Regular-shape nano round hole array structure and preparation method thereof

Abstract

The invention belongs to the technical field of nano structure preparation, and discloses a regular-shape nano round hole array structure and a preparation method thereof. According to the preparation method, large-area, uniformly and densely arranged nanoscale polystyrene microspheres are prepared on a target substrate by using an LB membrane method, and a high-quality two-dimensional colloidal crystal is formed; the morphology and size of the microspheres are controlled by using an inductively coupled plasma etching technology; depositing a target material on the surfaces of the obtained microspheres and the substrate by using a vacuum evaporation coating technology with good deposition directivity; and finally, stripping the polystyrene nanometer microspheres to prepare the nanometer circular hole array. According to the technical scheme disclosed by the invention, the nano round hole array structure with a regular shape can be prepared in a large area at low cost, and the method has relatively high universality; the prepared nano round hole array structure has the characteristics of regular shape, high consistency, uniform arrangement, controllable size and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of nanostructure preparation, and particularly relates to a regularly shaped nano-circular hole array structure and a preparation method thereof. Background Art

[0002] With the continuous development of nanotechnology, the nano-circular hole array, as an important structural form, has been widely applied in the fields of microelectronics, optics, optoelectronics, sensor technology, biomedicine, surface-enhanced Raman spectroscopy, microfluidic chips, solar cells, etc. The nano-circular hole array can not only regulate the properties of light, heat, electrons, etc., but also provide great application potential in sensing, data storage, information processing, etc.; further explanatory, by precisely designing the size, spacing, and arrangement of the holes, the nano-circular hole array can achieve precise control of light, electrons, molecules, etc., greatly expanding its potential in scientific research and industrial applications.

[0003] The preparation of nano-circular hole arrays is an important research direction in nanotechnology. The existing preparation methods mainly include lithography techniques, nanoimprinting, template methods, etc.; among them, lithography techniques (such as electron beam lithography) can define fine patterns at the nanoscale, but have the disadvantages of long time consumption, difficulty in preparing large-area uniform arrays, and high cost; the accuracy of laser etching is relatively low, and it is difficult to control the size and spacing of the holes, especially there are great challenges in the preparation of high-density hole arrays; the template method is simple and economical, but there are difficulties in preparing regularly shaped, highly consistent, and size-controllable circular hole arrays.

[0004] In summary, there is still a lack of effective methods for the preparation of regularly shaped, highly consistent, uniformly arranged, size-controllable, and large-area low-cost nano-circular hole arrays, and it is urgent to develop a new preparation method. Summary of the Invention

[0005] The purpose of the present invention is to provide a regularly shaped nano-circular hole array structure and a preparation method thereof to solve one or more of the above-mentioned technical problems. The technical solution disclosed by the present invention can prepare a regularly shaped nano-circular hole array structure with large area and low cost, has strong versatility, and the prepared nano-circular hole array has the characteristics of regular shape, high consistency, uniform arrangement, and size controllability.

[0006] To achieve the above object, the present invention adopts the following technical solutions: In the first aspect of the present invention, a preparation method of a regularly shaped nano-circular hole array structure is provided, including the following steps: Using the LB film method, a two-dimensional colloidal crystal composed of polystyrene nano-microspheres is prepared on a selected target substrate; On the prepared two-dimensional colloidal crystal, controlled dry etching is carried out by ICP etching method to obtain a microsphere array with a target size; Using the vacuum evaporation coating method, deposit the selected target material on the microsphere array of the target size and the substrate surface to obtain a microsphere array with controllable coating of the target material and the substrate surface; Based on the microsphere array with controllable coating of the target material and the substrate surface, perform microsphere peeling to obtain a nano-hole array structure with regular shape and target size.

[0007] A further improvement of the preparation method of the present invention lies in that In the step of obtaining a microsphere array of the target size by performing controllable dry etching on the prepared two-dimensional colloidal crystal by ICP etching method, Control the microsphere size by adjusting the process parameters in the ICP etching method; wherein, the process parameters include etching gas, ICP power, radio frequency power, etching gas flow rate, etching pressure and etching time.

[0008] A further improvement of the preparation method of the present invention lies in that In the step of controlling the microsphere size by adjusting the process parameters in the ICP etching method, the etching gas is O2, the ICP power is 50 - 400 W, the radio frequency power is 10 - 100 W, the O2 flow rate is 10 - 50 sccm, and the etching pressure is 10 - 50 mTorr.

[0009] A further improvement of the preparation method of the present invention lies in that In the step of using the vacuum evaporation coating method to deposit the selected target material on the microsphere array of the target size and the substrate surface to obtain a microsphere array with controllable coating of the target material and the substrate surface, Controllably coat the microsphere array and the substrate surface by adjusting the process parameters in the vacuum evaporation coating method; wherein, the process parameters include air pressure, deposition rate, substrate temperature and deposition time.

[0010] A further improvement of the preparation method of the present invention lies in that In the step of controllably coating the microsphere array and the substrate surface by adjusting the process parameters in the vacuum evaporation coating method, the air pressure is 10 -6 ~10 -4 Torr, the deposition rate is 0.1 - 1 nm / s, and the substrate temperature is 20 - 50 °C. A further improvement of the preparation method of the present invention lies in that The target substrate is silicon, gallium arsenide, gallium nitride, silicon carbide, germanium, sapphire, quartz, aluminum nitride, diamond, lithium niobate or glass.

[0011] A further improvement of the preparation method of the present invention lies in that The target material is a conductor, semiconductor or insulator; wherein, The conductor is Au, Ag, Cu, Al, Ti, Cr, Pt, Ni, Sn, W, Mo or an alloy; The semiconductor is Si, Ge, GaAs, GaN, CdS, CIGS or InP; The insulator is Al2O3, SiO2, MgF2, TiO2, Si3N4 or AlN.

[0012] In a second aspect of the present invention, a nanometer circular hole array structure with regular shape is provided, which is prepared by using the preparation method described in any one of the first aspects of the present invention.

[0013] A further improvement of the present invention lies in that the nanometer circular hole array structure with regular shape includes: a target substrate and a thin film having a nanometer circular hole array with regular shape on the target substrate.

[0014] A further improvement of the present invention lies in that in the nanometer circular hole array with regular shape, D is the diameter of the original nanosphere, and the value range of D is greater than 0 and less than or equal to 1000 nm; the hole pitch is D - d, where d is the diameter of the nanometer circular hole, and d is less than D; the value range of the hole thickness is greater than 0 and less than H / 2, where H is the height of the microsphere after etching.

[0015] Compared with the prior art, the present invention has the following beneficial effects: In the preparation method disclosed by the present invention, the Langmuir-Blodgett (LB) film method is used to prepare two-dimensional colloidal crystals. The process has excellent repeatability and can efficiently and controllably prepare high-quality two-dimensional colloidal crystals composed of polystyrene nanospheres on the target substrate. It has the characteristics of large-area uniform close packing, high coverage rate, and low defect rate, providing a prerequisite for the preparation of large-area and uniformly arranged circular hole arrays, and overcoming the deficiencies of existing traditional colloidal crystal preparation methods (such as spin coating method, manual method after self-assembly at the gas-liquid interface) that are difficult to prepare repeatedly and have more defects. In the colloidal crystal etching process step, the inductively coupled plasma (ICP) etching process is adopted. Compared with other etching process methods, such as the problem of microsphere aggregation resulting in non-uniform nano-circular hole arrays during oxygen plasma asher etching, and the reactive ion etching method being unable to achieve low-damage etching at an appropriate rate, which is not conducive to controlling the etching morphology and resulting in irregular shapes and poor consistency. By adjusting the ICP etching process parameters, the present invention can precisely control the microsphere size and obtain a microsphere array with regular shapes, high consistency, and uniform arrangement of the target size. In the process step of depositing the selected target material on the microsphere array of the target size and the substrate surface, the vacuum evaporation coating technology is adopted. Compared with other deposition technologies, such as the problem of poor directionality, inability to peel off microspheres, and difficulty in forming nano-circular holes during sputtering coating deposition, the present invention uses the vacuum evaporation coating technology to deposit the target material, with good deposition directionality, semi-coating the upper surface of the microspheres, realizing controllable coating of the microspheres and the substrate surface, and then a nano-circular hole array structure with regular shapes and controllable thickness can be obtained. Summarizing, the technical solution of the present invention fully combines the advantages of the three-step process. Finally, the prepared nano-circular hole array has regular shapes, high consistency, uniform arrangement, controllable size, and can be prepared in large areas at low cost, overcoming the problems of high cost, irregular shapes, and poor consistency existing in the preparation of other existing process methods, and forming a set of efficient and low-cost preparation solutions for regular-shaped nano-circular hole array structures. Brief Description of the Drawings

[0016] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art; obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0017] Figure 1 It is a flowchart showing the preparation method of a regular-shaped nano-circular hole array structure in an embodiment of the present invention; Figure 2It is an exemplary principle explanation diagram of a preparation method for a regularly shaped nano-circular hole array structure in an embodiment of the present invention; Figure 3 It is an SEM image of a two-dimensional colloidal crystal formed by polystyrene nano-microspheres prepared on a silicon substrate using the LB film method in Specific Embodiment 1 of the present invention; Figure 4 It is an SEM image of a polystyrene nano-microsphere array etched to the target size by ICP in Specific Embodiment 1 of the present invention; Figure 5 It is an SEM image of a polystyrene nano-microsphere array with Cr deposited by electron beam evaporation in Specific Embodiment 1 of the present invention; Figure 6 It is an SEM image of a nano-circular hole array with the target size left after stripping the polystyrene nano-microspheres in Specific Embodiment 1 of the present invention; The explanations of the reference numerals in the figure are as follows: 1. Langmuir-Blodgett film analyzer; 2. Target substrate; 3. Polystyrene nano-microspheres; 4. Target material. Specific Embodiments

[0018] To make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention; obviously, the described embodiments of the technical solutions are part of the embodiments of the present invention, not all of the embodiments.

[0019] Based on the technical solutions disclosed in the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention. In addition, the terms "include" and "have" and any variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or device that includes a series of steps or units does not necessarily have to be limited to those steps or units clearly listed, but may include other steps or units not clearly listed or inherent to these processes, methods, products, or devices.

[0020] Please refer to Figure 1 and Figure 2 , a preparation method for a regularly shaped nano-circular hole array structure provided by an embodiment of the present invention includes the following steps: Step 1, using the LB film method, prepare a two-dimensional colloidal crystal composed of polystyrene nano-microspheres on a selected target substrate; in a specific exemplary technical solution, a Langmuir-Blodgett film analyzer 1 can be used to prepare a large-area and uniformly densely packed polystyrene nano-microsphere 3 (i.e., a polystyrene microsphere at the nano-scale) on a selected target substrate 2 to form a high-quality two-dimensional colloidal crystal; Step 2: Based on the two-dimensional colloidal crystal obtained in Step 1, perform controllable dry etching through ICP etching technology to obtain a microsphere array of the target size. In a specific exemplary technical solution, the high-quality two-dimensional colloidal crystal formed by the obtained polystyrene nanospheres 3 can be subjected to controllable dry etching through ICP etching technology, with the etching gas being O2. By adjusting process parameters, a microsphere array of the target size with regular shapes and high consistency can be obtained. Further explanatory, by adjusting ICP etching process parameters, including etching gas, ICP power, RF power, etching gas flow rate, etching pressure, and etching time (explanatorily, the etching time is determined according to the target size), etc., the microsphere size can be precisely controlled to obtain a microsphere array of the target size with regular shapes, high consistency, and uniform arrangement. Step 3: Adopt vacuum evaporation coating technology to deposit the selected target material on the microsphere array of the target size after ICP etching and the substrate surface, and controllably coat the microsphere array of the target size and the substrate surface. In a specific exemplary technical solution, the microsphere array of the target size after ICP etching and the substrate surface can be used to deposit the target material 4 by using vacuum evaporation coating technology with good deposition directionality. By adjusting process parameters, including: air pressure, deposition rate, substrate temperature, and deposition time (explanatorily, the deposition time is determined according to the pore thickness), etc., controllable coating of the microspheres and the substrate surface can be achieved, so as to obtain a nano-hole array with regular shapes and controllable depths subsequently. Step 4: Based on the microsphere array and the substrate surface after controllable coating, perform microsphere peeling to obtain a nano-hole array structure with regular shapes and the target size. In a specific exemplary technical solution, the obtained sample can be subjected to microsphere peeling according to the deposited material and the substrate material by selecting a suitable microsphere peeling process, and after removing the microspheres, a nano-hole array of the target size with regular shapes, high consistency, and uniform arrangement is left.

[0021] The technical solution provided by the embodiments of the present invention can achieve the preparation of a nano-hole array structure with regular shapes, and can achieve large-area and low-cost preparation; the prepared nano-hole array structure with regular shapes includes a target substrate and a thin film with a nano-hole array with regular shapes on the target substrate. The nano-hole array has the advantages of regular shapes, high consistency, uniform arrangement, and controllable size. Summarizing, the technical solution of the embodiments of the present invention discloses a method for preparing a nano-hole array structure with regular shapes that is efficient and controllable by integrating the LB film method, ICP etching process, and vacuum evaporation coating technology. This method not only has excellent process repeatability but also can precisely control the microsphere size and the morphological characteristics of the nano-hole array according to requirements, providing a new technical approach for the preparation and application of micro-nano devices.

[0022] For further explanatory purposes, the LB film method is a technique that spreads and compresses a monolayer or a layer of nanoparticles at the gas-liquid interface and then transfers it onto a solid substrate. The present invention utilizes this technique to efficiently and controllably fabricate a high-quality two-dimensional colloidal crystal composed of polystyrene nanospheres on a target substrate; the fabricated two-dimensional colloidal crystal has the remarkable characteristics of large-area uniform close packing, high coverage rate, and low defect rate. This highly ordered arrangement of microspheres provides an ideal template for the subsequent fabrication of a large-area and uniformly arranged circular hole array; by precisely controlling parameters such as surface pressure, spreading speed, and transfer conditions during the LB film method preparation process, the high quality and repeatability of the colloidal crystal are ensured.

[0023] In a specific embodiment of the present invention, in the ICP etching step, the etching gas used is O2, the ICP power is 50 - 400 W, the radio frequency power is 10 - 100 W, the O2 flow rate is 10 - 50 standard cubic centimeters per minute (sccm), and the gas pressure is 10 - 50 mTorr; for explanatory purposes, when using an oxygen plasma asher for etching, there is a problem of microsphere aggregation, and the formed nano circular holes are arranged unevenly; reactive ion etching cannot achieve low-damage etching at an appropriate etching rate, which is not conducive to controlling the etching morphology and results in irregular shapes and poor consistency; in view of the above problems, the ICP etching method adopted in the embodiment of the present invention can achieve controllable etching with regular microsphere shapes and high consistency.

[0024] For explanatory purposes, inductively coupled plasma (ICP) etching is a technique that uses a high-frequency electric field to excite a gas to form a plasma and etches materials through physical and chemical actions; the present invention precisely regulates ICP etching process parameters, including the type and proportion of etching gas, ICP power, radio frequency power, etching gas flow rate, etching gas pressure, and etching time, to achieve precise control of the microsphere size; after the ICP etching treatment, the microsphere array has regular shapes, high consistency, uniform arrangement, and the size meets the design requirements, laying a solid foundation for the subsequent preparation of the nano circular hole array.

[0025] In a specific embodiment of the present invention, the vacuum evaporation coating gas pressure is 10 -6 ~10 -4 Torr, the deposition rate is 0.1 - 1 nm / s, and the substrate temperature is 20 - 50 °C; in addition, the vacuum evaporation coating technology used, according to different heating sources, includes but is not limited to: resistance heating, electron beam heating, laser heating, arc heating, and high-frequency induction heating. For explanatory purposes, sputtering coating has problems such as poor directionality, inability to peel off microspheres, and difficulty in forming nano circular holes; in view of the above problems, the vacuum evaporation coating adopted in the embodiment of the present invention can achieve controllable coating of microspheres and the substrate surface due to good deposition directionality, and thus obtain a nano circular hole array with regular shapes and controllable thickness.

[0026] Explanatorily, vacuum evaporation coating is a technique where, in a high-vacuum environment, a material is evaporated into a gaseous state by heating an evaporation source and then deposited onto the surface of a substrate to form a thin film; the present invention utilizes the good deposition directionality of the vacuum evaporation coating technique to ensure that the target material can be uniformly and controllably coated on the surface of the microspheres and the substrate; by precisely controlling the coating thickness and conditions and combining with the previous microsphere array template, a nano-hole array with regular shape and controllable thickness is finally obtained, and these hole arrays have broad application prospects in the fields of optics, electronics, biosensing, etc.

[0027] In the embodiment of the present invention, the prepared nano-hole array with regular shape includes a target substrate and a thin film with a nano-hole array; wherein, in the nano-hole array with regular shape, D is the diameter of the original nano-microspheres, and the value range of D is greater than 0 and less than or equal to 1000 nm; the hole pitch is D - d, where d is the diameter of the nano-holes, and d is less than D; the value range of the hole thickness is greater than 0 and less than H / 2, where H is the height of the microspheres after etching.

[0028] In the embodiment of the present invention, the target substrate includes but is not limited to: silicon (Si), gallium arsenide (GaAs), gallium nitride (GaN), silicon carbide (SiC), germanium (Ge), sapphire (Al2O3), quartz (SiO2), aluminum nitride (AlN), diamond (Diamond), lithium niobate (LiNbO3), glass, etc.; explanatorily, the target substrate is selected according to the actual situation for crystal structure and orientation, doping and conductivity, thickness and size, stress and stability, whether there is an oxide layer, etc. Additionally, the deposited target materials include but are not limited to: conductors (Au, Ag, Cu, Al, Ti, Cr, Pt, Ni, Sn, W, Mo, alloys, etc.), semiconductors (Si, Ge, GaAs, GaN, CdS, CIGS, InP, etc.), insulators (Al2O3, SiO2, MgF2, TiO2, Si3N4, AlN, etc.).

[0029] In summary, the embodiment of the present invention discloses an optimized method for preparing a nano-hole array with regular shape, which can prepare a nano-hole array with regular shape, high consistency, uniform arrangement, controllable size, large area and low cost. The general preparation method can be widely applied to the fields of microelectronics, optics, optoelectronics, sensor technology, biomedicine, surface-enhanced Raman spectroscopy, microfluidic chips, solar cells, etc. Specific Embodiment 1 A method for preparing a nano-hole array structure with regular shape provided by the embodiment of the present invention includes the following steps: Step 1: Use a Langmuir-Blodgett film analyzer to prepare a large-area, uniformly and densely packed two-dimensional colloidal crystal of polystyrene nanospheres with a diameter of 500 nm on a silicon (Si) substrate to form a high-quality two-dimensional colloidal crystal; Step 2: Perform controllable dry etching on the high-quality two-dimensional colloidal crystal of polystyrene nanospheres obtained in Step 1 by ICP etching technology. The etching gas is O2, the ICP power is 200 W, the radio frequency power is 50 W, the O2 flow rate is 40 sccm, the gas pressure is 20 mTorr, and the etching time is 100 s to obtain a microsphere array with a target size of 350 nm; Step 3: Deposit 50 nm thick Cr on the surface of the polystyrene nanosphere / Si substrate after ICP etching in Step 2 by vacuum evaporation coating technology. Specifically, it is electron beam evaporation, and the process parameters are: the base vacuum degree is 2×10 -3 Pa, the substrate temperature is 20 °C, the deposition rate is 0.1 nm / s, and the deposition time is 500 s to achieve controllable coating of the microspheres and the substrate surface, and then obtain a nanometer circular hole array with regular shape and controllable depth; Step 4: Perform a microsphere peeling process on the sample obtained in Step 3. Specifically, it is ultrasonic treatment in acetone solvent for 30 min. After removing the microspheres, a nanometer circular hole array with regular shape, high consistency, and uniform arrangement of the target size is left. Thus, a nanometer circular hole array with regular shape, high consistency, uniform arrangement, controllable size, large area, and low cost is prepared.

[0031] Please refer to Figures 3 to 6 , in the method of the embodiment of the present invention, Figure 3 is the SEM image of the two-dimensional colloidal crystal of polystyrene nanospheres with a diameter of 500 nm prepared on a silicon substrate by the LB film method; Figure 4 is the SEM image of the polystyrene nanosphere array etched to a diameter of 350 nm by ICP; Figure 5 is the SEM image of the polystyrene nanosphere array deposited with 50 nm thick Cr by electron beam evaporation; Figure 6 is the SEM image of the circular hole array with a diameter of 350 nm left after peeling off the polystyrene nanospheres.

[0032] It can be seen from Figures 3 to 6 that the two-dimensional colloidal crystal composed of polystyrene nanospheres prepared in the embodiment of the present invention is large-area, uniformly and densely packed, and the prepared Cr circular hole array has the characteristics of regular shape, high consistency, uniform arrangement, and controllable size. Specific Embodiment 2 A method for preparing a nanometer circular hole array structure with a regular shape provided by an embodiment of the present invention includes the following steps: Step 1: Use a Langmuir-Blodgett film analyzer to prepare large-area and uniformly close-packed polystyrene nanospheres with a diameter of 350 nm on a quartz (SiO2) substrate to form a high-quality two-dimensional colloidal crystal; Step 2: Carry out controllable dry etching on the high-quality two-dimensional colloidal crystal formed by the polystyrene nanospheres obtained in Step 1 through ICP etching technology. The etching gas is O2, the ICP power is 100 W, the radio frequency power is 50 W, the O2 flow rate is 30 sccm, the gas pressure is 20 mTorr, and the etching time is 80 s to obtain a microsphere array with a target size of 240 nm; Step 3: Deposit 30 nm thick Au on the surface of the polystyrene nanosphere / SiO2 substrate after ICP etching in Step 2. Specifically, it is electron beam evaporation. The process parameters are: the base vacuum degree is 2×10 -3 Pa, the substrate temperature is 20 °C, the growth rate is 0.2 nm / s, and the growth time is 150 s to achieve controllable coating of the microspheres and the substrate surface, and then obtain a nano-hole array with regular shape and controllable depth; Step 4: Carry out a microsphere stripping process on the sample obtained in Step 3. Specifically, heat it in an oxygen or air atmosphere in a 300 °C high-temperature furnace to remove the microspheres and leave a nano-hole array with regular shape, high consistency, and uniform arrangement of the target size. Thus, a nano-hole array with regular shape, high consistency, uniform arrangement, controllable size, large area, and low cost is prepared. Specific Example 3 A method for preparing a nano-hole array structure with regular shape provided by an embodiment of the present invention includes the following steps: Step 1: Use a Langmuir-Blodgett film analyzer to prepare large-area and uniformly close-packed polystyrene nanospheres with a diameter of 200 nm on a silicon substrate with an oxide layer (SiO2 / Si) to form a high-quality two-dimensional colloidal crystal; Step 2: Carry out controllable dry etching on the high-quality two-dimensional colloidal crystal formed by the polystyrene nanospheres obtained in Step 1 through ICP etching technology. The etching gas is O2, the ICP power is 100 W, the radio frequency power is 50 W, the O2 flow rate is 30 sccm, the gas pressure is 20 mTorr, and the etching time is 50 s to obtain a microsphere array with a target size of 130 nm; Step 3: Deposit 15 nm thick Al on the surface of the polystyrene nanosphere - SiO2 / Si substrate after ICP etching in Step 2. Specifically, it is resistance heating vacuum evaporation. The process parameters are: the base vacuum degree is 2×10 -3At Pa, substrate temperature of 20 °C, growth rate of 0.2 nm / s, and growth time of 75 s, controllable coating of the microspheres and the substrate surface is achieved, and then a nano-hole array with regular shape and controllable depth is obtained. Step 4: Perform a microsphere stripping process on the sample obtained in Step 3. Specifically, ultrasonicate in acetone solvent for 30 min, and after removing the microspheres, a nano-hole array with regular shape, high consistency, and uniform arrangement of the target size is left.

[0035] Thus, a nano-hole array with regular shape, high consistency, uniform arrangement, controllable size, large area, and low cost is prepared. Specific Example 4 A method for preparing a nano-hole array structure with regular shape provided by an embodiment of the present invention includes the following steps: Step 1: Use the LB film method to prepare a two-dimensional colloidal crystal composed of polystyrene nano-microspheres on a selected target substrate. Step 2: On the prepared two-dimensional colloidal crystal, perform controllable dry etching by ICP etching method to obtain a microsphere array of the target size. Step 3: Use the vacuum evaporation coating method to deposit the selected target material on the microsphere array of the target size and the substrate surface, and obtain a microsphere array with controllable coating of the target material and the substrate surface. Step 4: Based on the microsphere array with controllable coating of the target material and the substrate surface, perform microsphere stripping to obtain a nano-hole array structure with regular shape of the target size. Among them, the microsphere size is controlled by adjusting the process parameters in the ICP etching method. The etching gas is O2, the ICP power is 50 W, the radio frequency power is 10 W, the O2 flow rate is 10 sccm, and the etching pressure is 10 mTorr; the microsphere array and the substrate surface are controllably coated by adjusting the process parameters in the vacuum evaporation coating method. The pressure is 10 -6 Torr, the deposition rate is 0.1 nm / s, and the substrate temperature is 20 °C; the target substrate is aluminum nitride; the target material is Cu. Specific Example 5 A method for preparing a nano-hole array structure with regular shape provided by an embodiment of the present invention includes the following steps: Step 1: Use the LB film method to prepare a two-dimensional colloidal crystal composed of polystyrene nano-microspheres on a selected target substrate. Step 2: On the prepared two-dimensional colloidal crystal, perform controllable dry etching by ICP etching method to obtain a microsphere array of the target size. Step 3: Using the vacuum evaporation coating method, deposit the selected target material on the microsphere array of the target size and the substrate surface to obtain a microsphere array with controllable coating of the target material and the substrate surface; Step 4: Based on the microsphere array with controllable coating of the target material and the substrate surface, perform microsphere peeling to obtain a nano-hole array structure with regular shape and target size; Among them, the microsphere size is controlled by adjusting the process parameters in the ICP etching method. The etching gas is O2, the ICP power is 200 W, the radio frequency power is 50 W, the O2 flow rate is 30 sccm, and the etching pressure is 30 mTorr; the microsphere array and the substrate surface are controllably coated by adjusting the process parameters in the vacuum evaporation coating method. The pressure is 10 -5 Torr, the deposition rate is 0.5 nm / s, and the substrate temperature is 30 °C; the target substrate is glass; the target material is TiO2. Specific Example 6 A method for preparing a nano-hole array structure with regular shape provided by an embodiment of the present invention includes the following steps: Step 1: Using the LB film method, prepare a two-dimensional colloidal crystal composed of polystyrene nano-microspheres on the selected target substrate; Step 2: On the prepared two-dimensional colloidal crystal, perform controllable dry etching by the ICP etching method to obtain a microsphere array of the target size; Step 3: Using the vacuum evaporation coating method, deposit the selected target material on the microsphere array of the target size and the substrate surface to obtain a microsphere array with controllable coating of the target material and the substrate surface; Step 4: Based on the microsphere array with controllable coating of the target material and the substrate surface, perform microsphere peeling to obtain a nano-hole array structure with regular shape and target size; Among them, the microsphere size is controlled by adjusting the process parameters in the ICP etching method. The etching gas is O2, the ICP power is 400 W, the radio frequency power is 100 W, the O2 flow rate is 50 sccm, and the etching pressure is 50 mTorr; the microsphere array and the substrate surface are controllably coated by adjusting the process parameters in the vacuum evaporation coating method. The pressure is 10 -4 Torr, the deposition rate is 1 nm / s, and the substrate temperature is 50 °C; the target substrate is sapphire; the target material is Ge.

[0039] In summary, the embodiments of the present invention disclose an optimized method for preparing a nano-hole array with regular shapes, mainly including the following steps: preparing a large-area and uniformly densely packed nano-scale microsphere on a target substrate to form a high-quality two-dimensional colloidal crystal; using ICP etching to controllably etch the two-dimensional colloidal crystal to obtain a microsphere array with regular shapes and high consistency and a target size; depositing a target material by using a vacuum evaporation coating technology to achieve controllable coating of the microsphere and the substrate surface, and further obtaining a nano-hole array with regular shapes and controllable thickness; selecting a suitable microsphere stripping process according to the deposited material and the substrate material, and removing the microspheres to leave a nano-hole array with regular shapes, high consistency, uniform arrangement and a target size. The prepared array has the characteristics of regular shapes, high consistency, uniform arrangement, controllable size, large area and low cost. The general preparation method can be widely applied to the fields of microelectronics, optics, optoelectronics, sensor technology, biomedicine, surface-enhanced Raman spectroscopy, microfluidic chips, solar cells, etc.

[0040] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: the specific implementation manners of the present invention can still be modified or equivalently replaced, and any modification or equivalent replacement without departing from the spirit and scope of the present invention shall be covered by the protection scope of the claims of the present invention.

Claims

1. A method for preparing a regularly shaped nano-circular hole array structure, characterized in that: The following steps are involved: Using the LB film method, two-dimensional colloidal crystals composed of polystyrene nanospheres were prepared on the selected target substrate; On the prepared two-dimensional colloidal crystal, controllable dry etching is performed by ICP etching to obtain a microsphere array of target size; A vacuum evaporation coating method is used to deposit the selected target material on the microsphere array of target size and the substrate surface to obtain the microsphere array and the substrate surface with controllable coating of the target material; Based on the controllable coating of the target material on the microsphere array and the substrate surface, the microspheres are peeled off to obtain a nano-circular hole array structure with regular shape of the target size.

2. The method for preparing a regularly shaped nano-circular hole array structure according to claim 1, characterized in that: In the step of performing controllable dry etching on the prepared two-dimensional colloidal crystal by ICP etching to obtain a microsphere array of a target size, The size of the microspheres is controlled by adjusting the process parameters in the ICP etching method; wherein the process parameters include etching gas, ICP power, radio frequency power, etching gas flow rate, etching pressure and etching time.

3. The method for preparing a regularly shaped nano-circular hole array structure according to claim 2, characterized in that: In the step of controlling the size of the microspheres by adjusting the process parameters in the ICP etching method, the etching gas is O2, the ICP power is 50-400 W, the RF power is 10-100 W, the O2 flow rate is 10-50 sccm, and the etching pressure is 10-50 mTorr.

4. The method for preparing a regularly shaped nano-circular hole array structure according to claim 1, characterized in that: In the step of using a vacuum evaporation coating method to deposit a selected target material on a microsphere array of a target size and on a substrate surface to obtain a microsphere array and a substrate surface that are controllably coated with the target material, The microsphere array and the substrate surface are controllably coated by regulating the process parameters in the vacuum evaporation coating method; wherein the process parameters include gas pressure, deposition rate, substrate temperature and deposition time.

5. The method for preparing a regularly shaped nano-circular hole array structure according to claim 4, characterized in that: In the step of controlling the process parameters in the vacuum evaporation coating method to coat the microsphere array and the substrate surface, the gas pressure is 10 -6 ~10 -4 Torr, the deposition rate is 0.1~1 nm / s, and the substrate temperature is 20~50 ℃.

6. The method for preparing a regularly shaped nano-circular hole array structure according to claim 1, characterized in that: The target substrate is silicon, gallium arsenide, gallium nitride, silicon carbide, germanium, sapphire, quartz, aluminum nitride, diamond, lithium niobate or glass.

7. The method for preparing a regularly shaped nano-circular hole array structure according to claim 1, characterized in that: The target material is a conductor, a semiconductor or an insulator; wherein, The conductor is Au, Ag, Cu, Al, Ti, Cr, Pt, Ni, Sn, W, Mo or an alloy; The semiconductor is Si, Ge, GaAs, GaN, CdS, CIGS or InP; The insulator is Al2O3, SiO2, MgF2, TiO2, Si3N4 or AlN.

8. A nano-circular hole array structure with regular shape, characterized in that: The preparation method is described in any one of claims 1 to 7.

9. The regularly shaped nano-circular hole array structure according to claim 8, characterized in that: include: A target substrate and a thin film having a nano-circular hole array with regular shapes on the target substrate.

10. The regularly shaped nano-circular hole array structure according to claim 9, characterized in that: In the regularly shaped nano-circular hole array, D is the original diameter of the nano-microsphere, and the value range of D is greater than 0 and less than or equal to 1000 nm; the hole spacing is Dd, d is the diameter of the nano-circular hole, and d is less than D; the hole thickness ranges from greater than 0 to less than H / 2, and H is the height of the microsphere after etching.

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