Block copolymer assembly structure, nano functional material, preparation method and application

Abstract

This invention discloses a block copolymer assembly structure, a nanomaterial, a preparation method, and applications. The block copolymer assembly structure is formed by assembling at least one of PS-P2VP and PS-P4VP, with a morphology of either a horizontal columnar or vertical columnar structure. The PS blocks in PS-P2VP and / or the PS blocks in PS-P4VP form a continuous phase, while the P2VP blocks in PS-P2VP and / or the P4VP blocks in PS-P4VP form a columnar dispersed phase. In the horizontal columnar morphology, the columnar dispersed phase is arranged in an orderly manner parallel to the substrate surface. In the vertical columnar morphology, the columnar dispersed phase is arranged in an orderly manner perpendicular to the substrate surface. This block copolymer assembly structure has advantages such as uniform orientation, regular structure, and controllable processing, and can be used as a nanotemplate, functional layer for electronic devices, etc., showing broad application prospects in nanoimprinting, semiconductor devices, sensors, and other fields.

Description

Technical Field

[0001] This invention belongs to the field of nanomaterial self-assembly technology, specifically relating to a block copolymer assembly structure, nanofunctional materials, preparation methods, and applications. Background Technology

[0002] Block copolymers (BCPs) self-assembly, with their advantages of scalable preparation, uniform structure and size, and controllable morphology, have significant application value in fields such as nanotemplates, electronic devices, and biosensors. Among them, PS-P2VP and PS-P4VP, as typical diblock copolymers, can form ordered structures such as spherical, columnar, and layered structures through phase separation. In particular, the columnar structure, due to its high specific surface area and regular spatial arrangement, is an ideal precursor for the preparation of nanoarray materials.

[0003] Dynamic soft template assembly (DSA) technology, as a mild self-assembly method, achieves the ordered assembly of block copolymers by controlling the phase separation kinetics during solvent evaporation. Compared with traditional thermal annealing or solvent annealing, it features simpler processes, shorter processing times, and easier scalability. However, in existing DSA processes, the orientation control of block copolymers remains a key challenge: a single solvent system cannot simultaneously meet the solubility requirements of two blocks, resulting in chaotic orientation and poor uniformity of the assembled structure; traditional control methods (such as substrate modification and external force field induction) suffer from complex processes, high costs, and poor repeatability, limiting their practical application.

[0004] For example, when using a single good solvent to prepare PS-P2VP assembled structures in the prior art, random oriented columnar structures are easily formed; while complex substrate chemical modification can induce the formation of vertical columns, the modification process is cumbersome and it is difficult to achieve flexible switching between flat columns and vertical columns.

[0005] Therefore, developing a simple, efficient, and precisely controllable DSA assembly method for block copolymer orientation is of great significance for promoting the industrial application of block copolymer self-assembly technology. Summary of the Invention

[0006] The purpose of this invention is to provide a block copolymer assembly structure, a nanofunctional material, a preparation method, and an application. The block copolymer assembly structure has a directional arrangement of horizontal or vertical columnar shapes, with a regular structure and good uniformity.

[0007] To achieve the above objectives, a specific embodiment of the present invention provides the following technical solution:

[0008] A block copolymer assembly structure, wherein the block copolymer assembly structure is formed by assembling at least one of PS-P2VP and PS-P4VP, and the morphology of the block copolymer assembly structure is a horizontal columnar or vertical columnar;

[0009] In this phase, the PS blocks in PS-P2VP and / or the PS blocks in PS-P4VP form a continuous phase, and the P2VP blocks in PS-P2VP and / or the P4VP blocks in PS-P4VP form a columnar dispersed phase.

[0010] The block copolymer assembly structure has a horizontal columnar morphology, and the columnar dispersed phase is arranged in an orderly manner parallel to the substrate surface;

[0011] The block copolymer assembly structure has a vertical columnar morphology, and the columnar dispersed phase is arranged in an orderly manner perpendicular to the substrate surface.

[0012] In one or more embodiments of the present invention, in the supra-columnar morphology, the columnar dispersed phases formed by the P2VP blocks in PS-P2VP and / or the P4VP blocks in PS-P4VP are arranged in an orderly linear pattern; and / or,

[0013] In the vertical morphology, the columnar dispersed phases formed by the P2VP blocks in PS-P2VP and / or the P4VP blocks in PS-P4VP are arranged in a hexagonal ordered manner, and the top view shows an ordered lattice pattern.

[0014] In one or more embodiments of the present invention, in the flat columnar morphology and / or vertical columnar morphology, the column diameter of the columnar dispersed phase is 5nm-50nm, and the phase separation period is 10nm-100nm.

[0015] In one or more embodiments of the present invention, the number-average molecular weight of either PS-P2VP or PS-P4VP is 10,000-100,000, and the PDI is <1.2; and / or,

[0016] The mass ratio of PS blocks to P2VP blocks in the PS-P2VP is 3:7-7:3; and / or,

[0017] The mass ratio of the PS block to the P4VP block in the PS-P4VP is 3:7-7:3.

[0018] Another specific embodiment of the present invention provides the following technical solution:

[0019] A method for preparing a block copolymer assembly structure, the method comprising the following steps:

[0020] Choose a good solvent for PS blocks and a selective solvent for P2VP blocks and / or P4VP blocks;

[0021] A mixed solvent is obtained by mixing a good solvent and a selective solvent;

[0022] At least one of PS-P2VP and PS-P4VP is dispersed in a mixed solvent to obtain a mixed solution;

[0023] The mixed solution was coated onto the substrate surface, and after dynamic assembly and annealing, a block copolymer assembly structure was obtained.

[0024] In one or more embodiments of the present invention, the good solvent is at least one selected from toluene, styrene, chloroform, and tetrahydrofuran; and / or,

[0025] The selective solvent is at least one of ethanol, methanol, N,N-dimethylformamide, and water; and / or,

[0026] The substrate is one of silicon wafers, quartz wafers, glass wafers, and flexible polymer substrates, and the substrate is pre-treated with hydrophilic or hydrophobic treatment.

[0027] In one or more embodiments of the present invention, the dynamic assembly is carried out in a nitrogen or argon atmosphere at a temperature of 25°C-80°C for a time of 0.5h-10h; and / or,

[0028] In the dynamic assembly step, the solvent evaporation rate is 0.1 μL / min·cm. 2 -5μL / min·cm 2 ; and / or,

[0029] The annealing treatment is solvent annealing or thermal annealing. Solvent annealing involves holding the solution at 25°C-60°C for 1-12 hours in a saturated vapor atmosphere of a mixed solvent; thermal annealing involves holding the solution at 80°C-150°C for 0.5-5 hours in a nitrogen or argon atmosphere; and / or...

[0030] The coating method for the mixed solution is selected from spin coating, blade coating, or drop coating. Spin coating speed is 500 rpm-5000 rpm, spin coating time is 30 s-120 s, and spin coating thickness is 10 nm-80 nm. Blade coating thickness is 100 nm-500 nm. Drop coating amount is 0.1 μL / cm. 2 -1μL / cm 2 .

[0031] In one or more embodiments of the present invention, the concentration of the mixed solution is 0.5wt%-5wt%; and / or,

[0032] In the mixed solvent, the volume ratio of the good solvent to the selective solvent is 1:9-9:1; and / or,

[0033] In the mixed solvent, the volume percentage of the good solvent is ≥70%, and the morphology of the block copolymer assembly structure is a horizontal columnar shape; the volume percentage of the selective solvent is ≥50%, and the morphology of the block copolymer assembly structure is a vertical columnar shape.

[0034] Another specific embodiment of the present invention provides the following technical solution:

[0035] A nanofunctional material is formed from a block copolymer assembly structure or a block copolymer assembly structure prepared by the above-mentioned block copolymer assembly structure preparation method;

[0036] The nanomaterials are nanopore arrays, quantum dot arrays, or metal nanowire arrays.

[0037] Another specific embodiment of the present invention provides the following technical solution:

[0038] Applications of a block copolymer assembly structure, the block copolymer assembly structure or nanomaterial prepared by the above-mentioned block copolymer assembly structure preparation method, in nanoimprint templates, semiconductor devices, chemical sensors, and biodetection chips.

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] 1. Advantages of the assembly structure: By controlling the mixed solvent, the precise switching between the flat column and the vertical column structure is achieved. The structure has the characteristics of uniform orientation, controllable period and uniform size. The column diameter and period can be flexibly controlled by the molecular weight of the block copolymer and the ratio of the mixed solvent.

[0041] 2. Advantages of the preparation method: No complex substrate modification or external force field induction is required. Orientation control can be achieved simply by adjusting the composition of the mixed solvent and process parameters. The process is simple, low-cost, and has good repeatability, making it easy to scale up production.

[0042] 3. Application value: This assembly structure can be directly used as a nanotemplate to prepare functional materials such as nanopore arrays and metal nanowire arrays; it can also be used as a functional layer of electronic devices (such as the dielectric layer of semiconductor devices and the sensitive layer of sensors), and has broad application prospects in the fields of nanoimprinting, organic electronics, and biological detection. Attached Figure Description

[0043] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0044] Figure 1 This is a flowchart of a method for preparing a block copolymer assembly structure according to an embodiment of the present invention;

[0045] Figure 2 This is a SEM image of the block copolymer assembly structure in Example 1 of the present invention;

[0046] Figure 3 This is a SEM image of the block copolymer assembly structure in Example 2 of the present invention;

[0047] Figure 4 This is a SEM image of the block copolymer assembly structure in Comparative Example 2 of the present invention;

[0048] Figure 5 This is a SEM image of the block copolymer assembly structure in Comparative Example 3 of the present invention. Detailed Implementation

[0049] To enable those skilled in the art to better understand the technical solutions in this disclosure, the technical solutions in the embodiments of this disclosure are described clearly and completely below. Obviously, the described embodiments are only some embodiments of this disclosure, and not all embodiments. Based on the embodiments in this disclosure, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this disclosure.

[0050] One specific embodiment of the present invention provides a block copolymer assembly structure, which is formed by assembling at least one of PS-P2VP (polystyrene-b-poly2-vinylpyridine) and PS-P4VP (polystyrene-b-poly4-vinylpyridine). The morphology of the block copolymer assembly structure is a horizontal columnar or vertical columnar. Specifically, the PS blocks in PS-P2VP and / or the PS blocks in PS-P4VP form a continuous phase, and the P2VP blocks in PS-P2VP and / or the P4VP blocks in PS-P4VP form a columnar dispersed phase. In the horizontal columnar morphology, the columnar dispersed phase is arranged in an orderly manner parallel to the substrate surface; in the vertical columnar morphology, the columnar dispersed phase is arranged in an orderly manner perpendicular to the substrate surface.

[0051] Furthermore, in the horizontal columnar morphology, the columnar dispersed phases formed by P2VP blocks in PS-P2VP and / or P4VP blocks in PS-P4VP are arranged in an orderly linear pattern; in the vertical morphology, the columnar dispersed phases formed by P2VP blocks in PS-P2VP and / or P4VP blocks in PS-P4VP are arranged in a hexagonal orderly pattern, and the top view shows an ordered lattice pattern.

[0052] Furthermore, in the horizontal columnar morphology and / or vertical columnar morphology, the column diameter of the columnar dispersed phase is 5nm-50nm, and the phase separation period is 10nm-100nm.

[0053] The block copolymer assembly structure in this invention is arranged in a horizontal columnar or vertical columnar orientation, exhibiting excellent structural regularity and orientation uniformity.

[0054] Another specific embodiment of the present invention provides a method for preparing a block copolymer assembly structure, such as... Figure 1 As shown, the specific steps include the following:

[0055] Step 1: Prepare the mixed solvent system.

[0056] Specifically, a good solvent for the PS block is selected, which is at least one of toluene, styrene, chloroform, and tetrahydrofuran; a selective solvent for the P2VP block and / or P4VP block is selected, which is at least one of ethanol, methanol, N,N-dimethylformamide, and water. The good solvent and the selective solvent are mixed evenly at a volume ratio of 1:9 to 9:1 to obtain a mixed solvent.

[0057] In this step, the composition of the mixed solvent is key to controlling the orientation: a high proportion of good solvent for PS blocks facilitates PS block spreading, inducing the formation of flat columns from P2VP / P4VP blocks; a high proportion of selective solvent for P2VP / P4VP enhances the solvation of P2VP / P4VP blocks, promoting their growth along the vertical direction of the substrate and forming vertical columns. Specifically, in the mixed solvent, if the volume percentage of good solvent is ≥70%, the morphology of the block copolymer assembly structure is a flat column; if the volume percentage of selective solvent is ≥50%, the morphology of the block copolymer assembly structure is a vertical column.

[0058] Step 2: Prepare block copolymer solution.

[0059] Specifically, at least one of PS-P2VP and PS-P4VP is dissolved in a mixed solvent and ultrasonically dispersed for 10-30 minutes to obtain a mixed solution with a concentration of 0.5wt%-5wt%. The number average molecular weight of either PS-P2VP or PS-P4VP is 10,000-100,000, and the PDI is <1.2. The mass ratio of PS blocks to P2VP blocks in PS-P2VP is 3:7-7:3, and the mass ratio of PS blocks to P4VP blocks in PS-P4VP is also 3:7-7:3.

[0060] In this step, the concentration of the mixed solution affects the film thickness and structural compactness. Too low a concentration can lead to an incomplete structure, while too high a concentration may cause phase separation disorder.

[0061] Step 3, DSA assembly.

[0062] Specifically, a substrate is taken, which can be one of silicon wafer, quartz wafer, glass wafer, or flexible polymer substrate. The substrate is pre-treated with hydrophilic or hydrophobic treatment. The hydrophilic treatment method is oxygen plasma treatment or concentrated sulfuric acid-hydrogen peroxide mixture treatment. The hydrophobic treatment method is trimethylchlorosilane modification or fluorosilane modification.

[0063] The mixed solution was coated by spin coating (500 rpm-5000 rpm, 30 s-120 s, thickness 10 nm-80 nm), blade coating (100 nm-500 nm thickness), or drop coating (dropping amount 0.1 μL / cm). 2 -1μL / cm 2 The solvent was coated onto the pretreated substrate surface using a specific method. The solvent evaporation rate was controlled to be 0.1 μL / min·cm. 2 -5μL / min·cm 2 Dynamic assembly was performed at 25℃-80℃ for 0.5h-10h, allowing the block copolymers to gradually separate and orient themselves during solvent evaporation. Subsequent annealing was carried out: solvent annealing (using a mixed solvent saturated vapor atmosphere, holding at 25℃-60℃ for 1-12h) or thermal annealing (using nitrogen or argon protection, holding at 80℃-150℃ for 0.5-5h) to further optimize structural regularity and obtain the target assembled structure.

[0064] In this step, the annealing temperature affects the morphology of the block copolymer assembly structure. If the temperature is too low, molecular motion cannot be triggered, and no reaction occurs. If the temperature is too high, the molecular chains break, resulting in widespread disorder.

[0065] This invention regulates phase separation behavior by controlling the solvent system, and achieves precise switching between two orientation structures by controlling the solution concentration, solvent evaporation rate and annealing conditions. The process is simple and highly controllable.

[0066] Another specific embodiment of the present invention provides a nanofunctional material, which is obtained by etching, deposition or filling modification of a block copolymer assembly structure. The nanofunctional material is a nanopore array, a quantum dot array or a metal nanowire array.

[0067] Another specific embodiment of the present invention provides the application of block copolymer assembly structures or nanofunctional materials in nanoimprint templates, semiconductor devices, chemical sensors, and biological detection chips.

[0068] The present invention will be further described in detail below with reference to specific embodiments.

[0069] Example 1

[0070] The preparation method of the block copolymer assembly structure in this embodiment is as follows:

[0071] (1) Preparation of mixed solvent: Mix toluene (PS good solvent) and ethanol (P2VP selective solvent) at a volume ratio of 8:2 and stir evenly to obtain mixed solvent.

[0072] (2) Solution preparation: Select PS-P2VP (number average molecular weight 50,000, mass ratio of PS to P2VP 6:4), dissolve it in the above mixed solvent, and ultrasonically disperse it for 20 min to obtain a solution with a concentration of 2wt%.

[0073] (3) Substrate pretreatment: The silicon wafer is treated with oxygen plasma for 10 minutes (power 100W, oxygen flow rate 20sccm) to obtain a hydrophilic substrate.

[0074] (4) DSA assembly: The solution was spin-coated onto the silicon wafer surface at 2000 rpm to a thickness of 50 nm. The solvent evaporation rate was controlled at 0.5 μL / min·cm at 30 °C. 2 Dynamic assembly was performed for 30 minutes. Subsequently, solvent annealing was carried out at 40°C for 6 hours in a saturated vapor atmosphere of toluene-ethanol mixed solvent to obtain a flat-lying column assembly structure.

[0075] Characterization results: SEM image ( Figure 2 The data shows that the P2VP blocks form columnar phases with a diameter of about 20 nm, arranged in a hexagonal order parallel to the silicon wafer surface, with a phase separation period of about 45 nm; the structure is uniform and there are no obvious defects.

[0076] Example 2

[0077] The preparation method of the block copolymer assembly structure in this embodiment is as follows:

[0078] (1) Preparation of mixed solvent: Tetrahydrofuran (PS good solvent) and N,N-dimethylformamide (P4VP selective solvent) are mixed in a volume ratio of 4:6 and stirred evenly to obtain a mixed solvent.

[0079] (2) Solution preparation: Select PS-P4VP (number average molecular weight 30000, mass ratio of PS to P4VP 5:5), dissolve it in the above mixed solvent, and ultrasonically disperse it for 15 min to obtain a solution with a concentration of 1.5wt%.

[0080] (3) Substrate pretreatment: The quartz sheet was immersed in a 5 wt% trimethylchlorosilane toluene solution and modified with trimethylchlorosilane for 30 min to obtain a hydrophobic substrate.

[0081] (4) DSA assembly: The solution was spin-coated onto the surface of a quartz plate at 1500 rpm to a thickness of 50 nm. The solvent evaporation rate was controlled at 1 μL / min·cm at 50 °C. 2 Dynamic assembly was performed for 40 minutes. Subsequently, under nitrogen protection, it was thermally annealed at 120℃ for 2 hours to obtain the vertical column assembly structure.

[0082] Characterization results: SEM image ( Figure 3The results showed that the P4VP blocks formed columnar phases with a diameter of about 15 nm, which were regularly arranged perpendicular to the surface of the quartz plate, with a phase separation period of about 35 nm; this also verified the orderliness of the columnar phases.

[0083] Example 3

[0084] The preparation method of the block copolymer assembly structure in this embodiment is basically the same as that in Example 1, except that the mixed solvent is a mixture of toluene and ethanol in a volume ratio of 9:1.

[0085] Example 4

[0086] The preparation method of the block copolymer assembly structure in this embodiment is basically the same as that in Example 1, except that the mixed solvent is a mixture of toluene and ethanol in a volume ratio of 7:3.

[0087] Example 5

[0088] The preparation method of the block copolymer assembly structure in this embodiment is basically the same as that in Example 1, except that the mixed solvent is a mixture of toluene and ethanol in a volume ratio of 5:5.

[0089] Example 6

[0090] The preparation method of the block copolymer assembly structure in this embodiment is basically the same as that in Example 1, except that the mixed solvent is a mixture of toluene and ethanol in a volume ratio of 3:7.

[0091] Example 7

[0092] The preparation method of the block copolymer assembly structure in this embodiment is basically the same as that in Example 1, except that the mixed solvent is a mixture of toluene and ethanol in a volume ratio of 1:9.

[0093] Compared with Example 1, Examples 3-7 only changed the mixing ratio of toluene and ethanol in the mixed solvent. The results showed that when the volume percentage of toluene was ≥70% (such as the ratio of the two being 9:1, 8:2, 7:3), a flat column structure was formed; when the volume percentage of ethanol was ≥50% (such as the ratio of the two being 5:5, 3:7, 1:9), it gradually transformed into a vertical column structure, proving that the ratio of the mixed solvent is a key parameter for orientation control.

[0094] Example 8

[0095] The method for preparing the nanopore array in this embodiment is as follows:

[0096] Using the block copolymer assembly structure prepared in Example 2 as a template, the P4VP columnar phase was removed by plasma etching. The plasma etching conditions were oxygen (flow rate of 20 sccm), power of 80 W, and time of 3 min, to obtain a PS nanopore array.

[0097] Observations revealed that the obtained PS nanopore array has a pore size of approximately 15 nm and a pore spacing of approximately 35 nm, which can be used for subsequent metal deposition to prepare metal nanodot and line arrays for application in the electrode structure of semiconductor devices.

[0098] Comparative Example 1

[0099] The preparation method of the block copolymer assembly structure in this comparative example is basically the same as that in Example 1, except that toluene is used as the solvent.

[0100] The SEM characterization of the block copolymer assembly structure obtained in this comparative example shows that the columnar phase orientation is disordered, with no obvious horizontal or vertical arrangement, and the structure is not uniform, proving that it is difficult to achieve orientation control with a single solvent.

[0101] Comparative Example 2

[0102] The preparation method of the block copolymer assembly structure in this comparative example is basically the same as that in Example 1, except that ethanol is used as the solvent.

[0103] SEM characterization of the block copolymer assembly structure obtained in this comparative example is as follows: Figure 4 As shown in the figure, the block copolymer assembly structure exhibits poor uniformity and disordered orientation.

[0104] Comparative Example 3

[0105] The preparation method of the block copolymer assembly structure in this comparative example is basically the same as that in Example 1, except that the annealing temperature is 80℃.

[0106] The block copolymer assembly structure obtained in this comparative example is characterized by SEM as follows: Figure 5 As shown in the figure, the block copolymer assembly structure exhibits poor uniformity and widespread disorder.

[0107] In summary, this invention successfully achieved the precise fabrication of PS-P2VP / PS-P4VP flat-lying and vertical-pillar assembly structures by controlling the DSA process with mixed solvents. These structures exhibit excellent regularity and orientation uniformity. The fabrication method is simple, controllable, and easy to scale up, making it of significant application value in the fields of nanomaterials and electronic devices.

[0108] It will be apparent to those skilled in the art that this disclosure is not limited to the details of the exemplary embodiments described above, and that this disclosure can be implemented in other specific forms without departing from the spirit or essential characteristics of this disclosure. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of this disclosure is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within this disclosure.

[0109] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A block copolymer assembly structure, characterized in that, The block copolymer assembly structure is formed by assembling at least one of PS-P2VP and PS-P4VP, and the morphology of the block copolymer assembly structure is a horizontal columnar or vertical columnar; In this phase, the PS blocks in PS-P2VP and / or the PS blocks in PS-P4VP form a continuous phase, and the P2VP blocks in PS-P2VP and / or the P4VP blocks in PS-P4VP form a columnar dispersed phase. The block copolymer assembly structure has a horizontal columnar morphology, and the columnar dispersed phase is arranged in an orderly manner parallel to the substrate surface; The block copolymer assembly structure has a vertical columnar morphology, and the columnar dispersed phase is arranged in an orderly manner perpendicular to the substrate surface.

2. The block copolymer assembly structure according to claim 1, characterized in that, In the described planar columnar morphology, the columnar dispersed phases formed by the P2VP blocks in PS-P2VP and / or the P4VP blocks in PS-P4VP exhibit an orderly linear arrangement; and / or In the vertical morphology, the columnar dispersed phases formed by the P2VP blocks in PS-P2VP and / or the P4VP blocks in PS-P4VP are arranged in a hexagonal ordered manner, and the top view shows an ordered lattice pattern.

3. The block copolymer assembly structure according to claim 1, characterized in that, In the described horizontal columnar morphology and / or vertical columnar morphology, the column diameter of the columnar dispersed phase is 5nm-50nm, and the phase separation period is 10nm-100nm.

4. The block copolymer assembly structure according to claim 1, characterized in that, The number-average molecular weight of either PS-P2VP or PS-P4VP is 10,000-100,000, and the PDI is <1.2; and / or, The mass ratio of PS blocks to P2VP blocks in the PS-P2VP is 3:7-7:3; and / or, The mass ratio of the PS block to the P4VP block in the PS-P4VP is 3:7-7:

3.

5. A method for preparing the block copolymer assembly structure according to claim 1, characterized in that, The preparation method includes the following steps: Choose a good solvent for PS blocks and a selective solvent for P2VP blocks and / or P4VP blocks; A mixed solvent is obtained by mixing a good solvent and a selective solvent; At least one of PS-P2VP and PS-P4VP is dispersed in a mixed solvent to obtain a mixed solution; The mixed solution was coated onto the substrate surface, and after dynamic assembly and annealing, a block copolymer assembly structure was obtained.

6. The method for preparing the block copolymer assembly structure according to claim 5, characterized in that, The good solvent is at least one selected from toluene, styrene, chloroform, and tetrahydrofuran; and / or, The selective solvent is at least one of ethanol, methanol, N,N-dimethylformamide, and water; and / or, The substrate is one of silicon wafers, quartz wafers, glass wafers, and flexible polymer substrates, and the substrate is pre-treated with hydrophilic or hydrophobic treatment.

7. The method for preparing the block copolymer assembly structure according to claim 5, characterized in that, The dynamic assembly is carried out in a nitrogen or argon atmosphere at a temperature of 25℃-80℃ for 0.5h-10h; and / or, In the dynamic assembly step, the solvent evaporation rate is 0.1 μL / min·cm. 2 -5μL / min·cm 2 ; and / or, The annealing treatment is solvent annealing or thermal annealing. Solvent annealing involves holding the solution at 25°C-60°C for 1-12 hours in a saturated vapor atmosphere of a mixed solvent; thermal annealing involves holding the solution at 80°C-150°C for 0.5-5 hours in a nitrogen or argon atmosphere; and / or... The coating method for the mixed solution is selected from spin coating, blade coating, or drop coating. Spin coating speed is 500 rpm-5000 rpm, spin coating time is 30 s-120 s, and spin coating thickness is 10 nm-80 nm. Blade coating thickness is 100 nm-500 nm. Drop coating amount is 0.1 μL / cm. 2 -1μL / cm 2 .

8. The method for preparing the block copolymer assembly structure according to claim 5, characterized in that, The concentration of the mixed solution is 0.5wt%-5wt%; and / or, In the mixed solvent, the volume ratio of the good solvent to the selective solvent is 1:9-9:1; and / or, In the mixed solvent, the volume percentage of the good solvent is ≥70%, and the morphology of the block copolymer assembly structure is a horizontal columnar shape; the volume percentage of the selective solvent is ≥50%, and the morphology of the block copolymer assembly structure is a vertical columnar shape.

9. A nanomaterial, characterized in that, The block copolymer assembly structure is formed by the block copolymer assembly structure according to claim 1 or by the preparation method of the block copolymer assembly structure according to claim 5; The nanomaterials are nanopore arrays, quantum dot arrays, or metal nanowire arrays.

10. The application of the block copolymer assembly structure according to any one of claims 1-4, the block copolymer assembly structure prepared by the preparation method of the block copolymer assembly structure according to any one of claims 5-8, or the nanofunctional material according to claim 9 in nanoimprint templates, semiconductor devices, chemical sensors, and biodetection chips.

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