JP6986887B2 - Photoelectric conversion element for image sensor - Google Patents

Description

The present invention relates to a photoelectric conversion element for an image pickup device that can be used for an image pickup device, an optical sensor, or the like.

In recent years, there has been increasing interest in organic electronic devices. Its features are that it has a flexible structure and can increase the area, and that it enables an inexpensive and high-speed printing method in the electronic device manufacturing process. Typical devices include an organic EL element, an organic solar cell element, an organic photoelectric conversion element, an organic transistor element and the like. Organic EL elements are expected to be the main target for next-generation display applications as flat panel displays, and are being applied to mobile phone displays and TVs, and are being developed with the aim of further enhancing functionality. Research and development has been carried out on organic solar cell elements and the like as flexible and inexpensive energy sources, and on organic transistor elements and the like as flexible displays and inexpensive ICs.

For the development of organic electronics devices, the development of materials that make up the devices is extremely important. Therefore, many materials are being studied in each field, but they cannot be said to have sufficient performance, and materials useful for various devices are still being energetically developed. Among them, compounds having benzothioenobenzothiophene as a matrix have also been developed as organic electronics materials (Patent Documents 1 to 3), and when an alkyl derivative of benzothioenobenzothiophene is used, a semiconductor thin film is used in the printing process. However, since the number of fused rings is relatively small with respect to the alkyl chain length, a phase transition is likely to occur at a low temperature, and the heat resistance of the organic electronic device is inferior.

In recent years, among organic electronics, organic photoelectric conversion elements are expected to be applied to next-generation image pickup elements, and several groups have reported on them. For example, an example in which a quinacridone derivative or a quinazoline derivative is used for a photoelectric conversion element (Patent Document 4), an example in which a photoelectric conversion element using a quinacridone derivative is applied to an image pickup element (Patent Document 5), and a diketopyrrolopyrrole derivative are used. There is an example (Patent Document 6). Generally, it is considered that the performance of the image sensor is improved by aiming at the 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.

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

Japanese Unexamined Patent Publication No. 2008-258592 WO2008-047896 WO2010-098372 Japanese Patent No. 4945146 Japanese Patent No. 5022573 Japanese Unexamined Patent Publication No. 2008-290963

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

The present invention has been made in view of such a situation, and provides a photoelectric conversion element having excellent 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 problems, the present inventor has described the above by using a compound having a specific structure in the photoelectric conversion portion of the photoelectric conversion element for an image pickup element and having a specific visible light absorption end. We have found that the various problems of the above can be solved, and have completed the present invention.
That is, the present invention is as follows.
(1) (A) A first electrode film, (B) a second electrode film, and (C) a photoelectric conversion having a photoelectric conversion unit arranged between the first electrode film and the second electrode film. The following formula (1) in which the (C) photoelectric conversion unit is an element and the visible light absorption end is 410 nm or more.

(In the formula (1), n is the number of substituents R, each independently representing an integer of 0 to 4. R independently represents a hydrogen atom or a substituent, and when n is 2 or more, they are adjacent to each other. A photoelectric conversion element for an image pickup element having one or more organic thin film layers containing a compound represented by () R may be connected to each other to form a ring structure.
(2) The photoelectric conversion element for an image sensor according to the previous item (1), wherein the visible light absorption end of the compound represented by the formula (1) is 440 nm or more.
(3) The organic thin film layer containing the compound represented by the formula (1) possessed by the (C) photoelectric conversion unit is an organic layer other than the (c-1) photoelectric conversion layer and / or (c-2) the photoelectric conversion layer. The photoelectric conversion element for an image pickup element according to the preceding item (1) or (2).
(4) The above-mentioned item (3), wherein the photoelectric conversion layer (c-1) is an organic thin film layer containing an organic semiconductor material other than the compound represented by the formula (1) and the compound represented by the formula (1). Photoelectric conversion element for image sensor,
(5) The photoelectric conversion element for an image pickup device according to the previous item (4), wherein the organic semiconductor material other than the compound represented by the formula (1) is an n-type organic semiconductor material.
(6) The photoelectric conversion element for an image sensor according to any one of (3) to (5) above, wherein the organic layer other than the photoelectric conversion layer is an electron block layer.
(7) The photoelectric conversion element for an image sensor according to any one of (3) to (5) above, wherein the organic layer other than the photoelectric conversion layer is a hole block layer.
(8) The photoelectric conversion element for an image sensor according to any one of (3) to (5) above, wherein the organic layer other than the photoelectric conversion layer is an electron transport layer.
(9) The photoelectric conversion element for an image sensor according to any one of (3) to (5) above, wherein the organic layer other than the photoelectric conversion layer is a hole transport layer.
(10) Further, any one of (1) to (9) above, which has (D) a thin film transistor having a hole storage unit and (E) a signal reading unit for reading a signal corresponding to the charge accumulated in the thin film transistor. The photoelectric conversion element for an image sensor according to the section,
(11) The compound represented by the formula (1) is the following formula (2).

(In the formula (2), R represents the same meaning as R in the formula (1) described in the preceding paragraph (1)).
(12) An image pickup device in which the photoelectric conversion elements for an image pickup device according to any one of the preceding paragraphs (1) and (11) are arranged in a plurality of arrays, and (13) any one of the preceding paragraphs (1) and (11). An optical sensor including the photoelectric conversion element for an image sensor according to the first item or the image pickup element according to the previous item (12).

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

FIG. 1 shows a cross-sectional view illustrating an embodiment of a photoelectric conversion element for an image pickup device of the present invention. FIG. 2 is a plot of the wavelength and the light-dark ratio of the visible light absorption edge 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 the representative embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples.

The feature of the photoelectric conversion element for an image pickup element of the present invention is that the (C) photoelectric conversion unit (described later) of the photoelectric conversion element for an image pickup element is represented by the following formula (1) and the visible light absorption end is 410 nm. It is to have an organic thin film layer containing the above compounds.

In the formula (1), n is the number of substituents R and independently represents an integer of 0 to 4. Each of R independently represents a hydrogen atom or a substituent, and when n is 2 or more, adjacent Rs may be connected to each other to form a ring structure.

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

The alkyl group as a substituent represented by R in the formula (1) is not limited to any of linear, branched and cyclic, and its carbon number is not particularly limited, but usually has 1 to 8 carbon atoms. It is a linear or branched alkyl group, or a cyclic alkyl group having 5 or 6 carbon atoms.
Specific examples of the alkyl group as the 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. , Se-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, cyclopentyl group, cyclohexyl group and the like, and a linear or branched alkyl group having 1 to 4 carbon atoms is preferable. , A linear alkyl group having 1 to 3 carbon atoms is more preferable.

Specific examples of the alkoxy group as the substituent represented by R in the formula (1) include a methoxy group, an ethoxy group, a propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a t-butoxy group and 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-nonadecyloxy group, n-eicosyloxy group, docosyloxy group, n-pentacosyloxy group, n-octacocil Oxy group, n-tricontyloxy group, 5- (n-pentyl) decyloxy group, heneicosyloxy group, tricosyloxy group, tetracosyloxy group, hexacosyloxy group, heptacosyloxy group, nonacosyloxy Examples thereof include an alkoxy group having 1 to 36 carbon atoms such as a group, an n-triacontyloxy group, a squaryloxy group, a dotriacontyloxy group and a hexatriacontyloxy group, and an alkoxy group having 1 to 24 carbon atoms. Is more preferable, an alkoxy group having 1 to 20 carbon atoms is more preferable, an alkoxy group having 1 to 12 carbon atoms is further preferable, and an alkoxy group having 1 to 6 carbon atoms is particularly preferable. Most preferably, it is an alkoxy group having 1 to 4 carbon atoms.

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, a biphenyl group, a terphenyl group and a naphthyl group, a benzothienyl group, a naphthothenyl group and an anthra. Thienyl group, benzodithienyl group, dibenzothienyl group, benzotrithienyl group, thienothienyl group, benzofuranyl group, naphthofuranyl group, anthrafranyl group, benzodifuranyl group, dibenzofuranyl group, benzotrifuranyl group, quinolyl group, isoquinolyl group , Heterocyclic condensed aromatic groups such as benzopyrrolyl group, indolenyl group, benzoimidazolyl group, carbazolyl group, xanthenyl group and thioxanthenyl group, and aromatic hydrocarbon groups are preferable.
The aromatic group as the substituent represented by R in the formula (1) may have a substituent, and the substituent which may have the substituent is the same as the substituent represented by R in the formula (1). Things can be mentioned.

Specific examples of the halogen atom as the substituent represented by R in the formula (1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl-substituted amino group as the substituent represented by R in the formula (1) is not limited to any of the monoalkyl-substituted amino group and the dialkyl-substituted amino group, and the alkyl group in these alkyl-substituted amino groups is the formula (1). ) Is the same as the alkyl group as the substituent represented by R.

The aryl-substituted amino group as the substituent represented by R in the formula (1) is not limited to any of the monoaryl-substituted amino group and the diaryl-substituted amino group, and the aryl group in these aryl-substituted amino groups is the formula (1). ), The same as the aromatic hydrocarbon group described in the section of the substituent represented by R can be mentioned.
Examples of the acyl group as the substituent represented by R in the formula (1) include the aromatic hydrocarbon group described in the section of the substituent represented by R in the formula (1) and the term of the substituent represented by R in the formula (1). Examples thereof include a substituent in which the alkyl group described in 1 is bonded to a carbonyl group (= CO group).
Examples of the alkoxycarbonyl group as the substituent represented by R in the formula (1) include a substituent in which the alkoxy group as the substituent represented by the formula (1) is bonded to the carbonyl group.
The substituent represented by R in the formula (1) is preferably an alkyl group, an aromatic group, a halogen atom or an alkoxyl group, more preferably an alkyl group, an aromatic group or a halogen atom, and an alkyl group or an alkyl group or a halogen atom. It is more preferably an aromatic group, most preferably an aromatic group.

The substitution position of R in the above formula (1) is not particularly limited, but the 2-position, 3-position, and 6 in the BTBT ([1] benzothioeno [3,2-b] [1] benzothiophene) structure in the formula (1). It is preferably one or more places selected from the second and seventh places, and more preferably one or more places selected from the second and seventh places. Further, it is preferable that the compound represented by the formula (1) has a target form, for example, it has a substituent at the 2-position and the 7-position, and it has a substituent at the 3-position and the 6-position. That is, as the compound represented by the formula (1), the compound represented by the following general formula (2) is particularly preferable.

In the formula (2), R has the same meaning as R in the formula (1), and the preferred one is the same as R in the formula (1).
That is, as the compound represented by the formula (2), R in the formula (2) is preferably a preferable or most preferable form of R in the above-mentioned formula (1).

Further, when n is 2 or more, it is similarly preferable that adjacent Rs are connected to each other to form a ring structure, and it is more preferable that the formed ring structure has aromaticity, and the aromaticity is more preferable. It is more preferable to have a hydrocarbon ring. When forming a ring structure, it is preferable that the 2nd and 3rd positions in the BTBT structure in the formula (1) are connected and / or the 6th and 7th positions are connected, and the ring structure is formed. It is more preferable that the ring to be formed is a benzene ring. The ring structure formed by connecting adjacent Rs may have a substituent, and examples of the substituents that may have are the same as the substituent represented by R in the formula (1). , The preferred ones are the same.

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, in the case of a compound in which n of the formula (1) is 1 to 4, the method described in the following scheme can be mentioned. Using the nitrostilbene derivative (A) as a raw material, a benzothienobenzothiophene skeleton (D) is formed, and by reducing this, an aminated product (E) (a compound in which R in the formula (1) is an amino group) is obtained. Be done. If this compound (E) is halogenated, a halide (F) (a compound in which R is a halogen in the formula (1) and a compound in which R is iodine is described as an example in the following scheme) is obtained, and this compound ( If F) is further coupled with a boric acid derivative, it is possible to obtain a compound in which R in the formula (1) is an aromatic group or the like. According to the method of Patent Document 5, a compound in which R in the formula (1) is an aromatic group or the like can be produced from the corresponding benzaldehyde derivative in one step, which is more effective.
Further, in the case of a compound of the formula (1) in which n is 0 or a compound having no substituent and having a ring structure formed by connecting adjacent Rs, a stilbene derivative having no nitro group is used as a starting material for benzothiophene. The desired compound is obtained by forming the skeleton (D).

The method for purifying the compound represented by the formula (1) is not particularly limited, and known methods such as recrystallization, column chromatography, and vacuum sublimation purification can be adopted. Moreover, these methods can be combined as needed.

The visible light absorption edge means the absorption wavelength closer to the longest wavelength in the spectral waveform of the compound. The visible light absorption edge is measured using a solution in which the compound represented by the formula (1) is dissolved in a solvent or the like, the powder of the compound itself represented by the formula (1), and the compound represented by the formula (1). It may be carried out in any form such as the obtained thin film, but it is preferably carried out in the form of a solution or a thin film from the viewpoint of reproducibility, and more preferably in the form of a thin film when the solubility of the compound is extremely low. It is more preferable to use a thin film obtained by the vacuum vapor deposition method.

The visible light absorption edge of the compound represented by the formula (1) used in the photoelectric conversion element for an image pickup device of the present invention is usually 410 nm or more, preferably 420 nm or more, and more preferably 430 nm or more. It is more preferably 440 nm or more, and particularly preferably 450 nm or more.

The photoelectric conversion element for an image pickup element of the present invention (hereinafter, may be simply referred to as “photoelectric conversion element”) has two electrodes, (A) a first electrode film and (B) a second electrode film, which face each other. 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 the semiconductor reads out a signal corresponding to the charge, and the incident light amount corresponding to the absorption wavelength of the photoelectric conversion film unit. It is an element showing. A transistor for reading may be connected to the electrode film on the side where light is not incident. When a large number of photoelectric conversion elements are arranged in an array, they are image pickup elements because they also show incident position information in addition to the amount of incident light. Further, when 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 photoelectric conversion element when viewed from the light source side, a plurality of photoelectric conversion elements are laminated. You may use it. A multi-color image pickup device (full-color photodiode array) can be obtained by stacking and using a plurality of photoelectric conversion elements having different absorption wavelengths in the visible light region.

(C) The photoelectric conversion unit consists of a group consisting of (c-1) a photoelectric conversion layer, an electron transport layer, a hole transport layer, an electron block layer, a hole block layer, an anticrystallization layer, an interlayer contact improvement layer, and the like. It often consists of an organic layer other than one or more selected (c-2) photoelectric conversion layers. The organic thin film layer represented by the formula (1) of the photoelectric conversion element for an image pickup device of the present invention and containing a compound having a visible light absorption end of 410 nm or more is the (c-1) photoelectric conversion layer and (c-2). It is used for either or both of organic layers other than the photoelectric conversion layer.

The (A) first electrode film and (B) second electrode film of the photoelectric conversion element for an image pickup element of the present invention include the (c-1) photoelectric conversion layer included in the (C) photoelectric conversion unit described later. When it has a hole transport property, or an organic layer other than (c-2) photoelectric conversion layer (hereinafter, the organic layer other than the photoelectric conversion layer is also simply referred to as "(c-2)) organic layer" is positive. In the case of a hole transport layer having a hole transport property, it plays a role of extracting holes from the (c-1) photoelectric conversion layer and the (c-2) organic layer and collecting them, and also (C). ) When the (c-1) photoelectric conversion layer included in the photoelectric conversion unit has an electron transporting property, or when the (c-2) organic layer is an electron transporting layer, the (c-1) ) It plays a role of extracting electrons from the photoelectric conversion layer and the (c-2) organic layer and discharging them. Therefore, the materials that can be used as (A) the first electrode film and (B) the second electrode film are not particularly limited as long as they have a certain degree of conductivity, but the adjacent (c-1) photoelectric conversion layer is not particularly limited. And (c-2), it is preferable to select it in consideration of adhesion to the organic layer, electron affinity, ionization potential, stability and the like. Materials that can be used as the first electrode film (A) and the second electrode film (B) include, for example, tin oxide (NESA), indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), and the like. Conductive metal oxides; Metals such as gold, silver, platinum, chromium, aluminum, iron, cobalt, nickel and tungsten; Inorganic conductive substances such as copper iodide and copper sulfide; Conductive polymers such as polythiophene, polypyrrole and polyaniline ; Carbon and the like can be mentioned. If necessary, a plurality of these materials may be mixed and used, or a plurality of these materials may be laminated in two or more layers and used. The conductivity of the materials used for (A) the first electrode film and (B) the second electrode film is not particularly limited as long as it does not interfere with the light reception of the photoelectric conversion element more than necessary, but the signal strength and consumption of the photoelectric conversion element are not particularly limited. 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 300 Ω / □ or less functions sufficiently as (A) a first electrode film and (B) a second electrode film, but has a conductivity of about several Ω / □. Since commercially available products of the substrate provided with the ITO film having the above are 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 the method for forming a film such as ITO include a conventionally known vapor deposition method, electron beam method, sputtering method, chemical reaction method, coating method and the like. The ITO film provided on the substrate may be subjected to UV-ozone treatment, plasma treatment, or the like, if necessary.

Of the (A) first electrode film and (B) second electrode film, as the material of the transparent electrode film used for at least one of the side on which light is incident, ITO, IZO, SnO ₂ , ATO ( Antimonated 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 preferable to have.

Further, when a plurality of photoelectric conversion layers having different wavelengths to be detected are laminated, an electrode film used between the photoelectric conversion layers (this is other than (A) the first electrode film and (B) the second electrode film). The electrode film) needs to transmit light having a wavelength other than the light detected by each photoelectric conversion layer, and it is preferable to use a material that transmits 90% or more of the incident light for the electrode film. It is more preferable to use a material that transmits% or more of light.

The electrode film is preferably plasma-free. By producing these electrode films in a plasma-free manner, the influence of plasma on the substrate on which the electrode film is provided can be reduced, and the photoelectric conversion characteristics of the photoelectric conversion element can be improved. Here, plasma-free means that plasma is not 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 the plasma is reduced.

Examples of the device that does not generate plasma during the film formation of the electrode film include an electron beam vapor deposition apparatus (EB vapor deposition apparatus) and a pulse laser vapor deposition apparatus. Hereinafter, the method of forming a transparent electrode film using an EB vapor deposition apparatus is referred to as an EB vapor deposition method, and the 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 capable of realizing a state in which plasma can be reduced during film formation (hereinafter referred to as a plasma-free film forming apparatus), for example, an opposed target sputtering apparatus, an arc plasma vapor 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 fine cracks generated in the photoelectric conversion layer are covered with a dense film such as TCO (Transient Conductive Oxide), and between the film and the electrode film (second conductive film) on the opposite side of the transparent conductive film. It is thought that this is because the continuity of the Therefore, when a material such as Al, which is inferior in film quality, is used for the electrode, the leakage current is unlikely to increase. By controlling the film thickness of the electrode film according to the film thickness (crack depth) of the photoelectric conversion layer, it is possible to suppress an increase in leakage current.

Usually, when the conductive film is made thinner than a predetermined value, a rapid increase in resistance value occurs. The sheet resistance of the conductive film in the photoelectric conversion element for an image sensor of the present embodiment is usually 100 to 10000 Ω / □, and the degree of freedom in film thickness is large. Further, the thinner the transparent conductive film, the smaller the amount of light absorbed, and generally the higher the light transmittance. When the light transmittance is high, the amount of light absorbed by the photoelectric conversion layer is increased and the photoelectric conversion ability is improved, which is highly preferable.

The (C) photoelectric conversion unit included in the photoelectric conversion element for an image pickup device of the present invention includes at least an organic layer other than the (c-1) photoelectric conversion layer and the (c-2) photoelectric conversion layer.
(C) An organic semiconductor film is generally used for the (c-1) photoelectric conversion layer constituting the photoelectric conversion unit, but the organic semiconductor film may be one layer or a plurality of layers, and in the case of one layer. 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, there are about 2 to 10 layers, which is a structure in which any one of a P-type organic semiconductor film, an N-type organic semiconductor film, or a mixed film thereof (bulk heterostructure) is laminated, and the layers are layers. A buffer layer may be inserted in.
When the (c-1) photoelectric conversion layer is an organic thin film layer containing a compound represented by the formula (1), the organic thin film layer is an organic semiconductor material (p-type) other than the compound represented by the formula (1). It may contain a known semiconductor material such as a semiconductor material or an n-type semiconductor material), and the n-type organic semiconductor material is preferable as the organic semiconductor material which may contain the semiconductor material).

(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, and a polysilane compound, depending on the wavelength band to be absorbed. , Thiophen compounds, phthalocyanine compounds, cyanine compounds, merocyanine compounds, oxonor compounds, polyamine compounds, indol compounds, pyrrol compounds, pyrazole compounds, polyarylene compounds, carbazole derivatives, naphthalene derivatives, anthracene derivatives, chrysene derivatives, phenanthrene derivatives, pentacene derivatives, Use phenylbutadiene derivative, styryl derivative, quinoline derivative, tetracene derivative, pyrene derivative, perylene derivative, fluorantene derivative, quinacridone derivative, coumarin derivative, porphyrin derivative, fullerene derivative, metal complex (Ir complex, Pt complex, Eu complex, etc.). be able to.

In the photoelectric conversion element for an image pickup element of the present invention, the organic layer other than the (c-2) photoelectric conversion layer constituting the (C) photoelectric conversion unit is a layer other than the (c-1) photoelectric conversion layer, for example, electron transport. It is also used as a 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. In particular, by using it 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 that efficiently converts even weak light energy into an electric signal can be obtained. Therefore, it is preferable.

The electron transport layer has a role of transporting electrons generated in the (c-1) photoelectric conversion layer to (A) the first electrode film or (B) the second electrode film, and (c) from the electron transport destination electrode film. -1) It plays a role of blocking the movement of holes to the photoelectric conversion layer.
The hole transport layer has a role of transporting the generated holes from the (c-1) photoelectric conversion layer to (A) the first electrode film or (B) the second electrode film, and the hole transport destination electrode film. (C-1) It plays a role of blocking the movement of electrons to the photoelectric conversion layer.
The electron block layer prevents the movement of electrons from (A) the first electrode film or (B) the second electrode film to (c-1) the photoelectric conversion layer, and (c-1) in the photoelectric conversion layer. It plays a role in preventing recombination and reducing dark current.
The hole block layer prevents the movement of holes from (A) the first electrode film or (B) the second electrode film to (c-1) the photoelectric conversion layer, and (c-1) in the photoelectric conversion layer. It has the function of preventing recombination and reducing dark current.
The hole block layer is formed by laminating or mixing a hole blocking substance alone or two or more kinds. The hole-blocking substance is not limited as long as it is a compound capable of preventing holes from flowing out from the electrode to the outside of the device. Examples of the compound that can be used for the hole block layer include phenanthroline derivatives such as vasophenantroline and vasocuproin, silol derivatives, quinolinol derivative metal complexes, and oxazole derivatives, in addition to the compounds represented by the above general formula (1). , Oxazole derivative, quinoline derivative and the like, and one or more of these can be used.

An organic layer other than the photoelectric conversion layer (c-2) containing the compound represented by the general formula (1) can be particularly preferably used as a hole block layer. The film thickness of the hole block layer should be thick from the viewpoint of preventing leakage current, but the film thickness should be as thin as possible from the viewpoint of obtaining a sufficient amount of current when reading a signal at the time of light incident. .. In order to achieve both of these contradictory characteristics, it is generally preferable that the film thickness of the (C) photoelectric conversion unit containing (c-1) and (c-2) is about 5 to 500 nm. The function of the layer in which the compound represented by the general formula (1) is used depends on what other compound is used for the photoelectric conversion element.
Further, the hole block layer and the electron block layer preferably have high transmittance of the absorption wavelength of the photoelectric conversion layer so as not to interfere with the light absorption of the (c-1) photoelectric conversion layer, and may be used as a thin film. 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 has 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.

If the active layer used for the thin film transistor is formed of an oxide semiconductor, the mobility of electric charges is much higher than that of the active layer of amorphous silicon, and it can be driven at a low voltage. Further, if an oxide semiconductor is used, it is possible to form an active layer having higher light transmittance and flexibility than silicon. Further, since an oxide semiconductor, particularly an amorphous oxide semiconductor, can be uniformly formed at a low temperature (for example, room temperature), it is particularly advantageous when a flexible resin substrate such as plastic is used. Further, since a plurality of secondary light receiving pixels are laminated, 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 oxide semiconductors, particularly amorphous oxide semiconductors, are advantageous because they 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, In—O system) is preferable, and at least two of In, Ga and Zn are used. Oxides containing (for example, In—Zn—O system, In—Ga—O system, Ga—Zn—O system) are more preferable, and oxides containing In, Ga and Zn are further preferable. As the In-Ga-Zn-O-based oxide semiconductor, an oxide semiconductor whose composition in the crystalline state is represented by InGaO ₃ (ZnO) m (m is a natural number less than 6) is preferable, and InGaZnO ₄ is more preferable. .. A characteristic of the amorphous oxide semiconductor having this composition is that the electron mobility tends to increase as the electric conductivity increases.

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

Although a typical element structure of the photoelectric conversion element for an image pickup device of the present invention will be described in detail in FIG. 1, the present invention is not limited to these structures. In the example of 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. The layer and 6 represent the other electrode film (second electrode film or first electrode film), and 7 represents an insulating base material or a laminated photoelectric conversion element. The readout transistor (not shown in the figure) may be connected to either 2 or 6 electrode film. For example, if the photoelectric conversion layer 4 is transparent, the side opposite to the side on which light is incident is opposite. The film may be formed on the outside of the electrode film (upper side of the electrode film 2 or 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 block the absorption wavelength of the photoelectric conversion layer, the light is incident in the upper part (Fig. Either the insulating portion 1 side in 1) or the lower portion (insulated substrate 7 side in FIG. 1) may be used.

The method for forming an organic layer other than the (c-1) photoelectric conversion layer and (c-2) photoelectric conversion layer in the photoelectric conversion element for an image pickup device of the present invention generally includes resistance heating vapor deposition and electrons, which are vacuum processes. Beam vapor 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 and other printing. A soft lithography method such as a method or a microcontact printing method, or a method in which a plurality of these methods are combined can be adopted. The thickness of each layer cannot be limited because it depends on the resistance value and charge mobility of each substance, but is usually in the range of 1 to 5000 nm, preferably in the range of 3 to 1000 nm, and more preferably in the range of 5 to 500 nm. Is in the range of.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present 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 by a vapor deposition machine integrated with the glove box, and the photoelectric conversion element is installed in a closed bottle-type measuring chamber (manufactured by ALS Technology Co., Ltd.) in the glove box with a nitrogen atmosphere. Then, the current and voltage were applied and measured. Unless otherwise specified, the current and voltage application measurements were performed using a semiconductor parameter analyzer 4200-SCS (Keithley Instruments). Unless otherwise specified, the incident light was irradiated using PVL-3300 (manufactured by Asahi Spectroscopy Co., Ltd.) with an irradiation light wavelength of 550 nm and an irradiation light half width of 20 nm. Further, the ultraviolet-visible spectrophotometer UV-3150 (ultraviolet visible spectrophotometer UV-3150) was used for the vapor-deposited film prepared by using the compounds obtained in Synthesis Examples 1 to 16 and the compound used in place of the compound represented by the formula (1) in Examples. The visible light absorption edge was confirmed based on the spectral waveform measured using (manufactured by Shimadzu Corporation). The light-dark ratio in the examples shows the current value when light irradiation is performed divided by the current value in a dark place.

Synthesis Example 1 (Synthesis of 2,7-diphenyl [1] benzothiophene [3,2-b] [1] benzothiophene)
2,7-Diode [1] benzothiodeno [3,2-b] [1] benzothiophene (3.8 parts) synthesized in DMF (250 parts) by the method described in Japanese Patent No. 4945757, which is generally available. Phenylboronic acid (2.4 parts), tripotassium phosphate (27 parts) and tetrakis (triphenylphosphine) palladium (0.47 parts) were mixed and stirred at 90 ° C. for 6 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (250 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with acetone, dried, and then sublimated and purified to obtain No. 1 of the above specific example. The compound represented by 2 (2.5 parts, yield 83%) was obtained.

Synthesis Example 2 (2,7-bis ([1,1': 4', 1''-terphenyl] -4-yl) [1] benzothioenoe [3,2-b] [1] benzothiophene synthesis)
Except for the use of commonly available (1,1': 4', 1''-terphenyl) -4-ylboronic acid (5.4 parts) instead of phenylboronic acid (2.4 parts). According to Synthesis Example 1, No. 1 of the above specific example. The compound represented by 8 (3.7 parts, 69%) was obtained.

Synthesis Example 3 (2,7-bis (naphthalene-2-yl) [1] benzothioenoe [3,2-b] [1] benzothiophene synthesis)
According to Synthesis Example 1, No. 1 of the above specific example was used, except that generally available naphthalene-2-ylboronic acid (3.3 parts) was used instead of phenylboronic acid (2.4 parts). A compound represented by 9 (3.1 parts, yield 82%) was obtained.

Synthesis Example 4 (2,7-bis (4'-methyl- [1,1'-biphenyl] -4-yl) [1] benzothioenoe [3,2-b] [1] benzothiophene synthesis)
Except for the use of commonly available (4'-methyl- [1,1'-biphenyl] -4-yl) boronic acid (5.0 parts) instead of phenylboronic acid (2.4 parts). According to Synthesis Example 1, No. 1 of the above specific example. The compound represented by 21 (2.7 parts, 61%) was obtained.

Synthesis Example 5 (2,7-bis (2-fluoro- [1,1'-biphenyl] -4-yl) [1] benzothiophene [3,2-b] [1] benzothiophene synthesis)
Synthetic except that commonly available (2-fluoro- [1,1'-biphenyl] -4-yl) boronic acid (5.0 parts) was used instead of phenylboronic acid (2.4 parts). According to Example 1, No. of the above specific example. The compound represented by 23 (2.2 parts, 50%) was obtained.

Synthesis Example 6 (2,7-bis ([1,1': 3,1''-terphenyl] -4-yl) [1] benzothioenoe [3,2-b] [1] benzothiophene synthesis)
(Step 1) Synthesis of 2- ([1,1': 3,1''-terphenyl] -4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane synthesis Toluene (240 parts), commonly available 4-bromo-1,1': 3,1''-terphenyl (6.0 parts), bis (pinacolato) diboron (5.6 parts), potassium acetate (6 parts) 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 a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, 20 parts of silica gel was added, and the mixture was stirred for 5 minutes. Then, the solid content was filtered off and the solvent was removed under reduced pressure to remove 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) 2,7-Bis ([1,1': 3,1''-terphenyl] -4-yl) [1] Benzothioeno [3,2-b] [1] Synthesis of benzothiophene Phenylboron 2-([1,1': 3,1''-terphenyl] -4-yl) -4,4,5,5-tetra obtained in step 1 instead of acid (2.4 parts) Methyl-1,3,2-dioxaborolane (6.8 parts) was used, and water (8.0 parts) was added to the reaction system. The compound represented by 26 (2.6 parts, 46%) was obtained.

Synthesis Example 7 (2,7-bis ([1,1': 3', 1''-terphenyl] -5'-yl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene )
Synthetic except that the commonly available (2-fluoro- [1,1'-biphenyl] -4-yl) boronic acid (5.3 parts) was used instead of phenylboronic acid (2.4 parts). According to Example 1, No. of the above specific example. The compound represented by 27 (2.0 parts, 37%) was obtained.

Synthesis Example 8 (2,7-bis (benzo [b] furan-2-yl) [1] benzothioeno [3,2-b] [1] benzothiophene synthesis)
In accordance with Synthesis Example 1, except that generally available benzo [b] furan-2-ylboronic acid (1.9 parts) was used instead of phenylboronic acid (2.4 parts), the above specific example No. The compound represented by 29 (2.6 parts, 73%) was obtained.

Synthesis Example 9 (2,7-bis (benzo [b] thiophen-2-yl) [1] benzothioeno [3,2-b] [1] synthesis of benzothiophene)
In accordance with Synthesis Example 1, except that generally available benzo [b] thiophen-2-ylboronic acid (2.1 parts) was used instead of phenylboronic acid (2.4 parts), the above specific example No. The compound represented by 33 (2.7 parts, 70%) was obtained.

Synthesis Example 10 (2,7-bis (4- (benzo [b] furan-2-yl) phenyl) [1] benzothioenoe [3,2-b] [1] synthesis of benzothiophene)
(Step 3) Synthesis of 2- (4-bromophenyl) benzo [b] furan In DMF (920 parts), generally 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 under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (920 parts) was added, and the solid content was collected by filtration. The obtained solid content 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 part) was mixed and stirred at reflux temperature for 4 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, 20 parts of silica gel was added, and the mixture was stirred for 5 minutes. Then, the solid content was filtered off and the solvent was removed under reduced pressure to remove 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) 2,7-Bis (4- (benzo [b] furan-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene In DMF (200 parts), Water (6.0 parts), 2,7-diiodo [1] benzothiophene [3,2-b] [1] benzothiophene (3.0 parts) synthesized by the method described in Japanese Patent No. 4945757, in step 4. The obtained 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 under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (200 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with acetone, dried, and then sublimated and purified to obtain No. 1 of the above specific example. The compound represented by 83 (2.0 parts, yield 50%) was obtained.

Synthesis Example 11 (2,7-bis (4- (benzo [b] thiophen-2-yl) phenyl) [1] benzothioeno [3,2-b] [1] synthesis of benzothiophene)
(Step 6) Synthesis of 2- (4-bromophenyl) benzo [b] thiophene DMF (300 parts), generally available benzo [b] thiophene-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 under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (300 parts) was added, and the solid content was collected by filtration. The obtained solid content 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 part) was mixed and stirred at reflux temperature for 4 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, 20 parts of silica gel was added, and the mixture was stirred for 5 minutes. Then, the solid content was filtered off and the solvent was removed under reduced pressure to remove 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) 2,7-Bis (4- (benzo [b] thiophen-2-yl) phenyl) [1] benzothioeno [3,2-b] [1] synthesis of benzothiophene In DMF (170 parts), Water (5.0 parts), 2,7-diiodo [1] benzothiophene [3,2-b] [1] benzothiophene (2.6 parts) synthesized by the method described in Japanese Patent No. 4945757, in step 7. The obtained 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 under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (170 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with acetone, dried, and then sublimated and purified to obtain No. 1 of the above specific example. The compound represented by 87 (1.6 parts, yield 46%) was obtained.

Synthesis Example 12 (2,7-bis ([1,1'-biphenyl] -3-yl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
According to Synthesis Example 1, No. 1 of the above specific example was used, except that generally available 3-biphenylboronic acid (3.8 parts) was used instead of phenylboronic acid (2.4 parts). The compound represented by 6 (2.1 g, 51%) was obtained.

Synthesis Example 13 (2,7-bis (4-methylphenyl) [1] benzothioenoe [3,2-b] [1] benzothiophene synthesis)
According to Synthesis Example 1, No. 1 of the above specific example was used, except that generally available 4-methylphenylboronic acid (2.7 parts) was used instead of phenylboronic acid (2.4 parts). The compound represented by 12 (1.8 parts, 54%) was obtained.

Synthesis Example 14 (2,7-bis (naphthalene-1-yl) [1] benzothioenoe [3,2-b] [1] benzothiophene synthesis)
According to Synthesis Example 1, No. 1 of the above specific example was used, except that generally available naphthalene-1-ylboronic acid (3.3 parts) was used instead of phenylboronic acid (2.4 parts). The compound represented by 13 (2.7 parts, 72%) was obtained.

Synthesis Example 15 (2,7-bis (phenanthrene-9-yl) [1] benzothioenoe [3,2-b] [1] benzothiophene synthesis)
According to Synthesis Example 1, No. 1 of the above specific example was used, except that generally available phenanthrene-9-ylboronic acid (4.3 parts) was used instead of phenylboronic acid (2.4 parts). A compound represented by 15 (3.0 parts, 65%) was obtained.

Synthesis Example 16 (2,7-bis (4- (trifluoromethyl) phenyl) [1] benzothioenoe [3,2-b] [1] benzothiophene synthesis)
In accordance with Synthesis Example 1, except that generally available 4- (trifluoromethyl) phenylboronic acid (3.7 parts) was used instead of phenylboronic acid (2.4 parts), the above specific example No. The compound represented by 17 (2.7 parts, 67%) was obtained.

Synthesis Example 17 (2,7-bis (6-phenylnaphthalen-2-yl) [1] benzothioenoe [3,2-b] [1] benzothiophene synthesis)
(Step 9) Synthesis of 2-methoxy-6-phenylnaphthalene 2-bromo-6-methoxynaphthalene (25 parts) and phenyl in a mixed solution of toluene (250 parts), isopropyl alcohol (20 parts) and water (15 parts). 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 under a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, toluene and water were added, and the solution was separated. After distilling off the solvent 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 obtain 2-methoxy-6-phenylnaphthalene (developing solution; toluene / hexane = 1/6 (volume ratio)). 16.6 parts, yield 69%) was obtained.

(Step 10) Synthesis of 2-Hydroxy-6-Phenylnaphthalene 2-Methoxy-6-phenylnaphthalene (14.0 parts) and pyridine hydrochloride (86 parts) obtained in Step 9 are mixed and subjected to a nitrogen atmosphere. The mixture was stirred at 190 ° C. for 5 hours. The obtained reaction solution was cooled to room temperature, ethyl acetate and water were added, and the layers were separated. The solvent was distilled off under reduced pressure to obtain 2-hydroxy-6-phenylnaphthalene (13.0 parts, yield 99%).

(Step 11) Synthesis of 6-phenylnaphthalene-2-yl trifluoromethanesulfonate To a mixed solution of dichloromethane (200 parts) and triethylamine (12.0 parts), 2-hydroxy-6-phenylnaphthalene obtained in step 10 (step 11). 13.0 parts) was added, and after cooling to 0 ° C., trifluoromethanesulfonic anhydride (20.0 parts) was slowly added dropwise. After completion of the dropping, the temperature was raised to 25 ° C. and the mixture was stirred for 1 hour. Water was added to the obtained reaction solution, the solution was separated, and the solvent was distilled off under reduced pressure to obtain a brown solid. This solid is purified by silica gel column chromatography (developing solution; toluene) and the solvent is removed under reduced pressure to obtain 6-phenylnaphthalene-2-yl trifluoromethanesulfonate (20.5 parts, yield 99%). Obtained.

(Step 12) Synthesis of (6-phenylnaphthalene-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (350 parts) was added to 6- obtained in Step 11. Phenylnaphthalene-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 a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, and the solid content was filtered off to obtain a filtrate containing a product. Then, the residue was purified by silica gel column chromatography (developing solution; toluene), and the solvent was removed under reduced pressure to remove 6- (phenylnaphthalene-2-yl) -4,4,5,5-tetramethyl-1,3. , 2-Dioxaborolane (12.1 parts, yield 66%) was obtained.

(Step 13) 2,7-Bis (6-phenylnaphthalen-2-yl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene DMF (250 parts) and water (8.0 parts). ), 2,7-Diode [1] benzothiodeno [3,2-b] [1] benzothiophene (4.2 parts) synthesized by the method described in Japanese Patent No. 4945757, 6- obtained in step 12 (. Phenylnaphthalene-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 part) was mixed and stirred at 90 ° C. for 5 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (250 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with DMF and acetone, dried, and then sublimated and purified. A compound represented by 10 (3.0 parts, yield 56%) was obtained.

Synthesis Example 18 (2,7-bis (5'-phenyl- [1,1': 3', 1''-terphenyl] -4-yl) [1] benzothioeno [3,2-b] [1] Synthesis of benzothiophene)
(Step 14) (5'-Phenyl- [1,1': 3', 1''-terphenyl] -4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Synthesis of Toluene (510 parts), commonly available 4-bromo-5'-phenyl-1,1': 3', 1''-terphenyl (15.0 parts), bis (pinacolato) diboron (12). .0 parts), potassium acetate (7.5 parts) and [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (1.1 parts) mixed in a nitrogen atmosphere. The mixture was stirred at reflux temperature for 5 hours. The obtained reaction solution was cooled to room temperature, 50 parts of silica gel was added, and the mixture was stirred for 5 minutes. Then, the solid content was filtered off and the solvent was removed under reduced pressure (5'-phenyl- [1,1': 3', 1''-terphenyl] -4-yl) -4,4,5,5. 5-Tetramethyl-1,3,2-dioxaborolane (12.0 parts, yield 71%) was obtained.

(Step 15) 2,7-Bis (5'-Phenyl- [1,1': 3', 1''-Terphenyl] -4-yl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene 2,7-diiodo [1] benzothieno [3,2-b] [1] benzo synthesized in DMF (300 parts) with water (9.0 parts) by the method described in Patent No. 4945757. Thiophene (4.5 parts), obtained in step 14 (5'-phenyl- [1,1': 3', 1''-terphenyl] -4-yl) -4,4,5,5- Tetramethyl-1,3,2-dioxaborolane (9.9 parts), tripotassium phosphate (30.3 parts) and tetrakis (triphenylphosphine) palladium (0.6 parts) are mixed and 90 parts under a nitrogen atmosphere. The mixture was stirred at ° C for 6 hours. After cooling the obtained reaction solution to room temperature, water (300 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with acetone, dried, and then sublimated and purified to obtain No. 1 of the above specific example. The compound represented by 28 (2.0 parts, yield 26%) was obtained.

Synthesis Example 19 (2,7-bis (4- (benzo [d] thiazole-2-yl) phenyl) [1] benzothioenoe [3,2-b] [1] synthesis of benzothiophene)
(Step 16) Synthesis of 2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) phenyl) benzo [d] thiazole Toluene (240 parts) is generally used. 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 part) was mixed and stirred at reflux temperature for 4 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, 20 parts of silica gel was added, and the mixture was stirred for 5 minutes. Then, the solid content was filtered off and the solvent was removed under reduced pressure to remove 2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) phenyl) benzo [d. ] Thiazole (4.9 parts, yield 80%) was obtained.

(Step 17) 2,7-Bis (4- (benzo [d] thiazole-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene In DMF (170 parts), Water (5.0 parts), 2,7-diiodo [1] benzothiodeno [3,2-b] [1] benzothiophene (2.6 parts) synthesized by the method described in Japanese Patent No. 4945757, in step 16. 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 under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (170 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with acetone, dried, and then sublimated and purified to obtain No. 1 of the above specific example. The compound represented by 111 (1.8 parts, yield 52%) was obtained.

Synthesis Example 20 (2,7-bis (9,9-dimethyl-9H-fluorene-2-yl) [1] benzothioenoe [3,2-b] [1] benzothiophene synthesis)
(Step 18) Synthesis of 2- (9,9-dimethyl-9H-fluorene-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane In toluene (250 parts), 2 -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 a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, and the solid content was filtered off to obtain a filtrate containing a product. Then, by purifying by short silica gel column chromatography (developing solution; toluene) and removing the solvent under reduced pressure, 2- (9,9-dimethyl-9H-fluorene-2-yl) -4,4,5, 5-Tetramethyl-1,3,2-dioxaborolane (11.1 parts, yield 95%) was obtained.

(Step 19) 2,7-Bis (9,9-dimethyl-9H-fluorene-2-yl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene DMF (300 parts) with water. (10.0 parts), 2,7-diiodo [1] benzothiodeno [3,2-b] [1] benzothiophene (7.1 parts) synthesized by the method described in Japanese Patent No. 4945757, obtained in step 18. 2- (9,9-dimethyl-9H-fluorene-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (11.1 parts), tripotassium phosphate (11.1 parts) 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 solution to room temperature, water (250 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with acetone, dried, and then sublimated and purified to obtain No. 1 of the above specific example. The compound represented by 172 (6.2 parts, yield 69%) was obtained.

Synthesis Example 21 (2,7-bis (4- (9,9-dimethyl-9H-fluorene-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene)
(Step 20) Synthesis of 2- (9,9-dimethyl-9H-fluorene-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane In toluene (250 parts), 2 -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 a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, and the solid content was filtered off to obtain a filtrate containing a product. Then, by purifying by short silica gel column chromatography (developing solution; toluene) and removing the solvent under reduced pressure, 2- (9,9-dimethyl-9H-fluorene-2-yl) -4,4,5, 5-Tetramethyl-1,3,2-dioxaborolane (11.1 parts, yield 95%) was obtained.

(Step 21) Synthesis of 2- (4-bromophenyl) -9,9-dimethyl-9H-fluorene In a mixed solution of DMF (400 parts) and water (15 parts), 2- (9) obtained in step 20. , 9-dimethyl-9H-fluorene-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 solution was cooled to room temperature, water was added, and the produced white solid was collected by filtration. Purification with recrystallization (recrystallization solvent; acetone) gave 2- (4-bromophenyl) -9,9-dimethyl-9H-fluorene (26.7 parts, yield 98%).

(Step 22) Synthesis of 2- (4- (9,9-dimethyl-9H-fluorene-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (200) 2- (4-bromophenyl) -9,9-dimethyl-9H-fluorene (10.0 parts), bis (pinacolato) diboron (8.7 parts), potassium acetate (parts) obtained in step 21. 5.6 parts) and [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane addition (0.7 parts) were mixed and stirred at reflux temperature for 4 hours under a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, and the solid content was filtered off to obtain a filtrate containing a product. Then, it was purified by short silica gel column chromatography (developing solution; toluene), and the solvent was removed under reduced pressure to obtain a white solid. By further purifying this solid with recrystallization (recrystallization solvent; acetone / hexane), 2- (4- (9,9-dimethyl-9H-fluorene-2-yl) phenyl) -4,4,5, 5-Tetramethyl-1,3,2-dioxaborolane (8.3 parts, 73% yield) was obtained.

(Step 23) 2,7-Bis (4- (9,9-dimethyl-9H-fluorene-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene DMF (190) (Parts), water (7.0 parts), 2,7-diiodo [1] benzothiophene [3,2-b] [1] benzothiophene (3.7 parts) synthesized by the method described in Japanese Patent No. 4945757. , 2- (4- (9,9-dimethyl-9H-fluorene-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7) obtained in step 22 .5 parts), 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 solution to room temperature, water (200 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with DMF and acetone, dried, and then sublimated and purified. The compound represented by 174 (1.8 parts, yield 31%) was obtained.

Synthesis Example 22 (2,7-bis (4'-(pyridin-2-yl)-[1,1'-biphenyl] -4-yl) [1] benzothiophene [3,2-b] [1] benzothiophene Synthesis)
(Step 24) Synthesis of 4- (pyridin-2-yl) phenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2- (4) generally available in toluene (960 parts). -Bromophenyl) Pyridine (17.1 parts), Bis (Pinacholato) 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 a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, 80 parts of silica gel was added, and the mixture was stirred for 5 minutes. Then, the solid content was filtered off and washed with ethyl acetate. By removing the solvent in the obtained solution under reduced pressure, 4- (pyridin-2-yl) phenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (19.0 parts, yield) 92%) was obtained.

(Step 25) Synthesis of 2- (4'-bromo- [1,1'-biphenyl] -4-yl) pyridine In DMF (520 parts), water (18.0 parts), 4 obtained in step 24. -(Pyridine-2-yl) Phenyl-4,4,5,5-Tetramethyl-1,3,2-dioxaborolane (14.6 parts), commonly available para-bromoiodobenzene (14.6 parts) , Tripotassium phosphate (62.6 parts) and tetrakis (triphenylphosphine) palladium (1.6 parts) were mixed and stirred at 90 ° C. for 6 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (520 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with water and dried to obtain 2- (4'-bromo- [1,1'-biphenyl] -4-yl) pyridine (15.0 parts, yield 94%). rice field.

(Step 26) Synthesis of (4'-(pyridin-2-yl)-[1,1'-biphenyl] -4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (350 parts), 2- (4'-bromo- [1,1'-biphenyl] -4-yl) pyridine (8.0 parts) obtained in step 25, bis (pinacolato) diboron (7. 9 parts), potassium acetate (5.0 parts) and [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane addition (0.8 parts) are mixed and refluxed under a nitrogen atmosphere. The mixture was stirred at temperature for 5 hours. After cooling the obtained reaction solution to room temperature, 40 parts of silica gel was added, and the mixture was stirred for 5 minutes. Then, the solid content was filtered off and washed with ethyl acetate. By removing the solvent in the obtained solution under reduced pressure, (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 27) 2,7-Bis (4'-(pyridin-2-yl)-[1,1'-biphenyl] -4-yl) [1] benzothiophene [3,2-b] [1] benzothiophene Synthesis of 2,7-diiodo [1] benzothiophene [3,2-b] [1] benzothiophene synthesized by the method described in Japanese Patent No. 4945757 with water (9.0 parts) in DMF (300 parts). 4.5 parts), (4'-(pyridin-2-yl)-[1,1'-biphenyl] -4-yl) -4,4,5,5-tetramethyl-1 obtained in step 26. , 3,2-Dioxaborolane (8.2 parts), tripotassium phosphate (30.3 parts) and tetrakis (triphenylphosphine) palladium (0.6 parts) are mixed and heated at 90 ° C. for 6 hours under a nitrogen atmosphere. Stirred. After cooling the obtained reaction solution to room temperature, water (300 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with acetone, dried, and then sublimated and purified to obtain No. The compound represented by 181 (7.2 parts, 42%) was obtained.

Synthesis Example 23 (2,7-bis (4- (benzo [b] thiophen-2-yl) -2-methylphenyl) [1] benzothioeno [3,2-b] [1] synthesis of benzothiophene)
(Step 28) Synthesis of 2- (4-bromo-3-methylphenyl) benzo [b] thiophene A commonly available benzo [b] thiophene-2-ylboronic acid (5.0 parts) in DMF (300 parts). , 2-Bromo-5-iodotoluene (8.3 parts), tripotassium phosphate (34 parts) and tetrakis (triphenylphosphine) palladium (0.84 parts) were mixed and 6 at 90 ° C. under a nitrogen atmosphere. Stirred for hours. After cooling the obtained reaction solution to room temperature, water (300 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with methanol and dried to obtain 2- (4-bromo-3-methylphenyl) benzo [b] thiophene (5.7 parts, yield 67%).

(Step 29) Synthesis of 2- (4- (benzo [b] thiophen-2-yl) -2-methylphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (240) Part), 2- (4-bromo-3-methylphenyl) benzo [b] thiophene (5.6 parts), bis (pinacolato) diboron (5.6 parts), potassium acetate (3 parts) obtained in step 28. .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 a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, 20 parts of silica gel was added, and the mixture was stirred for 5 minutes. Then, the solid content was filtered off and the solvent was removed under reduced pressure to remove 2- (4- (benzo [b] thiophen-2-yl) -2-methylphenyl) -4,4,5,5-tetramethyl-. 1,3,2-dioxaborolane (5.6 parts, 87% yield) was obtained.

(Step 30) 2,7-Bis (4- (benzo [b] thiophen-2-yl) -2-methylphenyl) [1] benzothioeno [3,2-b] [1] synthesis of benzothiophene DMF (170) (Parts), water (5.0 parts), 2,7-diiodo [1] benzothiophene [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) obtained in step 29. .6 parts), tripotassium phosphate (18 parts) and tetrakis (triphenylphosphine) palladium (0.35 parts) were mixed and stirred at 90 ° C. for 6 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (170 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with acetone, dried, and then sublimated and purified to obtain No. 1 of the above specific example. The compound represented by 189 (1.2 parts, yield 35%) was obtained.

Synthesis Example 24 (2,7-bis (2,2'-vinaphthalene-6-yl) [1] benzothiophene [3,2-b] [1] benzothiophene synthesis)
(Step 31) Synthesis of 6-methoxy-2,2'-vinaphthalene 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 a reflux temperature for 5 hours under a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, water was added, and the formed solid was collected by filtration. The obtained solid was washed with methanol to obtain 6-methoxy-2,2'-vinaphthalene (13.5 parts, yield 98%).

(Step 32) Synthesis of 6-Hydroxy-2,2'-Binaphthalene 6-Methoxy-2,2'-Binaphthalene (13.0 parts) and pyridine hydrochloride (53 parts) obtained in Step 31 were mixed and mixed. The mixture was stirred at 190 ° C. for 5 hours under a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, ethyl acetate and water were added, and the layers were separated. By distilling off the solvent under reduced pressure, 6-hydroxy-2,2'-vinaphthalene (11.5 parts, yield 94%) was obtained.

(Step 33) Synthesis of 2,2'-binaphthyl-6-yltrifluoromethanesulfonate 6-hydroxy-2,2 obtained in step 32 in a mixed solution of dichloromethane (150 parts) and triethylamine (8.6 parts). '-Vinaphthalene (11.5 parts) was added, cooled to 0 ° C., and then trifluoromethanesulfonic anhydride (14.4 parts) was slowly added dropwise. After completion of the dropping, the temperature was raised to 25 ° C., and the mixture was stirred for 2 hours. Water and toluene were added to the obtained reaction solution, the layers were separated, and the solvent was distilled off under reduced pressure to obtain a brown solid. By suspending this solid in methanol (100 parts) and recovering the white solid by filtration, 2,2'-binaphthyl-6-yltrifluoromethanesulfonate (15.2 parts, yield 89%) was obtained. rice field.

(Step 34) Synthesis of (2,2'-binaphthyl-6-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (350 parts) was obtained in step 33. 2,2'-binaphthyl-6-yltrifluoromethanesulfonate (14.5 parts), bis (pinacolato) diboron (11.0 parts), potassium acetate (7.1 parts) and [1,1'-bis (1,1'-bis) Diphenylphosphino) ferrocene] Palladium (II) dichloride dichloromethane adduct (0.9 parts) was mixed and stirred at reflux temperature for 6 hours under a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, and the solid content was filtered off to obtain a filtrate containing a product. Then, the residue was purified by silica gel column chromatography (developing solution; toluene), and the solvent was removed under reduced pressure to obtain (2,2'-binaphthyl-6-yl) -4,4,5,5-tetramethyl-1. , 3,2-Dioxaborolane (13.5 parts, yield 99%) was obtained.

(Step 35) 2,7-Bis (2,2'-binaphthyl-6-yl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene DMF (180 parts) was added to water (8. 0 part), 2,7-diiodo [1] benzothiophene [3,2-b] [1] benzothiophene (3.3 parts) synthesized by the method described in Japanese Patent No. 4945757, obtained in step 34 (. 2,2'-binaphthyl-6-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6.6 parts), tripotassium phosphate (5.7 parts) and tetrakis (6 parts) Triphenylphosphine) palladium (0.4 part) was mixed, and the mixture was stirred at 80 ° C. for 5 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (200 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with DMF and acetone, dried, and then sublimated and purified. The compound represented by 184 (1.0 part, yield 20%) was obtained.

Synthesis Example 25 (2,7-bis (2-dibenzothiophene) [1] benzothioenoe [3,2-b] [1] benzothiophene synthesis)
(Step 36) Synthesis of 2- (dibenzothiophen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (250 parts) and 2-bromodibenzothiophene (10. 0 parts), 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) were mixed, and the mixture was stirred at a reflux temperature for 4 hours under a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, and the solid content was filtered off to obtain a filtrate containing a product. Then, by purifying by short silica gel column chromatography (developing solution; toluene) and removing the solvent under reduced pressure, 2- (dibenzothienyl-2-yl) -4,4,5,5-tetramethyl-1, 3,2-Dioxaborolane (11.5 parts, yield 98%) was obtained.

(Step 37) 2,7-Bis (2-dibenzothienyl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene DMF (230 parts), water (7.0 parts), patent No. 2,7-Diode [1] benzothiophene [3,2-b] [1] benzothiophene (4.5 parts) synthesized by the method described in No. 4945757, 2- (dibenzothienyl-2) obtained in step 36. -Il) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.0 parts), tripotassium phosphate (7.7 parts) and tetrakis (triphenylphosphine) palladium (0. 6 parts) were mixed and stirred at 90 ° C. for 5 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (250 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with acetone, dried, and then sublimated and purified to obtain No. 1 of the above specific example. A compound represented by 164 (2.0 parts, yield 37%) was obtained.

Synthesis Example 26 (2,7-bis (6- (benzo [b] thiophen-2-yl) naphthalene-2-yl) [1] benzothioeno [3,2-b] [1] synthesis of benzothiophene)
(Step 38) Synthesis of 2- (6-methoxynaphthalene-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 under a nitrogen atmosphere. .. The obtained reaction solution 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 39) Synthesis of 2- (6-hydroxy-2-yl) benzo [b] thiophene 2- (6-methoxynaphthalen-2-yl) benzo [b] thiophene (19.5 parts) obtained in step 38. ) And methylene chloride (100 parts) were mixed and stirred at 0 ° C. under a nitrogen atmosphere. A methylene chloride solution of 1 mol / L boron tribromide was slowly added dropwise to this solution, and the mixture was stirred at room temperature for 1 hour after the addition was completed. Water was added to the reaction solution and the solution was separated. The solvent was distilled off under reduced pressure, the obtained solid was suspended in methanol, and the white solid was recovered by filtration to recover 2- (6-methoxynaphthalen-2-yl) benzo [b] thiophene (17.9 parts). , Yield 97%) was obtained.

(Step 40) Synthesis of 6- (benzo [b] thiophen-2-yl) naphthalene-2-yl trifluoromethanesulfonate Obtained in step 39 in a mixed solution of dichloromethane (250 parts) and triethylamine (14.0 parts). 2- (6-Methoxynaphthalene-2-yl) benzo [b] thiophene (19.0 parts) was added, cooled to 0 ° C., and then trifluoromethanesulfonic anhydride (29.1 parts) was slowly added dropwise. did. After completion of the dropping, the temperature was raised to 25 ° C. and the mixture was stirred for 1 hour. Water was added to the obtained reaction solution, and the brown precipitate was collected by filtration. The precipitated solid was washed with methanol to obtain 6- (benzo [b] thiophen-2-yl) naphthalene-2-yl trifluoromethanesulfonate (27.5 parts, yield 98%).

(Step 41) Synthesis of 2- (6- (benzo [b] thiophen-2-yl) naphthalene-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (400) 6- (benzo [b] thiophen-2-yl) naphthalene-2-yl trifluoromethanesulfonate (27.0 parts), bis (pinacolato) diboron (20.1 parts) obtained in step 40. , Potassium acetate (13.0 parts) and [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (1.6 parts) are mixed, and the reflux temperature is 4 under a nitrogen atmosphere. Stirred for hours. The obtained reaction solution was cooled to room temperature, and the solid content was filtered off to obtain a filtrate containing a product. Then, it was purified by silica gel column chromatography (developing solution; toluene), and the solvent was removed under reduced pressure to obtain a white solid. By recrystallizing the obtained solid with toluene, 2- (6- (6- (benzo [b] thiophen-2-yl) naphthalene-2-yl) -4,4,5,5-tetramethyl- 1,3,2-dioxaborolane (18.0 parts, yield 71%) was obtained.

(Step 42) 2,7-Bis (6- (benzo [b] thiophen-2-yl) naphthalene-2-yl) [1] benzothioeno [3,2-b] [1] synthesis of benzothiophene DMF (260) (Parts), water (30.0 parts), 2,7-diiodo [1] benzothiophene [3,2-b] [1] benzothiophene (4.0 parts) synthesized by the method described in Japanese Patent No. 4945757. , 2- (6- (6- (benzo [b] thiophen-2-yl) naphthalene-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7) obtained in step 41. .9 parts), tripotassium phosphate (6.9 parts) and tetrakis (triphenylphosphine) palladium (0.52 parts) were mixed and stirred at 80 ° C. for 5 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (300 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with DMF and acetone, dried, and then sublimated and purified. The compound represented by 185 (0.6 part, yield 10%) was obtained.

Synthesis Example 27 (2,7-bis (4- (5-benzo [b] thienyl) phenyl) [1] benzothioenoe [3,2-b] [1] synthesis of benzothiophene)
(Step 43) Synthesis of 2- (benzo [b] thiophene-5-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane In toluene (200 parts), 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 solution was cooled to room temperature, and the solid content was filtered off to obtain a filtrate containing a product. Then, the residue was purified by short silica gel column chromatography (developing solution; toluene), and the solvent was removed under reduced pressure to obtain 2- (benzo [b] thiophene-5-yl) -4,4,5,5-tetramethyl. -1,3,2-dioxaborolane (11.7 parts, yield 96%) was obtained.

(Step 44) Synthesis of 5- (4-bromophenyl) benzo [b] thiophene To DMF (230 parts), 2- (benzo [b] thiophene-5-yl) -4,4 obtained in step 43. 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 solution was cooled to room temperature, water (200 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with water and methanol in this order to obtain 5- (4-bromophenyl) benzo [b] thiophene (12.0 parts, yield 94%).

(Step 45) Synthesis of 2- (4- (5-benzo [b] thienyl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (200 parts), step 44. 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 a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, and the solid content was filtered off to obtain a filtrate containing a product. Then, it was purified by short silica gel column chromatography (developing solution; toluene), and the solvent was removed under reduced pressure. By washing the obtained pale orange solid with methanol, 2- (4- (5-benzo [b] thienyl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane ( 7.4 parts, yield 53%) was obtained.

(Step 46) 2,7-Bis (4- (5-benzo [b] thienyl) phenyl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene DMF (200 parts) was added to water (200 parts). 10.0 parts), 2,7-diiodo [1] benzothiodeno [3,2-b] [1] benzothiophene (3.7 parts) synthesized by the method described in Japanese Patent No. 4945757, obtained in step 45. 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 solution to room temperature, water (150 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with acetone and DMF, dried, and then sublimated and purified. The compound represented by 105 (2.0 parts, yield 51%) was obtained.

Synthesis Example 28 (2,7-bis (4'-(2-naphthyl)-(1,1'-biphenyl) -4-yl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene )
(Step 47) Synthesis of 2- (4'-bromo- (1,1'-biphenyl) -4-yl) naphthalene DMF (100 parts) to 4- (2-naphthyl) phenylboronic acid (5.0 parts) , P-Iodo-bromobenzene (5.7 parts), tripotassium phosphate (8.6 parts) and tetrakis (triphenylphosphine) palladium (0.7 parts) were added, and the reflux temperature was 6 hours under a nitrogen atmosphere. Stirred. The obtained 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 48) Synthesis of 2- (4'-(2-naphthyl)-(1,1'-biphenyl) -4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (150 parts), 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) are mixed and refluxed under a nitrogen atmosphere. The mixture was stirred at temperature for 5 hours. The obtained reaction solution was cooled to room temperature, and the solid content was filtered off to obtain a filtrate containing a product. Then, the residue was purified by silica gel column chromatography (developing solution; toluene), and the solvent was removed under reduced pressure to obtain 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 49) 2,7-Bis (4'-(2-naphthyl)-(1,1'-biphenyl) -4-yl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene DMF (200 parts), water (10.0 parts), 2,7-diiodo [1] benzothiophene [3,2-b] [1] benzothiophene (3. 2 parts), 2- (4'-(2-naphthyl)-(1,1'-biphenyl) -4-yl) -4,4,5,5-tetramethyl-1,3 obtained in step 48 , 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 under a nitrogen atmosphere. .. After cooling the obtained reaction solution to room temperature, water (200 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with DMF and acetone, dried, and then sublimated and purified. The compound represented by 192 (0.5 part, yield 10%) was obtained.

Synthesis Example 29 (2,7-bis (4- (naphtho [1,2-b] thiophen-2-yl) phenyl) [1] benzothioenoe [3,2-b] [1] synthesis of benzothiophene)
(Step 50) Synthesis of 2- (4-bromophenyl) naphtho [1,2-b] thiophene 2- (naphtho [1,2-b] thiophene-synthesized with 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 solution to room temperature, water (190 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with methanol and dried to obtain 2- (4-bromophenyl) naphtho [1,2-b] thiophene (3.0 parts, yield 47%).

(Step 51) Synthesis of 2- (4- (naphtho [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 part) obtained in step 50. .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 a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, 20 parts of silica gel was added, and the mixture was stirred for 5 minutes. Then, the solid content was filtered off and the solvent was removed under reduced pressure to remove 2- (4- (naphtho [1,2-b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-. 1,3,2-dioxaborolane (2.2 parts, yield 69%) was obtained.

(Step 52) 2,7-Bis (4- (naphtho [1,2-b] thiophen-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene DMF (100) (Parts), water (2.6 parts), 2,7-diiodo [1] benzothiophene [3,2-b] [1] benzothiophene (1.2 parts) synthesized by the method described in Japanese Patent No. 4945757. , 2- (4- (Naft [1,2-b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2) obtained in step 51. .0 parts), tripotassium phosphate (8.1 parts) and tetrakis (triphenylphosphine) palladium (0.2 parts) were mixed and stirred at 80 ° C. for 5 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (100 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with acetone, dried, and then sublimated and purified to obtain No. 1 of the above specific example. A compound represented by 201 (0.4 parts, yield 26%) was obtained.

Synthesis Example 30 (2,7-bis (4- (benzo [d] oxazole-2-yl) phenyl) [1] benzothioenoe [3,2-b] [1] synthesis of benzothiophene)
(Step 53) Synthesis of 2- (Benzo [d] Oxazole-2-yl) Phenyl) -4,4,5,5-Tetramethyl-1,3,2-dioxaborolane Toluene (500 parts), 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 a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, 20 parts of silica gel was added, and the mixture was stirred for 5 minutes. Then, the solid content was filtered off and the solvent was removed under reduced pressure to remove (2- (benzo [d] oxazole-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-. Dioxaborolane (11.4 parts, 99% yield) was obtained.

(Step 54) 2,7-Bis (4- (benzo [d] oxazole-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene In DMF (430 parts), Water (11 parts), 2,7-diiodo [1] benzothiophene [3,2-b] [1] benzothiophene (4.9 parts) synthesized by the method described in Japanese Patent No. 4945757, obtained in step 53. (2- (Benzo [d] oxazole-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 under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (430 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with acetone, dried, and then sublimated and purified to obtain No. 1 of the above specific example. The compound represented by 112 (3.6 parts, yield 57%) was obtained.

Synthesis Example 31 (2,7-bis (4- (5-phenylbenzo [b] thiophen-2-yl) phenyl) [1] benzothioeno [3,2-b] [1] synthesis of benzothiophene)
(Step 55) Synthesis of 5-phenylbenzo [b] thiophene To 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 the mixture was stirred at 70 ° C. for 6 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (500 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with water and acetone and dried to obtain 5-phenylbenzo [b] thiophene (13.3 parts, yield 67%).

(Step 56) Synthesis of 2- (5-phenylbenzo [b] thiophen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane in tetrahydrofuran (300 parts), step 55 5-Phenylbenzo [b] thiophene (12.6 parts) obtained in 1) 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 under a nitrogen atmosphere. Pinacol isopropoxyboronic acid (16 parts) was added to the obtained mixed solution, and the mixture was stirred at room temperature for 12 hours. Water (100 parts) was added to the obtained reaction solution, and the solid content generated by distilling off the solvent under reduced pressure was collected by filtration. By washing the obtained solid content with water and drying it, 2- (5-phenylbenzo [b] thiophen-2-yl) -4,4,5,5-tetramethyl-1,3,2- Dioxaborolane (11.4 parts, 57% yield) was obtained.

(Step 57) Synthesis of 2- (4-bromophenyl) -5-phenylbenzo [b] thiophene To DMF (300 parts), water (8.0 parts), 2- (5-phenyl) obtained in step 56. 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 phosphate (36 parts) and tetrakis (triphenylphosphine) palladium (1.0 part) were mixed and stirred at 70 ° C. for 3 hours under a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, water (300 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with water and methanol in this order to obtain 2- (4-bromophenyl) -5-phenylbenzo [b] thiophene (9.2 parts, yield 85%).

(Step 58) 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.) obtained in step 57. 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 a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, 20 parts of silica gel was added, and the mixture was stirred for 5 minutes. Then, the solid content was filtered off and the solvent was removed under reduced pressure to remove 2- (4- (5-phenylbenzo [b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1. , 3,2-Dioxaborolane (5.2 parts, yield 55%) was obtained.

(Step 59) 2,7-Bis (4- (5-phenylbenzo [b] thiophen-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene DMF (200 parts) ), Water (5.0 parts), 2,7-diiodo [1] benzothiophene [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 58 Part), tripotassium phosphate (15 parts) and tetrakis (triphenylphosphine) palladium (0.4 parts) were mixed and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (200 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with acetone, dried, and then sublimated and purified to obtain No. 1 of the above specific example. A compound represented by 90 (1.5 parts, yield 50%) was obtained.

Synthesis Example 32 (2,7-bis (4- (3-dibenzo [b, d] furan) phenyl) [1] benzothioenoe [3,2-b] [1] synthesis of benzothiophene)
(Step 60) Synthesis of 2- (3-dibenzo [b, d] furan) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane In toluene (100 parts), 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) ) Dichloromethane dichloromethane adduct (0.5 part) was mixed, and the mixture was stirred at reflux temperature for 5 hours under a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, and the solid content was filtered off to obtain a filtrate containing a product. Then, the residue was purified by short silica gel column chromatography (developing solution; toluene), and the solvent was removed under reduced pressure to obtain 2- (3-dibenzo [b, d] furan) -4,4,5,5-tetramethyl. -1,3,2-dioxaborolane (3.8 parts, yield 64%) was obtained.

(Step 61) Synthesis of 3- (4-bromophenyl) dibenzo [b, d] furan To DMF (60 parts), 2- (3-dibenzo [b, d] furan) -4, obtained in step 60, 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 part) was mixed, and the mixture was stirred at 60 ° C. for 2 hours under a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, water (200 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with water and methanol in this order to obtain 3- (4-bromophenyl) dibenzo [b, d] furan (2.7 parts, yield 64%).

(Step 62) Synthesis of 2- (4- (3-dibenzo [b, d] furan) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane In 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 a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, and the solid content was filtered off to obtain a filtrate containing a product. Then, by purification by short silica gel column chromatography (developing solution; toluene), 2- (4- (3-dibenzo [b, d] furan) phenyl) -4,4,5,5-tetramethyl- 1,3,2-dioxaborolane (2.8 parts, 90% yield) was obtained.

(Step 63) 2,7-Bis (4- (3-dibenzo [b, d] furan) phenyl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene In DMF (80 parts), Water (8.0 parts), 2,7-diiodo [1] benzothiophene [3,2-b] [1] benzothiophene (1.5 parts) synthesized by the method described in Japanese Patent No. 4945757, in step 62. The obtained 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 solution to room temperature, water (100 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with acetone and DMF, dried, and then sublimated and purified to obtain No. 1 of the above specific example. The compound represented by 171 (0.9 parts, yield 41%) was obtained.

Synthesis Example 33 (2,7-bis (4- (3-dibenzo [b, d] thiophene) phenyl) [1] benzothioeno [3,2-b] [1] benzothiophene synthesis)
(Step 64) Synthesis of 2- (3-dibenzo [b, d] thiophene) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane In toluene (100 parts), 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) ) Dichloromethane addition (0.4 part) was mixed, and the mixture was stirred at reflux temperature for 4 hours under a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, and the solid content was filtered off to obtain a filtrate containing a product. Then, the residue was purified by short silica gel column chromatography (developing solution; toluene), and the solvent was removed under reduced pressure to obtain 2- (3-dibenzo [b, d] thiophene) -4,4,5,5-tetramethyl. -1,3,2-dioxaborolane (2.3 parts, yield 39%) was obtained.

(Step 65) Synthesis of 3- (4-bromophenyl) dibenzo [b, d] thiophene DMF (40 parts) was combined with 2- (3-dibenzo [b, d] thiophene) -4, obtained in step 64. 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 part) was mixed, and the mixture was stirred at 60 ° C. for 3 hours under a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, water (60 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with water and methanol in this order to obtain 3- (4-bromophenyl) dibenzo [b, d] thiophene (2.5 parts, yield 99%).

(Step 66) Synthesis of 2- (4- (3-dibenzo [b, d] thiophene) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane In 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 part) was mixed, and the mixture was stirred under a nitrogen atmosphere at a reflux temperature for 8 hours. The obtained reaction solution was cooled to room temperature, and the solid content was filtered off to obtain a filtrate containing a product. Then, by purification by short silica gel column chromatography (developing solution; toluene), 2- (4- (3-dibenzo [b, d] thiophene) phenyl) -4,4,5,5-tetramethyl- 1,3,2-dioxaborolane (2.0 parts, yield 71%) was obtained.

(Step 67) 2,7-Bis (4- (3-dibenzo [b, d] thiophene) phenyl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene In DMF (60 parts), Water (8.0 parts), 2,7-diiodo [1] benzothiophene [3,2-b] [1] benzothiophene (1.0 part) synthesized by the method described in Japanese Patent No. 4945757, in step 66. The obtained 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 under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (100 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with acetone and DMF, dried, and then sublimated and purified . A compound represented by 170 (0.4 part, yield 26%) was obtained.

Synthesis Example 34 (2,7-bis (4- (phenanthrene-2-yl) phenyl) [1] benzothioenoe [3,2-b] [1] synthesis of benzothiophene)
(Step 68) Synthesis of 2- (phenanthrene-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (130 parts) is commonly available with 2-bromophenanthrene (. 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 (1,1'-bis (diphenylphosphino) ferrocene) 0.28 part) was mixed, and the mixture was stirred at a reflux temperature for 6 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, 20 parts of silica gel was added, and the mixture was stirred for 5 minutes. Then, the solid content was filtered off and the solvent was removed under reduced pressure to remove 2- (phenanthrene-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.7 parts, Yield 96%) was obtained.

(Step 69) Synthesis of 2- (4-bromophenyl) phenanthrene DMF (90 parts) and water (2.4 parts) 2- (phenanthrene-2-yl) -4,4,5 obtained in step 68 , 5-Tetramethyl-1,3,2-dioxaborolane (2.7 parts), 2-bromo-5-iodotoluene (2.5 parts), tripotassium phosphate (10.7 parts) and tetrakis (triphenyl) Phenyl) palladium (0.28 part) was mixed and stirred at 70 ° C. for 2 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (90 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with methanol and dried to obtain 2- (4-bromophenyl) phenanthrene (2.9 parts, yield 100%).

(Step 70) Synthesis of 2- (4- (phenanthrene-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (120 parts) was obtained in step 69. 2- (4-Bromophenyl) phenanthrene (2.8 parts), bis (pinacolato) diboron (2.7 parts), potassium acetate (1.7 parts) and [1,1'-bis (diphenylphosphino) ) Phenanthrene] Palladium (II) dichloride dichloromethane adduct (0.25 parts) was mixed and stirred at reflux temperature for 5 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, 20 parts of silica gel was added, and the mixture was stirred for 5 minutes. Then, the solid content was filtered off and the solvent was removed under reduced pressure to remove 2- (4- (phenanthrene-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4,4,5,5-tetramethyl-1,3,2-dioxaborolane). 2.8 parts, yield 88%) was obtained.

(Step 71) 2,7-Bis (4- (phenanthrene-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene DMF (140 parts) was added to water (3. 6 parts), 2,7-diiodo [1] benzothiodeno [3,2-b] [1] benzothiophene (2.7 parts) synthesized by the method described in Japanese Patent No. 4945757, 2 obtained in step 70. -(4- (Phenanthrene-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 part) was mixed and stirred at 80 ° C. for 7 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (140 parts) was added, and the solid content was collected by filtration. The obtained solid content was washed with DMF and acetone, dried, and then sublimated and purified. The compound represented by 208 (0.8 parts, yield 38%) was obtained.

Example 1 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] benzothioeno [3,2-b] [1] benzothiophene (No. 2 obtained in Synthesis Example 1) on ITO transparent conductive glass (manufactured by Geomatec Co., Ltd., ITO film thickness 150 nm). (Compound represented by) was formed into a 50 nm film by resistance heating vacuum vapor deposition as a block layer. The visible light absorption edge of this block layer was 412 nm. Next, quinacridone was vacuum-formed on the block layer as a photoelectric conversion layer at 100 nm. Finally, a 100 nm vacuum film was formed on aluminum as an electrode on the photoelectric conversion layer to produce the photoelectric conversion element for an image pickup device of the present invention. The ITO and aluminum as electrodes, the contrast ratio at the time of applying a voltage of 5V was 1.4 × 10 ^5.

Example 2 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis ([1] , 1': 4', 1''-terphenyl] -4-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (represented by No. 8 obtained in Synthesis Example 2). where except that the compound) was used in performing the evaluation in accordance with example 1, the visible light absorption edge of the blocking layer is 453 nm, in contrast ratio is 1.4 × 10 ⁵ at the time of applying a voltage of 5V there were.

Example 3 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (naphthalene-) 2-Il) [1] Benzothiophene [3,2-b] [1] Evaluation according to Example 1 except that benzothiophene (compound represented by No. 9 obtained in Synthesis Example 3) was used. was carried out, visible light absorption edge of the blocking layer is 430 nm, the contrast ratio at the time of applying a voltage of 5V was 2.8 × 10 ^5.

Example 4 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (4') -Methyl- [1,1'-biphenyl] -4-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 21 obtained in Synthesis Example 4) where except for using were evaluated in accordance with example 1, the visible light absorption edge of the blocking layer is 441 nm, the contrast ratio at the time of applying a voltage of 5V was 1.2 × 10 ^5.

Example 5 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (2-) Fluoro- [1,1'-biphenyl] -4-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 23 obtained in Synthesis Example 5) is used. where except that the that was evaluated according to example 1, the visible light absorption edge of the blocking layer is 414 nm, the contrast ratio at the time of applying a voltage of 5V was 1.1 × 10 ^5.

Example 6 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis ([1] , 1': 3,1''-terphenyl] -4-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (compound represented by No. 26 obtained in Synthesis Example 6). ) where except for using that was evaluated according to example 1, the visible light absorption edge of the blocking layer is 445 nm, met contrast ratio is 1.1 × 10 ⁵ at the time of applying a voltage of 5V rice field.

Example 7 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis ([1] , 1': 3', 1''-terphenyl] -5'-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (represented by No. 27 obtained in Synthesis Example 7). When the evaluation was performed according to Example 1 except that the compound was used, the visible light absorption end of the block layer was 413 nm, and the light-dark ratio when a voltage of 5 V was applied was 7.0 × 10 ^4. Met.

Example 8 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (benzo [] b] Fran-2-yl) [1] Benzothiophene [3,2-b] [1] Example 1 except that benzothiophene (compound represented by No. 29 obtained in Synthesis Example 8) was used. were evaluated in accordance with the visible light absorption edge of the blocking layer is 446 nm, the contrast ratio at the time of applying a voltage of 5V is of 2.5 × 10 ^5.

Example 9 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (benzo [] b] Thiophene-2-yl) [1] Benzothiophene [3,2-b] [1] Example 1 except that benzothiophene (compound represented by No. 33 obtained in Synthesis Example 9) was used. were evaluated in accordance with the visible light absorption edge of the blocking layer is 449 nm, the contrast ratio at the time of applying a voltage of 5V was 2.2 × 10 ^5.

Example 10 (Preparation of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (4-) (Benzo [b] furan-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 83 obtained in Synthesis Example 10) was used. where was evaluated according to example 1 except, the visible light absorption edge of the blocking layer is 460 nm, the contrast ratio at the time of applying a voltage of 5V was 3.2 × 10 ^5.

Example 11 (Preparation of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (4-) (Benzo [b] thiophen-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 87 obtained in Synthesis Example 11) was used. where was evaluated according to example 1 except, the visible light absorption edge of the blocking layer is 461 nm, the contrast ratio at the time of applying a voltage of 5V was 6.7 × 10 ^5.

Example 12 (Preparation of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (6-bis) Phenylnaphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] In Example 1 except that benzothiophene (compound represented by No. 10 obtained in Synthesis Example 17) was used. according to was evaluated, visible light absorption edge of the blocking layer is 453 nm, the contrast ratio at the time of applying a voltage of 5V was 9.8 × 10 ^5.

Example 13 (Preparation of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (5') -Phenyl- [1,1': 3', 1''-terphenyl] -4-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (No. 1 obtained in Synthesis Example 18). When the evaluation was performed according to Example 1 except that the compound represented by 28) was used, the visible light absorption end of the block layer was 429 nm, and the light-dark ratio when a voltage of 5 V was applied was 5. It was 1 × 10 ^5.

Example 14 (Preparation of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (4-) (Benzo [d] thiazole-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 111 obtained in Synthesis Example 19) was used. where was evaluated according to example 1 except, the visible light absorption edge of the blocking layer is 463 nm, the contrast ratio at the time of applying a voltage of 5V is of 2.5 × 10 ^5.

Example 15 (Preparation of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (9, 9-dimethyl-9H-fluorene-2-yl) [1] Benzothiophene [3,2-b] [1] Except for the use of benzothiophene (compound represented by No. 172 obtained in Synthesis Example 20). where was evaluated in accordance with example 1, the visible light absorption edge of the blocking layer is 436 nm, the contrast ratio at the time of applying a voltage of 5V was 1.6 × 10 ^5.

Example 16 (Preparation of photoelectric conversion element and evaluation thereof)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (4-) (9,9-dimethyl-9H-fluorene-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 174 obtained in Synthesis Example 21) where except for using that was evaluated according to example 1, the visible light absorption edge of the blocking layer is 444 nm, the contrast ratio at the time of applying a voltage of 5V was 9.5 × 10 ⁵ ..

Example 17 (Preparation of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (4') -(Pyridine-2-yl)-[1,1'-biphenyl] -4-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (No. 181 obtained in Synthesis Example 22) When the evaluation was performed according to Example 1 except that the compound (represented) was used, the visible light absorption edge of the block layer was 455 nm, and the light-dark ratio when a voltage of 5 V was applied was 2.5 ×. It was 10 ^5.

Example 18 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (4-) (Benzo [b] thiophen-2-yl) -2-methylphenyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 189 obtained in Synthesis Example 23) where except for using that was evaluated according to example 1, the visible light absorption edge of the blocking layer is 442 nm, contrast ratio at the time of applying a voltage of 5V was 8.4 × 10 ⁵ ..

Example 19 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (2, 2'-Binaphthalene-6-yl) [1] Benzothiophene [3,2-b] [1] Examples except that benzothiophene (compound represented by No. 184 obtained in Synthesis Example 24) was used. were evaluated in accordance with 1, visible light absorption edge of the blocking layer is 458 nm, the contrast ratio at the time of applying a voltage of 5V was 1.6 × 10 ^6.

Example 20 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (2-) Dibenzothienyl) [1] Benzothiophene [3,2-b] [1] According to Example 1 except that the synthesis of benzothiophene (compound represented by No. 164 obtained in Synthesis Example 25) was used. was evaluated, visible light absorption edge of the blocking layer is 433 nm, the contrast ratio at the time of applying a voltage of 5V was 4.8 × 10 ^5.

Example 21 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (6-bis) (Benzo [b] thiophen-2-yl) Naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 185 obtained in Synthesis Example 26) except using the were evaluated in accordance with example 1, the visible light absorption edge of the blocking layer is 465 nm, met 3.8 × 10 ⁵ is the contrast ratio at the time of applying a voltage of 5V rice field.

Example 22 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (4-) (5-Benzo [b] thienyl) phenyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 105 obtained in Synthesis Example 27) was used except that it was used. were evaluated in accordance with example 1, the visible light absorption edge of the blocking layer is 444 nm, the contrast ratio at the time of applying a voltage of 5V was 4.4 × 10 ^5.

Example 23 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (4') -(2-naphthyl)-(1,1'-biphenyl) -4-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (represented by No. 192 obtained in Synthesis Example 28). As a result of evaluation according to Example 1, the visible light absorption end of the block layer was 460 nm, and the light-dark ratio when a voltage of 5 V was applied was 3.8 × 10. It was ^5.

Example 24 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (4-) (Naft [1,2-b] thiophen-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 201 obtained in Synthesis Example 29) except using the were evaluated in accordance with example 1, the visible light absorption edge of the blocking layer is 465 nm, the contrast ratio at the time of applying a voltage of 5V is 8.4 × 10 ⁵ met rice field.

Example 25 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (4-) (Benzo [d] oxazole-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 112 obtained in Synthesis Example 30) was used. Otherwise, were evaluated in accordance with example 1, the visible light absorption edge of the blocking layer is 464 nm, the contrast ratio at the time of applying a voltage of 5V was 3.5 × 10 ^5.

Example 26 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (4-) (5-Phenylbenzo [b] thiophen-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 90 obtained in Synthesis Example 31) except for using, were evaluated in accordance with example 1, the visible light absorption edge of the blocking layer is 461 nm, the contrast ratio at the time of applying a voltage of 5V was 1.0 × 10 ⁶ ..

Example 27 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (4-) (3-Dibenzo [b, d] furan) phenyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 171 obtained in Synthesis Example 32) was used. Otherwise, were evaluated in accordance with example 1, the visible light absorption edge of the blocking layer is 458 nm, the contrast ratio at the time of applying a voltage of 5V was 1.2 × 10 ^5.

Example 28 (Preparation of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (4-) (3-Dibenzo [b, d] thiophene) Phenyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene ( compound represented by No. 170 obtained in Synthesis Example 33) was used. Otherwise, were evaluated in accordance with example 1, the visible light absorption edge of the blocking layer is 456 nm, the contrast ratio at the time of applying a voltage of 5V was 9.2 × 10 ^5.

Example 29 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (4-) (Phenanthrene-2-yl) Phenyl) [1] Benzothiophene [3,2-b] [1] Performed except that benzothiophene (compound represented by No. 208 obtained in Synthesis Example 34) was used. were evaluated in accordance with example 1, the visible light absorption edge of the blocking layer is 453 nm, the contrast ratio at the time of applying a voltage of 5V was 5.7 × 10 ^5.

Comparative Example 1 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis ([1] , 1'-biphenyl] -3-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 6 obtained in Synthesis Example 12) was used except that it was used. were evaluated in accordance with example 1, the visible light absorption edge of the blocking layer is 407 nm, the contrast ratio at the time of applying a voltage of 5V was 1.8 × 10 ^3.

Comparative Example 2 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (4-) Methylphenyl) [1] Benzothiophene [3,2-b] [1] Evaluation was carried out according to Example 1 except that benzothiophene (compound represented by No. 12 obtained in Synthesis Example 13) was used. when went, visible light absorption edge of the blocking layer is 405 nm, the contrast ratio at the time of applying a voltage of 5V was 3.9 × 10 ^3.

Comparative Example 3 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (naphthalene-) 1-yl) [1] Benzothiophene [3,2-b] [1] Evaluation according to Example 1 except that benzothiophene (compound represented by No. 12 obtained in Synthesis Example 14) was used. was carried out, visible light absorption edge of the blocking layer is 408 nm, the contrast ratio at the time of applying a voltage of 5V was 2.4 × 10 ^2.

Comparative Example 4 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (phenanthrene-) 9-yl) [1] Benzothiophene [3,2-b] [1] Evaluation according to Example 1 except that benzothiophene (compound represented by No. 15 obtained in Synthesis Example 15) was used. was carried out, visible light absorption edge of the blocking layer is 404 nm, the contrast ratio at the time of applying a voltage of 5V was 6.9 × 10 ^2.

Comparative Example 5 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (4-) (Trifluoromethyl) phenyl) [1] Benzothiophene [3,2-b] [1] In Example 1 except that benzothiophene (compound represented by No. 17 obtained in Synthesis Example 16) was used. according to was evaluated, visible light absorption edge of the blocking layer is 409 nm, the contrast ratio at the time of applying a voltage of 5V was 7.8 × 10 ^1.

Comparative Example 6 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Diphenyl [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 2 obtained in Synthesis Example 1), 2,7-bis (9H-) Carbazole-9-yl)-[1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 81) was evaluated according to Example 1. , visible light absorption edge of the blocking layer is 402 nm, the contrast ratio at the time of applying a voltage of 5V was 4.7 × 10 ^0.

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

From the above evaluation results, the photoelectric conversion element for an image pickup device of the present invention, in which the photoelectric conversion unit is represented by the formula (1) and has an organic thin film layer containing a compound having a visible light absorption end of 410 nm or more, satisfies the above conditions. It is clear that it has better characteristics than the photoelectric conversion element for an image pickup element of the comparative example which does not have an organic thin film layer to satisfy.

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 is not only an organic image pickup element having high resolution and high responsiveness, but also an organic EL element and an organic solar cell. Expected to be applied to organic electronics devices such as devices and organic transistor devices, devices such as optical sensors, infrared sensors, ultraviolet sensors, X-ray sensors and photon counters, and cameras, video cameras, infrared cameras, etc. using them. Will be done.

Claims (13)

A photoelectric conversion element having (A) a first electrode film, (B) a second electrode film, and (C) a photoelectric conversion unit arranged between the first electrode film and the second electrode film. The following formula (1) indicates that the (C) photoelectric conversion unit has a visible light absorption end of 410 nm or more.

(In the formula (1), n is the number of substituents R, and n = 1. R represents a phenyl group having a substituent or a naphthyl group having a substituent, and the substituents are a benzofuranyl group and a benzothienyl group. It is selected from the group consisting of a group, a benzothiadyl group, a naphthothiol group, a benzoxazole group and a dibenzothienyl group, except when the substituent of the phenyl group having a substituent is a benzofuranyl group, a benzothienyl group or a benzothiazyl group. A photoelectric conversion element for an image pickup element having one or more organic thin film layers containing the compound represented by). The photoelectric conversion element for an image sensor according to claim 1, wherein the visible light absorption end of the compound represented by the formula (1) is 440 nm or more. (C) The organic thin film layer containing the compound represented by the formula (1) possessed by the photoelectric conversion unit is an organic layer other than the (c-1) photoelectric conversion layer and / or (c-2) photoelectric conversion layer. Item 2. The photoelectric conversion element for an image pickup element according to Item 1 or 2. (C-1) The image pickup device according to claim 3, wherein the photoelectric conversion layer is an organic thin film layer containing an organic semiconductor material other than the compound represented by the formula (1) and the compound represented by the formula (1). Photoelectric conversion element. The photoelectric conversion element for an image pickup element according to claim 4, wherein the organic semiconductor material other than the compound represented by the formula (1) is an n-type organic semiconductor material. (C-2) The photoelectric conversion element for an image sensor according to any one of claims 3 to 5, wherein the organic layer other than the photoelectric conversion layer is an electronic block layer. (C-2) The photoelectric conversion element for an image sensor according to any one of claims 3 to 5, wherein the organic layer other than the photoelectric conversion layer is a hole block layer. (C-2) The photoelectric conversion element for an image sensor according to any one of claims 3 to 5, wherein the organic layer other than the photoelectric conversion layer is an electron transport layer. (C-2) The photoelectric conversion element for an image sensor according to any one of claims 3 to 5, wherein the organic layer other than the photoelectric conversion layer is a hole transport layer. The image pickup device according to any one of claims 1 to 9, further comprising (D) a thin film transistor having a hole storage unit and (E) a signal reading unit for reading a signal corresponding to the charge stored in the thin film transistor. Photoelectric conversion element. The compound represented by the formula (1) is the following formula (2).

The photoelectric conversion element for an image sensor according to claim 1, wherein R is a compound represented by (in the formula (2), R has the same meaning as R in the formula (1) according to claim 1.). An image pickup device in which the photoelectric conversion elements for an image pickup device according to any one of claims 1 to 11 are arranged in a plurality of arrays. An optical sensor including the photoelectric conversion element for an image sensor according to any one of claims 1 and 11 or the image pickup element according to claim 12.

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