Compounds, compositions, films, photoelectric conversion elements, and CMOS image sensors

Abstract

Provided are a compound that can extend the absorption wavelength while maintaining light absorption properties, a composition, a film, a photoelectric conversion device, and a CMOS image sensor using the compound, in an A-D-A type non-fullerene acceptor material. 【Solution means】A compound represented by the following general formula (1). TIFF2026047588000050.tif29170 In general formula (1), each A is independently a methylidene group substituted with a cyano group or an electron-withdrawing group consisting of 1 to 3 rings, and Q 1 is independently an oxygen atom, a sulfur atom, a selenium atom, N-R 1 or CR 1 =CR 1 where Y 1 ~Y 4 are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group, a and b each independently represent an integer of 1 or more and 3 or less, and R 1 are each independently an aryl group optionally substituted with an alkyl group, an alkyl group, or an alkoxy group, and D is a condensed ring structure of 3 to 9 rings and has one or more specific structures.

Description

[Technical Field]

[0001] The present invention relates to compounds, compositions, films, photoelectric conversion elements, and CMOS image sensors suitable as semiconductor materials used in photoelectric conversion elements. [Background technology]

[0002] CMOS image sensors, which are equipped with photoelectric conversion elements, are used, for example, as image sensors in digital cameras and smartphones. CMOS image sensors include inorganic CMOS image sensors and organic CMOS image sensors, with inorganic CMOS image sensors using silicon photodiodes being the most commonly used. On the other hand, organic CMOS image sensors, by utilizing the high light absorption capacity of organic thin films, can achieve both high resolution and a wide dynamic range, as well as the incorporation of a global shutter that minimizes image distortion. Thus, organic CMOS image sensors are considered to be able to solve the problem of achieving both a high dynamic range and a global shutter, which is difficult for inorganic CMOS image sensors, and therefore there is a demand for materials suitable for organic CMOS image sensors.

[0003] Furthermore, in photoelectric conversion elements (hereinafter also referred to as "inorganic photoelectric conversion elements") used in inorganic CMOS image sensors, inexpensive silicon semiconductors are generally used for photoresponses up to an absorption wavelength of 1000 nm, but very expensive indium gallium arsenide (InGaAs) semiconductors are used when the absorption wavelength exceeds 1000 nm. Therefore, there is a demand for semiconductor materials that are inexpensive and can be used in the long-wavelength region, and organic semiconductor materials (hereinafter also referred to as "organic semiconductor materials") are attracting attention as candidates for such materials.

[0004] In photoelectric conversion elements (hereinafter also referred to as "organic photoelectric conversion elements") incorporated into organic CMOS image sensors, the photoelectric conversion capability and absorption wavelength range can be controlled by the molecular design of the p-type and n-type semiconductor materials used in the organic thin film (photoelectric conversion layer) that constitutes the photoelectric conversion element. In recent years, high photoelectric conversion capability has been reported in elements using non-fullerene acceptors as n-type semiconductor materials. In photoelectric conversion elements using non-fullerene acceptors, the role of controlling the absorption wavelength range is mainly played by the n-type semiconductor material. As n-type semiconductor materials (light-absorbing and electron-transporting materials), compounds having an electron acceptor (A) part and an electron donor (D) part, so-called ADA-type compounds (hereinafter also referred to as "ADA-type non-fullerene acceptor materials"), are known. The absorption wavelength of ADA-type compounds can be designed by reducing the HOMO-LUMO gap by selecting the electron-withdrawing properties of part A and the electron-donating properties of part D.

[0005] ADA-type compounds include a cyclopentadithiophene central donor (D) moiety and a thiophene ring (D) substituted with a specific substituent. 1 ), (D 2 ) with section D sandwiched between, AD 1 -DD 2 -A type compounds are known. For example, Non-Patent Literature 1 discloses a compound represented by the following formula (a) which is an A-D'-D-D'-A type compound, a compound represented by the following formula (b) which is an A-D'-DD”-A type compound, and a compound represented by the following formula (c) which is an AD”-DD”-A type compound. Here, D' represents a thiophene ring substituted with an alkoxy group, and D” represents a thiophene ring substituted with an alkyl group. According to Non-Patent Literature 1, the compound represented by the following formula (a) is said to achieve the longest absorption wavelength. The compound represented by the following formula (a) is a compound in which the alkyl group bonded to the thiophene ring in the D” portion of the compound represented by the following formula (b) or the following formula (c) is replaced with an alkoxy group, which is a strong electron-donating group, to form the D' portion.

[0006] [ka] [Prior art documents] [Non-patent literature]

[0007] [Non-Patent Document 1] Jaewon Lee, et al., “ACS Energy Lett.”, 2019, Vol. 4, pp. 1401-1409. [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] Incidentally, in ADA-type non-fullerene acceptor materials, molecular design guidelines are known to enhance the electron-donating properties of the D portion or the electron-withdrawing properties of the A portion in order to lengthen the absorption wavelength. However, if the electron-donating property of the D-part or the electron-withdrawing property of the A-part is too strong, the frontier orbital may become localized, leading to a dominance of intramolecular charge-transfer excitation and a decrease in absorbance. Since a decrease in absorbance leads to a decrease in photoelectric conversion characteristics, ADA-type compounds used in photoelectric conversion devices require molecular designs that can increase the absorption wavelength to longer wavelengths while maintaining absorbance and strengthening the electron-donating property of the D-part or the electron-withdrawing property of the A-part.

[0009] The present invention aims to provide a compound that can lengthen the absorption wavelength while maintaining absorbency in an ADA-type non-fullerene acceptor material, as well as a composition, film, photoelectric conversion element, and CMOS image sensor using this compound. [Means for solving the problem]

[0010] In view of the above problems, the present inventors have studied compounds capable of extending the absorption wavelength of a photoelectric conversion element. Specifically, in the D part of an A-D’-D-D”-type compound as shown in Non-Patent Document 1, the substituents were studied. As a result, it was found that by substituting the bridgehead position of the D part with an aryl group or heteroaryl group substituted with an amino group, the absorption wavelength can be extended, and the present invention has been completed.

[0011] That is, the present invention has the following aspects. [1] A compound represented by the following general formula (1).

[0012] [Chemical formula]

[0013] In general formula (1), each A is independently a methylidene group substituted with a cyano group or an electron-withdrawing group composed of 1 to 3 rings, and Q 1 is independently an oxygen atom, a sulfur atom, a selenium atom, N-R 1 or CR 1 =CR 1 and Y 1 ~Y 4 are each independently a hydrogen atom, an alkyl group, an alkoxy group or an ester group, a and b each independently represent an integer of 1 or more and 3 or less, and R 1 are each independently an aryl group which may be substituted with an alkyl group, an alkyl group or an alkoxy group, D is a condensed ring structure of 3 to 9 rings, and has one or more structures represented by the following general formula (2).

[0014] [Chemical formula]

[0015] In general formula (2), Ar 1Each of these is independently an alkyl group, an alkyl-substituted aryl group or heteroaryl group, an alkoxy-substituted aryl group or heteroaryl group, an amino-substituted aryl group or heteroaryl group, and at least one Ar 1 This is an aryl group or heteroaryl group substituted with an amino group.

[0016] [2] The compound of [1], represented by the following general formula (3).

[0017] [ka]

[0018] In general formula (3), A is independently a methylidene group substituted with a cyano group or an electron-withdrawing group consisting of 1-3 cyclic structures, and Q 1 Each of these is independently an oxygen atom, a sulfur atom, a selenium atom, and NR 1 or CR 1 =CR 1 And Ar 1 Each of these is independently an alkyl group, an alkyl-substituted aryl group or heteroaryl group, an alkoxy-substituted aryl group or heteroaryl group, an amino-substituted aryl group or heteroaryl group, and at least one Ar 1 is an aryl group or heteroaryl group substituted with an amino group, Ar 2 Each is independently an aryl group or a heteroaryl group, but at least one Ar 2 It is not necessary to have Y 1 ~Y 4 Each of them is independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group, and each of a and b independently represents an integer between 1 and 3, R 1 Each of these is independently an aryl group which may be substituted with an alkyl group, an alkyl group, or an alkoxy group.

[0019] [3] A compound of [1] or [2] represented by any of the following general formulas (1a) to (1i).

[0020] [ka]

[0021] In general formulas (1a) to (1i), A is independently a methylidene group substituted with a cyano group or an electron-withdrawing group consisting of 1 to 3 rings, and Q 1 Each of these is independently an oxygen atom, a sulfur atom, a selenium atom, and NR 1 or CR 1 =CR 1 And Ar 1 Each of these is independently an aryl group or heteroaryl group substituted with an amino group, and Y 1 ~Y 4 Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group, and R 1 Each of these is independently an aryl group which may be substituted with an alkyl group, an alkyl group, or an alkoxy group.

[0022] [4] Q in the general formula (1) above 1 A compound of any of the above [1] to [3], wherein each of the atoms is independently either an oxygen atom or a sulfur atom. [5] Y in the general formula (1) 1 and Y 3 One of them is a hydrogen atom, and the other is an alkyl group, alkoxy group, or ester group, Y 2 and Y 4 A compound of any of the above [1] to [4], wherein one of the atoms is a hydrogen atom and the other is an alkyl group, an alkoxy group, or an ester group. [6] Y in the general formula (1) 3 and Y 4 Y is a hydrogen atom, 1 and Y 2 A compound of any of the above [1] to [5], wherein each of the groups is independently an alkyl group, an alkoxy group, or an ester group. [7] Y in the general formula (1) 3 and Y 4 Y is a hydrogen atom, 1 and Y 2 A compound according to any one of the above [1] to [6], wherein is an alkoxy group. [8] The compound according to any one of [1] to [7] above, wherein A in the general formula (1) is independently a group represented by any one of the following general formulas (3a) to (3u).

[0023] [ka]

[0024] In general formulas (3a) to (3u), Z 1 ~Z 7 Each of these is independently an oxygen atom, a sulfur atom, or a dicyanomethylene group, and R 3 Each is independently a hydrogen atom or an alkyl group, and R 4 Each is independently a methyl group or a trifluoromethyl group, and X 1 Each is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, Ar is an aryl group, and V is independently a CX 2 or nitrogen atom, Q 2 Each of these is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or a CR atom. 5 =CR 5 Q 3 X is a sulfur atom, a carbon atom substituted with an alkyl or aryl group, a nitrogen atom substituted with an alkyl or aryl group, a silicon atom substituted with an alkyl or aryl group, or a germanium atom substituted with an alkyl or aryl group. 2 Each of these is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, and R 5 Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group.

[0025] [9] Z in the above general formulas (3a) to (3u) 1 is a dicyanomethylene group, Z 2 This is an oxygen atom, Z 3 is a sulfur atom or a dicyanomethylene group, Z 4 and Z 5 One of them is an oxygen atom, and the other is a dicyanomethylene group, Z 6 and Z7 The compound of [8] wherein is an oxygen atom.

[10] Any of the compounds [1] to [9] above, represented by the following general formula (4).

[0026] [ka]

[0027] In general formula (4), A is independently a methylidene group substituted with a cyano group or an electron-withdrawing group consisting of 1 to 3 rings, and W 2 Each of them is independently a sulfur atom or CH=CH, and R 2 Each of these is independently an alkyl group, an aryl group which may be substituted with an alkyl group or an alkoxy group, and Y 1 ~Y 4 Each of the elements is independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group, and each of the elements a and b independently represents an integer between 1 and 3.

[0028]

[11] W in the general formula (4) 2 CH=CH, R 2 is an alkyl group, Y 3 and Y 4 Y is a hydrogen atom, 1 and Y 2 The compound of

[10] wherein is an alkoxy group.

[12] The compound of

[10] or

[11] , wherein A in the general formula (4) is independently a group represented by the following general formulas (3m), (3n), (3o), or (3s).

[0029] [ka]

[0030] In general formulas (3m), (3n), (3о) and (3s), Z 4 and Z 5 Each of these is independently an oxygen atom, a sulfur atom, or a dicyanomethylene group, and X 1Each of these is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, and each of these is independently a CX 2 or nitrogen atom, X 2 Each of these is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group.

[0031]

[13] Z in the general formulas (3m), (3n), (3o), and (3s) 4 and Z 5 One of them is an oxygen atom, and the other is a dicyanomethylene group, X 1 Each of these is independently a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, and V is CX 2 or nitrogen atom, X 2 The compound of

[12] wherein is a hydrogen atom.

[14] A in the general formula (4) is a group represented by the general formula (3o), and Z in the general formula (3o) 4 and Z 5 One of them is an oxygen atom, and the other is a dicyanomethylene group, X 1 Each of these is independently a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, and V is CX 2 X 2 The compound of

[12] or

[13] wherein is a hydrogen atom.

[15] A composition containing any of the compounds described in [1] to

[14] above.

[16] A membrane containing any of the compounds described in [1] to

[14] above.

[17] A photoelectric element comprising the film described in

[16] .

[18] A CMOS image sensor equipped with the photoelectric conversion element described in

[17] above. [Effects of the Invention]

[0032] According to the present invention, it is possible to provide a compound that can lengthen the absorption wavelength while maintaining absorbency in an ADA-type non-fullerene acceptor material, as well as a composition, film, photoelectric conversion element, and CMOS image sensor using this compound. [Brief explanation of the drawing]

[0033] [Figure 1] It is a diagram for explaining the HOMO orbital and LUMO orbital of compound (X). [Figure 2] It is a diagram for explaining the HOMO orbital and LUMO orbital of compound (Y). [Figure 3] It is a cross-sectional view schematically showing an example of an embodiment of the photoelectric conversion element of the present invention.

Embodiments for Carrying Out the Invention

[0034] The preferred embodiments of the invention are given below to explain the present invention in more detail. However, the following description is an example of the embodiments of the present invention, and the present invention is not limited to the following description as long as it does not exceed the gist thereof. In this specification, "~" indicating a numerical range means including the numerical values described before and after it as the lower limit value and the upper limit value. Also, in the present invention, the wavy line in the general formula represents the bonding position with an adjacent group.

[0035] [Compound] The compound of the present invention is a compound represented by the following general formula (1) (hereinafter, also referred to as "compound (1)". The same applies hereinafter.).

[0036] [Chemical Formula]

[0037] In general formula (1), each A is independently a methylidene group substituted with a cyano group or an electron-withdrawing group consisting of 1 to 3 rings, and Q 1 is each independently an oxygen atom, a sulfur atom, a selenium atom, N-R 1 or CR 1 =CR 1 and Y 1 ~Y 4 are each independently a hydrogen atom, an alkyl group, an alkoxy group or an ester group, a and b each independently represent an integer of 1 or more and 3 or less, and R 1Each is independently an aryl group which may be substituted with an alkyl group, an alkyl group or an alkoxy group, D is a tricyclic to nonacyclic bridged ring structure, and has one or more structures represented by the following general formula (2).

[0038]

Chemical formula

[0039] In general formula (2), Ar 1 is each independently an alkyl group, an aryl group or heteroaryl group substituted with an alkyl group, an aryl group or heteroaryl group substituted with an alkoxy group, or an aryl group or heteroaryl group substituted with an amino group, and at least one Ar 1 [[ID=1⑥]]is an aryl group or heteroaryl group substituted with an amino group.

[0040] As compound (1), a compound represented by the following general formula (3) (compound (3)) is preferable.

[0041]

Chemical formula

[0042] In general formula (3), A is each independently a methylidene group substituted with a cyano group or an electron-withdrawing group consisting of monocyclic to tricyclic rings, and Q 1 is each independently an oxygen atom, a sulfur atom, a selenium atom, N-R 1 or CR 1 =CR 1 and Ar 1 is each independently an alkyl group, an aryl group or heteroaryl group substituted with an alkyl group, an aryl group or heteroaryl group substituted with an alkoxy group, or an aryl group or heteroaryl group substituted with an amino group, and at least one Ar 1 is an aryl group or heteroaryl group substituted with an amino group, Ar 2 is each independently an aryl group or heteroaryl group, but at least one Ar 2 may not be present, and Y1 ~Y 4 Each of them is independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group, and each of a and b independently represents an integer between 1 and 3, R 1 Each of these is independently an aryl group which may be substituted with an alkyl group, an alkyl group, or an alkoxy group.

[0043] The compounds of the present invention are AD as shown in Non-Patent Document 1. 1 -DD 2 -In the D portion of the type A compound, the bridgehead position of the D portion is substituted with an aryl group or heteroaryl group substituted with an amino group, thereby enabling the absorption wavelength to be extended.

[0044] The reason why the compound of the present invention can lengthen the absorption wavelength of the photoelectric conversion element is not clear, but it is presumed to be as follows. In conventional technology, amino groups are known not only to be strong electron-donating groups, but also to perturb the π-conjugated system of the entire molecule by distributing the HOMO on the amino group. For this reason, amino groups have not been used solely for the purpose of electron-donating without the distribution of the HOMO orbital. For example, when calculating the molecular orbital structure of compound (X) shown below using Wavefunction's Spartan 20 software, the CAM-B3LYP / 6-31G(d) method yields two degenerate HOMO levels, either distributed across the entire molecule or on the amino group, as shown in Figure 1. In this case, during the light absorption process, a charge-transfer transition occurs from the amino group with HOMO orbitals to the π skeleton of the main chain with LUMO orbitals, resulting in a decrease in oscillator intensity and consequently a decrease in absorbance.

[0045] [ka]

[0046] On the other hand, when the compound (Y) shown below was calculated using the CAM-B3LYP / 6-31G(d) method as a model structure, it was found that the distribution of the HOMO on the amino group can be almost suppressed by extending the π-conjugation by linking an aryl group or heteroaryl group to the π skeleton of the main chain, as shown in Figure 2. Thus, in the compound of the present invention, the amino group functions only as a strong electron-donating group with respect to the π skeleton of the main chain, resulting in π-π * It is presumed that this method allowed for the expression of only the sex transition, resulting in both the long-wavelength absorption of the material and high absorbance.

[0047] [ka]

[0048] In the general formula (1) above, D is a 3- to 9-ring fused ring structure and has one or more structures represented by the general formula (2) above. The fused ring structure of D is 3 to 9 rings, and from the viewpoint of solubility, 3 to 8 rings are preferred, and 3 to 6 rings are more preferred. The ring forming the fused ring structure of D is preferably an aromatic hydrocarbon ring or an aromatic heterocycle, which may be substituted. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring. The aromatic heterocycle is preferably a thiophene ring, a furan ring, a selenofene ring, a pyrrole ring, or a silole ring, more preferably a thiophene ring or a furan ring, and even more preferably a thiophene ring.

[0049] In the general formulas (1) and (3) above, A is independently a methylidene group substituted with a cyano group or an electron-withdrawing group consisting of 1 to 3 rings. A may be the same or different, but it is preferable that it be the same. A is preferably a group represented by any of the following general formulas (3a) to (3u), more preferably a group represented by the following general formulas (3m), (3n), (3o), or (3s), even more preferably a group represented by the following general formulas (3o) or (3s), and most preferably a group represented by the following general formula (3o).

[0050] [ka]

[0051] In general formulas (3a) to (3u), Z 1 ~Z 7 Each of these is independently an oxygen atom, a sulfur atom, or a dicyanomethylene group, and R 3 Each is independently a hydrogen atom or an alkyl group, and R 4 Each is independently a methyl group or a trifluoromethyl group, and X 1 Each is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, Ar is an aryl group, and V is independently a CX 2 or nitrogen atom, Q 2 Each of these is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or a CR atom. 5 =CR 5 Q 3 X is a sulfur atom, a carbon atom substituted with an alkyl or aryl group, a nitrogen atom substituted with an alkyl or aryl group, a silicon atom substituted with an alkyl or aryl group, or a germanium atom substituted with an alkyl or aryl group. 2 Each of these is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, and R 5 Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group.

[0052] In the general formulas (3a) to (3u), Z 1 ~Z 7 Each of these is independently an oxygen atom, a sulfur atom, or a dicyanomethylene group. Z 1 ~Z 7 It is thought that the presence of an oxygen atom, a sulfur atom, or a dicyanomethylene group allows it to act as an electron-withdrawing group in the acceptor moiety. Z in the general formulas (3c), (3l), (3t) 1 It is preferable that it is a dicyanomethylene group. In the above general formula (3d), Z 2It is preferably an oxygen atom, Z 3 Preferably, this is a sulfur atom or a dicyanomethylene group. Z in the general formula (3m), (3n), (3o), (3s) 4 and Z 5 Preferably, one of the atoms is an oxygen atom and the other is a dicyanomethylene group. In the above general formula (3p), Z 5 It is preferable that this is an oxygen atom or a dicyanomethylene group. In the above general formula (3r), Z 6 and Z 7 It is preferable that it is an oxygen atom.

[0053] In the general formulas (3a) to (3u), R 3 Each of these is independently a hydrogen atom or an alkyl group. 4 Each of these is independently a methyl group or a trifluoromethyl group. R 3 The number of carbon atoms in the alkyl group is preferably small from the standpoint of the material's conductivity. Therefore, R 3 The number of carbon atoms in the alkyl group is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, and particularly preferably 10 or less. 3 The alkyl group preferably has 1 or more carbon atoms, and more preferably 2 or more carbon atoms. R 3 The alkyl group may be linear or cyclic. If the alkyl group is linear, it may be linear or branched. R 3 They may be the same or different, but it is preferable that they be the same. R 4 They may be the same or different, but it is preferable that they be the same.

[0054] In the general formulas (3o), (3m), (3n), (3p), (3q), (3s) and (3u), X 1Each of these is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, and is preferably a fluorine atom, a chlorine atom, or a cyano group. 1 They may be the same or different, but it is preferable that they be the same.

[0055] Ar is an aryl group. The number of carbon atoms in the aryl group is preferably low from the viewpoint of the material's conductivity. Therefore, the number of carbon atoms in the aryl group is preferably 18 or less, more preferably 12 or less, even more preferably 10 or less, and particularly preferably 6. The lower limit of the number of carbon atoms in the aryl group is 6. The aryl group may or may not have substituents. That is, the aryl group is either unsubstituted or substituted. Examples of substituents include alkyl groups, alkoxy groups, ester groups, hydroxyl groups, amino groups, cyano groups, fluorine atoms, and chlorine atoms. In the general formulas (3e) and (3r) mentioned above, the Ar is preferably a phenyl group.

[0056] In the above general formulas (3a) to (3u), V is independently CX 2 Or it is a nitrogen atom. X 2 Each of these is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group. That is, V is a carbon atom, a carbon atom in which the hydrogen atom bonded to the carbon atom is replaced by a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, or a nitrogen atom. X 2 They may be the same or different, but it is preferable that they be the same. X 2 It is preferable that it is a hydrogen atom. Note X 2 CX when it is a hydrogen atom 2 This is also called an "unsubstituted carbon atom." 2 When CX is a fluorine atom, chlorine atom, bromine atom, or cyano group 2 These are also called "substituted carbon atoms." In the above general formulas (3o), (3p), (3q), (3s), and (3u), V is CX 2 or nitrogen atom, X 2 It is preferable that V is a hydrogen atom, that is, an unsubstituted carbon atom or nitrogen atom.

[0057] In the above general formulas (3a) to (3u), Q 2 Each of these is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or a CR atom. 5 =CR 5 That is the case. R 5 Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group. R 5 The number of carbon atoms in the alkyl group is preferably small from the standpoint of the material's conductivity. Therefore, R 5 The number of carbon atoms in the alkyl group is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, and particularly preferably 10 or less. 5 The alkyl group preferably has 2 or more carbon atoms, more preferably 4 or more, and even more preferably 6 or more. R 5 The alkyl group may be linear or cyclic. If the alkyl group is linear, it may be linear or branched.

[0058] R 5 The number of carbon atoms in the alkoxy group is preferably small in terms of the conductivity of the material. Therefore, R 5 The number of carbon atoms in the alkoxy group is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, and particularly preferably 10 or less. 5 The alkoxy group preferably has 2 or more carbon atoms, more preferably 4 or more, and even more preferably 6 or more. The alkoxy group has a structure in which an alkyl group is bonded to an oxygen atom, and the alkyl group bonded to the oxygen atom may be linear or cyclic. If the alkyl group bonded to the oxygen atom is linear, it may be linear or branched. Q in the general formulas (3c), (3l), (3t) 2 It is preferable that it be a sulfur atom.

[0059] R 5 Examples of ester groups include monovalent groups having an ester bond. Specifically, examples include the group represented by the following general formula (i). -COO-R 7 ...(i) In general formula (i), R 7 It is an alkyl group or an aryl group. R 7 As for the alkyl group, the R 5 The alkyl groups mentioned earlier are cited as examples in the explanation. R 7 The alkyl group may be linear or cyclic. If the alkyl group is linear, it may be linear or branched.

[0060] R 7 Examples of aryl groups include the aryl groups previously exemplified in the description of Ar. R 7 The aryl group may or may not have substituents. That is, R 7 The aryl group is either unsubstituted or substituted. Examples of substituents include alkyl groups, alkoxy groups, ester groups, hydroxyl groups, and amino groups.

[0061] In the above general formulas (3a) to (3u), Q 3 This is a sulfur atom, a carbon atom substituted with an alkyl or aryl group, a nitrogen atom substituted with an alkyl or aryl group, a silicon atom substituted with an alkyl or aryl group, or a germanium atom substituted with an alkyl or aryl group. A carbon atom substituted with an alkyl or aryl group is represented by the following general formula (ii). A nitrogen atom substituted with an alkyl or aryl group is represented by the following general formula (iii). A silicon atom substituted with an alkyl or aryl group is represented by the following general formula (iv). A germanium atom substituted with an alkyl or aryl group is represented by the following general formula (v).

[0062] [ka]

[0063] In general formulas (ii) to (v), R 8 ~R 14 Each of these is independently an alkyl group or an aryl group. R 8 ~R 14 As for the alkyl group, the R 5 The alkyl groups mentioned earlier are cited as examples in the explanation. R 8 ~R 14 Examples of aryl groups include the aryl groups previously exemplified in the description of Ar. R 8 ~R 14 The aryl group may or may not have substituents. That is, R 8 ~R 14 The aryl group is either unsubstituted or substituted. Examples of substituents include alkyl groups, alkoxy groups, ester groups, hydroxyl groups, and amino groups.

[0064] In terms of the ease of synthesis of compound (1), Q 3 In this material, it is preferable that the two alkyl or aryl groups possessed by the carbon atom, silicon atom, and germanium atom are identical. From the standpoint of synthesis cost, Q in the general formula (3t) 3 It is preferably a sulfur atom, a carbon atom substituted with an alkyl or aryl group, a nitrogen atom substituted with an alkyl or aryl group, or a silicon atom substituted with an alkyl or aryl group, more preferably a sulfur atom or a carbon atom substituted with an alkyl or aryl group, and even more preferably a sulfur atom. From the perspective of increasing solubility, Q in the general formula (3t) 3Preferably, the atom is a carbon atom substituted with an alkyl or aryl group, a nitrogen atom substituted with an alkyl or aryl group, a silicon atom substituted with an alkyl or aryl group, or a germanium atom substituted with an alkyl or aryl group.

[0065] A is more preferably a group represented by any of the general formulas (3m), (3n), (3o), and (3s). In particular, Z in the general formulas (3m), (3n), (3o), and (3s) 4 and Z 5 One of them is an oxygen atom, and the other is a dicyanomethylene group, X 1 is a fluorine atom, a chlorine atom, or a cyano group, and V is CX 2 or nitrogen atom, X 2 Preferably, it is a hydrogen atom. In particular, A is more preferably a group represented by the general formula (3o) or (3s), and even more preferably a group represented by the general formula (3o), and Z in the general formula (3o). 4 and Z 5 One of them is an oxygen atom, and the other is a dicyanomethylene group, X 1 Each of these is independently a fluorine atom, a chlorine atom, or a cyano group, and V is CX 2 or nitrogen atom, X 2 It is even more preferable that Z in the general formula (3o) is a hydrogen atom. In particular, in one aspect, 4 and Z 5 One of them is an oxygen atom, and the other is a dicyanomethylene group, X 1 Each of these is independently a fluorine atom, a chlorine atom, or a cyano group, and V is CX 2 X 2 It is particularly preferable that Z in the general formula (3o) is a hydrogen atom. 4 and Z 5 One of them is an oxygen atom, and the other is a dicyanomethylene group, X 1 The group is a cyano group, and V is CX 2 or nitrogen atom, X 2It is particularly preferable that the atom is a hydrogen atom. Among these, the Z atom in the general formula (3o) is particularly preferable. 4 and Z 5 One of them is an oxygen atom, and the other is a dicyanomethylene group, X 1 The group is a cyano group, and V is CX 2 X 2 It is most preferable that the atom is a hydrogen atom.

[0066] In the general formulas (1) and (3), Q 1 Each of these is independently an oxygen atom, a sulfur atom, a selenium atom, and NR 1 or CR 1 =CR 1 Therefore, Q 1 Each of these atoms is independently preferably an oxygen atom or a sulfur atom, with a sulfur atom being more preferable. R 1 Each of these is independently an aryl group which may be substituted with an alkyl group, an alkyl group, or an alkoxy group. R 1 The alkyl groups are, respectively, the R 5 The alkyl groups mentioned earlier are cited as examples in the explanation. R 1 The alkoxy group is the aforementioned R 5 The alkoxy group, which was exemplified earlier in the explanation, is one example. R 1 Examples of aryl groups include the aryl groups previously exemplified in the description of Ar. R 1 They may be the same or they may be different, but it is preferable that they be the same. Also, R 1 These elements may join together to form a ring.

[0067] In the above general formulas (2) and (3), Ar 1 Each of these is independently an alkyl group, an alkyl-substituted aryl group or heteroaryl group, an alkoxy-substituted aryl group or heteroaryl group, an amino-substituted aryl group or heteroaryl group, and at least one Ar 1is an aryl group or heteroaryl group substituted with an amino group. From the viewpoint of enhancing the electron-donating properties of the D portion, Ar 1 Preferably, these are aryl groups or heteroaryl groups substituted with amino groups. Here, the amino group may have at least one of its two hydrogen atoms substituted with a substituent, and an amino group in which both hydrogen atoms are substituted is preferred. In the present invention, even when at least one of the two hydrogen atoms is substituted with a substituent, it is still referred to as an "amino group". Examples of substituents include alkyl groups, aryl groups, and heteroaryl groups having 1 to 30 carbon atoms. The aryl and heteroaryl groups may be further substituted with alkyl or alkoxy groups having 1 to 30 carbon atoms. Among these, from the viewpoint of balancing solubility and device performance, phenyl groups which may be substituted with alkyl groups, alkyl groups, or alkoxy groups having 1 to 30 carbon atoms are preferred, and alkyl groups having 2 to 12 carbon atoms are more preferred. An amino group in which at least one of the two hydrogen atoms is replaced by an alkyl group is also specifically called an "alkylamino group." Examples of alkylamino groups include alkylamino groups having 1 to 30 carbon atoms, such as methylamino group, dimethylamino group, diethylamino group, ethylmethylamino group, dihexylamino group, dioctylamino group, and di(2-ethylhexyl)amino group.

[0068] Ar 1 Examples of the aryl group include the aryl groups previously exemplified in the description of Ar, with phenyl or naphthyl groups being preferred, and phenyl groups being even more preferred. Ar 1 Examples of heteroaryl groups include those produced by removing one hydrogen atom from any ring atom of a heteroarene such as thiophene, and heteroaryl groups containing an oxygen atom, a sulfur atom, or a selenium atom are preferred. 1The number of carbon atoms in the heteroaryl group is preferably 17 or less, more preferably 11 or less, even more preferably 9 or less, and particularly preferably 4. 1 The lower limit of the number of carbon atoms in the heteroaryl group is 4. From the viewpoint of ease of synthesis, a thienyl group is preferred.

[0069] In the above general formula (3), Ar 2 Each of these is independently an aryl group or a heteroaryl group. Ar 2 Examples of aryl groups include the aryl groups previously exemplified in the explanation of Ar, as well as phenyl groups and Ar 1 A cyclopentadienyl group having the is preferred. Ar 2 The heteroaryl group is the Ar 1 In the explanation, the heteroaryl group mentioned earlier is cited, and the thienyl group is preferred. From the standpoint of ease of synthesis, Ar 2 However, it is preferable that the phenyl group, the cyclopentadienyl group having Ar1, or the thienyl group are fused together in a 2- to 4-cyclic manner, either identically or differently. Compound (3) contains at least one Ar 2 It does not have to have. From the viewpoint of solubility, compound (3) has at least one Ar 2 Preferably, it does not have both Ar 2 It is more preferable that it does not have. In another embodiment, in terms of extending the absorption wavelength, compound (3) has both Ar 2 It is preferable that it has [this feature].

[0070] In the above general formulas (1) and (3), Y 1 ~Y 4 Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group. Y 1 ~Y 4 As for the alkyl group, the R 5 The alkyl groups mentioned earlier are cited as examples in the explanation. Y 1~Y 4 The alkyl group may be linear or cyclic. If the alkyl group is linear, it may be linear or branched. In terms of ease of synthesis, it is preferable that the alkyl group is linear or branched in which the carbon atoms bonded to the ring structure are primary carbon atoms. In terms of solubility of the material, it is preferable that the alkyl group is branched in which the carbon atoms bonded to the ring structure are primary carbon atoms, or that the alkyl group is linear, branched, or cyclic in which the carbon atoms bonded to the ring structure are secondary carbon atoms. In terms of ease of synthesis and solubility, it is even more preferable that the alkyl group is branched in which the carbon atoms bonded to the ring structure are primary carbon atoms.

[0071] Y 1 ~Y 4 The alkoxy group is the aforementioned R 5 The alkoxy group, which was exemplified earlier in the explanation, is one example. An alkoxy group has a structure in which an alkyl group is bonded to an oxygen atom, and the alkyl group bonded to the oxygen atom may be linear or cyclic. When the alkyl group bonded to the oxygen atom is linear, it may be linear or branched. In terms of ease of synthesis, it is preferable that the carbon atom bonded to the oxygen atom is a linear or branched alkyl group in which the carbon atom is a primary carbon atom. In terms of solubility of the material, it is preferable that the carbon atom bonded to the oxygen atom is a branched alkyl group in which the carbon atom is a primary carbon atom, or a linear, branched, or cyclic alkyl group in which the carbon atom bonded to the oxygen atom is a secondary carbon atom, more preferably a linear, branched, or cyclic alkyl group in which the carbon atom bonded to the oxygen atom is a secondary carbon atom, and even more preferably a linear or branched alkyl group in which the carbon atom bonded to the oxygen atom is a secondary carbon atom.

[0072] Y 1 ~Y 4 As for the ester group, the above R 5 In the explanation, the ester group exemplified earlier, that is, the group represented by the general formula (i) above, is an example. In the above general formula (i), R 7The alkyl group may be linear or cyclic. If the alkyl group is linear, it may be linear or branched. In terms of ease of synthesis, it is preferable that the alkyl group is linear or branched in which the carbon atom bonded to the oxygen atom is a primary carbon atom. In terms of solubility of the material, it is preferable that the alkyl group is branched in which the carbon atom bonded to the oxygen atom is a primary carbon atom, or linear, branched, or cyclic in which the carbon atom bonded to the oxygen atom is a secondary carbon atom, more preferably linear, branched, or cyclic in which the carbon atom bonded to the oxygen atom is a secondary carbon atom, and even more preferably linear or branched in which the carbon atom bonded to the oxygen atom is a secondary carbon atom.

[0073] Y 1 ~Y 4 They may be the same or different. In particular, Y is chosen because it is easy to form a lamellar structure in a film obtained using the compound of the present invention. 1 and Y 3 One of them is a hydrogen atom, and the other is an alkyl group, alkoxy group, or ester group, Y 2 and Y 4 Preferably, one of the atoms is a hydrogen atom, and the other is an alkyl group, an alkoxy group, or an ester group. Furthermore, in terms of extending the absorption wavelength, Y 1 and Y 2 Each of these is independently an alkyl group, an alkoxy group, or an ester group, Y 3 and Y 4 It is preferable that Y is a hydrogen atom. 1 and Y 2 Each of them is independently an alkoxy group, Y 3 and Y 4 It is more preferable that it is a hydrogen atom. In terms of ease of synthesis, Y 1 and Y 2 It is more preferable that they be identical.

[0074] In the general formulas (1) and (3) above, a and b each independently represent integers between 1 and 3. From the viewpoint of ease of composition, a and b are each preferably integers between 1 and 2, and more preferably 1.

[0075] As for compound (1), in one aspect, a compound represented by any of the following general formulas (1a) to (1i) is preferred. In another aspect, a compound represented by the following general formula (4) is preferred. In the following specification, the compound represented by general formula (1a) is also referred to as "compound (1a)". The same applies to compounds represented by other general formulas.

[0076] [ka]

[0077] In general formulas (1a) to (1i), A is independently a methylidene group substituted with a cyano group or an electron-withdrawing group consisting of 1 to 3 rings, and Q 1 Each of these is independently an oxygen atom, a sulfur atom, a selenium atom, and NR 1 or CR 1 =CR 1 And R 1 Each of these is independently an alkyl group, an aryl group which may be substituted with an alkyl group or an alkoxy group, and Ar 1 Each of these is independently an aryl group or heteroaryl group substituted with an amino group, and Y 1 ~Y 4 Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group.

[0078] [ka]

[0079] In general formula (4), A is independently a methylidene group substituted with a cyano group or an electron-withdrawing group consisting of 1 to 3 rings, and W 2 Each of them is independently a sulfur atom or CH=CH, and R 2Each of these is independently an alkyl group, an aryl group which may be substituted with an alkyl group or an alkoxy group, and Y 1 ~Y 4 Each of the elements is independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group, and each of the elements a and b independently represents an integer between 1 and 3.

[0080] In general formulas (1a) to (1i) and general formula (4), A is the same as A in general formula (1). In particular, A is preferably a group that is independently represented by any of the general formulas (3m), (3n), (3o), and (3s), and Z in general formulas (3m), (3n), (3o), and (3s). 4 and Z 5 One of them is an oxygen atom, and the other is a dicyanomethylene group, X 1 is a fluorine atom, a chlorine atom, or a cyano group, and V is CX 2 or nitrogen atom, X 2 It is more preferable that it be a hydrogen atom. In particular, A is more preferably a group represented by the general formula (3o) or (3s), and even more preferably a group represented by the general formula (3o), and Z in the general formula (3o). 4 and Z 5 One of them is an oxygen atom, and the other is a dicyanomethylene group, X 1 Each of these is independently a fluorine atom, a chlorine atom, or a cyano group, and V is CX 2 or nitrogen atom, X 2 It is even more preferable that Z in the general formula (3o) is a hydrogen atom. In particular, in one aspect, 4 and Z 5 One of them is an oxygen atom, and the other is a dicyanomethylene group, X 1 Each of these is independently a fluorine atom, a chlorine atom, or a cyano group, and V is CX 2 X 2 It is particularly preferable that Z in the general formula (3o) is a hydrogen atom. 4 and Z 5 One of them is an oxygen atom, and the other is a dicyanomethylene group, X 1The group is a cyano group, and V is CX 2 or nitrogen atom, X 2 It is particularly preferable that the atom is a hydrogen atom. Among these, the Z atom in the general formula (3o) is particularly preferable. 4 and Z 5 One of them is an oxygen atom, and the other is a dicyanomethylene group, X 1 The group is a cyano group, and V is CX 2 X 2 It is most preferable that the atom is a hydrogen atom.

[0081] Q in the above general formulas (1a) to (1i) 1 Q in the general formula (1) is 1 It is similar to that. In the above general formulas (1a) to (1i), Ar 1 This is Ar in the general formula (2) above. 1 It is similar to that. In the above general formulas (1a) to (1i) and the above general formula (4), Y 1 ~Y 4 Y in the general formula (1) is 1 ~Y 4 It is similar to that.

[0082] In the general formula (4) above, W 2 Each of these is independently a sulfur atom or CH=CH. From the viewpoint of ease of synthesis, W 2 CH=CH is preferable. R in the general formula (4) above 2 Each of these is independently an alkyl group, an aryl group which may be substituted with an alkyl group or an alkoxy group, or a heteroaryl group which may be substituted with an alkyl group or an alkoxy group. R 2 The alkyl groups are, respectively, the R 5 The alkyl groups mentioned earlier are cited as examples in the explanation. R 2 The alkoxy group is the aforementioned R 5 The alkoxy group, which was exemplified earlier in the explanation, is one example. R 2 Examples of aryl groups include the aryl groups previously exemplified in the description of Ar. R 2 Examples of heteroaryl groups include the aryl groups previously exemplified in the description of Ar. The values ​​of a and b in the aforementioned general formula (4) are the same as those of a and b in the aforementioned general formula (1).

[0083] Compound (4) is preferably a compound in which A in general formula (4) is independently represented by the group (3o) or (3s), and Z in general formulas (3o) and (3s). 4 and Z 5 Each of these is independently an oxygen atom, a sulfur atom, or a dicyanomethylene group, and X 1 Each of these is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, and each of V is independently CX 2 or nitrogen atom, X 2 Compounds in which each is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group are more preferred, and Z in the general formulas (3o) and (3s) 4 and Z 5 Compounds in which one of the atoms is an oxygen atom and the other is a dicyanomethylene group are even more preferred. In particular, A in the general formula (4) is a group represented by the general formula (3o), and Z in the general formula (3o) is a group represented by the general formula (3o). 4 and Z 5 One of them is an oxygen atom, and the other is a dicyanomethylene group, X 1 Each of these is independently a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, and V is CX 2 X 2 Compounds in which the atom is a hydrogen atom are particularly preferred.

[0084] Specific examples of compound (1) include the compound represented by the following formula, but compound (1) is not limited to these.

[0085] [ka]

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] The method for producing compound (1) is not particularly limited, but as an example of a method for producing compound (1), the method for producing compound (A) shown in the following formula will be specifically explained. In compound (A), Y is the same as Y in compound (1). 1 ~Y 4 It corresponds to one of the above, and X in compound (A) is X in the general formula (3o) above. 1 This corresponds to Z in compound (A), and Z in compound (A) is Z in the general formula (3o) above. 4 or Z 5 It corresponds to this.

[0092] [ka]

[0093] First, the compound (B), which is a 3-substituted thiophene, is reacted with lithium diisopropylamide (LDA) in a reaction solvent, and then N,N-dimethylformamide is reacted further to obtain the compound (C) shown below.

[0094] [ka]

[0095] The preferred ratio of raw materials is 0.9 to 1.5 equivalents of LDA and 0.9 equivalents or more of N,N-dimethylformamide relative to compound (B). N-formylpiperidine may be used instead of N,N-dimethylformamide. The reaction solvent is not particularly limited as long as it does not react with the starting compound. Examples include saturated aliphatic hydrocarbon solvents such as hexane; ether solvents such as tetrahydrofuran (THF), diethyl ether, cyclopentyl methyl ether, and methyl t-butyl ether; and aromatic hydrocarbon solvents such as toluene and xylene. The reaction temperature is preferably -78 to 50°C. The reaction time is preferably 10 minutes to 12 hours after adding LDA, and 10 minutes to 12 hours after adding N,N-dimethylformamide.

[0096] Compound (B) may be synthesized by known methods, or a commercially available product may be used. For example, compound (B), in which Y is an alkoxy group, the alkyl group bonded to the oxygen atom in the alkoxy group is linear, branched, or cyclic, and the carbon atom bonded to the oxygen atom is a secondary carbon atom, can be obtained by reacting commercially available 3-methoxythiophene with a secondary alcohol in a reaction solvent. Here, the secondary alcohol may be synthesized by known methods, or a commercially available product may be used. The preferred ratio of raw materials is 0.9 to 1.5 equivalents of secondary alcohol and 0.1 to 0.5 equivalents of sodium bisulfate relative to 3-methoxythiophene. The reaction solvent is not particularly limited as long as it does not react with the starting compound; for example, aromatic hydrocarbon solvents such as toluene and xylene can be used. The reaction temperature is preferably between room temperature and reflux temperature. The reaction time is preferably 1 to 24 hours.

[0097] Next, compound (C) and N-bromosuccinimide (NBS) are reacted in a reaction solvent to obtain compound (D) of the following formula.

[0098]

Chemical formula

[0099] The charging ratio of the raw materials is preferably 0.9 to 1.2 equivalents of NBS with respect to compound (C), and more preferably 0.9 to 1.05 equivalents. Note that bromine may be used instead of NBS. The reaction solvent is not particularly limited as long as it does not react with the raw material compounds. Examples thereof include saturated aliphatic hydrocarbon solvents such as hexane; ether solvents such as tetrahydrofuran (THF); aromatic hydrocarbon solvents such as toluene and xylene; halogen solvents such as chloroform; and N,N-dimethylformamide. The reaction temperature is preferably -78 to 50°C. The reaction time is preferably 10 minutes to 24 hours after adding NBS.

[0100] In the production of compound (A), compound (E) of the following formula may be used instead of compound (D). Compound (E) can be obtained, for example, as follows.

[0101] That is, first, compound (B) and lithium diisopropylamide (LDA) are reacted in a reaction solvent, and then 1,2-dibromo-1,1,2,2-tetrachloroethane is further reacted to obtain compound (D') of the following formula.

[0102]

Chemical formula

[0103] The charging ratio of the raw materials is preferably 0.9 to 1.5 equivalents of LDA with respect to compound (B), and preferably 0.9 equivalents or more of 1,2-dibromo-1,1,2,2-tetrachloroethane. The reaction solvent is not particularly limited as long as it does not react with the starting compound. Examples include saturated aliphatic hydrocarbon solvents such as hexane; ether solvents such as tetrahydrofuran (THF), diethyl ether, cyclopentyl methyl ether, and methyl t-butyl ether; and aromatic hydrocarbon solvents such as toluene and xylene. The reaction temperature is preferably -78 to 50°C. The reaction time is preferably 10 minutes to 12 hours after adding LDA, and 10 minutes to 12 hours after adding 1,2-dibromo-1,1,2,2-tetrachloroethane.

[0104] Next, compound (D') and lithium diisopropylamide (LDA) are reacted in a reaction solvent, and then N,N-dimethylformamide is further reacted to obtain compound (E) shown in the formula below.

[0105] [ka]

[0106] The preferred ratio of raw materials is 0.9 to 1.5 equivalents of LDA and 0.9 equivalents or more of N,N-dimethylformamide relative to compound (D'). N-formylpiperidine may be used instead of N,N-dimethylformamide. The reaction solvent is not particularly limited as long as it does not react with the starting compound. Examples include saturated aliphatic hydrocarbon solvents such as hexane; ether solvents such as tetrahydrofuran (THF), diethyl ether, cyclopentyl methyl ether, and methyl t-butyl ether; and aromatic hydrocarbon solvents such as toluene and xylene. The reaction temperature is preferably -78 to 50°C. The reaction time is preferably 10 minutes to 12 hours after adding LDA, and 10 minutes to 12 hours after adding N,N-dimethylformamide.

[0107] Next, in the reaction solvent, a cross-coupling reaction is carried out between at least one of compound (D) and compound (E) and compound (F) of the following formula to obtain compound (G) of the following formula. The method for producing compound (G) is not particularly limited, but for example, compound (G) can be produced by a method similar to the method described in literature such as Adv. Energy Mater., 2018, Vol. 8, p. 1801212.; J. Mater. Chem. C, 2020, Vol. 8, p. 15175.; ACS Energy Lett., 2019, Vol. 4, p. 1401.; and Japanese Patent Publication No. 2022-030124. An example of specific production conditions is as follows.

[0108] [ka]

[0109] The type of cross-coupling reaction between compound (D) and compound (E) and compound (F) is not particularly limited, and can be carried out by Stille coupling, Suzuki coupling, Negishi coupling, Kumada coupling, Hiyama coupling, etc. The cross-coupling reaction may be carried out in the presence of a catalyst such as a palladium catalyst, nickel catalyst, or copper catalyst. For example, when compound (D) or compound (E) is reacted with compound (F) by a Stille coupling reaction, the charging ratio of the raw materials is preferably 1.9 to 3.0 equivalents of compound (D) or compound (E) relative to compound (F). Furthermore, it is preferable to use a palladium catalyst in the Stille coupling reaction, and the palladium content in the catalyst is preferably 0.1 to 50 mol%. The reaction solvent is not particularly limited as long as it does not react with the starting compounds, and examples thereof include saturated aliphatic hydrocarbon solvents such as hexane; ether solvents such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran (THF), 1,4-dioxane; aromatic hydrocarbon solvents such as toluene, xylene; N,N-dimethylformamide (DMF), dimethyl sulfoxide, N-methyl-2-pyrrolidone and the like. The reaction temperature is preferably from 20°C to the reflux temperature of the reaction solvent. The reaction time is preferably 1 to 24 hours.

[0110] Compound (F) may be synthesized by referring to known methods (for example, Org. Lett. 2013, Vol. 15, p. 3102; Polym. Chem., 2013, Vol. 4, p. 5351-5360; J. Phys. Chem. C, 2011, Vol. 15, p. 2398-2405; Chem. Commun., 2012, Vol. 48, p. 11130-11132), or a commercially available product may be used. Further, a compound (F) corresponding to the cross-coupling reaction (where "L" in compound (F) is an alkyltin group, boric acid, boric acid ester group, zinc halide, magnesium halide, or silyl group, etc.) may be used. For example, a compound (F) in which L is an alkyltin group can be obtained by reacting commercially available 4H-cyclopenta[2,1-b:3,4-b']dithiophene with commercially available 4-bromo-N,N-dihexylaniline, and then reacting the resulting reaction product with an alkyltin compound such as trimethyltin chloride.

[0111]

Chemical formula

[0112] Next, in the reaction solvent, compound (G) and compound (I) are reacted in the presence of an acid catalyst or a base catalyst to obtain compound (A). The method for producing compound (A) is not particularly limited, but for example, under acid-catalyzed conditions, compound (A) can be produced by a method similar to that described in Japanese Patent Publication No. 2022-511781; Japanese Patent Publication No. 2023-500815, etc. On the other hand, under base-catalyzed conditions, compound (A) can be produced by a method similar to that described in Adv. Energy Mater., 2018, Vol. 8, p. 1801212.; J. Mater. Chem. C, 2020, Vol. 8, p. 15175.; ACS Energy Lett., 2019, Vol. 4, p. 1401., etc. An example of specific production conditions is as follows.

[0113] [ka]

[0114] Here, compound (I) can be synthesized by known methods (for example, Japanese Patent Publication No. 2022-511781, Japanese Patent Publication No. 2023-500815, Adv. Mater., 2017, Vol. 29, p. 1703080; Angew. Chem. Int. Ed., 2017, Vol. 56, p. 3045; J. Am. Chem. Soc., 2017, Vol. 139, pp. 1336-1343, etc.). Examples of acid catalysts include p-toluenesulfonic acid hydrate (PTSA·H2O). Examples of base catalysts include pyridine and piperidine. The preferred ratio of raw materials is 1.9 to 10 equivalents of compound (I) relative to compound (G). The preferred amount of acid catalyst is 2.1 to 11 equivalents. The preferred amount of base catalyst is 1 to 10% by mass relative to the reaction solvent. The reaction solvent is not particularly limited as long as it does not react with the starting compound. Examples include alcoholic solvents such as methanol and ethanol; aromatic hydrocarbon solvents such as toluene and xylene; and halogenated solvents such as chloroform. These may also be used in mixtures. The reaction temperature is preferably between room temperature and reflux temperature. The reaction time is preferably between 10 minutes and 24 hours.

[0115] In this way, compound (A) can be produced. Here, X in compound (A) is the same as X in the general formula (3o). 1 Thus, Z in compound (A) is Z in the general formula (3o). 4 or Z 5 This is the result.

[0116] The compounds of the present invention are suitable as n-type semiconductor materials (light-absorbing and electron-transporting materials) used in photoelectric conversion elements because they can maintain absorbance while extending the absorption wavelength. The applications of the compounds of the present invention are not limited to those described above. For example, since the compounds of the present invention also have excellent luminescence properties, they can be used in bioimaging, organic EL, near-infrared luminescent dyes for wavelength conversion films and compositions, etc.

[0117] [Composition] The composition of the present invention contains the above-described compound (1). Compound (1) may be used alone, or two or more compounds may be used in any proportion and combination. The content of compound (1) in the composition of the present invention is not particularly limited. However, when the composition of the present invention is used for forming the photoelectric conversion layer (active layer) of a photoelectric conversion element, it is preferable that the content of compound (1) be high in terms of light absorption, and low in terms of carrier balance. Therefore, the content of compound (1) in the composition of the present invention is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more, relative to the total amount (total mass) of all components other than the solvent. Furthermore, the content of compound (1) in the composition of the present invention is preferably 100% by mass or less, more preferably 90% by mass or less, even more preferably 75% by mass or less, and particularly preferably 60% by mass or less, relative to the total amount (total mass) of all components other than the solvent.

[0118] The composition of the present invention may further contain a solvent. A composition containing compound (1) and a solvent is suitable as an ink (active layer forming composition) for forming the photoelectric conversion layer (active layer) of a photoelectric conversion element. As a solvent, a liquid that does not react with compound (1) but dissolves compound (1) is preferred, such as aromatic hydrocarbon solvents like toluene and xylene; or halogenated solvents like dichloromethane and chloroform. If the composition of the present invention contains a solvent, the solvent may be used alone or two or more solvents in any proportion or combination. If the composition of the present invention contains a solvent, the content of compound (1) in the composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total mass of the composition of the present invention. Furthermore, the content of compound (1) is preferably 5.0% by mass or less, more preferably 3.5% by mass or less, and even more preferably 2.0% by mass or less, based on the total mass of the composition of the present invention.

[0119] When the composition of the present invention is used as an active layer forming composition, it is preferable that the composition further contains a p-type semiconductor material in addition to compound (1). The p-type semiconductor material is not limited to those used in the photoelectric conversion layer of organic photoelectric conversion elements, but examples include polymers described in the literature (ACS Energy Lett., 2019, Vol. 4, p. 1401. and Adv. Optical Mater., 2022, Vol. 10, p. 2200747.). When the composition of the present invention contains a p-type semiconductor material, the p-type semiconductor material may be used alone or two or more types may be used in any proportion and combination. The mass ratio of compound (1) to the p-type semiconductor material (compound (1) / p-type semiconductor material) is preferably 0.1 or higher, more preferably 0.5 or higher, and even more preferably 0.75 or higher. Furthermore, the mass ratio of compound (1) to the p-type semiconductor material is preferably 3.0 or lower, more preferably 2.0 or lower, and even more preferably 1.5 or lower.

[0120] The composition of the present invention may further contain components other than compound (1), a p-type semiconductor material, and a solvent (optional components), as long as they do not impair the effects of the present invention. Optional components include, for example, 1,8-diiodoctane and 1-chloronaphthalene. If the composition of the present invention contains optional components, these optional components may be used alone or in any combination of two or more components in any proportion. When an optional component is included, a higher content of the optional component is preferable in that the effects of including the optional component are more likely to manifest. On the other hand, a higher content of compound (1) is preferable in that the composition of the present invention is more likely to maintain suitable physical properties as a photoelectric conversion element. Therefore, when the composition of the present invention includes an optional component, the content of the optional component is preferably 0.1% by mass or more, and more preferably 0.3% by mass or more, relative to the total amount (total mass) of all components other than the solvent in the composition of the present invention. Furthermore, the content of the optional component is preferably 2.0% by mass or less, and more preferably 1.0% by mass or less, relative to the total amount (total mass) of all components other than the solvent in the composition of the present invention.

[0121] The compositions of the present invention can be obtained, for example, by dissolving compound (1) in a solvent and, if necessary, a p-type semiconductor material and one or more optional components. Furthermore, by removing the solvent from the obtained composition, a solvent-free composition of the present invention can be obtained.

[0122] The composition of the present invention is suitable as an ink (active layer forming composition) for forming the photoelectric conversion layer (active layer) of a photoelectric conversion element.

[0123] [film] The film of the present invention is a film containing the above-mentioned compound (1), and is also called an organic thin film. The film of the present invention can be obtained, for example, by removing the solvent from the composition of the present invention, which contains the solvent as described above. Specifically, it can be obtained by coating the composition of the present invention onto a substrate and then drying it. The content of compound (1) in the membrane is the same as the content of compound (1) relative to the total amount (total mass) of all components other than the solvent in the composition of the present invention described above. That is, the content of compound (1) relative to the total mass of the membrane is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more. Furthermore, the content of compound (1) relative to the total mass of the membrane is preferably 100% by mass or less, more preferably 90% by mass or less, even more preferably 75% by mass or less, and particularly preferably 60% by mass or less.

[0124] In terms of light absorption, a thicker film thickness is preferable. On the other hand, in terms of external quantum efficiency (EQE) when the film of the present invention is used as the photoelectric conversion layer (active layer) of a photoelectric conversion element, a thinner film thickness is preferable. Therefore, the film thickness is preferably 10 nm or more, and more preferably 100 nm or more. Furthermore, the film thickness is preferably 1000 nm or less, and more preferably 500 nm or less. The film thickness can be adjusted by the amount of composition applied to the substrate.

[0125] The method of applying the composition is not particularly limited, but examples include brush application, bar coating, spray coating, dip coating, spin coating, curtain coating, etc. The drying temperature after application is preferably 20 to 250°C. The drying time is preferably between 10 minutes and 5 hours.

[0126] The film of the present invention is suitable as a photoelectric conversion layer (active layer) of a photoelectric conversion element.

[0127] [Photoelectric conversion element] The photoelectric conversion element of the present invention is an element comprising the film of the present invention as described above, and is also called an organic photoelectric conversion element. Specifically, the photoelectric conversion element of the present invention comprises the film of the present invention as a photoelectric conversion layer (active layer). The structure of the photoelectric conversion element can adopt the structure of a known organic photoelectric conversion element. For example, one can refer to the description in Japanese Patent Application Publication No. 2007-324587. The specific structure is not particularly limited, but examples include an element having a laminated structure in which a photoelectric conversion layer (active layer) is sandwiched between a pair of electrodes.

[0128] An example of the photoelectric conversion element of the present invention will be described below with reference to Figure 1. Please note that, for the sake of clarity, the drawings used in the following description may show enlarged versions of key features, and the dimensional ratios of each component may differ from those of the actual components. Furthermore, the materials, dimensions, etc., exemplified in the following description are merely examples, and the present invention is not limited to them. It can be implemented with appropriate modifications without altering its essence.

[0129] The photoelectric conversion element 10 shown in Figure 1 has a structure in which a transparent electrode 12, a hole transport layer 13, a photoelectric conversion layer 14, an electron transport layer 15, and a metal electrode 16 are stacked in this order on a transparent substrate 11. Furthermore, the hole transport layer 13 and the electron transport layer 15 may be swapped in their positions. That is, the photoelectric conversion element may have a structure in which a transparent electrode, an electron transport layer, a photoelectric conversion layer (active layer), a hole transport layer, and a metal electrode are stacked on a transparent substrate in that order.

[0130] The transparent substrate 11 may be a substrate having an average transmittance of 80% or more in visible light of 450 nm or higher. Examples of materials for forming the transparent substrate 11 include glass; plastics such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, and polyethylene sulfide.

[0131] The transparent electrode 12 is an electrode having an average transmittance of 80% or more in visible light of 450 nm or higher. The material used to form the transparent electrode 12 is not particularly limited as long as it can form the transparent electrode 12, but examples include tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), tungsten-doped indium oxide (IWO), zinc-aluminum oxide (AZO), indium oxide (In2O3), zinc oxide (ZnO), titanium oxide (TiO2), and the like.

[0132] The metal electrode 16 is an electrode that is paired with the transparent electrode 12. The material constituting the metal electrode 16 is not particularly limited, but examples include metals or alloys thereof such as gold, platinum, silver, aluminum, nickel, titanium, magnesium, calcium, barium, sodium, chromium, copper, and cobalt. The metal electrode 16 is preferably a transparent electrode or a reflective electrode. That is, the photoelectric conversion element is preferably a laminated structure in which a photoelectric conversion layer (active layer) is sandwiched between a pair of electrodes (transparent or metal), and more preferably a laminated structure in which an electron transport layer, a photoelectric conversion layer (active layer), and a hole transport layer are sandwiched between a pair of electrodes (transparent or metal). In the case of a pair of transparent electrodes, the materials forming the electrodes may be of the same type or different types. The film thickness of the metal electrode 16 is not particularly limited, but approximately 10 nm is preferred from the viewpoint of improving transparency. If transparency is not required, a thickness of 40 nm or more is preferred, and 100 nm or more is more preferred, considering durability and other factors.

[0133] The method for forming the transparent electrode 12 and the metal electrode 16 is not particularly limited, but they can be formed by, for example, a dry process such as vacuum deposition or sputtering; or a wet process using conductive ink or the like.

[0134] There are no particular restrictions on the components and manufacturing methods when a hole transport layer 13 and an electron transport layer 15 are provided, and known technologies can be used. For example, components and manufacturing methods described in public documents such as International Publication No. 2013 / 171517, International Publication No. 2013 / 180230, or Japanese Patent Publication No. 2012-191194 can be used.

[0135] The photoelectric conversion layer 14 is a layer that absorbs light and separates electric charges. The photoelectric conversion layer 14 of the photoelectric conversion element of the present invention is a layer containing the compound (1) of the present invention described above. More specifically, it is the film of the present invention described above. The photoelectric conversion layer 14 can be formed, for example, by applying the above-described composition of the present invention to a layer that will be beneath the photoelectric conversion layer 14, such as the hole transport layer 13, and then drying it.

[0136] The photoelectric conversion element 10 can be obtained, for example, by forming a transparent electrode 12, a hole transport layer 13, a photoelectric conversion layer 14, an electron transport layer 15, and a metal electrode 16 on a transparent substrate 11 in this order.

[0137] The photoelectric conversion element of the present invention has a photoelectric conversion layer 14 containing compound (1), which allows for the absorption wavelength to be increased while maintaining absorbance, and thus provides high sensor sensitivity on the longer wavelength side.

[0138] [CMOS image sensor] The CMOS image sensor of the present invention comprises the photoelectric conversion element of the present invention described above. The structure of the CMOS image sensor can adopt the structure of a known CMOS image sensor. For example, one can refer to the description in Japanese Patent Application Publication No. 2021-57422, and is not particularly limited. More specifically, an example of a CMOS image sensor is one in which metal wiring, the photoelectric conversion element of the present invention, a color filter, and a microlens are stacked in this order on a substrate such as a silicon substrate. [Examples]

[0139] The present invention will be described in more detail below with reference to examples, but the following examples are not intended to limit the scope of the present invention.

[0140] [Synthesis of compound (1a-3o-1)] Compound (B-1) shown below was synthesized using the same method as described in the publicly available literature (New J. Chem., 2020, Vol. 44, p. 8032). Using the obtained compound (B-1), compound (C-1) was synthesized using the same method as described in the publicly available literature (J.Mater.Chem.A, 2020, Vol. 8, p. 5163). Compound (B-1) 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CDCl3, ppm): δ7.14(dd,1H), 6.74(dd,1H), 6.21(dd,1H), 4. 00(quin,1H), 1.71-1.58(m,4H), 1.50-1.28(m,6H), 0.95(t,3H), 0.88(t,3H). Compound (C-1) 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CDCl3, ppm): δ9.81(s,1H), 7.40(dd,1H), 6.73(m,1H), 4.0 3(quin,1H), 1.72-1.57(m,4H), 1.45-1.29(m,6H), 0.96(t,3H), 0.87(t,3H).

[0141] [ka]

[0142] Next, 4.99 g (20.7 mmol) of compound (C-1) was dissolved in 40 mL of acetonitrile. 3.73 g (20.9 mmol) of N-bromosuccinimide was slowly added. After stirring at room temperature for 1 hour, water and hexane were added, and the organic layer was washed three times with water. After drying over anhydrous sodium sulfate, the compound was purified by silica gel chromatography to obtain the compound (yield 98%). 1 1H-NMR analysis confirmed that the obtained compound was compound (D-1). 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CDCl3, ppm): δ9.70(s,1H), 7.33(s,1H), 4.10(quin,1H), 1.73-1.59(m,4H), 1.45-1.29(m,6H), 0.96(t,3H), 0.88(t,3H).

[0143] [ka]

[0144] Separately, potassium tert-butoxide (KOtBu, 0.33g, 2.96mmol) was added to a mixture of commercially available 4H-cyclopenta[2,1-b:3,4-b']dithiophene (0.220g, 1.23mmol), commercially available 4-bromo-N,N-dihexylaniline (1.01g, 2.96mmol), tris(dibenzylideneacetone)dipalladium(0)(Pd2(dba)3, 0.057g, 0.06mmol), triphenylphosphine (PPh3, 0.032g, 0.12mmol), and anhydrous toluene (5mL), and the mixture was stirred at 100°C for 8 hours. Water was added to the resulting mixture, and after extraction with ethyl acetate, the organic layer was dried over sodium sulfate. The organic layer was filtered, and the solvent was removed from the resulting solution. The crude product was purified by silica gel chromatography to obtain a viscous solid compound (yield 10%). 1 1H-NMR analysis confirmed that the obtained compound was compound (F-1-1) shown in the formula below. 1The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CD2Cl2, ppm): δ7.10(d,2H), 6.95(d,2H), 6.92(dd,4H), 6.38(dd,4H), 3.10(dd,8H), 1.48-1.38(m,8H), 1.19(m,24H), 0.79(m,12H).

[0145] [ka]

[0146] Compound (F-1-1) (0.13 g, 0.19 mmol) was dissolved in tetrahydrofuran (THF, 7 mL) and cooled in a dry ice acetone bath. Lithium diisopropylamide (0.41 mL, 1.01 M, 0.42 mmol) was slowly added dropwise. After stirring for 0.5 hours, trimethyltin chloride THF solution (0.16 mL, 0.42 mmol, 2.65 M) was added dropwise and stirred for 1 hour. After raising the temperature, water was added, and then ethyl acetate was added to extract the organic layer. After drying the extract over sodium sulfate, the solvent of the solution, which had been removed by filtration to obtain the solid compound (F-1) shown below. Compound (F-1) was not purified and was used directly in the next reaction.

[0147] Next, compound (F-1) and compound (D-1) (0.12 g, 0.39 mmol) were reacted, referring to the method described in Japanese Patent Publication No. 2022-030124. After removing the solvent under reduced pressure, the mixture was purified by silica gel column chromatography to obtain a solid compound (yield 85%). 1 1H-NMR analysis confirmed that the obtained compound was compound (G-1). 1 The H-NMR measurement data is shown below. 1H-NMR (400MHz, solvent: CD2Cl2, ppm): δ9.78(s,2H), 7.48(s,2H), 7.43(s,2H), 7.09(d,4H), 6.54(d,4H), 4.34( t,2H), 3.23(t,8H), 1.90-1.72(m,8H), 1.59-1.44(m,10H), 1.38-1.24(m,34H), 1.05(t,6H), 0.92(m,18H).

[0148] [ka]

[0149] Compound (I-1) shown below was synthesized separately using the method described in a publicly available document (Angew. Chem. Int. Ed., 2017, Vol. 56, p. 3045). 0.070 g (0.06 mmol) of compound (G-1) and 0.033 g (0.14 mmol) of compound (I-1) were placed in a reaction vessel, dissolved in 2.0 mL of chloroform, and then 0.08 mL of pyridine was added and the mixture was stirred at 60°C for 3 hours. After cooling, the solvent was removed by distillation, and the resulting crude product was purified using silica gel chromatography to obtain 0.086 g of the solid compound (yield 91%). 1 1H-NMR analysis confirmed that the obtained solid was compound (1a-3o-1). 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CD2Cl2, ppm): δ8.70(s,2H), 8.53(dd,2H), δ7.70-7.66(m,4H), 7.57(s,2H), 7.13(d,4H), 6.58(d,4H) , 4.47(t,2H), 3.26(t,8H), 1.93-1.77(m,8H), 1.63-1.47(m,10H), 1.40-1.25(m,34H), 1.08(t,6H), 0.94-0.90(m,18H).

[0150] [ka]

[0151] [Synthesis of compound (1a-3o-2)] Compound (G-1) was synthesized in the same manner as compound (1a-3o-1). Compound (I-2) shown below was synthesized separately using the same method as described in a publicly available document (Adv. Mater., 2017, Vol. 29, p. 1703080). 0.062 g (0.05 mmol) of compound (G-1) and 0.033 g (0.13 mmol) of compound (I-2) were placed in a reaction vessel, 1.8 mL of chloroform was added and stirred to dissolve, then 0.07 mL of pyridine was added and the mixture was stirred at 60°C for 3 hours. After cooling, the solvent was removed by distillation and the resulting crude product was purified using silica gel chromatography to obtain 0.073 g of the solid compound (yield 83%). 1 1H-NMR analysis confirmed that the obtained compound was compound (1a-3o-2). 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CD2Cl2, ppm): δ8.61(s,2H), 8.57(s,2H), δ7.79(s,2H), 7.57(s,2H), 7.39(br.s,2H), 7.01(d,4H), 6.67(d ,4H), 4.34(t,2H), 3.13(t,8H), 1.80-1.65(m,8H), 1.51-1.33(m,10H), 1.29-1.20(m,34H), 0.95(t,6H), 0.82-0.77(m,18H).

[0152] [ka]

[0153] [Synthesis of compound (1a-3o-3)] Compound (G-1) was synthesized in the same manner as compound (1a-3o-1). Separately, compound (I-3) of the following formula was synthesized by the method described in Japanese Patent Publication No. 2023-500815. 0.085 g (0.07 mmol) of compound (G-1) and 0.53 g (0.22 mmol) of compound (I-3) were placed in a reaction vessel, dissolved in 1.1 mL of toluene and 2.1 mL of ethanol, and then 0.062 g (0.33 mmol) of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at 65°C for 3 hours. After cooling, the organic layer was extracted with chloroform and water, the extract was dried over sodium sulfate, and the solvent was removed from the solution after removing the solids by filtration. The resulting crude product was purified using silica gel chromatography to obtain 0.103 g of the solid compound (yield 87%). 1 1H-NMR analysis confirmed that the obtained compound was compound (1a-3o-3). 1 The H-NMR measurement data is shown below. 1 H-NMR (400MHz, solvent: CD2Cl2, ppm): δ8.59(s,2H), 8.52(s,2H), δ7.76(s,2H), 7.56(s,2H), 7.43(br.s,2H), 7.04(d,4H), 6.58(d ,4H), 4.34(t,2H), 3.13(t,8H), 1.80-1.62(m,8H), 1.50-1.31(m,10H), 1.27-1.12(m,34H), 0.94(t,6H), 0.84-0.76(m,18H).

[0154] [ka]

[0155] [Synthesis of compound (N-1)] The compound (N-1) shown below was synthesized using the method described in the publicly available literature (ACS Energy Lett., 2019, Vol. 4, pp. 1401-1409).

[0156] [ka]

[0157] [Example 1] <Absorption Spectrum Measurement> 1.33 mg of compound (1a-3o-1) was weighed out and dissolved in 500 mL of spectroscopic chloroform, and 1.64 × 10⁻⁶ was measured. -6 A solution of M was prepared. The obtained solution was placed in an absorption cell, and the absorption spectrum was measured using a UV-Vis-Near-Infrared spectrophotometer (manufactured by JASCO Corporation, product name "V-770"). The maximum absorption wavelength and absorbance were confirmed from the obtained spectrum. The molar extinction coefficient was calculated from the absorbance and solution concentration. The results are shown in Table 1. The values ​​shown in Table 1 are based on the maximum absorption wavelength and molar extinction coefficient of compound (N-1) used in Comparative Example 1 described later.

[0158] [Example 2] A solution of the same concentration as in Example 1 was prepared, and the same measurements and results analysis were performed, except that compound (1a-3o-3) was used. The results are shown in Table 1.

[0159] [Comparative Example 1] A solution of the same concentration as in Example 1 was prepared, except for the use of compound (N-1), and the same measurements and results analysis were performed.

[0160] [Table 1]

[0161] As is clear from the results in Table 1, it was found that in Examples 1 and 2, the band gap was significantly narrower compared to Comparative Example 1, while the molar extinction coefficient was maintained. These results demonstrate that compound (1) of the present invention has the effect of suppressing CT absorption while enabling long-wavelength absorption.

[0162] [Example 3] <Manufacturing of photoelectric conversion elements> (Formation of hole transport layer) The surface of an ITO substrate, on which a transparent conductive film of indium tin oxide (ITO) was patterned onto a glass substrate as a transparent substrate and used as a transparent electrode, was treated with ozone for 10 minutes using an ultraviolet ozone cleaning machine (manufactured by Japan Laser Electronics Co., Ltd., product name "NL-UV253"). Separately, a composition for forming a hole transport layer was prepared by dissolving 60 mg of a polytriarylamine compound (hole transport polymer) represented by the following formula (H-1) in 1 mL of anisole. A hole transport layer-forming composition was spin-coated onto a transparent electrode of an ozone-treated ITO substrate at a rotation speed of 1000 rpm for 60 seconds, and then heated and dried at 240°C for 30 minutes to form a hole transport layer with a thickness of 300 nm.

[0163] [ka]

[0164] (Formation of the photoelectric conversion layer) As the p-type semiconductor material, a compound represented by the following formula (P-1) (weight-average molecular weight 80,000) was used. Compound (1a-3o-1) was used as the n-type semiconductor material. An active layer-forming composition, which is an organic semiconductor ink, was prepared by dissolving 0.11 g of p-type semiconductor material and 0.13 g of n-type semiconductor material in 9.68 mL of o-xylene. In the active layer-forming composition, the mass ratio of the n-type semiconductor material to the p-type semiconductor material (n-type semiconductor material / p-type semiconductor material) was 1.2. The solid content concentration of the active layer-forming composition was 25 mg / mL. Using the obtained active layer-forming composition, the hole transport layer was spin-coated at 1000 rpm per minute, followed by heat treatment (thermal annealing) at 120°C for 10 minutes to form a photoelectric conversion layer (active layer) consisting of an organic thin film with a thickness of 150 nm.

[0165] [ka]

[0166] (Formation of electron transport layer and metal electrode) A 40 nm thick electron transport layer was formed on a photoelectric conversion layer by depositing C60 fullerene (manufactured by Frontier Carbon Co., Ltd.) as an electron transport material in a vacuum. Next, aluminum was deposited in a vacuum as a metal electrode material on the electron transport layer to form a 100 nm thick metal electrode, thereby obtaining a photoelectric conversion element. The obtained photoelectric conversion elements were evaluated as follows.

[0167] <Rating> (Evaluation of external quantum efficiency (EQE)) The photoelectric conversion element was irradiated with a xenon lamp under a -5V applied voltage, and the external quantum efficiency was measured using an action spectrum measuring device (PEC-S20, manufactured by Pexel Technologies, Inc.).

[0168] (Measurement of dark current) The dark current was measured using a photoelectric conversion element when -5V was applied. A high-precision current measuring device (Keithley Instruments, product name "Keithley 6482") was used to measure the dark current.

[0169] [Examples 4 and 5] A photoelectric conversion element was manufactured in the same manner as in Example 3, except that compound (1a-3o-2) or compound (1a-3o-3) was used as the n-type semiconductor material, and the external quantum efficiency was measured when -5V was applied. Furthermore, the dark current of the obtained photoelectric conversion element was measured when -5V was applied, in the same manner as in Example 3.

[0170] Based on the above evaluations, the photoelectric conversion elements obtained in Examples 3 to 5 were confirmed to have photoelectric conversion capabilities with light ranging from 400 nm to 1100 nm. [Industrial applicability]

[0171] The compounds of the present invention can maintain absorbance while extending the absorption wavelength, making them useful as semiconductor materials for use in photoelectric conversion devices. [Explanation of Symbols]

[0172] 10 Photoelectric conversion element 11 Transparent substrate 12 Transparent electrode 13 Hole transport layer 14 Photoelectric conversion layer 15 Electron transport layer 16 Metal electrode

Claims

1. A compound represented by the following general formula (1). 【Chemistry 1】 In general formula (1), A is independently a methylidene group substituted with a cyano group or an electron-withdrawing group consisting of 1 to 3 rings, and Q １ Each of these is independently an oxygen atom, a sulfur atom, a selenium atom, and N-R １ or CR １ =CR １ Y １ ~Y ４ Each of them is independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group, and each of a and b independently represents an integer between 1 and 3, R １ Each of these is an aryl group which may be substituted with an alkyl group, an alkyl group or an alkoxy group, and D is a 3- to 9-cyclic fused ring structure which has one or more structures represented by the following general formula (2). 【Chemistry 2】 In the general formula (2), Ar １ is each independently an alkyl group, an aryl group or heteroaryl group substituted with an alkyl group, an aryl group or heteroaryl group substituted with an alkoxy group, or an aryl group or heteroaryl group substituted with an amino group, and at least one Ar １ is an aryl group or heteroaryl group substituted with an amino group.

2. The compound according to claim 1, represented by the following general formula (3). 【Transformation 3】 In general formula (3), A is independently a methylidene group substituted with a cyano group or an electron-withdrawing group consisting of 1 to 3 rings, and Q １ Each of these is independently an oxygen atom, a sulfur atom, a selenium atom, and N-R １ or CR １ =CR １ And Ar １ Each of these is independently an alkyl group, an alkyl-substituted aryl group or heteroaryl group, an alkoxy-substituted aryl group or heteroaryl group, an amino-substituted aryl group or heteroaryl group, and at least one Ar １ Ar is an aryl group or heteroaryl group substituted with an amino group. ２ Each is independently an aryl group or a heteroaryl group, but at least one Ar ２ It is not necessary to have Y １ ~Y ４ Each of them is independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group, and each of a and b independently represents an integer between 1 and 3, R １ Each of these is independently an aryl group which may be substituted with an alkyl group, an alkyl group, or an alkoxy group.

3. The compound according to claim 1, represented by any of the following general formulas (1a) to (1i). 【Chemistry 4】 In general formulas (1a) to (1i), A is independently a methylidene group substituted with a cyano group or an electron-withdrawing group consisting of 1 to 3 rings, and Q １ Each of these is independently an oxygen atom, a sulfur atom, a selenium atom, and N-R １ or CR １ =CR １ And Ar １ Each of these is independently an aryl group or heteroaryl group substituted with an amino group, and Y １ ~Y ４ Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group, and R １ Each of these is independently an aryl group which may be substituted with an alkyl group, an alkyl group, or an alkoxy group.

4. Q in the general formula (1) above １ The compound according to claim 1, wherein each of them is independently an oxygen atom or a sulfur atom.

5. Y in the general formula (1) １ and Y ３ One of them is a hydrogen atom, and the other is an alkyl group, an alkoxy group, or an ester group, Y ２ and Y ４ The compound according to claim 1, wherein one of the atoms is a hydrogen atom and the other is an alkyl group, an alkoxy group, or an ester group.

6. Y in the general formula (1) ３ and Y ４ Y is a hydrogen atom, １ and Y ２ The compound according to claim 1, wherein each of them is independently an alkyl group, an alkoxy group, or an ester group.

7. Y in the general formula (1) ３ and Y ４ Y is a hydrogen atom, １ and Y ２ The compound according to claim 1, wherein is an alkoxy group.

8. The compound according to claim 1, wherein A in the general formula (1) is independently a group represented by any of the following general formulas (3a) to (3u). 【Transformation 5】 In general formulas (3a) to (3u), Z １ ~Z ７ Each of these is independently an oxygen atom, a sulfur atom, or a dicyanomethylene group, and R ３ Each is independently a hydrogen atom or an alkyl group, and R ４ Each is independently a methyl group or a trifluoromethyl group, X １ Each is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, Ar is an aryl group, and V is independently C-X ２ or nitrogen atom, Q ２ Each is independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or CR ５ =CR ５ Q ３ X is a sulfur atom, a carbon atom substituted with an alkyl or aryl group, a nitrogen atom substituted with an alkyl or aryl group, a silicon atom substituted with an alkyl or aryl group, or a germanium atom substituted with an alkyl or aryl group. ２ Each of these is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, and R ５ Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group.

9. Z in the above general formulas (3a) to (3u) １ The group is a dicyanomethylene group, Z ２ This is an oxygen atom, Z ３ is a sulfur atom or a dicyanomethylene group, Z ４ and Z ５ One of them is an oxygen atom, and the other is a dicyanomethylene group, Z ６ and Z ７ The compound according to claim 8, wherein is an oxygen atom.

10. The compound according to claim 1, represented by the following general formula (4). 【Transformation 6】 In general formula (4), A is independently a methylidene group substituted with a cyano group or an electron-withdrawing group consisting of 1 to 3 rings, and W ２ Each of them is independently a sulfur atom or CH=CH, and R ２ Each of these is independently an alkyl group, an aryl group which may be substituted with an alkyl group or an alkoxy group, and Y １ ~Y ４ Each of the elements is independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group, and each of the elements a and b independently represents an integer between 1 and 3.

11. In the general formula (4) above, W ２ CH=CH, R ２ is an alkyl group, Y ３ and Y ４ Y is a hydrogen atom, １ and Y ２ The compound according to claim 10, wherein is an alkoxy group.

12. The compound according to claim 10, wherein A in the general formula (4) is independently a group represented by the following general formulas (3m), (3n), (3o), or (3s). 【Transformation 7】 In general formulas (3m), (3n), (3о) and (3s), Z ４ and Z ５ Each of these is independently an oxygen atom, a sulfur atom, or a dicyanomethylene group, and X １ Each of these is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, and each of these is independently C-X ２ or nitrogen atom, X ２ Each of these is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a cyano group.

13. In the above general formulas (3m), (3n), (3o), and (3s), Z ４ and Z ５ One of them is an oxygen atom, and the other is a dicyanomethylene group, X １ Each of these is independently a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, and V is C-X ２ or nitrogen atom, X ２ The compound according to claim 12, wherein is a hydrogen atom.

14. In the general formula (4), A is the group represented by the general formula (3o), and Z in the general formula (3o) ４ and Z ５ One of them is an oxygen atom, and the other is a dicyanomethylene group, X １ Each of these is independently a fluorine atom, a chlorine atom, a bromine atom, or a cyano group, and V is C-X ２ X ２ The compound according to claim 12, wherein is a hydrogen atom.

15. A composition containing the compound described in any one of claims 1 to 14.

16. A film containing the compound described in any one of claims 1 to 14.

17. A photoelectric conversion element comprising the film described in claim 16.

18. A CMOS image sensor comprising the photoelectric conversion element described in claim 17.

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