JPWO2016195091A1 - Thermoelectric conversion element - Google Patents

Abstract

The present invention provides a thermoelectric conversion element having excellent thermoelectric conversion performance and excellent bending resistance. The thermoelectric conversion element of the present invention includes an electrode, a treatment electrode that is fixed on the electrode and includes an adhesion layer having an aromatic ring, and a thermoelectric conversion layer that is in contact with the treatment electrode and includes carbon nanotubes.

Description

  The present invention relates to a thermoelectric conversion element.

Thermoelectric conversion materials capable of mutually converting thermal energy and electrical energy are used in thermoelectric conversion elements such as thermoelectric power generation elements and Peltier elements. Thermoelectric power generation using such thermoelectric conversion elements can directly convert thermal energy into electric power, does not require moving parts, and is used for wristwatches that operate at body temperature, power supplies for remote areas, power supplies for space, etc. It has been.
In recent years, carbon nanotubes (hereinafter also referred to as “CNT”) have attracted attention as thermoelectric conversion materials, and several techniques relating to thermoelectric conversion materials containing CNTs have been proposed (for example, Patent Document 1).

International Publication No. 2012/121133

On the other hand, in recent years, further improvement in the thermoelectric conversion performance of thermoelectric conversion elements has been demanded in order to improve the performance of equipment in which thermoelectric conversion elements are used.
When the present inventors produced a thermoelectric conversion element using the thermoelectric conversion material containing CNT as described in patent document 1, and evaluated the characteristic (power generation amount), it satisfy | fills the level currently requested | required. However, it was found that further improvement is necessary.

  In recent years, there has been an increasing demand for attaching a thermoelectric conversion element to the surface of a device having a curved surface and / or unevenness, and even when the thermoelectric conversion element is bent, its characteristics are not easily changed, and bending resistance is also required.

  In view of the above circumstances, an object of the present invention is to provide a thermoelectric conversion element that is excellent in thermoelectric conversion performance and also excellent in bending resistance.

As a result of intensive studies on the above problems, the present inventors have found that a desired effect can be obtained by using an electrode having a predetermined adhesion layer.
More specifically, the present inventors have found that the above object can be achieved by the following configuration.

(1) a treatment electrode including an electrode and an adhesion layer having an aromatic ring fixed on the electrode;
The thermoelectric conversion element which has a thermoelectric conversion layer which contacts a process electrode and contains a carbon nanotube.
(2) The thermoelectric conversion element according to (1), wherein the adhesion layer includes an organic compound having an aromatic ring.
(3) The organic compound has at least one adsorbing group selected from the group consisting of a thiol group, a disulfide group, a sulfonic acid group, an amino group, a carboxyl group, and a phosphoric acid group, and an aromatic ring. 1 compound or
-M (X) _3-n (R) Thermoelectric conversion according to (2), including a second compound having a group represented by _n and an aromatic ring, a hydrolyzate thereof, or a hydrolyzate condensate thereof. element.
M represents Si, Ti, or Zr. X represents a hydrolyzable group. R represents a monovalent organic group. n represents 0, 1 or 2. However, the monovalent organic group does not include a hydrolyzable group.
(4) The organic compound is a compound represented by formula (1) described later, a compound represented by formula (2) described later, a repeating unit represented by formula (3) described later, and formula (4) described later. Or a compound represented by the following formula (5), a hydrolyzate thereof, or a hydrolyzate condensate thereof: Conversion element.
(5) The organic compound is a compound represented by the formula (1) in which L in the formula (1) is a divalent linking group, or a formula in which L in the formula (5) is a divalent linking group. The thermoelectric conversion element according to (4), comprising the compound represented by (5), a hydrolyzate thereof, or a hydrolysis condensate thereof.
(6) The thermoelectric conversion element according to any one of (1) to (5), wherein the aromatic ring is a polycyclic aromatic ring.
(7) The thermoelectric conversion element according to (2), wherein the organic compound includes at least one selected from the group consisting of a thiol group, a disulfide group, a phosphate group, and a carboxyl group.

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in thermoelectric conversion performance, the thermoelectric conversion element which is excellent also in bending resistance can be provided.

It is sectional drawing of the 1st embodiment of the thermoelectric conversion element of this invention. The arrow in FIG. 1 shows the direction of the temperature difference provided when using the thermoelectric conversion element. It is sectional drawing of the 2nd embodiment of the thermoelectric conversion element of this invention. The arrow in FIG. 2 shows the direction of the temperature difference given when using the thermoelectric conversion element. It is a top view which shows notionally the 3rd embodiment of the thermoelectric conversion element of this invention. It is a front view which shows notionally the 3rd embodiment of the thermoelectric conversion element of this invention. It is a bottom view which shows notionally the 3rd embodiment of the thermoelectric conversion element of this invention. It is a conceptual diagram for demonstrating another example of the 3rd embodiment of the thermoelectric conversion element of this invention. It is a top view for demonstrating an example of the thermoelectric conversion module of this invention. It is a top view for demonstrating an example of the thermoelectric conversion module of this invention. It is a top view for demonstrating an example of the thermoelectric conversion module of this invention. It is a front view for demonstrating an example of the thermoelectric conversion module of this invention. It is a conceptual diagram which shows another example of the board | substrate used for the thermoelectric conversion element of this invention. It is a conceptual diagram which shows another example of the board | substrate used for the thermoelectric conversion module of this invention.

Below, the suitable aspect of the thermoelectric conversion element of this invention is demonstrated. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
One of the features of the thermoelectric conversion element of the present invention is that a processing electrode including an electrode and an adhesion layer having an aromatic ring fixed on the electrode is used. In the prior art, since the thermoelectric conversion layer using CNT has poor adhesion to the electrode in the prior art, voids are easily generated between the thermoelectric conversion layer and the electrode, and as a result, the thermoelectric conversion layer and the electrode It was found that the resistance between them increased and the thermoelectric properties deteriorated. Therefore, the present inventors have used a processing electrode including an adhesion layer having an aromatic ring, whereby the CNT contained in the thermoelectric conversion layer disposed in contact with the processing electrode and the adhesion layer on the surface of the processing electrode. It has been found that the aromatic ring derived from the interaction interacts to further improve the adhesion between the processing electrode and the thermoelectric conversion layer. In addition, as the adhesion between the processing electrode and the thermoelectric conversion layer is improved, the thermoelectric conversion layer becomes difficult to peel off from the processing electrode even when the thermoelectric conversion element is bent. As a result, characteristics (especially resistance value) are improved. It is also known that deterioration is suppressed.

<First Embodiment>
FIG. 1 conceptually shows a first embodiment of the thermoelectric conversion element of the present invention.
As shown in FIG. 1, the thermoelectric conversion element 1 </ b> A includes a substrate 2, a first processing electrode 3 </ b> A and a second processing electrode 4 </ b> A that are disposed on the substrate 2, and a first processing electrode on the substrate 2. The thermoelectric conversion layer 5 is disposed so as to be in contact with 3A and the second processing electrode 4A, and the protective substrate 6 is disposed on the thermoelectric conversion layer 5. When the thermoelectric conversion element 1 is used, a temperature difference is given in the direction of the arrow as shown in FIG.
The surface of the adhesion layer (not shown) is located on the surface 3as of the first processing electrode 3A in contact with the thermoelectric conversion layer 5 and the surface 4as of the second processing electrode 4A in contact with the thermoelectric conversion layer 5. That is, the first processing electrode 3A includes an electrode disposed on the substrate 2 and an adhesion layer that is fixed on the electrode and covers the electrode surface that is not in contact with the substrate 2, and the surface of the adhesion layer is on the surface 3as. To position. The second processing electrode 4A also includes an electrode disposed on the substrate 2 and an adhesion layer that is fixed on the electrode and covers the electrode surface that is not in contact with the substrate 2, and the surface of the adhesion layer is on the surface 4as. To position. Thus, the adhesion layer in the processing electrode is in contact with the thermoelectric conversion layer.
In the above embodiment, the first processing electrode 3A and the second processing electrode 4A are disposed on the substrate 2, but the positions thereof are not particularly limited as long as they are in contact with the thermoelectric conversion layer 5. Further, it is only necessary that at least a part of each of the first processing electrode 3 </ b> A and the second processing electrode 4 </ b> A is in contact with the thermoelectric conversion layer 5.
Hereinafter, each member which comprises a thermoelectric conversion element is explained in full detail.

[substrate]
The type of the substrate is not particularly limited as long as it functions to support various members to be described later. However, it is preferable to select a substrate that is not easily affected during the formation of the electrodes and the thermoelectric conversion layer.
Examples of such a substrate include a resin substrate, a glass substrate, a transparent ceramic substrate, and a metal substrate. Among these, a resin substrate is preferable from the viewpoint of cost and flexibility.
More specifically, examples of the resin substrate include polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-phthalenedicarboxyl. Polycycloolefin substrates such as polyester substrates made of a rate, ZEONOR film (trade name, manufactured by ZEON CORPORATION), Arton film (trade name, manufactured by JSR), Sumilite FS1700 (trade name, manufactured by Sumitomo Bakelite), Kapton ( Product name, Toray DuPont), Apical (trade name, manufactured by Kaneka), Upilex (trade name, manufactured by Ube Industries), Pomilan (trade name, manufactured by Arakawa Chemical Co., Ltd.) and other polyimide substrates, Pure Ace (product) Name, manufactured by Teijin Chemicals Ltd.), Elmec A polycarbonate substrate such as a trade name, manufactured by Kaneka), a polyether ether ketone substrate such as Sumilite FS1100 (trade name, manufactured by Sumitomo Bakelite), a polyphenyl sulfide substrate such as Torelina (trade name, manufactured by Toray), a polyacetal substrate, Examples include a polyamide substrate, a polyphenylene ether substrate, a polyolefin substrate (for example, a polyethylene substrate), a polystyrene substrate, a polyarylate substrate, a polysulfone substrate, a polyether sulfone substrate, a fluororesin substrate, and a liquid crystal polymer substrate. A polyimide substrate is preferable from the viewpoint of easy availability, heat resistance (preferably 100 ° C. or higher), and more excellent effects of the present invention.

  The thickness of the substrate is preferably 1 to 3000 μm, more preferably 5 to 1000 μm, still more preferably 5 to 1000 μm, and particularly preferably 5 to 800 μm from the viewpoints of handleability and durability.

In addition, as a resin substrate, the thermoelectric conversion characteristics of the thermoelectric conversion element are more excellent and / or the bending resistance of the thermoelectric conversion element is more excellent (hereinafter simply referred to as “the effect of the present invention is more excellent”). Preferably, a resin substrate whose surface is irradiated with energy rays is preferably used. A resin substrate that has been subjected to such treatment is more excellent in adhesion to the thermoelectric conversion layer.
The method of energy beam irradiation is not particularly limited. For example, corona treatment using corona discharge, plasma treatment exposed to a plasma atmosphere, ultraviolet irradiation treatment that performs ultraviolet irradiation (preferably UV (ultraviolet light that performs ultraviolet irradiation in an ozone atmosphere) ) Ozone treatment), and EB (Electoron Beam) irradiation treatment that irradiates an electron beam can be used, and preferred examples include plasma treatment, corona treatment, and UV ozone treatment.

[First processing electrode and second processing electrode]
The first processing electrode and the second processing electrode are members that are disposed in contact with a thermoelectric conversion layer described later and are electrically connected to the thermoelectric conversion layer.
The first processing electrode and the second processing electrode include an electrode and an adhesion layer having an aromatic ring fixed on the electrode. As will be described in detail later, such a treated electrode is obtained by surface-treating the electrode with a predetermined organic compound, and an aromatic ring is introduced on the surface of the electrode.
This adhesion layer is fixed on the electrode. Although fixing is described in detail later, it is intended that the adhesion layer is strongly adhered to the electrode by adsorbing or bonding a predetermined group contained in the adhesion layer to the electrode.
In addition, the presence of the aromatic ring in the adhesion layer improves the interaction with CNT, and as a result, the adhesion between the processing electrode and the thermoelectric conversion layer is further improved, and the thermoelectric conversion characteristics (particularly, power generation amount) are improved. .
In FIG. 1, both of the pair of electrodes are processing electrodes. However, the present invention is not limited to this mode, and at least one of the electrodes may be a predetermined processing electrode.
In the following, first, the configuration of the adhesion layer will be described in detail.

[Adhesion layer]
The adhesion layer is a layer having an aromatic ring fixed on the electrode. When this adhesion layer is interposed between the electrode and the thermoelectric conversion layer, the adhesion between them is further improved.
Note that the adhesion layer may cover the entire surface other than the surface in contact with the substrate of the electrode disposed on the substrate, or may cover a part thereof. That is, the adhesion layer may be fixed so as to cover at least a part of the electrode surface so as to be interposed between the electrode and the thermoelectric conversion layer.

The adhesion layer is fixed on the electrode. That is, it is intended that the adhesion layer is strongly adhered to the electrode when a predetermined group contained in the adhesion layer is adsorbed or bonded to the electrode. Here, examples of the predetermined group contained in the adhesion layer include an adsorbing group described later, and these groups can be adsorbed on the electrode surface. In addition, a group represented by -M (X) _3-n (R) _n , which will be described later, can be bonded to the electrode surface by hydrolysis (can form a chemical bond). In addition, these predetermined groups correspond to the group derived from the organic compound contained in an adhesion layer, for example.

The adhesion layer has an aromatic ring (aromatic ring group). An aromatic ring originates in the component (organic compound) which comprises an adhesion layer, for example.
The aromatic ring may be a hydrocarbon aromatic ring or a heteroaromatic ring.
Examples of the hydrocarbon aromatic ring include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, azulene ring, chrysene ring, perylene ring, triphenylene ring, pentalene ring, indacene ring, fluoranthene ring, and acephenanthrylene ring. , An asanthrylene ring, a naphthacene ring, a pentaphen ring, a pentacene ring, a hexaphen ring, and the like.
Examples of the heteroaromatic ring include furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, Pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring, triazine ring , Benzofuran ring, isobenzofuran ring, benzothiophene ring, indole ring, indoline ring, isoindole ring, benzoxazole ring, benzothiazole ring, indazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, cinno Ring, phthalazine ring, quinazoline ring, quinoxaline ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring, xanthene ring, acridine ring, phenanthridine ring, phenanthroline ring, phenazine ring, phenoxazine ring, thianthrene ring, indolizine ring, A quinolidine ring, a quinuclidine ring, a naphthyridine ring, a purine ring, a pteridine ring, etc. are mentioned.

The aromatic ring may be a monocyclic aromatic ring or a polycyclic aromatic ring (condensed polycyclic aromatic ring). Among these, a polycyclic aromatic ring is preferable and a polycyclic aromatic ring having 3 or more rings is more preferable in that the effect of the present invention is more excellent. The upper limit of the number of polycyclic aromatic rings is not particularly limited, but is often 10 or less, and more often 5 or less.
A polycyclic aromatic ring is a ring structure formed by condensation of two or more aromatic rings.

As one preferred embodiment of the adhesion layer, the adhesion layer preferably contains an organic compound having an aromatic ring (hereinafter also simply referred to as “organic compound”).
The organic compound may be a low molecular compound or a high molecular compound. In addition, a low molecular compound intends a compound with a molecular weight of 2000 or less, and a high molecular compound intends a compound with a molecular weight of more than 2000. In addition, when the molecular weight of the organic compound is polydispersed, it is determined whether the organic compound is a low molecular compound or a high molecular compound depending on whether the weight average molecular weight is 2000 or less or more than 2000.
Especially, a low molecular weight compound is preferable at the point by which generation | occurrence | production of a defect is suppressed more, when coat | covering the electrode surface.

  The organic compound includes an aromatic ring (aromatic ring group). That is, an aromatic ring structure is included. The definition of the aromatic ring is as described above.

As the organic compound, at least one kind of adsorptive group selected from the group consisting of a thiol group, a disulfide group, a sulfonic acid group, an amino group, a carboxyl group, and a phosphoric acid group in that the effect of the present invention is more excellent. And a first compound having an aromatic ring, or a second compound having a group represented by -M (X) _3-n (R) _n and an aromatic ring, a hydrolyzate thereof, or a hydrolysis condensate thereof Are preferred.
The adsorptive group contained in the first compound is adsorbed on the electrode surface and improves the adhesion between the electrode and the adhesion layer. Further, the second compound, its hydrolyzate, and its hydrolysis condensate can form a bond with the electrode surface. For example, the M-OH group in the hydrolyzed condensate of the second compound and the electrode surface A chemical reaction may be formed by the condensation reaction proceeding with the OH group.
As described above, the organic compound may contain an adsorptive group described later and a group represented by -M (X) _3-n (R) _n , and the effects of the present invention are more excellent. , A thiol group, a disulfide group, a phosphate group, and at least one selected from the group consisting of carboxyl groups are preferably included.

In addition, it is preferable that an optimal adsorptive group is selected by the material which comprises the electrode mentioned later. For example, when the material constituting the electrode is a material whose standard electrode potential E0 shown later is smaller than 0 V, the electrode surface is often partially oxidized, so that the adsorptive groups include carboxyl groups and phosphate groups. In the case where the standard electrode potential is greater than 0 V, the electrode surface is not oxidized. Therefore, the adsorptive group is preferably a thiol group or a disulfide group.
The standard electrode potential E0 is a standard electrode potential in an aqueous solution at 25 ° C., and is described in the Chemical Society of Japan, “Chemical Handbook (Basics II)”, Rev. 5, Maruzen, pp581-584 (2004). Numeric values can be used.

In addition, the group represented by -M (X) _3-n (R) _n is bonded to another group at the position of * as represented by * -M (X) _3-n (R) _n. To do.
-M (X) _3-n (R) In the group represented by _n , M represents Si (silicon atom), Ti (titanium atom) or Zr (zirconium atom). Especially, Si is preferable at the point which the effect of this invention is more excellent.
X represents a hydrolyzable group. The hydrolyzable group is a group that is directly connected to M and can proceed with a hydrolysis reaction and / or a condensation reaction, and examples thereof include an alkoxy group, a halogen atom, an acyloxy group, and an alkenyloxy group. Among these, an alkoxy group is preferable in terms of better handleability. The number of carbon atoms in the alkoxy group is not particularly limited, but 1 to 5 is preferable and 1 to 3 is more preferable in terms of excellent reactivity.
When there are a plurality of Xs, the plurality of Xs may be the same or different.

R represents a monovalent organic group (excluding a hydrolyzable group).
The monovalent organic group may be any organic group other than a hydrolyzable group and a hydroxyl group. For example, an alkyl group, a cycloalkyl group, an aryl group, an alkylcarbonyl group, a cycloalkylcarbonyl group, an arylcarbonyl group, an alkyloxy group Examples thereof include a carbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group, or a combination thereof. Especially, a C1-C6 alkyl group and an aryl group are mentioned preferably.
The monovalent organic group may include an aromatic ring.

  n represents 0, 1 or 2. Especially, 0 or 1 is preferable at the point which the effect of this invention is more excellent, and 0 is more preferable.

Moreover, the hydrolyzate of a 2nd compound intends the compound obtained by hydrolyzing the hydrolysable group in a 2nd compound. In addition, even if all the hydrolyzable groups are hydrolyzed (completely hydrolyzed), the hydrolyzate is partially hydrolyzed (partially hydrolyzed). Thing). That is, the hydrolyzate may be a complete hydrolyzate, a partial hydrolyzate, or a mixture thereof.
Moreover, the hydrolysis condensate of a 2nd compound intends the compound obtained by hydrolyzing the hydrolyzable group in a 2nd compound, and condensing the obtained hydrolyzate. The hydrolysis condensate may be partially hydrolyzed even if all hydrolyzable groups are hydrolyzed and the hydrolyzate is all condensed (completely hydrolyzed condensate). The functional group may be hydrolyzed and a part of the hydrolyzate may be condensed (partially hydrolyzed condensate). That is, the hydrolysis condensate may be a complete hydrolysis condensate, a partial hydrolysis condensate, or a mixture thereof.

The organic compound may contain other arbitrary functional groups.
For example, a divalent linking group may be included between the aromatic ring and the adsorptive group (or a group represented by -M (X) _3-n (R) _n ). The definition of a bivalent coupling group is as below-mentioned.

(Preferred embodiment)
As one of the preferred embodiments of the organic compound, the compound represented by the formula (1), the compound represented by the formula (2), or the formula (3) is preferable in that the effect of the present invention is more excellent. A compound (polymer) having a repeating unit represented by formula (4) and a compound represented by formula (5), a hydrolyzate thereof, or a hydrolysis condensate thereof.
Formula (1) X1-LY
Formula (2) YL-X2-LY
Formula (5) X3-LY

In formula (1) and formula (3), X1 represents a thiol group, a sulfonic acid group, an amino group, a carboxyl group, or a phosphoric acid group. Especially, as X1, a thiol group and a carboxyl group are more preferable.
In formula (2), X2 represents a disulfide group.

In formula (1) to formula (5), L represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent hydrocarbon group (a divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group. A divalent saturated hydrocarbon group may be used. May be linear, branched or cyclic, preferably has 1 to 20 carbon atoms, more preferably has 3 to 20 carbon atoms, and further preferably has 5 to 20 carbon atoms. Preferred examples include an alkylene group, and the divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, such as a phenylene group, in addition to alkenylene groups, It may be an alkynylene group.) Divalent heterocyclic group, —O—, —S—, —SO ₂ —, —NR _L —, —CO—, —COO—, —CONR _L —, —SO _{3 -, - SO 2 NR L} -, or two or more kinds of these pairs The combined group (e.g., alkyleneoxy group, an alkyleneoxy carbonyl group, an alkylene carbonyl group etc.) and the like. Among these, an alkylene group, —O—, —COO—, —SO ₃ —, or a combination thereof is preferable. Here, _RL represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).

In formula (1), formula (2), formula (4), and formula (5), Y represents a substituted or unsubstituted aromatic ring. The definition of the aromatic ring is as described above.
The aromatic ring represented by Y may be substituted with a substituent. As a substituent, the group (for example, alkyl group) illustrated as said monovalent organic group is mentioned, for example.

In formula (3) and formula (4), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group (preferably a methyl group).

In Formula (5), X3 represents a group represented by -M (X) _3-n (R) _n . The definitions of M, X, R, and n are as described above.
Moreover, the hydrolyzate of the compound represented by Formula (5) intends the compound obtained by hydrolyzing the hydrolyzable group in the compound represented by Formula (5). In addition, even if all the hydrolyzable groups are hydrolyzed (completely hydrolyzed), the hydrolyzate is partially hydrolyzed (partially hydrolyzed). Thing). That is, the hydrolyzate may be a complete hydrolyzate, a partial hydrolyzate, or a mixture thereof.
The hydrolysis condensate of the compound represented by formula (5) is obtained by hydrolyzing the hydrolyzable group in the compound represented by formula (5) and condensing the obtained hydrolyzate. Intended compounds. The hydrolysis condensate may be partially hydrolyzed even if all hydrolyzable groups are hydrolyzed and the hydrolyzate is all condensed (completely hydrolyzed condensate). The functional group may be hydrolyzed and a part of the hydrolyzate may be condensed (partially hydrolyzed condensate). That is, the hydrolysis condensate may be a complete hydrolysis condensate, a partial hydrolysis condensate, or a mixture thereof.

The weight average molecular weight of the compound (polymer) having the repeating unit represented by the formula (3) and the repeating unit represented by the formula (4) is not particularly limited, but is preferably from 3,000 to 500,000 from the viewpoint of handleability.
Although content in particular of the repeating unit represented by Formula (3) in a compound is not restrict | limited, 10-90 mol% is preferable with respect to all the repeating units, and 20-80 mol% is more preferable.
Although content in particular of the repeating unit represented by Formula (4) in a compound is not restrict | limited, 10-90 mol% is preferable with respect to all the repeating units, and 20-80 mol% is more preferable.
In addition, the compound (polymer) having the repeating unit represented by formula (3) and the repeating unit represented by formula (4) has other repeating units (repeating units derived from other copolymerization components). It may be.

  Specific examples of the organic compound (for example, the first compound and the second compound) include compounds shown in the following table.

(electrode)
As an electrode material which comprises the electrode in a process electrode, if it has required electrical conductivity, it can form with various materials.
Specifically, in various devices such as copper, silver, gold, platinum, nickel, aluminum, constantan, chromium, indium, iron, copper alloy, and other metal materials, indium tin oxide (ITO) or zinc oxide (ZnO) Examples include materials used as transparent electrodes. Especially, copper, gold | metal | money, silver, platinum, nickel, a copper alloy, aluminum, or a constantan etc. are illustrated preferably, and copper, gold | metal | money, silver, platinum, or nickel is illustrated more preferably.

(Process electrode manufacturing method)
The manufacturing method of the first treatment electrode and the second treatment electrode is not particularly limited. For example, the electrode is first formed, and then the electrode and the above-described organic compound (for example, the first compound or the second compound) are contacted. And a method for forming an adhesion layer. That is, the method of surface-treating the electrode surface using an organic compound is mentioned. By performing the above treatment, an adhesion layer is formed on the electrode. In other words, a treated electrode obtained by surface-treating an electrode with an organic compound having an aromatic ring is obtained.
At that time, when the organic compound has an adsorptive group, the adsorbing group derived from the organic compound in the adhesion layer is adsorbed on the electrode surface, and adhesion between the adhesion layer and the electrode is ensured. Also, if having a group which an organic compound is represented by _{-M (X) 3-n (} R) n, for example, _{-M (X)} of 3-n _(R) groups represented by _n hydrolysis As the condensation reaction proceeds and the formation of the hydrolyzate and hydrolysis condensate proceeds, a bond is formed between the electrode surface and the adhesion between the adhesion layer and the electrode is ensured.
The method for forming the electrode to be processed includes vapor deposition, printing (for example, screen printing, metal mask printing, ink jet printing, etc.), adhesive / adhesive according to the forming material of the first processing electrode and the second processing electrode. It may be performed by a known method such as pasting to a substrate through the like. The electrode pattern may be formed using a mask at the time of vapor deposition or printing, and may be formed by patterning by a known method such as etching, sand blasting, laser engraving, or electron beam method after the electrode is formed on the surface.

As a method for surface treatment of an electrode with an organic compound, a method of bringing an organic compound into contact with an electrode is preferable. For example, a method of immersing a substrate having an electrode in a solution containing the organic compound, or an organic compound on the electrode The method of apply | coating the solution containing is mentioned.
Various solvents may be contained in the solution. The kind in particular of solvent used is not restrict | limited, Water and an organic solvent are mentioned. The concentration of the organic compound in the solution is not particularly limited, but is preferably 0.01 to 100 mmol / L, more preferably 0.1 to 10 mmol / L in terms of productivity and reactivity.
The contact time between the electrode and the organic compound (or a solution containing the organic compound) is not particularly limited, and is preferably 1 to 72 hours, more preferably 10 to 48 hours, in that the effect of the present invention is more excellent.
After bringing the electrode into contact with the organic compound (or a solution containing the organic compound), the electrode surface may be washed with a solvent as necessary.

In addition to the above, the method of surface treatment of the electrode with an organic compound includes an embodiment using a base agent.
The base agent is a compound having the above-described adsorptive group or a group represented by -M (X) _3-n (R) _n and a reactive group, and after surface-treating the electrode with this base agent, Furthermore, the adhesion layer which has an aromatic ring can also be formed by surface-treating an electrode with the organic compound which has the bonding group and aromatic ring which react with the reactive group in a base agent.
The base agent includes an adsorptive group or a group represented by -M (X) _3-n (R) _n . The definitions of these groups are as described above.
Further, the base agent contains a reactive group. The reactive group may be any group capable of reacting with a binding group contained in an organic compound, such as a methacryloyl group, an acryloyl group, an epoxy group, a primary amino group, a secondary amino group, a styryl group, and a vinyl group. , A phenol group, an isocyanate group, a mercapto group, and a carboxyl group, and a methacryloyl group or an acryloyl group is preferable in that the reactivity is more excellent.
The binding group contained in the organic compound is preferably a functional group that can react with the reactive group of the base agent to form a chemical bond, such as a methacryloyl group, an acryloyl group, an epoxy group, a hydroxyl group, and styryl. Group, vinyl group, phenol group, isocyanate group and the like.
As a method for surface-treating the electrode with such a base material, first, a treatment for bringing the electrode into contact with the base material is performed. As a specific method, in the method of bringing the organic compound and the electrode into contact with each other, a method using a base agent instead of the organic compound can be mentioned.
Next, examples of the surface treatment method of the electrode surface-treated with the base material with an organic compound having a binding group and an aromatic ring include the methods described above.
Examples of suitable combinations of the reactive group and the binding group (reactive group: binding group) include, for example, (methacryloyl group: mercapto group), (acryloyl group: mercapto group), (mercapto group: Methacryloyl group), (mercapto group: acryloyl group), (epoxy group: carboxyl group), (isocyanate group: hydroxyl group) and the like.

[Thermoelectric conversion layer]
The thermoelectric conversion layer is a layer that is disposed on the substrate and is in contact with the first processing electrode and the second processing electrode, and exhibits excellent adhesion to the first processing electrode and the second processing electrode.
The thermoelectric conversion layer includes CNT. The CNT includes a single-layer CNT in which one carbon film (graphene sheet) is wound in a cylindrical shape, a two-layer CNT in which two graphene sheets are wound in a concentric shape, and a plurality of graphene sheets. There are multi-walled CNTs wound concentrically. In the present invention, single-walled CNTs, double-walled CNTs, and multilayered CNTs may be used alone or in combination of two or more. In particular, it is preferable to use single-walled CNT and double-walled CNT having excellent properties in terms of conductivity and semiconductor properties, and more preferably single-walled CNT.
Single-walled CNTs may be semiconducting or metallic, and both may be used in combination. When both semiconducting CNT and metallic CNT are used, the content ratio of both in the composition can be appropriately adjusted according to the use of the composition. The CNT may contain a metal or the like, or may contain a molecule such as fullerene.

  The average length of CNT is not particularly limited, and can be appropriately selected according to the application. Specifically, although it depends on the distance between the electrodes, the average length of the CNT is preferably 0.01 to 2000 μm, more preferably 0.1 to 1000 μm from the viewpoints of manufacturability, film formability, conductivity, and the like. 1 to 1000 μm is more preferable.

The diameter of the CNT is not particularly limited, but is preferably 100 nm or less, more preferably 50 nm or less, and preferably 15 nm or less from the viewpoints of durability, transparency, film formability, conductivity, and the like. The lower limit is not particularly limited, but is often 0.4 nm or more.
In particular, when single-walled CNT is used, the diameter is preferably 0.5 to 2.2 nm, and more preferably 1.0 to 2.2 nm.

In the present invention, CNTs modified or treated with CNTs can also be used. Modification or treatment methods include a method of encapsulating a ferrocene derivative or nitrogen-substituted fullerene (azafullerene), a method of doping an alkali metal (such as potassium) or a metal element (such as indium) into the CNT by an ion doping method, or CNT in a vacuum The method etc. which heat this are illustrated.
When CNT is used, in addition to single-walled CNT or multilayered CNT, carbon nanohorn, carbon nanocoil, carbon nanobead, graphite, graphene, and amorphous carbon such as amorphous carbon may be included.

  The content of CNT in the thermoelectric conversion layer is not particularly limited, but is preferably 5 to 80% by mass with respect to the total mass of the thermoelectric conversion layer in terms of more excellent performance of the thermoelectric conversion layer, and 5 to 70. It is more preferable that it is mass%, and it is further more preferable that it is 5-50 mass%.

The thermoelectric conversion layer may contain components other than CNT.
For example, the thermoelectric conversion layer may contain a resin material as a binder as necessary.
Various known non-conductive resin materials (polymers) can be used as the resin material.
Specifically, various known resin materials such as vinyl compounds, (meth) acrylate compounds, carbonate compounds, ester compounds, epoxy compounds, siloxane compounds, and gelatin can be used.
The content of the resin material is not particularly limited, but in terms of the mechanical strength of the thermoelectric conversion layer, the resin material / CNT mass ratio is preferably 0.5 to 10, more preferably 0.5 to 5, and preferably 1 to 4. Is more preferable.

The thermoelectric conversion layer may contain a dispersant (CNT dispersant) as necessary. A surfactant is preferably used as the dispersant.
As the surfactant, a known surfactant can be used as long as it has a function of dispersing CNTs. More specifically, various surfactants can be used as long as they have a group that dissolves in water, a polar solvent, or a mixture of water and a polar solvent and adsorbs CNTs.
Accordingly, the surfactant may be ionic or nonionic. The ionic surfactant may be any of cationic, anionic and amphoteric.
Examples of the anionic surfactant include alkylbenzene sulfonates such as dodecylbenzene sulfonic acid, aromatic sulfonic acid surfactants such as dodecyl phenyl ether sulfonate, monosoap anionic surfactants, ether sulfates Surfactants, phosphate surfactants, carboxylic acid surfactants such as sodium deoxycholate and sodium cholate, carboxymethyl cellulose and its salts (sodium salt, ammonium salt, etc.), polystyrene sulfonate ammonium salt, polystyrene Examples thereof include water-soluble polymers such as sulfonic acid sodium salt.
Examples of the cationic surfactant include alkylamine salts and quaternary ammonium salts. Examples of amphoteric surfactants include alkyl betaine surfactants and amine oxide surfactants.
Furthermore, examples of nonionic surfactants include sugar ester surfactants such as sorbitan fatty acid esters, fatty acid ester surfactants such as polyoxyethylene resin acid esters, and ether surfactants such as polyoxyethylene alkyl ethers. Etc. are exemplified.
Among these, ionic surfactants are preferably used, and among them, cholate or deoxycholate is preferably used.

  When the thermoelectric conversion layer contains a surfactant, the content is preferably low. Specifically, the surfactant / CNT mass ratio is preferably 5 or less, and more preferably 2 or less.

  In addition to the above, the thermoelectric conversion layer may contain dopants, antifoaming agents, drying inhibitors, fungicides, and the like.

The average thickness of the thermoelectric conversion layer is preferably 0.1 to 1000 μm and more preferably 1 to 100 μm from the viewpoint of imparting a temperature difference.
In addition, the average thickness of a thermoelectric conversion layer measures the thickness of the thermoelectric conversion layer in arbitrary 10 points | pieces, and calculates | requires them by arithmetic average.

The method for forming the thermoelectric conversion layer is not particularly limited, but as an example, CNT and a component such as a resin material or a surfactant added as necessary are dissolved or dispersed in a solvent such as water or an organic solvent. And a method using a CNT dispersion liquid.
The thermoelectric conversion layer can be formed by applying the CNT dispersion liquid onto the substrate having the first processing electrode and the second processing electrode and forming a film.
The film forming method is not particularly limited. For example, spin coating method, extrusion die coating method, blade coating method, bar coating method, screen printing method, stencil printing method, roll coating method, curtain coating method, spray coating method, dip coating. A known coating method such as a method or an ink jet method can be used.
In addition, when producing a thermoelectric conversion layer in a predetermined position, the method of apply | coating a CNT dispersion liquid in a pattern form can be used.
As an example, a method of pattern-printing a CNT dispersion liquid on a substrate is exemplified by a printing method. As the printing method, various known printing methods such as screen printing, metal mask printing, gravure printing, flexographic printing, and offset printing can be used.
In addition, it is also possible to use a method in which a mold or mask is provided at a predetermined position on the substrate, and a CNT dispersion liquid or paste is applied in a pattern using the mold or mask.
Moreover, after application | coating, a drying process is performed as needed. For example, the solvent can be volatilized and dried by blowing hot air.
Furthermore, you may implement the process which wash | cleans a thermoelectric conversion layer after application | coating as needed. In particular, by using a solvent that can dissolve other components (for example, a surfactant and a binder) without dissolving CNT during the cleaning treatment, the content of CNT in the thermoelectric conversion layer is improved, The performance of the thermoelectric conversion element can be further improved.

Furthermore, instead of applying a CNT dispersion or the like in a pattern, after applying and drying the CNT dispersion on the entire surface of the substrate, unnecessary portions are removed by etching such as laser engraving, sandblasting, electron beam method, plasma etching, etc. A method of forming the thermoelectric conversion layer by patterning by removing it can also be used.
Note that etching may be performed using a mask formed using photolithography, a metal mask, or the like, if necessary.

[Protection board]
The protective substrate is a substrate disposed on the thermoelectric conversion layer, and protects the thermoelectric conversion layer from the outside. The protective substrate may be disposed as necessary.
The kind in particular of a protective substrate is not restrict | limited, From the point of the bending resistance of a thermoelectric conversion element, a resin substrate is preferable. Specific examples of the resin substrate include the specific examples described for the resin substrate used as the substrate.

<Second Embodiment>
FIG. 2 conceptually shows a second embodiment of the thermoelectric conversion element of the present invention.
As shown in FIG. 2, the thermoelectric conversion element 1B is an element having a substrate 2, a first processing electrode 3B, a thermoelectric conversion layer 5, a second processing electrode 4B, and a protective substrate 6 in this order.
Here, the thermoelectric conversion element 1 </ b> B illustrated in FIG. 2 is a mode in which an electromotive force (voltage) is obtained using a temperature difference in a direction indicated by an arrow.

In the thermoelectric conversion element 1B according to the second embodiment, the same members as those of the thermoelectric conversion element 1 according to the first embodiment are used, but the arrangement positions thereof are different, and the thermoelectric conversion layer 5 is the first in the stacking direction of each layer. It is sandwiched between the first processing electrode 3B and the second processing electrode 4B. The first processing electrode 3B and the second processing electrode 4B are members made of the same material except that the shapes are different from those of the first processing electrode 3A and the second processing electrode 4A described above.
In the thermoelectric conversion element 1B, the surface of the adhesion layer (not shown) is positioned on the surface 3bs on the thermoelectric conversion layer 5 side of the first processing electrode 3B and the surface 4bs on the thermoelectric conversion layer 5 side of the second processing electrode 4B. In other words, the first processing electrode 3B has an electrode disposed on the substrate 2 and an adhesion layer fixed on the electrode and covering the electrode surface opposite to the substrate 2, and the surface of the adhesion layer is the surface 3bs. Located in. The second processing electrode 4B includes an electrode disposed on the substrate 6 and an adhesion layer fixed on the electrode and covering the electrode surface opposite to the substrate 6, and the surface of the adhesion layer is the surface 4bs. Located in.

<Third embodiment>
3A to 3C conceptually show a third embodiment of the thermoelectric conversion element of the present invention. 3A is a top view (a view of FIG. 3B viewed from above), FIG. 3B is a front view (a view of a substrate or the like to be described later), and FIG. 3C is a bottom view (FIG. 3B is viewed from below the view). It is a view).

As shown in FIGS. 3A to 3C, the thermoelectric conversion element 10 basically includes a first substrate 12, a thermoelectric conversion layer 16, a second substrate 20, a first processing electrode 26 and a second processing electrode 28. It is comprised.
Specifically, the thermoelectric conversion layer 16 is formed on the surface of the first substrate 12. Further, the thermoelectric conversion layer 16 is also referred to as a substrate surface direction of the first substrate 12 (hereinafter simply referred to as “surface direction”. In other words, the first substrate 12 and the second substrate 20 are stacked. The first processing electrode 26 and the second processing electrode 28 (electrode pair) are formed in contact with the thermoelectric conversion layer 16 so as to be sandwiched in a direction perpendicular to the direction.
The first processing electrode 26 and the second processing electrode 28 correspond to the electrodes having the above-described adhesion layer. Specifically, the surface of the first processing electrode 26 and the second processing electrode 28 that are in contact with the thermoelectric conversion layer 16 is the surface of an adhesion layer (not shown).
Although not shown in FIG. 3, an adhesive layer may be disposed between the first substrate 12 and the thermoelectric conversion layer 16 or between the second substrate 20 and the thermoelectric conversion layer 16.

  As shown in FIGS. 3A to 3C, the first substrate 12 includes a low thermal conductivity portion 12 a and a high thermal conductivity portion 12 b having a higher thermal conductivity than the low thermal conductivity portion 12 a. Similarly, the 2nd board | substrate 20 also has the high heat conductive part 20b whose heat conductivity is higher than the low heat conductive part 20a and the low heat conductive part 20a.

In the thermoelectric conversion element 10, the two substrates are arranged such that their high heat conduction portions are at different positions in the separation direction (that is, the energization direction) between the first processing electrode 26 and the second processing electrode 28.
The thermoelectric conversion element 10 has the 2nd board | substrate 20 stuck by the adhesion layer as a preferable aspect, and also the 1st board | substrate 12 and the 2nd board | substrate 20 have both a low heat conduction part and a high heat conduction part. The thermoelectric conversion element 10 has a configuration in which two substrates having a high heat conduction portion and a low heat conduction portion are used, and the high heat conduction portions of the two substrates are located at different positions in the plane direction, and the thermoelectric conversion layer is sandwiched between the two substrates. Have

  That is, the thermoelectric conversion element 10 is a thermoelectric conversion element (hereinafter also referred to as an in-plane type thermoelectric conversion element) that generates a temperature difference in the surface direction of the thermoelectric conversion layer and converts heat energy into electric energy. In the example shown, by using a substrate having a low thermal conductivity portion and a high thermal conductivity portion having a higher thermal conductivity than the low thermal conductivity portion, a temperature difference is caused in the surface direction of the thermoelectric conversion layer 16 to convert the thermal energy into electrical energy. Can be converted to

  In addition, the high heat conduction part or the low heat conduction part in the present invention indicates that the thermal conductivity is high or low with respect to the adjacent layer (adjacent high heat conduction part or low heat conduction part). The ratio of the thermal conductivity between the high heat conduction part and the low heat conduction part is preferably 100: 1 or more, more preferably 500: 1 or more, and still more preferably 1000: 1 or more.

  In the illustrated thermoelectric conversion element 10, the first substrate 12 and the second substrate 20 have the same configuration except that the arrangement positions and the directions of the front and back sides and the surface direction (substrate surface direction) are different. Therefore, in the following description, the first substrate 12 will be described as a representative example, unless the first substrate 12 and the second substrate 20 need to be distinguished.

In the illustrated thermoelectric conversion element 10, the first substrate 12 (second substrate 20) covers a region on one half of one surface of the plate-like material that becomes the low thermal conduction portion 12 a (low thermal conduction portion 20 a). It has a configuration in which the high heat conduction part 12b (high heat conduction part 20b) is laminated. In other words, in the first substrate 12, the high thermal conductivity portion 12 b is provided so as to cover the low thermal conductivity portion 12 a, that is, the half surface of the first substrate 12.
Accordingly, on one surface of the first substrate 12, a half region in the surface direction is the low heat conduction portion 12a, and the other half region is the high heat conduction portion 12b. Further, the entire surface of the other surface (12c) of the first substrate 12 becomes the low thermal conductive portion 12a. In the thermoelectric conversion element 10, the surface (12 c) of the first substrate 12 on which the high heat conductive portion 12 b of the low heat conductive portion 12 a is not formed becomes the formation surface of the thermoelectric conversion layer 16.

  In addition, in the thermoelectric conversion element of this invention, the 1st board | substrate 12 can utilize various structures other than the structure formed by laminating | stacking a high heat conduction part on the surface of a low heat conduction part. For example, as conceptually shown in FIG. 6A, the first substrate is formed with a concave portion in a half region of one surface of the plate-like material that becomes the low thermal conductive portion 12a, and the surface is uniform in the concave portion. The structure which incorporates the high heat conduction part 12b may be sufficient.

  As the low heat conduction part 12a and the low heat conduction part 20a, for example, a known resin substrate can be used. Examples of the resin substrate include the examples described in the first embodiment.

As long as the high heat conductive part 12b has a heat conductivity higher than the low heat conductive part 12a, the film and metal foil which consist of various materials are illustrated.
Specifically, various metals such as gold, silver, copper, and aluminum are exemplified in terms of thermal conductivity and the like. Of these, copper and aluminum are preferably used in terms of thermal conductivity, economy, and the like.

In the present invention, the thickness of the first substrate 12, the thickness of the low thermal conductive portion 12a, the thickness of the high thermal conductive portion 12b, etc. are the same as the forming material of the high thermal conductive portion 12b and the low thermal conductive portion 12a. What is necessary is just to set suitably according to a magnitude | size. In addition, the thickness of the 1st board | substrate 12 is the thickness of the low heat conductive part 12a of the area | region which does not have the high heat conductive part 12b. According to the study by the present inventors, the thickness of the first substrate 12 is preferably 2 to 100 μm, and more preferably 2 to 50 μm.
In addition, the size in the surface direction of the first substrate 12 (when viewed from the direction orthogonal to the substrate surface), the area ratio in the surface direction of the high heat conduction portion 12b in the first substrate 12, and the like are also included. What is necessary is just to set suitably according to the formation material of the part 12b, the magnitude | size of the thermoelectric conversion element 10, etc. FIG.

Furthermore, the position of the first substrate 12 in the surface direction of the high thermal conductive portion 12b is not limited to the illustrated example, and various positions can be used.
For example, in the 1st board | substrate 12, the high heat conductive part 12b may be included in the low heat conductive part 12a in the surface direction. Alternatively, a part of the high heat conduction unit 12b may be located at the end of the first substrate 12 in the plane direction, and the other region may be included in the low heat conduction unit 12a.
Further, the first substrate 12 may have a plurality of high heat conducting portions 12b in the surface direction.

In addition, the thermoelectric conversion element 10 shown to FIG. 3A-FIG. 3C is a preferable aspect which tends to produce the temperature difference between the 1st board | substrate 12 and the 2nd board | substrate 20, and the 1st board | substrate 12 and the 2nd board | substrate 20 are both The high heat conduction part 12b and the high heat conduction part 20b are located outside in the stacking direction.
However, the present invention may have a configuration in which the first substrate 12 and the second substrate 20 both have the high heat conduction portion 12b and the high heat conduction portion 20b located inside in the stacking direction. Alternatively, the first substrate 12 may be configured such that the high heat conductive portion 12b is positioned outside in the stacking direction, and the second substrate 20 is positioned such that the high heat conductive portion 20b is positioned inside in the stacking direction.
In the configuration in which the high heat conductive portion is formed of a conductive material such as metal and the high heat conductive portion is disposed inside the stacking direction, the high heat conductive portion, the first processing electrode 26, and the second processing electrode. 28 and at least one of the thermoelectric conversion layers 16 are electrically connected to each other, the insulating property between the high thermal conductivity portion and at least one of the first processing electrode 26, the second processing electrode 28, and the thermoelectric conversion layer 16 In order to ensure this, an insulating layer may be provided between them.

In the thermoelectric conversion element 10, the thermoelectric conversion layer 16 is formed on the surface (12 c) where the entire surface of the first substrate 12 is the low thermal conductive portion 12 a.
The aspect of the thermoelectric conversion layer 16 is the same as the aspect of the thermoelectric conversion layer 5 of the first embodiment described above, and includes at least CNT.
A second substrate 20 is provided on the thermoelectric conversion layer 16. The second substrate 20 is provided with the surface of the low heat conductive portion 20 a on which the high heat conductive portion 20 b is not formed facing the thermoelectric conversion layer 16.
The high thermal conductive portions 12b and 20b of both the substrates are arranged so as to efficiently generate a temperature difference in the surface direction of the thermoelectric conversion layer 16. That is, it is preferable that the high heat conductive portions 12b and 20b of both the substrates are arranged at different positions in the plane direction with respect to the thermoelectric conversion layer 16, and the boundary between the low heat conductive portion and the high heat conductive portion of both the substrates is More preferably, the conversion layer 16 is provided so as to coincide with the center of the surface direction, and it is further preferable that the boundary is spaced apart in the electrode separation direction.
The thermoelectric conversion layer 16 is connected to an electrode pair including the first processing electrode 26 and the second processing electrode 28 so as to be sandwiched in the surface direction.

The thermoelectric conversion element has a difference in carrier density in the direction of the temperature difference in the thermoelectric conversion layer inside the thermoelectric conversion layer due to a temperature difference caused by, for example, heating due to contact with a heat source. Occurs.
For example, a heat source is provided on the first substrate 12 side, and a temperature difference is generated between the high heat conductive portion 12b of the first substrate 12 and the high heat conductive portion 20b of the second substrate 20, thereby causing the inside of the thermoelectric conversion layer 16 to be inside. Therefore, a difference occurs in the carrier density in the direction of the temperature difference, and power is generated. Further, by connecting wiring to the first processing electrode 26 and the second processing electrode 28, electric power (electric energy) generated by heating is taken out.

  In the thermoelectric conversion element 10 of the present invention, the thickness of the thermoelectric conversion layer 16, the size in the surface direction, the area ratio in the surface direction with respect to the substrate, and the like depend on the forming material of the thermoelectric conversion layer 16, the size of the thermoelectric conversion element 10, etc. Accordingly, it may be set appropriately.

In the example shown in FIGS. 3A to 3C, the thermoelectric conversion layer 16 has a rectangular parallelepiped shape, but in the thermoelectric conversion element of the present invention, various shapes can be used for the thermoelectric conversion layer 16.
For example, the thermoelectric conversion layer may have a quadrangular pyramid shape or the like. Alternatively, it may be a columnar shape, a prism shape other than a square shape, a truncated cone, a truncated pyramid, an indefinite shape, or the like.

A first processing electrode 26 and a second processing electrode 28 are provided on the surface of the first substrate 12 so as to sandwich the thermoelectric conversion layer 16 in the surface direction.
In addition, in the thermoelectric conversion element of this invention, the shape of the 1st process electrode 26 and the 2nd process electrode 28 is not restrict | limited to the shape shown by FIG. 3A-FIG. 3C, and it is sufficient electroconductivity in the thermoelectric conversion layer 16. Various shapes can be used as long as they are connected.
For example, as conceptually shown in FIG. 4, the thermoelectric conversion layer 16 covers the end portions of the plate-like first processing electrode 30 and the second processing electrode 32 formed on the surface of the first substrate 12. Such a configuration may be adopted.

  The aspect of the 1st processing electrode 26 and the 2nd processing electrode 28 is synonymous with the 1st processing electrode 3 and the 2nd processing electrode 4 which were described in the 1st embodiment mentioned above.

  In addition, the thickness, size, shape, and the like of the first processing electrode 26 and the second processing electrode 28 are appropriately set according to the thickness, size, shape, and size of the thermoelectric conversion element 10 of the thermoelectric conversion layer 16. do it.

As described above, the thermoelectric conversion element 10 includes the adhesive layer disposed between the first substrate 12 and the thermoelectric conversion layer 16 and / or between the second substrate 20 and the thermoelectric conversion layer 16. Also good.
The material for forming the adhesive layer depends on the materials for forming the first substrate 12 (low heat conduction part 12a), the second substrate 20 (low heat conduction part 20a), the first processing electrode 26 and the second processing electrode 28, etc. Various things that can be attached are available.
Specific examples include acrylic resin, urethane resin, silicone resin, epoxy resin, rubber, EVA (Ethylene-Vinyl Acetate), α-olefin polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, gelatin, starch and the like. Moreover, you may form an adhesion layer using a commercially available double-sided tape and an adhesive film.
The thickness of the pressure-sensitive adhesive layer depends on the material for forming the pressure-sensitive adhesive layer, the material for forming the first substrate 12 and the second substrate 20, the size thereof, and the like, and is attributable to the thermoelectric conversion layer 16. What is necessary is just to set suitably the thickness which can fill a level | step difference.

In the illustrated thermoelectric conversion element 10, the high thermal conductive portion 12 b of the first substrate 12 and the high thermal conductive portion 20 b of the second substrate 20 face each other in the inter-electrode direction and abut the end portions thereof. Arranged at different positions.
In addition to this, various configurations can be used for the thermoelectric conversion element of the present invention.
For example, in the example shown in FIGS. 3A to 3C, the high heat conduction portion 12 b of the first substrate 12 is moved to the right side in the drawing, and the high heat conduction portion 20 b of the second substrate 20 is moved to the left side in the drawing, Both high heat conduction parts may be separated in the inter-electrode direction. Specifically, the high thermal conductive portion 12b of the first substrate 12 and the high thermal conductive portion 20b of the second substrate 20 are in the plane direction, the thermoelectric conversion layer in the direction in which the first processing electrode 26 and the second processing electrode 28 are separated from each other. The size of 16 is preferably 10 to 90% apart, more preferably 10 to 50% apart in the direction between the electrodes.
On the contrary, in the example shown in FIGS. 3A to 3C, the high heat conduction part 12b of the first substrate 12 is moved to the left side in the figure, and the high heat conduction part 20b of the second substrate 20 is moved to the right side in the figure, thereby A part of the high thermal conductivity portion of the substrate may overlap in the plane direction.

Alternatively, a circular high heat conduction part is formed on the first substrate, and a square high heat conduction part of the same size (diameter and length of one side coincides) is formed on the second substrate, and the center of both high heat conduction parts is faced. You may arrange | position both board | substrates so that it may correspond in a direction. Even in this configuration, although the distance is short, since the end (periphery) positions of the two high heat conducting portions are different in the surface direction, a temperature difference in the surface direction is generated in the thermoelectric conversion layer, and a temperature difference is generated in the thickness direction. Efficient power generation is possible compared to thermoelectric conversion elements.
That is, in the present invention, various configurations can be used for the first substrate and the second substrate as long as the high thermal conductivity portions do not completely overlap in the plane direction between the first substrate and the second substrate. In other words, when the first substrate and the second substrate are viewed from the direction perpendicular to the substrate surface, various configurations can be used as long as the high thermal conductivity portions of the first substrate and the second substrate do not completely overlap. is there.

<Thermoelectric conversion module>
5A to 5D conceptually show an example of the thermoelectric conversion module of the present invention in which a plurality of such thermoelectric conversion elements 10 of the present invention are connected in series. 5A to 5C are top views and FIG. 5D is a front view. As described in detail later, in the embodiment of the thermoelectric conversion module of FIGS. 5A to 5D, the first processing electrode 26 has an adhesion layer having the above-described electrode and an aromatic ring fixed on the electrode. Applicable.

In this example, each of the first substrate 12A and the second substrate 20A has a rectangular plate-like high heat conductive portion that extends in one direction on the surface of a rectangular plate-like low heat conductive material, and a side that contacts the low heat conductive portion of the square pillar. Are arranged in the direction orthogonal to the extending direction of the quadrangular prism at equal intervals.
That is, in the first substrate 12A and the second substrate 20A, the entire surface of one surface is a low heat conductive portion, and the other surface is a low heat conductive portion and a high heat conductive portion extending in one direction. It has a structure formed alternately at equal intervals in the orthogonal direction (see FIGS. 5A, 5C, and 5D).
Also in this example, the first substrate (second substrate) can use various configurations other than the configuration in which the high thermal conductivity portion is placed on the surface of the low thermal conductivity portion. For example, as conceptually shown in FIG. 6B, the first substrate has a groove extending in one direction (a direction perpendicular to the paper surface of FIG. 6B) in the rectangular plate-shaped low heat conducting portion 12a. Alternatively, the groove may be formed at equal intervals with the width of the groove in a direction orthogonal to the extending direction, and the high heat conducting portion 12b may be incorporated in the groove.

As shown in FIG. 5B, the thermoelectric conversion layer 16 has a rectangular surface shape, and the entire surface of the first substrate 12A is the surface (12c) on the side that is the low thermal conduction portion 12a (FIG. 5D is reversed upside down in the figure. The center of the thermoelectric conversion layer 16 and the boundary between the low heat conduction portion 12a and the high heat conduction portion 12b are aligned in the plane direction. The horizontal direction of the thermoelectric conversion layer 16 in FIG. 4B (hereinafter, also simply referred to as “lateral direction”) is set between 0.5 times and less than 2.0 times the width of the high thermal conductive portion 12b. The That is, the horizontal direction is an alternate arrangement direction of the low heat conduction portions 12a and the high heat conduction portions 12b.
The thermoelectric conversion layer 16 is formed at equal intervals every other boundary with respect to the boundary between the low thermal conductivity portion 12a and the high thermal conductivity portion 12b in the lateral direction. That is, the thermoelectric conversion layer 16 is formed at equal intervals with the same center as the distance of twice the width of the high thermal conductive portion 12b.
Further, the thermoelectric conversion layers 16 are arranged such that the rows of the thermoelectric conversion layers 16 arranged at equal intervals in the horizontal direction are arranged at equal intervals in the vertical direction of FIG. 5B (hereinafter also simply referred to as “vertical direction”). , Formed two-dimensionally. That is, the up and down direction is the extending direction of the low heat conduction portion 12a and the high heat conduction portion 12b.
Furthermore, as shown in FIG. 5B, the horizontal arrangement of the thermoelectric conversion layers 16 is formed so as to be shifted in the horizontal direction by the width of the high thermal conductive portion 12 b in the columns adjacent in the vertical direction. In other words, in the rows adjacent in the vertical direction, the thermoelectric conversion layers 16 are alternately formed with the horizontal centers corresponding to the widths of the high heat conduction portions 12b.

The thermoelectric conversion layers 16 are connected in series by the first processing electrode 26. Specifically, as shown in FIG. 5B, in the arrangement of the thermoelectric conversion layers 16 in the horizontal direction in the drawing, the first processing electrodes 26 (shown by shading for the sake of clarity) are connected to each thermoelectric conversion layer. 16 is provided so as to sandwich it horizontally. Thereby, the thermoelectric conversion layers 16 arranged in the horizontal direction are connected in series by the first processing electrode 26.
At the ends of the rows in the horizontal direction of the thermoelectric conversion layers 16, the thermoelectric conversion layers 16 in rows adjacent in the vertical direction are connected by the first processing electrode 26. The connection of the thermoelectric conversion layer 16 in the vertical direction by the first processing electrode 26 at the end of the horizontal row is such that the thermoelectric conversion layer 16 at one end is the thermoelectric conversion layer 16 at the same end of the upper row. The thermoelectric conversion layer 16 at the other end is connected to the thermoelectric conversion layer 16 at the same end in the lower row.
Thereby, all the thermoelectric conversion layers 16 are connected in series like the one line | wire folded in multiple times in the horizontal direction.

As conceptually shown in FIG. 5A, on the thermoelectric conversion layer 16 and the first processing electrode 26, the entire surface of the second substrate 20 </ b> A has a surface (20 c) on the side that is the low thermal conductive portion 20 a, and The second substrate 20A is laminated such that the boundary between the low heat conductive portion 20a and the high heat conductive portion 20b is coincident with the boundary between the low heat conductive portion 12a and the high heat conductive portion 12b of the first substrate 12A. This stacking is performed so that the high thermal conductive portion 12b of the first substrate 12A and the high thermal conductive portion 20b of the second substrate 20A are alternated.
Although not shown, an adhesive layer is formed on the thermoelectric conversion layer 16 and the first processing electrode 26 so as to cover the entire surface of the first substrate 12A prior to the lamination of the second substrate 20A.

Therefore, the low heat conduction part 12a of the first substrate 12A and the region of the second substrate 20A only with the high heat conduction part 20b are aligned in the plane direction and face each other, and the high heat conduction part 12b of the first substrate 12A and the second substrate 20A The region of only the low heat conducting portion 20a faces the surface direction in alignment.
Thereby, the thermoelectric conversion module of this invention formed by connecting two or more thermoelectric conversion elements 10 of this invention in series is comprised.

  In the above embodiment, the first processing electrode 26 includes the above-described electrode and an adhesion layer having an aromatic ring fixed on the electrode. In the above aspect, the adhesion layer in the first processing electrode 26 and the thermoelectric conversion layer 16 are in contact with each other.

Here, as described above, in the horizontal arrangement of the thermoelectric conversion layers 16, in the columns adjacent in the vertical direction, the horizontal center line of the thermoelectric conversion layers 16 is the high heat conduction portion 12b (that is, the high heat conduction portion 20b). This is formed by shifting in the horizontal direction by the width of. In other words, in the rows adjacent in the vertical direction, the thermoelectric conversion layers 16 are formed so that the horizontal center lines of the thermoelectric conversion layers 16 are staggered by the width of the high thermal conductivity portion 12b.
For this reason, the thermoelectric conversion layers 16 connected in series as a single folded line have all the thermoelectric conversion layers 16 in the flow in one direction of the connection direction, and one half of the thermoelectric conversion layers 16 is the high thermal conductivity of the first substrate 12A. The portion 12b faces the region of the second substrate 20A only of the low heat conduction portion 20a, and the other half faces the region of only the low heat conduction portion 12a of the first substrate 12A and the high heat conduction portion 20b of the second substrate 20A. .
For example, when viewed in the series connection direction from the top to the bottom of FIG. 5B, as shown in FIGS. 5A to 5C, all the thermoelectric conversion layers 16 have high thermal conductivity of the first substrate 12A in the upstream half. The portion 12b and the second substrate 20A face only the region of the low heat conduction portion 20a, and the downstream half faces the region of the first substrate 12A only of the low heat conduction portion 12a and the second substrate 20A of the high heat conduction portion 20b.
Therefore, when the heat source is arranged on the first substrate 12A side or the second substrate 20A side, the heat flow direction relative to the connection direction, that is, the flow direction of the generated electricity is the same in all the thermoelectric conversion layers 16 connected in series. And the thermoelectric conversion module can generate electricity properly.

(Method for manufacturing thermoelectric conversion module)
Below, an example of the manufacturing method of the thermoelectric conversion module shown to FIG. 5A-FIG. 5D is demonstrated. In addition, a thermoelectric conversion element can be manufactured according to the manufacturing method of this thermoelectric conversion module.

  First, a first substrate 12A (first substrate 12) having a low thermal conductivity portion 12a and a high thermal conductivity portion 12b, and a second substrate 20A (second substrate 20) having a low thermal conductivity portion 20a and a high thermal conductivity portion 20b are prepared. .

The first substrate 12A and the second substrate 20A may be manufactured by a known method using photolithography, etching, film formation technology, or the like.
For example, it can be produced by etching one surface of a copper polyimide film in which copper is laminated on both surfaces of the substrate, and etching the other surface so as to form a high heat conduction portion pattern. In addition, a sheet-like material of the substrate to be the low heat conduction part is prepared, and the belt-like high heat conduction part is attached to the sheet-like material in the direction orthogonal to the extending direction at equal intervals with the width of the belt. What is necessary is just to produce 1 board | substrate 12A and 2nd board | substrate 20A.
Commercially available products can also be used for the first substrate 12A and the second substrate 20A.

Next, the first processing electrode 26 is formed. Examples of the method for forming the first processing electrode 26 include the method for forming the first processing electrode 3 described in the first embodiment.
Next, the thermoelectric conversion layer 16 is formed so as to sandwich the first processing electrode 26 in the surface direction. Examples of the method for forming the thermoelectric conversion layer 16 include the method for forming the thermoelectric conversion layer 5 described in the first embodiment.

  Furthermore, the prepared second substrate 20A is attached to the thermoelectric conversion layer 16 with the surface (20c) on which the high heat conducting portion 20b is not formed, and a thermoelectric conversion module (thermoelectric conversion element 10) is manufactured. To do. In sticking, an adhesive layer may be used as necessary.

Such a thermoelectric conversion element and thermoelectric conversion module of the present invention can be used for various applications.
Examples include various power generation applications such as hot spring thermal generators, solar thermal generators, waste heat generators, and other devices (devices) such as wristwatch power supplies, semiconductor drive power supplies, and small sensor power supplies. The Moreover, as a use of the thermoelectric conversion element of this invention, sensor element uses, such as a thermal sensor and a thermocouple, are illustrated besides a power generation use.

  As described above, the thermoelectric conversion element and the thermoelectric conversion module of the present invention have been described in detail. However, the present invention is not limited to the above-described examples, and various improvements and modifications can be made without departing from the gist of the present invention. Of course it is good.

  Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention. However, the present invention is not limited to the following examples.

<Preparation of CNT dispersion>
To 20 mL of water, 500 mg of CNT (manufactured by Meijo Nanocarbon Co., Ltd.) and 1500 mg of sodium deoxycholate were added.
This solution was dispersed for 7 minutes using a bladed homogenizer. The obtained dispersion was further subjected to a stirring process for 5 minutes at a peripheral speed of 30 m / s using a high-speed rotating thin film dispersion method (Filmix, manufactured by Primex) to obtain a CNT dispersion.

<Manufacture of treated electrodes>
A first substrate 12A and a second substrate 20A in which copper stripes having a width of 0.5 mm and a thickness of 70 μm were formed on one surface of a polyimide film having a thickness of 25 μm and 15 × 12 cm were prepared (FIG. 5A). To FIG. 5D).
By vacuum deposition using a mask, 0.5 × can be formed so that 1785 thermoelectric conversion layers 16 can be formed in a 6 × 6 cm region of the surface of the first substrate 12A, which is the low thermal conductive portion 12a, as will be described later. A pattern of 1 mm electrodes (thickness 200 nm) was formed (see FIG. 5B). As shown in FIG. 5B, the electrode pattern is formed so that the boundary between the high thermal conductive portion 12b and the low thermal conductive portion 12a (the boundary of the copper stripe) coincides with the center of the 0.5 × 1 mm pattern. did. As shown in FIG. 5B, at the end of the row in the horizontal direction of the thermoelectric conversion layer 16, the electrode pattern is formed so that the thermoelectric conversion layers 16 in the row adjacent in the vertical direction are connected by the first processing electrode 26. Formed.
In addition, the material shown in Table 4 was used for the material of the used electrode in each Example and each comparative example.
The obtained substrate having an electrode was immersed in 100 mL of ethanol, subjected to ultrasonic cleaning, and dried at 100 ° C. for 1 hour. The washed substrate was immersed in an ethanol solution of an organic compound (5 mmol / L) used in each example shown in Table 4 at room temperature for 24 hours. Thereafter, the substrate was taken out, washed with ethanol, and then dried at 100 ° C. for 1 hour, whereby the surface of the electrode was subjected to surface treatment to obtain a first processing electrode 26 having an adhesion layer containing a predetermined component.
In addition, the group represented by -M (X) _3-n (R) _n is contained in the organic compound used in Examples 1-4, and in the adhesion layer formed in each Example, These organic compound hydrolysates and hydrolysis condensates were included.
Further, as will be described later, in Example 12, the surface treatment of the electrode was performed by a method different from the above.

The polymer used in Example 11 was synthesized by the following method.
<Benzyl methacrylate / methacrylic acid polymer>
In a 300 mL three-necked flask, 20 g of benzyl methacrylate, 10 g of methacrylic acid, and 70 g of methyl ethyl ketone were charged and heated to 75 ° C. in a nitrogen atmosphere. Thereafter, 0.5 g of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added and reacted for 2 hours. Furthermore, 0.25 g of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added and reacted for 2 hours. The obtained reaction solution was reprecipitated in methanol to obtain 25 g of the target polymer. The weight average molecular weight was 10,000 by GPC (Gel Permeation Chromatography) measurement.
The GPC measurement conditions were as follows.
Column: TSK-GEL SuperH manufactured by Tosoh Corporation
Column temperature: 40 ° C
Flow rate: 1 mL / min
Eluent: THF (tetrahydrofuran)

Moreover, in Example 12, the electrode surface treatment was performed by the following method.
The board | substrate which has an electrode was immersed in the ethanol solution of 2-carboxyethyl acrylate (5 mmol / L) for 24 hours at room temperature. Thereafter, the substrate was taken out, washed with ethanol, and then dried at 50 ° C. for 1 hour. Then, it was immersed in an ethanol solution of 2-mercaptonaphthalene (5 mmol / L) and triethylamine (5 mmol / L) at room temperature for 24 hours. Then, after washing with ethanol, the substrate was dried at 100 ° C. for 1 hour to perform surface treatment of the electrode, thereby obtaining a first treated electrode 26 having an adhesion layer containing a predetermined component.

<Manufacture of thermoelectric conversion elements>
Next, a CNT dispersion was applied between each first processing electrode 26 by screen printing to form 1785 patterns of 0.5 × 1 mm. The first substrate 12A on which the pattern was formed was heated on a hot plate at 50 ° C. for 30 minutes, and further heated at 130 ° C. for 2.5 hours to dry the pattern. Next, the first substrate 12A was immersed in ethanol for 14 hours. The 1st board | substrate 12A immersed in ethanol was heated for 30 minutes at 50 degreeC on the hotplate, and also the thermoelectric conversion layer 16 was produced by heating for 150 minutes at 130 degreeC.
The pattern was formed so that the boundary between the high heat conduction part 12b and the low heat conduction part 12a (the boundary between the copper stripes) and the center of the 0.5 × 1 mm pattern coincided. On the first substrate 12A, 1785 thermoelectric conversion layers 16 were connected in series by the first processing electrode 26 (see FIG. 5B).
On the other hand, a double-sided tape (adhesive transfer tape 8146-1, 3M) having a thickness of 25 μm was stuck as an adhesive layer on the surface of the second substrate 20A, which is the low thermal conductive portion 20a.
This double-sided tape was affixed so as to cover the thermoelectric conversion layer 16 and the first processing electrode 26 to produce a thermoelectric conversion module as shown in FIGS. 5A to 5D. In the second substrate 20A, the center of the thermoelectric conversion layer 16 and the boundary of the copper stripe coincide with each other, and the extending direction of the copper stripe of the second substrate 20A is the extending direction of the copper stripe of the first substrate 12A. Furthermore, the first substrate 12A and the second substrate 20A have a high heat conduction portion and a low heat conduction portion that alternate (in the plane direction, the copper stripe of the first substrate 12A and the copper of the second substrate 20A). The stripes were attached so that the stripes did not overlap.
The produced thermoelectric conversion module was placed on the hot plate with the first substrate 12A side down, and a Peltier element for temperature control was installed on the second substrate 20A.
A temperature difference of 10 ° C. was made between the first substrate 12A and the second substrate 20A of the thermoelectric conversion module by keeping the temperature of the hot plate constant at 100 ° C. and decreasing the temperature of the Peltier element.

<Evaluation>
(Evaluation of power generation (thermoelectric conversion characteristics))
The power generation amount of the produced thermoelectric conversion module was measured and evaluated according to the following evaluation criteria. The results are summarized in Table 4.
AAA: Power generation amount 35 μW or more AA: Power generation amount 30 μW or more and less than 35 μW A: Power generation amount 25 μW or more and less than 30 μW B: Power generation amount 20 μW or more and less than 25 μW C: Power generation amount 15 μW or more and less than 20 μW D: Power generation amount 15 μW or less

(Bend resistance evaluation)
The produced thermoelectric conversion module was set in a mandrel bending tester having a diameter of 32 mm, bent five times, and then the resistance value of the thermoelectric conversion module was measured to evaluate the bending resistance, and evaluated according to the following evaluation criteria. . The results are summarized in Table 4. In addition, the following resistance value variation rate (%) is {(resistance value of thermoelectric conversion module after bending test) − (resistance value of thermoelectric conversion module before bending test) / (resistance of thermoelectric conversion module after bending test). Value)} × 100.
AAA: Resistance value fluctuation rate of less than 5% AA: Resistance value fluctuation rate of 5% or more and less than 10% A: Resistance value fluctuation rate of 10% or more and less than 15% B: Resistance value fluctuation rate of 15% or more and less than 20% C: Resistance value fluctuation Rate 20% or more and less than 25% D: Resistance value fluctuation rate 25% or more

In Table 4, the columns of “Expression (1)”, “Expression (2)”, “Expression (3)”, “Expression (4)”, and “Expression (5)” are respectively the above-described Expression (1), Expression (2), The part applicable to each group in Formula (3), Formula (4), and Formula (5) is represented. However, in Comparative Examples 2, 3 and 5, there is no group corresponding to the “Y” column, but the structure of the compound used for comparison is shown.
In Table 4, “Et” represents an ethyl group, “iPr” represents an isopropyl group, “Bz” represents a benzene ring, “Np” represents a naphthalene ring, and “Py” represents a pyrene ring.

As shown in Table 4 above, it was confirmed that the thermoelectric conversion element using the predetermined treatment electrode was excellent in thermoelectric conversion performance (power generation amount) and also in bending resistance.
Especially, when the organic compound contains a thiol group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a disulfide group, or the like from the comparison of Examples 1 to 16 (more preferably, a thiol group, a carboxyl group, a phosphoric acid group, It was confirmed that the disulfide group), power generation amount and bending resistance were more excellent.
Moreover, it was confirmed from the comparison with Example 6 and Example 7 (or comparison with Example 14 and Example 16) that an effect is more excellent when an aromatic ring is a polycyclic aromatic ring.
Moreover, from the comparison with Example 8 and 9, when L was a bivalent coupling group in Formula (1), it was confirmed that an effect is more excellent.

  On the other hand, the desired effects were not obtained in Comparative Examples 1 to 5 in which the treatment with the predetermined organic compound was not performed and the adhesion layer was not provided.

1A, 1B, 10 Thermoelectric conversion element 2 Substrate 6 Protective substrate 12, 12A First substrate 12a, 20a Low heat conduction part 12b, 20b High heat conduction part 5, 16 Thermoelectric conversion layer 20, 20A Second substrate 3, 26, 30 First Processing electrode 4, 28, 32 Second processing electrode

Claims (7)

A treatment electrode including an electrode and an adhesion layer having an aromatic ring, which is fixed on the electrode;
The thermoelectric conversion element which has a thermoelectric conversion layer which contacts the said process electrode and contains a carbon nanotube.   The thermoelectric conversion element according to claim 1, wherein the adhesion layer includes an organic compound having an aromatic ring. A first compound in which the organic compound has at least one adsorptive group and an aromatic ring selected from the group consisting of a thiol group, a disulfide group, a sulfonic acid group, an amino group, a carboxyl group, and a phosphoric acid group Or
The thermoelectric conversion according to claim 2, comprising a second compound having a group represented by -M (X) _3-n (R) _n and an aromatic ring, a hydrolyzate thereof, or a hydrolyzed condensate thereof. element.
M represents Si, Ti, or Zr. X represents a hydrolyzable group. R represents a monovalent organic group. n represents 0, 1 or 2. However, the monovalent organic group does not include the hydrolyzable group. A compound in which the organic compound has a compound represented by the formula (1), a compound represented by the formula (2), a repeating unit represented by the formula (3), and a repeating unit represented by the formula (4); Or the thermoelectric conversion element of Claim 2 or 3 containing the compound represented by Formula (5), its hydrolyzate, or its hydrolysis condensate.
Formula (1) X1-LY
Formula (2) YL-X2-LY
Formula (5) X3-LY
In formula (1) and formula (3), X1 represents a thiol group, a sulfonic acid group, an amino group, a carboxyl group, or a phosphoric acid group.
In formula (2), X2 represents a disulfide group.
In formula (1), formula (2), formula (4), and formula (5), Y represents a substituted or unsubstituted aromatic ring.
In formula (1) to formula (5), L represents a single bond or a divalent linking group.
In formula (3) and formula (4), R ₁ and R ₂ each independently represents a hydrogen atom or an alkyl group.
In Formula (5), X3 represents a group represented by -M (X) _3-n (R) _n . M represents Si, Ti, or Zr. X represents a hydrolyzable group. R represents a monovalent organic group. n represents 0, 1 or 2. However, the monovalent organic group does not include the hydrolyzable group.   The organic compound is a compound represented by Formula (1) in which L in Formula (1) is a divalent linking group, or Formula (5) in which L in Formula (5) is a divalent linking group. The thermoelectric conversion element of Claim 4 containing the compound represented by this, its hydrolyzate, or its hydrolysis condensate.   The thermoelectric conversion element according to any one of claims 1 to 5, wherein the aromatic ring is a polycyclic aromatic ring.   The thermoelectric conversion element according to claim 2, wherein the organic compound includes at least one selected from the group consisting of a thiol group, a disulfide group, a phosphate group, and a carboxyl group.