CN114315416A

CN114315416A - Preparation method of interlinked nano-cone periodic array

Info

Publication number: CN114315416A
Application number: CN202111671267.XA
Authority: CN
Inventors: 赵晓宇; 安彤舸; 温嘉红; 张鉴; 郭筱洁; 王雅新; 钟家松; 张永军
Original assignee: Hangzhou Dianzi University
Current assignee: Hangzhou Dianzi University
Priority date: 2021-12-31
Filing date: 2021-12-31
Publication date: 2022-04-12
Anticipated expiration: 2041-12-31
Also published as: CN114315416B

Abstract

The invention belongs to the technical field of nano composite material synthesis, and particularly relates to a preparation method of a cyclic nano-cone periodic array. According to the invention, a novel interlinked nano-cone periodic array is prepared by combining a silicon dioxide colloid ball self-assembly technology, a plasma etching technology and a physical deposition technology, the preparation method can obtain interlinked nano-cone periodic arrays with different sizes by changing the size of a colloid ball, the plasma etching time and the thickness of deposited metal, the preparation method is simple, and the prepared interlinked nano-cone periodic array has the advantages of good uniformity, high order degree and strong repeatability, and can be effectively copied and applied in a large scale.

Description

Preparation method of interlinked nano-cone periodic array

Technical Field

The invention relates to the technical field of nano composite material synthesis, in particular to a preparation method of a cyclic nano-cone periodic array.

Background

The Surface Plasmon Resonance (SPR) is expected to enhance the photocatalytic energy conversion efficiency due to its unique characteristic of interaction between light and substances, and has attracted great attention in recent years. SPR is the effect of collective oscillation of valence electrons on the surface of metal (Au, Ag, Cu, Al, etc.) under the action of a certain external field (such as light). The metal nano particles with the SPR effect can controllably adjust the light absorption performance of the metal nano particles in a visible-near infrared region by controlling the size, components, morphology and other factors of the metal nano particles, so that the light capturing range is expected to be expanded. Nano-focusing is one of the important characteristics of surface plasmons, and the concept proposed by Stockman in 2004 refers to the phenomenon that when surface plasmons propagate along a tapered metal nanostructure, the propagation energy is highly converged at the tip of the tapered structure. The surface plasmon nano focusing effect makes it possible to form an electromagnetic field "hot spot" on the nanostructure tip by remote excitation and propagation. The nanometer focusing also has the characteristic that the focus size breaks through the nanometer scale, and the research enthusiasm is raised internationally in recent years. For example, in the aspect of enhancing the light-matter interaction, the metal conical nanostructure can be used as a probe by virtue of the action of nano focusing, so that the remote excitation and the highly sensitive spectrum detection of molecules are realized. In the field of near-field imaging, surface plasmon nanometer focusing on a metal needle point is utilized to realize the detection and scanning imaging of the transmitted surface plasmon to the near field of a measured object, and the method is widely applied to the related research of a scanning near-field optical microscope. Meanwhile, with the continuous improvement of the nano waveguide preparation process, different types of nano focusing waveguides are being developed gradually, and more feasible schemes are provided for the nano focusing waveguides which can be widely applied to various fields such as photonic elements, biological cell detection and the like. Babadjanyan and coworkers thereof, by analyzing the boundary problem of the metal microtip cone structure, believe that when SPPs are guided along the nanocone toward the diameter reduction direction thereof, the guided wave wavelength decreases to make focusing apparent, and there is a large field enhancement at the apex. At the same time they propose: the pipe diameter near the apex of the cone is very small, almost a few microns. Careful analysis of SPP scattering in this region without local effects has further confirmed the focusing characteristics of the cone. Besides being applied to a planar structure, the experimental implementation of the super-focusing structure is also very useful for the optical study of the lower surface of a near-field optical microscope.

The nanometer focusing effect utilizes the configuration of the tapered nanometer structure with gradually changed diameter to realize the convergence of photon energy in a nanometer space. Compared with a nano-gap coupling system, the conical nano-structure has higher structural stability and controllability, so that the conical nano-structure is applied to the field of spectrum scanning detection. The existing preparation method of the tapered nano structure has complicated steps and high cost, and becomes a difficulty which hinders the further development of the tapered nano structure.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a preparation method of a periodic array of interlinked nano-cones; the preparation method of the interlinked nano-cone periodic array has the advantages of simple steps, high operable space, short preparation period and low price, and the prepared interlinked nano-cone periodic array has the characteristics of large-area controllable construction, good uniformity, high order degree and strong repeatability and has the excellent performances of localized surface plasmon resonance and specific surface area increase.

In order to achieve the purpose, the invention adopts the following technical scheme: a method for preparing a periodic array of nanocones comprises the following steps:

(A) preparing a highly ordered silicon dioxide bead array on a Si substrate with a hydrophilic surface by using a self-assembly method;

(B) carrying out plasma etching on the silicon dioxide small ball array to obtain a interlinked nano cone periodic array;

(C) and depositing a layer of metal film on the surface of the sample by utilizing a magnetron sputtering technology.

The interlinked silver nanocone array structure is obtained through plasma etching and magnetron sputtering, the size of the nanocone can be adjusted by changing the size of the silicon dioxide pellet, the plasma etching time and the thickness of the sputtering metal layer, and the interlinked silver nanocone array structure has the advantages of simplicity in operation and high controllability.

Preferably, in step (A), the silica spheres have a radius of 500 nm.

Preferably, in step (B), the plasma etching gas is O₂Or CF₄The etching power is 50-150W, and the etching time is 8-14 min.

Preferably, in the step (C), the magnetron sputtering metal species are Ag, Au and Cu, and the sputtering thickness is 30-150 nm.

In the invention, the interlinked periodic array of the nano-cones is prepared, the periodic array has high order degree, good uniformity and strong repeatability, the preparation method is simple, the preparation period is short, and the array can be effectively copied and applied on a large scale, thereby widening the operable space for the subsequent nano-structure.

Drawings

FIG. 1 top view of a scanning electron microscope of a periodic array of interlinked nanocones in example 1.

FIG. 2 is a 45 ℃ scanning electron micrograph of a periodic array of interlinked nanopyramids of example 1.

Detailed Description

The invention is further described with reference to the following figures and detailed description.

Example 1

A method for preparing a periodic array of interlinked nanocones as described above, said method comprising the steps of:

(A) on a Si substrate 1 with a hydrophilic surface, a dense silicon dioxide globule array 2 is obtained by a self-assembly method, wherein the radius of the silicon dioxide globules is 500nm,

(B) carrying out plasma etching on the densely-arranged silicon dioxide pellet array, wherein etching gas is CF4, gas flux is 30sccm, working pressure is 2Pa, etching power is 150W, and etching time is 11min to obtain a periodic array of interlinked nano-cones, a top view of a scanning electron microscope is shown in figure 1, a 45-degree view of the scanning electron microscope is shown in figure 2, and adjacent nano-cones are connected with each other to form the periodic array of interlinked nano-cones as can be seen from figures 1 and 2;

(C) and depositing a silver film on the interlinked periodic array of the nanocones by magnetron sputtering, wherein the thickness of the silver film is 100 nm.

Example 2

(A) obtaining a dense silicon dioxide bead array on a Si substrate with a hydrophilic surface by using a self-assembly method, wherein the radius of the silicon dioxide beads is 500 nm;

(B) carrying out plasma etching on the densely-arranged silicon dioxide small ball array, wherein the etching gas is CF4, the gas flux is 30sccm, the working pressure is 2Pa, the etching power is 150W, and the etching time is 11min, so as to obtain a connected nano-cone periodic array;

(C) and depositing a layer of gold film on the interlinked periodic array of the nanocones by magnetron sputtering, wherein the thickness of the gold film is 100 nm.

Example 3

(B) performing plasma etching on the densely-arranged silicon dioxide pellet array, wherein the first-step etching gas is O2, the gas flux is 50sccm, the working pressure is 20Pa, the etching power is 50W, the etching time is 150s, the second-step etching gas is CF4, the gas flux is 30sccm, the working pressure is 2Pa, the etching power is 150W, and the etching time is 500s, so as to obtain the interlinked nano-cone periodic array;

The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.

Claims

1. A preparation method of a cyclic nanocone periodic array is characterized by comprising the following steps:

(A) obtaining a highly ordered silicon dioxide colloid ball array on a Si substrate with a hydrophilic surface by a self-assembly method;

(C) and depositing a layer of metal on the surface of the sample by utilizing a magnetron sputtering technology.

2. The method for preparing the cyclic nanocone periodic array according to claim 1, wherein in the step (A), the spherical radius of the silica colloid is 500-2000 nm.

3. The method for preparing the cyclic nanocone periodic array according to claim 1, wherein in the step (B), the plasma etching gas is O₂Or CF₄The etching power is 50-150W, and the etching time is 8-14 min.

4. The method for preparing the cyclic nanocone periodic array according to claim 1,

in the step (C), the metal layer is an Ag layer, an Au layer or a Cu layer.

5. The method for preparing the cyclic nanocone periodic array according to claim 1, wherein in the step (C), the thickness of the metal layer is 30 to 150 nm.