TWI481857B - Sensor chip, sensor cartridge, and analysis apparatus - Google Patents

Description

Perceptron, sensor, and analysis device

The present invention relates to a sensor wafer, a sensor, and an analysis device.

Priority is claimed on Japanese Patent Application No. 2009-281480, filed on Dec. 11, 2009, and Japanese Patent Application No. 2010-192838, filed on Aug.

In recent years, the demand for sensors used in medical diagnosis and food inspection has increased, and it has been required to develop a sensor technology that is small and can be sensed at high speed. In order to cope with this demand, various types of perceptrons represented by electrochemical methods have been studied. In these sensors, attention has been paid to the use of sensors using SPR (Surface Plasmon Resonance) from the standpoint of being integrable, low-cost, and not selecting a measurement environment.

Here, the surface plasmon refers to a vibration mode of an electron wave coupled to light by a boundary condition inherent to the surface. As a method of exciting a surface plasmon, there is a method of engraving a diffraction grating on a metal surface to couple light with a plasma or a method of using an attenuation wave. For example, as a configuration using a sensor having SPR, it is known to include a total reflection type germanium and a metal film formed in contact with a target substance on the surface of the crucible. According to this configuration, the presence or absence of adhesion of the antigen in the antigen-antibody reaction and the presence or absence of adhesion of the target substance are detected.

Moreover, there is a surface type plasmonics on the metal surface, and on the other hand, a local type surface plasmon exists in the metal particles. It is well known that when a surface plasmon of a local type, that is, a surface plasmon which is locally present on the fine structure of the surface, is excited, a significantly enhanced electric field is caused.

Therefore, for the purpose of improving the sensitivity of the sensor, a perceptron using localized surface Plasmon Resonance (LSPR) using metal microparticles or a metal nanostructure has been proposed. For example, in the transparent substrate on which metal fine particles are fixed in a film shape on the surface, light is measured, and the absorbance of light transmitted through the metal fine particles is measured, thereby detecting metal fine particles. The change of the nearby medium to detect the adsorption or accumulation of the target substance.

However, in Patent Document 1, it is difficult to uniformly form the size (size and shape) of the metal fine particles, and it is difficult to regularly arrange the metal fine particles. If the size or arrangement of the metal particles cannot be controlled, the absorption or resonance wavelength due to resonance also varies. Thereby, the width of the absorbance spectrum is broadened, and the peak intensity is lowered. Therefore, there is a limit to the change in the signal obtained by detecting the change in the medium in the vicinity of the metal fine particles, and the sensitivity of the sensor is also increased. Therefore, in the use of the substance to determine the substance according to the absorbance spectrum, the sensitivity of the sensor is not sufficient.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a sensory wafer, a sensor, and an analysis device that can determine a target substance according to a Raman spectroscopic spectrum by realizing an improvement in sensitivity of a sensor.

In order to solve the above problems, the present invention adopts the following constitution.

According to a first aspect of the present invention, a sensing wafer includes: a substrate having a planar portion; and a diffraction grating comprising: periodically arranging at intervals of 100 nm or more and 1000 nm or less a plurality of first protrusions in a first direction parallel to the plane portion; a plurality of base portions constituting a base of the base material between the adjacent two first protrusions; and a surface formed on the surface of the plurality of first protrusions a plurality of second protrusions; and a plurality of third protrusions formed on the plurality of base portions, the diffraction grating having a surface formed of a metal and formed on the planar portion and disposed with a target substance.

According to the first aspect of the present invention, the near-field enhanced by the surface plasmon resonance is excited by the surface of the same shape by the first protrusion, and the metal fine structure formed by the second protrusion and the third protrusion can be further formed. It exhibits enhanced surface enhanced Raman Scattering (SERS). Specifically, when light is incident on a surface on which a plurality of first protrusions, a plurality of second protrusions, and a plurality of third protrusions are formed, a vibration mode inherent to the surface caused by the plurality of first protrusions is generated (surface Electro-paste). As a result, the free electrons resonate with the vibration of the light, and the vibration of the electromagnetic waves is excited by the vibration of the free electrons. The vibration of the electromagnetic wave affects the vibration of the free electrons, and thus becomes a system of vibration coupling between the two, that is, a so-called surface plasmon polarized phonon (SPP: Surface Plasmon Polariton). Thereby, local surface plasmon resonance (LSPR: Localized Surface Plasmon Resonance) is excited in the vicinity of the plurality of second protrusions and the plurality of third protrusions. In this configuration, the distance between the adjacent two second projections and the distance between the adjacent two third projections are small, so that an extremely strong electric field is generated in the vicinity of the contact. Moreover, when 1 to several target substances are adsorbed at their joints, SERS is generated therefrom. Therefore, a steep SERS spectrum inherent to the target substance can be obtained. Thus, a perceptual wafer that achieves an increase in sensor sensitivity and that can be used to determine a target substance based on SERS spectroscopy can be provided. Further, the position of the resonance peak can be adjusted to an arbitrary wavelength by appropriately changing the period or height of the first projection, the height of the second projection, and the height of the third projection. Therefore, the wavelength of the light to be irradiated when the target substance is determined can be appropriately selected, thereby expanding the range of the measurement range.

In the sensor wafer of the present invention, the plurality of first protrusions are preferably periodically arranged in a second direction that intersects the first direction and is parallel to the plane portion. Thereby, the sensing can be performed under the plasmon resonance condition in which the first protrusion is formed to be periodically formed in a direction parallel to the plane portion of the substrate (the first direction). Thus, a perceptual wafer that achieves an increase in sensor sensitivity and that can be used to determine a target substance based on SERS spectroscopy can be provided. Further, in addition to the period of the first projection in the first direction, the period in the second direction may be appropriately changed. Therefore, the wavelength of the light to be irradiated when the target substance is determined can be appropriately selected, thereby expanding the range of the measurement range.

In the sensor wafer of the present invention, the plurality of second projections and the plurality of third projections are preferably periodically arranged in a third direction parallel to the planar portion. Thereby, the period of the second protrusion and the third protrusion can be appropriately changed. Therefore, the wavelength of the light to be irradiated when the target substance is determined can be appropriately selected, thereby expanding the range of the measurement range.

In the sensor wafer of the present invention, the plurality of second projections and the plurality of third projections are preferably periodically arranged in a fourth direction that intersects the third direction and is parallel to the planar portion. Thereby, the sensing can be performed under the plasmon resonance condition in which the second projection and the third projection are formed only in a direction parallel to the plane portion of the base material (the third direction). Thus, a perceptual wafer that achieves an increase in sensor sensitivity and that can be used to determine a target substance based on SERS spectroscopy can be provided. Further, in addition to the period of the third projection and the third projection in the third direction, the period in the fourth direction may be appropriately changed. Therefore, the wavelength of the light to be irradiated when the target substance is determined can be appropriately selected, thereby expanding the range of the measurement range.

In the sensor wafer of the present invention, the plurality of second protrusions and the plurality of third protrusions preferably include fine particles. Thus, a sensory wafer that achieves an improvement in sensor sensitivity and can determine a target substance based on SERS spectra can be provided.

In the sensor wafer of the present invention, the metal constituting the surface of the diffraction grating is preferably gold or silver. As a result, since gold or silver exhibits characteristics of SPP, LSPR, and SERS, SPP, LSPR, and SERS are easily expressed, and the target substance can be detected with high sensitivity.

According to a second aspect of the present invention, a sensor device includes: the sensor wafer described above; a transport unit that transports the target substance to a surface of the sensor wafer; and a placement unit that mounts the sensor wafer; The body is configured to receive the sensing wafer, the transporting portion, and the mounting portion, and an illumination window disposed at a position of the frame opposite the surface of the sensing wafer.

According to the second aspect of the present invention, since the sensor 匣 includes the above-described sensor wafer, the Raman scattered light can be selectively split to detect a target molecule. Therefore, it is possible to provide a sensor that determines the sensitivity of the sensor and determines the target substance based on the SERS spectrum.

According to a third aspect of the present invention, an analysis apparatus includes: the sensor wafer described above; a light source that emits light to the sensing wafer; and a photodetector that detects light obtained by the sensing wafer.

According to the third aspect of the present invention, since the analysis device includes the above-described sensor wafer, the Raman scattered light can be selectively split to detect a target molecule. Therefore, it is possible to provide an analysis device that can achieve an improvement in sensor sensitivity and can determine a target substance based on SERS spectra.

According to a fourth aspect of the invention, a sensor wafer includes: a substrate having a flat portion; and a diffraction grating formed by overlapping the first uneven shape, the second uneven shape, and the third uneven shape a composite pattern on the planar portion, and having a surface formed of a metal and having a target substance disposed thereon; the first uneven shape is a plurality of first convex shapes, and is periodically arranged at a period of 100 nm or more and 1000 nm or less The second uneven shape is formed by a plurality of second convex shapes which are periodically arranged on the plurality of first convex shapes at a period shorter than a period of the first uneven shape, and the third unevenness is formed. The shape is a plurality of third convex shapes, and is formed in a base portion which is periodically arranged between the adjacent two first convex shapes at a period shorter than a period of the first uneven shape.

According to the fourth aspect of the present invention, the near-field enhanced by the surface plasmon resonance is excited by the surface of the same shape by the first convex shape, and can be expressed by the metal fine structure formed by the second convex shape. Surface Enhanced Raman Scattering (SERS) with high enhancement. Specifically, when light is incident on the surface on which the first uneven shape and the second uneven shape are formed, a vibration mode (surface plasmon) inherent to the surface due to the first uneven shape is generated. As a result, the free electrons resonate with the vibration of the light, and the vibration of the electromagnetic waves is excited by the vibration of the free electrons. The vibration of the electromagnetic wave affects the vibration of the free electrons, and thus becomes a system of vibration coupling between the two, that is, a so-called surface plasmon polarized phonon (SPP: Surface Plasmon Polariton). Thereby, local surface plasmon resonance (LSPR: Localized Surface Plasmon Resonance) is excited in the vicinity of the second uneven shape. In this structure, the distance between the adjacent two second convex shapes is small, so that an extremely strong electric field is generated in the vicinity of the contact. Moreover, when 1 to several target substances are adsorbed at their joints, SERS is generated therefrom. Therefore, a steep SERS spectrum inherent to the target substance can be obtained. Thus, a perceptual wafer that achieves an increase in sensor sensitivity and that can be used to determine a target substance based on SERS spectroscopy can be provided. Further, the position of the resonance peak can be adjusted to an arbitrary wavelength by appropriately changing the period of the first convex shape, the height, the height of the second convex shape, and the height of the third convex shape. Therefore, the wavelength of the light to be irradiated when the target substance is determined can be appropriately selected, thereby expanding the range of the measurement range.

In the sensor wafer of the present invention, the plurality of first convex shapes are preferably periodically arranged in a first direction parallel to the planar portion, and are periodically arranged to intersect the first direction and the plane The second direction parallel to the department. Thereby, the sensing can be performed under the plasmon resonance condition in which the first convex shape is formed only periodically in a direction parallel to the planar portion of the substrate (the first direction). Thus, a perceptual wafer that achieves an increase in sensor sensitivity and that can be used to determine a target substance based on SERS spectroscopy can be provided. Further, in addition to the period of the first convex shape in the first direction, the period in the second direction may be appropriately changed. Therefore, the wavelength of the light to be irradiated when the target substance is determined can be appropriately selected, thereby expanding the range of the measurement range.

In the sensor wafer of the present invention, the plurality of second convex shapes and the plurality of third convex shapes are preferably periodically arranged in a third direction parallel to the planar portion. Thereby, the period of the second convex shape and the third convex shape can be appropriately changed. Therefore, the wavelength of the light to be irradiated when the target substance is determined can be appropriately selected, thereby expanding the range of the measurement range.

In the sensor wafer of the present invention, the plurality of second convex shapes and the plurality of third convex shapes are preferably periodically arranged in a fourth direction that intersects with the third direction and is parallel to the planar portion. Thereby, the sensing can be performed under the plasmon resonance condition in which the second convex shape and the third convex shape are formed only in a direction parallel to the planar portion of the base material (the third direction). Thus, a perceptual wafer that achieves an increase in sensor sensitivity and that can be used to determine a target substance based on SERS spectroscopy can be provided. Further, in addition to the period of the third convex shape and the third convex third direction, the period in the fourth direction may be appropriately changed. Therefore, the wavelength of the light to be irradiated when the target substance is determined can be appropriately selected, thereby expanding the range of the measurement range.

In the sensor wafer of the present invention, the plurality of second convex shapes and the plurality of third convex shapes preferably include fine particles. Thus, a sensory wafer that achieves an improvement in sensor sensitivity and can determine a target substance based on SERS spectra can be provided.

In the sensor wafer of the present invention, the metal constituting the surface of the diffraction grating is preferably gold or silver. As a result, since gold or silver exhibits characteristics of SPP, LSPR, and SERS, SPP, LSPR, and SERS are easily expressed, and the target substance can be detected with high sensitivity.

According to a fifth aspect of the present invention, a sensor device includes: the sensor wafer described above; a transport unit that transports the target substance to a surface of the sensor wafer; and a placement unit that mounts the sensor wafer; The body is configured to receive the sensing wafer, the transporting portion, and the mounting portion, and an illumination window disposed at a position of the frame opposite the surface of the sensing wafer.

According to the fifth aspect of the present invention, since the sensor 匣 includes the above-described sensor wafer, the Raman scattered light can be selectively split to detect a target molecule. Therefore, it is possible to provide a sensor that determines the sensitivity of the sensor and determines the target substance based on the SERS spectrum.

According to a sixth aspect of the invention, there is provided an analysis apparatus comprising: the sensor wafer described above; a light source that emits light to the sensing wafer; and a photodetector that detects light obtained by the sensing wafer.

According to the sixth aspect of the present invention, since the analysis device includes the above-described sensor wafer, the Raman scattered light can be selectively split to detect a target molecule. Therefore, it is possible to provide an analysis device that can achieve an improvement in sensor sensitivity and can determine a target substance based on SERS spectra.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. This embodiment is an embodiment of the present invention, and is not intended to limit the present invention, and may be arbitrarily changed within the scope of the technical idea of the present invention. Further, in the following drawings, in order to facilitate understanding of each configuration, the actual structure differs from the scale or number of each structure.

1A and 1B are schematic views showing a schematic configuration of a sensor wafer according to an embodiment of the present invention. 1A is a perspective view showing a schematic configuration of a sensor wafer, and FIG. 1B is a schematic cross-sectional view showing a sensor wafer. In FIG. 1B, the symbol P1 is the period of the first protrusion (first convex shape), the symbol P2 is the period of the second protrusion (second convex shape) and the third protrusion (third convex shape), and the symbol T1 is the first protrusion. The height (the depth of the groove), the symbol T2 is the height of the second protrusion (the depth of the groove), the symbol T3 is the height of the third protrusion (the depth of the groove), the symbol W1 is the width of the first protrusion, and the symbol W2 is adjacent. The distance between the two first protrusions.

15 and FIG. 16 are schematic diagrams showing a schematic configuration of a sensor wafer according to an embodiment of the present invention corresponding to FIG. 1B. In Fig. 15 and Fig. 16, the symbol P1 is the period of the first projection (first convex shape), and the symbol P2 is the period of the second projection (second convex shape) and the third projection (third convex shape), and the symbol T1 is The height of the first projection (depth of the groove), the symbol T2 is the height of the second projection (the depth of the groove), the symbol T3 is the height of the third projection (the depth of the groove), and the symbol W1 is the width of the first projection, symbol W2. It is the distance between two adjacent first protrusions.

The sensing wafer 1 is configured to dispose a target substance on a diffraction grating 9 formed on a substrate 10 containing metal, and utilize localized surface plasmon resonance (LSPR: Localized Surface Plasmon Resonance) and surface enhanced Raman scattering (SERS: Surface Enhanced Raman Scattering) to detect the above target substances.

The sensor wafer 1 is for arranging a target substance on the diffraction grating 9 formed on the substrate 10, and detecting the target substance by LSPR and SERS. The diffraction grating 9 includes a plurality of first protrusions 11 which are arranged in a first direction parallel to a plane portion of the substrate 10 at a period P1 of 100 nm or more and 1000 nm or less; a plurality of base portions 10a which are adjacent to each other A base of the base material 10 is formed between the two first projections 11; a plurality of second projections 12 are formed on the respective upper surfaces 11a of the plurality of first projections 11; and a plurality of third projections 13 are formed. On each of the plurality of base portions 10a. The diffraction grating 9 has a surface formed of a metal and is formed on the flat portion 10s of the substrate 10.

In other words, the diffraction grating 9 has a composite pattern in which the first uneven shape, the second uneven shape, and the third uneven shape are superposed in a direction perpendicular to the plane portion of the substrate 10, and has a surface formed of a metal; The uneven shape is formed by arranging a plurality of first convex shapes (first protrusions) 11 in a period P1 of 100 nm or more and 1000 nm or less, and the second uneven shape is a plurality of second convex shapes (second protrusions) 12 The period P2 which is shorter than the period of the first concavo-convex shape is periodically arranged on each of the plurality of first convex shapes 11, and the third concavo-convex shape is a plurality of third convex shapes and is smaller than the first concavo-convex shape The period P2 of which the period is short is arranged in the base portion between the adjacent two first convex shapes 11.

In addition, the "diffraction grating" as used herein means a structure in which a plurality of irregularities (plurality of protrusions) are periodically arranged.

Here, the term "planar portion" as used herein means the upper surface portion of the substrate. In other words, the "planar portion" refers to a surface portion on one side of a substrate on which a target substance is disposed. Further, the composite pattern formed by overlapping the first uneven shape, the second uneven shape, and the third uneven shape is formed at least on the upper surface portion of the substrate. Further, the surface portion on the other side of the other substrate, that is, the shape of the lower surface portion of the substrate is not particularly limited. However, in consideration of a processing step or the like to the planar portion (upper surface portion) of the substrate, it is preferable that the lower surface portion of the substrate be a plane parallel to the base portion of the planar portion and flat.

As a configuration of the diffraction grating 9, as shown in FIG. 1B, the base material 10, the first convex shape 11 and the second convex shape 12 each include a metal. In addition, as shown in FIG. 15, the base material 10 and the 1st convex shape 11 are formed with the insulating member of glass or resin, and the whole of the exposed part of the insulating member is covered with the metal film, and the metal film is formed with metal. The second convex shape 12 includes a third convex shape 13 of metal. Furthermore, as shown in FIG. 16 , the entire structure of the base material 10 , the first convex shape 11 , the second convex shape 12 , and the third convex shape 13 is formed by an insulating member, and the entire exposed portion of the insulating member is covered with a metal film. . That is, the diffraction grating 9 has a base portion 10a of the base material 10, at least the surfaces of the first convex shape 11, the second convex shape 12, and the third convex shape 13 which are formed of metal.

The substrate 10 has a structure in which a metal film of 150 nm or more is formed on a glass substrate, for example. This metal film is formed into the first protrusions 11, the second protrusions 12, and the third protrusions 13 by a manufacturing process to be described later. Further, in the present embodiment, the substrate 10 is formed of a metal film on the glass substrate, but the substrate is not limited thereto. For example, a substrate on which a metal film is formed on a quartz substrate or a sapphire substrate may be used as the substrate 10. Further, a plate containing a metal may be used as the substrate.

The first protrusions 11 are formed on the flat portion 10s of the substrate 10 with a specific height T1. The first protrusions 11 are arranged in a direction (first direction) parallel to the plane portion 10s of the substrate 10 at a period P1 shorter than the wavelength of the light. The period P1 is the sum of the width of the first protrusion 11 in the first direction (the horizontal direction in FIG. 1B) and the distance between the adjacent two first protrusions 11. Further, the first projections 11 have a convex shape in a cross-sectional rectangular shape, and the plurality of first projections 11 are formed in a line of view and a gap (striped shape).

Preferably, in the first protrusions 11, for example, the period P1 is set to a range of 100 to 1000 nm, and the height T1 is set to a range of 10 to 100 nm. Thereby, the first protrusions 11 can function as a structure for expressing the LSPR.

The width W1 of the first protrusions 11 in the first direction is larger than the distance W2 between the adjacent two first protrusions 11 (W1 > W2). Thereby, the space filling rate of the first protrusions 11 that excite the LSPR increases.

The second projections 12 have a specific height T2 and two or more of the upper surfaces 11a of the plurality of first projections 11 are formed. The third projections 13 have a specific height T3 and are formed in two or more of the plurality of base portions 10a.

The second protrusions 12 and the third protrusions 13 are arranged in a direction (third direction) parallel to the plane portion 10s of the substrate 10 at a period P2 shorter than the wavelength of light. The period P2 is a total of the width of the second projection 12 in the third direction (the horizontal direction in FIG. 1B) and the distance between the adjacent two second projections 12 (the third projection 13 in the third direction is single) The width is the sum of the distances between the two adjacent third protrusions 13). Thereby, the period P2 of the second projections 12 (third projections 13) is much shorter than the period P1 of the first projections 11.

It is preferable that the second protrusions 12 and the third protrusions 13 have a period P2 set to a value smaller than 500 nm, and heights T2 and T3 set to a value smaller than 200 nm. Thereby, the second projections 12 and the third projections 13 can function as a structure for exhibiting SERS.

In the present embodiment, the arrangement direction (first direction) of the first projections 11 is the same as the arrangement direction (third direction) of the second projections 12 and the third projections 13. Further, the second projections 12 and the third projections 13 are formed in a convex shape in a cross-sectional rectangular shape, and the plurality of second projections 12 and the plurality of third projections 13 are formed in a line of view and a gap (striped shape).

As the metal of the surface of the diffraction grating 9, for example, gold (Au), silver (Ag), copper (Cu), aluminum (Al), or alloys thereof are used. In the present embodiment, Au or Ag having characteristics of SPP, LSPR, and SERS is used. Thereby, SPP, LSPR, and SERS are easily expressed, and the target substance can be detected with high sensitivity.

Here, LSPR and SERS will be described. When light is incident on the surface of the sensor wafer 1, that is, the surface on which the plurality of first protrusions 11, the plurality of second protrusions 12, and the plurality of third protrusions 13 are formed, a surface generated by the plurality of first protrusions 11 is generated. Inherent vibration mode (surface plasmonics). However, the direction in which the incident light is polarized is orthogonal to the groove direction of the first projections 11 in advance. As a result, the vibration of the electromagnetic wave is excited by the vibration of the free electrons. Since the vibration of the electromagnetic wave affects the vibration of the free electrons, it becomes a system of vibration coupling between the two, that is, a so-called surface plasmon polarized phonon (SPP: Surface Plasmon Polariton). Further, in the present embodiment, the incident angle of light is substantially perpendicular to the surface of the sensing wafer 1, but the angle of incidence is not limited to the angle (vertical) if the condition of the SPP is excited.

The SPP propagates along the surface of the sensor wafer 1, specifically along the interface between the air and the second protrusions 12 and the third protrusions 13, and excites a strong local electric field in the vicinity of the second protrusions 12 and the third protrusions 13. The coupling of SPP is sensitive to the wavelength of light, and its coupling efficiency is high. In this way, the incident light from the air propagation mode excites local surface plasmon resonance (LSPR) via the SPP. Moreover, according to the relationship between LSPR and Raman scattered light, Surface Enhanced Raman Scattering (SERS) can be utilized.

2A and 2B are views showing a Raman scattering spectrometry. Fig. 2A shows the principle of Raman scattering spectrometry. Fig. 2B shows a Raman spectrum (relationship between Raman shift and Raman scattering intensity). In Fig. 2A, the symbol L represents incident light (light of a single wavelength), the symbol Ram represents Raman scattered light, the symbol Ray represents Rayleigh scattered light, and the symbol X represents a target molecule (target substance). In Fig. 2B, the horizontal axis represents the Raman shift. Further, the Raman shift refers to the difference between the vibration frequency of the Raman scattered light Ram and the vibration frequency of the incident light L, which takes a value peculiar to the structure of the target molecule X.

As shown in FIG. 2A, when a single-wavelength light L is irradiated to the target molecule X, light having a wavelength different from the wavelength of the incident light (Raman scattered light Ram) is generated in the scattered light. The energy difference between the Raman scattered light Ram and the incident light L corresponds to the energy level of the target molecule X or the energy of the rotational energy level or the electronic energy level. The target molecule X has a unique vibrational energy corresponding to its structure, and thus the target molecule X can be determined by using light L of a single wavelength.

For example, when the vibration energy of the incident light L is set to V1, the vibration energy consumed by the target molecule X is V2, and when the vibration energy of the Raman scattered light Ram is V3, V3 = V1 - V2. Furthermore, most of the incident light L also has the same amount of energy as before the collision after colliding with the target molecule X. This sinusoidal scattered light is referred to as Rayleigh scattered light Ray. For example, when the vibration energy of the Rayleigh scattered light Ray is V4, it becomes V4=V1.

According to the Raman spectrum shown in FIG. 2B, when the scattering intensity (spectral peak) of the Raman scattered light Ram is compared with the scattering intensity of the Rayleigh scattered light Ray, it is understood that the Raman scattered light Ram is weak. Thus, the Raman scattering spectrometry is a measurement method in which the recognition ability of the target molecule X is excellent but the sensitivity of the target molecule X is itself low. Therefore, in the present embodiment, in order to achieve high sensitivity, a surface-enhanced Raman scattering spectrometry (SERS spectrometry) is used (see FIG. 4).

3A and 3B are views showing a mechanism for electric field enhancement by LSPR. Fig. 3A is a schematic view showing when light is incident on the metal nanoparticles. Fig. 3B is a view showing an LSPR enhanced electric field. In Fig. 3A, reference numeral 100 is a light source, reference numeral 101 is a metal nanoparticle, and symbol 102 is light emitted from a light source. Symbol 103 in Fig. 3B is a surface local electric field.

As shown in FIG. 3A, when the light 102 is incident on the metal nanoparticles 101, the free electrons resonate with the vibration of the light 102. Furthermore, the diameter of the metal nanoparticles is smaller than the wavelength of the incident light. For example, the wavelength of light is 400 to 800 nm, and the diameter of metal nanoparticles is 10 to 100 nm. Further, Ag and Au were used as the metal nanoparticles.

As a result, a strong surface local electric field 103 is excited in the vicinity of the metal nanoparticle 101 in accordance with the resonance vibration of the free electrons (see FIG. 3B). As such, the LSPR can be excited by the incident light 102 on the metal nanoparticle 101.

Fig. 4 is a view showing the SERS spectroscopy. In Fig. 4, reference numeral 200 is a substrate, symbol 201 is a metal nanostructure, symbol 202 is a selective adsorption film, symbol 203 is an enhanced electric field, symbol 204 is a target molecule, symbol 211 is incident laser light, and symbol 212 is Raman scattered light. , symbol 213 is Rayleigh scattered light. Further, the adsorption film 202 is selected to adsorb the target molecule 204.

As shown in FIG. 4, when the laser light 211 is incident on the metal nanostructure 201, the free electrons resonate with the vibration of the laser light 211. The metal nanostructure 201 is smaller in size than the incident laser light. As a result, a strong surface local electric field is excited in the vicinity of the metal nanostructure 201 along with the resonance vibration of the free electrons. This inspires the LSPR. Moreover, when the distance between adjacent metal nanostructures 201 becomes small, a strong enhanced electric field 203 is generated near the junction. When 1 to several target molecules 204 are adsorbed at their junctions, SERS is generated therefrom. In this respect, it is also confirmed based on the result of the enhanced electric field generated between the two silver nanoparticles which are calculated using the EDTD (Finite Difference Time Domain) method. Therefore, the Raman scattered light can be selectively split to detect the target molecule with high sensitivity.

In the present embodiment, as described above, the first protrusions 11 are arranged in a direction parallel to the plane portion of the substrate 10 at a period P1 shorter than the wavelength of light, and the LSPR is excited. Further, in the present embodiment, the second projections 12 are formed on the upper surface 11a of the first projections 11, and the second projections 13 are formed in the base portion 10a to form the SERS. Specifically, based on the principle that Raman scattered light is generated when a single wavelength of light is irradiated to a target molecule, the target molecule is disposed between the adjacent two second protrusions 12 (third protrusions 13) and is connected thereto. An enhanced magnetic field is generated near the point, thereby generating a SERS. Thereby, compared with the Raman scattering spectroscopy, the SERS spectroscopy which can detect a target substance with high sensitivity can be used.

Fig. 5 is a graph showing the intensity of reflected light of the first projection unit. In Fig. 5, the horizontal axis represents the wavelength of light, and the vertical axis represents the intensity of reflected light. The height T1 of the first protrusion 11 was taken as a parameter (T1 = 20 nm, 30 nm, 40 nm). Further, in the configuration of the sensor wafer 1 of the present embodiment, the value obtained by subtracting the intensity of the reflected light from the incident light intensity (1.0) is the absorbance.

The light is incident perpendicularly to the first protrusions 11. The polarization direction of the light is a TM (Transverse Electric) polarization orthogonal to the polarization of the electric field component parallel to the groove (the direction in which the region between the adjacent first protrusions 11 extends). The period of the first protrusions 11 is 580 nm, and the resonance peak of the reflected light intensity exists at a wavelength of around 630 nm. This resonance peak is derived from SPP, and when the height T1 of the first protrusion 11 is increased, the resonance peak shifts to the long wavelength side (long wavelength region). It is understood that when the height T1 of the first protrusions 11 is 30 nm, the intensity of reflected light becomes the strongest, and the strongest absorption is exhibited.

Figure 6 is a graph showing the dispersion curve of SPP. In Fig. 6, the symbol C1 is a dispersion curve of SPP (exemplified by the value on the boundary surface between air and Au), and the symbol C2 is an open line. The period of the first protrusions 11 is 580 nm. The position of the lattice vector of the first protrusion 11 is shown on the horizontal axis (corresponding to 2 π/P on the horizontal axis of Fig. 6). If the line is extended upward from this position, it will intersect the dispersion curve of the SPP. The wavelength corresponding to the intersection can be obtained according to the following formula.

In the formula (1), P1 is the period of the first protrusions 11, E1 is the complex dielectric constant of air, and E2 is the complex dielectric constant of Au. If P1, E1, and E2 are substituted into the formula (1), λ = 620 nm is obtained (corresponding to w0 on the vertical axis of Fig. 6).

As the height T1 of the first protrusions 11 increases, the imaginary part of the wave number of the SPP becomes large. Thereby, the real part of the wave number of the SPP becomes small, and the intersection of the line extending from the position of the lattice vector and the dispersion curve of the SPP moves from the upper right direction to the lower left side. That is, the resonance peak shifts toward the long wavelength side.

Fig. 7 is a view showing a structure in which the first projections 11 and the second projections 12 (third projections 13) are superimposed, that is, a graph showing the intensity of reflected light of the sensor wafer 1 according to an embodiment of the present invention. In Fig. 7, the horizontal axis represents the wavelength of light and the vertical axis represents the intensity of reflected light. The height T2 of the second protrusions 12 (the height T3 of the third protrusions 13) was taken as a parameter (T2 (T3) = 0 nm, 40 nm, 80 nm). Furthermore, the graph of the parameter T2=0 of the figure is the same as the graph of the parameter T1=30 of FIG.

The light system is incident perpendicularly to the first protrusions 11. Furthermore, the height T1 of the first protrusions 11 is 30 nm. Further, the period P2 of the second projections 12 (third projections 13) is 97 nm. The resonance peak of the reflected light intensity exists near the wavelength of 730 nm. Compared with the spectrum of Patent Document 1, the width of the resonance peak is narrowed and becomes steep. The resonance peak is derived from the SPP, and the position of the resonance peak is shifted toward the long wavelength side by overlapping the second protrusion 12 (third protrusion 13) in the first protrusion 11. At this time, the steepness and gradient of the resonance peak are maintained. When the height T2 of the second protrusions 12 (the height of the third protrusions 13) is 40 nm, a strong local electric field can be excited toward the vicinity of the surface of the second protrusions 12 by irradiating light having a wavelength of 730 nm. Further, by appropriately changing the periods P1 and P2 and the heights T1 and T2 (T3) of the first projections 11 and the second projections 12 (third projections 13), the position of the resonance peak can be adjusted to an arbitrary wavelength.

FIG. 8 is a view schematically showing a case where the first convex shape 11 is not formed on the flat portion 10s of the base material 10, and only the second projections 12 (third projections 13) are formed on the flat surface portion 10s of the base material 10. That is, a view of the sensor wafer 2 in the case where a plurality of second protrusions 12 (third protrusions 13) are formed on the flat portion 10s of the substrate 10.

FIG. 9 is a graph showing the intensity of reflected light of the wafer 2 in the case where a plurality of second projections 12 (third projections 13) are formed on the flat portion 10s of the substrate 10. In Fig. 9, the horizontal axis represents the wavelength of light, and the vertical axis represents the intensity of reflected light. The height T2 of the second protrusions 12 (the height T3 of the third protrusions 13) was taken as a parameter (T2 (T3) = 0 nm, 40 nm, 80 nm). The TM polarized light is incident perpendicularly to the second protrusions 12 (third protrusions 13). Even if the figure is observed, it is confirmed that the resonance peak having a large intensity of reflected light is not obtained. According to the results, it is understood that when the first protrusions 11 are present, that is, when the SPP is not passed, the light energy can hardly be coupled to the second protrusions 12 (the third protrusions 13).

10A to 10F are views showing a manufacturing process of a sensor wafer. First, the Au film 31 is formed on the glass substrate 30 by vapor deposition or sputtering. Then, the resist 32 is applied to the Au film 31 by spin coating or the like (see FIG. 10A). At this time, the film thickness Ta of the Au film 31 is thickly formed to such an extent that the incident light does not permeate (for example, 100 nm).

Then, a resist pattern 32a having a period Pa of 580 nm is formed by a method such as imprint (see FIG. 10B). Next, the Au film 31 is etched to a specific depth D1 (for example, 30 nm) by dry etching using the resist pattern 32a as a mask. Thereafter, the first protrusion 31a is formed by removing the resist pattern 32a (see FIG. 10C).

Next, the resist 33 is applied by spin coating or the like on the Au film 31 on which the first convex shape 31a is formed (see FIG. 10D). Then, a resist pattern 33a having a period Pb of 97 nm is formed by a method such as imprint (see FIG. 10E). Next, using the resist pattern 33a as a mask, the Au film 31 on which the first protrusions 31a are formed is etched by a specific depth D2 (for example, 40 nm) by dry etching. Thereafter, the second protrusion 31b and the third protrusion 31c are formed by removing the resist pattern 33a (see FIG. 10F). The sensor wafer 3 of one embodiment of the present invention can be manufactured by the above steps.

According to the sensor wafer 1 of the embodiment of the present invention, the metal fine structure formed by the first protrusions 11 can excite the LSPR via the SPP, and the metal fine structure formed by the second protrusions 12 and the third protrusions 13 can be formed. Showing SERS. Specifically, when light is incident on the surface on which the plurality of first protrusions 11 , the plurality of second protrusions 12 , and the plurality of third protrusions 13 are formed, vibration inherent to the surface caused by the plurality of first protrusions 11 occurs. Modal (surface plasmonics). As a result, the free electrons resonate with the vibration of the light to excite the SPP, thereby exciting a strong surface local electric field in the vicinity of the second protrusions 12 and the third protrusions 13. Thereby, the LSPR is excited. In this configuration, the distance between the two adjacent second protrusions 12 (third protrusions 13) is small, so that an extremely strong electric field is generated in the vicinity of the contact. Moreover, when 1 to several target substances are adsorbed at their joints, SERS is generated therefrom. Therefore, it is possible to obtain a strength characteristic in which the width of the reflected light intensity spectrum is narrowed and the resonance peak is steep, so that the sensor sensitivity can be improved. Therefore, it is possible to provide a sensor wafer 1 for realizing the sensitivity of the sensor and determining the target substance based on the SERS spectrum. Further, by appropriately changing the period P1 or the height T1 of the first projection 11, the height T2 of the second projection 12, and the height T3 of the third projection 13, the position of the resonance peak can be matched with an arbitrary wavelength. Therefore, the wavelength of the light to be irradiated when the target substance is determined can be appropriately selected, thereby expanding the range of the measurement range.

In addition, since the second projections 12 and the third projections 13 are periodically arranged in the third direction parallel to the plane portion of the base material 10, the period of the second projections 12 and the third projections 13 can be appropriately changed. P2. Therefore, the wavelength of the light to be irradiated when the target substance is determined can be appropriately selected, thereby expanding the range of the measurement range.

Further, according to this configuration, since gold or silver is used as the metal on the surface of the diffraction grating 9, SPP, LSPR, and SERS are easily expressed, and the target substance can be detected with high sensitivity.

Further, according to this configuration, the duty ratio of the first projections 11 satisfies the relationship of W1>W2, and the space filling ratio of the first projections 11 that excite the LSPR increases, so that the relationship of W1<W2 can be satisfied. Sensing is performed under a wider plasmon resonance condition. Moreover, the energy of the light irradiated when the target substance is determined can be effectively utilized.

In the present embodiment, the first protrusion 11 is arranged in a direction (first direction) parallel to the plane portion of the substrate 10 at a period P1 shorter than the wavelength of the light, but the configuration is not limited thereto. . The sensor wafer 4 having a structure different from that of the first protrusion 11 of the present embodiment will be described with reference to Fig. 11 .

FIG. 11 is a perspective view showing a schematic configuration of the sensor wafer 4 having the first projections 41 different from the first projections 11. Further, in the figure, the illustration of the second projection and the third projection is omitted for convenience.

As shown in FIG. 11, the 1st protrusion 41 is formed in the planar part 40s of the base material 40. The first protrusions 41 are arranged in a direction (first direction) parallel to the plane portion of the substrate 40 at a period P3 shorter than the wavelength of light. Further, the first projections 41 are arranged in a second direction orthogonal to the first direction and parallel to the planar portion of the base material 40 at a period P4 shorter than the wavelength of light. Further, the second direction is not limited to a direction orthogonal to the first direction and parallel to the plane portion of the base material 40, and may be a direction intersecting the first direction and parallel to the plane portion of the base material 40.

According to this configuration, the SPP can be excited under a resonance condition in which the first projection is formed only in a direction parallel to the plane portion of the base material 10 (the first direction). Therefore, it is possible to provide a sensor wafer 4 for realizing the sensitivity of the sensor and determining the target substance based on the SERS spectrum. Further, in addition to the period P3 in the first direction of the first projection, the period P4 in the second direction may be appropriately changed. Therefore, the wavelength of the light to be irradiated when the target substance is determined can be appropriately selected, thereby expanding the range of the measurement range.

In the present embodiment, the second projections 12 and the third projections 13 are arranged in a direction (third direction) parallel to the plane portion of the base material 10 at a period P2 shorter than the wavelength of the light. Specifically, The arrangement direction of the first protrusions 11 (first direction) and the arrangement direction of the second protrusions 12 and the third protrusions 13 (third direction) are the same direction, but the invention is not limited thereto. The sensor wafers 5, 6, 7, and 8 having a structure different from the second protrusions 12 and the third protrusions 13 of the present embodiment will be described with reference to Figs. 12A to 13B.

FIG. 12A and FIG. 12B are perspective views showing a schematic configuration of a sensing wafer having second projections and third projections different from the second projections 12 and the third projections 13 described above. 12A shows the sensor wafer 5 having the second protrusions 52 and the third protrusions 53, and FIG. 12B shows the sensor wafer 6 having the second protrusions 62 and the third protrusions 63.

As shown in FIG. 12A, the second projections 52 are formed in two or more on the upper surface 51a of each of the plurality of first projections 51. The third projections 53 are formed in two or more of the plurality of base portions 50a. In the figure, the angle in which the arrangement direction (first direction) of the first protrusions 51 and the arrangement direction (third direction) of the second protrusions 53 and the third protrusions 53 intersect each other is 45 degrees as an example.

As shown in FIG. 12B, the second projections 62 are formed in two or more on the upper surface 61a of each of the plurality of first projections 61. The third projections 63 are formed in two or more of the plurality of base portions 60a. In the figure, the angle in which the arrangement direction (first direction) of the first protrusions 61 and the arrangement direction (third direction) of the second protrusions 63 and the third protrusions 63 intersect each other is 90 degrees as an example.

In this configuration, it is also possible to provide a sensory wafer that can improve the sensitivity of the sensor and determine the target substance based on the SERS spectrum.

As shown in FIG. 13A, the second projections 72 are formed in two or more upper surfaces 71a of a plurality of first projections (not shown). The third projections 73 are formed in two or more of the plurality of base portions 70a. Further, the second projections 72 and the third projections 73 are periodically arranged in a fourth direction that intersects with the third direction and is parallel to the planar portion of the base material. In the figure, as an example, the second projections 72 and the third projections 73 are configured to have a circular shape in plan view. Further, the second projections 72 and the third projections 73 may be arranged in a random manner without being periodic. Further, it is preferable that the interval between the second projections 72 and the interval between the third projections 73 are set in the range of zero to several tens of nm.

As shown in FIG. 13B, the second projections 82 are formed in two or more on the upper surface 81a of each of the plurality of first projections (not shown). The third projections 83 are formed in two or more of the plurality of base portions 80a. Further, the second projections 82 and the third projections 83 are periodically arranged in a fourth direction that intersects with the third direction and is parallel to the planar portion of the base material. In the figure, as an example, the second projections 82 and the third projections 83 are configured to have an elliptical shape in plan view. Further, the second projections 82 and the third projections 83 may be arranged in a random manner without being periodic. Further, it is preferable that the interval between the second projections 82 and the interval between the third projections 83 are set in the range of zero to several tens of nm.

According to this configuration, the density of the portion where the electric field is enhanced can be increased as compared with the case where the second projection and the third projection are formed only in the direction parallel to the plane portion of the base material (the third direction). Thus, a perceptual wafer that achieves an increase in sensor sensitivity and that can be used to determine a target substance based on SERS spectroscopy can be provided. Further, in addition to the period of the third projection and the third projection in the third direction, the period in the fourth direction may be appropriately changed. Therefore, the wavelength of the light to be irradiated when the target substance is determined can be appropriately selected, thereby expanding the range of the measurement range.

In the present embodiment, the second protrusions and the third protrusions are formed by patterning the Au film formed on the upper surface of the glass substrate, but the invention is not limited thereto. For example, the second protrusions and the third protrusions may be fine particles. In this configuration, it is also possible to provide a sensory wafer that can improve the sensitivity of the sensor and determine the target substance based on the SERS spectrum.

Further, in the present embodiment, the same metal (gold or silver) is used as the metal contained in the base material, the metal contained in the first projection, the metal contained in the second projection, and the metal contained in the third projection. It is not limited to this. For example, the metal contained in the substrate may be gold, the metal contained in the first protrusion may be silver, and the metal contained in the second protrusion (third protrusion) may be an alloy of gold and silver, and a different metal may be used in combination ( Gold, silver, copper, aluminum, or alloys of these).

(analytical device)

Fig. 14 is a schematic view showing an example of an analysis device having a sensor wafer according to an embodiment of the present invention. In addition, the arrow of FIG. 14 shows the conveyance direction of the target substance (not shown).

As shown in FIG. 14, the analysis device 1000 includes a sensor wafer 1001, a light source 1002, a photodetector 1003, a collimator lens 1004, a polarization control element 1005, a beam splitter 1006, an objective lens 1007, an objective lens 1008, and a transport unit 1010. The light source 1002 and the photodetector 1003 are electrically connected to a control device (not shown) via wiring.

Light source 1002 generates laser light that excites SPP, LSPR, and SERS. The laser light irradiated from the light source 1002 is parallel light to the collimator lens 1004, passes through the polarization control element 1005, is guided by the beam splitter 1006 in the direction of the sensing wafer 1001, and is collected by the objective lens 1007 and then incident on the sensing wafer 1001. At this time, a target substance (not shown) is placed on the surface of the sensor wafer 1001 (for example, a surface on which a metal nanostructure or a detection substance selection mechanism is formed). In addition, the target substance is introduced into the transport unit 1010 from the carry-in port 1011 by driving a fan (not shown), and is discharged from the discharge port 1012 to the outside of the transport unit 1010. Also, the size of the metallic nanostructure is smaller than the wavelength of the laser light.

When laser light is incident on the metal nanostructure, the free electrons resonate with the vibration of the laser light, thereby exciting a strong surface local electric field in the vicinity of the metal nanostructure, thereby exciting the LSPR. Moreover, when the distance between the adjacent metal nanostructures becomes small, an extremely strong electric field is generated in the vicinity of the joint, and if one or several target substances are adsorbed at the joint, SERS is generated therefrom.

The light (Raman scattered light or Rayleigh scattered light) obtained by sensing the wafer 1001 passes through the objective lens 1007, is guided by the beam splitter 1006 in the direction of the photodetector 1003, and is incident on the objective lens 1007 and then incident on the photodetector 1003. . Moreover, spectral information is obtained by spectral decomposition by the photodetector 1003.

According to this configuration, since the analysis device 1000 has the above-described sensor wafer of one embodiment of the present invention, it is possible to selectively split the Raman scattered light to detect the target molecule. Therefore, it is possible to provide an analysis device 1000 that can achieve an improvement in sensor sensitivity and can determine a target substance based on SERS spectra.

The analysis device 1000 includes a perceptron 匣 1100. The sensor device 1100 includes a sensor wafer 1001, a transport unit 1010 that transports a target substance to the surface of the sensor wafer 1001, a mounting unit 1101 on which the sensor wafer 1001 is placed, and a housing 1110 that houses the sensor. An illumination window 1111 is disposed at a position opposite to the sensing wafer 1001 of the housing 1110. The laser light irradiated from the light source 1002 is irradiated onto the surface of the sensing wafer 1001 through the irradiation window 1111. The sensor 匣 1100 is located above the analysis device 1000 and is configured to be detachable from the body portion of the analysis device 1000.

According to this configuration, since the sensing wafer according to the embodiment of the present invention is provided, it is possible to selectively split the Raman scattered light to detect the target molecule. Thus, a perceptron 匣 1100 that achieves an increase in sensor sensitivity and can determine a target substance from the SERS spectrum can be provided.

The analysis device according to an embodiment of the present invention can be widely applied to a sensing device used in the detection of drugs or explosives, medical or health diagnosis, and food inspection. Further, it can be used as a binding force sensor for detecting the presence or absence of adsorption of an antigen such as an antigen in an antigen-antibody reaction.

1, 2, 3, 4, 5, 6, 7, 8, 1001. . . Perceptual chip

9. . . Diffraction grating

10, 40, 50. . . Substrate

10a, 50a, 60a, 70a, 80a. . . Base portion

10s, 40s, 50s. . . Plane department

11, 31a, 41, 51, 61. . . First protrusion (first convex shape)

11a, 51a, 61a, 71a, 81a. . . Upper surface of the first protrusion 11

12, 31b, 52, 62, 72, 82. . . Second protrusion (second convex shape)

13, 31c, 53, 63, 73, 83. . . Third protrusion

30. . . glass substrate

31. . . Au film

32, 33. . . Resist

32a, 33a. . . Resist pattern

100, 1002. . . light source

101. . . Metal nanoparticle

102. . . Light emitted from a light source

103. . . Surface local electric field

200. . . Substrate

201. . . Metal nanostructure

202. . . Adsorption membrane

203. . . Enhanced electric field

204. . . Target molecule

211. . . Incident laser light

212, Ram. . . Raman scattered light

213, Ray. . . Rayleigh scattered light

1000. . . Analytical device

1003. . . Photodetector

1004. . . Collimating lens

1005. . . Polarized light control element

1006. . . Beam splitter

1007, 1008. . . Objective lens

1010. . . Transport department

1011. . . Move in

1012. . . Discharge

1100. . . Sensor 匣

1110. . . framework

1111. . . Illumination window

C1. . . SPP dispersion curve

C2. . . Bright line

D1, D2. . . Etching depth

L. . . Incident light

P1. . . Period of the first protrusion (first convex shape)

P2. . . Cycle of the second projection (second convex shape) and the third projection (third convex shape)

P3, P4. . . a shorter period of light wavelength

Pa, Pb. . . cycle

T1. . . Height of the first protrusion

T2. . . Height of the second protrusion

T3. . . Height of the third protrusion

W1. . . Width of the first protrusion

W2. . . Distance between two adjacent first protrusions

X. . . Target molecule

1A and 1B are schematic views showing a schematic configuration of a sensor wafer according to an embodiment of the present invention;

2A and 2B are views showing a Raman scattering spectrometry;

3A and 3B are views showing a mechanism for electric field enhancement by LSPR;

Figure 4 is a diagram showing the SERS spectroscopy;

Figure 5 is a graph showing the intensity of reflected light of the first protrusion unit;

Figure 6 is a graph showing the dispersion curve of SPP;

Figure 7 is a graph showing the intensity of reflected light of a sensor wafer according to an embodiment of the present invention;

Figure 8 is a schematic view showing a sensing wafer in which a plurality of second protrusions are formed on a planar portion of a substrate;

Figure 9 is a graph showing the intensity of reflected light of the sensor wafer of Figure 8;

10A to 10F are diagrams showing a manufacturing process of a sensor wafer;

Fig. 11 is a schematic block diagram showing a modification of the sensing wafer having the first projection;

12A and 12B are schematic configuration diagrams showing a modification of the sensing wafer having the second projection;

13A and 13B are schematic configuration diagrams showing a modification of the sensing wafer having the second projection;

Figure 14 is a schematic view showing an example of an analysis device;

Figure 15 is a schematic view showing a schematic configuration of a sensor wafer according to an embodiment of the present invention;

Fig. 16 is a schematic view showing a schematic configuration of a sensor wafer according to an embodiment of the present invention.

1. . . Perceptual chip

9. . . Diffraction grating

10. . . Substrate

10a. . . Base portion

10s. . . Plane department

11. . . First protrusion

11a. . . Upper surface of the first protrusion 11

12. . . Second protrusion

13. . . Third protrusion

P1. . . Period of the first protrusion (first convex shape)

P2. . . Cycle of the second projection (second convex shape) and the third projection (third convex shape)

T1. . . Height of the first protrusion

T2. . . Height of the second protrusion

T3. . . Height of the third protrusion

W1. . . Width of the first protrusion

W2. . . Distance between two adjacent first protrusions

Claims (16)

A sensing wafer comprising: a substrate having a planar portion; and a diffraction grating having a plurality of periodically arranged in a first direction parallel to the planar portion at a period of 100 nm or more and 1000 nm or less a plurality of first protrusions; a plurality of base portions constituting a base of the base material between the adjacent two first protrusions; a plurality of second protrusions formed on a surface of the plurality of first protrusions; and a plurality of third protrusions of the plurality of base portions, the diffraction grating having a surface formed of a metal, and being formed on the planar portion and disposed with a target substance; and the plurality of second protrusions are periodically arranged Further, the height of the second protrusion is 40 nm or more and less than 200 nm. The sensor wafer of claim 1, wherein the plurality of first protrusions are periodically arranged in a second direction that intersects the first direction and is parallel to the plane portion. The sensor wafer of claim 1, wherein the plurality of second protrusions and the plurality of third protrusions are periodically arranged in a third direction parallel to the plane portion. The sensor wafer of claim 3, wherein the plurality of second protrusions and the plurality of third protrusions are periodically arranged in a fourth direction that intersects the third direction and is parallel to the plane portion. The sensor wafer of claim 1, wherein the plurality of second protrusions and the plurality of third protrusions comprise fine particles. The sensor wafer of claim 1, wherein the metal constituting the surface of the diffraction grating is gold or silver. A sensor device comprising: the sensor wafer of claim 1; a transport unit that transports the target substance to a surface of the sensor wafer; a placement unit that mounts the sensor wafer; and a housing that accommodates the perception The wafer, the transfer portion, and the mounting portion, and the illumination window are disposed at a position of the frame opposite to the surface of the sensing wafer. An analysis apparatus comprising: the sensor wafer of claim 1; a light source that illuminates the sensor wafer; and a light detector that detects light obtained by the sensor wafer. A sensor wafer comprising: a substrate having a flat portion; and a diffraction grating having a composite pattern formed on the planar portion by overlapping the first uneven shape, the second uneven shape, and the third uneven shape, And having a surface formed of a metal and having a target substance; the first uneven shape is a plurality of first convex shapes, and is periodically arranged at a period of 100 nm or more and 1000 nm or less, and the second uneven shape is plural The second convex shape is periodically arranged on the plurality of first convex shapes at a period shorter than a period of the first uneven shape. The third uneven shape is a plurality of third convex shapes, and is periodically arranged in a period shorter than a period of the first uneven shape, and is periodically arranged in a base portion between the adjacent two first convex shapes. The height of the second convex shape is 40 nm or more and less than 200 nm. The sensor wafer of claim 9, wherein the plurality of first convex shapes are periodically arranged in a first direction parallel to the planar portion, and are periodically arranged to intersect the first direction and the planar portion Parallel to the second direction. The sensor wafer of claim 9, wherein the plurality of second convex shapes and the plurality of third convex shapes are periodically arranged in a third direction parallel to the planar portion. The sensor wafer of claim 11, wherein the plurality of second convex shapes and the plurality of third convex shapes are periodically arranged in a fourth direction that intersects the third direction and is parallel to the planar portion. The sensor wafer of claim 9, wherein the plurality of second convex shapes and the plurality of third convex shapes comprise fine particles. The sensor wafer of claim 9, wherein the metal constituting the surface of the diffraction grating is gold or silver. A sensor device comprising: a sensor wafer according to claim 9; a transport unit that transports the target substance to a surface of the sensor wafer; a placement unit that mounts the sensor wafer; and a housing that accommodates the perception Wafer, the above-mentioned transport unit, and the above And an illumination window disposed at a position of the frame opposite the surface of the sensing wafer. An analysis apparatus comprising: a sensor wafer as claimed in claim 9; a light source that illuminates the sensor wafer; and a light detector that detects light obtained by the sensor wafer.