KR20110134701A - 3d multilayer structures and method for preparing thereof - Google Patents
3d multilayer structures and method for preparing thereof Download PDFInfo
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Abstract
The present invention relates to a three-dimensional nanoparticle multilayer film structure and a method of manufacturing the same, and more particularly, to a multilayer film of the block copolymer by a layer-by-layer assembly of the block copolymer and UV irradiation in a vacuum atmosphere. The present invention relates to a structure, a method for manufacturing the same, and an optical sensor and a photocatalyst including the same.
Description
The present invention relates to a three-dimensional multilayer film structure and a method of manufacturing the same.
Self-assembly technology has recently been in the spotlight as a tool for manufacturing nanoscale devices such as medical, electronic / information, optical, or sensors. For example, two-dimensional or three-dimensional assemblies of monodisperse nanoparticles are widely used in functional coatings, dye-free paints, catalysts, luminescent materials, etc., templates for the growth of arranged micro or nanoporous materials, light splitting , Optical filters, photonic crystals, etc. have been utilized in optical materials and device applications.
Three-dimensional assemblies with periodicity of nano size have been studied very recently in the industry. In particular, research on the three-dimensional multilayer structure having periodicity is actively progressing. Typical methods for producing such three-dimensional multilayers include chemical vapor deposition, laser ablation deposition, and layer-by-layer assembly. Among the above methods, layer-by-layer assembly is the most common and widely used method of manufacturing a multilayer structure, in which a multilayer film is produced by electrostatic attraction between a positively charged material and a negatively charged material. Can be.
In the double block copolymer, two or more polymer chains are covalently linked through one end, and thus, each block has a tendency to phase-separate each block into its respective domain due to the limitation of the covalent bond point between the two blocks. Such a biblock copolymer can form a periodic nanostructure having a size of about 10 nm to 100 nm by spontaneous phase separation, the shape and size of the nanostructure is the molecular weight of the biblock copolymer, each block It is determined by the volume ratio of, the Flory-Huggins interaction coefficient between each block, and further dissolved in a solvent selective to one block spontaneously to form a nanometer spherical, cylindrical, etc. micelles Can be.
By using the self-assembly of the double block copolymer as described above, the size of the particles in the nanostructure of the double block copolymer may be limited to nanometer size without any treatment, and the arrangement of the particles may also be the size of the nanostructure. It is limited by the and spacing and can control the size and arrangement of the particles.
Among the multifunctional inorganic or semiconductor oxides, zinc oxide has a wide bandgap of 3.3 eV at room temperature, and has a large exciton binding energy of 60 meV, which is greater than the thermal energy of 24 meV, so that it is easy to emit light in the ultraviolet region by excitons. Do. Because of its excellent optical properties, zinc oxide has attracted much attention as an optical device such as an ultraviolet light emitting diode (Ultraviolet LED) or a laser diode (LD). Especially, zinc oxide nanostructures are used in optoelectronic devices, ultraviolet laser devices, chemical sensors, and solar cells. Potential applications in cells, photocatalysts are of increasing interest.
Recently, various semiconductors have been studied as representative photocatalysts including titanium dioxide, zinc oxide, cadmium sulfide, tungsten trioxide, and the like. Of these, titanium dioxide has been studied most widely as a photocatalyst, but recent studies have shown that zinc oxide can also be used as a highly efficient semiconductor photocatalyst. Moreover, zinc oxide is of great interest due to the decomposition and mineralization of environmental pollutants, and in order to increase the photodegradation efficiency, much research has been carried out regarding the size, shape and manufacturing method in the photocatalytic properties of zinc oxide. come.
On the other hand, photocatalysts formed by hybridization such as zinc oxide-titanium oxide and zinc oxide-gold are rapidly increasing interest due to their excellent photocatalytic activity. For example, Zheng et al. Have a silver / zinc oxide heterojunction nanocrystal as a photocatalyst. nanocrystal) promotes the separation of metallic silver nanoparticles and oxygen vacancies on the surface of the zinc oxide nanorods, resulting in light-induced electron-hole paris, resulting in increased photocatalytic activity. Proved [Y. Zheng, L. Zheng, Y. Zhan, X, Lin, Q. Zheng and K. Wei, Inorg.chem., 2007, 46, 6980].
In addition, hybrid noble metal / zinc oxide in which noble metal nanoparticles are introduced into zinc oxide is known to express improved properties that monocomponent zinc oxide does not have due to the induction effect of surface plasmon properties of noble metal nanoparticle components. It can be used in a wide range of light emitting materials and sensors.
In addition, periodic nanostructures, called photonic crystals or photonic bandgap materials, exhibit unusual optical properties due to their ability to reflect certain wavelength bands of visible light, It is applied to various fields including paint, ink, optical fiber, optical waveguide and optical computer. Existing methods for fabricating such a structure can be colloid self-assembly, photolithography, etc., and recently, block copolymer self-assembly has been used. However, in order to manufacture an optical bandgap material using a conventional block copolymer, a difficult procedure and technique such as synthesizing an ultra high molecular weight polymer or blending with a single polymer so that the repeating unit of the periodic structure has a size level of the visible light wavelength This was required.
Accordingly, the present inventors adopted a self-assembled double block copolymer reverse micelle as a basic unit and introduced a layer-by-layer assembly to sequentially fabricate reverse micelles to manufacture a multilayer membrane structure. In particular, unlike the layer-by-layer assembly generated by the electrostatic attraction of positive and negative charges, three-dimensional structure having various structures and components using stabilization by UV irradiation in a vacuum atmosphere The present invention has been completed by establishing a method for producing a multilayered film structure.
Accordingly, an object of the present invention is to provide a method for producing a multilayer film structure using a layer-by-layer assembly of a double block copolymer containing a metal or metal oxide nanoparticle precursor.
Another object of the present invention is to provide a multilayer film structure manufactured by the above production method.
In addition, another object of the present invention to provide a photocatalyst or an optical sensor comprising the multilayer structure.
The present invention for achieving the above object
a) a block copolymer carrying a metal or metal oxide nanoparticle precursor by applying a first mixed solution containing a reverse micelle of a block copolymer containing a hydrophilic block and a hydrophobic block and a metal or metal oxide nanoparticle precursor onto a substrate; Manufacturing a thin film; And
b) preparing a first block copolymer thin film on which the metal or metal oxide nanoparticles are supported by irradiating ultraviolet light in a vacuum atmosphere on the thin film;
It relates to a method for producing a multilayer film structure comprising a.
The manufacturing method of the multilayer film structure
c) a second mixed solution containing a reverse micelle of a block copolymer containing a hydrophilic block and a hydrophobic block and a metal or metal oxide nanoparticle precursor is coated on the first block copolymer thin film to support the metal or metal oxide precursor. Preparing a block copolymer thin film; And
d) irradiating the thin film of step c) with ultraviolet rays in a vacuum atmosphere to produce the second block copolymer thin film on which the metal or metal oxide nanoparticles are supported.
In addition,
c ') applying a second solution containing reverse micelles of a block copolymer containing a hydrophilic block and a hydrophobic block onto a substrate to prepare a block copolymer thin film;
d ') manufacturing a second block copolymer thin film by irradiating the thin film with ultraviolet light in a vacuum atmosphere;
It further comprises a, a), b), c '), d') or a step c '), d'), a), includes a method for producing a multilayer film structure performed in the order.
The present invention also relates to a multilayer membrane nanostructure in which one or more single layers in which at least one block copolymer on which metal or metal oxide nanoparticles are supported are arranged are stacked.
In addition,
A single layer in which one or more block copolymers carrying the metal or metal oxide nanoparticles are arranged; And
It comprises a multi-layered nano-structure in which a single layer in which one or more block copolymers are arranged is alternately stacked.
In addition, the present invention relates to a photocatalyst or an optical sensor including the multilayer film nanostructure.
The present invention provides a self-assembled double block containing a metal or metal oxide nanoparticle precursor, unlike a conventional method for manufacturing a multilayer structure by layer-by-layer assembly using electrostatic attraction between positive and negative charges. The multilayer structure may be prepared by layer-by-layer assembly of the copolymer and ultraviolet irradiation in a vacuum atmosphere. In addition, since a variety of metal or metal oxide nanoparticle precursors can be introduced, it is easy to manufacture a multilayer film structure having various structures and components, and thus may be usefully used in an industrial field requiring such a multilayer film structure.
1 is a schematic view showing a manufacturing process of a multilayer film structure according to an embodiment of the present invention ((a): hybrid metal or metal oxide nanoparticles / block copolymer multilayer film structure, (b) first 'monolayer group and agent Multi-layered structure in which 2 'monolayer groups are crossed].
Figure 2 is a schematic diagram showing the type of multilayer film structure according to an embodiment of the present invention ((a) hybrid metal or metal oxide nanoparticles / block copolymer multilayer film structure, (b) cross-laminated metal or metal oxide nanoparticles Block copolymer multi-layer structure, (c) multi-layered structure in which the first monolayer group and the second monolayer group cross each other.
3 is an atomic force microscope (AFM) photograph of a multilayer film structure according to an embodiment of the present invention [(a) Example 1, (b) Example 2, (c) Example 3, ( d) Example 4).
Figure 4 is a graph showing the X-ray reflectivity (X-ray reflectivity) results of the multilayer structure according to an embodiment of the present invention ((a) Example 1, (b) Example 2]. The black, white, red, green, and yellow curves in the graphs of (a) and (b) are the results of X-ray reflectance experiments for monomolecular, bilayer, trilayer, 4-layer, and 5-layer samples, respectively.
5 is a graph showing the spectrum of the local surface plasmon resonance (LSPR) characteristic peak of the silver nanoparticles / block copolymer multilayer film structure according to Example 5 of the present invention.
6 is an atomic force microscope (AFM) photograph showing the surface of a multilayer membrane structure according to Example 6 of the present invention [block copolymer layer: (a) one layer, (b) three layers, (c) five layers; Silver nanoparticle / block copolymer layer: (d) two layers, (e) four layers. (f) sixth floor].
7 is a photograph of the coating film according to the number of layers of the multilayer film structure according to Example 6 of the present invention.
8 is a transmission spectrum showing the photonic crystal characteristic of the multilayer structure according to Example 6 of the present invention.
Definitions of terms used in the present invention are as follows.
As used herein, the term “reverse micelle” refers to a micelle, in which a hydrophobic block is spontaneously located on the outside of a block copolymer, and a hydrophilic block is located on the inside of a block copolymer.
As used herein, the term "block copolymer thin film" means a monomolecular film in which one or more block copolymers are arranged.
Hereinafter, a method of manufacturing a multilayer film structure according to the present invention will be described in more detail step by step.
In the manufacturing method according to the present invention,
Step a) is applied to a substrate by applying a mixed solution containing a reverse micelle of a block copolymer containing a hydrophilic block and a hydrophobic block (an amphiphilic block copolymer) and a metal or metal oxide nanoparticle precursor onto a substrate to obtain metal or metal oxide nanoparticles. It is a step of preparing a block copolymer thin film on which the precursor is supported.
The hydrophilic block is preferably at least one polymer selected from the group consisting of polyvinylpyridine, polyethylene oxide, polyacrylic acid, polymethacrylic acid, polyvinyl alcohol, polyacrylamide and polystyrene sulfonic acid, wherein the hydrophobic block is polystyrene, One or more polymers selected from the group consisting of polyolefins, polyalkylacrylates, polyisoprene, polybutadiene, polysiloxane, polyimidazole, polylactide, polydimethylsiloxane and polylactone are preferred, but not limited thereto.
The amphiphilic block copolymers include polystyrene-block-poly (4-vinylpyridine) and polystyrene-block-poly (2-vinylpyridine), polystyrene-block-polyethylene oxide (PS-b-PEO), and polyisoprene-block. -Poly (2-vinylpyridine) (PI-b-P2VP), poly (2-vinylpyridine) -block-polydimethylsiloxane (P2VP-b-PDMA) and the like can be used, in particular polystyrene-block-poly (4-vinylpyridine) or polystyrene-block- (2-vinylpyridine) can be used.
In addition, reverse micelles can be formed using toluene, chloroform, tetrahydrofuran, dimethylformamide, benzene, haptan, xylene, or the like as a solvent for dissolving only hydrophobic blocks in the amphiphilic block copolymer.
In particular, the reverse micelles may contain 0.1 to 1.5% by weight of a block copolymer. If the block copolymer is less than 0.1% by weight, no defect-free uniform monolayer may be produced, and when the block copolymer is more than 1.5% by weight, the multimolecular film may be produced.
In addition, the metal includes not only noble metals such as gold, silver, platinum, palladium, etc., but also transition metals such as cobalt, nickel, iron, copper, and the like, and the metal oxides include titanium dioxide, zinc oxide, and the like. And metal nanoparticles modified with metal chlorides, metal nitrates, sol-gel precursors of metal oxides or hydrophilic ligands, and the like. At this time, the hydrophilic ligand is preferably a hydroxy group (-OH), a carboxy group (-COOH) and the like. As the precursor, for example, hydrogen tetrachloroaurate (HAuCl 4 ), lithium tetrachloroaurate (LiAuCl 4 ), silver nitrate (AgNO 3 ), silver acetate (CH 3 COOAg), zinc acetate dihydrate (zinc acetate hydrate) ), Zinc acetylacetonate monohydrate, zinc nitrate hexahydrate, and the like.
In order to mix the metal or metal oxide nanoparticle precursors with reverse micelles, a colloidal solution is used. The solvent used may include a corresponding metal salt or a metal or metal oxide nano, such as a lower alcohol having 1 to 4 carbon atoms, an organic solvent such as toluene or benzene. The solvent is not limited so long as it can dissolve the particles. The dissolved metal or metal oxide precursor as described above may selectively bind to the hydrophilic block portion of the block copolymer.
The reverse micelles and the metal or metal oxide nanoparticle precursor mixed solution may be mixed such that the content of the metal or metal oxide nanoparticles has a predetermined ratio in terms of uniformity and order of order of the nanostructure to be manufactured. Preferably, the mixture is prepared by mixing the reverse micelle solution and the metal or metal oxide colloidal solution such that the molar ratio of the metal or metal oxide nanoparticles to the hydrophilic block monomer is 0.1 to 0.7. If the molar ratio is less than 0.1, there is a problem in that the dispersion of the metal or metal oxide particles is not uniform in each reverse micelle. If the molar ratio is more than 0.7, the molar ratio is not included in the reverse micelle and the metal or metal oxide particles are combined to form agglomerates. There is a problem.
The substrate may be any one used in the art, but a silicon wafer, quartz, glass or mica is suitable.
The block copolymer thin film on which the metal or metal oxide nanoparticle precursor is supported is prepared by applying the mixed solution by a coating method used in the related art, and preferably prepared by spin coating. Spin coating conditions can be changed depending on the type of polymer used, molecular weight, solvent and the thickness of the monomolecular film, but in the present invention, the mixed solution is applied onto a substrate by spin coating at 1000 to 2500 rpm to form a metal or metal oxide nanoparticle precursor. To prepare a block copolymer thin film arranged regularly. If the spin coating is less than 1000 rpm, a reverse micelle array stacked in multiple layers may be formed. If the spin coating is more than 2500 rpm, a thin film having an appropriate thickness may not be formed.
In the manufacturing method according to the present invention, step b) is a step of preparing a first block copolymer thin film on which the metal or metal oxide nanoparticles are supported by irradiating ultraviolet rays in a vacuum atmosphere to the thin film prepared in step a).
Irradiating the amphiphilic block copolymer with ultraviolet rays in a vacuum atmosphere not only induces reduction of the metal precursor, but also irradiates with ultraviolet rays even when the temperature is changed or the use of a solvent which can harden the polymer and bring fluidity to the polymer. The structure, form, composition, etc., formed by the whole block copolymer can be maintained.
The vacuum atmosphere is preferably 10 -2 to 10 -7 mmHg, more preferably 10 -3 to 10 -5 mmHg.
In addition, the ultraviolet light is preferably irradiated for 1 to 2 hours at a wavelength of 250 to 260 nm and 20 to 30 J / cm 2 in a vacuum atmosphere. In the case of too strong or long irradiation, the block copolymer may not be removed or the metal state exhibiting optimal surface plasmon properties may not be induced. In the case of too weak or short irradiation, hardening of the block copolymer may occur. There is a problem that the structure is not maintained, or the metal precursor is not completely reduced when the multilayer film is not made completely.
As described above, the inverse of the block copolymer thin film on which the metal or metal oxide nanoparticles are additionally supported on the monolayer film of the block copolymer having the metal or metal oxide nanoparticles prepared through steps a) and b). The periodic multilayer film of the block copolymer on which the metal or the metal oxide nanoparticles are supported may be prepared by repeatedly applying the mixed solution containing the micelles and the metal or the metal oxide nanoparticle precursors and repeating the ultraviolet irradiation process in a vacuum atmosphere.
That is, the reverse micelle mixing is performed on the block copolymer thin film (monolayer film) on which the metal or metal oxide nanoparticles are supported, because a single molecule nanoparticle array having a uniform density is formed on the substrate through steps a) and b). By repeating the application of the solution and stabilization by ultraviolet irradiation in a vacuum atmosphere, a stacked three-dimensional nanostructure having a periodic structure can be manufactured. Therefore, the height and thickness of the three-dimensional nanostructures are controlled according to the number of repetitions, and if the type of the mixed solution is different for each layer, the three-dimensional nanostructures showing the periodicity of the arrangement and composition as well as the height and thickness can be manufactured. have.
More specifically, the manufacturing method of the present invention
c) applying a second mixed solution containing a reverse micelle of a block copolymer including a hydrophilic block and a hydrophobic block and a metal or metal oxide nanoparticle precursor onto the first block copolymer thin film prepared in step b) Or preparing a block copolymer thin film on which the metal oxide nanoparticle precursor is supported; And
d) preferably irradiating the thin film of step c) with ultraviolet rays in a vacuum atmosphere to repeat the step of manufacturing the second block copolymer thin film on which the metal or metal oxide nanoparticles are supported one or more times.
In one embodiment of the present invention, the first mixed solution and / or the second mixed solution may include only one component of the nanoparticle precursor, but includes two or more kinds of metals or metal oxide nanoparticle precursors. It is also possible to produce a multilayer film structure on which a metal or metal oxide composite is supported.
In another embodiment of the present invention, the metal or metal oxide nanoparticle precursor of the second mixed solution may be the same as the metal or metal oxide nanoparticle precursor of the first mixed solution.
In this case, it is possible to manufacture a multilayer film nanostructure in which a single layer in which one or more block copolymers carrying the same kind of metal or metal oxide nanoparticles are arranged is sequentially stacked.
In another embodiment of the present invention, the metal or metal oxide nanoparticle precursor of the second mixed solution may be different from the metal or metal oxide nanoparticle precursor of the first mixed solution.
In this case a single layer in which one or more block copolymers carrying the first metal or metal oxide nanoparticles are arranged and a single layer in which one or more block copolymers carrying the second metal or metal oxide nanoparticles are arranged The multilayered film nanostructures laminated alternately can be produced. In addition, it is possible to form an additional single layer on which the third and fourth metal or metal oxide nanoparticles are supported, and of course, the periodicity can also be freely controlled.
In another embodiment of the present invention, the step a) and b) may be repeated two or more times, and then the steps c) and d) may be repeated two or more times.
In this case, the first single layer group in which two or more single layers including the first metal or metal oxide nanoparticles are stacked and the second single in which two or more single layers including the second metal or metal oxide nanoparticles are stacked. Multilayer film nanostructures in which layer groups are alternately stacked may be manufactured.
The present invention also provides
c ') applying a second solution containing reverse micelles of a block copolymer containing a hydrophilic block and a hydrophobic block onto a substrate to prepare a block copolymer thin film;
d ') manufacturing a second block copolymer thin film by irradiating the thin film with ultraviolet light in a vacuum atmosphere;
It further comprises a, a), b), c '), d') or a step c '), d'), a), includes a method for producing a multilayer film structure performed in the order.
Steps c ') and d') skip the mixing process of the metal or metal oxide nanoparticle precursor in the process of steps a) and b), and perform the same process except adjusting the concentration of the block copolymer solution.
In the present invention, it is possible to control the thickness of the block copolymer thin film according to the concentration of the block copolymer, thereby controlling the periodicity of the thin film. The solution containing the reverse micelles may include 0.1 to 8.0 wt% of a block copolymer. If the block copolymer is less than 0.1% by weight, there is a problem that a uniform thin film without defects is not produced, and when the block copolymer is more than 8.0% by weight, there is a problem that a thin film is not produced. In the embodiment of the present invention, in the case of the solution containing reverse micelles containing no metal or metal oxide nanoparticle precursors for controlling the thickness of the thin film, the concentration of the block copolymer is 3.0 to 8.0 wt%, and the metal or metal oxide In the case of a solution containing reverse micelles containing the nanoparticle precursor, the concentration of the block copolymer was used at 0.1 to 1.5% by weight.
The invention also repeats steps a) and b) two or more times, steps c ') and d') two or more times or steps c ') and d') two or more times, step a ) And b) may be repeated two or more times to manufacture the multilayer nanostructure.
By repeating lamination as described above, a periodic multilayer film of the block copolymer thin film and the block copolymer thin film on which the metal or metal oxide nanoparticles are supported can be prepared.
In addition, the height and thickness of the three-dimensional nanostructure is controlled according to the number of repetitions of the thin film forming step, and if the type of the mixed solution for each layer is different, the three-dimensional nano shows the periodicity of the arrangement and composition as well as the height and thickness The structure can be prepared.
The present invention also relates to a multilayer membrane nanostructure in which at least one single layer on which one or more nanoblock copolymers carrying metal or metal oxide nanoparticles are arranged is stacked.
The present invention also provides a single layer comprising at least one block copolymer on which the metal or metal oxide nanoparticles are supported; And
It comprises a multi-layered nano-structure in which a single layer in which one or more block copolymers are arranged is alternately stacked.
In one embodiment of the present invention, the metal or metal oxide nanoparticles of each single layer may be the same or different kinds.
In the case where the metal or metal oxide nanoparticles of the single layer are the same, for example, a multilayer film nanostructure in which monomolecular films of block copolymers carrying gold (Au) nanoparticles are continuously stacked; A multilayer film nanostructure in which monomolecular films of a block copolymer on which zinc oxide (ZnO) nanoparticles are supported are sequentially stacked; Alternatively, a multi-layered film nanostructure in which monomolecular films of a block copolymer loaded with gold (Au) and zinc oxide (ZnO) nanocomposites are sequentially stacked may be formed.
When the metal or metal oxide nanoparticles of the single layer are different, for example, the monomolecular film of the block copolymer on which gold (Au) nanoparticles are supported and the block copolymer on which zinc oxide (ZnO) nanoparticles are supported A multilayer film nanostructure in which monomolecular films are alternately stacked; Alternatively, a multi-layered film nanostructure is formed in which a monomolecular film of a block copolymer loaded with gold (Au) and zinc oxide (ZnO) nanocomposites and a monomolecular film of a block copolymer loaded with zinc oxide (ZnO) nanoparticles are alternately stacked. can do. In this case, it is a matter of course that a monomolecular film including the third or fourth metal or metal oxide may be further formed.
In another embodiment of the present invention, two or more single layers including the first metal or metal oxide nanoparticles are stacked and two or more single layers including the second metal or metal oxide nanoparticles are stacked. The second single layer group may be formed by alternatingly stacking.
In this case, for example, the monomolecular membrane of the block copolymer carrying the zinc nanoparticles and the first monolayer group in which the monomolecular membrane of the block copolymer carrying gold (Au) nanoparticles is carried and the zinc oxide (ZnO) nanoparticles Successively stacked second monolayer groups may be formed by alternately stacking.
In another embodiment of the present invention, a first 'single layer group in which two or more single layers in which block copolymers are arranged is stacked and a second' in which two or more single layers including metal or metal oxide nanoparticles are stacked. Single layer groups can be stacked alternately to form.
In this case, for example, a first 'single layer group in which a single layer of block copolymer is continuously laminated and a second' single layer group in which a single layer of block copolymer in which silver nanoparticles are supported are alternately stacked are alternated. It can be formed by laminating.
The method for manufacturing a multilayered film nanostructure according to the present invention is simple in process and forms a nanostructure on which regular and orderly metal or metal oxide nanoparticles are supported, as well as the arrangement and configuration of the height and layer of each layer using a lamination technique. This controlled three-dimensional nanostructure is made possible, and by using the block copolymer as a template, the nanostructure can be produced without modifying the shape and periodicity of the structure formed by the block copolymer.
In addition, the present invention can control the thickness of the coating film by adjusting the concentration of the block copolymer reverse micelle solution and the speed of spin coating, through which it is possible to easily control the interlayer spacing of the nanoparticles. In particular, a photonic crystal exhibiting a photonic band gap may be manufactured by controlling the periodicity of the nanoparticles.
The invention also relates to a photocatalyst or an optical sensor comprising a multilayered film structure according to the invention.
The 3D multilayer film structure manufactured according to the present invention may exhibit improved photocatalyst and light sensing characteristics. Accordingly, the three-dimensional multilayer film structure according to the present invention is a photocatalyst, and can be usefully used in the field of an optical sensor or an optical device.
Hereinafter, the present invention will be described in more detail by way of examples. It should be noted, however, that the following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Example 1: gold nanoparticles / Block copolymer Multilayer film Fabrication of the Structure
1) Preparation of reverse micelle solution containing self-assembled double block copolymer
Polystyrene-block-poly (4-vinyl pyridine), PS-b-P4VP, Mnps = 41.5 kg / mol, Mnp4vp = 17.5 kg / mol, Mw / Mn = 1.07) Was dissolved in toluene at a concentration of 0.5% by weight to prepare a reverse micelle solution.
2) Preparation of reverse micelle solution containing gold nanoparticle precursor
Hydrogentetrachloroaurate (HAuCl 4 ) was added to the reverse micelle solution prepared in 1) such that the molar ratio of hydrogentetrachloroaurate (HAuCl 4 ) was 0.2 relative to poly (4-vinylpyridine). After stirring for 2 days at room temperature to prepare a self-assembled double block copolymer reverse micelle solution containing gold nanoparticle precursor.
3) Preparation of Gold Nanoparticle Precursor / Block Copolymer Monolayer
The reverse micelle solution containing the gold nanoparticle precursor prepared in 2) was spin coated on a silicon wafer at 2000 rpm for 60 seconds to prepare a gold nanoparticle precursor / block copolymer monolayer.
4) Manufacture of Gold Nanoparticles / Block Copolymer Monolayers
The wavelength of 254 nm and 25 J / cm 2 in the gold nanoparticle precursor / block copolymer monomolecular film of 3) Ultraviolet light having an intensity was irradiated under vacuum for 1 hour to prepare a gold nanoparticle / block copolymer monomolecular film having reduced self-assembled double block copolymer cured gold nanoparticle precursor.
5) Preparation of Gold Nanoparticles / Block Copolymer Multi-Layered Structures
3) and 4) were repeated to prepare a gold nanoparticle / block copolymer multilayer film structure.
Example 2: zinc oxide nanoparticles / Block copolymer Multilayer film Fabrication of the Structure
1) Preparation of reverse micelle solution containing self-assembled double block copolymer
Polystyrene-block-poly (4-vinyl pyridine), PS-b-P4VP, Mnps = 41.5 kg / mol, Mnp4vp = 17.5 kg / mol, Mw / Mn = 1.07) Was dissolved in toluene at a concentration of 0.5% by weight to prepare a reverse micelle solution.
2) Preparation of reverse micelle solution containing zinc oxide nanoparticle precursor
Zinc acetate dihydrate was added to the reverse micelle solution prepared in 1) so that the molar ratio of zinc acetate dihydrate to 0.5 (polyvinyl pyridine) was 0.5, and then at room temperature. After stirring for 2 days, a self-assembled double block copolymer reverse micelle solution containing a zinc oxide nanoparticle precursor was prepared.
3) Zinc Oxide Nanoparticle Precursor / Block Copolymer Monolayer
The reverse micelle solution containing the zinc oxide nanoparticle precursor prepared in 2) was spin coated on a silicon wafer at 2000 rpm for 60 seconds to prepare a zinc oxide nanoparticle precursor / block copolymer monolayer.
4) Zinc Oxide Nanoparticle / Block Copolymer Monolayer
The zinc oxide nanoparticle precursor / block copolymer monolayer of 3) was irradiated with ultraviolet rays having a wavelength of 254 nm and a 25 J / cm 2 intensity under vacuum for 1 hour under a vacuum to self-assembled zinc oxide nanoparticles. A block copolymer monomolecular film was prepared.
5) Preparation of Zinc Oxide Nanoparticles / Block Copolymer Multi-Layered Structures
3) and 4) were repeated to prepare a zinc oxide nanoparticle / block copolymer multilayer film structure.
Example 3: hybrid Gold / Zinc Oxide Nanoparticles / Block copolymer Multilayer film Fabrication of the Structure
1) Preparation of reverse micelle solution containing self-assembled double block copolymer
Polystyrene-block-poly (4-vinyl pyridine), PS-b-P4VP, Mnps = 41.5 kg / mol, Mnp4vp = 17.5 kg / mol, Mw / Mn = 1.07) Was dissolved in toluene at a concentration of 0.5% by weight to prepare a reverse micelle solution.
2) Preparation of reverse micelle solution containing gold nanoparticle precursor and zinc oxide nanoparticle precursor
Hydrogentetrachloroaurate (HAuCl 4 ) and zinc acetate dihydrate in reverse micelle solution prepared in 1) with respect to poly (4-vinylpyridine) hydrogentetrachloroaurate (HAuCl 4 ) And self-assembled double block copolymers containing gold nanoparticle precursors and zinc oxide nanoparticle precursors simultaneously by adding the molar ratio of zinc acetate dihydrate to 0.2 and 0.5, respectively, and then stirring at room temperature for 2 days. Reverse micelle solutions were prepared.
3) Hybrid gold / zinc oxide nano particle precursor / block copolymer monolayer
The reverse micelle solution containing the gold nanoparticle precursor and zinc oxide nanoparticle precursor prepared in 2) was spin coated at 2000 rpm for 60 seconds to prepare a hybrid gold / zinc oxide nanoparticle precursor / block copolymer monolayer.
4) Hybrid Gold / Zinc Oxide Nano Particle / Block Copolymer Monolayer
The wavelength of 254 nm and 25 J / cm 2 in the hybrid gold / zinc oxide nanoparticle precursor / block copolymer monolayer of 3). Ultraviolet rays having intensity were irradiated under vacuum for 1 hour to prepare hybrid gold / zinc oxide nanoparticles / block copolymer monomolecular membranes in which self-assembled double block copolymers were cured.
5) Manufacture of hybrid gold / zinc oxide nanoparticles / block copolymer multilayer film structure
3) and 4) were repeated to prepare a hybrid gold / zinc oxide nanoparticle / block copolymer multilayer film structure.
Example 4: Zinc Oxide Nanoparticles / Block copolymer Layer and gold nanoparticle / block copolymer layer Crossed there is Multilayer film Fabrication of the Structure
1) Preparation of reverse micelle solution containing self-assembled double block copolymer
Polystyrene-block-poly (4-vinyl pyridine), PS-b-P4VP, Mnps = 41.5 kg / mol, Mnp4vp = 17.5 kg / mol, Mw / Mn = 1.07) Was dissolved in toluene at a concentration of 0.5% by weight to prepare a reverse micelle solution.
2) Preparation of reverse micelle solution containing gold nanoparticle precursor
Hydrogentetrachloroaurate (HAuCl 4 ) was added to the reverse micelle solution prepared in 1) above so that the molar ratio of hydrogentetrachloroaurate (HAuCl 4 ) to poly (4-vinylpyridine) was 0.2. After stirring for 2 days at room temperature to prepare a self-assembled double block copolymer reverse micelle solution containing gold nanoparticle precursor.
3) Preparation of reverse micelle solution containing zinc oxide nanoparticle precursor
Zinc acetate dihydrate was added to the reverse micelle solution prepared in 1) so that the molar ratio of zinc acetate dihydrate to 0.5 (polyvinyl pyridine) was 0.5, and then at room temperature. After stirring for 2 days, a self-assembled double block copolymer reverse micelle solution containing a zinc oxide nanoparticle precursor was prepared.
4) Preparation of Gold Nanoparticle Precursor / Block Copolymer Monolayer
The reverse micelle solution containing the gold nanoparticle precursor prepared in 2) was spin coated at 2000 rpm for 60 seconds to prepare a gold nanoparticle precursor / block copolymer monolayer.
5) Manufacture of Gold Nanoparticles / Block Copolymer Monolayers
The gold nanoparticle precursor / block copolymer monolayer of 4) was irradiated with ultraviolet rays having a wavelength of 254 nm and a 25 J / cm 2 intensity under vacuum for 1 hour to cure the self-assembled double block copolymer. Copolymer monolayers were prepared.
6) Zinc Oxide Nanoparticle Precursor / Block Copolymer Monolayer
The reverse micelle solution containing the zinc oxide nanoparticle precursor prepared in 3) was spun at 2000 rpm for 60 seconds on the gold nanoparticle / block copolymer monolayer cured by the self-assembled double block copolymer prepared in 5). The coating prepared a zinc oxide nanoparticle precursor / block copolymer monolayer.
7) Zinc Oxide Nanoparticle / Block Copolymer Monolayer
The zinc oxide nanoparticles / block copolymer monolayer on the zinc oxide nanoparticle precursor / block copolymer of 6) was irradiated with ultraviolet rays having a wavelength of 254 nm and 25 J / cm 2 intensity under vacuum for 1 hour in a self-assembled double layer. The block copolymer was cured to prepare a zinc oxide nanoparticle / block copolymer monomolecular film in which the self-assembled double block copolymer was cured.
8) Fabrication of a multi-layered film structure in which a gold nanoparticle / block copolymer layer and a zinc oxide nanoparticle / block copolymer layer intersect
4), 5), 6) and 7) were repeated to prepare a multi-layered film structure in which the gold nanoparticle / block copolymer layer and the zinc oxide nanoparticle / block copolymer layer intersect.
Example 5: silver nanoparticles / Block copolymer Multilayer film Fabrication of the Structure
1) Preparation of reverse micelle solution containing self-assembled double block copolymer
Polystyrene-block-poly (4-vinyl pyridine), PS-b-P4VP, Mnps = 41.5 kg / mol, Mnp4vp = 17.5 kg / mol, Mw / Mn = 1.07) Was dissolved in toluene at a concentration of 0.5% by weight to prepare a reverse micelle solution.
2) Preparation of reverse micelle solution containing silver nanoparticle precursor
Silver nitrate (AgNO 3 ) was added to the reverse micelle solution prepared in 1) above so that the molar ratio of silver nitrate (AgNO 3 ) to poly (4-vinylpyridine) was 0.5, followed by stirring at room temperature for 2 days to obtain silver nanoparticles. Self-assembled double block copolymer reverse micelle solutions containing precursors were prepared.
3) Silver Nanoparticle Precursor / Block Copolymer Monolayer
The reverse micelle solution containing the silver nanoparticle precursor prepared in 2) was spin coated at 2000 rpm for 60 seconds to prepare a silver nanoparticle precursor / block copolymer monolayer.
4) Silver Nanoparticle / Block Copolymer Monolayer
The silver nanoparticle precursor / block copolymer monolayer of 3) was irradiated with ultraviolet rays having a wavelength of 254 nm and a 25 J / cm 2 intensity under vacuum for 1 hour to cure the self-assembled double block copolymer. Copolymer monolayers were prepared.
5) Preparation of silver nanoparticle / block copolymer multilayer film structure
3) and 4) were repeated to prepare a silver nanoparticle / block copolymer multilayer film structure.
Comparative example 1: silver nanoparticles / in the air atmosphere Block copolymer Multilayer film Fabrication of the Structure
In the same manner as in Example 5, in step 3) of Example 5, the silver nanoparticle precursor / block copolymer monolayer was irradiated with ultraviolet light having a wavelength of 254 nm and 25 J / cm 2 intensity under air for 1 hour. Nanoparticle / block copolymer multilayer membrane structures were prepared.
Example 6: Block copolymer Layer and silver nanoparticles / Block copolymer Layered Gyoza there is Multilayer film Preparation of Nanostructures
1) Preparation of polystyrene-block-poly (2-vinylpyridine) reverse micelle solution containing self-assembled double block copolymer
Polystyrene-block-poly (2-vinyl pyridine), PS-b-P2VP, Mnps = 50 kg / mol, Mnp2vp = 16.5 kg / mol, Mw / Mn = 1.09 Was dissolved in toluene at a concentration of 6% by weight to prepare a reverse micelle solution.
2) Preparation of polystyrene-block-poly (4-vinylpyridine) reverse micelle solution containing self-assembled double block copolymer
Polystyrene-block-poly (2-vinyl pyridine), PS-b-P4VP, Mnps = 41.5 kg / mol, Mnp4vp = 17.5 kg / mol, Mw / Mn = 1.07) Was dissolved in toluene at a concentration of 1% by weight to prepare a reverse micelle solution.
3) Preparation of reverse micelle solution containing silver nanoparticle precursor
Silver nitrate (AgNO 3 ) was added to the reverse micelle solution prepared in 2) so that the molar ratio of silver nitrate (AgNO 3 ) was 0.5, and then stirred at room temperature for 2 days to self-assemble double block air containing silver nanoparticle precursors. The combined reverse micelle solution was prepared.
4) Preparation of Block Copolymer Thin Film
The polystyrene-block-poly (2-vinylpyridine) reverse micelle solution prepared in 1) was spin coated at 1500 rpm for 60 seconds to prepare a block copolymer thin film.
5) Curing of Self-assembled Double Block Copolymer by UV Irradiation
The polystyrene-block-poly (2-vinylpyridine) thin film of 4) was irradiated with ultraviolet rays having a wavelength of 254 nm and 25 J / cm 2 intensity under vacuum for 1 hour to prepare a thin block copolymer cured thin film.
6) Silver Nanoparticle Precursor / Block Copolymer Monolayer
The reverse micelle solution containing the silver nanoparticle precursor prepared in 3) was spin coated at 1000 rpm for 60 seconds on the cured thin film of the block copolymer prepared in 5), thereby obtaining the silver nanoparticle precursor / block copolymer thin film. Was prepared.
7) Curing Self-Assembled Double Block Copolymer by UV Irradiation
The silver nanoparticle precursor / block copolymer thin film on the cured block copolymer thin film of 6) was irradiated with ultraviolet light having a wavelength of 254 nm and 25 J / cm 2 intensity under vacuum for 1 hour to obtain a self-assembled double block copolymer. A cured silver nanoparticle / block copolymer thin film was prepared.
8) Fabrication of a multilayer membrane structure in which a block copolymer thin film and a silver nanoparticle / block copolymer thin film intersect
4), 5), 6) and 7) were repeated to prepare a multilayer membrane structure in which the block copolymer thin film and the silver nanoparticle / block copolymer thin film intersect.
Experimental Example 1: Metal nanoparticles / by ultraviolet irradiation under vacuum atmosphere Block copolymer Fabrication of Multi-Layered Structures
The following experiments were performed to confirm the surface analysis of the metal or metal oxide nanoparticles / block copolymer multilayer film structure prepared through curing of the self-assembled block copolymer by ultraviolet irradiation in a vacuum atmosphere and the formation of the multilayer film structure.
The surface of each layer of the metal or metal oxide nanoparticle / block copolymer multilayer films of Examples 1, 2, 3, and 4 was observed in an atomic force microscope (AFM), and is shown in FIG. 3.
FIG. 3 (a) is an atomic force microscope (AFM) photograph of the surface of the gold nanoparticle / block copolymer multilayer film structure of Example 1, wherein one layer, three layers, and It is surface photograph of five levels.
Figure 3 (b) is an atomic force microscope (AFM) photograph of the surface of the zinc oxide nanoparticles / block copolymer multilayer film structure of Example 2, a
3 (c) is an atomic force microscope (AFM) photograph of the surface of the hybrid gold / zinc oxide nanoparticle / block copolymer multilayer film structure of Example 3, wherein the hybrid gold / zinc oxide nanoparticle / block copolymer multilayer film Surface photographs of the first, third and fifth layers of the structure.
FIG. 3D is an atomic force microscope (AFM) photograph of the surface of the multilayer film structure in which the zinc oxide nanoparticle / block copolymer layer and the gold nanoparticle / block copolymer layer of Example 4 intersect, and are oxidized. Surface photographs of one, three, five, and two, four, and six layers of zinc nanoparticles / block copolymers.
As can be seen in the atomic force microscope (AFM) photograph of FIG. 3, the nanoparticle / block copolymer array was observed. It was also found that the initial array was maintained as the layers of the multilayer film structure increased. This phenomenon indicates that the array is maintained even after spin coating the reverse micelle solution containing nanoparticles by curing the self-assembled double block copolymer of the nanoparticle / block copolymer monomolecular film first generated by ultraviolet irradiation.
X-ray reflectivity results of the nanoparticle / block copolymer multilayer film structures of Examples 1 and 2 are shown in FIG. 4. More specifically, the X-ray reflectivity (X-ray reflectivity) result of the gold nanoparticles / block copolymer multilayer film structure of Example 1 is shown in Figure 4 (a), the zinc oxide nanoparticles of Example 2 X-ray reflectivity of the block copolymer multilayer film structure (X-ray reflectivity) results are shown in Figure 4 (b). For reference, black, white, red, green, and yellow curves in the graphs of (a) and (b) are the results of X-ray reflectance experiments for monomolecular, bilayer, trilayer, four-layer, and five-layer films, respectively. As can be seen from the results, it can be seen that as the number of laminations increases, the thickness of the curve increases sequentially from decreasing oscillation of the curve.
From this, it was confirmed that a multi-layered membrane structure in which nanoparticles were introduced using the block copolymer as a template, and that curing of the self-assembled biblock copolymer by ultraviolet irradiation in a vacuum atmosphere is a very important factor in manufacturing the multilayered membrane structure. Could know. Furthermore, according to the kind of nanoparticle precursor added to the block copolymer reverse micelle solution, it was found that a multilayer film structure including various nanoparticles can be obtained, and the internal structure of the multilayer film can be easily controlled.
Experimental Example 2: silver nanoparticles according to UV irradiation environment Multilayer film Fabrication of the Structure
The following experiment was performed to confirm the fabrication and optical properties of the silver nanoparticle multilayer structure according to the UV irradiation environment.
Spectra of LSPR local surface plasmon resonance (LSPR) characteristic peaks of the silver nanoparticles / block copolymer multilayer film structures of Example 5 and Comparative Example 1 are shown in FIG. 5. In more detail, the local surface plasmon resonance (LSPR) characteristic peak of the silver nanoparticle / block copolymer multilayer film structure obtained by ultraviolet irradiation in the vacuum atmosphere of Example 5 is shown in FIG. 5 (a), and Comparative Example 1 The local surface plasmon resonance (LSPR) characteristic peak of the silver nanoparticles / block copolymer structure through ultraviolet irradiation in the air atmosphere of is shown in (b) of FIG. 5, and the two silver nanoparticles / block copolymer multilayer film structures The wavelength change of the local surface plasmon resonance (LSPR) characteristic peak for each layer of is shown in comparison with FIG.
As can be seen from the local surface plasmon resonance (LSPR) characteristic peak of FIG. 5, it can be seen that the silver nanoparticle precursor is reduced to silver nanoparticles by ultraviolet irradiation. In addition, it can be seen that the position of the characteristic peak of the local surface plasmon resonance (LSPR) of the silver nanoparticles is different depending on the ultraviolet irradiation environment. That is, when the silver nanoparticles / block copolymer multilayer film structure is manufactured by irradiating ultraviolet rays in a vacuum atmosphere, the block copolymer is cured as described in Experimental Example 1 from FIGS. 5 (a) and 5 (c). It was found that the multilayer film was formed sequentially. In this case, the presence of the polymer mattress generates a certain interval between the silver nanoparticles, thus reducing the coupling effect between the surface plasmon fields of the adjacent silver nanoparticles. On the other hand, when the thin film is irradiated with ultraviolet light while being exposed to air, the block copolymer is decomposed and the reduction of the silver precursor proceeds to produce a multilayer film in which pure silver nanoparticles are stacked. As can be seen from (b) and (c) of FIG. 5, the three-dimensional silver nanoparticle multilayer film has a relatively large surface plasmon resonance (LSPR) interaction effect due to the reduction of the distance between the silver nanoparticles. As the nanoparticles were sequentially stacked, it was found that the wavelength of the characteristic peak shifted to a longer wavelength.
Experimental Example 3: Block copolymer layer Silver nanoparticles / Block copolymer layer Crossed there is Multilayer film Manufacture of structures and Photonic crystal Property evaluation
The following experiments were carried out to evaluate the surface analysis and photonic crystal properties of the multi-layered film structure in which the block copolymer thin film and the silver nanoparticle / block copolymer thin film manufactured by curing the self-assembled double block copolymer by UV irradiation were performed. It was.
The surface of each layer of the photonic crystalline multilayer film nanostructure of Example 6 was observed in an atomic force microscope (AFM) and is shown in FIG. 6. More specifically, Figures 3 (a), (b) and (c) are surface photographs of one, three and five layers of the block copolymer thin film of Example 6, (d), (e) and ( f) is a surface photograph of two, four and six layers of the silver nanoparticle / block copolymer thin film of Example 6.
As can be seen in the atomic force microscope (AFM) photograph of FIG. 7, it can be seen that the array of the block copolymer thin film and the silver nanoparticle / block copolymer thin film is maintained even when the layer of the multilayer film structure is increased. This phenomenon indicates that the structure is maintained even after spin coating the reverse micelle solution containing nanoparticles by curing the block copolymer thin film first generated by ultraviolet irradiation.
In the case of the multilayer film structure in which the block copolymer thin film and the silver nanoparticle / block copolymer thin film of Example 6 intersect, the thickness of the block copolymer thin film is controlled by controlling the concentration of the block copolymer reverse micelle solution and the spin coating speed. In this case, the periodicity of the silver nanoparticle thin film can be adjusted. From this, a stop band called a photonic band gap is observed by preventing the transmission of electromagnetic waves in a specific wavelength range of the visible light region, and such a material is called a photonic crystal. .
The photograph of FIG. 7 is a photograph of each coating film of the photonic crystalline multilayer film nanostructure prepared in Example 6. The thickness of the thin film was measured by stylus method, X-ray reflectivity and ellipsometry. The total thickness of the final structure was about 350 nm. .
A spectrum showing the transmittance of the photonic crystalline multilayer film nanostructure of Example 6 is shown in FIG. 8. As can be seen from the spectrum of FIG. 8, it can be seen that the stop band appears in the visible light region. It can be seen that as the period becomes longer, that is, as the layer of the multilayer film increases, the position of the stop band moves toward the longer wavelength and a new stop band appears in the short wavelength region. From this, it can be seen that the multilayer film structure in which the block copolymer thin film prepared in Example 6 and the silver nanoparticles / block copolymer thin film intersect has a periodicity.
Claims (26)
b) preparing a first block copolymer thin film on which the metal or metal oxide nanoparticles are supported by irradiating ultraviolet light in a vacuum atmosphere on the thin film;
Method of manufacturing a multilayer film structure comprising a.
c) applying a second mixed solution containing a reverse micelle of the block copolymer containing a hydrophilic block and a hydrophobic block and a metal or metal oxide nanoparticle precursor on the first block copolymer thin film to obtain a metal or metal oxide nanoparticle precursor. Preparing a supported block copolymer thin film; And
d) preparing a multilayer film structure further comprising repeating at least one step of irradiating the thin film of step c) with ultraviolet light in a vacuum atmosphere to prepare a second block copolymer thin film on which the metal or metal oxide nanoparticles are supported. Way.
The first mixed solution is a method for producing a multilayer film structure comprising two or more metal or metal oxide nanoparticle precursors.
The metal or metal oxide nanoparticle precursor of the second mixed solution is the same or different from the metal or metal oxide nanoparticle precursor of the first mixed solution.
Repeating steps a) and b) two or more times, and repeating steps c) and d) two or more times.
c ') applying a second solution containing reverse micelles of a block copolymer containing a hydrophilic block and a hydrophobic block onto a substrate to prepare a block copolymer thin film;
d ') manufacturing a second block copolymer thin film by irradiating the thin film with ultraviolet light in a vacuum atmosphere;
The method of claim 1, further comprising steps a), b), c '), d') or c '), d'), a) and b).
Repeat steps a) and b) two or more times, repeat steps c ') and d') two or more times, or repeat steps c ') and d') two or more times, steps a) and b) Method of manufacturing a multilayer film nanostructure comprising the step of repeating two or more times.
Wherein said hydrophilic block is at least one polymer selected from the group consisting of polyvinylpyridine, polyethylene oxide, polyacrylic acid, polymethacrylic acid, polyvinyl alcohol, polyacrylamide and polystyrenesulfonic acid.
Wherein said hydrophobic block is at least one polymer selected from the group consisting of polystyrene, polyolefin, polyalkylacrylate, polyisoprene, polybutadiene, polysiloxane, polyimidazole, polylactide, polydimethylsiloxane and polylactone.
The metal is a manufacturing method of a multilayer film structure containing a precious metal or a transition metal.
The metal or metal oxide nanoparticle precursor is a metal chloride, a metal nitrate, a sol-gel precursor of a metal oxide or a metal or metal oxide nanoparticle modified with a hydrophilic ligand.
The hydrophilic ligand is a hydroxy group (-OH) or a carboxy group (-COOH) method for producing a multilayer film structure.
Method for producing a multilayer film structure comprising a molar ratio of the metal or metal oxide nanoparticles to 0.1 to 0.7 with respect to the hydrophilic block monomer.
The method of claim 1, wherein the first mixed solution is applied onto the substrate using spin coating at a speed of 1000 to 2500 rpm.
The ultraviolet rays are irradiated for 1 to 2 hours at a wavelength of 250 to 260 nm, 20 to 30 J / cm 2 The method of manufacturing a multilayer film structure.
A single layer in which one or more block copolymers carrying the metal or metal oxide nanoparticles are arranged; And
Multilayer membrane nanostructures in which a single layer in which one or more block copolymers are arranged is alternately stacked.
Multilayer film nanostructures of the same kind of metal or metal oxide nanoparticles in each single layer.
Multilayer film nanostructures of different types of metal or metal oxide nanoparticles in each single layer.
A multi-layered film nanostructure, in which a single layer comprising first metal or metal oxide nanoparticles and a single layer comprising second metal or metal oxide nanoparticles are alternately stacked.
The first single layer group in which two or more single layers including the first metal or metal oxide nanoparticles are stacked and the second single layer group in which two or more single layers including the second metal or metal oxide nanoparticles are stacked. Multi-layered nanostructures stacked alternately.
The metal or metal oxide nanoparticles of each single layer are two or more metal or metal oxide composites.
The first 'single layer group in which two or more single layers in which the block copolymers are arranged is stacked and the second' single layer group in which two or more single layers including metal or metal oxide nanoparticles are stacked are alternately stacked. Multi-layer nanostructures.
A multilayer film structure having photonic crystal properties.
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