JP2015170782A - Organic device and method of manufacturing organic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic device excellent in characteristics.SOLUTION: The organic device includes a first electrode, a second electrode, and an organic layer provided between the first electrode and the second electrode. The organic layer contains: a compound obtained by removing an insulating moiety from a first compound which has an organic semiconductor moiety having one rectifying property of an electron-donating property and an electron-accepting property, the insulating moiety, and a bonding moiety bonding them together and has a molecular weight dispersion of 1.6 or less; and a second compound which has an organic semiconductor moiety having a rectifying property different from that of the organic semiconductor moiety of the first compound.

Description

  The present invention relates to an organic device and a method for manufacturing the organic device.

  An organic device having a light emitting layer containing an organic compound as a material and an organic layer serving as an optically active layer can be reduced in weight, more flexible and transparent than a conventional device made of an inorganic compound such as silicon. It has attracted attention as a new device because it has a feature that it can be a structure rich in properties and can be manufactured at a lower cost.

  In such an organic device, in order to realize high characteristics, a structure in which the phase of the p-type semiconductor material and the phase of the n-type semiconductor material in the organic layer are phase-separated on the order of several tens of nm is generated, and the p-type is formed. The phase separation structure formed by the p-type semiconductor material and the n-type semiconductor material is optimized so that the phase of the semiconductor material and the phase of the n-type semiconductor material are in contact with each other and electrically connected to each other. Is considered important.

  In order to form an organic layer having a more optimal structure, for example, in an organic photoelectric conversion element, either a p-type semiconductor material or an n-type semiconductor material, a material having crystallinity, a material that self-organizes during film formation, etc. A technique for constructing a nanostructure using a material having a periodic structure and forming an optically active layer using the nanostructure as a template has been studied. (See Non-Patent Documents 1, 2, and 3.)

  Also, in organic light-emitting devices, providing a micro-mixed layer at the interface between an electron transport material (n-type semiconductor material) and a hole transport material (p-type semiconductor material) increases both contact interfaces and improves device characteristics. It is being considered to do. (See Non-Patent Document 4.)

Journal of Polymer Science Part B, 2011, 49, 1131-1156. Chem. Rev. 2010, 110, 146-177 The latest technology of organic thin film solar cell CM publication p63-71, p172-179, (2005) Japan Journal of Applied Physics, Vol. 46, no. 35, 2007, pp. L861-L863

  However, in the organic devices such as the organic photoelectric conversion element and the organic light emitting element disclosed in the above non-patent literature, the nanostructure formed by the p-type semiconductor material and the n-type semiconductor material in the organic layer is not optimized As a result, the characteristics such as the photoelectric conversion efficiency and the light emission efficiency are not always satisfactory.

  The present invention has been made in view of the above problems, and the object thereof is an organic device having an organic layer containing a highly ordered nanostructure and having high photoelectric conversion efficiency and light emission efficiency. And providing a manufacturing method thereof.

The present invention provides the following [1] to [20].
[1] having a first electrode, a second electrode, and an organic layer provided between the first electrode and the second electrode;
The organic layer has an organic semiconductor site having one of rectifying properties of electron donating property and electron accepting property, an insulating site, and a binding site for binding them, and the molecular weight dispersion is 1.6 or less. An organic device comprising: a compound obtained by removing an insulating part from a first compound; and a second compound having an organic semiconductor part having a rectifying characteristic different from that of the organic semiconductor part.
[2] The organic device according to [1], wherein the organic semiconductor portion of the first compound is electron-donating.
[3] The organic device according to [1] or [2], wherein the organic semiconductor portion of the first compound includes a hetero 5-membered ring.
[4] The organic device according to any one of [1] to [3], wherein the organic semiconductor portion of the first compound includes a thiophenediyl group which may have a substituent.
[5] The organic device according to any one of [1] to [4], wherein the organic semiconductor portion of the first compound has a structure represented by the following formula (1).
(In the formula (1), X represents a group represented by —C═C—, a group represented by —C≡C—, or a group represented by —N═N—, and m is 0 or 1. n. Is an integer equal to or greater than 1. R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and Z are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 3 to 3 carbon atoms. 20 cycloalkyl groups, monovalent aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, cycloalkoxy groups having 3 to 20 carbon atoms, 1 to 1 carbon atoms 20 alkylthio groups, a cycloalkylthio group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group which may have a substituent or a monovalent heterocyclic group which may have a substituent. Represents.)
[6] The organic device according to any one of [1] to [5], wherein the organic semiconductor portion of the first compound has a structure represented by the following formula (2) or the following formula (3).
(In the formula (2), Z is as defined in the formula (1). In the formula (3), R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and Z are the formula (1). (N is an integer of 2 or more)
[7] The organic device according to [6], wherein the organic semiconductor portion of the first compound has a structure represented by the formula (2), and the Z is an n-butyl group.
[8] The organic semiconductor portion of the first compound has a structure represented by the formula (3), the Z is a chlorine atom or a bromine atom, and the R ₀ , R ₁ , R ₂ , R ₃ and The organic device according to [6], wherein each R ₄ is a linear alkyl group.
[9] The organic device according to [8], wherein R _0, R ₁ , R ₂ , R ₃ and R ₄ are all n-hexyl groups.
[10] The organic semiconductor part of the first compound is a monovalent group having hydrophobicity, and the insulating part is a monovalent group derived from a hydrophilic polymer. [1] to [9] Organic device as described in any one of these.
[11] The organic device according to [10], wherein the monovalent group derived from the hydrophilic polymer is a monovalent group having a polyethylene oxide chain.
[12] The organic device according to any one of [1] to [11], including a structure in which the binding site is decomposed by treatment with light, heat, acid, or alkali.
[13] The organic device according to [12], wherein the structure of the binding site includes any one of an acetal bond, an ester bond, and an ether bond.
[14] The organic device according to any one of [1] to [13], wherein the first compound is a compound represented by the following formula (4), the following formula (5), or the following formula (6). .
(In Formula (4), X ₂ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a monovalent aliphatic non-valent having 2 to 20 carbon atoms. A saturated hydrocarbon group, an alkoxy group having 1 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a cycloalkylthio group having 3 to 20 carbon atoms, and a substituent. Represents a monovalent aromatic hydrocarbon group which may have or a monovalent heterocyclic group which may have a substituent, q and s are integers of 1 or more, in formula (5), p and n are each independently an integer of 1 or more, and in formula (6), r is an integer of 2 or more.)
[15] A polymer compound represented by the following formula (6).
(In formula (6), r is an integer of 2 or more.)
[16] In a method of manufacturing an organic device having a first electrode, a second electrode, and an organic layer provided between the first electrode and the second electrode,
The organic semiconductor part having an rectifying property of either one of electron donating property and electron accepting property, an insulating part, and a binding part for bonding them, and having a molecular weight dispersion of 1.6 or less After forming the layer containing the compound, the insulating portion is removed from the first compound by decomposing the binding site of the first compound in the layer, and then the organic semiconductor having a rectifying characteristic different from that of the organic semiconductor portion The manufacturing method of the organic device which adds the 2nd compound which has a site | part so that the said layer may be contacted, and forms the organic layer by filling the space | gap in the said layer produced by the removal of the said insulating site | part.
[17] An organic semiconductor portion having one of rectifying characteristics of either electron donating property or electron accepting property, an insulating portion, and a binding site for binding them, and having a molecular weight dispersion of 1.6 or less Forming a layer containing one compound, removing an insulating portion from the first compound in the layer, and adding a second compound having an organic semiconductor portion having a rectifying characteristic different from the organic semiconductor portion to the layer A thin film obtained by adding so as to come into contact.
[18] A photoelectric conversion element comprising the thin film according to [17].
[19] A light emitting device comprising the thin film according to [17].
[20] A sensor comprising the thin film according to [17].

  ADVANTAGE OF THE INVENTION According to this invention, it has an organic layer containing a highly regular nanostructure, and can provide the organic device excellent in luminous efficiency and photoelectric conversion efficiency.

FIG. 1 is a photograph showing an AFM image. FIG. 2 is a photograph showing an AFM image.

  Hereinafter, the organic device and the manufacturing method thereof of the present invention will be described in detail.

(Photoelectric conversion element)
The organic device of the present invention includes a first electrode, a second electrode, and an organic layer provided between the first electrode and the second electrode. A first organic semiconductor portion having an rectifying property of any one of electron donating properties and electron accepting properties, an insulating portion, and a binding site for bonding them, and having a molecular weight dispersion of 1.6 or less The compound from which the insulating part was removed from the compound and the 2nd compound which has the organic-semiconductor site | part of a rectification characteristic different from the organic-semiconductor site | part of a 1st compound are included.

  The component which comprises the organic device of this invention is demonstrated concretely.

(substrate)
The organic device of the present invention usually includes a substrate. The substrate that can be used may be a plate-like body that does not change thermally or chemically when the electrode is formed and when the organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. When the substrate is opaque, it is preferable that the electrode located on the opposite side of the substrate (that is, the electrode far from the substrate) is transparent or opaque.

(electrode)
The organic device includes a first electrode and a second electrode facing each other. At least one of the first electrode and the second electrode is a transparent or translucent electrode. One of the first electrode and the second electrode functions as an anode, and the other electrode functions as a cathode.

Examples of the material of the electrode functioning as the anode include metals and conductive oxides. Specific examples of the metal include Al, Au, Pt, Sn, Zn, Cu, Ag, Mo, and Ti. In order to increase the stability of the electrode, a different metal may be further added in addition to the metal. Examples of the conductive oxide that is a material of the electrode functioning as the anode include a conductive oxide having high conductivity near normal temperature (25 ° C.). Specific examples of the conductive oxide include ITO, SnO ₂ , ZnO, FTO (tin oxide added with fluorine), IZO (zinc oxide added with indium oxide), and Al-doped ZnO (AZO). , Ga-doped ZnO (GZO), and ATO (antimony-added tin oxide). Examples of the electrode forming method include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.

  As an electrode material that functions as an anode, polyaniline and derivatives thereof, organic materials such as polythiophene and derivatives thereof, and p-type semiconductor metal oxide materials such as molybdenum oxide and vanadium oxide may be used.

A transparent or translucent conductive thin film can be used as the cathode. Examples of the metal material that can form the cathode include aluminum, scandium, vanadium, zinc, silver, Pt, Sn, Cu, and Ti. Materials for the case where the cathode is a transparent electrode include ITO, SnO. ₂ , ZnO, FTO, IZO, AZO, GZO, and ATO.

(Organic layer)
The organic layer of the present invention is provided between the first electrode and the second electrode, and has an organic semiconductor part and an insulating part having a rectifying characteristic of either electron donating property or electron accepting property. And a rectifying characteristic that is different from the organic semiconductor part of the first compound and the compound from which the insulating part is removed from the first compound having a molecular weight dispersion of 1.6 or less And a second compound having an organic semiconductor moiety.
The organic layer may be, for example, an optically active layer that can obtain a photovoltaic effect by incident light. Further, the optically active layer may be a layer whose orientation can be controlled by incident light, for example, and which can control electrical characteristics, optical characteristics, and the like.

<First compound>
The first compound is a compound having an organic semiconductor site, an insulating site, and a binding site for bonding them, and having a molecular weight dispersion of 1.6 or less. The first compound is a compound in which the organic semiconductor part has a long structure, and when the coating film is formed, the organic semiconductor part and the insulating part exhibit a highly ordered nanostructure by self-organization, It is a compound that can maintain a highly ordered nanostructure composed of organic semiconductor sites even after the insulating sites are removed in the subsequent steps.

  The combination of the organic semiconductor site and the insulating site in the first compound is not particularly limited on the condition that a nanostructure as described later can be formed by self-assembly. In the first compound, it is preferable that the organic semiconductor portion has hydrophobicity and the insulating portion has hydrophilicity.

  Further, from the viewpoint of forming a nano structure having higher regularity, the first compound preferably has liquid crystallinity or crystallinity. From the viewpoint of enabling the orientation and the formed nanostructure to be controlled by external force, it is more preferable that at least the organic semiconductor portion of the first compound has only liquid crystallinity.

  Examples of nanostructures that can be formed by the first compound include nanoporous structures formed by arranging organic semiconductor sites in a nematic phase by self-organization, and organic semiconductor sites arranged in a smectic phase by self-organization. And nanocylinder arrays and nanorod arrays formed by From the viewpoint of securing a charge transport route, a nanoporous structure and a nanocylinder arrangement are preferable, and a nanocylinder arrangement is more preferable.

  The first compound capable of forming a nanoporous structure and a nanocylinder arrangement is such that the major axis of the self-organized organic semiconductor site is 30 ° to 90 ° with respect to the substrate surface from the viewpoint of facilitating transport of charge to the electrode. It is preferable to make an angle of °. This angle is more preferably 45 ° to 90 °, and particularly preferably 80 ° to 90 °.

  The diameter of the substantially cylindrical organic semiconductor portion constituting the nanoporous structure and the nanocylinder arrangement is preferably 10 nm to 50 nm from the viewpoint of photocharge separation. More preferably, it is 10 nm-20 nm.

  The first compound has an organic semiconductor site, an insulating site, and a binding site, and is preferably a block copolymer in which the organic semiconductor site and the insulating site are bonded by a binding site.

The rectifying property of the organic semiconductor portion is not limited, and may be p-type (electron donating property) or n-type (electron accepting property).
From the viewpoint of ease of synthesis, the organic semiconductor site is preferably an organic semiconductor site that is hydrophobic and has an electron donating property as described above.

  The electron-donating organic semiconductor site preferably contains a hetero 5-membered ring. Examples of electron-donating organic semiconductor sites include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophenes and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilanes and derivatives thereof, side chains or main chains. And monovalent groups derived from polysiloxane derivatives having aromatic amine residues, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, and the like. .

  The electron-donating organic semiconductor portion may contain a monocyclic structure or a condensed ring structure. In addition, the electron-donating organic semiconductor portion may have a structure in which two monocyclic structures or two condensed ring structures or a monocyclic structure and a condensed ring structure are bonded by a direct bond. The monocyclic structure and the condensed ring structure may contain an aromatic ring. The aromatic ring may be an aromatic carbocyclic ring such as a benzene ring or an aromatic heterocyclic ring.

  Examples of the electron-donating organic semiconductor moiety include a divalent aromatic group, a monovalent group including a structure in which a monocyclic aromatic ring or a polycyclic aromatic ring is connected by a direct bond, or a ring structure. And a monovalent group bonded to. The divalent aromatic group contained in the organic semiconductor region is capable of forming a 6π electron system, a 10π electron system, or a 14π electron system by supplying π electrons in addition to the six-membered ring. A structure in which an atom and a group represented by —C═C— are substituted may be included.

  Specific examples of the electron-donating organic semiconductor moiety include a fluorenediyl group which may have a substituent, a benzofluorenediyl group which may have a substituent, and a substituent. Dibenzofurandiyl group which may have, dibenzothiophenediyl group which may have substituent, benzodithiophenediyl group which may have substituent, thiophene diyl which may have substituent Group, an optionally substituted cyclopentadithiophenediyl group, an optionally substituted carbazolediyl group, an optionally substituted thiophenediyl group, and a substituent. An optionally substituted frangyl group, an optionally substituted pyrrole diyl group, an optionally substituted benzothiadiazole diyl group, and an optionally substituted trif A monovalent group comprising one or two or more divalent groups selected from the group consisting of nylaminediyl groups as a structural unit, wherein the structural units are bonded directly by a bond or bonded via a linking group. The group of is mentioned.

  In the present specification, examples of the substituent in the case of “may have a substituent” include a halogen atom, the number of carbon atoms in which one or more hydrogen atoms may be substituted with a halogen atom. 1 to 20 alkyl groups, one or more hydrogen atoms optionally substituted with a halogen atom, a cycloalkyl group having 3 to 20 carbon atoms, one or more hydrogen atoms substituted with a halogen atom Examples thereof include an alkoxy group having 1 to 20 carbon atoms and a cycloalkoxy group having 3 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a halogen atom.

  Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group. 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, dodecyl group and the like. The alkyl group in which one or more hydrogen atoms are substituted with a halogen atom is preferably an alkyl group substituted with a fluorine atom. Examples of the alkyl group substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group. Specific examples of the cycloalkyl group include a cyclohexyl group. The cycloalkyl group in which one or more hydrogen atoms are substituted with a halogen atom is preferably a cycloalkyl group substituted with a fluorine atom.

  The alkyl part in the alkoxy group may be linear or cyclic. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. Pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group and lauryloxy group. As the alkoxy group in which one or more hydrogen atoms are substituted with a halogen atom, an alkoxy group substituted with a fluorine atom is preferable. Examples of the alkoxy group substituted with a fluorine atom include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group. Specific examples of the cycloalkoxy group include a cyclohexyloxy group. As the alkoxy group in which one or more hydrogen atoms are substituted with a halogen atom, an alkoxy group substituted with a fluorine atom is preferable.

  From the viewpoint of enhancing the charge transporting property and from the viewpoint of facilitating the expression of a more regular nanostructure, the organic semiconductor portion preferably includes a structure in which three or more structural units are connected. As the structural unit, a thiophene diyl group or bithiophene which may have a substituent, a 3rd-position carbon atom and a 3′-position carbon atom bonded via a sulfur atom, an oxygen atom or a nitrogen atom It preferably includes a structure, and more preferably includes a thiophenediyl group which may have a substituent.

  Specifically, the organic semiconductor part preferably has a structure represented by the following formula (1).

In formula (1), X represents a group represented by —C═C—, a group represented by —C≡C—, or a group represented by —N═N—. m is 0 or 1. n is an integer of 1 or more. R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and Z are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a carbon atom. A monovalent aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and the number of carbon atoms 3 to 20 cycloalkylthio groups, a monovalent aromatic hydrocarbon group which may have a substituent or a monovalent heterocyclic group which may have a substituent.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and Z include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a tert-butyl group. , A hexyl group, an octyl group, and a cyclohexyl group. Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclohexyl group.

Examples of the monovalent aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms represented by R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and Z include, for example, a vinyl group, a 2-propenyl group, Examples include ethynyl group and 2-propynyl group.

Examples of the alkoxy group having 1 to 20 carbon atoms represented by R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and Z include, for example, methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group and An octyloxy group is mentioned, As a C3-C20 cycloalkoxy group, a cyclohexyloxy group is mentioned, for example.

Examples of the alkylthio group having 1 to 20 carbon atoms represented by R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and Z include, for example, methylthio group, ethylthio group, propylthio group, butylthio group, hexylthio group, and An octylthio group is mentioned, As a C3-C20 cycloalkylthio group, a cyclohexylthio group is mentioned, for example.

Examples of the monovalent aromatic hydrocarbon group optionally having a substituent represented by R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and Z include a phenyl group, a naphthyl group, and an anthracenyl group. And perylene-yl groups.

Examples of the monovalent heterocyclic group optionally having a substituent represented by R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and Z include a thienyl group, pyridyl group, furyl group, thiazolyl Group, pyrimidyl group, triazinyl group, quinolyl group and isoquinolyl group.

  In the structure represented by the formula (1), n is preferably 1 to 100.

  In the case where n is 1, the organic semiconductor portion preferably has a structure specifically represented by the following formula (2) from the viewpoint of orientation.

  In formula (2), Z is as defined above.

  When the organic semiconductor site has a structure represented by the formula (2), Z is preferably an n-butyl group.

  When n is an integer of 2 or more in the structure represented by the formula (1), the organic semiconductor site is specifically represented by the following formula (3) from the viewpoint of orientation and ease of synthesis. A structure is preferred.

In formula (3), R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and Z are as defined above. n is an integer of 2 or more.
When the organic semiconductor portion has the structure represented by the formula (3), R ₀ , R ₁ , R ₂ , R ₃ and R ₄ are all the same group from the viewpoint of enhancing the orientation such as crystallinity and liquid crystallinity. Preferably there is. Furthermore, from the viewpoint of enhancing solubility, R ₀ , R ₁ , R ₂ , R ₃ and R ₄ are preferably alkyl groups, and more preferably linear alkyl groups having no branches. R ₀ , R ₁ , R ₂ , R ₃ and R ₄ are more preferably an n-decyl group, an n-octyl group, an n-hexyl group and an n-butyl group, and particularly preferably an n-hexyl group. .

  When the organic semiconductor site has a structure represented by the formula (3), Z is preferably a hydrogen atom or a halogen atom from the viewpoint of enhancing the interaction between molecules. In view of ease of synthesis, a halogen atom is more preferable, and bromine is more preferable.

When the organic semiconductor portion has a structure represented by the formula (3), Z is a chlorine atom or a bromine atom, and R ₀ , R ₁ , R ₂ , R ₃ and R ₄ are all linear alkyl groups. It is preferable that R _0, R ₁ , R ₂ , R ₃ and R ₄ are all n-hexyl groups.

[Insulating part]
The insulating portion of the first compound is preferably a polymer whose main chain has a non-conjugated structure from the viewpoint of improving solubility. In addition, from the viewpoint of spontaneously phase-separating and self-integrating with an organic semiconductor site to develop a nanostructure, the organic semiconductor site is a monovalent group having hydrophobicity, and the insulating site is a monovalent group having hydrophilicity. It is preferably a group, and the insulating part is more preferably a monovalent group derived from a hydrophilic polymer.

  Specific examples of the insulating site include monovalent groups derived from hydrophilic polymers such as polyacrylic acid, polyvinyl alcohol, polyethylene oxide, polyacrylamide, polyethyleneimine, and polyvinylpyrrolidone. From the viewpoint of developing the nanostructure, a polymer having a small molecular weight dispersion that can constitute the insulating portion is preferable. Furthermore, from the viewpoint of easy availability, the monovalent group derived from a hydrophilic polymer that can form an insulating site is preferably a monovalent group having a polyethylene oxide chain. The molecular weight of polyethylene oxide that can be used is preferably 2000 to 100,000, more preferably 1000 to 50,000.

  Specifically, the monovalent group having a polyethylene oxide chain is preferably a structure represented by the following formula (A).

  In the formula (A), y is an integer of 1 or more, preferably 50 to 5000, and more preferably 100 to 2000.

[Binding site]
The binding site of the first compound can be easily decomposed by chemical treatment with acid, alkali, etc., physical treatment with heat, light, etc., or a combination thereof, and the organic semiconductor site and the insulating site can be separated. It has a structure. When the organic semiconductor portion and the insulating portion are separated, a structure derived from a part of the binding portion may remain in one or both of the organic semiconductor portion and the insulating portion.
Specific examples of the binding site include structures containing an acetal bond, an ester bond, an ether bond, a thioether bond, and the like. The binding site preferably has a structure containing an acetal bond from the viewpoint of ease of synthesis.

  Examples of the binding site include a divalent group having the following structure.

  From the viewpoint of ease of synthesis, the first compound may include a portion other than the organic semiconductor portion, the insulator portion, and the binding portion. Specific examples of sites other than organic semiconductor sites, insulator sites, and bond sites include saturated hydrocarbon groups such as ethylene and propylene, divalent aromatic hydrocarbon groups, and divalent heterocyclic groups. Of these, ethylene and triazine are preferable.

  A preferred structure of the first compound includes a block copolymer having a structure represented by the following formula (4), the following formula (5) and the following formula (6).

In formula (4), X ₂ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a monovalent aliphatic unsaturated group having 2 to 20 carbon atoms. It has a hydrocarbon group, an alkoxy group having 1 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a cycloalkylthio group having 3 to 20 carbon atoms, and a substituent. Represents a monovalent aromatic hydrocarbon group which may be substituted or a monovalent heterocyclic group which may have a substituent. From the viewpoint of synthesis, X ₂ is preferably a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group which may have a substituent. Among these, a halogen atom, a methyl group, an ethyl group, and a propyl group are more preferable, and a halogen atom is more preferable. q and s are integers of 1 or more. s is preferably 1 to 100, and more preferably 1 to 50. In formula (5), p and n are each independently an integer of 1 or more. q and p are each independently preferably 50 to 5000, and more preferably 100 to 2000. In formula (6), r is an integer of 2 or more. r is preferably 5 to 200, and more preferably 10 to 100.

  The first compound preferably has a smaller molecular weight dispersion (Mw / Mn), which is a ratio between the number average molecular weight (Mn) and the weight average molecular weight (Mw). The number average molecular weight (Mn) and the weight average molecular weight (Mw) mean a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

  The molecular weight dispersion of the first compound is 1.6 or less, preferably 1.5 or less, more preferably 1.3 or less, and even more preferably 1.2 or less.

  By reducing the molecular weight dispersion of the first compound as described above, it is possible to further increase the regularity (periodicity) of the arrangement of the obtained nanostructures, so the phase of the first compound and the phase of the second compound Can be optimized in a more preferred manner. As a result, the characteristics of the organic device can be further improved.

<Second compound>
The second compound is a compound having an organic semiconductor portion having a rectifying characteristic different from the organic semiconductor portion of the first compound. The organic semiconductor portion of the second compound preferably has n-type (electron accepting) rectification characteristics. Therefore, when the organic semiconductor part of the second compound has an n-type rectifying characteristic, the organic semiconductor part of the first compound has a p-type rectifying characteristic. Specific examples of the organic semiconductor portion of the second compound having n-type characteristics include monovalent groups derived from fullerene derivatives, perylene diimide derivatives, and naphthalene diimide derivatives. The organic semiconductor portion of the second compound is preferably a monovalent group derived from a fullerene derivative from the viewpoint of electron accepting properties.

Among the fullerene derivatives, fullerene derivatives such as C ₆₀ fullerene, C ₇₀ fullerene, phenyl C ₆₁ butyric acid methyl ester, phenyl C ₇₁ butyric acid methyl ester, or indene C ₆₀ bis adduct and indene C ₇₀ bis adduct are preferable. Among these, C ₇₀ fullerene, phenyl C ₆₁ butyric acid methyl ester, phenyl C ₇₁ butyric acid methyl ester, indene C ₆₀ bis adduct, and indene C ₇₀ bis adduct are more preferable.

(Middle layer)
The organic device of the present invention includes an intermediate layer having characteristics that enhance the efficiency of charge injection and / or transport between an organic layer and an electrode, film formability when forming an electrode, and when forming an electrode. You may have an intermediate | middle layer which has a function which improves a power generation characteristic, durability in a manufacturing process, etc., such as an intermediate | middle layer which has the characteristic which reduces the damage to a lower layer from an electrode.

  As the material of the intermediate layer, an organic material or a metal oxide material can be used. The intermediate layer can be formed using a vapor phase method such as an evaporation method, a sputtering method, or a laser ablation method, a wet method such as a sol-gel method, a spray coating method, a printing method, or a coating method. Examples of the layer having the property of increasing the efficiency of hole injection and / or transport include a layer containing poly (ethylenedioxythiophene) (PEDOT) / polystyrene sulfonic acid complex.

(Organic device manufacturing method)
The organic device manufacturing method of the present invention is a method of manufacturing an organic device having a first electrode, a second electrode, and an organic layer provided between the first electrode and the second electrode. And having an organic semiconductor portion having one of rectifying properties of electron donating property and electron accepting property, an insulating portion, and a binding portion for binding them, and having a molecular weight dispersion of 1.6 or less. After forming the layer containing the first compound, the insulating portion is removed by decomposing the binding site of the first compound in the layer, and then the organic compound having a rectifying characteristic different from the organic semiconductor portion of the first compound A second compound having a semiconductor site is added so as to contact the layer from which the insulating site has been removed, and the insulating site is removed by filling the voids in the layer generated by the removal of the insulating site. Including a first compound and a second compound Is a manufacturing method characterized by forming the machine layer. Here, adding to contact means, for example, vacuum-depositing the second organic compound or applying a solution containing the second compound by a coating method.

  Since the method for forming the first electrode and the second electrode (cathode and anode) has already been described, the organic layer forming step will be described here.

  The organic layer is a solution or dispersion liquid (hereinafter simply referred to as “liquid”) containing the first compound on a substrate provided with an intermediate layer bonded to the first electrode or the first electrode and the first electrode. .) Is applied to form a coating layer, and the formed coating layer is dried by a drying process to self-organize the organic semiconductor portion and the insulating portion to develop a regular nanostructure. A layer including a nanostructure including a nanocylinder arrangement as described is formed.

  Subsequently, the binding site is decomposed by the treatment such as the acid treatment already described to separate the organic semiconductor site and the insulating site, and the insulating site is removed from the first compound. Thereafter, by applying a solution containing the second organic compound on the layer from which the insulating portion has been removed from the first compound, the second gap is formed in the void generated by removing the insulating portion in the layer. It can be produced by filling with a compound.

  As described above, the layer containing the first compound can be formed by a coating method using the liquid containing the first compound. Examples of the coating method that can be used when forming the layer containing the first compound include a slit coating method, a capillary coating method, a gravure coating method, a micro gravure coating method, a bar coating method, a knife coating method, a nozzle coating method, Examples thereof include an ink jet coating method and a spin coating method.

  In the layer containing the first compound, in the step of drying the coating film, for example, an organic semiconductor site that is hydrophobic and an insulating site that is hydrophilic, for example, among the multiple first compounds included, Nanostructures are formed as a result of regular accumulation (arrangement) of sites having the same properties and self-organization. From this point of view, as a solvent that can be used to form a solution containing the first compound, it is preferable to select a solvent that exhibits good solubility in a hydrophobic site. Specific examples of such solvents include aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chloroform, chlorobenzene, and orthodichlorobenzene, and saturated hydrocarbon solvents such as hexane and octane. It is done. From the viewpoint of uniformity of the thickness of the formed layer and further refinement of the formed nanostructure, the solvent that can be used is more preferably an aromatic hydrocarbon solvent or a halogenated hydrocarbon solvent. As the solvent that can be used, toluene, xylene, chlorobenzene, and orthodichlorobenzene are more preferable.

  In order to obtain a higher-order nanostructure, heat treatment may be further performed on the formed layer containing the first compound.

  The insulating part in the layer containing the first compound is separated from the organic semiconductor part by decomposing the bonding part by treatment with acid, alkali, light, heat, etc., and is insulated from the first compound in the layer. Sex sites are removed. From the viewpoint of suppressing deterioration in characteristics of the organic device, treatment with an acidic solution or an alkaline solution is preferable, and treatment with an acidic aqueous solution or an alkaline aqueous solution is more preferable.

  Examples of the acidic solution include a solution of an organic acid such as hydrochloric acid, nitric acid, sulfuric acid stock solution or diluted solution, acetic acid, paratoluenesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid. From the viewpoint of maintaining the characteristics of the organic semiconductor portion remaining in the layer after the removal of the insulating portion, the acidic solution is preferably a dilute hydrochloric acid solution or an organic acid solution.

  Examples of the alkali solution include solutions of alkali metal halides such as potassium and sodium, carbonates, hydroxides, ammonia, trialkylamines, dimethylformamide, dimethylsulfoxide and the like. From the viewpoint of maintaining the characteristics of the organic semiconductor portion remaining in the layer after removal of the insulating portion, it is preferable to use a solution of an inorganic salt, and more preferably an aqueous solution of an inorganic salt.

  The insulating part separated from the organic semiconductor part is decomposed from the first compound layer by immersing the layer containing the first compound in a solvent in which the binding part is soluble or flowing the solvent. Can be removed. From the viewpoint of maintaining the nanostructure of the first compound layer, it is preferable to use a hydrophilic solvent such as water, alcohol or carboxylic acid as the solvent for removing the insulating portion separated from the organic semiconductor portion. .

The organic layer which is a thin film of the present invention has a nanostructure and is added so that the second compound is brought into contact with the first compound layer from which the insulating site has been removed, and the insulating site is removed. It is formed by filling the voids in the layer of the first compound generated by this with the second compound.
When a solution containing the second compound is used in forming the organic layer, a hydrophilic solvent such as water, alcohol or carboxylic acid is used as the solvent from the viewpoint of maintaining the nanostructure of the first compound layer. preferable. In forming the organic layer, the organic semiconductor site may be subjected to heat treatment and laser irradiation treatment to insolubilize the organic semiconductor site, and then the second compound solution may be applied.

(Usage mode of organic device)
The organic device of the present invention can be operated as a photoelectric conversion element by generating photovoltaic power between the electrodes by making light such as sunlight enter from the transparent or translucent electrode side. It can also be used as a photoelectric conversion module by integrating a plurality of photoelectric conversion elements.

  The photoelectric conversion element can be used as a module structure basically similar to a conventional photoelectric conversion module (solar cell module). In general, a photoelectric conversion module has a structure in which a photoelectric conversion element is formed on a support substrate such as metal or ceramic, and the photoelectric conversion element is covered with a filling resin or a protective glass to capture light from the opposite side of the support substrate. A transparent material such as tempered glass may be used for the support substrate, and a photoelectric conversion element may be formed thereon to take light from the transparent support substrate side. Specifically, a module structure called a super straight type, a substrate type, and a potting type, a substrate integrated module structure used in an amorphous silicon solar cell, and the like are known. Even in the photoelectric conversion module to which the photoelectric conversion element of the present invention is applied, these module structures can be appropriately selected depending on the purpose of use, the place of use, and the environment.

  The photoelectric conversion element of the present invention operates as a sensor (organic optical sensor) by causing light to enter from a transparent or translucent electrode side in a state where a voltage is applied between the electrodes, thereby generating a photocurrent. be able to. Furthermore, the organic photosensor is used as a light receiving unit, an output is detected by a signal current generated by the organic photosensor, and a drive circuit unit that reads the signal charge, and a wiring that electrically connects the organic photosensor and the drive circuit, Can be used as an organic image sensor.

  The organic layer which is a thin film of the present invention can also be used as a functional layer (e.g., a light emitting layer, a charge transport layer, a charge injection layer) of the light emitting element.

  Examples are given below to illustrate the present invention in more detail. The present invention is not limited to the following examples.

Synthesis Example 1 Synthesis of α- [1- (2-Chloroethoxy) ethyl] -ω-methoxypoly (oxy-1,2-ethanediyl) (PEO-acetal-Cl) According to the following scheme, PEO-acetal-Cl was synthesized. did.

Poly (ethyl oxide) methyl ether (PEO-OH, Aldrich, 6 g) was dissolved in dichloromethane / tetrahydrofuran (v / v = 1/1, 20 mL) and purified by precipitation dropwise in hexane (180 mL). . Purified PEO-OH (M _n (NMR) = 6.04 × 10 ³ , 5.00 g, 0.828 mmol) and pyridinium p-toluenesulfate (PPTS, 25 mg, 0.10 mmol) in an eggplant flask (volume 100 mL). After the inside atmosphere was replaced with nitrogen gas, azeotropic distillation (normal pressure, 170 ° C.) with dehydrated toluene (20 mL) was performed three times. Dehydrated dichloromethane (25 mL) was added, and the resulting solution was ice-cooled, and 2-chlorovinyl ether (CEVE, 0.55 mL, 0.58 g, 5.4 mmol) was added dropwise using a syringe, under a nitrogen gas atmosphere. Stir at 0 ° C. for 1 hour. After stopping the reaction with 5 wt% aqueous sodium carbonate solution (6 mL), the organic layer was washed with pure water (10 mL) and subsequently washed with saturated brine (20 mL). The target product was further extracted with dichloromethane (8 mL) from the aqueous layer obtained by each washing, dried over anhydrous magnesium sulfate, and filtered. The residual solvent was further distilled off with an evaporator, and the precipitated solid was dissolved in dichloromethane / tetrahydrofuran (v / v = 1/1, 16 mL) and then added dropwise to hexane (150 mL) to precipitate a white solid. The obtained white solid was collected by suction filtration and dried under reduced pressure in a desiccator to obtain PEO-acetal-Cl (white powder; M _n (NMR) = 6.08 × 10 ³ , yield 4.70 g, reaction rate 96). %, Yield 90%). The measurement result of ¹ H NMR is shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 4.84 (q, 1H,> CHCH ₃ ), 3.85 (m, 1H, —CH ₂ Cl), 3.74 (m, 1H, _{-CH 2 Cl), 3.80-3.48 (br} , 542H, - (OCH 2 CH 2) m -, -CH 2 CH 2 Cl), 3.38 (s, 3H, CH 3 O-), 1.35 (d, 3H,> CHCH ₃ ).

(Synthesis Example 2) Synthesis of α- [1- (2-Azidoethoxy) ethyl] -ω-methoxypoly (oxy-1,2-ethanediyl) (PEO-acetal-N ₃ ) PEO-acetal-N ₃ according to the following scheme Was synthesized.

PEO-acetal-Cl (M _n (NMR) = 6.08 × 10 ³ , 3.00 g, 0.493 mmol) and sodium azide (NaN ₃ , 393 mg, 6.05 mmol) were added to an eggplant flask (volume 30 mL). The atmosphere inside was replaced with nitrogen gas, dehydrated N, N-dimethylformamide (12 mL) was added, and the mixture was stirred at 80 ° C. for 24 hours. After the solvent was distilled off under reduced pressure, the residue was dissolved in pure water (15 mL). The target product was extracted twice with dichloromethane (10 mL), and the obtained organic layer was washed with saturated brine (15 mL). Then, the target product was extracted once more with dichloromethane (10 mL) from the obtained aqueous layer. Then, it dried with anhydrous magnesium sulfate and filtered. The resulting solution was concentrated to a total volume of 6 mL and added dropwise to hexane / diethyl ether (v / v = 1/1, 120 mL). The resulting white precipitate was collected by suction filtration, washed with diethyl ether, dissolved in dichloromethane (7 mL), and reprecipitated in hexane (120 mL). The precipitate collected by suction filtration was washed with hexane, and then dried under reduced pressure in a desiccator, whereby PEO-acetal-N ₃ (white powder; M _n (NMR) = 6.17 × 10 ³ , yield 2.31 g, reaction) To 100%, yield 76%). The measurement result of ¹ H NMR is shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 4.83 (q, 1H,> CHCH ₃ ), 3.85-3.45 (br, 548H, — (OCH ₂ CH ₂ ) _m −, _{-CH 2 CH 2 N 3),} 3.44-3.35 (m, 2H, -CH 2 N 3), 3.38 (s, 3H, CH 3 O-), 1.35 (d, 3H, > CHCH ₃ ).

(Synthesis Example 3) Synthesis of α-Ethynyl-ω-bromopoly (3-hexyl-2,5-thiophenedyl) (P3HT-C≡CH) P3HT-C≡CH was synthesized according to the following scheme.

After attaching a three-way cock to an eggplant flask (capacity 50 mL) and frame-drying, 2-Bromo-3-hexyl-5-iodothiophene (I-3HT-Br, Tokyo Kasei, 1.00 g, 2.68 mmol) was added, The internal atmosphere was replaced with nitrogen gas. After adding dehydrated tetrahydrofuran (THF, 13 mL) in a nitrogen stream and cooling with ice, 2.0M Isopropylmagnesium chloride THF solution (i-PrMgCl, Aldrich, 1.34 mL, 2.68 mmol) was slowly added dropwise under a nitrogen stream. And stirred at 0 ° C. for 1 hour. Next, dehydrated THF (13 mL) of [1,3-Bis (diphenyl-phosphino) propane] nickel (II) dichloride (Ni (dppp) Cl ₂ , Tokyo Kasei, 14.7 mg, 0.0271 mmol, 1.0 mol%) The dispersion was quickly added to the reaction solution at 0 ° C. under a nitrogen stream, returned to room temperature, and stirred for 2 hours. Then, 0.5M Bromoethylnymagnesium THF solution (HC≡CMgBr, Aldrich, 1.0 mL, 0.5 mmol) was added dropwise under a nitrogen stream and stirred at room temperature for 20 minutes, and finally methanol (26 mL) was added and stirred for 10 minutes. . The deposited purple solid was collected by suction filtration, and the resulting purple solid was thoroughly washed with methanol, acetone and hexane in this order, and then the purple solid was dissolved in chloroform, and insoluble matter was removed by suction filtration. The obtained filtrate was concentrated to 5 mL with an evaporator and reprecipitated in hexane (100 mL). The resulting precipitate was collected by suction filtration and dried under reduced pressure in a desiccator to give P3HT-C≡CH (M _n (NMR) = 1.91 × 10 ⁴ , M _n (GPC) as a glossy green solid. = 1.85 × 10 ⁴ , M _w (GPC) = 2.24 × 10 ⁴ , M _w / M _n (GPC) = 1.21, yield 212 mg, yield 48%). The measurement result of ¹ H NMR is shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 6.98 (s, 1H, Th—H), 6.89 (s, Th (—C≡CH) —H), 6.82 (d , Th (-Br) -H), 3.52 (s, -C≡CH), 2.81 (t, J = 7.73 Hz, 2H, Th-CH 2 -), 2.70 (t, _{Th (-C≡CH) -CH 2 -)} , 2.57 (t, Th (-Br) -CH 2 -), 1.71 (quint, J = 7.56 Hz, 2H, Th-CH 2 - _{CH 2 -), 1.44 (quint} , J = 6.93 Hz, 2H, Th- (CH 2) 2 -CH 2 -), 1.35 (m, 4H, - (CH 2) 2 -CH 3 ), 0.92 (t, J = 6.99 Hz, 3H, -CH 3).

Example 1 Synthesis of Poly (3-hexyl-2,5-thiophenedyl) -acetal-poly (ethyl oxide) (P3HT-acetal-PEO) P3HT-acetal-PEO was synthesized according to the following scheme.

P3HT-C≡CH (M _n (NMR) = 1.91 × 10 ⁴ , 180 mg, 0.00942 mmol), PEO-acetal-N ₃ (M _n (NMR) = 6.17 ×) in an eggplant flask (volume 20 mL). 10 ³ , 120 mg, 0.0194 mmol), copper (I) bromide (CuBr, 31 mg, 0.22 mmol), N, N, N ′, N ″, N ″ -Pentamethyldiethylenediamine (PMDETA, 0.10 mL, 0 .48 mmol) and dehydrated THF (6 mL) were added, and this cycle was repeated three times with one cycle of freezing treatment using liquid nitrogen, degassing treatment, and thawing treatment, followed by stirring under reflux for 20 hours under a nitrogen gas atmosphere. The solvent was distilled off with an evaporator, and pure water (30 mL) was added to the precipitated crude product containing the target component insoluble in water and methanol and washed. The remaining solid was collected by suction filtration, washed in this order with pure water and methanol, and then dried under reduced pressure, whereby P3HT-acetal-PEO (M _n (GPC) = 2.43), which is a greenish brown solid. × 10 ⁴ , M _w (GPC) = 3.05 × 10 ⁴ , M _w / M _n (GPC) = 1.26, yield 199 mg). The measurement result of ¹ H NMR is shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 7.80 (s, triazole), 6.98 (s, Th-H), 6.82 (d, Th (-Br) -H), 4.78 (q,> CHCH ₃ ), 3.80-3.48 (br,-(OCH ₂ CH ₂ ) _m- ), 3.38 (s, -OCH ₃ ), 2.80 (t, Th _{-CH 2 -), 2.57 (t} , Th (-Br) -CH 2 -), 1.71 (quint, Th-CH 2 -CH 2 -), 1.44 (quint, Th- (CH 2 _{) 2 -CH 2 -), 1.35} (m, - (CH 2) 2 -CH 3), 0.91 (t, -CH 2 CH 3).

(Example 2)
(1) Formation of P3HT-acetal-PEO thin film Ultrasonic cleaning using a neutral detergent is performed on a glass substrate (Matsunami Glass Ind., Ltd .; 22 × 26 mm, thickness 0.12 mm to 0.17 mm). Washing with running water for 20 minutes, washing with ultrasonic water using pure water for 20 minutes, washing with running water for 20 minutes, and washing with ultrasonic water using 2-propanol for 20 minutes were performed in this order. Next, UV-O ₃ treatment (30 minutes) was performed after drying (65 ° C., 60 minutes). Next, a 1 wt% toluene solution of P3HT-acetal-PEO was applied onto a glass substrate by a spin coating method (2000 rpm, 30 seconds) to form a coating film. After drying under reduced pressure in a desiccator, annealing was performed in vacuum (230 ° C. for 6 hours, heating rate 0.5 ° C./min) to form a P3HT-acetal-PEO thin film on the glass substrate.

  The obtained thin film was subjected to AFM (Atomic Force Microscope) measurement. The AFM measurement was performed in an atmospheric AC mode (dynamic mode) using an Agilent Technologies 5500 AFM (probe: Olympus OMCL-AC160TS-C3 (resonance frequency: 300 kHz)). The scanning range was 500 nm × 500 nm (256 × 256 points), and the scanning speed was 1.0 line / sec.

  The results are shown in FIG. FIG. 1 is a photograph showing an AFM image. As is clear from FIG. 1, the phase separation between the bright part (P3HT part which is an organic semiconductor part) shown whitish in the photograph and the dark part (polyethylene oxide part: PEO part which is an insulating part) shown blackish As a result, a highly ordered nanostructure was confirmed.

(2) Removal of PEO site from thin film of P3HT-acetal-PEO A second sample tube (capacity 10 mL) filled with water was stored in the first sample tube (capacity 50 mL). Therefore, trifluoroacetic acid (maximum 15 mL) was put outside the second sample tube. The board | substrate with which the thin film of P3HT-acetal-PEO was formed there was immersed there, and it left still for 3 hours, and cut | disconnected the acetal bond. After that, the substrate on which the P3HT-acetal-PEO thin film was formed was immersed in methanol (maximum 20 mL) in a third sample tube (capacity 50 mL) for 3 hours, rinsed with methanol, and then dried under reduced pressure. It was.

(Example 3) Preparation Example 1 of an organic photoelectric conversion element
A glass substrate on which an ITO film having a thickness of 150 nm is formed by sputtering is subjected to surface treatment by ozone UV treatment. Next, PEDOT: PSS (AI 4083 manufactured by Heraeus) is applied by spin coating, and is applied at 200 ° C. Heat treatment is performed for 10 minutes. A P3HT-acetal-PEO thin film was formed thereon by the method of Example 2, and C ₆₀ fullerene was vacuum deposited on the obtained thin film at a vacuum of 5 × 10 ⁻⁴ Pa or less to form an optically active layer. Can be formed. Subsequently, a metal electrode is vapor-deposited and an organic thin film solar cell can be obtained. When the obtained organic thin film solar cell is irradiated with a certain amount of light using a solar simulator, excellent photoelectric conversion characteristics are exhibited.

(Example 4) Preparation example 2 of an organic photoelectric conversion element
A glass substrate on which an ITO film having a thickness of 150 nm is formed by sputtering is subjected to surface treatment by ozone UV treatment. Next, PEDOT: PSS (AI 4083 manufactured by Heraeus) is applied by spin coating, and is applied at 200 ° C. Heat treatment is performed for 10 minutes. A thin film of P3HT-acetal-PEO is formed thereon by the method of Example 2, and the resulting thin film is irradiated with a low energy electron beam to crosslink, and then immersed in a solution containing the second compound. An optically active layer can be formed. Then, a metal electrode is vacuum-deposited at 5 * 10 <^-4> Pa or less, and an organic thin film solar cell can be obtained. When the obtained organic thin film solar cell is irradiated with a certain amount of light using a solar simulator, excellent photoelectric conversion characteristics are exhibited.

Synthesis Example 4 Synthesis of 2-Bromo-5-butyl-thiophene (Compound 2) Compound 2 was synthesized from Compound 1 according to the following scheme.

2-Butyl-thiophene (Compound 1) (7.09 g, 50.5 mmol) and tetrahydrofuran (50 mL) were mixed with N-bromosuccinimide (NBS) (9.00 g, 50.6 mmol, 1 eq.) In two portions. Separately added and stirred at room temperature for 3 hours. The reaction was then stopped with pure water, and the resulting solution was extracted with diethyl ether. The organic layer was washed and dried, and the solvent was distilled off to obtain a red liquid compound 2 (10.7 g, 49.0 mmol, yield 97%). The measurement result of ¹ H NMR is shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 6.84 (d, 1H), 6.53 (d, 1H), 2.74 (t, 2H), 1.64-1.57 ( sext, 2H), 1.41-1.34 (sext, 2H), 0.92 (t, 3H).

Synthesis Example 5 Synthesis of 2-Butyl-5- [2- (trimethylsilyl) ethyl] -thiophene (Compound 3) Compound 3 was synthesized from Compound 2 according to the following scheme.

To a mixture of PdCl ₂ (PPh ₃ ) ₂ (0.936 g, 1.33 mmol, 3 mol%) and copper iodide (0.300 g, 1.58 mmol, 3.5 mol%), 2-Bromo-5-butyl- A mixed solution of thiophene (compound 2) (9.78 g, 44.6 mmol), trimethylsilylacetylene (TMSA) (6.86 g, 69.8 mmol, 1.6 eq.) and triethylamine (50 mL) was added, and an argon gas atmosphere was added. And stirred at room temperature for 17 hours. The reaction was then stopped using hydrochloric acid and the black solid was filtered off. The resulting solution was extracted with diethyl ether, the organic layer was washed, dried and evaporated to give a black liquid. The resulting black liquid was purified by silica gel column chromatography (developing solvent: hexane) to obtain a reddish brown liquid compound 3 (8.03 g, 31.8 mmol, 71%). The measurement result of ¹ H NMR is shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 7.04 (d, 1H), 6.60 (d, 1H), 2.76 (t, 2H), 1.66-1.60 ( quint, 2H), 1.41-1.33 (sext, 2H), 0.91 (t, 3H), 0.23 (s, 9H).

Synthesis Example 6 Synthesis of 2-Butyl-5-ethylyl-thiophene (Compound 4) Compound 4 was synthesized from compound 3 according to the following scheme.

2-Butyl-5- [2- (trimethylsilyl) ethyl] -thiophene (compound 3) was added to a mixed solution of potassium carbonate (6.60 g, 47.8 mmol, 1.5 eq.) And methanol (200 mL) in a beaker. (8.03 g, 31.8 mmol) was added dropwise and stirred at room temperature for 20 hours. The solution was then extracted with chloroform. The organic layer was washed and dried, and the solvent was distilled off to obtain reddish brown liquid compound 4 (4.79 g, 29.2 mmol, yield 92%). The measurement result of ¹ H NMR is shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 7.09 (d, 1H), 6.63 (d, 1H), 3.28 (s, 1H), 2.77 (t, 2H) , 1.67-1.61 (quint, 2H), 1.42-1.34 (sext, 2H), 0.93 (t, 3H).

Synthesis Example 7 Synthesis of 2-Thiophenebutanol (Compound 6) Compound 6 was synthesized from compound 5 according to the following scheme.

A two-necked eggplant flask was charged with lithium aluminum hydride (LAH) (2.25 g, 59.4 mmol, 1 eq.) And diethyl ether (50 mL), and 2-Thiophenebutanoic Acid (Compound 5) (10.0 g, 58.7 mmol). ) And diethyl ether (10 mL) were added dropwise under ice cooling, and the mixture was refluxed at 50 ° C. for 3 hours under an argon gas atmosphere. Thereafter, the reaction was stopped using pure water (2.3 mL) for 30 minutes, and an aqueous sodium hydroxide solution (15%, 2.3 mL) and pure water (7.0 mL) were sequentially added. The precipitated white solid was filtered off, the obtained organic layer was dried and the solvent was distilled off to obtain a light yellow liquid compound 6 (9.06 g, yield 99%). The measurement result of ¹ H NMR is shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 7.11 (dd, 1H), 6.91 (dd, 1H), 6.79 (dd, 1H), 3.68 (q, 2H) , 2.87 (t, 2H), 1.78-1.74 (m, 2H), 1.67-1.61 (m, 2H).

Synthesis Example 8 Synthesis of Tetrahydro-2- [4- (2-thienyl) butoxy] -2H-pyran (Compound 7) Compound 7 was synthesized from compound 6 according to the following scheme.

2-Thiophenebutanol (compound 6) (2.00 g, 12.8 mmol) and 3,4-Dihydro-2H-pyran (DHP) (1.21 g, 14.3 mmol, 1.1 eq.) Were placed in an eggplant flask and salified. Aluminum (III) hexahydrate (AlCl ₃ .6H ₂ O, 33.1 mg, 0.137 mmol, 1 mol%) was added. After stirring at 30 ° C. for 30 minutes, the mixture was stirred at 60 ° C. for 4 and a half hours. Thereafter, the solution was passed through a silica gel short column (developing solvent: chloroform) and distilled under reduced pressure to obtain Compound 7 (2.88 g, 12.0 mmol, 94%) as a pale yellow liquid. The measurement result of ¹ H NMR is shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 7.10 (d, 1H), 6.91 (t, 1H), 6.79 (d, 1H), 4.58 (t, 1H) , 3.88-3.84 (m, 1H), 3.79-3.75 (m, 1H), 3.52-3.48 (m, 1H), 3.44-3.39 (m, 1H) 1H), 2.86 (t, 2H), 1.87-1.50 (m, 10H).

(Synthesis Example 9) Synthesis of Tetrahydro-2- [4- (5-bromo-2-thienyl) butoxy] -2H-pyran (Compound 8) Compound 8 was synthesized from Compound 7 according to the following scheme.

Tetrahydro-2- [4- (2-thienyl) butoxy] -2H-pyran (compound 7) (2.88 g, 12.0 mmol) and toluene (12 mL) were placed in a two-necked eggplant flask, and N-bromosuccinimide (NBS) was added. ) (2.14 g, 12.0 mmol, 1 eq.) Was added in two portions, and the mixture was stirred at room temperature for 4 hours under an argon gas atmosphere. Next, the reaction was stopped with pure water, and the organic layer was washed with pure water and saturated brine in that order, then dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a black liquid. The resulting black liquid was purified by silica gel column chromatography (developing solvent: chloroform) to obtain a crude product (4.26 g) as a reddish brown liquid. ^{As a result of 1} H NMR measurement, a part of the THP protecting group was removed (a crude product containing a compound from which the THP protecting group was removed is referred to as a crude product 8 ′).

  Compound 8 was obtained from crude product 8 'according to the following scheme.

In an eggplant flask, the crude product 8 ′ (4.26 g, 18.1 mmol: all calculated as 5-Bromo-2-thiophenebutanol) and 3,4-Dihydro-2H-pyran (DHP) (1.69 g, 20 0.1 mmol, 1.1 eq.) And aluminum (III) chloride hexahydrate (AlCl ₃ .6H ₂ O, 45.6 mg, 0.189 mmol, 1 mol%) were added, and the mixture was stirred at 60 ° C. for 3 hours. Then, it refine | purified by silica gel column chromatography (developing solvent: chloroform), and depressurizingly distilled, Compound 8 (3.33g, 10.4mmol, 87% of yield) of reddish brown liquid was obtained.

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 6.84 (d, 1H), 6.54 (d, 1H), 4.57 (t, 1H), 3.88-3.83 ( m, 1H), 3.78-3.74 (m, 1H), 3.52-3.48 (m, 1H), 3.42-3.38 (m, 1H), 2.79 (t, 2H), 1.85-1.51 (m, 10H).

Synthesis Example 10 Synthesis of Tetrahydro-2- [4- (5- [2- (trimethylsilyl) ethyl] -2-thionyl) butoxy] -2H-pyran (Compound 9) Synthesized.

PdCl ₂ (PPh ₃ ) ₂ (221 mg, 0.316 mmol, 3 mol%) and copper iodide (70.7 mg, 0.371 mmol, 3.6 mol%) were placed in a _two- necked eggplant flask. Tetrahydro-2- [4- (5-bromo-2-thienyl) butoxy] -2H-pyran (compound 8) (3.33 g, 10.4 mmol), trimethylsilylacetylene (TMSA) (1.46 g, 14.8 mmol, 1.4 eq.) And triethylamine (10 mL) were added, and the mixture was stirred at room temperature for 22 hours under an argon gas atmosphere. Subsequently, the solvent was distilled off under reduced pressure and subjected to silica gel column chromatography (developing solvent: chloroform). The obtained organic layer was extracted twice with chloroform and washed with pure water and saturated saline in this order. The extract was dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was further purified twice by silica gel column chromatography (developing solvent: chloroform) to obtain brown liquid compound 9 (3.29 g, 9.79 mmol, yield 94). %). The measurement result of ¹ H NMR is shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 7.04 (d, 1H), 6.62 (d, 1H), 4.57 (t, 1H), 3.87-3.83 ( m, 1H), 3.78-3.73 (m, 1H), 3.52-3.48 (m, 1H), 3.42-3.37 (m, 1H), 2.80 (t, 2H), 1.85-1.51 (m, 10H) 0.23 (s, 9H).

Synthesis Example 11 Synthesis of Tetrahydro-2- [4- (5-ethyl-2-thienyl) butoxy] -2H-pyran (Compound 10) Compound 10 was synthesized from compound 9 according to the following scheme.

In a two-necked eggplant flask, tetrahydro-2- [4- (5- [2- (trimethylsilyl) ethyl] -2-thionyl) butoxy] -2H-pyran (compound 9) (3.29 g, 9.79 mmol) and tetrahydrofuran ( 60 mL). Tetrabutylammonium Fluoride (TBAF) (11.0 mL, 11.0 mmol, 1.1 eq.) Was added dropwise under an argon gas atmosphere, and the mixture was stirred at room temperature for 1 hour. Subsequently, the mixture was filtered under reduced pressure, and the resulting organic layer was extracted with chloroform, washed with pure water and saturated brine in this order, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a black liquid. The resulting black liquid was purified by silica gel column chromatography (developing solvent: chloroform) to obtain a reddish brown liquid compound 10 (2.21 g, 8.34 mmol, yield 85%). The measurement result of ¹ H NMR is shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 7.09 (d, 1H), 6.65 (d, 1H), 4.57 (t, 1H), 3.88-3.83 ( m, 1H), 3.79-3.74 (m, 1H), 3.52-3.48 (m, 1H), 3.43-3.38 (m, 1H), 3.29 (s, 1H), 2.82 (t, 2H), 1.85-1.51 (m, 10H).

Synthesis Example 12 Synthesis of 5-Iodo-2,2 ′: 5 ′, 2 ″ -tertiophene (Compound 12) Compound 12 was synthesized from Compound 11 according to the following scheme.

In a two-necked eggplant flask, 2,2 ′: 5 ′, 2 ″ -Terthiophene (Compound 11) (1.00 g, 4.03 mmol) and N-Iodosuccinimide (NIS) (1.08 g, 4.81 mmol, 1.2 eq. The mixture was added with dehydrated chloroform (8 mL) and acetic acid (8 mL), and stirred for 18 and a half hours at room temperature in an argon gas atmosphere, and then the reaction was stopped with pure water, and chloroform was added. The organic layer was washed with pure water and saturated brine in this order, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a yellow solid, which was recrystallized using chloroform and hexane. To obtain a yellow solid compound 12 (1.44 g, 3.86 mmol, yield 96%) The measurement results of ¹ H NMR are shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 7.23 (dd, 1H), 7.17 (dd, 1H), 7.16 (d, 1H), 7.06 (d, 1H) , 7.03 (d, 1H), 7.02 (d, 1H), 6.84 (d, 1H).

Synthesis Example 13 Synthesis of 5-Bromo-5 ″ -iodo-2,2 ′: 5 ′, 2 ″ -tertiophene (Compound 13) Compound 13 was synthesized from compound 12 according to the following scheme.

  5-Ido-2,2 ′: 5 ′, 2 ″ -tertiophene (compound 12) (2.62 g, 7.00 mmol) and N-bromosuccinimide (NBS) (1.25 g, 7.02 mmol, 1 eq.). After putting into a two-necked eggplant flask, dehydrated chloroform (14 mL) and acetic acid (14 mL) were added, and the mixture was stirred for 19 and a half hours at room temperature in an argon gas atmosphere, then the reaction was stopped with pure water and extracted with chloroform. The obtained organic layer was washed with pure water and saturated brine in this order, and the washed organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a yellow solid, followed by chloroform and hexane. Was used to obtain Compound 13 (2.41 g, 5.33 mmol, yield 76%) of yellow needle crystals.

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 7.16 (d, 1H), 7.01-6.99 (m, 2H), 6.97 (d, 1H), 6.91 ( d, 1H), 6.83 (d, 1H).

Synthesis Example 14 Tetrahydro-2- (4- {5- [2- (5 ″ -bromo-2,2 ′: 5 ′, 2 ″ -tertiophene) -5-ethylnyl] -2-thienyl} butoxy) − Synthesis of 2H-pyran (Compound 14) Compound 14 was synthesized using Compound 10 and Compound 13 according to the following scheme.

Two-neck eggplant-shaped flask 5-Bromo-5 "-iodo- 2,2 ': 5', 2" -terthiophene ( Compound _{13) (1.36g, 3.01mmol),} PdCl 2 (PPh 3) 2 (65. 3 mg, 93.0 mol, 3.1 mol%), copper iodide (21.6 mg, 0.113 mmol, 3.8 mol%), tetrahydrofuran (60 mL) were added, and Tetrahydro-2- [4- (5-ethylny-2 -Thienyl) butoxy] -2H-pyran (compound 10) (0.795 g, 3.01 mmol, 1 eq.) And triethylamine (120 mL) were added dropwise in an ice bath under an argon gas atmosphere to room temperature. The mixture was stirred for 3 days while returning. Thereafter, the solvent was distilled off under reduced pressure, and dichloromethane was added. The obtained organic layer was washed with pure water and saturated saline in this order, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a black solid. Purification was performed by silica gel column chromatography (developing solvent: dichloromethane) twice to obtain orange solid compound 14 (0.929 g, 1.58 mmol, yield 52%).

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 7.14 (d, 1H), 7.10 (d, 1H), 7.07 (d, 1H), 7.05 (d, 1H) , 7.01 (d, 1H), 6.98 (d, 1H), 6.92 (d, 1H), 6.70 (d, 1H), 4.58 (t, 1H), 3.88- 3.84 (m, 1H), 3.80-3.75 (m, 1H), 3.53-3.49 (m, 1H), 3.44-3.40 (m, 1H), 85 (t, 2H), 1.85-1.51 (m, 10H).

(Synthesis Example 15) Tetrahydro-2- (4- {5- [2- (5- {5 "-[2- (5-butyl-2-thienyl) ethyl]]-2,2 ': 5', 2" Synthesis of -terthiophene} -yl) ethyl] -2-thienyl} butoxy) -2H-pyran (Compound 15) Compound 15 was synthesized using Compound 4 and Compound 14 according to the following scheme.

Tetrahydro-2- (4- {5- [2- (5 "-bromo-2,2 ': 5', 2" -tertiophene) -5-ethylnyl] -2-thienyl} butoxy)- 2H-pyran (compound 14) (0.901 g, 1.53 mmol), PdCl ₂ (PPh ₃ ) ₂ (37.4 mg, 53.3 mol, 3.5 mol%), copper iodide (11.3 mg, 59.3 μmol) 3.9 mol%) was added, and a mixed solution of 2-Butyl-5-ethylthiophene (Compound 4) (0.374 g, 2.28 mmol, 1.5 eq.) And triethylamine (90 mL) was added. After stirring at room temperature for 23 hours under an argon gas atmosphere, the solvent was distilled off under reduced pressure, and dichloromethane was added. The obtained organic layer was washed with pure water and then saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a black solid. The resulting black solid was purified by silica gel column chromatography (developing solvent: dichloromethane) to obtain orange solid compound 15 (0.938 g, 1.39 mmol, yield 91%).

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 7.14 (dd, 2H), 7.11 (d, 2H), 7.01 (s, 2H), 7.06 (d, 2H) , 6.70 (d, 1H), 6.68 (d, 1H), 4.58 (t, 1H), 3.89-3.84 (m, 1H), 3.80-3.75 (m 1H), 3.53-3.49 (m, 1H), 3.44-3.40 (m, 1H), 2.85 (t, 2H), 2.81 (t, 2H), 86-1.50 (m, 12H), 0.94 (t, 3H).

(Synthesis Example 16) 5- [2- (5- {5 "-[2- (5-Butyl-2-thienyl) ethyl] -2,2 ': 5', 2" -tertiophene} -yl) ethyl] Synthesis of 2-thiophenebutanol (Compound 16) Compound 16 was synthesized from compound 15 according to the following scheme.

Tetrahydro-2- (4- {5- [2- (5- {5 "-[2- (5-but-2-ylenyl) ethyl]]-2,2 ': 5', 2" -tertiophene} -yl ) Ethynyl] -2-thienyl} butoxy) -2H-pyran (compound 15) (0.211 g, 0.313 mmol) was dissolved in tetrahydrofuran (10 mL) and ethanol (10 mL) was added. Pyridinium p-Toluenesulfate (PPTS) (21.6 g, 86.0 μmol, 30 mol%) was added with stirring at 60 ° C. with stirring for 3 hours. Then, the obtained solution was distilled off under reduced pressure and purified by silica gel column chromatography (developing solvent: chloroform) to obtain orange solid compound 16 (180 mg, 0.306 mmol, yield 98%). The measurement result of ¹ H NMR is shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 7.14 (dd, 2H), 7.11 (d, 2H), 7.10 (s, 2H), 7.06 (d, 2H) , 6.70 (d, 1H), 6.68 (d, 1H), 3.68 (q, 2H), 2.85 (t, 2H), 2.81 (t, 2H), 1.81- 1.75 (quint, 2H), 1.69-1.62 (m, 4H), 1.43-1.36 (sext, 2H), 0.94 (t, 3H).

Synthesis Example 17 4- {5- [2- (5- {5 ″-[2- (5-Butyl-2-thienyl) ethyl]]-2,2 ′: 5 ′, 2 ″ -tertiophene} -yl ) Synthesis of ethyl] -2-thienyl} butyl methacrylate (Compound 17) Compound 17 was synthesized from Compound 16 according to the following scheme.

5- [2- (5- {5 "-[2- (5-Butyl-2-thienyl) ethyl]]-2,2 ': 5', 2" -tertiophene} -yl) ethyl] -2-thiophenebutanol ( Compound 16) (0.103 g, 0.174 mmol), triethylamine (0.480 mL, 3.45 mmol, 20 eq.), Tetrahydrofuran (20 mL), and a solution obtained by mixing hydroquinone as a polymerization inhibitor with methacryloyl chloride (0.330 mL, 3 .47 mmol, 20 eq.) And tetrahydrofuran (0.670 mL) were added dropwise under ice cooling. After stirring at room temperature for 4 hours, the reaction solution was dropped into a saturated aqueous sodium hydrogen carbonate solution to stop the reaction. Extracted with chloroform three times, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain an orange solid. The resulting orange solid was purified by silica gel column chromatography (developing solvent: chloroform) to obtain orange solid compound 17 (97.2 mg, 0.148 mmol, 85% yield). The measurement result of ¹ H NMR is shown below.

¹ H NMR (500 MHz, CDCl ₃ ): δ / ppm = 7.14 (dd, 2H), 7.11 (dd, 2H), 7.09 (s, 2H), 7.06 (d, 2H) , 6.70 (d, 1H), 6.68 (d, 1H), 6.11 (s, 1H), 5.56 (s, 1H), 4.18 (t, 2H), 2.86 ( t, 2H), 2.81 (t, 2H), 1.95 (s, 3H), 1.81-1.77 (m, 4H), 1.69-1.63 (quint, 2H), 1 .44-1.36 (sext, 2H), 0.94 (t, 3H).

Example 5 Synthesis of PEO-b-PTR5MA PEO-b-PTR5MA can be synthesized using Compound 17 and polyethylene oxide according to the following scheme.

(Example 6)
The compound of Example 5 is applied as a first compound on a glass substrate on which the ITO layer is patterned by spin coating or the like, and dried to form a thin film. After the heat treatment in an inert gas atmosphere or in a vacuum, the hydrophilic portion is cut and removed. The photoelectric conversion element is manufactured by drying again and impregnating the void formed after removing the hydrophilic portion with the second compound to form an optically active layer, and forming an electrode on the optically active layer. The produced photoelectric conversion element exhibits excellent photoelectric conversion efficiency.

Synthesis Example 18 Synthesis of Homopolymer of Compound 17 A homopolymer of Compound 17 was synthesized according to the following scheme.

4- {5- [2- (5- {5 ″-[2- (5-Butyl-2-thienyl) ethyl]]-2,2 ′: 5 ′, 2 ″ -tertiophene} -yl) ethylyl ] -2-thienyl} butyl methacrylate (compound 17) (75.0 mg, 0.114 mmol) was added, and 2,2′-Azobis (isobutyronitrile) (AIBN) (0.75 mg, 4.6 μmol, 1 wt%) and toluene A mixed solution with (0.75 mL) was added. Next, vacuum deaeration with Freeze-pump-thaw cycle was performed three times, and the tube was sealed and stirred at 60 ° C. for 18 hours. The eggplant flask containing the polymerization solution was placed in an ice bath to stop the polymerization reaction, and the polymerization solvent was removed to obtain an orange solid (96.2 mg). The obtained yellow solid was dissolved in chloroform and added dropwise to methanol to precipitate the solid, and the solid was collected by vacuum filtration and washed with acetone twice. The obtained brown solid was dissolved again in chloroform and added dropwise to hexane to precipitate the solid, and the solid was recovered by filtration under reduced pressure. The obtained solid was dried with a desiccator to obtain a purple solid (18.3 mg). The measurement results of ¹ H NMR and molecular weight (Mn, Mw) are shown below.

1H NMR (500 MHz, CDCl ₃ ): δ / ppm = 7.13-6.82 (br, 8H), 6.67-6.61 (br, 2H), 3.96-3.93 (br, 2H), 2.85-2.67 (br, 4H), 1.68-1.59 (br, 6H), 1.41-1.33 (br, 2H), 1.25 (s), 0 97-0.84 (br, 3H). Mn = 1.33 × 10 ⁴ , Mw = 2.05 × 10 ⁴ , Mw / Mn = 1.54

  The liquid crystallinity of the homopolymer of Compound 17 was confirmed using a polarizing microscope. A schlieren texture peculiar to the nematic phase could be observed at room temperature (25 ° C.), and it was confirmed that the homopolymer of Compound 17 was in a liquid crystal state. The homopolymer of Compound 17 had liquid crystallinity even when the temperature was raised to 200 ° C. When the temperature was maintained at 200 ° C., the entire image gradually became darker, and after 10 minutes the brightness did not change, so the temperature dropped. As the temperature decreased, the image regained its brightness and remained liquid crystalline even at room temperature. As a result, it was found that the homopolymer of Compound 17 exhibited a nematic phase over a wide temperature range from 25 ° C to 200 ° C. Therefore, the homopolymer of compound 17 can be suitably used as a material for a photoelectric conversion element and the like because its liquid crystallinity allows the morphology to be optimized by controlling its orientation by external force.

Synthesis Example 19 Synthesis of Block Copolymer (PEO-b-PTR5MA) A block copolymer (PEO-b-PTR5MA) was synthesized using Compound 17 according to the following scheme.

In a 10 mL eggplant flask, α- (2-Bromo-2-methyl-1-oxopropyl) -ω-methoxy-poly (oxy-1,2-ethanediyl) (PEOBr, 15.2 mg, 2.50 μmol), 4- {5 -[2- (5- {5 "-[2- (5-Butyl-2-thienyl) ethyl]]-2,2 ': 5', 2" -tertiophene} -yl) ethyl] -2-thienyl} butyl Methacrylate (compound 17, 131.8 mg, 0.2 mmol, 80 eq.) And Cu (I) Cl (1.2 mg, 12.1 μmol, 4.8 eq.) Were added, and the atmosphere was replaced with argon gas. Next, HMTETA (3.4 μL, 12.5 μmol, 5 eq.) And toluene (0.5 mL) were added for freeze degassing, and the mixture was stirred at 60 ° C. for 24 hours. Thereafter, the polymerization was stopped and the solvent was distilled off to obtain PEO-b-PTR5MA as the target product. When GPC measurement of the solid obtained after the termination of polymerization was performed, Mn = 1.93 × 10 ⁴ , Mw = 2.33 × 10 ⁴ , and Mw / Mn = 1.21.

  The obtained thin film was subjected to AFM (Atomic Force Microscope) measurement. The AFM measurement was performed in an atmospheric AC mode (dynamic mode) using an Agilent Technologies 5500 AFM (probe: Olympus OMCL-AC160TS-C3 (resonance frequency: 300 kHz)). The scanning range was 500 × 500 nm (256 × 256 points), and the scanning speed was 1.0 line / sec.

  The results are shown in FIG. FIG. 2 is a photograph showing an AFM image. As is clear from FIG. 2, the phase separation between the bright part (PTR5MA part which is an organic semiconductor part) shown as whitish and the dark part (polyethylene oxide part: PEO part which is an insulating part) shown as blackish in the photographic diagram. As a result, a highly ordered nanostructure was confirmed.

(Example 7) Production Example 3 of Organic Photoelectric Conversion Element
A glass substrate on which an ITO film having a thickness of 150 nm is formed by sputtering is subjected to surface treatment by ozone UV treatment. Next, PEDOT: PSS (AI 4083 manufactured by Heraeus) is applied by spin coating, and 200 ° C. And heat treatment for 10 minutes. A thin film of PEO-b-PTR5MA was formed thereon by the method of Example 2, and C ₆₀ fullerene was vacuum deposited on the obtained thin film at a vacuum degree of 5 × 10 ⁻⁴ Pa or less to form an optically active layer. Can be formed. Subsequently, a metal electrode is vapor-deposited and an organic thin film solar cell can be obtained. When the obtained organic thin film solar cell is irradiated with a certain amount of light using a solar simulator, excellent photoelectric conversion characteristics are exhibited.

(Example 8) Production Example 4 of Organic Photoelectric Conversion Element
A glass substrate on which an ITO film having a thickness of 150 nm is formed by sputtering is subjected to surface treatment by ozone UV treatment. Next, PEDOT: PSS (AI 4083 manufactured by Heraeus) is applied by spin coating, and 200 ° C. And heat treatment for 10 minutes. A thin film of PEO-b-PTR5MA is formed thereon by the method of Example 2, and the resulting thin film is irradiated with a low energy electron beam to crosslink, and then immersed in a solution containing the second compound. An optically active layer can be formed. Then, a metal electrode is vacuum-deposited with the vacuum degree of 5 * 10 <^-4> Pa or less, and an organic thin film solar cell can be obtained. When the obtained organic thin film solar cell is irradiated with a certain amount of light using a solar simulator, excellent photoelectric conversion characteristics are exhibited.

Example 9 Production Example 1 of Organic Light-Emitting Element
When an element is manufactured according to the method described in Example 3 and a current is applied, excellent light emission characteristics are exhibited.

Example 10 Production Example 2 of Organic Light-Emitting Element
When an element is manufactured according to the method described in Example 4 and a current is applied, excellent light emission characteristics are exhibited.

Example 11 Production Example 3 of Organic Light-Emitting Element
When an element is fabricated according to the method described in Example 7 and a current is applied, excellent light emission characteristics are exhibited.

Example 12 Production Example 4 of Organic Light-Emitting Element
When an element is manufactured according to the method described in Example 8 and a current is applied, excellent light emission characteristics are exhibited.

Claims (20)

A first electrode; a second electrode; and an organic layer provided between the first electrode and the second electrode;
The organic layer has an organic semiconductor site having one of rectifying properties of electron donating property and electron accepting property, an insulating site, and a binding site for binding them, and the molecular weight dispersion is 1.6 or less. An organic device comprising: a compound obtained by removing an insulating part from a first compound; and a second compound having an organic semiconductor part having a rectifying characteristic different from that of the organic semiconductor part.   The organic device according to claim 1, wherein the organic semiconductor portion of the first compound is electron-donating.   The organic device according to claim 1, wherein the organic semiconductor portion of the first compound includes a hetero 5-membered ring.   The organic device of any one of Claims 1-3 in which the organic-semiconductor site | part of a said 1st compound contains the thiophenediyl group which may have a substituent. The organic device of any one of Claims 1-4 whose organic-semiconductor site | part of a said 1st compound is a structure shown by following formula (1).
(In the formula (1), X represents a group represented by —C═C—, a group represented by —C≡C—, or a group represented by —N═N—, and m is 0 or 1. n. Is an integer equal to or greater than 1. R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and Z are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 3 to 3 carbon atoms. 20 cycloalkyl groups, monovalent aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, cycloalkoxy groups having 3 to 20 carbon atoms, 1 to 1 carbon atoms 20 alkylthio groups, a cycloalkylthio group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group which may have a substituent or a monovalent heterocyclic group which may have a substituent. Represents.) The organic device of any one of Claims 1-5 whose organic-semiconductor site | part of a said 1st compound is a structure shown by following formula (2) or following formula (3).
(In the formula (2), Z is as defined in the formula (1). In the formula (3), R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and Z are the formula (1). (N is an integer of 2 or more)   The organic device according to claim 6, wherein the organic semiconductor portion of the first compound has a structure represented by the formula (2), and the Z is an n-butyl group. The organic semiconductor part of the first compound has a structure represented by the formula (3), the Z is a chlorine atom or a bromine atom, and the R ₀ , R ₁ , R ₂ , R ₃ and R ₄ are The organic device according to claim 6, wherein each is a linear alkyl group. The organic device according to claim 8, wherein each of R _0, R ₁ , R ₂ , R ₃ and R ₄ is an n-hexyl group.   The organic semiconductor part of the first compound is a monovalent group having hydrophobicity, and the insulating part is a monovalent group derived from a polymer having hydrophilicity. Organic device as described in.   The organic device according to claim 10, wherein the monovalent group derived from the hydrophilic polymer is a monovalent group having a polyethylene oxide chain.   The organic device according to claim 1, wherein the binding site includes a structure that is decomposed by treatment with light, heat, acid, or alkali.   The organic device according to claim 12, wherein the structure of the binding site includes any one of an acetal bond, an ester bond, and an ether bond. The organic device according to any one of claims 1 to 13, wherein the first compound is a compound represented by the following formula (4), the following formula (5), or the following formula (6).
(In Formula (4), X ₂ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a monovalent aliphatic non-valent having 2 to 20 carbon atoms. A saturated hydrocarbon group, an alkoxy group having 1 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a cycloalkylthio group having 3 to 20 carbon atoms, and a substituent. Represents a monovalent aromatic hydrocarbon group which may have or a monovalent heterocyclic group which may have a substituent, q and s are integers of 1 or more, in formula (5), p and n are each independently an integer of 1 or more, and in formula (6), r is an integer of 2 or more.) The high molecular compound shown by following formula (6).
(In formula (6), r is an integer of 2 or more.) In a method for manufacturing an organic device having a first electrode, a second electrode, and an organic layer provided between the first electrode and the second electrode,
The organic semiconductor part having an rectifying property of either one of electron donating property and electron accepting property, an insulating part, and a binding part for bonding them, and having a molecular weight dispersion of 1.6 or less After forming the layer containing the compound, the insulating portion is removed from the first compound by decomposing the binding site of the first compound in the layer, and then the organic semiconductor having a rectifying characteristic different from that of the organic semiconductor portion The manufacturing method of the organic device which adds the 2nd compound which has a site | part so that the said layer may be contacted, and forms the organic layer by filling the space | gap in the said layer produced by the removal of the said insulating site | part.   A first compound having an organic semiconductor portion having an rectifying property of either one of electron donating property and electron accepting property, an insulating portion, and a binding site for binding them, and having a molecular weight dispersion of 1.6 or less And a second compound having an organic semiconductor portion having a rectifying characteristic different from that of the organic semiconductor portion is brought into contact with the layer, the insulating portion is removed from the first compound in the layer. A thin film obtained by adding so.   A photoelectric conversion element comprising the thin film according to claim 17.   A light emitting device comprising the thin film according to claim 17.   A sensor comprising the thin film according to claim 17.