JP2023107154A - Ink composition and photoelectric conversion device arranged by use of thereof - Google Patents

Abstract

To enhance the characteristic of a photoelectric conversion device.SOLUTION: An ink composition comprises: a semiconductor material including at least one p-type semiconductor material and at least one n-type semiconductor material; and two or more kinds of solvent including a first solvent and a second solvent having a boiling point higher than that of the first solvent, in which any one of the p-type semiconductor material and the n-type semiconductor material is a non-fullerene compound represented by the formula (I) below, and a polarity term P(B1)(MPa0.5) of Hansen solubility parameters of a compound including B1 in a state in which a terminal end formed by cutting a bond of A1 and B1 in the non-fullerene compound given by the formula (I) is terminated with a hydrogen atom, and a polarity term P(S2)(MPa0.5) of Hansen solubility parameters of the second solvent satisfy the requirement given by the following expression (III): A1-B1-(A1)n(I) |P(B1)-P(S2)|>3.2(MPa0.5)(III).SELECTED DRAWING: Figure 1

Description

The present invention relates to an ink composition and a photoelectric conversion device using the same.

Photoelectric conversion elements are attracting attention because they are extremely useful devices from the viewpoint of, for example, energy saving and reduction of carbon dioxide emissions.

A photoelectric conversion device is a device that includes at least a pair of electrodes consisting of an anode and a cathode, and an active layer provided between the pair of electrodes. In the photoelectric conversion element, at least one of the pair of electrodes is made of a transparent or translucent material, and light is allowed to enter the active layer from the side of the transparent or translucent electrode. Electric charges (holes and electrons) are generated in the active layer by the energy (hν) of light incident on the active layer, the generated holes move toward the anode, and the electrons move toward the cathode. Then, the charges that have reached the anode and cathode are taken out of the device.

BACKGROUND ART In recent years, various applications of organic photoelectric conversion elements containing an organic semiconductor material in an active layer have been investigated because of their characteristics such as light weight and easy enlargement of the area. Further improvements in the characteristics of organic photoelectric conversion elements are demanded. Therefore, various further organic semiconductor materials have been developed and reported.
Moreover, the active layer of the organic photoelectric conversion element is formed by applying and drying an ink composition containing an organic semiconductor material. A method of controlling the structure in the active layer by adding an additive (second solvent) to such an ink composition to obtain high photoelectric conversion properties has been investigated. For example, in Non-Patent Document 1, in an active layer using a fullerene derivative as an n-type semiconductor material, 1,8 -It is reported that the addition of diiodooctane (DIO) improves photoelectric conversion characteristics. Furthermore, the same technique is also applied in active layers using non-fullerene compounds (NFAs) as n-type semiconductor materials. (See, for example, Non-Patent Document 2.).

J. Am. Chem. Soc, 2008, 130, 3619-3623 J. Mater. Chem. A, 2020, 8, 23628-23636

Non-fullerene compounds can adjust the absorption wavelength range depending on the molecular design. Recently, many non-fullerene compounds with absorption in the near-infrared region have been reported, and are attracting attention as compounds that can handle near-infrared rays. . However, it is still difficult to say that the properties required for a photoelectric conversion device, which is a photodetector containing a non-fullerene compound, are sufficient.

Therefore, there is a demand for means capable of further improving the characteristics of photoelectric conversion elements.

As a result of intensive studies aimed at solving the above problems, the inventors of the present invention found that the above problems can be solved by manufacturing a photoelectric conversion element, particularly by combining predetermined solvents, and have completed the present invention. .

（式（ＩＶ）中、
Ａｒ^１及びＡｒ^２は、それぞれ独立して、置換基を有していてもよい芳香族炭素環又は置換基を有していてもよい芳香族複素環を表し、
Ｙは、直接結合、－Ｃ（＝Ｏ）－で表される基又は酸素原子を表し、
Ｒは、それぞれ独立して、
水素原子、
ハロゲン原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、
置換基を有していてもよいアルキルチオ基、
置換基を有していてもよいシクロアルキルチオ基、
置換基を有していてもよいアリールチオ基、
置換基を有していてもよい１価の複素環基、
置換基を有していてもよい置換アミノ基、
置換基を有していてもよいアシル基、
置換基を有していてもよいイミン残基、
置換基を有していてもよいアミド基、
置換基を有していてもよい酸イミド基、
置換基を有していてもよい置換オキシカルボニル基、
置換基を有していてもよいアルケニル基、
置換基を有していてもよいシクロアルケニル基、
置換基を有していてもよいアルキニル基、
置換基を有していてもよいシクロアルキニル基、
シアノ基、
ニトロ基、
－Ｃ（＝Ｏ）－Ｒ^ａで表される基、又は
－ＳＯ_２－Ｒ^ｂで表される基を表し、
Ｒ^ａ及びＲ^ｂは、それぞれ独立して、
水素原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、又は
置換基を有していてもよい１価の複素環基を表す。
複数あるＲは、互いに同一であっても異なっていてもよい。）
〔６〕 前記第１の構成単位が、下記式（Ｖ）で表される構成単位である、〔５〕に記載のインク組成物。

（式（Ｖ）中、
Ｙ及びＲは、前記定義のとおりであり、
Ｘ^１及びＸ^２は、それぞれ独立して、硫黄原子又は酸素原子を表し、
Ｚ^１及びＺ^２は、それぞれ独立して、＝Ｃ（Ｒ）－で表される基又は窒素原子を表す。）
〔７〕 前記第１の構成単位が、下記式（Ｖ－１）で表される構成単位である、〔６〕に記載のインク組成物。

（式（Ｖ－１）中、
Ｙは、－Ｃ（＝Ｏ）－で表される基又は酸素原子を表し、
Ｒは、それぞれ独立して、
水素原子、
ハロゲン原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、
置換基を有していてもよいアルキルチオ基、
置換基を有していてもよいシクロアルキルチオ基、
置換基を有していてもよいアリールチオ基、
置換基を有していてもよい１価の複素環基、
置換基を有していてもよい置換アミノ基、
置換基を有していてもよいアシル基、
置換基を有していてもよいイミン残基、
置換基を有していてもよいアミド基、
置換基を有していてもよい酸イミド基、
置換基を有していてもよい置換オキシカルボニル基、
置換基を有していてもよいアルケニル基、
置換基を有していてもよいシクロアルケニル基、
置換基を有していてもよいアルキニル基、
置換基を有していてもよいシクロアルキニル基、
シアノ基、
ニトロ基、
－Ｃ（＝Ｏ）－Ｒ^ａで表される基、又は
－ＳＯ_２－Ｒ^ｂで表される基を表し、
Ｒ^ａ及びＲ^ｂは、それぞれ独立して、
水素原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、又は
置換基を有していてもよい１価の複素環基を表す。
複数あるＲは、同一であっても異なっていてもよい。）
〔８〕 Ｂ^１が、下記式（ＶＩＩ－１）～式（ＶＩＩ－１６）で表される構造からなる群から選択されるいずれか１つの構造を有する２価の基である、〔６〕又は〔７〕に記載のインク組成物。

―ＣＵ１－ （ＶＩＩ－１）

－ＣＵ１－ＣＵ１－ （ＶＩＩ－２）

－ＣＵ１－ＣＵ２－ （ＶＩＩ－３）

－ＣＵ１－ＣＵ１－ＣＵ１－ （ＶＩＩ－４）

―ＣＵ１－ＣＵ２－ＣＵ１－ （ＶＩＩ－５）

―ＣＵ１－ＣＵ１－ＣＵ２－ （ＶＩＩ－６）

－ＣＵ１－ＣＵ２－ＣＵ２－ （ＶＩＩ－７）

―ＣＵ２－ＣＵ１－ＣＵ２－ （ＶＩＩ－８）

－ＣＵ１－ＣＵ１－ＣＵ１－ＣＵ１－ （ＶＩＩ－９）

－ＣＵ１－ＣＵ１－ＣＵ１－ＣＵ２－ （ＶＩＩ－１０）

－ＣＵ１－ＣＵ１－ＣＵ２－ＣＵ１－ （ＶＩＩ－１１）

－ＣＵ１－ＣＵ１－ＣＵ２－ＣＵ２－ （ＶＩＩ－１２）

－ＣＵ１－ＣＵ２－ＣＵ１－ＣＵ２－ （ＶＩＩ－１３）

－ＣＵ１－ＣＵ２－ＣＵ２－ＣＵ１－ （ＶＩＩ－１４）

－ＣＵ１－ＣＵ２－ＣＵ２－ＣＵ２－ （ＶＩＩ－１５）

－ＣＵ２－ＣＵ１－ＣＵ２－ＣＵ２－ （ＶＩＩ－１６）

（式（ＶＩＩ－１）～式（ＶＩＩ－１６）中、
ＣＵ１は、前記第１の構成単位を表し、
ＣＵ２は、前記第２の構成単位を表す。
ＣＵ１が２つ以上ある場合、２つ以上あるＣＵ１は、同一であっても異なっていてもよく、ＣＵ２が２つ以上ある場合、２つ以上あるＣＵ２は、同一であっても異なっていてもよい。）
〔９〕 前記ｐ型半導体材料が共役高分子化合物である、〔１〕～〔８〕のいずれか１つに記載のインク組成物。
〔１０〕 〔１〕～〔９〕のいずれか１つに記載のインク組成物を固化させた固化膜。
〔１１〕 第１電極と、第２電極と、該第１電極及び第２電極の間に設けられている活性層を含み、該活性層が〔１０〕に記載の固化膜である、光電変換素子。
〔１２〕 光検出素子である、〔１１〕に記載の光電変換素子。 Accordingly, the present invention provides the following [1] to [12].
[1] a semiconductor material comprising at least one p-type semiconductor material and at least one n-type semiconductor material;
two or more solvents, including a first solvent and a second solvent having a boiling point higher than the boiling point of the first solvent;
one of the p-type semiconductor material and the n-type semiconductor material is a non-fullerene compound represented by the following formula (I);
^The polarity term ^{P (} An ink composition in which B ¹ )(MPa ^0.5 ) and the polarity term P(S2)(MPa ^0.5 ) of the Hansen solubility parameter of the second solvent satisfy the condition represented by the following formula (III).

A ¹ -B ¹ -(A ¹ )n (I)
|P(B ¹ )−P(S2)|>3.2 (MPa ^0.5 ) (III)

(In formula (I),
A ¹ represents an electron-withdrawing group,
B ¹ represents a group comprising one or more structural units and constituting a π-conjugated system;
n is 0 or 1, and when n is 1, two A ¹ may be the same or different,
A compound containing A ¹ and a compound containing B ¹ having a hydrogen atom-terminated terminal obtained by severing the bond between A ¹ and B ¹ satisfy the condition represented by the following formula (II).

E _HOMO (B ¹ )−E _HOMO (A ¹ )>2.0 (eV) (II)

(In formula (II),
E _HOMO (B ¹ ) (eV) represents the energy level of the highest occupied orbital of a compound containing B ¹ having a hydrogen atom-terminated terminal formed by severing the bond between A ¹ and B ¹ ,
E _HOMO (A ¹ ) (eV) represents the energy level of the highest occupied orbital of a compound containing A ¹ , which is formed by severing the bond between A ¹ and B ¹ and terminated with a hydrogen atom. ))
[2] The ink composition of [1], wherein the second solvent has a boiling point higher than that of the first solvent by 30°C or more.
[3] The ink composition of [1] or [2], wherein the second solvent is an ether solvent, an aromatic hydrocarbon solvent, a ketone solvent, or an ester solvent.
[4] The ink composition according to any one of [1] to [3], wherein the non-fullerene compound represented by formula (I) is an n-type semiconductor material.
[5] In formula (I), the first structural unit, which is at least one of the one or more structural units contained in ^B1 , is a structural unit represented by formula (IV) below, and The remaining second structural unit other than the first structural unit is a divalent group containing an unsaturated bond, a divalent aromatic carbocyclic group or a divalent aromatic heterocyclic group, When there are two or more structural units, the two or more first structural units may be the same or different, and when there are two or more second structural units, the two or more second structural units The ink composition according to any one of [1] to [4], wherein the two structural units may be the same or different.

(In formula (IV),
Ar ¹ and Ar ² each independently represent an optionally substituted aromatic carbocyclic ring or an optionally substituted aromatic heterocyclic ring,
Y represents a direct bond, a group represented by -C(=O)- or an oxygen atom,
R are each independently
hydrogen atom,
halogen atom,
an optionally substituted alkyl group,
a cycloalkyl group optionally having a substituent,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
a cycloalkyloxy group optionally having a substituent,
an optionally substituted aryloxy group,
an optionally substituted alkylthio group,
a cycloalkylthio group optionally having a substituent,
an optionally substituted arylthio group,
a monovalent heterocyclic group optionally having a substituent,
a substituted amino group which may have a substituent,
an acyl group optionally having a substituent,
an imine residue optionally having a substituent,
an amide group optionally having a substituent,
an acid imide group optionally having a substituent,
a substituted oxycarbonyl group optionally having a substituent,
an optionally substituted alkenyl group,
a cycloalkenyl group optionally having a substituent,
an optionally substituted alkynyl group,
a cycloalkynyl group optionally having a substituent,
cyano group,
nitro group,
a group represented by —C(=O)—R ^a or a group represented by —SO ₂ —R ^b ,
R ^a and R ^b each independently
hydrogen atom,
an optionally substituted alkyl group,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
It represents an optionally substituted aryloxy group or an optionally substituted monovalent heterocyclic group.
Multiple R's may be the same or different. )
[6] The ink composition of [5], wherein the first structural unit is a structural unit represented by the following formula (V).

(In formula (V),
Y and R are as defined above;
X ¹ and X ² each independently represent a sulfur atom or an oxygen atom,
Z ¹ and Z ² each independently represent a group represented by =C(R)- or a nitrogen atom. )
[7] The ink composition of [6], wherein the first structural unit is a structural unit represented by the following formula (V-1).

(In formula (V-1),
Y represents a group represented by -C(=O)- or an oxygen atom,
R are each independently
hydrogen atom,
halogen atom,
an optionally substituted alkyl group,
a cycloalkyl group optionally having a substituent,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
a cycloalkyloxy group optionally having a substituent,
an optionally substituted aryloxy group,
an optionally substituted alkylthio group,
a cycloalkylthio group optionally having a substituent,
an optionally substituted arylthio group,
a monovalent heterocyclic group optionally having a substituent,
a substituted amino group which may have a substituent,
an acyl group optionally having a substituent,
an imine residue optionally having a substituent,
an amide group optionally having a substituent,
an acid imide group optionally having a substituent,
a substituted oxycarbonyl group optionally having a substituent,
an optionally substituted alkenyl group,
a cycloalkenyl group optionally having a substituent,
an optionally substituted alkynyl group,
a cycloalkynyl group optionally having a substituent,
cyano group,
nitro group,
a group represented by —C(=O)—R ^a or a group represented by —SO ₂ —R ^b ,
R ^a and R ^b each independently
hydrogen atom,
an optionally substituted alkyl group,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
It represents an optionally substituted aryloxy group or an optionally substituted monovalent heterocyclic group.
Plural R's may be the same or different. )
[8] B ¹ is a divalent group having any one structure selected from the group consisting of structures represented by the following formulas (VII-1) to (VII-16); [6] Or the ink composition according to [7].

-CU1- (VII-1)

-CU1-CU1- (VII-2)

-CU1-CU2- (VII-3)

-CU1-CU1-CU1- (VII-4)

-CU1-CU2-CU1- (VII-5)

-CU1-CU1-CU2- (VII-6)

-CU1-CU2-CU2- (VII-7)

-CU2-CU1-CU2- (VII-8)

-CU1-CU1-CU1-CU1- (VII-9)

-CU1-CU1-CU1-CU2- (VII-10)

-CU1-CU1-CU2-CU1- (VII-11)

-CU1-CU1-CU2-CU2- (VII-12)

-CU1-CU2-CU1-CU2- (VII-13)

-CU1-CU2-CU2-CU1- (VII-14)

-CU1-CU2-CU2-CU2- (VII-15)

-CU2-CU1-CU2-CU2- (VII-16)

(In the formulas (VII-1) to (VII-16),
CU1 represents the first structural unit,
CU2 represents the second structural unit.
When there are two or more CU1s, the two or more CU1s may be the same or different, and when there are two or more CU2s, the two or more CU2s may be the same or different. good. )
[9] The ink composition according to any one of [1] to [8], wherein the p-type semiconductor material is a conjugated polymer compound.
[10] A solidified film obtained by solidifying the ink composition according to any one of [1] to [9].
[11] A photoelectric conversion comprising a first electrode, a second electrode, and an active layer provided between the first electrode and the second electrode, wherein the active layer is the solidified film according to [10]. element.
[12] The photoelectric conversion device of [11], which is a photodetector.

According to the present invention, it is possible to provide a photoelectric conversion element with further improved characteristics by using a combination of predetermined solvents in a method for manufacturing a photoelectric conversion element.

FIG. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element.

Hereinafter, embodiments of the present invention will be described, and in particular, photoelectric conversion elements will be described with reference to the drawings. It should be noted that the drawings only schematically show the shape, size and arrangement of the constituent elements to the extent that the invention can be understood. The present invention is not limited by the following description, and each component can be changed as appropriate without departing from the gist of the present invention. Also, the configurations according to the embodiments of the present invention are not necessarily manufactured or used in the arrangement shown in the drawings.

Terms commonly used in the following description will be described first.

A "non-fullerene compound" refers to a compound that is neither a fullerene nor a fullerene derivative.

A “π-conjugated system” means a system in which π electrons are delocalized to multiple bonds.

The term “polymer compound” means a polymer having a molecular weight distribution and a polystyrene-equivalent number average molecular weight of 1×10 ³ or more and 1×10 ⁸ or less. In addition, the structural units contained in the polymer compound are 100 mol % in total.

A "structural unit" means a residue derived from a raw material compound (monomer) and present at least one in the compound and polymer compound of the present embodiment.

A "hydrogen atom" may be either a protium atom or a deuterium atom.

Examples of "halogen atoms" include fluorine, chlorine, bromine, and iodine atoms.

In the "optionally substituted" aspect, when all hydrogen atoms constituting the compound or group are unsubstituted, and when one or more hydrogen atoms are partially or entirely substituted by a substituent Both aspects are included.

Examples of "substituents" include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, cycloalkynyl groups, alkyloxy groups, cycloalkyloxy groups, alkylthio groups, cycloalkylthio groups, aryl groups, aryloxy groups, arylthio groups, monovalent heterocyclic groups, substituted amino groups, acyl groups, imine residues, amide groups, acid imide groups, substituted oxycarbonyl groups, cyano groups, alkylsulfonyl groups, and nitro groups mentioned. When referring to the number of carbon atoms in this specification, the number of carbon atoms usually does not include the number of carbon atoms of the substituent.

In this specification, unless otherwise specified, the "alkyl group" may be linear, branched, or cyclic. The number of carbon atoms in the linear alkyl group is generally 1-50, preferably 1-30, more preferably 1-20, not including the number of carbon atoms in the substituents. The number of carbon atoms in the branched or cyclic alkyl group is usually 3 to 50, preferably 3 to 30, more preferably 4 to 20, not including the number of carbon atoms in substituents.

Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isoamyl, 2-ethylbutyl, n- hexyl group, cyclohexyl group, n-heptyl group, cyclohexylmethyl group, cyclohexylethyl group, n-octyl group, 2-ethylhexyl group, 3-n-propylheptyl group, adamantyl group, n-decyl group, 3,7-dimethyl octyl group, 2-ethyloctyl group, 2-n-hexyl-decyl group, n-dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and eicosyl group.

The alkyl group may have a substituent. An alkyl group having a substituent is, for example, a group in which a hydrogen atom in the above-exemplified alkyl group is substituted with a substituent such as an alkyloxy group, an aryl group, or a fluorine atom.

Specific examples of substituted alkyl groups include trifluoromethyl, pentafluoroethyl, perfluorobutyl, perfluorohexyl, perfluorooctyl, 3-phenylpropyl, 3-(4-methylphenyl ) propyl group, 3-(3,5-dihexylphenyl)propyl group and 6-ethyloxyhexyl group.

A "cycloalkyl group" may be a monocyclic group or a polycyclic group. A cycloalkyl group may have a substituent. The number of carbon atoms in the cycloalkyl group is usually 3-30, preferably 12-19, not including the number of carbon atoms in the substituents.

Examples of cycloalkyl groups include unsubstituted alkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl and adamantyl groups, and hydrogen atoms in these groups are alkyl groups, alkyloxy groups, aryl groups, fluorine Groups substituted with substituents such as atoms are included.

Specific examples of substituted cycloalkyl groups include a methylcyclohexyl group and an ethylcyclohexyl group.

A "p-valent aromatic carbocyclic group" (p represents an integer of 1 or more) is a hydrogen atom directly bonded to a carbon atom constituting a ring from an optionally substituted aromatic hydrocarbon It means the remaining atomic groups excluding p atoms. The p-valent aromatic carbocyclic group may further have a substituent. In addition, the "aromatic carbocyclic ring" includes a structure in which two or more carbocyclic rings (aromatic rings) are crossed by a group (substituent) containing a hetero atom, for example.

"Aryl group" is a monovalent aromatic carbocyclic group, which is an optionally substituted aromatic hydrocarbon remaining after removing one hydrogen atom directly bonded to a carbon atom constituting the ring means the atomic group of

The aryl group may have a substituent. Specific examples of aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-pyrenyl, 2-pyrenyl, and 4-pyrenyl groups. , 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, and hydrogen atoms in these groups are alkyl groups, alkyloxy groups , an aryl group, and a group substituted with a substituent such as a fluorine atom.

The "alkyloxy group" may be linear, branched, or cyclic. The number of carbon atoms in the straight-chain alkyloxy group is generally 1-40, preferably 1-10, not including the number of carbon atoms in the substituents. The number of carbon atoms in the branched or cyclic alkyloxy group is usually 3-40, preferably 4-10, not including the number of carbon atoms in the substituents.

The alkyloxy group may have a substituent. Specific examples of alkyloxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tert-butyloxy, n-pentyloxy and n-hexyloxy groups. , cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, 3,7-dimethyloctyloxy group, 3-heptyldodecyloxy group, lauryl Examples include oxy groups and groups in which hydrogen atoms in these groups are substituted with alkyloxy groups, aryl groups, fluorine atoms and the like.

The cycloalkyl group included in the "cycloalkyloxy group" may be a monocyclic group or a polycyclic group. A cycloalkyloxy group may have a substituent. The number of carbon atoms in the cycloalkyloxy group is usually 3-30, preferably 12-19, not including the number of carbon atoms in the substituent.

Examples of cycloalkyloxy groups include unsubstituted cycloalkyloxy groups such as cyclopentyloxy, cyclohexyloxy, and cycloheptyloxy, and hydrogen atoms in these groups are fluorine atoms, alkyl groups, and the like. Substituted groups are included.

The number of carbon atoms in the "aryloxy group" is usually 6-60, preferably 6-48, not including the number of carbon atoms in the substituents.

The aryloxy group may have a substituent. Specific examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthracenyloxy group, a 9-anthracenyloxy group, a 1-pyrenyloxy group, and these groups. A group in which a hydrogen atom in is substituted with a substituent such as an alkyl group, an alkyloxy group, or a fluorine atom.

The "alkylthio group" may be linear, branched, or cyclic. The number of carbon atoms in the straight-chain alkylthio group is generally 1-40, preferably 1-10, not including the number of carbon atoms in the substituents. The number of carbon atoms in the branched or cyclic alkylthio group is usually 3-40, preferably 4-10, not including the number of carbon atoms in the substituents.

The alkylthio group may have a substituent. Specific examples of alkylthio groups include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, tert-butylthio, pentylthio, hexylthio, cyclohexylthio, heptylthio, octylthio, 2 -ethylhexylthio, nonylthio, decylthio, 3,7-dimethyloctylthio, laurylthio, and trifluoromethylthio groups.

The cycloalkyl group of the "cycloalkylthio group" may be a monocyclic group or a polycyclic group. A cycloalkylthio group may have a substituent. The number of carbon atoms in the cycloalkylthio group is usually 3-30, preferably 12-19, not including the number of carbon atoms in the substituent.

A cyclohexylthio group is mentioned as an example of the cycloalkylthio group which may have a substituent.

The number of carbon atoms in the "arylthio group" is usually 6-60, preferably 6-48, not including the number of carbon atoms in the substituents.

The arylthio group may have a substituent. Examples of the arylthio group include a phenylthio group and a C1-C12 alkyloxyphenylthio group (C1-C12 indicates that the number of carbon atoms in the group immediately following it is 1-12. The same applies below. .), C1-C12 alkylphenylthio groups, 1-naphthylthio groups, 2-naphthylthio groups, and pentafluorophenylthio groups.

"p-valent heterocyclic group" means p hydrogen atoms among the hydrogen atoms directly bonded to the carbon atoms or heteroatoms constituting the ring from the optionally substituted heterocyclic compound means the rest of the atomic groups excluding

The p-valent heterocyclic group may further have a substituent. The number of carbon atoms in the p-valent heterocyclic group is usually 2 to 30, preferably 2 to 6, not including the number of carbon atoms in the substituents.

Examples of substituents that the heterocyclic compound may have include halogen atoms, alkyl groups, aryl groups, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, monovalent heterocyclic groups, substituted amino groups, acyl groups, imine residues, amide groups, acid imide groups, substituted oxycarbonyl groups, alkenyl groups, alkynyl groups, cyano groups, and nitro groups. The p-valent heterocyclic group includes a "p-valent aromatic heterocyclic group".

"p-valent aromatic heterocyclic group", from an optionally substituted aromatic heterocyclic compound, out of the hydrogen atoms directly bonded to the carbon atoms or heteroatoms constituting the ring p means the remaining atomic groups excluding the hydrogen atoms of The p-valent aromatic heterocyclic group may further have a substituent.

Aromatic heterocyclic compounds include not only compounds in which the heterocycle itself exhibits aromaticity, but also compounds in which an aromatic ring is fused to a heterocycle, even if the heterocycle itself does not exhibit aromaticity. be.

Among aromatic heterocyclic compounds, specific examples of compounds in which the heterocycle itself exhibits aromaticity include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, and triazine. , pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphole.

Among aromatic heterocyclic compounds, specific examples of compounds in which the aromatic heterocyclic ring itself does not show aromaticity and the aromatic ring is fused to the heterocyclic ring include phenoxazine, phenothiazine, dibenzoborol, dibenzo Siloles, and benzopyrans.

The number of carbon atoms in the monovalent heterocyclic group is usually 2-60, preferably 4-20, not including the number of carbon atoms in the substituents.

The monovalent heterocyclic group may have a substituent, and specific examples of the monovalent heterocyclic group include thienyl, pyrrolyl, furyl, pyridyl, piperidyl, quinolyl, isoquinolyl group, pyrimidinyl group, triazinyl group, and groups in which hydrogen atoms in these groups are substituted with alkyl groups, alkyloxy groups, and the like.

A "substituted amino group" means an amino group having a substituent. Examples of substituents possessed by the amino group include alkyl groups, aryl groups, and monovalent heterocyclic groups, with alkyl groups, aryl groups, and monovalent heterocyclic groups being preferred. The substituted amino group usually has 2 to 30 carbon atoms.

Examples of substituted amino groups include dialkylamino groups such as dimethylamino group and diethylamino group; diphenylamino group, bis(4-methylphenyl)amino group, bis(4-tert-butylphenyl)amino group, bis(3, and diarylamino groups such as 5-di-tert-butylphenyl)amino group.

The "acyl group" may have a substituent. The number of carbon atoms in the acyl group is usually 2-20, preferably 2-18, not including the number of carbon atoms in the substituents. Specific examples of acyl groups include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, benzoyl, trifluoroacetyl, and pentafluorobenzoyl groups.

The term “imine residue” means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom or a nitrogen atom constituting a carbon atom-nitrogen atom double bond from an imine compound. An "imine compound" means an organic compound having a carbon atom-nitrogen atom double bond in the molecule. Examples of imine compounds include aldimines, ketimines, and compounds in which a hydrogen atom bonded to a nitrogen atom constituting a carbon atom-nitrogen double bond in aldimines is substituted with an alkyl group or the like.

The imine residue usually has 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Examples of imine residues include groups represented by the following structural formulas.

"Amido group" means an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from amide. The amide group usually has 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms. Specific examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, and a dibenzamide group. , a ditrifluoroacetamide group, and a dipentafluorobenzamide group.

An "acid imide group" means an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an acid imide. The number of carbon atoms in the acid imide group is generally 4-20. Specific examples of acid imide groups include groups represented by the following structural formulas.

"Substituted oxycarbonyl group" means a group represented by R'-O-(C=O)-. Here, R' represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

The number of carbon atoms in the substituted oxycarbonyl group is usually 2-60, preferably 2-48, not including the number of carbon atoms in the substituent.

Specific examples of substituted oxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl and hexyloxycarbonyl groups. group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, tri fluoromethoxycarbonyl, pentafluoroethoxycarbonyl, perfluorobutoxycarbonyl, perfluorohexyloxycarbonyl, perfluorooctyloxycarbonyl, phenoxycarbonyl, naphthoxycarbonyl, and pyridyloxycarbonyl groups.

An "alkenyl group" may be linear, branched, or cyclic. The number of carbon atoms in the straight-chain alkenyl group is usually 2-30, preferably 3-20, not including the number of carbon atoms in the substituents. The number of carbon atoms in the branched or cyclic alkenyl group is usually 3 to 30, preferably 4 to 20, not including the number of carbon atoms in substituents.

The alkenyl group may have a substituent. Specific examples of alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl and 5-hexenyl groups. , 7-octenyl groups, and groups in which hydrogen atoms in these groups are substituted with alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms.

A "cycloalkenyl group" may be a monocyclic group or a polycyclic group. A cycloalkenyl group may have a substituent. The number of carbon atoms in the cycloalkenyl group is usually 3-30, preferably 12-19, not including the number of carbon atoms in the substituents.

Examples of cycloalkenyl groups include unsubstituted cycloalkenyl groups such as cyclohexenyl, and groups in which hydrogen atoms in these groups are substituted with alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms. mentioned.

Examples of substituted cycloalkenyl groups include methylcyclohexenyl and ethylcyclohexenyl groups.

An "alkynyl group" may be linear, branched, or cyclic. The number of carbon atoms in the linear alkenyl group is usually 2 to 20, preferably 3 to 20, not including the number of carbon atoms in the substituents. The number of carbon atoms in the branched or cyclic alkenyl group is usually 4 to 30, preferably 4 to 20, not including the number of carbon atoms in the substituents.

The alkynyl group may have a substituent. Specific examples of alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, 3-butynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl and 5-hexynyl groups. , and groups in which hydrogen atoms in these groups are substituted with alkyloxy groups, aryl groups, and fluorine atoms.

A "cycloalkynyl group" may be a monocyclic group or a polycyclic group. A cycloalkynyl group may have a substituent. The number of carbon atoms in the cycloalkynyl group is generally 4-30, preferably 12-19, not including the number of carbon atoms in the substituents.

Examples of cycloalkynyl groups include unsubstituted cycloalkynyl groups such as cyclohexynyl groups, and groups in which hydrogen atoms in these groups are substituted with alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms. be done.

Examples of substituted cycloalkynyl groups include methylcyclohexynyl and ethylcyclohexynyl groups.

An "alkylsulfonyl group" may be linear or branched. The alkylsulfonyl group may have a substituent. The number of carbon atoms in the alkylsulfonyl group is usually 1-30, not including the number of carbon atoms in the substituents. Specific examples of alkylsulfonyl groups include methylsulfonyl, ethylsulfonyl, and dodecylsulfonyl groups.

The symbol "*" that can be attached to the chemical formula represents a bond.

"Ink composition (hereinafter sometimes simply referred to as ink)" means a liquid material used in a coating method, and is not limited to a colored liquid. In addition, "coating method" includes a method of forming a film (layer) using a liquid substance, for example, slot die coating method, slit coating method, knife coating method, spin coating method, casting method, micro gravure coating method. , gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, gravure printing method, flexographic printing method, offset printing method, inkjet coating method, dispenser printing method, A nozzle coating method and a capillary coating method can be mentioned.

The ink composition may be a solution or a dispersion such as a dispersion, an emulsion, a suspension, or the like.

"Absorption peak wavelength" is a parameter specified based on the absorption peak of the absorption spectrum measured in a predetermined wavelength range, and refers to the wavelength of the absorption peak with the highest absorbance among the absorption peaks of the absorption spectrum.

"External quantum efficiency" is also called EQE (External Quantum Efficiency), and is the number of electrons that can be taken out of the photoelectric conversion element among the generated electrons with respect to the number of photons irradiated to the photoelectric conversion element. is expressed as a ratio (%).

The ink composition of this embodiment comprises a semiconductor material comprising at least one p-type semiconductor material and at least one n-type semiconductor material;
two or more solvents, including a first solvent and a second solvent having a boiling point higher than the boiling point of the first solvent;
one of the p-type semiconductor material and the n-type semiconductor material is a non-fullerene compound represented by the following formula (I);
Polar ^{term P} ( ^{B 1} ) An ink composition in which (MPa ^0.5 ) and the polar term P(S2)(MPa ^0.5 ) of the Hansen solubility parameter of the second solvent satisfy the condition represented by the following formula (III): .

A ¹ -B ¹ -(A ¹ )n (I)
|P(B ¹ )−P(S2)|>3.2 (MPa ^0.5 ) (III)

(In formula (I),
A ¹ represents an electron-withdrawing group,
B ¹ represents a group comprising one or more structural units and constituting a π-conjugated system;
n is 0 or 1, and when n is 1, two A ¹ may be the same or different,
A compound containing A ¹ and a compound containing B ¹ having a hydrogen atom-terminated terminal obtained by severing the bond between A ¹ and B ¹ satisfy the condition represented by the following formula (II).

E _HOMO (B ¹ )−E _HOMO (A ¹ )>2.0 (eV) (II)

(In formula (II),
E _HOMO (B ¹ ) (eV) is a compound containing B ¹ obtained by severing the bond between B ¹ and A ¹ and terminated with a hydrogen atom (hereinafter sometimes simply referred to as a compound containing B ¹ ) represents the value of the energy level of the highest occupied orbital,
E _HOMO (A ¹ ) (eV) is a compound containing A ¹ obtained by severing the bond between A ¹ and B ¹ and terminated with a hydrogen atom (hereinafter sometimes simply referred to as a compound containing A ¹ ) represents the value of the energy level of the highest occupied orbital. ))

Compounds that are semiconductor materials that can be included in the ink composition of the present embodiment are described in detail below.

1. Non-Fullerene Compound First, a compound that can be used as a semiconductor material in the ink composition of the present embodiment will be described. The non-fullerene compound of the present embodiment can be suitably used as an n-type semiconductor material, particularly for the active layer of a photoelectric conversion device.

As already explained, whether the non-fullerene compound functions as a p-type semiconductor material or an n-type semiconductor material in the active layer depends on the energy level of the highest occupied molecular orbital (HOMO) of the selected compound. It can be determined relatively from the value or the lowest unoccupied molecular orbital (LUMO) energy level value.

The relationship between the HOMO and LUMO energy level values of the p-type semiconductor material contained in the active layer and the HOMO and LUMO energy level values of the n-type semiconductor material is used to function the photoelectric conversion element (light detection element). can be appropriately set within a range where

The non-fullerene compound of this embodiment is a compound represented by the following formula (I).

A ¹ -B ¹ -(A ¹ )n (I)

In formula (I),
A ¹ represents an electron-withdrawing group,
B ¹ represents a group comprising one or more structural units and constituting a π-conjugated system;
n is 0 or 1, and when n is 1, two A ¹ may be the same or different,
A compound containing A ¹ and a compound containing B ¹ having a hydrogen atom-terminated terminal obtained by severing the bond between A ¹ and B ¹ satisfy the condition represented by the following formula (II).

E _HOMO (B ¹ )−E _HOMO (A ¹ )>2.0 (eV) (II)

In formula (II),
E _HOMO (B ¹ ) (eV) represents the value of the energy level of the highest occupied orbital of a compound containing B ¹ that is terminated with a hydrogen atom and is formed by severing the bond between B ¹ and A ¹ ;
E _HOMO (A ¹ ) (eV) represents the energy level of the highest occupied orbital of a compound containing A ¹ , which is formed by severing the bond between B ¹ and A ¹ and terminated with a hydrogen atom.

The non-fullerene compound of the present embodiment is a non-fullerene compound represented by the above formula (I), wherein A ¹ which is an electron-withdrawing monovalent group is a monovalent or divalent group B 1 is a compound attached to one end or both ends of ¹ .

In the non-fullerene compound of the present embodiment, it is preferable that a π-conjugated system is formed throughout the non-fullerene compound including not only B ¹ but also A ¹ .

In the non-fullerene compound represented by formula (I) of the present embodiment, the compound containing A ¹ and the compound containing B ¹ satisfy the condition represented by formula (II). In other words, the non-fullerene compound represented by the above formula (I) has the energy level value (E _HOMO (B ¹ )) of the highest occupied molecular orbital (HOMO) of ^the compound containing B ¹ and the highest The difference between the occupied orbital (HOMO) and the energy level value (E _HOMO (A ¹ )) is greater than 2.0 eV.

In the non-fullerene compound of the present embodiment, the energy level value of the highest occupied orbital of the compound containing B ¹ (E _HOMO (B ¹ )) and the energy level value of the highest occupied orbital of the compound containing A ¹ (E _HOMO ( The difference from A ¹ )) can increase the bias of the electric charge in the ground state, and can generate a strong interaction between molecules, so that the charge transport property is improved, and the EQE is further improved. Therefore, it is preferably larger than 2.0 eV, more preferably larger than 2.2 eV.

The value of the energy level of the highest occupied molecular orbital (HOMO) can be calculated using any suitable conventionally known computational science method, for example, Gaussian16, which is a quantum chemical calculation program manufactured by Gaussian. Specifically, for a compound in which the terminal of ^B1 is terminated with a hydrogen atom and/or a compound in which the terminal of ^A1 is terminated with a hydrogen atom, structure optimization is performed by density functional theory at the B3LYP level using the quantum chemical calculation program. Then, the value calculated using 6-31G as the basis function can be used as the energy level value (unit: eV) of the highest occupied orbital.

In the above formula (I ⁾ , when n is 1 and two A ¹ are different from each other, two The average value of the energy level values of the highest occupied orbital in the compound can be taken as the highest occupied orbital energy value of the compound containing ^A1 .

Calculation examples of E _HOMO (A ¹ ) and E _HOMO (B ¹ ) are shown in Tables 1 to 3 below.

Specific examples of A ¹ and B ¹ that can constitute the non-fullerene compound of the present embodiment and the non-fullerene compound are described below.

(1) About A ¹ In the non-fullerene compound of the present embodiment, A ¹ is an electron-withdrawing monovalent group. When there are two A ¹ 's, the two A ¹ 's may be the same or different. The two A ¹ 's are preferably the same group from the viewpoint of facilitating the synthesis of the non-fullerene compound.

Examples of A ¹ include groups represented by —CH═C(—CN) ₂ and groups represented by the following formulas (a-1) to (a-9).

In formulas (a-1) to (a-7),
T represents an optionally substituted carbocyclic ring or an optionally substituted heterocyclic ring. Carbocyclic and heterocyclic rings may be monocyclic or condensed. When these rings have multiple substituents, the multiple substituents may be the same or different.

Examples of optionally substituted carbocyclic rings represented by T include aromatic carbocyclic rings, preferably aromatic carbocyclic rings. Specific examples of optionally substituted carbocyclic rings represented by T include benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring and phenanthrene ring, preferably benzene They are a ring, a naphthalene ring and a phenanthrene ring, more preferably a benzene ring and a naphthalene ring, still more preferably a benzene ring. These rings may have a substituent.

Examples of optionally substituted heterocyclic rings represented by T include aromatic heterocyclic rings, preferably aromatic carbocyclic rings. Specific examples of the optionally substituted heterocyclic ring represented by T include pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole and a thienothiophene ring, preferably a thiophene ring, a pyridine ring, a pyrazine ring, a thiazole ring, and a thienothiophene ring, more preferably a thiophene ring. These rings may have a substituent.

Examples of substituents that the carbocyclic or heterocyclic ring represented by T may have include halogen atoms, alkyl groups, alkyloxy groups, aryl groups, cyano groups and monovalent heterocyclic groups, preferably fluorine atom, chlorine atom, alkyloxy group having 1 to 6 carbon atoms and/or alkyl group having 1 to 6 carbon atoms.

X ⁴ , X ⁵ and X ⁶ each independently represents an oxygen atom, a sulfur atom, an alkylidene group or a group represented by =C(-CN) ₂ , preferably an oxygen atom, a sulfur atom, or =C(-CN) ₂ .

X ⁷ is a hydrogen atom or a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted alkyloxy group, an optionally substituted aryl group, or represents a monovalent heterocyclic group. ^X7 is preferably a cyano group.

R ^a1 , R ^a2 , R ^a3 , R ^a4 , and R ^a5 each independently represent a hydrogen atom, an optionally substituted alkyl group, a halogen atom, an optionally substituted alkyl represents an oxy group, an optionally substituted aryl group or a monovalent heterocyclic group, preferably an optionally substituted alkyl group or an optionally substituted aryl group is.

In formulas (a-8) and (a-9),
R ^a6 and R ^a7 each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or a substituted an alkyloxy group that may have a substituent, a cycloalkyloxy group that may have a substituent, a monovalent aromatic carbocyclic group that may have a substituent, or a monovalent that may have a substituent and a plurality of R ^a6 and R ^a7 may be the same or different.

Specific examples of the electron-withdrawing monovalent group represented by A ¹ include the following formulas (a-1-1) to (a-1-4), and formula (a-5-1), Examples thereof include groups represented by formula (a-6-1), formula (a-6-2) and formula (a-7-1).

Formula (a-1-1) to formula (a-1-4), and formula (a-5-1), formula (a-6-1), formula (a-6-2) and formula (a- 7-1) Medium,
multiple R ^a10 each independently represent a hydrogen atom or a substituent,
R ^a1 , R ^a2 , R ^a3 , R ^a4 and R ^a5 are each independently as defined above.

R ^a10 is preferably a hydrogen atom, a halogen atom, an alkyloxy group, a cyano group or an alkyl group. R ^a1 , R ^a2 , R ^a3 , R ^a4 and R ^a5 are preferably an optionally substituted alkyl group or an optionally substituted aryl group.

A ¹ and A ² are each independently preferably an electron-withdrawing group containing one or more selected from the group consisting of a cyano group, a carbonyl group and a thiocarbonyl group.

Preferred examples of the electron-withdrawing monovalent group represented by A ¹ include groups represented by the following formulae.

(2) B ¹ Specifically, B ¹ is a group containing a pair or more of atoms that are π-bonded to each other, and a π electron cloud spreads over the entire B ¹ .

B ¹ preferably has a structure represented by the following formula.

In the above formula,
Ar ^a , Ar ^b and Ar ^c are each independently a substituted aromatic carbocyclic ring which may contain a plurality of ring structures and may be condensed with a plurality of ring structures. or represents an aromatic heterocyclic ring which may have a substituent or may contain a plurality of ring structures and may be condensed with a plurality of ring structures,
Ar ^d and Ar ^e are each independently a divalent aromatic carbocyclic ring which may have a substituent, may contain a plurality of ring structures, and may have a plurality of condensed ring structures. represents a divalent aromatic heterocyclic group which may have a group or a substituent, may contain a plurality of ring structures and may be condensed with a plurality of ring structures,
When there are a plurality of each of A ^a , Ar ^b , A ^c , Ar ^d and ^Are , each of the plurality of A ^a , Ar ^b , A ^c , Ar ^{d and Are} may be the same but different. may be
x, y, z are 0, 1, 2 or 3;
i is 0, 1, 2 or 3;
k is 0 or an integer from 1 to 10,
m is 0 or an integer from 1 to 10;

More specifically, B ¹ is preferably a monovalent or divalent group containing one or more structural units and forming a π-conjugated system. Here, the monovalent group B ¹ is a group in which one end of the divalent group B ¹ is terminated with a hydrogen atom.

The first structural unit (hereinafter also referred to as first structural unit CU1), which is at least one of the one or more structural units contained in ^B1 , is a structural unit represented by the following formula (IV). and the remaining second structural unit other than the first structural unit (hereinafter also referred to as second structural unit CU2) is a divalent group containing an unsaturated bond, a divalent aromatic carbon A cyclic group or a divalent aromatic heterocyclic group is preferred.

In formula (I), when there are two or more first structural units, the two or more first structural units may be the same or different, and there are two or more second structural units In that case, the two or more second structural units may be the same or different.

In formula (IV),
Ar ¹ and Ar ² each independently represent an optionally substituted aromatic carbocyclic ring or an optionally substituted aromatic heterocyclic ring,
Y represents a direct bond, a group represented by -C(=O)- or an oxygen atom,
R are each independently
hydrogen atom,
halogen atom,
an optionally substituted alkyl group,
a cycloalkyl group optionally having a substituent,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
a cycloalkyloxy group optionally having a substituent,
an optionally substituted aryloxy group,
an optionally substituted alkylthio group,
a cycloalkylthio group optionally having a substituent,
an optionally substituted arylthio group,
a monovalent heterocyclic group optionally having a substituent,
a substituted amino group which may have a substituent,
an acyl group optionally having a substituent,
an imine residue optionally having a substituent,
an amide group optionally having a substituent,
an acid imide group optionally having a substituent,
a substituted oxycarbonyl group optionally having a substituent,
an optionally substituted alkenyl group,
a cycloalkenyl group optionally having a substituent,
an optionally substituted alkynyl group,
a cycloalkynyl group optionally having a substituent,
cyano group,
nitro group,
a group represented by —C(=O)—R ^a or a group represented by —SO ₂ —R ^b ,
R ^a and R ^b each independently
hydrogen atom,
an optionally substituted alkyl group,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
It represents an optionally substituted aryloxy group or an optionally substituted monovalent heterocyclic group.
Multiple R's may be the same or different.

In formula (IV), the aromatic carbocyclic ring that can constitute Ar ¹ and Ar ² is preferably a benzene ring and a naphthalene ring, more preferably a benzene ring and a naphthalene ring, still more preferably a benzene ring. These rings may have a substituent.

The aromatic heterocyclic ring that can constitute Ar ¹ and Ar ² is preferably an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a thienothiophene ring, a benzothiophene ring, a pyrrole ring, a phosphole ring, and a furan ring. , pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, quinoline ring, isoquinoline ring, carbazole ring, and dibenzophosphole ring, and phenoxazine ring, phenothiazine ring, dibenzoborol ring, dibenzosilol ring, and It is a benzopyran ring. These rings may have a substituent.

A halogen atom represented by R is preferably a fluorine atom.

The optionally substituted alkyl group represented by R is preferably an optionally substituted alkyl group having 1 to 20 carbon atoms, more preferably having a substituent. an optionally substituted alkyl group having 1 to 15 carbon atoms, more preferably an optionally substituted alkyl group having 1 to 12 carbon atoms, and still more preferably having a substituent is an alkyl group having 1 to 10 carbon atoms which may be

The substituent that the alkyl group represented by R may have is preferably a halogen atom, more preferably a fluorine atom and/or a chlorine atom.

The optionally substituted cycloalkyl group represented by R is preferably an optionally substituted cycloalkyl group having 3 to 10 carbon atoms, more preferably having a substituent. A cycloalkyl group having 5 to 6 carbon atoms which may be substituted, more preferably a cyclohexyl group which may have a substituent.

The optionally substituted aryl group represented by R is preferably an optionally substituted aryl group having 6 to 15 carbon atoms, more preferably an optionally substituted aryl group. phenyl group or naphthyl group.

The substituents that the aryl group represented by R may have are preferably halogen atoms (eg, chlorine atom, fluorine atom), alkyl groups having 1 to 12 carbon atoms (eg, methyl group, trifluoromethyl group, tert-butyl group, octyl group, dodecyl group), alkyloxy group having 1 to 12 carbon atoms (e.g., methoxy group, ethoxy group, octyloxy group), alkylsulfonyl group having 1 to 12 carbon atoms (e.g. , dodecylsulfonyl group), and/or a cyano group.

The optionally substituted alkyloxy group represented by R is preferably an optionally substituted alkyloxy group having 1 to 10 carbon atoms, more preferably having a substituent. an alkyloxy group having 1 to 8 carbon atoms which may be The group may have a substituent.

The optionally substituted aryloxy group represented by R is preferably an optionally substituted aryloxy group having 6 to 15 carbon atoms, more preferably having a substituent. phenyloxy group or anthracenyloxy group which may be substituted.

The substituent that the aryloxy group represented by R may have is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 6 carbon atoms. is a methyl group.

The optionally substituted alkylthio group represented by R is preferably an optionally substituted alkylthio group having 1 to 6 carbon atoms, and more preferably an optionally substituted alkylthio group. an alkylthio group having 1 to 3 carbon atoms, which may be optionally substituted, and more preferably a methylthio group or a propylthio group, which may have a substituent.

The optionally substituted arylthio group represented by R is preferably an optionally substituted arylthio group having 6 to 10 carbon atoms, more preferably an optionally substituted arylthio group. phenylthio group.

The substituent that the arylthio group represented by R may have is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably is a methyl group.

The optionally substituted monovalent heterocyclic group represented by R is preferably an optionally substituted 5- or 6-membered monovalent heterocyclic group. Examples of 5-membered monovalent heterocyclic groups include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, and pyrrolidinyl groups. Examples of 6-membered monovalent heterocyclic groups include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, piperidyl, piperazinyl, morpholinyl, and tetrahydropyranyl groups.

The optionally substituted monovalent heterocyclic group represented by R is more preferably a thienyl group, a furyl group, a thiazolyl group, an oxazolyl group, a pyridyl group, or a pyrazyl group, and these groups are It may have a substituent.

The substituent that the monovalent heterocyclic group represented by R may have is preferably an alkyl group having 1 to 12 carbon atoms (e.g., methyl group, trifluoromethyl group, propyl group, hexyl group, octyl group, dodecyl group).

The optionally substituted alkenyl group represented by R is preferably an optionally substituted alkenyl group having 2 to 10 carbon atoms, more preferably having a substituent is an alkenyl group having 2 to 6 carbon atoms which may be optionally substituted, and more preferably a 2-propenyl group or a 5-hexenyl group which may have a substituent.

The optionally substituted cycloalkenyl group represented by R is preferably an optionally substituted cycloalkenyl group having 3 to 10 carbon atoms, more preferably having a substituent. It is a cycloalkenyl group having 6 to 7 carbon atoms which may be substituted, more preferably a cyclohexenyl group or a cycloheptenyl group which may have a substituent.

The substituent that the cycloalkenyl group represented by R may have is preferably an alkyl group having 1 to 12 carbon atoms.

The optionally substituted alkynyl group represented by R is preferably an optionally substituted alkynyl group having 2 to 10 carbon atoms, more preferably having a substituent. is an alkynyl group having 5 to 6 carbon atoms which may be optionally substituted, and more preferably a 5-hexynyl group or a 3-methyl-1-butynyl group which may have a substituent.

The optionally substituted cycloalkynyl group represented by R is preferably an optionally substituted cycloalkynyl group having 6 to 10 carbon atoms, more preferably having a substituent. is a cycloalkynyl group having 7 to 8 carbon atoms which may be substituted, and more preferably a cycloheptynyl group or a cyclooctynyl group which may have a substituent.

The substituent that the cycloalkynyl group represented by R may have is preferably a C1-C12 alkyl group.

A plurality of Rs are each independently preferably an optionally substituted alkyl group, more preferably an optionally substituted alkyl group having 1 to 15 carbon atoms, More preferably, it is an optionally substituted alkyl group having 1 to 12 carbon atoms, and more preferably an optionally substituted alkyl group having 1 to 10 carbon atoms. It is particularly preferred that each of a plurality of Rs is an optionally substituted alkyl group having 1 to 10 carbon atoms.

In the group represented by —C(=O)—R ^a represented by R and the group represented by —SO ₂ —R ^b , R ^a is preferably a hydrogen atom, and R ^b is preferably is an optionally substituted alkyl group or an optionally substituted alkyloxy group, more preferably an optionally substituted alkyl group having 1 to 12 carbon atoms or An optionally substituted alkyloxy group having 1 to 12 carbon atoms, more preferably an optionally substituted alkyl group having 1 to 12 carbon atoms or having a substituent an alkyloxy group having 1 to 6 carbon atoms which may be substituted, and more preferably a methyl group, an ethyl group, a 2-methylpropyl group, an octyl group, a dodecyl group, or an ethoxy group; You may have a group.

Examples of structural units represented by formula (IV) include structural units represented by the following formulas.

In the above formula, R is as already explained.

The structural unit represented by the above formula (IV) that can constitute B ¹ is preferably a structural unit represented by the following formula (V).

In formula (V), Y and R are as already explained. X ¹ and X ² each independently represent a sulfur atom or an oxygen atom, and Z ¹ and Z ² each independently represent a group represented by =C(R)- or a nitrogen atom.

Examples of structural units represented by formula (V) include structural units represented by the following formula.

The structural unit represented by the formula (V) that can constitute B ¹ is an optionally substituted divalent polycyclic ring containing two or more thiophene rings and containing an sp3 carbon atom as a constituent element A condensed ring group is preferably a structural unit represented by the following formula (V-1).

In formula (V-1), Y and R are as defined above.

Preferred specific examples of the structural unit represented by formula (V-1) include structural units represented by the following formula.

Examples of suitable structural units represented by formula (V) that can constitute B ¹ also include structural units represented by the following formula (V-2).

In formula (V-2), X ¹ and X ² , Z ¹ and Z ² and R are as already explained.

Examples of structural units represented by formula (V-2) include structural units represented by formulas (V-2-1) to (V-2-16) below.

Preferred specific examples of the structural unit represented by formula (V-2) include structural units represented by the following formula.

In the present embodiment, ^B1 preferably contains one first structural unit (first structural unit CU1) represented by formula (IV) or formula (V) above.

As the second structural unit (second structural unit CU2) that B ¹ other than the structural unit represented by the above formula (IV) or formula (V) may contain, for example, a divalent group containing an unsaturated bond , divalent aromatic carbocyclic groups and divalent aromatic heterocyclic groups.

The second structural unit CU2 "a divalent group containing an unsaturated bond" is, for example, a group represented by -(CR=CR)n- (R is as defined above, n is 1 n is an integer equal to or greater than 1. The value of n is preferably 1 or 2, more preferably 1.), a group represented by -C≡C-, and a phenylene group.

Specific examples of the "divalent group containing an unsaturated bond" include ethene-1,2-diyl group, 1,3-butadiene-1,4-diyl group, acetylene-1,2-diyl group, and phenylene groups.

Specific examples of the “divalent aromatic heterocyclic group” which is the second structural unit CU2 include groups represented by the following formulas (101) to (191). These groups may further have a substituent.

In formulas (101) to (191), R has the same definition as above.

Specific examples of the "divalent aromatic carbocyclic group" that is the second structural unit CU2 include a phenylene group (e.g., the following formulas 1 to 3), a naphthalene-diyl group (e.g., the following formulas 4 to 13 ), anthracene-diyl group (e.g., formulas 14 to 19 below), biphenyl-diyl group (e.g., formulas 20 to 25 below), terphenyl-diyl group (e.g., formulas 26 to 28 below), condensed ring Compound groups (eg, formulas 29 to 35 below), fluorene-diyl groups (eg, formulas 36 to 38 below), and benzofluorene-diyl groups (eg, formulas 39 to 46 below) are included.

In Formulas 1 to 46, R has the same definition as above.

In the compound of the present embodiment, the second structural unit CU2 is selected from the group consisting of divalent groups containing unsaturated bonds and groups represented by the following formulas (VI-1) to (VI-12) Among them, structural units selected from the group consisting of groups represented by formulas (VI-10) to (VI-12) are more preferred.

In formulas (VI-1) to (VI-12), X ¹ , X ² , Z ¹ , Z ² and R are as defined above.
When there are two R's, the two R's may be the same or different.

A more specific preferred example of the second structural unit CU2 is a structural unit represented by the following formula. These structural units may further have a substituent.

In the compound of this embodiment, B ¹ contains one or more structural units, at least one of the one or more structural units is the first structural unit CU1, and The remaining structural unit is the second structural unit CU2.

The combination and arrangement of the first structural unit CU1 and the second structural unit CU2 contained in ^B1 are not particularly limited, provided that a π-conjugated system can be formed.

B ¹ is preferably a divalent group having any one structure selected from the group consisting of structures represented by formulas (VII-1) to (VII-16) below.

-CU1- (VII-1)

-CU1-CU1- (VII-2)

-CU1-CU2- (VII-3)

-CU1-CU1-CU1- (VII-4)

-CU1-CU2-CU1- (VII-5)

-CU1-CU1-CU2- (VII-6)

-CU1-CU2-CU2- (VII-7)

-CU2-CU1-CU2- (VII-8)

-CU1-CU1-CU1-CU1- (VII-9)

-CU1-CU1-CU1-CU2- (VII-10)

-CU1-CU1-CU2-CU1- (VII-11)

-CU1-CU1-CU2-CU2- (VII-12)

-CU1-CU2-CU1-CU2- (VII-13)

-CU1-CU2-CU2-CU1- (VII-14)

-CU1-CU2-CU2-CU2- (VII-15)

-CU2-CU1-CU2-CU2- (VII-16)

In formulas (VII-1) to (VII-16),
CU1 represents the first structural unit CU1,
CU2 represents the second structural unit CU2.
When there are two or more CU1s, the two or more CU1s may be the same or different, and when there are two or more CU2s, the two or more CU2s may be the same or different. may

Among the formulas (VII-1) to (VII-16), structures represented by formulas (VII-1) to (VII-8), formulas (VII-15) and formulas (VII-16) A divalent group having is preferred, formula (VII-1), formula (VII-3), formula (VII-7), formula (VII-8), formula (VII-15) and formula (VII-16) A divalent group having a structure represented by is more preferred.

The total number of the first structural unit CU1 and the second structural unit CU2 that can be contained in ^B1 is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 7 or less. Yes, preferably 5 or less, more preferably 4 or less.
The number of first structural units CU1 that can be contained in ^B1 is usually 5 or less, preferably 3 or less, and more preferably 1.
The number of second structural units CU2 that can be contained in ^B1 is usually 5 or less, preferably 3 or less, and more preferably 1 or less.

Specific preferred examples of B ¹ include divalent groups represented by the following formulas.

In the formula, R is as defined above.

(3) Specific Examples of Non-Fullerene Compound Specific examples of the non-fullerene compound represented by formula (I) of the present embodiment include compounds represented by the following formula.

More specific preferred examples of the non-fullerene compound represented by formula (I) of the present embodiment include compounds represented by formulas N-1 to N-7 below.

2. Method for producing a non-fullerene compound The non-fullerene compound of the present embodiment is produced by, for example, using two or more raw material compounds capable of constituting A ¹ and B ¹ already described, as shown in the synthesis examples described later. It can be produced (synthesized) by any suitable conventionally known method.

In this embodiment, the active layer of the photoelectric conversion element may contain only the non-fullerene compound of this embodiment as an n-type semiconductor material, and a compound other than the non-fullerene compound of this embodiment may be added to a further n-type semiconductor. It may be included as a material. Compounds other than the non-fullerene compounds of the present embodiment that can be included as further n-type semiconductor materials may be low-molecular-weight compounds or high-molecular-weight compounds.

Examples of n-type semiconductor materials (electron-accepting compounds) other than the low-molecular compound "non-fullerene compound of the present embodiment" include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, and naphthoquinone. and derivatives thereof, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, and phenanthrene derivatives such as bathocuproine are mentioned.

Examples of n-type semiconductor materials other than the "fullerene compound of the present embodiment", which is a polymer compound, include polyvinylcarbazole and its derivatives, polysilane and its derivatives, and polysiloxane derivatives having an aromatic amine structure in the side chain or main chain. , polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, and polyfluorene and its derivatives be done.

Compounds that are n-type semiconductor materials other than the "non-fullerene compound of the present embodiment" may include fullerene derivatives.

Here, the fullerene derivative refers to a compound in which at least a portion of fullerene ( _C60 fullerene, _C70 fullerene, _C76 fullerene, _C78 fullerene, and _C84 fullerene) is modified. In other words, it refers to a compound having one or more groups attached to the fullerene skeleton. Hereinafter, the fullerene derivative of _C60 fullerene may be particularly referred to as " _C60 fullerene derivative", and the fullerene derivative of _C70 fullerene may be referred to as " _C70 fullerene derivative".

A fullerene derivative that can be used as an n-type semiconductor material other than the "non-fullerene compound of the present embodiment" is not particularly limited as long as it does not impair the object of the present invention.

Specific examples of _C60 fullerene derivatives that can be used as n-type semiconductor materials other than the "non-fullerene compound of the present embodiment" include the following compounds.

In the formula, R is as defined above. When there are multiple Rs, the multiple Rs may be the same or different.

Examples of _C70 fullerene derivatives include the following compounds.

3. Photoelectric conversion element The photoelectric conversion element according to the present embodiment includes an anode, a cathode, and an active layer provided between the anode and the cathode and containing a p-type semiconductor material and an n-type semiconductor material, A photoelectric conversion device containing the compound of the present embodiment described above as the n-type semiconductor material.

According to the photoelectric conversion element of this embodiment, by having the above configuration, it is possible to effectively improve the characteristics of the photoelectric conversion element such as the external quantum efficiency and the photoelectric conversion efficiency.

Here, a configuration example that the photoelectric conversion element of this embodiment can take will be described. FIG. 1 is a diagram schematically showing the configuration of the photoelectric conversion element of this embodiment.

As shown in FIG. 1, the photoelectric conversion element 10 is provided on the support substrate 11 . The photoelectric conversion element 10 includes an anode 12 provided in contact with a support substrate 11, a hole transport layer 13 provided in contact with the anode 12, and a hole transport layer 13 provided in contact with the hole transport layer 13. an active layer 14 , an electron transport layer 15 provided in contact with the active layer 14 , and a cathode 16 provided in contact with the electron transport layer 15 . In this configuration example, a sealing member 17 is further provided so as to be in contact with the cathode 16 .
Constituent elements that can be included in the photoelectric conversion element of this embodiment will be specifically described below.

(substrate)
A photoelectric conversion element is usually formed on a substrate (support substrate). Further, it may be further sealed with a substrate (sealing substrate). One of a pair of electrodes, typically an anode and a cathode, is formed on the substrate. The material of the substrate is not particularly limited as long as it is a material that does not chemically change when the layer containing an organic compound is formed.

Materials for the substrate include, for example, glass, plastic, polymer film, and silicon. When an opaque substrate is used, the electrode on the opposite side of the electrode provided on the opaque substrate (in other words, the electrode on the far side from the opaque substrate) is preferably a transparent or translucent electrode. .

(electrode)
A photoelectric conversion element includes a pair of electrodes, an anode and a cathode. At least one of the anode and the cathode is preferably a transparent or translucent electrode in order to allow light to enter.

Examples of transparent or semi-transparent electrode materials include conductive metal oxide films and semi-transparent metal thin films. Specifically, indium oxide, zinc oxide, tin oxide, and their composites indium tin oxide (ITO), indium zinc oxide (IZO), conductive materials such as NESA, gold, platinum, silver, copper. ITO, IZO, and tin oxide are preferable as materials for transparent or translucent electrodes. Moreover, as the electrode, a transparent conductive film using an organic compound such as polyaniline and its derivatives, polythiophene and its derivatives as a material may be used. The transparent or translucent electrode can be either the anode or the cathode.

If one electrode of the pair of electrodes is transparent or translucent, the other electrode may be an electrode with low light transmittance. Examples of materials for electrodes with low light transmittance include metals and conductive polymers. Specific examples of low light transmissive electrode materials include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, Metals such as terbium, ytterbium, and alloys of two or more thereof, or one or more of these metals together with gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin alloys with one or more metals selected from the group consisting of graphite, graphite intercalation compounds, polyaniline and its derivatives, polythiophene and its derivatives. Alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys.

(active layer)
The active layer included in the photoelectric conversion element of the present embodiment is assumed to have a bulk heterojunction structure and includes a p-type semiconductor material and an n-type semiconductor material, and the active layer is an n-type semiconductor material. includes the non-fullerene compound of the present embodiment (details will be described later).

In this embodiment, the thickness of the active layer is not particularly limited. The thickness of the active layer can be any suitable thickness considering the balance between suppression of dark current and extraction of the generated photocurrent. The thickness of the active layer is preferably 100 nm or more, more preferably 150 nm or more, and even more preferably 200 nm or more, particularly from the viewpoint of further reducing dark current. Also, the thickness of the active layer is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 1 μm or less.

Here, a p-type semiconductor material that can be suitably used in combination with the n-type semiconductor material, which is the non-fullerene compound of the present embodiment, will be described as the material of the active layer according to the present embodiment.

The p-type semiconductor material is preferably a polymer compound having a predetermined polystyrene-equivalent weight-average molecular weight.

Here, the polystyrene equivalent weight average molecular weight means the weight average molecular weight calculated using a standard sample of polystyrene using gel permeation chromatography (GPC).

The polystyrene-equivalent weight-average molecular weight of the p-type semiconductor material is preferably 3,000 or more and 500,000 or less, particularly from the viewpoint of improving solubility in a solvent.

In the present embodiment, the p-type semiconductor material is a π-conjugated polymer compound (DA-type conjugated polymer It is also referred to as a compound.). It should be noted that which is the donor structural unit or which is the acceptor structural unit can be relatively determined from the energy level of the HOMO or LUMO.

Here, the donor structural unit is a structural unit with an excess of π electrons, and the acceptor structural unit is a structural unit with a π electron deficiency.

In the present embodiment, the structural unit that can constitute the p-type semiconductor material may be a structural unit in which a donor structural unit and an acceptor structural unit are directly bonded, or a donor structural unit and an acceptor structural unit. Structural units linked via spacers (groups or structural units) are also included.

Examples of p-type semiconductor materials that are polymer compounds include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives containing an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives. , polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyfluorene and its derivatives.

The p-type semiconductor material of this embodiment is preferably a polymer compound containing a structural unit represented by the following formula (VIII). A structural unit represented by the following formula (VIII) is usually a donor structural unit in the present embodiment.

In formula (VIII), Ar ⁵ and Ar ⁶ represent an optionally substituted trivalent aromatic heterocyclic group, and Z is represented by the following formulas (Z-1) to (Z-7). represents the group represented.

In formulas (Z-1) to (Z-7),
R is as defined above.
In each of formulas (Z-1) to (Z-7), when there are two R's, the two R's may be the same or different.

The aromatic heterocycles that can constitute Ar ⁵ and Ar ⁶ include, in addition to monocyclic rings and condensed rings in which the heterocycle itself exhibits aromaticity, even if the heterocycle itself does not exhibit aromaticity. A ring in which an aromatic ring is condensed to a heterocyclic ring is included.

Each of the aromatic heterocycles that can constitute Ar ⁵ and Ar ⁶ may be a monocyclic ring or a condensed ring. When the aromatic heterocycle is a condensed ring, all of the rings constituting the condensed ring may be aromatic condensed rings, or only some of the rings may be aromatic condensed rings. When these rings have multiple substituents, these substituents may be the same or different.

Specific examples of aromatic carbocyclic rings that can constitute Ar ⁵ and Ar ⁶ include benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring and phenanthrene ring, preferably benzene ring and naphthalene ring. It is a ring, more preferably a benzene ring or a naphthalene ring, still more preferably a benzene ring. These rings may have a substituent.

Specific examples of the aromatic heterocyclic ring include ring structures possessed by compounds already described as aromatic heterocyclic compounds, such as oxadiazole ring, thiadiazole ring, thiazole ring, oxazole ring, thiophene ring, pyrrole ring, phosphole ring, furan ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, quinoline ring, isoquinoline ring, carbazole ring, dibenzophosphole ring, phenoxazine ring, phenothiazine ring, dibenzoborol ring, dibenzo A silole ring and a benzopyran ring are included. These rings may have a substituent.

The structural unit represented by formula (VIII) is preferably a structural unit represented by formula (VIII-1), (VIII-2) or (VIII-3) below.

In formulas (VIII-1), (VIII-2) and (VIII-3), Ar ⁵ , Ar ⁶ and R are as defined above.

Specific examples of suitable structural units represented by formula (VIII) include structural units represented by the following formulae.

In the above formula, R is as defined above.
When there are two R's, the two R's may be the same or different.

More specific examples of preferred structural units represented by formula (VIII) include structural units represented by the following formulae.

The polymer compound that is the p-type semiconductor material in the present embodiment preferably contains a structural unit represented by the following formula (IX). A structural unit represented by the following formula (IX) is usually an acceptor structural unit in the present embodiment.

In formula (IX), Ar ⁷ represents a divalent aromatic heterocyclic group.

The number of carbon atoms in the divalent aromatic heterocyclic group represented by Ar ⁷ is generally 2-60, preferably 4-60, more preferably 4-20.

The divalent aromatic heterocyclic group represented by Ar ⁷ may have a substituent. Examples of the substituent that the divalent aromatic heterocyclic group represented by Ar ⁷ may have include a halogen atom, an optionally substituted alkyl group, and a optionally substituted aryl group, optionally substituted alkyloxy group, optionally substituted aryloxy group, optionally substituted alkylthio group, optionally substituted optionally substituted arylthio group, optionally substituted monovalent heterocyclic group, optionally substituted amino group, optionally substituted acyl group, optionally substituted optionally imine residue, optionally substituted amide group, optionally substituted acid imide group, optionally substituted oxycarbonyl group, substituent alkenyl groups optionally having a, alkynyl groups optionally having substituents, cyano groups, and nitro groups.

As the structural unit represented by the formula (IX), structural units represented by the following formulas (IX-1) to (IX-10) are preferable.

In formulas (IX-1) to (IX-10),
X ¹ , X ² , Z ¹ , Z ² and R are as defined above.
When there are two R's, the two R's may be the same or different.

Both X ¹ and X ² in formulas (IX-1) to (IX-10) are preferably sulfur atoms from the viewpoint of availability of starting compounds.

The structural units represented by formulas (IX-1) to (IX-10) can usually function as acceptor structural units as described above. However, it is not limited to this, and in particular structural units represented by formulas (IX-4), (IX-5) and (IX-7) can also function as donor structural units.

In the present embodiment, the p-type semiconductor material is preferably a π-conjugated polymer compound containing a structural unit containing a thiophene skeleton and containing a π-conjugated system.

Specific examples of the divalent aromatic heterocyclic group represented by Ar ⁷ include groups represented by the above formulas (101) to (191). These groups may further have a substituent.

The polymer compound that is the p-type semiconductor material of the present embodiment includes a structural unit represented by formula (VIII) as a donor structural unit and a structural unit represented by formula (IX) as an acceptor structural unit. A conjugated polymer compound is preferred.

In the polymer compound that is the p-type semiconductor material of the present embodiment, the polymer compound that is the p-type semiconductor material includes a structural unit represented by the already described formula (VIII) and a structure represented by the following formula (IX). A structure in which units are linked may be included as a structural unit.

The polymer compound that is the p-type semiconductor material of the present embodiment may contain two or more structural units represented by formula (VIII), and two or more structural units represented by formula (IX). may contain.

For example, from the viewpoint of improving solubility in a solvent, the polymer compound that is the p-type semiconductor material of the present embodiment may contain a structural unit represented by the following formula (X).

In formula (X), Ar ⁸ represents an arylene group.

The arylene group represented by Ar ⁸ means an atomic group remaining after removing two hydrogen atoms from an optionally substituted aromatic hydrocarbon. Aromatic hydrocarbons include compounds having condensed rings, and compounds in which two or more selected from the group consisting of independent benzene rings and condensed rings are bonded directly or via a divalent group such as a vinylene group. included.

Examples of the substituent that the aromatic hydrocarbon may have include the same substituents as those exemplified as the substituent that the heterocyclic compound may have.

The number of carbon atoms in the arylene group represented by Ar ⁸ is usually 6-60, preferably 6-20, not including the number of carbon atoms in the substituent. The number of carbon atoms in the arylene group including substituents is usually 6-100.

Examples of the arylene group represented by Ar ⁸ include a phenylene group (eg, the following formulas 1 to 3), a naphthalene-diyl group (eg, the following formulas 4 to 13), an anthracene-diyl group (eg, the following formulas 14 to formula 19), biphenyl-diyl groups (e.g., formulas 20 to 25 below), terphenyl-diyl groups (e.g., formulas 26 to 28 below), condensed ring compound groups (e.g., formulas 29 to 35 below ), fluorene-diyl groups (eg, formulas 36 to 38 below), and benzofluorene-diyl groups (eg, formulas 39 to 46 below).

In the formula, R is as defined above. Plural R's may be the same or different.

The structural unit represented by the formula (X) is preferably a structural unit represented by the following formulas (X-1) and (X-2).

In formula (X-1), R is as defined above. Two R's may be the same or different.

A structural unit constituting a polymer compound that is a p-type semiconductor material may be a structural unit in which two or more types of structural units selected from the above structural units are combined and linked.

When the polymer compound as the p-type semiconductor material contains the structural unit represented by formula (VIII) and/or the structural unit represented by formula (IX), the structural unit represented by formula (VIII) and the formula The total amount of structural units represented by (IX) is usually 20 mol% to 100 mol% when the amount of all structural units contained in the polymer compound is 100 mol%, and the charge as a p-type semiconductor material From the viewpoint of improving transportability, the content is preferably 40 mol % to 100 mol %, more preferably 50 mol % to 100 mol %.

Specific examples of the polymer compound that is the p-type semiconductor material of the present embodiment include polymer compounds represented by the following formulas (P-1) to (P-18).

In the above formula, R is as defined above. Plural R's may be the same or different.

If the polymer compound exemplified above is used as the p-type semiconductor material, it is possible to suppress the decrease in EQE during heat treatment in the manufacturing process of the photoelectric conversion element or the process of incorporating the photoelectric conversion element into a device to which the photoelectric conversion element is applied. can be further improved, and the heat resistance of the photoelectric conversion element can be improved.

(middle layer)
As shown in FIG. 1, the photoelectric conversion device of the present embodiment includes, for example, a charge transport layer (electron transport layer, hole transport layer, electron injection layer, An intermediate layer (buffer layer) such as a hole injection layer is preferably provided.

Examples of materials used for the intermediate layer include metals such as calcium, inorganic oxide semiconductors such as molybdenum oxide and zinc oxide, and PEDOT (poly(3,4-ethylenedioxythiophene)) and PSS (poly( 4-styrenesulfonate)) (PEDOT:PSS).

As shown in FIG. 1, the photoelectric conversion device preferably has a hole transport layer between the anode and the active layer. The hole transport layer has a function of transporting holes from the active layer to the electrode.

A hole-transporting layer provided in contact with an anode may be particularly referred to as a hole-injecting layer. A hole transport layer (hole injection layer) provided in contact with the anode has a function of promoting injection of holes into the anode. The hole transport layer (hole injection layer) may be in contact with the active layer.

The hole-transporting layer contains a hole-transporting material. Examples of hole-transporting materials include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing constitutional units having aromatic amine residues, CuSCN, CuI, NiO, tungsten oxide (WO ₃ ) and molybdenum oxide. (MoO ₃ ).

The intermediate layer can be formed by any suitable conventionally known forming method. The intermediate layer can be formed by a vacuum deposition method or a coating method similar to the method for forming the active layer.

In the photoelectric conversion element according to this embodiment, the intermediate layer is an electron transport layer, and the substrate (supporting substrate), anode, hole transport layer, active layer, electron transport layer, and cathode are laminated in this order so as to be in contact with each other. It is preferable to have a

As shown in FIG. 1, the photoelectric conversion device of this embodiment preferably has an electron transport layer as an intermediate layer between the cathode and the active layer. The electron transport layer has a function of transporting electrons from the active layer to the cathode. The electron transport layer may be in contact with the cathode. The electron transport layer may be in contact with the active layer.

An electron-transporting layer provided in contact with the cathode may be particularly referred to as an electron-injecting layer. An electron transport layer (electron injection layer) provided in contact with the cathode has a function of promoting injection of electrons generated in the active layer into the cathode.

The electron-transporting layer contains an electron-transporting material. Examples of electron-transporting materials include polyalkyleneimines and their derivatives, high-molecular compounds containing a fluorene structure, metals such as calcium, and metal oxides.

Examples of polyalkyleneimines and derivatives thereof include alkyleneimine having 2 to 8 carbon atoms, especially alkyleneimine having 2 to 8 carbon atoms, such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, octyleneimine. Examples include polymers obtained by conventionally polymerizing one or more of 2 to 4 alkyleneimines, and polymers chemically modified by reacting them with various compounds. Preferred polyalkyleneimines and derivatives thereof are polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE).

Examples of polymer compounds containing a fluorene structure include poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-ortho-2,7-(9 ,9′-dioctylfluorene)] (PFN) and PFN-P2.

Examples of metal oxides include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide and niobium oxide. As the metal oxide, a metal oxide containing zinc is preferable, and zinc oxide is particularly preferable.

Examples of other electron-transporting materials include poly(4-vinylphenol) and perylene diimide.

(sealing member)
Preferably, the photoelectric conversion element of the present embodiment further includes a sealing member, and is a sealed body sealed with the sealing member.
Any suitable conventionally known member can be used as the sealing member. Examples of the sealing member include a combination of a glass substrate as a substrate (sealing substrate) and a sealing material (adhesive) such as a UV curable resin.

The sealing member may be a sealing layer having a layer structure of one or more layers. Examples of layers constituting the sealing layer include gas barrier layers and gas barrier films.

The sealing layer is preferably formed of a material having a property of blocking moisture (water vapor barrier property) or a property of blocking oxygen (oxygen barrier property). Examples of suitable materials for the sealing layer include polyethylene trifluoride, polytrifluoroethylene chloride (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, ethylene-vinyl alcohol copolymer, and the like. Examples include organic materials, inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, and diamond-like carbon.

The sealing member is usually made of a material that can withstand heat treatment to which the photoelectric conversion element is applied, for example, when incorporated into a device of the following application examples.

(Use of photoelectric conversion element)
Applications of the photoelectric conversion device of this embodiment include photodetection devices and solar cells.
More specifically, the photoelectric conversion element of the present embodiment allows a photocurrent to flow by irradiating light from the transparent or translucent electrode side while a voltage (reverse bias voltage) is applied between the electrodes. and can be operated as a photodetector (optical sensor). Also, it can be used as an image sensor by integrating a plurality of photodetectors. Thus, the photoelectric conversion element of this embodiment can be suitably used as a photodetector.

Moreover, the photoelectric conversion element of this embodiment can generate a photovoltaic force between the electrodes by being irradiated with light, and can be operated as a solar cell. A solar cell module can also be obtained by integrating a plurality of photoelectric conversion elements.

(Application example of photoelectric conversion element)
The photoelectric conversion element according to the present embodiment is suitably applied as a light detection element to detection units provided in various electronic devices such as workstations, personal computers, personal digital assistants, entrance/exit management systems, digital cameras, and medical equipment. can do.

The photoelectric conversion element of the present embodiment is provided in the above-exemplified electronic device, for example, an image detection unit for a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor (e.g., an image sensor such as an X-ray sensor), a fingerprint Detection units of biometric information authentication devices that detect predetermined features of a part of a living body, such as detection units, face detection units, vein detection units, and iris detection units (e.g., near-infrared sensors), and optical biosensors such as pulse oximeters. It can be suitably applied to a detection unit or the like.

The photoelectric conversion element of this embodiment can be suitably applied as an image detection unit for a solid-state imaging device, and further to a time-of-flight (TOF) type distance measurement device (TOF type distance measurement device).

4. Method for Manufacturing Photoelectric Conversion Element The method for manufacturing the photoelectric conversion element of the present embodiment is not particularly limited. The photoelectric conversion element of this embodiment can be manufactured by combining the materials selected for forming the constituent elements with a suitable forming method.

The method for manufacturing the photoelectric conversion element of this embodiment can include a step including a heating process at a heating temperature of 100° C. or higher. More specifically, the active layer is formed by a step including a process of heating at a heating temperature of 100° C. or higher, and/or heated at a heating temperature of 100° C. or higher after the step of forming the active layer. can include steps including processing to be performed.

Hereinafter, as an embodiment of the present invention, a method for manufacturing a photoelectric conversion element having a structure in which a substrate (supporting substrate), an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are in contact with each other in this order will be described.

(Process of preparing substrate)
In this step, for example, a support substrate provided with an anode is prepared. Alternatively, a substrate provided with a conductive thin film made of the material for the electrode already described is obtained from the market, and if necessary, the conductive thin film is patterned to form an anode, thereby forming an anode. A coated support substrate can be provided.

In the method of manufacturing the photoelectric conversion element according to this embodiment, the method of forming the anode on the support substrate is not particularly limited. The anode is formed by any suitable conventionally known method such as a vacuum deposition method, a sputtering method, an ion plating method, a plating method, a coating method, etc., using the materials already described. layer, hole transport layer).

(Step of forming hole transport layer)
The method for manufacturing a photoelectric conversion element may include a step of forming a hole transport layer (hole injection layer) provided between the active layer and the anode.

A method for forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the process of forming the hole transport layer, it is preferable to form the hole transport layer by any suitable conventionally known coating method. The hole transport layer can be formed by, for example, a coating method using a coating liquid containing the material for the hole transport layer and a solvent, or a vacuum deposition method.

(Step of forming active layer)
In the method for manufacturing the photoelectric conversion element of this embodiment, the active layer is formed on the hole transport layer. The active layer, which is the main component, can be formed by any suitable conventionally known forming process. In this embodiment, the active layer is preferably produced by a coating method using an ink composition (ink, coating liquid).

The steps (i) and (ii) included in the step of forming the active layer, which is the main component of the photoelectric conversion element of the present invention, will be described below.

step (i)
Any suitable coating method can be used as a method for coating the ink composition onto the coating object. The coating method is preferably a slit coating method, a knife coating method, a spin coating method, a micro gravure coating method, a gravure coating method, a bar coating method, an inkjet printing method, a nozzle coating method, or a capillary coating method. A coating method, a capillary coating method, or a bar coating method is more preferable, and a slit coating method or a spin coating method is even more preferable.

The ink composition used in the method for producing a photoelectric conversion element of this embodiment contains at least one p-type semiconductor material and at least one n-type semiconductor material.

Therefore, the ink composition of the present embodiment is preferably an ink composition for forming an active layer of a photoelectric conversion element. The ink composition for forming the active layer of this embodiment will be described below. The ink composition for forming an active layer of the present embodiment is preferably an ink composition for forming a bulk heterojunction active layer. Therefore, the ink composition for forming the active layer includes a composition containing the already described non-fullerene compound of the present embodiment as the already described p-type semiconductor material or n-type semiconductor material. The ink composition for forming an active layer of the present embodiment includes the composition, and two or more solvents including a first solvent and a second solvent having a boiling point higher than that of the first solvent.

According to the ink composition for forming an active layer of the present embodiment, 2 By containing more than one kind of solvent, a better phase separation structure can be formed, and as a result, characteristics such as external quantum efficiency (EQE) can be further improved (details will be described later).

A mixed solvent in which a first solvent and a second solvent are combined is used for the ink composition for forming an active layer according to the present embodiment. Specifically, the ink composition of the present embodiment includes a main solvent (first solvent), which is a main component, and an additive solvent (second solvent).

Here, the first solvent and the second solvent that can be suitably used in the ink composition for forming the active layer of the present embodiment, the combination thereof, and the preparation of the ink composition will be described.

(1) First solvent As the first solvent, both the p-type semiconductor material and the n-type semiconductor material of the present embodiment, and one of the semiconductor materials is a non-fullerene compound represented by formula (I), It is preferable to use a good solvent capable of dissolving. The first solvent of this embodiment is preferably an aromatic hydrocarbon.

Examples of the first solvent include toluene, xylene (eg, o-xylene, m-xylene, p-xylene), o-dichlorobenzene, trimethylbenzene (eg, mesitylene, 1,2,4-trimethylbenzene (pseudocumene)). ), butylbenzene (eg n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (eg 1-methylnaphthalene), tetralin and indane.

The first solvent may be composed of only one solvent, or may be composed of two or more solvents. It is preferable to use only one solvent as the first solvent, as this makes it easier to prepare the ink composition.

The first solvent is preferably toluene, o-xylene, m-xylene, p-xylene, mesitylene, o-dichlorobenzene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butyl One or more selected from the group consisting of benzene, methylnaphthalene, tetralin and indane, more preferably toluene, o-xylene, m-xylene, p-xylene, o-dichlorobenzene, mesitylene, 1,2,4 -trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, tetralin, or indane.

(2) Second Solvent In the present embodiment, the second solvent is a solvent having a boiling point higher than that of the already explained first solvent. In addition, the second solvent is a compound containing ^B1 , which is obtained by severing the bond between ^B1 and ^A1 among the non-fullerene compounds represented by formula (I) described above and having the terminal terminated with a hydrogen atom. and the polar term P(B ¹ ) of the Hansen solubility parameter of the second solvent satisfy the condition represented by the following formula (III).

|P(B ¹ )−P(S2)|>3.2 (MPa ^0.5 ) (III)

In other words, the second solvent has a boiling point higher than that of the first solvent, and the absolute value of the difference between the polar term P(B ¹ ) and the polar term P(S2) is 3.2 (MPa ^0.5 ).

Here, the Hansen Solubility Parameter (HSP) used as an index for the second solvent will be described.

(i) Hansen Solubility Parameter Hansen Solubility Parameter (HSP) is a type of solubility parameter, and is used to search for solvents in organic compounds, investigate solubility when mixing multiple organic compounds, design formulations of additives, etc. is used for The organic compound also includes a polydisperse polymer compound.

The Hansen solubility parameter is attributed to the van der Waals interaction, a dispersion term D that can be an index of the dispersion force, a polar term P that is due to the electrostatic interaction, and can be an index of the force between the dipoles, a hydrogen bond, It contains three components of the hydrogen-bonding term H, which can be indicators of hydrogen-bonding strength, and these can be represented three-dimensionally.

For the definition and calculation method of the Hansen solubility parameter, see, for example, Charles M. et al. Hansen, Hansen Solubility Parameters: A Users Handbook, and B, John, Solubility Parameters: theory and application, The Book and paper group annual Vol. 3, and the calculation method can be appropriately applied to this embodiment as well.

In addition, the Hansen solubility parameters (dispersion term D, polar term P and hydrogen bonding term H) are calculated based on the chemical structure of the compound using commercially available computer software such as Hansen Solubility Parameters in Practice (HSPiP). be able to. Details of the calculation method will be described later.

As described above, the ink composition of the present embodiment is an ink composition containing at least one p-type semiconductor material, at least one n-type semiconductor material, and two or more solvents.

In the method for producing a photoelectric conversion element, particularly when forming an active layer having a bulk heterojunction structure, from the viewpoint of forming a good phase separation structure in the active layer, preparation of an ink composition for forming an active layer is performed. Therefore, it is necessary to select a solvent for suitably mixing the p-type semiconductor material and the n-type semiconductor material.

Here, the solvent to be selected is usually a good solvent having high solubility for the p-type semiconductor material and the n-type semiconductor material. However, in the present embodiment, in addition to the first solvent, which is a good solvent, the semiconductor material represented by the already described formula (I) has a lower solubility and a higher boiling point than the first solvent. A second solvent is also used.

After applying the ink composition of the present embodiment to form the active layer, the solvent must be removed after the application in order to complete the active layer.

According to the present embodiment, in the process of removing the solvent, the first solvent, which is a good solvent with a higher solubility and a lower boiling point, evaporates first, and when the first solvent evaporates, the first solvent In contrast, the second solvent, in which the non-fullerene compound represented by formula (I) has a lower solubility and a higher boiling point, mainly remains. Thus, after the first solvent, which is a good solvent with a lower boiling point, is first removed, the second solvent with a lower solubility of the non-fullerene compound represented by formula (I) and a higher boiling point remains, and then It is considered that the removal of the second solvent also greatly affects the formation of a good phase-separated structure. That is, it is possible to form a good phase separation structure by appropriately selecting a second solvent having a lower solubility of the non-fullerene compound represented by formula (I) and a higher boiling point than the first solvent. Conceivable.

According to the present embodiment, among the three components of the Hansen solubility parameter, by focusing on the polarity term (P) of the Hansen solubility parameter that can be an index of the force between dipoles, the first solvent and the second solvent are selected. A good phase separation structure can be formed, and the characteristics of the photoelectric conversion device, particularly EQE, can be improved.

(ii) Hansen Solubility Parameter Calculation Method Here, the polarity term (P) of the Hansen solubility parameter according to the present embodiment and |P(B ¹ )−P(S2)| A calculation method using the software HSPiP will be described.

First, after specifying the chemical structure of the compound to be calculated, the following steps 1) to 3) are performed. Here, among the non-fullerene compounds according to formula (I) already explained, the compound having the structure "A ¹ -B ¹ " will be explained as an example.

1) First, in the chemical structure of the specified compound, the bond between A ¹ and B ¹ is cleaved to cut out the A ¹ site and the B ¹ site, thereby forming a bond at the end of the B ¹ site is terminated by adding a hydrogen atom to each of the "compounds containing B ¹ ".

2) The polar term P(B ² ) of the Hansen Solubility Parameter for compounds containing the assumed B ¹ is then calculated using the computer software HSPiP.

3) Next, ^{|P(B 1 )} −P(S2)| calculate.

Here, as the value of P(S2) for the second solvent, the value described in "Hansen solubility parameters in practice 4th edition" may be used.

For example, when the second solvent is acetophenone, the value of P(S2) is 9.0 (MPa ^0.5 ).

If two or more solvents are used as the second solvent, the value for the solvent with the highest boiling point should be used.

Here, the calculation of the polarity term P(B ¹ ) will be described using compound N-1 as a specific example.

First, as in step 1) above, when the two bonds between A ¹ and B ¹ are cut in compound N-1, each bond formed in B ¹ is terminated by adding a hydrogen atom, represented by the following formula: Consider a compound (B ¹ ) that contains B ¹ .

Next, as in step 2) above, the polarity term P(B ¹ ) is calculated for compound B ¹ . When actually calculated as described above, P(B ¹ ) was 1.7 (MPa ^0.5 ).

Therefore, when the second solvent is, for example, acetophenone, the value of |P(B ¹ )−P(S2)|, which can be calculated according to step 3) above, can be calculated as 7.3.

In particular, the second solvent applied to the ink composition for forming the bulk heterojunction active layer of the photoelectric conversion device is a solvent in which the non-fullerene compound represented by the formula (I) described above is difficult to dissolve, that is, Preferably, the second solvent is a poor solvent for the non-fullerene compound represented by formula (I).More specifically, the second solvent has a solubility of the non-fullerene compound represented by formula (I) higher than 1 g/L. In addition, the difference between the polar term of the Hansen solubility parameter of the compound containing ^B1 and the polar term of the Hansen solubility parameter of the second solvent satisfies the relationship represented by the above formula (III) can be used.

The second solvent is not particularly limited as long as it satisfies the above requirements. The second solvent can be appropriately selected from conventionally known solvents in consideration of the properties of the selected first solvent. As for the second solvent, not only one type but also two or more types may be used.

By using a solvent that satisfies the above requirements as the second solvent, it is possible to form a better phase-separated structure, thereby improving the characteristics such as EQE of the manufactured photoelectric conversion device.

In the present embodiment, the value of |P(B ¹ )−P(S2)| More preferably, it is greater than .3.

In the present embodiment, the second solvent is a solvent having a boiling point higher than the boiling point of the first solvent by 30° C. or more from the viewpoint of forming a good phase separation structure and improving properties such as EQE. is preferred.

Preferably, the second solvent is an ether solvent, an aromatic hydrocarbon solvent, a ketone solvent or an ester solvent.

Examples of the second solvent include ether solvents such as 1,2-dimethoxybenzene, diphenyl ether and dibenzyl ether, and aromatic hydrocarbons such as 1,2,3,5-tetramethylbenzene, cyclohexylbenzene and 1-methylnaphthalene. Solvents include ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone and propiophenone, ester solvents such as ethyl acetate, butyl acetate, phenyl acetate, ethyl cellosolve acetate, methyl benzoate, butyl benzoate and benzyl benzoate. .

Table 4 below shows the second solvent that can be applied to the ink composition of the present embodiment and the value of the polar term P(S2) (unit: MPa ^0.5 ) of the Hansen solubility parameter.

As the second solvent, it is preferable to use, for example, acetophenone, butyl benzoate, methyl benzoate, and 1,2-dimethoxybenzene from the viewpoint of forming a better phase separation structure and further improving properties such as EQE.

(3) Combination of first solvent and second solvent Examples of suitable combinations of the first solvent and the second solvent are shown in Table 5 below together with boiling points (°C).

As described above, in the ink composition of the present embodiment, examples of suitable combinations of the first solvent and the second solvent include a combination of tetralin (first solvent) and butyl benzoate (second solvent), o - a combination of xylene (first solvent) and methyl benzoate (second solvent), a combination of o-xylene (first solvent) and acetophenone (second solvent), and pseudocumene (first solvent) and 1,2- A combination with dimethoxybenzene (second solvent) may be mentioned.

(4) Volume ratio of the first solvent and the second solvent The volume ratio of the first solvent, which is the main solvent, to the second solvent, which is the additive solvent (first solvent: second solvent), forms a better phase separation structure From the viewpoint of improving characteristics such as EQE as a A range is more preferable.

(5) Any Other Solvent The solvent may contain any other solvent other than the first and second solvents already described. When the total mass of all solvents contained in the ink composition is 100% by mass, the content of any other solvent is preferably 5% by mass or less, more preferably 3% by mass or less, and further Preferably, it is 1% by mass or less. Any other solvent preferably has a higher boiling point than the second solvent.

(6) Optional Components In addition to the first solvent, the second solvent, the p-type semiconductor material and the n-type semiconductor material, the ink composition contains a surfactant, an ultraviolet Optional ingredients such as absorbers, antioxidants, sensitizers to enhance the ability to generate charge from absorbed light, and light stabilizers to increase stability from UV light may be included.

(7) Concentration of p-type semiconductor material and n-type semiconductor material The concentration of the p-type semiconductor material and the n-type semiconductor material in the ink composition is arbitrary within a range that does not impair the object of the present invention, taking into consideration the solubility in the solvent. Any suitable concentration can be used.

The mass ratio (polymer/non-fullerene compound) of the “p-type semiconductor material” to the “n-type semiconductor material” in the ink composition is usually in the range of 1/0.1 to 1/10, preferably 1/0. 0.5 to 1/2, more preferably 1/1.5.

The total concentration of the “p-type semiconductor material” and “n-type semiconductor material” in the ink composition is usually 0.01% by mass or more, more preferably 0.02% by mass or more, and 0.25% by mass or more. More preferred. The total concentration of the "p-type semiconductor material" and "n-type semiconductor material" in the ink composition is usually 20% by mass or less, preferably 10% by mass or less, and 7.50% by mass or less. It is more preferable to have

The concentration of the “p-type semiconductor material” in the ink composition is usually 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.10% by mass or more. Also, the concentration of the "p-type semiconductor material" in the ink composition is usually 10% by mass or less, more preferably 5.00% by mass or less, and even more preferably 3.00% by mass or less.

The concentration of the "n-type semiconductor material" in the ink composition is usually 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.15% by mass or more. Also, the concentration of the "n-type semiconductor material" in the ink is usually 10% by mass or less, more preferably 5% by mass or less, and even more preferably 4.50% by mass or less.

(8) Preparation of Ink Composition In the present embodiment, the ink composition can be prepared by any suitable conventionally known method. For example, the first solvent, or the first solvent and the second solvent are mixed to prepare a mixed solvent, and the (conjugated) polymer compound (p-type semiconductor material) and the formula (I) are added to the resulting mixed solvent. A method of adding a compound (n-type semiconductor material), adding a p-type semiconductor material to the first solvent, adding an n-type semiconductor material to the second solvent, and then adding the first solvent and the first solvent to which each material was added. It can be prepared by, for example, a method of mixing two solvents.

The first solvent, the second solvent, the p-type semiconductor material and the n-type semiconductor material may be heated to a temperature equal to or lower than the boiling point of the solvent and mixed.

After mixing the first solvent and the second solvent with the p-type semiconductor material and the n-type semiconductor material, the resulting mixture may be filtered using a filter, and the resulting filtrate may be used as the solvent. As the filter, for example, a filter made of a fluororesin such as polytetrafluoroethylene (PTFE) can be used.

The ink composition for forming an active layer is applied to an application target selected according to the photoelectric conversion element and its manufacturing method. The ink composition for forming an active layer can be applied to a functional layer of a photoelectric conversion element, in which an active layer may exist, in the manufacturing process of the photoelectric conversion element. Therefore, the object to be coated with the ink composition for forming the active layer varies depending on the layer structure and the order of layer formation of the photoelectric conversion element to be manufactured. For example, when the photoelectric conversion element has a layer structure in which a substrate, an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are laminated, and the layer described further to the left is formed first. , the object to be coated with the ink composition for forming the active layer is the hole transport layer. Further, for example, the photoelectric conversion element has a layer structure in which a substrate, a cathode, an electron transport layer, an active layer, a hole transport layer, and an anode are laminated, and the layer described further to the left is formed first. In this case, the object to be coated with the ink composition for forming the active layer is the electron transport layer.

step (ii)
Any suitable method can be used as a method for removing the solvent from the coating film of the ink composition, that is, as a method for removing the solvent from the coating film and solidifying the coating film. Examples of methods for removing the solvent include direct heating using a hot plate under an inert gas atmosphere such as nitrogen gas, hot air drying, infrared heat drying, flash lamp annealing drying, and vacuum drying. and other drying methods.

In the method for manufacturing a photoelectric conversion element of the present embodiment, step (ii) is a step for volatilizing and removing the solvent, and is also called a pre-baking step (first heat treatment step).

The implementation conditions of the pre-baking process and the post-baking process, that is, conditions such as heating temperature and heat treatment time, can be arbitrarily suitable in consideration of the composition of the ink used, the boiling point of the solvent, and the like.

Specifically, in the method for manufacturing the photoelectric conversion element of the present embodiment, for example, the pre-baking process and the post-baking process can be performed using a hot plate in a nitrogen gas atmosphere.

The total heat treatment time in the pre-baking process and the post-baking process can be set to 1 hour, for example.

The heating temperature in the pre-baking process and the heating temperature in the post-baking process may be the same or different.

The heat treatment time can be, for example, 10 minutes or longer. Although the upper limit of the heat treatment time is not particularly limited, it can be set to, for example, 4 hours in consideration of the tact time and the like.

The thickness of the active layer can be any desired desired thickness by appropriately adjusting the solid content concentration in the ink composition and the conditions of the above step (i) and/or step (ii).

The step of forming the active layer may include other steps in addition to the steps (i) and (ii) provided that the objects and effects of the present invention are not impaired.

The method for manufacturing a photoelectric conversion element of the present embodiment may be a method for manufacturing a photoelectric conversion element including a plurality of active layers, or may be a method in which steps (i) and (ii) are repeated multiple times. good.

(Step of forming electron transport layer)
The method for manufacturing the photoelectric conversion element of this embodiment includes a step of forming an electron transport layer (electron injection layer) provided on the active layer.

A method for forming the electron transport layer is not particularly limited. From the viewpoint of making the step of forming the electron transport layer simpler, it is preferable to form the electron transport layer by any suitable conventionally known vacuum vapor deposition method.

(Cathode formation step)
The method of forming the cathode is not particularly limited. The cathode can be formed, for example, on the electron-transporting layer using any of the electrode materials exemplified above by a conventionally known suitable method such as coating, vacuum deposition, sputtering, ion plating, or plating. . Through the above steps, the photoelectric conversion element of this embodiment is manufactured.

(Step of forming sealing body)
In forming the sealing body, in the present embodiment, a conventionally known and suitable sealing material (adhesive) and substrate (sealing substrate) are used. Specifically, a sealing material such as a UV curable resin is applied to the support substrate so as to surround the manufactured photoelectric conversion element, and then the sealing material is bonded without gaps. A photoelectric conversion element sealed body can be obtained by sealing the photoelectric conversion element in the gap between the supporting substrate and the sealing substrate using a method suitable for the selected sealing material, such as light irradiation. .

5. Method for manufacturing an image sensor and a biometrics authentication device The photoelectric conversion device of the present embodiment, particularly the photodetector, can function by being incorporated in an image sensor, a biometrics authentication device (fingerprint authentication device, vein authentication device), as described above. .

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

In this example, the polymer compounds shown in Table 6 below were used as p-type semiconductor materials (electron-donating compounds), and the compounds shown in Tables 7 and 8 below were used as n-type semiconductor materials (electron-accepting compounds). used as

Polymer compound P-1, which is a p-type semiconductor material, was synthesized with reference to the method described in WO 2011/052709 and used.

Compounds N-1 to N-7, which are n-type semiconductor materials, were synthesized and used according to synthesis examples described later.

<Synthesis Example 1> (Synthesis of Compound 2)
Compound 2 represented by the following formula was synthesized using compound 1 represented by the following formula.

4.00 g (7.77 mmol) of compound 1 synthesized by the method described in the literature (Dyes and Pigments, 2015, 112, 145.) and tetrahydrofuran were added to a 300 mL four-necked flask whose internal atmosphere was replaced with nitrogen gas. 78 mL was added and cooled to -30°C.

Next, 1.31 g (7.38 mmol) of N-bromosuccinimide was added to a four-necked flask and stirred at -30°C for 6 hours.

Next, the obtained solution was warmed to room temperature, stirred at room temperature for another 3 hours to react, and then a 3% sodium sulfite aqueous solution was added to terminate the reaction.

After extracting the resulting reaction solution with hexane, the extract was washed with water and saturated aqueous sodium chloride solution to obtain an organic layer.

Next, the obtained organic layer was dried with magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

By purifying the resulting crude product with a silica gel column, 4.16 g (7.01 mmol, yield 94.9%) of compound 2 was obtained as a pale yellow oil.

The NMR spectrum of the obtained compound 2 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 7.16 (d, _JHH = 8.4Hz, 4H), 7.10 (d, _JHH = 8.4Hz, 4H), 6.98 (d, _JHH = 4.8Hz, 1H), 6 .75 (d, J _HH =4.8Hz, 1H), 6.42 (s, 1H), 2.58 (t, 4H), 1.63-1.57 (m, 4H), 1.36- 1.27 (br, 12H), 0.87 (t, 6H).

<Synthesis Example 2> (Synthesis of Compound 3)
Compound 3 represented by the following formula was synthesized using compound 2 represented by the following formula.

4.13 g (6.96 mmol) of Compound 2 and 70 mL of dehydrated tetrahydrofuran were added to a 100 mL three-necked flask in which the internal atmosphere was replaced with nitrogen gas, and the resulting solution was cooled to -70° C., then n-butyl 4.13 mL of lithium solution (1.64 mol/L, hexane solution) was added and stirred for 1 hour.

Next, while maintaining the reaction solution at -70°C, 1.01 g (9.74 mmol) of trimethoxyborane was added and stirred for 2 hours.

Next, a 10% by mass acetic acid aqueous solution (30 mL) was added to the obtained reaction solution, and a liquid separation operation was performed using ethyl acetate to extract an organic layer. Toluene (20 mL) and 1.25 g (10.4 mmol) of 2-hydroxymethylene-2-methyl-1,3-propanediol were added to the resulting organic layer, and dehydration was performed using a Dean-Stark tube for 30 minutes. gone. Further solvent was removed on a rotary evaporator to obtain 4.47 g of crude product of compound 3 as a green oil.

<Synthesis Example 3> (Synthesis of Compound 5)
Compound 5 represented by the following formula was synthesized using compound 3 and compound 4 represented by the following formula.

1.00 g (1.43 mmol) of compound 4 synthesized by the method described in JP-A-2013-43818 and 2.20 g (3 .43 mmol), 14 mL of tetrahydrofuran was added, and argon gas was bubbled for 30 minutes to deaerate.

Then, in a four-necked flask, 0.105 g (0.11 mmol, 8 mol%) of Tris (dibenzylideneacetone) dipalladium (0), 0.070 g (0.23 mmol, 16 mol%) of Tri-tert-butylphosphonium Tetrafluoroborate, and tetrahydrofuran. 5 mL was added and stirred for 5 minutes.

Next, 14 mL of a 3.0 M potassium phosphate aqueous solution was added to a four-necked flask, and the reaction solution was stirred while being heated in an oil bath at a set temperature of 50° C. for 3 hours.

After cooling the reaction solution, 100 mL of water and 100 mL of hexane were added to a four-necked flask, and the organic layer was washed with water three times and with a saturated aqueous sodium chloride solution once.

The resulting solution was dried using anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.

By purifying the resulting crude product with a silica gel column, 1.74 g (1.11 mmol, yield 78%) of compound 5 was obtained as a red oil.

The NMR spectrum of the obtained compound 5 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 7.38 (s, 1H), 7.23-7.18 (m, 8H), 7.14-7.10 (m, 8H), 7.03-7.00 (m, 2H), 6 .92 (s, 1H), 6.79-6.77 (m, 2H), 6.58 (s, 1H), 6.53 (s, 1H), 2.62-2.57 (m, 8H ), 2.19-2.11 (m, 2H), 1.71-1.56 (m, 10H), 1.37-1.25 (m, 28H), 1.25-1.08 (br , 36H), 0.89-0.83 (m, 18H).

<Synthesis Example 4> (Synthesis of Compound 6)
Compound 6 represented by the following formula was synthesized using compound 5 represented by the following formula.

窒素ガスで内部の雰囲気を置換した１００ｍＬ三つ口フラスコに、化合物５を１．７４ｇ（１．１１ｍｍｏｌ）、クロロホルムを１２ｍＬ入れ、常温で１０分間攪拌して化合物５を溶解させた。

1.74 g (1.11 mmol) of Compound 5 and 12 mL of chloroform were placed in a 100 mL three-necked flask in which the internal atmosphere was replaced with nitrogen gas, and the mixture was stirred at room temperature for 10 minutes to dissolve Compound 5 therein.

Next, 0.43 g (3.33 mmol) of (Chloromethylene)dimethyliminium chloride was put into a three-necked flask, and the mixture was heated and stirred in an oil bath at a set temperature of 65° C. for 2 hours.

After cooling the reaction solution, 20 mL of water was added, and the organic layer was separated and washed twice with a saturated sodium chloride aqueous solution. The obtained solution was dried using anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.

The resulting crude product was purified with a silica gel column to obtain 1.63 g (1.01 mmol, yield 90.6%) of Compound 6 as a dark red oil.

The NMR spectrum of the obtained compound 6 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 9.76 (s, 1H), 9.75 (s, 1H), 7.46 (s, 1H), 7.37 (s, 1H), 7.36 (s, 1H), 7.21- 7.12 (m, 16H), 7.00 (s, 1H), 6.61 (s, 1H), 6.58 (s, 1H), 2.63-2.58 (m, 8H), 2 .21-2.13 (m, 2H), 1.73-1.57 (m, 10H), 1.37-1.26 (m, 28H), 1.24-1.09 (br, 36H) , 0.89-0.83 (m, 18H).

<Synthesis Example 5> (Synthesis of Compound N-1)
Compound N-1 represented by the following formula was synthesized using compound 6 and compound 7 represented by the following formula.

0.57 g (0.35 mmol) of compound 6, 0.28 g (1.05 mmol) of compound 7, 10 mL of chloroform, and 0.003 g of pyridine ( 0.04 mmol), and the mixture was heated and stirred in an oil bath at 65°C for 2 hours.

The resulting solution was cooled to room temperature and water was added to stop the reaction. After the obtained solution was extracted with chloroform, it was washed twice with water and once with a saturated aqueous sodium chloride solution to obtain an organic layer.

Next, the obtained organic layer was dried with magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

The obtained crude product was purified with a silica gel column to obtain 0.64 g (0.30 mmol, yield 86.3%) of Compound N-1 as a dark blue-green solid.

The NMR spectrum of the obtained compound N-1 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 8.74 (s, 1H), 8.73 (s, 1H), 8.69 (s, 1H), 8.68 (s, 1H), 7.91 (s, 1H), 7.90 ( s, 1H), 7.49 (s, 2H), 7.46 (s, 1H), 7.21-7.14 (m, 16H), 7.03 (s, 1H), 6.67 (s , 1H), 6.64 (s, 1H), 2.64-2.59 (m, 8H), 2.24-2.17 (m, 2H), 1.99-1.86 (m, 8H ), 1.76-1.59 (m, 10H), 1.38-1.26 (m, 28H), 1.24-1.12 (br, 36H), 0.89-0.83 (m , 18H).

<Synthesis Example 6> (Synthesis of Compound 9)
Compound 9 represented by the following formula was synthesized from compound 8 represented by the following formula.

2.85 g (5.36 mmol) of compound 18 synthesized by the method described in paragraph [0271] of WO 2011/052709 and dehydrated tetrahydrofuran were added to a 100 mL three-necked flask whose internal atmosphere was replaced with nitrogen gas. After adding 27 mL and cooling the resulting solution to −70° C., 3.3 mL of n-butyllithium solution (1.64 mol/L, hexane solution) was added and stirred for 2 hours.

Next, while maintaining the reaction solution at -70°C, 0.83 g (8.04 mmol) of trimethoxyborane was added and stirred for 2 hours.

Next, a 10 wt % acetic acid aqueous solution (30 mL) was added to the obtained reaction solution, and a liquid separation operation was performed using ethyl acetate to extract an organic layer. Toluene (20 mL) and 1.29 g (10.72 mmol) of 2-hydroxymethylene-2-methyl-1,3-propanediol were added to the obtained organic layer, and dehydration was performed using a Dean-Stark tube for 30 minutes. gone. Further, the solvent was removed with a rotary evaporator to obtain 3.53 g of crude compound 19 as a green oil.

<Synthesis Example 7> (Synthesis of Compound 11)
Compound 11 represented by the following formula was synthesized using compound 9 and compound 10 represented by the following formula.

3.53 g (5.36 mmol) of the unpurified crude compound 9 obtained in Synthesis Example 6 was placed in a 100 mL four-necked flask in which the internal atmosphere was replaced with nitrogen gas, and Luminescence Technology Corp. 1.2 g (2.23 mmol) of the compound 10 purchased from the company and 22 mL of tetrahydrofuran were added, and degassed by bubbling argon gas for 30 minutes.

0.164 g (0.179 mmol, 8 mol%) of Tris(dibenzylideneacetone) dipalladium (0) and 0.109 g (0.357 mmol, 16 mol%) of Tri-tert-butylphosphonium Tetrafluoroborate were added to the resulting reaction solution. Stir for a minute.

Next, 22 mL of a 3.0 M potassium phosphate aqueous solution was further added to the reaction solution, and the resulting reaction solution was stirred while being heated in an oil bath at a set temperature of 75° C. for 1 hour.

After cooling the reaction mixture, 100 mL of water and 100 mL of hexane were added, and the mixture was washed three times with water and once with a saturated aqueous sodium chloride solution.

The resulting solution was dried over anhydrous sodium sulfate and then filtered, and the solvent was distilled off under reduced pressure. By purifying the resulting crude product with a silica gel column, 2.11 g (1.49 mmol, yield 67%) of Compound 11 was obtained as a dark red oil.

The NMR spectrum of the obtained compound 21 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 7.94 (s, 1H), 7.03 (dd, _JHH = 9.2Hz, 5.2Hz, 2H), 6.85 (s, 1H), 6.81 (s, 1H), 6. 68 (dd, _JHH = 5.2Hz, 1.6Hz, 2H), 4.37 (t, _JHH = 6.8Hz, 2H), 1.95-1.78 (m, 10H), 1.44 -1.22 (m, 100H), 0.86 (t, 15H).

<Synthesis Example 8> (Synthesis of Compound 12)
Compound 12 represented by the following formula was synthesized from compound 11 represented by the following formula.

1.5 g (1.06 mmol) of Compound 21 and 11 mL of dichloromethane were added and dissolved in a 100 mL four-necked flask whose internal atmosphere was replaced with nitrogen gas.

Next, 0.41 g (3.19 mmol) of (Chloromethylene)dimethyliminium chloride was added to the obtained reaction solution, and the mixture was heated and stirred in an oil bath at a set temperature of 40° C. for 3 hours.

Then, after cooling the obtained reaction solution, 20 mL of water was added, and the solution was washed twice with a saturated sodium chloride aqueous solution.

The resulting solution was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was purified with a silica gel column, yielding 1.44 g (0.4 g) of Compound 22 as a purple solid. 98 mmol, yield 92%).

The NMR spectrum of the obtained compound 22 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 9.78 (s, 1H), 9.77 (s, 1H), 7.95 (s, 1H), 7.29 (s, 1H), 7.28 (s, 1H), 6.90 ( s, 1H), 6.86 (s, 1H), 4.39 (t, J _HH = 7.2Hz, 2H), 1.97-1.79 (m, 10H), 1.46-1.22 (m, 100H), 0.86 (t, 15H).

<Synthesis Example 9> (Synthesis of compound N-2)
Compound N-2 represented by the following formula was synthesized using compound 12 and compound 13 represented by the following formula.

1.4 g (0.98 mmol) of compound 12, 0.78 g (2.95 mmol) of compound 13, 20 mL of chloroform, and 0.04 g of pyridine ( 0.49 mmol), and stirred while heating in an oil bath at 65°C for 2 hours.

Next, the obtained solution was cooled to normal temperature, and the reaction was stopped by adding water. After the resulting solution was extracted with chloroform, it was washed twice with water and once with a saturated aqueous sodium chloride solution.

Next, the obtained organic layer was dried with magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. By purifying the resulting crude product with a silica gel column, 1.5 g (0.77 mmol, yield 95%) of compound N-2 was obtained as a black solid.

The NMR spectrum of the obtained compound N-2 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 8.57-8.51 (m, 4H), 7.81 (s, 1H), 7.77 (s, 1H), 7.73 (s, 1H), 7.29 (br, 2H), 6.96 (s, 1H), 6.88 (s, 1H), 4.50 (t, J _HH = 7.2Hz, 2H), 2.08-1.93 (m, 10H), 1.59 -1.20 (m, 100H), 0.83 (t, 15H).

<Synthesis Example 10> (Synthesis of Compound 15)
Compound 15 represented by the following formula was synthesized using compound 14 represented by the following formula.

10.2 g (16.7 mmol) of compound 14 synthesized by the method described in paragraphs [0269] to [0274] of JP-A-2012-36357 is placed in a 300 mL three-necked flask whose internal atmosphere has been replaced with nitrogen gas. ), 170 mL of dehydrated tetrahydrofuran was added, the resulting solution was cooled to −70° C., 10.9 mL (17.5 mmol) of n-butyllithium solution (1.6 mol/L, hexane solution) was added, and the mixture was stirred for 1 hour. gone.

Next, while maintaining the reaction solution at -70°C, 4.39 g (23.4 mmol) of trimethoxyborane was added and stirred for 2 hours.

Next, 41.5 g of a 2% by mass aqueous acetic acid solution was added to the obtained reaction solution, and a liquid separation operation was performed using ethyl acetate to extract an organic layer. Toluene (20 mL) and 3.00 g (25.1 mmol) of 2-hydroxymethylene-2-methyl-1,3-propanediol were added to the obtained organic layer, and dehydration was performed using a Dean-Stark tube for 30 minutes. gone. Further solvent was removed on a rotary evaporator to obtain 11.2 g of crude product of compound 15 as a green oil.

<Synthesis Example 11> (Synthesis of Compound 17)
Compound 17 represented by the following formula was synthesized using compound 15 and compound 16 represented by the following formula.

2.45 g (3.50 mmol) of Compound 16 synthesized by the method described in paragraphs [0202] to [0205] of JP-A-2014-31364 is placed in a 300 mL four-necked flask whose internal atmosphere has been replaced with nitrogen gas. ), 5.30 g (8.05 mmol) of compound 15, and 100 mL of tetrahydrofuran were added, and degassed by bubbling argon gas for 30 minutes.

Then, in a four-necked flask, 0.160 g (0.175 mmol, 5 mol%) of Tris (dibenzylideneacetone) dipalladium (0), 0.213 g (0.700 mmol, 20 mol%) of Tri-tert-butylphosphonium Tetrafluoroborate, and tetrahydrofuran. 15 mL was added and stirred for 5 minutes.

Next, 12 mL of a 3.0 M potassium phosphate aqueous solution was added to a four-necked flask, and the reaction solution was stirred while being heated in an oil bath at a set temperature of 75° C. for 3 hours.

After cooling the reaction solution, 100 mL of water and 100 mL of hexane were added to a four-necked flask, and the organic layer was washed three times with water and once with a saturated aqueous sodium chloride solution for separation and washing.

The resulting solution was dried using anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure. By purifying the resulting crude product with a silica gel column, 4.97 g (3.11 mmol, yield 88.8%) of compound 17 was obtained as a red oil.

The NMR spectrum of the obtained compound 17 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 7.43 (s, 1H), 7.01 (d, _JHH = 5.2Hz, 1H), 7.00 (d, _JHH = 5.2Hz, 1H), 6.96 (s, 1H) , 6.82 (s, 1H), 6.79 (s, 1H), 6.67 (d, _JHH = 4.8Hz, 1H), 6.66 (d, _JHH = 4.8Hz, 1H) , 2.18 (m, 2H), 1.87 (m, 8H), 1.71 (m, 2H), 1.23 (br, 120H), 0.86 (m, 18H).

<Synthesis Example 12> (Synthesis of Compound 18)
Compound 18 represented by the following formula was synthesized using compound 17 represented by the following formula.

4.96 g (3.10 mmol) of compound 17 and 150 mL of dichloromethane were placed in a 300 mL three-necked flask whose internal atmosphere was replaced with nitrogen gas, and the mixture was stirred at room temperature for 10 minutes to dissolve compound 17 .

Next, 1.19 g (9.30 mmol) of (Chloromethylene)dimethyliminium chloride was put into a three-necked flask, and the mixture was heated and stirred in an oil bath with a set temperature of 40° C. for 2 hours.

After cooling the reaction solution, 20 mL of water was added, and the organic layer was separated and washed twice with a saturated sodium chloride aqueous solution. The obtained solution was dried using anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.

The obtained crude product was purified with a silica gel column to obtain 4.81 g (2.90 mmol, yield 93.7%) of compound 18 as a dark red solid.

The NMR spectrum of the obtained compound 18 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 9.783 (s, 1H), 9.775 (s, 1H), 7.53 (s, 1H), 7.28 (s, 1H), 7.27 (s, 1H), 7.06 ( s, 1H), 6.87 (s, 1H), 6.85 (s, 1H), 2.22 (m, 2H), 1.90 (m, 8H), 1.74 (m, 2H), 1.21 (br, 120H), 0.86 (m, 18H).

<Synthesis Example 13> (Synthesis of compound N-3)
Compound N-3 represented by the following formula was synthesized using compound 18 and compound 13 represented by the following formula.

0.828 g (0.500 mmol) of compound 18, 0.395 g (1.50 mmol) of compound 19, 25 mL of chloroform, and 0.396 g of pyridine ( 5.00 mmol), and the mixture was heated and stirred in an oil bath at 65°C for 2 hours.

The resulting solution was cooled to room temperature and water was added to stop the reaction. After the obtained solution was extracted with chloroform, it was washed twice with water and once with a saturated aqueous sodium chloride solution to obtain an organic layer.

Next, the obtained organic layer was dried with magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

The obtained crude product was purified with a silica gel column to obtain 0.752 g (0.350 mmol, yield 70.1%) of Compound N-3 as a dark blue-green solid.

The NMR spectrum of the obtained compound N-3 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 8.74 (s, 4H), 7.92 (s, 1H), 7.91 (s, 1H), 7.62 (s, 1H), 7.40 (s, 1H), 7.39 ( s, 1H), 7.15 (s, 1H), 6.93 (s, 1H), 6.91 (s, 1H), 2.26 (m, 2H), 1.93 (m, 8H), 1.79 (m, 2H), 1.20 (br, 120H), 0.86 (m, 18H).

<Synthesis Example 14> (Synthesis of Compound 21)
Compound 21 represented by the following formula was synthesized using compound 20 represented by the following formula.

5.02 g (12.0 mmol) of compound 20 synthesized by the method described in paragraphs [0261] to [0271] of International Publication No. 2011/052709 in a 300 mL four-necked flask whose internal atmosphere was replaced with nitrogen gas. , 100 mL of tetrahydrofuran was added and cooled to -30°C.

Next, 2.11 g (11.9 mmol) of N-bromosuccinimide was added to a four-necked flask and stirred at -30°C for 6 hours.

Next, the obtained solution was warmed to room temperature, stirred at room temperature for another 3 hours to react, and then a 3% sodium sulfite aqueous solution was added to terminate the reaction.

The obtained reaction solution was extracted with hexane, and then washed with water and saturated sodium chloride aqueous solution to obtain an organic layer.

Next, the obtained organic layer was dried with magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

By purifying the resulting crude product with a silica gel column, 4.66 g (9.36 mmol, yield 78.0%) of Compound 21 was obtained as a pale yellow oil.

The NMR spectrum of the obtained compound 21 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 6.98 (d, _JHH = 4.8Hz, 1H), 6.66 (s, 1H), 6.65 (d, _JHH = 4.8Hz, 1H), 1.87-1.74 ( m, 4H), 1.41-1.23 (br, 24H), 0.86 (t, 6H).

<Synthesis Example 15> (Synthesis of Compound 22)
Using compound 21 represented by the following formula, compound 22 represented by the following formula was synthesized.

4.59 g (9.23 mmol) of Compound 21 and 90 mL of dehydrated tetrahydrofuran were added to a 100 mL three-necked flask in which the internal atmosphere was replaced with nitrogen gas, and the resulting solution was cooled to -70° C., then n-butyl 5.8 mL of lithium solution (1.64 mol/L, hexane solution) was added and stirred for 1 hour.

Next, while maintaining the reaction solution at -70°C, 2.43 g (12.9 mmol) of trimethoxyborane was added and stirred for 2 hours.

Next, a 10% by mass acetic acid aqueous solution (30 mL) was added to the obtained reaction solution, and a liquid separation operation was performed using ethyl acetate to extract an organic layer. Toluene (20 mL) and 1.66 g (13.82 mmol) of 2-hydroxymethylene-2-methyl-1,3-propanediol were added to the obtained organic layer, and dehydration was performed using a Dean-Stark tube for 30 minutes. gone. Further solvent was removed on a rotary evaporator to obtain 5.00 g of crude product of compound 22 as a green oil.

<Synthesis Example 16> (Synthesis of Compound 24)
Compound 24 represented by the following formula was synthesized using compound 22 and compound 23 represented by the following formula.

1.65 g (2.80 mmol) of compound 23 synthesized by the method described in the literature (ACS Omega 2017, 2, 4347.) and 3.5 g (2.80 mmol) of compound 22 were placed in a 200 mL four-necked flask whose internal atmosphere was replaced with nitrogen gas. 83 g (7.00 mmol) and 93 mL of tetrahydrofuran were added, and degassed by bubbling argon gas for 30 minutes.

Then, in a four-necked flask, 0.128 g (0.140 mmol, 5 mol%) of Tris (dibenzylideneacetone) dipalladium (0), 0.170 g (0.560 mmol, 20 mol%) of Tri-tert-butylphosphonium Tetrafluoroborate, and tetrahydrofuran. 5 mL was added and stirred for 5 minutes.

Next, 9.3 mL of a 3.0 M potassium phosphate aqueous solution was added to a four-necked flask, and the reaction solution was heated and stirred in an oil bath at a set temperature of 50° C. for 3 hours.

After cooling the reaction solution, 100 mL of water and 100 mL of hexane were added to a four-necked flask, and the organic layer was washed with water three times and with a saturated aqueous sodium chloride solution once.

The resulting solution was dried using anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure. By purifying the resulting crude product with a silica gel column, 3.21 g (2.54 mmol, yield 90.6%) of compound 24 was obtained as a red oil.

The NMR spectrum of the obtained compound 24 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 7.44 (s, 1H), 7.03 (d, _JHH = 4.0Hz, 1H), 7.02 (d, _JHH = 4.0Hz, 1H), 6.97 (s, 1H) , 6.83 (s, 1H), 6.80 (s, 1H), 6.89 (d, _JHH = 4.8Hz, 1H), 6.68 (d, _JHH = 4.8Hz, 1H) , 2.23-2.16 (m, 2H), 1.94-1.81 (m, 8H), 1.77-1.69 (m, 2H), 1.44-1.11 (br, 72H), 0.86-0.80 (m, 18H).

<Synthesis Example 17> (Synthesis of Compound 25)
Compound 25 represented by the following formula was synthesized using compound 24 represented by the following formula.

3.41 g (2.70 mmol) of compound 24 and 80 mL of chloroform were placed in a 100 mL three-necked flask in which the internal atmosphere was replaced with nitrogen gas, and the mixture was stirred at room temperature for 10 minutes to dissolve compound 66 therein.

Next, 1.04 g (8.10 mmol) of (Chloromethylene)dimethyliminium chloride was placed in a three-necked flask, and the mixture was heated and stirred in an oil bath at a set temperature of 65° C. for 2 hours.

After cooling the reaction solution, 20 mL of water was added, and the organic layer was separated and washed twice with a saturated sodium chloride aqueous solution. The obtained solution was dried using anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.

The obtained crude product was purified with a silica gel column to obtain 2.97 g (2.25 mmol, yield 83.3%) of compound 25 as a dark red solid.

The NMR spectrum of the obtained compound 25 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 9.79 (s, 1H), 9.78 (s, 1H), 7.53 (s, 1H), 7.29 (s, 1H), 7.28 (s, 1H), 7.06 ( s, 1H), 6.87 (s, 1H), 2.25-2.17 (m, 2H), 1.96-1.84 (m, 8H), 1.78-1.71 (m, 2H), 1.44-1.12 (br, 72H), 0.87-0.79 (m, 18H).

<Synthesis Example 18> (Synthesis of Compound N-4)
Compound N-4 represented by the following formula was synthesized using compound 13 and compound 25 represented by the following formula.

0.858 g (0.650 mmol) of compound 67, 0.513 g (1.95 mmol) of compound 12, 30 mL of chloroform, and 0.514 g of pyridine ( 6.50 mmol), and the mixture was heated and stirred in an oil bath at 65°C for 2 hours.

The resulting solution was cooled to room temperature and water was added to stop the reaction. After the obtained solution was extracted with chloroform, it was washed twice with water and once with a saturated aqueous sodium chloride solution to obtain an organic layer.

Next, the obtained organic layer was dried with magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

The resulting crude product was purified with a silica gel column to obtain 0.967 g (0.534 mmol, yield 82.2%) of compound N-4 as a dark blue-green solid.

The NMR spectrum of the obtained compound N-4 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 8.74 (s, 4H), 7.92 (s, 1H), 7.91 (s, 1H), 7.63 (s, 1H), 7.40 (s, 1H), 7.38 ( s, 1H), 7.15 (s, 1H), 6.94 (s, 1H), 6.91 (s, 1H), 2.29-2.22(m, 2H), 1.99-1 .86 (m, 8H), 1.82-1.75 (m, 2H), 1.44-1.14 (br, 72H), 0.92-0.80 (m, 18H).

<Synthesis Example 19> (Synthesis of Compound 27)
Compound 27 represented by the following formula was synthesized using compound 26 represented by the following formula.

0.746 g (0.450 mmol) of compound 26 and 0.349 g (0.450 mmol) of (Tributyl (1,3-dioxolan-2-ylmethyl)phosphonium bromide) were placed in a 100 mL three-necked flask whose internal atmosphere was replaced with nitrogen gas. .945 mmol), 20 mL of tetrahydrofuran was added, and cooled to 0°C.

Next, 0.072 g (1.80 mmol) of sodium hydride was added, the temperature was raised to normal temperature, and the mixture was stirred for 1.5 hours.

The reaction solution was cooled to 0° C. again, 10% hydrochloric acid was added, the temperature was raised to normal temperature, and the mixture was stirred for 2 hours. 15 mL of hexane was further added to the reaction solution, and the organic layer was washed once with water and washed twice with a saturated aqueous sodium chloride solution. The obtained solution was dried using anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.

The resulting crude product was purified with a silica gel column to obtain 0.703 g (0.412 mmol, yield 91.4%) of compound 27 as a reddish-purple oil.

The NMR spectrum of the obtained compound 27 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 9.614 (d, _JHH = 8.0Hz, 1H), 9610 (d, _JHH = 8.0Hz, 1H), 7.50 (s, 1H), 7.433 (d, _JHH = 15 .6Hz, 1H), 7.426 (d, _JHH = 15.6Hz, 1H), 7.03 (s, 1H), 6.93 (s, 1H), 6.92 (s, 1H), 6 .85 (s, 1H), 6.83 (s, 1H), 6.457 (dd, _JHH = 8.0Hz, 15.6Hz, 1H), 6.453 (dd, _JHH = 8.0Hz, 15.6Hz, 1H), 2.24-2.17 (m, 2H), 1.95-1.82 (m, 8H), 1.78-1.70 (m, 2H), 1.41- 1.11 (br, 120H), 0.88-0.83 (m, 18H).

<Synthesis Example 20> (Synthesis of Compound N-5)
Compound N-5 represented by the following formula was synthesized using compound 13 and compound 27 represented by the following formula.

1.00 g (0.585 mmol) of compound 7, 0.462 g (0.585 mmol) of compound 13, 29 mL of chloroform, and 0.463 g of pyridine ( 5.85 mmol), and the mixture was heated and stirred in an oil bath at 65°C for 2 hours.

The resulting solution was cooled to room temperature and water was added to stop the reaction. After the obtained solution was extracted with chloroform, it was washed twice with water and once with a saturated aqueous sodium chloride solution to obtain an organic layer.

Next, the obtained organic layer was dried with magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

The resulting crude product was purified with a silica gel column to obtain 0.982 g (0.447 mmol, yield 76.4%) of compound N-5 as a dark blue-green solid.

The NMR spectrum of the obtained compound N-5 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 8.74 (s, 2H), 8.55-8.40 (m, 4H), 7.92 (s, 2H), 7.55 (s, 1H), 7.41 (d, J _HH = 14Hz, 2H), 7.06 (d, _JHH = 14Hz, 2H), 7.05 (s, 2H), 6.87 (s, 2H), 6.85 (s, 2H), 2.28- 2.20 (m, 2H), 1.93-1.89 (m, 8H), 1.81-1.74 (m, 2H), 1.27-1.14 (br, 120H), 0. 87-0.83 (m, 18H).

<Synthesis Example 21> (Synthesis of Compound 29)
Compound 29 represented by the following formula was synthesized from compound 28 represented by the following formula.

13.30 g (24.50 mmol) of compound 28 synthesized by the method described in paragraph [0203] of JP-A-2014-31364 and 490 mL of tetrahydrofuran were placed in a 1 L four-necked flask whose internal atmosphere was replaced with nitrogen gas. and cooled to 0°C.

Next, 4.361 g (24.50 mmol) of N-bromosuccinimide was added to a four-necked flask and stirred at 0° C. for 4 hours.

Next, the obtained solution was warmed to room temperature, stirred at room temperature for another 3 hours to react, and then a 3% sodium sulfite aqueous solution was added to terminate the reaction.

The obtained reaction solution was extracted with hexane, and then washed with water and saturated aqueous sodium chloride solution.

Next, the obtained organic layer was dried with magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

By purifying the resulting crude product with a silica gel column, 10.1 g (16.2 mmol, yield 66.3%) of compound 29 was obtained as a pale yellow oil.

The NMR spectrum of the obtained compound 29 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 7.44 (d, _JHH = 5.6Hz, 1H), 7.07 (d, _JHH = 5.6Hz, 1H), 6.95 (s, 1H), 2.16 (m, 2H) , 1.72 (m, 2H), 1.21 (br, 40H), 0.86 (t, 6H).

<Synthesis Example 22> (Synthesis of Compound 31)
Compound 31 represented by the following formula was synthesized using compound 29 and compound 30 represented by the following formula.

5.23 g (6.65 mmol) of compound 30 synthesized by the method described in paragraphs [0139] to [0141] of WO 2011/052709 is placed in a 300 mL four-necked flask whose internal atmosphere has been replaced with nitrogen gas. , 9.51 g (15.3 mmol) of compound 29 and 120 mL of tetrahydronaphthalene were added, and degassed by bubbling argon gas for 30 minutes.

Next, in a four-necked flask, 0.304 g (0.333 mmol, 5 mol%) of Tris(dibenzylideneacetone) dipalladium (0), 0.405 g (1.33 mmol, 20 mol%) of Tri-tert-butylphosphonium Tetrafluoroborate, tetrahydro 13 mL of naphthalene was added and stirred for 5 minutes.

Next, 22 mL of a 3.0 M potassium phosphate aqueous solution was further added to the four-necked flask, and the reaction solution was stirred while being heated in an oil bath at a set temperature of 75° C. for 1 hour.

After cooling the reaction solution, 100 mL of water and 100 mL of hexane were added, and the solution was separated and washed three times with water and once with a saturated aqueous sodium chloride solution.

The resulting solution was dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.

By purifying the resulting crude product with a silica gel column, 9.83 g (6.09 mmol, yield 91.7%) of Compound 31 was obtained as a dark red oil.

The NMR spectrum of the obtained compound 31 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 7.46 (d, _JHH = 5.2Hz, 1H), 7.45 (d, _JHH = 5.2Hz, 1H), 7.07 (d, _JHH = 5.2Hz, 1H), 7 .06 (d, _JHH = 5.2Hz, 1H), 7.02 (s, 1H), 6.98 (s, 1H), 6.86 (s, 1H), 6.84 (s, 1H) , 2.19 (m, 4H), 1.91 (m, 4H), 1.73 (m, 4H), 1.18 (br, 120H), 0.86 (t, 18H).

<Synthesis Example 23> (Synthesis of Compound 32)
Compound 32 represented by the following formula was synthesized from compound 31 represented by the following formula.

9.68 g (6.00 mmol) of Compound 31 and 120 mL of chloroform were placed in a 300 mL four-necked flask in which the internal atmosphere was replaced with nitrogen gas, and dissolved by stirring at room temperature for 10 minutes.

Next, 5.38 g (42.0 mmol) of (Chloromethylene)dimethyliminium chloride was put into a four-necked flask, and the mixture was heated and stirred in an oil bath set at a temperature of 65° C. for a total of 20 hours.

After cooling the reaction solution, 100 mL of water was added, and the solution was washed twice with a saturated sodium chloride aqueous solution.

The resulting solution was dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.

The resulting crude product was purified with a silica gel column to obtain 5.90 g (3.53 mmol, yield 58.9%) of compound 32 as purple oil.

The NMR spectrum of the obtained compound 32 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 9.91 (s, 2H), 8.08 (s, 1H), 8.07 (s, 1H), 7.06 (s, 1H), 7.02 (s, 1H), 6.93 ( s, 1H), 6.91 (s, 1H), 2.22 (m, 4H), 1.92 (m, 4H), 1.75 (m, 4H), 1.21 (br, 120H), 0.85 (t, 18H).

<Synthesis Example 24> (Synthesis of compound N-6)
Compound N-6 represented by the following formula was synthesized using compound 32 and compound 13 represented by the following formula.

2.25 g (1.35 mmol) of Compound 32, Adv. Mater. 2017, 29, 1703080. 0.888 g (3.38 mmol) of compound 13 synthesized by the method described in 1., 68 mL of chloroform, and 1.07 g (13.5 mmol) of pyridine were added, and the mixture was heated and stirred in an oil bath at 65°C for 2 hours.

The resulting solution was cooled to room temperature and water was added to stop the reaction. After the resulting solution was extracted with chloroform, it was washed twice with water and once with a saturated aqueous sodium chloride solution.

Next, the obtained organic layer was dried with magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

The resulting crude product was purified with a silica gel column to obtain 1.91 g (0.886 mmol, yield 65.6%) of compound N-6 as a dark blue-green solid.

The NMR spectrum of the obtained compound N-6 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 8.90 (s, 1H), 8.89 (s, 1H), 8.81 (s, 1H), 8.17 (s, 1H), 7.99 (s, 1H), 7.98 ( s, 1H), 7.11 (s, 1H), 7.07 (s, 1H), 6.98 (s, 1H), 6.98 (s, 1H), 2.25 (m, 4H), 1.94 (m, 4H), 1.77 (m, 4H), 1.24 (br, 120H), 0.86 (m, 18H).

<Synthesis Example 25> (Synthesis of compound c)
Using 2-bromo-3-(2-ethylhexyl)thiophene (compound a) and 2,5-dibromothiophene (compound b) represented by the following formula, compound c represented by the following formula was synthesized.

0.353 g (14.5 mmol) of magnesium, 10 mL of dehydrated diethyl ether, and a small amount of iodine were placed in a 50 mL four-necked flask whose internal atmosphere was replaced with nitrogen gas, and the mixture was stirred at room temperature.

Next, put 2.00 g (7.27 mmol) of 2-bromo-3-(2-ethylhexyl)thiophene and 10 mL of dehydrated diethyl ether into a dropping funnel, and adjust the dropping rate so that the internal temperature is 30° C. or lower. It was dropped little by little into a 50 mL four-necked flask.

Then, after heating under reflux for 2 hours in an oil bath at a set temperature of 43° C., the reaction solution was cooled to normal temperature, and the resulting solution was used as a Grignard reaction solution.

1.76 g (7.27 mmol) of 2,5-dibromothiophene, [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium (II ) and 20 mL of dehydrated diethyl ether were added and stirred.

After cooling with an ice water bath, the Grignard reaction solution was added dropwise to a 100 mL four-necked flask. After keeping the temperature for 2 hours, the 100 mL four-necked flask was removed from the ice water bath and the temperature of the reaction solution was raised to room temperature.

Next, 40 mL of water and 20 mL of heptane were added to the reaction liquid, and liquid separation washing was performed.

The obtained organic layer was dried using anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. By purifying the resulting crude product with a silica gel column, 1.48 g (4.14 mmol, yield 57.0%) of compound c was obtained as a yellow oil.

The NMR spectrum of the obtained compound c was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 7.19 (d, _JHH = 5.2Hz, 1H), 7.00 (d, _JHH = 3.9Hz, 1H), 6.89 (d, _JHH = 5.2Hz, 1H), 6 .84 (d, J _HH =3.9 Hz, 1 H), 2.64 (d, J _HH =7.2 Hz, 2 H), 1.62-1.51 (m, 1 H), 1.33-1. 16 (m, 8H), 0.90-0.80 (m, 6H).

<Synthesis Example 26> (Synthesis of compound e)
Compound e represented by the following formula was synthesized using compound c and compound d represented by the following formula.

1.46 g (4.09 mmol) of compound c and 1.42 g of compound d synthesized by the method described in International Publication No. 2014/112656 (1 .78 mmol), and 59 mL of tetrahydronaphthalene were added, and degassed by bubbling nitrogen gas for 30 minutes.

Then, put 0.0813 g (0.0888 mmol, 5 mol%) of Tris(dibenzylideneacetone) dipalladium (0) and 0.103 g (0.355 mmol, 20 mol%) of Tri-tert-butylphosphonium Tetrafluoroborate into a four-necked flask, Stirred for 5 minutes.

Next, 5.9 mL of a 3.0 M potassium phosphate aqueous solution was added to a four-necked flask, and the reaction solution was stirred while being heated in an oil bath at a set temperature of 75° C. for 1 hour.

After cooling the reaction solution, 103 mL of water and 103 mL of heptane were added to a four-necked flask, and the organic layer was washed with water three times and with a saturated sodium chloride aqueous solution once.

The resulting solution was dried using anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. By purifying the resulting crude product with a silica gel column, 1.81 g (1.67 mmol, yield 94.0%) of compound e was obtained as a red oil.

The NMR spectrum of the obtained compound e was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 7.19-7.17 (m, 2H), 7.09 (d, _JHH = 3.9Hz, 1H), 7.07 (d, _JHH = 3.9Hz, 1H), 7.01 ( d, J _HH =3.9Hz, 2H), 6.92-6.90 (m, 2H), 6.78 (s, 1H), 6.76 (s, 1H), 2.72 (m, 4H ), 1.95-1.81 (m, 4H), 1.68-1.64 (m, 2H), 1.42-1.23 (m, 56H), 0.91-0.83 (m , 18H).

<Synthesis Example 27> (synthesis of compound f)
Compound f represented by the following formula was synthesized using compound e represented by the following formula.

1.79 g (1.65 mmol) of compound e and 83 mL of dichloromethane were placed in a 100 mL four-necked flask whose internal atmosphere was replaced with nitrogen gas, and the mixture was stirred at room temperature for 10 minutes to dissolve compound e.

Next, 0.845 g (6.60 mmol) of (Chloromethylene)dimethyliminium chloride was added to a four-necked flask, and the mixture was heated and stirred for 24 hours in an oil bath set at a temperature of 49°C.

After cooling the reaction solution, 13 mL of water was added, and the organic layer was washed twice with a saturated aqueous solution of sodium hydrogencarbonate. The obtained solution was dried using anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

The resulting crude product was purified with a silica gel column to obtain 1.72 g (1.51 mmol, yield 91.4%) of compound f as dark red oil.

The NMR spectrum of the obtained compound f was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 9.84 (s, 2H), 7.56 (s, 1H), 7.55 (s, 1H), 7.19 (d, _JHH = 3.9Hz, 2H), 7.13 (d, _JHH = 3.9Hz, 1H), 7.11 (d, _JHH = 3.9Hz, 1H), 6.83 (s, 1H), 6.81 (s, 1H), 2.78-2. 75 (m, 4H), 1.96-1.82 (m, 4H), 1.70-1.68 (m, 2H), 1.40-1.23 (m, 56H), 0.90- 0.84 (m, 18H).

<Synthesis Example 28> (Synthesis of Compound N-7)
Compound N-7 represented by the following formula was synthesized using compound f and compound g represented by the following formula.

0.798 g (0.700 mmol) of compound f, 0.442 g (1.68 mmol) of compound g, 35 mL of chloroform, and 0.554 g of pyridine ( 7.00 mmol), and stirred while heating in an oil bath at 68° C. for 1.5 hours.

The resulting solution was cooled to ambient temperature and added to 210 mL of methanol. The resulting solution was filtered to obtain a crude product as a precipitate.

The resulting crude product was purified with a silica gel column to obtain 0.981 g (0.602 mmol, yield 86.0%) of compound N-7 as a black solid.

The NMR spectrum of the obtained compound N-7 was analyzed. The results are as follows.
[ ¹ H NMR (CDCl ₃ )]
δ 8.69 (s, 1H), 8.68 (s, 1H), 8.67 (s, 2H), 7.89 (s, 1H), 7.88 (s, 1H), 7.54 ( s, 1H), 7.53 (s, 1H), 7.38 (d, _JHH = 4.1Hz, 1H), 7.36 (d, _JHH = 4.0Hz, 1H), 7.08 ( d, _JHH = 4.3Hz, 1H), 7.05 (d, _JHH = 4.0Hz, 1H), 6.85 (s, 1H), 6.80 (s, 1H), 2.76- 2.72 (m, 4H), 1.96-1.92 (m, 4H), 1.74 (br, 2H), 1.41-1.23 (m, 56H), 0.95-0. 83 (m, 18H).

<Preparation Example 1> (Preparation of Ink I-1)
Tetralin was used as the first solvent, butyl benzoate was used as the second solvent, and a mixed solvent was prepared at a volume ratio of 97:3 between the first solvent and the second solvent. Polymer compound P-1, which is a p-type semiconductor material, was added to the prepared mixed solvent so as to have a concentration of 1.2% by mass with respect to the total mass of the ink, and compound N-1, which was an n-type semiconductor material, was added to the ink. (p-type semiconductor material / n-type semiconductor material = 1/1) to a concentration of 1.2% by mass with respect to the total mass of the mixed solution obtained by stirring at 60 ° C. for 8 hours Filtration was performed using a filter to obtain ink (I-1).

<Preparation Examples 2 to 17> (Preparation of Inks I-2 to I-17)
Inks (I-2) to (I-17) were obtained in the same manner as in Preparation Example 1, except that the combination of the solvent and the n-type semiconductor material shown in Table 9 below was used.

<Example 1> (Manufacture and evaluation of photoelectric conversion element)
(1) Production of a photoelectric conversion element and its encapsulant A glass substrate on which a 50 nm thick ITO thin film (anode) is formed by sputtering is prepared, and the glass substrate is subjected to ozone UV treatment as surface treatment. gone.

Next, the ink (I-1) was applied onto the ITO thin film by spin coating to form a coating film, and then heat-treated for 10 minutes using a hot plate heated to 100° C. in a nitrogen gas atmosphere. and dried to form an active layer. The thickness of the formed active layer was about 300 nm.

Next, ZnO (manufactured by Tayca, product name: HTD-711Z) was applied on the formed active layer by a spin coating method to form an electron transport layer having a thickness of about 50 nm.

Next, a silver (Ag) layer having a thickness of about 60 nm was formed on the formed electron transport layer to serve as a cathode.
A photoelectric conversion element was manufactured on the glass substrate by the above steps.

Next, a UV curable sealant as a sealing material was applied onto a glass substrate as a support substrate so as to surround the manufactured photoelectric conversion element, and the glass substrate as a sealing substrate was bonded. After that, by irradiating UV light, the photoelectric conversion element was sealed in the gap between the supporting substrate and the sealing substrate, thereby obtaining a sealed body of the photoelectric conversion element. The planar shape of the photoelectric conversion element sealed in the gap between the supporting substrate and the sealing substrate was a square of 2 mm×2 mm when viewed from the thickness direction. The resulting sealed body was designated as Sample 1.

(2) Evaluation of photoelectric conversion device (evaluation of external quantum efficiency)
A reverse bias voltage of −5 V is applied to the manufactured sample 1, and the external quantum efficiency (EQE) at a wavelength of 940 nm at this applied voltage is measured using a spectral sensitivity measurement device (CEP-2000, manufactured by Spectroscopy Instruments Co., Ltd.). and evaluated.

<Comparative Example 1>
A photoelectric conversion element was produced and evaluated in the same manner as in Example 1, except that ink (I-2) was used.

<Evaluation 1>
The relative percentage (EQE relative value, unit: %) of the EQE of the photoelectric conversion element according to Example 1 to the EQE value of the photoelectric conversion element according to Comparative Example 1 was 122%. That is, the EQE of the photoelectric conversion element according to Example 1 was higher than the EQE of the photoelectric conversion element according to Comparative Example 1. The results are also shown in Table 10 below.

<Example 2, Comparative Example 2, Reference Example 1>
Photoelectric conversion elements were produced and evaluated in the same manner as in Example 1, except that ink (I-3), ink (I-4), and ink (I-5) were used.

<Evaluation 2>
The EQE relative value of the photoelectric conversion element obtained in Example 1 with respect to the EQE value of the photoelectric conversion element according to Reference Example 1 was 118%, and the EQE relative value of the photoelectric conversion element according to Comparative Example 1 was 94%. . Although all the compounds used as n-type semiconductor materials were compound N-2, it was found that excellent EQE characteristics were obtained in Example 2. The results are also shown in Table 10 below.

<Examples 3 to 8, Comparative Example 3, Reference Examples 2 to 6>
Using the photoelectric conversion elements manufactured using the inks (I-6) to (I-17), comparisons were made between Examples and Comparative Examples for the reference example in the same manner as described above. The results are shown in Table 10 below.

As shown in Table 10 above, according to the photoelectric conversion element manufactured using the ink composition that satisfies the requirements of the present invention as the ink composition for forming the active layer, the ink composition that does not satisfy the requirements of the present invention was used. EQE was able to be improved compared with the photoelectric conversion element manufactured using it.

REFERENCE SIGNS LIST 10 photoelectric conversion element 11, 210 support substrate 12 anode 13 hole transport layer 14 active layer 15 electron transport layer 16 cathode 17 sealing member

Claims (12)

a semiconductor material comprising at least one p-type semiconductor material and at least one n-type semiconductor material;
two or more solvents, including a first solvent and a second solvent having a boiling point higher than the boiling point of the first solvent;
one of the p-type semiconductor material and the n-type semiconductor material is a non-fullerene compound represented by the following formula (I);
^The polarity term ^{P (} An ink composition in which B ¹ )(MPa ^0.5 ) and the polarity term P(S2)(MPa ^0.5 ) of the Hansen solubility parameter of the second solvent satisfy the condition represented by the following formula (III).

A ¹ -B ¹ -(A ¹ )n (I)
|P(B ¹ )−P(S2)|>3.2 (MPa ^0.5 ) (III)

(In formula (I),
A ¹ represents an electron-withdrawing group,
B ¹ represents a group comprising one or more structural units and constituting a π-conjugated system;
n is 0 or 1, and when n is 1, two A ¹ may be the same or different,
A compound containing A ¹ and a compound containing B ¹ having a hydrogen atom-terminated terminal obtained by severing the bond between A ¹ and B ¹ satisfy the condition represented by the following formula (II).

E _HOMO (B ¹ )−E _HOMO (A ¹ )>2.0 (eV) (II)

(In formula (II),
E _HOMO (B ¹ ) (eV) represents the energy level of the highest occupied orbital of a compound containing B ¹ having a hydrogen atom-terminated terminal formed by severing the bond between A ¹ and B ¹ ,
E _HOMO (A ¹ ) (eV) represents the energy level of the highest occupied orbital of a compound containing A ¹ , which is formed by severing the bond between A ¹ and B ¹ and terminated with a hydrogen atom. )) The ink composition according to claim 1, wherein the second solvent has a boiling point higher than that of the first solvent by 30°C or more. 3. The ink composition according to claim 1, wherein the second solvent is an ether solvent, an aromatic hydrocarbon solvent, a ketone solvent or an ester solvent. The ink composition according to any one of claims 1 to 3, wherein the non-fullerene compound represented by formula (I) is an n-type semiconductor material. In the formula (I), the first structural unit, which is at least one of the one or more structural units contained in ^B1 , is a structural unit represented by the following formula (IV), and the first The remaining second structural unit other than the structural unit is a divalent group containing an unsaturated bond, a divalent aromatic carbocyclic group or a divalent aromatic heterocyclic group, the first structural unit When there are two or more, the two or more first structural units may be the same or different, and when there are two or more of the second structural units, the two or more second structural units The ink composition according to any one of claims 1 to 4, wherein the units may be the same or different.

(In formula (IV),
Ar ¹ and Ar ² each independently represent an optionally substituted aromatic carbocyclic ring or an optionally substituted aromatic heterocyclic ring,
Y represents a direct bond, a group represented by -C(=O)- or an oxygen atom,
R are each independently
hydrogen atom,
halogen atom,
an optionally substituted alkyl group,
a cycloalkyl group optionally having a substituent,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
a cycloalkyloxy group optionally having a substituent,
an optionally substituted aryloxy group,
an optionally substituted alkylthio group,
a cycloalkylthio group optionally having a substituent,
an optionally substituted arylthio group,
a monovalent heterocyclic group optionally having a substituent,
a substituted amino group which may have a substituent,
an acyl group optionally having a substituent,
an imine residue optionally having a substituent,
an amide group optionally having a substituent,
an acid imide group optionally having a substituent,
a substituted oxycarbonyl group optionally having a substituent,
an optionally substituted alkenyl group,
a cycloalkenyl group optionally having a substituent,
an optionally substituted alkynyl group,
a cycloalkynyl group optionally having a substituent,
cyano group,
nitro group,
a group represented by —C(=O)—R ^a or a group represented by —SO ₂ —R ^b ,
R ^a and R ^b each independently
hydrogen atom,
an optionally substituted alkyl group,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
It represents an optionally substituted aryloxy group or an optionally substituted monovalent heterocyclic group.
Multiple R's may be the same or different. ) 6. The ink composition according to claim 5, wherein the first structural unit is a structural unit represented by formula (V) below.

(In formula (V),
Y and R are as defined above;
X ¹ and X ² each independently represent a sulfur atom or an oxygen atom,
Z ¹ and Z ² each independently represent a group represented by =C(R)- or a nitrogen atom. ) 7. The ink composition according to claim 6, wherein the first structural unit is a structural unit represented by the following formula (V-1).

(In formula (V-1),
Y represents a group represented by -C(=O)- or an oxygen atom,
R are each independently
hydrogen atom,
halogen atom,
an optionally substituted alkyl group,
a cycloalkyl group optionally having a substituent,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
a cycloalkyloxy group optionally having a substituent,
an optionally substituted aryloxy group,
an optionally substituted alkylthio group,
a cycloalkylthio group optionally having a substituent,
an optionally substituted arylthio group,
a monovalent heterocyclic group optionally having a substituent,
a substituted amino group which may have a substituent,
an acyl group optionally having a substituent,
an imine residue optionally having a substituent,
an amide group optionally having a substituent,
an acid imide group optionally having a substituent,
a substituted oxycarbonyl group optionally having a substituent,
an optionally substituted alkenyl group,
a cycloalkenyl group optionally having a substituent,
an optionally substituted alkynyl group,
a cycloalkynyl group optionally having a substituent,
cyano group,
nitro group,
a group represented by —C(=O)—R ^a or a group represented by —SO ₂ —R ^b ,
R ^a and R ^b each independently
hydrogen atom,
an optionally substituted alkyl group,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
It represents an optionally substituted aryloxy group or an optionally substituted monovalent heterocyclic group.
Plural R's may be the same or different. ) B ¹ is a divalent group having any one structure selected from the group consisting of structures represented by the following formulas (VII-1) to (VII-16), according to claim 6 or 7 The described ink composition.

-CU1- (VII-1)

-CU1-CU1- (VII-2)

-CU1-CU2- (VII-3)

-CU1-CU1-CU1- (VII-4)

-CU1-CU2-CU1- (VII-5)

-CU1-CU1-CU2- (VII-6)

-CU1-CU2-CU2- (VII-7)

-CU2-CU1-CU2- (VII-8)

-CU1-CU1-CU1-CU1- (VII-9)

-CU1-CU1-CU1-CU2- (VII-10)

-CU1-CU1-CU2-CU1- (VII-11)

-CU1-CU1-CU2-CU2- (VII-12)

-CU1-CU2-CU1-CU2- (VII-13)

-CU1-CU2-CU2-CU1- (VII-14)

-CU1-CU2-CU2-CU2- (VII-15)

-CU2-CU1-CU2-CU2- (VII-16)

(In the formulas (VII-1) to (VII-16),
CU1 represents the first structural unit,
CU2 represents the second structural unit.
When there are two or more CU1s, the two or more CU1s may be the same or different, and when there are two or more CU2s, the two or more CU2s may be the same or different. good. ) The ink composition according to any one of claims 1 to 8, wherein the p-type semiconductor material is a conjugated polymer compound. A solidified film obtained by solidifying the ink composition according to any one of claims 1 to 9. A photoelectric conversion device comprising a first electrode, a second electrode, and an active layer provided between the first electrode and the second electrode, wherein the active layer is the solidified film according to claim 10 . 12. The photoelectric conversion device according to claim 11, which is a photodetector.

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