JP6906388B2 - Photoelectric conversion element for image sensor - Google Patents

Description

The present invention relates to a photoelectric conversion element for an image sensor that can be used for an image sensor, 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 benzothiophenobenzothiophene as a matrix have also been developed as organic electronics materials (Patent Documents 1 to 3), and when an alkyl derivative of benzothiophenebenzothiophene is used, a semiconductor thin film is used in the printing process. However, since the number of condensed rings relative to the alkyl chain length is relatively small, a phase transition is likely to occur at a low temperature, and the heat resistance of the organic electronic device is inferior.

Further, among organic electronics in recent years, 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 imaging device (Patent Document 5), and a diketopyrrolopyrrole derivative are used. There is an example (Patent Document 6). In general, it is considered that the performance of an image sensor is improved by aiming at reducing dark current for the purpose of increasing contrast and power saving. Therefore, in order to reduce the leakage current from the photoelectric conversion unit in the dark, a method of inserting a hole block layer or an electron block layer between the photoelectric conversion unit and the electrode unit is used. Further, in order to effectively reduce the leakage current, it is necessary that the unevenness of the surface of each layer is small (Patent Document 7).

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 an electrode or a conductive film and another film in the constituent film of the device, respectively. It is a film that has the function of controlling the reverse movement of holes or electrons, and adjusts the leakage of unnecessary holes or electrons. Depending on the application of the device, heat resistance, transmission wavelength, film formation method, etc. 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 Japanese Unexamined Patent Publication No. 2012-23400

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

The present invention has been made in view of such a situation, and is a photoelectric conversion element excellent in hole or electron leakage prevention property, hole or electron transport property, 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 found that the above problems can be solved by using an organic thin film layer having high smoothness in the photoelectric conversion part of the photoelectric conversion element for an imaging element. The present invention has been completed.
That is, the present invention is as follows.
(1) (A) First electrode film, (B) Second electrode film, and (C) Photoelectric conversion having a photoelectric conversion unit arranged between the first electrode film and the second electrode film. A photoelectric conversion element for an imaging device, wherein the photoelectric conversion unit has one or more organic thin film layers having a surface roughness Ra and / or Sa of 7.0 nm or less.
(2) The photoelectric conversion element for an image sensor according to (1) above, wherein the photoelectric conversion unit has one or more organic thin film layers having a surface roughness Ra and / or Sa of 1.3 nm or more and 7.0 nm or less.
(3) The organic thin film layer having a surface roughness Ra and / or Sa of 7.0 nm or less of the (C) photoelectric conversion unit is other than the (c-1) photoelectric conversion layer and / or (c-2) photoelectric conversion layer. The photoelectric conversion element for an imaging element according to the previous item (1) or (2), which is an organic thin film layer of
(4) The photoelectric conversion element for an image sensor according to (3) above, wherein the photoelectric conversion layer contains a p-type organic semiconductor material and an n-type organic semiconductor material.
(5) (c-2) The photoelectric conversion element for an imaging element according to the previous item (3), wherein the organic thin film layer other than the photoelectric conversion layer is an electron block layer.
(6) (c-2) The photoelectric conversion element for an imaging element according to the previous item (3), wherein the organic thin film layer other than the photoelectric conversion layer is a hole block layer.
(7) (c-2) The photoelectric conversion element for an imaging element according to the previous item (3), wherein the organic thin film layer other than the photoelectric conversion layer is an electron transport layer.
(8) (c-2) The photoelectric conversion element for an imaging element according to the previous item (3), wherein the organic thin film layer other than the photoelectric conversion layer is a hole transport layer.
(9) Further, any one of (1) to (8) 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,
(10) (C) The organic thin film layer having a surface roughness Ra and / or Sa of 7.0 nm or less possessed by the photoelectric conversion unit is represented by the following formula (1).

(In the formula (1), n is the number of substituents R and independently represents an integer of 0 to 4. R each independently represents a substituent, and when n is 2 or more, adjacent Rs are adjacent to each other. The photoelectric conversion element for an image pickup device according to any one of (1) to (9) above, which contains a compound represented by (may be linked to form a ring structure).
(11) (C) The organic thin film layer having a surface roughness Ra and / or Sa of 7.0 nm or less possessed by the photoelectric conversion unit is represented by the following formula (2).

(In the formula (2), R represents the same meaning as R in the formula (1) according to claim 10.) The photoelectric conversion element for an image sensor according to the preceding item (10), which contains a compound represented by the compound.
(12) An image pickup device in which a plurality of photoelectric conversion elements for an image pickup device according to any one of the above items (1) and (11) are arranged in an array, and (13) any one of the above items (1) and (11). The photoelectric conversion element for an image sensor according to item 1 or an optical sensor including the image sensor 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 sensor of the present invention. FIG. 2 is a plot of the surface roughness and the light-dark ratio of the photoelectric conversion element for an image sensor in each Example and Comparative Example.

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

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

In the present invention, the method for measuring the smoothness of the organic thin film layer may be either a contact type or a non-contact type, but since the surface of the organic thin film layer is not damaged, a laser microscope, an atomic force microscope, an electron microscope and an electron microscope can be used. A non-contact measurement method such as a cross-sectional TEM is preferable.

The average surface roughness Ra and Sa are calculated from the measurement results of the smoothness of the organic thin film obtained by the above measurement method. Specifically, the average value of the linear arithmetic average roughness Ra of a plurality of portions randomly selected from the surface of the organic thin film layer, or the surface arithmetic average roughness Sa of the portion randomly selected from the surface of the organic thin film layer. Is the surface roughness of the present invention. When the average value of the linear arithmetic average roughness Ra is used, it is preferable that the number of measurement portions is large, and usually, the average value obtained by measuring a length of 2 μm or more at 5 or more locations is used. When the surface arithmetic average roughness Sa is used, the larger the area of the measurement portion is, the more preferable it is, usually 2 μm square or more, and an average value of a plurality of randomly selected locations may be used.

The surface roughness Ra and / or Sa of the organic thin film layer is usually 7.0 nm or less, preferably 6.0 nm or less, more preferably 5.0 nm or less, further preferably 4.5 nm or less, and 4.1 nm or less. It is particularly preferable, and most preferably 1.3 nm or more and 4.1 nm or less.

The photoelectric conversion element for an imaging 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 amount of incident light, a signal corresponding to the electric charge is read out by the semiconductor, and the amount of incident light corresponding to the absorption wavelength of the photoelectric conversion film unit. It is an element indicating. 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 sensor (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.

The (C) 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 anti-crystallization layer, an interlayer contact improvement layer, and the like. It often consists of one or more selected organic thin film layers other than the (c-2) photoelectric conversion layer. The organic thin film layer having a surface roughness Ra and / or Sa of 7.0 nm or less contained in the photoelectric conversion element for an imaging element of the present invention is an organic other than the (c-1) photoelectric conversion layer and the (c-2) photoelectric conversion layer. It may be any thin film layer, but it is preferably an organic thin film layer other than (c-2) photoelectric conversion layer.

The (A) first electrode film and (B) second electrode film included in the photoelectric conversion element for an imaging 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 transporting property, or an organic thin film layer other than the (c-2) photoelectric conversion layer (hereinafter, the organic thin film layer other than the photoelectric conversion layer is also simply referred to as "(c-2)) organic thin film layer". ) Is a hole transporting layer having a hole transporting property, it plays a role of extracting holes from the (c-1) photoelectric conversion layer and the (c-2) organic thin film layer and collecting them. Further, when the (c-1) photoelectric conversion layer included in the (C) photoelectric conversion unit has an electron transporting property, or when the (c-2) organic thin film layer is an electron transporting layer, the (c-2) organic thin film layer has an electron transporting property. It plays a role of extracting electrons from the (c-1) photoelectric conversion layer and the (c-2) organic thin film layer and discharging them. Therefore, the materials that can be used as the (A) first electrode film and (B) 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 in consideration of adhesion to the organic thin film layer, electron affinity, ionization potential, stability and the like. Examples of the material that can be used as the first electrode film (A) and the second electrode film (B) include tin oxide (NESA), indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). 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. 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 power consumption. 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 a commercially available product of a substrate having an ITO film having an ITO film is also available, it is desirable to use a substrate having such high conductivity. The thickness of the ITO film (electrode film) can be arbitrarily selected in consideration of conductivity, but is usually about 5 to 500 nm, preferably about 10 to 300 nm. Examples of 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 first electrode film (A) and the second electrode film (B), 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 ( Antimon-doped tin oxide), ZnO, AZO (Al-doped zinc oxide), GZO (gallium-doped zinc oxide), TiO ₂ , FTO (fluorine-doped tin oxide) and the like. (C-1) The transmittance of light incident through the transparent electrode film at the absorption peak wavelength of the photoelectric conversion layer is preferably 60% or more, more preferably 80% or more, and 95% or more. It is particularly 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 respective 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 in which the plasma is reduced.

Examples of the device that does not generate plasma when the electrode film is formed 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 having a film quality inferior to that of Al, such as Al, 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, an increase in leakage current can be suppressed.

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 very preferable.

The (C) photoelectric conversion unit included in the photoelectric conversion element for an imaging element of the present invention includes at least an organic thin film layer other than the (c-1) photoelectric conversion layer and the (c-2) photoelectric conversion layer.
An organic semiconductor film is generally used for the (c-1) photoelectric conversion layer constituting the (C) 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 (bulk heterostructure) thereof is laminated, and is an interlayer. A buffer layer may be inserted in.

(C-1) The organic semiconductor film of the photoelectric conversion layer has a triarylamine compound, a benzidine compound, a pyrazoline compound, a styrylamine compound, a hydrazone compound, a triphenylmethane compound, a carbazole compound, 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, pyrrole compounds, pyrazole compounds, polyarylene compounds, carbazole derivatives, naphthalene derivatives, anthracene derivatives, chrysene derivatives, phenanthrene derivatives, pentacene derivatives, Use phenylbutadiene derivatives, styryl derivatives, quinoline derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluorantene derivatives, quinacridone derivatives, coumarin derivatives, porphyrin derivatives, fullerene derivatives, metal complexes (Ir complex, Pt complex, Eu complex, etc.), etc. be able to.

In the photoelectric conversion element for an imaging element of the present invention, the organic thin film 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, an electron. It is also used as a transport layer, a hole transport layer, an electron block layer, a hole block layer, a crystallization prevention layer, an interlayer contact improvement layer, 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 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) plays a role of blocking the movement of electrons to the photoelectric conversion layer.
The electron block layer hinders 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 blocking layer hinders 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, oxaziazole derivatives, oxazole derivatives, quinoline derivatives, and the formula (1) described later. Examples thereof include the represented compounds, and one or more of these can be used.

From the viewpoint of preventing leakage current, the hole block layer should have a thick film thickness, but from the viewpoint of obtaining a sufficient amount of current when reading a signal at the time of light incident, the film thickness should be as thin as possible. .. 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.
Further, since the hole block layer and the electron block layer do not interfere with the light absorption of the (c-1) photoelectric conversion layer, the transmittance of the absorption wavelength of the photoelectric conversion layer is preferably high, and the hole block layer and the electron block layer are preferably 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, when 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 even more 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 electrical 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.

A typical element structure of the photoelectric conversion element for an image sensor of the present invention will be described in detail in FIG. 1, but 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, 6 represents 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 films. 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 layers (electron block layer, hole block layer, etc.) other than the photoelectric conversion layer constituting the photoelectric conversion element do not extremely block the absorption wavelength of the photoelectric conversion layer, the direction in which the light is incident is the upper part (Fig. Either the insulating portion 1 side in 1) or the lower portion (insulating substrate 7 side in FIG. 1) may be used.

The method for forming an organic thin film 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, which is a vacuum process. Electron beam deposition, sputtering, molecular lamination method, solution process casting, spin coating, dip coating, blade coating, wire bar coating, spray coating and other coating methods, inkjet printing, screen printing, offset printing, letterpress printing, etc. A soft lithography method such as a printing 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 7 to 5000 nm, preferably in the range of 5 to 1000 nm, and more preferably in the range of 3 to 500 nm. Is in the range of.

The material constituting the smooth organic thin film is not particularly limited, but preferably contains a compound represented by the following formula (1).

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

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

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

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 4 carbon atoms. It is a linear or branched alkyl group, or a cyclic alkyl group having 5 to 6 carbon atoms.
Specific examples of the alkyl group as 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 or 2 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-nonadesyloxy group, n-eicosyloxy group, docosyloxy group, n-pentacosyloxy group, n-octacosyl 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 squalyloxy group, a dotriacontyloxy group and a hexatriacontyloxy group, and an alkoxy group having 1 to 24 carbon atoms. It is more preferably an alkoxy group having 1 to 20 carbon atoms, further preferably an alkoxy group having 1 to 12 carbon atoms, and particularly preferably an alkoxy group having 1 to 6 carbon atoms. 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 phenyl group and naphthyl group and heterocyclic condensed aromatic groups, which are aromatic hydrocarbon groups. It is preferable to have.
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). ) Is the same as the aromatic hydrocarbon group described in the section of the substituent represented by R.
As the acyl group as the substituent represented by R in the formula (1), _{the aromatic hydrocarbon group described in the section of the substituent represented by R 1} and R ₂ in the formula (1) and R in the formula (1) are used. Examples thereof include a substituent in which the alkyl group described in the section of the substituent represented 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 R in the formula (1) is bonded to the carbonyl group.
The substituent represented by R in the formula (1) is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, a halogen atom or an alkoxyl group, and is a substituted or unsubstituted aromatic group. More preferably.

The substitution position of R in the above formula (1) is not particularly limited, but it is the 2nd and 7th positions in the BTBT ([1] benzothiophene [3,2-b] [1] benzothiophene) structure in the formula (1). Is preferable. That is, as the compound represented by the formula (1), the compound represented by the following general formula (2) is 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), the compound in which R in the formula (2) is preferable to the most preferable form of R in the above formula (1) is preferable.
The organic thin film other than the photoelectric conversion layer (c-2) containing the compound represented by the formula (1) is any of the above-mentioned electron transport layer, hole transport layer, electron block layer and hole block layer. However, it is preferable to use it for the hole block layer.

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

The compound represented by the formula (1) can be synthesized by a known method disclosed in Patent Document 1, Patent Document 6, and Non-Patent Document 1.
For example, 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. A benzothienobenzothiophene skeleton (D) is formed using a nitrostilbene derivative (A) as a raw material, and the benzothienobenzothiophene skeleton (D) is reduced to obtain an amination product (E) (a compound in which R is an amino group in the formula (1)). Be done. If this compound (E) is halogenated, a halide (F) (a compound in which R is halogen in the formula (1) and a compound in which R is iodine as an example is described in the following scheme) is obtained, and this compound ( By further coupling F) 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.

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 LS 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.) at an irradiation light wavelength of 550 nm and an irradiation light half width of 20 nm. The surface roughness of the thin-film film was measured using a laser microscope VK-X250 / 260 (Keyence) with a 150x lens and a laser light wavelength of 408 nm in a measurement range of 10 μm square. 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. In addition, "part" in an Example means mass part, and "%" means mass%.

Synthesis Example 1 (2,7-bis (naphthalene-2-yl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
2,7-Diiode [1] benzothiophene [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. Naphthalene-2-ylboronic acid (3.3 parts), tripotassium phosphate (27 parts) and tetrakis (triphenylphosphine) palladium (0.47 parts) were mixed and stirred at 90 ° C. for 6 hours under a nitrogen atmosphere. .. After cooling the obtained reaction solution to room temperature, water (250 parts) was added, and the solid content was filtered and separated. 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 9 (3.1 parts, yield 82%) was obtained.

Synthesis Example 2 (2,7-bis (4'-methyl- [1,1'-biphenyl] -4-yl) [1] benzothiophene [3,2-b] [1] benzothiophene synthesis)
Instead of naphthalene-2-ylboronic acid (3.3 parts), commonly available (4'-methyl- [1,1'-biphenyl] -4-yl) boronic acid (5.0 parts) was used. Other than that, No. 1 of the above specific example was obtained according to Synthesis Example 1. A compound represented by 21 (2.7 parts, yield 61%) was obtained.

Synthesis Example 3 (2,7-bis (2-fluoro- [1,1'-biphenyl] -4-yl) [1] benzothiophene [3,2-b] [1] benzothiophene synthesis)
Using commonly available (2-fluoro- [1,1'-biphenyl] -4-yl) boronic acid (5.0 parts) instead of naphthalene-2-ylboronic acid (3.3 parts). Except for the above-mentioned specific example No. The compound represented by 23 (2.2 parts, yield 50%) was obtained.

Synthesis Example 4 (2,7-bis ([1,1': 3,1''-terphenyl] -4-yl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
(Step 1) Synthesis of 2- ([1,1': 3,1''-terphenyl] -4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene ( 240 parts), commonly available 4-bromo-1,1': 3,1''-terphenyl (6.0 parts), bis (pinacolato) diboron (5.6 parts), potassium acetate (3. 5 parts) and [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.5 parts) were mixed and stirred at reflux temperature for 4 hours under a nitrogen atmosphere. The obtained reaction solution was cooled 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, yield 99%) was obtained.

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

Synthesis Example 5 (2,7-bis ([1,1': 3', 1''-terphenyl] -5'-yl) [1] Synthesis of benzothiophene [3,2-b] [1] benzothiophene )
Using commonly available (2-fluoro- [1,1'-biphenyl] -4-yl) boronic acid (5.3 parts) instead of naphthalene-2-ylboronic acid (3.3 parts). Except for the above, No. 1 of the above specific example according to Synthesis Example 1. A compound represented by 27 (2.0 parts, yield 37%) was obtained.

Synthesis Example 6 (2,7-bis (benzo [b] furan-2-yl) [1] benzothioeno [3,2-b] [1] synthesis of benzothiophene)
As described above in Synthesis Example 1, except that the generally available benzo [b] furan-2-ylboronic acid (1.9 parts) was used instead of naphthalene-2-ylboronic acid (3.3 parts). Specific example No. A compound represented by 29 (2.6 parts, yield 73%) was obtained.

Synthesis Example 7 (2,7-bis (benzo [b] thiophen-2-yl) [1] benzothioeno [3,2-b] [1] synthesis of benzothiophene)
As described above in Synthesis Example 1, except that the generally available benzo [b] thiophen-2-ylboronic acid (2.1 parts) was used instead of naphthalene-2-ylboronic acid (3.3 parts). Specific example No. A compound represented by 33 (2.7 parts, yield 70%) was obtained.

Synthesis Example 8 (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 filtered and separated. 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. The obtained reaction solution was cooled 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) Synthesis of 2,7-bis (4- (benzo [b] furan-2-yl) phenyl) [1] benzothioeno [3,2-b] [1] 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 (triphenylphosphene) 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 filtered and separated. 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 83 (2.0 parts, yield 50%) was obtained.

Synthesis Example 9 (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 In 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 filtered and separated. 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. The obtained reaction solution was cooled 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] Synthesis of benzothiophene [3,2-b] [1] Synthesis of benzothiophene In DMF (170 parts), Water (5.0 parts), 2,7-diiode [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 (triphenylphosphene) 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 filtered and separated. 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 87 (1.6 parts, yield 46%) was obtained.

Synthesis Example 10 (2,7-bis ([1,1'-biphenyl] -3-yl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
In accordance with 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 naphthalene-2-ylboronic acid (3.3 parts). A compound represented by 6 (2.1 parts, yield 51%) was obtained.

Synthesis Example 11 (2,7-bis ([1,1'-biphenyl] -2-yl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
In accordance with Synthesis Example 1, No. 1 of the above specific example was used, except that generally available 2-biphenylboronic acid (3.8 parts) was used instead of naphthalene-2-ylboronic acid (3.3 parts). A compound represented by No. 7 (2.4 parts, yield 57%) was obtained.

Synthesis Example 12 (2,7-bis (naphthalene-1-yl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
No. of the above specific example according to Synthesis Example 1 except that generally available naphthalene-1-ylboronic acid (3.3 parts) was used instead of naphthalene-2-ylboronic acid (3.3 parts). .. A compound represented by No. 13 (3.0 parts, yield 79%) was obtained.

Synthesis Example 13 (2,7-bis (phenanthrene-9-yl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
No. of the above specific example according to Synthesis Example 1 except that generally available phenanthrene-9-ylboronic acid (4.3 parts) was used instead of naphthalene-2-ylboronic acid (3.3 parts). .. A compound represented by No. 15 (3.0 parts, yield 65%) was obtained.

Synthesis Example 14 (2,7-bis (3,5-bis (trifluoromethyl) phenyl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
In Synthesis Example 1, except that the commonly available 3,5-bis (trifluoromethyl) phenylboronic acid (5.0 parts) was used instead of naphthalene-2-ylboronic acid (3.3 parts). According to the above specific example, No. The compound represented by 18 (3.6 parts, yield 70%) was obtained.

Synthesis Example 15 (2,7-bis (9H-carbazole-9-yl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
In Synthesis Example 1, except that the commonly available 3,5-bis (trifluoromethyl) phenylboronic acid (5.0 parts) was used instead of naphthalene-2-ylboronic acid (3.3 parts). According to the above specific example, No. A compound represented by 81 (3.6 parts, yield 70%) was obtained.

Synthesis Example 16 (2,7-bis (5'-phenyl- [1,1': 3', 1''-terphenyl] -4-yl) [1] benzothiophene [3,2-b] [1] Synthesis of benzothiophene)
(Step 9) (5'-Phenyl- [1,1': 3', 1''-terphenyl] -4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Synthesis of Toluene (510 parts), commonly available 4-bromo-5'-phenyl-1,1': 3', 1''-terphenyl (15.0 parts), bis (pinacolato) dichloromethane (12) .0 parts), potassium acetate (7.5 parts) and [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (1.1 parts) were mixed and prepared 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 10) 2,7-Bis (5'-Phenyl- [1,1': 3', 1''-Terphenyl] -4-yl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene 2,7-diiode [1] benzothieno [3,2-b] [1] benzo synthesized in DMF (300 parts) with water (9.0 parts) by the method described in Japanese Patent No. 4945757. Thiophene (4.5 parts), obtained in step 9 (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 in 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 filtered and separated. 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 28 (2.0 parts, yield 26%) was obtained.

Synthesis Example 17 (2,7-bis (4'-(pyridin-2-yl)-[1,1'-biphenyl] -4-yl) [1] benzothiophene [3,2-b] [1] benzothiophene Synthesis)
(Step 11) Synthesis of (4- (pyridin-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (960 parts) generally available 2- (4-Bromophenyl) Pyridine (17.1 parts), Bis (Pinacolato) diboron (22.4 parts), Potassium Acetate (14.1 parts) and [1,1'-Bis (Diphenylphosphino) Ferrocene] palladium (II) A dichloride dichloromethane adduct (2.3 parts) 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, 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 12) Synthesis of 2- (4'-bromo- [1,1'-biphenyl] -4-yl) pyridine In DMF (520 parts), water (18.0 parts) was obtained in step 11 (step 11). 4- (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 filtered and separated. 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 13) 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), bis (pinacolato) diboron (7. 9 parts), potassium acetate (5.0 parts) and [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.8 parts) 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 14) 2,7-Bis (4'-(pyridin-2-yl)-[1,1'-biphenyl] -4-yl) [1] benzothiophene [3,2-b] [1] benzothiophene Synthesis of (5'-phenyl- [1,1': 3', 1''-terphenyl] -4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (9) .9 parts) instead of (4'-(pyridin-2-yl)-[1,1'-biphenyl] -4-yl) -4,4,5,5-tetramethyl obtained in step 13. Except for the use of -1,3,2-dioxaborolane (8.2 parts), the synthesis was carried out according to step 10 to obtain No. 1 of the above specific example. The compound represented by 168 (7.2 parts, 42%) was obtained.

Synthesis Example 18 (2,7-bis (4- (benzo [d] thiazole-2-yl) phenyl) [1] benzothioenoe [3,2-b] [1] synthesis of benzothiophene)
(Step 15) 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 a reflux temperature for 4 hours under a nitrogen atmosphere. The obtained reaction solution was cooled 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- (4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) phenyl) benzo [d. ] Thiazole (4.9 parts, yield 80%) was obtained.

(Step 16) 2,7-Bis (4- (benzo [d] thiazole-2-yl) phenyl) [1] Synthesis of benzothiophene [3,2-b] [1] Synthesis of benzothiophene In DMF (170 parts), Water (5.0 parts), 2,7-diiode [1] benzothiophene [3,2-b] [1] benzothiophene (2.6 parts) synthesized by the method described in Japanese Patent No. 4945757, in step 15. The obtained 2- (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 filtered and separated. 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 111 (1.8 parts, yield 52%) was obtained.

Synthesis Example 19 (2,7-bis (4- (benzo [b] thiophen-2-yl) -2-methylphenyl) [1] benzothioeno [3,2-b] [1] synthesis of benzothiophene)
(Step 17) Synthesis of 2- (4-Bromo-3-methylphenyl) benzo [b] thiophene To DMF (300 parts), generally available benzo [b] thiophene-2-ylboronic acid (5.0 parts) , 2-Bromo-5-iodotoluene (8.3 parts), tripotassium phosphate (34 parts) and tetrakis (triphenylphosphene) 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 filtered and separated. 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 18) 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 17. .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. The obtained reaction solution was cooled 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, yield 87%) was obtained.

(Step 19) 2,7-Bis (4- (benzo [b] thiophen-2-yl) -2-methylphenyl) [1] benzothieno [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 18. .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 filtered and separated. 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 170 (1.2 parts, yield 35%) was obtained.

Synthesis Example 20 (2,7-bis (2-dibenzofuranyl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
(Step 20) Synthesis of 2- (dibenzofuran-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (150 parts) and 2-bromodibenzofuran (5.0 parts) ), Bis (pinacolato) diboron (6.2 parts), potassium acetate (4.0 parts) and [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.5 parts) ) 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- (dibenzofuran-2-yl) -4,4,5,5-tetramethyl-1,3. , 2-Dioxaborolane (3.8 parts, yield 64%) was obtained.

(Step 21) 2,7-Bis (2-dibenzofuranyl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene DMF (250 parts), water (8.0 parts), patent 2,7-Diiode [1] benzothiophene [3,2-b] [1] benzothiophene (4.7 parts) synthesized by the method described in No. 4945757, 2- (dibenzofuran-2) obtained in step 20. -Il) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.0 parts), tripotassium phosphate (8.1 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 filtered and separated. 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 165 (1.5 parts, yield 28%) was obtained.

Synthesis Example 21 (2,7-bis (9,9-dimethyl-9H-fluorene-2-yl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
(Step 22) Synthesis of 2- (9,9-dimethyl-9H-fluorene-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane 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) dichlorolide 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, the residue was purified by short silica gel column chromatography (developing solution; toluene), and the solvent was removed under reduced pressure to 2- (9,9-dimethyl-9H-fluorene-2-yl) -4,4,5,5. 5-Tetramethyl-1,3,2-dioxaborolane (11.1 parts, yield 95%) was obtained.

(Step 23) 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] benzothiophene [3,2-b] [1] benzothiophene (7.1 parts) synthesized by the method described in Japanese Patent No. 4945757, obtained in step 22. 2- (9,9-dimethyl-9H-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 filtered and separated. 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 166 (6.2 parts, yield 69%) was obtained.

Synthesis Example 22 (2,7-bis (4- (9,9-dimethyl-9H-fluorene-2-yl) phenyl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
(Step 24) Synthesis of 2- (9,9-dimethyl-9H-fluorene-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane 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) dichlorolide 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, the residue was purified by short silica gel column chromatography (developing solution; toluene), and the solvent was removed under reduced pressure to 2- (9,9-dimethyl-9H-fluorene-2-yl) -4,4,5,5. 5-Tetramethyl-1,3,2-dioxaborolane (11.1 parts, yield 95%) was obtained.

(Step 25) 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 24. , 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 26) 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 25. 5.6 parts) and [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.7 parts) were mixed and stirred at reflux temperature for 4 hours under a nitrogen atmosphere. The obtained reaction 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, yield 73%) was obtained.

(Step 27) 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 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 26. .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 filtered and separated. The obtained solid content was washed with DMF and acetone, dried, and then sublimated and purified. A compound represented by 167 (1.8 parts, yield 31%) was obtained.

Synthesis Example 23 (2,7-bis (6-phenylnaphthalene-2-yl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
(Step 28) 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 layers were 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 29) Synthesis of 2-Hydroxy-6-Phenylnaphthalene 2-Methoxy-6-phenylnaphthalene (14.0 parts) and pyridine hydrochloride (86 parts) obtained in Step 28 were 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 solution was separated. The solvent was distilled off under reduced pressure to obtain 2-hydroxy-6-phenylnaphthalene (13.0 parts, yield 99%).

(Step 30) 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 29 (step 30). 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 was purified by silica gel column chromatography (developing solution; toluene), and the solvent was removed under reduced pressure to obtain 6-phenylnaphthalene-2-yl trifluoromethanesulfonate (20.5 parts, yield 99%). Obtained.

(Step 31) 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 30. 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 32) 2,7-Bis (6-phenylnaphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene DMF (250 parts) and water (8.0 parts). ), 2,7-Diiode [1] benzothiophene [3,2-b] [1] benzothiophene (4.2 parts) synthesized by the method described in Japanese Patent No. 4945757, 6- obtained in step 31 (. 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 parts) 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 filtered and separated. 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 24 (2,7-bis (2,2'-binaphthalene-6-yl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
(Step 33) Synthesis of 6-methoxy-2,2'-binaphthalene In 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 produced solid was collected by filtration. The obtained solid was washed with methanol to obtain 6-methoxy-2,2'-binaphthalene (13.5 parts, yield 98%).

(Step 34) Synthesis of 6-hydroxy-2,2'-binaphthalene 6-methoxy-2,2'-binaphthalene (13.0 parts) and pyridine hydrochloride (53 parts) obtained in step 33 were mixed and mixed. The mixture was stirred at 190 ° C. for 5 hours in a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, ethyl acetate and water were added, and the solution was separated. By distilling off the solvent under reduced pressure, 6-hydroxy-2,2′-binaphthalene (11.5 parts, yield 94%) was obtained.

(Step 35) Synthesis of 2,2'-binaphthyl-6-yl trifluoromethanesulfonate 6-hydroxy-2,2 obtained in step 34 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 36) Synthesis of (2,2'-binaphthyl-6-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (350 parts) was obtained in step 35. 2,2'-binaphthyl-6-yl trifluoromethanesulfonate (14.5 parts), bis (pinacolato) diboron (11.0 parts), potassium acetate (7.1 parts) and [1,1'-bis (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 37) 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-diiode [1] benzothiophene [3,2-b] [1] benzothiophene (3.3 parts) synthesized by the method described in Japanese Patent No. 4945757, obtained in step 36 (. 2,2'-binaphthyl-6-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6.6 parts), tripotassium phosphate (5.7 parts) and tetrakis (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 filtered and separated. The obtained solid content was washed with DMF and acetone, dried, and then sublimated and purified. A compound represented by 169 (1.0 part, yield 20%) was obtained.

Synthesis Example 25 (2,7-bis (2-dibenzothioenyl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
(Step 38) 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 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- (dibenzothienyl-2-yl) -4,4,5,5-tetramethyl-1, 3,2-Dioxaborolane (11.5 parts, yield 98%) was obtained.

(Step 39) 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-Diiode [1] benzothiophene [3,2-b] [1] benzothiophene (4.5 parts) synthesized by the method described in No. 4945757, 2- (dibenzothienyl-2) obtained in step 38. -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 filtered and separated. 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 (1,1': 4', 1'': 4'', 1'''-quarterphenyl-4-yl)-[1] benzothioenoe [3,2-b] [1] Synthesis of benzothiophene)
(Step 40) Synthesis of 4-Bromo-1,1': 4', 1'': 4'', 1'''-Quarterphenyl In 100 parts of DMF, generally available 1,1': 4', 1 ''-Terphenylboronic acid 2.7 parts, 4-bromo-1-iodobenzene 2.8 parts, tripotassium phosphate 12 parts, tetrakis (triphenylphosphine) palladium 0.3 parts are mixed, and under a nitrogen atmosphere. , 90 ° C. for 6 hours. After cooling the obtained reaction solution to room temperature, 100 parts of water was added, and the solid content was filtered and separated. The obtained solid content was washed with methanol and dried to obtain 4-bromo-1,1': 4', 1'': 4'', 1'''-quarterphenyl (3.4 parts, yield). 88%) was obtained.

(Step 41) 2-([1,1': 4', 1'': 4'', 1'''-quarterphenyl] -4-yl) -4,4,5,5-tetramethyl-1 , 3,2-Dioxaborolane Synthesis In 100 parts of toluene, 3.0 parts of 4-bromo-1,1': 4', 1'': 4'', 1'''-quarterphenyl synthesized in step 40 , 2.4 parts of bis (pinacolato) diboron, 1.5 parts of potassium acetate and 0.2 parts of [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane additive are mixed to create a nitrogen atmosphere. Below, the mixture was stirred at reflux temperature for 7 hours. The obtained reaction solution was cooled 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': 4', 1'': 4'', 1'''-quarterphenyl] -4-yl)-. 4,4,5,5-Tetramethyl-1,3,2-dioxaborolane (1.3 parts, yield 38%) was obtained.

(Step 42) 2,7-Bis (1,1': 4', 1'': 4'', 1'''-Quarterphenyl-4-yl)-[1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene 2- ([1,1': 4', 1'': 4'', 1'''-quarterphenyl] -4-yl) obtained in step 41 in 30 parts of DMF. -4,4,5,5-tetramethyl-1,3,2-dioxaborolane 1.0 part, 2,7-diiodo [1] benzothiophene [3,2-b] [1] benzothiophene 0.46 part, 3.1 parts of tripotassium phosphate, 1.0 part of water and 0.055 part of tetrakis (triphenylphosphine) palladium (0) were mixed, and the mixture was stirred at 90 ° C. for 6 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, 30 parts of water was added, and the solid content was filtered and separated. 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 172 (0.1 part, yield 13%) was obtained.

Synthesis Example 27 (2,7-bis (6- (benzo [b] thiophen-2-yl) naphthalene-2-yl) [1] benzothioeno [3,2-b] [1] synthesis of benzothiophene)
(Step 43) Synthesis of 2- (6-methoxynaphthalene-2-yl) benzo [b] thiophene 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 44) Synthesis of 2- (6-hydroxy-2-yl) benzo [b] thiophene The 2- (6-methoxynaphthalene-2-yl) benzo [b] thiophene obtained in step 43 (19.5 parts) ) And methylene chloride (100 parts) were mixed and stirred at 0 ° C. in 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 completion of the addition. Water was added to the reaction solution to separate the solutions. 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-hydroxynaphthalene-2-yl) benzo [b] thiophene (17.9 parts). , Yield 97%) was obtained.

(Step 45) Synthesis of 6- (benzo [b] thiophen-2-yl) naphthalene-2-yl trifluoromethanesulfonate Obtained in step 44 in a mixed solution of dichloromethane (250 parts) and triethylamine (14.0 parts). 2- (6-Hydroxynaphthalene-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 give 6- (benzo [b] thiophen-2-yl) naphthalene-2-yl trifluoromethanesulfonate (27.5 parts, yield 98%).

(Step 46) Synthesis of 2- (6- (benzo [b] thiophen-2-yl) naphthalene-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (400) Part), 6- (benzo [b] thiophen-2-yl) naphthalene-2-yl trifluoromethanesulfonate (27.0 parts), bis (pinacolato) diboron (20.1 parts) obtained in step 45. , Potassium acetate (13.0 parts) and [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (1.6 parts) were mixed, and 4 at reflux temperature 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 47) 2,7-Bis (6- (benzo [b] thiophen-2-yl) naphthalene-2-yl) [1] benzothieno [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- (benzo [b] thiophen-2-yl) naphthalene-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7) obtained in step 46. .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 filtered and separated. The obtained solid content was washed with DMF and acetone, dried, and then sublimated and purified. A compound represented by 179 (0.6 parts, yield 10%) was obtained.

Synthesis Example 28 (2,7-bis (4- (5-benzo [b] thienyl) phenyl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
(Step 48) 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 49) Synthesis of 5- (4-bromophenyl) benzo [b] thiophene To DMF (230 parts), 2- (benzo [b] thiophene-5-yl) -4,4 obtained in step 48 5,5-Tetramethyl-1,3,2-dioxaborolane (11.5 parts), 1-bromo-4-iodobenzene (12.5 parts), tripotassium phosphate (18.7 parts) and tetrakis (tri) Phenylphosphine) palladium (1.6 parts) was mixed and stirred at 60 ° C. for 2 hours under a nitrogen atmosphere. The obtained reaction solution was cooled to room temperature, water (200 parts) was added, and the solid content was filtered and separated. 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 50) Synthesis of 2- (4- (5-benzo [b] thienyl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (200 parts), step 49. 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 51) 2,7-Bis (4- (5-benzo [b] thienyl) phenyl) [1] Synthesis of benzothiophene [3,2-b] [1] Synthesis of benzothiophene DMF (200 parts) was added to water (200 parts). 10.0 parts), 2,7-diiodo [1] benzothiophene [3,2-b] [1] benzothiophene (3.7 parts) synthesized by the method described in Patent No. 4945757, obtained in step 50. 2- (4- (5-benzo [b] thienyl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6.3 parts), tripotassium phosphate (6. 4 parts) and tetrakis (triphenylphosphine) palladium (0.5 parts) were mixed and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (150 parts) was added, and the solid content was filtered and separated. The obtained solid content was washed with acetone and DMF, dried, and then sublimated and purified. A compound represented by 187 (2.0 parts, yield 51%) was obtained.

Synthesis Example 29 (2,7-bis (4'-(2-naphthyl)-(1,1'-biphenyl) -4-yl) [1] Synthesis of benzothiophene [3,2-b] [1] benzothiophene )
(Step 52) 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 53) 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 54) 2,7-Bis (4'-(2-naphthyl)-(1,1'-biphenyl) -4-yl) [1] Synthesis of benzothiophene [3,2-b] [1] 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 53 , 2-Dioxaborolane (6.6 parts), tripotassium phosphate (5.5 parts) and tetrakis (triphenylphosphine) palladium (0.4 parts) were mixed and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere. .. After cooling the obtained reaction solution to room temperature, water (200 parts) was added, and the solid content was filtered and separated. The obtained solid content was washed with DMF and acetone, dried, and then sublimated and purified. A compound represented by 190 (0.5 part, yield 10%) was obtained.

Synthesis Example 30 (2,7-bis (4- (naphtho [1,2-b] thiophen-2-yl) phenyl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
(Step 55) 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 filtered and separated. 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 56) 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 55. .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. The obtained reaction solution was cooled 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 57) 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- (naphtho [1,2-b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2) obtained in step 56. .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 filtered and separated. 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 199 (0.4 part, yield 26%) was obtained.

Synthesis Example 31 (2,7-bis (4- (benzo [d] oxazole-2-yl) phenyl) [1] Synthesis of benzothiophene [3,2-b] [1] benzothiophene)
(Step 58) 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. The obtained reaction solution was cooled 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, yield 99%) was obtained.

(Step 59) 2,7-Bis (4- (benzo [d] oxazole-2-yl) phenyl) [1] Synthesis of 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 58. 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 the mixture was 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 filtered and separated. 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 112 (3.6 parts, yield 57%) was obtained.

Synthesis Example 32 (2,7-bis (4- (5-phenylbenzo [b] thiophen-2-yl) phenyl) [1] Synthesis of benzothiophene [3,2-b] [1] benzothiophene)
(Step 60) 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 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 filtered and separated. The obtained solid content was washed with water and acetone and dried to obtain 5-phenylbenzo [b] thiophene (13.3 parts, yield 67%).

(Step 61) Synthesis of 2- (5-phenylbenzo [b] thiophen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran (300 parts), step 60. 5-Phenylbenzo [b] thiophene (12.6 parts) obtained in the above was mixed. A normal butyllithium hexane solution (2.6 M, 28 parts) was added to the mixture cooled to 0 ° C., and the mixture was stirred under a nitrogen atmosphere for 1 hour. 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 62) Synthesis of 2- (4-bromophenyl) -5-phenylbenzo [b] thiophene DMF (300 parts) was mixed with water (8.0 parts), and 2- (5-phenyl) obtained in step 61 was added. 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 phosphate (36 parts) and tetrakis (triphenylphosphine) palladium (1.0 parts) 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 filtered and separated. 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 63) Synthesis of 2- (4- (5-phenylbenzo [b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (300 parts) ), 2- (4-Bromophenyl) -5-phenylbenzo [b] thiophene (8.5 parts), bis (pinacolato) diboron (6.9 parts), potassium acetate (4.) obtained in step 62. 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. The obtained reaction solution was cooled 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 64) 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 63 Part), tripotassium phosphate (15 parts) and tetrakis (triphenylphosphene) 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 filtered and separated. 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 33 (2,7-bis (4- (3-dibenzo [b, d] furan) phenyl) [1] Synthesis of benzothiophene [3,2-b] [1] benzothiophene)
(Step 65) Synthesis of 2- (3-dibenzo [b, d] furan) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (100 parts) was added to 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) ) Dichloroside 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 66) Synthesis of 3- (4-bromophenyl) dibenzo [b, d] furan To DMF (60 parts), 2- (3-dibenzo [b, d] furan) -4, obtained in step 65, 4,5,5-Tetramethyl-1,3,2-dioxaborolane (3.8 parts), 1-bromo-4-iodobenzene (3.7 parts), tripotassium phosphate (5.5 parts) and tetrakis (Triphenylphosphine) palladium (0.4 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 filtered and separated. 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 67) Synthesis of 2- (4- (3-dibenzo [b, d] furan) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane To 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 purifying with 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, yield 90%) was obtained.

(Step 68) Synthesis of 2,7-bis (4- (3-dibenzo [b, d] furan) phenyl) [1] benzothiophene [3,2-b] [1] 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 Patent No. 4945757, in step 67. 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 filtered and separated. The obtained solid content was washed with acetone and DMF, dried, and then sublimated and purified. A compound represented by 206 (0.9 parts, yield 41%) was obtained.

Synthesis Example 34 (2,7-bis (4- (3-dibenzo [b, d] thiophene) phenyl) [1] Synthesis of benzothiophene [3,2-b] [1] benzothiophene)
(Step 69) Synthesis of 2- (3-dibenzo [b, d] thiophene) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane To 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) ) Dichloride dichloromethane adduct (0.4 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 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 70) Synthesis of 3- (4-bromophenyl) dibenzo [b, d] thiophene To DMF (40 parts), 2- (3-dibenzo [b, d] thiophene) -4, obtained in step 69. 4,5,5-Tetramethyl-1,3,2-dioxaborolane (2.3 parts), 1-bromo-4-iodobenzene (2.1 parts), tripotassium phosphate (3.0 parts) and tetrakis (Triphenylphosphine) palladium (0.3 parts) was mixed, and 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 filtered and separated. 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 71) Synthesis of 2- (4- (3-dibenzo [b, d] thiophene) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (50 parts), 3- (4-Bromophenyl) dibenzo [b, d] thiophene (2.5 parts), bis (pinacolato) diboron (2.2 parts), potassium acetate (1.4 parts) and [ 1,1'-Bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.2 parts) was mixed and stirred at reflux temperature for 8 hours under 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 with 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 72) Synthesis of 2,7-bis (4- (3-dibenzo [b, d] thiophene) phenyl) [1] benzothieno [3,2-b] [1] benzothiophene In DMF (60 parts), Water (8.0 parts), 2,7-diiode [1] benzothieno [3,2-b] [1] benzothiophene (1.0 parts) synthesized by the method described in Japanese Patent No. 4945757, in step 71. 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 filtered and separated. The obtained solid content was washed with acetone and DMF, dried, and then sublimated and purified. A compound represented by 207 (0.4 part, yield 26%) was obtained.

Synthesis Example 35 (2,7-bis (4- (phenanthrene-2-yl) phenyl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
(Step 73) Synthesis of 2- (phenanthrene-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (130 parts) is commonly available with 2-bromophenanthrene (step 73). 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 part) 0.28 part) was mixed, and the mixture was stirred at reflux temperature for 6 hours under a nitrogen atmosphere. The obtained reaction solution was cooled 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 74) Synthesis of 2- (4-bromophenyl) phenanthrene DMF (90 parts) and water (2.4 parts) 2- (phenanthrene-2-yl) -4,4,5 obtained in step 73 , 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 the mixture was 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 filtered and separated. The obtained solid content was washed with methanol and dried to obtain 2- (4-bromophenyl) phenanthrene (2.9 parts, yield 100%).

(Step 75) Synthesis of 2- (4- (phenanthrene-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Toluene (120 parts) was obtained in step 74. 2- (4-Bromophenyl) phenanthrene (2.8 parts), bis (pinacolato) diboron (2.7 parts), potassium acetate (1.7 parts) and [1,1'-bis (diphenylphosphino) ) Phenanthrene] Phenanthrene (II) dichloride dichloromethane adduct (0.25 parts) was mixed and stirred at reflux temperature for 5 hours under a nitrogen atmosphere. The obtained reaction solution was cooled 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 76) 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-diiode [1] benzothiophene [3,2-b] [1] benzothiophene (2.7 parts) synthesized by the method described in Patent No. 4945757, 2 obtained in step 75. -(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 parts) 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 filtered and separated. The obtained solid content was washed with DMF and acetone, dried, and then sublimated and purified. A compound represented by 210 (0.8 parts, yield 38%) was obtained.

Synthesis Example 36 (2,7-bis (4- (naphtho [2,3-b] thiophen-2-yl) phenyl) [1] benzothiophene [3,2-b] [1] synthesis of benzothiophene)
(Step 77) Synthesis of 2- (4-bromophenyl) naphtho [2,3-b] thiophene 2- (Naft [1,2-b] thiophene-2-yl) -4,4,5,5-tetra 2- (Naft [2,3-b] thiophen-2-yl) -4,4,5,5-tetramethyl-1 synthesized by a known method instead of methyl-1,3,2-dioxaborolane , 3,2-Dioxaborolane was synthesized according to step 55 except that 2- (4-bromophenyl) naphtho [2,3-b] thiophene (3.5 parts, yield 55%). ) Was obtained.

(Step 78) Synthesis of 2- (4- (naphtho [2,3-b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2- ( In step 56, except that 2- (4-bromophenyl) naphtho [2,3-b] thiophene obtained in step 77 was used instead of 4-bromophenyl) naphtho [1,2-b] thiophene. By synthesizing according to the same procedure, 2- (4- (naphtho [2,3-b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane ( 3.7 parts, yield 58%) was obtained.

(Step 79) 2,7-Bis (4- (naphtho [2,3-b] thiophen-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Synthesis of benzothiophene 2- ( 4- (Naft [1,2-b] Thiophene-2-yl) Phenyl) -4,4,5,5-Tetramethyl-1,3,2-Dioxaborolane instead of 2- obtained in step 78 (4- (Naft [2,3-b] thiophen-2-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane according to step 57 except that dioxaborolane was used. By synthesizing, No. of the above specific example. A compound represented by 102 (0.6 parts, yield 39%) was obtained.

Example 1 (Preparation of photoelectric conversion element and its evaluation)
2,7-Bis (naphthalene-2-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (Synthesis Example 1) on ITO transparent conductive glass (manufactured by Geomatec Co., Ltd., ITO film thickness 150 nm) The compound (No. 9 represented by No. 9) obtained in (1) was formed into a 50 nm film by resistance heating vacuum deposition as a block layer. The average surface roughness Sa of this block layer was 1.7 nm. Next, quinacridone was vacuum-deposited on the block layer as a photoelectric conversion layer at 100 nm. Finally, aluminum was vacuum-deposited on the photoelectric conversion layer at 100 nm as an electrode to produce the photoelectric conversion element for an imaging device of the present invention. The ITO and aluminum as electrodes, the contrast ratio at the time of applying a voltage of 5V was 2.8 × 10 ^5.

Example 2 (Preparation of photoelectric conversion element and its evaluation)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (4'-methyl- [1,1'-biphenyl] -4-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (No. 21 obtained in Synthesis Example 2) As a result of evaluation according to Example 1 except that the compound represented by (compound) was used, the average surface roughness Sa of the block layer was 1.8 nm, and the light-dark ratio when a voltage of 5 V was applied. It was 1.2 × 10 ^5.

Example 3 (Preparation of photoelectric conversion element and its evaluation)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (2-fluoro- [1,1'-biphenyl] -4-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (No. 23 obtained in Synthesis Example 3) As a result of evaluation according to Example 1 except that the compound (represented) was used, the average surface roughness Sa of the block layer was 1.6 nm, and the light-dark ratio when a voltage of 5 V was applied was It was 1.1 × 10 ^5.

Example 4 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis ([1,1': 3,1 "-terphenyl] -4-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (No. obtained in Synthesis Example 4). When the evaluation was performed according to Example 1 except that the compound represented by 26) was used, the average surface roughness Sa of the block layer was 1.6 nm, and the brightness and darkness when a voltage of 5 V was applied. the ratio was 1.1 × 10 ^5.

Example 5 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis ([1,1': 3', 1 "-terphenyl] -5'-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (obtained in Synthesis Example 5) When the evaluation was performed according to Example 1 except that the compound represented by No. 27) was used, the average surface roughness Sa of the block layer was 1.6 nm, and when a voltage of 5 V was applied. the light-dark ratio was 7.0 × 10 ^4.

Example 6 (Preparation of photoelectric conversion element and evaluation thereof)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (benzo [b] furan-2-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (compound represented by No. 29 obtained in Synthesis Example 6) was used. was except that, were evaluated in accordance with example 1, the average surface roughness Sa of the blocking layer is 1.4 nm, the contrast ratio at the time of applying a voltage of 5V is 2.5 × 10 ⁵ there were.

Example 7 (Preparation of photoelectric conversion element and evaluation thereof)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (benzo [b] thiophen-2-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (compound represented by No. 33 obtained in Synthesis Example 7) was used. was except that, were evaluated in accordance with example 1, the average surface roughness Sa of the blocking layer is 1.7 nm, the contrast ratio at the time of applying a voltage of 5V is 2.2 × 10 ⁵ there were.

Example 8 (Preparation of photoelectric conversion element and evaluation thereof)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (4- (benzo [b] furan-2-yl) phenyl) [1] benzothiophene [3,2-b] [1] benzothiophene (represented by No. 83 obtained in Synthesis Example 8) As a result of evaluation according to Example 1, the average surface roughness Sa of the block layer was 1.7 nm, and the light-dark ratio when a voltage of 5 V was applied was 3. It was 2 × 10 ^5.

Example 9 (Preparation of photoelectric conversion element and evaluation thereof)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (4- (benzo [b] thiophen-2-yl) phenyl) [1] benzothiophene [3,2-b] [1] benzothiophene (represented by No. 87 obtained in Synthesis Example 9) As a result of evaluation according to Example 1, the average surface roughness Sa of the block layer was 4.1 nm, and the light-dark ratio when a voltage of 5 V was applied was 6. It was 7 × 10 ^5.

Example 10 (Preparation of photoelectric conversion element and evaluation thereof)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (5'-phenyl- [1,1': 3', 1''-terphenyl] -4-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (Synthetic example) When the evaluation was carried out according to Example 1 except that the compound represented by No. 28 obtained in No. 16 was used, the average surface roughness Sa of the block layer was 1.7 nm, which was 5 V. contrast ratio when applying the voltage was 5.1 × 10 ^5.

Example 11 (Preparation of photoelectric conversion element and evaluation thereof)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-bis (4'-(pyridine-2-yl)-[1,1'-biphenyl] -4-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (in Synthesis Example 17) When the evaluation was carried out according to Example 1 except that the obtained compound (represented by No. 168) was used, the average surface roughness Sa of the block layer was 2.4 nm, and a voltage of 5 V was applied. contrast ratio when the applied of 2.5 × 10 ^5.

Example 12 (Preparation of photoelectric conversion element and evaluation thereof)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (4- (benzo [d] thiazole-2-yl) phenyl) [1] benzothiophene [3,2-b] [1] benzothiophene (represented by No. 111 obtained in Synthesis Example 18). As a result of evaluation according to Example 1, the average surface roughness Sa of the block layer was 2.8 nm, and the light-dark ratio when a voltage of 5 V was applied was 2. It was 5 × 10 ^5.

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

Example 14 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (2-dibenzofuranyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 165 obtained in Synthesis Example 20) except that it was used. were evaluated in accordance with example 1, the average surface roughness Sa of the blocking layer is 1.8 nm, the contrast ratio at the time of applying a voltage of 5V is was 1.1 × 10 ^4.

Example 15 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalene-2-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (9,9-dimethyl-9H-fluorene-2-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (Represented by No. 166 obtained in Synthesis Example 21) When the evaluation was performed according to Example 1 except that the compound) was used, the average surface roughness Sa of the block layer was 2.1 nm, and the light-dark ratio when a voltage of 5 V was applied was 1.6. × was 10 ^5.

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

Example 17 (Preparation of photoelectric conversion element and evaluation thereof)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (6-phenylnaphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 10 obtained in Synthesis Example 23) was used. except that, were evaluated in accordance with example 1, the average surface roughness Sa of the blocking layer is 1.8 nm, the contrast ratio is 9.8 × 10 ⁵ meet at the time of applying a voltage of 5V rice field.

Example 18 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (2,2'-Binaphthalene-6-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 169 obtained in Synthesis Example 24) except for using, were evaluated in accordance with example 1, the average surface roughness Sa of the blocking layer is 1.9 nm, the contrast ratio is 1.6 × 10 upon application of a voltage of 5V ⁶ Met.

Example 19 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (2-dibenzothienyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 164 obtained in Synthesis Example 25) except that it was used. were evaluated in accordance with example 1, the average surface roughness Sa of the blocking layer is 2.1 nm, the contrast ratio at the time of applying a voltage of 5V was 4.8 × 10 ^5.

Example 20 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (1,1': 4', 1'': 4'', 1'''-Quarterphenyl-4-yl)-[1] Benzothiophene [3,2-b] [1] Benzothiophene When the evaluation was carried out according to Example 1 except that (the compound represented by No. 172 obtained in Synthesis Example 26) was used, the average surface roughness Sa of the block layer was 2.0 nm. , contrast ratio at the time of applying a voltage of 5V was 7.0 × 10 ^3.

Example 21 (Preparation of photoelectric conversion element and evaluation thereof)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1) is known instead of benzothiophene. No. synthesized by the method of No. When the evaluation was performed according to Example 1 except that the compound represented by 160 was used, the average surface roughness Sa of the block layer was 1.4 nm, and the light-dark ratio when a voltage of 5 V was applied. It was 2.4 × 10 ^3.

Example 22 (Preparation of photoelectric conversion element and its evaluation)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1) is known instead of benzothiophene. No. synthesized by the method of No. When the evaluation was performed according to Example 1 except that the compound represented by 173 was used, the average surface roughness Sa of the block layer was 1.5 nm, and the light-dark ratio when a voltage of 5 V was applied. It was 2.7 × 10 ^5.

Example 23 (Preparation of photoelectric conversion element and its evaluation)
No. 1 synthesized by a known method on ITO transparent conductive glass (manufactured by Geomatec Co., Ltd., ITO film thickness 150 nm). The compound represented by 160 was formed into a 200 nm film by resistance heating vacuum deposition. The average surface roughness Sa of this organic layer was 1.4 nm. Next, aluminum was vacuum-deposited at 100 nm as an electrode to produce a 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 3.3 × 10 ^5.

Example 24 (Preparation of photoelectric conversion element and evaluation thereof)
No. No. 1 synthesized by a known method instead of the compound represented by 160. When the evaluation was carried out according to Example 23 except that the compound represented by 176 was used, the average surface roughness Sa of the organic layer was 1.6 nm, and the light-dark ratio when a voltage of 5 V was applied. It was 2.3 × 10 ^5.

Example 25 (Preparation of photoelectric conversion element and evaluation thereof)
No. No. 1 synthesized by a known method instead of the compound represented by 160. When the evaluation was carried out according to Example 23 except that the compound represented by 175 was used, the average surface roughness Sa of the organic layer was 6.0 nm, and the light-dark ratio when a voltage of 5 V was applied. It was 5.7 × 10 ^4.

Example 26 (Preparation of Photoelectric Conversion Element and Evaluation thereof)
No. No. 1 synthesized by a known method instead of the compound represented by 160. When the evaluation was carried out according to Example 23 except that the compound represented by 177 was used, the average surface roughness Sa of the organic layer was 3.9 nm, and the light-dark ratio when a voltage of 5 V was applied. It was 5.1 × 10 ^3.

Example 27 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalene-2-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (6- (benzo [b] thiophen-2-yl) naphthalene-2-yl) [1] benzothieno [3,2-b] [1] benzothiophene (No. obtained in Synthesis Example 27). When the evaluation was performed according to Example 1 except that the compound represented by 179) was used, the average surface roughness Sa of the block layer was 1.6 nm, and the brightness and darkness when a voltage of 5 V was applied. the ratio was 3.8 × 10 ^5.

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

Example 29 (Preparation of photoelectric conversion element and evaluation thereof)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (4'-(2-naphthyl)-(1,1'-biphenyl) -4-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (obtained in Synthesis Example 29) When the evaluation was carried out according to Example 1 except that the compound represented by No. 190 was used, the average surface roughness Sa of the block layer was 1.8 nm, and a voltage of 5 V was applied. contrast ratio of time was 3.8 × 10 ^5.

Example 30 (Preparation of photoelectric conversion element and evaluation thereof)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (4- (naphtho [1,2-b] thiophen-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (No. obtained in Synthesis Example 30). When the evaluation was performed according to Example 1 except that the compound represented by 199) was used, the average surface roughness Sa of the block layer was 1.8 nm, and the brightness and darkness when a voltage of 5 V was applied. the ratio was 8.4 × 10 ^5.

Example 31 (Preparation of photoelectric conversion element and evaluation thereof)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (4- (benzo [d] oxazole-2-yl) phenyl) [1] benzothiophene [3,2-b] [1] benzothiophene (represented by No. 112 obtained in Synthesis Example 31). As a result of evaluation according to Example 1, the average surface roughness Sa of the block layer was 1.6 nm, and the light-dark ratio when a voltage of 5 V was applied was 3. It was 5 × 10 ^5.

Example 32 (Preparation of photoelectric conversion element and evaluation thereof)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (4- (5-phenylbenzo [b] thiophen-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (No. 90 obtained in Synthesis Example 32) As a result of evaluation according to Example 1 except that the compound represented by (compound) was used, the average surface roughness Sa of the block layer was 1.6 nm, and the light-dark ratio when a voltage of 5 V was applied. It was 1.0 × 10 ^6.

Example 33 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (4- (3-dibenzo [b, d] furan) phenyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (Represented by No. 206 obtained in Synthesis Example 33) As a result of evaluation according to Example 1, the average surface roughness Sa of the block layer was 1.7 nm, and the light-dark ratio when a voltage of 5 V was applied was 1. It was 2 × 10 ^5.

Example 34 (Preparation of photoelectric conversion element and evaluation thereof)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (4- (3-dibenzo [b, d] thiophene) phenyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (Represented by No. 207 obtained in Synthesis Example 34) As a result of evaluation according to Example 1, the average surface roughness Sa of the block layer was 1.7 nm, and the light-dark ratio when a voltage of 5 V was applied was 9. It was 2 × 10 ^5.

Example 35 (Preparation of photoelectric conversion element and evaluation thereof)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (4- (phenanthrene-2-yl) phenyl) [1] benzothiophene [3,2-b] [1] benzothiophene (compound represented by No. 210 obtained in Synthesis Example 35) except for using, were evaluated in accordance with example 1, the average surface roughness Sa of the blocking layer is 1.5 nm, the contrast ratio is 5.7 × 10 ⁵ at the time of applying a voltage of 5V Met.

Example 36 (Preparation of photoelectric conversion element and evaluation thereof)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (4- (naphtho [2,3-b] thiophen-2-yl) phenyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (No. 36 obtained in Synthesis Example 36). When the evaluation was performed according to Example 1 except that the compound represented by 102) was used, the average surface roughness Sa of the block layer was 1.6 nm, and the brightness and darkness when a voltage of 5 V was applied. the ratio was 4.5 × 10 ^5.

Comparative Example 1 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis ([1,1'-biphenyl] -3-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (Compound No. 6 obtained in Synthesis Example 10) ) Was evaluated according to Example 1. The average surface roughness Sa of the block layer was 52.5 nm, and the light-dark ratio when a voltage of 5 V was applied was 1.8 ×. It was 10 ^3.

Comparative Example 2 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis ([1,1'-biphenyl] -2-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (Compound No. 7 obtained in Synthesis Example 11) ) Was evaluated according to Example 1. The average surface roughness Sa of the block layer was 68.4 nm, and the light-dark ratio when a voltage of 5 V was applied was 1.5 ×. 10 was ^1.

Comparative Example 3 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (naphthalene-1-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 13 obtained in Synthesis Example 12) except that it was used. were evaluated in accordance with example 1, the average surface roughness Sa of the blocking layer is 89.9Nm, 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)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (phenanthrene-9-yl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (compound represented by No. 15 obtained in Synthesis Example 13) except that it was used. were evaluated in accordance with example 1, the average surface roughness Sa of the blocking layer is 73.3Nm, contrast ratio at the time of applying a voltage of 5V was 6.9 × 10 ^2.

Comparative Example 5 (Preparation of photoelectric conversion element and its evaluation)
Instead of 2,7-bis (naphthalen-2-yl) [1] benzothiophene [3,2-b] [1] benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (3,5-bis (trifluoromethyl) phenyl) [1] Benzothiophene [3,2-b] [1] Benzothiophene (Compound represented by No. 18 obtained in Synthesis Example 14) As a result of evaluation according to Example 1, the average surface roughness Sa of the block layer was 7.6 nm, and the light-dark ratio when a voltage of 5 V was applied was 2.0 × 10. It was ^2.

Comparative Example 6 (Manufacturing of photoelectric conversion element and its evaluation)
2,7-Bis (naphthalene-2-yl) [1] Benzothiophene [3,2-b] [1] Instead of benzothiophene (compound represented by No. 9 obtained in Synthesis Example 1), 2 , 7-Bis (9H-carbazole-9-yl)-[1] benzothiophene [3,2-b] [1] benzothiophene (compound represented by No. 81 obtained in Synthesis Example 15) was used. except that, were evaluated in accordance with example 1, the average surface roughness Sa of the blocking layer is 27.9Nm, met contrast ratio is 4.7 × 10 ⁰ at the time of applying a voltage of 5V rice field.

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

From the above evaluation results, the photoelectric conversion element for an imaging device of the present invention having an organic thin film layer having a surface roughness of 7.0 nm or less in the photoelectric conversion part has an organic thin film having a surface roughness of 7.0 nm or less in the photoelectric conversion part. It is clear that it has better characteristics than the photoelectric conversion element for an imaging element of the comparative example having no layer.

As described above, the photoelectric conversion element for an imaging device of the present invention has excellent performance in organic photoelectric conversion characteristics, and is not only an organic imaging element having high resolution and high responsiveness, but also an organic EL element and an organic solar cell. Expected to be applied to organic electronic devices such as elements and organic transistor elements, 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.

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

Claims (12)

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 photoelectric conversion unit is based on the following equation (1).

(In formula (1), n is the number of substituents R and n = 1. R represents a phenyl group having a naphthoenyl group.)
A photoelectric conversion element for an image sensor having one or more organic thin film layers having a surface roughness Ra and / or Sa of 7.0 nm or less containing a compound represented by. (C) The photoelectric conversion element for an image sensor according to claim 1, wherein the photoelectric conversion unit has one or more organic thin film layers having a surface roughness Ra and / or Sa of 1.3 nm or more and 7.0 nm or less. (C) The organic thin film layer having a surface roughness Ra and / or Sa of 7.0 nm or less contained in the photoelectric conversion unit is an organic thin film other than the (c-1) photoelectric conversion layer and / or (c-2) photoelectric conversion layer. The photoelectric conversion element for an imaging element according to claim 1 or 2, which is a layer. (C-1) The photoelectric conversion element for an image sensor according to claim 3, wherein the photoelectric conversion layer includes a p-type organic semiconductor material and an n-type organic semiconductor material. (C-2) The photoelectric conversion element for an imaging element according to claim 3, wherein the organic thin film layer other than the photoelectric conversion layer is an electron block layer. (C-2) The photoelectric conversion element for an imaging element according to claim 3, wherein the organic thin film layer other than the photoelectric conversion layer is a hole block layer. (C-2) The photoelectric conversion element for an imaging element according to claim 3, wherein the organic thin film layer other than the photoelectric conversion layer is an electron transport layer. (C-2) The photoelectric conversion element for an imaging element according to claim 3, wherein the organic thin film layer other than the photoelectric conversion layer is a hole transport layer. The image pickup device according to any one of claims 1 to 8, 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 accumulated in the thin film transistor. Photoelectric conversion element. (C) The organic thin film layer having a surface roughness Ra and / or Sa of 7.0 nm or less of the photoelectric conversion unit is represented by the following formula (2).

The photoelectric conversion element for an image sensor according to claim 1 , wherein R in the formula (2) has the same meaning as R in the formula (1) according to claim 1. An image pickup device in which a plurality of photoelectric conversion elements for an image pickup device according to any one of claims 1 to 10 are arranged in an array. An optical sensor including the photoelectric conversion element for an image sensor according to any one of claims 1 to 10 or the image sensor according to claim 11.

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