JP2010156581A - Multiphoton excitation device, and method for manufacturing same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve energy utilization efficiency by reducing energy disappearance caused by metal extinction generated in a compound by multiphoton excitation gold, in a multiphoton excitation device utilizing localized plasmon. <P>SOLUTION: This multiphoton excitation device including a substrate 13 including a dielectric layer 12 having a plurality of fine holes 15 opened at least on one surface, and a plurality of fine metal bodies 14 formed in the fine holes 15, is constituted so as to include a plurality of multiphoton excitation complex compounds expressed by a general formula D-L-A bonded to the surface of the fine metal bodies 14. In this case, D is a multiphoton excitation portion having a π-electron conjugate system capable of generating multiphoton excitation by absorbing light energy of irradiation light P, and A is a bonding portion bonding to the fine metal body 14, and L is a connection group for connecting the multiphoton excitation portion D to the bonding portion A. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a multiphoton excitation device using a π-electron conjugated material that can absorb light energy of irradiation light and generate multiphoton excitation, and a manufacturing method thereof.

Usually, an organic compound absorbs one photon energy corresponding to its excitation energy, and does not absorb one photon energy when one photon energy is less than the excitation energy. However, when the intensity of light is very strong (photon density is very high), there are two-photon excited compounds that generate an excited state by the sum of two photon energies. By utilizing this property, an excited state can be created only in a region where the photon density is high, or light having a shorter wavelength (higher energy) than the wavelength of irradiated light can be extracted. However, since the two-photon excitation efficiency is usually very small, a two-photon excitation compound having a higher two-photon excitation efficiency has been demanded. The two-photon absorption cross-section indicating the ease of two-photon absorption is usually very small and about 1 GM (Goepper Mayer: 1GM = 1 × 10 ⁻⁵⁰ cm ⁴ · s · molecule-1 · photon-1). However, two-photon excitation compounds having a relatively large two-photon absorption cross section of about several hundred to several thousand GM have been found in recent years. Examples of compounds having a relatively large two-photon absorption cross-sectional area are described or cited in Patent Document 1 and Non-Patent Document 1, for example.

Further, for example, Patent Document 2 teaches a method for efficiently generating two-photon excitation using an electric field enhancement effect by a localized plasmon. Since the region where this electric field enhancement effect reaches is limited to the vicinity of the metal body due to the light confinement effect by the localized plasmon, the two-photon excitation compound is fixed to the metal body via a linking group, thereby generating two-photon excitation. ing.
JP 2008-203573 A JP 2008-170418 A Yoshio Inagaki, Masanori Akiba, Laser Research vol.31, 392-396 (2003)

  However, when a metal body exists in the vicinity of a multi-photon excitation compound such as a two-photon excitation compound (a compound that absorbs two or more photon energies to form an excited state), energy transfer from the multi-photon excitation compound to the metal body Is a problem of so-called metal quenching, in which energy in the multiphoton excited compound is lost. When metal quenching occurs, even if multi-photon excitation can be efficiently generated due to the electric field enhancement effect, the energy in the multi-photon excitation compound is deprived by the metal body, resulting in a decrease in energy use efficiency.

  The present invention has been made in view of the above problems, and provides a multiphoton excitation device and a method for manufacturing the same that prevent metal quenching and can efficiently use energy generated in the multiphoton excitation compound. It is intended to do.

In order to solve the above problems, a multiphoton excitation device according to the present invention is:
A substrate comprising a dielectric layer having a plurality of micropores open on at least one surface;
A plurality of filling portions filled in the micropores and protruding portions formed on the filling portion so as to protrude from the surface of the dielectric layer and having a diameter capable of inducing localized plasmons due to irradiation light. A multiphoton excitation device comprising a fine metal body,
It has a plurality of multiphoton excited composite compounds represented by the following general formula (I) bonded to the surface of the protruding portion.
Formula (I): D-LA
Here, in the general formula (I), D represents a multiphoton excitation part having a π-electron conjugated system that can absorb the light energy of the irradiation light and cause multiphoton excitation, and A represents a coupling part that is coupled to the protrusion. L represents a linking group that links the multiphoton excitation part and the bond part.

  Here, the “diameter” capable of inducing localized plasmon means the maximum length of the protrusion in the direction parallel to the surface of the dielectric layer that is so small that localized plasmon is generated due to light irradiation. Shall.

  A “multiphoton excited composite compound” is a combination of a multiphoton excitation part that is a residue of a multiphoton excitation compound, a binding part that binds to a metal body, and a linking group that connects the multiphoton excitation part and the binding part. Means a compound formed by

  “Multi-photon excitation” means that n photons having energy 1 / n of the energy (excitation energy) required to make a transition from the ground state to a certain excited state are absorbed simultaneously, and a transition is made to the excited state. It means that. Here, n is a natural number of 2 or more. For example, when two photons having half the excitation energy are simultaneously absorbed and excited, this is called two-photon excitation. In this case, the wavelength of light necessary for two-photon excitation is twice the wavelength of light necessary for normal excitation.

  Furthermore, in the multiphoton excitation device according to the present invention, the bonding portion is preferably a sulfur-containing bonding portion that is bonded to the protruding portion by a sulfur atom. The linking group preferably has a main chain composed of an aliphatic chain.

And it is preferable that a coupling group contains the structure represented by the following general formula (II).
Formula (II):-(G _a -T _b ) _c-
Here, in the general formula (II), G represents —C (═O) —, —O—, —NR ₁ —, — (N-containing heterocycle) —, —S—, —SO—, —SO ₂ —. , -P (= O) <, or a divalent or trivalent partial linking group comprising these bonds, T represents an aliphatic group, a, b and c are each an integer of 0 to 2, 1 to An integer of 100 and an integer of 1 to 100 are represented. Here, R ₁ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms. When c is an integer of 2 or more, G and T and a and b may be the same or different for each c.

  The multiphoton excitation part is preferably a residue derived from a compound represented by the following general formula (III) or general formula (IV).

General formula (III):

General formula (IV):

Here, in general formula (III) or (IV), Y represents a methine group, a methylene group or an amine. These methine groups and methylene groups are at least one selected from the group consisting of a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and an aryl group having 6 to 18 carbon atoms. Each may be substituted with two substituents. i represents an integer of 1 to 4; R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms. R ₁₀₃ , R ₁₀₄ and R ₁₀₅ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms. j represents an integer of 0 to 3. R ₁₀₆ and R ₁₀₇ each independently represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. R ₁₀₈ , R ₁₀₉ , R ₁₁₀ and R ₁₁₁ are each independently a hydrogen atom, a halogen atom, a cyano group, an amino group, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. , An acyl group having 1 to 18 carbon atoms, an acylamino group having 1 to 18 carbon atoms, a carbamoyl group having 1 to 18 carbon atoms, a sulfonamide group having 1 to 18 carbon atoms, and a sulfamoyl group having 1 to 18 carbon atoms Group, an alkylamino group having 1 to 18 carbon atoms, or an arylamino group having 6 to 18 carbon atoms. Here, for R _{108 to} R ₁₁₁ , the groups listed above may be linked to each other to form a ring. _Further, any one of R 101 _{to R 111} may be at least one organic functional groups necessary to form the linking group. Furthermore, the alkyl group and alkoxy group described in this paragraph may have a partially unsaturated bond, be substituted with a hetero atom, or be branched. The aryl group includes a polycyclic aromatic hydrocarbon group.

  Furthermore, the multiphoton excitation part preferably emits light having a wavelength shorter than the wavelength of the irradiation light due to the multiphoton excitation.

And the multiphoton excitation part works as an energy donor that donates at least part of the energy obtained by the multiphoton excitation,
It has an energy acceptor coupled to the surface of the protrusion and accepts energy donated from an energy donor, and is configured such that a photochemical complex is formed by the energy donor and the energy acceptor. it can.

Furthermore, a method for producing a multiphoton excitation device according to the present invention includes:
A substrate including a dielectric layer having a plurality of micropores opened on at least one surface, a filling portion filled in the micropores, and formed on the filling portion so as to protrude from the surface of the dielectric layer and irradiated Prepare a plurality of fine metal bodies consisting of protrusions having diameters that can induce localized plasmons due to light,
A plurality of multiphoton excited composite compounds represented by the above general formula (I) are bonded to the surface of the protrusion.

And in the manufacturing method of the multiphoton excitation device according to the present invention,
The bond is a sulfur-containing bond containing a sulfur atom,
It is preferable to couple the linking group and the protruding portion with a sulfur atom.

In addition, the multiphoton excitation part acts as an energy donor that provides at least a part of the energy obtained by the multiphoton excitation,
An energy acceptor that accepts energy donated from the energy donor can be connected to the protrusion to form a photochemical complex composed of the energy donor and the energy acceptor.

  Furthermore, it is preferable to form the dielectric layer by subjecting the material to be anodized to anodization and forming a plurality of fine holes having openings on the anodized surface subjected to the anodization.

  The multiphoton excitation device and the manufacturing method thereof according to the present invention provide a multiphoton excitation part capable of generating multiphoton excitation via a linking group in the bonding of a multiphoton excitation composite compound to a fine metal body. It is comprised so that it may connect. Therefore, since the multiphoton excitation part and the fine metal body can be electronically isolated, the influence of metal quenching can be reduced. Thereby, in the multiphoton excitation device, it is possible to efficiently use the energy generated in the multiphoton excitation part in the multiphoton excitation composite compound.

  Hereinafter, although an embodiment of the present invention is described using a drawing, the present invention is not limited to this.

"Compound compound of multiphoton excitation part and linking group"
First, the compound Cd of the multiphoton excitation part, the linking group, and the bonding part in the present invention (hereinafter, multiphoton excitation composite compound) will be described. As shown in FIG. 1A, the multiphoton excited composite compound Cd is used by being bonded to a plurality of fine metal bodies 14 respectively formed in a plurality of fine holes 15 by a connecting portion. FIG. 1B is a schematic cross-sectional view showing a state in which the multiphoton excited composite compound Cd is bonded to the protruding portion 14 b of the fine metal body 14.

The multiphoton excited composite compound Cd includes a multiphoton excitation part D having a π-electron conjugated system capable of absorbing the light energy of the irradiation light P and causing multiphoton excitation, a coupling part A coupled to the protrusion 14b, and a multiphoton. It consists of a linking group L that connects the excitation part D and the bond part A, and is represented by the following general formula (I).
Formula (I): D-LA
Hereinafter, details of the multiphoton excitation part D, the linking group L, and the bonding part A will be described.

  First, the multiphoton excitation part D will be described. D in FIG. 1B represents a multiphoton excitation part composed of a multiphoton excitation compound residue having a multiphoton absorption cross section of 100 GM or more at a wavelength longer than 400 nm. In the multi-photon excitation device according to the present invention, the operation principle of the multi-photon excitation unit D that functions in response to only the near-field light (light with high photon density) enhanced by the electric field is as follows. Here, although two-photon excitation is specifically described as an example of multiphoton excitation, the present invention is not limited to this.

Usually, an organic compound absorbs one photon energy corresponding to its excitation energy, and does not absorb one photon energy when one photon energy is less than the excitation energy. However, when the intensity of light is very strong (photon density is very high), there are two-photon excited compounds that generate an excited state by the sum of two photon energies. The two-photon absorption cross-section indicating the ease of two-photon excitation is usually very small, about 1 GM (Goepper Mayer: 1 GM = 1 × 10 ⁻⁵⁰ cm ⁴ · s · molecule-1 · photon-1). Also, a substance having a relatively large two-photon absorption cross section of about several hundred to several thousand GM has been found. When such a substance is used, even light in a wavelength region having no light absorption band can be efficiently generated by two-photon excitation by irradiating light with very strong intensity such as a high-power laser.

  For example, a two-photon excitation compound that exhibits an absorption maximum wavelength of 1 photon at 400 nm and no absorption band at 800 nm is irradiated with a high-power laser with a wavelength of 800 nm, which is close to the excited state that occurs when 400 nm light is irradiated. An excited state can be created. If this two-photon excitation compound emits fluorescence of, for example, 430 nm when excited by light of 400 nm, fluorescence of 430 nm can be generated even when absorbing light of 800 nm. Furthermore, if a compound that absorbs light at 430 nm and emits fluorescence at 460 nm coexists, irradiation with high-power laser at 800 nm can generate fluorescence at 460 nm.

  In the present invention, a state in which the photon density is high is formed by near-field light whose electric field is enhanced by localized plasmons. Near-field light is light that is generated only in a region that is approximately the diameter of the protruding portion where localized plasmons are generated. Therefore, by using this near-field light, it is possible to excite only the two-photon excitation compound existing in the vicinity of the protrusion.

  In order for two-photon excitation to occur efficiently enough to meet the object of the present invention, the two-photon absorption cross section is preferably 100 GM or more, more preferably 1,000 GM or more, when expressed in units of GM for convenience. Particularly preferred is 100,000 GM to 1,000,000,000 GM. The two-photon absorption cross section can be measured by the fluorescence method or the Z-scan method described in the following non-patent document. The fluorescence method is described in C. Xu and W. W. Webb, Journal of The Optical Society of America, B, 13, 481 (1996). Regarding the Z-scan method, K. Kamada, K. Matsumoto, A. Yoshino, K. Ohta, Journal of The Optical Society of America, B, 20, 529 (2003), P. Audebert, K. Kamada, K. Matsunaga, K. Ohta, Chemical Physics Letters, 367, 62 (2003).

  Further, the two-photon absorption wavelength region preferably has a longer wave than 400 nm, and more preferably 500 to 1100 nm. It is preferable that the multiphoton excitation part D emits light having a wavelength shorter than the wavelength of irradiation light due to multiphoton excitation. In such a case, the multiphoton excitation device can be used as an optical element or a wavelength conversion element.

  Examples of the two-photon excitation compound having a two-photon absorption cross-section at a wavelength of longer than 400 nm of 100 GM or more include known light absorbers, for example, those described in the literature listed in the above [Background Art] section. It is done. Specifically, for example, chalcone compounds, dibenzylacetone compounds, merocyanine dyes, thiopyrylium dyes, pyrylium dyes, sialkylaminostilbene compounds, acridinium dyes, xanthene dyes, thiazene dyes, cyanine dyes, squalium dyes, Examples include xanthene dyes, triphenylmethane dyes, and thioxanthone.

  Other examples include polynuclear aromatic compounds such as anthracene, phenanthrene, and pyrene, polynuclear heteroaromatic compounds such as acridine, carbazole, and phenothiazine, and derivatives thereof. And the residue guide | induced from these compounds becomes the multiphoton excitation part D.

  Furthermore, a lissamine / rhodamine B sulfonyl chloride isomer mixture, which is a kind of xanthene dye as shown in the following chemical formula 3, is also preferable. Here, X is Cl or OH.

  Also, quadrupole type compounds (chemical formulas 4 and 5), dipole type (donor / acceptor type) compounds (chemical formulas 6, 7, 8 and 9), and linked compounds (chemical formulas 10 and 11) as shown below. A compound having a cross-conjugated system is particularly preferable (Non-patent Document 1). Here, the cross-conjugated system refers to a structure in which conjugated multiple bonds are branched in three directions.

  Moreover, it is also preferable that the multiphoton excitation part D is a residue derived from a dipolar compound represented by the following general formula (III) or a cross-conjugated compound represented by the general formula (IV).

General formula (III):

General formula (IV):

Here, in general formula (III) or (IV), Y represents a methine group, a methylene group or an amine. These methine groups and methylene groups are at least one selected from the group consisting of a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and an aryl group having 6 to 18 carbon atoms. Each may be substituted with two substituents. i represents an integer of 1 to 4; R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms. R ₁₀₃ , R ₁₀₄ and R ₁₀₅ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms. j represents an integer of 0 to 3. R ₁₀₆ and R ₁₀₇ each independently represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. R ₁₀₈ , R ₁₀₉ , R ₁₁₀ and R ₁₁₁ are each independently a hydrogen atom, a halogen atom, a cyano group, an amino group, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. , An acyl group having 1 to 18 carbon atoms, an acylamino group having 1 to 18 carbon atoms, a carbamoyl group having 1 to 18 carbon atoms, a sulfonamide group having 1 to 18 carbon atoms, and a sulfamoyl group having 1 to 18 carbon atoms Group, an alkylamino group having 1 to 18 carbon atoms, or an arylamino group having 6 to 18 carbon atoms. Here, for R _{108 to} R ₁₁₁ , the groups listed above may be linked to each other to form a ring. In addition, any one of R _{101 to} R ₁₁₁ has at least one functional group necessary for forming the linking group. Furthermore, the alkyl group and alkoxy group described in this paragraph may have a partially unsaturated bond, be substituted with a hetero atom, or be branched. The aryl group includes a polycyclic aromatic hydrocarbon group.

Preferred as Y is an unsubstituted methylene group (—CH ₂ —), —NH—, or —NR— (wherein R is an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms). , An acyl group having 2 to 18 carbon atoms, an alkylsulfonyl group having 1 to 18 carbon atoms, and an arylsulfonyl group having 6 to 18 carbon atoms). A thing preferable as R _{< 101>} , R _<102 > is a hydrogen atom or a C1-C6 alkyl group.

R ₁₀₃ , R ₁₀₄ and R ₁₀₅ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Two of R _{103, R 104} and _{R 105} may be bonded to form a ring. Particularly preferred is a hydrogen atom.

R ₁₀₆ and R ₁₀₇ are preferably alkyl groups having 1 to 6 carbon atoms, and may have a substituent. Preferred examples of the substituent include a hydroxyl group, an amino group, an acylamino group, a sulfonylamino group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxyl group, and a sulfonic acid group. R ₁₀₆ and R ₁₀₇ are particularly preferably an unsubstituted alkyl group having 1 to 4 carbon atoms or an alkyl group substituted with a hydroxy group.

Preferred as R ₁₀₈ , R ₁₀₉ , R ₁₁₀ and R ₁₁₁ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which are linked to each other or R ₁₀₆ or R ₁₀₇ to form a ring. May be. Particularly preferred is a hydrogen atom or an alkyl group linked to at least one of R ₁₀₆ or R ₁₀₇ to form a 5- to 6-membered ring.

The multiphoton excitation part D preferably has a hydrophilic group (for example, —OH, —COOH, —SO ₃ H, etc.), and particularly preferably —SO ₃ H. As a result, the hydrophilic group interacts with the surrounding solvent (especially a solvent having a high dielectric constant such as water) to prevent the linking group from bending and the multiphoton excitation part from contacting the fine metal body. be able to.

  Tables 1 and 2 below show specific examples of the two-photon absorption compounds represented by the general formulas (III) and (IV), respectively. However, the present invention is not limited to these. In the following table, Me represents a methyl group, and nPr represents an n-propyl group.

  As mentioned above, the example of the multiphoton excitation compound used as the group of the residue which comprises the multiphoton excitation part D was shown, However, A particularly preferable aspect is a xanthene dye as shown in the chemical formula 3 and the general formula (IV). It is a cross-conjugated compound represented.

  Next, the linking group will be described. The linking group L is a linking group for linking the multiphoton excitation part D and the coupling part A, and is used to electronically isolate the multiphoton excitation part D and the protruding part 14b (fine metal body 14). It is a linking group. Therefore, the linking group L does not include a conjugated multiple bond that is a π-conjugated system, that is, a bond in a molecular structure in which electrons are delocalized by the interaction of π orbitals in which unsaturated bonds and single bonds are alternately linked. It is preferable.

  The linking group L preferably has a main chain composed of an aliphatic chain. Thereby, it becomes possible to isolate the multiphoton excitation part D and the protrusion part 14b (fine metal body 14) more electronically. Here, the side chain may have a double bond or an unsaturated cyclic structure as long as the problem of the present invention can be solved.

  The linking group is a linking group containing at least one bond selected from the group consisting of a methylene bond, an ester bond, an amide bond, a sulfonamide bond, an ether bond, and a thioether bond so as not to form a conjugated multiple bond. preferable. Moreover, the coupling group which combines these bonds 2 or more may be sufficient. As a result, the atomic group of the multiphoton excitation part D and the protrusion 14b are not directly bonded by a covalent bond, and are not bonded by a conjugated bond. It is possible to form a state in which the portion 14b is electronically isolated by the linking group L and has a predetermined distance.

Or it is preferable that a coupling group contains the structure represented by the following general formula (II).
Formula (II):-(G _a -T _b ) _c-
Here, in the general formula (II), G represents —C (═O) —, —O—, —NR ₁ —, — (N-containing heterocycle) —, —S—, —SO—, —SO ₂ —. , -P (= O) <, or a divalent or trivalent partial linking group comprising these bonds. Here, R ₁ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms. T represents an aliphatic group. The aliphatic group has a linear, branched or cyclic structure and preferably has 1 to 200 carbon atoms, preferably 1 to 24 carbon atoms, and particularly preferably 2 to 18 carbon atoms. A, b, and c represent an integer of 0 to 2, an integer of 1 to 100, and an integer of 1 to 100, respectively. When c is an integer of 2 or more, G and T and a and b may be the same or different for each c. C is preferably 1 to 10, particularly preferably 1 or 2. Here, it is needless to say that the linking group represented by the general formula (II) preferably does not contain a conjugated multiple bond.

  By using the linking group as described above, (1) the multiphoton excitation part D and the coupling part A can be electrically insulated, and the multiphoton excitation state of the multiphoton excitation part D is deactivated. (2) It is possible to easily procure raw materials suitable for adjusting the distance between the multiphoton excitation part D and the coupling part A. (3) Multiphoton excitation part D and the linking group L, as well as raw materials with high reactivity can be used in the bond formation of the linking group L and the linking part A, so that the multiphoton excitation part D, the linking group can be easily and inexpensively without using an expensive noble metal catalyst. The effect that it becomes possible to synthesize | combine connection of L and the coupling | bond part A is acquired.

  Preferred examples of the linking group include an ester bond represented by the following formula (a) or (b), an amide bond represented by the following formulas (c) to (f), and a sulfone represented by the following formula (g). Examples include an amide bond, an ether bond, a thioether bond, and an amino bond. Here, the structure shown below may be reversed left and right.

  Here, in formulas (c) to (g), each R independently represents a hydrogen atom, an alkyl group, or an aryl group.

  Next, the coupling portion will be described. The coupling part A is for coupling to the projecting part 14b (fine metal body 14) and fixing the multiphoton excited composite compound Cd to the projecting part 14b.

The bonding portion A preferably has a sulfur-containing bonding portion that is bonded to the protruding portion 14b by a sulfur atom so that the bonding portion A can be easily bonded to the protruding portion 14b of the fine metal body 14 exposed on the substrate 13. . Thereby, the coupling group L and the protruding portion 14b can be bonded in a self-organized manner by the interaction between the sulfur atom contained in the sulfur-containing bonding portion and the protruding portion 14b which is a metal body. Here, the bonding portion is not limited to this as long as it has the same self-organization property as the sulfur atom with respect to the metal body. Such a bond having self-organization includes, for example, —SM (M is H, alkali metal, alkyl group, aryl group, heterocyclic group, S—R (R is a hydrogen atom, a halogen atom, a carbon atom) Represents an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.), -Se-M (M is the same as above), and the like. Furthermore, as another example, a ring structure containing — (— S—, —Se—, —S—S—, —Se—Se—, —S—Se—, —S—O— or —SO—S— is included. ),> C = S,> C = Se,-<ring> C = S,-<ring> C = Se,> P-, OP (-O) _2- and the like. . Here, “<ring> C” means a ring structure containing C. The bond having self-organization is particularly preferably a residue derived from a disulfide compound. Further, when A in the general formula (I) is -SS-, the linking group is bonded to both ends of the disulfide, and many linking groups are attached to the ends of each linking group. It is preferable to have a structure in which the photon excitation parts are coupled, that is, a structure such as DLSSL′-D ′. Here, L and L ′ and D and D ′ may be the same or different.

  Based on the above description of the multiphoton excitation part D, the linking group L, and the bonding part A, specific examples (exemplary compounds Cd-1 to Cd-30) of the multiphoton excitation composite compound Cd suitably used in the present invention are as follows. However, the present invention is not limited to these.

  Here, in the following table, (L) in the item of “multiphoton excitation part D” represents the part of the multiphoton excitation part D to which the linking group L is bonded. (D) and (A) in the item of “linking group L” represent the part of the linking group L to which the multiphoton excitation part D is bonded and the part of the linking group L to which the bonding part A is bonded, respectively. ing. (L) in the item “bonding part A” represents the part of the bonding part A to which the linking group L is bonded. In addition, “★” in the item “bonding part A” represents a structure further including the bonding part A, the linking group L, and the multiphoton excitation part D in the part of “★”. That is, it represents a compound having a symmetrical structure having a linking group L and a multiphoton excitation part D at both ends with a disulfide bond as the center.

  In the following table, Me represents a methyl group, Et represents an ethyl group, nPr represents an n-propyl group, and nHx represents an n-hexyl group.

  Further, Table 3 shows specific examples of the general formula (III).

Tables 4 and 5 show specific examples of the general formula (IV). Here, a in the item “R ₁₀₇ ” represents one (for example, the left side) R ₁₀₇ of the general formula (IV), and b represents the other (for example, the right side) R ₁₀₇ of the general formula (IV). In other words, compounds shown in table if there is distinction between a and b for R ₁₀₇ represents that it has an asymmetric structure, indicating that it has a symmetrical structure Without that distinction.

  A method for obtaining the multiphoton excited composite compound Cd is not particularly limited, and a compound having a multiphoton excitation part D having a chemical reaction active site and a binding part A (sulfur-containing compound) having a chemical reaction active site corresponding thereto. There is a method of forming a multiphoton excited composite compound Cd containing a linking group L by chemically reacting with a compound having a bonding portion). For example, a reactive group (for example, an electrophilic group such as —COOH, —COOR, —COCl, and —SO 2 Cl, or a nucleophilic group such as —OH and —NHR) is introduced into the multiphoton excited composite compound. The method of making it react with the sulfur-containing coupling | bond part which has a reactive group couple | bonded by reacting with these after that is mentioned.

"Multiphoton excitation device and fabrication method"
<First Embodiment of Multiphoton Excitation Device and Method for Producing the Same>
First, the configuration of the multiphoton excitation device 10 according to the present embodiment will be described. 1A and 1B are a schematic cross-sectional view showing the overall configuration of the multiphoton excitation device 10 according to the present embodiment, and a schematic cross-sectional view in the vicinity of a protruding portion of a fine metal body. The multi-photon excitation device 10 according to the present embodiment generates localized plasmons in a fine metal body having a mushroom structure by irradiation with irradiation light P, and multi-photon excitation is performed by near-field light enhanced by the electric field enhancement effect of the localized plasmons. It causes photon excitation.

  As shown in FIG. 1A and FIG. 1B, the multiphoton excitation device 10 is filled with a metal layer 11, a dielectric layer 12 having a plurality of fine holes 15 formed on the metal layer, and the fine holes 15. A plurality of fine portions each formed of a filled portion 14a and a projected portion 14b formed on the filled portion 14a so as to protrude from the surface of the dielectric layer 12 and having a diameter capable of inducing localized plasmons due to the irradiation light P. A metal body 14 and the above-described multiphoton excited composite compound Cd bonded to the protrusion 14b are provided.

  The metal layer 11 and the dielectric layer 12 serving as the substrate 13 are porous oxide materials obtained by anodizing a material to be anodized. When the anodized material is anodized, an oxidation reaction proceeds from the surface in a direction substantially perpendicular to the surface, and an anodized film 12 is generated. Such an anodized film 12 is described in paragraphs [0037] to [0043] and [0067] to [0069] of Patent Document 2.

  The fine hole 15 is a place where the fine metal body 14 is formed in the present invention. The cross-sectional shape, the hole diameter, and the arrangement pitch between adjacent micropores can be controlled by anodizing conditions, and are not particularly limited. Usually, the pitch W between the adjacent fine holes 15 can be controlled in the range of 10 to 500 nm, and the diameter of the fine holes 15 can be controlled in the range of 5 to 400 nm. Japanese Patent Application Laid-Open Nos. 2001-9800 and 2001-138300 disclose methods for finely controlling the formation position and the hole diameter of fine holes. By using these methods, the micropores having an arbitrary pore diameter and depth within the above range can be arranged almost regularly. The fine holes 15 may or may not be regularly arranged.

  The fine metal body 14 includes a filling portion 14a filled with fine holes and a protruding portion 14b at the upper portion of the filling portion protruding to the dielectric layer surface 12s. The fine metal body 14 only needs to have a diameter r of the protruding portion 14b that can induce localized plasmons. However, in consideration of the wavelength of the irradiation light P, the diameter of the protruding portion 14b is in the range of 10 nm to 300 nm. It is preferable that The protrusions 14b adjacent to each other are preferably separated from each other, and the average separation distance is more preferably in the range of several nm to 10 nm. When the average separation distance is within the above range, the electric field enhancement effect by the localized plasmon effect can be effectively obtained. The localized plasmon phenomenon is a phenomenon in which a free electric field in a convex portion resonates with an electric field of light and vibrates to generate a strong electric field around the convex portion. Therefore, the fine metal body 14 is an arbitrary metal having free electrons. Good. Since the multi-photon excitation device 10 irradiates the dielectric layer surface 12s with the irradiation light P including light having a wavelength capable of exciting the localized plasmon at the protrusion 14b, A metal that produces localized plasmons at a wavelength that substantially matches the absorption wavelength is preferable, and examples thereof include Au, Ag, Cu, Pt, Ni, and Ti. Au, Ag, and the like that have a high electric field enhancing effect are particularly preferable.

  Next, a manufacturing method of the multiphoton excitation device 10 according to the present embodiment will be described. In this method of manufacturing a multiphoton excitation device, a multiphoton excitation device 10 including a substrate 13 having micropores 15 and a fine metal body 14 having a mushroom structure formed in the micropores 15, and having a fine mushroom structure. The protrusion 14b of the metal body 14 protrudes from the dielectric layer surface 12s, and the multiphoton excitation device 10 having a structure in which a plurality of multiphoton excitation composite compounds are bonded to the protrusion 14b is manufactured (FIG. 2). The manufacturing method of the multiphoton excitation device 10 includes a step of forming a substrate 13 having a microhole 15 shown below, a step of forming a micrometal body 14 in the microhole 15, and a multiphoton in a protrusion 14 b of the micrometal body 14. It is roughly divided into a step of binding the excited complex compound.

  First, anodization is advanced from one surface of the anodized material to form the anodized film 12 having the fine holes 15 and the non-anodized portion 11 based on the anodized material (paragraph of Patent Document 2). [0037] to [0043]). In this way, the porous oxide material 13 composed of the anodized film 12 having the fine holes 15 and the non-anodized portion 11 can be formed, and this becomes the substrate of the multiphoton excitation device according to the present embodiment. Next, the fine holes 15 are filled with a plated metal material by plating the opening surface 12s of the anodized film 12 of the substrate 13 (see paragraph [0044] of Patent Document 2). Then, after a certain amount of time has passed, the filling portion 14a of the fine metal body 14 is formed, and further, by continuing the plating process, the plating metal material protrudes from the surface of the alumina layer, and the protrusion portion 14b of the fine metal body 14 Is formed (FIG. 2). By controlling the duration of the plating process, the diameter r of the protrusion 14b can be adjusted as appropriate.

  The multiphoton excited composite compound Cd is bonded to the protrusion 14b (fine metal body 14) by immersing the surface of the protrusion 14b formed above in a solution in which the multiphoton excited composite compound Cd is dissolved. Can be implemented. Thereafter, the substrate is taken out and washed with the same solvent as the above solvent. If necessary, the substrate is further washed with another solvent, and finally dried, whereby the multiphoton excited composite compound Cd is bonded to the protrusion 14b. Is completed. At this time, the solvent used immediately before drying is preferably a highly volatile solvent.

  As described above, in the multiphoton excitation device 10 according to the present embodiment, the multiphoton excitation unit capable of generating multiphoton excitation is connected to the fine metal body by the connecting group. Therefore, since the multiphoton excitation part and the fine metal body can be electronically isolated, the influence of metal quenching can be reduced. Thereby, in the multiphoton excitation device, it is possible to efficiently use the energy generated in the multiphoton excitation part in the multiphoton excitation composite compound.

  Furthermore, when the multiphoton excitation part has a hydrophilic group such as Cd-23 and Cd-24 among the multiphoton excitation complex compounds described in the present embodiment, the influence of metal quenching can be further reduced. it can. This is because when the hydrophilic group interacts with the surrounding solvent, the linking group is bent and the multiphoton excitation part can be prevented from contacting the fine metal body.

<Second Embodiment of Multiphoton Excitation Device and Method for Producing the Same>
First, the configuration of the multiphoton excitation device 30 according to the present embodiment will be described. FIG. 3 is a schematic cross-sectional view showing the overall configuration of the multiphoton excitation device 30 according to the present embodiment. The multiphoton excitation device 30 has substantially the same configuration as the multiphoton excitation device 10 according to the first embodiment. However, the multiphoton excitation composite compound Cd and energy from the multiphoton excitation composite compound Cd are applied to the protruding portion 14b. The difference is that a compound Ca containing an energy acceptor (hereinafter, a receptor complex compound) is simultaneously bonded. Therefore, the description of the same elements as those in the first embodiment of the multiphoton excitation device 30 is omitted unless particularly necessary. The multiphoton excitation device 30 according to the present embodiment generates fine metal body localized plasmons having a mushroom structure by irradiation with the irradiation light P, and multiphotons are generated by near-field light enhanced by the electric field enhancement effect of the localized plasmons. Multi-photon excitation is caused in the excitation part, and the energy stored by this excitation is transferred to the energy acceptor.

  As shown in FIG. 3, the multiphoton excitation device 30 includes a metal layer 11, a dielectric layer 12 having a plurality of fine holes 15 formed on the metal layer, and a filling portion filled in the fine holes 15. A plurality of fine metal bodies 14 formed of 14a and protruding portions 14b formed on the filling portion 14a so as to protrude from the surface of the dielectric layer 12 and having a diameter capable of inducing localized plasmons due to the irradiation light P; The multiphoton excited composite compound Cd bound to the projecting portion 14b and the acceptor composite compound Ca that receives energy from the multiphoton excited composite compound Cd similarly coupled to the projecting portion 14b are provided. Here, the multiphoton excitation part of the multiphoton excitation composite compound Cd functions as an energy donor that absorbs the energy of the irradiation light and provides at least a part of the energy. A photochemical complex Ce capable of causing energy transfer is formed by the energy donor in the multiphoton excited complex compound Cd and the energy acceptor in the acceptor complex compound Ca.

  The energy acceptor in the acceptor complex compound Ca is a part including a π-conjugated system that accepts energy from an energy donor (multiphoton excitation part). By binding the energy acceptor to the fine metal body through a linking group that does not contain a conjugated multiple bond, it is possible to prevent the received energy from quenching the metal. The structure of the energy acceptor is preferably selected so that the energy transfer efficiency from the energy donor is high. Further, the binding of the receptor complex compound Ca to the fine metal body is performed in a self-organized manner by immersing the surface of the protrusion 14b (fine metal body 14) in a solution in which the receptor complex compound Ca is dissolved. Can do. The specific method is the same as the binding method of the multiphoton excited composite compound Cd. Furthermore, by using a solution in which the multiphoton excitation complex compound Cd and the receptor complex compound Ca are dissolved, the multiphoton excitation complex compound Cd and the receptor complex compound Ca can be simultaneously bonded to the protrusion 14b.

  As shown in FIG. 3, when the irradiation light P is irradiated onto the multiphoton excitation device 30, the energy donor is excited by absorbing the light energy of the irradiation light P and emits electrons. The emitted excited electrons are then received by the energy acceptor, causing electron transfer, i.e. transfer of light energy. As described above, in the present embodiment, the irradiation light P is light including a wavelength that induces localized plasmons in the protrusions 14b, so that the light confinement effect in the vicinity of the protrusions 14b by the localized plasmons can be obtained. An electric field enhancement effect in the vicinity of the protrusion 14b can be obtained. Accordingly, the irradiation light P can be kept in the vicinity of the photochemical complex Ce for a longer time, and the irradiation light P can be absorbed by the photochemical complex Ce more efficiently. In particular, at the localized plasmon resonance wavelength, the electric field enhancement effect is 100 times or more, so that the absorption efficiency can be remarkably improved.

  As described above, the multiphoton excitation device 30 according to the present embodiment also connects the energy donor (multiphoton excitation unit) and the energy acceptor to the fine metal body by the linking group. Therefore, since the energy donor and energy acceptor and the fine metal body can be electronically isolated, the influence of metal quenching can be reduced. Thereby, in the multiphoton excitation device, it is possible to efficiently use the energy generated in the multiphoton excitation part in the multiphoton excitation composite compound.

  Examples of the multiphoton excitation apparatus according to the present invention and examples of wavelength conversion measurement performed using the multiphoton excitation apparatus according to the present invention are shown below.

<Synthesis Method of Multiphoton Excited Composite Compound>
As a synthesis example of a multiphoton excited composite compound, a method for synthesizing the compound Cd-21 will be described.
Cystamine dihydrochloride (Cystamine dihydrochroride, Chemical Abstracts Registry Number: 56-17-7; Aldrich reagent) 39 mg (170 mmol), anhydrous N, N-dimethylacetamide (Wako Pure Chemical Industries reagent) 2 ml, triethylamine (Wako Pure Chemicals) Reagents manufactured by Yakuhin Kogyo Co., Ltd.) 0.96 ml (6.94 mmol) and 200 mg (347 mmol) of Lissamine rhodamin B sulfonyl chloride mixed isomers (Invitrogen Reagent L-20) anhydrous N, N- Dimethylacetamide (9 ml) solution was added and stirred at room temperature for 5 hours and then at 50 ° C. for 30 minutes. The reaction mixture was poured into cooled 1.5M hydrochloric acid, and the resulting precipitate was washed with a small amount of cooled 1.5M hydrochloric acid and dried to obtain 83 mg (yield 39.6%) of compound Cd-21.
The mass spectrum was m / z +1233.59 and was consistent with the structure of Compound Cd-21. The emission maximum wavelengths when excited with light having an absorption maximum wavelength of ethanol solution and light at 520 nm were 562 nm and 590 nm, respectively.

<Example 1>
The multiphoton excited composite compound Cd-21 (the dye part is rhodamine 6G type) was dissolved in a water: ethanol (1: 1) mixed solution, and the surface of the fine metal body was immersed therein. Next, the surface of the fine metal body was washed with a water: ethanol (1: 1) mixture and dried. And when the laser beam of 1050 nm was irradiated to the surface of the fine metal body of this apparatus, light emission with a short wavelength of 570 to 600 nm could be observed.

<Example 2>
A solvent was prepared by adding 10-fold mol of a compound having the pigment part of compound Cd-21 as -CO-Ph to the compound Cd-21 solution shown in Example 1. And the apparatus was produced similarly to Example 1 and the same measurement was performed. As a result, light emission with a short wavelength of 570 to 600 nm could be observed by laser beam irradiation at 1050 nm.

(Comparative Example 1)
Compound Cd-21 was dissolved in a water: ethanol (1: 1) mixed solution, and this was put in a spectroscopic cell made of quartz, and the same measurement as in Example 1 was performed. As a result, light emission by 1050 nm laser light irradiation could not be observed.

(Comparative Example 2)
The same measurement as in Example 1 was performed without immersing the surface of the fine metal body in the solution of Compound Cd-21. As a result, light emission by 1050 nm laser light irradiation could not be observed.

(Comparative Example 3)
A surface plasmon electric field enhancing device having a gold film on one surface of the dielectric prism was used, and the amino group was modified on the gold film surface via a silane coupling agent. Then, a system in which the rhodamine 6G skeleton was bound to this amino group was constructed, and the same measurement as in Example 1 was performed. As a result, light emission by 1050 nm laser light irradiation could not be observed.

  From the above examples, it was demonstrated that metal quenching can be prevented and the energy generated in the multiphoton excited compound can be used efficiently.

  The multiphoton excitation device according to the present invention can be used as a biosensor for detecting a biological substance. For example, when the substance to be detected is present in the vicinity of the multiphoton excitation complex compound, an interaction occurs between them, so that the multiphoton excitation efficiency of the multiphoton excitation complex compound changes. Therefore, it becomes possible to detect the substance to be detected based on the change in the multiphoton excitation efficiency. Further, the multiphoton excitation device according to the present invention can be used as a wavelength conversion element when the multiphoton excitation unit emits light when returning from the excited state to the ground state. Furthermore, the multiphoton excitation device according to the present invention can be used as an artificial photosynthesis device utilizing energy transfer. When water molecules are brought into contact with the multiphoton excitation device and irradiated with light energy, the contacted water molecules are decomposed by the multiphoton excited complex material or photochemical complex that is in an excited state bonded to the surface. Is done. Thereby, oxygen and / or hydrogen can be generated. That is, oxygen can be artificially produced from water using the multiphoton excitation device according to the present invention. The water molecules may be contained in normal liquid water or water molecules contained in the air.

1 is a schematic cross-sectional view showing a multiphoton excitation device according to a first embodiment. Schematic showing the vicinity of a fine metal body of a multiphoton excitation device The figure which shows the board | substrate which has the fine metal body of a multiphoton excitation device Schematic sectional view showing a multiphoton excitation device according to the second embodiment

Explanation of symbols

DESCRIPTION OF SYMBOLS 10, 30 Multiphoton excitation apparatus 12 Dielectric layer 12s Surface of dielectric layer 13 Substrate 14 Fine metal body 14a Filling portion 14b Protrusion portion 15 Fine pore Ca receptor complex compound Cd Multiphoton excitation complex compound (energy donor)
Ce Photosystem complex A Coupling part D Multiphoton excitation part L Linking group P Irradiation light r Diameter of protrusion W Pitch between micropores

Claims (11)

A substrate comprising a dielectric layer having a plurality of micropores open on at least one surface;
A filling portion filled in the micropores, and a protruding portion formed on the filling portion so as to protrude from the surface of the dielectric layer and having a diameter capable of inducing localized plasmon due to irradiation light. A multi-photon excitation device comprising a plurality of fine metal bodies,
A multi-photon excitation device comprising a plurality of multi-photon excitation complex compounds represented by the following general formula (I) bonded to the surface of the protrusion.
Formula (I): D-LA
(In the above formula, D represents a multiphoton excitation part having a π-electron conjugated system capable of absorbing the light energy of the irradiation light and causing multiphoton excitation, A represents a bond part coupled to the protruding part, and L Represents a linking group for linking the multiphoton excitation part and the binding part.)   The multi-photon excitation device according to claim 1, wherein the coupling portion is a sulfur-containing coupling portion that is coupled to the protruding portion by a sulfur atom.   The multi-photon excitation device according to claim 1, wherein the linking group has a main chain composed of an aliphatic chain. The multi-photon excitation device according to claim 3, wherein the linking group includes a structure represented by the following general formula (II).
Formula (II):-(G _a -T _b ) _c-
(In the above formula, G represents —C (═O) —, —O—, —NR ₁ —, — (N-containing heterocycle) —, —S—, —SO—, —SO ₂ —, —P (= O) <or a divalent or trivalent partial linking group comprising these bonds, T represents an aliphatic group, a, b and c are each an integer from 0 to 2, an integer from 1 to 100 and 1 To an integer of 100 to 100. Here, R ₁ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and c is an integer of 2 or more. In this case, G and T and a and b for each c may be the same or different.) The multiphoton excitation device according to any one of claims 1 to 4, wherein the multiphoton excitation part is a residue derived from a compound represented by the following general formula (III) or general formula (IV): .
General formula (III):

General formula (IV):

(In general formula (III) or (IV), Y represents a methine group, a methylene group or an amine. These methine group and methylene group are a halogen atom, an alkyl group having 1 to 18 carbon atoms, and the number of carbon atoms. Each of them may be substituted with at least one substituent selected from the group consisting of an alkoxy group having 1 to 18 and an aryl group having 6 to 18 carbon atoms, i represents an integer of 1 to 4. R ₁₀₁ and R ₁₀₂ independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and R ₁₀₃ , R _104, and R ₁₀₅ each independently represents a hydrogen atom, a halogen atom, atom, _{.R 106} and _{R 107} .j represents an integer of 0 to 3 representing an alkyl group or an aryl group having 6 to 18 carbon atoms, 1 to 18 carbon atoms are each independently _{.R 108, R 109, R 110} , R 111 represents an alkyl group or an aryl group having 6 to 18 carbon atoms, atom number 1 to 18 are each independently a hydrogen atom, a halogen atom, a cyano group, an amino group, Hydroxyl group, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, acyl group having 1 to 18 carbon atoms, acylamino group having 1 to 18 carbon atoms, 1 to 18 carbon atoms A carbamoyl group, a sulfonamide group having 1 to 18 carbon atoms, a sulfamoyl group having 1 to 18 carbon atoms, an alkylamino group having 1 to 18 carbon atoms, or an arylamino group having 6 to 18 carbon atoms is represented here. in the _R 108 _{to R 111,} the groups listed above may form a ring. in _addition, any one of R 101 _{to R 111,} the communication It has at least one functional group necessary to form a group, and the alkyl group and alkoxy group described in this section are partially unsaturated, substituted with a hetero atom, or branched. The aryl group includes a polycyclic aromatic hydrocarbon group.)   The multiphoton excitation device according to any one of claims 1 to 5, wherein the multiphoton excitation unit emits light having a wavelength shorter than the wavelength of the irradiation light due to multiphoton excitation. The multiphoton excitation part serves as an energy donor that donates at least part of the energy obtained by multiphoton excitation,
An energy acceptor coupled to the surface of the protrusion for accepting energy donated from the energy donor;
The multiphoton excitation apparatus according to any one of claims 1 to 6, wherein a photochemical complex is formed by the energy donor and the energy acceptor. A substrate including a dielectric layer having a plurality of micropores opened on at least one surface, a filling portion filled in the micropores, and formed on the filling portion so as to protrude from the surface of the dielectric layer And preparing a plurality of fine metal bodies composed of protrusions having a diameter capable of inducing localized plasmons due to irradiation light,
A method for producing a multiphoton excitation device, wherein a plurality of multiphoton excitation complex compounds represented by the following general formula (I) are bonded to the surface of the protrusion.
Formula (I): D-LA
(In the above formula, D represents a multiphoton excitation part having a π-electron conjugated system capable of absorbing the light energy of the irradiation light and causing multiphoton excitation, A represents a bond part coupled to the protruding part, and L Represents a linking group for linking the multiphoton excitation part and the binding part.) The bond is a sulfur-containing bond containing a sulfur atom;
The method for producing a multiphoton excitation device according to claim 8, wherein the linking group and the protruding portion are bonded by the sulfur atom. The multiphoton excitation part serves as an energy donor that provides at least a part of the energy obtained by multiphoton excitation,
9. A photochemical complex comprising the energy donor and the energy acceptor is formed by connecting an energy acceptor that receives energy donated from the energy donor to the protrusion. Or a method for producing the multiphoton excitation device according to 9.   2. The dielectric layer is formed by subjecting the anodized material to anodization, and forming a plurality of micropores having openings in the anodized surface subjected to the anodization. A method for producing a multiphoton excitation device according to any one of 8 to 10.

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