WO2017200295A1 - 표면증강 라만산란 기판, 이를 포함하는 분자 검출용 소자 및 이의 제조방법 - Google Patents

표면증강 라만산란 기판, 이를 포함하는 분자 검출용 소자 및 이의 제조방법 Download PDF

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WO2017200295A1
WO2017200295A1 PCT/KR2017/005115 KR2017005115W WO2017200295A1 WO 2017200295 A1 WO2017200295 A1 WO 2017200295A1 KR 2017005115 W KR2017005115 W KR 2017005115W WO 2017200295 A1 WO2017200295 A1 WO 2017200295A1
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metal
raman scattering
film
enhanced raman
scattering substrate
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PCT/KR2017/005115
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English (en)
French (fr)
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WO2017200295A9 (ko
Inventor
이동한
이종민
윤일선
백종서
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충남대학교산학협력단
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Priority to US16/301,922 priority Critical patent/US11085881B2/en
Publication of WO2017200295A1 publication Critical patent/WO2017200295A1/ko
Publication of WO2017200295A9 publication Critical patent/WO2017200295A9/ko

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/02—Local etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F4/00—Processes for removing metallic material from surfaces, not provided for in group C23F1/00 or C23F3/00
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/256—Arrangements using two alternating lights and one detector
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/3103—Atomic absorption analysis
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N2021/258—Surface plasmon spectroscopy, e.g. micro- or nanoparticles in suspension
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N2021/3125—Measuring the absorption by excited molecules

Definitions

  • the present invention relates to a surface-enhanced Raman scattering substrate, a device for detecting molecules including the same, and a method for manufacturing the same, which enables the detection of molecules in detail and with high sensitivity, and obtains uniform detection results in a large area.
  • the present invention relates to a surface-enhanced Raman scattering substrate, a molecule for detecting molecules, and a method for manufacturing the same, which can be manufactured in an extremely low cost simple process.
  • SERS Surface Enhanced Raman Scattering
  • the SERS sensor is the most commonly studied, it is difficult to obtain reproducibility and accuracy of detection because the arrangement of metal nanoparticles has a random structure based on probability, which makes it difficult to obtain the reproducibility and accuracy of the detection.
  • the density of, etc. is not well defined, which makes it an obstacle to quantitative analysis.
  • the present invention provides surface enhanced Raman scattering substrates with precisely controlled hot spots, capable of quantitative analysis, and excellent measurement reliability and reproducibility.
  • Another object of the present invention is to have a uniform surface plasmon activity in a large area. High density hot spots are formed, providing a surface enhanced Raman scattering substrate with excellent sensitivity and commercial viability.
  • Another object of the present invention is to provide a surface enhanced Raman scattering substrate with a significant improvement in signal amplification by hot spots, since the material to be measured is located in or adjacent to the hot spots.
  • Another object of the present invention is to provide a method for manufacturing high quality surface enhancement Raman scattering substrates described above in an extremely simple method that requires no expensive equipment or high process control and low process construction costs. .
  • the surface-enhanced Raman Scattering (SERS) substrate includes an airborne type 1 metal nanoparticle, a support member for supporting the first metal nanoparticle, the first metal nanoparticle and nanoparticles. Forming a gap and forming the first metal
  • a second metal film is formed around the nanoparticles, and the first metal of the first metal nanoparticle and the second metal of the second metal film are metals on which surface plasmons are generated.
  • the first metal In the surface-enhanced Raman scattering substrate according to an embodiment of the present invention, the first metal.
  • the lower surface of the first metal nanoparticle which is the surface of the side supported by the support member, may be flat.
  • Nanogaps can be formed by the sides of the second metal film that includes the edges.
  • the nanogap may be a closed loop shape.
  • the support region forming the interface with the support member and the unsupported region exposed to the surface can coexist.
  • an area of 10 to 80% of the area of the lower surface may be interfacing with a supporting member.
  • the detection object may be located in a space defined by the first metal nanoparticle, including the unsupported area of the bottom surface of the nanoparticle, the side of the base metal film, and the side of the support member.
  • an airborne type 1 metal nanoparticle supported by a support member may be located inside the through-holes of the second metal film.
  • Nanoparticles, through-holes, and support members can be concentric with each other.
  • the surface-enhanced Raman scattering substrate may further include a second metal film and a lower film positioned under the airborne first metal nanoparticles.
  • the underlayer is the same material as the support member, and the support member may be extended from the underlayer.
  • a surface-enhanced Raman scattering substrate in accordance with one embodiment of the present invention.
  • Receptors that bind specifically to the substance to be detected may be formed on the surface of the underlying membrane or under the side of the support member, which is located below the suspended metal primary particles.
  • Surface enhancement Raman scattering according to an embodiment of the present invention. On the substrate , the support member
  • One or more may be selected from metal compounds and semiconductor compounds, and, independently of this, the lower layer may be selected from one or more from metal, metal compounds and semiconductor compounds.
  • the nanoparticles may be truncated particle shapes.
  • the size of the nanogap may be controlled by a factor of one or more selected factors that increases the length of the supporting member and the thickness of the second metal film.
  • Nanoparticles are based on projection shape, and the average diameter of the projection shape can be lOnm to 500nm.
  • the thickness of the second metal film may be 10 lOOnm.
  • the nanostructure density which is the number of the first metal nanoparticles, may be 1 to 100 / fim 2 .
  • a surface enhanced Raman scattering substrate according to an embodiment of the present invention the substrate being in the air
  • It includes a surface enhanced Raman scattering active area in which a floating type 1 metal nanoparticle is formed and a surface enhanced Raman scattering inactive area in which a floating type No. 1 metal nanoparticle is not formed, and two or more surface enhanced Raman scattering active areas may be spaced apart.
  • a first metal in a surface-enhanced Raman scattering substrate according to one embodiment of the present invention.
  • the first metal of the nanoparticles and the second metal of the second metal film may be metals in which surface plasmons occur independently of each other.
  • the first metal of the nanoparticles and the second metal of the second metal film may be, independently of each other, silver, gold, platinum, palladium, nickel, aluminum, copper, chromium or combinations thereof or alloys thereof.
  • the support member is Zr0 2 , ZnO, YF 3 , YbF 3 , Y 2 0 3 , Ti0 2 , ThF 4 , TbF 3 , Ta 2 0 5 , Ge0 2 , Te0 2 , SiC, diamond, SiO x ⁇ (Number of 0 ⁇ 2 Real, 0 ⁇ y ⁇ 1.5 Real), Si0 2 , SiO, SiN x (l ⁇ x ⁇ 1.5 Real), Sc 2 0 3, NdF 3, Na 3 AlF 6, MgF 2, LaF 3, Hf0 2, GdF 3, DyF 3, CeF 3, CaF 2, BaF 2, A1F 3, A1 2 0 3,
  • ITO Indium-Tin Oxide
  • the present invention provides a device for detecting molecules comprising the surface-enhanced Raman scattering substrate described above.
  • the device for detecting molecules includes a surface-enhanced Raman scattering substrate and a surface-enhanced Raman scattering substrate in the airborne type 1 metal nanoparticles, a support member for supporting a system 1 metal nanoparticles and at least second Form nano 3 ⁇ 4 with the first metal nanoparticles of the metal film, and inside the area surrounding the first metal nanoparticles
  • It may contain microfluidic channels configured to receive them.
  • a method for producing a surface-enhanced Raman scattering substrate according to the present invention comprises the steps of: a) forming a compound film which is a base metal compound or a semiconductor compound; b) forming a first metal film on the compound film, followed by heat treatment, to prepare a first metal nano island spaced apart from the compound film; c) using the first metal nano island as an etching mask; Isotropically etching the film to a certain depth; and d) forming a bimetallic film by depositing the first metal nanosum as a deposition mask and depositing a second metal on the etched compound film.
  • the metal compound or semiconductor compound of the compound film may be metal oxide, metal oxynitride, metal nitride, metal halide including metal fluoride, metal carbide, semiconductor oxide, semiconductor acid
  • metal oxide metal oxide
  • metal oxynitride metal nitride
  • metal halide including metal fluoride
  • metal carbide semiconductor oxide
  • semiconductor acid One or more may be selected from nitrides, semiconductor nitrides, semiconductor carbides and semiconductor materials.
  • step b) is performed by repeating the step b) forming the first metal film and b2) the heat treatment step. By doing so, it is possible to control the density of the first metal nanosum.
  • the isotropic etching may be wet etching.
  • dry etching may be further performed in steps c) and c) before isotropic etching or after isotropic etching.
  • the method of manufacturing a surface-enhanced Raman scattering substrate according to an embodiment of the present invention further includes forming a lower layer of a base metal film or a film of a metal compound or semiconductor compound different from the compound film, c)
  • the underlying film may be exposed to the surface in an area not protected by the etching mask by etching including isotropic etching of the step.
  • the etched compound film may remain by etching including isotropic etching in step c).
  • the step d) is performed by thermal evaporator or electron beam deposition (E-beam).
  • It can be a directional deposition with an evaporator.
  • the nanogap size can be controlled by controlling the etching depth of step c) and the deposition thickness of step d) at least one factor. have.
  • a patterned first metal film may be formed.
  • the thickness of the first metal film may be 1 to 50 nm.
  • a method of manufacturing a surface-enhanced Raman scattering substrate according to an embodiment of the present invention is a metal film exposed to the surface after step c), before step d), or after step d), or after step c).
  • the step of etching may further include forming a receptor on the surface of the remaining compound film and the support member that specifically binds the detection object.
  • the heat treatment in step c) may be performed by a rapid thermal process (RTP).
  • RTP rapid thermal process
  • the surface-enhanced Raman scattering substrate has hot spots formed by precisely controlled nano-gap, and has high density hot spots, which enables quantitative analysis of the object to be detected, sensitivity of measurement, Reliability and reproducibility have the advantage.
  • the surface-enhanced Raman scattering substrates in accordance with the present invention are in the order of nanometer orders.
  • the ultrafine nanogap is formed uniformly over a large area, which has the advantage of significantly improved detection intensity.
  • the surface-enhanced Raman scattering substrate according to the present invention has a fixed material located close to the hot spot or hot spot as the target material is located in the empty space defined under the airborne metal nanoparticles. This can significantly improve the detection strength.
  • the surface-enhanced Raman scattering substrate according to the present invention is only an airborne type metal.
  • the size of the nanogap is controlled by a rigid and easily adjustable factor of the length of the support member or the thickness of the metal film that supports the nanoparticles.
  • the surface-enhanced Raman scattering substrate according to the present invention is manufactured through a simple and low cost process. It is manufacturable and has the advantage of extremely good commerciality.
  • the method for producing the surface-enhanced Raman scattering substrate according to the present invention is carried out by deposition, heat treatment and
  • etching which is why the surface enhanced Raman scattering substrates are manufactured by easy and strictly controllable process variables. It also has the advantage of improving yield, and also has the advantage of reproducibly producing surface-enhanced Raman scattering substrates with constant surface plasmon activity, and significantly reducing defects caused by unintentional changes in surface plasmon activity. There is this.
  • the method of manufacturing the surface-enhanced Raman scattering substrate according to the present invention enables the manufacture of a substrate having SERS activity regardless of the uneven structure, even if an intentional uneven structure suitable for the use exists on the surface of the substrate, which is a physical support. there is an advantage, which is very advantageous considering the complexed with e 'micro channel forming or other detection elements.
  • the method of manufacturing the surface-enhanced Raman scattering substrate is based on the large area.
  • the substrate also has the advantage of being capable of producing substrates with homogeneous surface plasmon activity.
  • FIG. 1 is a cross-sectional view showing a cross section of a surface enhancement Raman scattering substrate according to an embodiment of the present invention.
  • FIG. 2 is another cross-sectional view showing a cross-section of a surface enhanced Raman scattering substrate according to an embodiment of the present invention.
  • FIG 3 illustrates an example of a first metal nanoparticle having a truncated spherical shape.
  • FIG. 4 is a perspective view showing in detail the through-pore region in the type 2 metal film.
  • FIG. 5 is a schematic diagram showing the positional relationship between the lower surface of the type 1 metal nanoparticle, the end surface of the support member, and the outer peripheral surface of the through-holes of the second metal film.
  • FIG. 6 is a perspective view showing only a supporting member for supporting the first metal nanoparticles.
  • FIG. 7 illustrates a support member including an upper support area and a lower support area.
  • FIG. 8 is a cross-sectional view showing a cross section of a surface augmented Raman scattering substrate according to an embodiment of the present invention.
  • FIG. 9 is a first metal patterned in a square pattern forming a matrix on a substrate
  • FIG. 10 shows a sample in which a base compound film and a metal layer are formed (FIG. 10 (a)), and
  • FIG. 11 is a scanning electron micrograph of the sample (Fig. 11 (a)) after the isotropic etching of the sample of Fig. 10 (b) and the sample on which the metal film is deposited (Fig. 11 (b)).
  • FIG. 12 shows the formation of the metal film and the formation of the metal film on the heat-treated sample (FIG. 12 (a)). Scanning electron micrographs of samples (FIG. 12 (b)) in which the density of metal nanoparticles were increased by heat treatment were observed.
  • FIG. 13 shows the formation of a patterned surface-enhanced Raman scattering active region by forming a patterned metal film (FIG. 13 (a)), followed by heat treatment to form a sample having the patterned surface enhancement Raman scattering active region. Scanning electron micrograph of observation of)).
  • FIG. 14 shows a dark field image of a sample prepared by depositing a metal film having the same thickness as that of the sample shown in FIG. 11 (b) after varying the depth of round etching of the compound film.
  • FIG. 15 is a scanning electron micrograph of the sample of FIG. 14.
  • FIG. 16 is a diagram showing a Raman scattering spectrum of a surface-enhanced Raman scattering substrate.
  • FIG. 17 shows the Raman scattering spectrum of a surface-enhanced Raman scattering substrate.
  • FIG. 19 shows the Raman scattering spectrum of the surface-enhanced Raman scattering substrate of FIG.
  • FIG. 20 is a scanning electron micrograph of the surface-enhanced Raman scattering substrate in which the lower layer is a metal film and the metals of the first metal nanoparticles and the second metal film are both Au.
  • FIG. 21 shows the Raman scattering spectrum of the surface-enhanced Raman scattering substrate of FIG.
  • the surface-enhanced Raman scattering (SERS) substrate according to the present invention is characterized in that the substrate contains an airborne type 1 metal nanoparticle, a support member supporting the first metal nanoparticle, a first metal nanoparticle and a nanogap. And a second metal film that forms and wraps the circumference of the first metal nanoparticle.
  • the second metal is independent of each other and the surface plasmon is generated by interaction with light
  • the first metal of the first metal nanoparticle and the second metal of the second metal film may be independently of each other silver, gold, platinum, palladium, nickel, aluminum, copper, creme or a combination thereof. Alloys may be used, but the present invention is not limited thereto, and may be a metal generating surface plasmon.
  • the airborne mass of the airborne type 1 metal nanoparticle is
  • the airborne flotation is formed on the lower side of the first metal nanoparticle
  • the support area supported by the support member in contact with the support member and the unsupported area (surface area) forming the surface coexist so that the lower side of the first metal nanoparticle is the first side. It can mean the side of the side where the metal nanoparticles are supported by the support site.
  • the first metal nanoparticles have a floating structure in the air, and the floating first metal
  • nanogap As a nanogap is formed between the second metal film surrounding the nanoparticles, it may have a closed loop hot spot, not a point hot spot.
  • LSPR Localized surface plasmon resonance
  • Closed-loop linear hot spots provide a linear LSPR generation area for closed-loop substrates.
  • the signal strength is remarkably increased by the linear LSPR generation region, which can improve detection sensitivity.
  • the airborne type 1 metal nanoparticle is formed by the support member.
  • the bottom surface of the first metal nanoparticle which is the side of the supported side, may be flat.
  • the floating part is not supported by the supporting member, but the bottom surface is not supported by the supporting member.
  • the lower surface of the flat plane is particularly advantageous with the second metal film to form a tightly controlled nanogap.
  • the detection intensity varies greatly with the small size variation of the nanogap.
  • the nano metal film is formed by the side surface of the second metal film including the edge of the second metal film which surrounds the first metal nanoparticle and the circumference of the metal nanoparticle. More specifically, nanogaps may be formed by, at least, the edges of the bottom surface and the edges of the second metal film surrounding the circumference of the first metal nanomip. Done
  • the nanogap is formed by the plane (bottom surface) and the plane (surface of the second metal film).
  • a strictly sized nanogap can be formed.
  • Extremely fine nanogaps of nanometer order can be formed.
  • FIG. 1 is a cross-sectional view showing a cross section of a surface-enhanced Raman scattering substrate according to an embodiment of the present invention. As shown in FIG. 1, the first metal nanoparticle 100 is
  • the support member 200 It is supported by the support member 200 and has an airborne type structure having an empty space E in the lower region of the first metal nanoparticle 100. Further, the second metal film 300 positioned on the substrate 500 is provided. The first metal nanoparticle (100) and the nano-gap (G) to form a silver first metal
  • the second metal film 300 is a film in which the through-hole pores (PP) are formed.
  • the first metal supported by the support member 200 inside the through-hole pores (PP) of the second metal film 300.
  • the second metal film 300 forms a nanogap G with the base metal 1 nanoparticles 100 and may have a structure surrounding the circumference of the U metal nanoparticles 100.
  • the second metal film forming a nanogap with the first metal nanoparticles
  • PP through hole
  • the first metal in an embodiment according to the present invention, as shown in FIG. 1, the first metal
  • the lower surface BS of the nanoparticle 100 may be a plane. At this time, the lower surface BS of the first metal nanoparticle 100 is a surface of the metal nanoparticle 100 supported by the support member 200. Can mean.
  • the bottom surface BS of the first metal nanoparticle 100 may be a plane parallel to the surface of the base 2 metal film, a plane parallel to the surface of the base 500, for example, a horizontal plane. .
  • the lower surface BS of the system 1 metal nanoparticle 100 is a flat plane, at least, the position within the nanogap closed curve formed in the shape of a closed curve along the edge of the lower surface BS Irrespective of its size, it may have an extremely uniform size. Accordingly, an extremely uniform and very strong local electric field may be formed between the first metal nanoparticle 100 and the second metal film 300 in the form of a closed loop.
  • two or more units can be located inside the through-hole pores PP of the second metal film 300, respectively.
  • the surface-enhanced Raman scattering substrates are arranged on the substrate 500 and spaced apart from each other.
  • the bottom face BS can be located in a single virtual plane VP, i.e. the bottom faces of the first metal nanoparticles 100 located on the surface enhanced Raman scattering substrate can be located in a single plane VP. .
  • nanogaps formed on surface-enhanced Raman scattering substrates can have extremely uniform sizes regardless of their position on the surface-enhanced Raman scattering substrates, and exhibit very uniform surface-enhanced Raman scattering activity even on large-area substrates. Can be.
  • the surface-enhanced Raman scattering substrate according to the embodiment of the present invention may have a uniform SERS activity even with a large-area substrate.
  • the hot spot is formed by the nanogap between the second metal film 300 and the first metal nanoparticle 100.
  • the hot spot includes the lower surface of the first metal nanoparticle 100. It may be formed by the surface of the first metal nanoparticle and the surface of the through-holes of the second metal film including the edge of the through-holes of the second metal film 300.
  • the hot spots formed on the substrate are derived from the planes, including the above-mentioned virtual planes (VP) and the surface planes including the pore surfaces of the second metal film 300, regardless of the position of the hot spots in the substrate. It is possible to have nanogaps of the same size with each other. Further, by adjusting one or more selected factors of the length (height) of the support member 200 and the thickness of the base 2 metal film 300, The size can be adjusted uniformly.
  • the lower surface of the first metal nanoparticle 100 being a flat surface
  • the lower surface is located at a strictly well-defined height
  • the thickness of the second metal film as the second metal film 300 also has a flat surface
  • the surface position of the second metal film can also be located at a strictly well-defined height.
  • the two elements forming the nanogap both have a strictly controlled position.
  • a precisely controlled size of nanogap can be formed.
  • the length (height) of the support member and the second metal only depend on the length of the support member or the thickness of the second metal film, as the position of the two elements forming the nanogap is determined. By adjusting a factor selected to one or more of the thicknesses of the membrane, the size of the nanogap can be precisely controlled.
  • the lower part of the first metal nanoparticle on the substrate can be As the faces are located in the same position (same plane), the size of the nano 3 ⁇ 4 can be controlled to be extremely uniform in the substrate.
  • the surface-enhanced Raman scattering substrates according to the present invention are ultra-fine nano nanometers in n order. Gap in large area Significantly improved detection with uniform size This has the advantage of strength. These ultra-small gaps and uniformly sized gaps can significantly improve detection sensitivity, device reliability (reproducibility of detection), and metallic materials of the first metal nanoparticles.
  • the local surface plasmon resonance (LSPR) wavelength of the substrate can also be easily adjusted by controlling the metal material of the metal film, the size of nano 3 ⁇ 4 and the size (average size) of the first metal nanoparticles.
  • the surface-enhanced Raman scattering substrate according to one embodiment of the present invention is formed by a hot spot formed by a notary floating-type primary metal nanoparticle and a type 2 metal membrane.
  • Well-controlled hotspots can be formed, and even large-area substrates can exhibit uniform plasmon activity.
  • the lower surface BS of the first metal nanoparticle 100 when the lower surface BS of the first metal nanoparticle 100 is a flat surface, as described above, the lower surface BS forms an interface with the support member 200.
  • the supporting area to be formed and the unsupported area exposed to the surface can coexist.
  • an empty space E may be formed under the first metal nanoparticle 100.
  • the second metal film 300 surrounding the first metal nanoparticle 100, as shown in FIG. 2, as the first metal nanoparticle 100 has a process-rich floating structure.
  • the first metal nanoparticle 100 comprising the support region 101 of the bottom surface BS of the first metal nanoparticle, and the side surface 201 of the support member 200.
  • the object to be detected may be located in space (E), i.e., the empty space (E) may be the space where the object is detected and detected by Raman scattering, and in this respect the empty space (E) may be referred to as the analysis space.
  • the side surface 301 of the second metal film 300 is, of course, large in the pore surface of the through-holes formed in the second metal film 300.
  • the ratio of the area of the support area forming the interface with the support member may directly affect the degree of formation of the empty space under the first metal nanoparticle. Therefore, the area ratio of the supporting region is preferably a ratio in which an empty space (E) can be formed so that the target object can exist in the hot spot region or the hot spot adjacent region while the first metal nanoparticle is physically stably supported.
  • an area of 10 to 80% of the lower surface area can be interfaced with the support member, that is, an area of the supporting area can be 10 to 80% of the area of the lower surface.
  • an area of the supporting area can be 10 to 80% of the area of the lower surface.
  • the area of the support area may be 30 to 80%, more preferably 40 to 80% of the area of the lower surface.
  • the lower surface is planar-type 1 metal.
  • the nanoparticle 100 may be truncated particle shape or plate shape.
  • the truncated particle shape may be a shape including a surface and a surface of a convex curved surface,
  • the plate may comprise a square (including a rectangle, a square), a polygonal plate such as a triangle, a circular plate or an oval plate.
  • the primary metal nanoparticle 100 may be a cut grain, and the cut grain may be a cut sphere ( It can be a truncated sphere shape or truncated cape e shape.
  • the cut plane shape or the truncated plane shape in the cut capsule shape can correspond to the underside described above, where the truncated sphere shape has a single curvature.
  • the cut surface includes not only the circle but also the rectangle sphere, the shape of the ellipse.
  • the cut capsule shape can be interpreted as a cylindrical or elliptical cylinder that is flat at one end and curved at the other end, and can also be interpreted as elongated in the vertical direction to the cut surface described above. to be.
  • the first metal nanoparticle 100 may be a laminated particle in which a metal (including a single alloy) or two or more metals in which a surface plasmon is generated is laminated.
  • the first metal nanoparticle 100 when the first metal nanoparticle 100 is a single metal region, the first metal nanoparticle may be It may be silver, gold, platinum, palladium, nickel, aluminum, copper, chromium or an alloy thereof having the above-mentioned cut off particle shape.
  • the monometallic nanoparticles 100 comprise a coating layer of 1-1 metal laminated to cover at least a portion of the 1-1 metal particles consisting of one plane and a convex surface and the convex surface of the 1-1 metal particles.
  • the first metal and the first metal may each be gold, platinum, palladium, nickel, aluminum, copper, cream, or an alloy thereof. More specifically, the first metal nanoparticle (100) ) Is a laminated granular particle, the surface having a constant curvature (first surface) 1-1 metal particles having a spherical spherical shape and having a curved surface (second surface) having the same or different curvature as the 1-1 metal particle, and a layer 1-2 metal coating layer laminated in contact with the first surface on the first surface of the system In this case, the primary metal
  • the nanoparticle 100 is in contact with the lower surface and the lower surface due to the cut surface of the 1-1 metal particle and in contact with the lower surface and the first surface due to the curved surface of the 1-1 metal particle. It may be a cut off particle having an upper surface derived from the second curved surface (see the first metal nanoparticle of FIG. 8).
  • the one-to-two metal coating layer is the second convex surface.
  • the first curved surface may have a concave surface that is transferred, and the thickness of the 1-2 metal coating layer may gradually become thinner from the center to the edge.
  • the thickness of the 1-2 metal coating layer may increase. In this case, it is, of course, possible for the laminated particles to be treated in the truncated capsule shape rather than in the truncated particle phase.
  • FIG 3 illustrates an example of a first metal nanoparticle having a truncated spherical shape.
  • the first metal nanoparticle 100 has a shape in which the lower portion of the sphere is cut off on the basis of the center of gravity of the sphere as shown in the example shown in Fig. 3 (a), and the center of the sphere as shown in the example shown in Fig. 3 (b). The upper part of the sphere is cut off on the basis of), as shown in the example shown in Fig. 3 (c).
  • the center (P) may have a truncated shape.
  • spheres should not be interpreted as being limited to true spheres.
  • a sphere can mean a three-dimensional sphere having a projection shape based on a projection shape and a circular to elliptic shape.
  • the limitations of the shape of the particles due to the process limits or the specific process methods that are implemented are difficult to be realized in the form of mathematically strict meanings, which is well known to those skilled in the field of nanostructures involving nanoparticles.
  • the projection direction of the projection shape is determined from the first metal nanoparticles.
  • the device is lowered from above with the first metal nanoparticle in the device It can mean the projection shape in the viewing direction.
  • the projection shape can be a projection shape based on parallel light.
  • FIG. 4 is a detailed view of the through-pore (PP) region in the second metal film 300
  • the shape of the through-hole pore (PP) can be defined by the first metal nanoparticle (100). With respect to the geometrical relationship between the first metal nanoparticle (100) and the through-hole pore (PP). For clarity, FIG. 4 shows the projection shape 1000 of the first metal nanoparticle 100 and the first metal nanoparticle 100 together.
  • the shape of the through-hole pore (PP) is made of the first metal.
  • the projection shape of the nanoparticle 100 can be compared with the projection shape 100.
  • the projection shape is the direction from the parallel light reference primary metal nanoparticle to the support member, that is, the first metal nanoparticle It is perpendicular to the lower surface (BS) and can refer to the shape projected in the direction of bird's-eye view, specifically, from the device looking upward from the device with the first metal nanoparticles upwards.
  • the metal nanoparticle 100 is viewed as a combination of cross-sections perpendicular to the projection direction
  • the projection shape is the longest radius in each of the cross-sectional directions of the radii in all directions (face directions) perpendicular to the projection direction from the cross-section centers of the cross sections. It may be a shape formed by these combinations.
  • the projection shape 1000 may vary depending on the position of the cut sphere of the cut sphere. If the spherical cut surface is located at the top of the sphere's center region as shown in Fig. 3 (b) or Fig. 3 (c), the projection shape (1000) may be the same as the bottom surface (BS). When located at the bottom of the sphere, such as 3 (a), the projection shape 100 may be identical to the cross section of the center of the sphere, i.e., the bottom face BS of the system 1 metal nanoparticles corresponding to FIG. 3 (c).
  • the through-holes (PP) of the system-based bimetallic film 300 may have a shape comparable to the projection shape ( ⁇ ) of the first metal nanoparticle 100 described above. Details of the configuration according to the present invention will be described in detail. In terms of shape, it has a shape that one shape differs from another shape. It can mean that different shapes have the same, enlarged or reduced shape. Specifically, the through-holes (PP) of the second metal film 300 may be substantially the same shape as the projection shape 1000 of the 11 metal nanoparticles 100.
  • nanoparticles of the airborne type first metal supported by the supporting member 200 are formed, and then, as a deposition mask, a system 2 metal is used.
  • the deposition metal of the second metal As the nanoparticles of the metal are used as the mask, the second particles are formed on the low 1 1 metal nanoparticles used as the mask. The metal may be deposited.
  • the first metal nanoparticle 100 provided on the substrate has only a slight or elongated shape in which the nanoparticles of the first metal used as the mask are deposited in the deposition direction. When the details of the scattering substrate are described in terms of manufacturing method, for the sake of clarity, the first metal nanoparticles are not specifically distinguished from the first metal nanoparticles and the first metal nanoparticles used as masks. Collectively referred to as particles.
  • the second metal film As described above, as the second metal film is formed by depositing the airborne type 1 metal nanoparticle as a deposition mask, the second metal film 300 has a shape that is projected onto the projection shape of the first metal nanoparticle 100. Through-holes can be formed. In terms of the manufacturing method, the formation of through-holes (PP) with the deposition mask of the first metal nanoparticle 100 has an important technical meaning.
  • a second metal film having a through-hole pore (PP) formed in the deposition mask of the first metal nanoparticle (100) as a projection shape of the metal nanoparticle (100) is formed, and the through-hole is formed.
  • the pore surface of the through-holes including the surface edges of the pores (PP) may form nanogaps with the bottom surface (BS) of the metal nanoparticles 100.
  • BS bottom surface
  • Strictly controlled hotspots can be formed, and furthermore, only tightly controlled hotspots can be present, and very fine nanogaps can be formed.
  • This self-aligned hotspot generation enables the measurement reliability and reliability of surface-enhanced Raman scattering substrates. In addition to remarkably improving reproducibility, the productivity of surface-enhanced Raman scattering substrates can be dramatically improved, and quality control can also be achieved very easily.
  • FIG 5 shows the bottom surface BS of the first metal nanoparticle, the cross section 210 of the support member, and the second metal.
  • the end face 210 of the support member has the shape of the galactic face BS.
  • the end face 210 of the support member may have a shape that corresponds to the shape of the bottom face BS regardless of the position of the end face.
  • Cross section 210 may mean a cross section in a direction perpendicular to the length direction of the support member.
  • the end face 210 of the support member may mean a cross section perpendicular to the projection direction described above, and more specifically, the end face 210 of the support member may mean a horizontal cross section of the support member.
  • the end surface 210 of the support member may have a shape substantially the same as that of the lower surface BS, but may have a reduced shape.
  • the reduction ratio is obtained by using the area of the lower surface BS as the circle of the same area.
  • the reduction ratio (/ 11 0 * 100) is 10 to 80%, preferably 30 to 80%, better than the area of the support member ( ⁇ ) / bottom surface ( ⁇ 0 2 ) * 100 (%) in contact with the lower surface.
  • the reduction ratio is 10 to 80%, preferably 30 to 80%, better than the area of the support member ( ⁇ ) / bottom surface ( ⁇ 0 2 ) * 100 (%) in contact with the lower surface.
  • the cross-section 210 of the supporting member has a shape substantially the same as that of the lower surface BS, but the manufacturing method of the structure having the reduced shape thereof is a material for forming the supporting member.
  • isotropic etching including wet etching, is not directional and is uniformly etched in all directions. Accordingly, when a film of the same material as the supporting member is etched, it is etched in the thickness direction of the film, simultaneously with the first metal nano Particles (Etching Mask) The same etching as 360-degree can be achieved. With this, the first metal nanoparticles is backed by a support member with the cross-sectional shape which will allow can have any structure of the air floating, Daewoong to the shape of the support bujaeui section galaxy surface (BS) Can have
  • the shape of the through-hole pore (PP) is formed of the first metal nanoparticle (100).
  • the end face 210 of the support member 200 may have a shape opposite to the shape of the lower surface BS.
  • the through-hole may be the bottom surface of the first metal nanoparticle or It can be shaped to cross the cross section of the center of the cutting sphere of a single metal nanoparticle.
  • the cross section of the support member can have a reduced size and a bottom surface.
  • the supporting members can be concentric with each other. This is related to the cross-sectional shape of the supporting member and the shape of the through-hole pores. It can be clearly understood.
  • the first metal nanoparticles act as a deposition mask to obtain through-holes.
  • the first metal nanoparticle-through-pore-supporting member is formed by isotropic etching to support the first metal nanoparticle in the form of air suspension by isotropic etching. Are concentric with each other.
  • the center of the outer circumferential surface 310 may have a concentric structure forming a single axis (shown in dashed lines in FIG. 5).
  • FIG. 6 illustrates only the support member 200 supporting the first metal nanoparticles 100.
  • the support member 200 may have a cross section that has a shape corresponding to the bottom surface of the first metal nanoparticle 100.
  • the support member 200 may have a side in contact with the first metal nanoparticle 100 as an upper side, and an opposing side in the upper side as a lower side, and an upper cross section may be smaller than a cross section in the lower side.
  • the supporting member 200 can increase its cross-sectional area from the upper side to the lower side and can continuously increase.
  • the side surface of the supporting member 200 can be a planar to curved surface, and the curved surface is concave. It can be a curved surface.
  • the supporting member may be formed by etching the first metal nanoparticles as an etching mask and isotropically etching the film of the supporting member material.
  • the upper part of the supporting member may be formed.
  • the length of the support member can be realized in orders of hundreds of nanometers order, The curved side by angle may not appear clearly, but the isotropic awakening member may have a concave surface side.
  • the empty space (E, analysis space) formed under the first metal nanoparticle is divided into the lower part. It may have a tapered hollow barrel shape that narrows in width.
  • the expression of the hollow bin means, of course, a space which is not substantially empty (the space of the supporting member).
  • the object may have a tapered hollow cylindrical shape that becomes narrower in width.
  • the object may be located in such an empty space.
  • SERS strength affects not only the SERS activity of the substrate itself, but also the position between the object and the hot spot.
  • Hot spots are formed between the edges of the mold pores and the surface of the second metal film including the pore surfaces of the through pores. In particular, in the case where the first metal nanoparticles are cut spheres, a hot closed loop shaped hot spot is formed.
  • the surface-enhanced Raman scattering intensity can be remarkably enhanced by placing the object in the minute void space (E) defined by the first metal nanoparticle and the second metal film forming the closed loop hot spot.
  • E minute void space
  • Including hot spots, matching the cross-sectional shape of the empty space with the shape of the hot spot can improve detection sensitivity and detection reliability (reproducibility).
  • FIG. 7 is a support member 200 having a step, in detail, the upper support region 210 and
  • FIG. 7 A perspective view showing in detail a support member 200 including a lower support region 220 and having a step between an upper support region 210 and a lower support region 220.
  • the upper support region 210 is illustrated.
  • Silver can be treated on the support member described above based on 1 to 6, and the lower support region 220 has a larger diameter than the upper support region.
  • It may be a column shape including a cylinder forming a step with the upper support area.
  • the shape of the upper support area 210 and the lower support area 220 may be defined by both the first metal nanoparticles 100.
  • the lower surface of the first metal nanoparticles (100) and the first metal nanoparticles is shown in FIG. (BS) Past 1 metal
  • the projection shape 1000 of the nanoparticles 100 is shown together.
  • the shape of the cross section (cross section in the longitudinal direction) of the upper support region 210 is shaped like the lower surface BS of the I metal nanoparticle 100, and in detail, the lower cross section.
  • the face (BS) may be in a reduced shape, where the reduction factor may be defined as R, R 0 * 100e3 ⁇ 4), as described above, which may be closely related to the length of the upper support area (210).
  • 3 ⁇ 4 can be directly related to the length of the upper support area 210.
  • R e may be substantially the same as the length of the upper support region 210.
  • the material for forming the support member including the upper support region is formed on the substrate in the form of a film (comparable to the compound film), and then the first metal nanoparticle is formed on the film (compound film).
  • the upper support region 210 can be fabricated by forming particles and isotropically etching the film (compound film) using the formed first metal nanoparticles as an etching mask. As such isotropic etching is oriented etching, When the etching is performed to the bottom of the first metal nanoparticle, which is a mask, it can be etched by R e in the depth direction of the film.
  • the length (height) may be substantially the same as R e, and may be substantially the same, where the actual identity is the same as that of the underlying mask and membrane under kinetic conditions such as fluidity of etchant and etching by-products. It is considered that the speed of etching in the depth direction can vary slightly depending on the etching time. Accordingly, the length of the etching in the horizontal direction (etching to the lower part of the first metal nanoparticle) and the length of the etching in the vertical direction are the same. It should be noted that the length is considered in consideration of the difference due to the kinetic variables during etching. Those who are involved in the semiconductor field to pattern the film or manufacture the device by using wet etching You will be able to clearly recognize the real identity.
  • the cross-section (cross-section in the longitudinal direction) of the lower support region 220 which forms a step with the upper support region 210 is the projection shape 100 and the Daeung of the first metal nanoparticle 100.
  • the cross-sectional shape of the lower support region 220 may be substantially the same shape as the projection shape 1000 of the first metal nanoparticle 100.
  • the second metal film 300 Through-hole pore also the first metal
  • the side surfaces of the lower support region 220 and the pore surfaces of the through-holes of the second metal film 300 can be adjacent to each other.
  • the film (compound film) located under the first metal nanoparticle is not etched, and the first metal nanoparticle ( A lower support region 220 can be fabricated, having substantially the same cross-sectional shape as the projection shape of the first metal nanoparticles, which is roughly the projection shape of 100.
  • the length of the lower support region 220 ie, Depth etched by directional etching may be appropriately controlled, and may be, for example, 10 nm to 5 ⁇ in practical terms, but the present invention is not limited thereto.
  • FIG. 8 is a cross-sectional view of a surface-enhanced Raman scattering substrate according to an embodiment of the present invention.
  • the substrate includes a second metal film 300 and an airborne first metal.
  • the lower layer 400 may be further disposed below the nanoparticle 100.
  • the surface-enhanced Raman scattering substrate may be a substrate 500, a lower layer 400 positioned on the substrate, and a lower layer 400.
  • Located in the through-holes of the second metal film 300, the second metal film 300, the through-holes formed therein, is supported by the support member 200, the second metal film 300 and the nano-gap An airborne type that may form 1 metal nanoparticles (100).
  • the lower film 400 may be a metal film (third metal film) or a film of the same material as the support member 200.
  • the lower film 400 is a film of the same material as the support member 200,
  • the support member 200 may be extended from the lower layer 400.
  • the extension of the support member 200 from the lower layer 400 indicates that the support member 200 and the lower layer 400 are physically integral.
  • the supporting member 200 can be interpreted as the protrusion of the lower part film 400.
  • the lower part film integrally with the supporting member and the supporting member is used to etch the first metal nanoparticles.
  • the film 400 is a film of the same material as the support member 200
  • the lower film may be a material selected from one or more of the metal compound and semiconductor compound described below.
  • the thickness of the lower film is not particularly limited but may be 10 nm or more. It can be 300 nm.
  • the present invention is not limited to the support member 200 and the lower layer 400 made of the same material.
  • the laminated film is formed.
  • the first metal nanoparticle By forming the first metal nanoparticle and selectively etching and removing the film of the material of the support member, it is possible to form the lower film support member of the heterogeneous material different from the support member. Accordingly, the support member and the lower film are different materials from each other.
  • the support member may be selected from one or more of metal compounds and semiconductor compounds, and, independently of this, the lower layer may be selected from one or more of metal, metal compounds and semiconductor compounds.
  • the lower layer may be a metal layer. If the lower layer is a metal layer, it is more advantageous to control the spread of light on the substrate. Specifically, the Raman scattering light surface-enhanced by hot spots on the Raman scattering substrate. It spreads in both the upper and lower directions of the silver (in all directions). However, if the lower film is a metal film, it prevents the Raman scattered light from propagating downward of the substrate, and most of the Raman scattered light in the hot spot is scattered.
  • the metal of the lower film is an alkali metal, a transition metal, or a metal before and after Metalloid, or an alloy of these (alloy) is the number of days.
  • the thickness of the metal film, which is the lower film is not particularly limited but may be 10 nm to 300 nm, and it is advantageous to be 50 nm to 300 nm in terms of effectively preventing light spreading to the underside of the substrate.
  • the lower side of the empty space E in the above-described empty space is formed by the lower layer 400, not the substrate 500. That is, when the support member is a support member without a step as in the example of Fig. 6, the lower side of the empty space E can be partitioned by the substrate 500 or the lower membrane 400, and the support member In the case of the supporting member having a step difference as shown in the example of FIG. 7, the empty space may be defined by the upper surface (step surface) of the lower support region 220 regardless of whether the lower film 400 exists.
  • Receptors that bind specifically can be formed.
  • the substrate may further include a receptor that specifically binds to the substance to be detected.
  • the receptor is located at least underneath the airborne type 1 metal nanoparticles. It may be formed on the surface of the substrate, the surface of the lower film, the upper surface of the lower support region, and / or the surface of the side of the support member. That is, it may mean the area of the underlying film or the area of the underlying film which is not covered, that is, exposed to the surface by the through-pore region of the bimetallic film.
  • the receptor includes a surface of the substrate; a surface of the substrate and a side surface of the support member;
  • E analysis space
  • the underlayer and the support member may be independently of each other, optically transparent or opaque, and may be electrically conductive or insulating. Is one or more selected from metal compounds and semiconductor compounds, and independently of this, the lower layer may be selected from one or more from metal, metal compounds and semiconductor compounds. More specifically, the supporting member may be selected from metal compounds and semiconductor compounds. It may be one or more than two substances selected, and the lower membrane may be of the same kind as the support member or may be a metal.
  • the metal of the metal film may be an alkali metal, a transition metal, a metal before or after a metal, a metalloid or an alloy thereof.
  • the metal of the metal film may be lithium, tin, potassium or ruby.
  • the metal compound of the membrane or support member may be metal oxide, metal oxynitride, metal
  • Nitrides metal halides including metal fluorides, metals
  • Carbides or mixtures thereof, and the semiconductor compound may be selected from semiconductor oxides, semiconductor oxynitrides, semiconductor nitrides, semiconductor carbides, and semiconductor materials, wherein the metal of the metal compound is a transition metal and The metal may include post-transition metals, and the semiconductor compound or semiconductor of the semiconductor material may include a group 4 semiconductor such as silicon (Si), germanium (Ge), or silicon germanium (SiGe).
  • the metal compound and the semiconductor compound are Zr0 2 , ZnO, YF 3) YbF 3 , Y 2 0 3 , Ti0 2 , ThF 4 , TbF 3 , Ta 2 0 5 , Ge0 2 , Te0 2 , SiC, diamond ( diamond), SiO x N y (0 ⁇ x ⁇ 2 real number, 0 ⁇ y ⁇ 1.5 real number), Si0 2 , SiO, SiN x (l ⁇ x ⁇ 1.5 real number), Sc 2 0 3 , NdF 3 , Na 3 AlF 6, MgF 2, LaF 3, Hf0 2, GdF 3, DyF 3, CeF 3, CaF 2, BaF 2, A1F 3, A1 2 0 3, ITO (Indium-Tin Oxide), AZO (Al doped Zinc Oxide), Ga doped Znic Oxide (GZO), Indium-Zinc Oxide (IZO), or a combination thereof.
  • ITO Indium-Tin Oxide
  • AZO Al do
  • the metal nanoparticles are based on the projection shape, and the average diameter of the projection shape (mean diameter of the circle converted into the same area as the projection shape) is It can be 10 nm to 500 nm, preferably 50 nm to 250 nm. Of course, if those 11 metal nanoparticles are truncated spherical, these sizes can, of course, be interpreted as one side of the population having an average diameter of 10 nm to 500 nm, preferably 50 nm to 250 nm.
  • the size of the first metal nanoparticles is not limited by the size of the particles, and the size of the first metal nanoparticles may be advantageous to enhance the plasmonic signal.
  • the length of the support member is adjusted in consideration of the length of the lower surface of the empty space (E) to be defined as close to the hot spot as possible while stably supporting the airborne type 1 metal nanoparticle.
  • the support member may
  • the lower surface of the empty space and the length (height) of the support member can be controlled independently of each other.
  • the length of the support member is 5 nm to ⁇ , more practically 10 nm to 500 nm. May be, but is not limited to.
  • the nanogap may have a length or a difference in the support member itself.
  • nano 3 ⁇ 4 is the order of the nanometer order (10 ° nm order).
  • the size of the nanogap includes the surface of the first metal nanoparticle including the bottom surface of the first metal nanoparticle and the surface of the second metal film including the pore surface of the through-type pores of the second metal film.
  • the first metal nanoparticle is cut or encapsulated in the lower part of the sphere, as shown in Figure 3 (a), it has the largest cross-sectional area at the bottom edge of the first metal nanoparticle.
  • the surface to the surface eg, the center surface of the sphere
  • it can be defined as the shortest distance between the lower surface area of the first metal nanoparticle and the pore surface of the through-hole of the second metal film. . ,
  • the thickness of the second metal film can be adjusted in consideration of the shape of the first metal nanoparticle, the length of the supporting member described above, and the size of the pre-designed nanogap.
  • the pore surface of the through-holes of the membrane may be a skewed surface, the thickness of the second metal membrane may be greater than the length of the supporting member, as the projection shape of the first metal nanoparticles in the manufacture of the second metal membrane plays a role of the mask.
  • the second metal in the deposition of the second metal for manufacturing the second metal film as shown in the example shown in FIG. 8, the second metal may be partially deposited on the first metal nanoparticles which perform the role of the mask.
  • the projected shape of the first metal nanoparticle acting as a mask may gradually increase. Accordingly, as in the manufacturing method described later, the metal nanoparticles acting as a mask at the start of the deposition of the second metal are referred to as the first metal nanosum 110, and the first metal nanosum by the deposition of the second metal ( When the portion deposited on top is referred to as a coating layer 120, the crab metal nanoparticles 100 may be cut particles in which the first metal nano islands 110 and the coating layer 120 are laminated. When the metal and the second metal are identical to each other, deposition proceeds, and the first metal nanoparticle contacts the bottom surface (BS) , the bottom surface, and is used as a mask.
  • BS bottom surface
  • the 110 s and can be transformed into a truncated particulate phase (100) having an upper surface (which may have the same curvature as the lower surface, 120 s) in contact with the lower surface (110s) and formed as the first metal is deposited.
  • the deposition proceeds and the first metal nano
  • the particles make contact with the lower surface (BS), the lower surface and the lower metal surface (1 10s) and the lower surface (110s) due to the curved surface of the first metal nanosum ( ⁇ 0) used as the mask. It may be a truncated particulate phase 100 having an upper surface 120s due to the curved surface.
  • the projection shape of the nanoparticles As the projection shape of the nanoparticles increases gradually, it may be formed as a tapered surface of the pore surface 301 of the through-holes in the second metal film 300, and in detail, the closer to the surface, The pores may be formed into tapered surfaces. More specifically, the lower part of the through-holes has a projection shape of the first metal nanoparticles (described later as one metal nano-isomer) at the time of the second metal deposition. The upper portion of the through-holes can have a size corresponding to the projection shape of the system 2 metal nanoparticles at the time when the deposition of the metal 2 is completed.
  • a pore surface can be formed into a raised surface.
  • the taper angle ( ⁇ ) between the pore surface and the substrate (or lower layer) May be 30 to 89 °, specifically 50 to 85 °.
  • the thickness of the second metal film may be controlled to be less than the thickness of the low metal film that is not physically in contact with the first metal nanoparticles.
  • the thickness (t) of the second metal film may be less than to (to is the thickness of the second metal film and the first metal nanoparticles contacting each other), and the thickness is controlled in consideration of the size of the designed nanogap under a condition of less than to.
  • the thickness of the second metal film may be from 0.5L to 5L, more specifically from 0.5L to 1.5L based on the length L of the supporting member, but is not limited thereto.
  • the thickness of the base 2 metal film may be equal to or greater than the length of the support member, that is, the thickness of the second metal film is 1 to 5L, specifically, based on the length (L) of the support member.
  • 1.1 L to 1.51 ⁇ 1 which means that the bottom surface of the first metal nanoparticle, the plane, is at the same or lower position than the film surface of the second metal film, and the first metal nanoparticle is In this case, a hot spot is formed between the surface of the first metal nanoparticle and the pore surface of the through-hole, which is inserted into the through-hole of the metal film.
  • Hot spots in the form of closed loops can be formed, which is more advantageous than the band-shaped hot spots, which not only amplify the signal more strongly than the line form, but also affect the process errors caused by the inevitable limitations of the manufacturing process. Relaxed, There sikilsu further improve the reliability of the plates.
  • the number of nanostructures, the number of primary metal nanoparticles per area, can be 1 to 400 / ⁇ 2 , specifically 10 to 100 / ⁇ 2 , more specifically 15 to 100 / ⁇ 2 .
  • the density of these nanostructures can be thought of as the hotspot density, the number of hotspots per unit area of the substrate. Hot spot density) can significantly improve the sensitivity of detection.
  • the Raman scattering active region may be a region in which an airborne type 1 metal nanoparticle is formed and a second metal film and a hot spot are formed, and the Raman scattering inactive region is a region in which the airborne type 1 metal nanoparticle is not formed.
  • a second metal film may or may not be formed in the Raman scattering non-active region.
  • the surface-enhanced Raman scattering substrate has two or more Raman scattering activities arranged in spaced apart from each other.
  • the object to be detected is not particularly limited, but may be a biochemical.
  • Biochemicals include cell constituents; genetic material; carbon compounds; substances that affect the metabolism of organisms; substances that affect the synthesis of matter in living organisms; substances that affect the transport or signaling of organisms; Specifically, biochemicals may include polymers, organic metal compounds, peptides, carbohydrates, proteins, protein complexes, lipids, metabolites, antigens, antibodies, enzymes, substrates, amino acids, aptamers, sugars, nucleic acids, and nucleic acid fragments. , PNA (Peptide Nucleic Acid), cell extracts, or combinations thereof. have.
  • Specific binding between the receptor and the detection target includes ionic bonds, covalent bonds, hydrogen bonds, coordination bonds or non-covalent bonds.
  • the receptor is an enzyme-substrate, antigen-antibody, protein-protein.
  • the present invention may be a substance capable of specifically binding to a detection target through complementary binding between DNAs.
  • Receptors can be used to detect conventional objects containing biochemicals.
  • any material known to be used in combination with the detection object to fix the detection object to one area of the sensor can be used.
  • the receptor forms at least an empty space (E).
  • SAM self-assembled monolayer
  • the self-assembled monomolecular film may include a chain group, a first reactor which is one end group of the chain group, and a second reactor which is another end group group of the chain group.
  • the first reactor may be a semi-group which spontaneously binds to the substrate. 2
  • the reaction can be a reaction that specifically binds to the analyte.
  • the first reactor is a thiol group ( -SH), a carboxyl group (-COOH) or an amine group (-NH 2 ).
  • a representative base material that spontaneously bonds with a thiol group and / or an amine group and is a metal oxide such as Au oxide, Ag oxide, Pd oxide, Pt oxide , Cu oxide, Zn oxide, Fe oxide or In oxide, and Si, Si0 2 (including amorphous glass) or indium tin oxide ( ⁇ ), etc.
  • the self-assembled monomolecular group includes an alkane chain group, specifically an C3-C20 alkane chain group, and the self-assembled monomolecular chain length. Detection zones that bind to the second functional group
  • the object can be placed inside the hot spot, i.e. by adjusting the length of the receptor formed in the void, the hot spot criterion, the position of the object to be bound to the receptor can be adjusted.
  • the second reaction group is similar to the first reaction agent described above with a thiol group, a carboxyl group or
  • the second half-ung group includes enzymes, substrates, antigens, antibodies, proteins, DNA, etc., bound to the end of the chain through functional groups such as thiol groups, carboxyl groups or amine groups. This is a well-known technique for workers in the field of biochemical detection.
  • the substrate 500 can serve as a support and is thermally and chemically stable.
  • the substrate may be in the form of a wafer or film, and a concave-convex structure may be formed on the surface in consideration of its use, such as a flat planar substrate, as well as a recess structure.
  • the substrate may be a semiconductor or ceramic.
  • silicon Si
  • Group IV semiconductors including germanium (Ge) or silicon germanium (SiGe)
  • Group 3-5 semiconductors including gallium arsenide (GaAs), indium phosphorus (InP) or gallium phosphorus (GaP);
  • Group 2-6 semiconductors including cadmium sulfide (CdS) or zinc telluride (ZnTe);
  • Group 4-6 semiconductors including lead sulfide (PbS); or two or more materials selected from them, each layer being a layered laminate.
  • Ceramic substrates include semiconductor oxides, semiconductor nitrides, and semiconductors.
  • a laminate of carbides, metal oxides, metal carbides, metal nitrides or two or more materials selected from them can be stacked in layers.
  • semiconductor oxides, semiconductor nitrides or semiconductors of semiconductor carbides can be composed of Group 4 semiconductors, 3-5 Foot semiconductors, group 2-6 semiconductors, group 4-6 semiconductors, or combinations thereof.
  • the present invention includes a device for detecting molecules including the surface-enhanced Raman scattering substrate described above, wherein the molecules may contain the biochemicals described above.
  • the device for detecting molecules includes a surface-enhanced Raman scattering substrate and a surface-enhancing Raman scattering substrate pore type 1 metal nanoparticles and a support member for supporting the first metal nanoparticles. And at least a microfluidic channel formed to form nanotubes with the first metal nanoparticles of the second metal film and to accommodate an area surrounding the first metal nanoparticles.
  • the device for detecting molecules is characterized in that the surface-enhanced Raman scattering substrate and the surface-enhanced Raman scattering substrate in the form of airborne crab 1 metal nanoparticles, the support for supporting the first metal nanoparticles It may include a well that forms a nanogap with the first metal nanoparticle of the member and at least the second metal film and accommodates therein an area surrounding the first metal nanoparticle.
  • the present invention includes a method of manufacturing the surface-enhanced Raman scattering substrate described above.
  • the method of manufacturing a surface-enhanced Raman scattering substrate comprises the steps of: a) forming a compound film which is a base metal compound or a semiconductor compound; b) forming a first metal film on the compound film, and then performing heat treatment to prepare a first metal nanoisland spaced apart from the compound film; c) isotropically etching the first metal nanosum with an etching mask and the compound film to a certain depth; and d) depositing a second metal film on the etched compound film with the first metal nanosum with a deposition mask.
  • the airborne flocculent 1 metal nanosum is prepared by etching in step c), and the airborne floc deposited on top of the first metal nanosum of the heavy metal flotation agent in step d). Sibling 1 metal nanoparticles and the enclosing them can produce a 2 metal film.
  • the manufacturing method according to the present invention includes the deposition-heat treatment-isotropic etching.
  • Etch-deposition The extremely simple and inexpensive, large-area manufacturing process allows precise control of the size of the hot spot, the shape of the hot spot, and the location of the hot spot, as described above. It is possible to manufacture high quality surface-enhanced Raman scattering substrates with remarkably enhanced and uniform SERS activity even in large areas.
  • precise control is possible, but using expensive equipment and masks, process construction cost and manufacturing cost are very high, and process maintenance is maintained.
  • design flexibility is also very limited, as it is difficult, and expensive new mask sets must be prepared to implement them again.
  • the nanogap is formed by metal nanoparticles formed in various sizes at random locations, and there is a limit that cannot precisely control the size of the nanogap. There are limitations such as relatively weak, difficult quantitative analysis, and poor reproducibility.
  • the method of manufacture according to the present invention overcomes the limitations of these prior arts, and allows the use of very inexpensive and simple processes, while allowing the size of the nanogap to be tightly controlled and having a very uniform nanogap in large areas. Can be manufactured.
  • step c when the compound film is etched to remain, the substrate film formed in step a) is supported by the Raman scattering substrate described above through etching including isotropic etching in step c).
  • the thickness of the compound film can be equal to the sum of the length of the supporting member and the thickness of the lower film described above.
  • the present invention can be limited to the same substance of the lower membrane and the supporting member.
  • step a) None is, of course. prior to step a), the base metal film, or the compound of step a)
  • a laminated film in which the second compound film, which is a substance of the underlying film, and the first compound film, which is a substance of the support member, may be formed.
  • the thickness of the second compound film may be It may be the thickness of the film, and the thickness of the lower compound film may correspond to the length of the supporting member described above.
  • the step of forming a base metal film before forming the compound film of step a) may be performed. That is, according to an embodiment of the present invention.
  • the manufacturing method may include forming a base metal film; forming a compound film on the metal film.
  • the metal film may also include sputtering and the like. It can be formed through conventional deposition such as chemical deposition such as physical deposition, plasma assist chemical vapor deposition, and the like.
  • etching including the isotropic etching of step C the compound film is converted into a supporting member and the metal is not protected by the etching mask.
  • the film can be exposed to the surface, i.e., by etching including the isotropic etching in step C), the compound film area under the etching mask is converted into a supporting member, and all the compound film areas except the lower part of the etching mask are removed and the metal is removed.
  • the film can be exposed to the surface.
  • the depth (etching depth) removed by etching including isotropic etching in step C) can be comparable to the thickness of the compound film.
  • the thickness of the base metal film may be the thickness of the lower film described above, and the thickness of the compound film may be equal to the length of the supporting member described above.
  • the first metal film is formed by forming a first metal film on the compound film and then thermally treating the first metal film.
  • the first metal film is also physically deposited such as sputtering or chemically deposited such as plasma assisted chemical vapor deposition. This is a well-known technique for those who are involved in the field of forming a film of uniform thickness through deposition.
  • the thickness of the first metal film formed on the compound film may be 50 nm or less, specifically, 1 to 50 nm, more specifically 1 to 30 nm, and more specifically, 5 to 20 nm. There is a risk that the size of the metal i island nanoparticles formed by heat treatment may be too small. Furthermore, if the thickness of the first metal film is excessively thick, even if a non-nano porous film is produced or nanoparticles are formed, There is a risk of particles being produced.
  • a compound metal patterned first metal film may be formed on the surface of a compound film to manufacture multiple surface-enhanced Raman scattering substrates by using a single substrate or by manufacturing a multiplexing substrate in which different detection objects are detected on a single substrate.
  • the first metal film is formed to form the surface-enhanced Raman scattering active region described above, and is formed in the form of a compound film in a pattern corresponding to the shape of the surface-enhanced Raman scattering active region and the arrangement of the designed surface-enhanced Raman scattering active region.
  • a patterned first metal film is an in-square support pattern that is arranged spaced apart from one another to form a matrix of MxN (M is at least one natural number and ⁇ is at least two natural numbers).
  • Fig. 9 shows an example of a first metal film 600 patterned in a square pattern forming a matrix of 2 ⁇ 3 matrix on the substrate. The portion where the substrate 1 metal film 600 is not formed is described above. Mansanran it is understood that the non-active areas can Daewoong.
  • Heat treatment for nano-islanding can be carried out with a rapid thermal process (RTP), which forms a first metal film instantaneously by thermal energy while maintaining the shape of the first metal film, which is a uniform thickness thin film. 1 of metal atoms This is because when homogenous diffusion occurs, more uniformly sized nano-islets can be manufactured, where the Rapid Thermal Process (RTP) is performed using conventional RTP equipment that is heated by light, such as tungsten-halogen lamps. Of course it can be.
  • RTP rapid thermal process
  • the heat treatment temperature for nano-islanding is 0.3T m to 0.9T m , specifically 0.5T m to () .8TV, based on the melting point of the first metal, T m (° C).
  • the above-mentioned silver degree is the temperature at which the fine nano islands are formed uniformly.
  • the heat treatment time is sufficient to allow sufficient material movement to form nano islands of the first metal in a reproducible manner.
  • the heat treatment time may vary somewhat depending on the thickness of the first metal film. It can be from 1 second to 5 minutes.
  • the heat treatment atmosphere may be carried out in a vacuum or inert atmosphere in the air, but the present invention is not limited by heat treatment time or heat treatment atmosphere.
  • the density of the finally obtained first metal nano-island can be increased.
  • the primary metal which has been nanosumming by the previous step (heat treatment step) already has an imig driving force.
  • the first metal film, which is almost consumed but newly formed on the compound film, has a sufficient driving force for granulation, so that, in the repeated heat treatment, nano-sums having similar sizes to those of the already formed nano-islets can be newly formed in the nano-sum formation area. have.
  • the density of the compound metal first metal nano island is repeated by repeating the unit process by forming the bl) first metal film and b2) the heat treatment step in one unit process.
  • This unit process can be repeated two to four times, but the number of repetitions can of course be adjusted appropriately, taking into account the density of the one metal nanoisle.
  • the thickness of the first metal film, which is repeatedly formed in the unit process is independently 30 nm or less, specifically 5 to 15 nm, and it is preferable to form a very thin type 1 metal film.
  • the metal compound film layer is subjected to the above-described heat treatment or repetition of the above-described unit process.
  • Extremely dense nano-islets of 10 or more / ⁇ 2 , specifically 40 / ⁇ 2, can be formed.
  • the first metal nanosum may have a mean diameter of 10 nm to 500 nm, preferably 50 nm to 250 n based on the projection shape.
  • the present invention is not limited to the size of the first metal nanosum, and the size of the first metal nanosum is sufficient for the plasmonic signal enhancement.
  • the airborne type 1 metal nano island can be manufactured, and an empty space (E, analysis space) can be formed under the nano island.
  • E analysis space
  • the support member described above based on FIGS. 1 to 6, that is, the support member having no step may be manufactured by wet etching, and in the case of the support member having the step described above based on FIG. 7, through wet etching Upper support areas can be manufactured.
  • step b) the case where isotropic etching including wet etching is performed in step b) and the case where directional etching and dry etching including dry etching are performed in combination will be described in detail.
  • the first metal nanoisle obtained in step b) is etched, and the compound film is wet-etched, so that the support member and the underlayer are supported.
  • Metal film or compound film remaining after etching can be produced at the same time.
  • the area of 10 to 80% may be etched to a depth that can interface with the support member, or to a depth that satisfies the reduction ratio as described above.
  • a support member having a length of 5 nm to 200 nm can be manufactured.
  • the remaining compound film after etching is formed by forming an underlayer or by etching the compound film (corresponding to the length of the designed support member). The thickness of the compound film) is removed, and the metal film exposed to the surface may form a lower film.
  • the etching solution may contain, for example, an etchant, sulfuric acid, nitric acid, boric acid, hydrogen fluoride, phosphoric acid, hydrochloric acid, or a combination thereof.
  • the etchant of the etch solution may be a single acid of hydrogen fluoride or a common acid of hydrogen fluoride and nitric acid.
  • the etchant of the etchant may be monoacid of phosphoric acid or common acid of phosphoric acid and hydrochloric acid, but the present invention is not limited to the etching solution.
  • Dry etching is a directional etching, by means of a mask that is a metal nanoparticle.
  • Non-screened areas can be etched away.
  • Dry etching includes plasma etching of etching targets by plasmaming gases containing halogen elements such as fluorine. Depending on the material, it may be carried out using a well-known dry etching method.
  • a supporting member and an underlayer (after dry etching) including an upper support region and a lower support region as shown in FIG.
  • the remaining compound film or metal film may be formed, in which case the compound film of step a) may have a thickness equal to the length of the designed upper support area and the designed lower support area. If the film is a compound film remaining after dry etching, the compound film of step a) may have a thickness that is the sum of the designed upper support area, the designed lower support area, and the designed lower film thickness.
  • a step of depositing a film of the second metal by using the first metal nano-sum suspended in the air by the support member may be performed.
  • the deposition of the second metal film is carried out by physical vapor deposition such as sputtering or the like. It can also be carried out through chemical deposition such as plasma assist chemical vapor deposition, but preferably, the second metal film can be formed by directional deposition including thermal evaporator or e-beam evaporator.
  • the use of the airborne type first metal nanosum having the directional deposition and the bottom surface of the plane as a deposition mask prevents the deposition and formation of nanoparticles of the second metal on the side of the support member.
  • the directional deposition of the second metal in the form of a film so as to have a uniform thickness on the basis of the first metal nano-isolated in the air floating state as a deposition mask In addition to precisely controlling the size of the nanogap, the nanogap can be formed in a self-aligned manner at the same time as the formation of the first metal nanoparticles and the second metal film.
  • the deposition prevents the formation of particulate secondary metal on the side of the support member, such that only a very fine nanogap controlled by the design can be present on the substrate.
  • the first metal which is obtained after the deposition is performed in step d), is a first metal.
  • Nanoparticles when the second metal and the first metal are the same, the surface curvature increases slightly in the deposition direction of the system I metal nanoscale used as the mask or slightly in the deposition direction.
  • the first metal nanoparticle may be referred to the laminated particles described above.
  • 1 Metallic nanoparticles may be truncated grains having a lower surface plane and a convex curved surface, and the truncated grains may be truncated spheres or truncated capsule shapes described above.
  • the first metal nanoparticles are the first metal nanosomes (particles of the above-mentioned 1-1 metal) and the convexities of the first metal nanosomes, which are composed of a plane lower surface and a convex surface.
  • the above-described customized particles can be produced comprising a coating layer of the second metal (coating layer of the above-mentioned 1-2 metal), covering at least a portion of the curved surface, wherein the first metal and the second metal are independent of each other.
  • the first metal and the second metal are independent of each other.
  • it can be gold, platinum, palladium, nickel, aluminum, copper, cream or their alloys.
  • High-density nanoparticles can be formed on substrates, even on large-area substrates.
  • the distribution of nanoparticles can be maintained uniformly.
  • the substrate according to the manufacturing method of the present invention has a large area even on a large-area substrate due to the uniform distribution of nanoparticles and the configuration of precisely controlled nanogaps.
  • the increased intensity of the average surface enhanced Raman scattering is maintained uniformly, allowing quantitative analysis of the analyte.
  • the thickness of the [211] -based bimetallic film can be 5 to 100 nm, and can be adjusted in consideration of the size of the pre-designed nanogap.
  • the metal nano-isolated in the air floating state is used as a deposition mask, and by directional deposition, the second metal is deposited in the form of a film to have a uniform uniform thickness.
  • the nanogap be precisely controlled in size, but also the formation of the first metal nanoparticles and the second metal film, the hot spots can be formed in a self-aligning manner, and the nanoparticles cause an uncontrollable gap on the side of the supporting member. Can be prevented from forming.
  • step c) the depth of the compound film during isotropic etching in step c) and the depth of step d)
  • the size of the nanogap formed in the self-aligned manner in step d) can be controlled.
  • the step of forming a receptor specifically binding to the object to be detected may be performed on the lower surface of the empty space and / or on the surface of the support member (including the side) defining the lower portion of the space (E).
  • the lower surface may of course be the surface of the substrate, the upper surface of the lower support region, the surface of the metal film exposed to the surface after etching in step c) or the surface of the compound film remaining after etching in step c).
  • the surface of the lower film (metal film or compound film remaining after etching) or the upper surface of the lower support region and / or the support member that partitions the void space Further steps may be taken to form a receptor on the side surface that specifically binds to the detection object.
  • This formation of the receptor introduces a solution containing the receptor into the empty space and chemically reacts with the support member and the underlying membrane. This can be achieved by binding and fixing.
  • any method of attaching a receptor commonly used in the field of sensors for detecting biochemicals can of course be used, and the present invention is not limited by the method of forming a specific receptor.
  • nanoparticles nanoparticles or first metal nanosums
  • Material of the support member size or shape of the support member; material or thickness of the underlying film;
  • Analytical material Receptor material; Substance or shape;
  • the column can refer to the above-mentioned Raman scattering substrate, and includes all of the above contents on Raman scattering substrate.
  • 10 (a) is a scanning electron microscope of a sample in which a silicon oxide layer having a thickness of 100 nm is formed on a substrate based on 2 cm X 2 cm of a silicon wafer, and an Ag film of 11 nm is formed on the silicon oxide layer.
  • 10 (b) shows the RTP equipment (Korea vacuum,
  • KVR-020 is a scanning electron microscope photograph of the sample heat-treated for 1 minute after the sample was heated up to 400 ° C. at a temperature rising rate of 15 ° C./sec.
  • the silicon oxide layer is formed of the cut grain type Ag nanoparticles.
  • the phase is well formed, and the Ag nanoparticles having an average size of 120 nm based on the projection shape are formed at a high density of 15 / ⁇ 2 .
  • FIG. 11 (a) is a sample obtained by wet etching a silicon oxide layer with a depth of 20 nm using the etching solution HF: NH 4 F l: 6 (v / v) for the sample of FIG. 10 (b).
  • HF NH 4 F l: 6 (v / v)
  • FIG. 10 (b) is a sample obtained by wet etching a silicon oxide layer with a depth of 20 nm using the etching solution HF: NH 4 F l: 6 (v / v) for the sample of FIG. 10 (b).
  • the etching rate of the etchant was 4 nm / sec, and the etching depth was adjusted by adjusting the etching time. Controlled.
  • FIG. 11 (b) shows a sample in which an Ag-type Ag nanoparticles of the sample of FIG. 11 (a) were used as a deposition mask, and a sample of 30 nm Ag was formed using an E-beam evaporator.
  • the deposition rate of the Ag film was 0.7 nm / sec, and the thickness of the deposited Ag film was controlled by controlling the deposition time.
  • the ring-shaped hot spots (nanogaps) between the nanoparticles are formed in a self-aligned manner.
  • the airborne type Ag nanoparticle lower robin space (E) is well defined through Fig. 11 (b).
  • the SERS activation structure of the airborne Ag nanoparticles and the Ag metal film according to the position of the silicon wafer was observed, and the device was fabricated in a large area of 2 cm X 2 cm. However, no significant changes in the SERS activity structure were observed.
  • the ultra-fine nanogap is uniformly formed even in large area, and Ag particles can be formed on the side of the supporting member by forming the Ag metal film by directional deposition. It can be seen that this is prevented.
  • FIG. 12 (a) shows that an Ag film having a thickness of 14 nm is formed on the silicon oxide layer, and then heated up to 400 ° C. at a temperature rising rate of 15 ° C./sec using RTP equipment for 1 minute.
  • Fig. 12 (b) again shows the Ag film of 14 nm thickness on the sample of Fig. 12 (a), the same as the sample of Fig. 12 (a) Scanning electron micrographs of Ag nanoparticles after heat treatment.
  • FIG. 13 (a) shows the observation of the silicon oxide phase patterned Ag film after formation thereof.
  • FIG. 13B is a scanning electron microscope photograph of Ag nanoparticles prepared by heat-treating the patterned Ag film in the same manner as the sample of FIG. 13A and 13B, an Ag film on only a dielectric film (compound film) was formed.
  • FIG. 14 shows the sample of FIG. 10 (b).
  • the etching time is controlled, the silicon oxide layer is etched to a depth of 32 nm, and an Ag film having a thickness of 30 nm is deposited using an E-beam evaporator. Observed the dark field image of the samples.
  • FIG. 15 is a scanning electron micrograph of the sample of FIG. 14, as seen from FIG. 15.
  • FIG. 16 shows that in the sample of FIG. 14, the etching depth of the silicon oxide layer is adjusted to 6 nm (sample A of FIG. 16), 24 nm (sample B of FIG. 16), or 32 nm (sample C of FIG. 16).
  • the surface-enhanced Raman scattering spectrum of the sample is also shown, and the surface-enhanced Raman scattering spectrum of the sample (Reference only Si0 2 / Si in FIG. 16) in which only the silicon oxide layer is formed before etching to the Si substrate by reference is also shown.
  • the experiment has a thiol functional group, which can form a strong chemical bond on the sample metal surface (Au, Ag, etc.), and a benzenethiol (Benzenethiol, C 6 H 6 SH) with weak photochemical reaction is used.
  • the prepared samples were kept in acetone or ethyl alcohol solution for at least 1 day to remove surface organic impurities, and each washed sample was returned for 1 day or more in 2mM benzene thiol solution (solvent: ethanol). . Strongly adsorbed by chemical bonding after reaction, only benzenethiol was applied to the sample surface.
  • the excess ethanol was washed with excess ethanol to remove excess benzenethiol that was physically adsorbed on the surface.
  • the sample was dried in nitrogen and stored in a closed container for Raman analysis.
  • the Raman signal is a Micro Raman system (Horiba, HR). -800) was used to measure the wavelength of 632.8 nm laser light.
  • the strong signal observed in the region of 1000-1100 cm 'and 1580 cm 1 shown in Fig. 16 corresponded to the SERS signal unique to benzenethiol. You can see
  • the intensity of the surface enhancement Raman scattering spectral peak varies as the size of the nanogap changes, and it is stronger than the C sample in the 1600 (cm ') wave range for the A and B samples. It can be seen that a peak occurs.
  • Figure 17 shows the surface enhancement Raman scattering spectrum of sample B of Figure 16, Figure 12 (b).
  • the surface enhancement Raman scattering spectrum of Sample E (etching depth and Ag film thickness is the same as Sample B) in which the Ag nanoparticle density is 1.5 times higher than that of Sample B is shown.
  • Fig. 1.7 the surface-enhanced Raman scattering spectrum of the sample (Reference only Si0 2 / Si in Fig. 17) in which only the silicon oxide layer was formed on the Si substrate before etching by reference is also shown.
  • the density of the hot spot is shown.
  • the peak of the 1600 (cnr ') frequency band is also 1.5 times increased by 1.5 times.
  • FIG. 18 is similar to the sample of FIG. 11 (b), but after forming an 11 nm Au film on the silicon oxide layer, RTP treatment at 550 ° C for 1 minute, 20 nm silicon oxide layer Scanning electron micrographs of samples wet-etched to depth and deposited with Au film (second metal film) at 30 nm thickness using an e-beam evaporator.
  • FIG. 19 shows surface enhancement Raman scattering using the sample of FIG. The Raman scattering experiment was performed in the same manner as in the example of Fig. 16. As can be seen from Fig. 19, a strong SERS signal could be measured using an ultra-low energy laser light of 8 W. Compared to the Raman signal of the board, we can measure the signal about 13 times stronger.
  • FIG. 20 illustrates a Raman scattering substrate manufactured by the same method as the sample of FIG. 18 except that a 50 nm thick Au film is formed on a silicon wafer and then a 20 nm silicon oxide layer is formed on an Au film. Scanning electron micrograph.
  • a 20 nm silicon oxide layer was formed on an Au film, and the Au film was formed and RTP heat treated in the same manner as in the sample shown in FIG. 18, and the etching solution (HF: NH 4 F (l: 6 (v / v)) was used to wet-etch the silicon oxide layer to a depth of 20 nm to remove all the silicon oxide layers other than the Au nanoparticle underneath, and then the airborne Au was the same as the sample of FIG.
  • FIG. 21 is a diagram showing the surface enhancement Raman scattering spectrum of FIG. 20 sample, and an example of FIG. The Raman scattering experiment was performed in the same manner. When the metal film was prepared in the lower film through the spectrum of FIG. It can be seen that the Raman scattering light loss is prevented and its strength is improved.

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Abstract

본 발명은 표면증강 라만산란 기판에 관한 것으로, 본 발명에 따른 표면증강 라만산란 기판은 공중 부유형 제1금속 나노입자, 상기 제1금속 나노입자를 지지하는 지지부재, 상기 제1금속 나노입자와 나노갭을 형성하며 상기 제1금속 나노입자의 둘레를 감싸는 제2금속 막을 포함하며, 상기 제1금속 나노입자의 제1금속 및 제2금속 막의 제2금속은 각각 표면 플라즈몬이 발생하는 금속일 수 있다.

Description

명세서
발명의명칭:표면증강라만산란기판，이를포함하는분자검출용 소자및이의제조방법
기술분야
[1] 본발명은표면증강라만산란기판，이를포함하는분자검출용소자및이의 제조방법에관한것으로，상세하게，고감도로분자검출이가능하며， 대면적에서도균일한검출결과를얻을수있으며，극히저가의간단한공정으로 제조가능한표면증강라만산란기판,분자검출용소자및이의제조방법에 관한것이다.
배경기술
[2] 표면증강라만산란 (SERS)분광법은금,은등의금속나노구조표면에흡착된 분자의라만산란세기가급격히 106 ~ 108배이상증가되는현상을이용한 분광법이다.백터량의데이터에의해한번의측정으로대량의정보를얻을수 있으며,단하나의분자를직접측정할수있을정도로초고감도의기술이며, 분자의진동상태,흑은분자구조에대한정보를직접적으로측정가능하여, 화학적 /생물학적 /생화학적분석을위한강력한분석방법으로인정받고있다.
[3] 표면증강라만산란분광의민감도，정량분석，측정의신뢰성및재현성을 위해서는엄밀하게잘규정된핫스팟이고밀도로형성되어야하며 ,
검출대상물이핫스팟과인접하여위치할수있어야한다.
[4] 또한,표면증강라만산란기판의상업화,즉,표면증강라만산란기판을저 비용으로대량생산하기위해서는리소그라피와같은고가의까다로운공정이 아닌증착이나열처리등간단한공정으로,대면적에서도，균일하게잘규정된 크기를갖는나노갭을고밀도로형성할수있는기술의개발이요구되고있다.
[5] 통상적으로,대한민국공개특허제 2013-0095718호와같이，나노입자를이용한
SERS센서가가장일반적으로연구되고있으나，금속나노입자의배열이확률에 의한랜덤구조를가지므로규정된구조를가질수없어검출의재현성및 정확성을획득하기어려운문제점이있다.나아가,핫스팟의위치나핫스팟의 밀도등이잘규정되지않아，정량분석에걸림돌이되고있다.
[6]
발명의상세한설명
기술적과제
[7] 본발명은정밀하게잘제어된핫스팟을가져,정량분석가능하며,측정의 신뢰성및재현성이우수한표면증강라만산란기판을제공하는것이다.
[8] 본발명의다른목적은대면적에서도균일하게극미세갭을갖는표면증강 라만산란기판을제공하는것이다.
[9] 본발명의또다른목적은대면적에서도균일한표면플라즈몬활성을가지며 고밀도의핫스팟이형성되어，측정의민감성및상업성이우수한표면증강 라만산란기판을제공하는것이다.
[10] 본발명의또다른목적은측정대상물질이핫스팟내또는핫스팟에인접하여 위치됨으로써,핫스팟에의한신호증강이현저하게향상된표면증강라만산란 기판을제공하는것이다.
[11] 본발명의또다른목적은，고가의장비나고도의공정제어가불필요하고,공정 구축비용이낮은극히간단한방법으로상술한고품질의표면증강라만산란 기판을제조할수있는제조방법을제공하는것이다.
[12]
과제해결수단
[13] 본발명에따른표면증강라만산란 (SERS; Surface-Enhanced Raman Scattering) 기판은공중부유형제 1금속나노입자，상기제 1금속나노입자를지지하는 지지부재，상기제 1금속나노입자와나노갭을형성하며상기제 1금속
나노입자의둘레를감싸는제 2금속막을포함하며，상기제 1금속나노입자의 제 1금속및제 2금속막의계 2금속은각각표면플라즈몬이발생하는금속이다.
[14] 본발명의일실시예에따른표면증강라만산란기판에있어 ,제 1.금속
나노입자에서，지지부재에의해지지되는측의면인제 1금속나노입자의 하부면은평면일수있다.
[15] 본발명의일실시예에따른표면증강라만산란기판에있어，제 1금속
나노입자와상기제 1금속나노입자의둘레를감싸는제 2금속막의
테두리 (edge)를포함하는제 2금속막의측면에의해나노갭이형성될수있다.
[16] 본발명의일실시예에따른표면증강라만산란기판에있어，나노갭은폐 루프형상일수있다.
[17] 본발명의일실시예에따른표면증강라만산란기판에있어,하부면은
지지부재와계면을형성하는지지영역과표면으로노출되는미지지영역이 공존할수있다.
[18] 본발명의일실시예에따른표면증강라만산란기판에있어，하부면의면적 기준， 10내지 80%의면적이지지부재와계면을이를수있다.
[19] 본발명의일실시예에따른표면증강라만산란기판에있어,제 1금속
나노입자의하부면의미지지영역을포함한제 1금속나노입자,계 2금속막의 측면，및지지부재의측면에의해규정되는공간에검출대상물이위치할수 있다.
[20] 본발명의일실시예에따른표면증강라만산란기판에있어，제 2금속막의 관통형기공내부에지지부재에의해지지되는공중부유형계 1금속나노입자가 위치할수있다.
[21 ] 본발명의일실시예에따른표면증강라만산란기판에있어,제 1금속
나노입자，관통형기공및지지부재는서로동심구조를이를수있다. [22] 본발명의일실시예에따른표면증강라만산란기판은제 2금속막및공중 부유형제 1금속나노입자하부에위치하는하부막을더포함할수있다.
[23] 본발명의일실시예에따른표면증강라만산란기판에있어，하부막은지지 부재와동일한물질이며，지지부재는하부막으로부터연장될수있다.
[24] 본발명의일실시예에따른표면증강라만산란기판에있어,하부막은
금속막 (제 3금속막)일수있다.
[25] 본발명의일실시예에따른표면증강라만산란기판에있어，적어도,공중
부유형제 1금속나노입자하부에위치하는하부막의표면또는지지부재의 측부표면에검출대상물질과특이적으로결합하는수용체가형성될수있다ᅳ [26] 본발명의일실시예에따른표면증강라만산란기판에있어，지지부재는
금속화합물및반도체화합물에서하나또는둘이상선택될수있으며,이와 독립적으로，상기하부막은금속，금속화합물및반도체화합물에서하나또는둘 이상선택될수있다.
[27] 본발명의일실시예에따른표면증강라만산란기판에있어,제 1금속
나노입자는잘린입자형상 (truncated particle shape)일수있다.
[28] 본발명의일실시예에따른표면증강라만산란기판에있어，나노갭의크기는
1 nm내지 lOOnm일수있다.
[29] 본발명의일실시예에따른표면증강라만산란기판에있어，지지부재의길이 및제 2금속막의두께증하나이상선택된인자 (factor)에의해,나노갭의크기가 조절될수있다.
[30] 본발명의일실시예에따른표면증강라만산란기판에있어，제 1금속
나노입자는투영 (projection)형상기준，투영형상의평균지름은 l Onm내지 500nm인일수있다.
[31] 본발명의일실시예에따른표면증강라만산란기판에있어,제 2금속막의 두께는 10지 lOOnm일수있다.
[32] 본발명의일실시예에따른표면증강라만산란기판에있어,단위면적당
제 1금속나노입자의수인나노구조체밀도는 1내지 100개 /fim2일수있다.
[33] 본발명의일실시예에따른표면증강라만산란기판에있어，기판은공중
부유형제 1금속나노입자가형성된표면증강라만산란활성영역및공증 부유형제 1금속나노입자가미형성된표면증강라만산란비활성영역을 포함하며，둘이상의표면증강라만산란활성영역이이격배열된것일수있다.
[34] 본발명의일실시예에따른표면증강라만산란기판에있어，제 1금속
나노입자의계 1금속및제 2금속막의제 2금속은서로독립적으로，표면 플라즈몬이발생하는금속일수있다.
[35] 본발명의일실시예에따른표면증강라만산란기판에있어,제 1금속
나노입자의제 1금속및제 2금속막의제 2금속은서로독립적으로,은,금,백금, 팔라디움，니켈,알루미늄,구리,크롬또는이들의조합또는이들의합금일수 있다. [36] 본발명의일실시예에따른표면증강라만산란기판에있어,지지부재는 Zr02, ZnO, YF3, YbF3, Y203, Ti02, ThF4, TbF3, Ta205, Ge02, Te02, SiC,다이아몬드， SiOx ^(0< ^2인실수， 0<y<1.5인실수), Si02, SiO, SiNx(l≤x≤1.5인실수)， Sc203, NdF3, Na3AlF6, MgF2, LaF3, Hf02, GdF3, DyF3, CeF3, CaF2, BaF2, A1F3, A1203,
ITO(Indium-Tin Oxide)또는이들의흔합물을포함할수있다.
[37] 본발명은상술한표면증강라만산란기판을포함하는분자검출용소자를
포함한다.
[38] 본발명의일실시예에따른분자검출용소자는상술한표면증강라만산란 기판및표면증강라만산란기판상공중부유형제 1금속나노입자，계 1금속 나노입자를지지하는지지부재및적어도제 2금속막의제 1금속나노입자와 나노 ¾을형성하며제 1금속나노입자의둘레를감싸는영역을내부에
수용하도록형성된미세유체채널을포함할수있다.
[39] 본발명에따른표면증강라만산란기판의제조방법은 a)기재상금속화합물 또는반도체화합물인화합물막을형성하는단계; b)상기화합물막상제 1금속 막을형성한후열처리하여화합물막상서로이격되어위치하는제 1금속나노 섬 (nano island)을제조하는단계； c)상기제 1금속나노섬을에칭마스크로，상기 화합물막을일정깊이까지등방에칭하는단계 ;및 d)상기제 1금속나노섬을 증착마스크로,에칭된화합물막상제 2금속을증착하여게 2금속막을형성하는 단계;를포함한다.
[40] 본발명의일실시예에따른표면증강라만산란기판의제조방법에있어，
화합물막의금속화합물또는반도체화합물은금속산화물 (oxide),금속 산질화물 (oxynitride),금속질화물 (nitride),금속불화물을포함하는금속 할로겐화물 (halide),금속탄화물 (carbide),반도체산화물，반도체산질화물, 반도체질화물，반도체탄화물，반도체물질에서하나또는둘이상선택될수 있다.
[41] 본발명의일실시예에따른표면증강라만산란기판의제조방법에있어 , b) 단계는, bl)제 1금속막을형성하는단계및 b2)열처리단계를단위공정으로, 단위공정올반복수행함으로써,제 1금속나노섬의밀도를제어할수있다.
[42] 본발명의일실시예에따른표면증강라만산란기판의제조방법에있어，등방 에칭은습식에칭일수있다.
[43] 본발명의일실시예에따른표면증강라만산란기판의제조방법에있어 , c) 단계에서 , c)단계에서，등방에칭전，또는등방에칭후,건식에칭이더수행될 수있다.
[44] 본발명의일실시예에따른표면증강라만산란기판의제조방법은기재상 금속막이거나,상기화함물막과상이한금속화합물또는반도체화합물의 막인하부막을형성하는단계를더포함하며， c)단계의등방에칭을포함하는 에칭에의해에칭마스크로보호되지않은영역에서하부막이표면으로노출될 수있다. [45] 본발명의일실시예에따른표면증강라만산란기판의제조방법에있어， c) 단계의등방에칭올포함하는에칭에의해，에칭된화합물막이잔류할수있다.
[46] 본발명의일실시예에따른표면증강라만산란기판의제조방법에있어， d) 단계의증착은열증착 (Thermal evaporator)또는전자빔증착 (E-beam
evaporator)을포함한방향성있는증착일수있다.
[47] 본발명의일실시예에따른표면증강라만산란기판의제조방법에있어， c) 단계의에칭깊이및 d)단계의증착두께증적어도하나의인자를제어하여, 나노갭크기가조절될수있다.
[48] 본발명의일실시예에따른표면증강라만산란기판의제조방법에있어, b) 단계에서,패턴화된제 1금속막이형성될수있다.
[49] 본발명의일실시예에따른표면증강라만산란기판의제조방법에있어， b) 단계에서,제 1금속막의두께는 1내지 50nm일수있다.
[50] 본발명의일실시예에따른표면증강라만산란기판의제조방법은 c)단계후 d)단계전，또는 d)단계후， c)단계의에칭후표면으로노출되는금속막또는 c) 단계의에칭후잔류하는화합물막과지지부재의표면에검출대상물과 특이적으로결합하는수용체를형성하는단계를더포함할수있다.
[51] 본발명의일실시예에따른표면증강라만산란기판의제조방법에있어， c) 단계의열처리는급속열처리공정 (RTP; rapid thermal process)에의해수행될수 있다.
발명의효과
[52] 본발명에따른표면증강라만산란기판은정밀하게그크기가제어된나노 갭에의해핫스팟이형성되며，고밀도의핫스팟을가짐에따라,검출대상물의 정량분석이가능하며 ,측정의민감성，신뢰성및재현성이우수한장점이있다.
[53] 또한,본발명에따른표면증강라만산란기판은나노미터오더 (order)의
극미세나노갭이대면적에서도균일하게형성되어,현저하게향상된검출 강도를갖는장점이있다.
[54] 또한,본발명에따른표면증강라만산란기판은공중부유형금속나노입자 하부에규정되는빈공간에검출대상물질이위치함에따라，검출대상물질이핫 스팟내지핫스팟과매우가깝게인접하여고정되어，검출강도를현저하게 향상시킬수있다.
[55] 또한,본발명에따른표면증강라만산란기판은단지공중부유형금속
나노입자를지지하는지지부재의길이나금속막의두께라는엄밀하고 용이하게조절가능한인자에의해나노갭의크기가제어됨에따라，
대면적에서도매우정밀하고균일하게제어된나노갭을갖는장점이있다.이에 따라대면적생산가능하면서도，제조되는대면적의기판이위치와무관하게 평균적으로균일한표면플라즈몬활성을가질수있는장점이있다.
[56] 또한，본발명에따른표면증강라만산란기판은저가의간단한공정을통해 제조가능하여,극히우수한상업성을갖는장점이있다.
[57] 본발명에따른표면증강라만산란기판의제조방법은，증착，열처리및
에칭이라는단지세종류의공정만으로상술한고품질의표면증강라만산란 기판을제조할수있는장점이있다.이에따라，용이하게제어할수있으며 엄밀하게제어가능한공정변수에의해표면증강라만산란기판이제조됨에 따라，생산성및수율을향상시킬수있는장점이있다.또한,일정한표면 플라즈몬활성을갖는표면증강라만산란기판을재현성있게제조할수있는 장점이있으며，의도치않는표면플라즈몬활성의변화에의한불량발생을 현저하게감소시킬수있는장점이있다.
[58] 또한,본발명에따른표면증강라만산란기판의제조방법은물리적지지체인 기재의표면에용도에부합한의도적요철구조가존재하더라도，요철구조와 무관하게 SERS활성을갖는기판의제조가가능한장점이있다.이는마'이크로 채널형성이나다른검출소자와의복합화를고려할때매우유리하다.
[59] 또한，본발명에따른표면증강라만산란기판의제조방법은대면적의
기재에도균질한표면플라즈몬활성을갖는기판의제조가가능한장점이있다. 도면의간단한설명
[60] 도 1은본발명의일실시예에따른표면증강라만산란기판의단면을도시한 일단면도이다.
[61 ] 도 2는본발명의일실시예에따른표면증강라만산란기판의단면을도시한 다른일단면도이다.
[62] 도 3은잘린구형상을갖는제 1금속나노입자의일예들을도시한일
사시도이다.
[63] 도 4는계 2금속막에서관통형기공영역을세부도시한일사시도이다.
[64] 도 5는계 1금속나노입자의하부면,지지부재의단면및제 2금속막의관통형 기공의외주면의위치관계를도시한일모식도이다.
[65] 도 6은제 1금속나노입자를지지하는지지부재만을도시한일사시도이다.
[66] 도 7은상부지지영역과하부지지영역을포함하는지지부재를도시한일
사시도이다.
[67] 도 8은본발명의일실시예에따른표면증강라만산란기판의단면을도시한 일단면도이다.
[68] 도 9는기재상 2X3매트릭스를형성하는사각패턴으로패턴화된제 1금속
막을도시한일예이다.
[69] 도 10은기재상화합물막및금속층이형성된샘플 (도 10(a))및이를
열처리한샘플 (도 10(b))을관찰한주사전자현미경사진이다.
[70] 도 11은도 10(b)의샘플을등방에칭한후의샘플 (도 11(a))및이에금속막을 증착한샘플 (도 11(b))을관찰한주사전자현미경사진이다.
[71] 도 12는금속막의형성및열처리된샘플 (도 12(a))에다시금속막을형성하고 열처리하여금속나노입자의밀도가증가된샘플 (도 12(b))을관찰한 주사전자현미경사진이다.
[72] 도 13은패턴화된금속막 (도 13(a))을형성한후，이를열처리하여패턴화된 표면증강라만산란활성영역을갖는샘플을제조하고，그활성영역 (도 13(b))을 관찰한주사전자현미경사진이다.
[73] 도 14는화합물막의둥방에칭깊이를달리한후도 11(b)의샘플과동일한 두께의금속막을증착하여제조된샘플의암시야상을도시한도면이다.
[74] 도 15는도 14의샘플을관찰한주사전자현미경사진이다.
[75] 도 16은표면증강라만산란기판의라만산란스펙트럼을도시한도면이다.
[76] 도 17은표면증강라만산란기판의라만산란스펙트럼을도시한다른
도면이다.
[77] 도 18은제 1금속나노입자및계 2금속막의금속이모두 Au인표면증강
라만산란기판을관찰한주사전자현미경사진이다.
[78] 도 19는도 18의표면증강라만산란기판의라만산란스펙트럼을도시한
도면이며，
[79] 도 20은하부막이금속막이며，제 1금속나노입자및제 2금속막의금속이모두 Au인표면증강라만산란기판을관찰한주사전자현미경사진이다.
[80] 도 21은도 20의표면증강라만산란기판의라만산란스펙트럼을도시한
도면이다.
[81]
발명의실시를위한형태
[82] 이하첨부한도면들을참조하여본발명에따른표면증강라만산란기판,이를 포함하는소자및기판의제조방법을상세히설명한다.다음에소개되는 도면들은당업자에게본발명의사상이층분히전달될수있도록하기위해 예로서제공되는것이다.따라서，본발명은이하제시되는도면들에한정되지 않고다른형태로구체화될수도있으며，이하제시돠는도면들은본발명의 사상을명확히하기위해과장되어도시될수있다.이때，사용되는기술용어및 과학용어에있어서다른정의가없다면,이발명이속하는기술분야에서 통상의지식을가진자가통상적으로이해하고있는의미를가지며，하기의설명 및첨부도면에서본발명의요지를불필요하게흐릴수있는공지기능및 구성에대한설명은생략한다.
[83] 본발명에따른표면증강라만산란 (SERS; Surface-Enhanced Raman Scattering) 기판은공중부유형제 1금속나노입자,제 1금속나노입자를지지하는지지부재， 제 1금속나노입자와나노갭을형성하며제 1금속나노입자의둘레를감싸는 제 2금속막을포함한다.
[84] 본발명을상술함에있어，제 1금속나노입자의계 1금속및계 2금속막의
제 2금속은서로독립적으로광과의상호작용에의해표면플라즈몬이발생하는 금속일수있다.구체적인일예로，계 1금속나노입자의제 1금속및제 2금속막의 제 2금속은서로독립적으로은,금,백금，팔라디움,니켈,알루미늄，구리，크름 또는이들의흔합물또는이들의합금등을들수있으나，이에한정되는것은 아니며，표면플라즈몬이발생하는금속이면무방하다.
[85] 본발명을상술함에있어，공중부유형제 1금속나노입자의공중부유는，
제 1금속나노입자의크기보다지지부재의크기가더작아，제 1금속나노입자가 지지부재에의해지지됨과동시에공중에떠있는영역이존재함을의미할수 있다.
[86] 구체적으로，공중부유는，제 1금속나노입자의하부측면에,지지부재와
접촉되어지지부재에의해지지되는지지영역과지지부재에의해지지되지 않아표면을형성하는미지지영역 (표면영역)이공존함을의미할수있다.이때， 제 1금속나노입자의하부측면은제 1금속나노입자가지지부지에의해 지지되는측의면을의미할수있다.
[87] 달리상술하면，공중부유는지지부재에의해지지되는계 1금속나노입자의 하부공간이모두지지부재로채워지지않고,지지부재와빈공간 (empty space)이 공존하는것을의미할수있다.
[88] 이러한공중부유구조에의해야기되는빈공간은검출대상물을핫
스팟 (hot-spot)생성영역으로가두는역할을수행하여,검출민감도，검출의 재현성및검출강도 (라만시그널강도)를현저하게향상시킬수있다.
[89] 또한，제 1금속나노입자가공중부유구조를가지며 ,부유하는제 1금속
나노입자의둘레를감싸는제 2금속막사이에나노갭이형성됨에따라, 점 (point)형핫스팟이아닌,폐루프 (closed loop)형핫스팟을가질수있다.
[90] 알려진바와같이,핫스팟 (hot-spot)은매우강한국소전기장이형성되며
국부적표면플라즈몬공명 (LSPR; localized surface plasmon resonance)이 발생하는영역을의미하며，표면플라즈몬이발생하는금속의나노구조간 접점이나나노갭등에의해형성될수있다.
[91] 폐루프형의선형핫스팟은기판이폐루프형의선형 LSPR발생영역을
가짐을의미하며，이러한선형 LSPR발생영역에의해라만신호강도가 현저하게증강되어,검출민감도를향상시킬수있다.
[92] 보다특징적으로，공중부유형제 1금속나노입자는상기지지부재에의해
지지되는측의면인제 1금속나노입자의하부면이평면일수있다.이러한경우, 공중부유는하부면이모두지지부재에의해지지되지않고，하부면에
지지부재에의해지지되는영역과지지부재에의해지지되지않는영역이 공존함을의미할수있다.
[93] 편평한 (flat)평면의하부면은제 2금속막과함께，엄밀하게제어된나노갭을 형성하는데특히유리하다.알려진바와같이，나노갭의미세한크기변화로도 검출강도가크게달라져，검출의재현성및민감도향상을위해잘규정된 나노갭을구현하고자하는연구가지속적으로이루어지고있다. [94] 제 1금속나노입자가평면의하부면을갖는경우,제 1금속나노입자와겨 금속 나노입자의둘레를감싸는제 2금속막의테두리 (edge)를포함하는제 2금속막의 측면에의해나노갭이형성될수있다.보다구체적으로,적어도，하부면의 테두리 (edge)와상기제 1금속나노밉자의둘레를감싸는제 2금속막의 테두리 (edge)에의해나노갭이형성될수있다.이는，서로이격된
평면 (하부면)과평면 (제 2금속막의표면)에의해나노갭이형성됨을의미하는 것이다.나노갭이두평면에의해형성됨에따라,엄밀하게그크기가제어된 나노갭이형성될수있으며，나노미터오더 (nm order)의극미세한나노갭이 형성될수있다.
[95] 도 1은본발명의일실시예에따른표면증강라만산란기판의단면을도시한 일단면도이다.도 1에도시한바와같이，제 1금속나노입자 (100)는
지지부재 (200)에의해지지되며,제 1금속나노입자 (100)하부영역에빈 공간 (E)을갖는공중부유형구조를가진다.또한,기재 (500)상위치하는제 2금속 막 (300)은제 1금속나노입자 (100)와나노갭 (G)을형성하며제 1금속
나노입자 (100)의둘레를감싸는구조를갖는다.
[96] 제 2금속막 (300)은관통형기공 (PP)이형성된막알수있다.제 2금속막 (300)의 관통형기공 (PP)내부에지지부재 (200)에의해지지되는제 1금속
나노입자 (100)가위치함으로써，제 2금속막 (300)은계 1금속나노입자 (100)와 나노갭 (G)을형성하며겨 U금속나노입자 (100)의둘레를감싸는구조를가질수 있다.이에,제 1금속나노입자와나노갭을형성하는제 2금속막의
테두리 (edge)를포함하는겨 12금속막의측면은，관통형기공 (PP)의
테두리 (edge)를포함하는관통형기공 (PP)의기공면을의미할수있다.
[97] 도 1에도시한일예와같이，본발명에따른일실시예에있어,제 1금속
나노입자 (100)의하부면 (BS)은평면일수있다.이때，제 1금속나노입자 (100)의 하부면 (BS)은금속나노입자 (100)에서지지부재 (200)에의해지지되는측의 면을의미할수있다.
[98] 상세하게,제 1금속나노입자 (100)의하부면 (BS)은계 2금속막의표면과평행한 평면,기재 (500)의표면과평행한평면，일예로，수평면 (horizontal plane)일수 있다.
[99] 계 1금속나노입자 (100)의하부면 (BS)이편평한 (flat)평면인경우，적어도, 하부면 (BS)의에지 (edge)를따라폐곡선형태로형성되는나노갭이폐곡선내 위치와무관하게극히균일한크기를가질수있다.이에따라，제 1금속 나노입자 (100)와제 2금속막 (300)사이에는폐루프형태의극히균일하며매우 강한국소전기장이형성될수있다.
[100] 또한，도 1에도시한일예와같이,공증부유형제 1금속나노입자 (100)및
지지부재 (200)를일단위체로하여,둘이상의단위체가각각계 2금속막 (300)의 관통형기공 (PP)내부에위치할수있다.
[101] 즉，표면증강라만산란기판은기재 (500)상，서로이격배열된다수개의관통형 기공 (PP)을갖는제 2금속막 (300)，관통형기공 (PP)내부각각에위치하며, 저 12금속막 (300)과나노갭을형성하는공증부유형제 1금속나노입자 (100)및 계 1금속나노입자 (100)를지지하는지지부재 (200)를포함할수있다.
[102] 이러한경우，관통형기공 (PP)각각에위치하는제 1금속나노입자 (100)의
하부면 (BS)은가상의단일한평면 (VP)내에위치할수있다.즉，표면증강 라만산란기판에위치하는제 1금속나노입자 (100)들의하부면들은단일한 평면 (VP)내에위치할수있다.
[103] 이에의해，표면증강라만산란기판에형성된나노갭들이표면증강라만산란 '기판상에서의위치와무관하게극히균일한크기를가질수있고，대면적의 기판에서도극히균일한표면증강라만산란활성을나타낼수있다.
[104] 상술한바와같이，본발명의일실시예에따른표면증강라만산란기판은, 대면적의기판일지라도균일한 SERS활성을가질수있다.
[105] 이는，핫스팟이제 2금속막 (300)과제 1금속나노입자 ( 100)간의나노갭에의해 형성됨에기인한것이다.상세하게,핫스팟이제 1금속나노입자 (100)의하부면을 포함하는제 1금속나노입자의표면과，제 2금속막 (300)의관통형기공의 에지 (edge)를포함하는제 2금속막의관통형기공면에의해형성될수있다. 기판에형성되는핫스팟은상술한가상의평면 (VP)과제 2금속막 (300)의 기공면을포함한표면이라는평면들로부터기인함에따라,기판내핫스팟의 위치와무관하게,기판에존재하는핫스팟은서로동일한크기의나노갭을 가질수있다.또한,단지，지지부재 (200)의길이 (높이)및계 2금속막 (300)의두께 중하나이상선택된인자 (factor)를조절함으로써,기판전체적으로나노 ¾의 크기가균일하게조절될수있다.
[106] 즉，제 1금속나노입자 (100)의하부면이평면임에따라,단지지지부재 (200)의 길이를조절함으로써,하부면 (에지를포함함)이엄밀하게잘규정된높이에 위치할수있다.또한,제 2금속막 (300)또한평면의표면을가짐에따라제 2금속 막의두께를조절함으로써제 2금속막의표면위치또한엄밀하게잘규정된 높이에위치할수있다.
[107] 이에따라,나노갭을형성하는두요소 (제 1금속나노입자의하부면및제 2금속 막의관통형기공면을포함한제 2금속막의표면)가모두엄밀하게잘제어된 위치를갖게되어,엄밀하게잘제어된크기의나노갭이형성될수있다.또한， 나노갭을형성하는두요소의위치가지지부재의길이나제 2금속막의두께에 의해결정됨에따라，단지지지부재의길이 (높이 )및제 2금속막의두께중하나 이상선택된인자 (factor)를조절함으로써，나노갭의크기가엄밀하게조절될수 있다.또한，상술한바와같이 ,대면적의기판이라할지라도기판상위치하는 제1금속나노입자의하부면들이서로동일한위치 (동일한평면)에위치함에 따라，나노 ¾의크기가기판전제적으로극히균일하게조절될수있다.또한,본 발명에따른표면증강라만산란기판은나노미터오더 ( n order)의극미세 나노갭이대면적에서도일정크기로균일하게형성되어,현저하게향상된검출 강도를갖는장점이있다.이러한극미세갭및균일한크기의갭은검출의 민감도，소자의신뢰성 (검출의재현성)을현저하게향상시킬수있다.또한， 제 1금속나노입자의금속물질，게 2금속막의금속물질，나노 ¾의크기， 제 1금속나노입자의크기 (평균크기)등을제어함으로써,기판의국부적표면 플라즈몬공명 (LSPR)파장또한용이하게조절할수있다.
[108] 상술한바와같이，본발명의일실시예에따른표면증강라만산란기판은공증 부유형제 1금속나노입자와계 2금속막에의해핫스팟이형성됨에따라， 표면증강라만산란기판에는기판전체적으로잘제어된핫스팟이형성될수 있다.또한,대면적의기판이라할지라도균일한플라즈몬활성을나타낼수 있다.
[109] 본발명에따른일실시예에있어，제 1금속나노입자 (100)의하부면 (BS)이 평면인경우，상술한바와같이,하부면 (BS)은지지부재 (200)와계면을형성하는 지지영역과표면으로노출되는미지지영역이공존할수있음은물론이다. 이러한미지지영역에의해제 1금속나노입자 (100)하부에빈공간 (E)이형성될 수있다.
[110] 상세하게,제 1금속나노입자 (100)가공증부유구조를가짐에따라，도 2에 도시한일예와같이，제 1금속나노입자 (100)를둘러싸는제 2금속막 (300)의 측면 (301)，제 1금속나노입자의하부면 (BS)의미지지영역 (101)을포함하는 계 1금속나노입자 (100)및지지부재 (200)의측면 (201)에의해규정되는빈 공간 (E)에검출대상물이위치할수있다.즉，빈공간 (E)은검출대상물이 위치하여라만산란에의해검출되는공간일수있으며，이러한측면에서빈 공간 (E)은분석공간으로지칭될수있다.이때，제 2금속막 (300)의측면 (301)은 제 2금속막 (300)에형성된관통형기공의기공면에대웅함은물론이다.
[111] 하부면의면적을기준으로,지지부재와계면을형성하는지지영역의면적 비율은곧제 1금속나노입자하부의빈공간형성정도에영향을미칠수있다. 이에，지지영역의면적비율은제 1금속나노입자가물리적으로안정하게 지지되면서도검출대상물이핫스팟영역내지핫스팟인접영역에존재할수 있도록하는빈공간 (E)이형성될수있는비율인것이좋다.
[112] 구체적인일예로,하부면의면적기준， 10내지 80%의면적이지지부재와 계면을이를수있다.즉，지지영역의면적은하부면면적의 10내지 80%일수 있다.제 1금속나노입자의안정적지지，검출대상물의핫스팟인근으로의위치 제어측면,검출대상물의용이한확보측면및후술하는제 2금속의증착시 지지부재측면에금속나노입자들이형성되는것을방지하는측면에서,좋게는 지지영역의면적은하부면면적의 30내지 80%,보다좋게는 40내지 80%일수 있다.
[113] 도 1또는도 2에에도시한일예와같이，하부면이평면인계 1금속
나노입자 (100)는，잘린입자상 (truncated particle shape)또는판상일수있다.잘린 입자상은평면과볼록한 (convex)곡면의표면을포함하는형상일수있고, 판상은사각 (직사각,정사각을포함함),삼각과같은다각형판,원형판또는 타원형판을포함할수있다.보다구체적으로제 1금속나노입자 ( 100)는잘린 입자상일수있으며,잘린입자상은잘린구 (truncated sphere)형상또는잘린 캡슐형상 (truncated capsuᅵ e shape)일수있다.잘린구형상또는잘린캡슐 형상에서잘려진평면이상술한하부면에대응될수있음은물론이다.이때， 잘린구형상은단일한곡률을갖는곡면뿐만아니라，서로상이한곡률을갖는 둘이상의곡면을갖는경우또한포함함을인지하여야하며，잘린면이원뿐만 아니라타원의형상인장방형구가잘린형태또한포함함을인지하여야한다. 또한，잘린캡슐형상은일단이평면이며다른일단이곡면인원통또는타원형 통으로해석될수있음은물론이며,상술한잘린구가잘려진면에수직인 방향으로늘려진 (elongated)형태로도해석될수있음은물론이다.
[114] 물질적으로,게 1금속나노입자 (100)는표면플라즈몬이발생하는단일한
금속 (단일한합금을포함함)또는표면플라즈몬이발생하는둘이상의금속이 적층된적층형입자일수있다.상세하게，제 1금속나노입자 (100)가단일한금속 영역인경우，제 1금속나노입자는상술한잘린입자상을갖는은，금,백금, 팔라디움，니켈,알루미늄，구리，크롬또는이들의합금일수있다.또한,제 1금속 나노입자 (100)가둘이상의금속이적층된적층형입자인경우，제 1금속 나노입자 (100)는일평면과볼록한 (convex)곡면으로이루어진제 1-1금속의입자 및제 1— 1금속입자의볼록한곡면의적어도일부를덮도록적층된제 1 -2금속의 코팅층을포함할수있다.이때,제 1-1금속과제 1-2금속은각각은,금，백금, 팔라디움，니켈，알루미늄，구리，크름또는이들의합금일수있다.보다 구체적으로,제 1금속나노입자 (100)가적층형입자상인경우，일정한곡률의 곡면 (제 1곡면)을갖는잘린구형상의제 1-1금속입자에，제 1-1금속입자와동일 내지상이한곡률의곡면 (제 2곡면)을갖는계 1-2금속코팅층이계 1곡면상부에 제 1곡면과접하여적층된구조를가질수있다.이러한경우，제 1금속
나노입자 (100)는계 1-1금속입자의잘린면으로부터기인한하부면，하부면과 접하며게 1-1금속입자의곡면으로부터기인한하부표면및제 1표면과접하며 제 1 -2금속코팅층의제 2곡면으로부터기인한상부표면을갖는잘린입자상일 수있다 (도 8의제 1금속나노입자참고).이때，제 1-2금속코팅층만을독립적으로 살피면,계 1-2금속코팅층은볼록한제 2곡면인표면과함께，계 1곡면이전사된 오목한표면을가질수있으며，제 1-2금속코팅층은중심에서가장자리로갈수록 그두께가점차적으로얇아질수있다.또한，제 1-2금속코팅층의두께증가하는 경우,적층형입자가잘린입자상보다는，잘린캡슐형상 (truncated capsule shape)에상웅할수있음은물론이다.
[115] 도 3은잘린구형상을갖는제 1금속나노입자의일예들을도시한일
사시도이다.제 1금속나노입자 (100)는도 3(a)에도시한예와같이구의 증심 (P)을기준으로구의하부가잘린형상,도 3(b)에도시한예와같이구의 중심 (P)을기준으로구의상부가잘린형상，도 3(c)에도시한일예와같이,구의 중심 (P)이잘린형상을가질수있다.
[1 16] 이때，잘린구형상의용어에있어,구 (sphere)가진구로한정되어해석되어서는 안된다.구 (sphere)는투영형상기준，원형내지타원형의투영형상을갖는 입체를의미할수있다.이는공정상의한계또는구현되는구체적공정 방법등에의해입자의형상이수학적으로엄밀한의미의진구형태로구현되기 어려운한계를고려한것이며，이는나노입자를포함하는나노구조체관련 분야에종사하는당업자에게는숙지된사실이다.본발명에따른세부구성을 상술함에있어，투영형상의투영방향은제 1금속나노입자에서
지지부재쪽으로의방향，달리말하면제 1금속나노입자의하부면 (BS)에 수직이며상부에서하부로의조감방향，구체적으로말하면,소자에서계 1금속 나노입자를상부로하여，소자를위에서내려다보는방향으로의투영형상을 의미할수있다.또한,투영형상은평행광기준의투영형상일수있음은 물론이다.
[117] 도 4는제 2금속막 (300)에서관통형기공 (PP)영역을세부도시한일
사시도이다.도 4에서관통형기공 (PP)의형상은제 1금속나노입자 (100)에의해 규정될수있다.이러한제 1금속나노입자 (100)과관통형기공 (PP)간의형상적 관계에대해보다명료한이해를위해，도 4에，제 1금속나노입자 (100)와제 1금속 나노입자 (100)의투영형상 (1000)을함께도시하였다.
[1.18] 도 4에도시한일예와같이 ,관통형기공 (PP)의형상은제 1금속
나노입자 (100)의투영 (projection)형상 (100)과대웅될수있다.상술한바와같이， 투영형상은평행광기준제 1금속나노입자에서지지부재쪽으로의방향,달리 말하면제 1금속나노입자의하부면 (BS)에수직이며상부에서하부로의조감 방향,구체적으로말하면,소자에서계 1금속나노입자를상부로하여소자를 위에서내려다보는방향으로투영된형상을의미할수있다.이에따라,제 1금속 나노입자 (100)를투영방향에수직인단면들의결합으로볼때，투영형상은상기 단면들의단면중심에서투영방향에수직인모든방향 (면방향)으로의 반지름들을중，각면방향에서가장긴반지름들이결합하여형성되는형상일수 있다.
[119] 일예로，도 3의일예와같이，제 1금속나노입자 (100)가잘린구형인경우,투영 형상 (1000)은잘린구형의잘린면의위치에따라달라질수있다.상세하게，잘린 구형의잘린면이도 3(b)또는도 3(c)와같이구의중심내지구의상부에 위치하는경우，투영형상 (1000)은하부면 (BS)과동일할수있다.잘린구형의 잘린면이도 3(a)와같이구의하부에위치하는경우,투영형상 (100)은구의 중심의단면,즉,도 3(c)에해당하는계 1금속나노입자의하부면 (BS)과동일할 수있다.
[120] 계 2금속막 (300)의관통형기공 (PP)은상술한제 1금속나노입자 (100)의투영 형상 (ωοο)과대웅하는형상을가질수있다.본발명에따른세부구성을 상술함에있어,일형상과다른형상이대웅하는형상을가진다함은，일형상과 다른형상이서로동일하거나확대또는축소된형상을가짐을의미할수있다. 구체적으로，제 2금속막 (300)의관통형기공 (PP)은겨 11금속나노입자 (100)의 투영형상 (1000)과실질적으로동일한형상일수있다.
[121] 이를제조방법적으로상술하면,지지부재 (200)에의해지지되는공중부유형 제 1금속의나노입자를형성한후，이를증착마스크로하여,계 2금속을
증착함으로써，계 2금속막 (300)이형성됨에기인하는것이다.이때，제 2금속의 증착시제】금속의나노입자가마스크로사용됨에따라，마스크로사용되는 저 1 1금속의나노입자상에도제 2금속이증착될수있다.최종적으로기판에 구비되는제 1금속나노입자 (100)는,마스크로사용되는계 1금속의나노입자가 증착방향으로조금커지거나늘어난 (elongated)형상일뿐임에따라，라만산란용 기판의세부구성을제조방법적측면에서상술하는경우，이해의명료함을위해， 마스크로사용되는제 1금속의나노입자와제 1금속나노입자를특별히구별하여 지칭하지않고제 1금속나노입자로통칭한다.
[122] 상술한바와같이 ,공중부유형제 1금속나노입자를증착마스크로제 2금속 막이형성됨에따라,제 2금속막 (300)에는，제 1금속나노입자 (100)의투영형상에 대웅되는형상으로관통형기공이형성될수있다.제조방법측면에서,제 1금속 나노입자 (100)를증착마스크로한관통형기공 (PP)의형성은중요한기술적 의미를갖는다.
[123] 상세하게，제 1금속나노입자 (100)를증착마스크로，금속나노입자 (100)의투영 형상에대웅되는형상의관통형기공 (PP)을갖는제 2금속막이형성되며,관통형 기공 (PP)의표면측에지 (도 4에서 edge로도시)를포함하는관통형기공의 기공면은금속나노입자 (100)의하부면 (BS)과나노갭을형성할수있다.즉, 제 1금속나노입자 (100)를증착마스크로제 2금속의막을형성함에따라，막의 형성과동시에핫스팟이저절로규정될수있다.
[124] 즉，핫스팟이제 1금속나노입자와제 2금속막사이에자기정렬 (self-align) 형태로형성될수있는것이다.
[125] 자기정렬형태의핫스팟생성에의해，기판상그형상및위치가모두
엄밀하게조절된핫스팟이형성될수있고,나아가，엄밀하게조절된핫스팟 만이존재할수있으며，극미세한나노갭이형성될수있다.이러한자기정렬 형태의핫스팟생성에의해，표면증강라만산란기판의측정신뢰성및 재현성을현저하게높일수있을뿐만아니라，표면증강라만산란기판의생산시 생산성을현저하게향상시킬수있으며，품질관리 (quality control)또한극히 용이하게이루어질수있다.
[126] 도 5는제 1금속나노입자의하부면 (BS),지지부재의단면 (210)，제 2금속
막 (300)의관통형기공의외주면 (310)을도시한일예이다.
[127] 도 5에도시한일예와같이，지지부재의단면 (210)은하부면 (BS)의형상과
대웅되는형상을가질수있다.상세하게，지지부재의단면 (210)은단면의위치와 무관하게하부면 (BS)의형상과대응되는형상을가질수있다.이때，지지부재의 단면 (210)은지지부재의길이방향에수직한방향으로의단면을의미할수있다. 상세하게，지지부재의단면 (210)은상술한투영방향에수직한단면을의미할수 있으며，보다상세하게，지지부재의단면 (210)은지지부재의수평단면을의미할 수있다.
[128] 상세하게,지지부재의단면 (210)은하부면 (BS)의형상과실질적으로동일한 형상을갖되,그크기가축소된형상을가질수있다.축소율은하부면 (BS)의 면적을동일면적의원으로환산시의원의반지름을 R。로하고，지지부재에서 계 1금속나노입자와접하거나인접한영역의단면의면적을동일한면적의 원으로환산시원의반지름을 ^으로할때, K/R^IOOC^로규정될수있다. 이때,축소율 ( /110*100)은하부면과접하는지지부재의면적 (πΐ )/하부면의 면적 (πΙ 0 2)*100(%)이 10내지 80%,좋게는 30내지 80%,보다좋게는 40내지 80%이되도록하는비율일수있다.
[129] 지지부재의단면 (210)은하부면 (BS)의형상과실질적으로동일한형상을갖되， 그크기가축소된형상을갖는구조를제조방법적으로상술하면,이러한구조는 지지부재형성을위한물질을막 (후술하는화합물막에상응할수있음)형태로 기재상부에형성한후,막 (화합물막)상저 1 1금속나노입자를형성하고,형성된 제 1금속나노입자를에칭마스크로하여，막 (화합물막)을등방에칭함에 기인한다.제 1금속나노입자를에칭마스크로한등방에칭에의해，상술한빈 공간 (Ε)을가지며지지부재에의해지지되는공중부유형제 1금속나노입자가 제조될수있다.이때,습식에칭을포함하는등방에칭은방향성이없어，모든 방향으로균일하게에칭이이루어진다.이에따라，지지부재와동일한물질의 막이에칭될때막의두께방향으로에칭됨과동시에 ,제 1금속나노입자 (에칭 마스크)하부로도전방위적으로동일하게에칭이이루어질수있다.이에의해， 제 1금속나노입자는지지부재에의해지지되며공중부유의구조를가질수 있게되며，지지부재의단면은하부면 (BS)의형상과대웅되는단면형상을가질 수있다.
[130] 상술한바와같이,관통형기공 (PP)의형상은제 1금속나노입자 (100)의
투영 (projection)형상과대응될수있으며,이와동시에상술한바와같이, 지지부재 (200)의단면 (210)은하부면 (BS)의형상과대웅되는형상을가질수 있다.
[131] 구체적일예로，제 1금속나노입자가잘린구형상인경우，관통형기공 (PP), 지지부재의단면,하부면은모두원형일수있다.관통형기공은제 1금속 나노입자의하부면또는게 1금속나노입자의잘린구의구중심을가로지르는 단면과대웅되는형태를가질수있다.또한，지지부재의단면은하부면이 축소된크기및하부면의형태를가질수있다.
[132] 또한，도 5에도시한일예와같이，제 1금속나노입자，관통형기공및
지지부재는서로동심구조를이를수있다.이는지지부재의단면형상및 관통형기공의형상관련하여，제조방법적측면에서상술한내용을참고하면 자명하게이해될수있다.
[133] 상세하게，제 1금속나노입자가증착마스크로작용하여관통형기공이
형성되고,제 1금속나노입자가에칭마스크로작용하여등방에칭에의해 제 1금속나노입자를공중부유형태로지지하는지지부재가형성됨에따라, 제 1금속나노입자-관통형기공-지지부재는서로동심구조를이루게된다.
[134] 도 5를참고하면,제 1금속나노입자의하부면 (BS)의중심，지지부재의임의의 위치에서의지지부재단면 (210)의중심,제 2금속막 (300)의관통형기공의 외주면 (310)의중심이단일한축 (도 5에점선으로도시)을이루는동심구조를 가질수있다.
[135] 도 6은제 1금속나노입자 (100)를지지하는지지부재 (200)만을도시한일
사시도이다.도 6의일예와같이,지지부재 (200)는제 1금속나노입자 (100)의 하부면과대응되는형상의단면을가질수있다.
[136] 또한，지지부재 (200)는제 1금속나노입자 ( 100)와접하는측을상부측으로하고， 상부측의대향측을하부측으로하여，상부측의단면이하부측의단면보다작을 수있다.상세하게,지지부재 (200)는상부측에서하부측방향으로그단면적이 증가할수있으며，연속적으로증가할수있다.또한，지지부재 (200)의측면은 평면내지곡면일수있고，곡면은오목한 (concave)한곡면일수있다.
[137] 제조방법적측면에서상술하면,제 1금속나노입자를에칭마스크로，지지부재 물질의막을등방에칭하여지지부재가형성될수있다.이에따라,일정 시간동안에칭을수행한다하더라도지지부재상부측일수록에칭액에노출되는 시간이길어지게되고，지지부재하부측일수록에칭액에보다짧은시간동안 노출되게된다.또한,지지부재의길이가수내지수백나노미터오더 (order)로도 구현될수있음에따라，둥방식각에의한곡면형측면이뚜렷하게나타나지 않을수도있으나，등방식각성에의해지지부재는오목한곡면의측면을가질 수있다.
[138] 상술한제 1금속나노입자의하부면,지지부재의형상및그단면형상，관통형 기공의형상에기반하여，제 1금속나노입자하부에형성되는빈공간 (E,분석 공간)은하부로갈수록그폭이좁아지는테이퍼된속빈통형상을가질수있다. 이때,빈공간을규정함에있어속빈의표현은실질적으로비어있지않은 공간 (지지부재의공간)을의미함은물론이다.
[139] 제 1금속나노입자가잘린구형상인경우,빈공간 (E,분석공간)은하부로
갈수록그폭이좁아지는테이퍼된속빈원통형상을가질수있다.상술한바와 같이,이러한빈공간에는검출대상물이위치할수있다. SERS강도는기판 자체의 SERS활성못지않게，검출대상물과핫스팟간의위치또한크게영향을 미친다.제 1금속나노입자의하부면에지 (edge)를포함하는계 1금속나노입자의 표면과제 2금속막의관통형기공의에지 (edge)및관통형기공의기공면을 포함한제 2금속막의표면사이에핫스팟이형성되는데，구체예로，제 1금속 나노입자가잘린구형상인경우，원형폐루프형태의핫스팟이형성될수있다, 이러한폐루프형태의핫스팟을형성하는제 1금속나노입자와제 2금속막에 의해구획되는미세한빈공간 (E)에검출대상물이위치함으로써표면증강 라만산란강도를현저하게증진시킬수있으며，빈공간이핫스팟을포함하고， 빈공간의단면형상과핫스팟의형상이일치함에따라,검출민감도및검출 신뢰성 (재현성)을향상시킬수있다.
[140] 도 7은단차를갖는지지부재 (200)，상세하게，상부지지영역 (210)과
하부지지영역 (220)을포함하며상부지지영역 (210)과하부지지영역 (220)간 단차를갖는지지부재 (200)를세부도시한일사시도이다.도 7의일예에서， 상부지지영역 (210)은도 1내지도 6을기반으로상술한지지부재에상웅할수 있으며 ,하부지지영역 (220)은상부지지영역보다큰직경을가지며
상부지지영역과단차를이루는원기등을포함한기둥형상일수있다.도 7과 같이 ,상부지지영역 (210)과하부지지영역 (220)의형상은모두제 1금속 나노입자 (100)에의해규정될수있다.이러한제 I금속나노입자 ( 100)와 지지부재 (200)간의형상적관계에대해보다명료한이해를위해,도 7에， 제 1금속나노입자 (100)，제 1금속나노입자의하부면 (BS)과게 1금속
나노입자 (100)의투영형상 (1000)을함께도시하였다.
[141] 도 7에도시한일예와같이，상부지지영역 (210)의단면 (길이방향의단면) 형상은제 I금속나노입자 (100)의하부면 (BS)과대웅되는형상,상세하게는 하부면 (BS)이축소된형상일수있다.이때，앞서상술한바와같이축소율은 R, R0*100e¾)로규정될수있다.상술한축소율은상부지지영역 (210)의길이와 깊은연관을가질수있다.상세하게， Re를 ^과 R。간의차로규정 (즉, R, = Ro-Re )하는경우， ¾는상부지지영역 (210)의길이와직접적인연관을가질수있다. 구체적인예로， Re는상부지지영역 (210)의길이와실질적으로동일할수있다.
[142] 이를제조방법적으로상술하면，상부지지영역을포함한지지부재형성을위한 물질을막 (화합물막에상웅할수있음)형태로기재상부에형성한후， 막 (화합물막)상제 1금속나노입자를형성하고，형성된제 1금속나노입자를 에칭마스크로하여，막 (화합물막)을등방에칭하여상부지지영역 (210)이 제조될수있다.이러한등방에칭은방향성없는에칭임에따라,마스크인 제 1금속나노입자하부로 의길이만큼에칭이이루어질때막의깊이 방향으로도 Re만큼에칭될수있다.이에의해，상부지지영역 (210)의
길이 (높이 )는 Re와실질적으로동일할수있으며 , 실질적으로동일할수 있다.이때，실질적동일이라함은，에천트，에칭부산물등의유동성등 동력학적 (kinetic)조건에의해에칭마스크하부와막의깊이방향으로의에칭 속도가에칭시간에따라미약하게나마어느정도달라질수있음을고려한 것이다.이에따라，수평방향으로의에칭 (제 1금속나노입자하부로의에칭 ) 길이와수직방향으로의에칭길이가서로동일함은에칭시의동력학적변수에 의한차이를고려한길이임을인지하여야한다.습식에칭을이용하여막을 패턴화하거나소자를제조하는반도체분야에종사하는종사자는이러한 실질적인동일함에대해명료하게인식할수있을것이다.
[143] 반면,상부지지영역 (210)과단차를이루는하부지지영역 (220)의단면 (길이 방향의단면)형상은제 1금속나노입자 (100)의투영 (projection)형상 (100)과 대웅될수있다.구체적으로,하부지지영역 (220)의단면형상은제 1금속 나노입자 (100)의투영형상 (1000)과실질적으로동일한형상일수있다.앞서 상술한바와같이 ,제 2금속막 (300)의관통형기공또한，제 1금속
나노입자 (100)의투영형상과실질적으로동일한형상을가질수있음에따라, 하부지지영역 (220)의측면과제 2금속막 (300)의관통형기공의기공면은서로 인접할수있다.
[144] 이를제조방법적으로상술하면，건식에칭과같은방향성에칭이수행됨에 따라，제 1금속나노입자하부에위치하는막 (화합물막)은에칭이이루어지지 않게되며,제 1금속나노입자 (100)의투영형상과대웅되는,실질적으로는 제 1금속나노입자의투영형상과동일한단면형상을갖는하부지지영역 (220)이 제조될수있다.이때，하부지지영역 (220)의길이 (즉,방향성있는에칭으로 식각되는깊이)는적절히조절될수있으며，실질적인일예로 10nm내지 5μπι일 수있으나,본발명이이에한정되는것은아니다.도 7을기반으로상술한 지지부재가구비되는경우，빈공간의하부는하부지지영역 (220)과
상부지지영역 (210)간단차면에의해규정될수있다.이는검출대상물이 위치하는빈공간의폭과빈공간의깊이가서로독립적으로제어될수있음을 의미하는것이다.
[145] 도 8은본발명의일실시예에따른표면증강라만산란기판의단면을도시한 일예이다.도 8에도시한예와같이 ,기판은제 2금속막 (300)및공중부유형 제 1금속나노입자 (100)하부에위치하는하부막 (400)을더포함할수있다.달리 상술하면，표면증강라만산란기판은기재 (500)，기재상부에위치하는 하부막 (400)，하부막 (400)상부에위치하며관통형기공이형성된제 2금속 막 (300)，제 2금속막 (300)의관통형기공에위치하고，지지부재 (200)에의해 지지되며,계 2금속막 (300)과나노갭을형성하는공중부유형게 1금속 나노입자 (100)를포함할수있다.
[146] 도 8의일예에서，하부막 (400)은금속막 (제 3금속막)또는지지부재 (200)와 동일한물질의막일수있다.
[147] 구체적으로，하부막 (400)이지지부재 (200)와동일한물질의막인경우，
지지부재 (200)는하부막 (400)으로부터연장된것일수있다.지지부재 (200)가 하부막 (400)으로부터연장되었다함은，지지부재 (200)와하부막 (400)이 물적으로일체인것을의미하여，지지부재 (200)가하부막 (400)의돌출부로해석 가능함을의미한다.제조방법적측면에서이를상술하면，지지부재및 지지부재와일체인하부막은，제 1금속나노입자를에칭마스크로하여,제 1금속 나노입자가형성된지지부재의물질의막 (화합물막)을일정깊이까지 에칭 (습식에칭또는습식에칭과건식에칭의순차적에칭)함에따라,동시에 제조될수있다.이에의해，지지부재물질의막 (화합물막)에서에칭후잔류하는 막은하부막으로， .에칭에의해형성되는제 1금속나노입자하부의기등은 지지부재로규정될수있다.하부막 (400)이지지부재 (200)와동일한물질의막인 경우,하부막은후술하는금속화합물및반도체화합물에서하나또는둘이상 선택되는물질일수있다.이때,하부막의두께는특별히한정되지않으나 10nm 내지 300nm일수있다.
[148] 그러나，본발명이지지부재 (200)와하부막 (400)이동일한물질로이루어진 것으로한정되는것은아니다.일예로,하부막과지지부재의물질의막이 적층된적층막을제조한후，적층막상제 1금속나노입자를형상하고이를 마스크로하여지지부재의물질의막을선택적으로에칭제거함으로써, 지지부재와상이한이종물질의하부막상지지부재를형성할수있다.이에 따라,지지부재및하부막은서로상이한물질일수있다.
[149] 구체적으로，지지부재는금속화합물및반도체화합물에서하나또는둘이상 선택되며，이와독립적으로,하부막은금속,금속화합물및반도체화합물에서 하나또는둘이상선택될수있다.유리하게 ,지지부재와상이한물질의 하부막의일예로，하부막은금속막일수있다.하부막이금속막인경우，기판상 광의퍼짐을제어할수있어보다유리하다.상세하게，라만산란기판에서핫 스팟에의해표면증강된라만산란광은상부및하부양방향으로 (전방향으로) 퍼져나가게된다.그러나,하부막이금속막인경우，기판의하부방향으로라만 산란광이진행하는것을방지하며，핫스팟에서증강된라만산란광의 대부분이라만산란기판의상부방향으로퍼져나가도록하여광의소실을 최소화할수있다.하부막이금속막인경우，하부막인금속막의금속은 알칼리금속，전이금속，전이후금속，준금속또는이들의합금 (alloy)일수있다. 하부막인금속막의두께는특별히한정되지않으나 10nm내지 300nm일수 있으며，기판하부로의광퍼짐을효과적으로방지하는측면에서 50nm내지 300nm인것이유리하다.
[150] 도 8의일예와같이，기판이하부막을더포함하는경우,상술한빈공간 (E, 분석공간)에서빈공간 (E)의하측은기재 (500)가아닌，하부막 (400)에의해 구획될수있다.즉，지지부재가도 6의일예와같이단차가존재하지않는 지지부재인경우,빈공간 (E)의하측은기재 (500)또는하부막 (400)에의해 구획될수있으며，지지부재가도 7의일예와같이단차가 ¾재하는지지부재인 경우，빈공간은하부막 (400)의존재여부와무관하게하부지지영역 (220)의상측 면 (단차면)에의해구획될수있다.
[151] 이러한빈공간의하측을구획하는기재 (500)영역또는하부막 (400)영역과, 지지부재 (200)중선택되는하나이상의구성요소에검출대상물질과
특이적으로결합하는수용체가형성될수있다.
[152] 즉，기판은검출대상물질과특이적으로결합하는수용체를더포함할수
있으며，수용체는，적어도，공중부유형제 1금속나노입자하부에위치하는 기재의표면，하부막의표면,하부지지영역의상측면및 /또는지지부재의측부 표면에형성될수있다.이때，제 1금속나노입자하부에위치하는하부막의 표면이나기재의표면은제 2금속막에의해덮이지않는，즉，게 2금속막의 관통형기공영역에의해표면으로노출되는하부막의영역또는기재의영역을 의미할수있다.
[153] 상세하게，수용체는기재의표면;기재의표면과지지부재의측부표면;
하부막의표면;하부막의표면과지지부재의측부표면;하부지지영역의상측 면;또는하부지지영역의상측면과상부지지영역의측부표면;에형성될수 있다.이러한수용체에의해검출대상물질이상술한빈공간 (E,분석공간)에 안정적으로고정될수있다.
[154] 본발명의일실시예에따른표면증강라만산란기판에있어，하부막및지지 부재는서로독립적으로，광학적으로투명또는불투명할수있으며，전기적으로 전도성또는절연성일수있다.상세하게,지지부재는금속화합물및반도체 화합물에서하나또는둘이상선택되며，이와독립적으로，상기하부막은금속, 금속화합물및반도체화합물에서하나또는둘이상선택될수있다.보다 구체적으로,지지부재는금속화합물및반도체화합물에서하나또는둘이상 선택되는물질일수있으며，하부막은지지부재와동종의물질이거나，금속일수 있다.
[155] 하부막이금속막인경우，금속막의금속은알칼리금속，전이금속，전이후금속， 준금속또는이들의합금 (alloy)일수있다.구체적으로,금속막의금속은리튬， 소듬,칼륨，루비듭,베릴륨，마그네슘，칼슴，스트론튬,바륨，스칸듐，이트륨， 란타넘,타이타늄，지르코늄,하프늄，바나듐，나이오븀，탄탈럼,크로뮴， 몰리브데넘,텅스텐，망간，철，루테늄，오스뮴，코발트，로듬，이리듬，니켈， 팔라듐,백금,구리,은，금,아연,알루미늄,갈륨,인듐,주석，납,비스무트，규소， 저마늄，안티모니，텔루륨또는이들의합금일수있다.하부막또는지지부재의 금속화합물은금속산화물 (oxide),금속산질화물 (oxynitride),금속
질화물 (nitride),금속불화물을포함하는금속할로겐화물 (halide),금속
탄화물 (carbide)또는이들의혼합물을포함할수있고，반도체화합물은반도체 산화물，반도체산질화물，반도체질화물,반도체탄화물，반도체물질에서하나 또는둘이상선택될수있다.이때,금속화합물의금속은전이금속및전이후 금속을포함할수있고，반도체화합물또는반도체물질의반도체는실리콘 (Si), 게르마늄 (Ge)또는실리콘게르마늄 (SiGe)등의 4족반도체를포함할수있다. 보다상세하게，금속화합물및반도체화합물은 Zr02, ZnO, YF3) YbF3, Y203, Ti02 ， ThF4, TbF3, Ta205, Ge02, Te02, SiC,다이아몬드 (diamond), SiOxNy(0<x<2인실수， 0<y<1.5인실수)， Si02, SiO, SiNx(l≤x≤1.5인실수)， Sc203, NdF3, Na3AlF6, MgF2, LaF3, Hf02, GdF3, DyF3, CeF3, CaF2, BaF2, A1F3, A1203, ITO(Indium-Tin Oxide), AZO(Al doped Zinc Oxide), GZO(Ga doped Znic Oxide), IZO(Indium-Zinc Oxide) 또는이들의흔합물을포함할수있다. [156] 본발명에따른일실시예에있어，제 1.금속나노입자는투영 (projection)형상 기준,투영형상의평균지름 (투영형상과동일한면적의원으로환산시환산된 원의평균지름)은 10nm내지 500nm,좋게는 50nm내지 250nm일수있다. 저 11금속나노입자가잘린구형상인경우,이러한크기는,평균지름이 10nm 내지 500nm,바람직하게는 50nm내지 250nm인구의일측이잘린것으로해석될 수있음은물론이다.그러나，본발명이계 1금속나노입자의크기에의해 한정되는것은아니며，제 1금속나노입자의크기는플라즈모닉신호강화에 유리한크기이면족하다.
[157] 본발명에따른일실시예에있어,지지부재의길이는공중부유형제 1금속 나노입자를안정적으로지지하면서가능한핫스팟에인접하도록빈공간 (E)의 하부면이규정될수있는길이를고려하여조절될수있으나,특별히한정되는 것은아니다.이는，상술한바와같이 ,지지부재가상부지지영역과
하부지지영역을포함하는경우，빈공간의하부면과지지부재의길이 (높이)가 서로독립적으로제어될수있기때문이다.실질적인일예로,지지부재의 길이는 5nm내지 Ιμηι,보다실질적으로는 10nm내지 500nm일수있으나，이에 한정되는것은아니다.
[158] 나노갭은단차가없는지지부재의경우지지부재자체의길이나,단차가
존재하는지지부재의경우상부지지영역의길이또는제 2금속막의두께를 조절하여그크기가조절될수있다.본발명의사상에따라단지지지부재의 길이나제 2금속막의두께를조절함으로써，나노갭의크기가제어됨에따라, 극미세한나노갭또한엄밀하게형성될수있으며，설계된크기로부터거의 오차를갖지않는나노갭이형성될수있다.효과적인플라즈모닉강화 측면에서나노 ¾은나노미터오더 (10° nm order)의크기를갖는극미세한나노 갭일수있으며，구체적으로 1 nm내지 95nm,보다구체적으로는 1내지 50nm, 보다더구체적으로는 5내지 20nm의극미세한나노갭일수있으나,본발명이 나노갭의크기에의해한정되는것은아니다.이때,나노갭의크기는제 1금속 나노입자의하부면에지를포함하는제 1금속나노입자의표면과계 2금속막의 관통형기공의기공면을포함하는제 2금속막의표면간의최단거리로규정될 수있다.일예로，제 1금속나노입자가도 3(a)와같이구의하부가잘린형상이나 잘린캡슐형인경우，제 1금속나노입자의하부면에지에서최대단면적을갖는 면 (일예로,구의중심면)까지의표면을제 1금속나노입자의하부표면영역으로 하여,계 1금속나노입자의하부표면영역과제 2금속막의관통형기공의 기공면간의최단거리로규정될수있다. ,
[159] 제 2금속막의두께는제 1금속나노입자의형상,상술한지지부재의길이및기 설계된나노갭의크기를고려하여조절될수있다.이때，도 8에도시한일예와 같이，계 2금속막의관통형기공의기공면은기울어진면일수있으며， 제 2금속막의두께가지지부재의길이보다클수있는데，이는제 2금속막제조시 제 1금속나노입자의투영형상이마스크의역할을수행하는데따른것이다. [160] 상세하게，도 8에도시한일예와같이제 2금속막을제조하기위한제 2금속의 증착시,마스크의역할을수행하는제 1금속나노입자에도제 2금속이일부 증착될수있다.이는계 2금속의증착이진행됨에따라마스크로작용하는 제 1금속나노입자의투영형상이점차적으로커지는효과를야기할수있다. 이에따라후술하는제조방법에서와같이，제 2금속증착이시작되는시점에서 마스크로작용하는금속나노입자를제 1금속나노섬 (110)으로하고,제 2금속의 증착에의해제 1금속나노섬 (110)상부에증착된부분을코팅층 (120)이라할때， 게 1금속나노입자 (100)는제 1금속나노섬 (110)과코팅층 (120)이적층된잘린 입자상일수있다.상세하게，제 1금속과제 2금속이서로동일한경우,증착이 진행되며,제 1금속나노입자는하부면 (BS),하부면과접하며마스크로사용되는 게 1금촉나노섬 (110)의곡면으로부터기인한하부표면 (110s)및하부 표면 (110s)과접하며제 1금속이증착됨에따라형성되는코팅층 (120)의상부 표면 (하부표면과동일내지상이한곡률을가질수있음， 120s)을갖는잘린 입자상 (100)으로변화될수있다.또한,제 1금속과제 2금속이서로상이한경우， 증착이진행되며계 1금속나노입자는하부면 (BS),하부면과접하며마스크로 사용되는제 1금속나노섬 (Π0)의곡면으로부터기인한하부표면 (1 10s)및하부 표면 (110s)과접하며게 2금속의코팅층 (110)의곡면으로부터기인한상부 표면 (120s)을갖는잘린입자상 (100)일수있다.
[161 ] 이와같이,게 2금속의증착이진행됨에따라마스크로작용하는제 1금속
나노입자의투영형상이점차적으로커지는효과를야기함에따라,제 2금속 막 (300)에서관통형기공의기공면 (301)이기을어진 (tapered)면으로형성될수 있으며，상세하게,표면에가까울수록기공이커지는형태로기울어진 (tapered) 면으로형성될수있다.보다구체적으로,관통형기공의하부는제 2금속증착 시점의제 1금속나노입자 (후술하는게 1금속나노섬)의투영형상에대웅하는 크기를가질수있으며，관통형기공의상부는게 2금속의증착이완료되는 시점의계 2금속나노입자의투영형상에대웅하는크기를가질수있다.
게 2금속의증착에의해마스크로작용하는나노입자의투영형상이점차적으로 커짐에따라기을어진면으로기공면이형성될수있는것이다.기공면과 기판 (또는하부막)간의각도인테이퍼각 (α)은 30내지 89°,구체적으로 50내지 85°일수있다.
[162] 본발명의일실시예에따른라만산란용기판에있어 ,제 2금속막의두께는 저 12금속막이제 1금속나노입자에물리적으로접촉되지않는두께미만으로 조절되면무방하다.상세하게,제 2금속막의두께 (t)는 to(to는제 2금속막과 제 1금속나노입자가서로접촉하는두께)미만일수있으며， to미만의조건하， 설계된나노갭의크기를고려하여그두께가제어될수있다.실질적이며비 한정적인일예로，제 2금속막의두께는지지부재의길이 (L)를기준으로 0.5L 내지 5L,보다구체적으로 0.5L내지 1.5L일수있으나，이에한정되는것은 아니다. [163] 좋게는，계 2금속막의두께는지지부재의길이와동일하거나지지부재의 길이보다더클수있다.즉,제 2금속막의두께는지지부재의길이 (L)을 기준으로 1내지 5L,구체적으로 1.1L내지 1.51^1수있다.이는평면인제 1금속 나노입자의하부면이，제 2금속막의막표면과동일하거나보다더낮은위치에 존재함을의미하는것이며,제 1금속나노입자가제 2금속막의관통형기공 내부에일부장입되어있음을의미하는것이다.이러한경우，관통형기공 내부에장입된제 1금속나노입자의표면과관통형기공의기공면간핫스팟이 형성되되，일정한폭을갖는띠형태의폐루프로핫스팟이형성될수있어보다 유리하다.이러한띠형태의핫스팟은선 (line)형태보다더욱강하게신호를 증폭시킬수있을뿐만아니라，제조공정의한계상어쩔수없이발생하는공정 오차들에의해미치는영향이완화되어，기판의안정성을보다더향상시킬수 있다.
[164] 본발명의일실시예에따른표면증강라만산란기판에있어，기판의단위
면적당제 1금속나노입자의수인나노구조체밀도는 1내지 400개 /μηι2, 구체적으로는 10내지 100개 /μπι2,보다더구체적으로는구체적으로는 15내지 100개 /μηι2일수있다.제 1금속나노입자와제 2금속의막에의해잘규정된폐 곡선형핫스팟이형성됨에따라，이러한나노구조체의밀도는곧기판의단위 면적당핫스팟의수인핫스팟밀도로간주될수있다.이러한고밀도의 나노구조체 (핫스팟밀도)에의해검출의민감성을현저하게향상시킬수있다.
[165] 본발명의일실시예에따른표면증강라만산란기판에있어，기판은라만산란 활성영역과라만산란비활성영역을포함할수있으며，둘이상의라만산란 활성영역이서로이격배열된것일수있다.
[166] 상세하게，라만산란활성영역은공중부유형제 1금속나노입자가형성되고 제 2금속막과핫스팟을형성하는영역일수있으며，라만산란비활성영역은 공중부유형계 1금속나노입자가미형성된영역일수있다.이때，라만산란비 활성영역에는제 2금속막이형성또는미형성될수있다.
[167] 즉,표면증강라만산란기판은서로이격배열된둘이상의라만산란활성
영역에의해,서로상이한검출대상물들이단일한기판을통해동시에검출및 분석될수있는，멀티플렉싱 (multiplexing)기판일수있다.이때，라만산란활성 영역별로,적어도빈공간 (E,분석공간)내부에서로상이한수용체가형성될수 있음은물론아다.
[168] 검출대상물은특별히한정되지않으나,생화학물질을대표적으로들수
있으며，생화학물질은세포구성물질；유전물질;탄소화합물;생물체의대사에 영향을미치는물질;생물체의물질합성에영향을미치는물질;생물체의물질 수송또는신호전달과정에영향을미치는물질;등을포함할수있다.상세하게, 생화학물질은고분자유기물，유기금속화합물，펩타이드,탄수화물，단백질， 단백질복합체，지질,대사체,항원,항체，효소，기질,아미노산，압타머，당,핵산， 핵산단편, PNA(Peptide Nucleic Acid),세포추출물,또는이들의조합등을들수 있다.
[169] 수용체와검출대상물간의특이적결합은이온결합,공유결합,수소결합，배위 결합또는비공유결합을포함하며,비한정적이며구체적일예로，수용체는 효소-기질，항원-항체，단백질-단백질또는 DNA간의상보적결합등을통해 검출대상물과특이적결합가능한물질일수있다.
[170] 수용체는생화학물질을포함하는검출대상물을검출하는종래의
센서분야에서，검출대상물과특이적으로결합하여검출대상물을센서의일 영역에고정시키는데사용되는것으로알려진어떠한물질이든사용가능하다.
[171] 구체적이며비한정적인일예로,수용체는적어도,빈공간 (E)을형성하는
하부막표면및 /또는지지부재측면에자기조립 (Self-Assembly)된
자기조립단분자막 (SAM; Self-Assembled Monolayer)을포함할수있다.
[172] 자기조립단분자막은사슬기，사슬기의일말단작용기인제 1반응기，사슬기의 다른일말단작용기인제 2반웅기를포함할수있다.제 1반응기는기재와 자발적으로결합하는반웅기일수있으며,제 2반웅기는분석대상물질과 특이적으로결합하는반웅기일수있다.자기조립은기재의물질및
자기조립단분자의제 1반웅기를적절히설계하여이루어질수있으며， 통상적으로알려진자기조립 (자기결합)되는기재물질별반웅기의셋 (set)을 이용할수있다.구체적인예로,제 1반응기는티올기 (-SH),카르복실기 (-COOH) 또는아민기 (-NH2)일수있다.티올기및 /또는아민기와자발적으로결합하는 대표적인기재물질로,금속산화물인 Au산화물， Ag산화물， Pd산화물， Pt산화물, Cu산화물, Zn산화물, Fe산화물또는 In산화물등을들수있으며， Si, Si02(비정질 유리를포함함)또는인듐틴산화물 (ΠΌ)등을들수있다.카르복실기와 자발적으로결합하는대표적인기재물질로， Si02, Ti02, Sn02, Zn산화물등을들 수있다.자기조립단분자의사슬기는알칸사슬기,구체적으로 C3-C20의알칸 사슬기를들수있으며,자기조립단분자의사슬기길이를조절함으로써， 제 2작용기에결합하는검출대상물을핫스팟내부에까지위치시킬수있다.즉, 빈공간에형성되는수용체의길이를조절함으로써,핫스팟기준，수용체와 결합하는검출대상물의위치가조절될수있다.
[173] 제 2반웅기는상술한제 1반웅기와유사하게티올기，카르복시기또는
아민기등의작용기일수있으나，이에한정되는것은아니다.계 2반웅기는 티올기，카르복시기또는아민기등의작용기를통해사슬기말단에결합된효소， 기질,항원，항체，단백질, DNA등을포함할수있으며，이는생화학물질을 검출하는분야에속하는종사자에게는주지관용의기술이다.
[174] 기재 (500)는지지체의역할을수행할수있으며，열적，화학적으로안정한
물질이면무방하다.거시적형상에서기재는웨이퍼또는필름 (film)의형상일수 있으며,편평한평면형기재뿐만아니라,리세스 (recess)구조등과같이용도를 고려하여표면에요철구조가형성된것일수있다.물질적으로,기재는 반도체나세라믹일수있다.반도체기재의비한정적인일예로，실리콘 (Si), 게르마늄 (Ge)또는실리콘게르마늄 (SiGe)을포함하는 4족반도체; 갈륨비소 (GaAs),인듐인 (InP)또는갈륨인 (GaP)을포함하는 3-5족반도체;
황화카드뮴 (CdS)또는텔루르화아연 (ZnTe)을포함하는 2-6족반도체 ;
황화납 (PbS)을포함하는 4-6족반도체；또는이들에서선택된둘이상의물질이 각층을이루며적층된적층체를들수있다.세라믹기재의비한정적인일예로， 반도체산화물，반도체질화물，반도체탄화물，금속산화물,금속탄화물， 금속질화물또는이들에서선택된둘이상의물질이각층을이루며적층된 적층체를들수있다.이때，반도체산화물，반도체질화물또는반도체탄화물의 반도체는 4족반도체, 3-5족반도체， 2-6족반도체, 4-6족반도체또는이들의 흔합물을포함할수있다.
[175] 본발명은상술한표면증강라만산란기판을포함하는분자검출용소자를 포함한다.이때,분자는상술한생화학물질을포함할수있음은물론이다.
[176ᅵ 구체예로，본발명의일실시예에따른분자검출용소자는상술한표면증강 라만산란기판및표면증강라만산란기판상공증부유형제 1금속나노입자， 제 1금속나노입자를지지하는지지부재및적어도제 2금속막의제 1금속 나노입자와나노 ¾을형성하며제 1금속나노입자의둘레를감싸는영역을 내부에수용하도록형성된미세유체채널을포함할수있다.
[177] 구체예로,본발명의일실시예에따른분자검출용소자는상술한표면증강 라만산란기판및표면증강라만산란기판상공중부유형게 1금속나노입자， 제 1금속나노입자를지지하는지지부재및적어도제 2금속막의제 1금속 나노입자와나노갭을형성하며제 1금속나노입자의둘레를감싸는영역을 내부에수용하는웰 (well)을포함할수있다.
[178] 본발명은상술한표면증강라만산란기판의제조방법을포함한다.
[179] 상세하게,본발명에따른표면증강라만산란기판의제조방법은 a)기재상 금속화합물또는반도체화합물인화합물막을형성하는단계; b)화합물막상 계 1금속막을형성한후열처리하여화합물막상이격되어위치하는제 1금속 나노섬 (nano island)을제조하는단계; c)제 1금속나노섬을에칭마스크로, 화합물막을일정깊이까지등방에칭하는단계;및 d)제 1금속나노섬을증착 마스크로，에칭된화합물막상제 2금속을증착하여제 2금속막을형성하는 단계;를포함한다.이때, c)단계의에칭에의해공중부유형제 1금속나노섬이 제조되며, d)단계에의해제 2금속이공중부유형제 1금속나노섬상부에증착된 공중부유형제 1금속나노입자및이를감싸는게 2금속막이제조될수있다.
[180] 즉，본발명에따른제조방법은증착 -열처리-등방에칭을포함하는
에칭 -증착이라는극히간단하고저렴하며,대면적제조가능한공정에의해 상술한바와같이핫스팟의크기,핫스팟의형상，핫스팟의위치등이정밀하게 제어되고,극미세한나노갭에의해라만산란신호가현저하게증강되며， 대면적에서도균일한 SERS활성을갖는고품질의표면증강라만산란기판을 제조할수있다ᅳ [181] 상세하게，종래와같이리소그라피를이용하여나노구조물간나노갭을 형성하는경우정밀한제어는가능하나고가의장비및마스크를사용함에따라, 공정구축비용과제조비가매우크며,공정의유지관리또한어렵고，나노 갭등을변경하고자하는경우다시이를구현할수있는고가의새로운마스크 세트가구비되어야하는등설계유연성또한매우떨어지는한계가있다.
[182] 또한，액상환원이나증착을이용하여금속나노입자들을형성하는경우，
저렴한공정이긴하나，랜덤한위치에다양한크기로형성되는금속나노입자에 의해나노갭이형성됨에따라,나노갭의크기를정밀하게제어할宁없는 한계가있으며,나노갭의분포또한넓어신호증강이상대적으로미약하고, 정량분석이어려우며및재현성이떨어지는등그한계가있다.
[183] 본발명에따른제조방법은이러한종래기술들의한계를극복한것으로，매우 저렴하고간단한공정을이용하면서도,나노갭의크기가엄밀하게제어될수 있으며，대면적에서도극히균일한나노갭을갖는기판을제조할수있다.
[184] 본발명에따른일실시예에있어 , a)기재상화합물막을형성하는단계는
스퍼터링등과같은물리적증착,플라즈마도움화학기상증착등과같은화학적 증착을통해수행될수있으며，이는증착을통해일정두께의막을형성하는 관련분야종사자에게는주지관용의기술이다. c)단계의등방에칭을포함하는 에칭시，화합물막이잔류하도록에칭하는경우， a)단계의기재상형성된 화합물막은 c)단계의등방에칭을포함한에칭을통해상술한라만산란용 기판의지지부재및하부막으로전환될수있다.이러한경우,화합물막의 두께는상술한지지부재의길이및하부막의두께를합한두께에상웅할수 있다.
[185] 그러나，본발명이하부막과지지부재가동일한물질인것으로한정될수
없음은물론이다 . a)단계전，기재상금속막이거나， a)단계의화합물
막 (제 1화합물막)과상이한금속화합물또는반도체화합물의막 (제 2화합물 막)인하부막을형성하는단계가더수행될수있으며， c)단계의등방에칭을 포함하는에칭에의해상기에칭마스크로보호되지않은영역에서하부막을 표면으로노출시킬수있다.이러한경우,노출된금속막또는제 2화합물막의 하부막이제조될수있다.
[186] 구체적으로,지지부재와하부막이서로상이한화합물 (금속화합물또는
반도체화합물)인경우 b)단계전,기재상，하부막의물질인제 2화합물막과 지지부재의물질인제 1화합물막이적층된적층막이형성될수있다.이러한 적층막의경우,제 2화합물막의두께는상술한하부막의두께일수있으며， 저 1 1화합물막의두께는상술한지지부재의길이에상응할수있다.
[187] 유리한일예인하부막이금속막인경우를보다상세히설명하면， a)단계의 화합물막형성전，기재상금속막을형성하는단계 ;가더수행될수있다.즉，본 발명의일실시예에따른제조방법은,기재상금속막을형성하는단계;금속막 상부로화합물막을형성하는단계를포함할수있다.금속막또한，스퍼터링등과 같은물리적증착，플라즈마도움화학기상증착등과같은화학적증착등과같은 통상의증착을통해형성될수있다. b)단계전,하부막 (금속막)과화합물막을 순차적으로형성하는경우， C)단계의등방에칭을포함하는에칭에의해， 화합물막은지지부재로전환되고에칭마스크로보호되지않은영역에서 금속막은표면으로노출될수있다.즉， C)단계의등방에칭을포함하는에칭에 의해에칭마스크하부에위치하는화합물막영역은지지부재로전환되고에칭 마스크하부이외의화합물막영역은모두제거되며금속막이표면으로노출될 수있다.이에， C)단계의등방에칭을포함하는에칭에의해제거되는깊이 (에칭 깊이)는화합물막두께에상웅할수있다. b)단계전，하부막 (금속막)과 화합물막을순차적으로형성하는경우，기재상금속막의두께는상술한 하부막의두께일수있으며，화합물막의두께는상술한지지부재의길이에 상웅할수있다.
[188] b)단계는화합물막상제 1금속막을형성한후이를열처리하여제 1금속나노 섬들을제조하는단계이다.제 1금속막또한스퍼터링등과같은물리적증착， 플라즈마도움화학기상증착등과같은화학적증착을통해수행될수있으며， 이는증착을통해일정두께의막을형성하는관련분야종사자에게는주지 관용의기술이다.
[189] 화합물막상형성되는제 1금속막의두께는 50nm이하,구체적으로는 1내지 50nm,보다구체적으로는 1내지 30nm,보다더구체적으로는 5내지 20nm일수 있다.제 금속막의두께가너무얇은경우열처리에의해형성되는제 i금속 나노섬의크기가너무작아질위험이있다.또한,제 1금속막의두께가과도하게 두꺼운경우나노섬이아닌다공막형태의막이제조되거나나노입자화가 이루어진다하더라도조대한입자가제조될위험이있다.
[190] 단일한기판에서서로상이한검출대상물들이검출되는멀티플렉싱기판의 제조또는단일한기재를이용하여다수개의표면증강라만산란기판을 제조하기위해화합물막상패턴화된제 1금속막이형성될수있다.패턴화된 제 1금속막은상술한표면증강라만산란활성영역을형성하기위한것으로，기 설계된표면증강라만산란활성영역에대응하는형상및기설계된표면증강 라만산란활성영역의배열에대웅하는패턴으로화합물막상에형성될수 있다.구체적이며비한정적인일예로,패턴화된제 1금속막은서로이격 배열되어 MxN(M은 1이상의자연수 , Ν은 2이상의자연수)매트릭스를형성하는 사각내지원형패턴을들수있다.도 9는기재상 2X3매트릭스를형성하는 사각패턴으로패턴화된제 1금속막 (600)을도시한일예이다.기재상제 1금속 막 (600)이형성되지않은부분은상술한표면증강라만산란비활성영역에 대웅할수있음은물론이다.
[191] 나노섬화를위한열처리는 RTP(Rapid Thermal Process)로수행될수있다.이는 균일한두께의박막인제 1금속막의형태를은전히유지한상태에서， 순간적으로，열에너지에의한계 1금속막을이루는제 1금속원자들의 이동 (diffusion)이발생할때,보다균일한크기의나노섬들이제조될수있기 때문이다.이때， RTP(Rapid Thermal Process)는텅스텐-할로겐램프와같이광에 의해가열되는통상의 RTP장비를이용하여수행될수있음은물론이다.
[192] 나노섬화를위한열처리온도는제 1금속의융점 (melting point)인 Tm(°C)을 기준으로， 0.3Tm내지 0.9Tm,구체적으로는 0.5Tm내지 ().8TV 수있다.상술한 은도는미세한나노섬이균일하게형성되기유리한온도이다.
[193] 열처리시간은물질이동이충분히발생하여재현성 있게제 1금속의나노 섬들이형성될수있는정도의시간이면족하다.제 1금속막의두께에따라어느 정도가변가능하나,구체적인일예로，열처리시간은 1초내지 5분일수있다. 열처리분위기는진공，공기내지불활성분위기에서수행될수있으나，본 발명이열처리시간이나열처리분위기에의해한정되는것은아니다.
[194] 본발명에따른일실시예에있어 ,상술한제 1금속막의형성및상술한나노 섬화를위한열처리를반복수행함으로써，최종적으로수득되는제 1금속나노 섬의밀도를증가시킬수있다.이러한반복수행을통해，나노섬의크기분포를 거의증가시키기않으면서도나노섬의밀도를현저하게증가시킬수있다.이는 반복수행시,전단계 (열처리단계)에의해나노섬화된제 1금속은이미그 구동력이거의소모된상태이나，화합물막상새로이형성된제 1금속막은 입자화의구동력을층분히가지고있어，반복수행되는열처리시，나노섬미 형성영역에,이미형성된나노섬과유사한크기를갖는나노섬들이새로이 형성될수있다.
[195] 다시상술하면， b)단계는 bl)제 1금속막을형성하는단계및 b2)열처리단계를 일단위공정으로,단위공정을반복수행함으로써,화합물막상제 1금속나노 섬의밀도 (단위면적당제 1금속나노섬의수)를증가시킬수있다.이러한단위 공정은 2내지 4회반복될수있으나，반복횟수는제조하고자하는게 1금속 나노섬의밀도를고려하여적절히조절될수있음은물론이다.이러한경우, 단위공정상반복형성되는제 1금속막의두께는독립적으로 30nm이하， 구체적으로는 5내지 15nm로,매우얇은계 1금속막을형성하는것이좋다.
[196] 상술한열처리또는상술한단위공정의반복을통해금속화합물막상
10개 /μιη2이상，구체적으로는 40개 /μπι2이상의극히고밀도의나노섬이형성될 수있다.
[197] 제 1금속막의열처리를통해제조되는계 1금속나노섬은평면인
하부면 (나노섬과화합물막간의계면)과볼록한 (convex)곡면의표면을 포함하는잘린입자상일수있으며,제 1금속나노섬은투영형상기준평균 지름이 10nm내지 500nm,좋게는 50nm내지 250 n일수있다.그러나,본 발명이제 1금속나노섬의크기에의해한정되는것은아니며，제 1금속나노섬의 크기는플라즈모닉신호강화에유리한크기이면족하다.
[198] 본발명에따른일실시예에있어， c)단계의에칭은등방에칭을포함할수 있다.이때，등방에칭은습식에칭일수있다.즉， c)단계는 b)단계에서수득되는 금속나노섬들을에칭마스크로하여 ,화합물막을일정깊이까지습식 에칭하는단계를포함할수있다. c)단계의에칭시，화합물막은제 1금속나노 섬의하부면 (에칭전나노섬과화합물막간의계면)의면적기준, 10내지 80%, 좋게는 30내지 80%，보다좋게는 40내지 80%의면적이지지부재와계면을이를 수있도록에칭될수있다.이때，상술한바와같이，화합물막하부에금속막을 형성하고습식에칭으로금속막을표면으로노출시키고자하는경우,습식 에칭되는일정깊이 (에칭깊이)는화합물막의두께에상웅할수있음은 물론이다.
[199] 습식에칭은방향성이없는등방에칭임에따라, c)단계의습식에칭에
의해공중부유형제 1금속나노섬이제조될수있는것이며，나노섬하부에빈 공간 (E,분석공간)이형성될수있다.
[200] 도 1내지도 6을기반으로상술한지지부재，즉,단차가없는지지부재는습식 에칭을통해제조될수있으며，도 7을기반으로상술한단차가존재하는 지지부재의경우,습식에칭을통해상부지지영역이제조될수있다.
[201] 이하, b)단계에서습식에칭을포함한등방에칭이수행되는경우와,건식 에칭을포함한방향성있는에칭과습식에칭이조합되어수행되는경우를각각 상술한다.
[202] 단차가없는지지부재를제조하고자하는경우, b)단계에서수득되는제 1금속 나노섬을에칭마스크로,화합물막이습식에칭됨으로써，제 1금속나노섬을 지지하는지지부재와하부막 (금속막또는에칭후잔류하는화합물막)이동시에 제조될수있다.
[203] 상세하게，습식에칭시제 1금속나노섬의하부면 (b)단계에서의제 1금속
나노섬과화합물막간의계면)의면적기준， 10내지 80%의면적이지지부재와 계면을이를수있는깊이로에칭되거나，상술한바와같은축소율을만족하는 깊이로에칭될수있다.일예로,화합물막이 5nm내지 200nm의깊이까지에칭 제거됨으로써， 5nm내지 200nm의길이를갖는지지부재가제조될수있다.이와 동시에에칭후잔류하는화합물막이하부막을형성하거나，또는에칭에의해 화합물막 (설계된지지부재의길이에해당하는두께를갖는화합물막)이 제거되며표면으로노출되는금속막이하부막을형성할수있다.
[204] 기판상존재하는모든제 1금속나노섬은화합물막의표면의잘규정된평면에 위치함에따라，에칭후공중부유하는제 1금속나노섬의하부면들은에칭 전의 화합물막표면이었던잘규정된단일한가상의평면상에위치할수있다.
[205] 습식에칭은화합물막의물질에따라，이미잘알려진에칭액을사용하여
수행될수있다.제거하고자하는물질에따라가변가능하나,구체적일예로, 에칭액은황산,질산，붕산，불화수소，인산,염산또는이들의흔합산인 에천트를함유할수있다.실질적인일예로，에칭하고자하는화합물막이 실리콘산화물을포함하는산화물막인경우，애칭액의에천트는불화수소의 단일산또는불화수소와질산의흔산일수있다.실질적인일예로，에칭하고자 하는화합물막이실리콘질화물을포함하는질화물막인경우，에칭액의 에천트는인산의단일산또는인산과염산의흔산일수있으나，본발명이 에칭액에의해한정되는것은아니다.
[206] 건식에칭은방향성있는에칭으로,금속나노입자인마스크에의해
스크린 (screen)되지않은영역을에칭제거할수있다.건식에칭은플루오르등 할로겐원소를포함하는가스를플라스마 (plasma)화하여식각대상물을 식각하는플라스마에칭 (plasma etching)등을들수있으며，화합물막의물질에 따라，이미잘알려진건식에칭방법을사용하여수행될수있다.습식에칭후 수행되는건식에칭에의해,도 7과같은상부지지영역과하부지지영역을 포함하는지지부재및하부막 (건식에칭후잔류하는화합물막또는금속막)이 형성될수있다.이때,하부막이금속막인경우 a)단계의화합물막은설계된 상부지지영역의길이와설계된하부지지영역의길이를합한두께를가질수 있다.이와달리하부막이건식에칭후잔류하는화합물막인경우， a)단계의 화합물막은설계된상부지지영역의길이,설계된하부지지영역의길이및 설계된하부막의두께를합한두께를가질수있다.
[207] 에칭이수행된후，지지부재에의해공중부유하는제 1금속나노섬을증착 마스크로하여제 2금속의막을증착하는단계가수행될수있다.게 2금속막의 증착은스퍼터링등과같은물리적증착，플라즈마도움화학기상증착등과같은 화학적중착올통해서도수행될수있으나，바람직하게는，제 2금속막은열 증착 (Thermal evaporator)또는전자빔증착 (E-beam evaporator)을포함한방향성 있는증착을통해형성될수있다.이러한방향성있는증착과평면의하부면을 갖는공중부유형제 1금속나노섬을증착마스크로사용하는것에의해 지지부재의측면에제 2금속의나노입자들이부착및형성되는것을방지할수 있다.
[208] 상술한바와같이,제 2금속의증착시，공중부유상태의제 1금속나노섬을 증착마스크로하여，기재상균일한두께를갖도록제 2금속을막형태로방향성 있는증착을수행함으로써,나노갭의크기가정밀히조절될수있을뿐만 아니라，제 1금속나노입자와제 2금속막의형성과동시에나노갭이자기정렬 방식으로형성될수있다.또한，제 1금속나노섬을이용한증착마스크및방향성 있는증착은지지부재의측부에입자상의제 2금속이형성되는것을방지하여, 기판에설계에따라제어된극미세나노갭만이존재할수있도록한다.
지지부재측부에부착된랜덤한입자 (제 2금속입자)들에의해야기되는나노
¾은랜덤한크기의갭을형성한다.이러한랜덤한크기의갭이존재하는경우 라만산란을이용한물질의정량분석이실질적으로매우어려워진다.그러나，본 발명의일실시예에따른제조방법은,방향성있는증착및공중부유상태의 금속나노입자의구조에의해，금속나노입자하부의지지부재측면에 제 2금속의나노입자들이형성되지않을수있으며，이는，라만산란용기판에 제어된크기의나노갭만이존재함을의미하는것이다. [209] d)단계에서증착이수행된후수득되는제 1금속나노섬인제 1금속
나노입자는，제 2금속과제 1금속이동일한경우마스크로사용된계 I금속나노 섬이증착방향으로표면곡률이조금커지거나,증착방향으로약간
늘어난 (elongated)형상일수있다.또한，제 2금속이제 2금속과상이한경우， 제 1금속나노입자는상술한적층형입자에상웅할수있다.상세하게，제 2금속과 게 1금속이동일한경우,제 1금속나노입자는하부면인평면과볼록한 (convex) 곡면의표면을갖는잘린입자상일수있으며，잘린입자상은상술한잘린 구 (truncated sphere)형상또는잘린캡술형상 (truncated capsule shape)일수있다. 제 2금속과제 1금속이상이한경우，제 1금속나노입자는평면인하부면과 볼록한 (convex)곡면으로이루어진제 1금속나노섬 (상술한제 1-1금속의입자)및 제 1금속나노섬의볼록한곡면의적어도일부를덮도록적층된제 2금속의 코팅층 (상술한제 1-2금속의코팅층)을포함하는상술한적춤형입자가제조될 수있다.이때，제 1금속및제 2금속은서로독립적으로은，금，백금，팔라디움， 니켈，알루미늄，구리,크름또는이들의합금일수있음은물론이다.
[210] 기판에는고밀도의나노입자가형성될수있어,대면적의기판에서도
나노입자의분포가균일하게유지될수있다.본발명의제조방법에따른기판은 이러한나노입자의균일한분포및정밀하게조절된나노갭 (만)이존재하는 구성에의해，대면적의기판에서도면적평균한표면증강라만산란의증강된 강도가일정하게유지되어분석대상물질의정량분석이이루어질수있다.
[211] 계 2금속막의두께는 5내지 lOOnm일수있으며,기설계된나노갭의크기를 고려하여조절될수있다.
[212] 상술한바와같이,게 2금속의증착시，공중부유상태의금속나노섬을증착 마스크로하고,방향성있는증착을이용하여,기재상균일한두께를갖도록 제 2금속을막형태로증착함으로써,나노갭의크기가정밀히조절될수있을 뿐만아니라，제 1금속나노입자와제 2금속막의형성과동시에핫스팟이자기 정렬방식으로형성될수있고，나아가지지부재측부에제어가불가능한갭을 야기하는나노입자들이형성되는것을방지할수있다.
[213] 또한， c)단계의등방에칭시의화합물막이에칭되는깊이및 d)단계의
증착시의제 2금속막의두께중적어도하나의인자를제어하여, d)단계에서 자기정렬방식으로형성되는나노갭의크기가조절될수있다.
[214] 에칭이수행되고제 2금속막의형성전，또는제 2금속막의형성후,빈
공간 (E)의하부를규정하는빈공간의하부면및 /또는지지부재의표면 (측면을 포함함)에검출대상물과특이적으로결합하는수용체를형성하는단계가더 수행될수있다.이때，빈공간의하부면은기재의표면,하부지지영역의상부 표면, c)단계의에칭후표면으로노출되는금속막의표면또는 c)단계의에칭후 잔류하는화합물막의표면일수있음은물론이다.
[215] 좋게는，제 2금속막의형성후，빈공간을구획하는하부막 (금속막또는에칭후 잔류하는화합물막)의표면이나하부지지영역의상부표면및 /또는지지부재의 측부표면에검출대상물과특이적으로결합하는수용체를형성하는단계가더 수행될수있다.이러한수용체형성은수용체를함유하는용액을빈공간에 유입시켜，수용체가유전체인지지부재와하부막과화학적으로결합하여 고정되도록함으로써이루어질수있다.그러나，생화학물질을검출하는센서 분야에서통상적으로사용되는수용체부착방법이면어떠한방법이든사용 가능함은물론이며，본발명이구체적인수용체의형성방법에의해한정되는 것은아니다.
[216] 상술한제조방법에서，제 1금속의물질;제 2금속의물질;제 1금속
나노입자 (나노입자,또는제 1금속나노섬)의크기，하부면,형상이나구조;
지지부재의물질，지지부재의크기나형상;하부막의물질이나두께;
분석대상물질;수용체물질;기재물질이나형상;둥은앞서상술한라만산란용 기판의내용을참고할수있으며，라만산란용기판에서상술한내용을모두 포함한다.
[217] 도 10(a)는실리콘웨이퍼 2 cm X 2 cm를기재로，기재상 lOOnm두께의실리콘 산화물층을형성하고，실리콘산화물층상에 11 nm의 Ag막을형성한샘플을 관찰한주사전자현미경사진이며,도 10(b)는 RTP장비 (Korea vacuum,
KVR-020)를이용하여제조된샘플을 15°C/sec의승온속도로열처리온도인 400°C까지승온한후， 1분동안열처리한샘플을관찰한주사전자현미경 사진이다.
[218] 도 10(b)에서알수있듯이잘린입자형 Ag나노입자들이실리콘산화물층
상에잘형성된것을알수있으며,투영형상기준평균 120 nm의크기를갖는 Ag나노입자들이 15개 /μπι2에이르는고밀도로형성된것을알수있다.
[219] 도 11(a)는도 10(b)의샘플을대상으로,에칭액 HF:NH4F l:6(v/v)을이용하여 20 nm의깊이로실리콘산화물층을습식에칭한샘플로，하부막으로부터연장된 지지부재및지지부재에의해지지되는공중부유형 Ag나노입자가제조되는 것을확인할수있다.이때,에칭액의식각률은 4 nm/sec였으며，에칭시간을 조절하여에칭되는깊이를제어하였다.
[220] 도 11(b)는도 11 (a)의샘플의공중부유형 Ag나노입자들을증착마스크로하여， E-beam evaporator를사용하여 30 nm의 Ag막을형성한샘플을관찰한
주사전자현미경사진이다.이때, Ag막의증착속도는 0.7 nm/sec로，증착시간을 조절하여증착되는 Ag막의두께를조절하였다.
[221] 도 11(b)에서도알수있듯이단지 Ag막을형성하는것으로 Ag막과 Ag
나노입자간의링형핫스팟 (나노갭)이자기정렬방식으로형성됨을알수 있다.또한도 11(b)를통해，공중부유형 Ag나노입자하부로빈공간 (E)이잘 규정되어있음을확인할수있다.또한,도 11(b)의샘플에서실리콘웨이퍼상 위치에따른공중부유형 Ag나노입자및 Ag금속막에의한 SERS활성구조를 관찰한결과， 2 cm X 2 cm에이르는넓은면적에서소자가제조되었음에도, 위치에따른유의미한 SERS활성구조의변화는관찰되지않았다. 주사전자현미경및 SERS활성관찰을통해，대면적에서도극미세한나노갭이 균일하게형성된것을알수있으며，방향성있는증착으로 Ag금속막을 제조함에따라,지지부재측면등에 랜덤한갭을형성할수있는 Ag입자들의 형성이방지됨을알수있다.
[222] 도 12는단위공정의반복에의한금속나노입자의밀도증가를관찰한
사진이다.상세하게,도 12(a)는실리콘산화물층상에 14 nm두께의 Ag막을 형성한후， RTP장비를이용하여 15°C/sec의승온속도로 400°C까지승온한후， 1 분동안열처리한샘플의표면을관찰한주사전자현미경사진이며，도 12(b)는 도 12(a)의샘플상에다시 14nm두께의 Ag막을형성하고，도 12(a)의샘플과 동일하게다시열처리를수행한후 Ag나노입자를관찰한주사전자현미경 사진이다.
[223] 도 12(a)및도 12(b)를통해알수있듯이,단위공정의반복에의해,입자의
크기나크기분포에는거의영향을미치지않으면서도， Ag나노입자의밀도가 1.5배증가함을확인할수있다.
[224] 도 13(a)는실리콘산화물상패턴화된 Ag막을형성한후이를관찰한
주사전자현미경사진이며，도 13(b)는패턴화된 Ag막을도 10의샘플과 동일하게열처리하여제조된 Ag나노입자를관찰한주사전자현미경사진이다. 도 13(a)및도 13(b)를통해，단지유전체막 (화합물막)상 Ag막을
패턴화함으로써，멀티플렉싱가능한표면증강라만산란기판이제조됨을알수 있다.
[225] 도 14는도 10(b)의샘플을대상으로，에칭시간을조절하여,실리콘산화물층을 32nm깊이로에칭한후， E-beam evaporator를사용하여 30 nm두께의 Ag막을 증착하여제조된샘플들의암시야상 (dark field image)을관찰한사진이다.
[226] 도 15는도 14의샘플을관찰한주사전자현미경사진이며，도 15에서알수
있듯이，동일한두께의 Ag막이형성되어도,에칭깊이를조절하여공중부유된 Ag나노입자의높이를제어함으로써，나노갭의크기가정밀하고균일하게 조절되는것을관찰할수있다.
[227] 도 16은도 14의샘플에서 ,실리콘산화물층의에칭깊이가 6 nm (도 16의 sample A), 24 nm (도 16의 sample B)또는 32 nm (도 16의 sample C)로조절된샘플의 표면증강라만산란스펙트럼을도시한도면이며，레퍼런스로 Si기판에에칭 전의실리콘산화물층만이형성된샘플 (도 16의 Reference only Si02/Si)의 표면증강라만산란스펙트럼또한함께도시하였다.라만산란실험을위해, 티올 (Thiol)작용기를가지고있어샘플금속표면 (Au, Ag등)에강한화학결합을 형성할수있으며，약한광화학반웅성을가진벤젠티올 (Benzenethiol, C6H6SH)을 이용하였다.상세하게，제작된샘플은아세톤또는에틸알코올용액에서 1일 이상보관하여표면에존재할수있는유기불순물들을제거한후,세척한 각각의샘플은 2mM벤젠티올용액 (용매:에탄올)에서 1일이상반웅시켰다. 반웅이후화학결합에의하여강하게흡착돤벤젠티올만이샘플표면에 잔류하도록과량의에탄올을이용하여세척하여표면에물리적으로흡착된 과량의벤젠티올을제거하였다.샘플은질소에서건조되어라만분석을위하여 밀폐용기에보관되었다.라만신호는마이크로라만시스템 (Horiba, HR-800)을 이용하여파장 632.8nm레이저광을샘플에조사하여측정하였다.도 16에서 나타난 1000-1100 cm '의영역과 1580 cm 1근처에서관찰되는강한신호는 벤젠티올고유의 SERS신호와일치함을알수있다.
[228] 도 16에서알수있듯이나노갭의크기가변화함에따라표면증강라만산란 스펙트럼상픽의강도가달라짐을확인할수있으며， A샘플및 B샘플의경우 1600(cm ')파수영역에서 C샘플보다도강한피크가발생함을알수있다.
[229] 도 17은도 16의샘플 B의표면증강라만산란스펙트럼과함께，도 12(b)의
샘플의예와동일한방법으로， Ag나노입자의밀도가샘플 B의 Ag나노입자 밀도보다 1.5배증가된샘플 E (에칭깊이및 Ag막의두께는샘플 B와동일)의 표면증강라만산란스펙트럼을도시한도면이다.도 1.7에서，레퍼런스로 Si 기판에에칭전의실리콘산화물층만이형성된샘플 (도 17의 Reference only Si02 /Si)의표면증강라만산란스펙트럼또한함께도시하였다.도 17에서알수 있듯이핫스팟의밀도가 1.5배증가하면서 1600(cnr')파수영역의피크또한 1.5배증가함올확인할수있다.
[230] 도 18은도 11(b)의샘플과유사하게제조하되 ,실리콘산화물층상에 11 nm의 Au막을형성한후， 550oC에서 1.분동안 RTP처리한후,실리콘산화물층을 20 nm깊이로습식에칭하고 e-beam evaporator를이용하여 30 nm두께로 Au 막 (제 2금속막)을증착한샘플을관찰한주사전자현미경사진이며，도 19는도 18의샘플을이용한표면증강라만산란스펙트럼을도시한도면이다.라만산란 실험은도 16의예와동일하게수행하였다.도 19에서알수있듯이 8 W의극히 낮은에너지의레이저광을이용하여측정함에도불구하고강한 SERS신호를 측정할수있었으며，실리콘기판의라만신호와비교하여볼때 13배정도강한 신호를측정할수있었다.
[231] 도 20은실리콘웨이퍼인기재상 50 nm두께의 Au막을형성한후, Au막상 20nm의실리콘산화물층을형성한것을제외하고도 18의샘풀과동일한 방법으로제조한라만산란용기판을관찰한주사전자현미경사진이다.
상세하게，실리콘웨이퍼인기재상 50nm두께의 Au막을형성한후, Au막상 20nm의실리콘산화물층을형성하고，도 18의샘플과동일하게 Au막형성및 RTP열처리한후，에칭액 (HF:NH4F(l:6(v/v))을이용하여 20 nm의깊이로실리콘 산화물층을습식에칭하여 Au나노입자하부이외의실리콘산화물층을모두 제거한후，도 18의샘플과동일하게공중부유형 Au나노입자들을증착 마스크로， 30 nm의 Au막을형성한샘플을관찰한주사전자현미경사진이다.도 21은도 20샘플의표면증강라만산란스펙트럼을도시한도면으로，도 20 샘풀을대상으로도 16의예와동일하게라만산란실험을수행하였다.도 21의 스펙트럼을통해，하부막으로금속막이구비되는경우,기판의하부로의 라만산란광손실이방지되어，그강도가향상되는것을확인할수있다.
[232] 이상과같이본발명에서는특정된사항들과한정된실시예및도면에의해 설명되었으나이는본발명의보다전반적인이해를돕기위해서제공된것일 뿐,본발명은상기의실시예에한정되는것은아니며，본발명이속하는 분야에서통상의지식을가진자라면이러한기재로부터다양한수정및변형이 가능하다.
[233] 따라서 ,본발명의사상은설명된실시예에국한되어정해져서는아니되며， 후술하는특허청구범위뿐아니라이특허청구범위와균등하거나등가적변형。 있는모든것들은본발명사상의범주에속한다고할것이다.

Claims

청구범위
[청구항 1] 공중부유형제 1금속나노입자，상기제 1금속나노입자를지지하는
지지부재,상기제 1금속나노입자와나노갭을형성하며상기게 1금속 나노입자의둘레를감싸는제 2금속막을포함하며,상기제 1금속 나노입자의계 1금속및제 2금속막의제 2금속은각각표면플라즈몬이 발생하는금속인표면증강라만산란기판.
[청구항 2] 제 1항에있어서,
제 1금속나노입자에서，상기지지부재에의해지지되는측의면인 제 1금속나노입자의하부면은평면인표면증강라만산란기판.
[청구항 3] 제 2항에있어서， '
상기제 1금속나노입자;와상기제 1금속나노입자의둘레를감싸는 계 2금속막의테두리 (edge)를포함하는제 2금속막의측면;에의해 나노갭이형성되는표면증강라만산란기판.
[청구항 4] 제 2항에있어서,
상기나노갭은폐루프형상인표면증강라만산란기판.
[청구항 5] 제 2항에있어서,
상기하부면은상기지지부재와계면을형성하는지지영역과표면으로 노출되는미지지영역이공존하는표면증강라만산란기판.
[청구항 6] 제 5항에있어서，
상기하부면의면적기준， 10내지 80%의면적이상기지지부재와계면을 이루는표면증강라만산란기판.
[청구항 7] 제 5항에있어서，
상기제 1금속나노입자의하부면의미지지영역을포함한제 1금속 나노입자，제 2금속막의측면，및지지부재의측면에의해규정되는 공간에검출대상물이위치하는표면증강라만산란기판.
[청구항 8] 제 5항에있어서，
상기제 2금속막의관통형기공내부에상기지지부재에의해지지되는 공중부유형제 1금속나노입자가위치하는표면증강라만산란기판.
[청구항 9] 제 8항에있어서，
상기게 1금속나노입자，상기관통형기공및상기지지부재는서로 동심구조를이루는표면증강라만산란기판.
[청구항 10] 제 2항에있어서，
상기소자는상기제 2금속막및공중부유형제 1금속나노입자하부에 위치하는하부막을더포함하는표면증강라만산란기판.
[청구항 11] 제 10항에있어서,
상기하부막은상기지지부재와동일한물질이며，상기지지부재는상기 하부막으로부터연장되는표면증강라만산란기판ᅳ [청구항】2] 제 10항에있어서，
상기하부막은금속막인표면증강라만산란기판.
[청구항 13] 제 10항에있어서, .
적어도,상기공증부유형제 1금속나노입자하부에위치하는상기 하부막의표면또는상기지지부재의측부표면에검출대상물질과 특이적으로결합하는수용체가형성된표면증강라만산란기판.
[청구항 I4] 제 10항에있어서,
상기지지부재는금속화합물및반도체화합물에서하나또는둘이상 선택되며,이와독립적으로,상기하부막은금속，금속화합물및 반도체화합물에서하나또는둘이상선택되는표면증강라만산란기판.
[청구항 15] 제 1항에있어서,
상기계 1금속나노입자는잘린입자형상 (truncated particle shape)인 표면증강라만산란기판.
[청구항 16] 제 1항내지제 15항중어느한항에있어서，
상기나노갭의크기는 1 nm내지 lOOnm인표면증강라만산란기판. [청구항 1.7] 제 1항내지제 15항중어느한항에있어서,
상기지지부재의길이및상기제 2금속막의두께중하나이상선택된 인자 (factor)에의해,상기나노갭의크기가조절되는표면증강라만산란 기판.
[청구항 18] 제 1항내지제 15항중어느한항에있어서,
상기제 1금속나노입자는투영 (projection)형상기준，투영형상의평균 지름은 10nm내지 500nm인표면증강라만산란기판.
[청구항 19] 제 1항내지제 15항중어느한항에있어서,
상기제 2금속막의두께는 5내지 lOOnm인표면증강라만산란기판.
[청구항 20] 제 1항내지제 15항중어느한항에있어서,
단위면적당상기제 1금속나노입자의수인나노구조체밀도는 1내지 100개 / μπι2인표면증강라만산란기판.
[청구항 21] 제 1항내지제 15항중어느한항에있어서,
상기기판은상기공중부유형제 1금속나노입자가형성된표면증강라만 산란활성영역및상기공중부유형제 1금속나노입자가미형성된 표면증강라만산란비활성영역을포함하며，둘이상의상기표면증강 라만산란활성영역이이격배열된표면증강라만산란기판.
[청구항 22] 제 1항내지제 15항중어느한항에있어서,
상기제 1금속나노입자의제 1금속및상기제 2금속막의제 2금속은서로 독립적으로，은，금,백금,팔라디움，니켈，알루미늄，구리,크롬또는 이들의조합또는이들의합금인표면증강라만산란기판.
[청구항 23] 제 1항내지제 15항중어느한항에따른표면증강라만산란기판을
포함하는분자검출용소자. [청구항 24] a)기재상금속화합물또는반도체화합물인화합물막을형성하는단계； b)상기화합물막상제 1금속막을형성한후열처리하여화합물막상 서로이격되어위치하는제 1금속나노섬 (nano island)를제조하는단계； c)상기제 1금속나노섬을에칭마스크로，상기화합물막을일정 깊이까지등방에칭하는단계;및
d)상기제 1금속나노섬을증착마스크로,에칭된화합물막상계 2금속을 증착하여제 2금속막을형성하는단계；
를포함하는표면증강라만산란기판의제조방법 .
[청구항 25] 제 24항에있어서，
상기 b)단계는,
bl)제 1금속막을형성하는단계및
b2)열처리단계
를단위공정으로,상기단위공정을반복수행함으로써，제 1금속나노 섬의밀도를제어하는표면증강라만산란기판의제조방법.
[청구항 26] 제 24항에있어서,
상기등방에칭은습식에칭인표면증강라만산란기판의제조방법.
[청구항 27] 제 24항에있어서,
상기 c)단계에서，상기둥방에칭전，또는등방에칭후，건식에칭이더 수행되는표면증강라만산란기판의제조방법 .
[청구항 28] 제 24항에있어서,
상기 a)단계전，
상기기재상금속막이거나，상기화합물막과상이한금속화합물또는 반도체화합물의막인하부막을형성하는단계를더포함하며，상기 c) 단계의등방에칭을포함하는에칭에의해상기에칭마스크로보호되지 않은영역에서하부막이표면으로노출되는표면증강라만산란기판의 제조방법ᅳ
[청구항 29] 제 24항에있어서，
상기 c)단계의등방에칭을포함하는에칭에의해，에칭된상기화합물 막이잔류하는표면증강라만산란기판의제조방법.
[청구항 30] ' 제 24항에있어서，
상기 d)단계의증착은열증착 (Thermal evaporator)또는전자빔
증착 (E-beam evaporator)을포함한방향성있는증착인표면증강라만산란 기판의제조방법.
[청구항 31] 제 24항에있어서，
상기 c)단계의에칭깊이및상기 d)단계의증착두께중적어도하나의 인자를제어하여，나노갭크기가조절되는표면증강라만산란기판의 제조방법.
[청구항 32] 제 24항에있어서， 상기 b)단계에서，패턴화된계 1금속막을형성하는표면증강라만산란 기판의제조방법.
[청구항 33] 제 24항에있어서，
상기 b)단계에서，제 1금속막의두께는 1내지 50nm인표면증강라만산란 기판의제조방법.
[청구항 34] 제 24항에있어서，서 ,
상기 c)단계후 d)단계전，또는 d)단계후,
등방에칭에의해수득되는하부막과지지부재의표면에검출대상물과 특이적으로결합하는수용체를형성하는단계를더포함하는표면증강 라만산란기판의제조방법.
[청구항 35] 제 24항에있어서，
상기 b)단계의열처리는급속열처리공정 (RTP; rapid thermal process)에 의해수행되는표면증강라만산란기판의제조방법 .
PCT/KR2017/005115 2016-05-17 2017-05-17 표면증강 라만산란 기판, 이를 포함하는 분자 검출용 소자 및 이의 제조방법 WO2017200295A1 (ko)

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