JP6051102B2 - Organic photoelectric conversion element and organic thin film solar cell - Google Patents

Description

The present invention is related to an organic photoelectric conversion device and an organic thin-film solar cells.

Organic semiconductor polymers have been actively researched in recent years in the electronics field. For example, it is used for an organic electroluminescence element that emits light when electricity is passed, an organic photoelectric conversion element that generates power by light irradiation, an organic thin film transistor element that controls the amount of current and voltage, and the like. In such an element, an organic semiconductor material in which a p-type conductivity / semiconductor material as an electron donating material and an n-type conductivity / semiconductor material as an electron-accepting material are combined is used as in the case of the inorganic semiconductor material.
In recent years, since fossil energy such as petroleum has a problem of releasing carbon dioxide into the atmosphere, demand for solar cells is increasing in order to protect the global environment by suppressing global warming. Known organic solar cells include wet dye-sensitized solar cells (Gretzel cells) and all-solid organic thin-film solar cells. Since the latter does not use an electrolytic solution, there is no need to consider evaporation or leakage of the electrolytic solution. Moreover, it is possible to give flexibility, and the structure and manufacture of the solar cell become simpler than the former.

However, the photoelectric conversion efficiency of the organic thin film solar cell is still insufficient. Since the photoelectric conversion efficiency is calculated by the short circuit current density (Jsc) × the open circuit voltage (Voc) × the fill factor (FF), it is necessary to improve each of them in order to increase the photoelectric conversion efficiency. In order to improve the short-circuit current density, a p-type conductive / semiconductor material having a narrow band gap that absorbs light in the near-infrared region (for example, a donor-acceptor type thiophene derivative polymer compound) is used. Is proportional to the difference between the highest occupied orbital (HOMO) level of p-type conductivity / semiconductor material and the lowest unoccupied orbital (LUMO) level of n-type conductivity / semiconductor material. It is important to use a semiconductor material. That is, in order to achieve both a high open-circuit voltage and a high short-circuit current density, development of a p-type conductive / semiconductor material having a deep HOMO level and a small band gap, that is, a deep LUMO level is required. In order to improve the fill factor, it is important to use a p-type conductive / semiconductor material having high carrier mobility, that is, strong association.
In order to improve photoelectric conversion efficiency, organic semiconductor polymers (p-type polymers) have been studied as p-type conductive / semiconductor materials from the above viewpoint. Conjugated polymers containing many heteroaromatic rings having different structures have been studied. For example, recently, polymers having a specific structural unit containing a benzothiadiazole ring have been studied or proposed (Patent Documents 1 and 2). Non-Patent Document 1).

JP 2012-107187 A International Publication No. 2012/054910 Pamphlet

Chemistry-A European Journal, 2012, 18, 12140-12151

Compared to dye-sensitized solar cells that use the same organic materials, organic thin-film solar cells have the advantages described above and, despite their wide application range, the photoelectric conversion efficiency is higher than that of dye-sensitized solar cells. The reality is that it does not reach the battery.
In order to further increase the photoelectric conversion efficiency, the present inventors have increased the LUMO level of the p-type semiconductor compound (reduces the band gap) and lengthens the absorption edge, thereby allowing light in the near-infrared region to be emitted. We thought it important to be able to perform photoelectric conversion. Therefore, the present inventors have examined many conventionally proposed heteroaromatic rings including the Patent Documents 1 and 2 and their substituents. As a result, it has been found that the above can be achieved by carefully selecting the heteroaromatic ring and adjusting the substituent and the substitution mode strictly. Furthermore, it has also been found that a photoelectric conversion element using the compound of the present invention as a P-type semiconductor has little variation in current when formed into an element and is excellent in production suitability.
That is, the present invention is excellent by developing a p-type organic semiconductor compound whose absorption edge in the absorption spectrum has a long wavelength (for example, near infrared region of 865 nm or more) in addition to deep LUMO level and band gap reduction. and to provide an organic photoelectric conversion device and an organic thin-film solar cells performance.

    That is, the subject of this invention was achieved by the following means.

(1) An organic photoelectric conversion device comprising a first electrode, a second electrode, and a photoelectric conversion layer disposed therebetween, wherein the polymer represented by the following formula (AB) in the photoelectric conversion layer An organic photoelectric conversion element containing

In the formula (AB), X is to table a sulfur atom.
Y ¹ and ^{Y 2} is hydrogen atom, -C≡CR ^y1 or - represents a ^{C (= O) R y 2} .
However, Y ¹ and Y ² are not simultaneously hydrogen atoms.
R ^y1 represents alkoxycarbonyl group, or an acyl group.
R ^y2 represents an A alkyl group or a cycloalkyl group.
Ar represents a group represented by the following formula (2).
n represents an integer of 2 to 2000.

In formula (2), Z ^a Is -C (R ^1Z ) (R ^2Z )-. Where R ^1Z And R ^2Z Each independently represents an alkyl group.

(2) Calculated value of the energy level of the highest occupied molecular orbital of structural units represented by Ar (HOMO) is an organic photoelectric conversion element according to at least -5.3 eV (1).

(3) Weight average molecular weight before Kipo Rimmer is 10,000 to 1,000,000 is (1) or an organic photoelectric conversion device according to (2) (4) the photoelectric conversion layer further contains a n-type semiconductor The organic photoelectric conversion device according to any one of (1) to ( 3 ).
( 5 ) The organic photoelectric conversion element according to ( 4 ), wherein the photoelectric conversion layer has a mixed layer of the polymer and the n-type semiconductor.
(6) the (1) to (5) Organic thin film solar cells comprising an organic photoelectric conversion device according to any one of.

In this specification, an aromatic ring is used to mean including an aromatic hydrocarbon ring and an aromatic heterocycle, and an alicyclic ring is an aliphatic hydrocarbon ring, which is a non-aromatic aliphatic hydrocarbon ring. And a heterocycle means a heterocycle including an aromatic group, and a heterocycle that is not an aromatic heterocycle is referred to as a non-aromatic heterocycle. Each of these rings may be monocyclic, polycyclic, or condensed.
In addition, in the case of a polycycle or a condensed ring, it may be composed of the same ring or different rings as described above.
Each of these rings may have a substituent unless otherwise specified.
In the present invention, in the same formula, a group including a substituent and a partial structure have the same symbol, that is, when a plurality of groups are present, it means that they may be the same as or different from each other. Further, adjacent groups may be bonded to each other to form a ring.
In the specification of the present application, the repeating unit or the structural unit such as a polymer or an oligomer may be any group as long as the defined group or partial structure is defined, and may not be exactly the same repeating unit. For example, when it is defined as an alkyl group, a unit of a methyl group and a unit of an ethyl group may be mixed in each unit.
Further, when a double bond is present, it may be either E-form or Z-form, and includes a mixture thereof. Similarly, when an optical isomer is present, any of these may be used as a mixture thereof. Is also included.

  By using the compound of the present invention having a deep LUMO level and a small band gap, that is, an absorption edge having a long wavelength (for example, a near-infrared region of 865 nm or more), an organic photoelectric that can photoelectrically convert light in the long wavelength region. A conversion element, an organic thin-film solar cell, a composition used therefor, a coating film, a compound, and a method for producing the compound can be provided. Furthermore, the organic photoelectric conversion element using the compound of the present invention has little variation in current value and is excellent in production suitability.

It is a side view which shows typically the structure of preferable embodiment of the organic thin-film solar cell of this invention.

The organic photoelectric conversion element of the present invention comprises a first electrode, a second electrode, and a photoelectric conversion layer disposed therebetween, and at least one layer of the photoelectric conversion layer has an excellent identification as an organic semiconductor It has the compound of.
First, specific compounds will be described.

<< Specific compounds >>
The specific compound is a compound containing a structural unit represented by the following formula (A).
The specific compound shown below is a dimer or more compound containing at least two repeating units shown below, and includes oligomers and polymers.

In formula (A), X represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, —N (R ^1X ) — or —C (R ^2X ) (R ^3X ) —. Here, R ^1X represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. R ^2X and R ^3X each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. R ^2X and R ^3X may combine with each other to form a ring structure.
Y ¹ is ^{-C≡CR y1, -C (= O)} OR y2, -C (= O) SR y2, -C (= S) OR y2, -C (= S) SR y2, -C (= O ) N (R ^y3 ) (R ^y4 ), -C (= S) N (R ^y3 ) (R ^y4 ), -C (= O) R ^y2 , -C (= S) R ^y2 , -CR ^y5 = C ^{(R y6) (R y7)} , - represents a CR y5 = ^{NR y8} or -N = ^{NR y9.}
Y ² is a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group, an alkenyl group, an alkynyl group, —C (═O) OR ^y2 , —C (═O) SR ^y2 , —C (═S) OR ^y2 , —C (= S) SR ^y2 , -C (= O) N (R ^y3 ) (R ^y4 ), -C (= S) N (R ^y3 ) (R ^y4 ), -C (= O) R ^y2 , -C ^{(= S) R y2, -CR} y5 = C (R y6) (R y7), - represents a CR y5 = ^{NR y8} or -N = ^{NR y9.}

R ^y1 represents a hydrogen atom, a fluorine atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxycarbonyl group, an acyl group, an aryl group or a heteroaryl group.
R ^y2 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group or a heteroaryl group.
R ^y3 and R ^y4 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group or a heteroaryl group.
R ^y5 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group or a heteroaryl group.
R ^y6 and R ^y7 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxycarbonyl group, an acyl group or a cyano group. However, either one of R ^y6 and R ^y7 is an alkoxycarbonyl group, an acyl group, or a cyano group.
R ^y8 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group or a heteroaryl group.
R ^y9 represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group or a heteroaryl group.

-N in X ^{(R 1X)} - ^{R 1X medium, -C (R 2X) (R} 3X) - alkyl group for ^{R 2X} and ^{R 3X} medium is a linear or branched alkyl group, 1 to carbon atoms 24 alkyl groups are preferable, and alkyl groups having 6 to 24 carbon atoms are more preferable. For example, methyl, ethyl, isopropyl, n-butyl, t-butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl N-octyl, 2-methylheptyl, 2-ethylhexyl, n-nonyl, n-decyl, 3,7-dimethyloctyl, isodecyl, n-undecyl, n-dodecyl, 2-butyloctyl, n-tridecyl, 3- Butyl nonyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-hexyldecyl, n-heptadecyl, n-octadecyl, n-nonade Sil, 2-octyldodecyl, n-icosyl, n-henecosyl, n-docosyl, n-tricosyl, n-tetracosyl, 2-decyltetradecyl.

The alkenyl group is preferably an alkenyl group having 2 to 24 carbon atoms, such as vinyl, allyl, isopropenyl, 2-butenyl, 3-butenyl, 5-hexenyl, 7-octenyl, 2-ethyl-5-hexenyl, 2- Examples include vinylhexyl, 3,7-dimethyl-7-octenyl, 11-dodecenyl, 13-tetradecenyl, and 9-octadecenyl.
The alkynyl group is preferably an alkynyl group having 2 to 24 carbon atoms, and examples thereof include ethynyl, 2-propynyl, 2-penten-4-ynyl, 5-hexynyl, 7-octynyl and 2-nonyl-3-butynyl.
The aryl group is preferably an aryl group having 6 to 18 carbon atoms, and examples thereof include phenyl and naphthyl.

  The heteroaryl group is preferably a heteroaryl group having 2 to 20 carbon atoms, more preferably a 5- or 6-membered heteroaryl group having at least one oxygen atom, sulfur atom, nitrogen atom or selenium atom, such as pyridyl, Pyridazyl, pyrimidyl, pyrazyl, triazyl, tetrazolyl, tetrazyl, imidazolyl, pyrazolyl, benzoimidazolyl, quinolyl, isoquinolyl, cinnolyl, quinoxalyl, thienyl, furyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, selenophenyl, selenazolyl, isoserazolyl It is done. These rings may be condensed with heteroaryl rings, or may be condensed with the above-mentioned aryl group.

Each of these groups may be further substituted with a substituent.
Examples of such substituents include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, aryl groups, heterocyclic groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, Alkylthio group, arylthio group, amino group, alkylamino group, anilino group, acylamino group, alkyl or aryl sulfonamide group, ureido group, carbamoyl group, sulfamoyl group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group Alkyl, aryl sulfonyl group, alkyl or aryl sulfinyl group, alkyl or aryl sulfonyloxy group, formyl group, cyano group, nitro group, sulfo group, carboxyl group, imino group, azo group, etc. And the like.

When R ^y1 is an aryl group, the aryl group preferably has an electron withdrawing group. The electron withdrawing group is preferably one having a Hammett constant σp> 0, for example, a halogen atom, a halogenated alkyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an alkanesulfonyl group, an alkoxysulfonyl group, an alkanesulfonyloxy group, Examples thereof include a sulfonamide group, a formyl group, a carboxyl group, a carbamoyl group, a cyano group, a nitro group, an imino group, and an azo group. The Hammett constant can be referred to Chemical Reviews 1991, 91, p165-195.
The heteroaryl group for R ^y1 is preferably pyridyl, pyridazyl, pyrimidyl, pyrazyl, triazyl, tetrazolyl, tetrazyl, imidazolyl, pyrazolyl, thienyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl.

R ^2X and R ^3X may be bonded to each other to form a ring structure. Such a ring is preferably a 5- or 6-membered ring, and may be a carbocyclic ring or a heterocyclic ring.

  X is preferably a sulfur atom, an oxygen atom, or a selenium atom, more preferably a sulfur atom or an oxygen atom, and particularly preferably a sulfur atom.

Y ¹ is ^{-C≡CR y1, -C (= O)} OR y2, -C (= O) SR y2, -C (= S) OR y2, -C (= S) SR y2, -C (= O ) N (R ^y3 ) (R ^y4 ), -C (= S) N (R ^y3 ) (R ^y4 ), -C (= O) R ^y2 , -C (= S) R ^y2 , -CR ^y5 = C (R ^y6 ) (R ^y7 ), —CR ^y5 = NR ^y8 , —N = NR ^y9 are represented, but —C≡CR ^y1 , —C (═O) OR ^y2 , —C (═O) N (R ^y3 ) ) (R ^y4 ), -C (= O) R ^y2 , -CR ^y5 = C (R ^y6 ) (R ^y7 ), -CR ^y5 = NR ^y8 , -N = NR ^y9 are preferred, -C≡CR ^y1 , ^{-C (= O) R y2,} -CR y5 = C (R y6) (R y7), - CR y5 = NR y8, -N = NR y9 is more preferable.

Y ² represents a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group, an alkenyl group, an alkynyl group, —C (═O) OR ^y2 , —C (═O) SR ^y2 , —C (═S) OR ^y2 , — C (= S) SR ^y2 , -C (= O) N ( ^Ry3 ) ( ^Ry4 ), -C (= S) N ( ^Ry3 ) ( ^Ry4 ), -C (= O) ^Ry2 ,- C (= S) R ^y2 , -CR ^y5 = C (R ^y6 ) (R ^y7 ), -CR ^y5 = NR ^y8 , -N = NR ^y9 , but a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group, An alkenyl group and an alkynyl group are preferable, a hydrogen atom, a fluorine atom, a chlorine atom, and an alkynyl group are more preferable, and a hydrogen atom and a fluorine atom are further preferable.

Here, the alkyl group, alkenyl group, and alkynyl group in R ^{y1 to} R ^{y9 have the same meaning as} the alkyl group, alkenyl group, and alkynyl group in R ^{1X to} R ^3X , and the preferred ranges are also the same.
Aryl group in ^{R y2} ~R ^y5, R ^y8 and ^{R y9,} the ^R 1X has the same meaning as the aryl group in ^{to R 3X,} and the preferred range is also the same.

The cycloalkyl group in R ^{y1 to} R ^y9 is preferably a ^{3- to} 7-membered cycloalkyl group, and preferably has 3 to 24 carbon atoms, and examples thereof include cyclopropyl, cyclohexyl, cyclopentyl, and cycloheptyl.

In the heteroaryl ring of the heteroaryl group in R ^{y2 to} R ^y5 , R ^y8, and R ^{y9, examples} of the hetero atom of the ring constituent atom include a sulfur atom, an oxygen atom, a nitrogen atom, and a selenium atom, which constitutes an aryl ring. The number of heteroatoms is preferably 1 to 4, more preferably 2 or 3, and particularly preferably 1 or 2.
The aromatic ring of the heteroaryl ring is preferably a 5-membered ring or a 6-membered ring, and may be monocyclic or condensed.
Heteroaryl rings include thiophene ring, thiazole ring, isothiazole ring, selenophene ring, pyrrole ring, furan ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, oxazole ring, isoxazole ring, oxadiazole ring, thiadiazole And a ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, and a tetrazine ring. These rings may be condensed with heteroaryl rings or may be condensed with an aryl group.

The alkoxycarbonyl group in R ^y1 , R ^y6 and R ^y7 is preferably an alkoxycarbonyl group having 2 to 24 carbon atoms. For example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, t-butoxycarbonyl, n-hexyloxycarbonyl, n-octyloxycarbonyl, 2-methylheptyloxycarbonyl N-heptyloxycarbonyl, 2-ethylhexyloxycarbonyl, n-octyloxycarbonyl, n-nonyloxycarbonyl, n-decyloxycarbonyl, n-dodecyloxycarbonyl, isodecyloxycarbonyl, 3,7-dimethyloctyloxy Carbonyl, 2-butyloctyloxycarbonyl, 3-butylnonyloxycarbonyl, 2-hexyldecyloxycarbonyl, 2-octyldodecyloxycarbonyl , N- octadecyloxycarbonyl, and a 2-decyltetradecyloxycarbonyl.

The acyl group in R ^y1 , R ^y6 and R ^y7 includes a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, an ^{alkynylcarbonyl} group, a cycloalkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and has 1 to 24 carbon atoms. Acyl groups are preferred, for example, formyl, acetyl, propionyl, butyryl, isobutyryl, pivaloyl, lauroyl, palmitoyl, stearoyl, acryloyl, methacryloyl, crotonoyl, oleyl, benzoyl, toluoyl, naphthoyl, cinnamoyl, furoyl, thienoyl, nicotinoyl, isonicotinoyl, Sanoyl.

R ^y1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxycarbonyl group, an acyl group, an aryl group or a heteroaryl group, but the alkyl group, alkenyl group, alkynyl group, alkoxycarbonyl group, acyl Group is preferable, and an alkyl group, an alkoxycarbonyl group, an acyl group, an aryl group, and a heteroaryl group are more preferable.
R ^y2 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group or a heteroaryl group, preferably an alkyl group, an alkenyl group or an alkynyl group, and more preferably an alkyl group.
R ^y3 and R ^y4 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group or a heteroaryl group, preferably a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, and more preferably an alkyl group. preferable.

R ^y5 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group or a heteroaryl group, preferably a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, more preferably a hydrogen atom or an alkyl group. Preferably, a hydrogen atom is particularly preferable.
R ^y6 and R ^y7 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxycarbonyl group, an acyl group, or a cyano group, and an alkyl group, an alkoxycarbonyl group, an acyl group, or a cyano group is preferable. However, one of R ^y6 and R ^y7 is an alkoxycarbonyl group, an acyl group, or a cyano group.
R ^y8 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group or a heteroaryl group, preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, an alkyl group, An aryl group and a heteroaryl group are more preferable.
R ^y9 represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group or a heteroaryl group, preferably an aryl group or a heteroaryl group.

Compounds having a structural unit represented by the previous SL (A) preferably further contains a structural unit represented by the following formula (B).

  In the formula (B), Ar represents an arylene group or a heteroarylene group.

As the arylene group in Ar, an arylene group having 6 to 18 carbon atoms is preferable, and examples thereof include phenylene and naphthylene.
In the heteroaryl ring of the heteroarylene group in Ar, examples of the hetero atom of the ring atom include a sulfur atom, an oxygen atom, a nitrogen atom, and a selenium atom, and the number of hetero atoms constituting the aryl ring is preferably 1 to 4, 2 or 3 is more preferable, and 1 is particularly preferable.
The aromatic ring of the heteroaryl ring is preferably a 5-membered ring or a 6-membered ring, and may be monocyclic or condensed.
Heteroaryl rings include thiophene ring, thiazole ring, isothiazole ring, selenophene ring, pyrrole ring, furan ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, oxazole ring, isoxazole ring, oxadiazole ring, thiadiazole A ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and a pyridazine ring.

The arylene group and heteroarylene group in Ar may have a substituent, and examples of the substituent include the substituents that the groups R ^{1 to} R ³ may have.
Examples of the substituent include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, amino groups, alkylamino groups, arylamino groups, acyl groups, alkoxy groups. A carbonyl group, an acyloxy group and a halogen atom are preferred, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group and an alkylamino group are more preferred, and an alkyl group and an alkoxy group are particularly preferred.

  In the present invention, a compound containing a structural unit in which the structural unit represented by the formula (A) and the structural unit represented by the general formula (B) are directly bonded to each other is preferable, and more preferably represented by the following formula (AB). It is a compound containing the structural unit.

Wherein (AB), X, ^{Y 1} and ^{Y 2,} the formula (A) have the same meanings as X, ^{Y 1} and ^{Y 2} in, and the preferred range is also the same. Ar has the same meaning as Ar in the formula (B), and the preferred range is also the same.
n represents an integer of 2 to 2000. n is preferably an integer of 10 to 2000.

In the present invention, Ar preferably has a calculated energy level of the highest occupied orbital (HOMO) of Ar of −5.3 eV or more, more preferably −5.3 to −4.6 eV. .
By setting the energy level of the highest occupied orbital (HOMO) of Ar to −5.3 to −4.6 eV, a compound having a preferable energy level and absorption wavelength can be obtained.
The energy level of the highest occupied orbital (HOMO) of Ar is a ring including a substituent that substitutes for the ring, and molecular orbital calculation software Gaussian09 is used for a ring in which a bond is replaced with a hydrogen atom. It is a calculated value obtained by using the basis function system 6-31G (d) in the B3LYP method by Gaussian.
For example, the energy levels of the most occupied occupancy (HOMO) of a typical ring are as follows. The calculation was performed with R = methyl. * Indicates a polymer main chain forming part.

Ar is preferably a heteroarylene group, and the heterocycle of the group preferably contains at least a thiophene ring. Further, the heterocycle of the heteroaryl group is preferably a condensed ring (preferably a condensed ring of 3 to 4 rings) rather than a single ring, and among these, a condensed ring containing a thiophene ring is preferable, and a ring condensed with a thiophene ring As an aromatic ring (benzene ring, naphthalene ring), cyclopentadiene ring, or a ring in which a non-conjugated carbon atom of the cyclopentadiene ring is replaced with a nitrogen atom, Si atom, or Ge atom (pyrrole ring, silacyclopentadiene ring, Germacyclopentadiene ring) is preferred. Here, the ring in which 3 to 4 rings are condensed is preferably a ring in which both sides of the central ring, that is, a ring having a bond of a repeating unit is a thiophene ring.
In particular, in the present invention, Ar may have a thiophene ring linked to a moiety linked to a benzene ring having Y ¹ and Y ² fused to a 5-membered ring containing ═N—X—N═ in formula (A). preferable.
Such preferable Ar is represented by the following formula (1).

In formula (1), D represents a group represented by formula (D1), (D2) or (D3).
W ¹ represents a sulfur atom, a selenium atom, an oxygen atom or —NR ^a —. W ² represents ^{═CR 1D} — or ^═N— , and R ^1D represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxycarbonyl group, an acyl group, or a halogen atom. me represents an integer of 0-2. md represents 0 or 1. However, when md is 0, me represents 1 or 2.

In the formula (D1), the rings A and C each independently represent a thiophene ring, and the ring B represents any one of the rings represented by the above formulas (B-1) to (B-3). L ^{1A to} L ^1C are each independently a single bond, —O—, —S—, —N (R ^a ) —, —C (═O) O—, —C (═S) O—, —C ( = O) S-, -SC (= O)-, -OC (= O)-, -OC (= S)-, -C (= O)-, -C (= S)-, -C (= O) N (R ^a ) —, —N (R ^a ) C (═O) —, —S (═O) —, —S (═O) ₂ —, —S (═O) ₂ O—, — OS (═O) ₂ —, —S (═O) ₂ N (R ^a ) —, —N (R ^a ) S (═O) ₂ —, an arylene group or a heteroarylene group is represented. Here, R ^a represents a hydrogen atom or a hydrocarbon group. R ^{1A to} R ^1C each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. mb represents an integer of 0 to 4, and ma and mc each independently represents 0 or 1.

Formula (B-1) in, ^{Z b is, -C (R 1Z) (R} 2Z) -, - C [= C (R 3Z) (R 4Z)] -, - Si (R 1Z) (R 2Z) —, —Ge (R ^1Z ) (R ^2Z ) — or —N (R ^a ) — is represented. Here, R ^1Z and R ^2Z each independently represent an alkyl group, an alkenyl group, or an alkynyl group. R ^3Z and R ^4Z each independently represents an alkyl group, an alkenyl group, an alkynyl group, an acyl group or an alkoxycarbonyl group. R ^a represents a hydrogen atom or a hydrocarbon group.

Wherein (D2) and (D3), ^{W 1} and ^{W 2} have the same meaning as ^{W 1} and ^{W 2} in the formula (1). The plurality of W ¹ , W ² and me in the formulas (1), (D2) and (D3) may be the same or different.
W ¹ is preferably a sulfur atom, a selenium atom, or an oxygen atom, and more preferably a sulfur atom.
W ² is preferably ^{═CR 1D} —.
R ^1D is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or a fluorine atom, more preferably a hydrogen atom or an alkyl group.
When md is 1, me is preferably 0 or 1. When md is 0, me is preferably 1 or 2.

In formula (D1), the arylene group or heteroarylene group in L ^{1A to} L ^1C is preferably a corresponding group in Ar.
L ^{1A to} L ^1C are preferably a single bond, —O—, —S—, —N (R ^a ) —, more preferably a single bond, —O—, —S—, and further a single bond, —O—. preferable.

The hydrocarbon group for R ^a is preferably an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, or an aryl group. Here, the alkyl group, the alkenyl group, the alkynyl group, and the aryl group are preferably the corresponding groups mentioned for R ^{1X to} R ^3X . The cycloalkyl group is a 3- to 6-membered ring, preferably a cycloalkyl group having 3 to 18 carbon atoms, and examples thereof include cyclopropyl, cyclopentyl, and cyclohexyl.
R ^a is preferably ^a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group, and more preferably an alkyl group.

The alkyl group, alkenyl group, and alkynyl group in R ^{1A to} R ^1C are preferably the corresponding groups listed for R ^{1X to} R ^3X .
R ^{1A to} R ^1C are preferably an alkyl group, and the alkyl group preferably has 1 to 24 carbon atoms, and more preferably 6 to 24 carbon atoms.

  ma and mc are preferably 0, and mb is preferably an integer of 0 to 2, more preferably 1 or 2.

Formula (B-1) in, ^{Z b is, -C (R 1Z) (R} 2Z) -, - C [= C (R 3Z) (R 4Z)] -, - Si (R 1Z) (R 2Z) —, —Ge (R ^1Z ) (R ^2Z ) — or —N (R ^a ) — is represented. Here, R ^1Z and R ^2Z each independently represent an alkyl group, an alkenyl group, or an alkynyl group. R ^3Z and R ^4Z each independently represents an alkyl group, an alkenyl group, an alkynyl group, an acyl group or an alkoxycarbonyl group. R ^a represents a hydrogen atom or a hydrocarbon group.

The alkyl group, alkenyl group and alkynyl group in R ^1Z , R ^2Z , R ^3Z and R ^4Z are preferably corresponding groups in R ^{1X to} R ^3X .
The acyl group in R ^3Z and R ^4Z is preferably an acyl group having 1 to 18 carbon atoms, more preferably an alkylcarbonyl group or an arylcarbonyl group, such as formyl, acetyl, propionyl, pivaloyl, myristylyl, stearoyl, acryloyl, or benzoyl. Can be mentioned.
The alkoxycarbonyl group in R ^3Z and R ^4Z is preferably an alkoxycarbonyl group having 2 to 18 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butyloxycarbonyl, s-butyloxycarbonyl, t-butyloxycarbonyl. 2-ethylhexyloxycarbonyl, 3,7-dimethyloctyloxycarbonyl, 2-butyloctyloxycarbonyl, 2-hexyldecyloxycarbonyl, 2-octyldodecyloxycarbonyl, 2-decyltetradecyloxycarbonyl, n-octadecyloxycarbonyl Is mentioned.

R ^1Z , R ^2Z , R ^3Z and R ^4Z are preferably alkyl groups, and among them, the alkyl group preferably has 1 to 24 carbon atoms, more preferably 6 to 24 carbon atoms.

Z ^{b is, -C (R 1Z) (R} 2Z) -, - Si (R 1Z) (R 2Z) -, - N (R a) -, - C [= C (R 3Z) (R 4Z)] ^-Is preferable, and -C ( ^R1Z ) ( ^R2Z )-, -Si ( ^R1Z ) ( ^R2Z )-, and -C [= C ( ^R3Z ) ( ^R4Z )]-are more preferable.
During and (D3) the formula (D2), ^{W 1} and ^{W 2} has the same meaning as ^{W 1} and ^{W 2} in the formula (1), and preferred ranges are also the same.

  The ring B is preferably a formula (B-1) or (B-2).

  The group represented by the above formula (1) is preferably a group represented by the following formulas (2) to (6).

Wherein (2), ^{Z a is, -C (R 1Z) (R} 2Z) -, - Si (R 1Z) (R 2Z) -, - Ge (R 1Z) (R 2Z) -, - C [= C (R ^3Z ) (R ^4Z )] — or —N (R ^a ) —. Here, R ^1Z and R ^2Z each independently represents an alkyl group, an alkenyl group or an alkynyl group, and R ^3Z and R ^4Z each independently represent an alkyl group, an alkenyl group, an alkynyl group, an acyl group or an alkoxycarbonyl group. Represents. R ^a represents a hydrogen atom or a hydrocarbon group.
Wherein ^{(3), L 1B, R} 1B , the formula (1) ^L 1B in ^is synonymous with ^{R 1B, R 3} is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an alkoxycarbonyl group Or represents a halogen atom.

In formula (4), R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an alkoxycarbonyl group or a halogen atom.
In formula (5), R ^5A and R ^5B each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an alkoxycarbonyl group or a halogen atom.
In formula (6), R ⁶ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an alkoxycarbonyl group or a halogen atom.

Here, —C (R ^1Z ) (R ^2Z ) —, —Si (R ^1Z ) (R ^2Z ) —, —Ge (R ^1Z ) (R ^2Z ) —, —N (R ^a ) — or —C [ = C (R ^3Z ) (R ^4Z )]-, and R ^1Z , R ^2Z , R ^a , R ^3Z , R ^4Z have the same ^{meanings as those} in the formula (1), and the preferred ranges are also the same.
In formula (3), R ³ is more preferably a hydrogen atom or an alkyl group.
In formula (4), R ⁴ is more preferably a hydrogen atom or an alkyl group.
In Formula (5), R ^5A is more preferably a hydrogen atom or an alkyl group, and R ^5B is more preferably a halogen atom or a hydrogen atom.
In formula (6), R ⁶ is more preferably a hydrogen atom or an alkyl group.

The compound including the structural unit represented by the formula (A), particularly the polymer, has a mass average molecular weight of preferably 10,000 or more, more preferably 10,000 to 1,000,000.
In particular, by increasing the mass average molecular weight in this way, the photoelectric conversion efficiency is improved.
The mass average molecular weight is a value measured using a GPC (gel filtration chromatography) method unless otherwise specified, and the molecular weight is a polystyrene equivalent mass average molecular weight. The gel packed in the column used in the GPC method is preferably a gel having an aromatic compound as a repeating unit, and examples thereof include a gel made of a styrene-divinylbenzene copolymer. It is preferable to use 2 to 6 columns connected together. Examples of the solvent used include halogen solvents such as chloroform, aromatic solvents such as toluene, chlorobenzene, 1,2-dichlorobenzene, and trichlorobenzene, ether solvents such as tetrahydrofuran, and amide solvents such as N-methylpyrrolidone. An aromatic solvent is preferable from the viewpoint of solubility of the polymer. The measurement is preferably performed at a solvent flow rate in the range of 0.1 to 2 mL / min, and more preferably in the range of 0.5 to 1.5 mL / min. The measurement temperature is appropriately changed depending on the boiling point of the solvent, but it is preferably 10 to 200 ° C, more preferably 20 to 150 ° C. The column and carrier to be used can be selected according to the physical properties of the polymer compound to be measured. In the present invention, column: TSK-GEL SUPER H-RC 6.0 * 150 + TSK-GEL BMHHR-H (20) 7.8 * 300 (two), solvent: 1,2-dichlorobenzene, temperature: 145 ° C. Flow rate: sample side: 1 mL / min, reference side: determined at 0.5 mL / min.

In the compound containing the structural unit represented by the formula (A), the polymer terminal or the bond of the structural unit is a hydrogen atom, a trialkyltin group (for example, a trimethyltin group or a tributyltin group), a halogen atom (fluorine) , Chlorine, bromine, iodine), —B (OH) ₂ , —B (OR ^x ) ₂ , trialkylsilyl group (eg, trimethylsilyl group, triethylsilyl group, etc.), aryl group (eg, phenyl group, tolyl group, A naphthyl group or the like, or a heteroaryl group (for example, a thienyl group, a 2-hexylthienyl group, a 3-hexylthienyl group, a thiazolyl group, a furyl group, or a pyridyl group) is preferable. The above R ^x represents an alkyl group, and a plurality of R ^x may be bonded to each other to form a ring.
These polymer ends are mainly based on the synthetic raw materials and the polymerization conditions.

In addition , the polymer in the compound containing the structural unit represented by the formula (A) may be obtained by any block, random or alternating polymerization method.
Incidentally, the particular compound used in the present invention is a polymer represented by the formula (AB) above, in the formula (AB), X is a sulfur atom, Y ¹ and Y ² are hydrogen atom, - C≡CR ^y1 or —C (═O) R ^y2 . However, Y ¹ and Y ² are not simultaneously hydrogen atoms. Here, R ^y1 is an alkoxycarbonyl group or an acyl group, and R ^y2 is an alkyl group or a cycloalkyl group. Ar is a group represented by the aforementioned formula (2), and in the formula (2), Z ^a is —C (R ^1Z ) (R ^2Z ) —. Here, R ^1Z and R ^2Z are each independently an alkyl group.
n is an integer of 2 to 2000.

Hereinafter, including the reference example shows the specific examples of the compound containing a structural unit represented by the formula (A). In the specific examples below, Me represents methyl and Et represents ethyl.

The compound containing the structural unit represented by the formula (A) is a coupling reaction, for example, Chemical Reviews, 2002, 102, 1359, Chemical Reviews, 2011, 111, 1493, Journal of Materials of Chemistry. , 2004, Vol. 14, p. 11 and the like.
Specifically, using a transition metal catalyst, Negishi coupling using a zinc reagent, Ueda-Kosugi-Still coupling using a tin reagent, Suzuki-Miyaura coupling using a boron reagent, a magnesium reagent are used. It can be synthesized using Kumada-Tamao-Coriu coupling, cross coupling such as Kashiyama coupling using a silicon reagent, Ullmann reaction using copper, Yamamoto polymerization using nickel, and the like. In the present invention, it is more preferable to use a right-Kosugi-Still coupling and a Suzuki-Miyaura coupling. As the transition metal catalyst, metals such as palladium, nickel, copper, cobalt, and iron (Journal of the American Chemical Society, 2007, Vol. 129, page 9844) can be used. Further, the metal may have a ligand, such as PPh ₃ , P (t-Bu) ₃ , P (o-tol) ₃ , P (2-furyl) ₃ , S-Phos, X-Phos, etc. A phosphorus ligand, an N-heterocyclic carbene ligand (Angewandte Chemie International Edition, 2002, 41, 1290) and the like are preferably used. The reaction may be performed under microwave irradiation as described in Macromolecular Rapid Communications, 2007, 28, 387.

Here, when Z ¹ and Z ² are a halogen atom and a perfluoroalkanesulfonyloxy group, Z ^a and Z ^b are a trialkyltin group, a trialkylsilyl group, or —B (ORα) ₂ , and Z ¹ and Z 2 ^{When 2} is a trialkyltin group, a trialkylsilyl group or —B (ORα) ₂ , Z ^a and Z ^b are a halogen atom or a perfluoroalkanesulfonyloxy group.

Incidentally, by adding a compound represented by Ar-V ¹ after polymerization may be carried out capping by reacting with the polymer end. Here, Ar represents an aryl group (for example, phenyl group, naphthyl group, tolyl group, etc.) or a heteroaryl group (for example, thienyl group, thiazolyl group, furyl group, pyridyl group, etc.). Ar may have a substituent such as an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, or a halogen atom.
V ¹ is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), perfluoroalkanesulfonyloxy group (eg, trifluoromethanesulfonyloxy group, nonafluorobutanesulfonyloxy group), trialkyltin group (e.g., trimethylstannyl group, a tributylstannyl group), trialkylsilyl groups (e.g., trimethylsilyl group, etc. triethylsilyl group), - represents a B (OR ^x) _2. Here, R ^x represents a hydrogen atom or an alkyl group. R ^x may be linked to form a ring.

  There are no particular limitations on the method of synthesizing the metal reactants such as tin reactant and boron reactant, which are raw materials, and they can be synthesized according to various known methods. For example, the tin reactant is Journal of the American Chemistry, 2009, 131, 7792, Journal of the American Chemistry, 2008, 130, 16144, European Patent Application No. 2407465, and the boron reactant is Jour. The compound can be synthesized with reference to the American Chemistry, pages 2012, 134, 539 and the like.

<< Compound Represented by Formula (M1) >>
The compound represented by the formula (M1) is useful and preferable as a synthesis raw material for synthesizing a compound containing the structural unit represented by the formula (A).

Wherein (M1), X, ^{Y 1} and ^{Y 2,} the formula (A) have the same meanings as X, ^{Y 1} and ^{Y 2} in, and the preferred range is also the same. Z ¹ and Z ² each independently represent a halogen atom, a perfluoroalkanesulfonyloxy group, a trialkyltin group, a trialkylsilyl group, or —B (ORα) ₂ . Here, Rα represents a hydrogen atom, an alkylsulfonyl group, an alkyl group, or an aryl group. Two Rαs may be bonded to each other to form a ring.

Here, the compound represented by the formula (M1) is a monomer, and the groups and symbols other than Z ¹ and Z ² are the same as those in the formula (A) as described above. The preferred range is also the same.

The alkylsulfonyl group for Rα in Z ¹ and Z ² is preferably a perfluoroalkanesulfonyl group, and particularly preferably a trifluoromethanesulfonyl group.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and the aryl group is preferably an aryl group having 6 to 10 carbon atoms.
Z ¹ and Z ² are preferably a halogen atom or a perfluoroalkane sulfonyloxy group, more preferably a bromine atom or an iodine atom, and particularly preferably a bromine atom.

Specific examples of the compound represented by the formula (M1) are shown below, but the present invention is not limited thereby. M ⁺ below represents a metal cation. In the specific examples below, Me represents methyl, Et represents ethyl, and Ph represents phenyl.

  The method of these compounds is not particularly limited and can be synthesized according to various known methods. For example, a compound represented by the formula (M1) can be synthesized using a compound represented by the following formula (M2) as a raw material.

Wherein (M2), X, ^{Y 2} has the same meaning as X, ^{Y 2} in the formula (M1), and the preferred range is also the same.
Z ³ and Z ⁴ each independently represents a fluorine atom, a chlorine atom, a bromine atom or a perfluoroalkanesulfonyloxy group.
When Z ³ and Z ⁴ are fluorine atoms, Y ³ represents a chlorine atom, a bromine atom, a perfluoroalkanesulfonyloxy group or an iodine atom, and when Z ³ and Z ⁴ are a chlorine atom or a perfluoroalkanesulfonyloxy group, Y ³ represents a bromine atom or an iodine atom, and when Z ³ and Z ⁴ are bromine, Y ³ represents an iodine atom.

Specifically, it is synthesized as follows. When Y ¹ is an acyl group, it can be synthesized as shown in the following reaction formula, for example, according to the synthesis method described in European Patent Application Publication No. 1782811.

When Y ¹ is a formyl group, it can be synthesized as shown in the following reaction formula, for example, according to the synthesis method described in Tetrahedron Letters, 2011, 52, p2383-2386.

When Y ¹ is an alkoxycarbonylethynyl group, it can be synthesized as shown in the following reaction formula, for example, according to the synthesis method described in International Publication No. 2006/131482.

Ｙ^１が（ヘテロ）アリールエチニル基の場合、例えば、国際公開第２００８／１２５５９９号パンフレットに記載の合成方法に従って、下記反応式のように合成できる。

When Y ¹ is a (hetero) arylethynyl group, it can be synthesized as shown in the following reaction formula, for example, according to the synthesis method described in International Publication No. 2008/125599.

When Y ¹ is an alkoxycarbonyl group, it can be synthesized as shown in the following reaction formula, for example, according to the synthesis method described in Tetrahedron Letters, 2012, 53, p3990-3993.

When Y ¹ is a thioester group, for example, it can be synthesized according to the synthesis method described in Journal of the American Chemical Society, 2010, 132, p3153-3158 as shown in the following reaction formula.

When Y ¹ is a carbamoyl group, it can be synthesized according to the following reaction formula according to the synthesis method described in Tetrahedron, 2011, 67, p2402-2406, for example.

When Y ¹ is an imino group, for example, it can be synthesized according to the synthesis method described in Journal of Catalysis, 2011, 283, p55-67 as shown in the following reaction formula.

<< set containing a specific compound Narubutsu >>
The composition containing the specific compound contains at least a compound containing the structural unit represented by the formula (A) and an organic solvent.
The composition containing the specific compound may be used for any purpose and purpose, but is preferably used as a composition for an organic semiconductor.
The organic solvent contained in the composition is not particularly limited, but ether solvents such as tetrahydrofuran, 1,4-dioxane, cyclopentylmethyl ether, benzene, toluene, ethylbenzene, xylene, mesitylene, anisole, thioanisole, pyridine, picoline, lutidine Aromatic solvents such as chloroform, dichloromethane, 1,2-dichloroethane, halogen solvents such as 1,1,2,2-tetrachloroethane, chlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, bromobenzene, Aromatic halogen solvents such as iodobenzene, trifluoromethylbenzene, fluorobenzene, difluorobenzene, etc. are mentioned. Tetrahydrofuran, toluene, chloroform, dichloromethane, chlorobenzene, o-dichloro Robenzen and 1,3,5-trichlorobenzene are preferred. These solvents may be used alone or as a mixed solvent of two or more.
In order to control the phase separation structure of the p-type semiconductor phase and the n-type semiconductor phase described later, an additive of 0.1% by mass to 10% by mass may be added to the solvent. Examples of the additive include diiodoalkane (for example, 1,8-diiodooctane, 1,6-diiodohexane, 1,10-diiododecane, etc.), alkanedithiol (for example, 1,8-octanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, etc.) and 1-chloronaphthalene.

The composition containing the specific compound is obtained by dissolving or dispersing the compound containing the structural unit represented by the formula (A) of the present invention in the organic solvent. Particularly, among the organic semiconductor polymers, the p-type organic semiconductor polymer is used. Useful as.
The composition containing the specific compound may contain the compound containing the structural unit represented by the formula (A) alone, but p other than the compound containing the structural unit represented by the formula (A). Type organic semiconductor compounds such as poly-3-hexylthiophene (P3HT), poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene (MEH-PPV), poly [2- Methoxy-5- (3 ′, 7′-dimethyloctyloxy) -1,4-phenylenevinylene] (MDMO-PPV), poly [(9,9-di-n-octylfluorenyl-2,7-diyl) ) -Alt- (benzo [2,1,3] thiadiazole-4,8-diyl)] (F8BT) or the like, or a compound other than a semiconductor may be used in combination. Examples of compounds other than semiconductors include other polymers such as polyester resins and methacrylic resins.

Particularly preferred as the compound or polymer to be used in combination is an n-type semiconductor (n-type semiconductor compound). As the n-type semiconductor (n-type semiconductor compound), those described later are preferable.
Use of an n-type semiconductor (n-type semiconductor compound) in combination is preferable for forming a photoelectric conversion layer of an organic photoelectric conversion element.

Although content of the compound containing the structural unit represented by Formula (A) is not specifically limited, When the mass of the whole composition is set to 100, it is preferable to make it contain 0.01-90 mass%, More preferably, 70% by mass is contained.

When an n-type organic semiconductor (n-type organic semiconductor compound) is used in combination, the n-type organic semiconductor (n-type organic semiconductor compound) is contained in an amount of 0.01 to 90% by mass when the total mass of the composition is 100. Is preferable, and it is more preferable to make it contain 0.1-70 mass%. About arbitrary p-type organic-semiconductor compounds other than the compound represented by the formula (I) of this invention, it is preferable to contain 0-50 mass%, and it is more preferable to contain 0-30 mass%. About compounds other than a semiconductor, although it is based also on the component, you may make it contain about 0-50 mass%.
Here, the content contained in the composition is 100% by mass in total although each component is within the above range.

Incidentally, the form of the set Narubutsu is not specifically limited, may be a flowable liquid and paste-like.

<< Coating film >>
The said composition containing a specific compound is preferably used for forming a coating film, and is used especially as a coating film of the organic-semiconductor material, especially the photoelectric converting layer of an organic photoelectric conversion element.
In order to form a coating film, it is preferable to apply a composition containing a specific compound by a spin coat method, a cast method, a spray method, a bar coat method, an ink jet method or the like.
Moreover, 0.01-1 micrometer is preferable and, as for the thickness of a coating film, 0.05-0.3 micrometer is more preferable.

<< Organic photoelectric conversion element and organic thin film solar cell >>
FIG. 1 is a side view schematically showing an example of the organic photoelectric conversion device of the present invention and an organic thin film solar cell using the organic photoelectric conversion device (hereinafter, referred to as an organic thin film solar cell or a solar cell as a representative). The solar cell 10 of the present embodiment includes a photoelectric conversion layer (bulk hetero bond layer) 3 including a compound including the structural unit represented by the formula (A). Organic thin-film solar cells are generally classified into pn bilayer junction or pin three-layer junction type organic thin film solar cells and bulk heterojunction type organic thin film solar cells, and any of them may be used in the present invention. Absent. Since high power generation efficiency can be easily obtained, it is particularly preferably applied to a bulk heterojunction organic thin film solar cell as shown in FIG.

In the organic thin-film solar cell of the present embodiment, the photoelectric conversion layer 3 is made of a compound containing the structural unit represented by the formula (A), a p-type semiconductor phase that is an electron-donating compound, and an n-type that is an electron-accepting compound. It consists of a semiconductor phase. The photoelectric conversion layer 3 is provided between the first electrode 11 and the second electrode 12.
In the present invention, the hole transport layer 21 is preferably provided between the first electrode and the photoelectric conversion layer, and the electron transport layer 22 is preferably provided between the second electrode and the photoelectric conversion layer. By providing these hole transport layer and electron transport layer, it is possible to extract charges generated in the photoelectric conversion layer more efficiently. In the solar cell of the present embodiment, the distinction between the upper and lower sides is not particularly important, but if necessary for convenience, the first electrode 11 side is positioned as the “up” or “top” side, and the second electrode 12 side is defined as “ Position it as “bottom” or “bottom”.

  Here, in order from the upper layer, the configuration of the substrate, the positive electrode, the hole transport layer, the photoelectric conversion layer, the electron transport layer, and the negative electrode is referred to as the forward configuration. The configuration of the layer and the positive electrode is referred to as a reverse configuration, and in the present invention, both the forward configuration and the reverse configuration are preferably applied.

  In the photoelectric conversion layer, the p-type semiconductor phase and the n-type semiconductor phase are mixed in a specific form as described above, and photoelectric conversion (charge separation) is performed at the interface. The form is not particularly limited, but as an ideal example, a state in which the phases are interdigitated in the order of nanometers as illustrated is preferable. In order to effectively create such a form, the p-type semiconductor polymer preferably has a specific compatibility or incompatibility with the n-type semiconductor polymer. The material that becomes the p-type semiconductor is not determined only by the specific physical properties, but is specified by the relative relationship with the material that becomes the n-type semiconductor. For example, when a typical fullerene is taken as an example of an n-type semiconductor material, a material having a higher electron donating property can be a p-type semiconductor material.

<Components of organic thin-film solar cells>
(N-type organic semiconductor)
The n-type organic semiconductor (n-type organic semiconductor compound) is not particularly limited, but is generally a π-electron conjugated system whose lowest orbital (LUMO) level is −3.5 to −4.5 eV. Perfluoro compounds in which hydrogen atoms of p-type organic semiconductor compounds are substituted with fluorine atoms (for example, perfluoropentacene or perfluorophthalocyanine), naphthalenetetracarboxylic anhydride, etc. Products, aromatic compounds such as naphthalene tetracarboxylic acid diimide, perylene tetracarboxylic acid anhydride, and perylene tetracarboxylic acid diimide, and polymer compounds containing the imidized product thereof as a skeleton.

Among these n-type organic semiconductor compounds, fullerene or a compound containing a structural unit represented by the formula (A), particularly a polymer organic semiconductor (p-type organic semiconductor compound) can be separated at high speed and efficiently. Its derivatives are preferred.
As fullerenes and derivatives thereof, C ₆₀ fullerene, C ₇₀ fullerene, C ₇₆ fullerene, C ₇₈ fullerene, C ₈₄ fullerene, C ₂₄₀ fullerene, C ₅₄₀ fullerene, mixed fullerene, fullerene nanotube, and some of them are hydrogen atoms. , Fullerene derivatives substituted by halogen atoms, substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, cycloalkyl groups, silyl groups, ether groups, thioether groups, amino groups, silyl groups, etc. Can be mentioned.

As the fullerene derivative, phenyl-C ₆₁ -butyric acid ester, diphenyl-C ₆₂ -bis (butyric acid ester), phenyl-C ₇₁ -butyric acid ester, phenyl-C ₈₅ -butyric acid ester or thienyl-C ₆₁ -butyric acid ester are preferable, The carbon number of the alcohol part of the butyric acid ester is preferably 1 to 30, more preferably 1 to 8, still more preferably 1 to 4, and most preferably 1.

Examples of preferred fullerene derivatives include phenyl-C ₆₁ -butyric acid methyl ester ([60] PCBM), phenyl-C ₆₁ -butyric acid n-butyl ester ([60] PCBnB), phenyl-C ₆₁ -butyric acid isobutyl ester ([60 PCBiB), phenyl-C ₆₁ -butyric acid n-hexyl ester ([60] PCBH), phenyl-C ₆₁ -butyric acid n-octyl ester ([60] PCBO), diphenyl-C ₆₂ -bis (butyric acid methyl ester) ( bis [60] PCBM), phenyl _{-C 71} - butyric acid methyl ester ([70] PCBM), phenyl _{-C 85} - butyric acid methyl ester ([84] PCBM), thienyl _{-C 61} - butyric acid methyl ester ([60] ThCBM _{), C 60} pyrrolidine tris _{acids, C 60} pyrrolidine tris San'e Glycol ester, N- methyl hula b pyrrolidine _(MP-C 60), (1,2 methanofullerene _C 60) -61- carboxylic acid, (1,2-methanofullerene _C 60) -61- carboxylic acid t- butyl ester And fullerene having a cyclic ether group such as US Pat. No. 7,329,709, and the like.

(P-type organic semiconductor compound)
In the present invention, a compound containing the structural unit represented by the formula (A) is used, but it may contain other p-type semiconductor compounds (for example, condensed polycyclic aromatic low molecular weight compounds, oligomers or polymers). Good.

  Examples of the condensed polycyclic aromatic low-molecular compound that is a p-type semiconductor compound include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumcam Compounds such as anthracene, bisanthene, zestrene, heptazeslen, pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bis Examples thereof include ethylene tetrathiafulvalene (BEDTTTTF) -perchloric acid complex, and derivatives and precursors thereof.

(Photoelectric conversion layer)
In the present invention, the composition for an organic semiconductor material is preferably used as a coating composition for a photoelectric conversion layer (particularly a bulk hetero layer). The mixing ratio of the p-type organic semiconductor compound that is an electron-donating material and the n-type semiconductor compound that is an electron-accepting material is preferably adjusted so as to increase the photoelectric conversion efficiency. It is selected from the range of ˜90: 10, preferably 20:80 to 80:20. As a method for forming such a mixed layer, for example, a co-evaporation method is used. Or it is also possible to produce by carrying out solvent application | coating using the solvent common to both organic materials. A coating method is preferable in order to increase the area of the interface where holes and electrons are separated by charge and to have high photoelectric conversion efficiency.

Here, for the purpose of promoting the phase separation of the electron donating region (donor) and the electron accepting region (acceptor) in the photoelectric conversion layer, crystallization of the organic material contained in the photoelectric conversion layer, and transparency of the electron transport layer, etc. You may heat-process (anneal) by the method. In the case of a dry film forming method such as vapor deposition, for example, there is a method of heating the substrate temperature during film formation to 30 ° C. to 150 ° C. In the case of a wet film forming method such as printing or coating, there is a method of setting the drying temperature after coating to 30 ° C. to 250 ° C. Moreover, you may heat at 30 degreeC-250 degreeC after completion | finish of a subsequent process, for example, formation of a metal negative electrode. By promoting phase separation, a charge transport path may be formed, and the photoelectric conversion efficiency may be improved.
In the present invention, a plurality of photoelectric conversion layers may be provided, but one photoelectric conversion layer is preferable.

(electrode)
The organic photoelectric conversion element according to the present invention has at least a first electrode and a second electrode. One of the first electrode and the second electrode is a positive electrode, and the rest is a negative electrode. Further, when a tandem configuration is adopted, the tandem configuration can be achieved by using an intermediate electrode. In the present invention, an electrode through which holes mainly flow is referred to as a positive electrode, and an electrode through which electrons mainly flow is referred to as a negative electrode. From the functional aspect of whether or not there is translucency, an electrode having translucency is referred to as a transparent electrode, and an electrode having no translucency is referred to as a counter electrode or a metal electrode. In the forward configuration of the present invention, the positive electrode is a translucent transparent electrode, and the negative electrode is a non-translucent counter electrode or metal electrode. In the reverse configuration, the negative electrode is a translucent transparent electrode, and the positive electrode is a non-translucent counter electrode or metal electrode. Both the first electrode and the second electrode can be transparent electrodes.

(First electrode)
The first electrode is a positive electrode. In the case of a forward-configured solar cell, it is preferably a transparent electrode that transmits visible to near-infrared light (380 to 800 nm). Examples of the material include transparent conductive metal oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), indium tungsten oxide (IWO), tin oxide, zinc oxide, and indium oxide, magnesium, aluminum, calcium, Ultrathin films of metal and metal alloys such as titanium, chromium, manganese, iron, copper, zinc, strontium, silver, indium, tin, barium, and bismuth, metal nanowires, and carbon nanotubes can be used. It is also possible to use a mesh electrode in which a metal such as silver is meshed to ensure light transmission. Also, a conductive material selected from the group consisting of polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene and polynaphthalene. A functional polymer can also be used. In addition, a plurality of these conductive compounds can be combined to form a positive electrode. In the case of using a transparent electrode in the forward configuration, the transmittance of the positive electrode is the thickness used for solar cells (for example, 0.2 μm thick), and the average light transmittance in the wavelength region of 380 nm to 800 nm is 75% or more. It is preferably some 85% or more. If light transmission is not required in the reverse configuration, metals such as chromium, cobalt, nickel, copper, molybdenum, palladium, silver, tantalum, tungsten, platinum, and gold, alloys thereof, transparent conductive oxide, polyaniline The positive electrode can be formed of a conductive polymer such as polythiophene or polypyrrole. Details of the suitable conductive polymer layer are disclosed in JP 2012-43835 A, polythiophene derivatives are preferable, and polyethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) is more preferable. These metals, transparent conductive oxides, and conductive polymers may be used alone, or two or more kinds may be mixed or laminated.

(Second electrode)
In the present invention, the second electrode is a negative electrode. The negative electrode may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination. As the conductive material for the negative electrode, a material having a small work function (4 eV or less) metal, alloy, electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the viewpoint of electron extraction performance and durability against oxidation, etc., a mixture of these metals and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The negative electrode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.

  In the reverse configuration, the second electrode is a transparent electrode. A transparent electrode that transmits light from visible light to near infrared light (380 to 800 nm) is preferable, and examples thereof include metals, metal oxides, conductive polymers, mixtures thereof, and laminated structures. Specific examples include transparent conductive oxides such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), and indium tungsten oxide (IWO), magnesium, aluminum, calcium, titanium, Examples thereof include ultrathin films of metals and metal alloys such as chromium, manganese, iron, copper, zinc, strontium, silver, indium, tin, barium, and bismuth, and conductive polymers such as polyaniline, polythiophene, and polypyrrole. Particularly preferable materials for the transparent conductive oxide are ITO, IZO, tin oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), zinc oxide, antimony-doped zinc oxide (AZO), and gallium-doped oxide. Zinc (GZO) can be used. In the case of a transparent electrode with a reverse configuration, the transmittance of the negative electrode is the thickness used for solar cells (for example, 0.2 μm thickness), and the average light transmittance in the wavelength region of 380 nm to 800 nm is 75% or more. It is preferably some 85% or more.

If a metal material is used as the negative electrode conductive material of the forward configuration and the positive electrode conductive material of the reverse configuration, the light reaching the metal electrode is reflected and reflected to the photoelectric conversion layer side, and the reflected light is absorbed again. Is preferable. The metal electrode may be a metal (eg, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), carbon nanoparticle, nanowire, or nanostructure. A dispersion is preferable because a transparent and highly conductive negative electrode can be formed by a coating method.
Moreover, when making the metal electrode side light-transmitting, for example, a conductive material suitable for a negative electrode such as aluminum and an aluminum alloy, silver and a silver compound is made thin with a film thickness of about 1 to 20 nm, and then the positive electrode A light-transmitting negative electrode can be obtained by providing the conductive light-transmitting material film mentioned in the description.

(Hall transport layer)
In the present invention, it is preferable to provide a hole transport layer between the first electrode and the photoelectric conversion layer. Examples of the conductive polymer that forms the hole transport layer include polythiophene, polypyrrole, polyaniline, polyphenylene vinylene, polyphenylene, polyacetylene, polyquinoxaline, polyoxadiazole, polybenzothiadiazole, and polymers having a plurality of these conductive skeletons. Can be mentioned.
Among these, polythiophene and its derivatives are preferable, and polyethylenedioxythiophene and polythienothiophene are particularly preferable. These polythiophenes are usually partially oxidized in order to obtain conductivity. The electrical conductivity of the conductive polymer can be adjusted by the degree of partial oxidation (doping amount). The larger the doping amount, the higher the electrical conductivity. Since polythiophene becomes cationic by partial oxidation, a counter anion for neutralizing the charge is required. Examples of such polythiophenes include polyethylene dioxythiophene (PEDOT-PSS) with polystyrene sulfonic acid as a counter ion and polyethylene dioxythiophene (PEDOT-TsO) with p-toluenesulfonic acid as a counter anion.

(Electron transport layer)
In the present invention, an electron transport layer is preferably provided between the second electrode and the photoelectric conversion layer, a hole transport layer is provided between the first electrode and the photoelectric conversion layer, and the photoelectric conversion layer and the second It is particularly preferable to provide an electron transport layer between the electrodes.
Examples of the electron transport material that can be used for the electron transport layer include an n-type semiconductor compound that is the electron accepting material mentioned in the photoelectric conversion layer, and Electron in Chemical Review, Vol. 107, pages 953 to 1010 (2007). -What is described as Transporting and Hole-Blocking Materials is mentioned. In the present invention, it is preferable to use an inorganic salt or an inorganic oxide. As the inorganic salt, alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride are preferable. Various metal oxides are preferably used as materials for electron transport layers with high stability. For example, lithium oxide, magnesium oxide, aluminum oxide, calcium oxide, titanium oxide, zinc oxide, strontium oxide, niobium oxide, ruthenium oxide, indium oxide Zinc oxide and barium oxide. Of these, relatively stable aluminum oxide, titanium oxide, and zinc oxide are more preferable. The film thickness of the electron transport layer is 0.1 to 500 nm, preferably 0.5 to 300 nm. The electron transport layer can be suitably formed by any of a wet film formation method by coating or the like, a dry film formation method by PVD method such as vapor deposition or sputtering, a transfer method, or a printing method.

  Note that holes generated in the photoelectric conversion layer do not flow to the negative electrode side in the electron transport layer having a HOMO level deeper than the HOMO level of the p-type semiconductor compound used in the photoelectric conversion layer. A hole blocking function having a rectifying effect is provided. More preferably, a material deeper than the HOMO level of the n-type semiconductor compound is used as the electron transport layer. Moreover, it is preferable to use a compound with high electron mobility from the characteristic of transporting electrons. Such an electron transport layer is also referred to as a hole block layer, and it is preferable to use an electron transport layer having such a function. Such materials include phenanthrene compounds such as bathocuproine, n-type semiconductor compounds such as naphthalene tetracarboxylic acid anhydride, naphthalene tetracarboxylic acid diimide, perylene tetracarboxylic acid anhydride, perylene tetracarboxylic acid diimide, and titanium oxide. N-type inorganic oxides such as zinc oxide and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used. Moreover, the layer which consists of a n-type semiconductor compound single-piece | unit used for the photoelectric converting layer can also be used.

(Support)
In the present invention, the support constituting the photovoltaic cell includes at least a first electrode (positive electrode), a photoelectric conversion layer, a second electrode (metal negative electrode), and in a more preferred embodiment, a first electrode (positive electrode), a hole. It is not particularly limited as long as it can form and hold a transport layer, a photoelectric conversion layer, an electron transport layer, and a second electrode (metal negative electrode). For example, glass, plastic film, etc. You can choose.

  In addition, a conventional layer may be applied to provide an easy adhesion layer / undercoat layer, functional layer, recombination layer, other semiconductor layer, protective layer, gas barrier layer, UV absorption layer, antireflection layer, etc. Good.

Although the organic thin film solar cell has been described with respect to the compound including the structural unit represented by the formula (A), in some embodiments, the compound including the structural unit represented by the formula (A) Can be used in any device and system. For example, field effect transistors, photodetectors (eg, infrared photodetectors), photovoltaic detectors, imaging devices (eg, RGB imaging devices for cameras or medical imaging systems), light emitting diodes (LEDs) (eg, Organic LEDs, or infrared or near-infrared LEDs), laser elements, conversion layers (eg, layers that convert visible emission into infrared emission), amplifiers and radiators for telecommunications (eg, fiber dopants), These compounds or polymers can be used in suitable organic semiconductor elements such as storage elements (eg holographic storage elements) as well as electrochromic elements (eg electrochromic displays).

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not construed as being limited thereto.

Example 1
[Creation of organic photoelectric conversion element using polymer P1]
(1) Synthesis of polymer P1 Polymer P1 was synthesized as follows.
-Synthesis | combination of monomer (1-5) Monomer (1-5) was synthesize | combined with the following reaction scheme.

Synthesis of Compound (1-2) In a glass reaction vessel, 5.00 g (17.0 mmol) of the compound (1-1) was dissolved in 40 mL of concentrated sulfuric acid. 2.17 g (25.5 mmol) of sodium nitrate was added and stirred at room temperature for 1 hour. The reaction solution was added to 200 mL of ice water, and the precipitated solid was collected by filtration. The obtained solid was dried under reduced pressure to obtain 5.46 g (16.1 mmol, yield 94.7%) of compound (1-2).

Data MS (EI) of compound (1-2) m / z 336 (M ⁺ ), 338 (M ⁺ +2), 340 (M ⁺ +4)
¹ H-NMR (CDCl ₃ ) δ [ppm] = 8.28 (1H, s)

Synthesis of Compound (1-3) Add 3.00 g (8.85 mmol) of Compound (1-2), 100 mL of acetic acid and 5.93 g of iron powder to a glass reaction vessel, and allow to react at 80 ° C. for 1 hour in an argon atmosphere. It was. The reaction solution was added to 300 mL of water, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure, dissolved in acetone and filtered through celite. The filtrate was concentrated under reduced pressure to obtain 2.50 g (8.09 mmol, yield 91.4%) of compound (1-3).

Data of compound (1-3) MS (EI) m / z 307 (M ⁺ ), 309 (M ⁺ +2), 311 (M ⁺ +4)
¹ H-NMR (CDCl ₃ ) δ [ppm] = 4.64 (2H, s) 7.46 (1H, s)

Synthesis of Compound (1-4) 4.25 g (13.8 mmol) of Compound (1-3), 276 mL of benzene, 35.0 g (138 mmol) of iodine, and 4.86 g (41.3 mmol) of isoamyl nitrite were made into a glass reaction vessel. And reacted at 80 ° C. for 3 hours under an argon atmosphere. After cooling, the mixture was poured into a 10% by mass aqueous sodium sulfite solution and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (hexane: toluene = 3: 1) to obtain 2.22 g (5.30 mmol, yield 38.4%) of compound (1-4).

Data of compound (1-4) MS (EI) m / z 417 (M ⁺ ), 419 (M ⁺ +2), 421 (M ⁺ +4)
¹ H-NMR (CDCl ₃ ) δ [ppm] = 8.24 (1H, s)

Synthesis of Compound (1-5) 0.856 g (2.04 mmol) of Compound (1-4), Tris (dibenzylideneacetone) dipalladium (0) chloroform adduct 106 mg (0.102 mmol), triphenylphosphine 107 mg (0. 408 mmol) and 0.81 g (2.24 mmol) of triethyl (1-ethoxyvinyl) tin were added to a glass reaction vessel, and the inside of the vessel was replaced with argon. Toluene (dehydrated) 15 mL was added and reacted at 110 ° C. for 3 hours under an argon atmosphere. After allowing to cool, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was concentrated under reduced pressure, the concentrate was dissolved in 25 mL of tetrahydrofuran, 15 mL of 1N hydrochloric acid was added, and the mixture was stirred at room temperature for 5 hours. Water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, and concentrated. The concentrate was purified by silica gel column chromatography and recycled GPC to obtain 302 mg (0.899 mmol, yield 44.1%) of compound (1-5).

Data of compound (1-5) MS (EI) m / z 334 (M ⁺ ), 336 (M ⁺ +2), 338 (M ⁺ +4)
¹ H-NMR (CDCl ₃ ) δ [ppm] = 2.79 (3H, s), 7.90 (1H, s)

・ Synthesis of polymer P1

  Compound (1-6) 221 mg (0.281 mmol), Compound (1-5) 90.0 mg (0.268 mmol), Tris (dibenzylideneacetone) dipalladium (0) chloroform adduct 5.55 mg (5.36 μmol), 6.53 mg (21.4 μmol) of o-tolylphosphine was added to a glass reaction vessel, and the inside of the vessel was replaced with argon. Toluene (5.4 mL, dehydrated) was added, and the mixture was reacted at 110 ° C. for 12 hours under an argon atmosphere. After allowing to cool, the reaction solution was poured into methanol for crystallization, and the resulting solid was collected by filtration and dried under reduced pressure. The solid was dissolved in chloroform, filtered through celite, and the solvent was distilled off under reduced pressure. The concentrate was purified by silica gel column chromatography and then subjected to Soxhlet extraction with acetone to remove impurities. The residue was dried under reduced pressure to obtain 155 mg (yield 91.2%) of polymer P1.

Data of polymer P1
¹ H-NMR (CDCl ₃ ) δ [ppm] = 0.79 (18H, m), 0.82-1.46 (20H, br), 1.80-2.20 (4H), 2.36 ( 3H, s), 7.18 (1H, br), 7.94 (1H, Br), 8.06 (1H, br)
GPC (o-dichlorobenzene) Mw = 28 × 10 ³ , Mn = 12 × 10 ³

Preparation of organic photoelectric conversion element (organic thin film solar cell) PEDOT-PSS (Nagase Chemtech PT-100) used as a hole transport layer is spin-coated (5000 rpm) on a glass-ITO substrate that has been cleaned and UV-ozone-treated. And heated at 200 ° C. for 10 minutes. A mixture of 10 mg of polymer P1 and 10 mg of PC ₇₁ BM was dissolved in 1 mL of chlorobenzene containing 3% by weight of 1.8-diiodooctane. The solution was applied onto the PEDOT-PSS layer by spin coating (1000 rpm, 40 seconds) and dried to prepare a photoelectric conversion layer. On the photoelectric conversion layer, an ethanol solution of titanium (IV) tetraisopropoxide (concentration: 4.3 μL / mL) was applied at 4000 rpm, and then aluminum was deposited to form an upper electrode, whereby an element was obtained.

Example 2
[Synthesis of Polymer P2]
(1) Synthesis of polymer P2 Polymer P2 was synthesized as follows.
-Synthesis | combination of monomer (2-1) Monomer (2-1) was synthesize | combined with the following reaction scheme.

Synthesis of Compound (2-1) 336 g (0.800 mmol) of Compound (1-4), 94.2 mg (0.960 mmol) of ethyl propiolate, 11.2 mg (16 μmol) of dichlorobis (triphenylphosphine) palladium, copper iodide 6.10 mg (32 μmol) and 221 mg (1.60 mmol) of potassium carbonate were added to a glass reaction vessel, and the atmosphere was replaced with argon. Tetrahydrofuran (dehydrated) 2 mL was added and reacted at 70 ° C. for 12 hours. After the reaction solution was concentrated, the concentrate was purified by silica gel column chromatography and recycle GPC to obtain 131 mg (0.336 mmol, yield 42.0%) of compound (2-1).

Data of compound (2-1) MS (EI) m / z (M ⁺ ) 388 (M ⁺ ), 390 (M ⁺ +2), 392 (M ⁺ +4)
¹ H-NMR (CDCl ₃ ) δ [ppm] = 1.39 (3H, t, J = 6.9 Hz), 4.36 (2H, q, J = 6.9 Hz), 7.96 (1H, s )

・ Synthesis of polymer P2

  Compound (1-6) 201 mg (0.256 mmol), Compound (2-1) 95 mg (0.244 mmol), Tris (dibenzylideneacetone) dipalladium (0) chloroform adduct 5.05 mg (4.88 μmol), o- 5.94 mg (19.5 μmol) of tolylphosphine was placed in a glass reaction vessel, and the inside of the vessel was purged with argon. Toluene (9.8 mL, dehydrated) was added and reacted at 110 ° C. for 12 hours under an argon atmosphere. After allowing to cool, the reaction solution was poured into methanol for crystallization, and the resulting solid was collected by filtration and dried under reduced pressure. The solid was Soxhlet extracted with acetone to remove impurities, and then extracted with chlorobenzene. After concentrating the chlorobenzene extraction solution, the concentrate was dispersed in methanol and collected by filtration to obtain 5.5 mg of polymer P2 (yield 3.3%).

Data of polymer P2 GPC (o-dichlorobenzene) Mw = 87 × 10 ³ , Mn = 50 × 10 ³

Example 3
[Synthesis of Polymer P3]
Polymer P3 was synthesized as follows.

  Compound (3-1) 174 mg (0.238 mmol), Compound (2-1) 88.5 mg (0.227 mmol), Tris (dibenzylideneacetone) dipalladium (0) chloroform adduct 4.70 mg (4.54 μmol), 5.53 mg (18.2 μmol) of o-tolylphosphine was placed in a glass reaction vessel, and the inside of the vessel was replaced with argon. Toluene 4.5 mL (dehydrated) was added, and the mixture was reacted at 110 ° C. for 12 hours under an argon atmosphere. After allowing to cool, the reaction solution was poured into methanol for crystallization, and the resulting solid was collected by filtration and dried under reduced pressure. The solid was Soxhlet extracted with acetone to remove impurities, and then extracted with chlorobenzene. After concentrating the chlorobenzene extraction solution, the concentrate was dispersed in methanol and collected by filtration to obtain 22 mg of polymer P3 (yield 15.4%).

Example 4
[Creation of organic photoelectric conversion element using polymer P4]
(1) Synthesis of Polymer P4 Polymer P4 was synthesized as follows.
・ Synthesis of monomer (4-4)

Synthesis of Compound (4-3) 2.5 g (35.7 mmol) of Compound (4-1), 8.68 g (39.3 mmol) of Compound (4-2), and 14 mL of N, N-dimethylformamide were placed in a glass reaction vessel. Then, 6.00 g (71.4 mmol) of sodium hydrogen carbonate was added, and the mixture was reacted at 80 ° C. for 6 hours and at 100 ° C. for 16 hours under an argon atmosphere. After allowing to cool, 50 mL of water was added, and the mixture was extracted twice with hexane. The organic layer was dried over anhydrous sodium sulfate and filtered, and the solvent was distilled off under reduced pressure. The concentrate was distilled under reduced pressure to obtain 2.00 g (9.51 mmol, yield 26.6%) of compound (4-3).

Data for compound (4-3) bp 82 ° C./0.75 Torr
¹ H-NMR (CDCl ₃ ) δ [ppm] = 0.85-0.92 (9H, m), 1.10-1.34 (6H, m), 1.42-1.59 (3H, m ), 1.66-1.75 (1H, m), 2.88 (1H, s), 4.17-4.30 (2H, m).

Synthesis of polymer P4

  Compound (3-1) 152 mg (0.209 mmol), Compound (4-4) 100 mg (0.199 mmol), Tris (dibenzylideneacetone) dipalladium (0) chloroform adduct 4.12 mg (3.98 μmol), o- 4.85 mg (15.9 μmol) of tolylphosphine was placed in a glass reaction vessel, and the inside of the vessel was replaced with argon. Toluene 4.0 mL (dehydrated) was added and reacted at 110 ° C. for 12 hours under an argon atmosphere. After allowing to cool, the reaction solution was poured into methanol for crystallization, and the resulting solid was collected by filtration and dried under reduced pressure. The solid was Soxhlet extracted with acetone to remove impurities, and then extracted with chlorobenzene. After concentrating the chlorobenzene extraction solution, the concentrate was dispersed in methanol and collected by filtration to obtain 29 mg (yield 19.6%) of polymer P4.

Data of polymer P4
¹ H-NMR (CDCl ₃ ) δ [ppm] = 0.67 (12H, m), 0.88 (9H, m), 0.90-2.20 (32H, m), 4.41 (2H, br), 8.05 (1H, br), 8.10 (1H, br), 8.61 (1H, br)
GPC (o-dichlorobenzene) Mw = 88 × 10 ³ , Mn = 12 × 10 ³

Preparation of organic photoelectric conversion element (organic thin-film solar cell) Except that 7.5 mg of polymer P4 and 10 mg of PC ₇₁ BM were dissolved in 1 mL of 3% by weight of o-dichlorobenzene containing 1.8-diiodooctane Was performed in the same manner as in Example 1 to obtain an element.

(Evaluation of polymer properties)
A single film was prepared by spin-coating a polymer chlorobenzene or o-dichlorobenzene solution at 1000 rpm, and the HOMO level was measured with an atmospheric photoelectron spectrometer (AC-3, manufactured by Riken Keiki Co., Ltd.). Further, the band gap was obtained from the absorption edge of the single film, the LUMO level was calculated from HOMO + band gap (BG), and the data is shown in Table 1.

(Photocell evaluation)
IPCE characteristics The element characteristics of each organic photoelectric conversion element described above were evaluated using a spectral sensitivity measurement device (CEP-2000 manufactured by Spectrometer Co., Ltd.) in a nitrogen atmosphere (100 mW / cm ² AM1.5G). With the above apparatus, the long wavelength end of the photoelectric conversion wavelength was calculated from the output IPCE spectrum.
Moreover, in order to investigate the difference between lots of organic photoelectric conversion elements, the short-circuit current density (mA / cm ² ) was calculated from the IPCE spectrum for 10 organic photoelectric conversion elements in which each organic photoelectric conversion element was repeatedly created under the same conditions. The variation was evaluated.

The obtained results were evaluated according to the following criteria.
A: Standard deviation less than 0.3 B: Standard deviation 0.3 or more to less than 0.6 C: Standard deviation 0.6 or more

  As shown in Table 1 above, all the polymers of the present invention have a deep LUMO level compared to the polymer of the comparative example. Moreover, it has a narrow band gap and the absorption edge has a long wavelength. Therefore, the organic photoelectric conversion element using the polymer of the present invention can photoelectrically convert light having a longer wavelength. That is, it is useful as a sensor that can photoelectrically convert long-wavelength light. Furthermore, as shown in Table 2 above, the organic photoelectric conversion element using the compound of the present invention has little variation in current value and is excellent in production suitability. From the above, it is clear that the compound of the present invention has preferable characteristics as a P-type organic semiconductor.

7 Transparent Support 10 Photoelectric Conversion Element (Bulk Heterojunction Organic Thin Film Solar Cell)
11 Transparent electrode (first electrode)
12 Counter electrode (second electrode)
21 hole transport layer 22 electron transport layer 3 photoelectric conversion layer 31 p-type semiconductor phase 32 n-type semiconductor phase L light P electric motor (winding machine)

Claims (6)

An organic photoelectric conversion element comprising a first electrode, a second electrode, and a photoelectric conversion layer disposed therebetween, wherein the photoelectric conversion layer contains a polymer represented by the following formula (AB) Organic photoelectric conversion element.

In the formula (AB), X is to table a sulfur atom.
Y ¹ and ^{Y 2} is hydrogen atom, -C≡CR ^y1 or - represents a ^{C (= O) R y 2} .
However, Y ¹ and Y ² are not simultaneously hydrogen atoms.
R ^y1 represents alkoxycarbonyl group, or an acyl group.
R ^y2 represents an A alkyl group or a cycloalkyl group.
Ar represents a group represented by the following formula (2).
n represents an integer of 2 to 2000.

In formula (2), Z ^a represents —C (R ^1Z ) (R ^2Z ) —. Here, R ^1Z and R ^2Z each independently represent an alkyl group. The organic photoelectric conversion element according to claim 1 calculated value of the energy level is not less than -5.3eV the highest occupied molecular orbital of structural units represented by Ar (HOMO). The weight average molecular weight before Kipo Rimmer is from 10,000 to 1,000,000 in an organic photoelectric conversion element according to claim 1 or 2, The photoelectric conversion layer further organic photoelectric conversion device according to any one of claims 1 to 3 containing n-type semiconductor. The organic photoelectric conversion element according to claim 4 , wherein the photoelectric conversion layer has a mixed layer of the polymer and the n-type semiconductor. The organic thin-film solar cell containing the organic photoelectric conversion element of any one of Claims 1-5 .

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