CN116854024B - Preparation method of single or multiple nanoscale pore channels based on silicon wafer - Google Patents
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 87
- 239000010703 silicon Substances 0.000 title claims abstract description 87
- 239000011148 porous material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 62
- 238000005530 etching Methods 0.000 claims abstract description 41
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000004140 cleaning Methods 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000010894 electron beam technology Methods 0.000 claims abstract description 16
- 239000011241 protective layer Substances 0.000 claims abstract description 16
- 239000003223 protective agent Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 40
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 40
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 31
- 229910052737 gold Inorganic materials 0.000 claims description 31
- 239000010931 gold Substances 0.000 claims description 31
- 239000002105 nanoparticle Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 239000001509 sodium citrate Substances 0.000 claims description 10
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 10
- 229940038773 trisodium citrate Drugs 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000002923 metal particle Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 230000001678 irradiating effect Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00087—Holes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00436—Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
- B81C1/00523—Etching material
- B81C1/00539—Wet etching
-
- 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
Abstract
The invention discloses a preparation method of single or multiple nanoscale pore channels based on a silicon wafer, which comprises the following steps: (1) Preparing metal nano particles with surfaces coated with organic protective agents; (2) After the metal nano particles are ultrasonically dispersed to a solvent, the metal nano particles are dripped on the surface of the silicon substrate; (3) Placing the silicon substrate in the step (2) under an electron beam to selectively irradiate single or multiple metal nano particles to form a compact protective layer wrapping the metal nano particles; (4) Removing the metal nanoparticles not protected by the dense protective layer; (5) calcining the silicon substrate in the step (4); (6) And transferring the calcined silicon substrate into etching liquid for etching, and cleaning and drying after etching to obtain single or multiple nano-scale silicon tunnels. The invention has simple process and realizes the regulation and control of the nano pore canal structure. Meanwhile, the preparation process is simple, the shape of the pore canal is adjustable, and the preparation method is expected to be widely applied in the fields of medicine, optics, sensing, micro-nano processing and the like.
Description
Technical Field
The invention belongs to the technical field of micro-nano processing of silicon substrates, and particularly relates to a preparation method of single or multiple nanoscale pore channels based on a silicon wafer.
Background
In recent years, as human beings continuously explore life sciences, studies on the aspects of biological macromolecule recognition, gene sequencing, protein mass spectrometry analysis and the like are more and more in progress, a nanopore sensing technology is attracting attention of scientists as a means for effectively detecting biological small molecules. The core component in the nanopore sensing technology is a solid nanopore, and the performance of the solid nanopore directly determines the performance index in detecting biomolecules.
At present, the solid nano-pore is prepared by adopting electron beams generated by a transmission electron microscope or ion beams generated by a focused ion beam microscope, and the preparation method has the advantages of high manufacturing cost, low efficiency and easy breakage. Therefore, there is a need to develop solid state nanopores with low cost, good stability, fast efficiency and good biocompatibility.
Disclosure of Invention
Aiming at the technical problems, the invention aims to provide a preparation method of a single or a plurality of nanoscale pore canals based on a silicon wafer, which has the advantages of simple process, low cost and adjustable pore canal shape.
The invention uses electron beam of scanning electron microscope to irradiate metal nanometer particles in the earlier stage of preparing nanometer pore canal. In the visual field of a scanning electron microscope, only one or more metal nanoparticles are ensured, after a period of irradiation, the protective agent and environmental carbon on the surfaces of the metal nanoparticles can be carbonized by electron beams, so that a layer of compact protective layer is formed on the surfaces of the single or more metal nanoparticles, the single or more metal nanoparticles are selectively protected, and after the single or more metal nanoparticles are soaked in aqua regia, other metal particles except the metal particles outside the protective layer are dissolved into metal ion solution, so that only the selected single or more metal nanoparticles are reserved. The single or multiple metal particles with the protective layer on the silicon substrate are subjected to subsequent high-temperature calcination, so that the protective layer on the surface of the metal particles can be removed, and only a single nano pore canal is etched on the silicon substrate in the subsequent etching process.
The technical scheme provided by the invention is as follows:
a preparation method of single or multiple nanoscale pore channels based on a silicon wafer comprises the following steps:
(1) Preparing metal nano particles coated with an organic protective agent;
(2) After the metal nano particles are ultrasonically dispersed to a solvent, the metal nano particles are dripped on the surface of the silicon substrate;
(3) Placing the silicon substrate in the step (2) under an electron beam to selectively irradiate single or multiple metal nano particles to form a protective layer for wrapping the metal nano particles;
(4) Removing the metal nanoparticles not protected by the dense protective layer;
(5) Calcining the silicon substrate in the step (4);
(6) And transferring the calcined silicon substrate into etching liquid for etching, and cleaning and drying after etching to obtain single or multiple nano-scale silicon tunnels.
Further, in the step (1), the metal nanoparticles are gold, silver or platinum nanoparticles.
Further, in the step (1), the organic protecting agent includes one or more of trisodium citrate, cetyltrimethylammonium bromide or cetyltrimethylammonium chloride.
Further, in the step (1), the metal nanoparticles have a particle size of 20 to 150% nm and a particle number of 1×10 7 Per liter to 1X 10 11 and/L.
Further, in the step (2), the solvent includes water, acetone and N, N-dimethylformamide.
In the step (3), the electron beam is generated by a scanning electron microscope, the accelerating voltage is 1-20 kv, and the irradiation time is 1-20 minutes. Preferably, the acceleration voltage is 5kv and the irradiation time is 5 minutes.
Further, in the step (4), the method for removing the metal nano particles not protected by the dense protective layer comprises soaking the metal nano particles in aqua regia and then drying the metal nano particles.
Further, the method for removing the metal nano particles which are not protected by the compact protection layer comprises the following steps: transferring the silicon substrate obtained in the step (3) into fresh aqua regia, soaking and drying. Preferably, the soaking time is 2 hours.
Further, in the step (5), the calcination temperature is 300-600 ℃ and the calcination time is 1-6 hours. Preferably, the calcination temperature is 400℃and the calcination time is 2 hours.
Further, in the step (6), the etching solution is a mixed solution of hydrofluoric acid, hydrogen peroxide and secondary water.
Further, the concentration of hydrofluoric acid in the etching liquid is 2-20M, and the concentration of hydrogen peroxide is 0.1-8M. Preferably, the concentration of hydrofluoric acid in the etching solution is 4-15M, and the concentration of hydrogen peroxide is 0.5-5M.
Further, in the step (6), the etching time is 1 to 7 hours.
Further, in the step (6), the etching time is 3 to 6 hours. Preferably, the etching time is 4 hours.
The invention has the beneficial effects that:
according to the invention, through electron irradiation of the metal nano particles, a compact protective layer can be selectively formed on the surfaces of single or multiple metal nano particles, and then the selected single or multiple metal nano particles are controlled to be etched, so that nano pore channels on single or multiple nano dimensions can be obtained on a silicon substrate. The invention has simple process, overcomes the defect that the traditional chemical etching can only etch single or multiple nano pore channels on the silicon substrate, and realizes the regulation and control of the nano pore channel structure. Meanwhile, the preparation process is simple, the shape of the pore canal is adjustable, and the preparation method is expected to be widely applied in the fields of medicine, optics, sensing, micro-nano processing and the like.
Drawings
The present invention is further illustrated by the accompanying drawings, which are not to be construed as limiting the invention in any way.
FIG. 1 is a schematic illustration of the presenting step (2) of one embodiment of the present invention;
FIG. 2 is a schematic diagram of the presenting step (3) of one embodiment of the present invention;
FIG. 3 is a schematic diagram of the presenting step (4) of one embodiment of the present invention;
FIG. 4 is a schematic illustration of the presenting step (5) of one embodiment of the present invention;
FIG. 5 is a schematic illustration of the presenting step (6) of one embodiment of the present invention;
in the figure: a silicon wafer 101; metal particles 102; an electron beam 201; metal particles 202 with a protective layer; removing the metal particles 301 of the protective layer; the metal particles assist in etching the single hole 401.
Detailed Description
The invention is further illustrated below in connection with specific examples, the content of which is not limited at all.
In the following examples, the metal nanoparticles were gold nanoparticles having a particle size of 80. 80 nm and a particle number of 3.76X10 10 The protective agent is trisodium citrate.
Example 1
The preparation method of the single nanoscale silicon pore canal comprises the following steps:
(1) Adopting a heating method, and reducing with trisodium citrate to prepare gold nanoparticles;
(2) After the gold nanoparticles are ultrasonically dispersed into water, the gold nanoparticles are dripped on the upper surface of a silicon substrate, as shown in figure 1;
(3) Placing the silicon substrate subjected to the step (2) under an electron beam of a scanning electron microscope to selectively irradiate single gold nano particles, and irradiating for 20 minutes under the condition of 1 kv; as shown in fig. 2;
(4) Transferring the silicon substrate subjected to the step (3) into fresh aqua regia, and soaking for 2 hours; as shown in fig. 3;
(5) Cleaning and drying the silicon substrate after the step (4) is completed, placing the silicon substrate into a muffle furnace, and calcining the silicon substrate for 3 hours at 300 ℃; as shown in fig. 4, the protective layer is removed;
(6) Transferring the silicon substrate subjected to the step (5) into etching liquid, and etching for 1 hour; the etching solution is a mixed solution of hydrofluoric acid, hydrogen peroxide and secondary water, the concentration of the hydrofluoric acid in the mixed solution is 13M, and the concentration of the hydrogen peroxide is 0.5M; and then the silicon nano pore canal with the single diameter of about 200nm can be obtained by secondary water cleaning and drying, as shown in figure 5.
Example 2
The preparation method of the single nanoscale silicon pore canal comprises the following steps:
(1) Adopting a heating method, and reducing with trisodium citrate to prepare gold nanoparticles;
(2) After the gold nano particles are ultrasonically dispersed into water, the gold nano particles are dripped on the upper surface of the silicon substrate;
(3) Placing the silicon substrate subjected to the step (2) under an electron beam of a scanning electron microscope to selectively irradiate single gold nano particles, and irradiating for 15 minutes under the condition of 2 kv;
(4) Transferring the silicon substrate subjected to the step (3) into fresh aqua regia, and soaking for 2 hours;
(5) Cleaning and drying the silicon substrate after the step (4) is completed, and then placing the silicon substrate into a muffle furnace for calcining for 5 hours at 400 ℃;
(6) Transferring the silicon substrate subjected to the step (5) into etching solution, and etching for 3 hours, wherein the etching solution is a mixed solution of hydrofluoric acid, hydrogen peroxide and secondary water, the concentration of the hydrofluoric acid in the mixed solution is 9M, and the concentration of the hydrogen peroxide is 2.6M; and (3) cleaning with water for the second time and drying to obtain a single silicon nano pore canal with the diameter of about 200 nm.
Example 3
The preparation method of the single nanoscale silicon pore canal comprises the following steps:
(1) Adopting a heating method, and reducing with trisodium citrate to prepare gold nanoparticles;
(2) After the gold nano particles are ultrasonically dispersed into water, the gold nano particles are dripped on the upper surface of the silicon substrate;
(3) Placing the silicon substrate subjected to the step (2) under an electron beam of a scanning electron microscope to selectively irradiate single gold nano particles, and irradiating for 15 minutes at 5 kv;
(4) Transferring the silicon substrate subjected to the step (3) into fresh aqua regia, and soaking for 2 hours;
(5) Cleaning and drying the silicon substrate after the step (4) is completed, and then placing the silicon substrate into a muffle furnace for calcining for 4 hours at 400 ℃;
(6) Transferring the silicon substrate subjected to the step (5) into etching solution, and etching for 5 hours, wherein the etching solution is a mixed solution of hydrofluoric acid, hydrogen peroxide and secondary water, the concentration of the hydrofluoric acid in the mixed solution is 4.6M, and the concentration of the hydrogen peroxide is 4.5M; and (3) cleaning with water for the second time and drying to obtain a single silicon nano pore canal with the diameter of about 200 nm.
Example 4
The preparation method of the single nanoscale silicon pore canal comprises the following steps:
(1) Adopting a heating method, and reducing with trisodium citrate to prepare gold nanoparticles;
(2) After the gold nano particles are ultrasonically dispersed into water, the gold nano particles are dripped on the upper surface of the silicon substrate;
(3) Placing the silicon substrate subjected to the step (2) under an electron beam of a scanning electron microscope to selectively irradiate single gold nano particles, and irradiating for 5 minutes at 10 kv;
(4) Transferring the silicon substrate subjected to the step (3) into fresh aqua regia, and soaking for 2 hours;
(5) Cleaning and drying the silicon substrate after the step (4) is completed, and then placing the silicon substrate into a muffle furnace for calcining for 2 hours at 600 ℃;
(6) Transferring the silicon substrate subjected to the step (5) into etching solution, and etching for 6 hours, wherein the etching solution is a mixed solution of hydrofluoric acid, hydrogen peroxide and secondary water, the concentration of the hydrofluoric acid in the mixed solution is 12M, and the concentration of the hydrogen peroxide is 1.3M; and (3) cleaning with water for the second time and drying to obtain a single silicon nano pore canal with the diameter of about 200 nm.
Example 5
The preparation method of the single nanoscale silicon pore canal comprises the following steps:
(1) Adopting a heating method, and reducing with trisodium citrate to prepare gold nanoparticles;
(2) After the gold nano particles are ultrasonically dispersed into water, the gold nano particles are dripped on the upper surface of the silicon substrate;
(3) Placing the silicon substrate subjected to the step (2) under an electron beam of a scanning electron microscope to selectively irradiate single gold nano particles, and irradiating for 2 minutes at 15 kv;
(4) Transferring the silicon substrate subjected to the step (3) into fresh aqua regia, and soaking for 2 hours;
(5) Cleaning and drying the silicon substrate after the step (4) is completed, placing the silicon substrate into a muffle furnace, and calcining the silicon substrate for 1 hour at 500 ℃;
(6) Transferring the silicon substrate subjected to the step (5) into etching solution, and etching for 1 hour, wherein the etching solution is a mixed solution of hydrofluoric acid, hydrogen peroxide and secondary water, the concentration of the hydrofluoric acid in the mixed solution is 7.6M, and the concentration of the hydrogen peroxide is 3M; and (3) cleaning with water for the second time and drying to obtain a single silicon nano pore canal with the diameter of about 200 nm.
Example 6
The preparation method of the single nanoscale silicon pore canal comprises the following steps:
(1) Adopting a heating method, and reducing with trisodium citrate to prepare gold nanoparticles;
(2) After the gold nano particles are ultrasonically dispersed into water, the gold nano particles are dripped on the upper surface of the silicon substrate;
(3) Placing the silicon substrate subjected to the step (2) under an electron beam of a scanning electron microscope to selectively irradiate single gold nano particles, and irradiating for 1 minute under 20 kv;
(4) Transferring the silicon substrate subjected to the step (3) into fresh aqua regia, and soaking for 2 hours;
(5) Cleaning and drying the silicon substrate after the step (4) is completed, and then placing the silicon substrate into a muffle furnace for calcining for 4 hours at 600 ℃;
(6) Transferring the silicon substrate subjected to the step (5) into etching solution, and etching for 7 hours, wherein the etching solution is a mixed solution of hydrofluoric acid, hydrogen peroxide and secondary water, the concentration of the hydrofluoric acid in the mixed solution is 6.1M, and the concentration of the hydrogen peroxide is 3.9M; and (3) cleaning with water for the second time and drying to obtain a single silicon nano pore canal with the diameter of about 200 nm.
Example 7
The preparation method of the plurality of nano-scale silicon pore canals comprises the following steps:
(1) Adopting a heating method, and reducing with trisodium citrate to prepare gold nanoparticles;
(2) After the gold nano particles are ultrasonically dispersed into water, the gold nano particles are dripped on the upper surface of the silicon substrate;
(3) Placing the silicon substrate subjected to the step (2) under an electron beam of a scanning electron microscope to selectively irradiate a plurality of gold nanoparticles, and irradiating for 1 minute under 20 kv;
(4) Transferring the silicon substrate subjected to the step (3) into fresh aqua regia, and soaking for 2 hours;
(5) Cleaning and drying the silicon substrate after the step (4) is completed, and then placing the silicon substrate into a muffle furnace for calcining for 4 hours at 600 ℃;
(6) Transferring the silicon substrate subjected to the step (5) into etching solution, and etching for 7 hours, wherein the etching solution is a mixed solution of hydrofluoric acid, hydrogen peroxide and secondary water, the concentration of the hydrofluoric acid in the mixed solution is 6.1M, and the concentration of the hydrogen peroxide is 3.9M; and (3) cleaning with water for the second time and drying to obtain a plurality of nano-scale silicon nano-pore channels with the diameters of about 200 nm.
The present invention is not limited to the above-mentioned embodiments, but any modifications, equivalents, improvements and modifications within the scope of the invention will be apparent to those skilled in the art.
Claims (10)
1. The preparation method of the single or multiple nanoscale pore canals based on the silicon wafer is characterized by comprising the following steps:
(1) Preparing metal nano particles with surfaces coated with organic protective agents;
(2) After the metal nano particles are ultrasonically dispersed to a solvent, the metal nano particles are dripped on the surface of the silicon substrate;
(3) Placing the silicon substrate in the step (2) under an electron beam to selectively irradiate single or multiple metal nano particles to form a compact protective layer wrapping the metal nano particles;
(4) Removing the metal nanoparticles not protected by the dense protective layer;
(5) Calcining the silicon substrate in the step (4);
(6) And transferring the calcined silicon substrate into etching liquid for etching, and cleaning and drying after etching to obtain single or multiple nano-scale silicon tunnels.
2. The method according to claim 1, characterized in that: in the step (1), the metal nano particles are gold, silver or platinum nano particles; the organic protective agent comprises one or more of trisodium citrate, cetyltrimethylammonium bromide or cetyltrimethylammonium chloride.
3. The method according to claim 1, characterized in that: in the step (1), the particle size of the metal nano particles is 20-150 nm, and the number of the particles is 1 multiplied by 10 7 Per liter to 1X 10 11 and/L.
4. The method according to claim 1, characterized in that: in the step (2), the solvent comprises water, acetone and N, N-dimethylformamide.
5. The method according to claim 1, characterized in that: in the step (3), the electron beam is generated by a scanning electron microscope, the accelerating voltage is 1-20 kv, and the irradiation time is 1-20 minutes.
6. The method according to claim 1, characterized in that: in the step (4), the method for removing the metal nano particles which are not protected by the compact protective layer comprises soaking the metal nano particles in aqua regia and then drying the metal nano particles.
7. The method according to claim 1, characterized in that: in the step (5), the calcination temperature is 300-600 ℃ and the calcination time is 1-6 hours.
8. The method according to claim 1, characterized in that: in the step (6), the etching solution is a mixed solution of hydrofluoric acid, hydrogen peroxide and secondary water, wherein the concentration of the hydrofluoric acid in the mixed solution is 2-20M, and the concentration of the hydrogen peroxide is 0.1-8M.
9. The method according to claim 8, wherein: the concentration of hydrofluoric acid in the etching liquid is 4-15M, and the concentration of hydrogen peroxide is 0.5-5M.
10. The method according to claim 1, characterized in that: in the step (6), the etching time is 1-7 hours.
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