JPWO2016052358A1 - Thermoelectric conversion element, conductive film, and organic semiconductor device - Google Patents

Abstract

An object of this invention is to provide the thermoelectric conversion element with high thermoelectromotive force, the electrically conductive film with high electrical conductivity, and the organic-semiconductor device using the said electrically conductive film. The thermoelectric conversion element of the present invention is a thermoelectric conversion element comprising a thermoelectric conversion layer containing a π-conjugated polymer, wherein the π-conjugated polymer has a repeating unit having a molecular weight of 150 or more and is doped with a carrier. It is a polymer, and the crystallinity of the thermoelectric conversion layer is 20% or more.

Description

  The present invention relates to a thermoelectric conversion element, a conductive film, and an organic semiconductor device.

Thermoelectric conversion materials that can mutually convert 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 materials and thermoelectric conversion elements can directly convert heat energy into electric power, does not require moving parts, operates at body temperature, power supplies for remote areas, power supplies for space, etc. It is used for.
For example, Patent Document 1 discloses an embodiment in which a conductive polymer is used for a thermoelectric conversion layer of a thermoelectric conversion element. In the example of Patent Document 1, a liquid mixture containing a conductive polymer is applied onto a substrate and heated to form a thermoelectric conversion layer.

JP 2013-84947 A

On the other hand, in recent years, further improvement in the thermoelectromotive force of thermoelectric conversion elements has been demanded in order to improve the performance of equipment in which thermoelectric conversion elements are used. In addition, since the conductivity of the thermoelectric conversion layer (conductive film) of the thermoelectric conversion element directly affects the performance of the thermoelectric conversion element (thermoelectromotive force, conversion efficiency, responsiveness, etc.), a conductive film having high conductivity is required. ing. Moreover, such a conductive film exhibiting high electrical conductivity is useful not only for thermoelectric conversion elements but also for organic semiconductor devices.
Under these circumstances, the inventors applied a solution of a conductive polymer (π-conjugated polymer) on a substrate with reference to the example of Patent Document 1 and heated to produce a conductive film. The rate does not necessarily meet the level required recently, and it was found that further improvement is necessary. Similarly, when a solution of a conductive polymer (π-conjugated polymer) is applied on a substrate and heated to form a thermoelectric conversion layer of the thermoelectric conversion element, the thermoelectromotive force of the thermoelectric conversion element is recently required. It has been found that further improvement is necessary, not necessarily satisfying the level.

  Then, in view of the said situation, this invention aims at providing the thermoelectric conversion element with high thermoelectromotive force, the electrically conductive film with high electrical conductivity, and the organic-semiconductor device using the said electrically conductive film.

As a result of intensive studies on the above problems, the present inventors have used a π-conjugated polymer having a repeating unit of a specific molecular weight and doped with carriers in the thermoelectric conversion layer (conductive film), and the thermoelectric conversion layer. It has been found that the above problem can be solved by specifying the crystallinity of (conductive film).
That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) A thermoelectric conversion element comprising a thermoelectric conversion layer containing a π-conjugated polymer,
The π-conjugated polymer has a repeating unit having a molecular weight of 150 or more and is a π-conjugated polymer doped with carriers.
The thermoelectric conversion element whose crystallinity degree of the said thermoelectric conversion layer is 20% or more.
(2) The π-conjugated polymer is a thiophene compound, a pyrrole compound, an aniline compound, an acetylene compound, a p-phenylene compound, a p-phenylene vinylene compound, a p-phenylene ethynylene compound, or a derivative thereof. The thermoelectric conversion element according to (1) above, which is a π-conjugated polymer having a repeating unit derived from at least one monomer selected from the group consisting of:
(3) The thermoelectric conversion element according to (1) or (2), wherein the π-conjugated polymer is a π-conjugated polymer containing at least two types of aromatic rings in a repeating unit.
(4) The thermoelectric conversion element according to any one of (1) to (3), wherein the π-conjugated polymer is a π-conjugated polymer containing an aromatic condensed ring in a repeating unit.
(5) The thermoelectric conversion element according to any one of (1) to (4), wherein the π-conjugated polymer has a repeating unit represented by the formula (1) described later.
(6) In the above formula (1), A is a divalent conjugated linking group obtained by removing two hydrogen atoms from any position of the compound represented by the formula (A1) described later. The thermoelectric conversion element according to 1.
(7) In the formula (A1), m is 1, and X ³¹ and X ⁴² are each independently a sulfur atom, an oxygen atom, or a —NR ^N2 — group, or X ³² and X ^41. Are each independently a sulfur atom, an oxygen atom, or a —NR ^N2 — group. Here, R ^N2 represents a hydrogen atom or an alkyl group.
(8) In the formula (A1), m is 1, n is an integer of 1 or more, and the A ring is a benzene ring, pyrrole ring, thiophene ring, pyridine ring, cyclopentadiene ring, or silole ring. The thermoelectric conversion element according to (6) or (7) above.
(9) In the above formula (Z), any one of the above (5) to (8), wherein the Hammett substituent constant σ _p value of the electron donating group represented by R ^Z1 is −0.20 or less. The thermoelectric conversion element according to 1.
(10) In the above formula (Z), R ^Z1 represents a hydroxy group or a salt thereof, a mercapto group or a salt thereof, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, amino The thermoelectric conversion element according to any one of (5) to (9), which is a group, an alkylamino group, an arylamino group, a heterocyclic amino group, or an aryl group substituted with these groups.
(11) The thermoelectric conversion element according to any one of (5) to (10), wherein Z in the formula (1) is a group represented by formula (Z1) described later.
(12) The thermoelectric conversion element according to any one of (5) to (11), wherein ^XZ1 is a sulfur atom, an oxygen atom, or a —NR ^N2 — group in the formula (Z). Here, R ^N2 represents a hydrogen atom or an alkyl group.
(13) The thermoelectric conversion element according to any one of (5) to (12), wherein Y is a single bond or a 2,5-thienyl group in the formula (1).
(14) In the formula (1), A is a divalent conjugated linking group obtained by removing two hydrogen atoms from any position of the compound represented by the formula (A1), and two Y are The thermoelectric conversion element according to any one of the above (5) to (13), wherein both are single bonds, and two Zs are groups represented by the formula (Z1a) described later.
(15) In the formula (A1), m is 1, and X ³¹ and X ⁴² are each independently a sulfur atom, an oxygen atom, or a —NR ^N2 — group, or X ³² and X ^41. Are each independently a sulfur atom, an oxygen atom, or a —NR ^N2 — group. Here, R ^N2 represents a hydrogen atom or an alkyl group.
(16) In the formula (A1), m is 1, n is an integer of 1 or more, and the A ring is a benzene ring, a pyrrole ring, a thiophene ring, a pyridine ring, a cyclopentadiene ring, or a silole ring. The thermoelectric conversion element according to (14) or (15) above.
(17) The thermoelectric conversion element according to any one of (1) to (16), wherein the thermoelectric conversion layer further contains an oxidizing agent.
(18) The thermoelectric conversion element according to any one of (1) to (17), wherein the π-conjugated polymer is obtained by polymerization by an oxidative polymerization method in the presence of an oxidizing agent.
(19) The thermoelectric according to (18), wherein the oxidizing agent is at least one compound selected from the group consisting of iron (III) salts, copper (II) salts, peroxides, and peracids. Conversion element.
(20) The above (1) to (19), wherein the π-conjugated polymer is obtained by polymerization by a template polymerization method in the presence of a π-conjugated polymer having a repeating unit different from the repeating unit and an oxidizing agent. The thermoelectric conversion element in any one.
(21) A π-conjugated polymer having a repeating unit different from the above repeating unit is a thiophene compound, a pyrrole compound, an aniline compound, an acetylene compound, a p-phenylene compound, a p-phenylene vinylene compound, or p-phenylene. The thermoelectric conversion element according to (20), which is a π-conjugated polymer having a repeating unit derived from at least one monomer selected from the group consisting of an ethynylene compound and a derivative thereof.
(22) A conductive film containing a π-conjugated polymer,
The π-conjugated polymer has a repeating unit having a molecular weight of 150 or more and is a π-conjugated polymer doped with carriers.
The electrically conductive film whose crystallinity degree of the said electrically conductive film is 20% or more.
(23) The conductive film according to (22), wherein the π-conjugated polymer has a repeating unit represented by Formula (1) described later.
(24) In the above formula (1), A is a divalent conjugated linking group in which two hydrogen atoms are removed from any position of the compound represented by the following formula (A1). The electrically conductive film of description.
(25) In the above formula (1), A is a divalent conjugated linking group obtained by removing two hydrogen atoms from any position of the compound represented by the above formula (A1), and two Y are The conductive film according to (23) or (24) above, wherein both are single bonds, and two Zs are groups represented by the formula (Z1a) described later.
(26) The electrically conductive film in any one of said (22)-(25) whose carrier concentration is 1 * 10 < ²⁴ > ^-3 * 10 < ²⁶ > piece / m < ³ >.
(27) An organic semiconductor device using the conductive film according to any one of (22) to (26).
(28) An organic semiconductor device comprising a base material, an electrode, and the conductive film according to any one of (22) to (26) in this order.

  As shown below, according to the present invention, a thermoelectric conversion element having a high thermoelectromotive force, a conductive film having a high conductivity, and an organic semiconductor device using the conductive film can be provided.

It is sectional drawing which shows typically an example of the thermoelectric conversion element of this invention. The arrows in FIG. 1 indicate the direction of the temperature difference applied when the element is used. It is sectional drawing which shows typically an example of the thermoelectric conversion element of this invention. The arrows in FIG. 2 indicate the direction of the temperature difference applied when the element is used. It is sectional drawing which shows typically an example (module) of the thermoelectric conversion element of this invention.

Below, the thermoelectric conversion element of this invention, an electrically conductive film, and an organic-semiconductor device are demonstrated.
In the present specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and includes a mixture thereof.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

  The present invention uses a π-conjugated polymer in which the thermoelectric conversion layer (conductive film) has a repeating unit molecular weight of 150 or more and is doped with carriers, and the thermoelectric conversion layer (conductive film) has a crystallinity of 20% or more. By doing so, it is based on the knowledge that the conductivity and the thermoelectromotive force are dramatically improved. The reason why the electrical conductivity and the thermoelectromotive force are dramatically improved is not clear, but by making the molecular weight and crystallinity of the repeating unit above a specific value as described above, in the thermoelectric conversion layer (conductive film), It is presumed that the interaction between the π-conjugated polymers forms a three-dimensional and dense carrier path of the π-conjugated polymer, and the carrier movement becomes extremely efficient.

[Thermoelectric conversion element]
The thermoelectric conversion element of the present invention includes a thermoelectric conversion layer containing a π-conjugated polymer. Here, the π-conjugated polymer is a π-conjugated polymer having a repeating unit having a molecular weight of 150 or more and doped with carriers (hereinafter also referred to as a specific π-conjugated polymer). The crystallinity of the thermoelectric conversion layer is 20% or more.
A preferred embodiment of the thermoelectric conversion element of the present invention is an element comprising a base material (substrate) and the thermoelectric conversion layer provided on the base material, and more preferably an electrode for electrically connecting them. More preferably, the device has a pair of electrodes provided on a substrate and the thermoelectric conversion layer between the electrodes.
In the thermoelectric conversion element of the present invention, the thermoelectric conversion layer may be one layer or two or more layers.

  First, the whole structure of the suitable aspect of the thermoelectric conversion element of this invention is demonstrated using FIGS. 1-3 which are sectional drawings which show typically an example of the thermoelectric conversion element of this invention.

The thermoelectric conversion element 10 shown in FIG. 1 is an element that includes a first base material 11, a first electrode 12, a thermoelectric conversion layer 14, a second electrode 13, and a second base material 15 in this order. It is. The thermoelectric conversion layer 14 contains a specific π-conjugated polymer.
Here, the thermoelectric conversion element 10 shown in FIG. 1 is an aspect which obtains an electromotive force (voltage) using the temperature difference of the direction shown by the arrow.

The thermoelectric conversion element 20 shown in FIG. 2 has a first electrode 22 and a second electrode 23 on a part of the first base material 21, and the first base material 21 and the first electrode 22. And it is an element provided on the 2nd electrode 23 with the thermoelectric conversion layer 24 and the 2nd base material 25 in this order. The thermoelectric conversion layer 24 contains a specific π-conjugated polymer.
Here, the thermoelectric conversion element 20 shown in FIG. 2 is an aspect which obtains an electromotive force (voltage) using the temperature difference of the direction shown by the arrow.

  In the present invention, as shown in FIG. 3, the base material 31 common to the thermoelectric conversion elements 30 adjacent to each other is used, the second electrode 33 in one thermoelectric conversion element 30, and other thermoelectric conversion elements adjacent to the second electrode 33. It is good also as the module 300 which connected each thermoelectric conversion element 30 in series by electrically connecting with 30 1st electrodes 32. The thermoelectric conversion layer 34 contains a specific π-conjugated polymer.

  Hereinafter, the thermoelectric conversion layer, the base material, and the electrode will be described in detail.

[Thermoelectric conversion layer]
As described above, the thermoelectric conversion layer contains a π-conjugated polymer (specific π-conjugated polymer) having a repeating unit having a molecular weight of 150 or more and doped with carriers.
Hereinafter, the specific π-conjugated polymer will be described in detail, and then the optional components that the thermoelectric conversion layer may contain and the method for manufacturing the thermoelectric conversion layer will be described in detail.

<Specific π-conjugated polymer>
The specific π-conjugated polymer is a π-conjugated polymer having a repeating unit having a molecular weight of 150 or more and doped with a carrier. Here, the π-conjugated polymer refers to a polymer having a structure in which the main chain is conjugated with a lone pair of π electrons or lone electrons.

The molecular weight of the repeating unit of the specific π-conjugated polymer is 150 or more. Especially, it is preferable that it is 200-2000, and it is more preferable that it is 250-1000.
The upper limit of the molecular weight of the repeating unit is not particularly limited, but is preferably 5000 or less.

The specific π-conjugated polymer includes a thiophene compound, a pyrrole compound, an aniline compound, an acetylene compound, a p-phenylene compound, a p-phenylene vinylene compound, a p-phenylene ethynylene compound, and a group thereof. A π-conjugated polymer having a repeating unit derived from at least one monomer selected from the above is preferable.
Here, p-phenylene is synonymous with 1,4-phenylene and intends a partial structure in which adjacent units are connected to the para-position (two positions of the 1-position and 4-position) of the benzene ring. In addition, p-phenylene vinylene intends a partial structure in which a vinylene group and one linking site to an adjacent unit are connected to the para-position (two positions of the first and fourth positions) of the benzene ring. Further, p-phenyleneethynylene intends a partial structure in which one ethynylene group and one linking site with an adjacent unit are connected to the para-position (two positions of the 1-position and 4-position) of the benzene ring.
The thiophene compound is intended to be thiophene or a compound having a partial structure in which another ring is condensed with thiophene. The same applies to pyrrole compounds, aniline compounds, acetylene compounds, p-phenylene compounds, p-phenylene vinylene compounds, and p-phenylene ethynylene compounds.
Moreover, a derivative intends the compound which has a substituent (for example, the substituent W mentioned later).

Preferable embodiments of the specific π-conjugated polymer include π-conjugated polymers containing at least two or more types of aromatic rings in the repeating unit.
Examples of the aromatic ring include an aryl ring and a heteroaryl ring. The aromatic ring may be a single ring or a condensed ring.
Examples of the aryl ring include a benzene ring and a naphthalene ring.
Examples of the heteroaryl ring include a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, an oxadiazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, an imidazole ring, a pyrazole ring, a triazole ring, and a furazane ring. , Tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, tetrazine 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, cinnoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring, acridine ring Phenanthridine ring, phenanthroline ring, phenazine ring, naphthyridine ring, purine ring and pteridine ring.
The aromatic ring may have a substituent (for example, substituent W described later).

Another preferred embodiment of the specific π-conjugated polymer includes a π-conjugated polymer containing an aromatic condensed ring in the repeating unit.
In the present specification, the aromatic condensed ring means a condensed ring in which aryl rings are condensed, a condensed ring in which heteroaryl rings are condensed, or a condensed ring in which an aryl ring and a heteroaryl ring are condensed. Specific examples of the aryl ring and heteroaryl ring are as described above.
The aromatic condensed ring may have a substituent (for example, substituent W described later).

  The specific π-conjugated polymer preferably has a repeating unit represented by the following formula (1). That is, the above-described repeating unit having a molecular weight of 150 or more is preferably represented by the following formula (1).

  In formula (1), A represents a divalent conjugated linking group having a condensed ring structure or a monocyclic structure.

Examples of the monocyclic ring constituting the condensed ring structure (that is, the monocyclic ring condensed to constitute the condensed ring structure) include a monocyclic hydrocarbon ring, aryl ring, heteroaryl ring and the like. Two or more of these may be condensed.
Examples of the monocyclic hydrocarbon ring include a cyclopentadiene ring.
Examples of the monocyclic aryl ring include a benzene ring.
Examples of the monocyclic heteroaryl ring include a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, an oxadiazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, an imidazole ring, a pyrazole ring, and a triazole ring. , Furazane ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, tetrazine ring and the like.
Examples of the ring constituting the condensed ring structure include naphthalene 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, cinnoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring, acridine ring, phenanthridine ring, phenanthroline ring, phenazine ring, naphthyridine ring, purine ring, pteridine A ring etc. are mentioned.
Specific examples of the ring constituting the monocyclic structure are the same as the single ring constituting the condensed ring structure described above.
The divalent conjugated linking group is intended to be a divalent linking group in which the conjugated system is linked from one bonding position to the other bonding position.

  As a suitable aspect of A in the said Formula (1), the bivalent conjugated coupling group remove | excluding two hydrogen atoms from the arbitrary positions of the compound represented by the following formula (A1) is mentioned, for example.

In the above formula (A1), X ^{31 to} X ³³ and X ^{41 to} X ⁴³ each independently represent a hetero atom, a hetero atom having a substituent (for example, substituent W described later), or —CH═CH— group. , = CH- group or -C (= O)-group. The hetero atom is not particularly limited, but specific examples include a nitrogen atom, an oxygen atom, a sulfur atom, and the like.
X ³¹ and X ⁴² are each independently a sulfur atom, an oxygen atom, or a —NR ^N2 — group, or X ³² and X ⁴¹ are each independently a sulfur atom, an oxygen atom, or It is preferably a —NR ^N2 — group. Here, ^RN2 represents a hydrogen atom or an alkyl group (preferably having 1 to 20 carbon atoms). The alkyl group may be linear, branched or cyclic.

In the above formula (A1), each of the monocycle containing X ^{31 to} X ³³ and the monocycle containing X ^{41 to} X ⁴³ represents an aromatic ring.
For example, when X ³¹ is a —CH═CH— group and X ³² and X ³³ are a ═CH— group, the monocycle containing X ^{31 to} X ³³ represents a benzene ring. ^{Furthermore, X 31} is a sulfur ^atom, when ^{X 32} and ^{X 33} are = CH- a ^group, monocyclic ring containing X 31 ^{to X 33} represents a thiophene ring.
The monocycle containing X ^{31 to} X ³³ and the monocycle containing X ^{41 to} X ⁴³ may have a substituent (for example, substituent W described later).

In the above formula (A1), the A ring represents a conjugated hydrocarbon ring or a conjugated heterocyclic ring.
Here, the conjugated hydrocarbon ring refers to a hydrocarbon ring having a conjugated structure. The conjugated heterocycle represents a heterocycle having a conjugated structure. The conjugated structure refers to a structure in which two “carbon atoms—carbon atoms (C—C) multiple bonds” are connected via a single bond. The conjugated structure is preferably a structure in which two C—C double bonds are connected via a single bond.
Examples of the conjugated hydrocarbon ring include a benzene ring and a cyclopentadiene ring.
Examples of the conjugated heterocyclic structure include a pyrrole ring, a thiophene ring, a pyridine ring, a silole ring, and a furan ring.
The A ring is preferably a benzene ring, a pyrrole ring, a thiophene ring, a pyridine ring, a cyclopentadiene ring, or a silole ring.
The A ring may have a substituent (for example, a substituent W described later).

  In the above formula (A1), n represents 0 or an integer of 1 or more. Especially, the integer of 1-5 is preferable. When n is an integer of 2 or more, a plurality of A rings may be the same or different. In addition, the number of A rings connected by condensing is represented.

In the above formula (A1), m represents 0 or 1.
When m is 0, the above formula (A1) is represented by the following formula (m = 0), and when m is 1, the above formula (A1) is represented by the following formula (m = 1).

When m is 1 and n is 0, it means that there is no A ring and a single ring containing X ^{31 to} X ³³ and a single ring containing X ^{41 to} X ⁴³ are condensed. That is, the above formula (A1) is represented by the following formula (n0).

  For example, when the compound represented by the formula (A1) is a compound represented by the following formula (A1-1), A in the formula (1) is represented by the following formula (A1-1). A divalent conjugated linking group in which two hydrogen atoms are removed from any position of the compound to be obtained. Such a divalent conjugated linking group is represented, for example, by the following formula (A-1): Group. Here, * represents a bonding position.

  When A in the formula (1) is a divalent conjugated linking group in which two hydrogen atoms are removed from any position of the compound represented by the formula (A1), the formula (1) is It is represented by the following formula (1a).

In the formula (1), Y represents a single bond, —CH═CH— group, —N═N— group, arylene group, heteroarylene group, or —NR ^N1 — group. Two Y in the above formula (1) may be the same or different.
6-20 are preferable and, as for carbon number of the said arylene group, 6-15 are more preferable. The arylene group is preferably a phenylene group or a naphthylene group.
The arylene group has a plurality of aromatic rings bonded to an atom capable of forming a conjugated system of the main chain, preferably a nitrogen atom, and may include a group bonded to the main chain through different aromatic rings. Examples of such a group include a divalent group obtained from triphenylamine, which is bonded to the main chain with a different phenyl group.
3-20 are preferable and, as for carbon number of the said heteroarylene group, 5-12 are more preferable. The heterocycle constituting the heteroarylene group is not particularly limited, but a 5-membered ring or a 6-membered ring is preferable. The heteroatom constituting the heterocycle is not particularly limited, but a sulfur atom, a nitrogen atom, an oxygen atom, A silicon atom, a selenium atom, etc. are mentioned suitably. Preferred examples of the heteroarylene group include a divalent thiophene ring, a divalent thiazole ring, a divalent oxazole ring, a divalent furan ring, a divalent pyrrole ring, a divalent selenophene ring, and a divalent thiazole ring. Divalent oxazole ring, divalent phosphole ring, divalent phospholine ring, divalent thiadiazole ring, divalent oxadiazole ring, divalent pyrazole ring, divalent imidazole ring, divalent pyridine ring Examples thereof include a divalent pyrazine ring, a divalent pyridazine ring, a divalent triazine ring, a divalent triazole ring, and a divalent tetrazine ring.
Y is preferably a single bond or a 2,5-thienyl group.

R ^N1 in the —NR ^N1 — group represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a heteroaryl group. Of these, an aliphatic hydrocarbon group is preferable. In addition, these groups may have a substituent (for example, the substituent W mentioned later).
The aliphatic hydrocarbon group may be linear, branched or cyclic. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (particularly having 1 to 20 carbon atoms), a linear or branched alkenyl group (particularly having 2 to 20 carbon atoms), Examples thereof include a linear or branched alkynyl group (particularly, having 2 to 20 carbon atoms).
As said aryl group (aromatic hydrocarbon group), a phenyl group, a tolyl group, a xylyl group, a naphthyl group etc. are mentioned, for example. The number of carbons is not particularly limited but is preferably 6-18.
Specific examples and preferred embodiments of the heteroaryl group are the same as the above-described heteroarylene group as Y. However, specific examples are those in which a divalent group is a monovalent group.

  In the above formula (1), Z represents a group represented by the following formula (Z). In the above formula (1), two Zs may be the same or different. However, Z is different from A in the above formula (1).

In the above formula (Z), X ^Z1 and X ^Z2 are each independently a hetero atom, a hetero atom having a substituent (for example, substituent W described later), a —CH═CH— group, or a ═CH— group. Represents. The hetero atom is not particularly limited, but specific examples include a nitrogen atom, an oxygen atom, a sulfur atom, and the like. X ^Z1 is preferably a sulfur atom, an oxygen atom, or a —NR ^N2 — group. Here, R ^N2 represents a hydrogen atom or an alkyl group. As an alkyl group, a linear or branched alkyl group (especially C1-C20) is mentioned, for example. The alkyl group may have a substituent (for example, substituent W described later).

In the above formula (Z), R ^Z1 represents an electron donating group.
In the present specification, the electron donating group means a substituent having a Hammett's substituent constant σ _p value of −0.15 or less.
Here, Hammett's substituent constant σ _p value will be described. Hammett's rule was found in 1935 by L.L. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include σ _p value and σ _m value, and these values can be found in many general books. A. Dean, “Lange's and book of Chemistry”, 12th edition, 1979 (McGraw-Hill) and “Areas of Chemistry”, No. 122, 96-103, 1979 (Nankodo). In this specification, the electron-donating group is limited or explained by Hammett's substituent constant σ _p, but this is limited only to those substituents having known values that can be found in the above documents. It does not mean that. Even if the value is unknown in the literature, it also includes a substituent that is included in the range when measured based on Hammett's rule.
Hammett substituent constant of the electron donating group represented by R ^Z1 from the viewpoint of promoting oxidation by shallowing the highest occupied orbital (HOMO orbital) when synthesizing a specific π-conjugated polymer by oxidation polymerization. The σ _p value is preferably −0.20 or less.
The lower limit of Hammett's substituent constant σ _p value of the electron donating group represented by R ^Z1 is not particularly limited, but is preferably −0.90 or more.

R ^Z1 is not particularly limited as long as it has a Hammett substituent constant σ _p value of −0.15 or less. Specific examples thereof include a hydroxy group or a salt thereof, a mercapto group or a salt thereof, an alkoxy group ( Preferably, it has 1 to 30 carbon atoms, an aryloxy group (preferably 6 to 20 carbon atoms), a heterocyclic oxy group, and an alkylthio group (RS-: R represents an alkyl group (preferably 1 to 30 carbon atoms)). ), An arylthio group (preferably having 6 to 20 carbon atoms), a heterocyclic thio group, an amino group, and an alkylamino group (R ¹ R ² N—: R ¹ and R ² are each independently a hydrogen atom or an alkyl group. (preferably having 1 to 30 carbon atoms). However, at least one of ^{R 1} and ^{R 2} represents an alkyl group.), an arylamino group (preferably 6 to 20 carbon atoms), heterocycle a Group, a polyethyleneoxyether group (see the structural formula below), a polyethyleneoxythioether group (see the structural formula below), a polyethyleneoxyamino group (see the structural formula below) or an aryl group substituted with these groups. Can be mentioned. Of these, an alkylthio group, an alkylamino group, and an alkoxy group are preferable, and an alkoxy group is more preferable.
The alkyl group is a substituent having a Hammett's substituent constant σ _p value of more than −0.15, and thus does not correspond to R ^Z1 .

In the above formula (Z), n represents an integer of 1 or more. Especially, the integer of 2-5 is preferable and 2 is more preferable. In addition, n represents the number which ^RZ1 substitutes. For example, π-conjugated polymers 1 to 7 used in the examples described later have an aspect in which n is 2, and π-conjugated polymer 8 used in an example described later has an aspect in which n is 1.
In the above formula (Z), when n is an integer of 2 or more, a plurality of R ^Z1 may be the same or different.
In the above formula (Z), when n is an integer of 2 or more, a plurality of R ^Z1 may be bonded to each other to form a ring. Here, “to form a ring by bonding to each other” means that two or more groups are bonded through a single bond with a hydrogen atom as a bond at an arbitrary hydrogen atom position to form a ring. Intended.
In the above formula (Z), * represents a bonding position.

As a suitable aspect of Z in the said Formula (1), group represented by a following formula (Z1) is mentioned, for example. In addition, the following formula (Z1) is an embodiment in which, in the above formula (Z), n is 2, two R ^Z1 are alkylthio groups or alkoxy groups, and two R ^Z1 are bonded to each other to form a ring. It is one mode.

In formula (Z1), ^XZ1 represents a heteroatom, a heteroatom having a substituent (for example, substituent W described later), a —CH═CH— group, or a ═CH— group. X ^Z3 represents an oxygen atom or a sulfur atom. Two ^XZ3 may be the same or different. R ^Z2 represents a hydrogen atom or a substituent (for example, substituent W described later). Two R ^Z2 may be the same or different. * Represents a binding position.

  Moreover, as a suitable aspect of group represented by the said formula (Z1), group represented by the following formula (Z1a) is mentioned, for example.

In the above formula (Z1a), R ^Z3 represents a hydrogen atom, an aryl group (preferably having 6 to 20 carbon atoms), a heteroaryl group (preferably having 5 to 20 ring atoms), or an alkyl group (preferably having 1 carbon atom). To 30), an alkoxy group (preferably having a carbon number of 1 to 30), a polyethyleneoxyether group (see the following structural formula), an alkylthio group (RS-: R represents an alkyl group (preferably having a carbon number of 1 to 30).) , A polyethyleneoxythioether group (see the structural formula below), an alkylamino group (R ¹ R ² N—: R ¹ and R ² each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 30 carbon atoms). However, at least one of R ¹ and R ² represents an alkyl group.) Or a polyethyleneoxyamino group (refer to the structural formula below).
In the following structural formulas, R represents a hydrogen atom or an alkyl group. n represents an integer of 1 or more (preferably an integer of 1 to 10). The wavy line represents the coupling position.

In the above formula (Z1a), two R ^Z3 may be the same or different. * Represents a binding position.

  In the above formula (1), * represents a bonding position.

  As a suitable aspect of the repeating unit represented by the above formula (1), for example, in the above formula (1), A represents two hydrogen atoms from any position of the compound represented by the above formula (A1). An excluded divalent conjugated linking group, wherein two Y are all single bonds, and two Z are both groups represented by the above formula (Z1a), that is, the following formula ( Examples thereof include the repeating unit represented by 1b).

A plurality of R ^Z3 in the formula (1b) may be the same or different.

The specific π-conjugated polymer may have another repeating unit other than the repeating unit represented by the above formula (1).
In the case where the specific π-conjugated polymer has a plurality of repeating units, the copolymerization mode is not particularly limited, and any of block copolymerization, alternating copolymerization, random copolymerization, and graft copolymerization may be used.
The other repeating unit may be a linking group, an atom, or a combination thereof, which can form a conjugated system of the main chain. Such another repeating unit is not particularly limited, but is preferably at least one repeating unit selected from the group consisting of an ethenylene group, an ethynylene group, an arylene group, and a heteroarylene group. Specific examples and preferred embodiments of the arylene group and heteroarylene group are the same as Y in the above-described formula (1).
The another repeating unit may have a substituent (for example, substituent W described later).

  The content of the repeating unit represented by the above formula (1) in the specific π-conjugated polymer is not particularly limited, but is preferably 10% by mass or more, and more preferably 30% by mass or more. The upper limit is not particularly limited, and is 100% by mass (that is, a homopolymer of a repeating unit represented by the above formula (1)).

The molecular weight of the specific π-conjugated polymer is not particularly limited, but is preferably 3000 to 200,000, more preferably 5000 to 150,000 in terms of weight average molecular weight (Mw).
In the present specification, the weight average molecular weight is a polystyrene equivalent value measured by GPC.

(Π-conjugated polymer doped with carrier)
As described above, the specific π-conjugated polymer is a π-conjugated polymer doped with carriers.
Here, with respect to the π-conjugated polymer, “carrier is doped” means that the electron is removed from the π orbit of the π-conjugated polymer and the π-conjugated polymer is positively charged (p-type doping), or π-conjugated. A state in which electrons are imparted to the π ^* orbit of the polymer and the π-conjugated polymer is negatively charged (n-type doping).
As a method for evaluating whether or not carriers are doped with respect to the π-conjugated polymer in the thermoelectric conversion layer (conductive film), a method of measuring the absorption spectrum of the thermoelectric conversion layer can be mentioned. In the absorption spectrum of the thermoelectric conversion layer, another absorption peak (B) derived from doping of the π-conjugated polymer appears at a wavelength longer than 100 nm from the absorption peak (A) derived from the undoped π-conjugated polymer. When the absorbance of the peak (B) is 0.05 times or more that of the peak (A), it can be determined that the π-conjugated polymer in the thermoelectric conversion layer is doped with carriers.
Even in a π-conjugated polymer without carrier doping, the absorption spectrum may shift to the longer wavelength side depending on the association state. Is this due to carrier doping by changing the addition amount of the oxidizing agent or reducing agent? It can be distinguished whether it is due only to the meeting status. That is, when the carrier concentration is changed by increasing or decreasing the addition amount of the oxidizing agent or reducing agent, the absorption peak of the undoped region (short wavelength side) and / or the absorption peak of the doped region is changed according to the carrier concentration. One to a plurality of absorption peaks of the polaron or bipolaron found on the long wavelength side are observed. On the other hand, the absorption peak on the long wavelength side due to the association of the undoped π-conjugated polymer has a different wavelength range from the absorption peak due to doping, and is generally more than the absorption peak due to doping (due to polaron or bipolaron). Since it is often on the short wavelength side, it is possible to distinguish both from the difference in wavelength range.
As a method for examining the absorption peak and wavelength of the π-conjugated polymer when the carrier is not doped, for example, a π-conjugated polymer polymerized by a method that does not use an oxidizing agent such as a coupling method is used for doping. The method of producing a thermoelectric conversion layer (electrically conductive film) without measuring the absorption spectrum is mentioned. The fact that the π-conjugated polymer in the thermoelectric conversion layer (conductive film) is not doped can also be confirmed by measuring the carrier concentration of the thermoelectric conversion layer (conductive film). The method for measuring the carrier concentration is as described later.
Whether the doping is p-type doping or n-type doping is determined by a Hall coefficient measured by a Hall effect measuring apparatus ResiTest 8300 (manufactured by Toyo Corporation). Specifically, when the Hall coefficient is a positive value, the doping of the π-conjugated polymer is determined as p-type doping. Further, when the Hall coefficient is a negative value, the doping of the π-conjugated polymer is determined as n-type doping.
As another method for determining whether the doping is p-type doping or n-type doping, as described in the literature (Macromolecules 2000, 33, 6787-6793), a method using a CV (cyclic voltammetry) method is also exemplified. (The p-type has a peak on the reduction side, and the n-type has a peak on the oxidation side).

(Production method)
The production method of the specific π-conjugated polymer is not particularly limited, and a known method can be used. For example, a method in which a π-conjugated monomer that becomes a repeating unit having a molecular weight of 150 or more after polymerization is polymerized by an oxidative polymerization method or a coupling polymerization method may be used. Of these, a method of polymerizing by an oxidative polymerization method is preferable.
The method for doping the carrier is not particularly limited, but a method of doping the carrier at the same time as the polymerization by oxidative polymerization of the monomer in the presence of an oxidant, or a method of polymerizing without using the oxidant and then using an oxidant or the like to The method of doping etc. are mentioned. Specific examples and preferred embodiments of the oxidizing agent are as described later.

(Preferred embodiment)
The specific π-conjugated polymer is preferably obtained by polymerization by an oxidative polymerization method in the presence of an oxidizing agent described later.
Among these, in order to further improve the crystallinity of the thermoelectric conversion layer, in the presence of a π-conjugated polymer having a repeating unit different from the above-described repeating unit having a molecular weight of 150 or more (hereinafter also referred to as a template polymer) and an oxidizing agent, It is preferably obtained by polymerization by a template polymerization method.
The template polymer includes a thiophene compound, a pyrrole compound, an aniline compound, an acetylene compound, a p-phenylene compound, a p-phenylene vinylene compound, a p-phenylene ethynylene compound, and a group thereof. A π-conjugated polymer having a repeating unit derived from at least one selected monomer is preferable.
The molecular weight of the template polymer is preferably 3000 to 200,000 in terms of weight average molecular weight, and more preferably 10,000 to 150,000.

  Specific examples of the π-conjugated polymer having a repeating unit having a molecular weight of 150 or more are shown below, but the present invention is not limited thereto.

The content of the specific π-conjugated polymer in the thermoelectric conversion layer is not particularly limited, but is preferably 10 to 80% by mass and more preferably 20 to 60% by mass in the thermoelectric conversion layer.
The thermoelectric conversion layer may contain two or more specific π-conjugated polymers.

<Optional component>
The thermoelectric conversion layer may contain components other than the specific π-conjugated polymer described above.
Such components may contain an oxidizing agent, a non-conjugated polymer, a reducing agent, a nano-conductive material, the above-described template polymer, an antioxidant, a light-resistant stabilizer, a heat-resistant stabilizer, a plasticizer, and the like.
As an antioxidant, Irganox 1010 (manufactured by Cigabi Nippon, Inc.), Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GM (Sumitomo Chemical Industries, Ltd.) Manufactured). Examples of the light-resistant stabilizer include TINUVIN 234 (manufactured by BASF), CHIMASSORB 81 (manufactured by BASF), and Siasorb UV-3853 (manufactured by Sun Chemical). IRGANOX 1726 (made by BASF) is mentioned as a heat-resistant stabilizer. Examples of the plasticizer include Adeka Sizer RS (manufactured by Adeka).

(Oxidant)
The thermoelectric conversion layer preferably further contains an oxidizing agent. The oxidizing agent functions as a dopant for the specific π-conjugated polymer described above.
Note that the dopant of the specific π-conjugated polymer is not limited to the oxidizing agent. Further, as described above, the carrier may be doped simultaneously with the polymerization by oxidative polymerization of the monomer in the presence of the oxidizing agent. That is, the oxidant is not an essential component in the thermoelectric conversion layer.
Although it does not restrict | limit especially as an oxidizing agent, The at least 1 sort (s) of compound selected from the group which consists of iron (III) salt, copper (II) salt, a peroxide, and a peracid is preferable.
Specific examples of the oxidizing agent include halogen (Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr, IF), Lewis acid (PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BCl ₃ , BBr ₃ , SO _3), the transition metal compound _{(FeCl 3, FeOCl, TiCl 4} , ZrCl 4, HfCl 4, NbF 5, NbCl 5, TaCl 5, MoF 5, MoCl 5, WF 6, WCl 6, UF 6, LnCl 3 (Ln = Latanoids such as La, Ce, Pr, Nd and Sm), XeOF ₄ , (NO ₂ ⁺ ) (SbF ₆ ⁻ ), (NO ₂ ⁺ ) (SbCl ₆ ⁻ ), AgClO ₄ , H ₂ IrCl ₆ , _{la (NO 3) 3 · 6H} 2 O), O 2, O 3, (NO 2 +) (BF 4 -), FSO 2 OOSO 2 F, iron (III) chloride hexahydrate , Anhydrous iron (III) chloride, iron (III) nitrate nonahydrate, anhydrous ferric nitrate, iron (III) sulfate n-hydrate (n = 3-12), iron (III) ammonium sulfate Hydrates, iron (III) salts of inorganic acids such as iron (III) perchlorate n hydrate (n = 1,6), iron (III) tetrafluoroborate; copper (II) chloride, copper sulfate (II), copper (II) salts of inorganic acids such as copper (II) tetrafluoroborate; nitrosonium tetrafluoroborate; persulfates such as ammonium persulfate, sodium persulfate, potassium persulfate; potassium periodate Periodate salts such as hydrogen peroxide, potassium hexacyanoferrate (III), tetraammonium cerium sulfate (IV) dihydrate; iron (III) salts of organic acids such as iron (III) p-toluenesulfonate ; Ferric organic sulfonate, etc. It is.
As the organic sulfonic acid of the ferric organic sulfonate, aromatic sulfonic acids such as benzene sulfonic acid or a derivative thereof, naphthalene sulfonic acid or a derivative thereof, anthraquinone sulfonic acid or a derivative thereof are preferably used.
Examples of the benzenesulfonic acid derivative in the benzenesulfonic acid or derivative thereof include toluenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, dodecylbenzenesulfonic acid, methoxybenzenesulfonic acid, ethoxybenzenesulfonic acid, Examples thereof include propoxybenzene sulfonic acid, butoxybenzene sulfonic acid, phenol sulfonic acid, cresol sulfonic acid, and benzene disulfonic acid. , Methyl naphthalene sulfonic acid, ethyl naphthalene sulfonic acid, propyl naphthalene sulfonic acid, butyl naphthalene sulfonic acid, etc. It is, as the anthraquinone sulfonic acid derivatives in anthraquinone sulfonic acid or its derivatives, e.g., anthraquinone disulfonic acid, anthraquinone-trisulfonic acid. Among these aromatic sulfonic acids, toluenesulfonic acid, methoxybenzenesulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, naphthalenetrisulfonic acid and the like are particularly preferable, and paratoluenesulfonic acid and methoxybenzenesulfonic acid are particularly preferable. .
The oxidizing agent is preferably an iron salt (III) of an inorganic acid or an organic acid, or a persulfate, more preferably ammonium persulfate or iron (III) p-toluenesulfonate, and further iron (III) p-toluenesulfonate. preferable.

  Although content in particular of the oxidizing agent in a thermoelectric conversion layer is not restrict | limited, It is preferable that it is 1-45 mass% in a thermoelectric conversion layer, and it is more preferable that it is 5-30 mass%.

(Non-conjugated polymer)
The thermoelectric conversion layer preferably further contains a non-conjugated polymer.
The non-conjugated polymer is not particularly limited as long as it is a polymer (polymer) that does not exhibit electrical conductivity in the conjugated structure of the polymer main chain. The definition of the conjugated structure is as described above. The non-conjugated polymer functions as a binder and increases the strength of the thermoelectric conversion layer.
The non-conjugated polymer is preferably a ring, group or atom in which the polymer main chain is selected from a heteroatom having an aromatic ring (carbocyclic aromatic ring, heteroaromatic ring), an ethynylene bond, an ethenylene bond and a lone pair of electrons. It is a polymer other than the polymer comprised from these, or the polymer which is incorporated in isolation even if these groups are included.
The non-conjugated polymer repeats a component derived from at least one compound selected from the group consisting of vinyl compounds, (meth) acrylate compounds, carbonate compounds, ester compounds, amide compounds, imide compounds, fluorine compounds and siloxane compounds. Non-conjugated polymers included as structures are preferred. These compounds may have a substituent (for example, the above-described substituent W).

Specific examples of vinyl compounds include styrene, vinyl pyrrolidone, vinyl carbazole, vinyl pyridine, vinyl naphthalene, vinyl phenol, vinyl acetate, styrene sulfonic acid, vinyl alcohol, vinyl triphenylamine and other vinyl arylamines, vinyl tributylamine. And vinyl trialkylamines. In addition to these, for example, olefins having 2 to 4 carbon atoms (ethylene, propylene, butene, etc.), which are olefins corresponding to the constituent components of polyolefin, can be mentioned.
Examples of the non-conjugated polymer containing a component derived from a vinyl compound as a repeating structure include polyvinyl pyrrolidone, polyvinyl carbazole, polyvinyl alcohol, poly (4-styrene sulfonic acid), and the like.

  Specific examples of (meth) acrylate compounds include unsubstituted alkyl group-containing hydrophobic acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, 2-hydroxyethyl acrylate, 1-hydroxyethyl acrylate, and 2-hydroxypropyl. Acrylate monomers such as acrylates, hydroxyl-containing acrylates such as 3-hydroxypropyl acrylate, 1-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 1-hydroxybutyl acrylate, and the like And methacrylate monomers in which the acryloyl group is replaced with a methacryloyl group.

Specific examples of polycarbonates containing repeating components derived from carbonate compounds include general-purpose polycarbonates composed of bisphenol A and phosgene, Iupizeta (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.), Panlite (trade name, Teijin Chemicals Ltd.) Manufactured) and the like.
Examples of the compound that can constitute the ester compound include polyalcohols, polycarboxylic acids, and hydroxy acids such as lactic acid. Specific examples of polyester include Byron (trade name, manufactured by Toyobo Co., Ltd.) and the like.
Specific examples of polyamides containing a structural component derived from an amide compound as a repeating structure include PA-100 (trade name, manufactured by T & K TOKA Corporation).
As a specific example of polyimide containing a constituent component corresponding to an imide compound as a repeating structure, Solpy 6,6-PI (trade name, manufactured by Solpy Kogyo Co., Ltd.) and the like can be given.
Specific examples of the fluorine compound include vinylidene fluoride and vinyl fluoride.
Specific examples of the polysiloxane containing a component derived from a siloxane compound as a repeating structure include polydiphenylsiloxane and polyphenylmethylsiloxane.

  Another preferred embodiment of the non-conjugated polymer includes, for example, polyalkylene glycol such as polyethylene glycol, polypropylene glycol, poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol).

The non-conjugated polymer preferably has an acid group. When the non-conjugated polymer has an acid group, the doping state of the specific π-conjugated polymer described above becomes more stable.
It is not particularly restricted but includes groups, carboxyl group (-COOH), a sulfo group _(-SO 3 H), a phosphonic acid group (-PO _{(OH) 2),} and aromatic hydroxyl group (-OH). Of these, a sulfo group is preferable.

  Moreover, it is also preferable that a nonconjugated polymer is the following compounds (P-1 to P-37). In P-1 to P-37, x, y, and z represent mol% of each monomer component, and Mw represents a weight average molecular weight.

  The molecular weight of the non-conjugated polymer is not particularly limited, but is preferably 5000 to 300,000, and more preferably 10,000 to 150,000 in terms of weight average molecular weight (Mw).

  Although content in particular of the nonconjugated polymer in a thermoelectric conversion layer is not restrict | limited, It is preferable that it is 10-65 mass% in a thermoelectric conversion layer, and it is more preferable that it is 15-50 mass%.

(Reducing agent)
The thermoelectric conversion layer may contain a reducing agent. The reducing agent serves to adjust the carrier concentration of the specific π-conjugated polymer described above.
The reducing agent is not particularly limited, and specific examples thereof include monocyclic aromatic compounds, nitrogen-containing aromatic compounds, sulfur-containing aromatic compounds, aromatic vinyl polymers, aromatic amines, aliphatic amines (for example, alkylamines). ), Nitro compound, thiol, metal complex salt, thiosulfate, sulfite, hyposulfite, boron compound, aluminum hydride complex, simple metal, reductase (reductase), and at least one selected from the group consisting of these derivatives And the like. More specifically, 1,1-bi-2-naphthol, 1,3-di (N-carbazol) propane (DCzPr), 1,4-di (N-carbazolyl) butane (DCzBu), 1,4- diazabicclo [2,2,2] octane, 2,3-dihydroxy-naphthol, 2,7-dihydroxy-naphthol, 2-naphthol, Cr (CN) ₆ ³⁻ , di (N-carbazolyl) methane (DCzMe), Eu ²⁺ , Fe (CN) ₆ ⁴⁻ , Fe ²⁺ , meso-2,4-di (N-carbazolyl) pentane (m-DCzPe), N, N, N ′, N′-tetramethyl-p-phenylenediamine, N, N, N ′, N′-tetramethylben Jin, N, N-diethylaniline, N, _{N-dimethylaniline, N-ethyl-carbazole (EtCz} ), Pt 2 (P 2 O 5) 4 H 8 4-, ReCl 8 2-, Tetrakis (dimethylamino) ethylene ( TDAE), trans-1,2-di (N-carbazolyl) cyclobutane (DCzCBu), anthracene, indene, oxadiazole, oxazole, kadricyclane, diazabicyclooctane, diphenylethylene, triethylamine, triphenylmethane, trimethoxybenzene, Naphthalene, norbornadiene, hydrazone, hydrazine, pyrene, phenanthrene, phenothiazine, perylene, methoxynaphthalene, sodium thiosulfate, sodium sulfite Sodium hydrogen sulfite, potassium hyposulfite, sodium borohydride, diborane, sodium cyanoborohydride, lithium triethylborohydride, lithium tri (boro-butyl) borohydride, diisobutylaluminum hydride, lithium aluminum hydride, hydrogenated Examples thereof include sodium bis (2-methoxyethoxy) aluminum, tributyltin hydride, reduced iron, and metal tin.

The reducing agent is an aliphatic amine (preferably an aliphatic amine having two or more alkylamino groups (R ¹ R ² N—: R ¹ and R ² each independently represents a hydrogen atom or an alkyl group)), It should be at least one compound selected from the group consisting of monocyclic aromatic compounds (preferably monocyclic aromatic compounds having a hydroxy group), hydrazine, and thiols (preferably dithiols having a hydroxy group). preferable.

  As another suitable aspect of a reducing agent, the compound represented by the following general formula (D1) is mentioned, for example.

In general formula (D1), R ¹ and R ¹ ′ each independently represents an alkyl group, and at least one of them is a secondary or tertiary alkyl group. R ² and R ² ′ each independently represent a hydrogen atom or a group that can be substituted on a benzene ring. L represents a —S— group or a —CHR ³ — group, and R ³ represents a hydrogen atom or an alkyl group. X and X ′ each independently represent a hydrogen atom or a group that can be substituted on a benzene ring.

  Although content in particular of the reducing agent in a thermoelectric conversion layer is not restrict | limited, It is preferable that it is 0.1-30 mass% in a thermoelectric conversion layer, and it is more preferable that it is 1-15 mass%.

(Nano conductive material)
The thermoelectric conversion layer may contain a nanoconductive material from the viewpoint of conductivity and physical strength.
As said nano electroconductivity material, the carbon material (henceforth a nano carbon material) which has electroconductivity, a metal material (henceforth a nano metal material) etc. are mentioned.
Among nanocarbon materials and nanometal materials, nanoconductive materials are preferably carbon nanotubes (hereinafter also referred to as CNT), carbon nanofibers, graphite, graphene and carbon nanoparticle nanocarbon materials, and metal nanowires, Carbon nanotubes are particularly preferred from the viewpoint of improving conductivity. The carbon nanotube may have a single-layer structure, a double-layer structure, or a multi-layer structure having one or more layers, but a single-layer structure or a double-layer structure is particularly preferable from the viewpoint of improving conductivity.
A nano electroconductivity material may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together as a nano electroconductive material, you may use together at least 1 type of nano carbon material and nano metal material, and may use together 2 types of nano carbon materials or nano metal materials, respectively. .
The content of the nanoconductive material in the thermoelectric conversion layer is not particularly limited, but is preferably 1 to 500% by mass, more preferably 10 to 100% by mass with respect to the specific π-conjugated polymer described above. .

  When the above-mentioned specific π-conjugated polymer is obtained by polymerization by the above-described template polymerization method, the total content of the above-mentioned specific π-conjugated polymer and the template polymer in the thermoelectric conversion layer is not particularly limited, It is preferable that it is 10-80 mass% in a thermoelectric conversion layer, and it is more preferable that it is 20-60 mass%.

  Although the thickness in particular of a thermoelectric conversion layer is not restrict | limited, It is preferable that it is 0.01-100 micrometers, and it is more preferable that it is 0.02-30 micrometers. The thickness of the thermoelectric conversion layer is obtained by measuring the thickness of the conductive film at arbitrary 10 points and arithmetically averaging them.

<Crystallinity>
As described above, the crystallinity of the thermoelectric conversion layer is 20% or more.
In the present specification, the crystallinity of the thermoelectric conversion layer is a value obtained by an X-ray diffraction method and is defined by the following equation.
Crystallinity (%) = (Integral intensity of crystalline peak of entire thermoelectric conversion layer) / (Sum of integral intensity of crystalline peak of amorphous thermoelectric layer and amorphous halo)
The degree of crystallinity is preferably 30% or more, more preferably 50% or more, and further preferably 60% or more.
The upper limit of the crystallinity is not particularly limited, but is 100%.
The method for setting the crystallinity of the thermoelectric conversion layer to 20% or more is not particularly limited, and examples thereof include a method of polymerizing a specific π-conjugated polymer by a template polymerization method and a method of performing a crystallization treatment.

<Method for manufacturing thermoelectric conversion layer>
Although the method for producing the thermoelectric conversion layer is not particularly limited, as a preferred embodiment, for example, after applying the conductive composition containing the above-described π-conjugated polymer having a repeating unit having a molecular weight of 150 or more on a substrate, The method of performing the crystallization process mentioned later is mentioned. The π-conjugated polymer may be a carrier doped or a carrier undoped, but is preferably a carrier doped. When the π-conjugated polymer is one in which the carrier is not doped, the carrier-doped π-conjugated polymer (specific π-conjugated polymer) can be obtained by adding a dopant such as the above-described oxidizing agent to the conductive composition. The thermoelectric conversion layer to contain can be formed.
The coating method is not particularly limited, and known coating methods such as spin coating, extrusion die coating, blade coating, bar coating, screen printing, stencil printing, roll coating, curtain coating, spray coating, dip coating, ink jet printing, etc. The method can be used.
After apply | coating a conductive composition on a board | substrate, you may provide a heating process and a drying process as needed, and may evaporate a solvent.

Examples of the crystallization treatment described above include crystallization treatment by pressurization and crystallization treatment by solvent vapor exposure.
Examples of the crystallization treatment when the specific π-conjugated polymer is obtained by polymerization by a template polymerization method include crystallization treatment by slow cooling, crystallization treatment by pressurization, and crystallization treatment by solvent vapor exposure. Among them, crystallization treatment by slow cooling or crystallization treatment by pressurization is preferable, and crystallization treatment by slow cooling is more preferable.
The conditions for the crystallization treatment by slow cooling are not particularly limited, but after heating for 1 to 30 minutes in a state where the temperature is raised to 100 to 200 ° C., it is gradually cooled to room temperature at a cooling rate of 0.5 to 5 ° C./min. Is preferred.
The conditions for the crystallization treatment by pressurization are not particularly limited, but after pressurizing for 10 seconds to 10 minutes at a pressure of 1 to 20 MPa and a temperature of 100 to 200 ° C., cooling to room temperature with the pressure applied. preferable. Although the method of pressurizing is not particularly limited, it is preferable to use a hot press.
The conditions for crystallization treatment by exposure to solvent vapor are not particularly limited, but exposure to an organic solvent (preferably a polar solvent such as acetone, tetrahydrofuran, chloroform, or dichloromethane) at room temperature for 1 to 60 minutes is preferred.

(Conductive composition)
The conductive composition contains a π-conjugated polymer having the above-described repeating unit having a molecular weight of 150 or more. Specific examples and preferred embodiments of the π-conjugated polymer are the same as those of the specific π-conjugated polymer described above except for carrier doping.
The content of the π-conjugated polymer in the composition is not particularly limited, but is preferably 10 to 80% by mass and more preferably 20 to 60% by mass with respect to the total solid content in the composition.

The conductive composition preferably further contains an oxidizing agent (for example, the oxidizing agent described above).
Although content in particular of the oxidizing agent in a composition is not restrict | limited, It is preferable that it is 1-45 mass% with respect to the total solid in a composition, and it is more preferable that it is 5-30 mass%.

The conductive composition may further contain a non-conjugated polymer (for example, the above-described non-conjugated polymer).
The content of the non-conjugated polymer in the composition is not particularly limited, but is preferably 10 to 65% by mass and more preferably 15 to 50% by mass with respect to the total solid content in the composition.

It is preferable that the conductive composition further contains a reducing agent (for example, the reducing agent described above).
The content of the reducing agent in the composition is not particularly limited, but is preferably 0.1 to 30% by mass, and more preferably 1 to 15% by mass with respect to the total solid content in the composition. .

The conductive composition may further contain a nanoconductive material (for example, the above-described nanoconductive material).
Although content in particular of the nano electroconductive material in a composition is not restrict | limited, It is preferable that it is 0.1-200 mg with respect to an electroconductive composition (5g), and it is more preferable that it is 1-50 mg.

The conductive composition preferably further contains a template polymer (for example, the above-described template polymer).
The total content of the π-conjugated polymer having a repeating unit having a molecular weight of 150 or more and the template polymer in the composition is not particularly limited, but is 10 to 80% by mass with respect to the total solid content in the composition. Is preferable, and it is more preferable that it is 20-60 mass%.

It is preferable that the conductive composition further contains a hydrophilic solvent.
The boiling point of the hydrophilic solvent is preferably a high boiling point (specifically, 130 ° C. or higher). By setting the hydrophilic solvent to a high boiling point, it is presumed that the evaporation rate of the solvent in the film-forming drying process is moderately suppressed, and as a result, the arrangement of the π-conjugated polymer is further promoted. The upper limit of the boiling point of the hydrophilic solvent is not particularly limited, but is preferably 300 ° C. or lower. In addition, a boiling point points out the boiling point in 1 atmosphere.

  The hydrophilic solvent is not particularly limited as long as it is a hydrophilic solvent. For example, an ether group-containing compound such as tetrahydrofuran, for example, a lactone group-containing compound such as γ-butyrolactone and γ-valerolactone, such as caprolactam and N-methylcaprolactam. N, N-dimethylacetamide, N-methylacetamide, N, N-dimethylformamide (DMF), N-methylformamide, N-methylformanilide, N-methylpyrrolidone (NMP), N-octylpyrrolidone, pyrrolidone and the like Amide or lactam group-containing compounds such as sulfolane (tetramethylene sulfone), sulfones and sulfoxides such as dimethyl sulfoxide (DMSO), eg sugars or sugar derivatives such as sucrose, glucose, fructose, lactose, etc. Sugar alcohols such as sorbitol, mannitol, furan derivatives such as 2-furancarboxylic acid, 3-furancarboxylic acid, and / or dialcohols or polyalcohols such as ethylene glycol, glycerol, diethylene glycol or triethylene glycol An aliphatic ether compound such as dimethoxyethane, diethylene glycol dimethyl ether or polyethylene glycol dialkyl ether, or a phenol compound such as dimethoxyphenol, m-cresol, o-cresol, p-cresol, phenol or naphthol is preferably used. These hydrophilic solvents may be used alone or in combination of two or more.

  The content of the hydrophilic solvent in the composition is not particularly limited, but is preferably 10% by mass or more, more preferably 50% by mass or more, and 100% by mass with respect to the total solid content in the composition. % Or more is more preferable. The upper limit is not particularly limited, but is preferably 10 times (1000% by mass) or less of the total solid content.

  The method for preparing the conductive composition is not particularly limited, and for example, it can be prepared by mixing the above-described components. More specifically, the reaction can be performed at normal temperature and pressure using a normal mixing apparatus or the like. For example, each component may be dissolved or dispersed by stirring, shaking, kneading in a solvent. Sonication may be performed to promote dissolution and dispersion.

(Another preferred embodiment of the method for producing a thermoelectric conversion layer)
As another preferred embodiment of the method for producing a thermoelectric conversion layer, for example, a composition containing a π-conjugated monomer that becomes a repeating unit having a molecular weight of 150 or more after polymerization and an oxidizing agent (for example, the oxidizing agent described above). After the monomer in the composition is polymerized by oxidative polymerization method by heating, the above-described crystallization treatment (for example, crystallization treatment other than crystallization treatment by slow cooling in the crystallization treatment described above) is performed. The method of giving is mentioned.
In addition, a template polymer (for example, the above-described template polymer) can be blended in the composition and polymerized by a template polymerization method. In this case, the crystallization treatment after polymerization may not be performed, but it is preferable to perform the crystallization treatment (for example, the crystallization treatment described above).

<Substituent W>
It describes about the substituent W in this specification.
Examples of the substituent W include a hydrogen atom, an alkyl group (for example, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc.), a cycloalkyl group (for example, cyclopentyl, Cyclohexyl, etc.), alkenyl groups (eg, vinyl, allyl, etc.), alkynyl groups (eg, ethynyl, propargyl, etc.), aromatic hydrocarbon ring groups (also called aromatic carbocycle, aryl, etc., for example, phenyl, p-chlorophenyl, etc. , Mesityl, tolyl, xylyl, naphthyl, anthryl, azulenyl, acenaphthenyl, fluorenyl, phenanthryl, indenyl, pyrenyl, biphenylyl, etc.), aromatic heterocyclic groups (5- or 6-membered aromatic heterocyclic groups are preferred, Ring heteroatoms are Sulfur atom, nitrogen atom, oxygen atom, silicon atom, boron, selenium atom is preferable, for example, pyridyl, pyrimidinyl, furyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrazolyl, pyrazinyl, triazolyl (for example, 1,2,4-triazole-1 -Yl, 1,2,3-triazol-1-yl, etc.), oxazolyl, benzoxazolyl, thiazolyl, isoxazolyl, isothiazolyl, furazanyl, thienyl, quinolyl, benzofuryl, dibenzofuryl, benzothienyl, dibenzothienyl, indolyl, carbazolyl , Carborinyl, diazacarbazolyl (in which one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), quinoxalinyl, pyridazinyl, triazinyl, quinazolinyl Phthalazinyl, borol, azaborine, etc.), a heterocyclic group (a non-aromatic heterocyclic group, which may be a saturated ring or an unsaturated ring, preferably a 5- or 6-membered ring, Sulfur atom, nitrogen atom, oxygen atom, silicon atom and selenium atom are preferable, for example, pyrrolidyl, imidazolidyl, morpholyl, oxazolidyl etc.), alkoxy group (for example, methoxy, ethoxy, propyloxy, pentyloxy, hexyloxy, octyloxy, Dodecyloxy etc.), cycloalkoxy groups (eg cyclopentyloxy, cyclohexyloxy etc.), aryloxy groups (eg phenoxy, naphthyloxy etc.), alkylthio groups (eg methylthio, ethylthio, propylthio, pentylthio, hexylthio, octylthio, dodo De Silthio, etc.), cycloalkylthio groups (eg, cyclopentylthio, cyclohexylthio, etc.), arylthio groups (eg, phenylthio, naphthylthio, etc.), alkoxycarbonyl groups (eg, methyloxycarbonyl, ethyloxycarbonyl, butyloxycarbonyl, octyloxycarbonyl) , Dodecyloxycarbonyl, etc.), aryloxycarbonyl groups (eg, phenyloxycarbonyl, naphthyloxycarbonyl, etc.), sulfamoyl groups (eg, aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylamino) Sulfonyl, octylaminosulfonyl, dodecylaminosulfonyl, phenylaminosulfonyl, naphthylaminos Honiru, 2-pyridyl aminosulfonyl, etc.),

An acyl group (for example, acetyl, ethylcarbonyl, propylcarbonyl, pentylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, dodecylcarbonyl, acryloyl, methacryloyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl, etc.), an acyloxy group (for example, Acetyloxy, ethylcarbonyloxy, butylcarbonyloxy, octylcarbonyloxy, dodecylcarbonyloxy, phenylcarbonyloxy, etc.), amide groups (eg, methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, Cyclohexylcarbonylamino, 2-ethylhexylcarbonylamino, octyl Carbonylamino, dodecylcarbonylamino, phenylcarbonylamino, naphthylcarbonylamino, etc.), carbamoyl groups (eg, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, octylaminocarbonyl, 2 -Ethylhexylaminocarbonyl, dodecylaminocarbonyl, phenylaminocarbonyl, naphthylaminocarbonyl, 2-pyridylaminocarbonyl, etc.), ureido groups (eg methylureido, ethylureido, pentylureido, cyclohexylureido, octylureido, dodecylureido, phenylureido, Naphthylureido, 2-pyridylaminoureido, etc.), sulfinyl groups (eg For example, methylsulfinyl, ethylsulfinyl, butylsulfinyl, cyclohexylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, phenylsulfinyl, naphthylsulfinyl, 2-pyridylsulfinyl, etc.), alkylsulfonyl groups (for example, methylsulfonyl, ethylsulfonyl, butylsulfonyl, Cyclohexylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, etc.), arylsulfonyl group or heteroarylsulfonyl group (eg, phenylsulfonyl, naphthylsulfonyl, 2-pyridylsulfonyl, etc.), amino group (amino group, alkylamino group, alkenylamino group) , Arylamino group, heterocyclic amino group, for example, amino, ethylamino, dimethylamino, butyla Mino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, naphthylamino, 2-pyridylamino, etc., cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl, triisopropylsilyl, triphenylsilyl) , Phenyldiethylsilyl, etc.).
Each of these groups may further have a substituent, and examples of the substituent include the above-described substituents. Examples thereof include an aralkyl group in which an alkyl group is substituted with an aryl group, and a hydroxyalkyl group in which an alkyl group is substituted with a hydroxy group. In addition, when the substituent W further has a plurality of substituents, the plurality of substituents may be bonded to each other to form a ring.

〔Base material〕
The thermoelectric conversion element of the present invention preferably includes a base material.
Although the kind of base material is not specifically limited, It is preferable to select the base material which is hard to be influenced at the time of formation of an electrode or the formation of a thermoelectric conversion layer.
Examples of such a substrate include glass, transparent ceramics, metal, and plastic film. Among these, a plastic film is preferable from the viewpoint of cost and flexibility.
Specific examples of the plastic film include polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-phthalenedicarboxylate, and bisphenol A. Polyester films such as polyester films with iso and terephthalic acid; polycycloolefin films such as ZEONOR film (manufactured by ZEON Corporation), ARTON film (manufactured by JSR Corporation), Sumilite FS1700 (manufactured by Sumitomo Bakelite Corporation); Kapton (Toray DuPont) ), Apical (Kaneka), Ubilex (Ube Industries), Pomilan (Arakawa Chemical), etc .; Pure Ace (Teijin Chemicals), Et Polycarbonate film, such as MEC (manufactured by Kaneka Corporation); polyether ether ketone film, such as SUMILITE FS1100 (manufactured by Sumitomo Bakelite); TORELINA (manufactured by Toray Industries, Inc.) and the like polyphenyl sulfide film such.
Of these, commercially available polyethylene terephthalate, polyethylene naphthalate, various polyimides and polycarbonate films are preferred from the viewpoints of availability, heat resistance of 100 ° C. or higher, economy and effects.

  In the present invention, the thickness of the substrate can be appropriately selected according to the purpose of use. For example, when a plastic film is used, it is generally preferable to use a substrate having a thickness of 5 to 500 μm. .

〔electrode〕
The thermoelectric conversion element of the present invention preferably includes an electrode.
The material of the electrode is not particularly limited. Examples of the material include transparent electrode materials such as ITO and ZnO; metal electrode materials such as silver, copper, gold, and aluminum; carbon materials such as CNT and graphene; PEDOT / PSS The organic material is mentioned. Alternatively, the electrode may be formed using a conductive paste in which conductive fine particles such as silver and carbon black are dispersed; a conductive paste containing metal nanowires such as silver, copper, and aluminum.

[Use]
The thermoelectric conversion element of the present invention is useful for thermoelectric power generation articles and the like.
Specific examples of thermoelectric power generation products include power generators such as hot spring thermal power generators, solar thermal power generators, and waste heat power generators, wristwatch power supplies, semiconductor drive power supplies, and small sensor power supplies.

[Conductive film]
The conductive film of the present invention is a conductive film containing a π-conjugated polymer.
Here, the π-conjugated polymer is the same as the specific π-conjugated polymer described above. Specific examples, preferred embodiments, and production methods of the specific π-conjugated polymer are as described above.
Further, the degree of crystallinity of the conductive film is 20% or more. The definition of crystallinity and a suitable aspect are the same as the thermoelectric conversion layer mentioned above.
The specific example, suitable aspect, and manufacturing method of the electrically conductive film of this invention are the same as the thermoelectric conversion layer mentioned above.

The conductive film of the present invention preferably has a carrier concentration of 1 × 10 ^{24 to} 3 × 10 ²⁶ / m ³ . Especially, it is preferable that it is 1 * 10 < ²⁶ > piece / m < ³ > or less, and it is more preferable that it is 5 * 10 < ²⁵ > piece / m < ³ > or less from the reason for which the temporal stability of the electrically conductive film obtained is more excellent. Among these, it is preferably 5 × 10 ²⁴ pieces / m ³ or more, more preferably 1 × 10 ²⁵ pieces / m ³ or more, because the conductivity of the obtained conductive film is higher.
In the present specification, the carrier concentration (number / m ³ ) and mobility (cm ² / Vs) of the conductive film are values measured using a Hall effect measuring device ResiTest 8300 (manufactured by Toyo Technica Co., Ltd.). .

  In addition, the thermoelectric conversion element of this invention mentioned above hits the thermoelectric conversion element which used the electrically conductive film of this invention for the thermoelectric conversion layer. The suitable aspect of the carrier concentration of the thermoelectric conversion layer is the same as that of the conductive film of the present invention.

[Organic semiconductor devices]
The organic semiconductor device of the present invention is an organic semiconductor device using the above-described conductive film of the present invention. Examples of such an organic semiconductor device include a thermoelectric conversion element, a photoelectric conversion element, an organic thin film transistor, an organic EL, a liquid crystal display, and a solar cell.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

<Example 1>
(Preparation of conductive film)
Iron (III) p-toluenesulfonate hexahydrate (525 mg) as an oxidizing agent, the following π-conjugated polymer 201 (590 mg), and pyridine (13 mg) as a polymerization rate regulator are dissolved in a diglyme solvent (4.5 g). The mixture was stirred at room temperature under a nitrogen atmosphere for 5.5 hours. After this mixed solution was ice-cooled, a π-conjugated monomer (221 mg) serving as a repeating unit of the following π-conjugated polymer 1 was added after polymerization, and the mixture was stirred at 0 ° C. for 10 minutes. This π-conjugated monomer solution was formed on a 3 cm × 4 cm glass substrate by spin coating, and then heated on a hot plate at 70 ° C. for 4 hours in the atmosphere to carry out an oxidative polymerization reaction. After the reaction, the film (oxidized polymer film) was cooled to room temperature, washed with ethanol, and heated on a hot plate at 70 ° C. for 15 minutes in a glove box in a nitrogen atmosphere. Thereafter, crystallization treatment by slow cooling (heating for 15 minutes in a state where the temperature is raised to 130 ° C. and then gradually cooling to room temperature at a cooling rate of 3 ° C./min) is performed to improve the crystallinity, and the π-conjugated polymer 1, conductive film containing iron (III) p-toluenesulfonate and π-conjugated polymer 201 (mass ratio of π-conjugated polymer 1, iron (III) p-toluenesulfonate and π-conjugated polymer 201 is about 18: 35:47). The manufacturing method is referred to as method A + B.

(Production of thermoelectric conversion element)
By the method A + B, a film thickness of 2.6 μm and a size of 8 mm × 8 mm are formed on the electrode surface on a glass substrate (thickness: 0.8 mm) having gold (thickness 20 nm, width: 5 mm) as a first electrode on one side surface. A conductive film to be a thermoelectric conversion layer was formed. Thereafter, a glass substrate (electrode thickness: 20 nm, electrode width: 5 mm, glass substrate thickness: 0.8 mm) on which gold was vapor-deposited as a second electrode was formed on the thermoelectric conversion layer. Were bonded at 80 ° C. so as to be in contact with the thermoelectric conversion layer, thereby producing a thermoelectric conversion element.
In the formation of the conductive film by the method A + B, single-walled carbon nanotubes were added to the π-conjugated monomer solution so that the content with respect to the obtained π-conjugated polymer was 30% by mass before film formation. Single-walled carbon nanotubes were dispersed by applying ultrasonic waves for 30 minutes.

<Example 2>
(Preparation of conductive film)
A conductive film containing π-conjugated polymer 1, iron (III) p-toluenesulfonate, and π-conjugated polymer 201 was obtained in the same manner as in Example 1 except that crystallization treatment by slow cooling was not performed. It was. The above production method is referred to as method B.

(Production of thermoelectric conversion element)
A thermoelectric conversion element was produced according to the same procedure as in Example 1 except that a conductive film to be a thermoelectric conversion layer was formed by Method B.
In the formation of the conductive film by Method B, single-walled carbon nanotubes were added to the π-conjugated monomer solution so that the content with respect to the obtained π-conjugated polymer was 30% by mass before film formation. Single-walled carbon nanotubes were dispersed by applying ultrasonic waves for 30 minutes.

<Example 3>
A conductive film and a thermoelectric conversion element were produced according to the same procedure as in Example 1 except that the following π conjugated polymer 203 was used instead of the π conjugated polymer 201.

<Examples 4 to 12, 17 to 32, Comparative Examples 1 and 6 to 9>
Instead of a π-conjugated monomer that becomes a repeating unit of π-conjugated polymer 1 after polymerization, a π-conjugated monomer that becomes a repeating unit of π-conjugated polymer described in the column of “first π-conjugated polymer” in Table 1 below is used after polymerization. The compounds described in the column of “Oxidizing agent” in Table 1 below are used in place of iron (III) hexahydrate of p-toluenesulfonate, and “secondary” in Table 1 below is used instead of π-conjugated polymer 201 A conductive film and a thermoelectric conversion element were produced in the same manner as in Example 2 except that the π-conjugated polymer described in the column “π-conjugated polymer” or polyvinylpyrrolidone was used.

<Example 13>
Instead of π-conjugated polymer 201, π-conjugated polymer 203 is used, and instead of crystallization treatment by slow cooling, pressure crystallization treatment (heating press machine (MP-WCL, manufactured by Toyo Seiki Seisakusho Co., Ltd.)) is used. The conductive film was subjected to the same procedure as in Example 1 except that the crystallinity was improved by pressurizing at 8 MPa at a temperature of 130 ° C. for 1 minute and then cooling to room temperature with the pressure applied. And the thermoelectric conversion element was produced. The method for manufacturing the conductive film is Method B + C.

<Example 14>
(Preparation of conductive film)
Iron (III) p-toluenesulfonate hexahydrate (525 mg) as an oxidizing agent and pyridine (13 mg) as a polymerization rate adjusting agent are dissolved in a diglyme solvent (4.5 g), and 5.5 hours at room temperature under a nitrogen atmosphere. Stir. After this mixed solution was ice-cooled, a π-conjugated monomer (221 mg) that becomes a repeating unit of the π-conjugated polymer 1 after polymerization was added, and the mixture was stirred at 0 ° C. for 10 minutes. This π-conjugated monomer solution was formed on a 5 cm × 5 cm PET substrate (thickness: 100 μm) by a drop cast method, and then heated on a hot plate at 70 ° C. for 6 hours in the atmosphere to carry out an oxidative polymerization reaction. After the reaction, the film (oxidized polymer film) was cooled to room temperature, washed with ethanol, and dried by heating on a hot plate at 70 ° C. for 15 minutes in the atmosphere. Then, the crystallization process by the pressurization mentioned above is performed, crystallinity degree is improved, and the electrically conductive film ((pi) conjugate polymer 1 and p-toluene containing (pi) conjugated polymer 1 and iron (III) p-toluenesulfonate. The mass ratio with iron (III) sulfonate was approximately 33:67). The production method is referred to as method C.

(Production of thermoelectric conversion element)
A thermoelectric conversion element was produced according to the same procedure as in Example 1 except that a conductive film to be a thermoelectric conversion layer was formed by Method C.
In the formation of the conductive film by Method C, single-walled carbon nanotubes were added to the π-conjugated monomer solution so that the content with respect to the obtained π-conjugated polymer was 30% by mass before film formation. Single-walled carbon nanotubes were dispersed by applying ultrasonic waves for 30 minutes.

<Example 15>
Use π-conjugated polymer 203 instead of π-conjugated polymer 201, and improve the crystallinity by performing crystallization treatment by solvent vapor exposure (exposure to acetone vapor for 30 minutes at room temperature) instead of crystallization treatment by slow cooling. A conductive film and a thermoelectric conversion element were produced according to the same procedure as in Example 1 except that. The method for manufacturing the conductive film is Method B + D.

<Example 16>
(Preparation of conductive film)
Iron (III) p-toluenesulfonate hexahydrate (525 mg) as an oxidizing agent and pyridine (13 mg) as a polymerization rate adjusting agent are dissolved in a diglyme solvent (4.5 g), and 5.5 hours at room temperature under a nitrogen atmosphere. Stir. After this mixed solution was ice-cooled, a π-conjugated monomer (221 mg) that becomes a repeating unit of the π-conjugated polymer 1 after polymerization was added, and the mixture was stirred at 0 ° C. for 10 minutes. This π-conjugated monomer solution was formed into a film on a 3 cm × 4 cm glass substrate by a drop cast method, and then heated on a hot plate at 70 ° C. for 6 hours in the atmosphere to carry out an oxidative polymerization reaction. After the reaction, the film (oxidized polymer film) was cooled to room temperature, washed with ethanol, and dried by heating on a hot plate at 70 ° C. for 15 minutes in the atmosphere. Thereafter, the crystallization treatment by the above-described solvent vapor exposure is performed to improve the crystallinity, and the conductive film containing π-conjugated polymer 1 and iron (III) p-toluenesulfonate (π-conjugated polymer 1 and p- The mass ratio with iron (III) toluenesulfonate was approximately 33:67). The above manufacturing method is referred to as Method D.

(Production of thermoelectric conversion element)
A thermoelectric conversion element was produced according to the same procedure as in Example 1 except that a conductive film to be a thermoelectric conversion layer was formed by Method D.
In addition, in formation of the electrically conductive film by Method D, single-walled carbon nanotubes were added to the π-conjugated monomer solution so that the content with respect to the obtained π-conjugated polymer was 30% by mass before film formation. Single-walled carbon nanotubes were dispersed by applying ultrasonic waves for 30 minutes.

<Comparative example 2>
(Method for producing conductive film)
The above-mentioned π-conjugated polymer 1 (10 mg) and the following π-conjugated polymer 201 (10 mg) obtained by prepolymerization by the coupling method described in Chemical Reviews 2009, 109, 5868-5923 are added to 1,4-dioxane (2 mL). The π-conjugated polymer solution is dissolved and formed on a glass substrate (3 cm × 4 cm) by spin coating under a nitrogen atmosphere, and then heated and dried on a hot plate at 130 ° C. for 60 minutes under a nitrogen atmosphere. By doing so, an undoped conductive film was obtained. The above manufacturing method is referred to as a manufacturing method X1.

(Production of thermoelectric conversion element)
A thermoelectric conversion element was produced according to the same procedure as in Example 1 except that a conductive film to be a thermoelectric conversion layer was formed by Method X1.
In the formation of the conductive film by the method X1, single-walled carbon nanotubes were added to the π-conjugated polymer solution so that the content with respect to the π-conjugated polymer was 30% by mass before film formation. Single-walled carbon nanotubes were dispersed by applying ultrasonic waves for 30 minutes.

<Comparative Example 3>
(Method for producing conductive film)
The above π-conjugated polymer 1 (10 mg) obtained by prepolymerization by the coupling method described in Chemical Reviews 2009, 109, 5868-5923 is dissolved in 1,4-dioxane (2 mL), and this π-conjugated polymer solution is dissolved. An undoped conductive film is formed by spin coating on a glass substrate (3 cm × 4 cm) in a nitrogen atmosphere, and then dried by heating on a hot plate at 130 ° C. for 60 minutes in a nitrogen atmosphere. Got. The above manufacturing method is referred to as a manufacturing method X2.

(Production of thermoelectric conversion element)
A thermoelectric conversion element was produced according to the same procedure as in Example 1 except that a conductive film to be a thermoelectric conversion layer was formed by Method X2.
In the formation of the conductive film by the method X2, single-walled carbon nanotubes were added to the π-conjugated polymer solution so that the content with respect to the π-conjugated polymer was 30% by mass before film formation. Single-walled carbon nanotubes were dispersed by applying ultrasonic waves for 30 minutes.

<Comparative example 4>
(Preparation of conductive film)
After polymerization, a π-conjugated monomer (500 mg) that becomes a repeating unit of the π-conjugated polymer 1 and p-toluenesulfonic acid iron (III) hexahydrate (600 mg) as an oxidizing agent are dissolved in diglyme (30 ml), and a room temperature nitrogen atmosphere Under stirring for 28 hours, the monomer was subjected to oxidative polymerization to synthesize the π-conjugated polymer 1. The reaction solution was reprecipitated in ethanol, and a black solid was taken out. The obtained black solid was sufficiently washed with pure water and ethanol by filtration under reduced pressure in a nitrogen atmosphere. Further, sodium dodecyl sulfate (80 mg) was added as a surfactant to the black solid (1.2 g) after washing, and the resulting mixture was dispersed in 250 ml of sufficiently deaerated pure water. Thereafter, dimethyl sulfoxide (boiling point: 189 ° C.) (5.5 ml) was added as a high-boiling hydrophilic solvent, and the mixture was stirred at room temperature under a nitrogen atmosphere for 2 hours. Π-conjugated polymer 1, iron p-toluenesulfonate (III) and dimethyl A conductive composition containing sulfoxide and water was obtained.

  The obtained conductive composition was applied on a 3 cm × 4 cm polyethylene terephthalate substrate (thickness: 75 μm), and then heated on a hot plate at 70 ° C. for 3 hours in the atmosphere. Then, after cooling at room temperature, it was washed with ethanol and heated on a hot plate at 70 ° C. for 15 minutes in a glove box under a nitrogen atmosphere. Then, the crystallization process by the slow cooling mentioned above was performed, the crystallinity degree was improved, and the electrically conductive film containing (pi) conjugated polymer 1 and p-toluenesulfonic acid iron (III) was obtained. The above production method is referred to as Method A.

(Production of thermoelectric conversion element)
A thermoelectric conversion element was produced according to the same procedure as in Example 1 except that a conductive film to be a thermoelectric conversion layer was formed by Method A.
In addition, in the formation of the conductive film by Method A, single-walled carbon nanotubes (4 mg) were added to the conductive composition (5 g) before applying the conductive composition. Single-walled carbon nanotubes were dispersed by applying ultrasonic waves for 30 minutes.

<Comparative Example 5>
Further, a conductive film and a thermoelectric conversion element were produced according to the same procedure as in Comparative Example 3 except that a mixed solution containing iron (III) p-toluenesulfonate hexahydrate (525 mg) was used as an oxidizing agent.

<Measurement of crystallinity>
About the obtained electrically conductive film, the crystallinity degree was calculated | required using the X ray diffraction method.
Specifically, measurement in the range of 2θ = 10 to 40 ° was performed using an X-ray diffractometer (D8 DISCOVER with GADDS Super Speed, manufactured by Bruker AXS). At this time, the profile in all directions of the sample was measured. According to the method of Hindeleh et al. (AM Hideleh and DJ Johnson, Polymer, 19, 27 (1978)), peaks were separated based on the omnidirectional diffraction curve of commercially available meta-aramid.
For the crystallinity, the crystalline peak and the amorphous halo were separated by profile fitting, the integrated intensities of the crystalline peak and the amorphous halo were obtained, and the crystallinity was calculated from the following formula. The results are shown in Table 1.
Crystallinity (%) = (Integral intensity of crystalline peak of entire conductive film) / (Sum of crystalline peak of conductive film and integrated intensity of amorphous halo) × 100
Note that the crystallinity corresponds to the crystallinity of the thermoelectric conversion layer.

<Evaluation>
(conductivity)
The electrical conductivity was evaluated for each produced conductive film. Specifically, the surface resistivity (unit: Ω / □) was measured using a “low resistivity meter: Loresta GP” (manufactured by Mitsubishi Chemical Analytech Co., Ltd.), and the film thickness ( Unit: cm) was measured, and the conductivity (S / cm) was calculated from the following formula. The results are shown in Table 1. The results were expressed as an index with the conductivity of Comparative Example 7 as 100. The larger the index, the higher the electrical conductivity and the better the performance of the thermoelectric conversion element. Note that “<1” is intended to be smaller than 1.
(Conductivity) = 1 / ((Surface resistivity) × (Film thickness))

(Mobility)
About the produced electrically conductive film, mobility (cm < ² > / Vs) was measured using Hall effect measuring apparatus ResiTest8300 (made by Toyo Technica Co., Ltd.). The results are shown in Table 1. The result was expressed as an index with the mobility of Comparative Example 7 as 100. The larger the index, the higher the mobility and the better.

(Thermo-electromotive force)
The thermoelectromotive force was evaluated about each produced thermoelectric conversion element. Specifically, the second electrode side of the thermoelectric conversion element is adhered on a hot plate (manufactured by AS ONE, model number: HP-2LA) having a set temperature of 55 ° C., and the set temperature of 25 ° C. is set on the first electrode side. A cold plate (manufactured by Nippon Digital Co., Ltd., model number: 980-127DL) was adhered. And the thermoelectromotive force (unit: V) which generate | occur | produced between the 1st electrode and the 2nd electrode was evaluated. The results are shown in Table 1. The results were expressed as an index with the thermoelectromotive force of Comparative Example 7 as 100. The larger the index, the higher the thermoelectromotive force, which is preferable. The thermoelectromotive forces of Comparative Examples 2 and 3 were below the detection limit and could not be measured.

  In Table 1, 1 to 15 and 101 to 103 for the “first π conjugated polymer” represent π conjugated polymers 1 to 15 and 101 to 103, respectively. The π-conjugated polymer 1 is as described above. Further, the π-conjugated polymers 2 to 15 and 101 to 103 are as follows. The π-conjugated polymers 1 to 15 correspond to π-conjugated polymers having a repeating unit having a molecular weight of 150 or more, and the π-conjugated polymers 101 to 103 do not correspond to a π-conjugated polymer having a repeating unit having a molecular weight of 150 or more.

The alkoxy groups of the π-conjugated polymers 1 and 4 to 11 (wherein two alkoxy groups are bonded to each other to form a ring), the alkylamino group of the π-conjugated polymer 2 and the alkoxy group of the π-conjugated polymer 3 are: , Both are substituents having Hammett's substituent constant σ _p value of −0.20 or less.

  In Table 1, “p-toluenesulfonic acid iron (III)” described in “Oxidizing agent” represents “p-toluenesulfonic acid iron (III) hexahydrate”.

  In Table 1, 201 to 206 and PEDOT: PSS for “second π-conjugated polymer” represent the following π-conjugated polymers 201 to 206 and PEDOT: PSS, respectively. PVP represents polyvinylpyrrolidone.

In Table 1, A to D, X, A + B, B + C, and B + D described in “Method” represent the above-described methods A to D, X, A + B, B + C, and B + D, respectively.
The characteristics of each method are as follows.
Method A: After polymerizing by a method other than the template polymerization method, a crystallization treatment by slow cooling is performed.
Method B: Polymerization is performed by a template polymerization method.
Method C: After polymerization by a method other than the template polymerization method, a crystallization treatment by pressure is performed.
-Method D: After polymerizing by a method other than the template polymerization method, a crystallization treatment by solvent vapor exposure is performed.
Method X1, X2: Neither crystallization treatment is performed after polymerization by a method other than the template polymerization method.
Method A + B: A crystallization treatment by slow cooling is performed after polymerization by the template polymerization method.
Method B + C: After polymerization by a template polymerization method, a crystallization treatment by pressure is performed.
Method B + D: After polymerization by a template polymerization method, a crystallization treatment by solvent vapor exposure is performed.

  In Table 1, “carrier concentration” is the carrier concentration of the conductive film (thermoelectric conversion layer). The method for measuring the carrier concentration is as described above.

Evaluation of “carrier doping” for the π-conjugated polymers described in “First π-conjugated polymers” in Table 1 in the conductive films (thermoelectric conversion layers) of Examples 1 to 32 and Comparative Examples 1 and 4 to 9. As a result, the carrier was doped. The evaluation method is as described above. Also, from the Hall coefficient measurement, all of the above dopings were p-type dopings.
In Comparative Examples 2 and 3, since a conductive film (thermoelectric conversion layer) is produced without doping using the π-conjugated polymer 1 polymerized by a coupling method without using an oxidizing agent, the comparative example The π-conjugated polymers described in “First π-conjugated polymer” in Table 1 in the conductive films (thermoelectric conversion layers) 2 and 3 correspond to π-conjugated polymers in which carriers are not doped.

  As described above, in Examples 1 to 32, the π-conjugated polymer described in “First π-conjugated polymer” in Table 1 in the conductive film (thermoelectric conversion layer) has a repeating unit having a molecular weight of 150 or more, and is a carrier. Is a doped π-conjugated polymer. That is, in Examples 1 to 32, the π-conjugated polymer of the conductive film (thermoelectric conversion layer) corresponds to the specific π-conjugated polymer described above.

As can be seen from Table 1, the present example in which the conductive film (thermoelectric conversion layer) contains a specific π-conjugated polymer and the crystallinity thereof is 20% or more showed high conductivity and thermoelectromotive force. .
From the comparison of Examples 1 to 17, Examples 1 to 13, 15 and 17 in which the degree of crystallinity of the conductive film (thermoelectric conversion layer) was 30% or more showed higher thermoelectromotive force and mobility. Among them, Examples 1, 3, 4, and 17 in which the degree of crystallinity of the conductive film (thermoelectric conversion layer) was 65% or more showed higher mobility. Among them, Examples 1 and 3 in which the degree of crystallinity of the conductive film (thermoelectric conversion layer) was 75% or more showed higher conductivity and mobility.
From the comparison of Examples 1 to 17, Examples 1 to 13, 15 and 17 which are polymers obtained by polymerizing the specific π-conjugated polymer by the template polymerization method show higher thermoelectromotive force and mobility. It was.
From a comparison between Examples 1 and 2, Example 1 in which crystallization treatment by slow cooling was performed after polymerization by the template polymerization method showed higher conductivity and mobility.
From the comparison of Examples 3, 12, 13, and 15, Examples 3 and 13 in which crystallization treatment was performed by slow cooling or pressurization after polymerization by the template polymerization method showed higher mobility. Especially, Example 3 which performed the crystallization process by slow cooling after superposing | polymerizing by the template polymerization method showed higher electrical conductivity and mobility.
From the comparison with Examples 18 to 32, Examples 18 to 28 and 30 to 32 in which the specific π-conjugated polymer has a repeating unit having a molecular weight of 300 or more showed higher conductivity and mobility. Among them, the specific π-conjugated polymer has a repeating unit represented by the above formula (1), and in the above formula (1), A is an arbitrary position of the compound represented by the above formula (A1). A divalent conjugated linking group in which two hydrogen atoms are removed from each other, two Y's are single bonds, and two Z's are both groups represented by the formula (Z1a) described above. In the formula (A1), m is 1, and X ³¹ and X ⁴² are each independently a sulfur atom, an oxygen atom, or a —NR ^N2 — group, or X ³² and X ⁴¹ are Independently, Example 21, which is a sulfur atom, an oxygen atom, or a —NR ^N2 — group, showed a higher thermoelectromotive force.

  On the other hand, Comparative Examples 1 to 5 in which the degree of crystallinity of the conductive film (thermoelectric conversion layer) is less than 20%, and the degree of crystallinity of the conductive film (thermoelectric conversion layer) is 20% or more, but the repetition of the π-conjugated polymer In Comparative Example 6 in which the unit molecular weight was less than 150, the conductivity and the thermoelectromotive force were low.

10, 20, 30 Thermoelectric conversion element 11, 21 First substrate 12, 22, 32 First electrode 13, 23, 33 Second electrode 14, 24, 34, Thermoelectric conversion layer 15, 25 Second group Material 31 Base material 300 Module

Claims (28)

A thermoelectric conversion element comprising a thermoelectric conversion layer containing a π-conjugated polymer,
The π-conjugated polymer is a π-conjugated polymer having a repeating unit having a molecular weight of 150 or more and doped with carriers.
The thermoelectric conversion element whose crystallinity degree of the said thermoelectric conversion layer is 20% or more.   The π-conjugated polymer is a group consisting of thiophene compounds, pyrrole compounds, aniline compounds, acetylene compounds, p-phenylene compounds, p-phenylene vinylene compounds, p-phenylene ethynylene compounds, and derivatives thereof. The thermoelectric conversion element according to claim 1, wherein the thermoelectric conversion element is a π-conjugated polymer having a repeating unit derived from at least one monomer selected from the group.   The thermoelectric conversion element according to claim 1 or 2, wherein the π-conjugated polymer is a π-conjugated polymer containing at least two kinds of aromatic rings in a repeating unit.   The thermoelectric conversion element according to any one of claims 1 to 3, wherein the π-conjugated polymer is a π-conjugated polymer containing an aromatic condensed ring in a repeating unit. The thermoelectric conversion element according to any one of claims 1 to 4, wherein the π-conjugated polymer has a repeating unit represented by the following formula (1).
In formula (1), A represents a divalent conjugated linking group having a condensed ring structure or a monocyclic structure. Y represents a single bond, a —CH═CH— group, a —N═N— group, an arylene group, a heteroarylene group, or a —NR ^N1 — group. Here, R ^N1 represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a heteroaryl group. Two Ys may be the same or different. Z represents a group represented by the following formula (Z). Two Z's may be the same or different. However, Z is different from A. * Represents a binding position.
In formula (Z), X ^Z1 and X ^Z2 each independently represent a hetero atom, a hetero atom having a substituent, a —CH═CH— group, or a ═CH— group. R ^Z1 represents an electron donating group. n represents an integer of 1 or more. When n is an integer of 2 or more, a plurality of R ^Z1 may be the same or different. When n is an integer of 2 or more, a plurality of R ^Z1 may combine with each other to form a ring. * Represents a binding position. The thermoelectric conversion according to claim 5, wherein A in the formula (1) is a divalent conjugated linking group obtained by removing two hydrogen atoms from any position of the compound represented by the following formula (A1). element.
In formula (A1), X ^{31 to} X ³³ and X ^{41 to} X ⁴³ each independently represent a hetero atom, a hetero atom having a substituent, a —CH═CH— group, a —CH— group, or —C ( ═O) — represents a group. A ring represents a conjugated hydrocarbon ring or a conjugated heterocyclic ring. n represents 0 or an integer of 1 or more. When n is an integer of 2 or more, a plurality of A rings may be the same or different. m represents 0 or 1; In the formula (A1), m is 1, and X ³¹ and X ⁴² are each independently a sulfur atom, an oxygen atom, or a —NR ^N2 — group, or X ³² and X ⁴¹ are each The thermoelectric conversion element according to claim 6, which is independently a sulfur atom, an oxygen atom, or a —NR ^N2 — group. Here, R ^N2 represents a hydrogen atom or an alkyl group.   In the formula (A1), m is 1, n is an integer of 1 or more, and the A ring is a benzene ring, a pyrrole ring, a thiophene ring, a pyridine ring, a cyclopentadiene ring, or a silole ring. The thermoelectric conversion element according to 6 or 7. The thermoelectric according to any one of claims 5 to 8, wherein a Hammett substituent constant σ _p value of the electron donating group represented by R ^Z1 in the formula (Z) is -0.20 or less. Conversion element. In the formula (Z), R ^Z1 represents a hydroxy group or a salt thereof, a mercapto group or a salt thereof, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, or an alkyl The thermoelectric conversion element according to any one of claims 5 to 9, which is an amino group, an arylamino group, a heterocyclic amino group, or an aryl group substituted with these groups. The thermoelectric conversion element according to any one of claims 5 to 10, wherein Z in the formula (1) is a group represented by the following formula (Z1).
In the formula (Z1), ^XZ1 represents a heteroatom, a heteroatom having a substituent, a —CH═CH— group, or a ═CH— group. X ^Z3 represents an oxygen atom or a sulfur atom. Two ^XZ3 may be the same or different. R ^Z2 represents a hydrogen atom or a substituent. Two R ^Z2 may be the same or different. * Represents a binding position. In the formula ^{(Z), X Z1} is a sulfur atom, an oxygen atom, or ^{-NR N2} - a group, the thermoelectric conversion device according to any one of claims 5-11. Here, R ^N2 represents a hydrogen atom or an alkyl group.   The thermoelectric conversion element according to any one of claims 5 to 12, wherein, in the formula (1), Y is a single bond or a 2,5-thienyl group. In the formula (1), A is a divalent conjugated linking group obtained by removing two hydrogen atoms from any position of the compound represented by the formula (A1). The thermoelectric conversion element according to any one of claims 5 to 13, which is a bond, and two Zs are groups represented by the following formula (Z1a).
In the formula (Z1a), R ^Z3 represents a hydrogen atom, an aryl group, a heteroaryl group, an alkyl group, an alkoxy group, a polyethyleneoxyether group, an alkylthio group, a polyethyleneoxythioether group, an alkylamino group, or a polyethyleneoxyamino group. . Two R ^Z3 may be the same or different. * Represents a binding position. In the formula (A1), m is 1, and X ³¹ and X ⁴² are each independently a sulfur atom, an oxygen atom, or a —NR ^N2 — group, or X ³² and X ⁴¹ are each The thermoelectric conversion element according to claim 14, which is independently a sulfur atom, an oxygen atom, or a -NR ^N2- group. Here, R ^N2 represents a hydrogen atom or an alkyl group.   In the formula (A1), m is 1, n is an integer of 1 or more, and the A ring is a benzene ring, a pyrrole ring, a thiophene ring, a pyridine ring, a cyclopentadiene ring, or a silole ring. The thermoelectric conversion element according to 14 or 15.   The thermoelectric conversion element according to claim 1, wherein the thermoelectric conversion layer further contains an oxidizing agent.   The thermoelectric conversion element according to any one of claims 1 to 17, wherein the π-conjugated polymer is obtained by polymerization by an oxidative polymerization method in the presence of an oxidizing agent.   The thermoelectric conversion element according to claim 18, wherein the oxidizing agent is at least one compound selected from the group consisting of iron (III) salts, copper (II) salts, peroxides, and peracids.   The π-conjugated polymer is obtained by polymerizing by a template polymerization method in the presence of a π-conjugated polymer having a repeating unit different from the repeating unit and an oxidizing agent. Thermoelectric conversion element.   A π-conjugated polymer having a repeating unit different from the repeating unit is a thiophene compound, a pyrrole compound, an aniline compound, an acetylene compound, a p-phenylene compound, a p-phenylene vinylene compound, or a p-phenylene ethynylene compound. The thermoelectric conversion element according to claim 20, which is a π-conjugated polymer having a repeating unit derived from at least one monomer selected from the group consisting of a compound and a derivative thereof. a conductive film containing a π-conjugated polymer,
The π-conjugated polymer is a π-conjugated polymer having a repeating unit having a molecular weight of 150 or more and doped with carriers.
The electrically conductive film whose crystallinity degree of the said electrically conductive film is 20% or more. The electrically conductive film according to claim 22, wherein the π-conjugated polymer has a repeating unit represented by the following formula (1).
In formula (1), A represents a divalent conjugated linking group having a condensed ring structure or a monocyclic structure. Y represents a single bond, a —CH═CH— group, a —N═N— group, an arylene group, a heteroarylene group, or a —NR ^N1 — group. Here, R ^N1 represents a hydrogen atom or a hydrocarbon group. Two Ys may be the same or different. Z represents a group represented by the following formula (Z). Two Z's may be the same or different. However, Z is different from A. * Represents a binding position.
In formula (Z), X ^Z1 and X ^Z2 each independently represent a hetero atom, a hetero atom having a substituent, a —CH═CH— group, or a ═CH— group. R ^Z1 represents an electron donating group. n represents an integer of 1 or more. When n is an integer of 2 or more, a plurality of R ^Z1 may be the same or different. When n is an integer of 2 or more, a plurality of R ^Z1 may combine with each other to form a ring. * Represents a binding position. 24. The conductive film according to claim 23, wherein, in the formula (1), A is a divalent conjugated linking group obtained by removing two hydrogen atoms from any position of the compound represented by the following formula (A1). .
In formula (A1), X ^{31 to} X ³³ and X ^{41 to} X ⁴³ each independently represent a hetero atom, a hetero atom having a substituent, a —CH═CH— group, a —CH— group, or —C ( ═O) — represents a group. A ring represents a conjugated hydrocarbon ring or a conjugated heterocyclic ring. n represents 0 or an integer of 1 or more. When n is an integer of 2 or more, a plurality of A rings may be the same or different. m represents 0 or 1; In the formula (1), A is a divalent conjugated linking group obtained by removing two hydrogen atoms from any position of the compound represented by the formula (A1). The conductive film according to claim 23 or 24, which is a bond, and two Zs are groups represented by the following formula (Z1a).
In the formula (Z1a), R ^Z3 represents a hydrogen atom, an aryl group, a heteroaryl group, an alkyl group, an alkoxy group, a polyethyleneoxyether group, an alkylthio group, a polyethyleneoxythioether group, an alkylamino group, or a polyethyleneoxyamino group. . Two R ^Z3 may be the same or different. * Represents a binding position. The conductive film according to claim 22, wherein the carrier concentration is 1 × 10 ^{24 to} 3 × 10 ²⁶ / m ³ .   The organic-semiconductor device using the electrically conductive film of any one of Claims 22-26.   An organic-semiconductor device provided with a base material, an electrode, and the electrically conductive film of any one of Claims 22-26 in this order.