METHOD FOR LASER-INDUCED GROWTH OF NANO-UNITS TO FORM ORIENTED, CHIRAL, AND COMPLEX STRUCTURES
20220126364 · 2022-04-28
Assignee
Inventors
Cpc classification
C23C14/16
CHEMISTRY; METALLURGY
B82Y30/00
PERFORMING OPERATIONS; TRANSPORTING
B22F9/20
PERFORMING OPERATIONS; TRANSPORTING
B82Y40/00
PERFORMING OPERATIONS; TRANSPORTING
International classification
B22F9/20
PERFORMING OPERATIONS; TRANSPORTING
C23C14/16
CHEMISTRY; METALLURGY
Abstract
A method for laser-induced growth of nano-units to form oriented, chiral, and complex structures is provided. Through a laser-induced photochemical reaction, a metal precursor undergoes photolysis to produce inorganic nanoparticles, and these nanoparticles are orientally deposited on a substrate along a polarization direction in a linearly polarized laser to form fusiform nano-units. Through mixed polarized light generated by a vortex plate, the nano-units can grow rapidly and form a specific arrangement to obtain special three-dimensional (3D) nanostructures with chiral features and complex patterns. This method can be implemented in a room temperature environment, has the characteristics of simple operation, short reaction time, high repeatability, long storage time, low cost, and controllable orientations and sites, and shows promising application prospects in the fields of optical devices, chiral catalysis, sensing, integrated circuits, and the like.
Claims
1. A method for laser polarization-induced growth of fusiform gold nano-units, comprising the following steps: step 1. preparation of a gold substrate with a thermal evaporation instrument, vapor-depositing chromium on a silicon substrate as an adhesion layer, and vapor-depositing a gold layer to obtain a gold film as the substrate; and cutting the substrate into small pieces, and storing the small pieces in a dry box for further use; step 2. preparation of a sample taking a small piece of the gold film, adding an appropriate amount of a chloroauric acid solution dropwise on the gold film with a pipette, and covering with a cover glass such that the gold film is completely immersed in the chloroauric acid solution to obtain the sample; step 3. laser-induced oriented growth of single fusiform gold nanoparticles coupling a linearly polarized laser into an optical microscope, and focusing the linearly polarized laser on a surface of the gold film in the sample through an objective lens to conduct irradiation for 10 s to 25 s at an irradiation power of 3 mW to 6 mW, wherein a direction of the linearly polarized laser can be adjusted to obtain fusiform gold nanoparticles with a corresponding orientation.
2. The method according to claim 1, further comprising the following steps: step 4. laser polarization-induced chiral growth of fusiform gold converting 446 nm linearly polarized light into mixed polarized light by aligning a fast axis of a vortex plate in a degree ranging from 30° to 60° to the polarization, and focusing the mixed polarized light on a surface of the gold film in the sample through an objective lens to conduct irradiation for 90 s to 180 s at an irradiation power of 5 mW to 6 mW to obtain a chiral nanostructure composed of multiple fusiform gold nano-units.
3. The method according to claim 1, further comprising the following steps: step 5. laser polarization-induced growth of fusiform gold nano-units to form a complex pattern converting linearly polarized light into radially or angularly polarized light by aligning a fast axis of a vortex plate either parallel or vertical to the polarization, and focusing the radially or angularly polarized light on a surface of the gold film in the sample through an objective lens to conduct irradiation for 90 s to 180 s at an irradiation power of 5 mW to 6 mW to obtain a complex pattern nanostructure composed of multiple fusiform gold nano-units.
4. The method according to claim 1, wherein in step 1, a chromium layer of 3 nm is first vapor-deposited as an adhesion layer, and then a gold layer of 50 nm to 100 nm is vapor-deposited.
5. The method according to claim 1, wherein in steps 3, 4 and 5, the laser has a wavelength of 400 nm to 460 nm.
6. A method for laser polarization-induced growth of platinous/palladium oxide fusiform/circular nano-pillars, comprising the following steps: step 1. preparation of a sample soaking a silicon wafer in an aminopropyltriethoxysilane (APTS) solution for a few minutes, and cleaning the silicon wafer with deionized water; and adding an appropriate amount of a Pt or Pd precursor solution dropwise on the silicon wafer, and covering with a cover glass such that the silicon wafer is completely immersed in the Pt or Pd precursor solution to obtain the sample; step 2. laser-induced oriented growth of fusiform/circular pillars coupling a linearly polarized laser into an optical microscope, and focusing the linearly polarized laser on a surface of the silicon wafer in the sample through an objective lens to conduct irradiation for no less than 10 s at an irradiation power of 2 mW to 22 mW, wherein a direction of the linearly polarized laser can be adjusted to obtain fusiform nano-pillars with a corresponding orientation; or coupling a circularly polarized laser into an optical microscope, and focusing the circularly polarized laser on a surface of the silicon wafer in the sample through an objective lens to conduct irradiation for no less than 10 s at an irradiation power of 2 mW to 22 mW to obtain circular nano-pillars.
7. The method according to claim 6, further comprising the following steps: step 3. laser-induced growth to form a complex pattern converting linearly polarized light into radially or angularly polarized light through a vortex plate, and focusing the radially or angularly polarized light on a surface of the silicon wafer in the sample through an objective lens for irradiation to obtain a complex pattern nanostructure composed of multiple fusiform nano-units.
8. The method according to claim 6, further comprising the following steps: step 4. induced chiral growth of fusiform pillars through any of the following modes: mode 1: coupling a linearly polarized laser into an optical microscope, and focusing the linearly polarized laser on a surface of the silicon wafer in the sample through an objective lens for irradiation, wherein an irradiation site of the laser is fixed, and a polarization direction of the laser is adjusted through a half-wave plate (HWP) to make fusiform nano-units with different orientations grow at the same site and thus obtain a spiral chiral nanostructure formed from superposition of the fusiform nano-units with different orientations; and mode 2: converting a linearly polarized laser into a mixed polarized laser by aligning a fast axis of a vortex plate in a degree ranging from 30° to 60° to the polarization, and focusing the mixed polarized laser on a surface of the silicon wafer in the sample through an objective lens for irradiation to obtain a chiral nanostructure composed of multiple fusiform nano-units.
9. The method according to claim 6, wherein the laser has a wavelength of 400 nm to 460 nm or of 500 nm to 550 nm; when the laser wavelength of 400 nm to 460 nm is adopted, the power is in a range of 2 mW to 6 mW and a irradiation time is in a range of 10 s to 60 s; and when the laser wavelength of 500 nm to 550 nm is adopted, the power is in a range of 8 mW to 22 mW and the irradiation time is no less than 20 s.
10. The method according to claim 6, wherein in step 1, the Pt precursor is any one from the group consisting of K.sub.2PtCl.sub.4, K.sub.2PtCl.sub.6, and Pt(acac).sub.2.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE EMBODIMENTS
[0077] Specific embodiments of the method for laser-induced growth of nano-units to form oriented, chiral, and complex structures involved in the present disclosure will be described in detail below with reference to the accompanying drawings.
Example 1
[0078] 1) Preparation of a Gold Substrate
[0079] With a thermal evaporation instrument, a chromium layer of 3 nm was vapor-deposited on a silicon substrate as an adhesion layer, and then a gold layer of 100 nm was vapor-deposited to obtain a gold film. The prepared gold film substrate was cut into small pieces each of about 1 cm.sup.2, and stored in a dry box.
[0080] 2) Preparation of a Sample
[0081] A small piece of the gold film was taken, cleaned with alcohol, and blow-dried; an appropriate amount of a chloroauric acid solution (10 mmol/L to 20 mmol/L) was added dropwise on the gold film with a pipette; and then the gold film was covered with a cover glass such that the gold film was completely immersed in the chloroauric acid solution.
[0082] 3) Laser-Induced Oriented Growth of Fusiform Gold Nanoparticles
[0083] A linearly polarized laser was coupled into an optical microscope and then focused on a surface of the gold film sample prepared in 2) through a 100× objective lens (numerical aperture: 0.8) for irradiation. The irradiation laser was linearly polarized light with a wavelength of 446 nm, an irradiation power could be adjusted in a range of 3 mW to 6 mW, and an irradiation time could be adjusted in a range of 15 s to 25 s.
[0084] A polarization direction of the laser could be changed to obtain fusiform gold nanoparticles with different orientations.
[0085] 4) Laser Polarization-Induced Growth of Fusiform Gold to Form a Chiral/Complex Pattern
[0086] The 446 nm linearly polarized light was converted into radially polarized light, angularly polarized light, and mixed polarized light using a vortex plate, and then focused on a surface of the gold film sample prepared in 2) through a 100× objective lens (numerical aperture: 0.8) for irradiation. An irradiation power could be adjusted in a range of 5 mW to 6 mW and an irradiation time could be adjusted in a range of 120 s to 180 s to finally form different chiral/complex patterns on the gold film.
[0087] Specifically, in this example, a 10 mmol/L HAuCl.sub.4 solution was added dropwise. The gold film sample prepared in 2) was placed under a microscope, and under the same laser irradiation conditions (4 mW, 15 s), irradiation was conducted in varying polarization directions to obtain a test sample group 1.sup.#, where the varying polarization directions had included angles of 0°, 30°, 60°, and 90°, with a horizontal direction, respectively.
[0088] The gold film sample prepared in 2) was placed under a microscope, and irradiation was conducted with a 446 nm laser at a power of 4 mW for different times to obtain a test sample group 2.sup.#.
[0089] The gold film sample prepared in 2) was placed under a microscope, and the HAuCl.sub.4 solution was irradiated for 120 s with radially polarized light and angularly polarized light of 446 nm and mixed polarized light of the two at an irradiation power of 5 mW to obtain a test sample group 3.sup.#.
[0090] SEM images of the obtained fusiform gold nanostructure test samples (No. 1.sup.#), change of growth of the fusiform gold nanostructure with time (No. 2.sup.#), and temperature and electric field simulation diagrams were shown in
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Example 2
[0095] 1) Preparation of a Sample
[0096] A silicon wafer of 1 cm.sup.2 was taken, rinsed with alcohol, and then blow-dried. 1 μL of APTS was pipetted with a pipette and added to 1 mL of deionized water, and a resulting mixture was thoroughly mixed to obtain an APTS solution. The cleaned silicon wafer was soaked in the APTS solution for 10 min, and then cleaned with deionized water, such that laser-induced platinous oxide nanoparticles could be firmly adsorbed on the substrate. An appropriate amount of a K.sub.2PtCl.sub.4 solution (5 mmol/L to 30 mmol/L) was added dropwise on the treated silicon wafer, and then the silicon wafer was covered with a cover glass such that the silicon wafer was completely immersed in the K.sub.2PtCl.sub.4 solution.
[0097] 2) Laser-Induced Oriented Growth of Platinous Oxide Pillars
[0098] A linearly polarized laser was coupled into an optical microscope and then focused on a surface of the silicon substrate through a 100× or 50× objective lens (numerical aperture: 0.8 or 0.5) for irradiation. The irradiation laser may have a wavelength of 446 nm or 532 nm. When a laser with a wavelength of 446 nm was used for irradiation, an irradiation power was in a range of 2 mW to 6 mW and an irradiation time was in a range of 10 s to 60 s. When a laser with a wavelength of 523 nm was used for irradiation, an irradiation power was in a range of 8 mW to 22 mW and an irradiation time was no less than 20 s. Under the above irradiation conditions, fusiform nano-pillars with an obvious orientation could be obtained. When the 446 nm laser was used for irradiation (3 mW, 30 s), a polarization direction of the linearly polarized laser could be changed to obtain fusiform nano-pillars with different orientations. Under the same light conditions, the linearly polarized light was adjusted into circularly polarized light with a quarter wave plate to induce the generation of circular pillars.
[0099] 3) Laser Polarization-Induced Chiral Growth of Platinous Oxide Fusiform Pillars
[0100] A laser with a wavelength of 446 nm was selected, a laser power was preferably controlled in the range of 2 mW to 3 mW, and an irradiation time was preferably controlled in the range of 8 s to 15 s. The irradiation site and power of the laser were fixed, and the polarization direction of the laser was adjusted through an HWP to make fusiform nano-pillars with different orientations grow at the same site, such that a spiral chiral nanostructure obtained from superposition of the fusiform nano-pillars with different orientations.
[0101] 4) Laser Polarization-Induced Growth of Platinous Oxide Pillars to Form a Chiral/Complex Pattern
[0102] The 446 nm linearly polarized light was converted into radially polarized light, angularly polarized light, and mixed polarized light using a vortex plate, and then focused on a surface of the silicon substrate prepared in 1) through a 100× objective lens (numerical aperture: 0.8) for irradiation. An irradiation power could be adjusted in a range of 4 mW to 6 mW and an irradiation time could be adjusted in a range of 60 s to 90 s to finally form different chiral/complex patterns on the silicon substrate.
[0103] Specifically, in Example 2, a 20 mmol/L potassium tetrachloroplatinate solution was used. The sample obtained in 1) was placed under a microscope, and linearly polarized and circularly polarized lasers (with a wavelength of 446 nm) each were used for irradiation to obtain a test sample group 4.sup.#.
[0104] The sample obtained in 1) was placed under a microscope, a laser with a wavelength of 446 nm was used for irradiation, and the polarization direction of the laser was changed (0°, 45°, 90°, and 180°) to obtain a test sample group 5.sup.#.
[0105] The sample obtained in 1) was placed under a microscope, a laser with a wavelength of 446 nm was used for irradiation, and the polarization direction of the laser was changed (0°, 120°, and 240°) to conduct irradiation multiple times at the same site to obtain a test sample group 6.sup.#.
[0106] The sample obtained in 1) was placed under a microscope, the 446 nm linearly polarized light was converted into radially polarized light, angularly polarized light, and mixed polarized light with a vortex plate, and then the potassium tetrachloroplatinate solution was irradiated with these three kinds of polarized light to obtain a test sample group 7.sup.#.
[0107] SEM images of the obtained platinous oxide nanostructure samples (No. 4-7.sup.#) were shown in
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[0112] The above examples merely illustrate the technical solutions of the present disclosure. The method for laser-induced growth of nano-units to form oriented, chiral, and complex structures involved in the present disclosure is not only limited to contents described in the above examples, but is subject to a scope defined by the claims. Any modifications, supplementations, or equivalent replacements made by a person skilled in the part based on the examples shall fall within the protection scope of the present disclosure.