JP2018166200A - Photoelectric conversion element for imaging element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoelectric conversion element excellent in hole or electron leakage preventing property, hole or electron transporting property, heat resistance against process temperature, visible light transparency, and the like.SOLUTION: A photoelectric conversion element for an imaging element, includes (A) a first electrode film, (B) a second electrode film, and (C) a photoelectric conversion unit disposed between the first electrode film and the second electrode film, and the photoelectric conversion unit has one or more organic thin film layers having a surface roughness Ra and/or Sa of 7.0 nm or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an image sensor photoelectric conversion element that can be used in an image sensor, an optical sensor, and the like.

  In recent years, interest in organic electronics devices has increased. Its features include a flexible structure and a large area, and further enabling an inexpensive and high-speed printing method in the electronic device manufacturing process. Typical devices include organic EL elements, organic solar cell elements, organic photoelectric conversion elements, organic transistor elements, and the like. Organic EL elements are expected as main targets for next-generation display applications as flat panel displays, and are applied to mobile phone displays, TVs, etc., and development aimed at further enhancement of functionality is being continued. Research and development have been made on organic solar cell elements and the like as flexible and inexpensive energy sources, and organic transistor elements and the like on flexible displays and inexpensive ICs.

  In developing an organic electronic device, it is very important to develop a material constituting the device. For this reason, many materials have been studied in each field, but they cannot be said to have sufficient performance, and even now, materials that are useful for various devices are being actively developed. Among them, compounds having benzothienobenzothiophene as a mother skeleton have also been developed as organic electronics materials (Patent Documents 1 to 3). When an alkyl derivative of benzothienobenzothiophene is used, a semiconductor thin film is formed by a printing process. However, it has a problem that the organic electronics device is inferior in heat resistance due to a relatively small number of condensed rings with respect to the alkyl chain length, which tends to cause a phase transition at a low temperature.

  In recent organic electronics, organic photoelectric conversion elements are expected to be developed into next-generation imaging elements, and reports have been made by several groups. For example, an example in which a quinacridone derivative or a quinazoline derivative is used as a photoelectric conversion element (Patent Document 4), an example in which a photoelectric conversion element using a quinacridone derivative is applied to an imaging element (Patent Document 5), and a diketopyrrolopyrrole derivative There is an example (Patent Document 6). In general, it is considered that the performance of an imaging device is improved by aiming at reduction of dark current for the purpose of high contrast and power saving. Therefore, in order to reduce the leakage current from the photoelectric conversion unit in the dark, a method of inserting a hole block layer or an electron block layer between the photoelectric conversion unit and the electrode unit is used. Further, in order to effectively reduce the leakage current, the unevenness of the surface of each layer needs to be small (Patent Document 7).

  The hole blocking layer and the electron blocking layer are generally widely used in the field of organic electronics devices, and are arranged at the interface between the electrode or the conductive film and the other films in the component film of the device, respectively. It is a film that has the function of controlling the reverse movement of holes or electrons, and adjusts the leakage of unnecessary holes or electrons. Depending on the application of the device, heat resistance, transmission wavelength, film formation method, etc. These are selected and used in consideration of the characteristics. However, the required performance of materials especially for photoelectric conversion elements is high, and the conventional hole blocking layer or electron blocking layer is sufficient in terms of leakage current prevention characteristics, heat resistance to process temperature, transparency to visible light, etc. It cannot be said that it has a good performance and has not been utilized commercially.

JP 2008-2558592 A WO2008 / 047896 WO2010 / 098372 Japanese Patent No. 4945146 Japanese Patent No. 5022573 JP 2008-290963 A JP2012-23400A

J. Am. Chem. Soc., 2006, 128 (39), 12604.

  The present invention has been made in view of such circumstances, and is a photoelectric conversion element excellent in hole or electron leakage prevention characteristics, hole or electron transport characteristics, heat resistance to process temperature, visible light transparency, and the like. The purpose is to provide.

As a result of diligent efforts to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a highly smooth organic thin film layer in the photoelectric conversion part of the photoelectric conversion element for an image sensor, The present invention has been completed.
That is, the present invention is as follows.
(1) (A) First electrode film, (B) Second electrode film, and (C) Photoelectric conversion having a photoelectric conversion part disposed between the first electrode film and the second electrode film A photoelectric conversion element for an imaging element, wherein the photoelectric conversion part has one or more organic thin film layers having a surface roughness Ra and / or Sa of 7.0 nm or less,
(2) (C) The photoelectric conversion part for an imaging element according to the above item (1), in which the photoelectric conversion unit has one or more organic thin film layers having a surface roughness Ra and / or Sa of 1.3 nm or more and 7.0 nm or less,
(3) (C) The organic thin film layer having a surface roughness Ra and / or Sa of 7.0 nm or less included in the photoelectric conversion part is other than (c-1) the photoelectric conversion layer and / or (c-2) the photoelectric conversion layer. The photoelectric conversion element for an image sensor according to the item (1) or (2), which is an organic thin film layer of
(4) (c-1) The photoelectric conversion element for an image pickup device according to (3), wherein the photoelectric conversion layer includes a p-type organic semiconductor material and an n-type organic semiconductor material,
(5) (c-2) The photoelectric conversion element for an image pickup device according to (3), wherein the organic thin film layer other than the photoelectric conversion layer is an electron block layer,
(6) (c-2) The photoelectric conversion element for an image pickup device according to item (3), wherein the organic thin film layer other than the photoelectric conversion layer is a hole blocking layer,
(7) (c-2) The photoelectric conversion element for an image pickup device according to item (3), wherein the organic thin film layer other than the photoelectric conversion layer is an electron transport layer,
(8) (c-2) The photoelectric conversion element for an imaging element according to the above item (3), wherein the organic thin film layer other than the photoelectric conversion layer is a hole transport layer,
(9) Any one of (1) to (8) further including (D) a thin film transistor having a hole accumulating portion and (E) a signal reading portion for reading a signal corresponding to the electric charge accumulated in the thin film transistor. The photoelectric conversion element for an image sensor according to the item,
(10) (C) The organic thin film layer having a surface roughness Ra and / or Sa of 7.0 nm or less of the photoelectric conversion part is represented by the following formula (1).

(In formula (1), n is the number of substituents R, and each independently represents an integer of 0 to 4. R represents a substituent independently, and when n is 2 or more, adjacent Rs are The photoelectric conversion element for an imaging device according to any one of the above items (1) to (9), comprising a compound represented by:
(11) (C) The organic thin film layer having a surface roughness Ra and / or Sa of 7.0 nm or less included in the photoelectric conversion portion is represented by the following formula (2).

(In Formula (2), R represents the same meaning as R in Formula (1) according to Claim 10). The photoelectric conversion element for an image sensor according to (10), comprising the compound represented by
(12) An imaging device in which the photoelectric conversion elements for the imaging device according to any one of (1) to (11) are arranged in an array, and (13) any of (1) to (11) An optical sensor including the photoelectric conversion element for an imaging element according to one item or the imaging element according to the preceding item (12).

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a photoelectric conversion element for an imaging element that is excellent in required characteristics such as hole or electron leakage prevention and transportability, and further heat resistance and visible light transparency.

FIG. 1 is a cross-sectional view illustrating an embodiment of a photoelectric conversion element for an image sensor according to the present invention. FIG. 2 is a plot of the surface roughness and the light / dark ratio of the photoelectric conversion element for an image sensor in each example and comparative example.

  The contents of the present invention will be described in detail. The description of the constituent elements described below is based on typical embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples.

  The first feature of the photoelectric conversion element for an image sensor of the present invention is that it has an organic thin film layer having high smoothness.

  In the present invention, the method for measuring the smoothness of the organic thin film layer may be either a contact type or a non-contact type, but since it does not damage the surface of the organic thin film layer, a laser microscope, an atomic force microscope, an electron microscope, and Non-contact measurement methods such as cross-sectional TEM are preferred.

  The average surface roughness Ra and Sa are calculated from the measurement result of the smoothness of the organic thin film obtained by the above measurement method. Specifically, the average value of the line arithmetic average roughness Ra of a plurality of portions randomly selected from the surface of the organic thin film layer, or the surface arithmetic average roughness Sa of a portion selected randomly from the surface of the organic thin film layer. Is the surface roughness of the present invention. When the average value of the linear arithmetic average roughness Ra is used, the number of measurement parts is preferably as large as possible, and an average value obtained by measuring five or more lengths of 2 μm or more is usually used. When the surface arithmetic average roughness Sa is used, the area of the measurement portion is preferably as large as possible, and is usually 2 μm square or more, and an average value at a plurality of locations selected at random may be used.

  The surface roughness Ra and / or Sa of the organic thin film layer is usually 7.0 nm or less, preferably 6.0 nm or less, more preferably 5.0 nm or less, still more preferably 4.5 nm or less, and 4.1 nm or less. Particularly preferred is 1.3 nm or more and 4.1 nm or less.

  The photoelectric conversion element for an image sensor according to the present invention (hereinafter, also simply referred to as “photoelectric conversion element”) has two electrodes, that is, an opposing (A) first electrode film and (B) second electrode film. An element in which (C) a photoelectric conversion unit is arranged between the films, and light is incident on the photoelectric conversion unit from above (A) the first electrode film or (B) the second electrode film. . (C) The photoelectric conversion unit generates electrons and holes according to the incident light amount, and a signal according to the charge is read out by a semiconductor, and the incident light amount according to the absorption wavelength of the photoelectric conversion film unit. It is an element which shows. In some cases, a reading transistor is connected to the electrode film on which light is not incident. In the case where a large number of photoelectric conversion elements are arranged in an array, the photoelectric conversion element is an imaging element because it indicates incident position information in addition to the incident light quantity. If the photoelectric conversion element arranged closer to the light source does not shield (transmit) the absorption wavelength of the photoelectric conversion element arranged behind the light source when viewed from the light source side, a plurality of photoelectric conversion elements are stacked. It may be used. By laminating and using a plurality of photoelectric conversion elements having different absorption wavelengths in the visible light region, a multicolor imaging element (full color photodiode array) can be obtained.

  (C) The photoelectric conversion part is (c-1) from the group consisting of a photoelectric conversion layer, an electron transport layer, a hole transport layer, an electron block layer, a hole block layer, a crystallization prevention layer, an interlayer contact improvement layer, and the like. It is often composed of one or a plurality of (c-2) organic thin film layers other than the selected photoelectric conversion layer. The organic thin film layer having a surface roughness Ra and / or Sa of 7.0 nm or less included in the photoelectric conversion element for an image pickup device of the present invention is organic other than (c-1) photoelectric conversion layer and (c-2) photoelectric conversion layer. Although it may be any of the thin film layers, (c-2) an organic thin film layer other than the photoelectric conversion layer is preferable.

  (A) 1st electrode film and (B) 2nd electrode film which the photoelectric conversion element for image sensors of this invention has are contained in the (C) photoelectric conversion part mentioned later (c-1) photoelectric conversion layer In the case of having a hole transport property, (c-2) Organic thin film layer other than the photoelectric conversion layer (hereinafter, the organic thin film layer other than the photoelectric conversion layer is also simply referred to as “(c-2)) organic thin film layer”. ) Is a hole transporting layer having a hole transporting property, it plays a role of collecting and collecting holes from the (c-1) photoelectric conversion layer and the (c-2) organic thin film layer. In addition, when (c-1) the photoelectric conversion layer included in the photoelectric conversion part (C-1) has an electron transporting property, or (c-2) the organic thin film layer is an electron transporting layer having an electron transporting property, It serves to take out electrons from the (c-1) photoelectric conversion layer and the (c-2) organic thin film layer and discharge them. Therefore, the material that can be used as the (A) first electrode film and the (B) second electrode film is not particularly limited as long as it has a certain degree of conductivity, but the adjacent (c-1) photoelectric conversion layer. (C-2) It is preferable to select in consideration of adhesion to the organic thin film layer, electron affinity, ionization potential, stability, and the like. Examples of materials that can be used for (A) the first electrode film and (B) the second electrode film include tin oxide (NESA), indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Conductive metal oxide; metals such as gold, silver, platinum, chromium, aluminum, iron, cobalt, nickel and tungsten; inorganic conductive materials such as copper iodide and copper sulfide; conductive polymers such as polythiophene, polypyrrole and polyaniline Carbon etc. are mentioned. A plurality of these materials may be used as a mixture as necessary, or a plurality of these materials may be laminated in two or more layers. The conductivity of the material used for (A) the first electrode film and (B) the second electrode film is not particularly limited as long as it does not obstruct the light reception of the photoelectric conversion element more than necessary, but the signal intensity and consumption of the photoelectric conversion element It is preferable that it is as high as possible from the viewpoint of electric power. For example, an ITO film having a sheet resistance value of 300Ω / □ or less functions well as (A) the first electrode film and (B) the second electrode film, but has a conductivity of several Ω / □. Since a commercial product of a substrate provided with an ITO film having the above is also available, it is desirable to use a substrate having such high conductivity. The thickness of the ITO film (electrode film) can be arbitrarily selected in consideration of conductivity, but is usually about 5 to 500 nm, preferably about 10 to 300 nm. Examples of a method for forming a film such as ITO include conventionally known vapor deposition methods, electron beam methods, sputtering methods, chemical reaction methods, and coating methods. If necessary, the ITO film provided on the substrate may be subjected to UV-ozone treatment, plasma treatment, or the like.

Among the materials for the transparent electrode film used on at least one of the light incident side of (A) the first electrode film and (B) the second electrode film, ITO, IZO, SnO ₂ , ATO ( Antimony-doped tin oxide), ZnO, AZO (Al-doped zinc oxide), GZO (gallium-doped zinc oxide), TiO ₂ , FTO (fluorine-doped tin oxide), and the like. (C-1) The transmittance of light incident through the transparent electrode film at the absorption peak wavelength of the photoelectric conversion layer is preferably 60% or more, more preferably 80% or more, and 95% or more. It is particularly preferred.

  When a plurality of photoelectric conversion layers having different wavelengths to be detected are stacked, the electrode films used between the respective photoelectric conversion layers (this is other than (A) the first electrode film and (B) the second electrode film) It is necessary to transmit light having a wavelength other than the light detected by each photoelectric conversion layer, and the electrode film is preferably made of a material that transmits 90% or more of incident light. It is more preferable to use a material that transmits at least% of light.

  The electrode film is preferably made plasma-free. By producing these electrode films without plasma, the influence of plasma on the substrate on which the electrode films are provided is reduced, and the photoelectric conversion characteristics of the photoelectric conversion element can be improved. Here, plasma-free means that no plasma is generated when the electrode film is formed, or the distance from the plasma generation source to the substrate is 2 cm or more, preferably 10 cm or more, more preferably 20 cm or more, and reaches the substrate. It means a state where plasma is reduced.

  Examples of an apparatus that does not generate plasma when forming an electrode film include an electron beam vapor deposition apparatus (EB vapor deposition apparatus) and a pulse laser vapor deposition apparatus. Hereinafter, a method of forming a transparent electrode film using an EB vapor deposition apparatus is referred to as an EB vapor deposition method, and a method of forming a transparent electrode film using a pulse laser vapor deposition apparatus is referred to as a pulse laser vapor deposition method.

  As an apparatus that can realize a state in which plasma can be reduced during film formation (hereinafter referred to as a plasma-free film formation apparatus), for example, an opposed target sputtering apparatus, an arc plasma deposition apparatus, or the like can be considered.

  When the transparent conductive film is an electrode film (for example, the first conductive film), a DC short circuit or an increase in leakage current may occur. One of the causes is that a fine crack generated in the photoelectric conversion layer is covered with a dense film such as TCO (Transparent Conductive Oxide), and is between the electrode film (second conductive film) opposite to the transparent conductive film. This is thought to be due to increased conduction. For this reason, when a material such as Al that is inferior in film quality is used for the electrode, an increase in leakage current is unlikely to occur. By controlling the film thickness of the electrode film according to the film thickness (crack depth) of the photoelectric conversion layer, an increase in leakage current can be suppressed.

  Usually, when the conductive film is made thinner than a predetermined value, the resistance value increases rapidly. The sheet resistance of the conductive film in the photoelectric conversion element for an image sensor according to the present embodiment is usually 100 to 10,000 Ω / □, and the degree of freedom in film thickness is large. In addition, the thinner the transparent conductive film, the smaller the amount of light that is absorbed and the higher the light transmittance. High light transmittance is very preferable because light absorbed by the photoelectric conversion layer is increased and the photoelectric conversion performance is improved.

The (C) photoelectric conversion unit included in the photoelectric conversion element for an image sensor of the present invention includes at least an organic thin film layer other than (c-1) a photoelectric conversion layer and (c-2) a photoelectric conversion layer.
(C) An organic semiconductor film is generally used for the photoelectric conversion layer constituting the photoelectric conversion part. (C-1) The organic semiconductor film may be a single layer or a plurality of layers. A P-type organic semiconductor film, an N-type organic semiconductor film, or a mixed film thereof (bulk heterostructure) is used. On the other hand, in the case of a plurality of layers, it is about 2 to 10 layers, and has a structure in which any one of a P-type organic semiconductor film, an N-type organic semiconductor film, or a mixed film (bulk heterostructure) is laminated. A buffer layer may be inserted in

  (C-1) The organic semiconductor film of the photoelectric conversion layer has a triarylamine compound, a benzidine compound, a pyrazoline compound, a styrylamine compound, a hydrazone compound, a triphenylmethane compound, a carbazole compound, a polysilane compound depending on the wavelength band to be absorbed. Thiophene compound, phthalocyanine compound, cyanine compound, merocyanine compound, oxonol compound, polyamine compound, indole compound, pyrrole compound, pyrazole compound, polyarylene compound, carbazole derivative, naphthalene derivative, anthracene derivative, chrysene derivative, phenanthrene derivative, pentacene derivative, Phenylbutadiene derivatives, styryl derivatives, quinoline derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives, quinacridin Emissions derivatives, coumarin derivatives, porphyrin derivatives, fullerene derivatives and metal complexes (Ir complexes, Pt complexes, Eu complexes, etc.), or the like can be used.

  In the photoelectric conversion element for an image sensor of the present invention, (C) the organic thin film layer other than the photoelectric conversion layer constituting the photoelectric conversion unit is (c-1) a layer other than the photoelectric conversion layer, for example, an electron It is also used as a transport layer, a hole transport layer, an electron block layer, a hole block layer, a crystallization prevention layer, an interlayer contact improvement layer, or the like. In particular, when used as one or more thin film layers selected from the group consisting of an electron transport layer, a hole transport layer, an electron block layer and a hole block layer, an element capable of efficiently converting into an electric signal even with weak light energy can be obtained. Therefore, it is preferable.

The electron transport layer (c-1) transports electrons generated in the photoelectric conversion layer to (A) the first electrode film or (B) the second electrode film, and from the electrode transport destination electrode film (c -1) It plays the role of blocking the movement of holes to the photoelectric conversion layer.
The hole transport layer has the role of transporting the generated holes from (c-1) the photoelectric conversion layer to (A) the first electrode film or (B) the second electrode film, and the hole transport destination electrode film. (C-1) plays the role of blocking the movement of electrons to the photoelectric conversion layer.
The electron blocking layer prevents movement of electrons from (A) the first electrode film or (B) second electrode film to (c-1) the photoelectric conversion layer, and (c-1) within the photoelectric conversion layer. It serves to prevent recombination and reduce dark current.
The hole blocking layer prevents movement of holes from (A) the first electrode film or (B) second electrode film to (c-1) the photoelectric conversion layer, and (c-1) in the photoelectric conversion layer. It has a function of preventing recombination at the time and reducing dark current.
The hole blocking layer is formed by laminating or mixing hole blocking substances alone or in combination. The hole blocking substance is not limited as long as it is a compound that can prevent holes from flowing out of the element from the electrode. Examples of compounds that can be used for the hole blocking layer include phenanthroline derivatives such as bathophenanthroline and bathocuproin, silole derivatives, quinolinol derivative metal complexes, oxadiazole derivatives, oxazole derivatives, quinoline derivatives, and formula (1) described below. The compound etc. which are represented are mentioned, Among these, 1 type, or 2 or more types can be used.

From the standpoint of preventing leakage current, the hole blocking layer should be thick, but from the standpoint of obtaining a sufficient amount of current when reading the signal at the time of light incidence, the thickness should be as thin as possible. . In order to make these contradictory characteristics compatible, it is generally preferable that the thickness of the (C) photoelectric conversion portion including (c-1) and (c-2) is about 5 to 500 nm.
In addition, the hole blocking layer and the electron blocking layer are preferably (c-1) high in transmittance of the absorption wavelength of the photoelectric conversion layer and used in a thin film so as not to prevent light absorption of the photoelectric conversion layer. preferable.

  The thin film transistor outputs a signal to the signal reading unit based on the electric charge generated by the photoelectric conversion unit. The thin film transistor includes a gate electrode, a gate insulating film, an active layer, a source electrode, and a drain electrode, and the active layer is formed of a silicon semiconductor, an oxide semiconductor, or an organic semiconductor.

  When an active layer used for a thin film transistor is formed using an oxide semiconductor, charge mobility is much higher than that of an amorphous silicon active layer, and it can be driven at a low voltage. In addition, when an oxide semiconductor is used, it is possible to form an active layer that is usually more light transmissive than silicon and has flexibility. An oxide semiconductor, particularly an amorphous oxide semiconductor, can be uniformly formed at a low temperature (for example, room temperature), and thus is particularly advantageous when a flexible resin substrate such as a plastic is used. Further, since a plurality of secondary light receiving pixels are stacked, the lower secondary light receiving pixels are affected when the upper secondary light receiving pixels are formed. In particular, the photoelectric conversion layer is easily affected by heat, but an oxide semiconductor, particularly an amorphous oxide semiconductor, is advantageous because it can be formed at a low temperature.

As the oxide semiconductor for forming the active layer, an oxide containing at least one of In, Ga, and Zn (for example, an In—O system) is preferable, and at least two of In, Ga, and Zn are used. Oxides containing (for example, In—Zn—O, In—Ga—O, and Ga—Zn—O) are more preferable, and oxides including In, Ga, and Zn are more preferable. As the In—Ga—Zn—O-based oxide semiconductor, an oxide semiconductor whose composition in a crystalline state is represented by InGaO ₃ (ZnO) m (m is a natural number less than 6) is preferable, and InGaZnO ₄ is particularly preferable. . As an amorphous oxide semiconductor having this composition, the electron mobility tends to increase as the electrical conductivity increases.

  The signal reading unit reads a charge generated and accumulated in the photoelectric conversion unit or a voltage corresponding to the charge.

  Although the typical element structure of the photoelectric conversion element for image sensors of this invention is demonstrated in detail in FIG. 1, this invention is not limited to these structures. In the embodiment of FIG. 1, 1 is an insulating part, 2 is one electrode film (first electrode film or second electrode film), 3 is an electron block layer, 4 is a photoelectric conversion layer, and 5 is a hole block. A layer, 6 represents the other electrode film (second electrode film or first electrode film), 7 represents an insulating base material, or a stacked photoelectric conversion element. The readout transistor (not shown in the drawing) only needs to be connected to either the electrode film 2 or 6, for example, if the photoelectric conversion layer 4 is transparent, the side opposite to the light incident side The film may be formed outside the electrode film (on the upper side of the electrode film 2 or on the lower side of the electrode film 6). If the thin film layer (electron block layer, hole block layer, etc.) other than the photoelectric conversion layer constituting the photoelectric conversion element does not extremely shield the absorption wavelength of the photoelectric conversion layer, the direction in which light is incident is the upper side (Fig. 1 or the lower portion (insulating substrate 7 side in FIG. 1).

  In the method for forming an organic thin film layer other than the (c-1) photoelectric conversion layer and the (c-2) photoelectric conversion layer in the photoelectric conversion element for an image pickup device of the present invention, generally, resistance heating vapor deposition that is a vacuum process, Electron beam deposition, sputtering, molecular lamination method, solution process casting, spin coating, dip coating, blade coating, wire bar coating, spray coating and other coating methods, inkjet printing, screen printing, offset printing, letterpress printing, etc. A soft lithography technique such as a printing method or a microcontact printing method, or a combination of these techniques may be employed. The thickness of each layer depends on the resistance value and charge mobility of each substance and cannot be limited, but is usually in the range of 7 to 5000 nm, preferably in the range of 5 to 1000 nm, more preferably in the range of 3 to 500 nm. Range.

  Although the material which comprises the smooth organic thin film is not specifically limited, It is preferable that the compound represented by following formula (1) is included.

  In the above formula (1), n is the number of substituents R, and each independently represents an integer of 0 to 4. R each independently represents a substituent. When n is 2 or more, adjacent substituents may be linked to form a ring structure.

The substituent represented by R in formula (1) is not particularly limited, but a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aromatic group, a halogen atom, a hydroxyl group, a mercapto group, Examples thereof include a nitro group, an alkyl-substituted amino group, an aryl-substituted amino group, an unsubstituted amino group (NH ₂ group), an acyl group, an alkoxycarbonyl group, a cyano group, and an isocyano group.

Here, the “substituted or unsubstituted alkyl group” means an alkyl group in which a hydrogen atom on the alkyl group is substituted with a substituent or an alkyl group in which a hydrogen atom on the alkyl group is not substituted with a substituent. . When the alkyl group has a substituent, it suffices if it has at least one substituent, and the position of substitution and the number of substituents are not particularly limited. The same applies to a substituted or unsubstituted alkoxy group and a substituted or unsubstituted aromatic group.
As the substituent of the alkyl group, alkoxy group and aromatic group as the substituent represented by R in Formula (1), the substituent represented by R in Formula (1) (substituted or unsubstituted alkyl group, substituted Or unsubstituted alkoxy group, substituted or unsubstituted aromatic group, halogen atom, hydroxyl group, mercapto group, nitro group, alkyl-substituted amino group, aryl-substituted amino group, unsubstituted amino group (NH ₂ group), acyl group , Alkoxycarbonyl group, cyano group and isocyano group).

The alkyl group as a substituent represented by R in the formula (1) is not limited to any of linear, branched and cyclic, and the carbon number is not particularly limited, but usually has 1 to 4 carbon atoms. It is a linear or branched alkyl group or a cyclic alkyl group having 5 to 6 carbon atoms.
Specific examples of the alkyl group as a substituent represented by R in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, and a tert-butyl group. , Sec-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, cyclopentyl group, cyclohexyl group and the like, preferably a linear or branched alkyl group having 1 to 4 carbon atoms. More preferably, it is a linear alkyl group having 1 or 2 carbon atoms.

  Specific examples of the alkoxy group as the substituent represented by R in the formula (1) include methoxy group, ethoxy group, propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, t-butoxy group, n -Pentyloxy group, iso-pentyloxy group, t-pentyloxy group, sec-pentyloxy group, n-hexyloxy group, iso-hexyloxy group, n-heptyloxy group, sec-heptyloxy group, n-octyl Oxy group, n-nonyloxy group, sec-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy Group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyl Xyl group, n-eicosyloxy group, docosyloxy group, n-pentacosyloxy group, n-octacosyloxy group, n-tricontyloxy group, 5- (n-pentyl) decyloxy group, heneicosyloxy Group, tricosyloxy group, tetracosyloxy group, hexacosyloxy group, heptacosyloxy group, nonacosyloxy group, n-triacontyloxy group, squaryloxy group, dotriacontyloxy group and hexatria Examples thereof include alkoxy groups having 1 to 36 carbon atoms such as a contyloxy group, preferably alkoxy groups having 1 to 24 carbon atoms, more preferably alkoxy groups having 1 to 20 carbon atoms, and 1 carbon atom. Is more preferably an alkoxy group having 1 to 12 carbon atoms, particularly preferably an alkoxy group having 1 to 6 carbon atoms, And most preferably from 1 to 4 alkoxy groups.

Specific examples of the aromatic group as the substituent represented by R in the formula (1) include aromatic hydrocarbon groups such as a phenyl group and a naphthyl group, and heterocyclic condensed aromatic groups. Preferably there is.
Specific examples of the halogen atom as the substituent represented by R in Formula (1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl-substituted amino group as a substituent represented by R in the formula (1) is not limited to either a monoalkyl-substituted amino group or a dialkyl-substituted amino group. The alkyl group in these alkyl-substituted amino groups is represented by the formula (1 The same thing as the alkyl group as a substituent which R of R) represents is mentioned.

The aryl-substituted amino group as a substituent represented by R in the formula (1) is not limited to either a monoaryl-substituted amino group or a diaryl-substituted amino group. The aryl group in these aryl-substituted amino groups is represented by the formula (1 The same thing as the aromatic hydrocarbon group described in the term of the substituent which R represents is.
Examples of the acyl group as the substituent represented by R in Formula (1) include the aromatic hydrocarbon group described in the section of the substituent represented by R ₁ and R ₂ in Formula (1), and R in Formula (1). The substituent which the alkyl group described in the term of the substituent to represent couple | bonded with the carbonyl group (= CO group) is mentioned.
Examples of the alkoxycarbonyl group as a substituent represented by R in Formula (1) include a substituent in which an alkoxy group as a substituent represented by R in Formula (1) is bonded to a carbonyl group.
The substituent represented by R in formula (1) is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, a halogen atom or an alkoxyl group, and is a substituted or unsubstituted aromatic group. More preferably.

  The substitution position of R in the above formula (1) is not particularly limited, but is the 2nd and 7th positions in the BTBT ([1] benzothieno [3,2-b] [1] benzothiophene) structure in the formula (1). Is preferred. That is, the compound represented by the formula (1) is preferably a compound represented by the following general formula (2).

In formula (2), R represents the same meaning as R in formula (1), and preferred one is also the same as R in formula (1).
That is, as the compound represented by the formula (2), R in the formula (2) is preferably the most preferable embodiment of the R in the formula (1) described above.
The organic thin film other than the photoelectric conversion layer (c-2) comprising the compound represented by the formula (1) is any of the above-described electron transport layer, hole transport layer, electron block layer, and hole block layer. However, it is preferably used for the hole blocking layer.

  Specific examples of the compound represented by the formula (1) are shown below, but the present invention is not limited to these specific examples.

The compound represented by the formula (1) can be synthesized by a known method disclosed in Patent Document 1, Patent Document 6, and Non-Patent Document 1.
For example, when n in the formula (1) is a compound of 1 to 4, the methods described in the following schemes can be mentioned. Using the nitrostilbene derivative (A) as a raw material, a benzothienobenzothiophene skeleton (D) is formed and reduced to obtain an aminated product (E) (a compound in which R in the formula (1) is an amino group). It is done. If this compound (E) is halogenated, a halide (F) (a compound in which R in the formula (1) is a halogen, and in the following scheme, a compound in which R is iodine is described as an example) is obtained. If F) is further coupled with a boric acid derivative, it is possible to obtain a compound in which R in formula (1) is an aromatic group or the like. In addition, according to the method of patent document 5, since R in Formula (1) can manufacture a compound, such as an aromatic group, from a corresponding benzaldehyde derivative in one step, it is more effective.
In addition, in the case of a compound of formula (1) where n is 0 or adjacent Rs are linked to form a ring structure and does not have a substituent, a stilbene derivative having no nitro group is used as a starting material. A desired compound is obtained by forming the skeleton (D).

  The purification method of the compound represented by Formula (1) is not particularly limited, and known methods such as recrystallization, column chromatography, and vacuum sublimation purification can be employed. These methods can be combined as necessary.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated still in detail, this invention is not limited to these examples.
The block layer described in the examples may be either a hole block layer or an electron block layer. The photoelectric conversion element is manufactured using a vapor deposition unit integrated with the glove box, and the photoelectric conversion element is installed in a sealed bottle-type measurement chamber (manufactured by ALS Technology) in a glove box in a nitrogen atmosphere. Then, current voltage application measurement was performed. Current voltage application measurement was performed using a semiconductor parameter analyzer 4200-SCS (Keithley Instruments) unless otherwise specified. Irradiation of incident light was performed using PVL-3300 (manufactured by Asahi Spectroscopic Co., Ltd.) at an irradiation light wavelength of 550 nm and an irradiation light half width of 20 nm unless otherwise specified. Further, the surface roughness of the deposited film was measured in a measuring range of 10 μm square using a laser microscope VK-X250 / 260 (Keyence) with a 150 × lens and a laser beam wavelength of 408 nm. The light / dark ratio in the examples indicates a value obtained by dividing the current value in the case of light irradiation by the current value in a dark place. In the examples, “part” means mass part, and “%” means mass%.

Synthesis Example 1 (Synthesis of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene)
2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (3.8 parts) synthesized by the method described in Japanese Patent No. 4945757, generally available in DMF (250 parts) Naphthalen-2-ylboronic acid (3.3 parts), tripotassium phosphate (27 parts) and tetrakis (triphenylphosphine) palladium (0.47 parts) were mixed and stirred at 90 ° C. for 6 hours in a nitrogen atmosphere. . After cooling the obtained reaction liquid to room temperature, water (250 parts) was added, and solid content was separated by filtration. The obtained solid content was washed with acetone and dried, followed by purification by sublimation, whereby No. in the above specific example. 9 (3.1 parts, yield 82%) represented by 9 was obtained.

Synthesis Example 2 (Synthesis of 2,7-bis (4′-methyl- [1,1′-biphenyl] -4-yl) [1] benzothieno [3,2-b] [1] benzothiophene)
Instead of naphthalen-2-ylboronic acid (3.3 parts), the commonly available (4′-methyl- [1,1′-biphenyl] -4-yl) boronic acid (5.0 parts) was used. Except for the above, according to Synthesis Example 1, No. 21 (2.7 parts, 61% yield) represented by 21 was obtained.

Synthesis Example 3 (Synthesis of 2,7-bis (2-fluoro- [1,1′-biphenyl] -4-yl) [1] benzothieno [3,2-b] [1] benzothiophene)
Instead of naphthalen-2-ylboronic acid (3.3 parts), commonly available (2-fluoro- [1,1′-biphenyl] -4-yl) boronic acid (5.0 parts) was used. Except for the above-mentioned specific example No. 23 (2.2 parts, 50% yield) was obtained.

Synthesis Example 4 (Synthesis of 2,7-bis ([1,1 ′: 3,1 ″ -terphenyl] -4-yl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 1) Synthesis of 2-([1,1 ′: 3,1 ″ -terphenyl] -4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene ( 240 parts), commonly available 4-bromo-1,1 ′: 3,1 ″ -terphenyl (6.0 parts), bis (pinacolato) diboron (5.6 parts), potassium acetate (3. 5 parts) and [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.5 parts) were mixed and stirred at reflux temperature for 4 hours under nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, 20 parts of silica gel was added and stirred for 5 minutes. Thereafter, the solid content was filtered off and the solvent was removed under reduced pressure to give 2-([1,1 ′: 3,1 ″ -terphenyl] -4-yl) -4,4,5,5-tetramethyl. -1,3,2-dioxaborolane (6.9 parts, 99% yield) was obtained.

(Step 2) Synthesis of 2,7-bis ([1,1 ′: 3,1 ″ -terphenyl] -4-yl) [1] benzothieno [3,2-b] [1] benzothiophene Naphthalene- Instead of 2-ylboronic acid (3.3 parts), 2-([1,1 ′: 3,1 ″ -terphenyl] -4-yl) -4,4,5,5 obtained in step 1 No. of the above specific example according to Synthesis Example 1 except that 5-tetramethyl-1,3,2-dioxaborolane (6.8 parts) was used and water (8.0 parts) was added to the reaction system. . 26 (2.6 parts, yield 46%) represented by 26 was obtained.

Synthesis Example 5 (2,7-bis ([1,1 ′: 3 ′, 1 ″ -terphenyl] -5′-yl) [1] benzothieno [3,2-b] [1] synthesis of benzothiophene )
Instead of naphthalen-2-ylboronic acid (3.3 parts), the commonly available (2-fluoro- [1,1′-biphenyl] -4-yl) boronic acid (5.3 parts) was used Except for the above-mentioned specific example No. 27 was obtained (2.0 parts, yield 37%).

Synthesis Example 6 (Synthesis of 2,7-bis (benzo [b] furan-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene)
According to Synthesis Example 1, except that benzo [b] furan-2-ylboronic acid (1.9 parts), which is generally available, was used instead of naphthalen-2-ylboronic acid (3.3 parts) No. of specific example. 29 was obtained (2.6 parts, yield 73%).

Synthesis Example 7 (Synthesis of 2,7-bis (benzo [b] thiophen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene)
According to Synthesis Example 1, except that benzo [b] thiophen-2-ylboronic acid (2.1 parts), which is generally available, was used instead of naphthalen-2-ylboronic acid (3.3 parts) No. of specific example. 33 (2.7 parts, yield 70%) represented by 33 was obtained.

Synthesis Example 8 (Synthesis of 2,7-bis (4- (benzo [b] furan-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 3) Synthesis of 2- (4-bromophenyl) benzo [b] furan To DMF (920 parts), commonly available benzo [b] furan-2-ylboronic acid (14.8 parts), para-bromo Iodobenzene (25.8 parts), tripotassium phosphate (110 parts) and tetrakis (triphenylphosphine) palladium (2.8 parts) were mixed and stirred at 90 ° C. for 6 hours in a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (920 parts) was added, and solid content was fractionated by filtration. The obtained solid was washed with methanol and dried to obtain 2- (4-bromophenyl) benzo [b] furan (6.6 parts, yield 26%).

(Step 4) Synthesis of 2- (4- (benzo [b] furan-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (240 parts) 2- (4-Bromophenyl) benzo [b] furan (5.0 parts), bis (pinacolato) diboron (5.6 parts), potassium acetate (3.5 parts) and [1, 1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.5 parts) was mixed and stirred at reflux temperature for 4 hours under nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, 20 parts of silica gel was added and stirred for 5 minutes. Thereafter, the solid content is filtered off and the solvent is removed under reduced pressure to give 2- (4- (benzo [b] furan-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3, 2-Dioxaborolane (5.2 parts, 88% yield) was obtained.

(Step 5) Synthesis of 2,7-bis (4- (benzo [b] furan-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene In DMF (200 parts), Water (6.0 parts), 2,7-diiodo [1] benzothieno [3,2-b] [3] benzothiophene (3.0 parts) synthesized by the method described in Japanese Patent No. 4945757, in Step 4 The resulting 2- (4- (benzo [b] furan-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.0 parts), triphosphate Potassium (20 parts) and tetrakis (triphenylphosphine) palladium (0.4 parts) were mixed and stirred at 90 ° C. for 6 hours in a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (200 parts) was added and solid content was separated by filtration. The obtained solid content was washed with acetone and dried, followed by purification by sublimation, whereby No. in the above specific example. 83 (2.0 parts, 50% yield) was obtained.

Synthesis Example 9 (Synthesis of 2,7-bis (4- (benzo [b] thiophen-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 6) Synthesis of 2- (4-bromophenyl) benzo [b] thiophene To DMF (300 parts), generally available benzo [b] thiophen-2-ylboronic acid (5.0 parts), para-bromo Iodobenzene (7.9 parts), tripotassium phosphate (34 parts), and tetrakis (triphenylphosphine) palladium (0.84 parts) were mixed and stirred at 90 ° C. for 6 hours in a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (300 parts) was added and solid content was fractionated by filtration. The obtained solid was washed with methanol and dried to obtain 2- (4-bromophenyl) benzo [b] thiophene (5.7 parts, yield 70%).

(Step 7) Synthesis of 2- (4- (benzo [b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (240 parts) 2- (4-Bromophenyl) benzo [b] thiophene (5.3 parts), bis (pinacolato) diboron (5.6 parts), potassium acetate (3.5 parts) and [1, 1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.5 parts) was mixed and stirred at reflux temperature for 4 hours under nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, 20 parts of silica gel was added and stirred for 5 minutes. Thereafter, the solid content is filtered off and the solvent is removed under reduced pressure to give 2- (4- (benzo [b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3, 2-Dioxaborolane (4.5 parts, 73% yield) was obtained.

(Step 8) Synthesis of 2,7-bis (4- (benzo [b] thiophen-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene In DMF (170 parts), Water (5.0 parts), 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (2.6 parts) synthesized by the method described in Japanese Patent No. 4945757, in Step 7 The resulting 2- (4- (benzo [b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.5 parts), triphosphate Potassium (18 parts) and tetrakis (triphenylphosphine) palladium (0.35 parts) were mixed and stirred at 90 ° C. for 6 hours in a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (170 parts) was added and solid content was separated by filtration. The obtained solid content was washed with acetone and dried, followed by purification by sublimation, whereby No. in the above specific example. The compound represented by 87 (1.6 parts, yield 46%) was obtained.

Synthesis Example 10 (Synthesis of 2,7-bis ([1,1′-biphenyl] -3-yl) [1] benzothieno [3,2-b] [1] benzothiophene)
In place of naphthalen-2-ylboronic acid (3.3 parts), no. 6 (2.1 parts, 51% yield) was obtained.

Synthesis Example 11 (Synthesis of 2,7-bis ([1,1′-biphenyl] -2-yl) [1] benzothieno [3,2-b] [1] benzothiophene)
In place of naphthalen-2-ylboronic acid (3.3 parts), No. of the above specific example was used according to Synthesis Example 1 except that 2-biphenylboronic acid (3.8 parts), which is generally available, was used. 7 (2.4 parts, yield 57%) represented by 7 was obtained.

Synthesis Example 12 (Synthesis of 2,7-bis (naphthalen-1-yl) [1] benzothieno [3,2-b] [1] benzothiophene)
Instead of naphthalen-2-ylboronic acid (3.3 parts), No. of the above specific example was used according to Synthesis Example 1 except that naphthalen-1-ylboronic acid (3.3 parts), which is generally available, was used. . 13 (3.0 parts, 79% yield) was obtained.

Synthesis Example 13 (Synthesis of 2,7-bis (phenanthren-9-yl) [1] benzothieno [3,2-b] [1] benzothiophene)
In place of naphthalen-2-ylboronic acid (3.3 parts), no phenanthrene-9-ylboronic acid (4.3 parts) was used in the same manner as in Synthesis Example 1 except that phenanthrene-9-ylboronic acid (4.3 parts) was used. . 15 was obtained (3.0 parts, yield 65%).

Synthesis Example 14 (Synthesis of 2,7-bis (3,5-bis (trifluoromethyl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene)
Synthetic Example 1 except that instead of naphthalen-2-ylboronic acid (3.3 parts), generally available 3,5-bis (trifluoromethyl) phenylboronic acid (5.0 parts) was used. In accordance with the above specific example No. 18 (3.6 parts, 70% yield) was obtained.

Synthesis Example 15 (Synthesis of 2,7-bis (9H-carbazol-9-yl) [1] benzothieno [3,2-b] [1] benzothiophene)
Synthetic Example 1 except that instead of naphthalen-2-ylboronic acid (3.3 parts), generally available 3,5-bis (trifluoromethyl) phenylboronic acid (5.0 parts) was used. In accordance with the above specific example No. 81 (3.6 parts, yield 70%) represented by 81 was obtained.

Synthesis Example 16 (2,7-bis (5′-phenyl- [1,1 ′: 3 ′, 1 ″ -terphenyl] -4-yl) [1] benzothieno [3,2-b] [1] Synthesis of benzothiophene)
(Step 9) (5′-Phenyl- [1,1 ′: 3 ′, 1 ″ -terphenyl] -4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Synthesis of Toluene (510 parts) with commonly available 4-bromo-5′-phenyl-1,1 ′: 3 ′, 1 ″ -terphenyl (15.0 parts), bis (pinacolato) diboron (12 0.0 part), potassium acetate (7.5 parts) and [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (1.1 parts), and under nitrogen atmosphere, Stir at reflux for 5 hours. After cooling the obtained reaction liquid to room temperature, 50 parts of silica gel was added and stirred for 5 minutes. Thereafter, the solid content is filtered off and the solvent is removed under reduced pressure to give (5′-phenyl- [1,1 ′: 3 ′, 1 ″ -terphenyl] -4-yl) -4,4,5,5. 5-tetramethyl-1,3,2-dioxaborolane (12.0 parts, 71% yield) was obtained.

(Step 10) 2,7-bis (5′-phenyl- [1,1 ′: 3 ′, 1 ″ -terphenyl] -4-yl) [1] benzothieno [3,2-b] [1] Synthesis of benzothiophene DMF (300 parts), water (9.0 parts), 2,7-diiodo [1] benzothieno [3,2-b] [1] benzo synthesized by the method described in Japanese Patent No. 4945757 Thiophene (4.5 parts), (5′-phenyl- [1,1 ′: 3 ′, 1 ″ -terphenyl] -4-yl) -4,4,5,5-obtained in step 9 Tetramethyl-1,3,2-dioxaborolane (9.9 parts), tripotassium phosphate (30.3 parts), and tetrakis (triphenylphosphine) palladium (0.6 parts) were mixed and mixed under a nitrogen atmosphere. Stir at 6 ° C. for 6 hours. After cooling the obtained reaction liquid to room temperature, water (300 parts) was added and solid content was fractionated by filtration. The obtained solid content was washed with acetone and dried, followed by purification by sublimation, whereby No. in the above specific example. 28 was obtained (2.0 parts, yield 26%).

Synthesis Example 17 (2,7-bis (4 ′-(pyridin-2-yl)-[1,1′-biphenyl] -4-yl) [1] benzothieno [3,2-b] [1] benzothiophene Synthesis)
(Step 11) Synthesis of (4- (pyridin-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (960 parts) is generally available in 2- (4-Bromophenyl) pyridine (17.1 parts), bis (pinacolato) diboron (22.4 parts), potassium acetate (14.1 parts) and [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) Dichloride dichloromethane adduct (2.3 parts) was mixed and stirred at reflux temperature for 5 hours under nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, 80 parts of silica gel was added and stirred for 5 minutes. Thereafter, the solid content was filtered off and washed with ethyl acetate. The solvent in the resulting solution was removed under reduced pressure to give (4- (pyridin-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (19.0 parts, Yield 92%) was obtained.

(Step 12) Synthesis of 2- (4′-bromo- [1,1′-biphenyl] -4-yl) pyridine DMF (520 parts) was obtained in Step 11 with water (18.0 parts) ( 4- (Pyridin-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (14.6 parts), commonly available para-bromoiodobenzene (14.6) Part), tripotassium phosphate (62.6 parts) and tetrakis (triphenylphosphine) palladium (1.6 parts) were mixed and stirred at 90 ° C. for 6 hours in a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (520 parts) was added, and solid content was separated by filtration. The obtained solid was washed with water and dried to obtain 2- (4′-bromo- [1,1′-biphenyl] -4-yl) pyridine (15.0 parts, yield 94%). It was.

(Step 13) Synthesis of (4 ′-(pyridin-2-yl)-[1,1′-biphenyl] -4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (350 parts) was added 2- (4′-bromo- [1,1′-biphenyl] -4-yl) pyridine (8.0 parts), bis (pinacolato) diboron (7. 9 parts), potassium acetate (5.0 parts) and [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.8 parts) were mixed and refluxed under a nitrogen atmosphere. Stir at temperature for 5 hours. After cooling the obtained reaction liquid to room temperature, 40 parts of silica gel was added and stirred for 5 minutes. Thereafter, the solid content was filtered off and washed with ethyl acetate. The solvent in the resulting solution was removed under reduced pressure to give (4 ′-(pyridin-2-yl)-[1,1′-biphenyl] -4-yl) -4,4,5,5-tetramethyl- 1,3,2-dioxaborolane (9.0 parts, yield 97%) was obtained.

(Step 14) 2,7-bis (4 ′-(pyridin-2-yl)-[1,1′-biphenyl] -4-yl) [1] benzothieno [3,2-b] [1] benzothiophene Synthesis of (5′-phenyl- [1,1 ′: 3 ′, 1 ″ -terphenyl] -4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (9 (4 ′-(pyridin-2-yl)-[1,1′-biphenyl] -4-yl) -4,4,5,5-tetramethyl obtained in Step 13 -1,3,2-dioxaborolane (8.2 parts) was used except that the synthesis was carried out according to Step 10 to obtain the No. in the above specific example. The compound represented by 168 (7.2 parts, 42%) was obtained.

Synthesis Example 18 (Synthesis of 2,7-bis (4- (benzo [d] thiazol-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 15) Synthesis of 2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) phenyl) benzo [d] thiazole In toluene (240 parts), Available 2- (4-bromophenyl) benzo [d] thiazole (5.3 parts), bis (pinacolato) diboron (5.6 parts), potassium acetate (3.5 parts) and [1,1'- [Bis (diphenylphosphino) ferrocene] palladium (II) dichloride Dichloromethane adduct (0.5 parts) was mixed and stirred at reflux temperature for 4 hours under nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, 20 parts of silica gel was added and stirred for 5 minutes. Thereafter, the solid content is filtered off, and the solvent is removed under reduced pressure to give 2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) phenyl) benzo [d ] Thiazole (4.9 parts, 80% yield) was obtained.

(Step 16) Synthesis of 2,7-bis (4- (benzo [d] thiazol-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene In DMF (170 parts), Water (5.0 parts), 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (2.6 parts) synthesized by the method described in Japanese Patent No. 4945757, The obtained 2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) phenyl) benzo [d] thiazole (4.5 parts), tripotassium phosphate (18 parts) and tetrakis (triphenylphosphine) palladium (0.35 parts) were mixed and stirred at 90 ° C. for 6 hours in a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (170 parts) was added and solid content was separated by filtration. The obtained solid content was washed with acetone and dried, followed by purification by sublimation, whereby No. in the above specific example. The compound represented by 111 (1.8 parts, 52% yield) was obtained.

Synthesis Example 19 (Synthesis of 2,7-bis (4- (benzo [b] thiophen-2-yl) -2-methylphenyl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 17) Synthesis of 2- (4-bromo-3-methylphenyl) benzo [b] thiophene To DMF (300 parts), generally available benzo [b] thiophen-2-ylboronic acid (5.0 parts) , 2-bromo-5-iodotoluene (8.3 parts), tripotassium phosphate (34 parts) and tetrakis (triphenylphosphine) palladium (0.84 parts) were mixed at 90 ° C. under a nitrogen atmosphere. Stir for hours. After cooling the obtained reaction liquid to room temperature, water (300 parts) was added and solid content was fractionated by filtration. The obtained solid was washed with methanol and dried to obtain 2- (4-bromo-3-methylphenyl) benzo [b] thiophene (5.7 parts, yield 67%).

(Step 18) Synthesis of 2- (4- (benzo [b] thiophen-2-yl) -2-methylphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (240 2- (4-bromo-3-methylphenyl) benzo [b] thiophene (5.6 parts), bis (pinacolato) diboron (5.6 parts), potassium acetate (3 parts) 0.5 part) and [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.5 part) were mixed and stirred at reflux temperature for 4 hours under nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, 20 parts of silica gel was added and stirred for 5 minutes. Thereafter, the solid content is filtered off and the solvent is removed under reduced pressure to give 2- (4- (benzo [b] thiophen-2-yl) -2-methylphenyl) -4,4,5,5-tetramethyl- 1,3,2-dioxaborolane (5.6 parts, yield 87%) was obtained.

(Step 19) Synthesis of 2,7-bis (4- (benzo [b] thiophen-2-yl) -2-methylphenyl) [1] benzothieno [3,2-b] [1] benzothiophene DMF (170 Part)), water (5.0 parts), 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (2.6 parts) synthesized by the method described in Japanese Patent No. 4945757 2- (4- (Benzo [b] thiophen-2-yl) -2-methylphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4 .6 parts), tripotassium phosphate (18 parts) and tetrakis (triphenylphosphine) palladium (0.35 parts) were mixed and stirred at 90 ° C. for 6 hours in a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (170 parts) was added and solid content was separated by filtration. The obtained solid content was washed with acetone and dried, followed by purification by sublimation, whereby No. in the above specific example. The compound represented by 170 (1.2 parts, yield 35%) was obtained.

Synthesis Example 20 (Synthesis of 2,7-bis (2-dibenzofuranyl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 20) Synthesis of 2- (dibenzofuran-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (150 parts) was added 2-bromodibenzofuran (5.0 parts). ), Bis (pinacolato) diboron (6.2 parts), potassium acetate (4.0 parts) and [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.5 parts) ) And stirred at reflux temperature for 4 hours under a nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, solid content was separated by filtration, and a filtrate containing the product was obtained. Subsequently, it is purified by short silica gel column chromatography (developing solution; toluene), and the solvent is removed under reduced pressure to give 2- (dibenzofuran-2-yl) -4,4,5,5-tetramethyl-1,3. , 2-dioxaborolane (3.8 parts, yield 64%) was obtained.

(Step 21) Synthesis of 2,7-bis (2-dibenzofuranyl) [1] benzothieno [3,2-b] [1] benzothiophene DMF (250 parts), water (8.0 parts), patent 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (4.7 parts) synthesized by the method described in No. 4945757, 2- (dibenzofuran-2 obtained in Step 20) -Yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.0 parts), tripotassium phosphate (8.1 parts) and tetrakis (triphenylphosphine) palladium (0. 6 parts) was mixed and stirred at 90 ° C. for 5 hours under a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (250 parts) was added, and solid content was separated by filtration. The obtained solid content was washed with acetone and dried, followed by purification by sublimation, whereby No. in the above specific example. The compound represented by 165 (1.5 parts, yield 28%) was obtained.

Synthesis Example 21 (Synthesis of 2,7-bis (9,9-dimethyl-9H-fluoren-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 22) Synthesis of 2- (9,9-dimethyl-9H-fluoren-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (250 parts) -Bromo-9,9-dimethylfluorene (10.0 parts), bis (pinacolato) diboron (11.2 parts), potassium acetate (7.2 parts) and [1,1'-bis (diphenylphosphino) ferrocene Palladium (II) dichloride dichloromethane adduct (0.9 parts) was mixed and stirred at reflux temperature for 3 hours under nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, solid content was separated by filtration, and a filtrate containing the product was obtained. Subsequently, it is purified by short silica gel column chromatography (developing solution; toluene), and the solvent is removed under reduced pressure to give 2- (9,9-dimethyl-9H-fluoren-2-yl) -4, 4, 5, 5-tetramethyl-1,3,2-dioxaborolane (11.1 parts, 95% yield) was obtained.

(Step 23) Synthesis of 2,7-bis (9,9-dimethyl-9H-fluoren-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene DMF (300 parts) is mixed with water. (10.0 parts), 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (7.1 parts) synthesized by the method described in Japanese Patent No. 4945757, obtained in Step 22. 2- (9,9-dimethyl-9H-fluoren-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (11.1 parts), tripotassium phosphate ( 12.2 parts) and tetrakis (triphenylphosphine) palladium (0.9 parts) were mixed and stirred at 90 ° C. for 4 hours under a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (250 parts) was added, and solid content was separated by filtration. The obtained solid content was washed with acetone and dried, followed by purification by sublimation, whereby No. in the above specific example. The compound represented by 166 (6.2 parts, yield 69%) was obtained.

Synthesis Example 22 (Synthesis of 2,7-bis (4- (9,9-dimethyl-9H-fluoren-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 24) Synthesis of 2- (9,9-dimethyl-9H-fluoren-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (250 parts) -Bromo-9,9-dimethylfluorene (10.0 parts), bis (pinacolato) diboron (11.2 parts), potassium acetate (7.2 parts) and [1,1'-bis (diphenylphosphino) ferrocene Palladium (II) dichloride dichloromethane adduct (0.9 parts) was mixed and stirred at reflux temperature for 3 hours under nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, solid content was separated by filtration, and a filtrate containing the product was obtained. Subsequently, it is purified by short silica gel column chromatography (developing solution; toluene), and the solvent is removed under reduced pressure to give 2- (9,9-dimethyl-9H-fluoren-2-yl) -4, 4, 5, 5-tetramethyl-1,3,2-dioxaborolane (11.1 parts, 95% yield) was obtained.

(Step 25) Synthesis of 2- (4-bromophenyl) -9,9-dimethyl-9H-fluorene To a mixed solution of DMF (400 parts) and water (15 parts), 2- (9 , 9-dimethyl-9H-fluoren-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (25.0 parts), 1-bromo-4-iodobenzene (22. 0 part), tripotassium phosphate (33.2 parts) and tetrakis (triphenylphosphine) palladium (2.7 parts) were added, and the mixture was stirred at 50 ° C. for 2.5 hours under a nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, water was added, and the produced white solid was collected by filtration. 2- (4-Bromophenyl) -9,9-dimethyl-9H-fluorene (26.7 parts, yield 98%) was obtained by purification with recrystallization (recrystallization solvent; acetone).

(Step 26) Synthesis of 2- (4- (9,9-dimethyl-9H-fluoren-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (200 Parts) 2- (4-bromophenyl) -9,9-dimethyl-9H-fluorene (10.0 parts), bis (pinacolato) diboron (8.7 parts), potassium acetate ( 5.6 parts) and [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.7 parts) were mixed and stirred at reflux temperature for 4 hours under a nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, solid content was separated by filtration, and a filtrate containing the product was obtained. Subsequently, it refine | purified by the short silica gel column chromatography (developing liquid; toluene), and white solid was obtained by removing a solvent under reduced pressure. This solid was further purified by recrystallization (recrystallization solvent; acetone / hexane) to give 2- (4- (9,9-dimethyl-9H-fluoren-2-yl) phenyl) -4,4,5,5. 5-tetramethyl-1,3,2-dioxaborolane (8.3 parts, yield 73%) was obtained.

(Step 27) Synthesis of 2,7-bis (4- (9,9-dimethyl-9H-fluoren-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene DMF (190 Part)), water (7.0 parts), 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (3.7 parts) synthesized by the method described in Japanese Patent No. 4945757 2- (4- (9,9-dimethyl-9H-fluoren-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7 0.5 part), tripotassium phosphate (6.4 parts) and tetrakis (triphenylphosphine) palladium (0.5 parts) were mixed and stirred at 90 ° C. for 3 hours under a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (200 parts) was added and solid content was separated by filtration. The obtained solid content was washed with DMF and acetone, dried, and then subjected to sublimation purification. 167 (1.8 parts, 31% yield) was obtained.

Synthesis Example 23 (Synthesis of 2,7-bis (6-phenylnaphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 28) Synthesis of 2-methoxy-6-phenylnaphthalene To a mixed solution of toluene (250 parts), isopropyl alcohol (20 parts) and water (15 parts), 2-bromo-6-methoxynaphthalene (25 parts), phenyl Boronic acid (15.4 parts), tripotassium phosphate (44.8 parts) and tetrakis (triphenylphosphine) palladium (3.7 parts) were added, and the mixture was stirred at reflux temperature for 4 hours in a nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, toluene and water were added, and liquid separation was carried out. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (developing solution; toluene / hexane = 1/6 (volume ratio)), and the solvent was removed under reduced pressure to give 2-methoxy-6-phenylnaphthalene ( 16.6 parts, yield 69%).

(Step 29) Synthesis of 2-hydroxy-6-phenylnaphthalene 2-Methoxy-6-phenylnaphthalene (14.0 parts) obtained in Step 28 and pyridine hydrochloride (86 parts) were mixed, and under a nitrogen atmosphere, Stir at 190 ° C. for 5 hours. The obtained reaction liquid was cooled to room temperature, ethyl acetate and water were added, and liquid separation was carried out. The solvent was distilled off under reduced pressure to obtain 2-hydroxy-6-phenylnaphthalene (13.0 parts, yield 99%).

(Step 30) Synthesis of 6-phenylnaphthalen-2-yl trifluoromethanesulfonate 2-hydroxy-6-phenylnaphthalene (200) obtained in Step 29 in a mixed solution of dichloromethane (200 parts) and triethylamine (12.0 parts) 13.0 parts) was added and cooled to 0 ° C., and then trifluoromethanesulfonic anhydride (20.0 parts) was slowly added dropwise. After completion of dropping, the temperature was raised to 25 ° C. and stirred for 1 hour. Water was added to the obtained reaction liquid, liquid separation was performed, and the solvent was distilled off under reduced pressure to obtain a brown solid. This solid was purified by silica gel column chromatography (developing solution; toluene), and the solvent was removed under reduced pressure to obtain 6-phenylnaphthalen-2-yl trifluoromethanesulfonate (20.5 parts, yield 99%). Obtained.

(Step 31) Synthesis of (6-phenylnaphthalen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (350 parts) Phenylnaphthalen-2-yl trifluoromethanesulfonate (19.5 parts), bis (pinacolato) diboron (16.9 parts), potassium acetate (10.9 parts) and [1,1′-bis (diphenylphosphino) Ferrocene] palladium (II) dichloride dichloromethane adduct (1.4 parts) was mixed and stirred at reflux temperature for 4 hours under nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, solid content was separated by filtration, and a filtrate containing the product was obtained. Subsequently, the residue is purified by silica gel column chromatography (developing solution; toluene), and the solvent is removed under reduced pressure to give 6- (phenylnaphthalen-2-yl) -4,4,5,5-tetramethyl-1,3. , 2-dioxaborolane (12.1 parts, 66% yield) was obtained.

(Step 32) Synthesis of 2,7-bis (6-phenylnaphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene DMF (250 parts) was mixed with water (8.0 parts). ), 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (4.2 parts) synthesized by the method described in Japanese Patent No. 4945757, 6- ( Phenylnaphthalen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.0 parts), tripotassium phosphate (7.2 parts) and tetrakis (triphenylphosphine) Palladium (0.54 parts) was mixed and stirred at 90 ° C. for 5 hours under a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (250 parts) was added, and solid content was separated by filtration. The obtained solid content was washed with DMF and acetone, dried, and then subjected to sublimation purification. 10 (3.0 parts, yield 56%) was obtained.

Synthesis Example 24 (Synthesis of 2,7-bis (2,2′-binaphthalen-6-yl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 33) Synthesis of 6-methoxy-2,2′-binaphthalene To DMF (250 parts), 2-bromo-6-methoxynaphthalene (11.5 parts), 2-naphthylboronic acid (10.0 parts), Tripotassium phosphate (20.6 parts) and tetrakis (triphenylphosphine) palladium (1.7 parts) were added, and the mixture was stirred at reflux temperature for 5 hours under a nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, water was added, and the produced solid was collected by filtration. The obtained solid was washed with methanol to obtain 6-methoxy-2,2′-binaphthalene (13.5 parts, yield 98%).

(Step 34) Synthesis of 6-hydroxy-2,2′-binaphthalene 6-Methoxy-2,2′-binaphthalene (13.0 parts) obtained in Step 33 and pyridine hydrochloride (53 parts) were mixed, The mixture was stirred at 190 ° C. for 5 hours under a nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, ethyl acetate and water were added, and liquid separation was carried out. The solvent was distilled off under reduced pressure to obtain 6-hydroxy-2,2′-binaphthalene (11.5 parts, yield 94%).

(Step 35) Synthesis of 2,2′-binaphthyl-6-yl trifluoromethanesulfonate 6-hydroxy-2,2 obtained in Step 34 to a mixed solution of dichloromethane (150 parts) and triethylamine (8.6 parts) '-Binaphthalene (11.5 parts) was added, and after cooling to 0 ° C, trifluoromethanesulfonic anhydride (14.4 parts) was slowly added dropwise. After completion of dropping, the temperature was raised to 25 ° C. and stirred for 2 hours. Water and toluene were added to the obtained reaction liquid, liquid separation was performed, and the solvent was distilled off under reduced pressure to obtain a brown solid. This solid was suspended in methanol (100 parts), and a white solid was collected by filtration to obtain 2,2′-binaphthyl-6-yl trifluoromethanesulfonate (15.2 parts, yield 89%). It was.

(Step 36) Synthesis of (2,2′-binaphthyl-6-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (350 parts) was obtained in Step 35. 2,2′-binaphthyl-6-yl trifluoromethanesulfonate (14.5 parts), bis (pinacolato) diboron (11.0 parts), potassium acetate (7.1 parts) and [1,1′-bis ( Diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.9 parts) was mixed and stirred at reflux temperature for 6 hours under nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, solid content was separated by filtration, and a filtrate containing the product was obtained. Subsequently, it is purified by silica gel column chromatography (developing solution; toluene), and the solvent is removed under reduced pressure to obtain (2,2′-binaphthyl-6-yl) -4,4,5,5-tetramethyl-1 , 3,2-dioxaborolane (13.5 parts, 99% yield) was obtained.

(Step 37) Synthesis of 2,7-bis (2,2′-binaphthyl-6-yl) [1] benzothieno [3,2-b] [1] benzothiophene To DMF (180 parts), water (8. 0 part), 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (3.3 parts) synthesized by the method described in Japanese Patent No. 4945757, obtained in step 36 ( 2,2′-binaphthyl-6-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6.6 parts), tripotassium phosphate (5.7 parts) and tetrakis ( Triphenylphosphine) palladium (0.4 parts) was mixed and stirred at 80 ° C. for 5 hours under a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (200 parts) was added and solid content was separated by filtration. The obtained solid content was washed with DMF and acetone, dried, and then subjected to sublimation purification. 169 (1.0 parts, 20% yield) was obtained.

Synthesis Example 25 (Synthesis of 2,7-bis (2-dibenzothienyl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 38) Synthesis of 2- (dibenzothiophen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (250 parts) was added 2-bromodibenzothiophene (10. 0 part), bis (pinacolato) diboron (11.6 parts), potassium acetate (7.5 parts) and [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0. 9 parts) was mixed and stirred at reflux temperature for 4 hours under a nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, solid content was separated by filtration, and a filtrate containing the product was obtained. Subsequently, it is purified by short silica gel column chromatography (developing solution; toluene), and the solvent is removed under reduced pressure to give 2- (dibenzothienyl-2-yl) -4,4,5,5-tetramethyl-1, 3,2-Dioxaborolane (11.5 parts, 98% yield) was obtained.

(Step 39) Synthesis of 2,7-bis (2-dibenzothienyl) [1] benzothieno [3,2-b] [1] benzothiophene DMF (230 parts) with water (7.0 parts), Patent No. 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (4.5 parts) synthesized by the method described in No. 4945757, 2- (dibenzothienyl-2 obtained in step 38 -Yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.0 parts), tripotassium phosphate (7.7 parts) and tetrakis (triphenylphosphine) palladium (0. 6 parts) was mixed and stirred at 90 ° C. for 5 hours under a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (250 parts) was added, and solid content was separated by filtration. The obtained solid content was washed with acetone and dried, followed by purification by sublimation, whereby No. in the above specific example. The compound represented by 164 (2.0 parts, yield 37%) was obtained.

Synthesis Example 26 (2,7-bis (1,1 ′: 4 ′, 1 ″: 4 ″, 1 ′ ″-quarterphenyl-4-yl)-[1] benzothieno [3,2-b] [1] Synthesis of benzothiophene)
(Step 40) Synthesis of 4-bromo-1,1 ′: 4 ′, 1 ″: 4 ″, 1 ′ ″-Quaterphenyl 1,1 ′: 4 ′, 1 commonly available in 100 parts of DMF '' -Terphenylboronic acid 2.7 parts, 4-bromo-1-iodobenzene 2.8 parts, tripotassium phosphate 12 parts, tetrakis (triphenylphosphine) palladium 0.3 parts were mixed, and under nitrogen atmosphere , And stirred at 90 ° C. for 6 hours. After cooling the obtained reaction liquid to room temperature, 100 parts of water was added, and solid content was separated by filtration. The obtained solid was washed with methanol and dried to give 4-bromo-1,1 ′: 4 ′, 1 ″: 4 ″, 1 ′ ″-quarterphenyl (3.4 parts, yield). 88%).

(Step 41) 2-([1,1 ′: 4 ′, 1 ″: 4 ″, 1 ′ ″-quarterphenyl] -4-yl) -4,4,5,5-tetramethyl-1 , 3,2-Dioxaborolane Synthesis of 4-bromo-1,1 ′: 4 ′, 1 ″: 4 ″, 1 ′ ″-quarterphenyl 3.0 parts synthesized in Step 40 on 100 parts of toluene Bis (pinacolato) diboron 2.4 parts, potassium acetate 1.5 parts and [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct 0.2 part The mixture was stirred at reflux temperature for 7 hours. After cooling the obtained reaction liquid to room temperature, 20 parts of silica gel was added and stirred for 5 minutes. Thereafter, the solid content is filtered off and the solvent is removed under reduced pressure to give 2-([1,1 ′: 4 ′, 1 ″: 4 ″, 1 ′ ″-quarterphenyl] -4-yl)- 4,4,5,5-Tetramethyl-1,3,2-dioxaborolane (1.3 parts, 38% yield) was obtained.

(Step 42) 2,7-bis (1,1 ′: 4 ′, 1 ″: 4 ″, 1 ′ ″-quarterphenyl-4-yl)-[1] benzothieno [3,2-b] [1] Synthesis of benzothiophene 2-([1,1 ′: 4 ′, 1 ″: 4 ″, 1 ′ ″-quarterphenyl] -4-yl) obtained in Step 41 was added to 30 parts of DMF. -4,4,5,5-tetramethyl-1,3,2-dioxaborolane 1.0 part, 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene 0.46 part, 3.1 parts of tripotassium phosphate, 1.0 part of water and 0.055 part of tetrakis (triphenylphosphine) palladium (0) were mixed and stirred at 90 ° C. for 6 hours in a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, 30 parts of water was added, and solid content was separated by filtration. The obtained solid content was washed with acetone and dried, followed by purification by sublimation, whereby No. in the above specific example. 172 (0.1 parts, 13% yield) was obtained.

Synthesis Example 27 (Synthesis of 2,7-bis (6- (benzo [b] thiophen-2-yl) naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 43) Synthesis of 2- (6-methoxynaphthalen-2-yl) benzo [b] thiophene To DMF (600 parts), 2-bromo-6-methoxynaphthalene (22.5 parts), benzo [b] thiophene 2-boronic acid (20.3 parts), tripotassium phosphate (40.3 parts) and tetrakis (triphenylphosphine) palladium (2.3 parts) were added, and the mixture was stirred at 70 ° C. for 6 hours in a nitrogen atmosphere. . The obtained reaction liquid was cooled to room temperature, water was added, and the produced solid was collected by filtration. The obtained solid was washed with methanol to obtain 2- (6-methoxynaphthalen-2-yl) benzo [b] thiophene (19.7 parts, yield 72%).

(Step 44) Synthesis of 2- (6-hydroxy-2-yl) benzo [b] thiophene 2- (6-methoxynaphthalen-2-yl) benzo [b] thiophene obtained in Step 43 (19.5 parts) ) And methylene chloride (100 parts) were mixed and stirred at 0 ° C. under a nitrogen atmosphere. To this solution, a 1 mol / L boron tribromide methylene chloride solution was slowly added dropwise, and after completion of the addition, the mixture was stirred at room temperature for 1 hour. Water was added to the reaction solution to separate it. The solvent was distilled off under reduced pressure, the obtained solid was suspended in methanol, and a white solid was collected by filtration to give 2- (6-hydroxynaphthalen-2-yl) benzo [b] thiophene (17.9 parts). Yield 97%).

(Step 45) Synthesis of 6- (benzo [b] thiophen-2-yl) naphthalen-2-yl trifluoromethanesulfonate Obtained in Step 44 in a mixed solution of dichloromethane (250 parts) and triethylamine (14.0 parts). 2- (6-hydroxynaphthalen-2-yl) benzo [b] thiophene (19.0 parts) was added, and after cooling to 0 ° C., trifluoromethanesulfonic anhydride (29.1 parts) was slowly added dropwise. did. After completion of dropping, the temperature was raised to 25 ° C. and stirred for 1 hour. Water was added to the obtained reaction solution, and a brown precipitate was collected by filtration. This precipitated solid was washed with methanol to obtain 6- (benzo [b] thiophen-2-yl) naphthalen-2-yl trifluoromethanesulfonate (27.5 parts, yield 98%).

(Step 46) Synthesis of 2- (6- (benzo [b] thiophen-2-yl) naphthalen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (400 6- (benzo [b] thiophen-2-yl) naphthalen-2-yl trifluoromethanesulfonate (27.0 parts), bis (pinacolato) diboron (20.1 parts) obtained in Step 45 , Potassium acetate (13.0 parts) and [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (1.6 parts). Stir for hours. The obtained reaction liquid was cooled to room temperature, solid content was separated by filtration, and a filtrate containing the product was obtained. Subsequently, it refine | purified by silica gel column chromatography (developing liquid; toluene), and the white solid was obtained by removing a solvent under reduced pressure. The obtained solid was purified by recrystallization from toluene, whereby 2- (6- (benzo [b] thiophen-2-yl) naphthalen-2-yl) -4,4,5,5-tetramethyl- 1,3,2-dioxaborolane (18.0 parts, yield 71%) was obtained.

(Step 47) Synthesis of 2,7-bis (6- (benzo [b] thiophen-2-yl) naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene DMF (260 Part)), water (30.0 parts), 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (4.0 parts) synthesized by the method described in Japanese Patent No. 4945757 2- (6- (Benzo [b] thiophen-2-yl) naphthalen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7 9 parts), tripotassium phosphate (6.9 parts) and tetrakis (triphenylphosphine) palladium (0.52 parts) were mixed and stirred at 80 ° C. for 5 hours in a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (300 parts) was added and solid content was fractionated by filtration. The obtained solid content was washed with DMF and acetone, dried, and then subjected to sublimation purification. 179 (0.6 parts, 10% yield) was obtained.

Synthesis Example 28 (Synthesis of 2,7-bis (4- (5-benzo [b] thienyl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 48) Synthesis of 2- (benzo [b] thiophen-5-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (200 parts) was mixed with 5-bromobenzo [b ] Thiophene (10.0 parts), bis (pinacolato) diboron (14.3 parts), potassium acetate (9.2 parts) and [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane The adduct (1.1 parts) was mixed and stirred at reflux temperature for 2 hours under a nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, solid content was separated by filtration, and a filtrate containing the product was obtained. Subsequently, the residue is purified by short silica gel column chromatography (developing solution; toluene), and the solvent is removed under reduced pressure to give 2- (benzo [b] thiophen-5-yl) -4,4,5,5-tetramethyl. -1,3,2-dioxaborolane (11.7 parts, yield 96%) was obtained.

(Step 49) Synthesis of 5- (4-bromophenyl) benzo [b] thiophene DMF (230 parts) was added to 2- (benzo [b] thiophen-5-yl) -4,4, obtained in Step 48. 5,5-tetramethyl-1,3,2-dioxaborolane (11.5 parts), 1-bromo-4-iodobenzene (12.5 parts), tripotassium phosphate (18.7 parts) and tetrakis (tri Phenylphosphine) palladium (1.6 parts) was mixed and stirred at 60 ° C. for 2 hours under a nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, water (200 parts) was added, and solid content was collected by filtration. The obtained solid was washed with water and methanol in this order to obtain 5- (4-bromophenyl) benzo [b] thiophene (12.0 parts, yield 94%).

(Step 50) Synthesis of 2- (4- (5-benzo [b] thienyl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Step 49 in toluene (200 parts) 5- (4-Bromophenyl) benzo [b] thiophene (12.0 parts), bis (pinacolato) diboron (14.5 parts), potassium acetate (9.3 parts) and [1,1 ′ -Bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (1.2 parts) was mixed and stirred at reflux temperature for 4 hours under nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, solid content was separated by filtration, and a filtrate containing the product was obtained. Subsequently, the residue was purified by short silica gel column chromatography (developing solution; toluene), and the solvent was removed under reduced pressure. The obtained pale orange solid was washed with methanol to give 2- (4- (5-benzo [b] thienyl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane ( 7.4 parts, yield 53%).

(Step 51) Synthesis of 2,7-bis (4- (5-benzo [b] thienyl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene In DMF (200 parts), water ( 10.0 parts), 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (3.7 parts) synthesized by the method described in Japanese Patent No. 4945757, obtained in step 50 2- (4- (5-benzo [b] thienyl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6.3 parts), tripotassium phosphate (6. 4 parts) and tetrakis (triphenylphosphine) palladium (0.5 parts) were mixed and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (150 parts) was added and solid content was separated by filtration. The obtained solid content was washed with acetone and DMF, dried, and then subjected to sublimation purification. The compound represented by 187 (2.0 parts, yield 51%) was obtained.

Synthesis Example 29 Synthesis of 2,7-bis (4 ′-(2-naphthyl)-(1,1′-biphenyl) -4-yl) [1] benzothieno [3,2-b] [1] benzothiophene )
(Step 52) Synthesis of 2- (4′-bromo- (1,1′-biphenyl) -4-yl) naphthalene 4- (2-naphthyl) phenylboronic acid (5.0 parts) into DMF (100 parts) , P-iodo-bromobenzene (5.7 parts), tripotassium phosphate (8.6 parts) and tetrakis (triphenylphosphine) palladium (0.7 parts) were added, and the mixture was refluxed for 6 hours under a nitrogen atmosphere. Stir. The resulting reaction solution was cooled to room temperature, water was added, and the precipitated solid was collected by filtration. The obtained solid was washed with methanol and dried to obtain 2- (4′-bromo- (1,1′-biphenyl) -4-yl) naphthalene (7.0 parts, yield 97%). .

(Step 53) Synthesis of 2- (4 ′-(2-naphthyl)-(1,1′-biphenyl) -4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (150 parts) was added 2- (4′-bromo- (1,1′-biphenyl) -4-yl) naphthalene (7.0 parts), bis (pinacolato) diboron (6. 1 part), potassium acetate (3.9 parts) and [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.5 parts) were mixed and refluxed under a nitrogen atmosphere. Stir at temperature for 5 hours. The obtained reaction liquid was cooled to room temperature, solid content was separated by filtration, and a filtrate containing the product was obtained. Subsequently, the residue is purified by silica gel column chromatography (developing solution; toluene), and the solvent is removed under reduced pressure to give 2- (4 ′-(2-naphthyl)-(1,1′-biphenyl) -4-yl). -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6.6 parts, yield 80%) was obtained.

(Step 54) Synthesis of 2,7-bis (4 ′-(2-naphthyl)-(1,1′-biphenyl) -4-yl) [1] benzothieno [3,2-b] [1] benzothiophene DMF (200 parts), water (10.0 parts), 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene synthesized by the method described in Japanese Patent No. 4945757 (3. 2 parts), 2- (4 ′-(2-naphthyl)-(1,1′-biphenyl) -4-yl) -4,4,5,5-tetramethyl-1,3 obtained in step 53 , 2-dioxaborolane (6.6 parts), tripotassium phosphate (5.5 parts) and tetrakis (triphenylphosphine) palladium (0.4 parts) were mixed and stirred at 80 ° C. for 6 hours in a nitrogen atmosphere. . After cooling the obtained reaction liquid to room temperature, water (200 parts) was added and solid content was separated by filtration. The obtained solid content was washed with DMF and acetone, dried, and then subjected to sublimation purification. The compound represented by 190 (0.5 parts, yield 10%) was obtained.

Synthesis Example 30 (Synthesis of 2,7-bis (4- (naphtho [1,2-b] thiophen-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 55) Synthesis of 2- (4-bromophenyl) naphtho [1,2-b] thiophene 2- (Naphtho [1,2-b] thiophene- synthesized by DMF (190 parts) by a known method 2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6.0 parts), para-bromoiodobenzene (5.5 parts), water (5.0 parts), Tripotassium phosphate (22.9 parts) and tetrakis (triphenylphosphine) palladium (0.6 parts) were mixed and stirred at 70 ° C. for 4 hours under a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (190 parts) was added and solid content was separated by filtration. The obtained solid was washed with methanol and dried to obtain 2- (4-bromophenyl) naphtho [1,2-b] thiophene (3.0 parts, yield 47%).

(Step 56) Synthesis of 2- (4- (naphth [1,2-b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (110 2- (4-bromophenyl) naphtho [1,2-b] thiophene (2.8 parts), bis (pinacolato) diboron (2.5 parts), potassium acetate (1) .6 parts) and [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.22 parts) were mixed and stirred at reflux temperature for 4 hours under nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, 20 parts of silica gel was added and stirred for 5 minutes. Thereafter, the solid content was filtered off and the solvent was removed under reduced pressure to give 2- (4- (naphth [1,2-b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl- 1,3,2-dioxaborolane (2.2 parts, 69% yield) was obtained.

(Step 57) Synthesis of 2,7-bis (4- (naphtho [1,2-b] thiophen-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene DMF (100 Part)), water (2.6 parts), 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (1.2 parts) synthesized by the method described in Japanese Patent No. 4945757 2- (4- (Naphtho [1,2-b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2 0.0 part), tripotassium phosphate (8.1 parts) and tetrakis (triphenylphosphine) palladium (0.2 parts) were mixed and stirred at 80 ° C. for 5 hours in a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (100 parts) was added and solid content was separated by filtration. The obtained solid content was washed with acetone and dried, followed by purification by sublimation, whereby No. in the above specific example. The compound represented by 199 (0.4 parts, yield 26%) was obtained.

Synthesis Example 31 (Synthesis of 2,7-bis (4- (benzo [d] oxazol-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 58) Synthesis of 2- (Benzo [d] oxazol-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (500 parts) was subjected to 2- ( 4-Bromophenyl) benzo [d] oxazole (10 parts), bis (pinacolato) diboron (10.8 parts), potassium acetate (6.9 parts) and [1,1′-bis (diphenylphosphino) ferrocene] Palladium (II) dichloride dichloromethane adduct (1.0 part) was mixed and stirred at reflux temperature for 4 hours under nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, 20 parts of silica gel was added and stirred for 5 minutes. Thereafter, the solid content is filtered off, and the solvent is removed under reduced pressure to give 2- (benzo [d] oxazol-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane. (11.4 parts, yield 99%) was obtained.

(Step 59) Synthesis of 2,7-bis (4- (benzo [d] oxazol-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene In DMF (430 parts), Water (11 parts), 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (4.9 parts) synthesized by the method described in Japanese Patent No. 4945757, obtained in step 58 2- (Benzo [d] oxazol-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8.0 parts), tripotassium phosphate (34 parts) And tetrakis (triphenylphosphine) palladium (0.8 parts) were mixed and stirred at 80 ° C. for 5 hours in a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (430 parts) was added and solid content was separated by filtration. The obtained solid content was washed with acetone and dried, followed by purification by sublimation, whereby No. in the above specific example. The compound represented by 112 (3.6 parts, yield 57%) was obtained.

Synthesis Example 32 (Synthesis of 2,7-bis (4- (5-phenylbenzo [b] thiophen-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 60) Synthesis of 5-phenylbenzo [b] thiophene In DMF (500 parts), 5-bromobenzo [b] thiophene (20 parts), phenylboronic acid (13.7 parts), tripotassium phosphate (113 parts) ) And tetrakis (triphenylphosphine) palladium (3.0 parts) were mixed and stirred at 70 ° C. for 6 hours under a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (500 parts) was added and solid content was separated by filtration. The obtained solid was washed with water and acetone and dried to obtain 5-phenylbenzo [b] thiophene (13.3 parts, yield 67%).

(Step 61) Synthesis of 2- (5-phenylbenzo [b] thiophen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Step 60 in tetrahydrofuran (300 parts) 5-Phenylbenzo [b] thiophene (12.6 parts) obtained in the above was mixed. A normal butyllithium hexane solution (2.6 M, 28 parts) was added to the mixture cooled to 0 ° C., and the mixture was stirred for 1 hour in a nitrogen atmosphere. Isopropoxyboronic acid pinacol (16 parts) was added to the resulting mixture and stirred at room temperature for 12 hours. Water (100 parts) was added to the resulting reaction solution, and the solid content produced by distilling off the solvent under reduced pressure was collected by filtration. The obtained solid was washed with water and dried to give 2- (5-phenylbenzo [b] thiophen-2-yl) -4,4,5,5-tetramethyl-1,3,2- Dioxaborolane (11.4 parts, 57% yield) was obtained.

(Step 62) Synthesis of 2- (4-bromophenyl) -5-phenylbenzo [b] thiophene DMF (300 parts), water (8.0 parts), 2- (5-phenyl) obtained in Step 61 Benzo [b] thiophen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (10 parts), 1-bromo-4-iodobenzene (8.4 parts), phosphorus Tripotassium acid (36 parts) and tetrakis (triphenylphosphine) palladium (1.0 part) were mixed and stirred at 70 ° C. for 3 hours in a nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, water (300 parts) was added, and solid content was collected by filtration. The obtained solid was washed with water and methanol in this order to obtain 2- (4-bromophenyl) -5-phenylbenzo [b] thiophene (9.2 parts, yield 85%).

(Step 63) Synthesis of 2- (4- (5-phenylbenzo [b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (300 parts 2- (4-bromophenyl) -5-phenylbenzo [b] thiophene (8.5 parts), bis (pinacolato) diboron (6.9 parts), potassium acetate (4. 4 parts) and [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.64 parts) were mixed and stirred at reflux temperature for 6 hours under nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, 20 parts of silica gel was added and stirred for 5 minutes. Thereafter, the solid content is filtered off and the solvent is removed under reduced pressure to give 2- (4- (5-phenylbenzo [b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1 3,2-dioxaborolane (5.2 parts, 55% yield) was obtained.

(Step 64) Synthesis of 2,7-bis (4- (5-phenylbenzo [b] thiophen-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene DMF (200 parts ), Water (5.0 parts), 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (1.8 parts) synthesized by the method described in Japanese Patent No. 4945757, 2- (4- (5-phenylbenzo [b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.5) obtained in step 63. Part), tripotassium phosphate (15 parts) and tetrakis (triphenylphosphine) palladium (0.4 parts) were mixed and stirred at 80 ° C. for 6 hours in a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (200 parts) was added and solid content was separated by filtration. The obtained solid content was washed with acetone and dried, followed by purification by sublimation, whereby No. in the above specific example. 90 (1.5 parts, 50% yield) was obtained.

Synthesis Example 33 (Synthesis of 2,7-bis (4- (3-dibenzo [b, d] furan) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 65) Synthesis of 2- (3-dibenzo [b, d] furan) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (100 parts) was mixed with 3-bromodibenzo [ b, d] furan (5.0 parts), bis (pinacolato) diboron (6.2 parts), potassium acetate (4.0 parts) and [1,1′-bis (diphenylphosphino) ferrocene] palladium (II ) Dichloride dichloromethane adduct (0.5 parts) was mixed and stirred at reflux temperature for 5 hours under nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, solid content was separated by filtration, and a filtrate containing the product was obtained. Subsequently, it is purified by short silica gel column chromatography (developing solution; toluene), and the solvent is removed under reduced pressure to give 2- (3-dibenzo [b, d] furan) -4,4,5,5-tetramethyl. -1,3,2-dioxaborolane (3.8 parts, yield 64%) was obtained.

(Step 66) Synthesis of 3- (4-bromophenyl) dibenzo [b, d] furan To DMF (60 parts), 2- (3-dibenzo [b, d] furan) -4, obtained in Step 65, 4,5,5-tetramethyl-1,3,2-dioxaborolane (3.8 parts), 1-bromo-4-iodobenzene (3.7 parts), tripotassium phosphate (5.5 parts) and tetrakis (Triphenylphosphine) palladium (0.4 parts) was mixed and stirred at 60 ° C. for 2 hours under a nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, water (200 parts) was added, and solid content was collected by filtration. The obtained solid was washed with water and methanol in this order to obtain 3- (4-bromophenyl) dibenzo [b, d] furan (2.7 parts, yield 64%).

(Step 67) Synthesis of 2- (4- (3-dibenzo [b, d] furan) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (50 parts) 3- (4-Bromophenyl) dibenzo [b, d] furan (2.7 parts), bis (pinacolato) diboron (2.5 parts), potassium acetate (1.6 parts) and [ 1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.2 parts) was mixed and stirred at reflux temperature for 8 hours under nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, solid content was separated by filtration, and a filtrate containing the product was obtained. Subsequently, 2- (4- (3-dibenzo [b, d] furan) phenyl) -4,4,5,5-tetramethyl- is purified by short silica gel column chromatography (developing solution; toluene). 1,3,2-dioxaborolane (2.8 parts, yield 90%) was obtained.

(Step 68) Synthesis of 2,7-bis (4- (3-dibenzo [b, d] furan) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene In DMF (80 parts), Water (8.0 parts), 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (1.5 parts) synthesized by the method described in Japanese Patent No. 4945757, in step 67 The resulting 2- (4- (3-dibenzo [b, d] furan) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.8 parts), triphosphate Potassium (2.6 parts) and tetrakis (triphenylphosphine) palladium (0.2 parts) were mixed and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (100 parts) was added and solid content was separated by filtration. The obtained solid content was washed with acetone and DMF, dried, and then subjected to sublimation purification. The compound represented by 206 (0.9 parts, yield 41%) was obtained.

Synthesis Example 34 (Synthesis of 2,7-bis (4- (3-dibenzo [b, d] thiophene) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 69) Synthesis of 2- (3-dibenzo [b, d] thiophene) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (100 parts) was mixed with 3-bromodibenzo [ b, d] thiophene (5.0 parts), bis (pinacolato) diboron (5.8 parts), potassium acetate (3.7 parts) and [1,1′-bis (diphenylphosphino) ferrocene] palladium (II ) Dichloride dichloromethane adduct (0.4 parts) was mixed and stirred at reflux temperature for 4 hours under nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, solid content was separated by filtration, and a filtrate containing the product was obtained. Subsequently, it is purified by short silica gel column chromatography (developing solution; toluene), and the solvent is removed under reduced pressure to give 2- (3-dibenzo [b, d] thiophene) -4,4,5,5-tetramethyl. -1,3,2-dioxaborolane (2.3 parts, 39% yield) was obtained.

(Step 70) Synthesis of 3- (4-bromophenyl) dibenzo [b, d] thiophene To DMF (40 parts), 2- (3-dibenzo [b, d] thiophene) -4, obtained in Step 69, 4,5,5-tetramethyl-1,3,2-dioxaborolane (2.3 parts), 1-bromo-4-iodobenzene (2.1 parts), tripotassium phosphate (3.0 parts) and tetrakis (Triphenylphosphine) palladium (0.3 parts) was mixed and stirred at 60 ° C. for 3 hours under a nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, water (60 parts) was added, and solid content was collected by filtration. The obtained solid was washed with water and methanol in this order to obtain 3- (4-bromophenyl) dibenzo [b, d] thiophene (2.5 parts, yield 99%).

(Step 71) Synthesis of 2- (4- (3-dibenzo [b, d] thiophene) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (50 parts) 3- (4-Bromophenyl) dibenzo [b, d] thiophene (2.5 parts), bis (pinacolato) diboron (2.2 parts), potassium acetate (1.4 parts) and [ 1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.2 parts) was mixed and stirred at reflux temperature for 8 hours under nitrogen atmosphere. The obtained reaction liquid was cooled to room temperature, solid content was separated by filtration, and a filtrate containing the product was obtained. Subsequently, 2- (4- (3-dibenzo [b, d] thiophene) phenyl) -4,4,5,5-tetramethyl- is purified by short silica gel column chromatography (developing solution; toluene). 1,3,2-dioxaborolane (2.0 parts, 71% yield) was obtained.

(Step 72) Synthesis of 2,7-bis (4- (3-dibenzo [b, d] thiophene) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene In DMF (60 parts), Water (8.0 parts), 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (1.0 part) synthesized by the method described in Japanese Patent No. 4945757, in Step 71 The resulting 2- (4- (3-dibenzo [b, d] thiophene) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.0 parts), triphosphate Potassium (1.8 parts) and tetrakis (triphenylphosphine) palladium (0.1 parts) were mixed and stirred at 80 ° C. for 6 hours in a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (100 parts) was added and solid content was separated by filtration. The obtained solid content was washed with acetone and DMF, dried, and then subjected to sublimation purification. The compound represented by 207 (0.4 parts, yield 26%) was obtained.

Synthesis Example 35 (Synthesis of 2,7-bis (4- (phenanthren-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 73) Synthesis of 2- (phenanthren-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (130 parts) was prepared with 2-bromophenanthrene, which is generally available ( 2.4 parts), bis (pinacolato) diboron (3.0 parts), potassium acetate (1.9 parts) and [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct ( 0.28 parts) was mixed and stirred at reflux temperature for 6 hours under a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, 20 parts of silica gel was added and stirred for 5 minutes. Thereafter, the solid content was filtered off and the solvent was removed under reduced pressure to give 2- (phenanthren-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.7 parts, Yield 96%) was obtained.

(Step 74) Synthesis of 2- (4-bromophenyl) phenanthrene 2- (phenanthren-2-yl) -4,4,5 obtained in Step 73 of water (2.4 parts) in DMF (90 parts) , 5-tetramethyl-1,3,2-dioxaborolane (2.7 parts), 2-bromo-5-iodotoluene (2.5 parts), tripotassium phosphate (10.7 parts) and tetrakis (triphenyl) Phosphine) palladium (0.28 parts) was mixed and stirred at 70 ° C. for 2 hours under a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (90 parts) was added and solid content was separated by filtration. The obtained solid was washed with methanol and dried to obtain 2- (4-bromophenyl) phenanthrene (2.9 parts, yield 100%).

(Step 75) Synthesis of 2- (4- (phenanthren-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (120 parts) was obtained in Step 74. 2- (4-bromophenyl) phenanthrene (2.8 parts), bis (pinacolato) diboron (2.7 parts), potassium acetate (1.7 parts) and [1,1′-bis (diphenylphosphino) ) Ferrocene] palladium (II) dichloride dichloromethane adduct (0.25 parts) was mixed and stirred at reflux temperature for 5 hours under nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, 20 parts of silica gel was added and stirred for 5 minutes. Thereafter, the solid content is filtered off and the solvent is removed under reduced pressure to give 2- (4- (phenanthren-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane ( 2.8 parts, yield 88%).

(Step 76) Synthesis of 2,7-bis (4- (phenanthren-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene To DMF (140 parts), water (3. 6 part), 2,7-diiodo [1] benzothieno [3,2-b] [1] benzothiophene (2.7 parts) synthesized by the method described in Japanese Patent No. 4945757, 2 obtained in Step 75 -(4- (phenanthren-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.7 parts), tripotassium phosphate (3.6 parts) and Tetrakis (triphenylphosphine) palladium (0.26 parts) was mixed and stirred at 80 ° C. for 7 hours under a nitrogen atmosphere. After cooling the obtained reaction liquid to room temperature, water (140 parts) was added and solid content was separated by filtration. The obtained solid content was washed with DMF and acetone, dried, and then subjected to sublimation purification. The compound represented by 210 (0.8 parts, yield 38%) was obtained.

Synthesis Example 36 (Synthesis of 2,7-bis (4- (naphtho [2,3-b] thiophen-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene)
(Step 77) Synthesis of 2- (4-bromophenyl) naphtho [2,3-b] thiophene 2- (Naphtho [1,2-b] thiophen-2-yl) -4,4,5,5-tetra 2- (Naphtho [2,3-b] thiophen-2-yl) -4,4,5,5-tetramethyl-1 synthesized by a known method instead of methyl-1,3,2-dioxaborolane , 3,2-dioxaborolane, except that 2- (4-bromophenyl) naphtho [2,3-b] thiophene (3.5 parts, yield 55%) )

(Step 78) Synthesis of 2- (4- (naphth [2,3-b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2- ( Instead of 4-bromophenyl) naphtho [1,2-b] thiophene, the process proceeds to step 56 except that 2- (4-bromophenyl) naphtho [2,3-b] thiophene obtained in step 77 was used. 2- (4- (naphth [2,3-b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane ( 3.7 parts, yield 58%).

(Step 79) Synthesis of 2,7-bis (4- (naphth [2,3-b] thiophen-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene 2- ( 4- (Naphtho [1,2-b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane instead of 2- (Similar to Step 57, except that 4- (naphth [2,3-b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane was used. By performing the synthesis, No. The compound represented by 102 (0.6 parts, yield 39%) was obtained.

Example 1 (Preparation of photoelectric conversion element and evaluation thereof)
2,7-bis (naphthalen-2-yl) [1] benzothieno [3, 2-b] [1] benzothiophene (Synthesis Example 1) The compound represented by No. 9 obtained in (1) was formed as a block layer by 50 nm by resistance heating vacuum deposition. The block layer had an average surface roughness Sa of 1.7 nm. Next, quinacridone was formed into a 100 nm vacuum film as a photoelectric conversion layer on the block layer. Finally, 100 nm of aluminum was vacuum-deposited as an electrode on the photoelectric conversion layer to produce a photoelectric conversion element for an image sensor according to the present invention. Using ITO and aluminum as electrodes, the contrast ratio when a voltage of 5 V was applied was 2.8 × 10 ⁵ .

Example 2 (Preparation of photoelectric conversion element and its evaluation)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (4′-methyl- [1,1′-biphenyl] -4-yl) [1] benzothieno [3,2-b] [1] benzothiophene (No. 21 obtained in Synthesis Example 2) Except for using the compound represented by formula (1), the evaluation was performed according to Example 1, and the average surface roughness Sa of the block layer was 1.8 nm, and the light-dark ratio when a voltage of 5 V was applied. Was 1.2 × 10 ⁵ .

Example 3 (Preparation of photoelectric conversion element and its evaluation)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (2-fluoro- [1,1′-biphenyl] -4-yl) [1] benzothieno [3,2-b] [1] benzothiophene (No. 23 obtained in Synthesis Example 3) When the evaluation was performed according to Example 1 except that the compound represented) was used, the average surface roughness Sa of the block layer was 1.6 nm, and the contrast ratio when a voltage of 5 V was applied was It was 1.1 × 10 ⁵ .

Example 4 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis ([1,1 ′: 3,1 ″ -terphenyl] -4-yl) [1] benzothieno [3,2-b] [1] benzothiophene (No. obtained in Synthesis Example 4). Except for using the compound represented by No. 26), the evaluation was performed according to Example 1, and the average surface roughness Sa of the block layer was 1.6 nm, and the light and darkness when a voltage of 5 V was applied. The ratio was 1.1 × 10 ⁵ .

Example 5 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis ([1,1 ′: 3 ′, 1 ″ -terphenyl] -5′-yl) [1] benzothieno [3,2-b] [1] benzothiophene (obtained in Synthesis Example 5) Except for using the compound represented by No. 27), the evaluation was performed according to Example 1, and the average surface roughness Sa of the block layer was 1.6 nm, and a voltage of 5 V was applied. The light-to-dark ratio was 7.0 × 10 ⁴ .

Example 6 (Preparation of photoelectric conversion element and its evaluation)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (benzo [b] furan-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 29 obtained in Synthesis Example 6) Except for the above, when evaluated according to Example 1, the average surface roughness Sa of the block layer is 1.4 nm, and the contrast ratio when a voltage of 5 V is applied is 2.5 × 10 ⁵ . there were.

Example 7 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (benzo [b] thiophen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 33 obtained in Synthesis Example 7) Except for the above, when evaluated according to Example 1, the average surface roughness Sa of the block layer is 1.7 nm, and the contrast ratio when a voltage of 5 V is applied is 2.2 × 10 ⁵ . there were.

Example 8 (Preparation of photoelectric conversion element and its evaluation)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (4- (benzo [b] furan-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene (represented by No. 83 obtained in Synthesis Example 8) Except for using this compound, the average surface roughness Sa of the block layer was 1.7 nm, and the contrast ratio when a voltage of 5 V was applied was 3. It was 2 × 10 ⁵ .

Example 9 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (4- (benzo [b] thiophen-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene (represented by No. 87 obtained in Synthesis Example 9) Except for using this compound), the average surface roughness Sa of the block layer was 4.1 nm, and the light / dark ratio when a voltage of 5 V was applied was 6. It was 7 × 10 ⁵ .

Example 10 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (5′-phenyl- [1,1 ′: 3 ′, 1 ″ -terphenyl] -4-yl) [1] benzothieno [3,2-b] [1] benzothiophene (Synthesis Example Except for using the compound represented by No. 28 obtained in No. 16), the average surface roughness Sa of the block layer was 1.7 nm when evaluated in accordance with Example 1. The contrast ratio when a voltage was applied was 5.1 × 10 ⁵ .

Example 11 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (4 ′-(pyridin-2-yl)-[1,1′-biphenyl] -4-yl) [1] benzothieno [3,2-b] [1] benzothiophene (in Synthesis Example 17) Except for using the obtained compound represented by No. 168), the evaluation was performed according to Example 1, and the average surface roughness Sa of the block layer was 2.4 nm, and a voltage of 5 V was applied. When applied, the contrast ratio was 2.5 × 10 ⁵ .

Example 12 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (4- (benzo [d] thiazol-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene (represented by No. 111 obtained in Synthesis Example 18) Except for using this compound, the average surface roughness Sa of the block layer was 2.8 nm, and the contrast ratio when a voltage of 5 V was applied was 2. It was 5 × 10 ⁵ .

Example 13 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (4- (benzo [b] thiophen-2-yl) -2-methylphenyl) [1] benzothieno [3,2-b] [1] benzothiophene (No. obtained in Synthesis Example 19). Except for using the compound represented by 170, the evaluation was performed according to Example 1, and the average surface roughness Sa of the block layer was 1.7 nm, and the light and darkness when a voltage of 5 V was applied. The ratio was 8.4 × 10 ⁵ .

Example 14 (Preparation of photoelectric conversion element and its evaluation)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (2-dibenzofuranyl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 165 obtained in Synthesis Example 20) was used. As a result of evaluation in accordance with Example 1, the average surface roughness Sa of the block layer was 1.8 nm, and the light / dark ratio when a voltage of 5 V was applied was 1.1 × 10 ⁴ .

Example 15 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (9,9-dimethyl-9H-fluoren-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (represented by No. 166 obtained in Synthesis Example 21) Except that the compound) was used, the evaluation was performed according to Example 1. As a result, the average surface roughness Sa of the block layer was 2.1 nm, and the contrast ratio when a voltage of 5 V was applied was 1.6. × 10 ⁵

Example 16 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (4- (9,9-dimethyl-9H-fluoren-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene (No. obtained in Synthesis Example 22). Except that the compound represented by 167) was used, the evaluation was performed according to Example 1. As a result, the average surface roughness Sa of the block layer was 2.0 nm, and light and dark when a voltage of 5 V was applied. The ratio was 9.5 × 10 ⁵ .

Example 17 (Production and Evaluation of Photoelectric Conversion Element)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (6-phenylnaphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (compound represented by No. 10 obtained in Synthesis Example 23) was used. Except for the above, when the evaluation was performed according to Example 1, the average surface roughness Sa of the block layer was 1.8 nm, and the contrast ratio when a voltage of 5 V was applied was 9.8 × 10 ^5. It was.

Example 18 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (2,2′-binaphthalen-6-yl) [1] benzothieno [3,2-b] [1] benzothiophene (compound represented by No. 169 obtained in Synthesis Example 24) When evaluated according to Example 1 except that it was used, the average surface roughness Sa of the block layer was 1.9 nm, and the light / dark ratio when a voltage of 5 V was applied was 1.6 × 10 ^6. Met.

Example 19 (Production and Evaluation of Photoelectric Conversion Element)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (2-dibenzothienyl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 164 obtained in Synthesis Example 25), As a result of evaluation according to Example 1, the average surface roughness Sa of the block layer was 2.1 nm, and the contrast ratio when a voltage of 5 V was applied was 4.8 × 10 ⁵ .

Example 20 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (1,1 ′: 4 ′, 1 ″: 4 ″, 1 ′ ″-quarterphenyl-4-yl)-[1] benzothieno [3,2-b] [1] benzothiophene Except for using (the compound represented by No. 172 obtained in Synthesis Example 26), the evaluation was performed according to Example 1, and the average surface roughness Sa of the block layer was 2.0 nm. The contrast ratio when a voltage of 5 V was applied was 7.0 × 10 ³ .

Example 21 (Preparation of photoelectric conversion element and evaluation thereof)
In place of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1) No. synthesized by the method of Except that the compound represented by 160 was used, the evaluation was performed according to Example 1. As a result, the average surface roughness Sa of the block layer was 1.4 nm, and the contrast ratio when a voltage of 5 V was applied. Was 2.4 × 10 ³ .

Example 22 (Preparation of photoelectric conversion element and evaluation thereof)
In place of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1) No. synthesized by the method of Except that the compound represented by 173 was used, the evaluation was performed according to Example 1. As a result, the average surface roughness Sa of the block layer was 1.5 nm, and the contrast ratio when a voltage of 5 V was applied. Was 2.7 × 10 ⁵ .

Example 23 (Preparation of photoelectric conversion element and its evaluation)
No. 1 synthesized by a known method on ITO transparent conductive glass (manufactured by Geomat Co., Ltd., ITO film thickness 150 nm). A compound represented by 160 was formed to a thickness of 200 nm by resistance heating vacuum deposition. The average surface roughness Sa of this organic layer was 1.4 nm. Next, aluminum was formed into a 100-nm vacuum film as an electrode, and the photoelectric conversion element for image sensors of this invention was produced. The light / dark ratio was 3.3 × 10 ⁵ when a voltage of 5 V was applied using ITO and aluminum as electrodes.

Example 24 (Preparation of photoelectric conversion element and evaluation thereof)
No. No. 160 synthesized by a known method instead of the compound represented by 160. Except that the compound represented by 176 was used, the evaluation was performed according to Example 23. The average surface roughness Sa of the organic layer was 1.6 nm, and the light / dark ratio when a voltage of 5 V was applied. Was 2.3 × 10 ⁵ .

Example 25 (Production and Evaluation of Photoelectric Conversion Element)
No. No. 160 synthesized by a known method instead of the compound represented by 160. Except that the compound represented by 175 was used, evaluation was performed according to Example 23. The average surface roughness Sa of the organic layer was 6.0 nm, and the light / dark ratio when a voltage of 5 V was applied. Was 5.7 × 10 ⁴ .

Example 26 (Production and Evaluation of Photoelectric Conversion Element)
No. No. 160 synthesized by a known method instead of the compound represented by 160. Except that the compound represented by 177 was used, the evaluation was performed according to Example 23. The average surface roughness Sa of the organic layer was 3.9 nm, and the light-dark ratio when a voltage of 5 V was applied. Was 5.1 × 10 ³ .

Example 27 (Production and Evaluation of Photoelectric Conversion Element)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (6- (benzo [b] thiophen-2-yl) naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (No. obtained in Synthesis Example 27). Except for using the compound represented by 179), the evaluation was performed according to Example 1, and the average surface roughness Sa of the block layer was 1.6 nm, and the light and darkness when a voltage of 5 V was applied. The ratio was 3.8 × 10 ⁵ .

Example 28 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (4- (5-benzo [b] thienyl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene (compound represented by No. 187 obtained in Synthesis Example 28) ) Was used according to Example 1, and the average surface roughness Sa of the block layer was 1.6 nm, and the contrast ratio when a voltage of 5 V was applied was 4.4 ×. 10 ⁵ .

Example 29 (Production and Evaluation of Photoelectric Conversion Element)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (4 ′-(2-naphthyl)-(1,1′-biphenyl) -4-yl) [1] benzothieno [3,2-b] [1] benzothiophene (obtained in Synthesis Example 29) When the evaluation was performed according to Example 1 except that the compound represented by No. 190 was used, the average surface roughness Sa of the block layer was 1.8 nm, and a voltage of 5 V was applied. The contrast ratio was 3.8 × 10 ⁵ .

Example 30 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (4- (naphth [1,2-b] thiophen-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene (No. obtained in Synthesis Example 30). Except for using the compound represented by 199), the evaluation was performed according to Example 1, and the average surface roughness Sa of the block layer was 1.8 nm, and the light and darkness when a voltage of 5 V was applied. The ratio was 8.4 × 10 ⁵ .

Example 31 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (4- (benzo [d] oxazol-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene (represented by No. 112 obtained in Synthesis Example 31) Except for using this compound, the average surface roughness Sa of the block layer was 1.6 nm, and the light / dark ratio when a voltage of 5 V was applied was 3. It was 5 × 10 ⁵ .

Example 32 (Production and Evaluation of Photoelectric Conversion Element)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (4- (5-phenylbenzo [b] thiophen-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene (No. 90 obtained in Synthesis Example 32) Except for using the compound represented by formula (1), the evaluation was performed according to Example 1, and the average surface roughness Sa of the block layer was 1.6 nm, and the contrast ratio when a voltage of 5 V was applied. Was 1.0 × 10 ⁶ .

Example 33 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (4- (3-dibenzo [b, d] furan) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene (represented by No. 206 obtained in Synthesis Example 33) Except for using this compound, the average surface roughness Sa of the block layer was 1.7 nm, and the contrast ratio when a voltage of 5 V was applied was 1. It was 2 × 10 ⁵ .

Example 34 (Production and Evaluation of Photoelectric Conversion Element)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (4- (3-dibenzo [b, d] thiophene) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene (represented by No. 207 obtained in Synthesis Example 34) The compound was evaluated according to Example 1 except that the average surface roughness Sa of the block layer was 1.7 nm, and the light / dark ratio when a voltage of 5 V was applied was 9. It was 2 × 10 ⁵ .

Example 35 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (4- (phenanthren-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene (compound represented by No. 210 obtained in Synthesis Example 35) When evaluated according to Example 1 except that it was used, the average surface roughness Sa of the block layer was 1.5 nm, and the contrast ratio when a voltage of 5 V was applied was 5.7 × 10 ^5. Met.

Example 36 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (4- (naphth [2,3-b] thiophen-2-yl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene (No. obtained in Synthesis Example 36). Except for using the compound represented by No. 102), the evaluation was performed according to Example 1, and the average surface roughness Sa of the block layer was 1.6 nm, and the light and darkness when a voltage of 5 V was applied. The ratio was 4.5 × 10 ⁵ .

Comparative Example 1 (Production and Evaluation of Photoelectric Conversion Element)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis ([1,1′-biphenyl] -3-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 6 obtained in Synthesis Example 10) ) Was used according to Example 1 except that the average surface roughness Sa of the block layer was 52.5 nm, and the light / dark ratio when a voltage of 5 V was applied was 1.8 ×. 10 ³ .

Comparative Example 2 (Production and Evaluation of Photoelectric Conversion Element)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis ([1,1′-biphenyl] -2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 7 obtained in Synthesis Example 11) ) Was used according to Example 1, and the average surface roughness Sa of the block layer was 68.4 nm, and the contrast ratio when a voltage of 5 V was applied was 1.5 ×. 10 was ¹ .

Comparative Example 3 (Production and Evaluation of Photoelectric Conversion Element)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (naphthalen-1-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 13 obtained in Synthesis Example 12) As a result of evaluation in accordance with Example 1, the average surface roughness Sa of the block layer was 89.9 nm, and the contrast ratio when a voltage of 5 V was applied was 2.4 × 10 ² .

Comparative Example 4 (Production and Evaluation of Photoelectric Conversion Element)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (phenanthren-9-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 15 obtained in Synthesis Example 13) was used. As a result of evaluation in accordance with Example 1, the average surface roughness Sa of the block layer was 73.3 nm, and the contrast ratio when a voltage of 5 V was applied was 6.9 × 10 ² .

Comparative Example 5 (Production and Evaluation of Photoelectric Conversion Element)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (3,5-bis (trifluoromethyl) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene (compound represented by No. 18 obtained in Synthesis Example 14) When the evaluation was performed according to Example 1 except that the average surface roughness Sa of the block layer was 7.6 nm, the light / dark ratio when a voltage of 5 V was applied was 2.0 × 10. ² .

Comparative Example 6 (Production and Evaluation of Photoelectric Conversion Element)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (the compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (9H-carbazol-9-yl)-[1] benzothieno [3,2-b] [1] benzothiophene (compound represented by No. 81 obtained in Synthesis Example 15) was used. Except for the above, the evaluation was performed according to Example 1. As a result, the average surface roughness Sa of the block layer was 27.9 nm, and the contrast ratio when a voltage of 5 V was applied was 4.7 × 10 ^0. It was.

  The light / dark ratio obtained in the evaluation of the above examples clearly shows excellent characteristics as a photoelectric conversion element for an image sensor.

  From the above evaluation results, the photoelectric conversion element for an image sensor according to the present invention having an organic thin film layer with a surface roughness of the photoelectric conversion part of 7.0 nm or less is an organic thin film with a surface roughness of the photoelectric conversion part of 7.0 nm or less. It is apparent that the characteristics are superior to those of the photoelectric conversion element for the image pickup element of the comparative example having no layer.

  As described above, the photoelectric conversion element for an image pickup device of the present invention has excellent performance in organic photoelectric conversion characteristics, and includes an organic EL device and an organic solar cell as well as an organic image pickup device having high resolution and high response. Expected to be applied to fields such as organic electronics devices such as devices and organic transistor devices, optical sensors, infrared sensors, ultraviolet sensors, X-ray sensors, photon counters, and cameras, video cameras, infrared cameras, etc. Is done.

DESCRIPTION OF SYMBOLS 1 Insulation part 2 Upper electrode 3 Electron block layer or hole transport layer 4 Photoelectric conversion part 5 Hole block layer or electron transport layer 6 Lower electrode 7 Insulating base material or other photoelectric conversion element

Claims (13)

A photoelectric conversion element having (A) a first electrode film, (B) a second electrode film, and (C) a photoelectric conversion unit disposed between the first electrode film and the second electrode film. In addition, the photoelectric conversion element for an imaging element, in which the photoelectric conversion unit has one or more organic thin film layers having a surface roughness Ra and / or Sa of 7.0 nm or less. (C) The photoelectric conversion element for image sensors of Claim 1 in which a photoelectric conversion part has one or more organic thin film layers whose surface roughness Ra and / or Sa are 1.3 nm or more and 7.0 nm or less. (C) The organic thin film layer having a surface roughness Ra and / or Sa of 7.0 nm or less of the photoelectric conversion part is (c-1) an organic thin film other than the photoelectric conversion layer and / or (c-2) the photoelectric conversion layer. The photoelectric conversion element for an image sensor according to claim 1, wherein the photoelectric conversion element is a layer. (C-1) The photoelectric conversion element for an image pickup device according to claim 3, wherein the photoelectric conversion layer includes a p-type organic semiconductor material and an n-type organic semiconductor material. (C-2) The organic thin film layer other than the photoelectric conversion layer is an electronic block layer, The photoelectric conversion element for an image pickup device according to claim 3. (C-2) The photoelectric conversion element for an image pickup device according to claim 3, wherein the organic thin film layer other than the photoelectric conversion layer is a hole blocking layer. (C-2) The organic thin film layer other than the photoelectric conversion layer is an electron transport layer, The photoelectric conversion element for an image pickup device according to claim 3. (C-2) The organic thin film layer other than the photoelectric conversion layer is a hole transport layer, The photoelectric conversion element for an image pickup device according to claim 3. The image pickup device according to any one of claims 1 to 8, further comprising (D) a thin film transistor having a hole accumulating portion and (E) a signal reading portion for reading a signal corresponding to the electric charge accumulated in the thin film transistor. Photoelectric conversion element. (C) The organic thin film layer having a surface roughness Ra and / or Sa of 7.0 nm or less of the photoelectric conversion part is represented by the following formula (1).

(In formula (1), n is the number of substituents R, and each independently represents an integer of 0 to 4. R represents a substituent independently, and when n is 2 or more, adjacent Rs are The photoelectric conversion element for an imaging device according to any one of claims 1 to 9, comprising a compound represented by the following formula: (C) The organic thin film layer having a surface roughness Ra and / or Sa of 7.0 nm or less included in the photoelectric conversion portion is represented by the following formula (2).

The photoelectric conversion element for an imaging element according to claim 10, comprising a compound represented by the formula (2), wherein R represents the same meaning as R in the expression (1) according to claim 10. An image sensor in which a plurality of photoelectric conversion elements for an image sensor according to any one of claims 1 to 11 are arranged in an array. An optical sensor including the photoelectric conversion element for an imaging element according to any one of claims 1 to 11 or the imaging element according to claim 12.

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