JP2015010825A - Localized plasmon resonance chip - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a localized plasmon resonance chip useful for achieving a high level of sensing accuracy.SOLUTION: A 10 nm to 100 nm thick gold (Au) nano thin-film layer 2a is formed over a substrate 1 consisting of glass, polyethylene terephthalate (PET) and other materials; a dielectric nano particle layer 3 formed of particles of 10 nm to 200 nm in grain size is arranged over the layer 2a; a 10 nm to 100 nm thick silver (Ag) nano thin-film layer 4 is formed over the layer 3; and a 10 nm to 100 nm thick gold (Au) nano thin-film layer 5 is formed over the layer 4. Instead of the Au nano thin-film layer 2a, a 10 nm to 100 nm thick silver (Ag) nano thin-film layer 2b is formed ((B) in Fig. 1).

Description

  The present invention relates to a localized plasmon resonance (LPR) biosensor used for medical diagnosis, medical examination, food inspection, and the like, and more particularly to a localized plasmon resonance chip.

  In recent years, surface plasmon resonance (SPR) biosensors with a Kretschmann arrangement using prisms have been developed as small-sized, low-cost, high-speed sensing biosensors in medical diagnosis, medical examination, food inspection, and the like.

  Furthermore, recently, a localized plasmon resonance (LPR) biosensor not using a prism has been attracting attention as a biosensor for high-sensitivity sensing. As a conventional localized plasmon resonance biosensor, there are a transmission type shown in FIG. 10 (refer to Patent Document 1) and a reflection type shown in FIG.

  In FIG. 10, 101 is a light source, 102 is a collimator lens, 103 is a localized plasmon resonance chip having a surface plasmon resonance unit 103a, 104 is a measurement apparatus including a spectroscope and a multi-channel analyzer and configured by a microcomputer. In this case, the light L1 from the light source 101 is converted into parallel light by the collimator lens 102 and vertically transmitted through the localized plasmon resonance chip 103, and the measurement apparatus 104 transmits the localized plasmon from the light L1 transmitted through the localized plasmon resonance chip 103. The absorbance of the resonance chip 103 is measured. In the measuring apparatus 104, the absorbance may be obtained as an absorption spectrum by subtracting the transmitted light spectrum of the light L1 transmitted through the localized plasmon resonance chip 103 from the light source spectrum of the light source 101. It may be used. The change in the refractive index (dielectric constant) of the medium in the vicinity of the surface plasmon resonance portion 103a of the localized plasmon resonance chip 103 can be detected with high accuracy by the shift amount of the absorption peak wavelength of the absorption spectrum or the transmission dip wavelength of the transmitted light spectrum. it can.

  On the other hand, in FIG. 11, 201 is a light source, 202 is a collimator lens, 203 is a beam splitter, 204 is a localized plasmon resonance chip having a surface plasmon resonance part 204a, 205 includes a spectroscope and a multichannel analyzer, and is constituted by a microcomputer. Measuring device. In this case, the light L2 from the light source 201 is converted into parallel light by the collimator lens 202, is transmitted through the beam splitter 203, is reflected by the localized plasmon resonance chip 204, is further reflected by the beam splitter 203, and enters the measuring device 205. . In the measuring apparatus 205, the absorbance of the localized plasmon resonance chip 204 is measured from the light L2 reflected by the localized plasmon resonance chip 204. In the measuring apparatus 205, the absorbance may be obtained as an absorption spectrum by subtracting the reflected light spectrum of the light L2 reflected by the localized plasmon resonance chip 204 from the light source spectrum of the light source 201, but the reflected light spectrum is directly obtained. It may be used. The change in the refractive index (dielectric constant) of the medium in the vicinity of the surface plasmon resonance portion 204a of the localized plasmon resonance chip 204 can be detected with high accuracy by the shift amount of the absorption peak wavelength of the absorption spectrum or the reflection dip wavelength of the reflected light spectrum.

  The medium in the vicinity of the surface plasmon resonance portions 103a and 204a is initially a sensor substance that specifically binds to a target substance such as an antigen substance, for example, an antibody substance. 204a. After the combination, the medium becomes a sensor substance plus a target substance, and thus the refractive index (dielectric constant) of the medium changes before and after the combination. As a result, the target substance can be quantitatively detected with high accuracy by detecting the change in the refractive index (dielectric constant) of the medium with high accuracy.

  In any of the localized plasmon resonance biosensors of FIGS. 10 and 11, the lights L1 and L2 are directly incident perpendicularly to the surface plasmon resonance portions 103a and 204a of the localized plasmon resonance chips 103 and 204. In the surface plasmon resonance biosensor, light is incident obliquely on the bottom surface of the prism. Therefore, the localized plasmon resonance biosensor is superior to the surface plasmon resonance biosensor in terms of miniaturization.

  The surface plasmon resonance portions 103a and 204a of the localized plasmon resonance chips 103 and 204 shown in FIGS. 10 and 11 are formed of a metal nano thin film layer or a metal nanoparticle layer made of one kind of metal such as Au, Ag, Cu, and Al. For example, the metal nano thin film layer is manufactured by forming a metal thin film having a through hole on a transparent substrate using a nanoimprint technique or a lithography technique (see Patent Document 1). In addition, the metal nanoparticle layer is dispersed and deposited on a smooth glass substrate via a dielectric such as a silane coupling agent by electrophoretic deposition (EPD) method. In this case, each particle of the metal nanoparticle layer is spherical and rod-shaped. Shape, triangular shape, and other polygonal shapes (see Non-Patent Document 1).

  FIG. 12 is a graph showing the absorption spectrum S1 or the transmitted / reflected light spectrum S2 obtained by the measuring devices 104 and 205 shown in FIGS. As shown in FIG. 12, since the surface plasmon resonance portions 103a and 204a of the localized plasmon resonance chips 103 and 204 of FIGS. 10 and 11 are formed of a metal nano thin film layer or metal nano particle layer made of one kind of metal, Only a peak-like absorption peak wavelength or a valley-like transmission / reflection dip wavelength is observed. Changes in the refractive index (dielectric constant) of the medium are detected according to the shift amount of the absorption peak wavelength or transmission / reflection dip wavelength.

JP 2003-270132 A

Masaaki Kurita, “Precious Metals Used in Localized Plasmon Resonance Biosensors and Their Applications”, Surface Technology, Vol.62, No.6, 2011, pp.28-30

  However, in the above-described conventional localized plasmon resonance biosensor, the absorption spectrum in the measuring devices 104 and 205 is absorbed at one absorption peak wavelength or transmitted by a metal nano thin film layer or metal nanoparticle layer made of one kind of metal. Since only the / reflected dip wavelength is expressed, if this absorption peak wavelength or the absorption spectrum near the transmitted / reflected dip wavelength or the transmitted / reflected light spectrum becomes unstable in the manufacture of the localized plasmon resonance biosensor, the sensing accuracy There is a problem that decreases.

  For example, even if the surface plasmon resonance portions 103a and 204a are the same metal, the thickness of the metal nano thin film layer, the particle size of the metal nano particle layer, the shape such as a spherical shape, a lot shape, and a triangular shape, and the aggregated state are As a result, the absorption spectrum or the transmitted / reflected light spectrum becomes a crushed mountain shape or a gentle valley shape, and the sensing accuracy decreases.

  Further, although halogen lamps and light emitting diode (LED) elements are used as the light sources 101 and 201, the light sources 101 and 201 vary in manufacturing. As a result, the absorption spectrum or the transmitted / reflected light spectrum is crushed or loose. It becomes a valley shape, and the sensing accuracy also decreases.

  In order to solve the above-described problem, a localized plasmon resonance chip according to the present invention includes a substrate, a non-planar first metal layer of a nanometer order that is disposed on the substrate and includes the first metal, And a second metal layer having a non-planar shape of nanometer order including a second metal different from the first metal and disposed on the first metal layer. The absorption peak wavelength that appears in the absorption spectrum due to the two kinds of metals or the transmission / reflection dip wavelength that appears in the transmitted / reflected light spectrum is two places.

  And a nanometer-order first metal particle randomly disposed on the substrate and including a first metal and a second metal particle having a second metal different from the first metal. It comprises. The absorption peak wavelength that appears in the absorption spectrum due to the two kinds of metals or the transmission / reflection dip wavelength that appears in the transmitted / reflected light spectrum is two places. Further, even if the first metal particle and the second metal particle are made of the same metal, and the shape of the first metal particle is different from the shape of the second metal particle, the absorption peak wavelength or the transmission / reflection dip wavelength. Are two places.

  According to the present invention, since the absorption peak wavelength of the absorption spectrum or the dip wavelength of the transmitted light / reflected light spectrum is two places, the refractive index of the medium (depending on the shift amount of the two absorption peak wavelengths or the transmitted / reflected dip wavelength) (Dielectric constant) change can be detected, that is, if one absorption peak wavelength is crushed and the other absorption peak wavelength is sharp, or one transmission / reflection dip wavelength is If the other transmission / reflection dip wavelength has a sharp valley shape even if it is slow, a change in the refractive index (dielectric constant) of the medium can be detected, and therefore the sensing accuracy can be improved.

1 is a sectional view showing a first embodiment of a localized plasmon resonance chip according to the present invention. It is sectional drawing which shows the example of a change of FIG. It is sectional drawing which shows 2nd Embodiment of the localized plasmon resonance chip concerning this invention. It is sectional drawing which shows the example of a change of FIG. The localized plasmon resonance chip of FIG. 1 (A), (B), FIG. 2, FIG. 3, (A), (B) or FIG. 4 is applied to the localized plasmon resonance biosensor of FIG. 10 (or FIG. 11). It is a graph which shows the transmitted-light / reflected-light spectrum and absorption spectrum which are obtained with a measuring device when it does. It is sectional drawing which shows 3rd Embodiment of the localized plasmon resonance chip concerning this invention. It is sectional drawing which shows 4th Embodiment of the localized plasmon resonance chip concerning this invention. It is sectional drawing which shows 5th Embodiment of the localized plasmon resonance chip | tip concerning this invention. It is sectional drawing which shows the local plasmon resonance chip | tip formed from three or more different metals. It is a figure which shows the conventional transmission type | mold local plasmon resonance biosensor. It is a figure which shows the conventional reflection type localized plasmon resonance biosensor. It is a graph which shows the absorption spectrum obtained with the measuring apparatus of FIG. 10, FIG.

  FIG. 1 is a sectional view showing a first embodiment of a localized plasmon resonance chip according to the present invention.

  In FIG. 1A, a gold (Au) nano thin film layer 2a having a thickness of 10 nm to 100 nm is formed on a substrate 1 made of glass, polyethylene terephthalate (PET) or the like, and a spherical diameter of 10 nm is formed thereon. A dielectric nanoparticle layer 3 composed of particles of ˜200 nm is disposed, a silver (Ag) nano thin film layer 4 having a thickness of 10 nm to 100 nm is formed thereon, and a gold ( Au) Nano thin film layer 5 is formed.

  In FIG. 1B, a silver (Ag) nano thin film layer 2b having a thickness of 10 nm to 100 nm is formed in place of the Au nano thin film layer 2a of FIG.

  In FIG. 1, due to the presence of the dielectric nanoparticle layer 3, the Ag nano thin film layer 4 and the Au nano thin film layer 5 have a non-plate shape, that is, an uneven shape, and cause localized plasmon resonance. The Au nano thin film layer 2a or the Ag nano thin film layer 2b is flat, but interacts with the localized plasmon resonance of the Au nano thin film layer 5 or the Ag nano thin film layer 4 via the dielectric nanoparticle layer 3. Causes localized plasmon resonance.

  In FIG. 2 showing a modified example of FIGS. 1A and 1B, the Au nano thin film layer 2a in FIG. 1A or the Ag nano thin film layer 2b in FIG. The dielectric nanoparticle layer 3 is directly disposed on the substrate 1.

  The dielectric nanoparticle layer 3 in FIGS. 1A, 1B, and 2 has an action of amplifying an electric field generated by surface plasmon resonance, and therefore, the absorption peak or transmitted / reflected light of the developed absorption spectrum. Spectral transmission / reflection dip can be increased.

  In FIGS. 1A and 1B, the Au nano thin film layer 2a (or Ag nano thin film layer 2b), the Ag nano thin film layer 4 and the Au nano thin film layer 5 are in the ultraviolet to near-infrared region of light and surface plasmon resonance. Wake up. In this case, since these nano thin film layers are made of two kinds of metals, that is, Au and Ag, as described later, two absorption peak wavelengths are expressed in the absorption spectrum, or two transmitted / reflected spectra are transmitted / reflected. A dip wavelength is developed.

  Also in FIG. 2, the Ag nano thin film layer 4 and the Au nano thin film layer 5 that cause surface plasmon resonance are made of two kinds of metals, that is, Au and Ag, so that two absorption peak wavelengths are expressed in the absorption spectrum, Alternatively, two transmitted / reflected dip wavelengths are expressed in the transmitted light / reflected light spectrum. However, since the Au nano thin film layer 2a and the Ag nano thin film layer 2b do not exist, the absorption peak or transmission / reflection dip that appears is slightly reduced.

  FIG. 3 is a sectional view showing a second embodiment of the localized plasmon resonance chip according to the present invention.

  In FIG. 3A, a gold (Au) nano thin film layer 2a having a thickness of 10 nm to 100 nm is formed on a substrate 1, and silver (Ag) nano particles comprising particles having a spherical diameter of 10 nm to 200 nm are formed thereon. The particle layer 3 ′ is disposed, and a gold (Au) nano thin film layer 5 having a thickness of 10 nm to 100 nm is formed thereon.

  In FIG. 3B, a silver (Ag) nano thin film layer 2b having a thickness of 10 nm to 100 nm is formed in place of the Au nano thin film layer 2a of FIG.

  In FIG. 3, the Ag nanoparticle layer 3 ′ is non-planar and thus causes localized plasmon resonance. The Au nano thin film layer 5 is non-planar, that is, an uneven shape due to the presence of the Ag nanoparticle layer 3 ′, and causes localized plasmon resonance. Furthermore, although the Au nano thin film layer 2a or the Ag nano thin film layer 2b is flat, it interacts with the Au nano thin film layer 5 or the Ag nanoparticle layer 3 'to cause localized plasmon resonance.

  In FIG. 4 showing a modified example of FIG. 3A and FIG. 3B, the Au nano thin film layer 2a in FIG. 3A or the Ag nano thin film layer 2b in FIG. 1, an Ag nanoparticle layer 3 ′ is directly disposed on the surface.

  In FIGS. 3A and 3B, the Au nano thin film layer 2a (or Ag nano thin film layer 2b), the Ag nano particle layer 3 ′, and the Au nano thin film layer 5 are formed of light and surface plasmons in the ultraviolet to near infrared region. Cause resonance. In this case, since these nano thin film layer and nano particle layer are made of two kinds of metals, that is, Au and Ag, as described later, two absorption peak wavelengths are expressed in the absorption spectrum, or 2 in the transmitted / reflected light spectrum. Two transmission / reflection dip wavelengths are developed.

  Also in FIG. 4, the Ag nanoparticle layer 3 ′ and Au nano thin film layer 5 that cause surface plasmon resonance are made of two kinds of metals, that is, Au and Ag, so that two absorption peak wavelengths are also expressed in the absorption spectrum. Alternatively, two transmitted / reflected dip wavelengths are expressed in the transmitted / reflected light spectrum. However, since the Au nano thin film layer 2a and the Ag nano thin film layer 2b do not exist, the absorption peak or transmission / reflection dip that appears is slightly reduced.

  FIG. 5 shows the localized plasmon resonance biochip of FIG. 10 (or FIG. 11) and the localized plasmon resonance chip of FIG. 10 (or FIG. 11). It is a graph which shows the light absorption spectrum and transmitted light spectrum (or reflected light spectrum) which are obtained with the measuring devices 104 and 205 when applied to a sensor.

  For the light source spectrum S0 of the light source 101 (201) shown in FIG. 5A, an absorption spectrum S1 shown in FIG. 5B and a transmitted / reflected light spectrum S2 shown in FIG. 5C are obtained. It is done. Therefore, by subtracting the transmitted / reflected light spectrum S2 shown in FIG. 5C from the light source spectrum S0 shown in FIG. 5A, an absorption spectrum S1 shown in FIG. 5B is obtained. In the absorption spectrum S1 of FIG. 12, there is one absorption peak or transmission / reflection dip, whereas in the absorption spectrum S1 or transmission / reflection light spectrum of FIG. 5, the absorption peak or transmission / reflection dip is There are two. As shown in FIG. 5A, the light source spectrum S0 is larger than the transmitted / reflected light spectrum S2.

  In the first and second embodiments described above, the nano thin film layer 5 may be other than Au. However, in the case of Au, in order to prevent deterioration of other metals such as Ag, Cu, and Ag as the outermost layer. It acts as a coating layer. Further, the particles of the dielectric nanoparticle layer 3 and the Ag nanoparticle layer 3 ′ do not need to be completely in close contact with each other, and 1 to 3 particles may be separated. Furthermore, the Ag nano thin film layer 2b, the Ag nano particle layer 3 ', and the Ag nano thin film layer 4 may be other metals such as copper (Cu) and aluminum (Al). Furthermore, the dielectric nanoparticle layer 3 and the Ag nanoparticle layer 3 ′ may have a rod shape other than a spherical shape, a triangular shape, or other polygonal shapes.

  FIG. 6 is a sectional view showing a third embodiment of the localized plasmon resonance chip according to the present invention.

  6A, a silver (Ag) nano thin film layer 4 ′ having a thickness of 10 nm to 100 nm is formed on the convex portion of the substrate 1 on which holes 1a having a depth of 50 to 500 nm are nano-imprinted. Then, a gold (Au) nano thin film layer 5 ′ having a thickness of 10 nm to 100 nm is formed.

  In FIG. 6B, an Ag nano thin film layer 4 ′ and an Au nano thin film layer 5 ′ are also formed in the concave portion of the substrate 1 in addition to the convex portion of the substrate 1 in FIG.

  In FIG. 6, the Ag nano thin film layer 4 ′ and the Au nano thin film layer 5 ′ are non-plate-like, that is, discretely formed, and thus cause localized plasmon resonance.

  In FIG. 6, the Ag nano thin film layer 4 ′ and the Au nano thin film layer 5 ′ cause surface plasmon resonance with light in the ultraviolet to near infrared region. In this case, since these nano thin film layers are made of two kinds of metals, that is, Au and Ag, as in the first and second embodiments, two absorption peak wavelengths are expressed in the absorption spectrum, or transmitted light / Two transmitted / reflective dips are developed in the reflected light spectrum.

  In the third embodiment described above, the Au nano thin film layer 5 'serves as a coating layer for preventing the deterioration of the Ag nano thin film layer 4' as the outermost layer. Further, the Ag nano thin film layer 4 ′ may be made of another metal such as Cu or Al.

  FIG. 7 is a sectional view showing a fourth embodiment of the localized plasmon resonance chip according to the present invention.

  In FIG. 7A, a silver (Ag) nanoparticle layer 3 ′ composed of particles having a sphere diameter of 10 nm to 200 nm and a gold (Au) nanoparticle layer 3 composed of particles having a sphere diameter of 10 nm to 200 nm are formed on a substrate 1. ”Are arranged at random.

  In FIG. 7B, holes 1a having a depth of 50 nm to 500 nm are nanoimprinted on the substrate 1 of FIG.

  In FIG. 7, the Ag nanoparticle layer 3 ′ and the Au nanoparticle layer 3 ″ are formed in a non-plate shape, that is, discretely, and thus cause localized plasmon resonance.

  7A and 7B, the Ag nanoparticle layer 3 ′ and the Au nanoparticle layer 3 ″ cause surface plasmon resonance with light in the ultraviolet to near infrared region. In this case, these nanoparticle layers are Since it consists of two kinds of metals, that is, Au and Ag, as in the first, second, and third embodiments, two absorption peak wavelengths are expressed in the absorption spectrum, or two in the transmitted / reflected light spectrum. A transmission / reflection dip wavelength is developed.

  In the fourth embodiment described above, the Ag nanoparticle layer 3 ′ and the Au nanoparticle layer 3 ″ do not need to be in close contact with each other. Also, the Ag nanoparticle layer 3 ′ and Au The nanoparticle layer 3 ″ may be two different kinds of metals. Further, the Ag nanoparticle layer 3 ′ and the Au nanoparticle layer 3 ″ may have a rod shape other than a spherical shape, a triangular shape, or other polygonal shapes.

  FIG. 8 is a sectional view showing a fifth embodiment of the localized plasmon resonance chip according to the present invention.

  In FIG. 8A, a gold (Au) nanoparticle layer 3 ″ a made of spherical particles having a spherical diameter of 10 nm to 200 nm and gold made of rod-like particles having a long side length of 10 nm to 200 nm are formed on the substrate 1. The (Au) nanoparticle layer 3 ″ b is randomly arranged.

  In FIG. 8B, holes 1a having a depth of 50 nm to 500 nm are nano-imprinted on the substrate 1 in FIG.

  In FIG. 8, since the Au nanoparticle layer 3 ″ a and the Au nanoparticle layer 3 ″ b are formed in a non-plate shape, that is, discretely, local plasmon resonance occurs.

  In FIGS. 8A and 8B, the Au nanoparticle layer 3 ″ a and the Au nanoparticle layer 3 ″ b cause surface plasmon resonance with light in the ultraviolet to near infrared region. In this case, since these nanoparticle layers have different particle shapes made of the same metal, that is, Au, as in the first, second, third, and fourth embodiments, the absorption spectrum has two absorption peak wavelengths. Or express two transmitted / reflected dip wavelengths in the transmitted / reflected light spectrum.

  In the fifth embodiment described above, the Au nanoparticle layer 3 ″ a and the Au nanoparticle layer 3 ″ b do not need to be in close contact with each other. The Au nanoparticle layer 3 ″ a and the Au nanoparticle layer 3 ″ b may be silver (Ag), copper (Cu), aluminum (Al), or the like other than gold. Furthermore, the Au nanoparticle layer 3 ″ a and the Au nanoparticle layer 3 ″ b may have any two different shapes such as a spherical shape, a rod shape, a triangular shape, and other polygonal shapes.

  In the first, second, third, and fourth embodiments described above, two different metals such as Au and Ag are used, but three or more different metals may be used. For example, a localized plasmon resonance chip obtained by adding a copper (Cu) nano thin film layer 6 having a thickness of 10 nm to 100 nm to the localized plasmon resonance chip shown in FIGS. Shown in A) and (B). In this case, three absorption peak wavelengths are expressed in the absorption spectrum, or three transmission / reflection dip wavelengths are expressed in the transmitted light / reflected light spectrum.

  The nanometer order in the present invention means a thickness of 10 nm to 100 nm in the case of a thin film layer, and in the case of particles, a sphere diameter, a length of a long side of a rod or a length of a triangle of 10 nm to 200 nm. means.

  It should be noted that the present invention can be applied to any modifications within the obvious range of the first to fifth embodiments described above.

  The localized plasmon resonance biosensor having the localized plasmon resonance chip according to the present invention can be used for security (explosives, narcotics) in addition to the above-described medical diagnosis, health check, food inspection, and the like. Further, in addition to the quantification of an antigen substance that is a target substance in an antigen-antibody reaction, it can be used for quantification of a specific substance in selective binding of DNA or the like.

1: Substrate 1a: Hole 2a: Au nano thin film layer 2b: Ag nano thin film layer 3: Dielectric nano particle layer 3 ′: Ag nano particle layer 3 ″: Au nano particle layer 4, 4 ′: Ag nano thin film layer 5, 5 ': Au nano thin film layer 6: Cu nano thin film layer 101: Light source 102: Collimator lens 103: Localized plasmon resonance chip 103a: Surface plasmon resonance unit 104: Measuring device 201: Light source 202: Collimator lens 203: Beam splitter 204: Localized plasmon resonance chip 204a: surface plasmon resonance unit 205: measuring device
S0: Light source spectrum
S1: Absorption spectrum
S2: Transmitted light / reflected light spectrum
L1, L2: Light

For example, even if the surface plasmon resonance portions 103a and 204a are the same metal, the thickness of the metal nano thin film layer, the particle size of the metal nano particle layer, the shape such as a spherical shape, a rod shape, and a triangular shape, and the aggregated state are As a result, the absorption spectrum or the transmitted / reflected light spectrum becomes a crushed mountain shape or a gentle valley shape, and the sensing accuracy decreases.

1 is a sectional view showing a first embodiment of a localized plasmon resonance chip according to the present invention. It is sectional drawing which shows the example of a change of FIG. It is sectional drawing which shows 2nd Embodiment of the localized plasmon resonance chip concerning this invention. It is sectional drawing which shows the example of a change of FIG. The localized plasmon resonance chip of FIG. 1 (A), (B), FIG. 2, FIG. 3, (A), (B) or FIG. 4 is applied to the localized plasmon resonance biosensor of FIG. 10 (or FIG. 11). It is a graph which shows the transmitted-light / reflected-light spectrum and absorption spectrum which are obtained with a measuring device when it does. It is sectional drawing which shows 3rd Embodiment of the localized plasmon resonance chip concerning this invention. It is sectional drawing which shows 4th Embodiment of the localized plasmon resonance chip concerning this invention. It is sectional drawing which shows 5th Embodiment of the localized plasmon resonance chip | tip concerning this invention. It is sectional drawing which shows the local plasmon resonance chip | tip formed from three or more different metals. It is a figure which shows the conventional transmission type | mold local plasmon resonance biosensor. It is a figure which shows the conventional reflection type localized plasmon resonance biosensor. 12 is a graph showing an absorption spectrum and a transmitted / reflected light spectrum obtained by the measuring apparatus of FIGS. 10 and 11.

In the first and second embodiments described above, the nano thin film layer 5 may be other than Au. However, in the case of Au, in order to prevent deterioration of other metals such as Ag, Cu, and Al as the outermost layer. It acts as a coating layer. The particles of the dielectric nanoparticle layer 3 and the Ag nanoparticle layer 3 ′ do not need to be completely in close contact with each other, and may be separated from 1 to 3 particles. Furthermore, the Ag nano thin film layer 2b, the Ag nano particle layer 3 ′, and the Ag nano thin film layer 4 may be other metals such as copper (Cu) and aluminum (Al). Furthermore, the dielectric nanoparticle layer 3 and the Ag nanoparticle layer 3 ′ may have a rod shape other than a spherical shape, a triangular shape, or other polygonal shapes.

Claims (14)

A substrate,
A non-planar non-planar first metal layer disposed on the substrate and comprising a first metal;
A localized plasmon resonance chip comprising: a second metal layer having a non-planar shape of nanometer order, which is disposed on the first metal layer and includes a second metal different from the first metal. The first and second metal layers comprise metal thin film layers,
The localized plasmon resonance chip according to claim 1, further comprising a dielectric particle layer disposed between the substrate and the first metal layer. And a third metal layer in a nanometer order, which is disposed between the substrate and the dielectric particle layer, and includes any one of the first and second metals.
The localized plasmon resonance chip according to claim 2, wherein the third metal layer comprises a metal thin film layer. The first metal layer is a metal particle layer;
The localized plasmon resonance chip according to claim 1, wherein the second metal layer includes a metal thin film layer. Furthermore, it is disposed between the substrate and the first metal layer, and comprises a third metal layer having a flat plate shape of nanometer order including any of the first and second metals,
The localized plasmon resonance chip according to claim 4, wherein the third metal layer is a metal thin film layer. The substrate is processed with irregularities at a depth of 50 to 500 nm,
2. The localized plasmon resonance chip according to claim 1, wherein the first and second metal layers include a metal thin film layer formed on a convex portion of the substrate.   The localized plasmon resonance chip according to claim 6, wherein the first and second metal layers further include a metal thin film layer formed on a concave portion of the substrate. The first metal is one of silver (Ag), copper (Cu) and aluminum (Al);
The localized plasmon resonance chip according to claim 1, wherein the second metal is gold (Au). A substrate,
First nanometer order metal particles randomly arranged on the substrate and comprising a second metal different from the first metal and comprising a second metal different from the first metal. Localized plasmon resonance chip.   The localized plasmon resonance chip according to claim 9, wherein the substrate is processed to be uneven at a depth of 50 to 500 nm. The first metal is one of silver (Ag), copper (Cu) and aluminum (Al);
The localized plasmon resonance chip according to claim 9, wherein the second metal is gold (Au). A substrate,
A first metal particle having a nanometer order including a certain metal, and a second metal particle having a nanometer order including the metal, and the shape of the first metal particle; A localized plasmon resonance chip in which the shape of the second metal particle is different.   The localized plasmon resonance chip according to claim 12, wherein the substrate is processed to be uneven. The localized plasmon resonance chip according to claim 12, wherein the metal is one of gold (Au), silver (Ag), copper (Cu), and aluminum (Al).

Images