CN115465835A - Large-area anisotropic ordered nano array and preparation method thereof - Google Patents

Large-area anisotropic ordered nano array and preparation method thereof Download PDF

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Publication number
CN115465835A
CN115465835A CN202211138034.8A CN202211138034A CN115465835A CN 115465835 A CN115465835 A CN 115465835A CN 202211138034 A CN202211138034 A CN 202211138034A CN 115465835 A CN115465835 A CN 115465835A
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China
Prior art keywords
substrate
silane
anisotropic
solution
nanosphere
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CN202211138034.8A
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Chinese (zh)
Inventor
聂志鸿
王亚子
李红艳
叶顺盛
杨帆
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Yiwu Research Institute Of Fudan University
Fudan University
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Yiwu Research Institute Of Fudan University
Fudan University
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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
    • B82B3/0061—Methods for manipulating nanostructures
    • B82B3/0066—Orienting nanostructures
    • 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
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B1/001—Devices without movable or flexible 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
    • B82B3/0009—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
    • B82B3/0009—Forming specific nanostructures
    • B82B3/0019—Forming specific nanostructures without movable or flexible elements

Abstract

The invention relates to a large-area anisotropic ordered nano array and a preparation method thereof, wherein the method comprises the following steps: modifying the anisotropic magnetic nanoparticles to make the surfaces of the magnetic nanoparticles carry negative charges to obtain a nanoparticle solution with the negative charges; sequentially carrying out silane modification and nanosphere photoetching technology treatment on the matrix to form positive-charge periodic sites on the surface of the matrix to obtain a patterned matrix; and (3) placing the patterned substrate in a nanoparticle solution with negative charges, applying a magnetic field, and adsorbing and orienting to obtain the large-area anisotropic ordered nano array. Compared with the prior art, the array structure prepared by the invention has the collective response characteristic depending on the orientation of the nano particles, and the method is simple, low in cost and suitable for large-area production.

Description

Large-area anisotropic ordered nano array and preparation method thereof
Technical Field
The invention relates to the field of nanoparticle self-assembly, in particular to a large-area anisotropic ordered nano array and a preparation method thereof.
Background
Anisotropic NPs can exhibit shape-dependent optical, magnetic, and electrical properties compared to spherical Nanoparticles (NPs). For example, the gold nanorods have two surface plasmon resonance modes of transverse direction and longitudinal direction, and have polarization-dependent optical response characteristics; the longitudinal axis of the magnetic nanorods is more easily magnetized with respect to its transverse axis and tends to align with the direction of the external magnetic field. The anisotropic nano particles are used as structural units, and a periodically ordered array structure is constructed by adopting a certain technical means, so that abundant collective electromagnetic properties can be obtained. In particular, non-close packed anisotropic nanoparticle arrays have shown significant utility in a variety of fields such as holographic techniques, optical lenses, and chiral detection. There are two main methods for preparing such nanoparticle arrays: top-down lithography and bottom-up self-assembly. Compared with the traditional photoetching technology, the colloid self-assembly has unique advantages, such as flexible operation, low cost, large-area preparation and the like.
Nevertheless, the single self-assembly technique still cannot realize the controllable preparation of non-close-packed, ordered and anisotropic array structure, and usually needs to be used together with the traditional lithography technique, and its basic idea is: periodic "topographical traps" are created on a substrate using photolithography techniques, and anisotropic NPs are placed in these traps by capillary forces, electric field forces, or DNA recognition. However, these methods require precise matching of nano-scale traps and anisotropic NPs in three-dimensional space, which makes them less flexible in practical applications. How to control the position and orientation of the anisotropic NPs on the substrate with high precision and flexibility remains a great challenge.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a large-area anisotropic ordered nano array which can control the position and orientation of anisotropic NPs on a substrate with high precision and flexibility, has simple process and low price and is suitable for large-scale production and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of large-area anisotropic ordered nano-arrays comprises the following steps:
modifying the anisotropic magnetic nanoparticles to make the surfaces of the magnetic nanoparticles have negative charges so as to obtain a nanoparticle solution with the negative charges;
sequentially carrying out silane modification and nanosphere photoetching technology treatment on the matrix to form positive-charge periodic sites on the surface of the matrix to obtain a patterned matrix;
and (3) placing the patterned substrate in a nanoparticle solution with negative charges, applying a magnetic field, and adsorbing and orienting to obtain the large-area anisotropic ordered nano array.
Furthermore, the shape of the anisotropic magnetic nanoparticles comprises an ellipsoid, a prism or a rhombohedron, the material is an iron-based, cobalt-based or nickel-based material, the diameter is 20-100nm, and the length is 50-800nm.
Such as iron oxides, cobalt oxides, nickel oxides, and the like.
Further, the modifying agent used in the modification process includes a carboxyl compound, a phosphorus compound, or a hydroxyl compound. Specifically, polyacrylic acid, sodium hypophosphite or dextran is included.
Further, the substrate comprises a silicon wafer or a quartz wafer.
Further, the silane used in the silane modification includes an aminosilane coupling agent.
Furthermore, the nanospheres are polystyrene nanospheres with the size of 200-1000nm.
Further, the specific process of forming the patterned substrate includes the following steps:
(1) Placing the substrate in a silane solution, reacting, and drying to complete silane modification;
(2-1) dispersing the nanospheres into a solvent to prepare a nanosphere solution;
(2-2) injecting the nanosphere solution to form a compact single-layer nanosphere film, and transferring the film onto a silane-modified substrate;
and (2-3) heating, plasma etching and cleaning the substrate in sequence, and then finishing the nanosphere photoetching technology treatment to form the patterned substrate with periodic sites.
Further, the silane solution comprises an alcohol solution of silane, and the solvent comprises alcohol and/or water.
Furthermore, the strength of the magnetic field is 600-6000Gs, and the time of adsorption orientation is 2-12h.
A large area anisotropic ordered nanoarray prepared as described above.
Compared with the prior art, the invention has the following advantages:
(1) The invention can control the position and orientation of anisotropic NPs on the substrate with high precision and flexibility;
(2) The array structure prepared by the invention has collective response characteristics depending on the orientation of the nano particles, and the method is simple, low in price and suitable for large-area production.
Drawings
FIG. 1 is a flow chart of the preparation of anisotropic ordered nanoarrays in the examples;
FIG. 2 is an SEM image of an anisotropic ordered nanoarray of example 2, wherein A is a low magnification SEM image, B is a high magnification SEM image, and the inset in A is a macroscopic optical photograph of the ordered nanoarray.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
A preparation method of large-area anisotropic ordered nano-arrays is characterized by comprising the following steps:
(1) Modifying the anisotropic magnetic nanoparticles to make the surfaces of the anisotropic magnetic nanoparticles have negative charges; the anisotropy is one of an ellipsoid, a prism and a rhombohedron; the magnetic nano particles are made of one of iron series, cobalt series and nickel series materials, the diameter of the nano particles is 20-100nm, and the length of the nano particles is 50-800nm; the modifier of the nano particles is one of a carboxyl compound, a phosphorus compound and a hydroxyl compound.
(2) Sequentially carrying out silane modification and nanosphere photoetching technology treatment on the substrate to form positive-charge periodic sites on the surface of the substrate; the substrate is one of a silicon wafer or a quartz wafer; the silane is an aminosilane coupling agent; the nanospheres are polystyrene nanospheres, and the size of the nanospheres is 200-1000nm.
(3) And (3) placing the patterned substrate in a nanoparticle solution with negative charges, applying a horizontal magnetic field, and performing adsorption orientation to obtain the anisotropic ordered nano array. The intensity of the magnetic field is 600-6000Gs; the time of adsorption orientation is 2-12h.
Example 1
A preparation method of a large-area anisotropic ordered nano array comprises the following steps:
mixing Co with diameter of 20nm and length of 50nm 3 O 4 And (3) placing the nano prism into the dextran solution, and stirring for 12 hours. Putting the silicon wafer into an ethanol solution containing 3-aminopropyltrimethoxysilane (the volume fraction is 0.2 percent), reacting for 30min, washing the silicon wafer with ethanol, and drying the silicon wafer in a 120 ℃ oven for 1.5h. Dispersing Polystyrene (PS) nanospheres with the size of 200nm into a mixed solution of ethanol and deionized water (volume ratio is 1. And (3) drying the silicon wafer in a drying oven at 110 ℃ for 5min, treating for 60s by using a plasma cleaning machine, then putting the silicon wafer into ethanol, and ultrasonically removing the PS nanospheres on the silicon wafer to form a periodic site structure. Immersing silicon wafer with periodic sites into Co 3 O 4 Placing the nanometer prism solution between two magnets, setting the magnetic field strength at 6000Gs, standing for 12h, taking out the silicon wafer, washing with deionized water,obtaining the anisotropic ordered nano array.
Example 2
A preparation method of large-area anisotropic ordered nano-arrays comprises the following steps:
mixing Fe with the diameter of 90nm and the length of 326nm 3 O 4 And (3) placing the nano ellipsoid in a polyacrylic acid solution, and stirring for 12 hours. Putting the silicon chip into an ethanol solution containing 3-aminopropyltrimethoxysilane (the volume fraction is 0.2 percent), reacting for 30min, washing the silicon chip with ethanol, and drying the silicon chip in a 120 ℃ drying oven for 1.5h. Dispersing PS nanospheres with the size of 700nm into a mixed solution of ethanol and deionized water (volume ratio is 1. And (3) drying the silicon wafer in a drying oven at 110 ℃ for 5min, treating for 60s by using a plasma cleaning machine, then putting the silicon wafer into ethanol, and ultrasonically removing the PS nanospheres on the silicon wafer to form a periodic site structure. Immersing a silicon wafer having periodic sites in Fe 3 O 4 And (3) placing the nano ellipsoid solution between two magnets, setting the magnetic field intensity to be 5800Gs, standing for 8h, taking out the silicon wafer, and washing the silicon wafer with deionized water to obtain the anisotropic ordered nano array.
Example 3
A preparation method of a large-area anisotropic ordered nano array comprises the following steps:
NiO nano rhombohedron with the diameter of 100nm and the length of 800nm is put into sodium hypophosphite monohydrate solution and stirred for 12h. Putting the quartz plate into an ethanol solution containing 3-aminopropyltriethoxysilane (volume fraction of 0.2%), reacting for 30min, washing with ethanol, and oven drying at 120 deg.C for 1.5h. Dispersing PS nanospheres with the size of 1000nm into a mixed solution of ethanol and deionized water (the volume ratio is 1. And (3) drying the quartz plate in a drying oven at 110 ℃ for 5min, treating for 60s by using a plasma cleaning machine, then putting into ethanol, and ultrasonically removing the PS nanospheres on the quartz plate to form a periodic site structure. And (3) immersing a quartz plate with periodic sites into the NiO nano rhombohedral solution, placing the solution between two magnets, setting the magnetic field intensity to be 600Gs, standing for 2h, taking out the quartz plate, and washing the quartz plate by using deionized water to obtain the anisotropic ordered nano array.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.

Claims (10)

1. A preparation method of large-area anisotropic ordered nano-arrays is characterized by comprising the following steps:
modifying the anisotropic magnetic nanoparticles to make the surfaces of the magnetic nanoparticles have negative charges so as to obtain a nanoparticle solution with the negative charges;
sequentially carrying out silane modification and nanosphere photoetching technology treatment on the substrate to form periodic sites with positive charges on the surface of the substrate to obtain a patterned substrate;
and (3) placing the patterned substrate in a nanoparticle solution with negative charges, applying a magnetic field, and adsorbing and aligning to obtain the large-area anisotropic ordered nano array.
2. The method according to claim 1, wherein the anisotropic magnetic nanoparticles have an ellipsoidal, prismatic or rhombohedral shape, are made of iron, cobalt or nickel materials, have a diameter of 20-100nm and a length of 50-800nm.
3. The method of claim 1, wherein the modifier used in the modification process comprises a carboxyl compound, a phosphorus compound, or a hydroxyl compound.
4. The method of claim 1, wherein the substrate comprises a silicon wafer or a quartz plate.
5. The method of claim 1, wherein the silane used in the silane modification comprises an aminosilane coupling agent.
6. The method of claim 1, wherein the nanospheres are polystyrene nanospheres with a size of 200-1000nm.
7. The method of claim 1, wherein the step of forming the patterned substrate comprises the steps of:
(1) Placing the substrate in a silane solution, reacting, and drying to complete silane modification;
(2-1) dispersing the nanospheres into a solvent to prepare a nanosphere solution;
(2-2) injecting the nanosphere solution to form a compact single-layer nanosphere film, and transferring the film onto a silane modified substrate;
and (2-3) heating, plasma etching and cleaning the substrate in sequence, and then finishing the nanosphere photoetching technology treatment to form the patterned substrate with periodic sites.
8. The method of claim 7, wherein the silane solution comprises an alcohol solution of silane, and the solvent comprises alcohol and/or water.
9. The method of claim 1, wherein the magnetic field has a strength of 600-6000Gs and the time of the adsorption orientation is 2-12h.
10. A large area anisotropic ordered nanoarray prepared by the method of any one of claims 1 to 9.
CN202211138034.8A 2022-09-19 2022-09-19 Large-area anisotropic ordered nano array and preparation method thereof Pending CN115465835A (en)

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Application Number Priority Date Filing Date Title
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