CN107417945B - Micro-nano ordered array structure and preparation method thereof - Google Patents
Micro-nano ordered array structure and preparation method thereof Download PDFInfo
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Abstract
The invention provides a micro-nano ordered array structure and a preparation method thereof, wherein the preparation method comprises the following steps: A) assembling a monolayer colloid particle film on the surface of a block copolymer film, wherein the block copolymer can generate phase separation; B) removing the block copolymer which is not shielded by the colloid particles by etching by taking the assembled colloid particles as a mask plate; C) and removing the colloidal particles on the surface of the etched block copolymer film to obtain the substrate with the micro-nano ordered array structure. The method provided by the invention can be used for preparing the substrate with the micro-nano ordered array structure, and the micro-nano ordered array structure has higher resolution, so that the method has good application prospects in the fields of biological detection, cell behavior research, microelectronics and the like. The method is simple, easy to operate, easy to realize and good in repeatability.
Description
Technical Field
The invention relates to the field of surface patterning, in particular to a micro-nano ordered array structure and a preparation method thereof.
Background
The multi-scale ordered nanostructure is widely concerned by researchers in recent years, and has an ordered structure with nanoscale and micron/submicron scale, so that the multi-scale ordered nanostructure presents unique advantages in biological detection, cell spreading, differentiation, research of proliferation behaviors, biosensors, biochips, microelectronic devices and construction of super-hydrophobic and super-hydrophilic surfaces. The introduction of more detailed nano-patterned structures in the large-scale ordered patterned micro-regions facilitates better control of the behavior in each small micro-region. As in the biological field, the ordered structure in micrometer scale is beneficial for us to study the growth adhesion behavior of single cells, and the Nano-lattice in each micro-region can allow us to more finely adjust the type, orientation, density, order degree and the like of extracellular factors in patterning, so as to provide a very good platform for better understanding the relationship between cell behavior and extracellular factors (Nano lett.2015,15,1457; Nano lett.2014,14,5539; Nano lett.201313, 5619), and also allow us to control cell behavior through surface modification (ACS Nano,2012,6, 7227). Due to the matching of the size of the protein with a plurality of biological macromolecules, the ordered structure of the nanometer scale is also beneficial to controlling the orientation of the biological macromolecules (Angew chem. int.Ed.Engl.2008,47,9618) on the molecular level, such as the inactivation caused by the burying of the active center of the protein can be avoided, and the practical application of the protein in the fields of biosensor preparation, biochips and the like is facilitated.
Several different approaches have been tried to build multi-scale micro-nano ordered structures, for example, de-wetting of block copolymer films, although multi-level structures can be built, the island structures formed by de-wetting tend to be not uniform in size (Macromolecules 2012,45, 1492). Park proposes a method for controlling dewetting to prepare micro-nano structures, and obtains a structure with micro-nano scale simultaneously ordered (Advanced Materials 2008,20,522), however, the micro-scale is usually over ten microns. The simplest and most direct method is to combine self-assembled micelle solution of block copolymer with nano-imprinting, however, the method is limited by ink diffusion and the like in the nano-imprinting process, the patterning precision after imprinting is not high, and a regular array structure is difficult to form in each micro-area due to the limitation of the method.
Disclosure of Invention
In view of the above, the present invention provides a micro-nano ordered array structure and a preparation method thereof, and the preparation method provided by the present invention can prepare the micro-nano ordered array structure, and the array structure has wide applications in the biological field.
The invention provides a preparation method of a micro-nano ordered array structure, which comprises the following steps:
A) assembling a monolayer colloid particle film on the surface of a block copolymer film, wherein the block copolymer can generate phase separation;
B) removing the block copolymer which is not shielded by the colloid particles by etching by taking the assembled colloid particles as a mask plate;
C) and removing the colloidal particles on the surface of the etched block copolymer film to obtain the substrate with the micro-nano ordered array structure.
Preferably, the single-layer colloidal particle film in the step a) is prepared according to the following method:
the single-layer colloidal particle film was obtained by assembling a dispersion of colloidal particles, water, and an aqueous solution containing a surfactant.
Preferably, the step a) is specifically:
and (3) dewatering the surface of the block copolymer film, treating the block copolymer film by adopting plasma, and then assembling the block copolymer film and the single-layer colloidal particle film to obtain the assembled colloidal particles.
Preferably, the step a) is specifically:
and the surface of the segmented copolymer film is hydrophilic, and the segmented copolymer film is directly assembled with the single-layer colloid particle film to obtain the assembled colloid particles.
Preferably, the single-layered colloidal particle film is selected from a single-layered polystyrene colloidal particle film, a single-layered silica colloidal particle film, a single-layered polymethylmethacrylate colloidal particle film, or a single-layered metal colloidal particle film.
Preferably, the material of the block copolymer film is selected from polystyrene, polymethyl methacrylate, polystyrene-poly 4-vinylpyridine block copolymer, polystyrene-poly 2-vinylpyridine block copolymer, polydimethylsiloxane, polyethylene, polypropylene, polybutadiene, polyisoprene, polythiophene or polyfluorene.
Preferably, the block copolymer thin film further comprises, before being assembled with the single-layer colloidal particle film:
and complexing the segmented copolymer film with a metal precursor to obtain a metal precursor-complexed segmented copolymer film, and assembling the metal precursor-complexed segmented copolymer film with the single-layer colloidal particle film.
Preferably, the metal precursor is selected from metal salt compounds.
Preferably, the method further comprises, after removing the colloidal particles:
and complexing the product without the colloid particles with a metal precursor, and etching again to obtain the substrate with the micro-nano ordered array structure.
The invention provides a micro-nano ordered array structure, which is prepared by the preparation method of the technical scheme.
The invention provides a preparation method of a micro-nano ordered array structure, which comprises the following steps: A) assembling a monolayer colloid particle film on the surface of a block copolymer film, wherein the block copolymer can generate phase separation; B) removing the block copolymer which is not shielded by the colloid particles by etching by taking the assembled colloid particles as a mask plate; C) and removing the colloidal particles on the surface of the etched block copolymer film to obtain the substrate with the micro-nano ordered array structure. The method provided by the invention can be used for preparing the micro-nano ordered array structure, and the resolution of the provided micro-nano ordered array structure can reach 5-100 nm due to the phase separation based on the nano scale of the block copolymer. The micro-nano ordered array structure has the resolution of nano scale, so the micro-nano ordered array structure has good application prospect in the fields of biological detection, cell behavior research, microelectronics and the like. The method is simple, easy to operate, easy to realize and good in repeatability.
Drawings
FIG. 1 is a basic schematic diagram of a block copolymer film with a micro-nano ordered array structure prepared by the invention;
FIG. 2 is an atomic force microscope image of a block copolymer film with a micro-nano ordered array structure prepared in example 1 of the present invention;
FIG. 3 is an atomic force microscope image of a block copolymer film with a micro-nano ordered array structure prepared in example 2 of the present invention;
FIG. 4 is a scanning electron microscope image of a micro-nano ordered array structure of gold nanoparticles prepared in example 3 of the present invention;
FIG. 5 is a scanning electron microscope image of a micro-nano ordered array structure of gold nanoparticles prepared in example 4 of the present invention;
FIG. 6 is a scanning electron microscope image of a micro-nano ordered array structure of platinum nanoparticles prepared in example 5 of the present invention;
FIG. 7 is a scanning electron microscope image of a micro-nano ordered array structure of platinum nanoparticles prepared in example 6 of the present invention;
FIG. 8 is a scanning electron microscope image of a micro-nano ordered array structure of gold nanoparticles prepared in example 7 of the present invention;
FIG. 9 is a confocal laser microscopy image of a fluorescein isothiocyanate labeled protein array prepared in example 7 of the present invention.
Detailed Description
The invention provides a preparation method of a micro-nano ordered array structure, which comprises the following steps:
A) assembling a monolayer colloid particle film on the surface of a block copolymer film, wherein the block copolymer can generate phase separation;
B) removing the block copolymer which is not shielded by the colloid particles by etching by taking the assembled colloid particles as a mask plate;
C) and removing the colloidal particles on the surface of the etched block copolymer film to obtain the substrate with the micro-nano ordered array structure.
The method provided by the invention can be used for preparing the micro-nano ordered array structure, and the micro-nano ordered array structure has higher resolution, namely the resolution of nano scale (5-100 nm), so that the method has good application prospect in the fields of biological detection, cell behavior research, microelectronics and the like. The method is simple, easy to operate, easy to realize and good in repeatability. The micro-nano ordered array structure is a substrate with a micro-nano ordered array structure; in a specific embodiment of the invention, the micro-nano ordered array structure can be a block copolymer film with a micro-nano ordered array structure; the micro-nano ordered array structure can also be a micro-nano ordered array structure of metal nanoparticles.
The present invention assembles a single layer colloid particle film on the surface of a block copolymer film, and the block copolymer can generate phase separation. In the present invention, the single-layered colloidal particle film is preferably selected from a single-layered polystyrene colloidal particle film, a single-layered silica colloidal particle film, a single-layered polymethylmethacrylate colloidal particle film, or a single-layered metal colloidal particle film. In the present invention, the particle diameter of the colloidal particles in the single-layer colloidal particle film is preferably 200nm to 5 μm; in a specific embodiment of the present invention, the raw material of the single-layer colloidal particle film is specifically 250nm polystyrene colloidal particles, 1 μm polystyrene colloidal particles, 3.8 μm polystyrene colloidal particles, 1.9 μm polystyrene colloidal particles or 250nm silica colloidal particles. In the present invention, the single-layered colloidal particle film is preferably prepared according to the following method:
the single-layer colloidal particle film was obtained by assembling a dispersion of colloidal particles, water, and an aqueous solution containing a surfactant.
In the present invention, the dispersion of colloidal particles is preferably an aqueous dispersion of colloidal particles. The source of the dispersion of colloidal particles in the present invention is not particularly limited, and the dispersion of colloidal particles may be prepared by any method known to those skilled in the art, such as commercially available methods or self-preparation methods known to those skilled in the art. In the embodiment of the present invention, the aqueous dispersion of colloidal particles is preferably diluted with alcohol and sonicated to uniformly disperse the colloidal particles.
The invention preferably drops the dispersion liquid of colloid particles on the surface of the silicon chip, immerses the silicon chip in water and takes out the silicon chip; the volume ratio of the alcohol to the water is preferably 0.01 to 1: 1. The colloidal particles on the silicon wafer are transferred to the surface of water. And dripping the water solution containing the surfactant onto the surface of water, and extruding the colloidal particles to assemble under the action of surface tension to obtain the single-layer colloidal particle film. In the present invention, the surfactant in the surfactant-containing aqueous solution includes a cationic surfactant, an anionic surfactant, or a nonionic surfactant. In the present invention, the surfactant is preferably sodium dodecylbenzenesulfonate, sodium dodecylsulfate or sodium dioctyl sulfosuccinate.
In the present invention, the material of the block copolymer film is preferably selected from polystyrene, polymethyl methacrylate, polystyrene-poly 4-vinylpyridine block copolymer, polystyrene-poly 2-vinylpyridine block copolymer, polydimethylsiloxane, polyethylene, polypropylene, polybutadiene, polyisoprene, polythiophene or polyfluorene. In the invention, the molecular weight and the preparation condition of the block copolymer film can regulate and control the nanoscale ordered structure with the micro-nano ordered array structure. In the present invention, the molecular weight of the polystyrene-poly 4-vinylpyridine block copolymer is preferably from 1000g/mol to 100000 g/mol; the molecular weight of the polystyrene-poly 2-vinylpyridine block copolymer is preferably 2000g/mol to 400000 g/mol.
In the invention, the block copolymer film can be an ordered block copolymer monolayer micelle film obtained by spin coating, and can also be a copolymer film with an ordered phase separation structure obtained after annealing.
In the present invention, the step of preparing a block copolymer thin film by a spin coating method comprises:
dissolving the block copolymer to obtain a block copolymer solution;
carrying out constant temperature and cooling on the segmented copolymer solution to obtain a micelle solution;
and spin-coating the micelle solution to obtain the segmented copolymer film.
The block copolymer is dissolved to obtain a block copolymer solution. In the present invention, the block copolymer is preferably selected from polystyrene, polymethyl methacrylate, polystyrene-poly 4-vinylpyridine block copolymer, polystyrene-poly 2-vinylpyridine block copolymer, polydimethylsiloxane, polyethylene, polypropylene, polybutadiene, polyisoprene, polythiophene or polyfluorene. The solvent for dissolving the block copolymer in the present invention is not particularly limited as long as the block copolymer can be dissolved. In one embodiment of the present invention, the solvent dissolving the polystyrene-poly 4-vinylpyridine block copolymer is preferably o-xylene. In the present invention, the mass concentration of the block copolymer solution is preferably 0.3 to 0.6 wt%, and more preferably 0.5 wt%.
After the segmented copolymer solution is obtained, the segmented copolymer solution is subjected to constant temperature and cooling to obtain the micelle solution. The invention is preferably thermostated in an oven well known to the person skilled in the art; the constant temperature is preferably 50-90 ℃; the constant temperature time is preferably 2 to 10 hours. In one embodiment of the present invention, the polystyrene-poly 4-vinylpyridine block copolymer solution is preferably thermostatted at 80 ℃ for 3 h.
In the invention, if the surface of the block copolymer film is hydrophobic, the block copolymer film is treated by adopting plasma and then assembled with the single-layer colloidal particle film to obtain the assembled colloidal particles.
The invention preferably adopts oxygen plasma or air plasma for etching treatment; the power of the block copolymer film for etching treatment is preferably 5W-100W, and more preferably 18W; the pressure for etching the block copolymer film is preferably 5Pa to 50 Pa; the time for etching the block copolymer film is preferably 1 to 20s, and more preferably 9 to 11 s.
In the present invention, if the surface of the block copolymer film is hydrophilic, the block copolymer film is directly assembled with the single-layer colloidal particle film to obtain an assembled colloidal particle.
In the specific embodiment of the invention, the single-layer colloid particle film of the water-air interface is fished on the block copolymer film, and the moisture in the single-layer colloid particle film is volatilized for 2 to 4 hours at the temperature of 15 to 30 ℃.
The assembled colloid particles are used as a mask plate, and the block copolymer which is not shielded by the colloid particles is removed by etching. According to the invention, the block copolymer which is not shielded by the colloid particles is removed by etching preferably by adopting oxygen plasma; the present invention more preferably treats the block copolymer film with plasma in a direction perpendicular to the block copolymer film to etch away the block copolymer not masked by the colloidal particles. Meanwhile, the colloid particles can be etched to be smaller, and the size of the patterned area can be effectively changed along with the change of etching time. In the present invention, the time for removing the block copolymer not blocked by the colloidal particles by etching is preferably 60s to 150 s.
According to the invention, colloidal particles on the surface of the etched segmented copolymer film are removed, and the substrate with the micro-nano ordered array structure is obtained. The invention removes the colloid particles on the surface of the etched block copolymer film by an ultrasonic method. The present invention preferably performs sonication in deionized water. In the invention, the time of the ultrasonic treatment is preferably 5-10 s.
In the present invention, the block copolymer thin film preferably further comprises, before being assembled with the single-layer colloidal particle film:
and complexing the segmented copolymer film with a metal precursor to obtain a metal precursor-complexed segmented copolymer film, and assembling the metal precursor-complexed segmented copolymer film with the single-layer colloidal particle film. In the present invention, the metal precursor is present in the form of a polymer containing a metal precursor or a polymer capable of complexing a metal precursor; the polymer containing the metal precursor or the polymer capable of complexing the metal precursor is selected from polyferrocenyldimethylsilane, polyvinylpyridine, polyacrylic acid, polystyrene sulfonate or polyvinylamine. In the invention, the complexing time is preferably 8-15 min, and more preferably 10 min. In the present invention, the metal precursor is preferably selected from metal salt compounds; the metal salt compound is preferably selected from chloroauric acid, chloroplatinic acid, chloropalladic acid, ferric trichloride or silver nitrate.
In the invention, when the unmasked block copolymer is etched, the metal precursor is reduced into metal nanoparticles, and after colloid particles are removed, an array structure with the metal nanoparticles and the block copolymer alternately arranged periodically can be obtained. According to the invention, residual block copolymers are preferably cleaned by using a dimethylformamide solvent, so that a metal array structure with complementary patterns, namely a substrate with a micro-nano ordered array structure, is obtained.
In certain embodiments of the present invention, the removing of the colloidal particles further comprises:
and complexing the product without the colloid particles with a metal precursor, and etching again to obtain the substrate with the micro-nano ordered array structure. In some embodiments of the present invention, the substrate having the micro-nano ordered array structure is a micro-nano array structure of ordered metal nanoparticles. In the invention, the re-etching preferably adopts oxygen plasma; the power of the re-etching is preferably 50W; the pressure of the re-etching is preferably 10 Pa; the re-etching time is preferably 60 s.
In the invention, a schematic diagram of the preparation of the block copolymer film with the micro-nano ordered array structure is shown in figure 1, and figure 1 is a basic schematic diagram of the block copolymer film with the micro-nano ordered array structure prepared by the invention;
firstly, preparing a block copolymer film, then assembling colloid particles on the surface of the block copolymer film, and transferring the pattern of the colloid particles to the surface of the block copolymer film by using plasma.
Path a: and (3) obtaining a patterned block copolymer micelle microarray (A1) after the steps are carried out, further complexing a metal precursor in the block copolymer microarray, and combining with secondary plasma etching to obtain the micro-nano ordered array structure (A2) of the metal particles.
And a path B: pre-complexing a metal salt precursor in a segmented copolymer film before assembling colloidal particles, then assembling the colloidal particles, then operating according to the steps to obtain an array structure (B1) of patterned metal nanoparticles and segmented copolymer micelle colloid arrangement, and further washing away residual polymers by using a solvent to obtain a micro-nano ordered array structure (B2) of the metal particles.
The invention provides a preparation method of a micro-nano ordered array structure, which comprises the following steps: A) assembling a monolayer colloid particle film on the surface of a block copolymer film, wherein the block copolymer can generate phase separation; B) removing the block copolymer which is not shielded by the colloid particles by etching by taking the assembled colloid particles as a mask plate; C) and removing the colloidal particles on the surface of the etched block copolymer film to obtain the substrate with the micro-nano ordered array structure. The method provided by the invention can be used for preparing the micro-nano ordered array structure, and the micro-nano ordered array structure has higher resolution and nano-scale resolution, so that the method has good application prospects in the fields of biological detection, cell behavior research, microelectronics and the like. The method is simple, easy to operate, easy to realize and good in repeatability.
In order to further illustrate the present invention, the following will describe a micro-nano ordered array structure and a preparation method thereof in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Dissolving a polystyrene-poly 4-vinylpyridine segmented copolymer (molecular weight: 9.8 k-10 k) in a selective solvent o-xylene to prepare a 0.5 wt% solution, placing the prepared solution in an oven at 80 ℃ for 3h to promote the copolymer to be fully dissolved, then naturally cooling the solution to room temperature to obtain a milky micellar solution with Tyndall phenomenon and certain transparency, and cooling and stabilizing the micellar solution for 24h for use. And dripping 30 mu L of prepared micelle solution on a cleaned silicon wafer, and spin-coating to prepare the ordered copolymer monolayer micelle film. In order to promote the assembly of the colloidal particle membrane on the surface of the micelle membrane, the monolayer micelle membrane prepared in the first step is subjected to oxygen plasma etching (18W,50Pa,10s), and hydrophilic groups such as carboxyl groups and hydroxyl groups are introduced on the surface of the membrane, so that the surface of the micelle membrane becomes hydrophilic.
Preparing an aqueous solution of sodium dodecyl sulfate with the mass fraction of 1 wt%, diluting an aqueous dispersion of 1 mu m polystyrene colloidal particles with the mass fraction of 10 wt% to 5 wt% by using ethanol, and performing ultrasonic treatment in the aqueous solution for 5min to uniformly disperse the aqueous dispersion for later use. A well-cleaned glass petri dish (phi: 15cm) was prepared and charged with deionized water. A piece of cleaned 2cm × 2cm silicon wafer was picked up, and 15 μ L of the polystyrene colloidal particle dispersion was pipetted by a pipette and dropped on the surface of the silicon wafer until spread uniformly. Slowly immersing the silicon wafer paved with the colloidal particles into a surface dish filled with deionized water in a slightly inclined manner, and taking out the silicon wafer after the colloidal particles on the silicon wafer are basically and completely transferred to the surface of the aqueous solution when the silicon wafer is completely immersed. And (3) transferring 30 mu L of sodium dodecyl sulfate solution by using a liquid transfer gun, dropwise adding the sodium dodecyl sulfate solution on the surface of the aqueous solution, and extruding the colloidal particles under the action of surface tension for assembly to obtain a monolayer ordered colloidal particle array.
And fishing the colloid particle membrane assembled on the water-air interface on the micelle membrane, and slowly volatilizing the water in the colloid particle membrane at room temperature until the colloid particle membrane is completely dried. The thin film assembled with the micelle monolayer and the colloid particle monolayer was treated with oxygen plasma (50W,10Pa), and the length of the treatment time determined the area of the patterned micro domains. And (3) ultrasonically treating the film subjected to the plasma etching in deionized water for 5-10 s to remove colloid particles assembled on the surface of the film, and obtaining the micro-nano array structure of the polymer. Structural characterization referring to fig. 2, fig. 2 is an atomic force microscope image of the block copolymer film with a micro-nano ordered array structure prepared in example 1 of the present invention.
Example 2
Dissolving a polystyrene-poly 4-vinylpyridine segmented copolymer (molecular weight: 102 k-98 k) in a selective solvent o-xylene to prepare a 0.5 wt% solution, placing the prepared solution in an oven at 80 ℃ for 3h to promote the copolymer to be fully dissolved, then naturally cooling the solution to room temperature to obtain a milky micellar solution with Tyndall phenomenon and certain transparency, and cooling and stabilizing the micellar solution for 24h for use. And dripping 30 mu L of prepared micelle solution on a cleaned silicon wafer, and spin-coating to prepare the ordered copolymer monolayer micelle film. In order to promote the assembly of the colloidal particle membrane on the surface of the micelle membrane, the monolayer micelle membrane prepared in the first step is subjected to oxygen plasma etching (18W,50Pa,10s), and hydrophilic groups such as carboxyl groups and hydroxyl groups are introduced on the surface of the membrane, so that the surface of the micelle membrane becomes hydrophilic.
Preparing 1 wt% of sodium dodecyl sulfate aqueous solution, diluting 10 wt% of 1.9-micron polystyrene colloid particle aqueous dispersion to 5 wt% by using ethanol, and performing ultrasonic treatment in the aqueous solution for 5min to uniformly disperse the polystyrene colloid particle aqueous dispersion for later use. A well-cleaned glass petri dish (phi: 15cm) was prepared and charged with deionized water. A piece of cleaned 2cm × 2cm silicon wafer was picked up, and 15 μ L of the polystyrene colloidal particle dispersion was pipetted by a pipette and dropped on the surface of the silicon wafer until spread uniformly. Slowly immersing the silicon wafer paved with the colloidal particles into a surface dish filled with deionized water in a slightly inclined manner, and taking out the silicon wafer after the colloidal particles on the silicon wafer are basically and completely transferred to the surface of the aqueous solution when the silicon wafer is completely immersed. And (3) transferring 30 mu L of sodium dodecyl sulfate solution by using a liquid transfer gun, dropwise adding the sodium dodecyl sulfate solution on the surface of the aqueous solution, and extruding the colloidal particles under the action of surface tension for assembly to obtain a monolayer ordered colloidal particle array.
And fishing the colloid particle membrane assembled on the water-air interface on the micelle membrane, and slowly volatilizing the water in the colloid particle membrane at room temperature until the colloid particle membrane is completely dried. The thin film assembled with the micelle monolayer and the colloid particle monolayer was treated with oxygen plasma (50W,10Pa), and the length of the treatment time determined the area of the patterned micro domains. And (3) ultrasonically treating the film subjected to the plasma etching in deionized water for 5-10 s to remove colloid particles assembled on the surface of the film, and obtaining the micro-nano array structure of the polymer. Structural characterization referring to fig. 3, fig. 3 is an atomic force microscope image of the block copolymer film with the micro-nano ordered array structure prepared in example 2 of the present invention.
Example 3
Dissolving a polystyrene-poly 4-vinylpyridine segmented copolymer (molecular weight: 9.8 k-10 k) in a selective solvent o-xylene to prepare a 0.5 wt% solution, placing the prepared solution in an oven at 80 ℃ for 3h to promote the copolymer to be fully dissolved, then naturally cooling the solution to room temperature to obtain a milky micellar solution with Tyndall phenomenon and certain transparency, and cooling and stabilizing the micellar solution for 24h for use. And dripping 30 mu L of prepared micelle solution on a cleaned silicon wafer, and spin-coating to prepare the ordered copolymer monolayer micelle film. In order to promote the assembly of the colloidal particle membrane on the surface of the micelle membrane, the monolayer micelle membrane prepared in the first step is subjected to oxygen plasma etching (18W,50Pa,10s), and hydrophilic groups such as carboxyl groups and hydroxyl groups are introduced on the surface of the membrane, so that the surface of the micelle membrane becomes hydrophilic.
Preparing an aqueous solution of sodium dodecyl sulfate with the mass fraction of 1 wt%, diluting an aqueous dispersion of 1 mu m polystyrene colloidal particles with the mass fraction of 10 wt% to 5 wt% by using ethanol, and performing ultrasonic treatment in the aqueous solution for 5min to uniformly disperse the aqueous dispersion for later use. A well-cleaned glass petri dish (phi: 15cm) was prepared and charged with deionized water. A piece of cleaned 2cm × 2cm silicon wafer was picked up, and 15 μ L of the polystyrene colloidal particle dispersion was pipetted by a pipette and dropped on the surface of the silicon wafer until spread uniformly. Slowly immersing the silicon wafer paved with the colloidal particles into a surface dish filled with deionized water in a slightly inclined manner, and taking out the silicon wafer after the colloidal particles on the silicon wafer are basically and completely transferred to the surface of the aqueous solution when the silicon wafer is completely immersed. And (3) transferring 30 mu L of sodium dodecyl sulfate solution by using a liquid transfer gun, dropwise adding the sodium dodecyl sulfate solution on the surface of the aqueous solution, and extruding the colloidal particles under the action of surface tension for assembly to obtain a monolayer ordered colloidal particle array.
And fishing the colloid particle membrane assembled on the water-air interface on the micelle membrane, and slowly volatilizing the water in the colloid particle membrane at room temperature until the colloid particle membrane is completely dried. The thin film assembled with the micelle monolayer and the colloid particle monolayer was treated with oxygen plasma (50W,10Pa), and the length of the treatment time determined the area of the patterned micro domains. And ultrasonically treating the film subjected to the plasma etching in deionized water for 5-10 s to remove colloid particles assembled on the surface of the film. The patterned film is further immersed into a chloroauric acid aqueous solution (concentration: 10mM) to complex metal salt for 10min, and combined with the next oxygen plasma etching (50W,10Pa,60s), the micro-nano structure of the gold nanoparticles can be obtained. Structural characterization referring to fig. 4, fig. 4 is a scanning electron microscope image of the micro-nano ordered array structure of gold nanoparticles prepared in embodiment 3 of the present invention.
Example 4
Dissolving a polystyrene-poly 4-vinylpyridine segmented copolymer (molecular weight: 9.8 k-10 k) in a selective solvent o-xylene to prepare a 0.5 wt% solution, placing the prepared solution in an oven at 80 ℃ for 3h to promote the copolymer to be fully dissolved, then naturally cooling the solution to room temperature to obtain a milky micellar solution with Tyndall phenomenon and certain transparency, and cooling and stabilizing the micellar solution for 24h for use. And dripping 30 mu L of prepared micelle solution on a cleaned silicon wafer, and spin-coating to prepare the ordered copolymer monolayer micelle film. In order to promote the assembly of the colloidal particle membrane on the surface of the micelle membrane, the monolayer micelle membrane prepared in the first step is subjected to oxygen plasma etching (18W,50Pa,10s), and hydrophilic groups such as carboxyl groups and hydroxyl groups are introduced on the surface of the membrane, so that the surface of the micelle membrane becomes hydrophilic.
Preparing 1 wt% of sodium dodecyl sulfate aqueous solution, diluting 10 wt% of 250nm polystyrene colloidal particle aqueous dispersion to 5 wt% by using ethanol, and performing ultrasonic treatment in the aqueous solution for 5min to uniformly disperse the aqueous dispersion for later use. A well-cleaned glass petri dish (phi: 15cm) was prepared and charged with deionized water. A piece of cleaned 2cm × 2cm silicon wafer was picked up, and 15 μ L of the polystyrene colloidal particle dispersion was pipetted by a pipette and dropped on the surface of the silicon wafer until spread uniformly. Slowly immersing the silicon wafer paved with the colloidal particles into a surface dish filled with deionized water in a slightly inclined manner, and taking out the silicon wafer after the colloidal particles on the silicon wafer are basically and completely transferred to the surface of the aqueous solution when the silicon wafer is completely immersed. And (3) transferring 30 mu L of sodium dodecyl sulfate solution by using a liquid transfer gun, dropwise adding the sodium dodecyl sulfate solution on the surface of the aqueous solution, and extruding the colloidal particles under the action of surface tension for assembly to obtain a monolayer ordered colloidal particle array.
And fishing the colloid particle membrane assembled on the water-air interface on the micelle membrane, and slowly volatilizing the water in the colloid particle membrane at room temperature until the colloid particle membrane is completely dried. The thin film assembled with the micelle monolayer and the colloid particle monolayer was treated with oxygen plasma (50W,10Pa, 80s), and the length of the treatment time determined the area of the patterned micro-domains. And ultrasonically treating the film subjected to the plasma etching in deionized water for 5-10 s to remove colloid particles assembled on the surface of the film. Further immersing the patterned film into a chloroauric acid aqueous solution (concentration: 10mmol/L) for 10min, and combining with another oxygen plasma etching (50W,10Pa,60s), the block copolymer containing the gold nanoparticles and having the micro-nano ordered array structure can be obtained. Structural characterization referring to fig. 5, fig. 5 is a scanning electron microscope image of the micro-nano ordered array structure of gold nanoparticles prepared in embodiment 4 of the present invention.
Example 5
Dissolving a polystyrene-poly 2-vinylpyridine segmented copolymer (molecular weight: 102 k-97 k) in a selective solvent o-xylene to prepare a 0.5 wt% solution, placing the prepared solution in an oven at 80 ℃ for 3h to promote the copolymer to be fully dissolved, then naturally cooling the solution to room temperature to obtain a milky micellar solution with Tyndall phenomenon and certain transparency, and cooling and stabilizing the micellar solution for 24h for use. And dripping 30 mu L of prepared micelle solution on a cleaned silicon wafer, and spin-coating to prepare the ordered copolymer monolayer micelle film. The film was further immersed in an aqueous solution of chloroplatinic acid (concentration: 10mM) in which a metal salt was complexed for 10 min. In order to promote the assembly of the colloidal particle membrane on the surface of the micelle membrane, the monolayer micelle membrane prepared in the first step is subjected to oxygen plasma etching (18W,50Pa,10s), and hydrophilic groups such as carboxyl groups and hydroxyl groups are introduced on the surface of the membrane, so that the surface of the micelle membrane becomes hydrophilic.
Preparing an aqueous solution of sodium dodecyl sulfate with the mass fraction of 1 wt%, diluting an aqueous dispersion of 1 mu m polystyrene colloidal particles with the mass fraction of 10 wt% to 5 wt% by using ethanol, and performing ultrasonic treatment in the aqueous solution for 5min to uniformly disperse the aqueous dispersion for later use. A well-cleaned glass petri dish (phi 15cm) was prepared and filled with deionized water. A piece of cleaned 2cm × 2cm silicon wafer was picked up, and 15 μ L of the polystyrene colloidal particle dispersion was pipetted by a pipette and dropped on the surface of the silicon wafer until spread uniformly. Slowly immersing the silicon wafer paved with the colloidal particles into a surface dish filled with deionized water in a slightly inclined manner, and taking out the silicon wafer after the colloidal particles on the silicon wafer are basically and completely transferred to the surface of the aqueous solution when the silicon wafer is completely immersed. And (3) transferring 30 mu L of sodium dodecyl sulfate solution by using a liquid transfer gun, dropwise adding the sodium dodecyl sulfate solution on the surface of the aqueous solution, and extruding the colloidal particles under the action of surface tension for assembly to obtain a monolayer ordered colloidal particle array.
And fishing the colloidal particle membrane assembled on the water-air interface on the micelle membrane, and slowly volatilizing the water in the colloidal particle membrane at room temperature until the colloidal particle membrane is completely dried. The thin film in which the micelle monolayer and the colloidal particle monolayer were assembled was treated with oxygen plasma (50W,10Pa,60 s). And (3) removing colloid particles assembled on the surface of the film after the plasma etching in deionized water by ultrasonic for 5-10 s to obtain a patterned structure in which platinum nanoparticles and a copolymer are alternately and periodically arranged, then immersing the film in DMF (dimethyl formamide) to remove residual polymers by ultrasonic for 20-30 s to obtain a patterned structure complementary with the structure and the shape in the example 1 or 2, and referring to the characterization of figure 6, figure 6 is a scanning electron microscope image of the micro-nano ordered array structure of the platinum nanoparticles prepared in the example 5 of the invention.
Example 6
Dissolving a polystyrene-poly 2-vinylpyridine segmented copolymer (molecular weight: 102 k-97 k) in a selective solvent o-xylene to prepare a 0.5 wt% solution, placing the prepared solution in an oven at 80 ℃ for 3h to promote the copolymer to be fully dissolved, then naturally cooling the solution to room temperature to obtain a milky micellar solution with Tyndall phenomenon and certain transparency, and cooling and stabilizing the micellar solution for 24h for use. And dripping 30 mu L of prepared micelle solution on a cleaned silicon wafer, and spin-coating to prepare the ordered copolymer monolayer micelle film. The film was further immersed in an aqueous solution of chloroplatinic acid (concentration: 10mmol/L) to complex the metal salt for 10 min. In order to promote the assembly of the colloidal particle membrane on the surface of the micelle membrane, the monolayer micelle membrane prepared in the first step is subjected to oxygen plasma etching (18W,50Pa,10s), and hydrophilic groups such as carboxyl groups and hydroxyl groups are introduced on the surface of the membrane, so that the surface of the micelle membrane becomes hydrophilic.
Preparing 1 wt% of sodium dodecyl sulfate aqueous solution, diluting 10 wt% of 250nm silica colloidal particle aqueous dispersion to 5 wt% by using ethanol, and performing ultrasonic treatment in the aqueous solution for 5min to uniformly disperse the aqueous dispersion for later use. A well-cleaned glass petri dish (phi 15cm) was prepared and filled with deionized water. A cleaned 2cm × 2cm silicon wafer was picked up, and 15 μ L of the silica colloidal particle dispersion was pipetted by a pipette and dropped on the surface of the silicon wafer until spread uniformly. Slowly immersing the silicon wafer paved with the colloidal particles into a surface dish filled with deionized water in a slightly inclined manner, and taking out the silicon wafer after the colloidal particles on the silicon wafer are basically and completely transferred to the surface of the aqueous solution when the silicon wafer is completely immersed. And (3) transferring 30 mu L of sodium dodecyl sulfate solution by using a liquid transfer gun, dropwise adding the sodium dodecyl sulfate solution on the surface of the aqueous solution, and extruding the colloidal particles under the action of surface tension for assembly to obtain a monolayer ordered colloidal particle array.
And fishing the colloidal particle membrane assembled on the water-air interface on the micelle membrane, and slowly volatilizing the water in the colloidal particle membrane at room temperature until the colloidal particle membrane is completely dried. The thin film in which the micelle monolayer and the colloidal particle monolayer were assembled was treated with oxygen plasma (50W,10Pa,60 s). And (3) removing colloid particles assembled on the surface of the film after the plasma etching in deionized water by ultrasonic for 5-10 s to obtain a patterned structure in which platinum nanoparticles and a copolymer are alternately and periodically arranged, then immersing the film in DMF (dimethyl formamide) to remove residual polymers by ultrasonic for 20-30 s to obtain a patterned structure complementary with the structure and the shape in the example 1 or 2, and referring to the figure 7 for characterization, the figure 7 is a scanning electron microscope image of the micro-nano ordered array structure of the platinum nanoparticles prepared in the embodiment 6 of the invention.
Example 7
Dissolving a polystyrene-poly 4-vinylpyridine segmented copolymer (molecular weight: 9.8 k-10 k) in a selective solvent o-xylene to prepare a 0.5 wt% solution, placing the prepared solution in an oven at 80 ℃ for 3h to promote the copolymer to be fully dissolved, then naturally cooling the solution to room temperature to obtain a milky micellar solution with Tyndall phenomenon and certain transparency, and cooling and stabilizing the micellar solution for 24h for use. And dripping 30 mu L of the prepared micelle solution on a cleaned quartz plate, and spin-coating to prepare the ordered copolymer monolayer micelle film. In order to promote the assembly of the colloidal particle membrane on the surface of the micelle membrane, the prepared monolayer micelle membrane is subjected to oxygen plasma etching (18W,50Pa,10s), and hydrophilic groups such as carboxyl, hydroxyl and the like are introduced on the surface of the membrane, so that the surface of the micelle membrane becomes hydrophilic.
Preparing 1 wt% of sodium dodecyl sulfate aqueous solution, diluting 10 wt% of 3.8-micron polystyrene colloid particle aqueous dispersion to 5 wt% by using ethanol, and performing ultrasonic treatment in the aqueous solution for 5min to uniformly disperse the polystyrene colloid particle aqueous dispersion for later use. A well-cleaned glass petri dish (phi: 15cm) was prepared and charged with deionized water. A piece of cleaned 2cm × 2cm silicon wafer was picked up, and 15 μ L of the polystyrene colloidal particle dispersion was pipetted by a pipette and dropped on the surface of the silicon wafer until spread uniformly. Slowly immersing the silicon wafer paved with the colloidal particles into a surface dish filled with deionized water in a slightly inclined manner, and taking out the silicon wafer after the colloidal particles on the silicon wafer are basically and completely transferred to the surface of the aqueous solution when the silicon wafer is completely immersed. And (3) transferring 30 mu L of sodium dodecyl sulfate solution by using a liquid transfer gun, dropwise adding the sodium dodecyl sulfate solution on the surface of the aqueous solution, and extruding the colloidal particles under the action of surface tension for assembly to obtain a monolayer ordered colloidal particle array.
And fishing the colloid particle membrane assembled on the water-air interface on the micelle membrane, and slowly volatilizing the water in the colloid particle membrane at room temperature until the colloid particle membrane is completely dried. The thin film in which the micelle monolayer and the colloidal particle monolayer were assembled was treated with oxygen plasma (50W,10 Pa). And ultrasonically treating the film subjected to the plasma etching in deionized water for 5-10 s to remove colloid particles assembled on the surface of the film. The patterned film is further immersed into a chloroauric acid aqueous solution (concentration: 10mmol/L) for 10min, and combined with another oxygen plasma etching (50W,10Pa,60s), a micro-nano ordered array structure of the gold nanoparticles can be obtained. FIG. 8 is a scanning electron microscope image of a micro-nano ordered array structure of gold nanoparticles prepared in example 7 of the present invention.
The quartz plate with the gold array is placed in a steam atmosphere of 3-Aminopropyltriethoxysilane (APTES) and treated for 2 hours at the temperature of 50 ℃, silane molecules are grafted on the surface of the quartz plate, and then the grafted quartz plate is soaked. N-hydroxysuccinimide capped polyethylene oxide (PEG-NHS) was grafted with polyethylene glycol (PEG) molecules in dichloromethane for 24 h. The quartz plate was then reacted for 2h in an aqueous solution of mercaptopropionic acid and the carboxyl groups were activated in a PBS buffer solution (pH 7.4) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride-N-hydroxysuccinimide (EDCI/NHS). Finally, the quartz plate is soaked in PBS buffer solution (pH 7.4) of BSA to bind protein molecules, and reacted with phosphate buffer solution (PBS, pH 7.4) of Fluorescein Isothiocyanate (FITC) to label patterned Bovine Serum Albumin (BSA) molecules, and characterization of the obtained protein array is shown in fig. 9, which is a confocal laser microscope image of the fluorescein isothiocyanate labeled protein array prepared in example 7.
The embodiment shows that the invention provides a preparation method of a micro-nano ordered array structure, which comprises the following steps: A) assembling a monolayer colloid particle film on the surface of a block copolymer film, wherein the block copolymer can generate phase separation; B) removing the block copolymer which is not shielded by the colloid particles by etching by taking the assembled colloid particles as a mask plate; C) and removing the colloidal particles on the surface of the etched block copolymer film to obtain the substrate with the micro-nano ordered array structure. The method provided by the invention can be used for preparing the micro-nano ordered array structure, and the micro-nano ordered array structure has higher resolution, namely the resolution of nano scale (5-100 nm), so that the method has good application prospect in the fields of biological detection, cell behavior research, microelectronics and the like. The method is simple, easy to operate, easy to realize and good in repeatability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A preparation method of a micro-nano ordered array structure comprises the following steps:
A) assembling a monolayer colloid particle film on the surface of a block copolymer film, wherein the block copolymer can generate phase separation;
B) removing the block copolymer which is not shielded by the colloid particles by using the assembled colloid particles as a mask plate through plasma etching;
C) removing colloid particles on the surface of the etched block copolymer film to obtain a substrate with a micro-nano ordered array structure;
the single-layer colloidal particle film in the step A) is prepared according to the following method:
assembling the dispersion liquid of the colloidal particles, water and an aqueous solution containing a surfactant to obtain a single-layer colloidal particle film;
the step A) is specifically as follows:
the surface of the block copolymer film is hydrophobic, the block copolymer film is treated by adopting plasma and then assembled with the single-layer colloid particle film to obtain assembled colloid particles or the step A) is specifically as follows:
and the surface of the segmented copolymer film is hydrophilic, and the segmented copolymer film is directly assembled with the single-layer colloid particle film to obtain the assembled colloid particles.
2. The method of claim 1, wherein the single colloidal particle film is selected from the group consisting of a single polystyrene colloidal particle film, a single silica colloidal particle film, a single polymethyl methacrylate colloidal particle film, and a single metal colloidal particle film.
3. The method according to claim 1, wherein the block copolymer film is made of a material selected from the group consisting of a polystyrene-poly-4-vinylpyridine block copolymer and a polystyrene-poly-2-vinylpyridine block copolymer.
4. The method according to claim 1, wherein the block copolymer film before being assembled with the monolayer film of colloidal particles further comprises:
and complexing the segmented copolymer film with a metal precursor to obtain a metal precursor-complexed segmented copolymer film, and assembling the metal precursor-complexed segmented copolymer film with the single-layer colloidal particle film.
5. The method of claim 4, wherein the metal precursor is selected from metal salt compounds.
6. The method of claim 1, wherein the removing of the colloidal particles further comprises:
and complexing the product without the colloid particles with a metal precursor, and etching again to obtain the substrate with the micro-nano ordered array structure.
7. A micro-nano ordered array structure prepared by the preparation method of any one of claims 1 to 6.
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