprinting, the hardness of the imprinting pattern formed according to the uniaxial stress feedback data of the imprinting equipment and the strain synchronous measurement is HB = 17.1 MPa, and the hardness of the processing surface is greater than the hardness of the imprinting pattern formed in step 2-1), which indicates that the complete and effective target imprinting pattern is formed and the target imprinting pattern formed in step 2-1) is retained, and the result shows that effective work hardening is generated and the hardness is further increased.

[0098] SEM characterization of the target sample, the characterization results are shown in Figure 8. As shown in the results of Figure 8, it shows very good processing results, the formed imprint pattern is ordered and clean, and the good nanometer grating structure can be effectively maintained after the imprinting process of 2-2), while in the existing nanometer grating preparation scheme, the preparation is usually carried out by photolithography or chemical etching, which has high cost and difficulty, and the manufacturing of good products is also relatively limited. As for the technical scheme of the present application, firstly, it can ignore the manufacturing difficulty problem caused by small scale or high aspect ratio, because for the technical scheme of the present application, only the adjustment to the appropriate parameters can very effectively form the imprint for the required nanometer grating structure. In addition, the nanometer grating structure constructed by the existing photolithography or chemical etching is relatively "fragile", because there is another important research and development direction in the existing nanometer grating medium field, that is, to further construct a three-dimensional structure based on nanometer grating, that is, to realize five-dimensional optical storage by adding the three-dimensional spatial degree of freedom to the two variables of nanometer grating delay and polarization angle for data coding, so as to further improve the storage capacity. If the existing nanometer grating wants to further form a three-dimensional structure, it can be used in combination with a multilayer composite or a deposition method, but on the one hand, the former has high cost and great difficulty, and it is difficult to ensure the good cooperation of the fine structure, and the latter will damage the previously formed nanometer grating structure. For the technical scheme of the present application, the previously formed nanometer grating structure itself is work hardened, and no corrosive substances are introduced during the multi-stage cross-scale structure processing, and the unique parameter control form of the present application can very effectively ensure the integrity of the structure, as shown in Figure 8, the previously formed nanometer grating remains clear, complete and does not deform after forming a three-dimensional structure in combination, it can be seen that the cross-scale processing method of the present application has the characteristics of very simple and efficient and excellent effect compared with the conventional cross-scale processing method.

[0099] As can be seen from the above examples, compared with the traditional technical scheme, the technical scheme of the present application can realize the hierarchical processing of cross-scale precision micro-nano structure and macro structure with very high efficiency, and after further research, it is expected to be effectively used for ultra-fine semiconductor chip processing, which has extremely great development potential and research value. At present, the technology can also be effectively used in most fine industrial fields and part of the processing and manufacturing of semiconductors. Compared with the traditional photolithography technology, the present application is more environmentally friendly (no photoresist), more precise (precision reaches 5 nanometers), larger processing range (size span range can reach 10 6 ~10 8 ), lower cost (no need for optical system), and more material applicability (materials with work hardening ability can be used).

Claims

1.A method for manufacturing high-precision cross-scale 3D structure, characterized in that, the method comprises: selecting a processing substrate, and performing multiple imprinting processes on the processing substrate; the imprinting process selects an imprinting mold, the imprinting mold is aligned with the surface to be processed of the processing substrate, the processing substrate is fixed, and a pressure is applied to the imprinting mold towards the surface to be processed, so that the processing substrate is processed by the imprinting mold, and after each imprinting process, a single or multiple imprinting patterns composed of a target 3D structure are formed; the hardness of the imprinting mold is greater than the hardness of the surface to be processed; during the multiple imprinting processes, the scale of the target 3D structure is formed from small to large in turn; during the multiple imprinting processes, bidirectional conversion is performed according to the topography requirements of the target 3D structure and / or the mechanical properties of the formed imprinting pattern and the operating parameters of the imprinting work, and when the mechanical properties do not meet the processing requirements, physical and / or chemical treatment is performed to strengthen the mechanical properties; during the multiple imprinting processes, physical and / or chemical methods can be used to realize the deposition of target materials, so that the target materials form secondary 3D structures. 2.The method for manufacturing high-precision cross-scale 3D structure according to claim 1, characterized in that, the processing substrate is a material with ductility; the material with ductility includes carbon and / or semiconductor and / or metal and / or alloy and / or metal compound and / or organic material and / or ceramic. 3.The method for manufacturing high-precision cross-scale 3D structure according to claim 1, characterized in that, before the imprinting process, if the target 3D structure is a structure protruding from the substrate, a imprinting mold with a groove structure is used for the imprinting process; before the imprinting process, if the target 3D structure is a structure recessed from the substrate, a imprinting mold with a protruding structure is used for the imprinting process. 4.The method for manufacturing high-precision cross-scale 3D structure according to claim 1 or 3, characterized in that, the mechanical property is the hardness of the surface to be processed; the operating parameter of the imprinting work is the pressure. From the second press process, the hardness of the surface to be processed before the press process is H0, and the conversion hardness H of the pressure used in the press process is ensured by pressure hardness conversion F satisfies H F ≤ H0, and the hardness of the surface to be processed after the press process is H0+△H, and the maximum conversion hardness H that can be tolerated in the next press process is estimated with H0+△H F-max , and the maximum conversion hardness H that can be tolerated in the next press process is estimated with H0+△H F-max The upper limit value of the pressure in the next press process is calculated by pressure hardness conversion. when the converted hardness H F when the condition H F < H0, the current imprinting process is determined to be unqualified, and the pressure used in the current imprinting process is reduced to a converted hardness H F when the condition H F < H0, the current imprinting process is determined to be unqualified, and the pressure used in the current imprinting process is reduced to a converted hardness H 5.The method for manufacturing high-precision cross-scale 3D structure according to claim 1, characterized in that, the target material constituting the secondary 3D structure is carbon and / or semiconductor and / or metal and / or alloy and / or metal compound and / or organic material and / or ceramic. 6.An application of the manufacturing method according to any one of claims 1 to 5, characterized in that, the manufacturing method is used for manufacturing semiconductor and / or flexible electronic material and / or catalytic material and / or optical material, or for coloring treatment. 7.The application according to claim 6, characterized in that, the manufacturing method is also used for manufacturing a material mold, and the material mold is used for manufacturing nanostructures and / or microstructures and / or macrostructures with specific topographic characteristics.

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