TW202115063A - Photoelectric conversion element - Google Patents

Abstract

The present invention improves heat resistance. A photoelectric conversion element 10 which includes a positive electrode 12, a negative electrode and an active layer 14 provided between said positive and negative electrodes, wherein the active layer contains an n-type semiconductor material and a p-type semiconductor material, the n-type semiconductor material is a compound represented by formula (I), and the p-type semiconductor material is a polymer compound containing a structural unit represented by formula (II). (In formula (I), R1 and R2 are as defined in the description.) (In formula (II), Ar1, Ar2 and Z are as defined in the description.).

Description

Photoelectric conversion element

The present invention relates to a photoelectric conversion element and its manufacturing method, as well as compounds that can be used for these.

Photoelectric conversion elements are extremely useful devices from the viewpoints of, for example, saving energy and reducing carbon dioxide emissions, and are attracting attention.

The photoelectric conversion element is an element including at least a pair of electrodes composed 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 semi-transparent material, and light enters the active layer from the side of the transparent or semi-transparent electrode. With the energy (hν) of the light incident on the active layer, charges (holes and electrons) are generated in the active layer, the generated holes move to the anode, and the electrons move to the cathode. Then, the charge reaching the anode and the cathode is extracted to the outside of the element.

By mixing n-type semiconductor material (electron-accepting compound) and p-type semiconductor material (electron-donating compound), it has the activity of a phase-separated structure composed of a phase containing n-type semiconductor material and a phase containing p-type semiconductor material The layer is also called a bulk heterojunction active layer.

It is known that in a photoelectric conversion element including such a bulk heterojunction active layer, a fullerene derivative, namely C60 PCBM ([6,6]-phenyl-C61 butyric acid methyl ester) is used as an n-type semiconductor The form of the material (refer to Patent Document 1 and Non-Patent Document 1). [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2019/082844 [Non-Patent Literature]

[Non-Patent Document 1] "Advanced Materials (adv.mater.)" 2014, 26, 5831.

[The problem to be solved by the invention] However, in the photoelectric conversion element of Patent Document 1, for example, the characteristics of the photoelectric conversion element may be due to heat treatment such as the manufacturing process of the photoelectric conversion element or the reflow step performed when mounting the photoelectric conversion element to a device to which the photoelectric conversion element is applied. decline.

In the photoelectric conversion element of Non-Patent Document 1, although the heat resistance is improved by further adding an additive as the material of the bulk heterojunction active layer, it is considered that the manufacturing process of the photoelectric conversion element, the time of mounting to the device, etc. The heating temperature is also difficult to say that the heat resistance is sufficient. Therefore, it is required to further improve the heat resistance to the heat treatment in the manufacturing step and the heat resistance of the photoelectric conversion element itself. [Means to solve the problem]

The inventors of the present invention conducted diligent studies to solve the above-mentioned problems, and as a result, found that heat resistance can be improved by using a predetermined semiconductor material as the material of the bulk heterojunction active layer, thereby completing the present invention. That is, the present invention provides the following [1] to [19]. [1] A photoelectric conversion element, comprising an anode, a cathode, and an active layer provided between the anode and the cathode, wherein: The active layer includes an n-type semiconductor material and a p-type semiconductor material, The n-type semiconductor material is a compound represented by the following formula (I), The p-type semiconductor material is a polymer compound containing a structural unit represented by the following formula (II).

（式（I）中， R₁ 表示氫原子、鹵素原子、可具有取代基的烷基、可具有取代基的烷氧基、可具有取代基的1價芳香族烴基或可具有取代基的1價芳香族雜環基，多個R₁ 可相同亦可不同。 R₂ 表示氫原子、鹵素原子、可具有取代基的烷基、可具有取代基的烷氧基、可具有取代基的1價芳香族烴基或可具有取代基的1價芳香族雜環基，多個R₂ 可相同亦可不同。）[化1]

(In formula (I), R ₁ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted monovalent aromatic hydrocarbon group, or an optionally substituted 1 A valent aromatic heterocyclic group, a plurality of R ₁ may be the same or different. R ₂ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted monovalent The aromatic hydrocarbon group or the monovalent aromatic heterocyclic group which may have a substituent, and a plurality of R ₂ may be the same or different.)

（式（II）中， Ar¹ 及Ar² 表示3價芳香族雜環基， Z表示下述式（Z-1）～式（Z-7）所表示的基。）[化2]

(In formula (II), Ar ¹ and Ar ² represent a trivalent aromatic heterocyclic group, and Z represents a group represented by the following formulas (Z-1) to (Z-7).)

（式（Z-1）～式（Z-7）中， R表示氫原子、鹵素原子、烷基、芳基、烷氧基、芳氧基、烷硫基、芳硫基、1價雜環基、取代胺基、醯基、亞胺殘基、醯胺基、醯亞胺（acid imide）基、取代氧基羰基、烯基、炔基、氰基或硝基，在式（Z-1）～式（Z-7）的各式中，當存在兩個R時，兩個R彼此可相同亦可不同）。 [2]如[1]所述的光電轉換元件，其中R₁ 及R₂ 中的至少一個是氟原子、含有氟原子作為取代基的烷基、含有氟原子作為取代基的烷氧基、含有氟原子作為取代基的1價芳香族烴基或含有氟原子作為取代基的1價芳香族雜環基。 [3]如[1]或[2]所述的光電轉換元件，其中R₁ 是包含一個以上的氟原子作為取代基的烷基， R₂ 是氫原子。 [4]如[3]所述的光電轉換元件，其中R₁ 是由-CH₂ (CF₂ )₂ CF₃ 所表示的基， R₂ 是氫原子。 [5]如[2]所述的光電轉換元件，其中R₁ 是可具有取代基的烷基， 多個R₂ 中的兩個以上是包含一個以上的氟原子作為取代基的烷基。 [6]如[1]至[5]中任一項所述的光電轉換元件，其中所述活性層藉由包括在165℃以上的加熱溫度下加熱的處理的步驟來形成。 [7]如[1]至[6]中任一項所述的光電轉換元件，其是光檢測元件。 [8]一種影像感測器，包括如[7]所述的光電轉換元件，且 所述影像感測器藉由包括包含在165℃以上的加熱溫度下加熱所述光電轉換元件的處理的步驟的製造方法來製造。 [9]一種生物體認證裝置，包括如[7]所述的光電轉換元件，且 所述生物體認證裝置藉由包括包含在165℃以上的加熱溫度下加熱所述光電轉換元件的處理的步驟的製造方法來製造。 [10]一種光電轉換元件的製造方法，是製造如[1]至[5]中任一項所述的光電轉換元件的方法，其中 形成所述活性層的步驟包括：步驟（i），將含有所述n型半導體材料及所述p型半導體材料的油墨塗佈在塗佈對象上而獲得塗膜；以及步驟（ii），自獲得的塗膜中除去溶劑。 [11]如[10]所述的光電轉換元件的製造方法，其更包括在165℃以上的加熱溫度下加熱的步驟。 [12]如[11]所述的光電轉換元件的製造方法，其中在165℃以上的加熱溫度下加熱的步驟於所述步驟（ii）之後實施。 [13]一種化合物，其由下述式（I）表示。[化3]

(In formulas (Z-1) to (Z-7), R represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic ring Group, substituted amine group, amide group, imine residue, amide group, acid imide group, substituted oxycarbonyl group, alkenyl group, alkynyl group, cyano group or nitro group, in the formula (Z-1 ) ~ Formula (Z-7), when two Rs are present, the two Rs may be the same or different from each other). [2] The photoelectric conversion element according to [1], wherein _{at least one of R 1} and R ₂ is a fluorine atom, an alkyl group containing a fluorine atom as a substituent, an alkoxy group containing a fluorine atom as a substituent, and A monovalent aromatic hydrocarbon group having a fluorine atom as a substituent or a monovalent aromatic heterocyclic group having a fluorine atom as a substituent. [3] The photoelectric conversion element according to [1] or [2], wherein R ₁ is an alkyl group containing one or more fluorine atoms as a substituent, and R ₂ is a hydrogen atom. [4] The photoelectric conversion element according to [3], wherein R ₁ is a group represented by -CH ₂ (CF ₂ ) ₂ CF _{3 , and R 2} is a hydrogen atom. [5] The photoelectric conversion element according to [2], wherein R ₁ is an alkyl group which may have a substituent _{, and two or more of the plurality of R 2} are alkyl groups containing one or more fluorine atoms as a substituent. [6] The photoelectric conversion element according to any one of [1] to [5], wherein the active layer is formed by a step including a process of heating at a heating temperature of 165° C. or more. [7] The photoelectric conversion element according to any one of [1] to [6], which is a light detecting element. [8] An image sensor comprising the photoelectric conversion element as described in [7], and the image sensor includes a step of heating the photoelectric conversion element at a heating temperature of 165°C or higher The manufacturing method to manufacture. [9] A biometric authentication device comprising the photoelectric conversion element as described in [7], and the biometric authentication device includes a step of heating the photoelectric conversion element at a heating temperature of 165°C or higher The manufacturing method to manufacture. [10] A method of manufacturing a photoelectric conversion element, which is a method of manufacturing the photoelectric conversion element as described in any one of [1] to [5], wherein the step of forming the active layer includes: step (i): The ink containing the n-type semiconductor material and the p-type semiconductor material is coated on the coating object to obtain a coating film; and step (ii), removing the solvent from the obtained coating film. [11] The method of manufacturing a photoelectric conversion element as described in [10], which further includes a step of heating at a heating temperature of 165°C or higher. [12] The method of manufacturing a photoelectric conversion element according to [11], wherein the step of heating at a heating temperature of 165° C. or higher is performed after the step (ii). [13] A compound represented by the following formula (I).

（式（I）中， R₁ 是包含一個以上的氟原子作為取代基的烷基，多個R₁ 可相同亦可不同。 R₂ 表示氫原子、鹵素原子、可具有取代基的烷基、可具有取代基的烷氧基、可具有取代基的1價芳香族烴基或可具有取代基的1價芳香族雜環基，多個R₂ 可相同亦可不同） [14]如[13]所述的化合物，其中R₁ 是由-CH₂ (CF₂ )₂ CF₃ 所表示的基， R₂ 是氫原子。 [15]一種化合物，其由下述式（I）表示。[化4]

(In formula (I), R ₁ is an alkyl group containing one or more fluorine atoms as a substituent, and a plurality of R ₁ may be the same or different. R ₂ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, An alkoxy group that may have a substituent, a monovalent aromatic hydrocarbon group that may have a substituent, or a monovalent aromatic heterocyclic group that may have a substituent, multiple R ₂ may be the same or different) [14] such as [13] In the compound, R ₁ is a group represented by -CH ₂ (CF ₂ ) ₂ CF _{3 and R 2} is a hydrogen atom. [15] A compound represented by the following formula (I).

（式（I）中， R₁ 表示氫原子、鹵素原子、可具有取代基的烷基、可具有取代基的烷氧基、可具有取代基的1價芳香族烴基或可具有取代基的1價芳香族雜環基，多個R₁ 可相同亦可不同。 R₂ 表示氫原子、鹵素原子、可具有取代基的烷基、可具有取代基的烷氧基、可具有取代基的1價芳香族烴基或可具有取代基的1價芳香族雜環基，多個R₂ 可相同亦可不同） [16]如[15]所述的化合物，其中R₁ 是可具有取代基的烷基， 多個R₂ 中的兩個以上是包含一個以上的氟原子作為取代基的烷基。 [17]如[15]或[16]所述的化合物，其由下述式（N-4）表示。[化5]

(In formula (I), R ₁ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted monovalent aromatic hydrocarbon group, or an optionally substituted 1 A valent aromatic heterocyclic group, a plurality of R ₁ may be the same or different. R ₂ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted monovalent The aromatic hydrocarbon group or the monovalent aromatic heterocyclic group which may have a substituent, and a plurality of R ₂ may be the same or different) [16] The compound according to [15], wherein R ₁ is an alkyl group which may have a substituent , Two or more of the plurality of R ₂ are alkyl groups containing one or more fluorine atoms as substituents. [17] The compound according to [15] or [16], which is represented by the following formula (N-4).

[18]一種組成物，含有n型半導體材料及p型半導體材料，且所述n型半導體材料是如[13]至[17]中任一項所述的化合物。 [19]一種油墨，包含如[18]所述的組成物。[化6]

[18] A composition containing an n-type semiconductor material and a p-type semiconductor material, and the n-type semiconductor material is the compound according to any one of [13] to [17]. [19] An ink comprising the composition as described in [18].

In addition, the photoelectric conversion element of the present invention may be in the form of the following [X]. [X] A photoelectric conversion element, comprising an anode, a cathode, and an active layer provided between the anode and the cathode, wherein: The active layer includes an n-type semiconductor material and a p-type semiconductor material, The n-type semiconductor material is a compound represented by the following formula (I), The p-type semiconductor material is a polymer compound containing a structural unit represented by the following formula (II).

（式（I）中， R₁ 表示氫原子、鹵素原子、可具有取代基的烷基、可具有取代基的烷氧基、可具有取代基的1價芳香族烴基或可具有取代基的1價芳香族雜環基，多個R₁ 可相同亦可不同。 R₂ 表示氫原子、鹵素原子、可具有取代基的烷基、可具有取代基的烷氧基、可具有取代基的1價芳香族烴基或可具有取代基的1價芳香族雜環基，多個R₂ 可相同亦可不同。）[化7]

(In formula (I), R ₁ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted monovalent aromatic hydrocarbon group, or an optionally substituted 1 A valent aromatic heterocyclic group, a plurality of R ₁ may be the same or different. R ₂ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted monovalent The aromatic hydrocarbon group or the monovalent aromatic heterocyclic group which may have a substituent, and a plurality of R ₂ may be the same or different.)

（式（II）中， Ar¹ 及Ar² 表示3價芳香族雜環基， Z表示下述式（Z-1）～式（Z-7）所表示的基）[化8]

(In formula (II), Ar ¹ and Ar ² represent a trivalent aromatic heterocyclic group, and Z represents a group represented by the following formulas (Z-1) to (Z-7))

（式（Z-1）～式（Z-7）中， R表示氫原子、鹵素原子、烷基、芳基、烷氧基、芳氧基、烷硫基、芳硫基、1價雜環基、取代胺基、醯基、亞胺殘基、醯胺基、醯亞胺基、取代氧基羰基、烯基、炔基、氰基或硝基，在式（Z-1）～式（Z-7）的各式中，當存在兩個R時，兩個R彼此可相同亦可不同。） 但是，所述p型半導體材料與所述n型半導體材料的組合將後述的P-1及後述的N-1的情況除外。 [發明的效果][化9]

(In formulas (Z-1) to (Z-7), R represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic ring Group, substituted amine group, amide group, imine residue, amide group, amide group, substituted oxycarbonyl group, alkenyl group, alkynyl group, cyano group or nitro group, in formula (Z-1) ~ formula ( In each formula of Z-7), when there are two Rs, the two Rs may be the same or different from each other.) However, the combination of the p-type semiconductor material and the n-type semiconductor material will be P-1 described later Except for the case of N-1 described later. [Effects of the invention]

According to the present invention, it is possible to improve the heat resistance of the heat treatment in the manufacturing step of the photoelectric conversion element or the mounting to the device to which the photoelectric conversion element is applied.

Hereinafter, the photoelectric conversion element according to the embodiment of the present invention will be described with reference to the drawings. In addition, the drawings 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 to the following description, and each constituent element can be appropriately changed without departing from the gist of the present invention. In addition, the structure of the embodiment of the present invention is not necessarily limited to be manufactured or used in the configuration shown in the drawings.

First, the terms commonly used in the following description will be explained.

The "polymer compound" refers to a polymer having a molecular weight distribution and a polystyrene-converted number average molecular weight of 1×10 ³ or more and 1×10 ⁸ or less. In addition, the total of the structural units contained in the polymer compound is 100 mol%.

"Structural unit" refers to the presence of one or more residues derived from raw material monomers in a polymer compound.

The "hydrogen atom" may be a light hydrogen atom or a heavy hydrogen atom.

Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The form of "may have substituents" includes two forms: a case where all hydrogen atoms constituting a compound or a group are unsubstituted, and a case where part or all of one or more hydrogen atoms are substituted with a substituent.

The "alkyl" may be any of linear, branched, and cyclic. The number of carbon atoms of the linear alkyl group excluding the substituent is usually 1-50, preferably 1-30, more preferably 1-20. The carbon number of the branched or cyclic alkyl group excluding the carbon number of the substituent is usually 3-50, preferably 3-30, more preferably 4-20. The alkyl group may have a substituent.

Specific examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, isopentyl, 2-ethylbutyl Base, n-hexyl, cyclohexyl, n-heptyl, cyclohexylmethyl, cyclohexylethyl, n-octyl, 2-ethylhexyl, 3-n-propylheptyl, adamantyl, n-decyl, 3, 7-dimethyloctyl, 2-ethyloctyl, 2-n-hexyl-decyl, n-dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and other alkanes One or more hydrogen atoms such as trifluoromethyl, pentafluoroethyl, -CH ₂ (CF ₂ ) ₂ CF ₃ , perfluorobutyl, perfluorohexyl, perfluorooctyl, etc. are replaced by fluorine atoms The alkyl group, 3-phenylpropyl, 3-(4-methylphenyl)propyl, 3-(3,5-di-n-hexylphenyl)propyl, 6-ethyloxyhexyl, etc. Substituent alkyl group.

The "aromatic hydrocarbon group (aryl group)" refers to an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon that may have a substituent. The aromatic hydrocarbon group may have a substituent.

Specific examples of aromatic hydrocarbon groups include: phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-pyrenyl, 2-pyrenyl, 4 -Pyrenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 2-phenylphenyl, 3-phenylphenyl, 4-phenylphenyl, and more alkyl, alkoxy, Substituent groups such as aryl groups and fluorine atoms.

The "alkoxy group" may be any of linear, branched, and cyclic. The carbon number of the linear alkoxy group excluding the carbon number of the substituent is usually 1-40, preferably 1-10. The number of carbon atoms of the branched or cyclic alkoxy group excluding the substituent is usually 3-40, preferably 4-10. The alkoxy group may have a substituent.

Specific examples of alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, N-hexyloxy, cyclohexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, 3,7-dimethyloctyloxy, and laurel Oxy.

The number of carbon atoms of the "aryloxy group" excluding the substituent is usually 6-60, preferably 6-48. The aryloxy group may have a substituent.

Specific examples of aryloxy groups include phenoxy, 1-naphthyloxy, 2-naphthyloxy, 1-anthryloxy, 9-anthryloxy, 1-pyrenyloxy, And a group further having substituents such as an alkyl group, an alkoxy group, and a fluorine atom.

"Alkylthio" may be any of linear, branched, and cyclic. The carbon number of the linear alkylthio group excluding the carbon number of the substituent is usually 1-40, preferably 1-10. The number of carbon atoms of the branched and cyclic alkylthio groups excluding the substituents is usually 3-40, preferably 4-10. The alkylthio group may have a substituent.

Specific examples of alkylthio groups include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, tertiary butylthio, pentylthio, and hexylthio. , Cyclohexylthio, heptylthio, octylthio, 2-ethylhexylthio, nonylthio, decylthio, 3,7-dimethyloctylthio, laurylthio, and trifluoromethylthio base.

The number of carbon atoms of the "arylthio group" excluding the substituent is usually 6-60, preferably 6-48. The arylthio group may also have a substituent.

Examples of arylthio groups include: phenylthio, C1 to C12 alkoxyphenylthio (here, "C1 to C12" means that the group described immediately after that has 1 to 12 carbon atoms. The following The same is also true.), C1-C12 alkylphenylthio, 1-naphthylthio, 2-naphthylthio, and pentafluorophenylthio.

"P-valent heterocyclic group" (p represents an integer of 1 or more) means that p hydrogen atoms in the hydrogen atoms directly bonded to the carbon atoms or heteroatoms constituting the ring are removed from the heterocyclic compound which may have a substituent The remaining atomic group. The "p-valent heterocyclic group" includes the "p-valent aromatic heterocyclic group". The "p-valent aromatic heterocyclic group" refers to an atomic group remaining after removing p hydrogen atoms from the hydrogen atoms directly bonded to the carbon atoms or heteroatoms constituting the ring from the aromatic heterocyclic compound which may have a substituent.

Examples of substituents that the heterocyclic compound may have include halogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, monovalent heterocyclic groups, and substituted amino groups. , Amino groups, imine residues, amide groups, amide groups, substituted oxycarbonyl groups, alkenyl groups, alkynyl groups, cyano groups and nitro groups.

Among the aromatic heterocyclic compounds, in addition to compounds in which the heterocyclic ring itself exhibits aromaticity, even if the heterocyclic ring itself does not exhibit aromaticity, the aromatic ring is fused with the heterocyclic ring.

Among the aromatic heterocyclic compounds, specific examples of compounds in which the heterocyclic ring itself exhibits aromaticity include: oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphocyclopentadiene, Furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphine.

Among the aromatic heterocyclic compounds, specific examples of compounds in which the aromatic heterocyclic ring itself does not exhibit aromaticity and the aromatic ring and the heterocyclic ring are condensed include: phenoxazine, phenothiazine, and dibenzo Borocyclopentadiene, dibenzosilole, and benzopyran.

The number of carbon atoms of the monovalent heterocyclic group excluding the number of carbon atoms of the substituent is usually 2-60, preferably 4-20.

The monovalent heterocyclic group may have a substituent. Specific examples of the monovalent heterocyclic group include thienyl, pyrrolyl, furyl, pyridyl, piperidinyl, quinolinyl, isoquinolinyl, A pyrimidinyl group, a triazinyl group, and a group further having substituents such as an alkyl group and an alkoxy group.

"Substituted amino group" refers to an amino group having a substituent. As the substituent which the amino group has, an alkyl group, an aryl group, and a monovalent heterocyclic group are preferable. The number of carbon atoms of the substituted amino group is usually 2-30.

Examples of substituted amino groups include dialkylamino groups such as dimethylamino and diethylamino, diphenylamino, bis(4-methylphenyl)amino, and bis(4- Diarylamino groups such as tertiary butylphenyl)amino and bis(3,5-di-tertiarybutylphenyl)amino.

The number of carbon atoms of the "acyl group" is usually 2-20, preferably 2-18. Specific examples of the acyl group include acetyl group, propyl group, butyryl group, isobutyryl group, trimethyl acetyl group, benzyl group, trifluoroacetyl group, and pentafluorobenzyl group.

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

The number of carbon atoms of the imine residue is usually 2-20, preferably 2-18. As an example of the imine residue, the group represented by the following structural formula can be mentioned.

[化10]

"Amino group" refers to an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an amide. The number of carbon atoms of the amide group is usually 1-20, preferably 1-18. Specific examples of the amide group include: formamide group, acetamide group, acrylamide group, butyramide group, benzamide group, trifluoroacetamide group, and pentafluorobenzamide group Group, dimethyl amide, diacetyl amide, dipropylene amide, dibutyl amide, dibenzyl amide, di-trifluoroacetamide, and di-pentafluorobenzamide Amine group.

The "amido" refers to a group of atoms remaining after removing one hydrogen atom bonded to a nitrogen atom from the amido. The number of carbon atoms of the imino group is usually 4-20. As a specific example of an imino group, the group represented by the following structural formula can be mentioned.

[化11]

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

The number of carbon atoms of the "substituted oxycarbonyl group" is usually 2-60, and preferably 2-48.

Specific examples of the substituted oxycarbonyl group include: methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, and tertiary butoxycarbonyl , Pentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, 3,7- Dimethyloctoxycarbonyl, dodecyloxycarbonyl, trifluoromethoxycarbonyl, pentafluoroethoxycarbonyl, perfluorobutoxycarbonyl, perfluorohexyloxycarbonyl, perfluorooctoxycarbonyl , Phenoxycarbonyl, naphthoxycarbonyl, and pyridyloxycarbonyl.

The "alkenyl group" may be any of linear, branched, and cyclic. The number of carbon atoms of the linear alkenyl group excluding the substituent is usually 2-30, preferably 3-20. The number of carbon atoms of the branched or cyclic alkenyl group excluding the substituent is usually 3-30, preferably 4-20. 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-hexyl Alkenyl, 5-hexenyl, 7-octenyl, and groups further having substituents such as alkyl and alkoxy.

The "alkynyl group" may be any of linear, branched, and cyclic. The number of carbon atoms of the linear alkynyl group excluding the substituent is usually 2-20, preferably 3-20. The number of carbon atoms of the branched or cyclic alkynyl group excluding the substituent is usually 4-30, preferably 4-20. 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, and 1 -Hexynyl, 5-hexynyl, and groups further having substituents such as alkyl and alkoxy.

"EQE" refers to the external quantum efficiency (External Quantum Efficiency), which is a ratio (%) representing the value of the number of generated electrons that can be extracted to the outside of the photoelectric conversion element relative to the number of photons irradiated to the photoelectric conversion element.

1. Photoelectric conversion element The photoelectric conversion element of this embodiment includes an anode, a cathode, and an active layer provided between the anode and the cathode. In the photoelectric conversion element, The active layer includes an n-type semiconductor material and a p-type semiconductor material, The n-type semiconductor material is a compound represented by the following formula (I), The p-type semiconductor material is a polymer compound containing a structural unit represented by the following formula (II).

（式（I）中， R₁ 表示氫原子、鹵素原子、可具有取代基的烷基、可具有取代基的烷氧基、可具有取代基的1價芳香族烴基或可具有取代基的1價芳香族雜環基，多個R₁ 可相同亦可不同。 R₂ 表示氫原子、鹵素原子、可具有取代基的烷基、可具有取代基的烷氧基、可具有取代基的1價芳香族烴基或可具有取代基的1價芳香族雜環基，多個R₂ 可相同亦可不同）[化12]

(In formula (I), R ₁ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted monovalent aromatic hydrocarbon group, or an optionally substituted 1 A valent aromatic heterocyclic group, a plurality of R ₁ may be the same or different. R ₂ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted monovalent Aromatic hydrocarbon group or monovalent aromatic heterocyclic group which may have a substituent, multiple R ₂ may be the same or different)

（式（II）中， Ar¹ 及Ar² 表示3價芳香族雜環基， Z表示下述式（Z-1）～式（Z-7）所表示的基）[化13]

(In formula (II), Ar ¹ and Ar ² represent a trivalent aromatic heterocyclic group, and Z represents a group represented by the following formulas (Z-1) to (Z-7))

（式（Z-1）～式（Z-7）中， R表示氫原子、鹵素原子、烷基、芳基、烷氧基、芳氧基、烷硫基、芳硫基、1價雜環基、取代胺基、醯基、亞胺殘基、醯胺基、醯亞胺基、取代氧基羰基、烯基、炔基、氰基或硝基，在式（Z-1）～式（Z-7）的各式中，當存在兩個R時，兩個R彼此可相同亦可不同）。[化14]

(In formulas (Z-1) to (Z-7), R represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic ring Group, substituted amine group, amide group, imine residue, amide group, amide group, substituted oxycarbonyl group, alkenyl group, alkynyl group, cyano group or nitro group, in formula (Z-1) ~ formula ( In each formula of Z-7), when two Rs are present, the two Rs may be the same or different from each other).

According to the photoelectric conversion element of this embodiment, by including the structure, it is possible to effectively improve the heat resistance of the photoelectric conversion element in the manufacturing steps or heat treatment when it is installed in a device to which the photoelectric conversion element is applied.

Here, a description will be given of a configuration example that can be adopted for the photoelectric conversion element of the present embodiment. FIG. 1 is a diagram schematically showing the structure of the photoelectric conversion element of this embodiment.

As shown in FIG. 1, the photoelectric conversion element 10 is provided on the supporting substrate 11. The photoelectric conversion element 10 includes an anode 12 provided in contact with the supporting substrate 11, a hole transport layer 13 provided in contact with the anode 12, and an active electrode provided in contact with the hole transport layer 13. The layer 14, the electron transport layer 15 provided in contact with the active layer 14, and the 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. Hereinafter, the constituent elements that can be included in the photoelectric conversion element of the present embodiment will be specifically described.

(Substrate) The photoelectric conversion element is usually formed on a substrate (supporting substrate). In addition, it may be further sealed by the substrate (sealing substrate). One of a pair of electrodes including a cathode and an anode is usually 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.

Examples of the material of the substrate include glass, plastic, polymer film, and silicon. When an opaque substrate is used, it is preferable that the electrode on the side opposite to the electrode provided on the side of the opaque substrate (in other words, the electrode on the side away from the opaque substrate) is a transparent or semitransparent electrode.

(electrode) The photoelectric conversion element includes an anode and a cathode as a pair of electrodes. At least one of the anode and the cathode is preferably a transparent or semi-transparent electrode to allow light to be incident.

Examples of materials for transparent or semi-transparent electrodes include conductive metal oxide films and semi-transparent metal thin films. Specifically, indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO), indium zinc oxide (Indium Zinc Oxide, IZO), NESA, and other conductive compounds that are composites of these can be cited. Sexual materials, gold, platinum, silver, copper. As the material of the transparent or semi-transparent electrode, ITO, IZO, and tin oxide are preferred. In addition, as the electrode, a transparent conductive film using organic compounds such as polyaniline and its derivatives, and polythiophene and its derivatives as materials can be used. The transparent or semi-transparent electrode can be an anode or a cathode.

If one electrode of the pair of electrodes is transparent or semi-transparent, 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 materials for electrodes with low light transmittance include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, and europium. , Ytterbium, ytterbium and other metals and alloys of two or more of these metals; or one or more of these metals is selected from gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and Alloys of one or more metals in the group consisting of tin; graphite, graphite intercalation compounds, polyaniline and its derivatives, polythiophene and its derivatives. Examples of 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 of this embodiment includes an n-type semiconductor material (electron-accepting compound) and a p-type semiconductor material (electron-donating compound). Which of the n-type semiconductor material and the p-type semiconductor material is relatively determined according to the energy level of the highest occupied orbital (Highest Occupied Molecular Orbital, HOMO) or the lowest unoccupied molecular orbital (LUMO) of the selected compound One.

In this embodiment, the thickness of the active layer is not particularly limited. In consideration of the balance between suppression of dark current and extraction of generated photocurrent, it may be any suitable thickness. The active layer of this embodiment is formed by a process including a process of heating at a heating temperature of 165° C. or higher (the details will be described later).

Here, an n-type semiconductor material and a p-type semiconductor material suitable as materials for the active layer of the photoelectric conversion element of this embodiment will be described.

(1) n-type semiconductor material The photoelectric conversion element of this embodiment is characterized by including an n-type semiconductor material as an active layer. In this embodiment, the n-type semiconductor material is a compound represented by the following formula (I).

[化15]

[In formula (I), R ₁ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted monovalent aromatic hydrocarbon group, or an optionally substituted 1 Valence aromatic heterocyclic group. A plurality of R ₁ may be the same or different.

In the formula (I), R _{1 is} preferably an alkyl group which may have a substituent. R _{1 is} preferably one or more of _{the group represented by -(CH 2} ) _n CH ₃ , the group represented by -CH(C _n H _2n+1 ) ₂ or the group represented by -(CH ₂ ) _n CH ₃ The alkyl group in which the hydrogen atom of is replaced by a fluorine atom is more preferably a group represented by -(CH ₂ )(CF ₂ ) _n-1 CF ₃ . Furthermore, n refers to an integer, and when R ₁ is a group represented by -(CH ₂ ) _n CH ₃ , the lower limit of n is preferably 1, more preferably 5, and still more preferably 7, n The upper limit is preferably 30, more preferably 25, and still more preferably 15. In addition, when R ₁ is a group represented by -(CH ₂ )(CF ₂ ) _n-1 CF ₃ , the lower limit of n is preferably 1, more preferably 3, and the upper limit of n is preferably It is 10, more preferably 7, and even more preferably 5.

R ₂ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted monovalent aromatic hydrocarbon group, or an optionally substituted monovalent aromatic heterocyclic group. From the viewpoint of energy level, R _{2 is} preferably an electron withdrawing group, more preferably a halogen atom, an alkyl group containing one or more halogen atoms as a substituent, or an alkoxy group containing one or more halogen atoms as a substituent, A monovalent aromatic hydrocarbon group containing more than one halogen atom as a substituent or a monovalent aromatic heterocyclic group containing more than one halogen atom as a substituent, and more preferably a bromine atom, a fluorine atom, or a fluorine atom containing more than one as Substituent alkyl groups, alkoxy groups containing more than one fluorine atom as a substituent, monovalent aromatic hydrocarbon groups containing more than one fluorine atom as a substituent, or monovalent aromatic hydrocarbon groups containing more than one fluorine atom as a substituent The heterocyclic group is preferably an alkyl group containing more than one fluorine atom as a substituent. A plurality of R ₂ may be the same or different.

In formula (I), it is preferable _{that at least one of R 1} and R ₂ is a fluorine atom, an alkyl group containing a fluorine atom as a substituent, an alkoxy group containing a fluorine atom as a substituent, or a fluorine atom as a substituent. The monovalent aromatic hydrocarbon group or the monovalent aromatic heterocyclic group _{containing a fluorine atom as a substituent is more preferably R 1} is an alkyl group containing one or more fluorine atoms as a substituent, and R ₂ is a hydrogen atom.

As an example of an n-type semiconductor material that can be preferably used in this embodiment, a compound in which R ₁ is a group represented by _{-CH 2} (CF ₂ ) ₂ CF _{3 and R 2} is a hydrogen atom can be cited. As a further example of the n-type semiconductor material that can be preferably used in this embodiment, R ₁ is an alkyl group which may have a substituent _{, and two or more of the plurality of R 2} are those containing more than one fluorine atom as a substituent. The compound of the alkyl group, more specifically, R ₁ is a group represented by -CH(C ₅ H ₁₁ ) _{2 , R 2} is a hydrogen atom or a group represented by _{-CF 3 , and two} of a plurality of R 2 More than one compound is a group represented by _{-CF 3.}

As specific examples of n-type semiconductor materials that can be suitably used in this embodiment, compounds represented by the following formulas (N-1) to (N-13) can be cited.

[化16]

[化17]

[化18]

[化19]

[化20]

As the compound represented by the above formula (I), it is preferable to use the compound represented by the above formula (N-1) to (N-3) because it can improve heat resistance, suppress the decrease of EQE, or further increase EQE, and further The increase in dark current is suppressed or the dark current is further reduced, so that these balances are good.

(P-type semiconductor material) The p-type semiconductor material can be a low-molecular compound or a high-molecular compound.

Examples of p-type semiconductor materials that are low-molecular-weight compounds include phthalocyanine, metal phthalocyanine, porphyrin, metalloporphyrin, oligothiophene, fused tetrabenzene, fused pentacene, and fluorene.

When the p-type semiconductor material is a polymer compound, the polymer compound has a predetermined weight average molecular weight in terms of polystyrene.

Here, the weight average molecular weight in terms of polystyrene refers to the weight average molecular weight calculated using gel permeation chromatography (GPC) and using a standard sample of polystyrene.

From the viewpoint of improving the solubility in a solvent, the weight average molecular weight in terms of polystyrene of the p-type semiconductor material is preferably 20,000 or more and 200,000 or less, more preferably 30,000 or more and 180,000 or less, and still more preferably 40,000 or more and Below 150,000.

As for the p-type semiconductor material as a polymer compound, for example, polyvinyl carbazole and its derivatives, polysilane and its derivatives, polysiloxane containing aromatic amine structure in the side chain or main chain Alkyl derivatives, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene and its derivatives, polythiophene and its derivatives, polyfluorene and its derivatives Things.

The p-type semiconductor material as the polymer compound is preferably a polymer compound containing a structural unit containing a thiophene skeleton.

The p-type semiconductor material is preferably a polymer compound containing a structural unit represented by the following formula (II) and/or a structural unit represented by the following formula (III).

[化21]

In the formula (II), Ar ¹ and Ar ² represent a trivalent aromatic heterocyclic group, and Z represents a group represented by the following formulas (Z-1) to (Z-7).

[化22]

In formulas (Z-1) to (Z-7), R represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and a monovalent heterocyclic group , Substituted amine group, amide group, imine residue, amide group, amide group, substituted oxycarbonyl group, alkenyl group, alkynyl group, cyano group or nitro group. In each of formulas (Z-1) to (Z-7), when there are two Rs, the two Rs may be the same or different from each other.

[化23]

In the formula (III), Ar ³ represents a divalent aromatic heterocyclic group.

The structural unit represented by formula (II) is preferably a structural unit represented by the following formula (II-1).

[化24]

In the formula (II-1), Z has the same meaning as above.

Examples of the structural unit represented by the formula (II-1) include structural units represented by the following formulas (501) to (505).

[化25]

In the above formulas (501) to (505), R has the same meaning as described above. When there are two Rs, the two Rs may be the same or different.

The ^{number of carbon atoms which the divalent aromatic heterocyclic group represented by Ar 3} has is 2-60 normally, Preferably it is 4-60, More preferably, it is 4-20. The divalent aromatic heterocyclic group represented by ^{Ar 3 may have a substituent.} Examples of the substituent that the divalent aromatic heterocyclic group represented by Ar ³ may have include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and a monovalent Heterocyclic groups, substituted amino groups, amide groups, imine residues, amide groups, amide groups, substituted oxycarbonyl groups, alkenyl groups, alkynyl groups, cyano groups, and nitro groups.

Examples of the divalent aromatic heterocyclic group represented by Ar ³ include groups represented by the following formulas (101) to (185).

[化26]

[化27]

[化28]

[化29]

In formula (101) to formula (185), R has the same meaning as described above. When there are a plurality of Rs, the plurality of Rs may be the same or different from each other.

The structural unit represented by the above formula (III) is preferably a structural unit represented by the following formula (III-1) to formula (III-6).

[化30]

In formula (III-1) to formula (III-6), X ¹ and X ² each independently represent an oxygen atom or a sulfur atom, and R represents the same meaning as described above. When there are a plurality of Rs, the plurality of Rs may be the same or different from each other.

^{From the viewpoint of availability of the raw material compound, X 1} and X ² in the formulas (III-1) to (III-6) are preferably both sulfur atoms.

The polymer compound as a p-type semiconductor material may include two or more structural units represented by formula (II), or two or more structural units represented by formula (III).

In order to improve the solubility in a solvent, the polymer compound as a p-type semiconductor material may contain a structural unit represented by the following formula (IV).

[化31]

In the formula (IV), Ar ⁴ represents an arylene group.

The ^{arylene group represented by Ar 4} refers to an atomic group remaining after removing two hydrogen atoms from an optionally substituted aromatic hydrocarbon. Aromatic hydrocarbons also 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 through divalent groups such as vinylidene groups.

As an example of the substituent which an aromatic hydrocarbon may have, the substituent similar to the substituent illustrated as a substituent which a heterocyclic compound may have is mentioned.

The number of carbon atoms of the part other than the substituent in the arylene group is usually 6-60, preferably 6-20. The number of carbon atoms of the arylene group including the substituent is usually about 6-100.

As examples of the arylene group, phenylene (for example, the following formulas 1 to 3), naphthalene-diyl (for example, the following formulas 4 to 13), and anthracene-diyl (for example, the following formulas 14 to 3) 19), biphenyl-diyl (for example, the following formula 20 to formula 25), terphenyl-diyl (for example, the following formula 26 to 28), condensed ring compound group (for example, the following formula 29 to 35), Fluorene-diyl (for example, the following formulae 36 to 38), and benzofluorene-diyl (for example, the following formulae 39 to 46).

[化32]

[化33]

[化34]

[化35]

[化36]

[化37]

[化38]

[化39]

The structural unit constituting the polymer compound as the p-type semiconductor material may be two selected from the structural unit represented by the formula (II), the structural unit represented by the formula (III), and the structural unit represented by the formula (IV) A structural unit formed by combining two or more of the above structural units.

When the polymer compound as the p-type semiconductor material contains the structural unit represented by the formula (II) and/or the structural unit represented by the formula (III), the amount of all the structural units contained in the polymer compound is 100 When mol%, the total amount of the structural unit represented by formula (II) and the structural unit represented by formula (III) is usually 20 mol% to 100 mol%, in order to improve the charge transport as a p-type semiconductor material For reasons of sex, it is preferably 40 mol% to 100 mol%, more preferably 50 mol% to 100 mol%.

Specific examples of the polymer compound as the p-type semiconductor material include polymer compounds represented by the following formulas (P-1) to (P-10).

[化40]

[化41]

[化42]

Among the specific examples of the polymer compound as the p-type semiconductor material, it is preferable to use the polymer compound represented by the formula P-1 because it can improve heat resistance, suppress the decrease of EQE, or further increase the EQE, thereby suppressing The dark current increases or further reduces the dark current, so that these balances are good.

(middle layer) As shown in FIG. 1, the photoelectric conversion element of this embodiment preferably includes, for example, an intermediate layer (buffer layer) such as a charge transport layer (electron transport layer, hole transport layer, electron injection layer, hole injection layer) as a It is a component that improves the photoelectric conversion efficiency and other characteristics.

In addition, examples of materials used in 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-styrene sulfonate)) mixture (PEDOT:PSS)

As shown in FIG. 1, it is preferable that the photoelectric conversion element includes a hole transport layer between the anode and the active layer. The hole transport layer has the function of transporting holes from the active layer to the electrode.

The hole transport layer provided in contact with the anode is sometimes called a hole injection layer in particular. The hole transport layer (hole injection layer) provided in contact with the anode has a function of promoting the injection of holes into the anode. The hole transport layer (hole injection layer) may be connected to the active layer.

The hole transport layer contains a hole transport material. Examples of hole-transporting materials include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing structural 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 preferred forming method known in the past. The intermediate layer can be formed by a vacuum evaporation method or a coating method similar to the formation method of the active layer.

The photoelectric conversion element of this embodiment preferably has a structure in which the intermediate layer is an electron transport layer, and the substrate (support substrate), anode, hole transport layer, active layer, electron transport layer, and cathode are stacked in order to be in contact with each other. .

As shown in FIG. 1, the photoelectric conversion element of this embodiment preferably includes 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 connected to the cathode. The electron transport layer may also be connected to the active layer.

The electron transport layer provided in contact with the cathode is sometimes specifically called an electron injection layer. The 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 transport layer contains an electron transport material. Examples of electron-transporting materials include polyalkyleneimine and its derivatives, polymer compounds containing a fluorene structure, metals such as calcium, and metal oxides.

Examples of polyalkyleneimine and its derivatives include: ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentenimine, hexeneimine, hepteneimine Alkyleneimines having 2-8 carbon atoms such as amines and octeneimines, especially polymers obtained by polymerizing one or two or more of alkyleneimines having 2 to 4 carbon atoms by a conventional method, And the polymers chemically modified by reacting these with various compounds. As polyalkyleneimine and its derivatives, polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE) are preferred.

As an example of a polymer compound containing a fluorene structure, poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-o- 2,7-(9,9-dioctylfluorene)] (PFN) and PEN-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, zinc-containing metal oxides are preferred, and zinc oxide is particularly preferred.

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

(Sealing member) The photoelectric conversion element of this embodiment preferably further includes a sealing member, and a sealed body sealed by the sealing member is formed. As the sealing member, any suitable conventionally known member can be used. As an example of the sealing member, a combination of a glass substrate as a substrate (sealing substrate) and a sealing material (adhesive) such as an ultraviolet (UV) curable resin can be cited.

The sealing member may be a sealing layer with more than one layer structure. Examples of the layer constituting the sealing layer include a gas barrier layer and a gas barrier film.

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 materials suitable as sealing layer materials include: polytrifluoroethylene, polychlorotrifluoroethylene (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, Organic materials such as ethylene-vinyl alcohol copolymers, and inorganic materials such as silicon oxide, silicon nitride, alumina and diamond-like carbon.

The sealing member is generally made of a material that can withstand the heat treatment performed when mounting the photoelectric conversion element to, for example, devices of the following application examples.

(Use of photoelectric conversion element) Examples of uses of the photoelectric conversion element of the present embodiment include photodetection elements and solar cells. More specifically, with regard to the photoelectric conversion element of this embodiment, by irradiating light from the side of a transparent or semi-transparent electrode in a state where a voltage (reverse bias voltage) is applied between the electrodes, a photocurrent can flow and it can be used as The light detection element (light sensor) works. In addition, it can also be used as an image sensor by integrating a plurality of light detecting elements. In this way, the photoelectric conversion element of this embodiment can be particularly preferably used as a photodetection element.

In addition, the photoelectric conversion element of the present embodiment can generate a photoelectromotive force between the electrodes by irradiating light, and can operate as a solar cell. It is also possible to manufacture a thin-film solar cell module by integrating a plurality of photoelectric conversion elements.

(Application example of photoelectric conversion element) The photoelectric conversion element of this embodiment can be suitably used as a light detection element for detection units included in various electronic devices such as workstations, personal computers, portable information terminals, entry and exit management systems, digital cameras, and medical equipment.

The photoelectric conversion element of the present embodiment can be suitably applied to images for solid-state imaging devices such as X-ray imaging devices and complementary metal oxide semiconductor (Complementary Metal Oxide Semiconductor, CMOS) image sensors that are included in the above-exemplified electronic devices. Detection unit (image sensor), fingerprint detection unit, face detection unit, vein detection unit, iris detection unit and other detection units that detect some specific features of living bodies, detection units of optical biosensors such as pulse oximeters, etc. in.

The following is a configuration example of an image detection unit for a solid-state imaging device and a fingerprint detection unit for a biometric authentication device (for example, a fingerprint authentication device) in the detection portion of the photoelectric conversion element according to the embodiment of the present invention, which can be suitably applied to the drawings. Be explained.

(Image Inspection Department) FIG. 2 is a diagram schematically showing a configuration example of an image detection unit for a solid-state imaging device.

The image detection unit 1 includes: a CMOS transistor substrate 20; an interlayer insulating film 30 provided to cover the CMOS transistor substrate 20; a photoelectric conversion element 10 according to an embodiment of the present invention provided on the interlayer insulating film 30; The interlayer wiring portion 32 provided as an insulating film 30 and electrically connecting the CMOS transistor substrate 20 and the photoelectric conversion element 10; a sealing layer 40 provided so as to cover the photoelectric conversion element 10; and a color filter provided on the sealing layer 40器50.

The CMOS transistor substrate 20 has any conventionally-known preferable structure in accordance with the design.

The CMOS transistor substrate 20 includes a transistor, a capacitor, etc. formed within the thickness of the substrate, and includes functional elements such as a CMOS transistor circuit (MOS transistor circuit) for realizing various functions.

Examples of functional elements include floating propagation (Floating Diffusion) elements, reset transistors, output transistors, and selection transistors.

Using such functional elements, wiring, etc., a signal readout circuit and the like are fabricated on the CMOS transistor substrate 20.

The interlayer insulating film 30 may be made of any suitable insulating material known in the past, such as silicon oxide, insulating resin, and the like. The interlayer wiring portion 32 may be made of any conventionally known conductive material (wiring material), such as copper and tungsten. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed at the same time as the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.

As long as it can prevent or suppress the permeation of harmful substances such as oxygen and water that may degrade the function of the photoelectric conversion element 10, the sealing layer 40 may be composed of any conventionally-known material. The sealing layer 40 may have the same structure as the sealing member 17 already described.

As the color filter 50, it is possible to use, for example, a primary color filter composed of any conventionally-known material and corresponding to the design of the image detection unit 1. In addition, as the color filter 50, a complementary color filter that can be thinner than the primary color filter may be used. As complementary color filters, for example, three types (yellow, cyan, magenta), three types (yellow, cyan, transparent), three types (yellow, transparent, magenta), and (transparent, cyan, magenta) can be used. These three kinds of color filters are combined. These may be able to generate color image data as a condition, and constitute any preferred configuration corresponding to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20.

The light received by the photoelectric conversion element 10 through the color filter 50 is converted by the photoelectric conversion element 10 into an electrical signal corresponding to the amount of received light, and is output to the photoelectric conversion in the form of the received light signal, that is, the electrical signal corresponding to the photographic subject through the electrode Component 10 outside.

Next, the received light signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 through the interlayer wiring portion 32, and is read out by a signal readout circuit fabricated on the CMOS transistor substrate 20. In addition, any preferred conventionally known functional unit performs signal processing to generate image information based on the subject.

(Fingerprint Detection Department) Fig. 3 is a diagram schematically showing a configuration example of a fingerprint detection unit integrally formed with a display device.

The display device 2 of the portable information terminal includes: a fingerprint detection unit 100 including the photoelectric conversion element 10 of the embodiment of the present invention as a main component; and a display panel provided on the fingerprint detection unit 100 for displaying a predetermined image部200。 Department 200.

In this configuration example, the fingerprint detection unit 100 is provided in an area substantially coincident with the display area 200 a of the display panel unit 200. In other words, the display panel part 200 is integrally laminated above the fingerprint detection part 100.

When fingerprint detection is performed only in a partial area of the display area 200a, only the fingerprint detection unit 100 may be provided corresponding to the partial area.

The fingerprint detection unit 100 includes the photoelectric conversion element 10 of the embodiment of the present invention as a functional unit that exhibits a substantial function. The fingerprint detection unit 100 can include a protection film (protection film), a support substrate, a sealing substrate, a sealing member, a barrier film, a band pass filter, and infrared cutoff in a manner corresponding to a design that can obtain desired characteristics. Any preferred conventionally known members such as films. The fingerprint detection unit 100 may also adopt the structure of the image detection unit described above.

The photoelectric conversion element 10 may be included in the display area 200a in any manner. For example, the plurality of photoelectric conversion elements 10 may be arranged in a matrix.

As described above, the photoelectric conversion element 10 is provided on the support substrate 11, and the support substrate 11 is provided with electrodes (anode or cathode) in a matrix, for example.

The light received by the photoelectric conversion element 10 is converted by the photoelectric conversion element 10 into an electrical signal corresponding to the amount of received light, and is output to the outside of the photoelectric conversion element 10 in the form of the received light signal, that is, the electrical signal corresponding to the photographed fingerprint. .

In this configuration example, the display panel unit 200 is configured in the form of an organic electroluminescence display panel (organic EL (electroluminescence) display panel) including a touch sensor panel. In place of the organic EL display panel, the display panel unit 200 may be constituted by, for example, a display panel having any preferred conventionally known structure, such as a liquid crystal display panel including a light source such as a backlight.

The display panel part 200 is provided on the fingerprint detection part 100 described above. The display panel section 200 includes an organic electroluminescence element (organic EL element) 220 as a functional section that exerts a substantial function. The display panel unit 200 may further include any preferred conventionally known substrates (support substrate 210 or sealing substrate 240) such as glass substrates (support substrate 210 or sealing substrate 240), sealing members, barrier films, circular polarizers and other polarizing plates in a manner corresponding to desired characteristics. Any preferred conventionally known components such as the touch sensor panel 230.

In the configuration example described above, the organic EL element 220 is used as a light source for pixels in the display area 200 a, and is also used as a light source for fingerprint imaging in the fingerprint detection unit 100.

Here, the operation of the fingerprint detection unit 100 will be briefly described. When performing fingerprint authentication, the fingerprint detection section 100 uses light emitted from the organic EL element 220 of the display panel section 200 to detect the fingerprint. Specifically, the light emitted from the organic EL element 220 passes through the constituent elements existing between the organic EL element 220 and the photoelectric conversion element 10 of the fingerprint detection unit 100, and is in contact with the surface of the display panel unit 200 in the display area 200a. The skin (finger surface) of the fingertip of the finger placed in the way reflects. At least a part of the light reflected by the finger surface passes through the constituent elements existing therebetween, is received by the photoelectric conversion element 10, and is converted into an electrical signal corresponding to the amount of light received by the photoelectric conversion element 10. Then, the converted electrical signal constitutes image information related to the fingerprint on the finger surface.

The portable information terminal including the display device 2 performs fingerprint authentication by comparing the obtained image information with pre-recorded fingerprint data for fingerprint authentication by any preferred procedure known in the past.

When mounting the photoelectric conversion element of the present embodiment to the device of the application example described above, heat treatment such as a reflow step for mounting on a wiring board or the like may be performed. For example, when manufacturing an image sensor, a process including heating the photoelectric conversion element at a heating temperature of 165° C. or higher may be performed.

According to the photoelectric conversion element of this embodiment, the n-type semiconductor material already described is used as the material of the active layer. In this way, in the process of forming the active layer (details will be described later), in the process of manufacturing the photoelectric conversion element after the active layer is formed, or in mounting the manufactured photoelectric conversion element to an image sensor or biometric authentication In the device, it is effective whether it is heated at a heating temperature of 165°C or higher, or heated at a heating temperature of 200°C or higher, or further processed at a heating temperature of 220°C or higher. Improve heat resistance. As a result, the decrease in EQE can be suppressed or the EQE can be further improved, thereby suppressing the increase in the dark current or further reducing the dark current.

Specifically, regarding the EQE, the EQE value of the photoelectric conversion element whose heating temperature in the post-baking step in the active layer formation step of the method of manufacturing the photoelectric conversion element is 100°C is based on the value of the EQE of the post-baking step. The value obtained by dividing the EQE value of the photoelectric conversion element whose heating temperature is changed to a higher temperature (for example, 165°C or higher) (hereinafter referred to as "EQE _heat /EQE _{100 °C} ") is preferably 0.9 or more, more preferably It is 1.0 or more.

EQE _heat /EQE _{100 °C,} for example, when the temperature of the post-baking step is set to 165°C and the heating time is set to 1 hour, it is preferably 0.9 or more, and more preferably 1.0 or more.

Regarding the EQE of the sealing body of the photoelectric conversion element, the EQE value of the sealing body of the sealing body of the photoelectric conversion element is not additionally heat-treated at the time of mounting, using the sealing body that has been heat-treated at 165°C or higher. The value obtained by dividing the EQE value and normalizing it (hereinafter referred to as "EQE _heat /EQE _unheat ") is preferably 0.9 or more, and more preferably 1.0 or more.

For example, when the temperature of the additional heating treatment is 165°C and the heating time is 1 hour, EQE _heat /EQE _{unheat is} preferably 0.9 or more, more preferably 1.0 or more.

Regarding the dark current, the value of the dark current of the photoelectric conversion element whose heating temperature in the post-baking step is 100°C is based on the value of the photoelectric conversion element whose heating temperature in the post-baking step is changed to a higher temperature (for example, 165°C or higher) The value of the dark current obtained by dividing and normalizing the value (hereinafter referred to as "dark current _heat /dark current _{100 °C} ") is preferably 1.10 or less.

For example, when the temperature of the post-baking step is set to 165°C and the heating time is set to 1 hour, the dark current _heat /dark current _{100 °C is} preferably 1.10 or less.

Regarding the dark current of the sealed body of the photoelectric conversion element, the value of the dark current of the sealed body of the photoelectric conversion element that has not been additionally heated at the time of mounting is used. The value of the dark current of the sealing body obtained by dividing and normalizing it (hereinafter referred to as "dark current _heat /dark current _unheat ") is preferably 1.10 or less.

For example, when the temperature of the additional heating treatment is set to 165°C and the heating time is set to 1 hour, the dark current _heat /dark current _{unheat is more} preferably 1.10.

2. Manufacturing method of photoelectric conversion element The manufacturing method of the photoelectric conversion element of this embodiment is not specifically limited. The photoelectric conversion element of this embodiment can be manufactured by combining a forming method suitable for materials selected when forming the constituent elements.

The method of manufacturing the photoelectric conversion element of the present embodiment includes a step including a process of heating at a heating temperature of 165° C. or higher. More specifically, the active layer is formed by a step including a process of heating at a heating temperature of 165°C or higher, 200°C or higher, or 220°C or higher, and/or after the step of forming the active layer, may include It is a process of heating at a heating temperature of 200°C or higher, 200°C or higher, or 220°C or higher.

Hereinafter, as an embodiment of the present invention, a method of manufacturing a photoelectric conversion element having a structure in which a substrate (support 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.

(Steps to prepare the substrate) In this step, for example, a supporting substrate provided with an anode is prepared. In addition, a substrate provided with a conductive thin film formed of the electrode material described above is obtained from the market, and an anode is formed by patterning the conductive thin film as needed, and a support substrate provided with the anode can be prepared.

In the method of manufacturing the photoelectric conversion element of the present embodiment, the method of forming the anode when forming the anode on the supporting substrate is not particularly limited. The anode can be formed by any preferred method known in the past, such as vacuum evaporation, sputtering, ion plating, plating, coating, etc., on the structure where the anode should be formed (such as a supporting substrate). , Active layer, hole transport layer).

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

The method of forming the hole transport layer is not particularly limited. From the viewpoint of making the hole transport layer forming step easier, it is preferable to form the hole transport layer by any preferred coating method known in the past. The hole transport layer can be formed by, for example, a coating method or a vacuum deposition method using a coating solution containing the material and solvent of the hole transport layer described above.

(Steps of forming active layer) In the method of manufacturing a photoelectric conversion element of this embodiment, an active layer is formed on the hole transport layer. The active layer as the main constituent element can be formed by any preferred conventionally known forming steps. In this embodiment, the active layer is preferably produced by a coating method using ink (coating liquid).

Hereinafter, the step (i) and the step (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.

Step (i) As a method of applying the ink to the coating object, any preferred coating method can be used. The coating method is preferably a slit coating method, a knife coating method, a spin coating method, a microgravure coating method, a gravure printing method, a bar coating method, an inkjet printing method, a nozzle coating method, or a capillary coating method. The cloth method is more preferably a slit coating method, a spin coating method, a capillary coating method or a bar coating method, and still more preferably a slit coating method or a spin coating method.

The ink for forming the active layer may be a solution, or a dispersion, such as a dispersion, an emulsion (emulsion), or a suspension (suspension). Hereinafter, the ink for forming an active layer will be described. Furthermore, the ink for forming the bulk heterojunction active layer will be described as an example. Therefore, the ink for forming an active layer contains a composition containing an n-type semiconductor material and a p-type semiconductor material, and further contains at least one or two or more solvents.

The ink for forming an active layer may contain only one type of n-type semiconductor material and p-type semiconductor material, or may contain two or more types in combination in any ratio.

The ink used to form the active layer of the present embodiment can improve heat resistance, suppress the decrease of EQE or increase EQE, suppress the increase or decrease of dark current, and can improve the balance of EQE and dark current characteristics. It is preferable to include a composition containing the compounds N-1 to N-3 as an n-type semiconductor material and the polymer compound P-1 as a p-type semiconductor material.

The ink for forming an active layer of the present embodiment preferably uses a mixed solvent composed of a first solvent and a second solvent, which will be described later, as a solvent. Specifically, when the ink for forming an active layer contains two or more solvents, it is preferable to contain a main solvent (first solvent) as a main component, and another additive solvent (the first solvent) added to improve solubility, etc. Two solvents).

Hereinafter, the first solvent and the second solvent that can be suitably used in the ink for forming an active layer of the present embodiment, and a combination of these will be described.

(1) The first solvent The first solvent is preferably a solvent that can dissolve the p-type semiconductor material. The first solvent in this embodiment is an aromatic hydrocarbon.

As for the aromatic hydrocarbon as the first solvent, for example, toluene, xylene (for example, o-xylene, meta-xylene, p-xylene), trimethylbenzene (for example, mesitylene, 1,2,4-trimethylbenzene) Methylbenzene (pseudocumene), butylbenzene (such as n-butylbenzene, second butylbenzene, tertiary butylbenzene), methylnaphthalene (such as 1-methylnaphthalene), tetrahydronaphthalene, indane.

The first solvent may be composed of one kind of aromatic hydrocarbon, or may be composed of two or more kinds of aromatic hydrocarbons. The first solvent is preferably composed of an aromatic hydrocarbon.

The first solvent is preferably selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, second-butylbenzene, and third-butylbenzene , Methyl naphthalene, tetrahydronaphthalene, and indane, more preferably toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethyl Benzene, n-butylbenzene, second-butylbenzene, third-butylbenzene, methylnaphthalene, tetrahydronaphthalene, or indane.

(2) The second solvent The second solvent is a solvent selected from the viewpoint of easier implementation of the manufacturing process and further improvement of the characteristics of the photoelectric conversion element. Examples of the second solvent include ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone, and phenylacetone, ethyl acetate, butyl acetate, phenyl acetate, and ethyl cyrus acetic acid. Ester solvents such as esters, methyl benzoate, butyl benzoate, and benzyl benzoate.

From the viewpoint of reducing dark current, the second solvent is preferably acetophenone, phenylacetone, or butyl benzoate.

(3) Combination of the first solvent and the second solvent As examples of preferred combinations of the first solvent and the second solvent, the combination of tetralin and ethyl benzoate, tetralin and propyl benzoate, and tetralin and butyl benzoate are more preferred. The combination of hydronaphthalene and butyl benzoate.

(4) The weight ratio of the first solvent to the second solvent From the viewpoint of further improving the solubility of the n-type semiconductor material and the p-type semiconductor material, the weight ratio of the first solvent as the main solvent to the second solvent as the additional solvent (first solvent: second solvent) is preferably The range of 85:15～99:1.

(5) Any other solvent The solvent may include any other solvents other than the first solvent and the second solvent. When the total weight of all solvents contained in the ink is 100% by weight, the content of any other solvent is preferably 5% by weight or less, more preferably 3% by weight or less, and still more preferably 1% by weight or less. As any other solvent, a solvent having a higher boiling point than the second solvent is preferred.

(6) Arbitrary ingredients In the ink, in addition to the first solvent, the second solvent, the n-type semiconductor material, and the p-type semiconductor material, surfactants, ultraviolet absorbers, antioxidants, and additives may be included within the limits that do not impair the purpose and effects of the present invention. Optional components such as a sensitizer that sensitizes the function of generating charges by using absorbed light, and a light stabilizer that increases the stability with respect to ultraviolet rays.

(7) Concentration of n-type semiconductor material and p-type semiconductor material The total concentration of the n-type semiconductor material and the p-type semiconductor material in the ink is preferably 0.01% by weight or more and 20% by weight or less, more preferably 0.01% by weight or more and 10% by weight or less, and more preferably 0.01% by weight or more and 5% by weight or less , Especially preferably, it is not less than 0.1% by weight and not more than 5% by weight. In the ink, the n-type semiconductor material and the p-type semiconductor material can be dissolved or dispersed. The n-type semiconductor material and the p-type semiconductor material are preferably at least partially dissolved, and more preferably completely dissolved.

In this embodiment, a material with high heat resistance is used as the n-type semiconductor material, so a solvent with a higher boiling point can also be used as the solvent. Therefore, the selection range of raw materials in the photoelectric conversion element manufacturing step is expanded, so that the photoelectric conversion element can be manufactured more simply and easily.

(8) Preparation of ink The ink can be prepared by a known method. For example, it can be prepared by the following method: a method of mixing a first solvent and a second solvent to prepare a mixed solvent, adding an n-type semiconductor material and a p-type semiconductor material to the obtained mixed solvent; adding to the first solvent For the p-type semiconductor material, the n-type semiconductor material is added to the second solvent, and then the first solvent and the second solvent added with each material are mixed.

The first solvent and the second solvent can be mixed with the n-type semiconductor material and the p-type semiconductor material by heating to a temperature below the boiling point of the solvent.

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

The ink for forming the active layer is coated on a coating object selected according to the photoelectric conversion element and its manufacturing method. The ink for forming the active layer may be coated on the functional layer of the photoelectric conversion element in which the active layer may exist in the manufacturing step of the photoelectric conversion element. Therefore, the application target of the ink for forming an active layer differs depending on the layer structure of the photoelectric conversion element to be manufactured and the order of layer formation. For example, when a 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 on the left is formed first, the active layer forming ink The coating object is the hole transport layer. In addition, for example, when a 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 on the left is formed first, the active layer is formed The coating object with the ink is the electron transport layer.

Step (ii) As the method of removing the solvent from the coating film of the ink, that is, the method of removing the solvent from the coating film and curing, any preferable method can be adopted. Examples of the method of removing the solvent include a method of directly heating using a hot plate under an inert gas atmosphere such as nitrogen, a hot air drying method, an infrared heating drying method, a flash lamp annealing drying method, and a drying method under reduced pressure.

In the method of manufacturing the photoelectric conversion element of this embodiment, step (ii) is a step for volatilizing and removing the solvent, and is also referred to as a pre-baking step (first heat treatment step). In the method of manufacturing the photoelectric conversion element of the present embodiment, it is preferable that after step (ii), a post-baking step (second heat treatment step) is performed followed by a pre-baking step to form a cured film by heat treatment. .

Regarding the implementation conditions of the pre-baking step and the post-baking step, that is, conditions such as heating temperature, heat treatment time, etc., considering the composition of the ink used, the boiling point of the solvent, etc., any preferable conditions may be adopted.

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

The heating temperature in the pre-baking step and the post-baking step is usually about 100°C. However, in the manufacturing method of the photoelectric conversion element of the present embodiment, since the above-mentioned n-type semiconductor material is used as the material of the active layer, the heating temperature in the pre-baking step and/or the post-baking step can be further increased. Specifically, the heating temperature in the pre-baking step and/or the post-baking step can be preferably set to 165°C or higher, more preferably 200°C or higher, and still more preferably 220°C or higher. The upper limit of the heating temperature is 250°C, more preferably 300°C or less.

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

The heating temperature in the pre-baking step and the heating temperature in the post-baking step may be the same or different. The heat treatment time may be 10 minutes or more, for example. The upper limit of the heat treatment time is not particularly limited, but it may be 4 hours, for example, in consideration of the gap time and the like.

The thickness of the active layer can be achieved by appropriately adjusting the solid content concentration in the coating liquid and the conditions of the above step (i) and/or step (ii).

In addition to the steps (i) and (ii) described above, the step of forming the active layer may also include other steps, provided that the purpose and effects of the present invention are not impaired.

The manufacturing method of the photoelectric conversion element of this embodiment may be a method of manufacturing a photoelectric conversion element including a plurality of active layers, or a method of repeating steps (i) and (ii) multiple times.

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

The method of forming the electron transport layer is not particularly limited. From the viewpoint of simplifying the formation process of the electron transport layer, it is preferable to form the electron transport layer by any preferred vacuum vapor deposition method known in the past.

(Steps of forming the cathode) The method of forming the cathode is not particularly limited. The cathode can be formed on the electron transport layer by any conventionally known method such as coating method, vacuum evaporation method, sputtering method, ion plating method, and plating method. Through the above steps, the photoelectric conversion element of this embodiment is manufactured.

(Steps of forming the sealing body) When forming a sealing body, in this embodiment, the conventionally well-known arbitrary preferable sealing material (adhesive) and a board|substrate (sealing substrate) are used. Specifically, after coating a sealing material such as UV curable resin on the supporting substrate so as to surround the periphery of the manufactured photoelectric conversion element, it is suitable for bonding with the sealing material without gaps, and irradiation with UV light. In the method of the selected sealing material, the photoelectric conversion element is sealed in the gap between the support substrate and the sealing substrate, whereby a sealed body of the photoelectric conversion element can be obtained.

3. Manufacturing method of image sensor and biometric authentication device As the photoelectric conversion element of the present embodiment, the photodetection element, in particular, can be installed in an image sensor or a biometric authentication device to function as described above.

Such image sensors and biometric authentication devices can be manufactured by a manufacturing method including the steps of heating the photoelectric conversion element (the sealing body of the photoelectric conversion element) at a heating temperature of 165°C or higher .

Specifically, when the photoelectric conversion element is mounted in an image sensor or a biometric authentication device, for example, by performing a reflow step that is carried out when mounting on a wiring board, it can be performed at 165°C or higher and 200°C or higher. , And then heat treatment at a heating temperature of 220°C or higher. However, according to the photoelectric conversion element of this embodiment, since the n-type semiconductor material already described is used as the material of the active layer, the heat resistance can be effectively improved. As a result, the EQE of the mounted photoelectric conversion element can be suppressed from decreasing or the EQE can be further improved, thereby suppressing the increase of dark current or further reducing the dark current, and thus can improve the characteristics of the detection accuracy in the manufactured image sensor and the biometric authentication device.

The heat treatment time may be 10 minutes or more, for example. The upper limit of the heat treatment time is not particularly limited, but it can be set to 4 hours, for example, in consideration of the lead time.

[Example] Hereinafter, in order to further describe the present invention in detail, examples are shown. The present invention is not limited to the embodiments described below.

In the following Examples, the n-type semiconductor material (electron-accepting compound) shown in Table 1 below and the p-type semiconductor material (electron-donating compound) shown in Table 2 below were used.

[Table 1]

[Table 2]

Regarding compound N-1, which is an n-type semiconductor material, diPDI (trade name, manufactured by 1-material company) is commercially available and used. Regarding the compound N-2 as an n-type semiconductor material, it was synthesized and used by the method described in ≪Journal of Materials Chemistry (J.Mater.Chem.C)≫, 2016, 4, 4134-4137. The compound N-3, which is an n-type semiconductor material, was synthesized by the methods described in Synthesis Example 1 and Synthesis Example 2 below, and used. Regarding compound N-4 as an n-type semiconductor material, it was synthesized by the method described in Synthesis Example 3 below, and used. Regarding the compound N-14, which is an n-type semiconductor material, E100 (trade name, manufactured by Frontier Carbon) was used on the market. Regarding the polymer compound P-1 as a p-type semiconductor material, it was synthesized and used with reference to the method described in International Publication No. 2011/052709. Regarding the polymer compound P-2 as a p-type semiconductor material, it is synthesized and used with reference to the method described in International Publication No. 2013/051676. Regarding the polymer compound P-3, which is a p-type semiconductor material, PTB7-Th (trade name, manufactured by 1-material company) is commercially available and used. Regarding the polymer compound P-4 as a p-type semiconductor material, P3HT (trade name, manufactured by SIGMA-ALDRICH) is commercially available and used.

<Synthesis Example 1> (Synthesis of Compound N-3) As described below, a compound 2 represented by the following formula was synthesized from a compound 1 represented by the following formula, and a compound 3 represented by the following formula was further synthesized using the obtained compound 2.

[化43]

In a 200 mL four-necked flask in which the internal atmosphere was replaced with nitrogen, 9.81 g (25.0 mmol) of compound 1, 100 mL of concentrated sulfuric acid, and 0.63 g (2.50 mmol) of iodine were added, and the mixture was heated and stirred at 60° C. for 30 minutes.

4.22 g (26.3 mmol) of bromine was added dropwise to the heated solution, and the mixture was further heated and stirred at 82° C. for 21 hours to cause a reaction.

After the reaction, the obtained reaction liquid was cooled to normal temperature, poured into 300 mL of saturated sodium sulfite aqueous solution, and filtered to obtain the produced solid.

The obtained solid was washed with 300 mL of methanol and dried under reduced pressure, thereby obtaining 11.2 g of a crude product of Compound 2 as a red-black solid.

3.53 g of the obtained crude product of compound 2 was put into a 300 mL four-necked flask whose internal atmosphere was replaced with nitrogen, 150 mL of dehydrated N-methyl-2-pyrrolidone, and 4.85 g (24.0 mmol) of hexafluorobutylamine were added. ) Stir to obtain a uniform solution.

After 3.06 g (51.0 mmol) of acetic acid was added dropwise to the obtained solution, the solution was heated to 90° C., heated and stirred for 4.5 hours to cause reaction.

After the reaction, the obtained reaction liquid was cooled to normal temperature, 500 mL of 2.0 M hydrochloric acid was injected, and the generated solid was filtered to obtain a solid.

Anhydrous magnesium sulfate was added to a solution obtained by dissolving the obtained solid in chloroform, stirred and filtered, thereby obtaining a crude product.

By refining the obtained crude product with a silica gel column (developing solvent chloroform), 894 mg (1.07 mmol, yield 14.3%) of compound 3 was obtained as a red and black solid.

The 1H nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) spectrum of the obtained compound 3 was analyzed. The results are as follows. [1H NMR (400 MHz, CDCl3)] δ 9.84 (d, 1H), 9.01 (s, 1H), 8.80 (d, 3H), 8.68 (d, 2H), 5.04 (m, 4H).

Synthesis Example 2 Compound 4 represented by the following formula was synthesized from Compound 3 represented by the following formula.

[化44]

In a 100 mL three-necked flask in which the internal atmosphere was replaced with nitrogen, 708 mg (0.850 mmol) of compound 3, 540 mg (8.50 mmol) of copper powder, and 17.0 mL of dehydrated dimethyl sulfoxide were added.

The obtained solution was heated and stirred at 100°C for 6 hours to be reacted, thereby obtaining a reaction liquid. The obtained reaction liquid was cooled to normal temperature, poured into 100 mL of water, and the generated solid was filtered to obtain a crude product.

The crude product obtained was purified with a silica gel column (developing solvent chloroform/toluene) and further purified by circulating GPC (developing solvent chloroform) to obtain 193 mg (0.129 mmol, yield 30.2%) of the compound as a red-black solid 4.

The 1H NMR spectrum of the obtained compound 4 was analyzed. The results are as follows. [1H NMR (400 MHz, CDCl3)] δ 8.89 (m, 8H), 8.49 (d, 2H, JHH=8.0 Hz), 8.30 (s, 2H), 8.26 (d, 2H, JHH=8.0 Hz), 4.97 (t, 4H), 4.94 (t, 4H).

<Synthesis Example 3> (Synthesis of Compound N-4) Compound 6 (Compound N-4) represented by the following formula was synthesized from Compound 5 represented by the following formula.

[化45]

In a 100 mL three-necked flask with the internal atmosphere replaced with nitrogen, 295 mg (0.190 mmol) was added and synthesized according to the method described in ≪Journal of Materials Chemistry (J.Mater.Chem.C)≫, 2016, 4, 4134-4137 Compound 5, 107 mg (0.399 mmol) 4,4'-di-tert-butyl-2,2'-bipyridine, 367 mg (0.399 mmol) (trifluoromethyl) tris(triphenylphosphine) copper ( I) 15 mL dehydrated toluene to obtain a solution.

The obtained solution was heated and stirred at 80°C (bath temperature) for 8 hours while allowing it to react. After the completion of the reaction, the obtained reaction liquid was cooled to room temperature, and washed with water and 10% acetic acid water.

The organic layer obtained by liquid separation washing was dried with anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a crude product. By refining the crude product with a silica gel column, 228 mg (0.149 mmol, yield 78.4%) of the target compound 6 was obtained as a dark brown solid.

The NMR spectrum of the obtained compound 6 was analyzed. The results are as follows. [1H NMR (400 MHz, CDCl3)] δ 9.10 (br, 2H), 8.78 (br, 2H), 8.67 (m, 2H), 8.27 (m, 6H), 5.13 (br, 4H), 2.16 (br, 8H), 1.78 (br, 8H), 1.21 (br, 48H), 0.78 (t, 24H). [19F NMR (400 MHz, CDCl3)] δ -55.1

<Preparation Example 1> (Preparation of Ink I-1) Tetrahydronaphthalene was used as the first solvent, butyl benzoate was used as the second solvent, and the volume ratio of the first solvent and the second solvent was set to 97:3 to prepare a mixed solvent.

In the obtained mixed solvent, the concentration of the compound N-1 as the n-type semiconductor material with respect to the total weight of the ink is 2% by weight, and the polymer compound P-1 as the p-type semiconductor material with respect to the ink The total weight is 2% by weight (n-type semiconductor material/p-type semiconductor material = 1/1), and the mixed solution obtained by stirring at 60°C for 8 hours is filtered with a filter to obtain ink (I -1).

<Preparation Example 2~Preparation Example 5 and Comparative Preparation Example 1~Comparative Preparation Example 3> Except that the n-type semiconductor material and the p-type semiconductor material were used in the combination shown in Table 3 below, the same method as Preparation Example 1 was used to perform ink (I-2) to ink (I-5) and ink (C). -1) ~ Preparation of ink (C-3).

[Table 3] (Table 3) Ink n-type semiconductor material p-type semiconductor material Preparation Example 1 I-1 N-1 P-1 Preparation Example 2 I-2 N-2 P-1 Preparation Example 3 I-3 N-3 P-1 Preparation Example 4 I-4 N-1 P-2 Preparation Example 5 I-5 N-4 P-1 Comparative Preparation Example 1 C-1 N-14 P-1 Comparative Preparation Example 2 C-2 N-2 P-3 Comparative Preparation Example 3 C-3 N-2 P-4

<Example 1> (Manufacturing and evaluation of photoelectric conversion element) (1) Manufacturing of photoelectric conversion elements and their sealing bodies As described below, a photoelectric conversion element and its sealing body are manufactured. In addition, for the evaluation described later, a plurality of photoelectric conversion elements and their sealing bodies were manufactured for each example (and comparative example).

A glass substrate on which an ITO thin film (anode) was formed to a thickness of 50 nm by a sputtering method was prepared, and the glass substrate was subjected to ozone UV treatment as a surface treatment.

Next, the ink (I-1) was applied on the ITO thin film by a spin coating method to form a coating film, and then heated in a nitrogen atmosphere using a hot plate heated to 100°C for 10 minutes to dry it (pre-baking step) ).

Furthermore, under a nitrogen atmosphere, on a hot plate heated to 100° C., the structure in which the anode and the active layer were sequentially laminated on the glass substrate was heated for 50 minutes (post-baking step) to form the active layer. The thickness of the formed active layer is approximately 250 nm.

Next, in a resistance heating vapor deposition apparatus, a calcium (Ca) layer was formed with a thickness of about 5 nm on the formed active layer as an electron transport layer.

Then, a silver (Ag) layer was formed with a thickness of about 60 nm on the formed electron transport layer as a cathode. Through the above steps, a photoelectric conversion element was manufactured on a glass substrate. The obtained structure was used as sample 1.

Next, a UV curable sealant as a sealing material was applied to the glass substrate as a supporting substrate to surround the periphery of the manufactured photoelectric conversion element, and after bonding the glass substrate as the sealing substrate, UV light was irradiated The light detection element is sealed in the gap between the support 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 support substrate and the sealing substrate when viewed from the thickness direction is a square of 2 mm×2 mm.

(2) Evaluation of photoelectric conversion elements Apply a -2.5V reverse bias voltage to the sealed body of the manufactured photoelectric conversion element, and use a solar simulator (CEP-2000, manufactured by Spectrometer) and a digital source meter (SourceMeter) (Keithley 2450 digital source). The meter (KEITHLEY 2450 Source Meter), manufactured by Keithley Instruments (Keithley Instruments), measured and evaluated the external quantum efficiency (EQE) and dark current under the applied voltage.

Regarding EQE, first, in a state where a reverse bias voltage of -2.5V is applied to the sealed body of the photoelectric conversion element, a certain number of photons (1.0×10 ¹⁶ ) per 20 nm in the wavelength range of 300 nm to 1200 nm is irradiated Measure the current value of the generated current, and obtain the EQE spectrum with a wavelength of 300 nm to 1200 nm by a well-known method.

Next, the measured value at the wavelength (λmax) closest to the absorption peak wavelength among the obtained multiple measured values per 20 nm is taken as the value (%) of EQE.

When evaluating the EQE of the photoelectric conversion element, the EQE value of the photoelectric conversion element (Sample 1) whose heating temperature in the subsequent baking step is 100°C is based on the value, and the photoelectric conversion element whose heating temperature in the post-baking step is changed is used. The EQE value of (Sample 2) was divided and the normalized obtained value (EQE _heat /EQE _{100 °C} ) was evaluated. The results are shown in Table 4 and Figure 4 below. Fig. 4 is a graph showing the relationship between _{heating temperature and EQE heat} /EQE _{100 °C.}

[Table 4] (Table 4) Ink Heat resistance EQE _heat /EQE _{100 ℃} Example 1 I-1 ○(220℃) 1.14 (220℃)

It can be seen from Table 4 and FIG. 4 that for "Sample 2" of Example 1, the EQE value does not decrease when the heating temperature in the post-baking step is 220°C, but the EQE tends to increase instead. Therefore, the evaluation of heat resistance can be said to be "good (○)" in the range of 100°C to 220°C.

<Example 2 to Example 5 and Comparative Example 1 to Comparative Example 3> (Manufacturing and Evaluation of Photoelectric Conversion Element) Except that ink (I-2) to ink (I-5) and ink (C-1) to ink (C-3) were used instead of ink (I-1), the photoelectric conversion was produced in the same manner as in Example 1 already described. The sealed body of the component. In addition, except that in any of Examples 2 to 5 and Comparative Examples 1 to 3, "Sample 1" in which the heating temperature in the post-baking step was set to 100°C was prepared, for In Comparative Example 1, three "Sample 2" in which the heating temperature in the post-baking step was changed to 120°C (Sample 2-1), 130°C (Sample 2-2), and 140°C (Sample 2-3) were further prepared. "For Comparative Example 2 and Comparative Example 3, two "Sample 2" were prepared in which the heating temperature in the post-baking step was changed to 150°C (Sample 2-1) and 180°C (Sample 2-2). Evaluation. The results are shown in Table 5 and Figure 4 below.

[Table 5] (Table 5) Ink Heat resistance EQE _heat /EQE _{100 ℃} Example 2 I-2 ○(220℃) 1.28 (220℃) Example 3 I-3 ○(220℃) 1.15 (220℃) Example 4 I-4 ○(220℃) 1.01 (220℃) Example 5 I-5 ○(220℃) 1.19 (220℃) Comparative example 1 C-1 ×(140℃) 0.98 (120°C) 0.98 (130°C) 0.71 (140°C) Comparative example 2 C-2 ×(150℃～180℃) 0.88 (150℃) 0.87 (180℃) Comparative example 3 C-3 ×（165℃～180℃） 1.00 (150℃) 0.74 (180℃)

It can be seen from Table 5 and Figure 4 that for the "Sample 2" of Example 2 to Example 5, at the heating temperature of 220°C in the post-baking step, _{the value of "EQE heat} /EQE _{100 °C} " exceeds 1.0, so EQE The value of is not decreased by the heat treatment in the post-baking step, but has a tendency to increase. Therefore, the heat resistance evaluation of "Sample 2" using EQE as an index can be said to be "good (○)" in the range of 100°C to 220°C. On the other hand, regarding the evaluation of the heat resistance of "Sample 2" of Comparative Example 1 to Comparative Example 3, especially according to Fig. 4, it can be seen that at least in the range of more than 165°C and less than 180°C, "EQE _heat /EQE _{100 ℃} The value of "is less than 0.9, so the value of EQE decreases due to the heat treatment in the post-baking step. Therefore, the heat resistance evaluation of Comparative Example 1-Comparative Example 3 using EQE as an index is "poor (×)".

Regarding the dark current, in the dark state where no light is irradiated, a voltage of -10 V to 2 V is applied to the sealed body of the photoelectric conversion element, and the current value when a voltage of -2.5 V is applied using a known method is obtained as the dark current Value.

When evaluating the dark current of the photoelectric conversion element, the value of the dark current of the photoelectric conversion element (Sample 1) whose heating temperature in the subsequent baking step is 100°C is based on the value of the photoelectric conversion element with the heating temperature changed in the post-baking step. The value of the dark current of the conversion element (Sample 2) was divided to normalize the obtained value (dark current _heat /dark current _{100 °C} ) for evaluation. The evaluation results of Examples 1 to 4 are shown in Table 6 and FIG. 5 below. Fig. 5 is a graph showing the relationship between _{heating temperature and dark current heat} /dark current _{100 °C.}

[Table 6] (Table 6) Heat resistance Dark current _heat /Dark current _{100 ℃} Example 1 ○(220℃) 0.36 (220℃) Example 2 ○(220℃) 1.05 (220℃) Example 3 ○(220℃) 0.42 (220℃) Example 4 ○(220℃) 0.42 (220℃)

It can be seen from Table 6 and FIG. 5 that for "Sample 2" of Examples 1 to 4, _{the value of "dark current heat} /dark current _{100 °C} " at 220°C is 1.10 or less. In particular, in Example 1, Example 3, and Example 4, it was 0.50 or less, so the value of dark current was significantly reduced. Therefore, from the viewpoint of dark current, the evaluation of the heat resistance of Examples 1 to 4 can also be said to be "good (○)" within the range of 100°C to 220°C.

For Comparative Example 1 to Comparative Example 3, the dark current was evaluated in the same manner as in the above-mentioned Example 1 to Example 4. Among them, in addition to any one of Comparative Example 1 to Comparative Example 3, the sample 1 in which the heating temperature in the post-baking step was set to 100°C was prepared, and for Comparative Example 1, the post-baking was further prepared. The heating temperature in the step is changed to four "Sample 2" of 120°C (Sample 2-1), 130°C (Sample 2-2), 140°C (Sample 2-3) and 150°C (Sample 2-4), For Comparative Example 2 and Comparative Example 3, "Sample 2" in which the heating temperature in the post-baking step was changed to 150°C was prepared and evaluated. The results are shown in Table 7 and Figure 5 below.

[Table 7] (Table 7) Heat resistance Dark current _heat /Dark current _{100 ℃} Comparative example 1 ×(140℃) 1.12 (120℃) 1.20 (130℃) 2.03 (140℃) 3.78 (150℃) Comparative example 2 ×(150℃) 1.46 (150°C) Comparative example 3 ×(150℃) 4.78 (150°C)

It can be seen from Table 7 and Figure 5 that for the "Sample 2" of Comparative Example 1 to Comparative Example 3, the "dark current _heat / dark current _{100 ℃} " is within the range of 120°C or higher (at least 120°C or higher and 150°C or lower). The value exceeds 1.10, so the value of the dark current increases due to the heat treatment in the post-baking step. Therefore, from the viewpoint of dark current, the evaluation of the heat resistance of Comparative Example 1 to Comparative Example 3 is also "poor (×)".

<Example 6> (Manufacture and evaluation of photoelectric conversion element) (1) Manufacturing of photoelectric conversion elements Except that the post-baking step was not performed, a plurality of photoelectric conversion elements were manufactured in the same manner as in Example 1, and a sealing step was performed on the manufactured photoelectric conversion elements to manufacture a sealed body of a plurality of photoelectric conversion elements.

(2) Evaluation of photoelectric conversion elements By subjecting the sealed body of the manufactured photoelectric conversion element to an additional heating treatment using a hot plate for 10 minutes in a nitrogen atmosphere, it simulates the assumption that the photoelectric conversion element is installed in application targets such as image sensors, biometric authentication devices, etc.的热处理。 Heat treatment. In addition, in Example 6, the sealed body that was not subjected to the additional heat treatment was used as the sample 1, and the sealed body that was subjected to the additional heat treatment was used as the sample 2.

Next, using the package after the additional heat treatment, the measured value of EQE was obtained in the same manner as in Example 1, and the evaluation of EQE was performed.

Specifically, based on the EQE value of the sealed body (sample 1) without additional heat treatment, the EQE value of the plurality of sealed bodies (sample 2) that were heated and the heating temperature was changed was divided by the EQE value. Calculate and normalize the obtained value (EQE _heat /EQE _unheat ) for evaluation. In addition, for "Sample 2", the heating temperature was changed to 170°C (Sample 2-1), 180°C (Sample 2-2), 190°C (Sample 2-3), and 200°C (Sample 2- 4) 4 "Sample 2". The results are shown in Table 8 and Figure 6. Fig. 6 is a graph showing the relationship between the heating temperature of the sealing body and "EQE _heat /EQE _unheat".

[Table 8] (Table 8) Ink Heat resistance EQE _heat /EQE _unheat Example 6 I-1 ○(170℃～200℃) 1.04 (170℃) 1.08 (180℃) 1.03 (190℃) 1.00 (200℃)

It can be seen from Table 8 and Fig. 6 that for the "Sample 2" of Example 6, the EQE value did not decrease in the range of 170°C to 200°C for the heating temperature of the sealing body, especially when the heating temperature was 170°C to 200°C. In the range of 180°C, the EQE value tends to increase instead. Therefore, the evaluation of heat resistance can be said to be "good (○)" in the range of 100°C to 200°C. Furthermore, as shown in FIG. 6, the value of EQE tends to decrease in the range of 180°C to 200°C, but the value of EQE of the photoelectric conversion element of Example 1 is in the range of 180°C to 200°C The increase is believed to be due to the lack of heat resistance of the additional components after the formation of the active layer, especially the sealing member to the heating temperature, or the interface between the anode and the active layer, the interface between the active layer and the electron transport layer, and/ Or the lack of heat resistance due to chemical changes caused at the interface between the electron transport layer and the cathode.

1: Image detection department 2: display device 10: photoelectric conversion element 11.210: Support substrate 12: anode 13: Hole transmission layer 14: Active layer 15: Electron transport layer 16: cathode 17: Sealing member 20: CMOS transistor substrate 30: Interlayer insulating film 32: Interlayer wiring part 40: Sealing layer 50: color filter 100: Fingerprint detection department 200: Display panel section 200a: display area 220: Organic EL element 230: Touch sensor panel 240: Sealing substrate

Fig. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element. Fig. 2 is a diagram schematically showing a configuration example of a video detection unit. Fig. 3 is a diagram schematically showing a configuration example of a fingerprint detection unit. Fig. 4 is a graph showing the relationship between _{heating temperature and EQE heat} /EQE _{100 °C.} Fig. 5 is a graph showing the relationship between _{heating temperature and dark current heat} /dark current _{100 °C. Fig. 6 is a graph showing} the relationship between the heating temperature of the sealing body and EQE _heat /EQE unheat.

10: photoelectric conversion element

11: Support substrate

12: anode

13: Hole transmission layer

14: Active layer

15: Electron transport layer

16: cathode

17: Sealing member

Claims (19)

A photoelectric conversion element, comprising an anode, a cathode, and an active layer disposed between the anode and the cathode, the active layer including an n-type semiconductor material and a p-type semiconductor material, and the n-type semiconductor material is as follows The compound represented by formula (I),

(In formula (I), R ₁ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted monovalent aromatic hydrocarbon group, or an optionally substituted 1 A valent aromatic heterocyclic group, a plurality of R ₁ may be the same or different, R ₂ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted monovalent An aromatic hydrocarbon group or a monovalent aromatic heterocyclic group which may have a substituent, and a plurality of R ₂ may be the same or different) The p-type semiconductor material is a polymer compound containing a structural unit represented by the following formula (II) ,

(In formula (II), Ar ¹ and Ar ² represent a trivalent aromatic heterocyclic group, and Z represents a group represented by the following formulas (Z-1) to (Z-7))

(In formulas (Z-1) to (Z-7), R represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic ring Group, substituted amine group, amide group, imine residue, amide group, amide group, substituted oxycarbonyl group, alkenyl group, alkynyl group, cyano group or nitro group, in formula (Z-1) ~ formula ( In each formula of Z-7), when two Rs are present, the two Rs may be the same or different from each other). The photoelectric conversion element according to claim 1, wherein _{at least one of R 1} and R ₂ is a fluorine atom, an alkyl group containing a fluorine atom as a substituent, an alkoxy group containing a fluorine atom as a substituent, or a fluorine atom as a substituent. A substituted monovalent aromatic hydrocarbon group or a monovalent aromatic heterocyclic group containing a fluorine atom as a substituent. The photoelectric conversion element according to claim 1 or 2, wherein R ₁ is an alkyl group containing one or more fluorine atoms as a substituent, and R ₂ is a hydrogen atom. The photoelectric conversion element according to claim 3, wherein R ₁ is a group represented by -CH ₂ (CF ₂ ) ₂ CF _{3 , and R 2} is a hydrogen atom. The photoelectric conversion element according to claim 2, wherein R ₁ is an alkyl group which may have a substituent _{, and two or more of the plurality of R 2} are an alkyl group containing one or more fluorine atoms as a substituent. The photoelectric conversion element according to any one of claims 1 to 5, wherein the active layer is formed by a step including a process of heating at a heating temperature of 165°C or higher. The photoelectric conversion element according to any one of claim 1 to claim 6, which is a light detecting element. An image sensor comprising the photoelectric conversion element according to claim 7, and The image sensor is manufactured by a manufacturing method including a step of heating the photoelectric conversion element at a heating temperature of 165° C. or higher. A biometric authentication device, comprising the photoelectric conversion element according to claim 7, and The biometric authentication device is manufactured by a manufacturing method including a step of heating the photoelectric conversion element at a heating temperature of 165°C or higher. A method of manufacturing a photoelectric conversion element is a method of manufacturing the photoelectric conversion element according to any one of claim 1 to claim 5, The step of forming the active layer includes: step (i), coating an ink containing the n-type semiconductor material and the p-type semiconductor material on the coating object to obtain a coating film; and step (ii), from The solvent is removed from the obtained coating film. The method of manufacturing a photoelectric conversion element according to claim 10, which further includes a step of heating at a heating temperature of 165°C or higher. The method of manufacturing a photoelectric conversion element according to claim 11, wherein the step of heating at a heating temperature of 165° C. or higher is performed after the step (ii). A compound represented by the following formula (I),

(In formula (I), R ₁ is an alkyl group containing one or more fluorine atoms as a substituent, and a plurality of R ₁ may be the same or different, and R ₂ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, For the optionally substituted alkoxy group, the optionally substituted monovalent aromatic hydrocarbon group, or the optionally substituted monovalent aromatic heterocyclic group, a plurality of R ₂ may be the same or different). The compound according to claim 13, wherein R ₁ is a group represented by -CH ₂ (CF ₂ ) ₂ CF _{3 , and R 2} is a hydrogen atom. A compound represented by the following formula (I),

(In formula (I), R ₁ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted monovalent aromatic hydrocarbon group, or an optionally substituted 1 A valent aromatic heterocyclic group, a plurality of R ₁ may be the same or different, R ₂ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted monovalent The aromatic hydrocarbon group or the monovalent aromatic heterocyclic group which may have a substituent, and a plurality of R ₂ may be the same or different). The compound according to claim 15, wherein R ₁ is an alkyl group which may have a substituent _{, and two or more of the plurality of R 2} are an alkyl group containing one or more fluorine atoms as a substituent. The compound described in claim 15 or claim 16, which is represented by the following formula (N-4),

. A composition containing an n-type semiconductor material and a p-type semiconductor material, and the n-type semiconductor material is the compound according to any one of claim 13 to claim 17. An ink comprising the composition described in claim 18.

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