CN114654083A - Method for manufacturing and assembling alloy nanoparticles into colored patterns by utilizing laser thermal induction - Google Patents
Method for manufacturing and assembling alloy nanoparticles into colored patterns by utilizing laser thermal induction Download PDFInfo
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- CN114654083A CN114654083A CN202210386655.1A CN202210386655A CN114654083A CN 114654083 A CN114654083 A CN 114654083A CN 202210386655 A CN202210386655 A CN 202210386655A CN 114654083 A CN114654083 A CN 114654083A
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- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/08—Devices involving relative movement between laser beam and workpiece
- B23K26/082—Scanning systems, i.e. devices involving movement of the laser beam relative to the laser head
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- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
- B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
- B23K26/062—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam
- B23K26/0622—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam by shaping pulses
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
- B23K26/362—Laser etching
Abstract
The invention relates to a method for manufacturing and assembling alloy nano particles into a colored pattern by utilizing laser thermal induction, wherein a single-layer alloy nano film or at least two layers of metal nano films on a substrate are scanned point by using laser with the power of 150-200 mW, the laser power is adjusted point by point, alloy nano particles with the particle size of 5-40 nm and the distance of 5-100 nm can be prepared, and the alloy nano particles are induced in situ to be assembled into the colored pattern. The method can accurately assemble the alloy nano particles on the surface of the substrate while forming the alloy nano particles to form colored patterns capable of adding information, is suitable for manufacturing and assembling large-area alloy nano particles, does not need a template, is simple to operate, high in controllability, green, efficient and pollution-free, and has clear colored patterns, few defects and higher resolution.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and relates to a method for manufacturing and assembling alloy nano particles into colored patterns by utilizing laser thermal induction.
Background
Currently, the related applications of nanostructures as coding materials have been developed in a variety of fields, such as biomolecule detection and analysis, clinical diagnosis and tracking, food quality and safety assessment, anti-counterfeiting, and forensic marking. Since the volume of the nanoparticles is very small, encoding using the nanoparticles may have advantages of high density, high cryptology, and high sensitivity.
With the continuous progress of nanotechnology, nanoparticles can be prepared by various methods, such as wet chemical method, mechanical grinding method or liquid laser irradiation method, but the above preparation methods mostly prepare nanoparticles from solution, which causes many limitations in encoding application. For example, for producing self-assembled nanoparticle arrays using chemical processes, while the diameter of the nanoparticles can be adjusted by selecting reactants and controlling reaction conditions, control of the inter-particle distance needs to be achieved by other modifying molecules during nanoparticle assembly; dielectric swallow et al (DOI:10.16152/j. cnki. xdxbzr.2016-03-012) self-assemble silver nanoparticles on gold surface by chemical plating method by using organic molecules cetyl mercaptan and 1, 10-decanedithiol as modifying molecules, to obtain regular and ordered patterned silver nanoparticle monolayer, which easily brings interference signal, thus affecting further application of self-assembled product; and when large-area assembly is involved, the chemical process often faces the problem that it is difficult to accurately control the array, at present, it is very difficult to realize particle self-assembly in the range of hundred nanometers by using the chemical process, and the method is easy to generate structural defects and destroy the integrity of the array, and finally affects the patterning effect.
In the application fields of plasma, catalysis and the like, the requirement of directly forming a nanoparticle array on a dry substrate is often met, and the self-assembly of nanoparticles and patterning are often realized by utilizing a photoetching method; CN103820826A discloses a preparation method of a morphology-controllable silver nanosheet assembly structure array and application of a product thereof, the method comprises the steps of firstly steaming gold on an inert conductive substrate, then coating a positive photoresist on the inert conductive substrate and drying to obtain the inert conductive substrate coated with a positive photoresist and a gold film, then covering a photoetching plate with ordered array light-transmitting patterns on the inert conductive substrate, and sequentially carrying out ultraviolet exposure, developing rinsing and drying treatment to obtain the inert conductive substrate coated with the positive photoresist and the gold film with the ordered array light-transmitting patterns, and then taking the inert conductive substrate as a positive electrode, placing the inert conductive substrate in a silver electrolyte and standing to obtain the morphology-controllable silver nanosheet assembly structure array; however, the photolithography process requires the intervention of a template, and is complex in process and flow, so that the efficiency is low, the price is high, and the large-scale application is difficult to realize.
In addition to the above problems, it is difficult to precisely assemble nanoparticles with different sizes and spacings into a specific pattern structure in the same period of time in both of the above methods. Therefore, there is still a need to develop a simple and convenient nanoparticle patterning assembly method, which can realize highly controllable patterning assembly of nanoparticles with different sizes and spacing on a larger size scale.
Disclosure of Invention
In view of the problems of complex nanoparticle assembly process, poor controllability and the like in the prior art, the present invention aims to provide a method for manufacturing and assembling alloy nanoparticles into a colored pattern by using laser thermal induction, wherein a single layer of metal nano-film or at least two layers of metal nano-films on a substrate are scanned point by using a laser with a power of 150-200 mW, and the laser power is adjusted point by point, so that the alloy nanoparticles can be manufactured and assembled into the colored pattern. The method can accurately assemble the alloy nano particles on the surface of the substrate while forming the alloy nano particles to form the colored pattern capable of adding information, is suitable for manufacturing and assembling large-area alloy nano particles, does not need a template, is simple to operate, high in controllability, green, efficient and pollution-free, and has clear colored pattern, few defects and higher resolution.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for producing and assembling alloy nanoparticles into a colored pattern using laser thermal induction, the method comprising the steps of:
(1) preparing a nano film on a substrate; the nano film comprises a single-layer alloy nano film and/or at least two layers of metal nano films;
(2) scanning the nano film in the step (1) point by using laser, adjusting the laser power point by point according to the gray value change of a target pattern, and manufacturing and assembling alloy nano particles into a colored pattern; the adjusting range of the laser power is 150-200 mW.
When the alloy nano-film is subjected to scanning thermal induction by using laser direct writing, the nano-film is heated and dehumidified under the irradiation of laser to be changed into a molten thermodynamically unstable state, the complete nano-film is finally split into small liquid drops with a certain centering distance under the competitive action of surface tension and intermolecular force, and the small liquid drops are condensed to form nano-particles; the invention can control the grain size and the spacing of the alloy nano particles by changing the laser power, and the arrays formed by the alloy nano particles with different grain sizes and spacings have different absorption and reflection capacities on light waves, thereby presenting the color and the brightness which are distinguished from the nano film in a macroscopic view; it is worth explaining that the nanoparticle arrays with the same component can present the same color, but have different brightness and saturation due to different particle sizes and spacing sizes of the nanoparticles, so that the invention can assemble the alloy nanoparticle arrays with different brightness and saturation into colored patterns by adjusting the laser power point by point in the point-by-point scanning process, and the obtained colored patterns are clear, have few defects and have higher resolution, thereby effectively realizing surface coding regulation and additional information; the method is suitable for manufacturing and assembling large-area alloy nanoparticles, does not need a template, is simple to operate, has high controllability, is green, efficient and pollution-free.
The nano film in the step (1) can be a single-layer metal alloy nano film, such as a single-layer Ag/Cu alloy film; the nano-particles prepared by using any one of the nano-films in the invention are alloy nano-particles, and the components of the alloy nano-particles are independent of the lamination sequence in the nano-films.
The specific power value of the laser power at each scanning point in the step (2) is determined by the gray value of a pixel point corresponding to the pre-written pattern, and the gray value range can be automatically matched with the set adjustment range of the laser power through a system algorithm, the method is set in a mode that the maximum gray value is matched with the maximum laser power, the laser power corresponding to the pixel point with the gray value of 0 is 0mW, namely, the position with the gray value of 0 is not subjected to laser scanning; in addition, the density of the scanning points is determined by the density of the pixel points of the pre-written pattern.
In the step (2), the laser power is adjusted in a range of 150 to 200mW, for example, 150mW, 155mW, 160mW, 165mW, 170mW, 175mW, 180mW, 185mW, 190mW, 195mW, or 200mW, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
The invention influences the energy of the laser beam by changing the laser power, and further influences the action process of the laser beam and the nano film, and realizes the preparation of nano particles with different particle sizes and intervals.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferred embodiment of the present invention, the material of the nano thin film in step (1) includes a combination of at least two of Au, Ag, Cu, Al or Co, and typical but non-limiting examples of the combination include a combination of Au and Ag, a combination of Au and Cu, a combination of Au and Al, a combination of Au and Co, a combination of Ag and Cu, a combination of Ag and Al, a combination of Ag and Co, a combination of Cu and Al, a combination of Cu and Co, a combination of Al and Co, and the like; for example, a combination of Au and Ag may be constructed as a single-layer Au/Ag alloy thin film, or a double-layer metal nano thin film composed of an Au nano thin film and a Cu nano thin film in any order of lamination, and a person skilled in the art may construct a combination of at least two of Au, Ag, Cu, Al, or Co as a single-layer alloy nano thin film or at least two-layer metal nano thin film according to actual needs and should be consistent with the present invention.
As a preferable technical scheme of the invention, in the at least two layers of metal nano films in the step (1), the thickness of each layer is at least 2 nm.
Preferably, the total thickness of the nano-film in step (1) is 4 to 50nm, such as 4nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm or 50nm, but not limited to the recited values, and other values not recited in the above range are also applicable.
When the nano film in the step (1) is at least two layers of metal nano films, the proportion of the content of each component in the obtained alloy nano particles can be adjusted by adjusting the thickness of each layer, but the thickness of each layer is at least more than 2nm, and the requirement that the total thickness of the nano film meets the requirement of 4-50 nm when at least two layers of metal nano films are adopted is emphasized; specifically, if the thickness of each layer is less than 2nm, so that the total thickness of the metal nano-film is less than 4nm, the laser-induced pattern may be less effective due to the poor film-forming property of the film; if the thickness of only one metal layer in the metal nano-film is less than 2nm, the content of the metal component in the alloy nano-particles may be too low to be detected due to the mass loss caused in the laser-induced process.
As a preferred technical scheme of the invention, the substrate in the step (1) comprises any one or a combination of at least two of a glass sheet, a silicon sheet or a quartz sheet, preferably a glass sheet, and typical but non-limiting examples of the combination comprise a combination of a glass sheet and a silicon sheet, a combination of a glass sheet and quartz or a combination of a silicon sheet and quartz.
As a preferred technical solution of the present invention, the method for preparing the nano thin film in step (1) includes any one or a combination of at least two of magnetron sputtering, thermal evaporation or ion sputtering, preferably magnetron sputtering, and typical but non-limiting examples of the combination include a combination of magnetron sputtering and thermal evaporation, a combination of magnetron sputtering and ion sputtering, or a combination of thermal evaporation and ion sputtering.
In a preferred embodiment of the present invention, the gradation writing level of the laser beam in the step (2) is 8 to 24 bits, for example, 8 bits, 10 bits, 12 bits, 14 bits, 16 bits, 18 bits, 20 bits, 22 bits, or 24 bits, but the gradation writing level is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
Preferably, the wavelength of the laser in the step (2) is 500-595 nm.
The laser used in the invention is selected from lasers in yellow-green light wave band (500-595 nm), the typical laser wavelength is 532nm, and lasers in other wavelengths in the yellow-green light wave band also include 543nm, 558nm or 561nm, but not limited to the values listed, and other values in the above range are also applicable to the invention.
Preferably, the frequency of the laser in step (2) is 250 to 1000Hz, such as 250Hz, 300Hz, 400Hz, 500Hz, 600Hz, 700Hz, 800Hz, 900Hz, or 1000Hz, but not limited to the values listed, and other values not listed in the above range are also applicable.
Preferably, the pulse width of the laser in step (2) is 30-3000 ns, such as 30ns, 100ns, 500ns, 1000ns, 1500ns, 2000ns, 2500n or 3000ns, but not limited to the listed values, and other values in the above range are also applicable.
As a preferred technical solution of the present invention, the point-by-point scanning manner in step (2) includes raster point-by-point scanning.
Preferably, the speed of the point-by-point scanning in the step (2) is 0.1-30 μm s-1For example 0.1 μm · s-1、0.5μm·s-1、1μm·s-1、5μm·s-1、10μm·s-1、15μm·s-1、20μm·s-1、25μm·s-1Or 30 μm · s-1And the like, but are not limited to the recited values, and other values not recited within the above numerical ranges are also applicable.
Preferably, the accuracy of the positioning of the point-by-point scanning in step (2) is 1 to 5nm, such as 1nm, 1.5nm, 2nm, 2.5nm, 3nm, 3.5nm, 4nm, 4.5nm or 5nm, but not limited to the recited values, and other values not recited in the above range of values are also applicable.
In a preferred embodiment of the present invention, the alloy nanoparticles in step (2) have a particle size of 5 to 40nm, for example, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm or 40nm, and a pitch of 5 to 100nm, for example, 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm or 100nm, but the invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
As a preferable technical scheme of the invention, the size specification of the colored pattern in the step (2) is more than or equal to 20 mu m multiplied by 20 mu m; for example, 20. mu. m.times.20. mu.m, 30. mu. m.times.20. mu.m, 100. mu. m.times.100. mu.m, 140. mu. m.times.120. mu.m, or 200. mu. m.times.200. mu.m, etc., but the numerical values are not limited to the above-mentioned values, and other numerical values not listed in the above-mentioned numerical range are also applicable.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) preparing a nano film with the total thickness of 4-50 nm on a substrate; the nano film comprises a single-layer alloy nano film and/or at least two layers of metal nano films; the material of the nano film comprises the combination of at least two of Au, Ag, Cu, Al or Co; in the at least two layers of metal nano films, the thickness of each layer is at least 2 nm; the substrate comprises any one or a combination of at least two of a glass sheet, a silicon sheet or a quartz sheet; the method for preparing the nano film comprises any one or combination of at least two of magnetron sputtering, thermal evaporation or ion sputtering;
(2) setting the gray scale writing level of laser to be 8-24 bit, the wavelength to be 500-595 nm, the frequency to be 250-1000 Hz, and the pulse width to be 30-3000 ns, and using the laser to perform the step (1)The nano film is scanned point by point, the scanning mode comprises raster point by point scanning, and the scanning speed is 0.1-30 mu m.s-1The positioning precision of the point-by-point scanning is 1-5 nm; adjusting the laser power point by point in the process of scanning point by point according to the gray value change of the target pattern, and manufacturing and assembling alloy nanoparticles into a colored pattern; the adjusting range of the laser power is 150-200 mW; the particle size of the alloy nano particles is 5-40 nm, and the distance between the alloy nano particles is 5-100 nm; the size specification of the colored pattern is more than or equal to 20 mu m multiplied by 20 mu m.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) according to the invention, alloy nanoparticles with different sizes and intervals can be prepared by utilizing a mode of dehumidifying a laser direct-writing heat-induced nano film and adjusting the laser power point by point during scanning, and the alloy nanoparticles are accurately assembled on the surface of a substrate to form a colored pattern capable of adding information, so that the obtained colored pattern is clear, has few defects and has higher resolution;
(2) the method is suitable for manufacturing, assembling and patterning the alloy nanoparticles with larger size and specification, does not need a template, has high controllability, has the advantages of greenness, high efficiency, no pollution and simple operation, and has great application potential in the aspect of realizing the coding field with high safety and high resolution.
Drawings
FIG. 1 is an optical micrograph of a colored pattern A obtained in example 1;
FIG. 2 is a scanning electron microscope photograph of a colored pattern A obtained in example 1, in a frame indicated by an arrow;
FIG. 3 is an optical micrograph of a colored pattern B obtained in example 2;
FIG. 4 is a spectrum of light absorption of the colored pattern C obtained in examples 3-6 and the nano-film without laser heat induction;
FIG. 5 is a scanning electron microscope photograph of the resulting colored pattern C of examples 3-6;
FIG. 6 is an optical micrograph of a colored pattern A obtained in examples 7 to 10;
FIG. 7 is an optical micrograph of a colored pattern A obtained in comparative example 1;
FIG. 8 is a scanning electron microscope photograph of a colored pattern A obtained in comparative example 1 at the frame indicated by the arrow.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The present embodiment provides a method for fabricating and assembling nanoparticles into a colored pattern using laser thermal induction, the method comprising the steps of:
(1) using magnetron sputtering, firstly preparing an Ag nano layer with the thickness of 15nm on one side of a glass sheet, and then preparing a Cu nano layer with the thickness of 15nm on one side of the Ag nano layer to form a double-layer metal nano film with the total thickness of 30 nm;
(2) importing a pre-written pattern A into a system, setting the specification size of the pattern to be 140 Mum multiplied by 120 Mum, and generating a written file A, wherein the written file A comprises a scanning path, scanning points and laser power corresponding to each scanning point; then, the gray scale writing level of the laser was set to 16bit, the wavelength was 558nmm, the frequency was 625Hz, the pulse width was 3000ns, and the scanning speed was set to 15 μm · s-1And (2) controlling the laser to execute the scanning path by using a PZT focusing actuator, scanning the double-layer metal nano film in the step (1) point by point, adjusting the laser power at each scanning point by using an acousto-optic modulator, and enabling the adjustment range of the laser power to be 150-200 mW, so that the nano particles are prepared and are assembled into the colored pattern A.
Example 2
The present embodiment provides a method for fabricating and assembling nanoparticles into a colored pattern using laser thermal induction, the method comprising the steps of:
(1) preparing a single-layer Ag/Cu alloy nano film with the thickness of 50nm on one side of a glass sheet by using ion sputtering;
(2) importing a pre-written pattern B into a system, setting the specification size of the pattern to be 100 Mum multiplied by 100 Mum, and generating a written file B, wherein the written file B comprises scanning paths, scanning points and laser power corresponding to each scanning point; then, the gray scale writing level of the laser is set to 24bit, the wavelength is 532nm, the frequency is 1000Hz, the pulse width is 3000ns, and the scanning speed is set to 1 μm s-1And (2) controlling the laser to execute the scanning path by using a PZT focusing actuator, scanning the single-layer Ag/Cu alloy nano film in the step (1) point by point, setting the laser power of a scanning point corresponding to a pixel point with the gray value of 0 in the pre-written pattern B to be 0mW, and setting the laser power to be 200mW by using an acousto-optic modulator for a scanning point corresponding to a pixel point with the gray value of not 0, so that the nano particles are prepared and are assembled into the colored pattern B at the same time.
Example 3
The present embodiment provides a method for fabricating and assembling nanoparticles into a colored pattern using laser thermal induction, the method comprising the steps of:
(1) preparing a Cu nano layer with the thickness of 2nm on one side of a glass sheet by using thermal evaporation, and then preparing an Ag nano layer with the thickness of 2nm on one side of the Cu nano layer to form a double-layer metal nano film with the total thickness of 4 nm;
(2) importing a square pre-written pattern C into a system, setting the specification size of the pattern to be 20 Mum multiplied by 20 Mum, and generating a written file C, wherein the written file C comprises scanning paths, scanning points and laser power corresponding to each scanning point; then, the gray scale writing level of the laser is set to 8bit, the wavelength is 532nm, the frequency is 250Hz, the pulse width is 30ns, and the scanning speed is set to 0.5 Mum.s-1And (2) controlling the laser to execute the scanning path by using a PZT focusing actuator, scanning the double-layer metal nano film in the step (1) point by point, and keeping the laser power at 150mW at each scanning point by using an acousto-optic modulator, so as to prepare nano particles and assemble the nano particles into a square colored pattern C.
Example 4
This example provides a method for fabricating and assembling nanoparticles into a colored pattern using laser thermal induction, which is identical to example 3 except that the laser power is maintained at 160mW at each scanning point using an acousto-optic modulator in step (2).
Example 5
This example provides a method for fabricating and assembling nanoparticles into a colored pattern using laser thermal induction, which is identical to example 3 except that the laser power was maintained at 170mW at each scanning point using an acousto-optic modulator in step (2).
Example 6
This example provides a method for fabricating and assembling nanoparticles into a colored pattern using laser thermal induction, which is identical to example 3 except that the laser power is maintained at 180mW at each scanning point using an acousto-optic modulator in step (2).
Example 7
The present example provides a method for fabricating and assembling nanoparticles into a colored pattern using laser thermal induction, which is identical to example 1 except that the pattern size is set to 30 μm × 20 μm in step (1) and the laser power is adjusted to a range of 150 to 180mW in step (2).
Example 8
The present example provides a method for fabricating and assembling nanoparticles into a colored pattern using laser thermal induction, which is identical to example 1 except that the pattern size is set to 30 μm × 20 μm in step (1) and the laser power is adjusted to a range of 150 to 190mW in step (2).
Example 9
The present example provides a method for fabricating and assembling nanoparticles into a colored pattern using laser thermal induction, which is identical to example 1 except that the pattern size is set to 30 μm × 20 μm in step (1) and the laser power is adjusted to a range of 150 to 160mW in step (2).
Example 10
The present example provides a method for fabricating and assembling nanoparticles into a colored pattern using laser thermal induction, which is identical to example 1 except that the pattern size is set to 30 μm × 20 μm in step (1) and the laser power is adjusted to a range of 150 to 170mW in step (2).
Comparative example 1
The present comparative example provides a method for fabricating and assembling nanoparticles into a colored pattern using laser thermal induction, the method comprising the steps of:
(1) preparing an Ag nano layer with the thickness of 7nm on one side of a glass sheet by magnetron sputtering, and preparing a Cu nano layer with the thickness of 3nm on one side of the Ag nano layer to form a double-layer metal nano film with the total thickness of 10 nm;
(2) importing a pre-written pattern A into a system, setting the specification size of the pattern to be 140 Mum multiplied by 120 Mum, and generating a written file A, wherein the written file A comprises a scanning path, scanning points and laser power corresponding to each scanning point; then, the gray scale writing level of the laser is set to 24bit, the wavelength is 561nmm, the frequency is 1000Hz, the pulse width is 3000ns, and the scanning speed is set to 30 μm · s-1And (2) controlling the laser to execute the scanning path by using a PZT focusing actuator, scanning the double-layer metal nano film in the step (1) point by point, adjusting the laser power at each scanning point by using an acousto-optic modulator, and enabling the adjustment range of the laser power to be 200-230 mW, so that the nano particles are prepared and are assembled into the colored pattern A.
Fig. 1 is an optical micrograph of the colored pattern a obtained in example 1, and it can be seen that the obtained colored pattern a is a wolf head pattern of 140 μm × 120 μm, and the change of the light and shade intensity of each scanning point in the pattern is obvious, so that the wolf hair can be clearly shown, which verifies that the assembling of the nanoparticles by using the method of the present invention has high flexibility and controllability, and the obtained pattern has few defects and high resolution;
FIG. 2 is a scanning electron microscope image of a square frame indicated by an arrow in the colored pattern A obtained in example 1, which contains scanning sites scanned with different laser powers, and the nanoparticles of the scanning sites exhibit different particle sizes and spacing sizes, so that the nanoparticles in a plurality of scanning site areas are combined and exhibit the variation of "density" in the image;
fig. 3 is an optical micrograph of the colored pattern B obtained in example 2, and it can be seen that the obtained colored pattern B is a two-dimensional code pattern at 100 μm × 100 μm, which can be scan-verified, and the obtained information is "National Center for nanoscience and technology";
examples 3 to 6 each gave a colored pattern C of 20 μm × 20 μm in a square geometry, which was obtained by controlling the laser power at all scanning points in step (2) to a constant value, but the constant laser power values used in examples 3 to 6 were successively increased to 150mW, 160mW, 170mW and 180mW, respectively, and as the power was increased, the square geometry finally obtained was blue, but the brightness gradually decreased and the color gradually deepened; FIG. 4 is an absorption spectrum of the colored pattern C obtained in examples 3 to 6 and the double-layered metal nano-film used in step (1); wherein a is the result of example 3, b is the result of example 4, c is the result of example 5, d is the result of example 6, and e is the absorption curve of the double-layered metal nano-film used in step (1) of examples 3-6 without laser heat induction; it is obvious from the absorption graph that the absorption curves obtained by the nano-particles prepared by different laser powers are different, and the absorption peak value within 600nm is obviously shifted, so that the change of the color and brightness degree of the obtained pattern can be observed macroscopically;
FIG. 5 is a scanning electron micrograph of a colored pattern C obtained in examples 3-6, wherein a is taken from example 3, b is taken from example 4, C is taken from example 5, and d is taken from example 6; the particle size and the distance of the nano particles prepared by different laser powers are changed, the difference is obvious, the distance between the nano particles obtained by using smaller laser power is smaller, the stacking density is larger, and the distance between the nano particles obtained by using smaller laser power can be effectively increased when the laser power is increased;
FIG. 6 is an optical micrograph of the resulting colored pattern A of examples 7-10, wherein a is taken from example 7, b is taken from example 8, c is taken from example 9, and d is taken from example 10; compared with the embodiment 1, the embodiments 7 to 10 assemble the nanoparticles into the wolf head pattern under the smaller dimension specification, at this time, the adjustment range of the laser power affects the definition and resolution of the pattern, the larger the adjustment range of the laser power is, the larger the difference between the size and the spacing of the nanoparticles formed in the scanning point area is, so that a slight difference can be shown in the pattern, for example, the adjustment range of the laser power is 150 to 180mW in the embodiment 7, and the adjustment range of the laser power is 150 to 190mW in the embodiment 8, so that the wolf head patterns obtained by the two are clearer and more complete, while the wolf head patterns obtained by the embodiments 9 and 10 are more fuzzy, and the loss of part of the pattern details exists;
FIG. 7 is an optical micrograph of a colored pattern A obtained in comparative example 1, although it can be seen that the obtained colored pattern A is a wolf-shaped pattern of 140 μm × 120 μm, but the change of the light and shade intensity of each scanning point in the pattern is not obvious, and the detail features of the obtained pattern are blurred because the comparative example 1 adopts an excessively high laser power adjustment range of 200-230 mW, under high laser power, the metal nano-film can cause aging reaction of alloy nano-particles during the cooling process after being heated and melted to form nano-particles, FIG. 8 is a scanning electron microscope image of a square frame indicated by an arrow in FIG. 7, and it can be seen from the image that small particles gradually decrease and large particles continuously increase due to aging, so that it is difficult to accurately control the particle size and the distance of the alloy nano-particles obtained at each scanning point, and finally the assembled pattern is blurred, the resolution is severely reduced;
in summary, the present invention utilizes a laser direct writing thermal induced alloy nano-film dewetting manner, and adjusts the laser power point by point during scanning, so as to prepare alloy nano-particles with different sizes and spacings, and simultaneously, precisely assemble the alloy nano-particles on the surface of the substrate to form a colored pattern capable of adding information, wherein the obtained colored pattern is clear, has few defects, and has high resolution; the method is suitable for manufacturing, assembling and patterning the alloy nanoparticles with larger size and specification, does not need a template, has high controllability, has the advantages of greenness, high efficiency, no pollution and simple operation, and has great application potential in the aspect of realizing the coding field with high safety and high resolution.
The present invention is described in detail with reference to the above embodiments, but the present invention is not limited to the above detailed structural features, that is, the present invention is not meant to be implemented only by relying on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that, in the above embodiments, the various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present invention does not separately describe various possible combinations.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A method for fabricating and assembling alloy nanoparticles into a colored pattern using laser thermal induction, the method comprising the steps of:
(1) preparing a nano film on a substrate; the nano film comprises a single-layer alloy nano film and/or at least two layers of metal nano films;
(2) scanning the nano film in the step (1) point by using laser, adjusting the laser power point by point according to the gray value change of a target pattern, and manufacturing and assembling alloy nano particles into a colored pattern; the adjusting range of the laser power is 150-200 mW.
2. The method of claim 1, wherein the material of the nano-film of step (1) comprises a combination of at least two of Au, Ag, Cu, Al, or Co.
3. The method according to claim 1 or 2, wherein in the at least two layers of metal nanofilms of step (1), each layer has a thickness of at least 2 nm;
preferably, the total thickness of the nano film in the step (1) is 4-50 nm.
4. The method of any one of claims 1 to 3, wherein the substrate of step (1) comprises any one or a combination of at least two of a glass sheet, a silicon sheet or a quartz sheet, preferably a glass sheet.
5. The method according to any one of claims 1 to 4, wherein the method for preparing the nano thin film in step (1) comprises any one or a combination of at least two of magnetron sputtering, thermal evaporation or ion sputtering, preferably magnetron sputtering.
6. The method according to any one of claims 1 to 5, wherein the gray scale writing level of the laser in the step (2) is 8 to 24 bits;
preferably, the wavelength of the laser in the step (2) is 500-595 nm;
preferably, the frequency of the laser in the step (2) is 250-1000 Hz;
preferably, the pulse width of the laser in the step (2) is 30-3000 ns.
7. The method according to any one of claims 1-6, wherein the point-by-point scanning of step (2) comprises raster point-by-point scanning;
preferably, the speed of the point-by-point scanning in the step (2) is 0.1-30 μm s-1；
Preferably, the positioning precision of the point-by-point scanning in the step (2) is 1-5 nm.
8. The method according to any one of claims 1 to 7, wherein the alloy nanoparticles in the step (2) have a particle size of 5 to 40nm and a pitch of 5 to 100 nm.
9. The method according to any one of claims 1 to 8, wherein the size specification of the colored pattern of step (2) is not less than 20 μm x 20 μm.
10. A method according to any one of claims 1-9, characterized in that the method comprises the steps of:
(1) preparing a nano film with the total thickness of 4-50 nm on a substrate; the nano film comprises a single-layer alloy nano film and/or at least two layers of metal nano films; the material of the nano film comprises the combination of at least two of Au, Ag, Cu, Al or Co; in the at least two layers of metal nano films, the thickness of each layer is at least 2 nm; the substrate comprises any one or a combination of at least two of a glass sheet, a silicon sheet or a quartz sheet; the method for preparing the nano film comprises any one or the combination of at least two of magnetron sputtering, thermal evaporation and ion sputtering;
(2) setting the gray scale writing level of laser to be 8-24 bit, the wavelength to be 500-595 nm, the frequency to be 250-1000 Hz and the pulse width to be 30-3000 ns, using the laser to perform point-by-point scanning on the nano film in the step (1), wherein the point-by-point scanning mode comprises grating point-by-point scanning, and the point-by-point scanning speed is 0.1-30 Mum.s-1The positioning precision of the point-by-point scanning is 1-5 nm; adjusting the laser power point by point in the process of scanning point by point according to the gray value change of the target pattern, and manufacturing and assembling alloy nanoparticles into a colored pattern; the adjusting range of the laser power is 150-200 mW; the alloy nanoparticlesThe particle size of the particles is 5-40 nm, and the distance is 5-100 nm; the size specification of the colored pattern is more than or equal to 20 mu m multiplied by 20 mu m.
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