Patent Grant
12030118
This application is a National Stage Patent Application of PCT International Patent Application No. PCT/KR2020/018597 (filed on Dec. 17, 2020) under 35 U.S.C. § 371, which claims priority to Korean Patent Application No. 10-2019-0168555 (filed on Dec. 17, 2019), which are all hereby incorporated by reference in their entirety.
The present invention relates to a plasmonic hierarchical structure having a nanogap formed therein and a method for producing the same, and more particularly, to a plasmonic hierarchical structure having a nanogap formed therein, which may be easily produced using 3D printing technology, has a nanogap formed between metal nanoparticles having excellent plasmonic properties so that a gap mode resonance may be formed in the plasmonic hierarchical structure, and is applicable to an electronic device, a chemical sensor, an optical switch, or a waveguide, and a method for producing the same.
The unique optical properties of metals are at the core of many areas of research and applications, including plasmonics, metamaterials, superlensing and subdiffraction focusing, optical antennas and surface enhanced Raman scattering. One important length scale inherent in metamaterials and plasmonics research activities in the microwave, terahertz, infrared, visible and ultraviolet ranges is the gap width of metal, which is called a nanogap.
The term “nanogap” generally refers to a gap having a width ranging from several nanometers to several tens or hundreds of nanometers as known in the art, even though the size thereof is not limited to a specific range. In general, the nanogap is applicable to an electrode or a sensor. In particular, the nanogap is essential in order to measure changes in electrical properties at the molecular level.
However, since complex process steps should be performed to form this nanogap, practical difficulties exist in using the nanogap directly in industrial applications.
Therefore, the present inventors have made efforts to overcome the above-described problems, and as a result, have recognized that it is urgent to develop a plasmonic hierarchical structure having nanogap formed therein, which may be easily produced using 3D printing technology, and a method for producing the same, thereby completing the present invention.
An object of the present invention is to provide a plasmonic hierarchical structure which shows little difference in the surface charge distribution because even when a defect occurs in the structure, it is recognized that virtual metal nanoparticles exist at the location of the defect due to a metal nanoparticle cluster forming the structure, and which may have a similar charge distribution even in dipole mode coupling.
Another object of the present invention is provide a method for producing a plasmonic hierarchical structure, which may produce a metal nanoparticle hierarchical structure having a nanogap formed therein while having a high aspect ratio, unlike conventional production methods based on lithography or self-assembly, and may produce a heterogeneous nanoparticle hierarchical structure having various optical properties by mixing metal nanoparticles with silica (SiO2) nanoparticles or CdSe quantum dots.
Objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned herein may be clearly understood by those of ordinary skill in the art from the following description of the invention.
To achieve the above objects, the present invention provides a plasmonic hierarchical structure having a nanogap formed therein, and a method for producing the same.
Hereinafter, the present specification will be described in more detail.
The present invention provides a plasmonic hierarchical structure having a nanogap formed between metal nanoparticles.
In the present invention, the nanogap may have a width of 1 nm to 100 nm.
In the present invention, the metal nanoparticles may comprise at least one selected from the group consisting of gold (Au), silver (Ag), copper (Cu), platinum (Pt), and palladium (Pd).
In the present invention, the plasmonic hierarchical structure may further comprise silica (SiO2) nanoparticles or CdSe quantum dots.
The present invention also provides a method for producing a plasmonic hierarchical structure comprising steps of:
In the present invention, the metal nanoparticles may comprise at least one selected from the group consisting of gold (Au), silver (Ag), copper (Cu), platinum (Pt), and palladium (Pd).
In the present invention, step (S1) may comprise mixing a silica (SiO2) nanoparticle or CdSe quantum dot solution with the metal nanoparticle solution and injecting the mixture into the micropipette.
In the present invention, step (S2) may comprise steps of:
In the present invention, step (S3) may comprise steps of:
In the present invention, the meniscus may be formed to have a volume of 10 to 500 fL.
All details mentioned in the plasmonic hierarchical structure and the production method therefor are equally applied unless they are contradictory.
The plasmonic hierarchical structure of the present invention shows little difference in the surface charge distribution because even when a defect occurs in the structure, it is recognized that virtual metal nanoparticles exist at the location of the defect due to a metal nanoparticle cluster forming the structure, and may have a similar charge distribution even in dipole mode coupling.
In addition, in the plasmonic hierarchical structure of the present invention, the metal nanoparticles may collectively exhibit a nanogap effect, and thus a gap plasmon mode may be formed, and a metal nanoparticle mode may be suppressed, and even when the nanogap is 30 nm or more, the localized plasmon resonance wavelength may appear at a long wavelength (about 780 nm or more).
In addition, in the plasmonic hierarchical structure of the present invention, when quantum dots are added to the plasmonic hierarchical structure and weak light (402 nm wavelength and 2 kW/cm2) is incident on the structure, the quantum dots may be heated, the emission wavelength may be shifted to a longer wavelength, and a strong plasmonic effect may appear in the plasmonic hierarchical structure.
In the method for producing a plasmonic hierarchical structure according to the present invention, it is possible to produce a metal nanoparticle hierarchical structure having a nanogap formed therein while having a high aspect ratio, unlike a conventional production method based on lithography or self-assembly.
In addition, in the method for producing a plasmonic hierarchical structure according to the present invention, it is possible to produce a heterogeneous nanoparticle hierarchical structure by mixing metal nanoparticles with silica (SiO2) nanoparticles, thereby controlling the width of the formed nanogap.
In addition, in the method for producing a plasmonic hierarchical structure according to the present invention, it is possible to produce a heterogeneous nanoparticle hierarchical structure by mixing metal nanoparticles with CdSe quantum dots, whereby the plasmonic effect of the plasmonic hierarchical structure may be imparted to the quantum dots, thereby improving the optical properties of the structure.
Effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned herein will be clearly understood by those skilled in the art from the following description and the appended claims.
The terms used in the present specification are currently widely used general terms selected in consideration of their functions in the present invention, but they may change depending on the intents of those skilled in the art, precedents, or the advents of new technology. Additionally, in certain cases, there may be terms arbitrarily selected by the applicant, and in this case, their meanings are described in a corresponding description part of the invention. Accordingly, the terms used in the present invention should be defined based on the meaning of the term and the entire contents of the present invention, rather than the simple term name.
Unless otherwise defined, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The terms used in general and defined in dictionaries should be interpreted as having meanings identical to those specified in the context of related technology. Unless definitely defined in the present application, the terms should not be interpreted as having ideal or excessively formative meanings.
A numerical range includes numerical values defined in the range. Every maximum numerical limitation given throughout the present specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout the present specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
Hereinafter, embodiments of the present invention will be described in detail, but it is obvious that the present invention is not limited by the following embodiments.
Plasmonic Hierarchical Structure Having Nanogap Formed Therein
The present invention provides a plasmonic hierarchical structure having a nanogap formed between metal nanoparticles.
As used herein, the term “nanogap” refers to a gap having a width ranging from several nanometers to several tens or hundreds of nanometers as known in the art, even though the size thereof is not limited to a specific range.
As used herein, the term “plasmon” means a type of quasiparticle consisting of free electrons collectively vibrating within the metal, and refers to waves of electrons.
Referring to
The plasmonic hierarchical structure may be in the form of a free-standing structure having a large aspect ratio. The free-standing structure is a structure which dose not an additional support for supporting the structure and in which a three-dimensional structure is formed in a vertical direction.
The metal nanoparticles may be nanoparticles comprising at least one selected from the group consisting of gold (Au), silver (Ag), copper (Cu), platinum (Pt) and palladium (Pd). Preferably, the metal nanoparticles may be nanoparticles comprising at least one selected from the group consisting of gold and silver. Most preferably, the metal nanoparticles may be gold nanoparticles.
When the surfaces of the metal nanoparticles having a size smaller than the wavelength of light are irradiated with light, a surface plasmon, which is a phenomenon of collective vibration of electrons caused by the interaction of light and electrons, may be formed at the boundary between the surface of the metal nanoparticle and a dielectric. Due to the surface plasmon formed on the metal nanoparticles, an electric field on the surfaces of the metal nanoparticles increases, and localized surface plasmon resonance (LSPR) characteristics appear.
The plasmonic hierarchical structure may have a width of 100 nm to 10 μm, preferably 100 nm to 2 μm, most preferably 500 nm to 1 μm.
The nanogap included in the plasmonic hierarchical structure may have a width of 1 nm to 100 nm, preferably 1 nm to 50 nm, most preferably 5 nm to 30 nm.
Even when the nanogap formed in the plasmonic hierarchical structure according to the present invention is 30 nm or more, the localized plasmon resonance wavelength may appear at a long wavelength (about 780 nm or more).
The nanogap may form a gap mode resonance that occurs when the gap between the metal nanoparticles decreases to a nanometer (nm) scale. The gap mode resonance may maximize electric field amplification in the wavelength range in which the gap mode resonance occurs. Thus, the plasmonic hierarchical structure may be used as a plasmonic device in the above-described wavelength range. In addition, since the wavelength range in which the gap mode resonance occurs may be changed in response to an external environment, the plasmonic hierarchical structure itself may be applied as a sensor.
In addition, since the metal nanoparticles collectively exhibit the nanogap effect, a gap plasmon mode may be formed, and the metal nanoparticle mode may be suppressed.
The plasmonic hierarchical structure may be formed as a heterogeneous nanoparticle hierarchical structure by additionally comprising silica (SiO2) nanoparticles or CdSe quantum dots in addition to the metal nanoparticles.
In the case of the heterogeneous nanoparticle hierarchical structure which is a plasmonic hierarchical structure comprising the metal nanoparticles and the silica nanoparticles, it is possible to control the width of the nanogap existing in the structure. More specifically, the heterogeneous nanoparticle hierarchical structure, which is a plasmonic hierarchical structure formed by mixing the metal nanoparticles with the silica nanoparticles, has a relatively increased nanogap width compared to the nanogap width of the plasmonic hierarchical structure comprising only the metal nanoparticles, and thus may be shifted to a relatively short wavelength (shifted to blue). In general, since the optical properties of the nanogap are maximized in the wavelength range in which the gap plasmon resonance occurs, it is very important to control the wavelength range in which the gap plasmon resonance occurs. In other words, the heterogeneous nanoparticle hierarchical structure, which is a plasmonic hierarchical structure comprising the metal nanoparticles mixed with the silica nanoparticles, may be very favorable for the fabrication of applied devices, because it indicates that it is possible to control the wavelength range in which the gap plasmon resonance occurs.
In addition, in the case of the heterogeneous nanoparticle hierarchical structure which is a plasmonic hierarchical structure comprising the metal nanoparticles and CdSe quantum dots, the width of the band gap of the quantum dot decreases with increasing temperature, and thus the photo-luminescence spectrum of the plasmonic hierarchical structure comprising the metal nanoparticles and the CdSe quantum dots may be shifted to a longer wavelength (shifted to red).
The plasmonic hierarchical structure of the present invention shows little difference in the surface charge distribution because even when a defect occurs in the structure, it is recognized that virtual metal nanoparticles exist at the location of the defect due to a metal nanoparticle cluster forming the structure, and may have a similar charge distribution even in dipole mode coupling.
Method for Producing Plasmonic Hierarchical Structure
present invention also provides a method for producing a plasmonic hierarchical structure comprising steps of:
The plasmonic hierarchical structure is the same as mentioned above.
The method for producing a plasmonic hierarchical structure may be performed through 3D printing, more specifically, a meniscus-guided 3D printing technique.
Step (S1) may be a step of injecting a metal nanoparticle solution into a micropipette. More specifically, step (S1) may be a step of injecting a metal nanoparticle solvent into a micropipette having a nozzle formed therein.
The metal nanoparticles may be nanoparticles comprising at least one selected from the group consisting of gold (Au), silver (Ag), copper (Cu), platinum (Pt) and palladium (Pd). Preferably, the metal nanoparticles may be nanoparticles comprising at least one selected from the group consisting of gold and silver. Most preferably, the metal nanoparticles may be gold nanoparticles.
The micropipette may be a glass capillary puller having a nozzle. When the glass capillary puller is used, it is possible to control the injection rate of the metal nanoparticle solution.
The micropipette may have a diameter of 1 to 5 μm, preferably 2 to 4 μm.
In step (S1), a silica (SiO2) nanoparticle or CdSe quantum dot solution may be mixed with the metal nanoparticle solution and injected into the micropipette, thereby producing a heterogeneous nanoparticle hierarchical structure as a plasmonic hierarchical structure.
Step (S2) may comprise steps of:
More specifically, as the micropipette comes into contact with the substrate and the micropipette moves from the contact point in a specific direction, for example, a vertical direction, at a predetermined speed, a predetermined flow rate of the metal nanoparticle solution may be released from the nozzle at the tip of the micropipette.
Step (S3) may comprise steps of:
More specifically, the meniscus may be formed by the surface tension of the metal nanoparticle solution released from the vicinity of the nozzle at the tip of the micropipette. A plasmonic hierarchical structure may be deposited on the substrate by evaporation of a solvent present in the metal nanoparticle solution from the meniscus surface. While the micropipette is moved upward, the surface tension of the meniscus formed at the tip of the nozzle may act to minimize the surface area of the metal nanoparticle solution, and may pull the metal nanoparticle solution in the nozzle so that the metal nanoparticle solution may be released of the nozzle without interruption, thereby depositing a plasmonic hierarchical structure on the substrate.
As the nozzle at the tip of the micropipette is moved in any direction, a plasmonic hierarchical structure corresponding to the movement trajectory may be produced.
The meniscus may be formed to have a volume of 10 to 500 fL.
According to the method for producing a plasmonic hierarchical structure according to the present invention, it is possible to produce a metal nanoparticle hierarchical structure having a nanogap formed therein while having a high aspect ratio, unlike conventional production methods based on lithography or self-assembly, and it is possible to produce a heterogeneous nanoparticle hierarchical structure having various optical properties by mixing metal nanoparticles with silica (SiO2) nanoparticles or CdSe quantum dots.
The advantages and features of the present invention, and the way of attaining them, will become apparent with reference to the examples described in detail below. However, the present invention is not limited to the examples disclosed below and may be embodied in a variety of different forms; rather, these examples are provided so that this disclosure of the present invention will be thorough and complete, and will fully convey the scope of the present invention to those skilled in the art. The scope of the present invention will be defined by the appended claims.
A solution containing gold nanoparticles (NanoXact Gold Nanospheres—Polystyrene—100 nm, Nanocomposix, San Diego, CA 92111, USA) at a concentration of 1 mg/ml was injected into a micropipette having a diameter of 3 μm. Next, the micropipette was brought into contact with a substrate, and the metal nanoparticle solution was released from the contact point between the micropipette and the substrate. A femtoliter-scale meniscus was formed by the surface tension of the released metal nanoparticle solution, and a plasmonic hierarchical structure was deposited on the substrate by evaporation of the metal nanoparticle solution present on the meniscus surface, thereby producing plasmonic hierarchical structure 1 having a curved shape.
A solution containing gold nanoparticles (NanoXact Gold Nanospheres—Polystyrene—100 nm, Nanocomposix, San Diego, CA 92111, USA) at a concentration of 1 mg/ml was injected into a micropipette having a diameter of 3 μm. Next, the micropipette was brought into contact with a substrate, and the metal nanoparticle solution was released from the contact point between the micropipette and the substrate. A femtoliter-scale meniscus was formed by the surface tension of the released metal nanoparticle solution, and a plasmonic hierarchical structure was deposited on the substrate by evaporation of the metal nanoparticle solution present on the meniscus surface, thereby producing plasmonic hierarchical structure 2 having a simple columnar shape.
A solution containing gold nanoparticles (NanoXact Gold Nanospheres—Polystyrene—100 nm, Nanocomposix, San Diego, CA 92111, USA) at a concentration of 1 mg/ml was mixed with 20 nm silica nanoparticles (Nanocs Inc., New York, NY 10001, USA), and the mixture and toluene were placed and mixed in a centrifuge. At this time, the gold nanoparticles and silica nanoparticles were mixed together at concentration ratios of 100:0, 100:5 and 100:10. Each of the three mixtures of the gold nanoparticles and the silica nanoparticles was injected into a micropipette having a diameter of 3 μm. Next, each of the micropipettes was brought into contact with a substrate, and each of the metal nanoparticle solutions was released from the contact point between each micropipette and each substrate. A meniscus was formed by the surface tension of each of the released metal nanoparticle solutions, and the metal nanoparticle solution existing on each of the meniscus surfaces was evaporated and a plasmonic hierarchical structure was deposited on each of the substrates, thereby producing plasmonic hierarchical structures 3A, 3B and 3C.
A solution containing gold nanoparticles (NanoXact Gold Nanospheres—Polystyrene—100 nm, Nanocomposix, San Diego, CA 92111, USA) at a concentration of 1 mg/ml was mixed with colloidal CdSe quantum dots having an emission peak at 620 nm and a concentration of 5 mg/ml. The mixture was injected into a micropipette having a diameter of 3 μm. Next, the micropipette was brought into contact with a substrate, and the metal nanoparticle solution was released from the contact point between the micropipette and the substrate. A meniscus was formed by the surface tension of the released metal nanoparticle solution, and a plasmonic hierarchical structure was deposited on the substrate by evaporation of the metal nanoparticle solution present on the meniscus surface, thereby producing plasmonic hierarchical construct 4.
In order to confirm whether a nanogap is present in the plasmonic hierarchical structure according to the present invention, whether or not the nanogap would be formed was examined by performing measurement with a scanning electron microscope (SEM) (Hitachi S-4700, PNU center for Research facilities, Busan, Korea) and a transmission electron microscope (TEM) for plasmonic hierarchical structure 1 produced in Example 1. The results are shown in
Referring to
In order to confirm the consistency of the 3D self-assembly method for producing a plasmonic hierarchical structure according to the present invention, the plasmonic hierarchical structure 2 produced in Example 2 was divided into five points (points 1 to 5) and then subjected to focused ion beam (FIB) milling (Helios NanoLab™, FEI, Eindhoven, 55651, Netherlands) and then to dark field scattering measurement. The results are shown in
Referring to
In order to analyze the optical properties of the plasmonic hierarchical structure of the present invention depending on the presence or absence of metal nanoparticle defects, simulation using the 3D finite element method (3D FEM) with COMSOL Multiphysics was performed on plasmonic hierarchical structure 1 produced in Example 1. The results are shown in
Referring to
In addition, referring to
From the above results, it can be confirmed that optical properties of the plasmonic hierarchical structure did not change depending on the presence or absence of metal nanoparticle defects in the plasmonic hierarchical structure, suggesting that virtual metal nanoparticles are recognized to exist in the plasmonic hierarchical structure.
In order to examines changes in nanogap control ability and short wavelength shift (shift to blue) depending on the amount of silica nanoparticles included in a heterogeneous nanoparticle hierarchical structure which is a plasmonic hierarchical structure comprising gold nanoparticles and silica nanoparticles, scattering characteristic analysis and 3D FDTD simulation were performed on the three plasmonic hierarchical structures produced in Example 3. The results are shown in
4.1 Analysis of Scattering Characteristics
Referring to
4.2 3D FDTD Simulation Results
Referring to
From the above results, it can be confirmed that, in the heterogeneous nanoparticle hierarchical structure, which is a plasmonic hierarchical structure comprising gold nanoparticles and silica nanoparticles, it is possible to control the wavelength range in which a gap plasmon resonance occurs.
In order to evaluate the effects of addition of quantum dots on photoluminescence (PL) and plasmonic heating, weak light with a wavelength of 402 nm and a laser source power of 2 kW/cm2 was applied to plasmonic layer structure 4 produced in Example 4. As a result, it could be confirmed that, as the quantum dots included in plasmon hierarchical structure 4 were heated, the emission wavelength was shifted to a longer wavelength (shifted to red). This signal is similar to a photoluminescence signal measured after heating quantum dots to 100° C. or higher, and it is known that the temperature can increase when the plasmonic concentration phenomenon occurs, suggesting that a strong plasmonic effect appeared in the plasmonic hierarchical structure.
While the present invention has been described with reference to the illustrative embodiments, those skilled in the art to which the present invention pertains will appreciate that that the present invention may be embodied in other specific forms without departing from the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above are considered to be illustrative in all respects and not restrictive.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2019-0168555 | Dec 2019 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2020/018597 | 12/17/2020 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2021/125853 | 6/24/2021 | WO | A |
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| Number | Date | Country | |
|---|---|---|---|
| 20220317042 A1 | Oct 2022 | US |
