TW202245283A

TW202245283A - Ink composition and method for producing same

Info

Publication number: TW202245283A
Application number: TW111114582A
Authority: TW
Inventors: 横井優季; 片倉史郎
Original assignee: 日商住友化學股份有限公司
Priority date: 2021-04-21
Filing date: 2022-04-18
Publication date: 2022-11-16
Also published as: JP2022166501A; WO2022224893A1; CN117242913A

Abstract

Provided is an ink composition which requires no trial and error to make it possible to more reliably carry out filtration without clogging a filter in a production step and which is unlikely to cause an electrical defect such as electrical insulation or a short circuit. Also provided is a method for producing an ink composition which makes it possible to more improve the efficiency of producing an ink composition and the efficiency of producing a photoelectric conversion element. An ink composition for producing a photoelectric conversion element comprises a p-type semiconductor material, an n-type semiconductor material, and a solvent, wherein the p-type semiconductor material contains a polymer compound which has a z average molecular weight of less than 5.0*105. The p-type semiconductor material preferably contains a polymer compound which has a weight-average molecular weight of more than 6.0*104.

Description

油墨組成物及其製造方法Ink composition and its manufacturing method

本發明是有關於一種用於形成光電轉換元件的功能層的油墨組成物及其製造方法。The present invention relates to an ink composition for forming a functional layer of a photoelectric conversion element and a manufacturing method thereof.

就例如節能、減少二氧化碳的排出量的觀點而言，光電轉換元件是極其有用的器件，而備受關注。A photoelectric conversion element is an extremely useful device from the viewpoint of, for example, energy saving and carbon dioxide emission reduction, and has attracted attention.

已知於製造光電轉換元件例如光檢測元件（有機光電二極體（organic photodiode，OPD））時，應用如下製造方法，即藉由將光電轉換元件製造用油墨組成物塗敷於塗佈對象上的塗佈法來形成活性層、電子傳輸層、電洞傳輸層等功能層（參照非專利文獻1）。 [現有技術文獻] [專利文獻] It is known that when manufacturing a photoelectric conversion element such as a photodetection element (organic photodiode (OPD)), a manufacturing method is applied by applying an ink composition for manufacturing a photoelectric conversion element to an object to be coated. Functional layers such as an active layer, an electron transport layer, and a hole transport layer are formed by a coating method (refer to Non-Patent Document 1). [Prior art literature] [Patent Document]

[非專利文獻1]斯卓貝爾（Strobel） 2019 可撓性印刷電子（Flexible and Printed Electronics，Flex. Print. Electron.） 4 043001[Non-Patent Document 1] Strobel 2019 Flexible and Printed Electronics (Flex. Print. Electron.) 4 043001

[發明所欲解決之課題] 於使用油墨組成物並藉由塗佈法形成功能層的光電轉換元件中，例如在形成本體異質接合（bulk heterojunction）型的活性層的情況下，活性層形成用的油墨組成物中通常包含p型半導體材料、n型半導體材料以及溶劑。此種油墨組成物中若混入異物，則有可能於使用該油墨組成物形成的活性層中成為絕緣、短路等電性缺陷的原因。因此，於油墨組成物的製造時，通常在使p型半導體材料與n型半導體材料溶解於溶劑中之後，利用具有規定孔徑的過濾器進行過濾處理。 [Problem to be Solved by the Invention] In a photoelectric conversion element that uses an ink composition and forms a functional layer by a coating method, for example, in the case of forming a bulk heterojunction type active layer, the ink composition for active layer formation usually contains p type semiconductor material, n-type semiconductor material and solvent. If such an ink composition is mixed with foreign matter, it may cause electrical defects such as insulation and short circuit in the active layer formed using the ink composition. Therefore, in the production of the ink composition, the p-type semiconductor material and the n-type semiconductor material are usually dissolved in a solvent, and then filtered through a filter having a predetermined pore size.

然而，於所述先前的油墨組成物中，根據p型半導體材料及/或n型半導體材料的不同選擇，亦有當過濾時過濾器堵塞而根本無法進行過濾，從而無法製造光電轉換元件的情況。 [解決課題之手段] However, in the above-mentioned conventional ink composition, depending on the selection of the p-type semiconductor material and/or n-type semiconductor material, the filter may be clogged during filtration and filtration may not be performed at all, thereby making it impossible to manufacture photoelectric conversion elements. . [Means to solve the problem]

本發明者等人為解決上述課題進行了努力研究，結果發現，於使過濾器堵塞的油墨組成物中的成分中包含p型半導體材料的超高分子量成分。然而，該超高分子量成分於油墨組成物中僅包含極少量，自所製備的油墨組成物中去除極其困難。對此，本發明者等人發現，若將用作原料的p型半導體材料的超高分子量成分的含量管理為一定程度以下，使油墨組成物中所含的p型半導體材料的z平均分子量成為規定範圍，則可解決上述課題，從而完成了本發明。The inventors of the present invention conducted diligent research to solve the above-mentioned problems, and as a result, found that an ultrahigh-molecular-weight component of a p-type semiconductor material is included in components of an ink composition that clogs a filter. However, the ultra-high molecular weight component is only contained in a very small amount in the ink composition, and it is extremely difficult to remove it from the prepared ink composition. In contrast, the inventors of the present invention found that if the content of the ultrahigh molecular weight component of the p-type semiconductor material used as a raw material is controlled to be below a certain level, the z-average molecular weight of the p-type semiconductor material contained in the ink composition becomes If the range is specified, the above-mentioned problems can be solved, and the present invention has been completed.

因此，本發明提供下述[1]～[9]。 [1] 一種光電轉換元件製造用油墨組成物，為包含p型半導體材料、n型半導體材料、以及溶劑的油墨組成物，其中，所述p型半導體材料包含z平均分子量小於5.0×10 ⁵的高分子化合物。 [2] 如[1]所述的光電轉換元件製造用油墨組成物，其中，所述p型半導體材料包含重量平均分子量大於6.0×10 ⁴的高分子化合物。 [3] 如[1]或[2]所述的光電轉換元件製造用油墨組成物，其中，所述p型半導體材料包含含有具有噻吩骨架的構成單元的高分子化合物。 [4] 如[3]所述的光電轉換元件製造用油墨組成物，其中，所述p型半導體材料包含具有施體/受體結構的高分子化合物。 [5] 如[1]至[4]中任一項所述的光電轉換元件製造用油墨組成物，其中，所述溶劑包含芳香族烴。 [6] 如[1]至[5]中任一項所述的光電轉換元件製造用油墨組成物，其中，所述n型半導體材料包含富勒烯衍生物。 [7] 如[1]至[5]中任一項所述的光電轉換元件製造用油墨組成物，其中，所述n型半導體材料包含非富勒烯化合物。 [8] 一種光電轉換元件製造用油墨組成物的製造方法，是如[1]至[7]中任一項所述的油墨組成物的製造方法，且包括利用孔徑0.5 μm以下的過濾器對所述油墨組成物進行過濾的步驟。 [9] 一種光電轉換元件製造用油墨組成物的製造方法，包括：準備步驟，準備作為p型半導體材料的多種高分子化合物；篩選步驟，於所述準備步驟中所準備的所述高分子化合物中，篩選z平均分子量小於5.0×10 ⁵的高分子化合物作為p型半導體材料；以及將所述篩選步驟中篩選出的p型半導體材料與n型半導體材料以及溶劑混合，製造油墨組成物的步驟。 [發明的效果] Therefore, the present invention provides the following [1] to [9]. [1] An ink composition for producing a photoelectric conversion element, which is an ink composition comprising a p-type semiconductor material, an n-type semiconductor material, and a solvent, wherein the p-type semiconductor material comprises an ink having a z-average molecular weight of less than 5.0×10 ⁵ polymer compound. [2] The ink composition for producing a photoelectric conversion element according to [1], wherein the p-type semiconductor material includes a polymer compound having a weight average molecular weight of more than 6.0×10 ⁴ . [3] The ink composition for producing a photoelectric conversion element according to [1] or [2], wherein the p-type semiconductor material includes a polymer compound including a constituent unit having a thiophene skeleton. [4] The ink composition for producing a photoelectric conversion element according to [3], wherein the p-type semiconductor material includes a polymer compound having a donor/acceptor structure. [5] The ink composition for producing a photoelectric conversion element according to any one of [1] to [4], wherein the solvent contains an aromatic hydrocarbon. [6] The ink composition for producing a photoelectric conversion element according to any one of [1] to [5], wherein the n-type semiconductor material contains a fullerene derivative. [7] The ink composition for producing a photoelectric conversion element according to any one of [1] to [5], wherein the n-type semiconductor material contains a non-fullerene compound. [8] A method for producing an ink composition for producing a photoelectric conversion element, which is the method for producing an ink composition according to any one of [1] to [7], and includes using a filter with a pore size of 0.5 μm or less to The step of filtering the ink composition. [9] A method for producing an ink composition for producing a photoelectric conversion element, comprising: a preparation step of preparing a plurality of polymer compounds as p-type semiconductor materials; a screening step of preparing the polymer compounds prepared in the preparation step wherein, screening a polymer compound with a z-average molecular weight of less than 5.0×10 ⁵ as a p-type semiconductor material; and mixing the p-type semiconductor material screened in the screening step with an n-type semiconductor material and a solvent to produce an ink composition . [Effect of the invention]

根據本發明，可提供一種油墨組成物，其無需進行反覆試驗，便可於製造步驟中在不會使過濾器堵塞的情況下更切實地進行過濾，且不易產生絕緣、短路等電性缺陷，進而可提供一種油墨組成物的製造方法，其可使油墨組成物的製造效率、進而使光電轉換元件的製造效率進一步提高。According to the present invention, it is possible to provide an ink composition that can filter more reliably without clogging the filter during the manufacturing process without trial and error, and is less prone to electrical defects such as insulation and short circuit, Furthermore, it is possible to provide a method for producing an ink composition, which can further improve the production efficiency of the ink composition and further the production efficiency of the photoelectric conversion element.

以下，參照圖式來說明本發明的實施方式。再者，圖式只不過以能夠理解發明的程度概略性地示出了構成要素的形狀、大小及配置。本發明並不受以下記述的限定，各構成要素能夠於不脫離本發明的主旨的範圍內適宜變更。於用於以下說明的圖式中，對於同樣的構成要素標記相同的符號表示，有時省略重覆的說明。另外，本發明的實施方式的結構不必限於以圖示例的配置使用。Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, the drawings only schematically show the shape, size, and arrangement of constituent elements to the extent that the invention can be understood. The present invention is not limited to the description below, and each component can be appropriately changed within a range not departing from the spirit of the present invention. In the drawings used for the following description, the same components are denoted by the same symbols, and overlapping descriptions may be omitted. In addition, the configurations of the embodiments of the present invention are not necessarily limited to the configurations exemplified in the drawings to be used.

1.共同術語的說明於本說明書中，「高分子化合物」是指具有分子量分佈，且聚苯乙烯換算的數量平均分子量為1×10 ³以上且1×10 ⁸以下的聚合物。高分子化合物中所含的構成單元合計為100莫耳%。 1. Explanation of Common Terms In this specification, a "polymer compound" refers to a polymer having a molecular weight distribution and having a polystyrene-equivalent number average molecular weight of 1×10 ³ to 1×10 ⁸ . The total of the constituent units contained in the polymer compound is 100 mol%.

於本說明書中，「構成單元」是指於高分子化合物中存在一個以上的單元、且為源自單量體化合物（單體）的單元。In this specification, a "constituent unit" refers to a unit derived from a monomeric compound (monomer) in which one or more units exist in a polymer compound.

於本說明書中，「氫原子」可為氕原子，亦可為氘原子。In this specification, a "hydrogen atom" may be a protium atom or a deuterium atom.

於本說明書中，作為「鹵素原子」的例子，可列舉：氟原子、氯原子、溴原子及碘原子。In this specification, examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

「可具有取代基」的形態包括：構成化合物或基的所有氫原子未經取代的情況、及一個以上的氫原子的部分或全部經取代基取代的情況此兩種形態。The form of "may have a substituent" includes two forms: a case where all hydrogen atoms constituting a compound or a group are not substituted, and a case where a part or all of one or more hydrogen atoms are substituted with a substituent.

作為取代基的例子，可列舉：鹵素原子、烷基、環烷基、烯基、環烯基、炔基、環炔基、烷基氧基、環烷基氧基、烷硫基、環烷硫基、芳基、芳氧基、芳硫基、一價雜環基、取代胺基、醯基、亞胺殘基、醯胺基、醯亞胺基、取代氧基羰基、氰基、烷基磺醯基、及硝基。Examples of substituents include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, cycloalkynyl groups, alkyloxy groups, cycloalkyloxy groups, alkylthio groups, and cycloalkane groups. Thio group, aryl group, aryloxy group, arylthio group, monovalent heterocyclic group, substituted amino group, acyl group, imine residue, amido group, imide group, substituted oxycarbonyl group, cyano group, alkane Sulfonyl, and nitro.

於本說明書中，「烷基」可具有取代基。「烷基」只要無特別說明，則可為直鏈狀、分支狀及環狀中的任一者。直鏈狀的烷基的碳原子數不包括取代基的碳原子數，且通常為1～50，較佳為1～30，更佳為1～20。分支狀或環狀的烷基的碳原子數不包括取代基的碳原子數，且通常為3～50，較佳為3～30，更佳為4～20。In this specification, "alkyl" may have a substituent. "Alkyl" may be any of linear, branched and cyclic, unless otherwise specified. The number of carbon atoms of the linear alkyl group is usually 1-50, preferably 1-30, more preferably 1-20, excluding the carbon number of the substituent. The carbon number of the branched or cyclic alkyl group does not include the carbon number of the substituent, and is usually 3-50, preferably 3-30, more preferably 4-20.

作為烷基的具體例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正戊基、異戊基、2-乙基丁基、正己基、環己基、正庚基、環己基甲基、環己基乙基、正辛基、2-乙基己基、3-正丙基庚基、金剛烷基、正癸基、3,7-二甲基辛基、2-乙基辛基、2-正己基-癸基、正十二烷基、十四烷基、十六烷基、十八烷基、二十烷基等未經取代的烷基；三氟甲基、五氟乙基、全氟丁基、全氟己基、全氟辛基、3-苯基丙基、3-(4-甲基苯基)丙基、3-(3,5-二-正己基苯基)丙基、6-乙氧基己基等經取代的烷基。Specific examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-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, etc. Substituted alkyl; trifluoromethyl, pentafluoroethyl, perfluorobutyl, perfluorohexyl, perfluorooctyl, 3-phenylpropyl, 3-(4-methylphenyl)propyl, Substituted alkyl groups such as 3-(3,5-di-n-hexylphenyl)propyl and 6-ethoxyhexyl.

「環烷基」可為單環的基，亦可為多環的基。環烷基可具有取代基。環烷基的碳原子數不包括取代基的碳原子數，且通常為3～30，較佳為3～20。"Cycloalkyl" may be a monocyclic group or a polycyclic group. A cycloalkyl group may have a substituent. The number of carbon atoms in the cycloalkyl group does not include the number of carbon atoms in the substituent, and is usually 3-30, preferably 3-20.

作為環烷基的例子，可列舉：環戊基、環己基、環庚基、金剛烷基等不具有取代基的烷基、及該些基中的氫原子被烷基、烷基氧基、芳基、氟原子等取代基取代而成的基。Examples of cycloalkyl groups include: cyclopentyl, cyclohexyl, cycloheptyl, adamantyl and other unsubstituted alkyl groups, and the hydrogen atoms in these groups are replaced by alkyl, alkyloxy, A group substituted with a substituent such as an aryl group or a fluorine atom.

作為具有取代基的環烷基的具體例，可列舉甲基環己基、乙基環己基。Specific examples of the cycloalkyl group having a substituent include a methylcyclohexyl group and an ethylcyclohexyl group.

「烯基」可為直鏈狀，亦可為分支狀。烯基可具有取代基。烯基的碳原子數不包括取代基的碳原子數，且通常為2～30，較佳為2～20。"Alkenyl" may be linear or branched. An alkenyl group may have a substituent. The number of carbon atoms in the alkenyl group does not include the number of carbon atoms in the substituent, and is usually 2-30, preferably 2-20.

作為烯基的例子，可列舉：乙烯基、1-丙烯基、2-丙烯基、2-丁烯基、3-丁烯基、3-戊烯基、4-戊烯基、1-己烯基、5-己烯基、7-辛烯基等不具有取代基的烯基、及該些基中的氫原子被烷基氧基、芳基、氟原子等取代基取代而成的基。Examples of alkenyl include vinyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, 3-pentenyl, 4-pentenyl, 1-hexene Alkenyl groups without substituents such as 5-hexenyl and 7-octenyl groups, and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyloxy groups, aryl groups, and fluorine atoms.

「環烯基」可為單環的基，亦可為多環的基。環烯基可具有取代基。環烯基的碳原子數不包括取代基的碳原子數，且通常為3～30，較佳為3～20。"Cycloalkenyl" may be a monocyclic group or a polycyclic group. A cycloalkenyl group may have a substituent. The number of carbon atoms of the cycloalkenyl group does not include the number of carbon atoms of the substituent, and is usually 3-30, preferably 3-20.

作為環烯基的例子，可列舉：環己烯基等不具有取代基的環烯基、及該些基中的氫原子被烷基、烷基氧基、芳基、氟原子等取代基取代而成的基。Examples of cycloalkenyl groups include cycloalkenyl groups without substituents such as cyclohexenyl groups, and hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms. The base formed.

作為具有取代基的環烯基的例子，可列舉甲基環己烯基及乙基環己烯基。Examples of the cycloalkenyl group having a substituent include a methylcyclohexenyl group and an ethylcyclohexenyl group.

「炔基」可為直鏈狀，亦可為分支狀。炔基可具有取代基。炔基的碳原子數不包括取代基的碳原子數，且通常為2～30，較佳為2～20。"Alkynyl" may be linear or branched. The alkynyl group may have a substituent. The number of carbon atoms of the alkynyl group does not include the number of carbon atoms of the substituent, and is usually 2-30, preferably 2-20.

作為炔基的例子，可列舉：乙炔基、1-丙炔基、2-丙炔基、2-丁炔基、3-丁炔基、3-戊炔基、4-戊炔基、1-己炔基、5-己炔基等不具有取代基的炔基、及該些基中的氫原子被烷基氧基、芳基、氟原子等取代基取代而成的基。Examples of the alkynyl group include: ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, 3-butynyl, 3-pentynyl, 4-pentynyl, 1- Alkynyl groups without substituents such as hexynyl and 5-hexynyl, and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyloxy groups, aryl groups, and fluorine atoms.

「環炔基」可為單環的基，亦可為多環的基。環炔基可具有取代基。環炔基的碳原子數不包括取代基的碳原子數，且通常為4～30，較佳為4～20。"Cycloalkynyl" may be a monocyclic group or a polycyclic group. The cycloalkynyl group may have a substituent. The number of carbon atoms in the cycloalkynyl group does not include the number of carbon atoms in the substituent, and is usually 4-30, preferably 4-20.

作為環炔基的例子，可列舉環己炔基等不具有取代基的環炔基、及該些基中的氫原子被烷基、烷基氧基、芳基、氟原子等取代基取代而成的基。Examples of the cycloalkynyl group include cycloalkynyl groups without substituents such as cyclohexynyl groups, and those in which hydrogen atoms are substituted by substituents such as alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms. into the base.

作為具有取代基的環炔基的例子，可列舉甲基環己炔基及乙基環己炔基。Examples of the cycloalkynyl group having a substituent include a methylcyclohexynyl group and an ethylcyclohexynyl group.

「烷基氧基」可為直鏈狀，亦可為分支狀。烷基氧基可具有取代基。烷基氧基的碳原子數不包括取代基的碳原子數，且通常為1～30，較佳為1～20。"Alkyloxy" may be linear or branched. An alkyloxy group may have a substituent. The carbon number of the alkyloxy group does not include the carbon number of the substituent, and is usually 1-30, preferably 1-20.

作為烷基氧基的例子，可列舉：甲氧基、乙氧基、正丙基氧基、異丙基氧基、正丁基氧基、異丁基氧基、第三丁基氧基、正戊基氧基、正己基氧基、正庚基氧基、正辛基氧基、2-乙基己基氧基、正壬基氧基、正癸基氧基、3,7-二甲基辛基氧基、3-庚基十二烷基氧基、月桂基氧基等不具有取代基的烷基氧基、及該些基中的氫原子被烷基氧基、芳基、氟原子等取代基取代而成的基。Examples of alkyloxy include: methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tert-butyloxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, 3,7-dimethyl octyloxy, 3-heptyldodecyloxy, lauryloxy and other unsubstituted alkyloxy groups, and the hydrogen atoms in these groups are replaced by alkyloxy, aryl, fluorine atoms A group substituted by other substituents.

「環烷基氧基」所具有的環烷基可為單環的基，亦可為多環的基。環烷基氧基可具有取代基。環烷基氧基的碳原子數不包括取代基的碳原子數，且通常為3～30，較佳為3～20。The cycloalkyl group contained in the "cycloalkyloxy" may be a monocyclic group or a polycyclic group. A cycloalkyloxy group may have a substituent. The carbon number of the cycloalkyloxy group does not include the carbon number of the substituent, and is usually 3-30, preferably 3-20.

作為環烷基氧基的例子，可列舉環戊基氧基、環己基氧基、環庚基氧基等不具有取代基的環烷基氧基、及該些基中的氫原子被氟原子、烷基等取代基取代而成的基。Examples of cycloalkyloxy groups include cycloalkyloxy groups without substituents such as cyclopentyloxy, cyclohexyloxy, and cycloheptyloxy, and cycloalkyloxy groups in which hydrogen atoms are replaced by fluorine atoms. A group substituted with substituents such as an alkyl group.

「烷硫基」可為直鏈狀，亦可為分支狀。烷硫基可具有取代基。烷硫基的碳原子數不包括取代基的碳原子數，且通常為1～30，較佳為1～20。"Alkylthio" may be linear or branched. The alkylthio group may have a substituent. The number of carbon atoms in the alkylthio group does not include the number of carbon atoms in the substituent, and is usually 1-30, preferably 1-20.

作為可具有取代基的烷硫基的例子，可列舉：甲硫基、乙硫基、正丙硫基、異丙硫基、正丁硫基、異丁硫基、第三丁硫基、正戊硫基、正己硫基、正庚硫基、正辛硫基、2-乙基己硫基、正壬硫基、正癸硫基、3,7-二甲基辛硫基、3-庚基十二烷硫基、月桂基硫基及三氟甲硫基。Examples of alkylthio groups that may have substituents include: methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, t-butylthio, n-butylthio, Pentylthio, n-hexylthio, n-heptylthio, n-octylthio, 2-ethylhexylthio, n-nonylthio, n-decylthio, 3,7-dimethyloctylthio, 3-heptylthio Dodecylthio, Laurylthio and Trifluoromethylthio.

「環烷硫基」所具有的環烷基可為單環的基，亦可為多環的基。環烷硫基可具有取代基。環烷硫基的碳原子數不包括取代基的碳原子數，且通常為3～30，較佳為3～20。The cycloalkyl group possessed by the "cycloalkylthio group" may be a monocyclic group or a polycyclic group. The cycloalkylthio group may have a substituent. The number of carbon atoms of the cycloalkylthio group does not include the number of carbon atoms of the substituent, and is usually 3-30, preferably 3-20.

作為可具有取代基的環烷硫基的例子，可列舉環己硫基。As an example of the cycloalkylthio group which may have a substituent, a cyclohexylthio group is mentioned.

「p價芳香族碳環基」是指自可具有取代基的芳香族烴除去p個與構成環的碳原子直接鍵結的氫原子後殘留的原子團。p價芳香族碳環基可進而具有取代基。The "p-valent aromatic carbocyclic group" refers to an atomic group remaining after removing p hydrogen atoms directly bonded to carbon atoms constituting the ring from an aromatic hydrocarbon which may have a substituent. The p-valent aromatic carbocyclic group may further have a substituent.

「芳基」是指一價芳香族碳環基。芳基可具有取代基。芳基的碳原子數不包括取代基的碳原子數，且通常為6～60，較佳為6～48。"Aryl" means a monovalent aromatic carbocyclic group. The aryl group may have a substituent. The carbon number of the aryl group does not include the carbon number of the substituent, and is usually 6-60, preferably 6-48.

作為芳基的例子，可列舉：苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-芘基、2-芘基、4-芘基、2-芴基、3-芴基、4-芴基、2-苯基苯基、3-苯基苯基、4-苯基苯基等不具有取代基的芳基、及該些基中的氫原子被烷基、烷基氧基、芳基、氟原子等取代基取代而成的基。Examples of the aryl group include: phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrene Aryl groups without substituents such as 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 2-phenylphenyl, 3-phenylphenyl, 4-phenylphenyl, and these groups A group in which hydrogen atoms are substituted by substituents such as alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms.

「芳氧基」可具有取代基。芳氧基的碳原子數不包括取代基的碳原子數，且通常為6～60，較佳為6～48。"Aryloxy" may have a substituent. The carbon number of the aryloxy group does not include the carbon number of the substituent, and is usually 6-60, preferably 6-48.

作為芳氧基的例子，可列舉：苯氧基、1-萘基氧基、2-萘基氧基、1-蒽基氧基、9-蒽基氧基、1-芘基氧基等不具有取代基的芳氧基、及該些基中的氫原子被烷基、烷基氧基、氟原子等取代基取代而成的基。Examples of aryloxy groups include: phenoxy, 1-naphthyloxy, 2-naphthyloxy, 1-anthracenyloxy, 9-anthracenyloxy, 1-pyrenyloxy, etc. An aryloxy group having a substituent, and a group in which a hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group, or a fluorine atom.

「芳硫基」可具有取代基。芳硫基的碳原子數不包括取代基的碳原子數，且通常為6～60，較佳為6～48。"Arylthio" may have a substituent. The number of carbon atoms of the arylthio group does not include the number of carbon atoms of the substituent, and is usually 6-60, preferably 6-48.

作為可具有取代基的芳硫基的例子，可列舉：苯硫基、C1～C12烷基氧基苯硫基、C1～C12烷基苯硫基、1-萘硫基、2-萘硫基及五氟苯硫基。「C1～C12」表示緊隨其後記載的基的碳原子數為1～12。進而，「Cm～Cn」表示緊隨其後記載的基的碳原子數為m～n。以下同樣。Examples of arylthio groups that may have substituents include: phenylthio, C1-C12 alkyloxyphenylthio, C1-C12 alkylphenylthio, 1-naphthylthio, 2-naphthylthio and pentafluorophenylthio. "C1-C12" means that the carbon number of the group described immediately after is 1-12. Furthermore, "Cm to Cn" means that the number of carbon atoms of the group described immediately thereafter is m to n. Same below.

「p價雜環基」（p表示1以上的整數）是指自可具有取代基的雜環式化合物除去與構成環的碳原子或雜原子直接鍵結的氫原子中的p個氫原子後殘留的原子團。「p價雜環基」中包括「p價芳香族雜環基」。「p價芳香族雜環基」是指自可具有取代基的芳香族雜環式化合物除去與構成環的碳原子或雜原子直接鍵結的氫原子中的p個氫原子後殘留的原子團。"p-valent heterocyclic group" (p represents an integer of 1 or more) refers to a heterocyclic compound which may have substituents except p hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring residual atoms. 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 among hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring from an aromatic heterocyclic compound which may have substituents.

芳香族雜環式化合物中，除了包含雜環本身顯示芳香族性的化合物以外，亦包含雜環本身不顯示芳香族性但於雜環中縮環有芳香環的化合物。Aromatic heterocyclic compounds include compounds in which the heterocycle itself does not exhibit aromaticity but are condensed with an aromatic ring in the heterocycle, in addition to compounds in which the heterocycle itself is aromatic.

芳香族雜環式化合物中，作為雜環本身顯示芳香族性的化合物的具體例，可列舉：噁二唑、噻二唑、噻唑、噁唑、噻吩、吡咯、磷雜環戊二烯、呋喃、吡啶、吡嗪、嘧啶、三嗪、噠嗪、喹啉、異喹啉、咔唑及二苯並磷雜環戊二烯。Among aromatic heterocyclic compounds, specific examples of compounds in which the heterocycle itself exhibits aromaticity include: oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan , pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole and dibenzophosphole.

芳香族雜環式化合物中，作為雜環本身不顯示芳香族性而於雜環上縮環有芳香環的化合物的具體例，可列舉：啡噁嗪、啡噻嗪、二苯並硼雜環戊二烯、二苯並噻咯及苯並吡喃。Among the aromatic heterocyclic compounds, as specific examples of compounds in which the heterocyclic ring itself does not show aromaticity but has an aromatic ring condensed on the heterocyclic ring, phenanthoxazine, phenanthiazine, dibenzoborin Pentadiene, dibenzosilazole and benzopyran.

p價雜環基可具有取代基。p價雜環基的碳原子數不包括取代基的碳原子數，且通常為2～60，較佳為2～20。The p-valent heterocyclic group may have a substituent. The number of carbon atoms of the p-valent heterocyclic group does not include the number of carbon atoms of the substituent, and is usually 2-60, preferably 2-20.

作為一價雜環基的例子，可列舉：一價芳香族雜環基（例如噻吩基、吡咯基、呋喃基、吡啶基、喹啉基、異喹啉基、嘧啶基、三嗪基）、一價非芳香族雜環基（例如哌啶基、哌嗪基）、及該些基中的氫原子被烷基、烷基氧基、氟原子等取代基取代而成的基。Examples of monovalent heterocyclic groups include: monovalent aromatic heterocyclic groups (such as thienyl, pyrrolyl, furyl, pyridyl, quinolinyl, isoquinolyl, pyrimidyl, triazinyl), Monovalent non-aromatic heterocyclic groups (eg, piperidinyl, piperazinyl), and groups in which hydrogen atoms in these groups are substituted by substituents such as alkyl groups, alkyloxy groups, and fluorine atoms.

「取代胺基」是指具有取代基的胺基。作為胺基所具有的取代基，較佳為烷基、芳基、及一價雜環基。取代胺基的碳原子數不包括取代基的碳原子數，且通常為2～30。"Substituted amino group" refers to an amino group having a substituent. As a substituent which an amino group has, an alkyl group, an aryl group, and a monovalent heterocyclic group are preferable. The carbon number of the substituted amino group does not include the carbon number of the substituent, and is usually 2-30.

作為取代胺基的例子，可列舉：二烷基胺基（例如二甲基胺基、二乙基胺基）、二芳基胺基（例如二苯基胺基、雙(4-甲基苯基)胺基、雙(4-第三丁基苯基)胺基、雙(3,5-二-第三丁基苯基)胺基）。Examples of substituted amino groups include: dialkylamine groups (such as dimethylamino groups, diethylamine groups), diarylamine groups (such as diphenylamine groups, bis(4-methylphenylamine groups), base) amino group, bis(4-tert-butylphenyl)amino group, bis(3,5-di-tert-butylphenyl)amino group).

「醯基」可具有取代基。醯基的碳原子數不包括取代基的碳原子數，且通常為2～20，較佳為2～18。作為醯基的具體例，可列舉：乙醯基、丙醯基、丁醯基、異丁醯基、三甲基乙醯基、苯甲醯基、三氟乙醯基及五氟苯甲醯基。"Acyl group" may have a substituent. The number of carbon atoms in the acyl group does not include the number of carbon atoms in the substituent, and is usually 2-20, preferably 2-18. Specific examples of the acyl group include acetyl, propionyl, butyryl, isobutyryl, trimethylacetyl, benzoyl, trifluoroacetyl and pentafluorobenzoyl.

「亞胺殘基」是指自亞胺化合物除去一個與構成碳原子-氮原子雙鍵的碳原子或氮原子直接鍵結的氫原子後殘留的原子團。「亞胺化合物」是指分子內具有碳原子-氮原子雙鍵的有機化合物。作為亞胺化合物的例子，可列舉醛亞胺、酮亞胺及醛亞胺中的與構成碳原子-氮原子雙鍵的氮原子鍵結的氫原子被烷基等的取代基取代而成的化合物。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 atom double bond from an imine compound. "Imine compound" refers to an organic compound having a carbon atom-nitrogen atom double bond in the molecule. Examples of imine compounds include aldimines, ketimines, and aldimines in which the hydrogen atom bonded to the nitrogen atom constituting the carbon atom-nitrogen double bond is substituted by a substituent such as an alkyl group. compound.

亞胺殘基的碳原子數通常為2～20，較佳為2～18。作為亞胺殘基的例子，可列舉下述結構式所表示的基。The number of carbon atoms of the imine residue is usually 2-20, preferably 2-18. As an example of an imine residue, the group represented by the following structural formula is mentioned.

[化1]

[chemical 1]

「醯胺基」是指自醯胺除去一個與氮原子鍵結的氫原子後殘留的原子團。醯胺基的碳原子數通常為1～20左右，較佳為1～18。作為醯胺基的具體例，可列舉：甲醯胺基、乙醯胺基、丙醯胺基、丁醯胺基、苯甲醯胺基、三氟乙醯胺基、五氟苯甲醯胺基、二甲醯胺基、二乙醯胺基、二丙醯胺基、二丁醯胺基、二苯甲醯胺基、二-三氟乙醯胺基、及二-五氟苯甲醯胺基。"Amido 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 in the amide group is usually about 1-20, preferably 1-18. Specific examples of the amide group include formamide, acetamide, acrylamide, butyramide, benzamide, trifluoroacetamide, and pentafluorobenzamide. Diformamide, diacetylamide, diacrylamide, dibutyrylamide, dibenzamide, di-trifluoroacetamide, and di-pentafluorobenzyl Amino.

「醯亞胺基」是指自醯亞胺除去一個與氮原子鍵結的氫原子後殘留的原子團。醯亞胺基的碳原子數通常為4～20。作為醯亞胺基的具體例，可列舉以下所示的基。The "imide group" refers to an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an imide. The number of carbon atoms in the imide group is usually 4-20. Specific examples of the imide group include groups shown below.

[化2]

[Chem 2]

「取代氧基羰基」是指R'-O-(C=O)-所表示的基。此處，R'表示烷基、芳基、芳烷基、或一價雜環基。"Substituted oxycarbonyl" refers to 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.

取代氧基羰基的碳原子數通常為2～60，較佳的是碳原子數為2～48。The number of carbon atoms in the substituted oxycarbonyl group is usually 2 to 60, preferably 2 to 48 carbon atoms.

作為取代氧基羰基的具體例，可列舉：甲氧基羰基、乙氧基羰基、丙氧基羰基、異丙氧基羰基、丁氧基羰基、異丁氧基羰基、第三丁氧基羰基、戊基氧基羰基、己基氧基羰基、環己基氧基羰基、庚基氧基羰基、辛基氧基羰基、2-乙基己基氧基羰基、壬基氧基羰基、癸基氧基羰基、3,7-二甲基辛基氧基羰基、十二烷基氧基羰基、三氟甲氧基羰基、五氟乙氧基羰基、全氟丁氧基羰基、全氟己基氧基羰基、全氟辛基氧基羰基、苯氧基羰基、萘氧基羰基、及吡啶氧基羰基。Specific examples of the substituted oxycarbonyl group include: methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, tert-butoxycarbonyl , Pentyloxycarbonyl, Hexyloxycarbonyl, Cyclohexyloxycarbonyl, Heptyloxycarbonyl, Octyloxycarbonyl, 2-Ethylhexyloxycarbonyl, Nonyloxycarbonyl, Decyloxycarbonyl , 3,7-dimethyloctyloxycarbonyl, dodecyloxycarbonyl, trifluoromethoxycarbonyl, pentafluoroethoxycarbonyl, perfluorobutoxycarbonyl, perfluorohexyloxycarbonyl, Perfluorooctyloxycarbonyl, phenoxycarbonyl, naphthyloxycarbonyl, and pyridyloxycarbonyl.

「烷基磺醯基」可為直鏈狀，亦可為分支狀。烷基磺醯基可具有取代基。烷基磺醯基的碳原子數不包括取代基的碳原子數，且通常為1～30。作為烷基磺醯基的具體例，可列舉：甲基磺醯基、乙基磺醯基及十二烷基磺醯基。"Alkylsulfonyl" may be linear or branched. The alkylsulfonyl group may have a substituent. The number of carbon atoms of the alkylsulfonyl group does not include the number of carbon atoms of the substituent, and is usually 1-30. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a dodecylsulfonyl group.

化學式中標註的「*」表示鍵結鍵。"*" marked in the chemical formula indicates a bond.

「π共軛系」是指π電子非局部存在化於多個鍵上的體系。The "π-conjugated system" means a system in which π-electrons are non-localized in a plurality of bonds.

「(甲基)丙烯酸基」中包含丙烯酸基、甲基丙烯酸基及該些的組合。The "(meth)acryl group" includes an acryl group, a methacryl group, and combinations thereof.

於本說明書中，「油墨組成物」是指用於塗佈法的液狀的組成物，並不限定於已著色的液體。另外，「塗佈法」是指使用以油墨組成物為代表的液狀物質來形成膜的方法。In this specification, an "ink composition" refers to a liquid composition used in a coating method, and is not limited to a colored liquid. In addition, the "coating method" refers to a method of forming a film using a liquid substance typified by an ink composition.

「油墨組成物」可為溶液，亦可為分散液、乳液（乳濁液）、懸浮液（懸濁液）等分散液。The "ink composition" may be a solution, or may be a dispersion such as a dispersion, emulsion (emulsion), or suspension (suspension).

2.油墨組成物本實施方式的油墨組成物是一種光電轉換元件製造用油墨組成物，且為含有p型半導體材料、n型半導體材料、以及溶劑的油墨組成物，其中，p型半導體材料包含z平均分子量小於5.0×10 ⁵的高分子化合物。 2. Ink composition The ink composition of the present embodiment is an ink composition for manufacturing a photoelectric conversion element, and is an ink composition containing a p-type semiconductor material, an n-type semiconductor material, and a solvent, wherein the p-type semiconductor material contains High molecular compounds with an average molecular weight of less than 5.0×10 ⁵ .

如上所述，本實施方式的油墨組成物是一種光電轉換元件製造用油墨組成物，且較佳為活性層形成用的油墨組成物。As described above, the ink composition of this embodiment is an ink composition for producing a photoelectric conversion element, and is preferably an ink composition for forming an active layer.

以下，對本實施方式的油墨組成物中可包含的成分進行具體說明。Hereinafter, components that may be included in the ink composition of the present embodiment will be specifically described.

此處，p型半導體材料包含至少一種供電子性化合物，n型半導體材料包含至少一種受電子性化合物。油墨組成物中所含的半導體材料作為p型半導體材料及n型半導體材料中的哪一個發揮功能可根據所選擇的化合物的最高佔據分子軌域（Highest Occupied Molecular Orbital，HOMO）能階的值或最低未佔分子軌域（Lowest Unoccupied Molecular Orbital，LUMO）能階的值相對地決定。Here, the p-type semiconductor material contains at least one electron-donating compound, and the n-type semiconductor material contains at least one electron-accepting compound. Whether the semiconductor material contained in the ink composition functions as a p-type semiconductor material or an n-type semiconductor material can be determined according to the value of the highest occupied molecular orbital (Highest Occupied Molecular Orbital, HOMO) energy level of the selected compound or The value of the lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbital, LUMO) energy level is relatively determined.

p型半導體材料的HOMO及LUMO的能階的值與n型半導體材料的HOMO及LUMO的能階的值的關係可適宜設定於由油墨組成物形成的（固化）膜發揮光電轉換功能、光檢測功能等規定功能的範圍內。The relationship between the energy level values of HOMO and LUMO of the p-type semiconductor material and the value of the energy level of HOMO and LUMO of the n-type semiconductor material can be set appropriately so that the (cured) film formed by the ink composition can perform photoelectric conversion function, light detection, etc. within the scope of specified functions.

（1）p型半導體材料於本實施方式中，p型半導體材料可為低分子化合物亦可為高分子化合物。 (1) p-type semiconductor material In this embodiment, the p-type semiconductor material can be a low-molecular compound or a high-molecular compound.

關於作為低分子化合物的p型半導體材料，例如可列舉：酞菁、金屬酞菁、卟啉、金屬卟啉、低聚噻吩、稠四苯、稠五苯及紅螢烯。The p-type semiconductor material which is a low-molecular compound includes, for example, phthalocyanine, metallophthalocyanine, porphyrin, metalloporphyrin, oligothiophene, condensed tetraphenyl, fused pentacene, and rubrene.

本實施方式的油墨組成物可包含的p型半導體材料較佳為包含具有含有施體構成單元（亦稱為D構成單元。）以及受體構成單位（亦稱為A構成單位。）的施體/受體結構的π共軛系高分子化合物（亦稱為D-A型共軛高分子化合物。）。The p-type semiconductor material that can be included in the ink composition of this embodiment preferably includes a donor having a donor constituting unit (also referred to as a D constituting unit.) and an acceptor constituting unit (also referred to as an A constituting unit.) π-conjugated macromolecular compounds with /receptor structure (also known as D-A conjugated macromolecular compounds.).

此處，施體構成單元是π電子過剩的構成單元，受體構成單元是π電子欠缺的構成單元。Here, the donor constituent unit is a constituent unit with an excess of π electrons, and the acceptor constituent unit is a constituent unit with a deficiency of π electrons.

於本實施方式中，可構成p型半導體材料的構成單元中亦包括施體構成單元與受體構成單元直接鍵結而成的構成單元、以及施體構成單元與受體構成單元經由任意較佳的間隔物（基或構成單元）鍵結而成的構成單元。In this embodiment, the constituent units that can constitute the p-type semiconductor material also include constituent units formed by direct bonding of the donor constituent unit and the acceptor constituent unit, and the donor constituent unit and the acceptor constituent unit via any preferred A constituent unit formed by bonding spacers (groups or constituent units).

關於作為高分子化合物的p型半導體材料，例如可列舉：聚乙烯基咔唑及其衍生物、聚矽烷及其衍生物、於側鏈或主鏈中包含芳香族胺結構的聚矽氧烷衍生物、聚苯胺及其衍生物、聚噻吩及其衍生物、聚吡咯及其衍生物、聚苯乙炔及其衍生物、聚伸噻吩乙炔及其衍生物、聚芴及其衍生物。作為p型半導體材料，較佳為使用含有具有噻吩骨架的構成單元的高分子化合物。Regarding the p-type semiconductor material as a polymer compound, for example, polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives containing aromatic amine structures in the side chain or main chain, etc. substances, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythiophene acetylene and its derivatives, polyfluorene and its derivatives. As the p-type semiconductor material, it is preferable to use a polymer compound containing a constituent unit having a thiophene skeleton.

就進一步提高油墨組成物的穩定性的觀點而言，進而就進一步提高光電轉換元件的外部量子效率的觀點而言，p型半導體材料較佳為包含下述式（I）所表示的構成單元及/或下述式（II）所表示的構成單元的高分子化合物。From the viewpoint of further improving the stability of the ink composition, and further from the viewpoint of further improving the external quantum efficiency of the photoelectric conversion element, the p-type semiconductor material preferably includes a constituent unit represented by the following formula (I) and /or a polymer compound of a structural unit represented by the following formula (II).

[化3]

[Chem 3]

式（I）中，Ar ¹及Ar ²分別獨立地表示可具有取代基的三價芳香族雜環基，Z表示下述式（Z-1）～式（Z-7）中的任一者所表示的基。 In formula (I), Ar ¹ and Ar ² each independently represent a trivalent aromatic heterocyclic group which may have substituents, and Z represents any one of the following formulas (Z-1) to (Z-7) The base represented.

[化4]

[chemical 4]

式（II）中，Ar ³表示二價芳香族雜環基。 In formula (II), Ar ³ represents a divalent aromatic heterocyclic group.

[化5]

[chemical 5]

式（Z-1）～式（Z-7）中，R表示：氫原子、鹵素原子、可具有取代基的烷基、可具有取代基的環烷基、可具有取代基的烯基、可具有取代基的環烯基、可具有取代基的炔基、可具有取代基的環炔基、可具有取代基的芳基、可具有取代基的烷基氧基、可具有取代基的環烷基氧基、可具有取代基的芳氧基、可具有取代基的烷硫基、可具有取代基的環烷硫基、可具有取代基的芳硫基、可具有取代基的一價雜環基、可具有取代基的取代胺基、可具有取代基的亞胺殘基、可具有取代基的醯胺基、可具有取代基的醯亞胺基、可具有取代基的取代氧基羰基、氰基、硝基、 -C(=O)-R ^c所表示的基、或 -SO ₂-R ^d所表示的基， R ^c及R ^d分別獨立地表示：氫原子、可具有取代基的烷基、可具有取代基的環烷基、可具有取代基的芳基、可具有取代基的烷基氧基、可具有取代基的環烷基氧基、可具有取代基的芳氧基、或可具有取代基的一價雜環基。 In formulas (Z-1) to (Z-7), R represents: a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an alkenyl group that may have a substituent, an optional Cycloalkenyl group which may have substituent, alkynyl group which may have substituent, cycloalkynyl group which may have substituent, aryl group which may have substituent, alkyloxy group which may have substituent, cycloalkane group which may have substituent An oxy group, an aryloxy group that may have a substituent, an alkylthio group that may have a substituent, a cycloalkylthio group that may have a substituent, an arylthio group that may have a substituent, a monovalent heterocyclic ring that may have a substituent A group, a substituted amino group that may have a substituent, an imine residue that may have a substituent, an amido group that may have a substituent, an imide group that may have a substituent, a substituted oxycarbonyl group that may have a substituent, A cyano group, a nitro group, a group represented by -C(=O)-R ^c , or a group represented by -SO ₂ -R ^d , R ^c and R ^d each independently represent a hydrogen atom, a group that may have a substituent Alkyl group, cycloalkyl group which may have substituent, aryl group which may have substituent, alkyloxy group which may have substituent, cycloalkyloxy group which may have substituent, aryloxy group which may have substituent, Or a monovalent heterocyclic group which may have a substituent.

式（Z-1）～式（Z-7）中，於存在兩個R時，存在兩個的R可相同亦可不同。In the formula (Z-1) to the formula (Z-7), when there are two Rs, the two Rs may be the same or different.

式（Z-1）～式（Z-7）中的R較佳為氫原子、烷基或芳基，更佳為氫原子或烷基，進而佳為氫原子或碳原子數1～40的烷基，更佳為氫原子或碳原子數1～30的烷基，特佳為氫原子或碳原子數1～20的烷基。該些基可具有取代基。於存在多個R時，存在多個的R彼此可相同亦可不同。R in formula (Z-1) to formula (Z-7) is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or a carbon number of 1 to 40 The alkyl group is more preferably a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. These groups may have a substituent. When a plurality of R exists, the plurality of R may be the same as or different from each other.

式（I）所表示的構成單元較佳為下述式（I-1）所表示的構成單元。The structural unit represented by formula (I) is preferably a structural unit represented by the following formula (I-1).

[化6]

[chemical 6]

式（I-1）中，Z表示與前述相同的含義。In formula (I-1), Z represents the same meaning as above.

作為式（I-1）所表示的構成單元的例子，可列舉下述式（501）～式（505）所表示的構成單元。Examples of the structural unit represented by formula (I-1) include structural units represented by the following formula (501) to formula (505).

[化7]

[chemical 7]

所述式（501）～式（505）中，R表示與前述相同的含義。於存在兩個R時，兩個R彼此可相同亦可不同。In the formula (501) to formula (505), R represents the same meaning as above. When there are two Rs, the two Rs may be the same or different from each other.

所述式（II）中，Ar ³所表示的二價芳香族雜環基的碳原子數通常為2～60，較佳為4～60，更佳為4～20。Ar ³所表示的二價芳香族雜環基可具有取代基。作為Ar ³所表示的二價芳香族雜環基可具有的取代基的例子，可列舉：鹵素原子、烷基、芳基、烷氧基、芳氧基、烷硫基、芳硫基、一價雜環基、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、氰基及硝基。 In the formula (II), the number of carbon atoms in the divalent aromatic heterocyclic group represented by Ar ³ is usually 2-60, preferably 4-60, more preferably 4-20. The divalent aromatic heterocyclic group represented by Ar ³ may have a substituent. Examples ^of substituents that the divalent aromatic heterocyclic group represented by Ar may include: a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a valent heterocyclic group, substituted amine group, acyl group, imine residue, amide group, imide group, substituted oxycarbonyl group, alkenyl group, alkynyl group, cyano group and nitro group.

作為Ar ³所表示的二價芳香族雜環基的例子，可列舉下述式（101）～式（190）所表示的基。 Examples of the divalent aromatic heterocyclic group represented by Ar ³ include groups represented by the following formula (101) to formula (190).

[化8]

[chemical 8]

[化9]

[chemical 9]

[化10]

[chemical 10]

[化11]

[chemical 11]

式（101）～式（190）中，R表示與前述相同的含義。於存在多個R時，多個R彼此可相同亦可不同。In Formula (101) to Formula (190), R represents the same meaning as above. When a plurality of R exists, the plurality of R may be the same as or different from each other.

作為所述式（II）所表示的構成單元，較佳為下述式（II-1）～式（II-6）所表示的構成單元。As a structural unit represented by the said formula (II), the structural unit represented by following formula (II-1) - a formula (II-6) is preferable.

[化12]

[chemical 12]

式（II-1）～式（II-6）中，X ¹及X ²分別獨立地表示氧原子或硫原子，R表示與前述相同的含義。於存在多個R時，多個R彼此可相同亦可不同。 In formulas (II-1) to (II-6), X ¹ and X ² each independently represent an oxygen atom or a sulfur atom, and R represents the same meaning as above. When a plurality of R exists, the plurality of R may be the same as or different from each other.

就原料化合物的獲取性的觀點而言，式（II-1）～式（II-6）中的X ¹及X ²均較佳為硫原子。 From the viewpoint of availability of raw material compounds, both X ¹ and X ² in formulas (II-1) to (II-6) are preferably sulfur atoms.

作為p型半導體材料的高分子化合物可包含兩種以上的式（I）的構成單元，亦可包含兩種以上的式（II）的構成單元。The polymer compound as a p-type semiconductor material may contain two or more structural units of the formula (I), and may contain two or more structural units of the formula (II).

就提高相對於溶劑的溶解性的觀點而言，作為p型半導體材料的高分子化合物亦可包含下述式（III）所表示的構成單元。From the viewpoint of improving solubility in a solvent, the polymer compound as a p-type semiconductor material may contain a structural unit represented by the following formula (III).

[化13]

[chemical 13]

式（III）中，Ar ⁴表示伸芳基。 In formula (III), Ar ⁴ represents an arylylene group.

Ar ⁴所表示的伸芳基是指自可具有取代基的芳香族烴除去兩個氫原子後殘留的原子團。芳香族烴中亦包括具有縮合環的化合物、選自由獨立的苯環及縮合環所組成的群組中的兩個以上直接或經由伸乙烯基等二價基鍵結而成的化合物。 The aryl group represented by Ar ⁴ refers to an atomic group remaining after removing two hydrogen atoms from an aromatic hydrocarbon which may have a substituent. 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 via divalent groups such as vinylene groups.

作為芳香族烴可具有的取代基的例子，可列舉與作為雜環式化合物可具有的取代基而列舉的所述例同樣的取代基。Examples of the substituent that the aromatic hydrocarbon may have include the same substituents as those mentioned above as the substituent that the heterocyclic compound may have.

伸芳基中的除取代基以外的部分的碳原子數通常為6～60，較佳為6～20。含取代基在內的伸芳基的碳原子數通常為6～100。The number of carbon atoms in the part other than the substituent in the arylen group is usually 6-60, preferably 6-20. The number of carbon atoms in the aryl group including substituents is usually 6-100.

作為伸芳基的例子，可列舉：伸苯基（例如，下述式1～式3）、萘-二基（例如，下述式4～式13）、蒽-二基（例如，下述式14～式19）、聯苯-二基（例如，下述式20～式25）、聯三苯-二基（例如，下述式26～式28）、縮合環化合物基（例如，下述式29～式35）、芴-二基（例如，下述式36～式38）、及苯並芴-二基（例如，下述式39～式46）。Examples of aryl groups include: phenylene groups (for example, the following formulas 1 to 3), naphthalene-diyl groups (for example, the following formula 4 to formula 13), anthracene-diyl groups (for example, the following formulas Formula 14 to Formula 19), biphenyl-diyl group (for example, the following formula 20 to formula 25), terphenyl-diyl group (for example, the following formula 26 to formula 28), condensed ring compound group (for example, the following formula Formula 29 to Formula 35), fluorene-diyl groups (eg, Formula 36 to Formula 38 below), and benzofluorene-diyl groups (eg, Formula 39 to Formula 46 below).

[化14]

[chemical 14]

[化15]

[chemical 15]

[化16]

[chemical 16]

[化17]

[chemical 17]

[化18]

[chemical 18]

[化19]

[chemical 19]

[化20]

[chemical 20]

[化21]

[chem 21]

式1～式46中，R與前述為相同含義。於存在多個R時，存在多個的R彼此可相同亦可不同。In Formula 1 to Formula 46, R has the same meaning as above. When a plurality of R exists, the plurality of R may be the same as or different from each other.

於作為p型半導體材料的高分子化合物包含式（I）所表示的構成單元及/或式（II）所表示的構成單元的情況下，當將高分子化合物所包含的所有構成單元的量設為100莫耳%時，式（I）所表示的構成單元與式（II）所表示的構成單元的合計量通常為20莫耳%～100莫耳%，出於提高作為p型半導體材料的電荷傳輸性的原因，較佳為40莫耳%～100莫耳%，更佳為50莫耳%～100莫耳%。In the case where a polymer compound as a p-type semiconductor material includes a structural unit represented by formula (I) and/or a structural unit represented by formula (II), when the amount of all the structural units contained in the polymer compound is set to When it is 100 mol%, the total amount of the structural unit represented by the formula (I) and the structural unit represented by the formula (II) is usually 20 mol% to 100 mol%, in order to improve the p-type semiconductor material It is preferably 40 mol % to 100 mol %, more preferably 50 mol % to 100 mol % due to charge transportability.

作為p型半導體材料的高分子化合物的較佳具體例可列舉下述式P-1～式P-10所表示的高分子化合物。Preferable specific examples of the polymer compound as a p-type semiconductor material include polymer compounds represented by the following formulas P-1 to P-10.

[化22]

[chem 22]

[化23]

[chem 23]

[化24]

[chem 24]

[化25]

[chem 25]

於本實施方式的油墨組成物中，p型半導體材料包含z平均分子量小於5.0×10 ⁵的高分子化合物。 In the ink composition of this embodiment, the p-type semiconductor material includes a polymer compound with a z-average molecular weight of less than 5.0×10 ⁵ .

於本實施方式的油墨組成物中，就提高光電轉換效率的觀點、更具體而言例如使外部量子效率（External Quantum Efficiency，EQE）成為較佳為50%以上的觀點而言，p型半導體材料較佳為包含重量平均分子量大於6.0×10 ⁴的高分子化合物，就兼顧光電轉換效率與過濾性的觀點而言，更佳為包含z平均分子量小於5.0×10 ⁵、且重量平均分子量大於6.0×10 ⁴的高分子化合物。 In the ink composition of this embodiment, from the viewpoint of improving the photoelectric conversion efficiency, more specifically, for example, from the viewpoint of making the external quantum efficiency (External Quantum Efficiency, EQE) preferably 50% or more, the p-type semiconductor material Preferably, it contains a polymer compound with a weight average molecular weight of more than 6.0×10 ⁴ , and more preferably contains a z average molecular weight of less than 5.0×10 ⁵ and a weight average molecular weight of more than 6.0× 10 ⁴ polymer compounds.

於本實施方式的油墨組成物中，就使外部量子效率成為較佳為50%以上的觀點而言，p型半導體材料的z平均分子量（Mz）較佳為大於1.5×10 ⁵。 In the ink composition of the present embodiment, the z-average molecular weight (Mz) of the p-type semiconductor material is preferably greater than 1.5×10 ⁵ from the viewpoint of making the external quantum efficiency preferably 50% or more.

另外，於本實施方式的油墨組成物中，作為p型半導體材料的高分子化合物的重量平均分子量通常為1×10 ³～5×10 ⁵，就提高於溶劑中的溶解性的觀點而言，較佳為1×10 ³～3×10 ⁵。 In addition, in the ink composition of the present embodiment, the weight-average molecular weight of the polymer compound as a p-type semiconductor material is usually 1×10 ³ to 5×10 ⁵ , and from the viewpoint of improving solubility in a solvent, Preferably it is 1×10 ³ to 3×10 ⁵ .

於本實施方式中，z平均分子量（Mz）及重量平均分子量（Mw）是可藉由使用先前公知的任意較佳的裝置而實施的凝膠滲透層析法（Gel Permeation Chromatography，GPC）來測定的、聚苯乙烯換算的平均分子量。In this embodiment, z-average molecular weight (Mz) and weight-average molecular weight (Mw) can be measured by gel permeation chromatography (Gel Permeation Chromatography, GPC) using any previously known preferred device The average molecular weight in terms of polystyrene.

本實施方式的油墨組成物可包含僅一種作為p型半導體材料的化合物（高分子化合物），亦可以任意的組合的形式包含兩種以上。The ink composition of the present embodiment may contain only one compound (polymer compound) as a p-type semiconductor material, or may contain two or more compounds in any combination.

此處，z平均分子量（Mz）是將分子量的平方用作權重的加權平均分子量，且是具有與重量平均分子量（Mw）相比更容易受到高分子量的分子存在的影響的傾向的參數。Here, the z-average molecular weight (Mz) is a weighted average molecular weight using the square of the molecular weight as a weight, and is a parameter that tends to be more easily affected by the presence of molecules with a higher molecular weight than the weight-average molecular weight (Mw).

於本實施方式中，作為高分子化合物的p型半導體材料的z平均分子量（Mz）可藉由將該高分子化合物的合成步驟中的條件設為規定條件而調節至所述較佳範圍內。In the present embodiment, the z-average molecular weight (Mz) of the p-type semiconductor material which is a polymer compound can be adjusted within the above-mentioned preferable range by setting the conditions in the synthesis steps of the polymer compound to predetermined conditions.

具體而言，例如，於上述例示的高分子化合物的合成步驟中，可藉由適宜調整作為原料的多種單體的投入組成（混合比）、適宜調整所使用的觸媒量、適宜調整反應溶液的濃度等，將z平均分子量（Mz）調節至上述較佳範圍內。更具體而言，例如參考「網絡聚合物（Network Polymer）、2009、30、261中記載的概要」等來適宜調節z平均分子量（Mz）即可。Specifically, for example, in the synthesis steps of the above-mentioned exemplified polymer compounds, by appropriately adjusting the input composition (mixing ratio) of various monomers as raw materials, appropriately adjusting the amount of catalyst used, and appropriately adjusting the reaction solution concentration, etc., adjust the z-average molecular weight (Mz) to the above-mentioned preferred range. More specifically, the z-average molecular weight (Mz) may be appropriately adjusted with reference to, for example, the summary described in "Network Polymer (Network Polymer), 2009, 30, 261".

根據使用z平均分子量（Mz）如已說明般的p型半導體材料的本實施方式的油墨組成物，無需進行反覆試驗，便可於製造步驟中在不會使過濾器堵塞的情況下更切實地進行過濾，且不易產生絕緣、短路等電性缺陷，進而，可使油墨組成物的製造效率、進而使光電轉換元件的製造效率進一步提高。According to the ink composition of the present embodiment using the p-type semiconductor material having the z-average molecular weight (Mz) as already described, it is possible to more reliably perform the process without clogging the filter in the manufacturing process without trial and error. Filtration is performed, and electrical defects such as insulation and short circuit are less likely to occur, and further, the production efficiency of the ink composition, and furthermore, the production efficiency of the photoelectric conversion element can be further improved.

（2）n型半導體材料本實施方式的油墨組成物可包含的n型半導體材料可為低分子化合物，亦可為高分子化合物。 (2) n-type semiconductor material The n-type semiconductor material that may be included in the ink composition of this embodiment may be a low-molecular compound or a high-molecular compound.

關於作為低分子化合物的n型半導體材料（受電子性化合物）的例子，可列舉：噁二唑衍生物、蒽醌二甲烷及其衍生物、苯醌及其衍生物、萘醌及其衍生物、蒽醌及其衍生物、四氰基蒽醌二甲烷及其衍生物、芴酮衍生物、二苯基二氰基乙烯及其衍生物、聯苯醌衍生物、8-羥基喹啉及其衍生物的金屬錯合物、C ₆₀富勒烯等的富勒烯及其衍生物即富勒烯衍生物（以下，有時稱為富勒烯化合物。）以及2,9-二甲基-4,7-聯苯-1,10-啡啉等菲衍生物。 Examples of n-type semiconductor materials (electron-accepting compounds) that are low-molecular compounds include: oxadiazole derivatives, anthraquinone dimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives , anthraquinone and its derivatives, tetracyanoanthraquinone dimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, 8-hydroxyquinoline and its derivatives Metal complexes of derivatives, fullerenes such as C ₆₀ fullerenes and their derivatives, fullerene derivatives (hereinafter sometimes referred to as fullerene compounds.) and 2,9-dimethyl- 4,7-biphenyl-1,10-phenanthrene derivatives such as phenanthrene.

關於作為高分子化合物的n型半導體材料的例子，可列舉：聚乙烯基咔唑及其衍生物、聚矽烷及其衍生物、於側鏈或主鏈中具有芳香族胺結構的聚矽氧烷衍生物、聚苯胺及其衍生物、聚噻吩及其衍生物、聚吡咯及其衍生物、聚苯乙炔及其衍生物、聚伸噻吩乙炔及其衍生物、聚喹啉及其衍生物、聚喹噁啉及其衍生物以及聚芴及其衍生物。Examples of n-type semiconductor materials as polymer compounds include: polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane having an aromatic amine structure in the side chain or main chain Derivatives, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienyl acetylene and its derivatives, polyquinoline and its derivatives, Quinoxaline and its derivatives and polyfluorene and its derivatives.

作為n型半導體材料，較佳為選自富勒烯及富勒烯衍生物中的一種以上，更佳為富勒烯衍生物。The n-type semiconductor material is preferably one or more selected from fullerenes and fullerene derivatives, more preferably fullerene derivatives.

作為富勒烯的例子，可列舉：C ₆₀富勒烯、C ₇₀富勒烯、C ₇₆富勒烯、C ₇₈富勒烯及C ₈₄富勒烯。作為富勒烯衍生物的例子，可列舉該些富勒烯的衍生物。富勒烯衍生物是指富勒烯的至少一部分經修飾的化合物。 Examples of fullerenes include _C60 fullerene, _C70 fullerene, _C76 fullerene, _C78 fullerene, and _C84 fullerene. Examples of fullerene derivatives include these fullerene derivatives. The fullerene derivative refers to a compound in which at least a part of fullerene has been modified.

作為富勒烯衍生物的例子，可列舉下述式所表示的化合物。As an example of a fullerene derivative, the compound represented by the following formula is mentioned.

[化26]

[chem 26]

式中， R ^a表示烷基、芳基、一價雜環基或具有酯結構的基。存在多個的R ^a彼此可相同亦可不同。 In the formula, R ^a represents an alkyl group, an aryl group, a monovalent heterocyclic group or a group having an ester structure. A plurality of R ^a may be the same or different from each other.

R ^b表示烷基或芳基。存在多個的R ^b彼此可相同亦可不同。 R ^b represents an alkyl group or an aryl group. Plural R ^b may be the same or different from each other.

作為R ^a所表示的具有酯結構的基的例子，可列舉下述式所表示的基。 As an example of the group which has an ester structure represented by R ^a , the group represented by the following formula is mentioned.

[化27]

[chem 27]

式中，u1表示1～6的整數。u2表示0～6的整數。R ^e表示烷基、芳基或一價雜環基。 In the formula, u1 represents an integer of 1-6. u2 represents an integer of 0-6. R ^e represents an alkyl group, an aryl group or a monovalent heterocyclic group.

作為C ₆₀富勒烯衍生物的例子，可列舉下述的化合物。 Examples of _C60 fullerene derivatives include the following compounds.

[化28]

[chem 28]

作為C ₇₀富勒烯衍生物的例子，可列舉下述的化合物。 Examples of _C70 fullerene derivatives include the following compounds.

[化29]

[chem 29]

作為富勒烯衍生物的具體例，可列舉：[6,6]-苯基-C61丁酸甲酯（C60PCBM、[6,6]-Phenyl C61 butyric acid methyl ester）、[6,6]-苯基-C71丁酸甲酯（C70PCBM、[6,6]-Phenyl C71 butyric acid methyl ester）、[6,6]-苯基-C85丁酸甲酯（C84PCBM、[6,6]-Phenyl C85 butyric acid methyl ester）、及[6,6]-噻吩基-C61丁酸甲酯（[6,6]-Thienyl C61 butyric acid methyl ester）。Specific examples of fullerene derivatives include [6,6]-phenyl-C61 butyric acid methyl ester (C60PCBM, [6,6]-Phenyl C61 butyric acid methyl ester), [6,6]- Phenyl-C71 butyric acid methyl ester (C70PCBM, [6,6]-Phenyl C71 butyric acid methyl ester), [6,6]-phenyl-C85 butyric acid methyl ester (C84PCBM, [6,6]-Phenyl C85 butyric acid methyl ester), and [6,6]-thienyl-C61 butyric acid methyl ester ([6,6]-Thienyl C61 butyric acid methyl ester).

本實施方式的油墨組成物中可包含的n型半導體材料中包含並非富勒烯化合物的化合物。於本說明書中，將並非富勒烯化合物的n型半導體材料稱為「非富勒烯化合物」。作為非富勒烯化合物，多種化合物是公知的，可於本實施方式中使用先前公知的任意較佳非富勒烯化合物作為n型半導體材料。The n-type semiconductor material that can be included in the ink composition of this embodiment includes a compound other than a fullerene compound. In this specification, an n-type semiconductor material that is not a fullerene compound is called a "non-fullerene compound". Various non-fullerene compounds are known, and any previously known non-fullerene compound may be used as an n-type semiconductor material in this embodiment mode.

本實施方式的油墨組成物可包含僅一種作為n型半導體材料的化合物，亦可包含多種。The ink composition of this embodiment may contain only one kind of compound as an n-type semiconductor material, or may contain multiple kinds thereof.

於本實施方式中，作為n型半導體材料的非富勒烯化合物較佳為包含苝四羧酸二醯亞胺結構的化合物。關於作為非富勒烯化合物的包含苝四羧酸二醯亞胺結構的化合物的例子，可列舉下述式所表示的化合物。In this embodiment, the non-fullerene compound as the n-type semiconductor material is preferably a compound containing a diimide structure of perylenetetracarboxylate. As an example of the compound containing the perylene tetracarboxylic acid diimide structure which is a non-fullerene compound, the compound represented by the following formula is mentioned.

[化30]

[chem 30]

[化31]

[chem 31]

[化32]

[chem 32]

[化33]

[chem 33]

式中，R如所述定義般。存在多個的R彼此可相同亦可不同。In the formula, R is as defined above. Plural R may be the same or different from each other.

於本實施方式中，n型半導體材料較佳為包含下述式（V）所表示的化合物。下述式（V）所表示的化合物是包含苝四羧酸二醯亞胺結構的非富勒烯化合物。In this embodiment, the n-type semiconductor material preferably includes a compound represented by the following formula (V). The compound represented by the following formula (V) is a non-fullerene compound containing a perylenetetracarboxylic diimide structure.

[化34]

[chem 34]

所述式（V）中，R ¹表示氫原子、鹵素原子、可具有取代基的烷基、可具有取代基的環烷基、可具有取代基的烷基氧基、可具有取代基的環烷基氧基、可具有取代基的芳基、或可具有取代基的一價芳香族雜環基。存在多個的R ¹彼此可相同亦可不同。 In the formula (V), R represents ^a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an alkyloxy group that may have a substituent, a ring that may have a substituent An alkyloxy group, an aryl group which may have a substituent, or a monovalent aromatic heterocyclic group which may have a substituent. A plurality of R ¹ may be the same or different from each other.

較佳的是，存在多個的R ¹分別獨立地為可具有取代基的烷基。 Preferably, R ¹ present in plural are each independently an alkyl group which may have a substituent.

R ²表示氫原子、鹵素原子、可具有取代基的烷基、可具有取代基的環烷基、可具有取代基的烷基氧基、可具有取代基的環烷基氧基、可具有取代基的芳基、或可具有取代基的一價芳香族雜環基。存在多個的R ²可相同亦可不同。 R ² represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, or a cycloalkyloxy group which may have a substituent aryl group, or a monovalent aromatic heterocyclic group which may have a substituent. Plural R ² may be the same or different.

作為式（V）所表示的化合物的較佳例，可列舉下述式所表示的化合物。Preferable examples of the compound represented by formula (V) include compounds represented by the following formula.

[化35]

[chem 35]

於本實施方式中，n型半導體材料較佳為包含下述式（VI）所表示的化合物。In this embodiment, the n-type semiconductor material preferably includes a compound represented by the following formula (VI).

A ¹-B ¹⁰-A ²（VI） A ¹ -B ¹⁰ -A ² (VI)

式（VI）中， A ¹及A ²分別獨立地表示拉電子性基，B ¹⁰表示包含π共軛系的基。 In formula (VI), A ¹ and A ² each independently represent an electron-withdrawing group, and B ¹⁰ represents a group including a π-conjugated system.

關於作為A ¹及A ²的拉電子性基的例子，可列舉-CH=C(-CN) ₂所表示的基、及下述式（a-1）～式（a-9）所表示的基。 Examples of electron-withdrawing groups as A ¹ and A ² include groups represented by -CH=C(-CN) ₂ and groups represented by the following formulas (a-1) to (a-9). base.

[化36]

[chem 36]

式（a-1）～式（a-7）中， T表示可具有取代基的碳環、或可具有取代基的雜環。碳環及雜環可為單環，亦可為縮合環。於該些環具有多個取代基的情況下，存在多個的取代基可相同亦可不同。 In formula (a-1) ~ formula (a-7), T represents a carbocyclic ring which may have a substituent, or a heterocyclic ring which may have a substituent. Carbocyclic and heterocyclic rings may be monocyclic or condensed rings. When these rings have a plurality of substituents, the plurality of substituents may be the same or different.

關於作為T的可具有取代基的碳環的例子，可列舉芳香族碳環。作為T的可具有取代基的碳環較佳為芳香族碳環。關於作為T的可具有取代基的碳環的具體例，可列舉：苯環、萘環、蒽環、稠四苯環、稠五苯環、芘環及菲環，較佳為苯環、萘環及菲環，更佳為苯環及萘環，進而佳為苯環。該些環可具有取代基。Examples of the carbocycle that may have a substituent as T include an aromatic carbocycle. The carbocycle which may have a substituent as T is preferably an aromatic carbocycle. Specific examples of carbocycles that may have substituents as T include: benzene ring, naphthalene ring, anthracene ring, condensed tetraphenyl ring, condensed pentaphenyl ring, pyrene ring, and phenanthrene ring, preferably benzene ring, naphthalene ring ring and phenanthrene ring, more preferably benzene ring and naphthalene ring, still more preferably benzene ring. These rings may have a substituent.

關於作為T的可具有取代基的雜環的例子，可列舉芳香族雜環，較佳為芳香族雜環。關於作為T的可具有取代基的雜環的具體例，可列舉：吡啶環、噠嗪環、嘧啶環、吡嗪環、吡咯環、呋喃環、噻吩環、咪唑環、噁唑環、噻唑環及噻吩並噻吩環，較佳為噻吩環、吡啶環、吡嗪環、噻唑環及噻吩並噻吩環，更佳為噻吩環。該些環可具有取代基。Examples of the heterocyclic ring which may have a substituent as T include an aromatic heterocyclic ring, preferably an aromatic heterocyclic ring. Specific examples of heterocyclic rings that may have substituents as T include pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, pyrrole rings, furan rings, thiophene rings, imidazole rings, oxazole rings, and thiazole rings. and a thienothiophene ring, preferably a thiophene ring, a pyridine ring, a pyrazine ring, a thiazole ring and a thienothiophene ring, more preferably a thiophene ring. These rings may have a substituent.

關於作為T的碳環或雜環可具有的取代基的例子，可列舉鹵素原子、烷基、烷基氧基、芳基及一價雜環基，較佳為氟原子及/或碳原子數1～6的烷基。Examples of substituents that the carbocyclic or heterocyclic ring as T may have include halogen atoms, alkyl groups, alkyloxy groups, aryl groups, and monovalent heterocyclic groups, preferably fluorine atoms and/or carbon atoms 1 to 6 alkyl groups.

X ⁴、X ⁵及X ⁶分別獨立地表示氧原子、硫原子、亞烷基或=C(-CN) ₂所表示的基，較佳為氧原子、硫原子或=C(-CN) ₂所表示的基。 X ⁴ , X ⁵ and X ⁶ independently represent an oxygen atom, a sulfur atom, an alkylene group or a group represented by =C(-CN) ₂ , preferably an oxygen atom, a sulfur atom or =C(-CN) ₂ The base represented.

X ⁷表示氫原子、鹵素原子、氰基、可具有取代基的烷基、可具有取代基的烷基氧基、可具有取代基的芳基或一價雜環基。 ^X7 represents a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted alkyloxy group, an optionally substituted aryl group, or a monovalent heterocyclic group.

R ^a1、R ^a2、R ^a3、R ^a4及R ^a5分別獨立地表示氫原子、可具有取代基的烷基、鹵素原子、可具有取代基的烷基氧基、可具有取代基的芳基或一價雜環基，較佳為可具有取代基的烷基或可具有取代基的芳基。 R ^a1 , R ^a2 , R ^a3 , R ^a4 and R ^a5 each independently represent a hydrogen atom, an optionally substituted alkyl group, a halogen atom, an optionally substituted alkyloxy group, an optionally substituted aryl group, or The monovalent heterocyclic group is preferably an alkyl group which may have a substituent or an aryl group which may have a substituent.

[化37]

[chem 37]

式（a-8）及式（a-9）中，R ^a6及R ^a7分別獨立地表示氫原子、鹵素原子、可具有取代基的烷基、可具有取代基的環烷基、可具有取代基的烷基氧基、可具有取代基的環烷基氧基、可具有取代基的一價芳香族碳環基或可具有取代基的一價芳香族雜環基，存在多個的R ^a6及R ^a7可相同亦可不同。 In formula (a-8) and formula (a-9), R ^a6 and R ^a7 independently represent a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, or a cycloalkyl group that may have a substituent An alkyloxy group, a cycloalkyloxy group that may have a substituent, a monovalent aromatic carbocyclic group that may have a substituent, or a monovalent aromatic heterocyclic group that may have a substituent, there are multiple R ^a6 and R ^a7 may be the same or different.

關於作為A ¹及A ²的拉電子性基，較佳為下述的式（a-1-1）～式（a-1-4）以及式（a-6-1）及式（a-7-1）中的任一者所表示的基，更佳為式（a-1-1）所表示的基。此處，存在多個的R ^a10分別獨立地表示氫原子或取代基，較佳為表示氫原子、鹵素原子、氰基或可具有取代基的烷基。R ^a3、R ^a4及R ^a5分別獨立地與前述為相同含義，且較佳為分別獨立地表示可具有取代基的烷基或可具有取代基的芳基。 Regarding the electron ^- withdrawing groups as A1 and A2, the following formulas (a- ^1-1 ) to (a-1-4) and formula (a-6-1) and formula (a- The group represented by any one of 7-1) is more preferably a group represented by formula (a-1-1). Here, R ^a10 present in plurality each independently represents a hydrogen atom or a substituent, and preferably represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R ^a3 , R ^a4 , and R ^a5 each independently have the same meaning as above, and each independently preferably represents an alkyl group that may have a substituent or an aryl group that may have a substituent.

[化38]

[chem 38]

關於作為B ¹⁰的包含π共軛系的基的例子，可列舉後述的式（VII）所表示的化合物中的-(S ¹) _n1-B ¹¹-(S ²) _n2-所表示的基。 Examples of the group including a π-conjugated system as B ¹⁰ include a group represented by -(S ¹ ) _n1 -B ¹¹ -(S ² ) _n2 - in a compound represented by formula (VII) described later.

於本實施方式中，n型半導體材料較佳為下述式（VII）所表示的化合物。 A ¹-(S ¹) _n1-B ¹¹-(S ²) _n2-A ²（VII） In this embodiment, the n-type semiconductor material is preferably a compound represented by the following formula (VII). A ¹ -(S ¹ ) _n1 -B ¹¹ -(S ² ) _n2 -A ² (VII)

式（VII）中，A ¹及A ²分別獨立地表示拉電子性基。A ¹及A ²的例子及較佳例與關於所述式（VI）中的A ¹及A ²加以說明的例子及較佳例相同。 In formula (VII), A ¹ and A ² each independently represent an electron-withdrawing group. Examples and preferred examples ^of A1 and ^A2 are the same as those described for A1 and A2 in the ^formula (VI ⁾ .

S ¹及S ²分別獨立地表示可具有取代基的二價碳環基、可具有取代基的二價雜環基、-C(R ^s1)=C(R ^s2)-所表示的基（此處，R ^s1及R ^s2分別獨立地表示氫原子、或取代基（較佳為氫原子、鹵素原子、可具有取代基的烷基、或可具有取代基的一價雜環基。））、或-C≡C-所表示的基。 S ¹ and S ² each independently represent a divalent carbocyclic group that may have a substituent, a divalent heterocyclic group that may have a substituent, a group represented by -C(R ^s1 )=C(R ^s2 )- (here , R ^s1 and R ^s2 independently represent a hydrogen atom or a substituent (preferably a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, or a monovalent heterocyclic group that may have a substituent.)), or a group represented by -C≡C-.

由S ¹及S ²表示的、可具有取代基的二價碳環基及可具有取代基的二價雜環基可為縮合環。於二價碳環基或二價雜環基具有多個取代基的情況下，存在多個的取代基可相同亦可不同。 ^The divalent carbocyclic group which may have a substituent and the divalent heterocyclic group which may have a substituent represented by S1 and S2 may be ^a condensed ring. When a divalent carbocyclic group or a divalent heterocyclic group has a plurality of substituents, the substituents present in a plurality may be the same or different.

式（VII）中，n1及n2分別獨立地表示0以上的整數，較佳為分別獨立地表示0或1，更佳為均表示0或1。In formula (VII), n1 and n2 each independently represent an integer of 0 or more, preferably each independently represent 0 or 1, and more preferably both represent 0 or 1.

作為二價碳環基的例子，可列舉二價芳香族碳環基。Examples of the divalent carbocyclic group include a divalent aromatic carbocyclic group.

作為二價雜環基的例子，可列舉二價芳香族雜環基。Examples of the divalent heterocyclic group include a divalent aromatic heterocyclic group.

於二價芳香族碳環基或二價芳香族雜環基為縮合環的情況下，構成縮合環的環的全部可為具有芳香族性的縮合環，亦可僅一部分為具有芳香族性的縮合環。When the divalent aromatic carbocyclic group or the divalent aromatic heterocyclic group is a condensed ring, all of the rings constituting the condensed ring may be aromatic condensed rings, or only part of them may be aromatic. Condensation ring.

作為S ¹及S ²的例子，可列舉作為已說明的Ar ³所表示的二價芳香族雜環基的例子而列舉的、式（101）～式（190）中的任一者所表示的基、及該些基中的氫原子被取代基取代而成的基。 As examples of S ¹ and S ² , those represented by any one of formula (101) to formula (190) listed as examples of the divalent aromatic heterocyclic group represented by Ar ³ described above can be mentioned. groups, and groups in which hydrogen atoms in these groups are replaced by substituents.

S ¹及S ²較佳為分別獨立地表示下述式（s-1）或式（s-2）所表示的基。 S ¹ and S ² preferably each independently represent a group represented by the following formula (s-1) or formula (s-2).

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式（s-1）及式（s-2）中， X ³表示氧原子或硫原子。 In formula (s-1) and formula (s-2), X ³ represents an oxygen atom or a sulfur atom.

R ^a10如所述定義般。 R ^a10 is as defined above.

S ¹及S ²較佳為分別獨立地為式（142）、式（148）、或者式（184）所表示的基、或該些基中的氫原子被取代基取代而成的基，更佳為所述式（142）或者式（184）所表示的基、或式（184）所表示的基中的一個氫原子被烷基氧基取代而成的基。 S ¹ and S ² are preferably each independently a group represented by formula (142), formula (148), or formula (184), or a group in which hydrogen atoms in these groups are replaced by substituents, more Preferably, it is a group represented by the above-mentioned formula (142) or formula (184), or a group in which one hydrogen atom in the group represented by the formula (184) is replaced by an alkyloxy group.

B ¹¹為選自由碳環結構及雜環結構所組成的群組中的兩個以上的結構的縮合環基，並且表示不含鄰-迫位縮合結構且可具有取代基的縮合環基。 B ¹¹ is a condensed ring group of two or more structures selected from the group consisting of a carbocyclic structure and a heterocyclic structure, and represents a condensed ring group that does not contain an ortho-peri condensation structure and may have a substituent.

B ¹¹所表示的縮合環基亦可包含將彼此相同的兩個以上的結構縮合而成的結構。 The condensed ring group represented by B ¹¹ may include a structure obtained by condensing two or more structures that are the same as each other.

於B ¹¹所表示的縮合環基具有多個取代基的情況下，存在多個的取代基可相同亦可不同。 When the condensed ring group represented by B ¹¹ has a plurality of substituents, the plurality of substituents may be the same or different.

作為可構成由B ¹¹表示的縮合環基的碳環結構的例子，可列舉下述式（Cy1）或式（Cy2）所表示的環結構。 Examples of carbocyclic structures that can constitute the condensed ring group represented by B ¹¹ include ring structures represented by the following formula (Cy1) or formula (Cy2).

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作為可構成由B ¹¹表示的縮合環基的雜環結構的例子，可列舉下述式（Cy3）～式（Cy10）中的任一者所表示的環結構。 Examples of the heterocyclic structure that can constitute the condensed ring group represented by B ¹¹ include a ring structure represented by any one of the following formula (Cy3) to formula (Cy10).

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式（VII）中，B ¹¹較佳為選自由所述式（Cy1）～式（Cy10）所表示的結構所組成的群組中的兩個以上的結構的縮合環基，並且為不含鄰-迫位縮合結構且可具有取代基的縮合環基。B ¹¹亦可包含式（Cy1）～式（Cy10）所表示的結構中的兩個以上的相同結構縮合而成的結構。 In formula (VII), B ¹¹ is preferably a condensed ring group of two or more structures selected from the group consisting of structures represented by formula (Cy1) to formula (Cy10), and does not contain ortho - a condensed ring group having a peri-condensed structure and which may have a substituent. B ¹¹ may also include a structure obtained by condensing two or more identical structures among the structures represented by formula (Cy1) to formula (Cy10).

B ¹¹更佳為選自由式（Cy1）～式（Cy6）及式（Cy8）所表示的結構所組成的群組中的兩個以上的結構的縮合環基，並且為不含鄰-迫位縮合結構且可具有取代基的縮合環基。 B ¹¹ is more preferably a condensed ring group of two or more structures selected from the group consisting of structures represented by formula (Cy1) to formula (Cy6) and formula (Cy8), and does not contain an ortho-perine position A condensed ring group having a condensed structure and which may have a substituent.

作為B ¹¹的縮合環基可具有的取代基較佳為可具有取代基的烷基、可具有取代基的芳基、可具有取代基的烷基氧基及可具有取代基的一價雜環基。由B ¹¹表示的縮合環基可具有的芳基例如可經烷基取代。 The substituent that the condensed ring group of ^B11 may have is preferably an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkyloxy group that may have a substituent, and a monovalent heterocyclic ring that may have a substituent. base. The aryl group that the condensed ring group represented by B ¹¹ may have, for example, may be substituted with an alkyl group.

作為B ¹¹的縮合環基的例子可列舉：下述式（b-1）～式（b-14）所表示的基、及該些基中的氫原子被取代基（較佳為可具有取代基的烷基、可具有取代基的芳基、可具有取代基的烷基氧基或可具有取代基的一價雜環基）取代而成的基。關於作為B ¹¹的縮合環基，較佳為下述式（b-2）或式（b-3）所表示的基、或該些基中的氫原子被取代基（較佳為可具有取代基的烷基、可具有取代基的芳基、可具有取代基的烷基氧基或可具有取代基的一價雜環基）取代而成的基，更佳為下述式（b-2）或式（b-3）所表示的基。 Examples of the condensed ring group of ^B11 include groups represented by the following formulas (b-1) to (b-14), and the hydrogen atoms in these groups are substituted (preferably may have substitution A group substituted with an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, or a monovalent heterocyclic group which may have a substituent). Regarding the condensed ring group as ^B11 , it is preferably a group represented by the following formula (b-2) or formula (b-3), or a hydrogen atom in these groups is substituted (preferably may have a substitution A group substituted with an alkyl group, an aryl group that may have a substituent, an alkyloxy group that may have a substituent, or a monovalent heterocyclic group that may have a substituent), more preferably the following formula (b-2 ) or the group represented by formula (b-3).

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[chem 43]

式（b-1）～式（b-14）中， R ^a10如所述定義般。 In formula (b-1) - formula (b-14), R ^a10 is as defined above.

式（b-1）～式（b-14）中，存在多個的R ^a10分別獨立地較佳為可具有取代基的烷基、或可具有取代基的芳基。 In formulas (b-1) to (b-14), R ^a10 present in plural is each independently preferably an alkyl group which may have a substituent or an aryl group which may have a substituent.

作為式（VI）或式（VII）所表示的化合物的例子，可列舉下述式所表示的化合物。Examples of the compound represented by formula (VI) or formula (VII) include compounds represented by the following formula.

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[chem 44]

所述式中，R如所述定義般，X表示氫原子、鹵素原子、氰基或可具有取代基的烷基。In the formula, R is as defined above, and X represents a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group.

所述式中，R較佳為氫原子、可具有取代基的烷基、可具有取代基的芳基或可具有取代基的烷基氧基。In the formula, R is preferably a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkyloxy group.

作為式（VI）或式（VII）所表示的化合物，可列舉下述式所表示的化合物。Examples of the compound represented by formula (VI) or formula (VII) include compounds represented by the following formulas.

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[chem 45]

於本實施方式的油墨組成物中，n型半導體材料除了包含所述非富勒烯化合物以外，亦可進而組合包含已說明的富勒烯及富勒烯衍生物（富勒烯化合物）。In the ink composition of the present embodiment, the n-type semiconductor material may further include the above-described fullerene and fullerene derivatives (fullerene compound) in combination in addition to the non-fullerene compound.

作為本實施方式中的n型半導體材料的較佳具體例，可列舉下述式所表示的化合物。Preferable specific examples of the n-type semiconductor material in this embodiment include compounds represented by the following formulas.

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[chem 46]

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[chem 47]

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[chem 48]

（3）溶劑本實施方式的油墨組成物可包含芳香族烴作為溶劑。該芳香族烴可具有取代基。作為芳香族烴，特佳為可溶解已說明的p型半導體材料的化合物。 (3) Solvent The ink composition of this embodiment may contain an aromatic hydrocarbon as a solvent. The aromatic hydrocarbon may have a substituent. The aromatic hydrocarbon is particularly preferably a compound capable of dissolving the p-type semiconductor material already described.

作為可用作溶劑的芳香族烴，例如可列舉：甲苯、二甲苯（例如鄰二甲苯、間二甲苯、對二甲苯）、三甲基苯（例如均三甲苯、1,2,4-三甲基苯（假枯烯（pseudocumene）））、丁基苯（例如正丁基苯、第二丁基苯、第三丁基苯）、甲基萘（例如1-甲基萘）、1,2,3,4-四氫萘（四氫萘（tetralin））、二氫茚、1-氯萘、氯苯及二氯苯（1,2-二氯苯）。Examples of aromatic hydrocarbons usable as solvents include toluene, xylene (e.g. o-xylene, m-xylene, p-xylene), trimethylbenzene (e.g. mesitylene, 1,2,4-trimethylbenzene) Methylbenzene (pseudocumene), butylbenzene (e.g. n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (e.g. 1-methylnaphthalene), 1, 2,3,4-Tetralin (tetralin), indene, 1-chloronaphthalene, chlorobenzene and dichlorobenzene (1,2-dichlorobenzene).

溶劑可僅包含一種芳香族烴，亦可包含兩種以上的芳香族烴。The solvent may contain only one kind of aromatic hydrocarbon, or may contain two or more kinds of aromatic hydrocarbons.

可構成溶劑的芳香族烴較佳為選自由甲苯、鄰二甲苯、間二甲苯、對二甲苯、均三甲苯、1,2,4-三甲基苯、正丁基苯、第二丁基苯、第三丁基苯、甲基萘、四氫萘、1-氯萘、氯苯及二氯苯（1,2-二氯苯）所組成的群組中的一種以上，更佳為甲苯、鄰二甲苯、間二甲苯、對二甲苯、均三甲苯、1,2,4-三甲基苯、正丁基苯、第二丁基苯、第三丁基苯、甲基萘、四氫萘、二氫茚、1-氯萘、氯苯或二氯苯（鄰二氯苯）。Aromatic hydrocarbons that can constitute solvents are preferably selected from toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, second-butyl At least one selected from the group consisting of benzene, tert-butylbenzene, methylnaphthalene, tetrahydronaphthalene, 1-chloronaphthalene, chlorobenzene and dichlorobenzene (1,2-dichlorobenzene), more preferably toluene , o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, second-butylbenzene, third-butylbenzene, methylnaphthalene, four Hydronaphthalene, indane, 1-chloronaphthalene, chlorobenzene or dichlorobenzene (o-dichlorobenzene).

本實施方式的油墨組成物可包含鹵化烷基作為溶劑。作為可用作溶劑的鹵化烷基，例如可列舉氯仿。The ink composition of this embodiment may contain a halogenated alkyl group as a solvent. As a halogenated alkyl group usable as a solvent, chloroform is mentioned, for example.

本實施方式的油墨組成物中，作為溶劑，較佳為包含選自由甲苯、鄰二甲苯、間二甲苯、對二甲苯、均三甲苯、1,2,4-三甲基苯、正丁基苯、第二丁基苯、第三丁基苯、甲基萘、四氫萘、二氫茚、1-氯萘、氯苯或二氯苯（1,2-二氯苯）及氯仿所組成的群組中的一種以上。In the ink composition of this embodiment, as a solvent, it is preferable to contain a solvent selected from toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butyl Composed of benzene, 2-butylbenzene, 3-butylbenzene, methylnaphthalene, tetrahydronaphthalene, indene, 1-chloronaphthalene, chlorobenzene or dichlorobenzene (1,2-dichlorobenzene) and chloroform More than one of the groups of .

於本實施方式的油墨組成物中，除了使用所述溶劑以外，亦可組合使用另外的溶劑。In the ink composition of the present embodiment, other solvents may be used in combination in addition to the solvents described above.

於本實施方式中，作為另外的溶劑的例子，可列舉：芳香族羰基化合物、芳香族酯化合物及含氮雜環式化合物。In this embodiment, examples of another solvent include aromatic carbonyl compounds, aromatic ester compounds, and nitrogen-containing heterocyclic compounds.

作為芳香族羰基化合物，例如可列舉：可具有取代基的苯乙酮、可具有取代基的苯丙酮、可具有取代基的苯丁酮、可具有取代基的環己基苯酮（cyclohexyl phenone）、可具有取代基的二苯甲酮。Examples of the aromatic carbonyl compound include: acetophenone which may have a substituent, propiophenone which may have a substituent, acetophenone which may have a substituent, cyclohexyl phenone which may have a substituent (cyclohexyl phenone), Benzophenone which may have a substituent.

作為芳香族酯化合物，例如可列舉：可具有取代基的甲基苯甲酸酯（苯甲酸甲酯）、可具有取代基的苯甲酸乙酯、可具有取代基的苯甲酸丙酯、可具有取代基的苯甲酸丁酯、可具有取代基的苯甲酸異丙酯、可具有取代基的苯甲酸苄酯、可具有取代基的苯甲酸環己酯、可具有取代基的苯甲酸苯基酯。As the aromatic ester compound, for example, methyl benzoate (methyl benzoate) which may have a substituent, ethyl benzoate which may have a substituent, propyl benzoate which may have a substituent, Butyl benzoate with substituent, isopropyl benzoate with substituent, benzyl benzoate with substituent, cyclohexyl benzoate with substituent, phenyl benzoate with substituent .

作為含氮雜環式化合物，例如可列舉：可具有取代基的吡啶、可具有取代基的喹啉、可具有取代基的喹噁啉、可具有取代基的1,2,3,4-四氫喹啉、可具有取代基的嘧啶、可具有取代基的吡嗪及可具有取代基的喹唑啉。As the nitrogen-containing heterocyclic compound, for example, pyridine which may have a substituent, quinoline which may have a substituent, quinoxaline which may have a substituent, 1,2,3,4-tetra Hydroquinoline, pyrimidine which may have a substituent, pyrazine which may have a substituent, and quinazoline which may have a substituent.

含氮雜環式化合物亦可具有與環結構直接鍵結的取代基。The nitrogen-containing heterocyclic compound may have a substituent directly bonded to the ring structure.

作為含氮雜環式化合物的環結構（例如喹啉環結構、1,2,3,4-四氫喹啉環結構、喹噁啉環結構）可具有的取代基，例如可列舉碳原子數1～5的烷基、碳原子數1～5的烷氧基、鹵素基及烷硫基。Examples of substituents that may be included in ring structures of nitrogen-containing heterocyclic compounds (such as quinoline ring structures, 1,2,3,4-tetrahydroquinoline ring structures, and quinoline ring structures) include, for example, the number of carbon atoms Alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, halogen group and alkylthio group.

作為包含吡啶環結構的含氮雜環式化合物，例如可列舉可具有取代基的吡啶、可具有取代基的喹啉及可具有取代基的異喹啉。As a nitrogen-containing heterocyclic compound containing a pyridine ring structure, the pyridine which may have a substituent, the quinoline which may have a substituent, and the isoquinoline which may have a substituent are mentioned, for example.

作為包含吡嗪環結構的含氮環式化合物，例如可列舉可具有取代基的吡嗪、可具有取代基的喹噁啉。As a nitrogen-containing ring compound containing a pyrazine ring structure, the pyrazine which may have a substituent, and the quinoxaline which may have a substituent are mentioned, for example.

作為包含四氫吡啶環結構的含氮環式化合物，例如可列舉可具有取代基的1,2,3,4-四氫喹啉、及可具有取代基的1,2,3,4-四氫異喹啉。Examples of nitrogen-containing ring compounds containing a tetrahydropyridine ring structure include 1,2,3,4-tetrahydroquinoline which may have substituents, and 1,2,3,4-tetrahydroquinoline which may have substituents. Hydroisoquinoline.

作為包含嘧啶環結構的含氮環式化合物，例如可列舉可具有取代基的嘧啶、及可具有取代基的喹唑啉。As a nitrogen-containing ring compound containing a pyrimidine ring structure, the pyrimidine which may have a substituent, and the quinazoline which may have a substituent are mentioned, for example.

於本實施方式中，溶劑可進而包含芳香族羰基化合物、芳香族酯化合物或含氮雜環式化合物中的僅一種、亦可進而包含選自該些中的兩種以上來作為另外的溶劑。In this embodiment, the solvent may further include only one of aromatic carbonyl compounds, aromatic ester compounds, or nitrogen-containing heterocyclic compounds, or may further include two or more selected from these as another solvent.

於本實施方式中，就環境保護的觀點而言，溶劑較佳為使用不含鹵素的溶劑。In this embodiment, from the viewpoint of environmental protection, it is preferable to use a halogen-free solvent as the solvent.

（溶劑與另外的溶劑的重量比）於本實施方式的油墨組成物包含所述溶劑及所述另外的溶劑時，就進一步提高p型半導體材料及n型半導體材料的溶解性的觀點而言，溶劑相對於另外的溶劑的重量比（溶劑/另外的溶劑）較佳為設為80/20～99.9/0.1的範圍。 (weight ratio of solvent to additional solvent) When the ink composition of this embodiment contains the solvent and the other solvent, from the viewpoint of further improving the solubility of the p-type semiconductor material and the n-type semiconductor material, the weight ratio of the solvent to the other solvent ( solvent/another solvent) is preferably in the range of 80/20 to 99.9/0.1.

（油墨組成物中溶劑的重量百分率）於將油墨組成物的總重量設為100質量%時，就進一步提高p型半導體材料及n型半導體材料的溶解性的觀點而言，油墨組成物中所含的溶劑的總重量較佳為90質量%以上，更佳為92質量%以上，進而佳為95質量%以上，就進一步提高油墨組成物中的p型半導體材料及n型半導體材料的濃度而容易形成一定厚度以上的層的觀點而言，較佳為99.9質量%以下。 (weight percent of solvent in ink composition) When the total weight of the ink composition is 100% by mass, the total weight of the solvent contained in the ink composition is preferably 90% from the viewpoint of further improving the solubility of the p-type semiconductor material and the n-type semiconductor material. Mass % or more, more preferably 92 mass % or more, and more preferably 95 mass % or more, from the viewpoint of further increasing the concentration of the p-type semiconductor material and n-type semiconductor material in the ink composition to easily form a layer with a certain thickness or more. In other words, it is preferably 99.9% by mass or less.

油墨組成物除了包含已說明的溶劑及另外的溶劑以外，亦可更包含任意溶劑。於將油墨組成物中所含的全部溶劑的合計重量設為100重量%時，任意溶劑的含有率較佳為10質量%以下，更佳為5質量%以下，進而佳為3重量%以下。作為任意溶劑，較佳為使用沸點較另外的溶劑高的溶劑。The ink composition may further contain an optional solvent in addition to the solvents described above and other solvents. When the total weight of all solvents contained in the ink composition is 100% by weight, the content of the optional solvent is preferably at most 10% by mass, more preferably at most 5% by mass, and even more preferably at most 3% by mass. As an optional solvent, it is preferable to use a solvent having a higher boiling point than another solvent.

（油墨組成物中p型半導體材料及n型半導體材料的濃度）油墨組成物中的、p型半導體材料與n型半導體材料的合計濃度根據所需要的功能層（活性層）的厚度、所期望的特性等，可設為任意較佳的濃度。p型半導體材料與n型半導體材料的合計濃度較佳為0.01質量%以上，更佳為0.1質量%以上，且較佳為10質量%以下，更佳為5質量%以下，進而佳為0.01質量%以上且20質量%以下，特佳為0.01質量%以上且10重量%以下，進而特佳為0.01質量%以上且5質量%以下，尤其較佳為0.1質量%以上且5質量%以下。 (concentration of p-type semiconductor material and n-type semiconductor material in the ink composition) The total concentration of the p-type semiconductor material and the n-type semiconductor material in the ink composition can be set to any preferred concentration according to the required thickness of the functional layer (active layer), desired characteristics, and the like. The total concentration of the p-type semiconductor material and the n-type semiconductor material is preferably at least 0.01% by mass, more preferably at least 0.1% by mass, and is preferably at most 10% by mass, more preferably at most 5% by mass, still more preferably at most 0.01% by mass % to 20 mass %, particularly preferably 0.01 mass % to 10 mass %, more preferably 0.01 mass % to 5 mass %, especially preferably 0.1 mass % to 5 mass %.

於油墨組成物中，p型半導體材料及n型半導體材料可溶解亦可分散。於油墨組成物中，p型半導體材料及n型半導體材料較佳為至少一部分溶解，更佳為全部溶解。In the ink composition, the p-type semiconductor material and the n-type semiconductor material can be dissolved or dispersed. In the ink composition, the p-type semiconductor material and the n-type semiconductor material are preferably at least partially dissolved, more preferably completely dissolved.

（p型半導體材料相對於n型半導體材料的重量比（p/n比））油墨組成物中的p型半導體材料相對於n型半導體材料的重量比（p型半導體材料/n型半導體材料）較佳為1/9以上，更佳為1/5以上，進而佳為1/3以上，且較佳為9/1以下，更佳為5/1以下，進而佳較佳為3/1以下。 (weight ratio of p-type semiconductor material to n-type semiconductor material (p/n ratio)) The weight ratio of the p-type semiconductor material to the n-type semiconductor material in the ink composition (p-type semiconductor material/n-type semiconductor material) is preferably 1/9 or more, more preferably 1/5 or more, and still more preferably 1/9. 3 or more, and preferably 9/1 or less, more preferably 5/1 or less, still more preferably 3/1 or less.

3.油墨組成物的製造方法本實施方式的油墨組成物的製造方法包括如下步驟：利用孔徑0.5 μm以下的過濾器，對如上所述般選擇p型半導體材料、n型半導體材料及溶劑而製備的油墨組成物進行過濾。 3. Manufacturing method of ink composition The manufacturing method of the ink composition of this embodiment includes the step of filtering the ink composition prepared by selecting the p-type semiconductor material, the n-type semiconductor material and the solvent as described above through a filter having a pore diameter of 0.5 μm or less.

另外，本實施方式的油墨組成物的製造方法亦可為一種光電轉換元件製造用油墨組成物的製造方法，包括：準備步驟，準備作為p型半導體材料的多種高分子化合物；篩選步驟，於所述準備步驟中所準備的高分子化合物中，篩選z平均分子量小於5.0×10 ⁵的高分子化合物作為p型半導體材料；以及將所述篩選步驟中篩選出的p型半導體材料與n型半導體材料以及溶劑混合，製造油墨組成物的步驟。 In addition, the manufacturing method of the ink composition of this embodiment can also be a manufacturing method of an ink composition for photoelectric conversion element manufacturing, including: a preparation step, preparing a variety of polymer compounds as p-type semiconductor materials; a screening step, in the Among the polymer compounds prepared in the above preparatory step, screening the polymer compound with z-average molecular weight less than 5.0×10 ⁵ as the p-type semiconductor material; and combining the p-type semiconductor material screened in the screening step with the n-type semiconductor material And solvent mixing, the step of making ink composition.

篩選z平均分子量小於5.0×10 ⁵的高分子化合物作為p型半導體材料的篩選步驟可設為如下的篩選步驟：針對準備步驟中所準備的高分子化合物，例如藉由已說明的測定方法測定z平均分子量，基於所測定的z平均分子量進行篩選。 The screening step for screening polymer compounds with an average z average molecular weight of less than 5.0×10 ⁵ as a p-type semiconductor material can be set as the following screening step: For the polymer compounds prepared in the preparatory step, for example, by measuring z Molecular weight average, screening is based on the measured z-average molecular weight.

於本實施方式中，油墨組成物可藉由先前公知的任意較佳的方法來製造。特別是於使用兩種以上的溶劑的情況下，例如可藉由如下製造方法等來製造，即，於將已說明的溶劑及另外的溶劑混合而製備混合溶劑後向混合溶劑中添加p型半導體材料及n型半導體材料來製造的方法；以及製備於溶劑中添加p型半導體材料而成的（第一）組成物，與此不同地製備於另外的溶劑中添加n型半導體材料而成的（第二）組成物，將所獲得的兩種以上組成物混合而製備（製造）的方法，換言之，為製備組成物的步驟包括製備兩種以上的組成物的步驟、且製備油墨組成物的步驟包括將兩種以上的組成物混合的步驟的製造方法。In this embodiment, the ink composition can be produced by any previously known preferred method. In particular, when two or more solvents are used, it can be produced by, for example, a production method such as adding a p-type semiconductor to the mixed solvent after mixing the above-described solvent and another solvent to prepare a mixed solvent. material and an n-type semiconductor material; and a (first) composition prepared by adding a p-type semiconductor material to a solvent, and differently prepared by adding an n-type semiconductor material to another solvent ( 2) Composition, a method of preparing (manufacturing) by mixing two or more obtained compositions, in other words, the step of preparing a composition includes a step of preparing two or more compositions, and a step of preparing an ink composition A production method including a step of mixing two or more components.

於製備油墨組成物時，亦可將溶劑（及另外的溶劑）與p型半導體材料及n型半導體材料加溫至溶劑的沸點以下的溫度來進行混合。When preparing the ink composition, the solvent (and another solvent) and the p-type semiconductor material and the n-type semiconductor material may be heated to a temperature below the boiling point of the solvent for mixing.

於本實施方式中，製備油墨組成物的步驟較佳為於0℃以上且200℃以下的條件下進行，較佳為於0℃以上且100℃以下的條件下進行。In this embodiment, the step of preparing the ink composition is preferably carried out under the condition of not less than 0°C and not more than 200°C, preferably not less than 0°C and not more than 100°C.

於本實施方式中，對所製備的油墨組成物進行過濾的步驟、具體而言於製備（製造）油墨組成物時，將溶劑（及另外的溶劑）與p型半導體材料及n型半導體材料混合後，使用具有規定孔徑的過濾器，依照常法對所獲得的混合物（油墨組成物）進行過濾即可。In this embodiment, the step of filtering the prepared ink composition, specifically, mixing the solvent (and another solvent) with the p-type semiconductor material and the n-type semiconductor material when preparing (manufacturing) the ink composition Then, the obtained mixture (ink composition) may be filtered according to a conventional method using a filter having a predetermined pore size.

於本實施方式中，作為過濾中可使用的過濾器，例如可列舉由纖維素乙酸酯、玻璃纖維、聚偏二氟乙烯（polyvinylidene fluoride，PVdF）、聚四氟乙烯（polytetrafluoroethylene，PTFE）等氟樹脂形成的過濾器。In this embodiment, as a filter usable for filtration, for example, a filter made of cellulose acetate, glass fiber, polyvinylidene fluoride (polyvinylidene fluoride, PVdF), polytetrafluoroethylene (polytetrafluoroethylene, PTFE), etc. Filter made of fluororesin.

於本實施方式中，就過濾器的獲取性、過濾的效率、抑制所形成的功能層（活性層）中的缺陷產生的觀點而言，可使用的過濾器的孔徑較佳為1 μm以下，更佳為0.5 μm以下，進而佳為0.45 μm以下，且較佳為0.1 μm以上，更佳為0.4 μm以上，較佳為0.1 μm～0.5 μm，更佳為0.1 μm～0.5 μm。In this embodiment, from the viewpoint of filter availability, filtration efficiency, and suppression of defects in the formed functional layer (active layer), the pore size of the filter that can be used is preferably 1 μm or less. More preferably 0.5 μm or less, further preferably 0.45 μm or less, and preferably 0.1 μm or more, more preferably 0.4 μm or more, preferably 0.1 μm to 0.5 μm, more preferably 0.1 μm to 0.5 μm.

4.油墨組成物的用途本實施方式的油墨組成物通常用於形成包含p型半導體材料及n型半導體材料的膜。 4. Application of ink composition The ink composition of this embodiment is generally used to form a film containing a p-type semiconductor material and an n-type semiconductor material.

本實施方式的油墨組成物可較佳地用於形成光電轉換元件中所含的活性層。特別是，本實施方式的油墨組成物可特佳地用於形成在使用時被施加反向偏壓的光檢測元件中所含的活性層。The ink composition of this embodiment can be suitably used to form an active layer included in a photoelectric conversion element. In particular, the ink composition of the present embodiment can be particularly suitably used to form an active layer included in a photodetection element to which a reverse bias is applied during use.

5.油墨組成物的固化膜使用本實施方式的油墨組成物形成膜後，自膜中除去溶劑而使膜固化，藉此可形成油墨組成物的固化膜。油墨組成物的固化膜可較佳地用於形成光檢測元件中所含的功能層、特別是活性層。油墨組成物的固化膜可藉由任意較佳的製造方法來製造。 5. Cured film of ink composition After forming a film using the ink composition of this embodiment, the solvent is removed from the film to cure the film, thereby forming a cured film of the ink composition. A cured film of the ink composition can be preferably used to form a functional layer, particularly an active layer, contained in a photodetection element. The cured film of the ink composition can be produced by any preferred production method.

於本實施方式中，油墨組成物的固化膜的製造方法包括將油墨組成物塗佈於塗佈對象上而獲得塗膜的步驟（i）、以及自所獲得的塗膜去除溶劑的步驟（ii）。以下，對步驟（i）及步驟（ii）進行說明。In the present embodiment, the method for producing a cured film of the ink composition includes the step (i) of applying the ink composition to the object to be coated to obtain a coating film, and the step (ii) of removing the solvent from the obtained coating film ). Hereinafter, step (i) and step (ii) are demonstrated.

[步驟（i）] 於步驟（i）中，作為將油墨組成物塗佈於塗佈對象上的方法，可使用已說明的先前公知的任意的塗佈法。於本實施方式中，作為塗佈法，較佳為狹縫塗佈法、刮刀塗佈法、旋塗法、微凹版塗佈法、凹版塗佈法、棒塗法、噴墨塗佈法、噴嘴塗佈法或毛細管塗佈法，更佳為狹縫塗佈法、旋塗法、毛細管塗佈法或棒塗法，進而佳為狹縫塗佈法或旋塗法。 [step (i)] In the step (i), as a method of applying the ink composition to the object to be coated, any previously known coating method described above can be used. In the present embodiment, the coating method is preferably a slit coating method, a knife coating method, a spin coating method, a micro gravure coating method, a gravure coating method, a bar coating method, an inkjet coating method, The nozzle coating method or the capillary coating method is more preferably a slit coating method, a spin coating method, a capillary coating method or a bar coating method, further preferably a slit coating method or a spin coating method.

於步驟（i）中，油墨組成物被塗佈於任意的塗佈對象上。於光電轉換元件的製造步驟中，例如可將油墨組成物塗佈於電極（陽極或陰極）、電子傳輸層或電洞傳輸層等光電轉換元件可包含的功能層上。In step (i), the ink composition is applied to an arbitrary object to be applied. In the manufacturing steps of the photoelectric conversion device, for example, the ink composition can be coated on the functional layers that the photoelectric conversion device can include such as electrodes (anode or cathode), electron transport layer or hole transport layer.

[步驟（ii）] 於步驟（ii）中，作為自藉由步驟（i）形成的油墨組成物的塗膜去除溶劑的方法，可使用任意較佳的方法。作為去除溶劑的方法的例子，可列舉：熱風乾燥法、紅外線加熱乾燥法、閃光燈退火乾燥法、減壓乾燥法等乾燥法。 [step (ii)] In the step (ii), any preferred method can be used as a method of removing the solvent from the coating film of the ink composition formed in the step (i). Examples of the method for removing the solvent include drying methods such as a hot air drying method, an infrared heating drying method, a flash lamp annealing drying method, and a reduced-pressure drying method.

6.光電轉換元件（1）光電轉換元件的結構本實施方式的光電轉換元件包括第一電極、第二電極以及設置於該第一電極與該第二電極之間的活性層，該活性層是已說明的固化膜。 6. Photoelectric conversion element (1) Structure of photoelectric conversion element The photoelectric conversion element of this embodiment includes a first electrode, a second electrode, and an active layer provided between the first electrode and the second electrode, and the active layer is the cured film described above.

以下，參照圖式對本實施方式的光電轉換元件的構成例進行具體說明。Hereinafter, a configuration example of the photoelectric conversion element of the present embodiment will be specifically described with reference to the drawings.

圖1是示意性地表示光電轉換元件的構成例的圖。FIG. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element.

如圖1所示，光電轉換元件10設置於支持基板11上。光電轉換元件10包括：以與支持基板11相接的方式設置的第一電極12、以與第一電極12相接的方式設置的電子傳輸層13、以與電子傳輸層13相接的方式設置的活性層14、以與活性層14相接的方式設置的電洞傳輸層15、以及以與電洞傳輸層15相接的方式設置的第二電極16。於所述構成例中，以與第一電極16相接的方式進而設置有密封構件17。As shown in FIG. 1 , the photoelectric conversion element 10 is disposed on a support substrate 11 . The photoelectric conversion element 10 includes: a first electrode 12 provided in contact with the support substrate 11 , an electron transport layer 13 provided in contact with the first electrode 12 , and an electron transport layer 13 provided in contact with the electron transport layer 13 . The active layer 14, the hole transport layer 15 provided in contact with the active layer 14, and the second electrode 16 provided in contact with the hole transport layer 15. In the configuration example described above, a sealing member 17 is further provided so as to be in contact with the first electrode 16 .

以下，對本實施方式的光電轉換元件中可包含的構成要素進行具體說明。Hereinafter, constituent elements that may be included in the photoelectric conversion element of the present embodiment will be specifically described.

（基板）光電轉換元件通常形成於基板（支持基板）上。另外，亦存在進而由基板（密封基板）密封的情況。於基板上通常形成包括第一電極及第二電極的一對電極中的一個。基板的材料只要為形成特別是包含有機化合物的層時不發生化學變化的材料則並無特別限定。 (substrate) A photoelectric conversion element is usually formed on a substrate (supporting substrate). In addition, there is also a case where it is further sealed with a substrate (sealing substrate). One of a pair of electrodes including a first electrode and a second electrode 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 change chemically when forming a layer including an organic compound.

作為基板的材料，例如可列舉玻璃、塑膠、高分子膜、矽。於使用不透明的基板的情況下，較佳為與設置於不透明的基板側的電極相反之側的電極（換言之，遠離不透明基板之側的電極）為透明或半透明的電極。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 opaque substrate (in other words, the electrode on the side away from the opaque substrate) be a transparent or semitransparent electrode.

（電極）光電轉換元件包括作為一對電極的第一電極及第二電極。為了使光入射，第一電極及第二電極中的至少一個電極較佳為設為透明或半透明的電極。 (electrode) The photoelectric conversion element includes a first electrode and a second electrode as a pair of electrodes. In order to allow light to enter, at least one of the first electrode and the second electrode is preferably a transparent or semitransparent electrode.

作為透明或半透明的電極的材料的例子，可列舉導電性的金屬氧化物膜、半透明的金屬薄膜。具體而言，可列舉：氧化銦、氧化鋅、氧化錫、及作為該些的複合物的銦錫氧化物（Indium Tin Oxide，ITO）、銦鋅氧化物（Indium Zinc Oxide，IZO）、奈塞（NESA）等導電性材料、金、鉑、銀、銅。作為透明或半透明的電極的材料，較佳為ITO、IZO、氧化錫。另外，作為電極，可採用使用聚苯胺及其衍生物、聚噻吩及其衍生物等有機化合物作為材料的透明導電膜。透明或半透明的電極可為第一電極亦可為第二電極。Examples of materials for transparent or semitransparent electrodes include conductive metal oxide films and semitransparent metal thin films. Specifically, indium oxide, zinc oxide, tin oxide, and indium tin oxide (Indium Tin Oxide, ITO), indium zinc oxide (Indium Zinc Oxide, IZO), Nesser (NESA) and other conductive materials, gold, platinum, silver, copper. As a material of the transparent or translucent electrode, ITO, IZO, and tin oxide are preferable. In addition, as an electrode, a transparent conductive film using an organic compound such as polyaniline and its derivatives, polythiophene and its derivatives as a material can be used. The transparent or translucent electrode can be the first electrode or the second electrode.

若一對電極中的一個電極為透明或半透明，則另一電極可為透光性低的電極。作為透光性低的電極的材料的例子，可列舉金屬、及導電性高分子。作為透光性低的電極的材料的具體例，可列舉：鋰、鈉、鉀、銣、銫、鎂、鈣、鍶、鋇、鋁、鈧、釩、鋅、釔、銦、鈰、釤、銪、鋱、鐿等金屬以及該些中的兩種以上的合金，或者該些中的一種以上的金屬與選自由金、銀、鉑、銅、錳、鈦、鈷、鎳、鎢及錫所組成的群組中的一種以上的金屬的合金，石墨、石墨層間化合物、聚苯胺及其衍生物、聚噻吩及其衍生物。作為合金，可列舉：鎂-銀合金、鎂-銦合金、鎂-鋁合金、銦-銀合金、鋰-鋁合金、鋰-鎂合金、鋰-銦合金、及鈣-鋁合金。If one of the pair of electrodes is transparent or translucent, the other electrode may be an electrode with low light transmittance. Examples of materials for electrodes with low translucency include metals and conductive polymers. Specific examples of materials for electrodes with low translucency include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, Metals such as europium, uranium, and ytterbium, and alloys of two or more of them, or one or more of these metals and metals selected from gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin Alloys of more than one metal in the group consisting of graphite, graphite interlayer compounds, polyaniline and its derivatives, polythiophene and its derivatives. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

（活性層）本實施方式的光電轉換元件包含已說明的油墨組成物的固化膜作為活性層。本實施方式的活性層具有本體異質接合型的結構。 (active layer) The photoelectric conversion element of this embodiment includes the cured film of the ink composition described above as an active layer. The active layer of this embodiment has a bulk heterojunction structure.

於本實施方式中，活性層的厚度並無特別限定。例如活性層的厚度可考慮到暗電流的抑制與所產生的光電流的導出的平衡而設為任意較佳的厚度。特別是就進一步減少暗電流的觀點而言，活性層的厚度較佳為100 nm以上，更佳為100 nm以上，進而佳為200 nm以上。另外，活性層的厚度較佳為5 μm以下，更佳為1 μm以下，進而佳為600 nm以下。In this embodiment, the thickness of the active layer is not particularly limited. For example, the thickness of the active layer can be set to any preferred thickness in consideration of the balance between the suppression of dark current and the derivation of generated photocurrent. In particular, from the viewpoint of further reducing dark current, the thickness of the active layer is preferably at least 100 nm, more preferably at least 100 nm, and still more preferably at least 200 nm. In addition, the thickness of the active layer is preferably not more than 5 μm, more preferably not more than 1 μm, and still more preferably not more than 600 nm.

（中間層）如圖1所示，本實施方式的光電轉換元件中，作為用於提高光電轉換效率等的特性的構成要素，例如較佳為包括電荷傳輸層（電子傳輸層、電洞傳輸層、電子注入層、電洞注入層）等中間層（緩衝層）。 (middle layer) As shown in FIG. 1 , in the photoelectric conversion element of the present embodiment, it is preferable to include, for example, a charge transport layer (electron transport layer, hole transport layer, electron injection layer, etc.) , hole injection layer) and other intermediate layers (buffer layers).

另外，作為中間層中使用的材料的例子，可列舉：鈣等金屬、氧化鉬、氧化鋅等無機氧化物半導體、及PEDOT（聚(3,4-乙烯二氧噻吩)）與PSS（聚(4-苯乙烯磺酸鹽)）的混合物（PEDOT：PSS）。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-styrenesulfonate)) (PEDOT:PSS).

中間層可藉由先前公知的任意較佳的形成方法來形成。中間層可藉由真空蒸鍍法或與活性層的形成方法相同的塗佈法來形成。The intermediate layer can be formed by any preferred forming method known previously. The intermediate layer can be formed by vacuum deposition or the same coating method as the active layer.

如圖1所示，本實施方式的光電轉換元件較佳為於第一電極與活性層之間包括電子傳輸層。電子傳輸層具有自活性層向電極傳輸電子的功能。As shown in FIG. 1 , the photoelectric conversion element of this embodiment preferably includes an electron transport layer between the first electrode and the active layer. The electron transport layer has a function of transporting electrons from the active layer to the electrode.

於另一實施方式中，光電轉換元件亦可不包括電子傳輸層。In another embodiment, the photoelectric conversion element may not include an electron transport layer.

有時將與第一電極相接地設置的電子傳輸層特別地稱為電子注入層。與第一電極相接地設置的電子傳輸層（電子注入層）具有促進電子向第一電極注入的功能。電子傳輸層（電子注入層）亦可與活性層相接。The electron transport layer provided in contact with the first electrode is sometimes specifically referred to as an electron injection layer. The electron transport layer (electron injection layer) provided in contact with the first electrode has a function of promoting injection of electrons into the first electrode. The electron transport layer (electron injection layer) may also be in contact with the active layer.

電子傳輸層包含電子傳輸性材料。作為電子傳輸性材料的例子，可列舉：聚伸烷基亞胺及其衍生物、包含芴結構的高分子化合物、鈣等金屬、金屬氧化物。The electron transport layer contains an electron transport material. Examples of the electron-transporting material include polyalkyleneimines and derivatives thereof, polymer compounds containing a fluorene structure, metals such as calcium, and metal oxides.

作為聚伸烷基亞胺及其衍生物的例子，可列舉藉由常規方法將伸乙基亞胺、伸丙基亞胺、伸丁基亞胺、二甲基伸乙基亞胺、伸戊基亞胺、伸己基亞胺、伸庚基亞胺、伸辛基亞胺等碳原子數2～8的伸烷基亞胺、特別是碳原子數2～4的伸烷基亞胺的一種或兩種以上聚合而獲得的聚合物、以及使該些與各種化合物反應並進行化學改質而得的聚合物。作為聚伸烷基亞胺及其衍生物，較佳為聚乙烯亞胺（polyethyleneimine，PEI）及乙氧基化聚乙烯亞胺（polyethylenimine ethoxylated，PEIE）。Examples of polyalkyleneimine and derivatives thereof include ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, One of alkylene imines with 2 to 8 carbon atoms, especially alkylene imines with 2 to 4 carbon atoms, such as alkylimine, hexyl imine, heptyl imine, and octyl imine. or polymers obtained by polymerization of two or more types, and polymers obtained by reacting these with various compounds and chemically modifying them. As polyalkyleneimine and its derivatives, polyethyleneimine (polyethyleneimine, PEI) and ethoxylated polyethyleneimine (polyethyleneimine ethoxylated, PEIE) are preferable.

作為包含芴結構的高分子化合物的例子，可列舉聚[(9,9-雙(3'-(N,N-二甲基胺基)丙基)-2,7-芴)-鄰-2,7-(9,9'-二辛基芴)]（poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)，PFN）及PFN-P2。Examples of polymer compounds containing a fluorene structure include poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-o-2 ,7-(9,9'-dioctylfluorene)] (poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7 -(9,9-dioctylfluorene), PFN) and PFN-P2.

作為金屬氧化物的例子，可列舉：氧化鋅、鎵摻雜氧化鋅、鋁摻雜氧化鋅、氧化鈦及氧化鈮。作為金屬氧化物，較佳為包含鋅的金屬氧化物，其中較佳為氧化鋅。Examples of metal oxides include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide, and niobium oxide. As the metal oxide, a metal oxide containing zinc is preferable, and zinc oxide is preferable among them.

作為其他電子傳輸性材料的例子，可列舉聚(4-乙烯基苯酚)、苝二醯亞胺。Examples of other electron-transporting materials include poly(4-vinylphenol) and perylenediimide.

本實施方式的光電轉換元件較佳為中間層為電子傳輸層，且具有基板（支持基板）、第一電極、電子傳輸層、活性層、電洞傳輸層、第二電極以按照此順序彼此相接的方式積層的結構。The photoelectric conversion element of this embodiment preferably has an intermediate layer that is an electron transport layer, and has a substrate (supporting substrate), a first electrode, an electron transport layer, an active layer, a hole transport layer, and a second electrode in this order. Layered structure in a connected manner.

如圖1所示，本實施方式的光電轉換元件較佳為於第二電極與活性層之間包括電洞傳輸層作為中間層。電洞傳輸層具有自活性層向第二電極傳輸電洞的功能。電洞傳輸層可與第二電極相接。電洞傳輸層亦可與活性層相接。As shown in FIG. 1 , the photoelectric conversion element of this embodiment preferably includes a hole transport layer as an intermediate layer between the second electrode and the active layer. The hole transport layer has the function of transporting holes from the active layer to the second electrode. The hole transport layer may be in contact with the second electrode. The hole transport layer can also be in contact with the active layer.

於另一實施方式中，光電轉換元件亦可不包括電洞傳輸層。In another embodiment, the photoelectric conversion element may not include a hole transport layer.

有時將與第二電極相接地設置的電洞傳輸層特別地稱為電洞注入層。與第二電極相接地設置的電洞傳輸層（電洞注入層）具有促進活性層中產生的電洞向第二電極注入的功能。The hole transport layer arranged in contact with the second electrode is sometimes called a hole injection layer in particular. The hole transport layer (hole injection layer) provided in contact with the second electrode has a function of promoting injection of holes generated in the active layer to the second electrode.

電洞傳輸層包含電洞傳輸性材料。作為電洞傳輸性材料的例子，可列舉：聚噻吩及其衍生物、芳香族胺化合物、包含具有芳香族胺殘基的構成單元的高分子化合物、CuSCN、CuI、NiO、氧化鎢（WO ₃）及氧化鉬（MoO ₃）。 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 constituent units having aromatic amine residues, CuSCN, CuI, NiO, tungsten oxide (WO ₃ ) and molybdenum oxide (MoO ₃ ).

（密封構件）本實施方式的光電轉換元件更包括密封構件，且較佳為形成為由所述密封構件密封而得的密封體。 (sealing member) The photoelectric conversion element of this embodiment further includes a sealing member, and is preferably formed as a sealed body sealed with the sealing member.

密封構件可使用任意較佳的先前公知的構件。作為密封構件的例子，可列舉作為基板（密封基板）的玻璃基板與紫外線（ultraviolet，UV）硬化性樹脂等密封材（接著劑）的組合。As the sealing member, any preferable previously known member can be used. Examples of the sealing member include a combination of a glass substrate as a substrate (sealing substrate) and a sealing material (adhesive) such as an ultraviolet (ultraviolet, UV) curable resin.

密封構件亦可為一層以上的層結構的密封層。作為構成密封層的層的例子，可列舉阻氣層、阻氣性膜。The sealing member may be a sealing layer having a layer structure of one or more layers. Examples of the layer constituting the sealing layer include a gas barrier layer and a gas barrier film.

密封層較佳為由具有阻擋水分的性質（水蒸氣阻隔性）或阻擋氧的性質（氧阻隔性）的材料形成。關於作為密封層而較佳的材料的材料的例子，可列舉：三氟化聚乙烯、聚三氟化氯乙烯（poly(chlorotrifluoroethylene)，PCTFE）、聚醯亞胺、聚碳酸酯、聚對苯二甲酸乙二酯、脂環式聚烯烴、乙烯-乙烯醇共聚物等有機材料、氧化矽、氮化矽、氧化鋁、類金剛石碳（diamond-like carbon）等無機材料等。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 for the sealing layer include: polyethylene trifluoride, poly(chlorotrifluoroethylene), PCTFE), polyimide, polycarbonate, polyparaphenylene Organic materials such as ethylene dicarboxylate, alicyclic polyolefin, and ethylene-vinyl alcohol copolymer, and inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, and diamond-like carbon.

密封構件由可耐受加熱處理的材料構成，所述加熱處理通常可於組裝至應用光電轉換元件的、例如後述的應用例的器件中時實施。The sealing member is made of a material that can withstand heat treatment that can usually be performed when assembling a photoelectric conversion element, such as an application example described later, in a device.

（2）光電轉換元件的製造方法本實施方式的光電轉換元件可藉由先前公知的任意較佳的製造方法來製造。本實施方式的光電轉換元件只要將對形成構成要素時所選擇的材料而言較佳的步驟加以組合來製造即可。 (2) Manufacturing method of photoelectric conversion element The photoelectric conversion element of this embodiment can be manufactured by any previously known preferable manufacturing method. The photoelectric conversion element of the present embodiment may be produced by combining steps that are preferable for the materials selected when forming the constituent elements.

以下，作為本發明的實施方式，對具有基板（支持基板）、第一電極、電洞傳輸層、活性層、電子傳輸層、第二電極按照此順序彼此相接的結構的光電轉換元件的製造方法進行說明。Hereinafter, as an embodiment of the present invention, a photoelectric conversion element having a structure in which a substrate (supporting substrate), a first electrode, a hole transport layer, an active layer, an electron transport layer, and a second electrode are in contact with each other in this order is described. The method is explained.

（準備基板的步驟）於本步驟中，例如準備設置有第一電極的支持基板。另外，自市場獲取設置有由已說明的電極的材料形成的導電性薄膜的基板，視需要對導電性薄膜進行圖案化而形成第一電極，藉此可準備設置有第一電極的支持基板。 (Procedure for preparing substrate) In this step, for example, a support substrate provided with a first electrode is prepared. In addition, a substrate provided with a conductive thin film made of the electrode material described above is obtained from the market, and the conductive thin film is patterned as necessary to form a first electrode, whereby a supporting substrate provided with the first electrode can be prepared.

於本實施方式的光電轉換元件的製造方法中，於支持基板上形成第一電極時的第一電極的形成方法並無特別限定。第一電極可藉由真空蒸鍍法、濺射法、離子鍍法、鍍敷法、塗佈法等先前公知的任意較佳的方法將已說明的材料形成於應形成第一電極的結構（例如支持基板、活性層、電洞傳輸層）上。In the method for manufacturing a photoelectric conversion element according to this embodiment, the method for forming the first electrode when forming the first electrode on the support substrate is not particularly limited. The first electrode can be formed on the structure where the first electrode should be formed by any previously known preferred method such as vacuum evaporation method, sputtering method, ion plating method, plating method, coating method, etc. ( Such as supporting substrate, active layer, hole transport layer).

（電洞傳輸層的形成步驟）光電轉換元件的製造方法可包括形成設置於活性層與第一電極之間的電洞傳輸層（電洞注入層）的步驟。 (Formation step of the hole transport layer) The method of manufacturing a photoelectric conversion element may include a step of forming a hole transport layer (hole injection layer) provided between the active layer and the first electrode.

電洞傳輸層的形成方法並無特別限定。就進一步簡化電洞傳輸層的形成步驟的觀點而言，較佳為藉由先前公知的任意較佳的塗佈法形成電洞傳輸層。電洞傳輸層例如可藉由使用塗佈液的塗佈法或真空蒸鍍法來形成，所述塗佈液包含已說明的可構成電洞傳輸層的材料及溶劑。The method for forming the hole transport layer is not particularly limited. From the viewpoint of further simplifying the formation steps of the hole transport layer, it is preferable to form the hole transport layer by any of the previously known preferable coating methods. The hole transport layer can be formed by, for example, a coating method using a coating solution containing the materials and solvents that can constitute the hole transport layer described above, or a vacuum evaporation method.

（活性層的形成步驟）於本實施方式的光電轉換元件的製造方法中，於電洞傳輸層上形成活性層。活性層可藉由任意較佳的先前公知的形成步驟來形成。於本實施方式中，活性層可藉由使用已說明的油墨組成物的塗佈法來製造。 (Active layer formation step) 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 can be formed by any preferred previously known formation steps. In this embodiment, the active layer can be produced by the coating method using the ink composition described above.

活性層可以與已說明的「固化膜」同樣的方式形成。本實施方式中，可藉由包括將包含p型半導體材料、n型半導體材料以及溶劑的油墨組成物塗佈於電洞傳輸層上來形成塗膜的步驟、繼而使所述塗膜乾燥的步驟的步驟，來形成活性層。The active layer can be formed in the same manner as the "cured film" described above. In this embodiment mode, a coating film may be formed by coating an ink composition including a p-type semiconductor material, an n-type semiconductor material, and a solvent on the hole transport layer, and then drying the coating film. step to form the active layer.

（電子傳輸層的形成步驟）本實施方式的光電轉換元件的製造方法可包括形成以與活性層相接的方式設置的電子傳輸層（電子注入層）的步驟。 (Formation step of electron transport layer) The method of manufacturing a photoelectric conversion element according to this embodiment may include the step of forming an electron transport layer (electron injection layer) provided in contact with the active layer.

電子傳輸層的形成方法並無特別限定。就進一步簡化電子傳輸層的形成步驟的觀點而言，較佳為藉由先前公知的任意較佳的真空蒸鍍法來形成電子傳輸層。The method for forming the electron transport layer is not particularly limited. From the viewpoint of further simplifying the formation steps of the electron transport layer, it is preferable to form the electron transport layer by any preferred vacuum evaporation method known previously.

（第二電極的形成步驟）第二電極的形成方法並無特別限定。第二電極例如可利用上述例示的電極的材料，藉由塗佈法、真空蒸鍍法、濺射法、離子鍍法、鍍敷法等先前公知的任意較佳的方法形成。藉由以上的步驟，製造本實施方式的光電轉換元件。 (Formation step of the second electrode) The method for forming the second electrode is not particularly limited. For example, the second electrode can be formed by any of the previously known preferred methods such as coating method, vacuum evaporation method, sputtering method, ion plating method, plating method, etc. using the materials of the electrodes exemplified above. Through the above steps, the photoelectric conversion element of this embodiment is manufactured.

（密封體的形成步驟）當形成密封體時，於本實施方式中，使用先前公知的任意較佳的密封材（接著劑）及基板（密封基板）。具體而言，以包圍所製造的光電轉換元件的周邊的方式，於支持基板上塗佈例如UV硬化性樹脂等密封材後藉由密封材無間隙地進行貼附，然後使用對所選擇的密封材而言較佳的照射UV光等方法，將光電轉換元件密封於支持基板與密封基板的間隙中，藉此可獲得光電轉換元件的密封體。 (Sealing Body Formation Step) When forming the sealing body, in this embodiment, any conventionally known preferable sealing material (adhesive) and substrate (sealing substrate) are used. Specifically, a sealing material such as UV curable resin is coated on a support substrate so as to surround the periphery of the produced photoelectric conversion element, and then the sealing material is attached without gaps, and then the selected sealing material is used. A method such as irradiating UV light, which is preferable for the material, seals the photoelectric conversion element in the gap between the support substrate and the sealing substrate, whereby a sealed body of the photoelectric conversion element can be obtained.

（3）光電轉換元件的用途作為本實施方式的光電轉換元件的用途，可列舉光檢測元件、太陽電池。 (3) Applications of photoelectric conversion elements Examples of applications of the photoelectric conversion element of this embodiment include photodetection elements and solar cells.

更具體而言，本實施方式的光電轉換元件於對電極間施加電壓（反向偏壓）的狀態下自透明或半透明的電極側照射光，藉此可使光電流流通，可作為光檢測元件（光感測器）運作。另外，亦可藉由將多個光檢測元件整合而用作圖像感測器。本實施方式的光電轉換元件尤其可較佳地用作光檢測元件。More specifically, in the photoelectric conversion element of this embodiment, when a voltage (reverse bias) is applied between the electrodes, light is irradiated from the side of the transparent or semitransparent electrode, thereby allowing photocurrent to flow, and can be used as a photodetector. components (light sensors) operate. In addition, it can also be used as an image sensor by integrating a plurality of photodetection elements. The photoelectric conversion element of this embodiment can be used particularly preferably as a photodetection element.

另外，本實施方式的光電轉換元件藉由照射光，可使電極間產生光電動勢，可作為太陽電池運作。亦可藉由將多個光電轉換元件整合而製成太陽電池模組。In addition, the photoelectric conversion element of this embodiment can generate photoelectromotive force between electrodes by irradiating light, and can operate as a solar cell. A solar cell module can also be made by integrating multiple photoelectric conversion elements.

（4）光電轉換元件的應用例本實施方式的光電轉換元件作為光檢測元件而可較佳地應用於工作站、個人電腦、便攜式資訊終端、存取控制系統、數位相機、及醫療設備等各種電子裝置所包括的檢測部中。 (4) Application examples of photoelectric conversion elements The photoelectric conversion element of this embodiment can be preferably used as a photodetection element in detection units included in various electronic devices such as workstations, personal computers, portable information terminals, access control systems, digital cameras, and medical equipment.

本實施方式的光電轉換元件可較佳地應用於上述例示的電子裝置所包括的例如X射線攝像裝置及互補式金氧半導體（complementary metal oxide semiconductor，CMOS）圖像感測器等固態攝像裝置用的圖像檢測部（例如X射線感測器等圖像感測器）、指紋檢測部、面部檢測部、靜脈檢測部及虹膜檢測部等檢測生物體的一部分規定特徵的生物體資訊認證裝置的檢測部（例如近紅外線感測器）、脈衝氧量計（pulse oxymeter）等光學生物感測器的檢測部等中。The photoelectric conversion element of this embodiment can be suitably applied to solid-state imaging devices such as X-ray imaging devices and complementary metal oxide semiconductor (CMOS) image sensors included in the electronic devices exemplified above. A biometric information authentication device that detects a part of a predetermined feature of a living body such as an image detection unit (such as an image sensor such as an X-ray sensor), a fingerprint detection unit, a face detection unit, a vein detection unit, and an iris detection unit In detection units (such as near-infrared sensors), detection units of optical biosensors such as pulse oxymeters, and the like.

本實施方式的光電轉換元件亦可作為固態攝像裝置用的圖像檢測部，進而較佳地應用於飛行時間（Time-of-flight，TOF）型距離測定裝置（TOF型測距裝置）。The photoelectric conversion element of the present embodiment can also be used as an image detection unit for a solid-state imaging device, and can be preferably applied to a time-of-flight (TOF) distance measuring device (TOF distance measuring device).

TOF型測距裝置中藉由利用光電轉換元件接收來自光源的放射光於測定對象物中被反射而得的反射光來測定距離。具體而言，檢測自光源放射出的照射光被測定對象物反射並作為反射光返回之前的飛行時間，以求出至測定對象物為止的距離。TOF型中存在直接TOF方式以及間接TOF方式。直接TOF方式中直接測量自光源照射光的時刻與利用光電轉換元件接收反射光的時刻的差，間接TOF方式中藉由將依存於飛行時間的電荷累積量的變化換算成時間變化來測量距離。間接TOF方式中所使用的藉由電荷累積獲得飛行時間的測距原理中，有根據來自光源的放射光與被測定對象反射的反射光的相位求出飛行時間的連續波（特別是正弦波）調製方式以及脈衝調製方式。In the TOF type distance measuring device, the distance is measured by using a photoelectric conversion element to receive reflected light obtained by reflecting light emitted from a light source on a measurement target object. Specifically, the flight time until the irradiation light emitted from the light source is reflected by the object to be measured and returned as reflected light is detected to obtain the distance to the object to be measured. The TOF type includes a direct TOF method and an indirect TOF method. In the direct TOF method, the difference between the time when light is irradiated from the light source and the time when the reflected light is received by the photoelectric conversion element is directly measured. In the indirect TOF method, the change of the charge accumulation amount depending on the flight time is converted into a time change to measure the distance. In the ranging principle of obtaining the time-of-flight by charge accumulation used in the indirect TOF method, there is a continuous wave (especially a sine wave) that calculates the time-of-flight based on the phase of the emitted light from the light source and the reflected light reflected by the object to be measured. modulation and pulse modulation.

以下，參照圖式對可較佳地應用本實施方式的光電轉換元件的檢測部中、固態攝像裝置用的圖像檢測部及X射線攝像裝置用的圖像檢測部、生物體認證裝置（例如指紋認證裝置或靜脈認證裝置等）用的指紋檢測部及靜脈檢測部以及TOF型測距裝置（間接TOF方式）的圖像檢測部的構成例進行說明。In the following, among the detection units of the photoelectric conversion element to which this embodiment can be preferably applied, the image detection unit for solid-state imaging devices, the image detection unit for X-ray imaging devices, and biometric authentication devices (such as A configuration example of a fingerprint detection unit and a vein detection unit for a fingerprint authentication device or a vein authentication device, and an image detection unit of a TOF distance measuring device (indirect TOF method) will be described.

（固態攝像裝置用的圖像檢測部）圖2是示意性地表示固態攝像裝置用的圖像檢測部的構成例的圖。 (Image detection unit for solid-state imaging devices) FIG. 2 is a diagram schematically showing a configuration example of an image detection unit for a solid-state imaging device.

圖像檢測部1包括：CMOS電晶體基板20；以覆蓋CMOS電晶體基板20的方式設置的層間絕緣膜30；設置於層間絕緣膜30上的本發明實施方式的光電轉換元件10；以貫通層間絕緣膜30的方式設置、且將CMOS電晶體基板20與光電轉換元件10電性連接的層間配線部32；以覆蓋光電轉換元件10的方式設置的密封層40；以及設置於密封層40上的濾色器50。The image detection unit 1 includes: a CMOS transistor substrate 20; an interlayer insulating film 30 arranged to cover the CMOS transistor substrate 20; a photoelectric conversion element 10 according to an embodiment of the present invention arranged on the interlayer insulating film 30; The interlayer wiring part 32 provided in the form of an insulating film 30 and electrically connecting the CMOS transistor substrate 20 and the photoelectric conversion element 10; the sealing layer 40 provided in a manner covering the photoelectric conversion element 10; and the sealing layer 40 provided on the sealing layer 40 color filter 50 .

CMOS電晶體基板20以與設計相應的形態包括先前公知的任意較佳的結構。The CMOS transistor substrate 20 includes any previously known preferable structure in a form corresponding to the design.

CMOS電晶體基板20包括於基板的厚度內形成的電晶體、電容器等，包括用於實現各種功能的CMOS電晶體電路（金屬氧化物半導體（metal oxide semiconductor，MOS）電晶體電路）等功能元件。The CMOS transistor substrate 20 includes transistors, capacitors, etc. formed within the thickness of the substrate, and includes functional components such as CMOS transistor circuits (metal oxide semiconductor (MOS) transistor circuits) for realizing various functions.

作為功能元件，例如可列舉：浮動擴散元件（floating diffusion）、重置電晶體（reset transistor）、輸出電晶體、選擇電晶體。Examples of functional elements include floating diffusion elements (floating diffusion), reset transistors (reset transistors), output transistors, and selection transistors.

藉由此種功能元件、配線等，於CMOS電晶體基板20上製作出訊號讀出電路等。A signal readout circuit and the like are fabricated on the CMOS transistor substrate 20 by such functional elements, wiring, and the like.

層間絕緣膜30可由例如氧化矽、絕緣性樹脂等先前公知的任意較佳的絕緣性材料構成。層間配線部32可由例如銅、鎢等先前公知的任意較佳的導電性材料（配線材料）構成。層間配線部32例如可為與配線層的形成同時形成的孔內配線，亦可為與配線層分開形成的埋入插頭。The interlayer insulating film 30 can be made of any previously known preferable insulating material such as silicon oxide, insulating resin, and the like. The interlayer wiring portion 32 can be made of any conventionally known preferable conductive material (wiring material), such as copper and tungsten, for example. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed simultaneously with the formation of the wiring layer, or may be a buried plug formed separately from the wiring layer.

以可防止或抑制有可能使光電轉換元件10發生功能劣化的氧、水等有害物質的滲透為條件，密封層40可由先前公知的任意較佳的材料構成。密封層40可設為與已說明的密封構件17同樣的結構。The sealing layer 40 may be made of any previously known preferable material on the condition that 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 have the same structure as the sealing member 17 described above.

作為濾色器50，可使用由先前公知的任意較佳的材料構成、且與圖像檢測部1的設計相對應的例如原色濾色器。另外，作為濾色器50，亦可使用與原色濾色器相比可減薄厚度的補色濾色器。作為補色濾色器，例如可使用（黃色、青色、品紅色）此三種、（黃色、青色、透明）此三種、（黃色、透明、品紅色）此三種、及（透明、青色、品紅色）此三種組合而成的濾色器。以可生成彩色圖像資料為條件，該些可設為與光電轉換元件10及CMOS電晶體基板20的設計相對應的任意較佳的配置。As the color filter 50 , for example, a color filter of primary colors that is made of any conventionally known preferable material and that corresponds to the design of the image detection unit 1 can be used. In addition, as the color filter 50 , a complementary color filter that can be thinner than a primary color filter can also be used. As the complementary color filter, for example, three types of (yellow, cyan, magenta), three types of (yellow, cyan, transparent), three types of (yellow, transparent, magenta), and (transparent, cyan, magenta) can be used. A color filter made of these three combinations. On the condition that color image data can be generated, these can be set to any preferred arrangement corresponding to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20 .

光電轉換元件10經由濾色器50所接收的光由光電轉換元件10轉換成與光接收量相應的電訊號，經由電極以光接收訊號、即與拍攝對象相對應的電訊號的形式輸出至光電轉換元件10外。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 light received, and output to the photoelectric signal through the electrodes in the form of a light reception signal, that is, an electrical signal corresponding to the subject. conversion element 10 outside.

繼而，自光電轉換元件10輸出的光接收訊號經由層間配線部32被輸入至CMOS電晶體基板20，藉由於CMOS電晶體基板20上製作出的訊號讀出電路被讀出，藉由未圖示的另外的任意較佳的先前公知的功能部進行訊號處理，藉此生成基於拍攝對象的圖像資訊。Then, the light-receiving 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. Any other preferable previously known functional part performs signal processing, thereby generating image information based on the subject.

（指紋檢測部）圖3是示意性地表示與顯示裝置一體地構成的指紋檢測部的構成例的圖。 (Fingerprint Detection Department) 3 is a diagram schematically showing a configuration example of a fingerprint detection unit configured integrally with a display device.

便攜式資訊終端的顯示裝置2包括：包括本發明實施方式的光電轉換元件10作為主要構成要素的指紋檢測部100；以及設置於該指紋檢測部100上並顯示規定圖像的顯示面板部200。The display device 2 of the portable information terminal includes: a fingerprint detection unit 100 including the photoelectric conversion element 10 according to the embodiment of the present invention as a main component; and a display panel unit 200 provided on the fingerprint detection unit 100 and displaying a predetermined image.

所述構成例中，於與顯示面板部200的顯示區域200a一致的區域設置有指紋檢測部100。換言之，於指紋檢測部100的上方一體地積層有顯示面板部200。In the configuration example, the fingerprint detection unit 100 is provided in an area corresponding to the display area 200 a of the display panel unit 200 . In other words, the display panel unit 200 is integrally laminated above the fingerprint detection unit 100 .

當於顯示區域200a中的僅一部分區域進行指紋檢測時，僅與該部分區域對應地設置指紋檢測部100即可。When fingerprint detection is performed on only a part of the display area 200a, it is only necessary to provide the fingerprint detection unit 100 corresponding to the part of the area.

指紋檢測部100包括本發明實施方式的光電轉換元件10作為發揮本質性功能的功能部。指紋檢測部100能夠以與可獲得所期望的特性的設計相對應的形態包括未圖示的保護膜（protection film）、支持基板、密封基板、密封構件、阻隔膜、帶通濾波器、紅外線截止膜等任意較佳的先前公知的構件。指紋檢測部100中亦可採用已說明的圖像檢測部的結構。The fingerprint detection unit 100 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs an essential function. The fingerprint detection unit 100 can include a protection film (not shown), a support substrate, a sealing substrate, a sealing member, a barrier film, a band-pass filter, an infrared cutoff film, etc., in a form corresponding to a design that can obtain desired characteristics. Any preferable conventionally known member such as a film. The fingerprint detection unit 100 may also adopt the structure of the image detection unit described above.

光電轉換元件10能夠以任意的形態包含於顯示區域200a內。例如，多個光電轉換元件10可配置為矩陣狀。The photoelectric conversion element 10 can be included in the display region 200 a in any form. For example, a plurality of photoelectric conversion elements 10 may be arranged in a matrix.

如已說明般，光電轉換元件10設置於支持基板11上，於支持基板11上例如以矩陣狀設置有電極（第一電極或第二電極）。As already described, the photoelectric conversion element 10 is provided on the support substrate 11 , and electrodes (first electrodes or second electrodes) are provided, for example, in a matrix on the support substrate 11 .

光電轉換元件10所接收的光由光電轉換元件10轉換成與光接收量相應的電訊號，並經由電極以光接收訊號、即與所拍攝的指紋相對應的電訊號的形式輸出至光電轉換元件10外。The light received by the photoelectric conversion element 10 is converted by the photoelectric conversion element 10 into an electrical signal corresponding to the received light amount, and output to the photoelectric conversion element in the form of a light received signal, that is, an electrical signal corresponding to the photographed fingerprint, through the electrodes. 10 outside.

顯示面板部200於所述構成例中以包括觸控感測器面板的有機電致發光顯示面板（有機EL顯示面板）的形式構成。代替有機EL顯示面板，顯示面板部200例如亦可由包括背光源等光源的液晶顯示面板等具有任意較佳的先前公知的結構的顯示面板構成。The display panel unit 200 is configured as an organic electroluminescent display panel (organic EL display panel) including a touch sensor panel in the configuration example described above. Instead of an organic EL display panel, the display panel unit 200 may be configured 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.

顯示面板部200設置於已說明的指紋檢測部100上。顯示面板部200包括有機電致發光元件（有機EL元件）220作為發揮本質性功能的功能部。顯示面板部200能夠以與所期望的特性相對應的形態進一步包括任意較佳的先前公知的玻璃基板等基板（支持基板210或密封基板240）、密封構件、阻隔膜、圓偏光板等偏光板、觸控感測器面板230等任意較佳的先前公知的構件。The display panel unit 200 is provided on the fingerprint detection unit 100 described above. The display panel section 200 includes an organic electroluminescent element (organic EL element) 220 as a functional section that performs an essential function. The display panel unit 200 may further include any preferred conventionally known substrate such as a glass substrate (support substrate 210 or sealing substrate 240 ), a sealing member, a barrier film, a polarizing plate such as a circular polarizing plate, etc., in a form corresponding to desired characteristics. , touch sensor panel 230 and other preferred previously known components.

於以上說明的構成例中，有機EL元件220被用作顯示區域200a中的畫素的光源，並且亦被用作指紋檢測部100中的指紋拍攝用的光源。In the configuration examples 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 capturing fingerprints in the fingerprint detection unit 100 .

此處，對指紋檢測部100的動作進行簡單說明。Here, the operation of the fingerprint detection unit 100 will be briefly described.

於執行指紋認證時，指紋檢測部100使用自顯示面板部200的有機EL元件220放射的光對指紋進行檢測。具體而言，自有機EL元件220放射的光透過存在於有機EL元件220與指紋檢測部100的光電轉換元件10之間的構成要素，而由手指的指尖的皮膚（指表面）反射，所述手指的指尖是以與顯示區域200a內的顯示面板部200的表面相接的方式載置。由指表面反射的光中的至少一部分透過存在於其間的構成要素而由光電轉換元件10接收，並被轉換成與光電轉換元件10的光接收量相應的電訊號。然後，由轉換後的電訊號構成與指表面的指紋相關的圖像資訊。When performing fingerprint authentication, the fingerprint detection unit 100 detects a fingerprint using light emitted from the organic EL element 220 of the display panel unit 200 . Specifically, the light emitted from the organic EL element 220 passes through the constituent elements present between the organic EL element 220 and the photoelectric conversion element 10 of the fingerprint detection unit 100, and is reflected by the skin (finger surface) of the fingertip of the finger, so The fingertip of the finger is placed so as to be in contact with the surface of the display panel unit 200 in the display region 200 a. At least a part of the light reflected by the finger surface is received by the photoelectric conversion element 10 through the constituent elements present therebetween, and is converted into an electric signal corresponding to the amount of light received by the photoelectric conversion element 10 . Then, image information related to the fingerprint on the finger surface is formed from the converted electric signal.

包括顯示裝置2的便攜式資訊終端藉由先前公知的任意較佳的步驟，將所獲得的圖像資訊與預先記錄的指紋認證用的指紋資料進行比較來進行指紋認證。The portable information terminal including the display device 2 performs fingerprint authentication by comparing the obtained image information with the pre-recorded fingerprint data for fingerprint authentication through any preferred steps known in the past.

（X射線攝像裝置用的圖像檢測部）圖4是示意性地表示X射線攝像裝置用的圖像檢測部的構成例的圖。 (Image detection unit for X-ray imaging equipment) FIG. 4 is a diagram schematically showing a configuration example of an image detection unit for an X-ray imaging device.

X射線攝像裝置用的圖像檢測部1包括：CMOS電晶體基板20；以覆蓋CMOS電晶體基板20的方式設置的層間絕緣膜30；設置於層間絕緣膜30上的本發明實施方式的光電轉換元件10；以貫通層間絕緣膜30的方式設置、且將CMOS電晶體基板20與光電轉換元件10電性連接的層間配線部32；以覆蓋光電轉換元件10的方式設置的密封層40；設置於密封層40上的閃爍體42；以覆蓋閃爍體42的方式設置的反射層44；以及以覆蓋反射層44的方式設置的保護層46。The image detection unit 1 for an X-ray imaging device includes: a CMOS transistor substrate 20; an interlayer insulating film 30 provided to cover the CMOS transistor substrate 20; The element 10; the interlayer wiring part 32 provided to penetrate the interlayer insulating film 30 and electrically connect the CMOS transistor substrate 20 to the photoelectric conversion element 10; the sealing layer 40 provided to cover the photoelectric conversion element 10; The scintillator 42 on the sealing layer 40 ; the reflective layer 44 provided to cover the scintillator 42 ; and the protective layer 46 provided to cover the reflective layer 44 .

CMOS電晶體基板20以與設計相應的方式包括先前公知的任意較佳的結構。The CMOS transistor substrate 20 includes any previously known preferable structure in a manner corresponding to the design.

CMOS電晶體基板20包括於基板的厚度內形成的電晶體、電容器等，包括用於實現各種功能的CMOS電晶體電路（MOS電晶體電路）等功能元件。The CMOS transistor substrate 20 includes transistors, capacitors, and the like formed within the thickness of the substrate, and includes functional elements such as CMOS transistor circuits (MOS transistor circuits) for realizing various functions.

作為功能元件，例如可列舉浮動擴散元件、重置電晶體、輸出電晶體、選擇電晶體。Examples of functional elements include floating diffusion elements, reset transistors, output transistors, and selection transistors.

閃爍體42可由與X射線攝像裝置用的圖像檢測部1的設計相對應的先前公知的任意較佳的材料構成。作為閃爍體42的較佳材料的例子，可使用CsI（碘化銫）或NaI（碘化鈉）、ZnS（硫化鋅）、GOS（硫氧化釓）、GSO（矽酸釓）等無機材料的無機結晶，或蒽、萘、二苯乙烯等有機材料的有機結晶，或使二苯基噁唑（PPO）或聯三苯（TP）等有機材料溶解於甲苯、二甲苯、二噁烷等有機溶劑中而成的有機液體，氙或氦等氣體，塑膠等。The scintillator 42 can be made of any previously known preferable material corresponding to the design of the image detection unit 1 for an X-ray imaging device. As an example of a preferable material of the scintillator 42 , inorganic materials such as CsI (cesium iodide) or NaI (sodium iodide), ZnS (zinc sulfide), GOS (gillium oxysulfide), and GSO (gillium silicate) can be used. Inorganic crystals, or organic crystals of organic materials such as anthracene, naphthalene, and stilbene, or dissolving organic materials such as diphenyloxazole (PPO) or terphenyl (TP) in organic materials such as toluene, xylene, and dioxane Organic liquids in solvents, gases such as xenon or helium, plastics, etc.

以閃爍體42將所入射的X射線轉換成具有以可見區域為中心的波長的光並可生成圖像資料為條件，所述構成要素可設為與光電轉換元件10及CMOS電晶體基板20的設計相對應的任意較佳的配置。On the condition that the scintillator 42 converts the incident X-rays into light having a wavelength centered on the visible region and can generate image data, the constituent elements can be set to be compatible with the photoelectric conversion element 10 and the CMOS transistor substrate 20 Design corresponding arbitrary preferred configurations.

反射層44反射由閃爍體42轉換的光。反射層44可減少轉換後的光的損失，增大檢測靈敏度。另外，反射層44亦可阻擋自外部直接入射的光。The reflective layer 44 reflects the light converted by the scintillator 42 . The reflective layer 44 can reduce the loss of the converted light and increase the detection sensitivity. In addition, the reflective layer 44 can also block light directly incident from outside.

以可防止或抑制有可能使閃爍體42發生功能劣化的氧、水等有害物質的滲透為條件，保護層46可由先前公知的任意較佳的材料構成。The protective layer 46 can be made of any previously known preferred material on the condition that it can prevent or suppress the permeation of harmful substances such as oxygen and water that may degrade the function of the scintillator 42 .

此處，對具有所述結構的X射線攝像裝置用的圖像檢測部1的動作進行簡單說明。Here, the operation of the image detection unit 1 for the X-ray imaging device having the above configuration will be briefly described.

當X射線或γ射線等的放射線能量入射至閃爍體42時，閃爍體42吸收放射線能量，並轉換為以可見區域為中心的自紫外區域至紅外區域的波長的光（螢光）。然後，藉由閃爍體42轉換的光由光電轉換元件10接收。When radiation energy such as X-rays or γ-rays enters the scintillator 42 , the scintillator 42 absorbs the radiation energy and converts it into light (fluorescence) having wavelengths from the ultraviolet region to the infrared region centering on the visible region. Then, the light converted by the scintillator 42 is received by the photoelectric conversion element 10 .

如此，經由閃爍體42而由光電轉換元件10接收的光藉由光電轉換元件10轉換為與光接收量相應的電訊號，經由電極以光接收訊號、即與拍攝對象相對應的電訊號的形式輸出至光電轉換元件10外。作為檢測對象的放射線能量（X射線）可自閃爍體42側、光電轉換元件10側的任一側入射。In this way, the light received by the photoelectric conversion element 10 via the scintillator 42 is converted by the photoelectric conversion element 10 into an electric signal corresponding to the amount of light received, and the light received signal, that is, an electric signal corresponding to the subject is passed through the electrodes. output to the outside of the photoelectric conversion element 10 . Radiation energy (X-rays) to be detected may enter from either the scintillator 42 side or the photoelectric conversion element 10 side.

（靜脈檢測部）圖5是示意性地表示靜脈認證裝置用的靜脈檢測部的構成例的圖。 (Vein Detection Department) 5 is a diagram schematically showing a configuration example of a vein detection unit for the vein authentication device.

靜脈認證裝置用的靜脈檢測部300包括：蓋部306，劃分出在測定時供作為測定對象的手指（例如，一個以上的手指的指尖、手指及手掌）***的***部310；光源部304，設置於蓋部306、且對測定對象照射光；光電轉換元件10，經由測定對象接收自光源部304照射的光；支持基板11，支持光電轉換元件10；以及玻璃基板302，以與支持基板11夾著光電轉換元件10而相向的方式配置、且以規定的距離自蓋部306分離，並與蓋部306一同劃分出***部306。The vein detection unit 300 for the vein authentication device includes: a cover portion 306, which defines an insertion portion 310 for inserting a finger (for example, fingertips, fingers, and palms of more than one finger) as a measurement object during measurement; a light source portion 304 , which is arranged on the cover part 306 and irradiates light to the measuring object; the photoelectric conversion element 10 receives the light irradiated from the light source part 304 through the measuring object; the supporting substrate 11 supports the photoelectric converting element 10; and the glass substrate 302 is connected with the supporting substrate 11 is disposed so as to face each other across the photoelectric conversion element 10 , is separated from the cover portion 306 by a predetermined distance, and defines the insertion portion 306 together with the cover portion 306 .

於所述構成例中，示出了光源部304以於使用時夾著測定對象與光電轉換元件10分離的方式和蓋部306一體地構成的透過型攝影方式，但光源部304未必需要位於蓋部306側。In the configuration example described above, the transmission type imaging method in which the light source unit 304 is integrally formed with the cover unit 306 in such a manner that the light source unit 304 is separated from the photoelectric conversion element 10 with the object to be measured is shown, but the light source unit 304 does not necessarily need to be located on the cover unit. part 306 side.

以可將來自光源部304的光有效率地照射至測定對象為條件，亦可設為例如自光電轉換元件10側照射測定對象的反射型攝影方式。On the condition that the light from the light source unit 304 can be efficiently irradiated to the measurement object, for example, a reflective imaging method may be adopted in which the measurement object is irradiated from the photoelectric conversion element 10 side.

靜脈檢測部300包括本發明的實施方式的光電轉換元件10作為發揮本質性功能的功能部。靜脈檢測部300能夠以與可獲得所期望的特性的設計相對應的形態包括未圖示的保護膜（protection film）、密封構件、阻隔膜、帶通濾波器、紅外線透過濾光片、可見光截止膜、手指放置導件等任意較佳的先前公知的構件。靜脈檢測部300中亦可採用已說明的圖像檢測部1的結構。The vein detection unit 300 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs an essential function. The vein detecting unit 300 can include a not-shown protection film (protection film), a sealing member, a barrier film, a bandpass filter, an infrared transmission filter, a visible light cutoff filter, etc. Any preferred previously known member such as a film, a finger placement guide, and the like. The configuration of the image detection unit 1 described above may also be employed in the vein detection unit 300 .

光電轉換元件10能夠以任意的形態被包含。例如，多個光電轉換元件10可配置為矩陣狀。The photoelectric conversion element 10 can be included in any form. For example, a plurality of photoelectric conversion elements 10 may be arranged in a matrix.

光電轉換元件10所接收的光由光電轉換元件10轉換成與光接收量相應的電訊號，並經由電極以光接收訊號、即與所拍攝的靜脈相對應的電訊號的形式輸出至光電轉換元件10外。The light received by the photoelectric conversion element 10 is converted by the photoelectric conversion element 10 into an electrical signal corresponding to the received light amount, and output to the photoelectric conversion element in the form of a light received signal, that is, an electrical signal corresponding to the photographed vein through the electrodes. 10 outside.

於靜脈檢測時（使用時），測定對象可與光電轉換元件10側的玻璃基板302接觸，亦可不接觸。During vein detection (in use), the measurement object may or may not be in contact with the glass substrate 302 on the side of the photoelectric conversion element 10 .

此處，對靜脈檢測部300的動作進行簡單說明。Here, the operation of the vein detection unit 300 will be briefly described.

於靜脈檢測時，靜脈檢測部300使用自光源部304放射的光來檢測測定對象的靜脈圖案。具體而言，自光源部304放射的光透過測定對象並轉換為與光電轉換元件10的光接收量相應的電訊號。然後，由轉換後的電訊號構成測定對象的靜脈圖案的圖像資訊。In vein detection, the vein detection unit 300 detects the vein pattern of the measurement target using the light emitted from the light source unit 304 . Specifically, the light emitted from the light source unit 304 passes through the measurement object and is converted into an electrical signal corresponding to the amount of light received by the photoelectric conversion element 10 . Then, the image information of the vein pattern of the measurement object is formed from the converted electric signal.

於靜脈認證裝置中，藉由先前公知的任意較佳的步驟，將所獲得的圖像資訊與預先記錄的靜脈認證用的靜脈資料進行比較，進行靜脈認證。In the vein authentication device, the vein authentication is performed by comparing the obtained image information with the pre-recorded vein data for vein authentication by any preferred steps known in the past.

（TOF型測距裝置用圖像檢測部）圖6是示意性地表示間接方式的TOF型測距裝置用圖像檢測部的構成例的圖。 (Image detection unit for TOF distance measuring device) 6 is a diagram schematically showing a configuration example of an image detection unit for an indirect TOF distance measuring device.

TOF型測距裝置用圖像檢測部400包括：CMOS電晶體基板20；以覆蓋CMOS電晶體基板20的方式設置的層間絕緣膜30；設置於層間絕緣膜30上的本發明實施方式的光電轉換元件10；以夾著光電轉換元件10的方式分離地配置的兩個浮動擴散層402；以覆蓋光電轉換元件10以及浮動擴散層402的方式設置的絕緣層40；以及設置於絕緣層40上並相互分離地配置的兩個光閘（photo gate）404。The image detection unit 400 for a TOF distance measuring device includes: a CMOS transistor substrate 20; an interlayer insulating film 30 provided to cover the CMOS transistor substrate 20; The element 10; the two floating diffusion layers 402 arranged separately to sandwich the photoelectric conversion element 10; the insulating layer 40 provided to cover the photoelectric conversion element 10 and the floating diffusion layer 402; and the insulating layer 40 provided on the insulating layer 40 and Two photo gates (photo gates) 404 are arranged separately from each other.

絕緣層40的一部分自分離的兩個光閘404的間隙露出，其餘的區域被遮光部406遮蔽。CMOS電晶體基板20與浮動擴散層402藉由以貫通層間絕緣膜30的方式設置的層間配線部32電性連接。A part of the insulating layer 40 is exposed from the gap between the two separated shutters 404 , and the remaining area is shielded by the light shielding portion 406 . The CMOS transistor substrate 20 and the floating diffusion layer 402 are electrically connected by the interlayer wiring portion 32 penetrating the interlayer insulating film 30 .

於所述構成例中，絕緣層40可設為由氧化矽構成的場氧化膜等先前公知的任意較佳的結構。In the configuration example, the insulating layer 40 may be any previously known preferable structure such as a field oxide film made of silicon oxide.

光閘404可由例如多晶矽等先前公知的任意較佳的材料構成。The shutter 404 can be made of any previously known preferred material such as polysilicon.

TOF型測距裝置用圖像檢測部400包括本發明的實施方式的光電轉換元件10作為發揮本質性功能的功能部。TOF型測距裝置用圖像檢測部400能夠以與可獲得所期望的特性的設計相對應的形態包括未圖示的保護膜（protection film）、支持基板、密封基板、密封構件、阻隔膜、帶通濾波器、紅外線截止膜等任意較佳的先前公知的構件。The image detection unit 400 for a TOF distance measuring device includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs an essential function. The image detection unit 400 for a TOF distance measuring device can include a not-illustrated protection film (protection film), support substrate, sealing substrate, sealing member, barrier film, Any preferable conventionally known member such as a band-pass filter and an infrared cut film.

此處，對TOF型測距裝置用圖像檢測部400的動作進行簡單說明。Here, the operation of the image detection unit 400 for a TOF distance measuring device will be briefly described.

自光源照射光，來自光源的光自測定對象反射，藉由光電轉換元件10接收反射光。於光電轉換元件10與浮動擴散層402之間設置有兩個光閘404，藉由交替施加脈衝，將由光電轉換元件10產生的訊號電荷傳送至兩個浮動擴散層402中的任一者，電荷蓄積於浮動擴散層402。若相對於打開兩個光閘404的時機，光脈衝以等分跨越的方式抵達，則蓄積於兩個浮動擴散層402的電荷量成為等量。若相對於光脈衝到達其中一個光閘404的時機，光脈衝延遲到達另一個光閘404，則蓄積於兩個浮動擴散層402的電荷量之間產生差異。Light is irradiated from the light source, the light from the light source is reflected from the measurement object, and the reflected light is received by the photoelectric conversion element 10 . Two shutters 404 are provided between the photoelectric conversion element 10 and the floating diffusion layer 402. By alternately applying pulses, the signal charge generated by the photoelectric conversion element 10 is transmitted to either of the two floating diffusion layers 402, and the charge accumulated in the floating diffusion layer 402 . When the light pulses arrive at the timings of opening the two shutters 404 in equal intervals, the amounts of charges accumulated in the two floating diffusion layers 402 become equal. If the light pulse arrives at the other shutter 404 with a delay relative to the timing at which the light pulse arrives at the other shutter 404 , a difference occurs between the amounts of charges accumulated in the two floating diffusion layers 402 .

蓄積於浮動擴散層402的電荷量的差依存於光脈衝的延遲時間。由於至測定對象為止的距離L使用光的往返時間td以及光的速度c而處於L=（1/2）ctd的關係，因此若可根據兩個浮動擴散層402的電荷量之差來推測延遲時間，則可求出至測定對象為止的距離。The difference in the amount of charge accumulated in the floating diffusion layer 402 depends on the delay time of the light pulse. Since the distance L to the measurement object is in the relationship of L=(1/2)ctd using the round-trip time td of light and the speed of light c, if the delay can be estimated from the difference between the charge amounts of the two floating diffusion layers 402 time, the distance to the measurement object can be obtained.

光電轉換元件10所接收的光的光接收量作為蓄積於兩個浮動擴散層402的電荷量之差而被轉換為電訊號，並以光接收訊號、即與測定對象相對應的電訊號的形式輸出至光電轉換元件10外。The received light amount of the light received by the photoelectric conversion element 10 is converted into an electric signal as a difference between the charge amounts accumulated in the two floating diffusion layers 402, and is converted into an electric signal in the form of a light received signal, that is, an electric signal corresponding to the measurement object. output to the outside of the photoelectric conversion element 10 .

繼而，自浮動擴散層402輸出的光接收訊號經由層間配線部32被輸入至CMOS電晶體基板20，藉由於CMOS電晶體基板20上製作出的訊號讀出電路被讀出，藉由未圖示的另外的任意較佳的先前公知的功能部進行訊號處理，藉此生成基於測定對象的距離資訊。Then, the light-receiving signal output from the floating diffusion layer 402 is input to the CMOS transistor substrate 20 through the interlayer wiring portion 32, and is read out by a signal readout circuit formed on the CMOS transistor substrate 20. Any other preferable conventionally known functional unit performs signal processing to generate distance information based on the measurement object.

7.光檢測元件如上所述，本實施方式的光電轉換元件可具有光檢測功能，所述光檢測功能是可將所照射的光轉換為與光接收量相應的電訊號，並經由電極輸出至外部電路。因此，本發明實施方式的光電轉換元件可特佳地應用作具有光檢測功能的光檢測元件。此處，本實施方式的光檢測元件可為光電轉換元件本身，亦可除了包括光電轉換元件以外更包括用於電壓控制等的功能元件。 [實施例] 7. Light detection element As described above, the photoelectric conversion element of the present embodiment may have a photodetection function of converting irradiated light into an electrical signal corresponding to the amount of light received, and outputting the signal to an external circuit via electrodes. Therefore, the photoelectric conversion element of the embodiment of the present invention can be particularly preferably applied as a photodetection element having a photodetection function. Here, the photodetection element of this embodiment may be the photoelectric conversion element itself, and may further include functional elements for voltage control and the like in addition to the photoelectric conversion element. [Example]

以下，為了更詳細地說明本發明而示出實施例。本發明並不限定於下述的實施例。Hereinafter, examples are shown in order to describe the present invention in more detail. The present invention is not limited to the following examples.

＜半導體材料＞作為材料P-1，使用參考WO2013/051676中記載的方法所合成的材料。＜Semiconductor Materials＞ As material P-1, a material synthesized by referring to the method described in WO2013/051676 was used.

作為材料P-2，自市場獲取1-材料（1-material）公司製造的商品名：PCE-10來使用。As the material P-2, a product name: PCE-10 manufactured by 1-material (1-material) Co., Ltd. was obtained from the market and used.

作為材料N-1，自市場獲取前沿碳（Frontier Carbon）公司製造的商品名：E100來使用。As the material N-1, a trade name: E100 manufactured by Frontier Carbon was obtained from the market and used.

作為材料N-2，自市場獲取1-材料（1-material）公司製造的商品名：DiPDI來使用。As material N-2, the trade name: DiPDI manufactured by 1-material (1-material) company was obtained from the market, and used.

作為材料N-3，自市場獲取1-材料（1-material）公司製造的商品名：ITIC來使用。As material N-3, the trade name: ITIC manufactured by 1-material (1-material) company was obtained from the market, and it used.

將本實施例中使用的作為所述p型半導體材料的材料P-1及材料P-2、以及作為n型半導體材料的材料N-1～材料N-3的具體結構示於下述表1及表2中。The specific structures of material P-1 and material P-2 as the p-type semiconductor material used in this example, and material N-1 to material N-3 as n-type semiconductor material are shown in the following Table 1 and Table 2.

[表1] （表1）符號化學結構 P型半導體材料 P-1

P-2

[Table 1] (Table 1)

symbol chemical structure P-type semiconductor material P-1

P-2

[表2] （表2）符號化學結構 n型半導體材料 N-1

N-2

N-3

[Table 2] (Table 2)

symbol chemical structure n-type semiconductor material N-1

N-2

N-3

＜分子量的測定＞ p型半導體材料的z平均分子量（Mz）、重量平均分子量（Mw）是藉由凝膠滲透層析法（GPC）（島津製作所公司製造，LC-20AT），作為聚苯乙烯換算的z平均分子量（Mz）、重量平均分子量（Mw）而求出。以下，進行具體說明。＜Measurement of Molecular Weight＞ The z-average molecular weight (Mz) and weight-average molecular weight (Mw) of the p-type semiconductor material are the z-average molecular weights in terms of polystyrene by gel permeation chromatography (GPC) (manufactured by Shimadzu Corporation, LC-20AT). (Mz) and weight average molecular weight (Mw) were obtained. Hereinafter, a specific description will be given.

使用鄰二氯苯作為GPC的流動相，以1.0 mL/min的流速流動。作為管柱，使用昭和電工公司製造的Shodex KD-806M，作為保護柱，使用昭和電工公司製造的Shodex KD-G。Use o-dichlorobenzene as the mobile phase of GPC at a flow rate of 1.0 mL/min. Shodex KD-806M manufactured by Showa Denko was used as the column, and Shodex KD-G manufactured by Showa Denko was used as the guard column.

作為檢測器，使用UV-vis檢測器（島津製作所公司製造，SPD-M20A）及差示折射率檢測器（島津製作所公司製造，RID-10A）。As a detector, a UV-vis detector (manufactured by Shimadzu Corporation, SPD-M20A) and a differential refractive index detector (manufactured by Shimadzu Corporation, RID-10A) were used.

將測定對象的化合物（聚合物）在作為溶劑的1-氯萘中混合至成為0.05質量%的濃度，藉由在80℃下攪拌2小時使其溶解而製成溶解液。The compound (polymer) to be measured was mixed to a concentration of 0.05% by mass in 1-chloronaphthalene as a solvent, and dissolved by stirring at 80° C. for 2 hours to prepare a solution.

將所獲得的溶解液作為樣品注入至所述測定裝置（GPC）中10 μL，藉此測定z平均分子量（Mz）、重量平均分子量（Mw）。10 μL of the obtained solution was injected into the measurement device (GPC) as a sample, and the z-average molecular weight (Mz) and the weight-average molecular weight (Mw) were measured.

＜實施例1＞ [油墨組成物的製備] 於1,2,3,4-四氫萘中，以相對於油墨組成物的總質量成為0.8質量%的方式混合作為p型半導體材料的材料P-1，且以相對於油墨組成物的質量成為1.6質量%的方式混合作為n型半導體材料的材料N-1，於60℃下攪拌6小時，藉此獲得油墨組成物（I-1）。 <Example 1> [Preparation of ink composition] In 1,2,3,4-tetralin, material P-1, which is a p-type semiconductor material, was mixed in such a manner that it became 0.8% by mass relative to the total mass of the ink composition, and the mass of the ink composition was The material N-1 which is an n-type semiconductor material was mixed so that it might become 1.6 mass %, and it stirred at 60 degreeC for 6 hours, and the ink composition (I-1) was obtained.

[油墨組成物的過濾性試驗] 使用如上所述般製備的油墨組成物，進行油墨組成物的過濾性試驗。具體而言，使用具有規定孔徑的過濾器，對油墨組成物是否能夠透過該過濾器進行評價。即，於油墨組成物可透過過濾器而可進行過濾的情況下，評價為過濾性良好（○），將油墨組成物無法透過過濾器、過濾器堵塞而無法進行過濾的情況評價為過濾性不良（×）。 [Filterability Test of Ink Composition] Using the ink composition prepared as described above, the filterability test of the ink composition was carried out. Specifically, a filter having a predetermined pore size was used to evaluate whether or not the ink composition could pass through the filter. That is, when the ink composition can pass through the filter and can be filtered, it is evaluated as good filterability (◯), and when the ink composition cannot pass through the filter or the filter is clogged and cannot be filtered, it is evaluated as poor filterability (×).

更具體而言，將如上所述般製備的油墨組成物（I-1）10 g加入至設置有孔徑0.5 μm的PTFE過濾器的不鏽鋼支架（愛多邦得科（Advantec）東洋公司製造，KS047）中以進行過濾試驗。More specifically, 10 g of the ink composition (I-1) prepared as described above was added to a stainless steel holder provided with a PTFE filter with a pore size of 0.5 μm (manufactured by Advantec Toyo Co., KS047 ) for filtration tests.

作為結果，油墨組成物I-1在不會使PTFE過濾器堵塞的情況下透過，過濾結束。因此，過濾性被評價為良好（○）。將結果亦示於表1中。As a result, the ink composition I-1 passed through without clogging the PTFE filter, and the filtration was completed. Therefore, the filterability was evaluated as good (◯). The results are also shown in Table 1.

＜實施例2～實施例6及比較例1＞除了使用具有下述表3所示的z平均分子量（Mz）及重量平均分子量（Mw）的材料P-1作為p型半導體材料以外，與實施例1同樣地實施油墨組成物的製備及過濾試驗。將結果亦示於下述表3中。 <Example 2 to Example 6 and Comparative Example 1> Preparation of the ink composition and filtration test were carried out in the same manner as in Example 1, except that material P-1 having the z-average molecular weight (Mz) and weight-average molecular weight (Mw) shown in Table 3 below was used as the p-type semiconductor material. . The results are also shown in Table 3 below.

[表3] （表3）油墨組成物 p型半導體材料的 z平均分子量（Mz）重量平均分子量（Mw）過濾性實施例1 I-1 1.4×10 ⁵ 5.2×10 ⁴ 〇實施例2 I-2 1.5×10 ⁵ 5.7×10 ⁴ 〇實施例3 I-3 2.5×10 ⁵ 8.2×10 ⁴ 〇實施例4 I-4 3.2×10 ⁵ 1.1×10 ⁵ 〇實施例5 I-5 4.4×10 ⁵ 1.4×10 ⁵ 〇實施例6 I-6 4.5×10 ⁵ 1.4×10 ⁵ 〇比較例1 I-7 5.1×10 ⁵ 1.3×10 ⁵ × [Table 3] (Table 3) ink composition z-average molecular weight (Mz) of p-type semiconductor materials Weight average molecular weight (Mw) Filterability Example 1 I-1 1.4×10 ⁵ 5.2×10 ⁴ 〇 Example 2 I-2 1.5×10 ⁵ 5.7×10 ⁴ 〇 Example 3 I-3 2.5×10 ⁵ 8.2×10 ⁴ 〇 Example 4 I-4 3.2×10 ⁵ 1.1×10 ⁵ 〇 Example 5 I-5 4.4×10 ⁵ 1.4×10 ⁵ 〇 Example 6 I-6 4.5×10 ⁵ 1.4×10 ⁵ 〇 Comparative example 1 I-7 5.1×10 ⁵ 1.3×10 ⁵ x

＜實施例7＞ [油墨組成物] 使用材料P-1作為p型半導體材料，以相對於油墨組成物的總質量成為2.0質量%的方式混合材料P-1，且以相對於油墨組成物的總質量成為1.0質量%的方式混合作為n型半導體材料的材料N-1，除此以外，與實施例1同樣地進行而製備油墨組成物（I-8）。 <Example 7> [Ink composition] Using material P-1 as a p-type semiconductor material, material P-1 was mixed in such a manner that it became 2.0% by mass relative to the total mass of the ink composition, and mixed in such a manner that it became 1.0% by mass relative to the total mass of the ink composition as An ink composition (I-8) was prepared in the same manner as in Example 1 except for material N-1 which is an n-type semiconductor material.

[油墨組成物的過濾性試驗] 與實施例1同樣地進行過濾性試驗。 [Filterability Test of Ink Composition] A filterability test was performed in the same manner as in Example 1.

作為結果，油墨組成物I-8在不會使PTFE過濾器堵塞的情況下透過，過濾結束。因此，過濾性被評價為良好（○）。將結果亦示於下述表4中。As a result, the ink composition I-8 permeated without clogging the PTFE filter, and the filtration was completed. Therefore, the filterability was evaluated as good (◯). The results are also shown in Table 4 below.

[表4] （表4）油墨組成物 p型半導體材料的z平均分子量（Mz）重量平均分子量（Mw）過濾性實施例7 I-8 1.4×10 ⁵ 5.2×10 ⁴ 〇 [Table 4] (Table 4) ink composition z-average molecular weight (Mz) of p-type semiconductor materials Weight average molecular weight (Mw) Filterability Example 7 I-8 1.4×10 ⁵ 5.2×10 ⁴ 〇

＜實施例8及比較例2＞使用具有下述表3所示的z平均分子量（Mz）及重量平均分子量（Mw）的材料P-1作為p型半導體材料，使用材料N-2作為n型半導體材料，以相對於油墨組成物的總質量成為1質量%的方式混合材料P-1，以相對於油墨組成物的總質量成為0.3質量%的方式混合材料N-2，並使用將鄰二甲苯（97質量%）與苯乙酮（3質量%）混合而成的混合溶劑作為溶劑來進行混合，除此以外，與實施例1同樣地進行而製備油墨組成物（I-9）及油墨組成物（I-10），實施過濾性試驗。將結果示於下述表5中。 <Example 8 and Comparative Example 2> Using material P-1 having the z-average molecular weight (Mz) and weight-average molecular weight (Mw) shown in Table 3 below as the p-type semiconductor material, and material N-2 as the n-type semiconductor material, relative to the ink composition Material P-1 was mixed so that the total mass of the ink composition became 1% by mass, Material N-2 was mixed so that the total mass of the ink composition became 0.3% by mass, and o-xylene (97% by mass) and styrene A mixed solvent obtained by mixing ketones (3% by mass) was used as a solvent, except that the ink composition (I-9) and the ink composition (I-10) were prepared in the same manner as in Example 1, and implemented. Filterability test. The results are shown in Table 5 below.

[表5] （表5）油墨組成物 p型半導體材料的z平均分子量（Mz）重量平均分子量（Mw）過濾性實施例8 I-9 3.2×10 ⁵ 1.1×10 ⁴ 〇比較例2 I-10 5.1×10 ⁵ 1.3×10 ⁵ × [Table 5] (Table 5) ink composition z-average molecular weight (Mz) of p-type semiconductor materials Weight average molecular weight (Mw) Filterability Example 8 I-9 3.2×10 ⁵ 1.1×10 ⁴ 〇 Comparative example 2 I-10 5.1×10 ⁵ 1.3×10 ⁵ x

＜實施例9及比較例3＞使用具有下述表4所示的z平均分子量（Mz）及重量平均分子量（Mw）的材料P-1作為p型半導體材料，使用材料N-3作為n型半導體材料，以相對於油墨組成物的總質量成為1.0質量%的方式混合材料P-1，以相對於油墨組成物的總質量成為1.0質量%的方式混合材料N-3，並使用鄰二甲苯作為溶劑來進行混合，除此以外，與實施例1同樣地進行而製備油墨（I-11）及油墨（I-12），實施過濾性試驗。將結果示於下述表6中。 <Example 9 and Comparative Example 3> Using material P-1 having the z-average molecular weight (Mz) and weight-average molecular weight (Mw) shown in Table 4 below as the p-type semiconductor material, and material N-3 as the n-type semiconductor material, relative to the ink composition Material P-1 is mixed so that the total mass of the ink composition becomes 1.0% by mass, Material N-3 is mixed so that the total mass of the ink composition becomes 1.0% by mass, and mixed using ortho-xylene as a solvent, except that , Ink (I-11) and ink (I-12) were prepared in the same manner as in Example 1, and a filterability test was implemented. The results are shown in Table 6 below.

[表6] （表6）油墨組成物 p型半導體材料的z平均分子量量（Mz）重量平均分子量（Mw）過濾性實施例9 I-11 3.2×10 ⁵ 1.1×10 ⁵ 〇比較例3 I-12 5.1×10 ⁵ 1.3×10 ⁵ × [Table 6] (Table 6) ink composition The z-average molecular weight (Mz) of p-type semiconductor materials Weight average molecular weight (Mw) Filterability Example 9 I-11 3.2×10 ⁵ 1.1×10 ⁵ 〇 Comparative example 3 I-12 5.1×10 ⁵ 1.3×10 ⁵ x

＜實施例10及比較例4＞使用具有下述表4所示的z平均分子量（Mz）及重量平均分子量（Mw）的材料P-2作為p型半導體材料，以相對於油墨組成物的總質量成為0.8質量%的方式混合材料P-2，除此以外，與實施例1同樣地進行而製備油墨組成物（I-13）及油墨組成物（I-14），實施過濾性試驗。將結果示於下述表7中。 <Example 10 and Comparative Example 4> Using material P-2 having z-average molecular weight (Mz) and weight-average molecular weight (Mw) shown in Table 4 below as a p-type semiconductor material, the materials were mixed so as to become 0.8% by mass relative to the total mass of the ink composition P-2, except for this, the ink composition (I-13) and the ink composition (I-14) were prepared in the same manner as in Example 1, and the filterability test was implemented. The results are shown in Table 7 below.

[表7] （表7）油墨組成物 p型半導體材料的z平均分子量（Mz）重量平均分子量（Mw）過濾性實施例10 I-13 4.4×10 ⁵ 1.2×10 ⁵ 〇比較例4 I-14 1.0×10 ⁶ 2.7×10 ⁵ × [Table 7] (Table 7) ink composition z-average molecular weight (Mz) of p-type semiconductor materials Weight average molecular weight (Mw) Filterability Example 10 I-13 4.4×10 ⁵ 1.2×10 ⁵ 〇 Comparative example 4 I-14 1.0×10 ⁶ 2.7×10 ⁵ x

如根據以上的實施例及比較例而明確般，油墨組成物的過濾性無法藉由重量平均分子量（Mw）來控制，另外可知，雖然觀察不到與油墨組成物中使用的n型半導體材料的種類、溶劑、及濃度的相關性，但若將p型半導體材料的z平均分子量（Mz）設為所述規定範圍內，則無需進行反覆試驗，便可於不使過濾器堵塞的情況下使油墨組成物的過濾性提高。As is clear from the above Examples and Comparative Examples, the filterability of the ink composition cannot be controlled by the weight average molecular weight (Mw), and it can be seen that although no interaction with the n-type semiconductor material used in the ink composition is observed type, solvent, and concentration, but if the z-average molecular weight (Mz) of the p-type semiconductor material is within the specified range, it can be used without clogging the filter without repeated experiments. The filterability of the ink composition is improved.

＜實施例11＞ [光電轉換元件的製造及評價] （1）光電轉換元件的製造（陰極的形成）準備利用濺鍍法以100 nm的厚度形成有ITO膜的玻璃基板（以下，將包含製造中途的玻璃基板的積層體簡稱為玻璃基板。）。對該玻璃基板進行利用臭氧UV處理的清潔處理，形成陰極。 <Example 11> [Manufacture and evaluation of photoelectric conversion elements] (1) Manufacture of photoelectric conversion elements (cathode formation) A glass substrate on which an ITO film was formed to a thickness of 100 nm by a sputtering method was prepared (hereinafter, a laminate including a glass substrate in production is simply referred to as a glass substrate.). The glass substrate was cleaned by ozone UV treatment to form a cathode.

（電子傳輸層的形成）接著，將清洗完畢的玻璃基板於將聚乙烯亞胺80%乙氧基化水溶液（西格瑪奧德里奇（Sigma-Aldrich）公司製造，37質量%水溶液）以成為0.1質量%的方式溶解於水中而成的溶液中浸漬5分鐘，提起玻璃基板後放置於加熱板上，於大氣中於100℃、10分鐘的條件下使塗膜乾燥。 (Formation of electron transport layer) Next, the cleaned glass substrate was dissolved in water so that 0.1% by mass of polyethyleneimine 80% ethoxylated aqueous solution (manufactured by Sigma-Aldrich, 37% by mass aqueous solution) was dissolved in water. The resulting solution was immersed for 5 minutes, the glass substrate was lifted, placed on a hot plate, and the coating film was dried in the air at 100° C. for 10 minutes.

藉由水對乾燥後的玻璃基板進行清洗，將清洗後的玻璃基板放置於加熱板上，於大氣中於100℃、10分鐘的條件下使陰極上的塗膜乾燥，將塗膜設為電子傳輸層。Clean the dried glass substrate with water, place the cleaned glass substrate on a heating plate, and dry the coating film on the cathode in the atmosphere at 100°C for 10 minutes, and set the coating film as an electronic transport layer.

（活性層的形成）接著，藉由槽模塗佈法將實施例1的油墨組成物（I-1）塗佈於電子傳輸層上形成塗膜後，進行5分鐘真空乾燥處理（壓力10 Pa、70℃），將塗膜作為活性層。將形成有活性層的玻璃基板放置於加熱板上，於100℃、12分鐘的條件下使活性層乾燥。乾燥後的活性層的厚度為200 nm。 (formation of active layer) Next, the ink composition (I-1) of Example 1 was coated on the electron transport layer to form a coating film by the slot die coating method, and vacuum drying was performed for 5 minutes (pressure 10 Pa, 70°C). The coating film acts as the active layer. The glass substrate on which the active layer was formed was placed on a hot plate, and the active layer was dried at 100° C. for 12 minutes. The thickness of the dried active layer was 200 nm.

（陽極的形成）繼而，藉由旋塗法將聚(3,4-乙烯二氧噻吩)/聚苯乙烯磺酸溶解於水中而成的懸濁液（賀利氏（Heraeus）公司製造，克里歐斯F HC索拉爾（Clevios F HC Solar））塗佈於活性層上，形成塗膜。將形成有塗膜的玻璃基板放入烘箱中，於85℃、30分鐘的條件下使塗膜乾燥而設為陽極。乾燥後的陽極的厚度約為120 nm。藉由以上步驟，製造實施例11的光電轉換元件。 (formation of anode) Then, by spin coating poly(3,4-ethylenedioxythiophene)/polystyrene sulfonic acid dissolved in water suspension (manufactured by Heraeus, Creos F HC Solar (Clevios F HC Solar)) is coated on the active layer to form a coating film. The glass substrate on which the coating film was formed was put into an oven, and the coating film was dried on the conditions of 85 degreeC and 30 minutes, and it was set as an anode. The thickness of the dried anode is about 120 nm. Through the above steps, the photoelectric conversion element of Example 11 was produced.

[光電轉換元件的評價] （外部量子效率（EQE）的評價）於對如上所述般製造的光電轉換元件施加2 V的反向偏壓的狀態下，使用分光靈敏度測定裝置（分光計器公司製造，商品名：CEP-2000型），測定對光電轉換元件照射800 nm的單色光（光子數：5×10 ¹⁴）而產生的電流值，藉由公知的手法求出EQE。將結果示於表8中。 [Evaluation of Photoelectric Conversion Element] (Evaluation of External Quantum Efficiency (EQE)) A spectroscopic sensitivity measuring device (manufactured by Spectrometer Co. , trade name: CEP-2000 type), measured the current value generated by irradiating the photoelectric conversion element with 800 nm monochromatic light (number of photons: 5×10 ¹⁴ ), and obtained EQE by a known method. The results are shown in Table 8.

＜實施例2～實施例14＞除了使用油墨組成物I-2作為活性層的材料以外，與實施例11同樣地進行而製造光電轉換元件，求出EQE。將結果示於表8中。 <Example 2 to Example 14> A photoelectric conversion element was produced in the same manner as in Example 11 except that ink composition I-2 was used as the material of the active layer, and EQE was obtained. The results are shown in Table 8.

[表8] （表8）油墨組成物 EQE（%）實施例11 I-1 45 實施例12 I-2 42 實施例13 1-3 54 實施例14 I-4 52 [Table 8] (Table 8) ink composition EQE (%) Example 11 I-1 45 Example 12 I-2 42 Example 13 1-3 54 Example 14 I-4 52

如表8所示，可確認使用油墨組成物I-1及油墨組成物I-2作為活性層的材料的光電轉換元件無問題地發揮功能。特別是可確認使用p型半導體材料的重量平均分子量大於6.0×10 ⁴的油墨組成物I-3及油墨組成物I-4作為活性層的材料的光電轉換元件可獲得更高的EQE。 As shown in Table 8, it was confirmed that the photoelectric conversion elements using the ink composition I-1 and the ink composition I-2 as the material of the active layer functioned without any problem. In particular, it was confirmed that photoelectric conversion elements using ink composition I-3 and ink composition I-4 in which the weight average molecular weight of the p-type semiconductor material was greater than 6.0×10 ⁴ as the material of the active layer obtained higher EQE.

1:圖像檢測部 2:顯示裝置 10:光電轉換元件 11、210:支持基板 12:第一電極 13:電子傳輸層 14:活性層 15:電洞傳輸層 16:第二電極 17:密封構件 20:CMOS電晶體基板 30:層間絕緣膜 32:層間配線部 40:密封層 42:閃爍體 44:反射層 46:保護層 50:濾色器 100:指紋檢測部 200:顯示面板部 200a:顯示區域 220:有機EL元件 230:觸控感測器面板 240:密封基板 300:靜脈檢測部 302:玻璃基板 304:光源部 306:蓋部 310:***部 400:TOF型測距裝置用圖像檢測部 402:浮動擴散層 404:光閘 406:遮光部 1: Image detection department 2: Display device 10: Photoelectric conversion element 11, 210: support substrate 12: The first electrode 13: Electron transport layer 14: active layer 15: Hole transport layer 16: Second electrode 17: sealing member 20: CMOS transistor substrate 30: interlayer insulating film 32:Interlayer wiring part 40: sealing layer 42: scintillator 44: reflective layer 46: protective layer 50: Color filter 100:Fingerprint detection department 200: Display panel part 200a: display area 220: Organic EL element 230: Touch sensor panel 240: sealed substrate 300: Vein Detection Department 302: glass substrate 304: Light source department 306: cover 310: insertion part 400: Image detection unit for TOF distance measuring device 402: floating diffusion layer 404: shutter 406: shading part

圖1是示意性地表示光電轉換元件的構成例的圖。圖2是示意性地表示圖像檢測部的構成例的圖。圖3是示意性地表示指紋檢測部的構成例的圖。圖4是示意性地表示X射線攝像裝置用的圖像檢測部的構成例的圖。圖5是示意性地表示靜脈認證裝置用的靜脈檢測部的構成例的圖。圖6是示意性表示間接方式的飛行時間（time-of-flight，TOF）型測距裝置用圖像檢測部的構成例的圖。 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 an image detection unit. FIG. 3 is a diagram schematically showing a configuration example of a fingerprint detection unit. FIG. 4 is a diagram schematically showing a configuration example of an image detection unit for an X-ray imaging device. 5 is a diagram schematically showing a configuration example of a vein detection unit for the vein authentication device. 6 is a diagram schematically showing a configuration example of an image detection unit for an indirect time-of-flight (TOF) distance measuring device.

10:光電轉換元件 10: Photoelectric conversion element

11:支持基板 11: Support substrate

12:第一電極 12: The first electrode

13:電子傳輸層 13: Electron transport layer

14:活性層 14: active layer

15:電洞傳輸層 15: Hole transport layer

16:第二電極 16: Second electrode

17:密封構件 17: sealing member

Claims

一種光電轉換元件製造用油墨組成物，為包含p型半導體材料、n型半導體材料、以及溶劑的油墨組成物，其中，所述p型半導體材料包含z平均分子量小於5.0×10 ⁵的高分子化合物。 An ink composition for manufacturing a photoelectric conversion element, which is an ink composition comprising a p-type semiconductor material, an n-type semiconductor material, and a solvent, wherein the p-type semiconductor material comprises a polymer compound with a z-average molecular weight of less than 5.0×10 ⁵ .

如請求項1所述的光電轉換元件製造用油墨組成物，其中，所述p型半導體材料包含重量平均分子量大於6.0×10 ⁴的高分子化合物。 The ink composition for producing photoelectric conversion elements according to claim 1, wherein the p-type semiconductor material includes a polymer compound with a weight average molecular weight greater than 6.0×10 ⁴ .

如請求項1或請求項2所述的光電轉換元件製造用油墨組成物，其中，所述p型半導體材料包含含有具有噻吩骨架的構成單元的高分子化合物。The ink composition for producing a photoelectric conversion element according to claim 1 or claim 2, wherein the p-type semiconductor material includes a polymer compound including a constituent unit having a thiophene skeleton.

如請求項3所述的光電轉換元件製造用油墨組成物，其中，所述p型半導體材料包含具有施體/受體結構的高分子化合物。The ink composition for producing a photoelectric conversion element according to claim 3, wherein the p-type semiconductor material includes a polymer compound having a donor/acceptor structure.

如請求項1至請求項4中任一項所述的光電轉換元件製造用油墨組成物，其中，所述溶劑包含芳香族烴。The ink composition for producing a photoelectric conversion element according to any one of claim 1 to claim 4, wherein the solvent contains an aromatic hydrocarbon.

如請求項1至請求項5中任一項所述的光電轉換元件製造用油墨組成物，其中，所述n型半導體材料包含富勒烯衍生物。The ink composition for producing a photoelectric conversion element according to any one of claim 1 to claim 5, wherein the n-type semiconductor material includes a fullerene derivative.

如請求項1至請求項5中任一項所述的光電轉換元件製造用油墨組成物，其中，所述n型半導體材料包含非富勒烯化合物。The ink composition for producing a photoelectric conversion element according to any one of claims 1 to 5, wherein the n-type semiconductor material contains a non-fullerene compound.

一種光電轉換元件製造用油墨組成物的製造方法，是如請求項1至請求項7中任一項所述的油墨組成物的製造方法，且包括利用孔徑0.5 μm以下的過濾器對所述油墨組成物進行過濾的步驟。A method for manufacturing an ink composition for manufacturing a photoelectric conversion element, which is the method for manufacturing an ink composition as described in any one of claim 1 to claim 7, and includes using a filter with a pore size of 0.5 μm or less to filter the ink The step of filtering the composition.

一種光電轉換元件製造用油墨組成物的製造方法，包括：準備步驟，準備作為p型半導體材料的多種高分子化合物；篩選步驟，於所述準備步驟中所準備的所述高分子化合物中，篩選z平均分子量小於5.0×10 ⁵的高分子化合物作為p型半導體材料；以及將所述篩選步驟中篩選出的p型半導體材料與n型半導體材料以及溶劑混合，製造油墨組成物的步驟。 A method for manufacturing an ink composition for manufacturing a photoelectric conversion element, comprising: a preparation step of preparing a plurality of polymer compounds as p-type semiconductor materials; a screening step of screening among the polymer compounds prepared in the preparation step A polymer compound with a z-average molecular weight of less than 5.0×10 ⁵ is used as a p-type semiconductor material; and a step of mixing the p-type semiconductor material screened in the screening step with an n-type semiconductor material and a solvent to produce an ink composition.