KR20160070568A - Plasmonic Paper and its Manufacturing Method - Google Patents

Plasmonic Paper and its Manufacturing Method Download PDF

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Publication number
KR20160070568A
KR20160070568A KR1020140177698A KR20140177698A KR20160070568A KR 20160070568 A KR20160070568 A KR 20160070568A KR 1020140177698 A KR1020140177698 A KR 1020140177698A KR 20140177698 A KR20140177698 A KR 20140177698A KR 20160070568 A KR20160070568 A KR 20160070568A
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KR
South Korea
Prior art keywords
plasmonic
paper
present
nanostructure
plasmon resonance
Prior art date
Application number
KR1020140177698A
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Korean (ko)
Inventor
정기훈
정혁진
강민희
박문성
Original Assignee
한국과학기술원
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 한국과학기술원 filed Critical 한국과학기술원
Priority to KR1020140177698A priority Critical patent/KR20160070568A/en
Priority to PCT/KR2015/013299 priority patent/WO2016093569A1/en
Publication of KR20160070568A publication Critical patent/KR20160070568A/en

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/02—Metal coatings
    • D21H19/08—Metal coatings applied as vapour, e.g. in vacuum
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating
    • D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/02—Patterned paper

Abstract

The present invention relates to a plasmonic paper and a method for producing the same. More particularly, the present invention relates to a plasmonic paper and a method for producing the plasmonic paper, To a plasmonic paper capable of detecting a high sensitivity of a biochemical sample including biomolecules, and a method for producing the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasmonic paper,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasmonic paper and a method for producing the same, and more particularly, to a plasmonic paper having a plasmonic nanostructure formed on a paper surface and a method for producing the same.

There are a lot of free electrons inside the conductor metal, and free electrons are not bound to metal atoms, so they can easily respond to specific external stimuli.

Especially, when the size of the metal becomes nano-sized, the surface plasmon resonance (SPR) characteristic is exhibited by the behavior of such free electrons, so that it has a unique optical property.

The surface plasmon resonance refers to a phenomenon in which, when light is incident between the surface of metal nanoparticles as a conductor and a dielectric such as air or water, free electrons on the surface of the metal collectively vibrate due to resonance with an electromagnetic field of a specific energy of light.

In this case, a surface plasmon generated in a nanometer-sized metal structure is referred to as Localized Surface Plasmon Resonance (LSPR), and the local surface plasmon resonance can be detected by biosensor .

Surface enhanced Raman scattering, metal enhancement fluorescence, and local surface plasmon resonance mutation can be used to detect the local surface plasmon resonance and to use it for precision detection of a molecule or a biosensor.

The surface enhanced Raman scattering refers to a phenomenon in which Raman scattering is amplified from 10 to 7 to 9 by local surface plasmon resonance occurring on a rough metal surface.

To describe Raman scattering more precisely, each molecule has its own vibration and rotation quantized energy state according to its molecular structure. When a molecule is irradiated with a short-wavelength light, Depending on the energy state, it absorbs the light, becomes excited state, and then returns to the ground state while emitting energy in the original light form.

At this time, the phenomenon of releasing red-shifted light from various light emitted is called Stokes-Raman Shift, and this phenomenon is called Raman scattering.

That is, since each molecule has a unique energy state according to its molecular structure, Raman scattering represents a unique property of the material, and even if only one molecule is present, a Raman scattering signal appears. There is an easy advantage.

The Metal Enhanced Fluorescence refers to a phenomenon in which a fluorescent signal is amplified using local surface plasmon resonance like surface enhancement Raman scattering described above.

The local surface plasmon resonance mutation can be used for precise detection of molecules by detecting that the wavelength of local surface plasmon resonance is changed finely using the optical refraction index depending on the concentration of the sample.

In order to utilize the above-described surface-enhanced Raman scattering, metal enhancement fluorescence and local surface plasmon resonance mutation, a plasmonic nanostructure should be formed on the test substance.

However, in general, in order to form a plasmonic nanostructure on a test material, it is difficult to form a large-area plasmonic nanostructure because a plasmonic nanostructure must be formed on a limited test material. Plasmonic nanostructure formation for Raman scattering There is a problem that it takes a lot of time.

In addition, conventional plasmonic substrates are not flexible enough to form various types of plasmonic structures and are expensive.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above problems, and it is an object of the present invention to provide a plasmonic nanostructure by inducing local surface plasmon resonance on a paper surface, The present invention provides a plasmonic paper capable of detecting a high sensitivity of a biochemical sample including biomolecules and a method for producing the same.

The plasmonic paper and the method of manufacturing the same according to the present invention are characterized by forming a subject material of paper including cellulose and a plasmonic nanostructure on the surface of the subject material, And the formed plasmon materials are spaced apart from each other.

Particularly, the plasmonic nanostructure is characterized in that the particles of the particles are spaced apart from each other by a distance of less than a wavelength.

The plasmon material may be selected from the group consisting of a metal, an alloy, a conductive oxide including indium tin oxide (ITO), a semiconductor including silicon, a nitride semiconductor, an oxide semiconductor, an amorphous semiconductor, a low molecular compound, Or more.

The plasmon material includes at least one selected from the group consisting of silver, gold, platinum, aluminum, iron, zinc, copper, tin and nickel, and an alloy selected from bronze and brass.

In addition, in the method for producing a plasmonic paper, a deposition step of depositing and applying a plasmon material on the surface of the object material; And a granulation step of granulating the plasmon material deposited in the deposition step.

In addition, the deposition step is characterized by depositing the plasmon material to a thickness of 1 nm to 50 nm.

The above-mentioned granulation step is characterized in that a heat treatment method is used at 30 ° C to 160 ° C.

The granulating step may be performed in any one of inert gas, vacuum, and air.

Further, the inert gas may be any one selected from nitrogen, argon, helium, neon, krypton, and xenon.

The plasmonic paper according to the present invention and the method of producing the same can obtain the amplification effect of fluorescence and Raman scattering and the mutation sensitivity of local surface plasmon resonance by forming a plasmonic nanostructure that induces local surface plasmon resonance on the paper surface , And high sensitivity of biological samples including biomolecules can be detected.

In particular, the plasmonic paper and the method of manufacturing the same according to the present invention can form a plasmonic paper having a plasmonic nanostructure that induces local surface plasmon resonance, thereby mass-producing a plasmonic sensing substrate having a large-area local surface plasmon resonance structure .

In addition, the plasmonic paper according to the present invention and the method for producing the same can form a plasmonic paper having a plasmonic nanostructure that induces local surface plasmon resonance, so that a high sensitivity can be measured with a very small amount of sample solution There are advantages.

In addition, the plasmonic paper according to the present invention and the method for producing the same have the advantage of being applicable to various plasmonic sensing by forming a plasmonic paper on which a plasmonic nanostructure for inducing local surface plasmon resonance is formed.

In addition, the plasmonic paper and the method of manufacturing the same according to the present invention can form a plasmonic paper in which the plasmonic nanostructure inducing local surface plasmon resonance is formed only on the surface of the paper. Therefore, absorption of natural moisture hygroscopic nature) without any influence on the environment.

In addition, the plasmonic paper and the method of manufacturing the same according to the present invention can form a plasmonic paper in which a plasmonic nanostructure that induces local surface plasmon resonance is formed on the surface of paper, so that the substrate is formed of paper and is flexible, There is an advantage that it is easy to form a structure.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a plasmonic paper according to the present invention.
2 shows a method for producing a plasmonic paper according to the present invention.
3 is another diagram showing a method for producing a plasmonic paper according to the present invention.
4 is a graph showing the density of nano-islands and the wavelength of local surface plasmon resonance according to the thickness of the plasmonic material according to the present invention.
5 is a view showing a result of a heat treatment test in the granulation step in the method for producing a plasmonic paper according to the present invention.

Hereinafter, a plasmonic paper having the above-described characteristics and a method of manufacturing the same will be described in detail with reference to the accompanying drawings.

Prior to this, terms and words used in the present specification and claims should not be construed in a conventional or dictionary sense, and the inventor should appropriately define the concept of the term to describe its invention in the best possible way The present invention should be construed in accordance with the spirit and concept of the present invention.

Therefore, the embodiments described in the present specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention, and not all of the technical ideas of the present invention are described. Therefore, It is to be understood that equivalents and modifications are possible.

FIG. 1 is a view showing a plasmonic paper according to the present invention, FIG. 2 is a view showing a method for producing a plasmonic paper according to the present invention, and FIG. 3 is a view for explaining a method for producing a plasmonic paper according to another embodiment FIG. 4 is a view showing the density of a nano-island and the wavelength of local surface plasmon resonance according to the thickness of the plasmon material according to the present invention. Fig. 6 is a graph showing the results of the heat treatment test in the intermediate granulation step. Fig.

The plasmonic papers according to the present invention can be obtained by forming a plasmonic nanostructure 200 that induces local surface plasmon resonance in a target material (paper) 100, thereby improving the amplification effect of fluorescence and Raman scattering and the sensitivity of local surface plasmon resonance And therefore, a plasmonic paper capable of detecting a high sensitivity of a biochemical sample including biomolecules.

1, the plasmonic paper according to the present invention is characterized in that a plasmonic nanostructure 200 is formed on the surface of a subject material 100 made of paper containing cellulose, The mononic nanostructure 200 is characterized in that the particles of the particles 210 are spaced apart.

More specifically, the object material 100 is formed of paper containing cellulosic material, which is used in large quantities as paper or textile fibers. The object material 100 is formed of a paper material, So that a high sensitivity can be measured even with a very small amount of sample solution.

Further, since the substrate is formed of a paper material, the substrate on which the plasmonic structure is formed is flexible, so that various types of plasmonic structures can be formed, and a plasmonic structure can be easily formed.

In addition, the plasmonic paper according to the present invention is advantageous in terms of cost as compared with conventional substrates having a high price because the substrate is made of a material 100 made of a paper material.

The plasmonic nanostructure 200 is characterized in that the particles 210 of particles are granulated to form a nano island and the nano-islands are formed on the surface of the object material 100 do.

At this time, it is recommended that the spacing distance between the nano-sized islands, that is, the period of the plasmonic nanostructure 200 is spaced apart by a wavelength smaller than the wavelength of light for induction of Raman scattering. However, As shown in FIG.

The plasmon material 210 may be selected from the group consisting of a metal, an alloy, a conductive oxide including indium tin oxide (ITO), a semiconductor including silicon, a nitride semiconductor, an oxide semiconductor, an amorphous semiconductor, a low molecular compound, Or more.

That is, at least one of the materials described above may be used, or two or more may be used in combination.

It is recommended to form the plasmon material 210 with silver (Ag) on the metal. However, if it is a substance capable of inducing local surface plasmon resonance, gold (Au), platinum (Pt), aluminum (Al) (Fe), zinc (Zn), copper (Cu), tin (Sn), nickel (Ni)

An alloy of the metals described above is used for the alloy forming the plasmonic material 210, and bronze which is an alloy of copper and tin and copper and a brass which is a zinc alloy are available.

Parylene may be used for the low-molecular compound, and a carbon-carbon compound, carbon nanotube (CNT), graphite, graphene, or the like may be used for the carbon compound.

As described above, since the plasmonic nanostructure 200 is formed on the surface of the subject material 100 made of paper, the plasmonic paper according to the present invention can be used for the amplification effect of fluorescence and Raman scattering and the sensitivity of mutation of local surface plasmon resonance It is possible to detect a high sensitivity of a biochemical sample including biomolecules, and it is also advantageous in mass production of a plasmonically sensing substrate having a large-area local surface plasmon resonance structure.

In particular, the plasmonic paper according to the present invention can form a plasmonic nanostructure 200 on a target material 100 of a paper material having good water absorption, and can measure a high sensitivity with a very small amount of sample solution And it is advantageous to variously apply to the formation of plasmonic sensing by using the material 100 made of paper instead of the test substance in which the conventional plasmonic nanostructure 200 is formed.

The method of producing the plasmonic paper described above will be described in detail with reference to the accompanying drawings.

2 to 3, a method of manufacturing a plasmonic paper according to the present invention includes a deposition step S100 of depositing and applying a plasmon material 210 on the surface of the object material 100, (S200) for granulating the plasmon material (210) deposited in the step (S100).

As shown in FIGS. 2 to 3 (b), the deposition step S100 is a step of depositing a plasmon material 210 on the surface of the object material 100, and is formed to have a thickness of 1 nm to 50 nm .

As shown in FIGS. 2 to 3 (c), the granulating step is a step of granulating the plasmon material 210 deposited on the surface of the object material 100 to form a separated nano island , And as described above, the nano-islands are formed so as to be spaced apart from each other by a distance equal to or less than the light wavelength.

At this time, in the method of granulating the plasmon material 210 in the granulation step, the plasmon material 210 may be granulated using a heat treatment method. In addition to the above-described method, a known technique such as laser processing, It goes without saying that various embodiments of the granulation method are possible.

The above-described method of granulating is a conventional technique known in the art, so a detailed description thereof will be omitted.

However, in order to granulate the plasmonic material 210 using the heat treatment, it is recommended to perform the granulation at a temperature of 30 ° C to 160 ° C.

In addition, the granulation step may perform the granulation of the plasmonic material 210 in the air, but may perform the granulation of the plasmonic material 210 in a vacuum or an inert gas to enhance the stability of the granulation operation .

<Deposition Thickness of Plasmonic Material Deposited in the Deposition Step of Plasmonic Paper Manufacturing Method According to the Present Invention>

4 is a graph showing the density of nano-islands and the wavelength of local surface plasmon resonance according to the thickness of the plasmon material 210 according to the present invention.

At this time, the thickness of the plasmon material 210 is formed to a thickness ranging from 1 nm to 50 nm as described above, and the plasmon material 210 used is used as silver.

As shown in FIG. 4, when the thickness of the plasmon material 210 is 10 nm, the density of the formed nano-islands is the highest, and when the thickness is 10 nm, the wavelength of the local surface plasmon resonance is the largest .

That is, the thickness of the plasmon material 210 may be in the range of 1 nm to 50 nm depending on the wavelength of the local surface plasmon resonance to be output and the test environment, but the wavelength of the local surface plasmon resonance It is recommended that the plasmonic material 210 be deposited to a particle size of 10 nm as described above.

&Lt; Temperature for heat treatment of plasmon material in the method of producing plasmonic paper according to the present invention &

Since the subject material is formed of a paper material containing cellulose and the cellulose is an organic material, the plasmatic paper according to the present invention is characterized in that in the method of producing a plasmonic paper according to the present invention, the subject material is heat- Must be granulated.

That is, the optical noise (absorption, fluorescence, Raman scattering) of the substrate of the paper material due to thermal deformation significantly increases in the cellulose as the organic material, so that it is difficult to detect the highly sensitive surface enhanced Raman spectroscopic signal.

Accordingly, Applicant has found through the test that the heat treatment temperature of 30 ° C to 160 ° C capable of measuring a high-sensitivity surface enhanced Raman signal while minimizing noise of the substrate due to heat treatment.

&Lt; Embodiment by Combination of Plasmonic Paper and Chromatography According to the Present Invention >

The plasmonic paper according to the present invention can separate the mixed material by combination with paper chromatography and perform the plasmonic characteristic detection.

As shown in Figure 6a, after chromatographic separation of the plasmonic species, the molecules separated at the color sensing locations of the fuel molecules (CR, TB, CV) in the aqueous mixture are clearly distinguishable, respectively, The absorption peak can be confirmed.

In addition, after chromatographic separation, measurements of surface enhanced Raman scattering can be performed without labeling.

As shown in Fig. 6 (b), after the chromatographic separation, the fluorescence signal of the dye molecules mixed at a very low concentration is absorbed by the plasmonic paper to show a clear division. Fig. 6 (c) And the measurement of the surface enhanced Raman scattering and the metal enhancement fluorescence is shown.

That is, the plasmonic paper according to the present invention is advantageous in that it can separate the mixed material using paper chromatography and perform ultra-high sensitivity plasmonic detection.

This can not be realized with a conventional plasmonic sensor. The plasmonic paper according to the present invention has a plasmonic structure on a flexible paper material, which is advantageous in various fields.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention. It is to be understood that various changes and modifications may be made without departing from the scope of the appended claims.

100: Target substance
200: Plasmonic nanostructure
210: plasmonic substance
S100: deposition step
S200: granulation step

Claims (9)

A subject material made of a paper material containing cellulose,
Wherein a plasmonic nanostructure is formed on the surface of the target material,
The plasmonic nanostructure
Wherein the particulate plasmonic materials are spaced apart.
The method according to claim 1,
The plasmonic nanostructure
Wherein the particles of the plasmonic material are spaced apart from each other by a distance less than a wavelength of light.
The method according to claim 1,
The plasmonic material
A nitride semiconductor, an oxide semiconductor, an amorphous semiconductor, a low-molecular compound, and a carbon compound, which is selected from the group consisting of a metal, an alloy, a conductive oxide including indium tin oxide (ITO) Plasmonic paper.
The method of claim 3,
The plasmonic material
Silver and at least one metal selected from gold, platinum, aluminum, iron, zinc, copper, tin and nickel,
Bronze, and brass. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
A method for producing a plasmonic paper according to any one of claims 1 to 4,
A deposition step of depositing and applying a plasmon material on the surface of the target material; And
And a granulation step of granulating the plasmon material deposited in the deposition step.
6. The method of claim 5,
The deposition step
Wherein the plasmon material is deposited to a thickness of 1 nm to 50 nm.
6. The method of claim 5,
The granulating step
Characterized in that a heat treatment method is used at 30 캜 to 160 캜.
6. The method of claim 5,
The granulating step
An inert gas, an inert gas, a vacuum, and an atmosphere.
The method according to claim 6,
The inert gas
Nitrogen, argon, helium, neon, krypton, and xenon.
KR1020140177698A 2014-12-10 2014-12-10 Plasmonic Paper and its Manufacturing Method KR20160070568A (en)

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KR1020140177698A KR20160070568A (en) 2014-12-10 2014-12-10 Plasmonic Paper and its Manufacturing Method
PCT/KR2015/013299 WO2016093569A1 (en) 2014-12-10 2015-12-07 Plasmonic paper and manufacturing method therefor

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KR20190121427A (en) * 2018-04-18 2019-10-28 경희대학교 산학협력단 A substrate for surface enhanced raman scattering and fabricating method of the same
KR20200089987A (en) * 2019-01-18 2020-07-28 경희대학교 산학협력단 A substrate for surface enhanced raman scattering and fabricating method of the same
KR20200089986A (en) * 2019-01-18 2020-07-28 경희대학교 산학협력단 A transparent substrate for surface enhanced raman scattering and fabricating method of the same

Family Cites Families (4)

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Publication number Priority date Publication date Assignee Title
KR101108699B1 (en) * 2009-09-10 2012-01-25 한국과학기술원 Manufacturing method for surface enhanced raman scattering patch with biocompatibility using hydrogel and surface enhanced raman scattering method in using the patch
KR101229065B1 (en) * 2011-07-01 2013-02-04 포항공과대학교 산학협력단 A method of manufacturing substrate for surface-enhanced raman scattering spectroscope and the substrate manufactured by the method
KR101352503B1 (en) * 2012-01-17 2014-01-20 서울대학교산학협력단 Metal nano particles on a substrate and method for fabricating the same
KR101475291B1 (en) * 2013-04-09 2014-12-22 한국과학기술원 chromatography substrate with surface enhanced Raman scattering nano-structure and fabricating method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190121427A (en) * 2018-04-18 2019-10-28 경희대학교 산학협력단 A substrate for surface enhanced raman scattering and fabricating method of the same
KR20200089987A (en) * 2019-01-18 2020-07-28 경희대학교 산학협력단 A substrate for surface enhanced raman scattering and fabricating method of the same
KR20200089986A (en) * 2019-01-18 2020-07-28 경희대학교 산학협력단 A transparent substrate for surface enhanced raman scattering and fabricating method of the same

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