WO2022236922A1 - Method and apparatus for preparing large-area array nano-needle structure - Google Patents

Method and apparatus for preparing large-area array nano-needle structure Download PDF

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WO2022236922A1
WO2022236922A1 PCT/CN2021/100664 CN2021100664W WO2022236922A1 WO 2022236922 A1 WO2022236922 A1 WO 2022236922A1 CN 2021100664 W CN2021100664 W CN 2021100664W WO 2022236922 A1 WO2022236922 A1 WO 2022236922A1
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nano
liquid
particles
gold
area
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PCT/CN2021/100664
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汪家道
马原
李轩
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清华大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0009—Forming specific nanostructures
    • B82B3/0014—Array or network of similar nanostructural elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0004—Apparatus specially adapted for the manufacture or treatment of nanostructural devices or systems or methods for manufacturing the same
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0042—Assembling discrete nanostructures into nanostructural devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

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  • the present application relates to the technical field of nanoneedle preparation, in particular to a method and device for preparing a large array nanoneedle structure.
  • micro- and nano-needle structures Due to the "size effect” and other effects, the micro- and nano-needle structures have many unique characteristics in terms of light, electricity, magnetism, force, etc., and have gradually become a research hotspot. It has been widely used in interpretation and other fields.
  • photolithography, chemical etching, laser processing, and 3D printing technologies are common methods for preparing micro- and nano-needle structures.
  • photolithography is a method of preparing micro- and nano-structures by using surface ultraviolet light masking materials, which is highly dependent on the preparation of high-precision mask plates, which is expensive and difficult to achieve large-scale preparation.
  • Chemical etching is a method of preparing nanoneedles by using chemical etchant to non-uniformly etch the substrate, but it is seriously affected by thermodynamics, the preparation is highly random, the shape of nanoneedles cannot be precisely controlled, and the preparation accuracy is poor.
  • Laser processing and 3D printing technology have attracted much attention in the preparation of microneedle structures, but due to the limitation of their own processing precision, it is difficult to realize the preparation of nanometer-sized structures, and the processing process is very time-consuming, and it is difficult to achieve large-area preparation, thus limiting the nanoneedle structure. wide application of the structure. Therefore, it is of great significance to study a nanoneedle structure preparation technology that can be prepared in a large area, with strong controllability and high precision.
  • This application aims to solve one of the technical problems in the related art at least to a certain extent.
  • one purpose of the present application is to propose a method for preparing a large-area nanoneedle structure, which has the advantages of large preparation area, high preparation precision, strong controllability, and strong stability.
  • Another purpose of the present application is to propose a device for preparing a large array nanoneedle structure.
  • an embodiment of the present application proposes a method for preparing a large area array nanoneedle structure, including:
  • a gold-plated layer is prepared on the surface of the particle structure by electron beam evaporation, and the particles are removed by ultrasonic cleaning to form a periodic surface in which the gold-plated layer and silicon substrates are alternately arranged;
  • the nano-column structure is non-uniformly etched by sulfur hexafluoride reactive ion etching technology to form a large array nano-needle structure.
  • a large area array nanoneedle structure preparation device including:
  • the driving module is used to drive micro-nano particles to form a large-area self-assembled structure at the liquid-air interface by using a tension gradient, and transfer the large-area self-assembled structure to the surface of the silicon substrate;
  • the adjustment module is used to adjust the diameter of the particles in the large-area self-assembled structure by using oxygen reactive ion etching technology to form a periodic micro-nano particle structure;
  • the processing module is used to prepare a gold-plated layer on the surface of the particle structure by electron beam evaporation, and remove the particles by ultrasonic cleaning to form a periodic surface of the gold-plated layer and silicon substrates alternately arranged;
  • the first etching module is used to place the silicon substrate in a hydrofluoric acid/hydrogen peroxide mixed solution for gold catalytic etching to form a nano-column structure;
  • the second etching module is used for performing non-uniform etching on the nano-column structure to form a large array nano-needle structure by using sulfur hexafluoride reactive ion etching technology.
  • the preparation method and device of the large-area nanoneedle structure based on the large-area self-assembly of micro-nanoparticles driven by tension gradients realizes large-area micro-nanoparticle masks through the technology of large-area self-assembly of micro-nanoparticles driven by tension gradients Plate preparation, combined with reactive ion etching technology, electron beam evaporation technology, and catalytic etching technology, finally realizes the preparation of large-area nanoneedle structures. It has the advantages of large preparation area, strong controllability, and strong stability. It has extremely high application value and practical significance in the fields of micro- and nano-structure preparation, super-hydrophobic surface preparation, light field regulation, and cell transfection.
  • Fig. 1 is a schematic flow chart of a method for preparing a large array nanoneedle structure according to an embodiment of the present application
  • Fig. 2 is a physical diagram of a self-assembled structure of large-area micro-nanoparticles according to one embodiment of the present application;
  • Fig. 3 is an electron micrograph of a self-assembled structure of large-area micro-nanoparticles according to one embodiment of the present application
  • Fig. 4 is according to an embodiment of the present application electron beam evaporation and the periodic surface schematic diagram of the gold-plated layer that forms after removing particle, silicon substrate alternately arranged;
  • FIG. 5 is a schematic diagram of a nanocolumn structure formed after gold catalytic etching according to an embodiment of the present application
  • FIG. 6 is a schematic diagram of a nanoneedle structure after sulfur hexafluoride reactive ion etching according to an embodiment of the present application
  • Fig. 7 is a schematic structural diagram of a device for preparing a large array nanoneedle structure according to an embodiment of the present application.
  • Fig. 1 is a schematic flowchart of a method for preparing a large array nanoneedle structure according to an embodiment of the present application.
  • the preparation method of the large array nanoneedle structure comprises the following steps:
  • step S1 the tension gradient is used to drive micro-nano particles to form a large-area self-assembled structure at the liquid-air interface, and the large-area self-assembled structure is transferred to the surface of the silicon substrate.
  • the colloidal dispersion of hydrophobic polystyrene particles is added dropwise into the liquid pool, and the hydrophobic polystyrene particles spread on the liquid-air interface to form a loose particle monolayer structure.
  • immerse the heating plate whose temperature is much higher than the liquid surface temperature on one side of the liquid pool at a certain speed, and form a temperature gradient from high to low along the heating plate, so the liquid-air interface forms a tension gradient (liquid-air interface) Tension decreases with increasing temperature), thereby inducing the Marangoni effect.
  • the loose particles at the liquid-air interface quickly aggregate to the side away from the heating plate and form a densely arranged large-area self-assembled structure of polystyrene particles at the liquid-air interface.
  • the above-mentioned large-area self-assembled structure at the liquid-air interface is transferred to the surface of the silicon substrate by means of oblique fishing.
  • the hydrophobic micro- and nano-polystyrene particles have a diameter of 100 nm-50 ⁇ m.
  • the size of the liquid pool is 4cm 2 -1m 2 .
  • the liquid in the liquid pool is deionized water with a depth of 1mm-10cm.
  • the temperature of the heating plate is 40°C-100°C, and its power is 5w-200w.
  • the preparation area of the large-area micro-nano particle self-assembled structure is 1 cm 2 -1 m 2 .
  • Step S2 using oxygen reactive ion etching technology to adjust the diameter of particles in the large-area self-assembled structure to form a periodic micro-nano particle structure.
  • the diameter of the particles in the large-area self-assembled structure is adjusted to an appropriate size by using oxygen reactive ion etching technology to form a non-closely arranged periodic micro-nanoparticle structure.
  • the power of the oxygen reactive ion etching technology is 20w-100w, the etching time is 30s-10min, and the diameter of the particles after the reaction is 95%-5% of the original diameter.
  • step S3 electron beam evaporation is used to prepare a gold-plated layer on the surface of the particle structure, and ultrasonic cleaning is used to remove the particles to form a periodic surface in which the gold-plated layer and silicon substrates are alternately arranged.
  • the gold plating speed of the electron beam is The thickness of the gold layer is 1nm-100nm.
  • the solvent used for ultrasonic cleaning is an organic solvent, such as toluene, xylene and the like.
  • Step S4 placing the silicon substrate in a mixed solution of hydrofluoric acid/hydrogen peroxide to perform gold catalytic etching to form a nano-column structure.
  • the ratio of hydrofluoric acid to hydrogen peroxide in the hydrofluoric acid/hydrogen peroxide mixed solution is 20:1 to 2:1
  • the etching time is 10 min-60 min
  • the height of the formed nano-column is 200nm-3 ⁇ .
  • Step S5 using sulfur hexafluoride reactive ion etching technology to perform non-uniform etching on the nano-column structure to form a large-area nano-needle structure.
  • the power of sulfur hexafluoride reactive ion etching technology is 20w-200w, and the etching time is 3s-5min.
  • Silicon wafers were selected as substrates, 900nm polystyrene microspheres were used as self-assembled units, and a 90°C, 50w heating plate was selected to induce a gradient of liquid-air interfacial tension.
  • a self-assembled structure with a large area and dense arrangement is prepared by using the self-assembly method of micro-nanoparticles driven by tension gradient, as shown in Figure 2 and Figure 3.
  • the oxygen reactive ion etching power was set to 50w, and the etching time was set to 3min to obtain a non-closely arranged periodic micro-nanoparticle structure.
  • a 20nm gold-plated layer was prepared on the surface of non-closely arranged periodic particle structure by electron beam evaporation.
  • the particles were removed by ultrasonic cleaning to form a periodic surface with gold-plated layers and silicon substrates alternately arranged, as shown in FIG. 4 .
  • it was placed in a hydrofluoric acid/hydrogen peroxide mixed solution (hydrofluoric acid:hydrogen peroxide ratio of 4:1) for catalytic etching for 30 minutes to form a nanocolumn structure with a height of about 1200 nm, as shown in FIG. 5 .
  • the sulfur hexafluoride reactive ion etching power was set to 50w, and the etching time was set to 20s to obtain a nanoneedle structure, as shown in FIG. 6 .
  • the preparation of large-area micro-nanoparticle mask plates is realized through the tension gradient-driven large-area self-assembly technology of micro-nanoparticles, combined with reactive ion etching technology, electron beam evaporation Plating technology and catalytic etching technology finally realize the preparation of large array nanoneedle structure.
  • It has the advantages of large preparation area, high preparation precision, strong controllability, strong stability, etc., wherein the preparation area can reach 1m 2 , which is hundreds of times the preparation area of existing nano needles.
  • the preparation has strong controllability, and can realize the controllable processing of the nanoneedle bottom diameter (100-1000nm) and the nanoneedle height (200-3 ⁇ m).
  • Fig. 7 is a schematic structural diagram of a device for preparing a large array nanoneedle structure according to an embodiment of the present application.
  • the device for preparing a nanoneedle structure in a large area array includes: a driving module 701 , an adjusting module 702 , a processing module 703 , a first etching module 704 and a second etching module 705 .
  • the driving module 701 is used to drive micro-nano particles to form a large-area self-assembled structure at the liquid-air interface by using a tension gradient, and transfer the large-area self-assembled structure to the surface of the silicon substrate.
  • the adjustment module 702 is used to adjust the particle diameter in the large-area self-assembled structure by using oxygen reactive ion etching technology to form a periodic micro-nano particle structure.
  • the processing module 703 is used to prepare a gold-plated layer on the surface of the particle structure by electron beam evaporation, and remove the particles by ultrasonic cleaning to form a periodic surface in which the gold-plated layer and silicon substrates are alternately arranged.
  • the first etching module 704 is used for placing the silicon substrate in a hydrofluoric acid/hydrogen peroxide mixed solution to perform gold catalytic etching to form a nano-column structure.
  • the second etching module 705 is used for performing non-uniform etching on the nano-column structure to form a large array nano-needle structure by using sulfur hexafluoride reactive ion etching technology.
  • the drive module 701 is specifically used for,
  • the colloidal dispersion of hydrophobic polystyrene particles is added dropwise to the liquid pool, and the hydrophobic polystyrene particles spread on the liquid-air interface to form a loose particle monolayer structure;
  • the heating plate whose temperature is higher than the liquid surface temperature on one side of the liquid pool, form a temperature gradient from high to low along the heating plate from near to far, form a tension gradient at the liquid-gas interface, induce the Marangoni effect, and the liquid-gas interface Driven by the Marangoni effect, the loose particles quickly aggregate to the side away from the heating plate and form a densely arranged large-area self-assembled structure of polystyrene particles at the liquid-air interface;
  • the large-area self-assembled structure of the liquid-air interface is transferred to the surface of the silicon substrate by oblique fishing.
  • the micro and nano particles have a diameter of 100 nm-50 ⁇ m.
  • the power of the oxygen reactive ion etching technology is 20w-100w, the etching time is 30s-10min, and the diameter of the particles after reaction is 95%-5% of the original diameter.
  • the gold plating speed of the electron beam is The thickness of the gold layer is 1nm-100nm.
  • the preparation of large-area micro-nanoparticle mask plates is realized through the tension gradient-driven large-area self-assembly technology of micro-nanoparticles, combined with reactive ion etching technology, electron beam evaporation Plating technology and catalytic etching technology finally realize the preparation of large array nanoneedle structure.
  • It has the advantages of large preparation area, high preparation precision, strong controllability, strong stability, etc., wherein the preparation area can reach 1m 2 , which is hundreds of times the preparation area of existing nano needles.
  • the preparation has strong controllability, and can realize the controllable processing of the nanoneedle bottom diameter (100-1000nm) and the nanoneedle height (200-3 ⁇ m).
  • first and second are used for descriptive purposes only, and cannot be interpreted as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features.
  • the features defined as “first” and “second” may explicitly or implicitly include at least one of these features.
  • “plurality” means at least two, such as two, three, etc., unless otherwise specifically defined.

Abstract

A method for preparing a large-area array nano-needle structure, comprising: using a tension gradient to drive micro and nano-particles to form a large-area self-assembled structure at a liquid-gas interface, and transferring same to the surface of a silicon substrate; adjusting the particle diameter in the large-area self-assembled structure by using oxygen reactive ion etching technology so as to form a non-closely arranged periodic micro and nano-particle structure; preparing a gold-plated layer on the surface of the non-closely arranged periodic particle structure by using electron beam evaporation; then removing the particles by using ultrasonic cleaning so as to form a periodic surface made by alternately arranging the gold-plated layer and the silicon substrate; placing the substrate in a hydrofluoric acid/hydrogen peroxide mixed solution for gold-catalyzed etching so as to form a nano-pillar structure; and finally, performing non-uniform etching on the nano-pillar structure by using sulfur hexafluoride reactive ion etching technology so as to form a large-area array nano-needle structure. The method has a large preparation area, high preparation precision, strong shape controllability and high preparation stability.

Description

大面阵纳米针结构制备方法及装置Preparation method and device of large array nanoneedle structure
相关申请的交叉引用Cross References to Related Applications
本申请要求清华大学于2021年05月12日提交的、发明名称为“大面阵纳米针结构制备方法及装置”的、中国专利申请号“202110517417.5”的优先权。This application claims the priority of the Chinese patent application number "202110517417.5" submitted by Tsinghua University on May 12, 2021, the title of the invention is "Preparation Method and Device for Large Area Array Nanoneedle Structure".
技术领域technical field
本申请涉及纳米针制备技术领域，特别涉及一种大面阵纳米针结构制备方法及装置。The present application relates to the technical field of nanoneedle preparation, in particular to a method and device for preparing a large array nanoneedle structure.
背景技术Background technique
微、纳米针结构由于“尺寸效应”等作用使其在光、电、磁、力等方面具有诸多独特特性，并逐渐成为研究热点，在光子晶体、超疏水表面制备，细胞转染、药物缓释等领域中得到了广泛的应用。目前光刻，化学刻蚀，激光加工，3D打印技术等是制备微、纳米针结构的常用方法。其中光刻技术是利用表面紫外光掩蔽物进行微、纳米结构制备的方法，其高度依赖于高精度掩膜板的制备，制备价格昂贵且难以实现大面积制备。化学刻蚀是利用化学刻蚀剂对基底进行非均匀刻蚀制备纳米针的方法，但是其受热力学影响严重，制备随机性强，无法精确的控制纳米针形貌，制备精度差。激光加工，3D打印技术在微米针结构制备中备受关注，但是其受到自身加工精度的限制难以实现纳米尺寸的结构制备，且加工过程十分耗时，难以实现大面积制备，因而限制了纳米针结构的广泛应用。因此研究一种能够大面积制备，可控性强，精度高的纳米针结构制备技术具有重要意义。Due to the "size effect" and other effects, the micro- and nano-needle structures have many unique characteristics in terms of light, electricity, magnetism, force, etc., and have gradually become a research hotspot. It has been widely used in interpretation and other fields. At present, photolithography, chemical etching, laser processing, and 3D printing technologies are common methods for preparing micro- and nano-needle structures. Among them, photolithography is a method of preparing micro- and nano-structures by using surface ultraviolet light masking materials, which is highly dependent on the preparation of high-precision mask plates, which is expensive and difficult to achieve large-scale preparation. Chemical etching is a method of preparing nanoneedles by using chemical etchant to non-uniformly etch the substrate, but it is seriously affected by thermodynamics, the preparation is highly random, the shape of nanoneedles cannot be precisely controlled, and the preparation accuracy is poor. Laser processing and 3D printing technology have attracted much attention in the preparation of microneedle structures, but due to the limitation of their own processing precision, it is difficult to realize the preparation of nanometer-sized structures, and the processing process is very time-consuming, and it is difficult to achieve large-area preparation, thus limiting the nanoneedle structure. wide application of the structure. Therefore, it is of great significance to study a nanoneedle structure preparation technology that can be prepared in a large area, with strong controllability and high precision.
发明内容Contents of the invention
本申请旨在至少在一定程度上解决相关技术中的技术问题之一。This application aims to solve one of the technical problems in the related art at least to a certain extent.
为此，本申请的一个目的在于提出一种大面阵纳米针结构制备方法，该方法具有制备面积大，制备精度高，可控性强，稳定性强等优势。Therefore, one purpose of the present application is to propose a method for preparing a large-area nanoneedle structure, which has the advantages of large preparation area, high preparation precision, strong controllability, and strong stability.
本申请的另一个目的在于提出一种大面阵纳米针结构制备装置。Another purpose of the present application is to propose a device for preparing a large array nanoneedle structure.
为达到上述目的，本申请一方面实施例提出了一种大面阵纳米针结构制备方法，包括：In order to achieve the above purpose, an embodiment of the present application proposes a method for preparing a large area array nanoneedle structure, including:
利用张力梯度驱动微、纳米颗粒在液气界面形成大面积自组装结构，并将所述大面积自组装结构转移至硅基板表面；Using the tension gradient to drive micro-nano particles to form a large-area self-assembled structure at the liquid-air interface, and transfer the large-area self-assembled structure to the surface of the silicon substrate;
利用氧气反应离子刻蚀技术对所述大面积自组装结构中的颗粒直径进行调整，形成周期性微、纳米颗粒结构；Using oxygen reactive ion etching technology to adjust the diameter of particles in the large-area self-assembled structure to form a periodic micro-nano particle structure;
利用电子束蒸镀在所述颗粒结构表面制备镀金层，利用超声清洗方式去除颗粒形成镀金层、硅基底交替排布的周期性表面；A gold-plated layer is prepared on the surface of the particle structure by electron beam evaporation, and the particles are removed by ultrasonic cleaning to form a periodic surface in which the gold-plated layer and silicon substrates are alternately arranged;
将所述硅基板放置于氢氟酸/双氧水混合溶液中进行金催化刻蚀形成纳米柱结构；placing the silicon substrate in a hydrofluoric acid/hydrogen peroxide mixed solution for gold catalytic etching to form a nanocolumn structure;
利用六氟化硫反应离子刻蚀技术对所述纳米柱结构进行非均匀刻蚀形成大面阵纳米针结构。The nano-column structure is non-uniformly etched by sulfur hexafluoride reactive ion etching technology to form a large array nano-needle structure.
为达到上述目的，本申请另一方面实施例提出了一种大面阵纳米针结构制备装置，包括：In order to achieve the above purpose, another embodiment of the present application proposes a large area array nanoneedle structure preparation device, including:
驱动模块，用于利用张力梯度驱动微、纳米颗粒在液气界面形成大面积自组装结构，并将所述大面积自组装结构转移至硅基板表面；The driving module is used to drive micro-nano particles to form a large-area self-assembled structure at the liquid-air interface by using a tension gradient, and transfer the large-area self-assembled structure to the surface of the silicon substrate;
调整模块，用于利用氧气反应离子刻蚀技术对所述大面积自组装结构中的颗粒直径进行调整，形成周期性微、纳米颗粒结构；The adjustment module is used to adjust the diameter of the particles in the large-area self-assembled structure by using oxygen reactive ion etching technology to form a periodic micro-nano particle structure;
处理模块，用于利用电子束蒸镀在所述颗粒结构表面制备镀金层，利用超声清洗方式去除颗粒形成镀金层、硅基底交替排布的周期性表面；The processing module is used to prepare a gold-plated layer on the surface of the particle structure by electron beam evaporation, and remove the particles by ultrasonic cleaning to form a periodic surface of the gold-plated layer and silicon substrates alternately arranged;
第一刻蚀模块，用于将所述硅基板放置于氢氟酸/双氧水混合溶液中进行金催化刻蚀形成纳米柱结构；The first etching module is used to place the silicon substrate in a hydrofluoric acid/hydrogen peroxide mixed solution for gold catalytic etching to form a nano-column structure;
第二刻蚀模块，用于利用六氟化硫反应离子刻蚀技术对所述纳米柱结构进行非均匀刻蚀形成大面阵纳米针结构。The second etching module is used for performing non-uniform etching on the nano-column structure to form a large array nano-needle structure by using sulfur hexafluoride reactive ion etching technology.
本申请实施例的基于张力梯度驱动微、纳米颗粒大面积自组装的大面阵纳米针结构制备方法及装置，通过张力梯度驱动微、纳米颗粒大面积自组装技术实现大面积微纳米颗粒掩膜板制备，结合反应离子刻蚀技术，电子束蒸镀技术，催化刻蚀技术最终实现大面阵纳米针结构的制备。具有制备面积大以及可控性强，稳定性强等优势。在微、纳米结构制备，超疏水表面制备、光场调控、细胞转染等领域具有极高的应用价值和实际意义。The preparation method and device of the large-area nanoneedle structure based on the large-area self-assembly of micro-nanoparticles driven by tension gradients in the embodiments of the present application realizes large-area micro-nanoparticle masks through the technology of large-area self-assembly of micro-nanoparticles driven by tension gradients Plate preparation, combined with reactive ion etching technology, electron beam evaporation technology, and catalytic etching technology, finally realizes the preparation of large-area nanoneedle structures. It has the advantages of large preparation area, strong controllability, and strong stability. It has extremely high application value and practical significance in the fields of micro- and nano-structure preparation, super-hydrophobic surface preparation, light field regulation, and cell transfection.
本申请附加的方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本申请的实践了解到。Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application.
附图说明Description of drawings
本申请上述的和/或附加的方面和优点从下面结合附图对实施例的描述中将变得明显和容易理解，其中：The above and/or additional aspects and advantages of the present application will become apparent and easy to understand from the following description of the embodiments in conjunction with the accompanying drawings, wherein:
图1为根据本申请一个实施例的大面阵纳米针结构制备方法流程示意图；Fig. 1 is a schematic flow chart of a method for preparing a large array nanoneedle structure according to an embodiment of the present application;
图2为根据本申请一个实施例的大面积微、纳米颗粒自组装结构实物图；Fig. 2 is a physical diagram of a self-assembled structure of large-area micro-nanoparticles according to one embodiment of the present application;
图3为根据本申请一个实施例的大面积微、纳米颗粒自组装结构电镜图；Fig. 3 is an electron micrograph of a self-assembled structure of large-area micro-nanoparticles according to one embodiment of the present application;
图4为根据本申请一个实施例的电子束蒸镀并去除颗粒后形成的镀金层、硅基底交替 排布的周期性表面示意图；Fig. 4 is according to an embodiment of the present application electron beam evaporation and the periodic surface schematic diagram of the gold-plated layer that forms after removing particle, silicon substrate alternately arranged;
图5为根据本申请一个实施例的金催化刻蚀后形成的纳米柱结构示意图；FIG. 5 is a schematic diagram of a nanocolumn structure formed after gold catalytic etching according to an embodiment of the present application;
图6为根据本申请一个实施例的六氟化硫反应离子刻蚀后的纳米针结构示意图；FIG. 6 is a schematic diagram of a nanoneedle structure after sulfur hexafluoride reactive ion etching according to an embodiment of the present application;
图7为根据本申请一个实施例的大面阵纳米针结构制备装置结构示意图。Fig. 7 is a schematic structural diagram of a device for preparing a large array nanoneedle structure according to an embodiment of the present application.
具体实施方式Detailed ways
下面详细描述本申请的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本申请，而不能理解为对本申请的限制。Embodiments of the present application are described in detail below, examples of which are shown in the drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the figures are exemplary, and are intended to explain the present application, and should not be construed as limiting the present application.
下面参照附图描述根据本申请实施例提出的大面阵纳米针结构制备方法及装置。The method and device for preparing a large array nanoneedle structure according to the embodiments of the present application will be described below with reference to the accompanying drawings.
首先将参照附图描述根据本申请实施例提出的大面阵纳米针结构制备方法。Firstly, the method for preparing a large array nanoneedle structure according to the embodiments of the present application will be described with reference to the accompanying drawings.
图1为根据本申请一个实施例的大面阵纳米针结构制备方法流程示意图。Fig. 1 is a schematic flowchart of a method for preparing a large array nanoneedle structure according to an embodiment of the present application.
如图1所示，该大面阵纳米针结构制备方法包括以下步骤：As shown in Figure 1, the preparation method of the large array nanoneedle structure comprises the following steps:
步骤S1，利用张力梯度驱动微、纳米颗粒在液气界面形成大面积自组装结构，并将大面积自组装结构转移至硅基板表面。In step S1, the tension gradient is used to drive micro-nano particles to form a large-area self-assembled structure at the liquid-air interface, and the large-area self-assembled structure is transferred to the surface of the silicon substrate.
具体地，首先将疏水聚苯乙烯颗粒胶体分散液滴加至液池中，疏水聚苯乙烯颗粒在液气界面铺展形成松散的颗粒单层结构。随后将温度远高于液面温度的加热板以一定的速度浸没于液池一侧，沿加热板由近及远形成由高到低的温度梯度，因此液气界面形成张力梯度(液气界面张力随温度的升高而降低)，从而诱发马兰戈尼效应。液气界面松散的颗粒在马兰戈尼效应的带动下(流体曳力)向远离加热板一侧快速聚集并形成密集排列的液气界面聚苯乙烯颗粒大面积自组装结构。最后通过倾斜捞取的方式将上述液气界面大面积自组装结构转移至硅基板表面。Specifically, firstly, the colloidal dispersion of hydrophobic polystyrene particles is added dropwise into the liquid pool, and the hydrophobic polystyrene particles spread on the liquid-air interface to form a loose particle monolayer structure. Then immerse the heating plate whose temperature is much higher than the liquid surface temperature on one side of the liquid pool at a certain speed, and form a temperature gradient from high to low along the heating plate, so the liquid-air interface forms a tension gradient (liquid-air interface) Tension decreases with increasing temperature), thereby inducing the Marangoni effect. Driven by the Marangoni effect (fluid drag), the loose particles at the liquid-air interface quickly aggregate to the side away from the heating plate and form a densely arranged large-area self-assembled structure of polystyrene particles at the liquid-air interface. Finally, the above-mentioned large-area self-assembled structure at the liquid-air interface is transferred to the surface of the silicon substrate by means of oblique fishing.
可选地，疏水的微、纳米聚苯乙烯颗粒直径为100nm-50μm。Optionally, the hydrophobic micro- and nano-polystyrene particles have a diameter of 100 nm-50 μm.
可选地，液池尺寸为4cm 2-1m 2。 Optionally, the size of the liquid pool is 4cm 2 -1m 2 .
可选地，液池中的液体为去离子水，其深度为1mm-10cm。Optionally, the liquid in the liquid pool is deionized water with a depth of 1mm-10cm.
可选地，加热板温度为40℃-100℃，其功率为5w-200w。Optionally, the temperature of the heating plate is 40°C-100°C, and its power is 5w-200w.
可选地，大面积微、纳米颗粒自组装结构的制备面积为1cm 2-1m 2。 Optionally, the preparation area of the large-area micro-nano particle self-assembled structure is 1 cm 2 -1 m 2 .
步骤S2，利用氧气反应离子刻蚀技术对大面积自组装结构中的颗粒直径进行调整，形成周期性微、纳米颗粒结构。Step S2, using oxygen reactive ion etching technology to adjust the diameter of particles in the large-area self-assembled structure to form a periodic micro-nano particle structure.
具体地，利用氧气反应离子刻蚀技术将大面积自组装结构中的颗粒直径调整至合适大小，以形成非紧密排列的周期性微、纳米颗粒结构。Specifically, the diameter of the particles in the large-area self-assembled structure is adjusted to an appropriate size by using oxygen reactive ion etching technology to form a non-closely arranged periodic micro-nanoparticle structure.
可选地，氧气反应离子刻蚀技术功率为20w-100w，刻蚀时间为30s-10min，反应后颗 粒的直径为原始直径的95％-5％。Optionally, the power of the oxygen reactive ion etching technology is 20w-100w, the etching time is 30s-10min, and the diameter of the particles after the reaction is 95%-5% of the original diameter.
步骤S3，利用电子束蒸镀在颗粒结构表面制备镀金层，利用超声清洗方式去除颗粒形成镀金层、硅基底交替排布的周期性表面。In step S3, electron beam evaporation is used to prepare a gold-plated layer on the surface of the particle structure, and ultrasonic cleaning is used to remove the particles to form a periodic surface in which the gold-plated layer and silicon substrates are alternately arranged.
可选地，电子束的镀金速度为
Figure PCTCN2021100664-appb-000001
金层厚度为1nm-100nm。 Optionally, the gold plating speed of the electron beam is
Figure PCTCN2021100664-appb-000001
The thickness of the gold layer is 1nm-100nm.
可选地，超声清洗时的溶剂为有机溶剂，可以是甲苯，二甲苯等。Optionally, the solvent used for ultrasonic cleaning is an organic solvent, such as toluene, xylene and the like.
步骤S4，将硅基板放置于氢氟酸/双氧水混合溶液中进行金催化刻蚀形成纳米柱结构。Step S4, placing the silicon substrate in a mixed solution of hydrofluoric acid/hydrogen peroxide to perform gold catalytic etching to form a nano-column structure.
可选地，氢氟酸/双氧水混合溶液中氢氟酸与双氧水比例为20：1至2：1，刻蚀时间为10min-60min，形成纳米柱高度为200nm-3μ。Optionally, the ratio of hydrofluoric acid to hydrogen peroxide in the hydrofluoric acid/hydrogen peroxide mixed solution is 20:1 to 2:1, the etching time is 10 min-60 min, and the height of the formed nano-column is 200nm-3μ.
步骤S5，利用六氟化硫反应离子刻蚀技术对纳米柱结构进行非均匀刻蚀形成大面阵纳米针结构。Step S5, using sulfur hexafluoride reactive ion etching technology to perform non-uniform etching on the nano-column structure to form a large-area nano-needle structure.
可选地，六氟化硫反应离子刻蚀技术功率为20w-200w，刻蚀时间为3s-5min。Optionally, the power of sulfur hexafluoride reactive ion etching technology is 20w-200w, and the etching time is 3s-5min.
下面通过一个具体实施例对本申请的大面阵纳米针结构制备方法进行说明。The preparation method of the large array nanoneedle structure of the present application will be described below through a specific example.
选用硅片为基底，900nm聚苯乙烯微球为自组装单元，选用90℃，50w加热板诱导液气界面张力梯度。利用张力梯度驱动微、纳米颗粒自组装方法制备大面积紧密排列的自组装结构，如图2和图3所示。将氧气反应离子刻蚀功率设置为50w，刻蚀时间设置为3min，获得非紧密排列的周期性微、纳米颗粒结构。利用电子束蒸镀在非紧密排列的周期性颗粒结构表面制备20nm后的镀金层。随后利用甲苯作为有机溶剂，通过超声清洗的方式去除颗粒以形成镀金层、硅基底交替排布的周期性表面，如图4所示。随后将其放置于氢氟酸/双氧水混合溶液(氢氟酸：双氧水为4：1)中催化刻蚀30min以形成约1200nm高的纳米柱结构，如图5所示。最后将六氟化硫反应离子刻蚀功率设置为50w，刻蚀时间设置为20s获得纳米针结构，如图6所示。Silicon wafers were selected as substrates, 900nm polystyrene microspheres were used as self-assembled units, and a 90°C, 50w heating plate was selected to induce a gradient of liquid-air interfacial tension. A self-assembled structure with a large area and dense arrangement is prepared by using the self-assembly method of micro-nanoparticles driven by tension gradient, as shown in Figure 2 and Figure 3. The oxygen reactive ion etching power was set to 50w, and the etching time was set to 3min to obtain a non-closely arranged periodic micro-nanoparticle structure. A 20nm gold-plated layer was prepared on the surface of non-closely arranged periodic particle structure by electron beam evaporation. Then, using toluene as an organic solvent, the particles were removed by ultrasonic cleaning to form a periodic surface with gold-plated layers and silicon substrates alternately arranged, as shown in FIG. 4 . Then it was placed in a hydrofluoric acid/hydrogen peroxide mixed solution (hydrofluoric acid:hydrogen peroxide ratio of 4:1) for catalytic etching for 30 minutes to form a nanocolumn structure with a height of about 1200 nm, as shown in FIG. 5 . Finally, the sulfur hexafluoride reactive ion etching power was set to 50w, and the etching time was set to 20s to obtain a nanoneedle structure, as shown in FIG. 6 .
根据本申请实施例提出的大面阵纳米针结构制备方法，通过张力梯度驱动微、纳米颗粒大面积自组装技术实现大面积微纳米颗粒掩膜板制备，结合反应离子刻蚀技术，电子束蒸镀技术，催化刻蚀技术最终实现大面阵纳米针结构的制备。具有制备面积大，制备精度高，可控性强，稳定性强等优势，其中制备面积可达1m 2，是现有纳米针制备面积的数百倍。其制备可控性强，能够实现纳米针底端直径(100-1000nm)，纳米针高度(200-3μm)的可控加工。 According to the preparation method of the large-area nanoneedle structure proposed in the embodiment of the present application, the preparation of large-area micro-nanoparticle mask plates is realized through the tension gradient-driven large-area self-assembly technology of micro-nanoparticles, combined with reactive ion etching technology, electron beam evaporation Plating technology and catalytic etching technology finally realize the preparation of large array nanoneedle structure. It has the advantages of large preparation area, high preparation precision, strong controllability, strong stability, etc., wherein the preparation area can reach 1m 2 , which is hundreds of times the preparation area of existing nano needles. The preparation has strong controllability, and can realize the controllable processing of the nanoneedle bottom diameter (100-1000nm) and the nanoneedle height (200-3μm).
其次参照附图描述根据本申请实施例提出的大面阵纳米针结构制备装置。Next, the device for preparing a large area array nanoneedle structure according to the embodiments of the present application will be described with reference to the accompanying drawings.
图7为根据本申请一个实施例的大面阵纳米针结构制备装置结构示意图。Fig. 7 is a schematic structural diagram of a device for preparing a large array nanoneedle structure according to an embodiment of the present application.
如图7所示，该大面阵纳米针结构制备装置包括：驱动模块701、调整模块702、处理模块703、第一刻蚀模块704和第二刻蚀模块705。As shown in FIG. 7 , the device for preparing a nanoneedle structure in a large area array includes: a driving module 701 , an adjusting module 702 , a processing module 703 , a first etching module 704 and a second etching module 705 .
驱动模块701，用于利用张力梯度驱动微、纳米颗粒在液气界面形成大面积自组装结构， 并将大面积自组装结构转移至硅基板表面。The driving module 701 is used to drive micro-nano particles to form a large-area self-assembled structure at the liquid-air interface by using a tension gradient, and transfer the large-area self-assembled structure to the surface of the silicon substrate.
调整模块702，用于利用氧气反应离子刻蚀技术对大面积自组装结构中的颗粒直径进行调整，形成周期性微、纳米颗粒结构。The adjustment module 702 is used to adjust the particle diameter in the large-area self-assembled structure by using oxygen reactive ion etching technology to form a periodic micro-nano particle structure.
处理模块703，用于利用电子束蒸镀在颗粒结构表面制备镀金层，利用超声清洗方式去除颗粒形成镀金层、硅基底交替排布的周期性表面。The processing module 703 is used to prepare a gold-plated layer on the surface of the particle structure by electron beam evaporation, and remove the particles by ultrasonic cleaning to form a periodic surface in which the gold-plated layer and silicon substrates are alternately arranged.
第一刻蚀模块704，用于将硅基板放置于氢氟酸/双氧水混合溶液中进行金催化刻蚀形成纳米柱结构。The first etching module 704 is used for placing the silicon substrate in a hydrofluoric acid/hydrogen peroxide mixed solution to perform gold catalytic etching to form a nano-column structure.
第二刻蚀模块705，用于利用六氟化硫反应离子刻蚀技术对纳米柱结构进行非均匀刻蚀形成大面阵纳米针结构。The second etching module 705 is used for performing non-uniform etching on the nano-column structure to form a large array nano-needle structure by using sulfur hexafluoride reactive ion etching technology.
优选地，驱动模块701，具体用于，Preferably, the drive module 701 is specifically used for,
将疏水聚苯乙烯颗粒胶体分散液滴加至液池中，疏水聚苯乙烯颗粒在液气界面铺展形成松散的颗粒单层结构；The colloidal dispersion of hydrophobic polystyrene particles is added dropwise to the liquid pool, and the hydrophobic polystyrene particles spread on the liquid-air interface to form a loose particle monolayer structure;
将温度高于液面温度的加热板浸没于液池一侧，沿加热板由近及远形成由高到低的温度梯度，在液气界面形成张力梯度，诱发马兰戈尼效应，液气界面松散的颗粒在马兰戈尼效应的带动下向远离加热板的一侧快速聚集并形成密集排列的液气界面聚苯乙烯颗粒大面积自组装结构；Immerse the heating plate whose temperature is higher than the liquid surface temperature on one side of the liquid pool, form a temperature gradient from high to low along the heating plate from near to far, form a tension gradient at the liquid-gas interface, induce the Marangoni effect, and the liquid-gas interface Driven by the Marangoni effect, the loose particles quickly aggregate to the side away from the heating plate and form a densely arranged large-area self-assembled structure of polystyrene particles at the liquid-air interface;
通过倾斜捞取的方式将液气界面的大面积自组装结构转移至硅基板表面。The large-area self-assembled structure of the liquid-air interface is transferred to the surface of the silicon substrate by oblique fishing.
优选地，微、纳米颗粒直径为100nm-50μm。Preferably, the micro and nano particles have a diameter of 100 nm-50 μm.
优选地，氧气反应离子刻蚀技术功率为20w-100w，刻蚀时间为30s-10min，反应后颗粒的直径为原始直径的95％-5％。Preferably, the power of the oxygen reactive ion etching technology is 20w-100w, the etching time is 30s-10min, and the diameter of the particles after reaction is 95%-5% of the original diameter.
优选地，，电子束的镀金速度为
Figure PCTCN2021100664-appb-000002
金层厚度为1nm-100nm。 Preferably, the gold plating speed of the electron beam is
Figure PCTCN2021100664-appb-000002
The thickness of the gold layer is 1nm-100nm.
需要说明的是，前述对方法实施例的解释说明也适用于该实施例的装置，此处不再赘述。It should be noted that the foregoing explanations of the method embodiment are also applicable to the device of this embodiment, and details are not repeated here.
根据本申请实施例提出的大面阵纳米针结构制备装置，通过张力梯度驱动微、纳米颗粒大面积自组装技术实现大面积微纳米颗粒掩膜板制备，结合反应离子刻蚀技术，电子束蒸镀技术，催化刻蚀技术最终实现大面阵纳米针结构的制备。具有制备面积大，制备精度高，可控性强，稳定性强等优势，其中制备面积可达1m 2，是现有纳米针制备面积的数百倍。其制备可控性强，能够实现纳米针底端直径(100-1000nm)，纳米针高度(200-3μm)的可控加工。 According to the large-area array nanoneedle structure preparation device proposed in the embodiment of the present application, the preparation of large-area micro-nanoparticle mask plates is realized through the tension gradient-driven large-area self-assembly technology of micro-nanoparticles, combined with reactive ion etching technology, electron beam evaporation Plating technology and catalytic etching technology finally realize the preparation of large array nanoneedle structure. It has the advantages of large preparation area, high preparation precision, strong controllability, strong stability, etc., wherein the preparation area can reach 1m 2 , which is hundreds of times the preparation area of existing nano needles. The preparation has strong controllability, and can realize the controllable processing of the nanoneedle bottom diameter (100-1000nm) and the nanoneedle height (200-3μm).
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。在本申请的描述中，“多个”的含义是至少两个，例如两个，三 个等，除非另有明确具体的限定。In addition, the terms "first" and "second" are used for descriptive purposes only, and cannot be interpreted as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features. Thus, the features defined as "first" and "second" may explicitly or implicitly include at least one of these features. In the description of the present application, "plurality" means at least two, such as two, three, etc., unless otherwise specifically defined.
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本申请的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。In the description of this specification, descriptions referring to the terms "one embodiment", "some embodiments", "example", "specific examples", or "some examples" mean that specific features described in connection with the embodiment or example , structure, material or characteristic is included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the described specific features, structures, materials or characteristics may be combined in any suitable manner in any one or more embodiments or examples. In addition, those skilled in the art can combine and combine different embodiments or examples and features of different embodiments or examples described in this specification without conflicting with each other.
尽管上面已经示出和描述了本申请的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本申请的限制，本领域的普通技术人员在本申请的范围内可以对上述实施例进行变化、修改、替换和变型。Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limitations on the present application, and those skilled in the art can make the above-mentioned The embodiments are subject to changes, modifications, substitutions and variations.

Claims (10)

  1. 一种大面阵纳米针结构制备方法，其特征在于，包括以下步骤：A method for preparing a large-area nanoneedle structure, characterized in that it comprises the following steps:
    利用张力梯度驱动微、纳米颗粒在液气界面形成大面积自组装结构，并将所述大面积自组装结构转移至硅基板表面；Using the tension gradient to drive micro-nano particles to form a large-area self-assembled structure at the liquid-air interface, and transfer the large-area self-assembled structure to the surface of the silicon substrate;
    利用氧气反应离子刻蚀技术对所述大面积自组装结构中的颗粒直径进行调整，形成周期性微、纳米颗粒结构；Using oxygen reactive ion etching technology to adjust the diameter of particles in the large-area self-assembled structure to form a periodic micro-nano particle structure;
    利用电子束蒸镀在所述颗粒结构表面制备镀金层，利用超声清洗方式去除颗粒形成镀金层、硅基底交替排布的周期性表面；A gold-plated layer is prepared on the surface of the particle structure by electron beam evaporation, and the particles are removed by ultrasonic cleaning to form a periodic surface in which the gold-plated layer and silicon substrates are alternately arranged;
    将所述硅基板放置于氢氟酸/双氧水混合溶液中进行金催化刻蚀形成纳米柱结构；placing the silicon substrate in a hydrofluoric acid/hydrogen peroxide mixed solution for gold catalytic etching to form a nanocolumn structure;
    利用六氟化硫反应离子刻蚀技术对所述纳米柱结构进行非均匀刻蚀形成大面阵纳米针结构。The nano-column structure is non-uniformly etched by sulfur hexafluoride reactive ion etching technology to form a large array nano-needle structure.
  2. 根据权利要求1所述的方法，其特征在于，利用张力梯度驱动微、纳米颗粒在液气界面形成大面积自组装结构，并将所述大面积自组装结构转移至硅基板表面，包括：The method according to claim 1, characterized in that, using a tension gradient to drive micro-nano particles to form a large-area self-assembled structure at the liquid-air interface, and transferring the large-area self-assembled structure to the surface of the silicon substrate, comprising:
    将疏水聚苯乙烯颗粒胶体分散液滴加至液池中，所述疏水聚苯乙烯颗粒在液气界面铺展形成松散的颗粒单层结构；Adding the colloidal dispersion of hydrophobic polystyrene particles into the liquid pool dropwise, the hydrophobic polystyrene particles spread at the liquid-air interface to form a loose particle monolayer structure;
    将温度高于液面温度的加热板浸没于液池一侧，沿加热板由近及远形成由高到低的温度梯度，在液气界面形成张力梯度，诱发马兰戈尼效应，液气界面松散的颗粒在马兰戈尼效应的带动下向远离加热板的一侧快速聚集并形成密集排列的液气界面聚苯乙烯颗粒大面积自组装结构；Immerse the heating plate whose temperature is higher than the liquid surface temperature on one side of the liquid pool, form a temperature gradient from high to low along the heating plate from near to far, form a tension gradient at the liquid-gas interface, induce the Marangoni effect, and the liquid-gas interface Driven by the Marangoni effect, the loose particles quickly aggregate to the side away from the heating plate and form a densely arranged large-area self-assembled structure of polystyrene particles at the liquid-air interface;
    通过倾斜捞取的方式将液气界面的所述大面积自组装结构转移至硅基板表面。The large-area self-assembled structure at the liquid-air interface is transferred to the surface of the silicon substrate by means of oblique fishing.
  3. 根据权利要求1所述的方法，其特征在于，所述微、纳米颗粒直径为100nm-50μm。The method according to claim 1, characterized in that the diameter of the micro and nano particles is 100nm-50μm.
  4. 根据权利要求1所述的方法，其特征在于，所述氧气反应离子刻蚀技术功率为20w-100w，刻蚀时间为30s-10min，反应后颗粒的直径为原始直径的95％-5％。The method according to claim 1, characterized in that the power of the oxygen reactive ion etching technology is 20w-100w, the etching time is 30s-10min, and the diameter of the particles after reaction is 95%-5% of the original diameter.
  5. 根据权利要求1所述的方法，其特征在于，所述电子束的镀金速度为
    Figure PCTCN2021100664-appb-100001
    金层厚度为1nm-100nm。     method according to claim 1, is characterized in that, the gold-plating speed of described electron beam is
    Figure PCTCN2021100664-appb-100001
    The thickness of the gold layer is 1nm-100nm.
  6. 一种大面阵纳米针结构制备装置，其特征在于，包括：A device for preparing a large area array nanoneedle structure, characterized in that it includes:
    驱动模块，用于利用张力梯度驱动微、纳米颗粒在液气界面形成大面积自组装结构，并将所述大面积自组装结构转移至硅基板表面；The driving module is used to drive micro-nano particles to form a large-area self-assembled structure at the liquid-air interface by using a tension gradient, and transfer the large-area self-assembled structure to the surface of the silicon substrate;
    调整模块，用于利用氧气反应离子刻蚀技术对所述大面积自组装结构中的颗粒直径进行调整，形成周期性微、纳米颗粒结构；The adjustment module is used to adjust the diameter of the particles in the large-area self-assembled structure by using oxygen reactive ion etching technology to form a periodic micro-nano particle structure;
    处理模块，用于利用电子束蒸镀在所述颗粒结构表面制备镀金层，利用超声清洗方式 去除颗粒形成镀金层、硅基底交替排布的周期性表面；The processing module is used to utilize electron beam evaporation to prepare a gold-plated layer on the surface of the particle structure, and use ultrasonic cleaning to remove the particles to form a periodic surface of the gold-plated layer and silicon substrates alternately arranged;
    第一刻蚀模块，用于将所述硅基板放置于氢氟酸/双氧水混合溶液中进行金催化刻蚀形成纳米柱结构；The first etching module is used to place the silicon substrate in a hydrofluoric acid/hydrogen peroxide mixed solution for gold catalytic etching to form a nano-column structure;
    第二刻蚀模块，用于利用六氟化硫反应离子刻蚀技术对所述纳米柱结构进行非均匀刻蚀形成大面阵纳米针结构。The second etching module is used for performing non-uniform etching on the nano-column structure to form a large array nano-needle structure by using sulfur hexafluoride reactive ion etching technology.
  7. 根据权利要求6所述的装置，其特征在于，所述驱动模块，具体用于，The device according to claim 6, wherein the drive module is specifically used for:
    将疏水聚苯乙烯颗粒胶体分散液滴加至液池中，所述疏水聚苯乙烯颗粒在液气界面铺展形成松散的颗粒单层结构；Adding the colloidal dispersion of hydrophobic polystyrene particles into the liquid pool dropwise, the hydrophobic polystyrene particles spread at the liquid-air interface to form a loose particle monolayer structure;
    将温度高于液面温度的加热板浸没于液池一侧，沿加热板由近及远形成由高到低的温度梯度，在液气界面形成张力梯度，诱发马兰戈尼效应，液气界面松散的颗粒在马兰戈尼效应的带动下向远离加热板的一侧快速聚集并形成密集排列的液气界面聚苯乙烯颗粒大面积自组装结构；Immerse the heating plate whose temperature is higher than the liquid surface temperature on one side of the liquid pool, form a temperature gradient from high to low along the heating plate from near to far, form a tension gradient at the liquid-gas interface, induce the Marangoni effect, and the liquid-gas interface Driven by the Marangoni effect, the loose particles quickly aggregate to the side away from the heating plate and form a densely arranged large-area self-assembled structure of polystyrene particles at the liquid-air interface;
    通过倾斜捞取的方式将液气界面的所述大面积自组装结构转移至硅基板表面。The large-area self-assembled structure at the liquid-air interface is transferred to the surface of the silicon substrate by means of oblique fishing.
  8. 根据权利要求6所述的装置，其特征在于，所述微、纳米颗粒直径为100nm-50μm。The device according to claim 6, characterized in that, the diameter of the micro and nano particles is 100 nm-50 μm.
  9. 根据权利要求6所述的装置，其特征在于，所述氧气反应离子刻蚀技术功率为20w-100w，刻蚀时间为30s-10min，反应后颗粒的直径为原始直径的95％-5％。The device according to claim 6, characterized in that the power of the oxygen reactive ion etching technology is 20w-100w, the etching time is 30s-10min, and the diameter of the particles after reaction is 95%-5% of the original diameter.
  10. 根据权利要求6所述的装置，其特征在于，所述电子束的镀金速度为
    Figure PCTCN2021100664-appb-100002
    金层厚度为1nm-100nm。     The device according to claim 6, wherein the gold plating speed of the electron beam is
    Figure PCTCN2021100664-appb-100002
    The thickness of the gold layer is 1nm-100nm.
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