Preparation method of female template and preparation method of material with nano-structure shape

Abstract

The invention discloses a preparation method of a female template, the female template, a preparation method of a material with a nano-structure shape and the material with the nano-structure shape. The method comprises the following steps: constructing a filler film for copying a structural shape on a first surface of a substrate material; stripping the filler film from the surface of the substrate material, and depositing a conductive metal layer on the surface of the filler film to form a conductive filler film; performing electrochemical deposition on the first surface of the conductive filler film to form a female template metal layer; and removing the conductive filler film, and making the remaining female template metal layer into the female template. According to the invention, the electrodeposited nickel metal layer is introduced as a female template raw material, and the prepared female template has flexibility and keeps a multi-element pattern form with high precision by utilizing the physicochemical properties of nickel; and the use frequency of cyclic imprinting is far greater than that of an organic polymer flexible female template and a silicon-based rigid female template in the prior art, so that the stability of a female template preparation process is remarkably improved.

Description

Technical Field

[0001] This application relates to a method for preparing a master template, a master template, a method for preparing a material with a nanostructure shape, and a material with a nanostructure shape, belonging to the field of nanoimprint technology. Background Technology

[0002] Cold nanoimprint lithography (CNIL) is a template-based nanoscale pattern replication technology that transfers nanostructure patterns from a template to the surface of a substrate material, achieving high-precision, large-area nanopattern fabrication. Unlike photolithography and other technologies that rely on photochemical reactions, CNIL primarily achieves pattern transfer through physical imprinting and material deformation at room temperature or lower.

[0003] Currently, among related technologies, nano cold embossing technology is mainly suitable for manufacturing micro and nano structures with simple geometric configurations. However, when applied to complex three-dimensional nanostructures, its manufacturing efficiency is insufficient. Moreover, the master plate used for embossing has poor durability and is difficult to process. In addition, it cannot meet the process requirements of accurately, faithfully, and with high throughput to replicate shapes and structures. Summary of the Invention

[0004] This application proposes a method for preparing a master template, a master template, a method for preparing a material with a nanostructure shape, and a material with a nanostructure shape.

[0005] The master template preparation method in this application embodiment, wherein the master template is suitable for nano-cold embossing, specifically includes: Based on a pre-treated substrate material having a preset structural shape, a filler film for replicating the structural shape is constructed on the first surface of the substrate material, wherein the first surface of the substrate material has the preset structural shape; The filler film is peeled off from the surface of the substrate material, and a conductive metal layer is deposited on the surface of the filler film to form a conductive filler film; Electrochemical deposition is performed on the first surface of the conductive filler film to form a master template metal layer, wherein the master template metal layer is a nickel metal layer, and the first surface of the conductive filler film has the predetermined structural shape; Remove the conductive filler film and use the remaining master template metal layer to form the master template.

[0006] In some embodiments, the substrate material includes an aluminum plate or sheet, and the pretreatment method of the substrate material includes: The surface of the substrate material is rinsed with a preset organic solvent and an inorganic solvent, wherein the organic solvent includes acetone and / or ethanol, and the inorganic solvent includes ultrapure water. The filler film includes a polymethyl methacrylate film.

[0007] In some embodiments, performing electrochemical deposition on the first surface of the conductive filler film to form a master template metal layer includes: Based on a preset mixed electrodeposition plating solution, electrodeposition is performed sequentially on the first surface of the conductive filler film at a first current density within a first time period, at a second current density within a second time period, and at a third current density within a third time period. The first current density, the second current density, and the third current density increase in sequence, the first duration range is less than the second duration range, and the third duration range is greater than or equal to the second duration range. The mixed electrodeposition plating solution includes nickel sulfate hexahydrate, nickel chloride hexahydrate, and boric acid, with the concentration ratio of nickel sulfate hexahydrate, nickel chloride hexahydrate, and boric acid being (24~25):(7~7.5):(7.5~8).

[0008] In some embodiments, removing the conductive filler film and forming the remaining master template metal layer into the master template includes: The conductive filler film on which the master template metal layer is formed is placed in a first organic solvent within a fourth time period to remove the conductive filler film; The remaining metal layer surface of the master template is rinsed with a second organic solvent and an inorganic solvent and then dried to produce the master template. The first organic solvent includes acetone or dichloromethane, the second organic solvent includes ethanol, and the inorganic solvent includes ultrapure water.

[0009] The master template for nano-cold embossing in this application is prepared according to the master template preparation method described in the above embodiments.

[0010] The method for preparing materials with nanostructured shapes in the embodiments of this application includes: Imprinting is performed on a pre-selected carrier material based on the master template to form a shape complementary to a preset structural shape on the first surface of the carrier material, wherein the master template is prepared according to the master template preparation method in the above embodiments, and the carrier material is an aluminum sheet or an aluminum plate. Anodizing is performed on the first surface of the carrier material to form an anodized layer on the first surface of the carrier material having a shape complementary to the preset structural shape; Based on the anodic oxide layer, a mask for nanocold embossing is prepared; Imprinting is performed on a pre-selected target base material based on the mask, so that the target base material has the nanostructure shape; Remove the mask remaining on the target base material to form the imprinted target base material into the target material with the nanostructure shape.

[0011] In some embodiments, the preparation of a mask for nano-cold embossing based on the anodic oxide layer includes: A filler film is constructed on the anodic oxide layer, and the remaining carrier material is removed to form a filler composite oxide layer, wherein the filler film comprises a polymethyl methacrylate film; The filler film included in the filler composite oxide layer is removed to form the mask.

[0012] In some embodiments, removing the mask remaining on the target base material to form the imprinted target base material into the target material having the nanostructure shape includes: The target base material with residual mask is immersed in chromic acid of a preset concentration to remove the residual mask; The remaining target base material is rinsed with an inorganic solvent, including ultrapure water, to obtain the target material.

[0013] In some embodiments, the process of constructing a filler film on the anodic oxide layer and removing the remaining carrier material to form a filler composite oxide layer further includes: Phosphoric acid pore-expanding is performed on the anodic oxide layer to adjust the structural morphology and structural dimensions to be complementary to the preset structural shape.

[0014] The nanostructured material in this application embodiment is prepared according to the nanostructured material preparation method described in the above embodiment.

[0015] The beneficial effects of this application are: the master template preparation method in the embodiments of this application introduces an electrodeposited nickel metal layer as the raw material of the master template. By utilizing the physicochemical properties of metallic nickel, the prepared master template is flexible and can maintain the multi-dimensional micro-nano pattern morphology with high precision. At the same time, it can also make its cyclic imprinting use number far greater than that of organic polymer flexible master templates and silicon-based rigid master templates in the current related technologies, which significantly improves the stability of the master template preparation process. Attached Figure Description

[0016] Figure 1 This is one of the flowcharts illustrating the master template preparation method in the embodiments of this application; Figure 2 This is one of the application scenarios of the master template preparation method in the embodiments of this application; Figure 3 This is the second schematic diagram of the application scenario of the master template preparation method in the embodiments of this application; Figure 4 This is the third schematic diagram illustrating the application scenario of the master template preparation method in the embodiments of this application; Figure 5 This is the fourth schematic diagram illustrating the application scenario of the master template preparation method in the embodiments of this application; Figure 6 This is the fifth schematic diagram illustrating the application scenario of the master template preparation method in the embodiments of this application; Figure 7 This is the second flowchart illustrating the method for preparing the master template in the embodiments of this application; Figure 8 This is the sixth schematic diagram illustrating the application scenario of the master template preparation method in the embodiments of this application; Figure 9 This is one of the flowcharts illustrating a method for preparing materials with nanostructured shapes in the embodiments of this application; Figure 10 This is a second schematic flowchart of a method for preparing materials with nanostructure shapes in the embodiments of this application; Figure 11 This is the third schematic flowchart of the method for preparing materials with nanostructure shapes in the embodiments of this application. Detailed Implementation

[0017] Please see Figure 1 The master template prepared by the master template preparation method in this application is suitable for nano-cold embossing. The method specifically includes the following steps: Step 01: Based on a pre-treated substrate material with a predetermined structural shape, a filler film for replicating the structural shape is constructed on the first surface of the substrate material. The first surface of the substrate material has a predetermined structural shape.

[0018] Specifically, the master template preparation method in this application is mainly used to prepare a master template for nano-cold embossing. The master template has a preset structural shape for performing nano-cold embossing. The preset structural shape is generally a three-dimensional structural shape, such as repetitive smooth protrusions, repetitive spherical protrusions, etc. The main logic of the master template preparation method is to use a filler film to replicate the preset structural shape on the substrate material, and further use electrochemical deposition to form a master template with the same preset structural shape on the filler film that has replicated the preset structural shape. This achieves the replication of the preset structural shape on the substrate material, and at the same time, the filler film and nickel metal are used to form a master template with high accuracy and durability in replicating the structural shape.

[0019] For example, a substrate material with a predetermined structural shape should first be selected, and the surface of the substrate material should be pretreated before constructing the filler film to avoid negative impacts from other substances originally present on the substrate material surface on the preparation process. Based on this, in some embodiments, the pretreatment of the substrate material includes: Rinse the surface of the substrate material with a pre-selected organic and inorganic solvent. The organic solvents include acetone and / or ethanol, and the inorganic solvents include ultrapure water; The filler film includes polymethyl methacrylate film, and the substrate material includes aluminum sheet or aluminum plate.

[0020] Specifically, the pretreatment of the substrate material surface described above generally involves rinsing with solutions of different properties. For example, the cleaning process is typically performed as follows: first, the substrate material surface is rinsed with an organic solvent such as acetone or ethanol to dissolve and remove impurities that are easily soluble in organic solvents but poorly soluble in water. Then, the substrate material surface is rinsed again with an inorganic solvent such as ultrapure water to dissolve and remove the organic solvents such as acetone and ethanol, as well as other water-soluble impurities, thus completing the rinsing process. The purpose of using ultrapure water is to minimize the amount of residue left on the substrate material surface. Furthermore, to improve the rinsing effect, the substrate material surface can be rinsed first with acetone and then with ethanol sequentially, and finally rinsed with ultrapure water. The specific rinsing steps and the solvents used can be adjusted according to the actual needs of rinsing the substrate material surface.

[0021] Furthermore, considering the ease or difficulty of forming the preset structural shape on the base material, the base material should not be too hard. For example, the base material can be aluminum sheet or aluminum plate. By utilizing the lower hardness of aluminum, the processing difficulty of the preset structural shape can be reduced.

[0022] The substrate material can be prepared by hard-pressing the original aluminum sheet or plate with a mold and then etching it. Assuming the intended structural shape is a periodic pit, the preparation method of the substrate material can be seen in the following example: In some examples, the original aluminum sheet or plate is first hard-pressed using a mold with periodic protrusions (that is, complementary shapes that are complementary to the preset structural shape). The pressure is 6~7MPa and maintained for 2 minutes to obtain an aluminum sheet or plate with periodic pits initially pressed on the surface.

[0023] Next, the pressed aluminum sheet or aluminum plate is anodized. The above anodizing is generally carried out at 5°C and 160V, using a mixed oxidation solution of phosphoric acid-ethylene glycol-ultrapure water with a mass ratio of 1:200:400 for 4 hours. This can obtain micro-nano structures with an oxide layer on the aluminum plate or aluminum sheet (the shape of which corresponds to the preset structure shape).

[0024] Finally, the aluminum plate or sheet with the oxide layer is immersed in chromic acid solution for at least 8 hours to obtain a micro-nano structure with completely etched anodized aluminum. The surface is then rinsed sequentially with organic solvents such as acetone and / or ethanol, and inorganic solvents such as ultrapure water, to obtain the substrate material described in the above embodiments. Please refer to... Figure 2 , Figure 2 The longitudinal section of a base material with a pre-defined structural shape of periodic pits is schematically shown.

[0025] Given the pre-treated substrate material in the example above, a filler material, such as polymethyl methacrylate (PMMA), is spin-coated multiple times onto the surface of the substrate material with a predetermined structural shape (corresponding to the first surface). The PMMA is then applied to a certain thickness. After spin-coating, the substrate material is dried in a 60°C oven to form a filler film. Since the filler material is spin-coated onto the surface of the substrate material with the predetermined structural shape, the dried filler film can replicate the predetermined structural shape of the substrate material through shape complementarity. This replicated shape can then be used to further prepare a master template with the same shape. Please... Figure 2 Further reference Figure 3 , Figure 3 The diagram schematically shows a longitudinal section of the substrate material after the formation of the filler film, due to Figure 2 The shown preset structural shape is a periodic pit, therefore Figure 3 The complementary shapes exhibited by the filler film formed in the process are periodic protrusions.

[0026] Please continue reading. Figure 1The method for preparing the master template in the embodiments of this application further includes: Step 02: Peel the filler film from the surface of the substrate material and deposit a conductive metal layer on the surface of the filler film to form a conductive filler film.

[0027] Specifically, based on the above embodiments, the role of the substrate material has been completed. Next, the formed filler film can be peeled off from the substrate material using methods currently available in related technologies. It should be noted that although the peeling method can be arbitrarily selected, it is necessary to ensure the integrity of the complementary shapes on the surface of the filler film as much as possible during peeling. Please... Figure 3 Further reference Figure 4 , Figure 4 The longitudinal section of the filler film after peeling is schematically shown.

[0028] Next, after peeling the filler film from the substrate material, a master template is constructed using the surface of the filler film as a reference. Since the master template is made of metal, it is generally formed using methods such as electrochemical deposition. However, the filler film itself has strong insulating properties (PMMA), so it is necessary to first modify the conductivity of the filler film.

[0029] Therefore, exemplarily, a conductive metal layer is deposited on the complete surface of the filler film to form a conductive filler film. This conductive metal layer creates a conductive path on the surface of the filler film, preparing for subsequent electrochemical deposition processes. In some examples, the conductive metal layer can be deposited using vapor phase physical deposition (VPD), which can be achieved through techniques such as magnetron sputtering. This allows for deposited conductive metal particles with larger sizes and weaker adhesion. Specifically, the deposited conductive metal layer is generally a layer formed from a single conductive metal element. The specific conductive metal element chosen can be selected based on the actual situation; commonly used conductors such as copper and silver are generally suitable. Please... Figure 4 Based on the above, refer to Figure 5 , Figure 5 The longitudinal section of the conductive filler film obtained after vapor phase physical deposition is schematically shown.

[0030] Please continue reading. Figure 1 The method for preparing the master template in the embodiments of this application further includes: Step 03: Perform electrochemical deposition on the first surface of the conductive filler film to form a master template metal layer, wherein the master template metal layer is a nickel metal layer. The first surface of the conductive filler film has a shape that is complementary to the preset structural shape.

[0031] Specifically, based on the above embodiments, after obtaining the conductive filler film, electrochemical deposition can then be performed on a surface of the conductive filler film with a complementary shape corresponding to the preset structural shape (corresponding to the first surface of the conductive filler film) to form a master template metal layer, which serves as the main base of the formed master template. Since the strength and hardness of the master template material used for imprinting should be greater than the strength and hardness of the material being imprinted during the imprinting process, the selection of the master template material typically requires properties or characteristics such as high hardness, high tensile strength, low coefficient of thermal expansion, smooth surface for easy processing, and strong corrosion resistance. If the strength and hardness of the master template material are insufficient, it may be unable to effectively shape the carrier material during the imprinting process, thus affecting the final imprinting effect. Among many metals, nickel metal has unique advantages in constructing micro / nano structures. Through deposition or electrochemical methods, diverse and stable micro / nano structures can be constructed on its surface. The controllability and ease of operation in this construction process are significant. For example, the master template metal layer is an electrochemically deposited nickel metal layer, and the master template subsequently manufactured is also a nickel metal plate.

[0032] Regarding the specific method of electrochemical deposition, in some embodiments, step 03 specifically includes: Based on a preset mixed electrodeposition plating solution, electrodeposition is performed sequentially on the first surface of a conductive filler film at a first current density within a first time period, at a second current density within a second time period, and at a third current density within a third time period. The first current density, the second current density, and the third current density increase in sequence, the first time range is less than the second time range, and the third time range is greater than or equal to the second time range. The mixed electrodeposition plating solution includes nickel sulfate hexahydrate, nickel chloride hexahydrate, and boric acid, with the concentration ratio of nickel sulfate hexahydrate, nickel chloride hexahydrate, and boric acid being (24~25):(7~7.5):(7.5~8).

[0033] Specifically, based on the above embodiments, the exemplary method for depositing the master template metal layer using electrochemical deposition is as follows: Using a pre-defined mixed electrodeposition plating solution as the nickel source, a master template metal layer with a pre-defined structural shape is deposited on the complementary side (corresponding to the first surface of the conductive filler film) of the conductive filler film using the principle of electrodeposition. The mixed electrodeposition plating solution is generally a mixed aqueous solution of nickel sulfate hexahydrate (NiSO4·6H2O), nickel chloride hexahydrate (NiCl2·6H2O), and boric acid (H3BO3). The concentration ratio of the three components in the solution is approximately (24~25):(7~7.5):(7.5~8). The proportions of the three components can be arbitrarily selected within their respective given ranges. For example, in some examples, the concentration of nickel sulfate hexahydrate (NiSO4·6H2O) is 99.88 g / L, the concentration of nickel chloride hexahydrate (NiCl2·6H2O) is 28.52 g / L, and the concentration of boric acid (H3BO3) is 30.92 g / L. Such a concentration ratio is within the range given above. For example, a mixed electrodeposition plating solution for depositing the master template metal layer can be formed by mixing nickel sulfate hexahydrate (NiSO4·6H2O) at a concentration of 96 g / L, nickel chloride hexahydrate (NiCl2·6H2O) at a concentration of 28 g / L, and boric acid (H3BO3) at a concentration of 30 g / L, or nickel sulfate hexahydrate (NiSO4·6H2O) at a concentration of 100 g / L, nickel chloride hexahydrate (NiCl2·6H2O) at a concentration of 30 g / L, and boric acid (H3BO3) at a concentration of 32 g / L, etc., in the above embodiments.

[0034] The electrodeposition process typically employs a staged, constant-current method to achieve electrochemical deposition of nickel. For instance, in some examples, nickel electrodeposition is achieved in three stages: the first stage uses a relatively low current density to perform preliminary electrodeposition over a short period, such as 1 mA / cm². 2 The first stage involves continuous deposition for 1 hour at a higher current density than the first stage. The second stage uses a higher current density and re-deposition over a longer duration; for example, if the first stage is complete, redeposition can be performed at 3 mA / cm². 2 The third stage involves continuous deposition for 2 hours at a current density of 5 mA / cm². Compared to the second stage, the third stage further increases the current density, performing the final stage deposition within a duration no less than that of the second stage to form a complete nickel master template metal layer. For example, this can be achieved by depositing the final stage at a current density of 5 mA / cm². 2 Under specific current density conditions, continuous deposition for 2 hours resulted in a nickel-based master template metal layer with a predetermined structural shape. Please... Figure 5 Further reference Figure 6 , Figure 6 The diagram schematically shows a longitudinal section of a conductive filler film that has formed a master template metal layer after electrodeposition.

[0035] Please continue reading. Figure 1 The method for preparing the master template in the embodiments of this application further includes the following steps: Step 04: Remove the conductive filler film and use the remaining master template metal layer to make the master template.

[0036] Specifically, based on the above embodiments, when the master template metal layer has been deposited, for example, it is only necessary to peel the conductive filler film from the master template metal layer to remove the conductive filler film. The remaining master template metal layer only needs to be slightly cleaned to obtain a flexible nickel metal plate that serves as a master template in nano cold imprinting technology.

[0037] Please see Figure 7 In some implementations, step 04 specifically includes: Step 041: The conductive filler film with the mother template metal layer formed is placed in the first organic solvent within a fourth time period to remove the conductive filler film; Step 042: Rinse the remaining metal layer surface of the master template with a second organic solvent and an inorganic solvent, and then dry it to form the master template. The first organic solvent includes acetone or dichloromethane, the second organic solvent includes ethanol, and the inorganic solvent includes ultrapure water.

[0038] Specifically, based on the above embodiments, for the removal of the conductive filler film, for example, the solubility of PMMA can be utilized by using organic solvents such as acetone or dichloromethane to dissolve the PMMA, thereby removing the conductive filler film. Therefore, when removing the conductive filler film, the conductive filler film with the mother template metal layer can be statically immersed in an organic solvent environment such as acetone or dichloromethane for a period of time. After the conductive filler film is completely dissolved in the solvent environment, the remaining mother template metal layer is transferred out, and then the subsequent surface treatment process is performed.

[0039] It is important to note that the conductive filler film is obtained by vapor deposition of a conductive metal layer on the surface of a PMMA film. However, as described in the above embodiments, the vapor deposition process is performed using methods such as magnetron sputtering. The resulting conductive metal layer has relatively large conductive metal particles, leading to a relatively loose microstructure. Furthermore, these conductive metal particles have weak adhesion to the PMMA film. Therefore, in principle, when the conductive filler film is dissolved using organic solvents such as acetone or dichloromethane, the conductive metal layer on the surface of the conductive filler film not only does not hinder the dissolution of PMMA, but is also dispersed into the organic solvent along with the dissolving PMMA, hardly adhering to the master template metal layer. From an empirical perspective, for example, scanning electron microscopy examination of the surface of the master template metal layer immediately after being removed from the organic solvent environment reveals that the amount of conductive metal layer residue on the master template metal layer is almost zero.

[0040] After removing the conductive filler film, the remaining master template metal layer is transferred from the organic solvent. Next, the residual organic solvent and other impurities on the surface of the master template metal layer need to be treated to ensure that the final master template has a precise predetermined structural shape. Therefore, for example, the surface of the master template metal layer is preferentially rinsed with ethanol to remove residual organic solvents such as acetone or dichloromethane, as well as other impurities that are poorly soluble in water. Then, the surface of the master template metal layer is rinsed again with ultrapure water to remove residual ethanol and other water-soluble impurities from the previous rinse. Finally, the rinsed master template metal layer is transferred to a drying oven to dry, thereby obtaining a nickel master template with a predetermined structural shape. Please... Figure 6 Further reference Figure 8 , Figure 8 The longitudinal section of the master template obtained after removing the conductive filler film is schematically shown.

[0041] The nickel master template prepared by the method described above not only maintains a high-precision preset structural shape through deposition on a PMMA film but also ensures a certain degree of flexibility, effectively improving wear resistance and stress resistance compared to silicon-based rigid templates. Furthermore, the master template prepared by the above embodiments utilizes the inherent physicochemical properties of elemental nickel, making it more durable than current polymer flexible templates. Experimental verification shows that the master template prepared by the method described above generally has a cyclic imprinting life of no less than 400 cycles.

[0042] Thus, the master template preparation method in this application introduces an electrodeposited nickel metal layer as the raw material of the master template. By utilizing the physicochemical properties of nickel, the prepared master template is flexible enough to maintain the multi-dimensional micro-nano pattern morphology with high precision. At the same time, it can also make its cyclic imprinting use number far greater than that of organic polymer flexible master templates and silicon-based rigid master templates in the current related technologies, which significantly improves the stability of the master template preparation process.

[0043] The master template for nano-cold embossing in this application is prepared according to the master template preparation method described in the above embodiments.

[0044] This application also proposes a method for preparing materials with nanostructured shapes. Please refer to [link to relevant documentation]. Figure 9 The methods specifically include: Step 001: Based on the master template, perform imprinting on the pre-selected carrier material to form a shape complementary to the preset structural shape on the first surface of the carrier material. The master template is prepared according to the master template preparation method in the above embodiments, and the carrier material is aluminum sheet or aluminum plate.

[0045] Specifically, this application further proposes an application of the master template prepared by the master template preparation method in the above embodiments in the field of nano cold imprinting technology. Specifically, it proposes a method for preparing materials with nanostructure shapes. The core logic of this method is to use the master template with a preset structural shape prepared according to the method in the above embodiments as the template for imprinting. After the initial imprinting, a mask is prepared, so that the mask has a complementary shape that is complementary to the preset structural shape. Then, the mask is further used to perform imprinting, thereby preparing a material with a nanostructure shape similar to or the same as the preset structural shape.

[0046] For example, a carrier material is first selected. The carrier material mainly serves as the raw material for the mask. Considering the ease of imprinting, the surface processing of the carrier material after imprinting, and the ease of further imprinting using the generated mask, the carrier material can still be aluminum sheet or aluminum plate.

[0047] Having selected a carrier material, the imprinting of the carrier material based on the master template can be performed using currently available nanoimprinting technology. For example, based on the master template prepared in the above embodiments, imprinting is performed on the first surface of the carrier material at a pressure of 7-9 MPa at room temperature for 2 minutes, thereby forming a complementary shape on the first surface of the carrier material that is complementary to the preset structural shape of the master template. For instance, in the example given above, the preset structural shape of the master template is periodic pits, then the complementary shape on the first surface of the carrier material after imprinting is a periodic protrusion.

[0048] Please continue reading. Figure 9 The method for preparing materials with nanostructured shapes in the embodiments of this application further includes: Step 002: Perform anodizing on the first surface of the carrier material to form an anodized layer with a shape complementary to the preset structural shape on the first surface of the carrier material.

[0049] Specifically, after imprinting using the master template, the complementary shape portions formed by imprinting need to be anodized to form an anodized layer, thereby enhancing the strength and hardness of the subsequently generated mask. For the specific implementation of anodizing, in some examples, a constant-voltage anodizing method can be used, applying a constant voltage of 100~140V to the complementary shape portions of the first surface of the aluminum plate or sheet for 4~6 hours. This oxidation process yields a long-range ordered anodized aluminum template layer (corresponding to the anodized layer, hereinafter referred to as the AAO layer).

[0050] Please continue reading. Figure 9 The method for preparing materials with nanostructured shapes in the embodiments of this application further includes: Step 003: Based on the anodic oxide layer, prepare a mask for nano-cold embossing.

[0051] Further, please refer to Figure 10 Step 003 specifically includes: Step 0032: Construct a filler film on the anodic oxide layer and remove the remaining carrier material to form a filler composite oxide layer. The filler film includes polymethyl methacrylate film; Step 0033: Remove the filler film included in the filler composite oxide layer to form a mask.

[0052] Specifically, based on the above embodiments, after obtaining the AAO, it is necessary to separate the AAO from other parts of the carrier material to form a mask for further imprinting preparation of the target material. Considering that the complementary shape of the AAO should be maintained when removing the carrier material other than the AAO, so as to avoid negatively affecting the structural shape of the mask and the nanostructure shape of the target material, the same PMMA film as in the above master template preparation method can be used to fix the complementary shape of the AAO, thereby fixing and protecting the complementary shape.

[0053] In some examples, PMMA is spin-coated multiple times onto the complementary shape of the AAO to achieve a certain thickness. After spin-coating, the entire carrier material is dried in a 60°C oven, allowing the PMMA and AAO to form a filled composite oxide layer. At this point, the filled composite oxide layer remains integrated with the remaining carrier material. The substrate portion of the carrier material, excluding the filled composite oxide layer, is then removed. Based on the above examples, the substrate portion other than the filled composite oxide layer is elemental aluminum, which can be achieved by a displacement reaction between aluminum and an aqueous solution of a metal salt with weaker metallic properties than aluminum. For example, a copper chloride solution can be used to react with the aluminum substrate on the carrier material, excluding the filler composite oxide layer, to induce a displacement reaction. During the displacement reaction, the reaction can be maintained by stirring constantly and peeling off the copper precipitated on the surface of the aluminum substrate. Eventually, all the remaining aluminum substrate on the carrier material can be removed, leaving only the filler composite oxide layer. The main component of the AAO layer is aluminum oxide, which hardly reacts with the copper chloride solution. Therefore, after removing the aluminum substrate, it is only necessary to rinse with ultrapure water to wash away the copper chloride solution.

[0054] When the aluminum substrate is removed, leaving only the filler composite oxide layer, the PMMA layer simply needs to be peeled off from the AAO layer. The remaining AAO layer after peeling is the mask with complementary shapes. The specific method for removing the PMMA layer is similar to the master template preparation method in the above embodiments; the PMMA layer is dissolved using an organic solvent such as acetone or dichloromethane. After dissolution, the remaining AAO layer is transferred from the organic solvent and rinsed successively with ethanol and ultrapure water to obtain the aforementioned mask.

[0055] Please continue reading. Figure 11 In some implementations, the method further includes the following step before step 0032: Step 0031: Perform phosphoric acid pore enlargement on the anodic oxide layer to adjust the structural morphology and structural dimensions to complement the preset structural shape.

[0056] Specifically, based on the above embodiments, for example, since there may be various different requirements for the morphology and size of the nanostructure on the final target material in the process of practical application, the complementary shape of the AAO layer can be appropriately modified when preparing the target material. This can directly change the morphology and size of the structure of the mask, thereby indirectly changing the morphology and size of the nanostructure on the target material.

[0057] For example, exemplarily, the AAO layer can be enlarged and etched using phosphoric acid enlargement. During the enlargement process, the morphology and size of the complementary shapes of the AAO layer can be adjusted by controlling the enlargement time, thereby directly adjusting the morphology and size of the structure on the mask derived from the AAO layer. The specific implementation method of phosphoric acid enlargement can refer to the relevant implementation methods in the current related technologies according to the actual situation, and this application does not make specific limitations.

[0058] Please continue reading. Figure 9 The method for preparing materials with nanostructured shapes in the embodiments of this application further includes: Step 004: Perform imprinting on a pre-selected target base material based on a mask to give the target base material a nanostructure shape.

[0059] Specifically, based on the above embodiments, the obtained mask has a complementary shape that is complementary to the preset structural shape of the master template. Then, by using the mask as an imprinting template to perform further imprinting, a nanostructure shape that is the same as or similar to the preset structural shape of the master template can be obtained, and thus a target material with the above-mentioned nanostructure shape can be prepared.

[0060] Therefore, it is necessary to first select the target base material required for the preparation of the target material. Considering the application scenario of the target material and the strength and hardness of the AAO layer, the target base material mentioned above can still be aluminum sheet or aluminum plate.

[0061] Based on the selected target base material, the imprinting of the target base material with the mask prepared according to the above embodiments can still adopt a nanoimprinting method similar to that in the above examples. For example, based on the master template prepared in the above embodiments, imprinting is performed on the first surface of the target base material at a pressure of 7~9MPa at room temperature for 2 minutes, thereby forming the above-mentioned nanostructure shape on the first surface of the target base material.

[0062] Please continue reading. Figure 9 The method for preparing materials with nanostructured shapes in the embodiments of this application further includes: Step 005: Remove the mask remaining on the target base material to form the imprinted target base material into a target material with a nanostructure shape.

[0063] Specifically, based on the above implementation method, after imprinting on the target base material using a mask, the method of removing the mask from the target base material can be selected according to the actual situation. After removing the mask from the target base material, the target material with the above-mentioned nanostructure shape is obtained.

[0064] In some embodiments, step 005 further includes: Step 0051: Immerse the target base material with residual masking in chromic acid of a preset concentration to remove the residual masking. Step 0052: Rinse the remaining target base material with an inorganic solvent, including ultrapure water, to obtain the target material.

[0065] Specifically, regarding the method of mask removal, a chemical approach can be used to select a substance that dissolves and removes the mask without affecting or having minimal impact on the target base material. In some examples, a chromic acid solution of a preset concentration can be selected to treat the target base material with residual mask. As shown in the above example, the mask originates from anodized aluminum oxide (AAO), while the target base material is an aluminum sheet or plate. Since chromic acid is a strong oxidizing acid, in the environment of the chromic acid solution, the surface of the target base material will quickly passivate and form a dense alumina layer. The alumina layer has a regular atomic arrangement and low porosity, making it difficult for chromic acid to react chemically with the alumina layer. Ultimately, this can prevent the elemental aluminum in the target base material from reacting with chromic acid. However, anodized aluminum oxide has a loose and porous ordered structure with numerous channels and surface defects, allowing it to react and dissolve rapidly in the chromic acid solution. Based on the above principle, chromic acid can specifically remove the mask. Generally, the concentration of chromic acid solution can be set to 60%. If the concentration of chromic acid is too high, it increases the threat to the alumina layer formed by passivation, and the shape of the nanostructure on the target base material may not be maintained. If the concentration of chromic acid is too low, it may lead to incomplete mask removal and reduce the preparation efficiency of the target material, ultimately affecting the shape of the nanostructure formed on the target material. In addition to chromic acid, other substances with similar effects, capable of directionally removing the AAO mask and preserving the shape of the target base material and its nanostructures as much as possible, can be selected according to the actual situation to achieve mask removal.

[0066] After removing the residual mask, inorganic materials such as ultrapure water are used to remove the residual chromic acid solution and other water-soluble impurities on the target base material, thereby obtaining the target material with the above-mentioned nanostructure shape.

[0067] The nanostructured material in this application embodiment is prepared according to the nanostructured material preparation method described in the above embodiment.

[0068] The above description is merely a preferred embodiment of this application and is not intended to limit this application in any way. Although this application has disclosed the preferred embodiment as above, it is not intended to limit this application. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the technical solution of this application. Any simple modifications, equivalent substitutions, and improvements made to the above embodiments without departing from the technical solution of this application, based on the technical essence of this application and within the spirit and principles of this application, shall still fall within the protection scope of the technical solution of this application.

Claims

1. A method for preparing a master template, wherein the master template is suitable for nano-cold embossing, characterized in that, The method includes: Based on a pre-treated substrate material having a preset structural shape, a filler film for replicating the structural shape is constructed on the first surface of the substrate material, wherein the first surface of the substrate material has the preset structural shape; The filler film is peeled off from the surface of the substrate material, and a conductive metal layer is deposited on the surface of the filler film to form a conductive filler film; Electrochemical deposition is performed on the first surface of the conductive filler film to form a master template metal layer, wherein the master template metal layer is a nickel metal layer, and wherein the first surface of the conductive filler film has a shape complementary to the preset structural shape; Remove the conductive filler film and use the remaining master template metal layer to form the master template.

2. The method according to claim 1, characterized in that, The substrate material includes aluminum sheet or aluminum plate, and the pretreatment method of the substrate material includes: The surface of the substrate material is rinsed with a preset organic solvent and an inorganic solvent, wherein the organic solvent includes acetone and / or ethanol, and the inorganic solvent includes ultrapure water. The filler film includes a polymethyl methacrylate film.

3. The method according to claim 1, characterized in that, The electrochemical deposition performed on the first surface of the conductive filler film to form a master template metal layer includes: Based on a preset mixed electrodeposition plating solution, electrodeposition is performed sequentially on the first surface of the conductive filler film at a first current density within a first time period, at a second current density within a second time period, and at a third current density within a third time period. The first current density, the second current density, and the third current density increase in sequence, the first duration range is less than the second duration range, and the third duration range is greater than or equal to the second duration range. The mixed electrodeposition plating solution includes nickel sulfate hexahydrate, nickel chloride hexahydrate, and boric acid, with the concentration ratio of nickel sulfate hexahydrate, nickel chloride hexahydrate, and boric acid being (24~25):(7~7.5):(7.5~8).

4. The method according to claim 1, characterized in that, The step of removing the conductive filler film and forming the remaining master template metal layer into the master template includes: The conductive filler film on which the master template metal layer is formed is placed in a first organic solvent within a fourth time period to remove the conductive filler film; The remaining metal layer surface of the master template is rinsed with a second organic solvent and an inorganic solvent and then dried to produce the master template. The first organic solvent includes acetone or dichloromethane, the second organic solvent includes ethanol, and the inorganic solvent includes ultrapure water.

5. A master template for nano-cold embossing, characterized in that, The master template is prepared according to the master template preparation method according to any one of claims 1-4.

6. A method for preparing a material with a nanostructure shape, characterized in that, The material preparation method includes: Imprinting is performed on a pre-selected carrier material based on the master template to form a shape complementary to a preset structural shape on the first surface of the carrier material, wherein the master template is prepared according to the master template preparation method according to any one of claims 1-4, and the carrier material is an aluminum sheet or an aluminum plate. Anodizing is performed on the first surface of the carrier material to form an anodized layer on the first surface of the carrier material having a shape complementary to the preset structural shape; Based on the anodic oxide layer, a mask for nanocold embossing is prepared; Imprinting is performed on a pre-selected target base material based on the mask, so that the target base material has the nanostructure shape; Remove the mask remaining on the target base material to form the imprinted target base material into the target material with the nanostructure shape.

7. The method according to claim 6, characterized in that, The preparation of a mask for nano-cold embossing based on the anodic oxide layer includes: A filler film is constructed on the anodic oxide layer, and the remaining carrier material is removed to form a filler composite oxide layer, wherein the filler film comprises a polymethyl methacrylate film; The filler film included in the filler composite oxide layer is removed to form the mask.

8. The method according to claim 6, characterized in that, The step of removing the mask remaining on the target base material to form the imprinted target base material into the target material with the nanostructure shape includes: The target base material with residual mask is immersed in chromic acid of a preset concentration to remove the residual mask; The remaining target base material is rinsed with an inorganic solvent, including ultrapure water, to obtain the target material.

9. The method according to claim 7, characterized in that, The process of constructing a filler film on the anodic oxide layer and removing the remaining carrier material to form a filler composite oxide layer further includes: Phosphoric acid pore-expanding is performed on the anodic oxide layer to adjust the structural morphology and structural dimensions to be complementary to the preset structural shape.

10. A material having a nanostructure shape, characterized in that, The material is prepared according to the material preparation method with nanostructure shape as described in any one of claims 6-9.

Images