Photoelectric conversion film and electronic device

Abstract

The present disclosure provides a photoelectric conversion film including a transparent compound that does not absorb visible light; and an organic dye compound that absorbs green light in a wavelength band greater than or equal to 450 nm and less than or equal to 600 nm.

Description

[0001] This application is a divisional application of patent application No. 201580020332.9, whose application date is April 8, 2015 and whose invention name is "Photoelectric conversion film, photoelectric conversion element and electronic device".

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims the benefit of priority from Japanese Priority Patent Application JP 2014-099816 filed on May 13, 2014, and Japanese Priority Patent Application JP 2015-000695 filed on January 6, 2015, the entire contents of each of which are hereby incorporated by reference herein. Technical Field

[0004] The present disclosure relates to a photoelectric conversion film, a photoelectric conversion element, and an electronic device. Background Art

[0005] Recently, a solid-state image sensor having a multilayer structure in which photoelectric conversion films made of organic materials are stacked has been proposed.

[0006] For example, Patent Document 1 discloses a solid-state image sensor in which organic photoelectric conversion films for absorbing blue light, green light, and red light are sequentially stacked. In the solid-state image sensor disclosed in Patent Document 1, a signal of each color is extracted by photoelectrically converting light corresponding to the color in each organic photoelectric conversion film.

[0007] In addition, Patent Document 2 discloses a solid-state image sensor in which an organic photoelectric conversion film for absorbing green light and a silicon photodiode are sequentially stacked. In the solid-state image sensor disclosed in Patent Document 2, a signal of green light is extracted using the organic photoelectric conversion film, and signals of blue light and red light separated by using the difference in light penetration depth of the silicon photodiode are extracted.

[0008] On the other hand, in the field of solar cells, in order to achieve high photoelectric conversion efficiency, a technology has been proposed in which two types of organic materials are mixed so that at least one material becomes crystalline particles and the photoelectric conversion film is formed as a bulk heterogeneous mixed film. Specifically, as disclosed in Patent Document 3, a technology has been proposed in which a p-type photoelectric conversion material and an n-type photoelectric conversion material are co-deposited so that the photoelectric conversion film is formed as a bulk heterogeneous mixed film.

[0009] Citation list

[0010] Patent Literature

[0011] [PTL 1] JP 2003-234460A

[0012] [PTL 2] JP 2005-303266A

[0013] [PTL 3] JP 2002-76391A Summary of the invention

[0014] Technical issues

[0015] Here, since the spectral characteristics of the photoelectric conversion film formed as a bulk heterogeneous mixed film using two types of organic materials are affected by the spectral characteristics of the two types of organic materials mixed, the wavelength band of the absorbed light may become wider. Therefore, in the photoelectric conversion film formed as a bulk heterogeneous mixed film, it is difficult to selectively absorb light in a specific wavelength range and to have suitable spectral characteristics as a photoelectric conversion film for a solid-state image sensor. Therefore, it is difficult to increase the sensitivity of the solid-state image sensor using such an organic photoelectric conversion film.

[0016] In view of the above problems, the present disclosure provides an improved novel photoelectric conversion film capable of increasing the sensitivity of a solid-state image sensor, a solid-state image sensor including the photoelectric conversion film, and an electronic device including the solid-state image sensor.

[0017] Technical solutions to the problem

[0018] According to one embodiment of the present disclosure, there is provided a photoelectric conversion film including a quinacridone derivative represented by the general formula (1) and a subphthalocyanine derivative represented by the general formula (2).

[0019] [Chemical formula 1]

[0020]

[0021] In the general formula (1), R1 to R 10 Each is independently selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and R1 to R2 10 At least two adjacent groups in the aryl or heteroaryl groups are condensed to form an aryl or heteroaryl group.

[0022] [Chemical formula 2]

[0023]

[0024] In the general formula (2), R 11 ~R 16each is independently selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, wherein X is selected from halogen, hydroxy, thiol, imido, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkylthio, and substituted or unsubstituted arylthio, and wherein R 11 ~R 16 At least one of represents fluorine.

[0025] According to another embodiment of the present disclosure, there is provided a photoelectric conversion film including a transparent compound that does not absorb visible light and is represented by at least one of the following general formula (3) and general formula (4).

[0026] [Chemical formula 3]

[0027]

[0028] In the general formula (3), R 21 ~R 32 Each is independently selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and R 21 ~R 32 At least two adjacent groups in the aryl or heteroaryl groups are condensed to form an aryl or heteroaryl group.

[0029] In the general formula (4), R 41 ~R 48 Each is independently selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, imido, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and R 41 ~R 48At least two adjacent groups in the formula (A) are condensed to form an aryl or heteroaryl group, and each of Ar1 to Ar4 is independently one of a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group.

[0030] In addition, according to another embodiment of the present disclosure, a photoelectric conversion element is provided, which includes: a photoelectric conversion film; a pair of electrodes arranged on both sides of the photoelectric conversion film, with the photoelectric conversion film sandwiched therebetween; and a hole blocking layer arranged between the photoelectric conversion film and one of the electrodes, wherein the difference between the ionization potential of the hole blocking layer and the work function of one of the electrodes is greater than or equal to 2.3 eV.

[0031] According to another embodiment of the present disclosure, since the photoelectric conversion film can selectively absorb light of a specific wavelength band, suitable spectral characteristics for a solid-state image sensor can be obtained.

[0032] Advantageous Effects of the Invention

[0033] As described above, according to one or more embodiments of the present disclosure, there are provided a photoelectric conversion film capable of increasing the sensitivity of a solid-state image sensor, a solid-state image sensor including the photoelectric conversion film, and an electronic device including the solid-state image sensor.

[0034] It should be noted that the above-mentioned effects are not necessarily limitative, and any effects desired to be introduced into the present specification or other effects that can be expected from the present specification may be exhibited together with or instead of these effects. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 Explanatory diagrams respectively illustrating a solid-state image sensor (A) including a photoelectric conversion element according to an embodiment of the present disclosure and a solid-state image sensor (B) according to a comparative example are shown.

[0036] Figure 2 is a schematic diagram illustrating an exemplary photoelectric conversion element according to an embodiment of the present disclosure.

[0037] Figure 3A A graph showing the evaluation results of changes in spectral characteristics of Example 4.

[0038] Figure 3B A graph showing the evaluation results of the change in spectral characteristics of Comparative Example 7.

[0039] Figure 3C A graph showing the evaluation results of the change in spectral characteristics of Comparative Example 8.

[0040] Figure 3D A graph showing the evaluation results of the change in spectral characteristics of Comparative Example 9.

[0041] Figure 3E A graph showing evaluation results of changes in spectral characteristics of a reference example.

[0042] Figure 4 A graph showing the IPCE measurement results of Example 8 and Comparative Example 19.

[0043] Figure 5 Graph showing the spectral characteristics of BTB compounds.

[0044] Figure 6 : is a schematic diagram showing the structure of a solid-state image sensor to which the photoelectric conversion element according to the embodiment of the present disclosure is applied.

[0045] Figure 7 is a cross-sectional view showing an outline of a unit pixel in a solid-state image sensor to which the photoelectric conversion element according to an embodiment of the present disclosure is applied.

[0046] Figure 8 : is a block diagram showing the configuration of an electronic device to which the photoelectric conversion element according to an embodiment of the present disclosure is applied. DETAILED DESCRIPTION

[0047] Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. It should be noted that in the present specification and the accompanying drawings, the same reference numerals are used to represent constituent elements having substantially the same function and structure, and repeated description of these constituent elements is omitted.

[0048] Hereinafter, the description will be given in the following order.

[0049] 1. Overview of Photoelectric Conversion Element According to Embodiments of the Present Disclosure

[0050] 2. First Implementation Method

[0051] 2.1. Configuration of the Photoelectric Conversion Film According to the First Embodiment

[0052] 2.2. Configuration of Photoelectric Conversion Element According to First Embodiment

[0053] 2.3. Examples according to the first embodiment

[0054] 3. Second Implementation Method

[0055] 3.1. Configuration of the photoelectric conversion film according to the second embodiment

[0056] 3.2. Configuration of Photoelectric Conversion Element According to Second Embodiment

[0057] 3.3. Example according to the second embodiment

[0058] 4. Third Implementation Method

[0059] 4.1. Configuration of Photoelectric Conversion Element According to Third Embodiment

[0060] 4.2 Examples according to the third embodiment

[0061] 5. Application Examples of the Photoelectric Conversion Element According to the Embodiments of the Present Disclosure

[0062] 5.1. Structure of solid-state image sensors

[0063] 5.2. Composition of electronic equipment

[0064] 6. Summary

[0065] 1. Overview of Photoelectric Conversion Element According to Embodiments of the Present Disclosure

[0066] Will refer to Figure 1 An outline of a photoelectric conversion element according to an embodiment of the present disclosure is described. Figure 1 (A) in FIG. 1 is an explanatory diagram showing a solid-state image sensor including a photoelectric conversion element according to an embodiment of the present disclosure. Figure 1 (B) in FIG. 1 is an explanatory diagram showing a solid-state image sensor according to a comparative example.

[0067] Hereinafter, in this specification, when it is described that "light of a certain wavelength is absorbed", it means that about 70% or more of the light of the wavelength is absorbed. In addition, conversely, when it is described that "light of a certain wavelength is transmitted" or "light of a certain wavelength is not absorbed", it means that about 70% or more of the light of the wavelength is transmitted and about 30% or less of the light is absorbed.

[0068] First, a solid-state image sensor according to a comparative example will be described. Figure 1 As shown in FIG. 2(B) , the solid-state image sensor 5 according to the comparative example includes photodiodes 7R, 7G, and 7B and color filters 6R, 6G, and 6B formed on the photodiodes 7R, 7G, and 7B.

[0069] The filters 6R, 6G, and 6B are films that selectively transmit light of a specific wavelength. For example, the filter 6R is a film that selectively transmits red light 2R having a wavelength greater than or equal to 600 nm. The filter 6G is a film that selectively transmits green light 2G having a wavelength greater than or equal to 450 nm and less than 600 nm. The filter 6B is a film that selectively transmits blue light 2B having a wavelength greater than or equal to 400 nm and less than 450 nm.

[0070] In addition, the photodiodes 7R, 7G, and 7B are photodetectors for absorbing light in a wide band (for example, the absorption wavelength of the silicon photodiode is 190 nm to 1100 nm). For this reason, when each of the photodiodes 7R, 7G, and 7B is used, it is difficult to extract the signal of each color such as red, green, and blue separately. Therefore, in the solid-state image sensor according to the comparative example, light other than the light corresponding to each color is absorbed by the filters 6R, 6G, and 6B, and only the light corresponding to each color is selectively transmitted, so that the colors are separated, and the signal of each color is extracted by the photodiodes 7R, 7G, and 7B.

[0071] Therefore, in the solid-state image sensor 5 according to the comparative example, since most of the light is absorbed by the filters 6R, 6G and 6B, the photodiodes 7R, 7G and 7B may substantially use only 1 / 3 of the incident light for photoelectric conversion. Therefore, in the solid-state image sensor 5 according to the comparative example, it is difficult to increase the detection sensitivity of each color.

[0072] Next, a solid-state image sensor 1 including a photoelectric conversion element according to an embodiment of the present disclosure will be described. Figure 1 As shown in (A) in the figure, a solid-state image sensor 1 including a photoelectric conversion element according to an embodiment of the present disclosure has the following structure: a green photoelectric conversion element 3G configured to absorb green light 2G, a blue photoelectric conversion element 3B configured to absorb blue light 2B, and a red photoelectric conversion element 3R configured to absorb red light 2R are stacked in sequence.

[0073] For example, the green photoelectric conversion element 3G is an organic photoelectric conversion element that selectively absorbs green light having a wavelength greater than or equal to 450 nm and less than 600 nm. The blue photoelectric conversion element 3B is an organic photoelectric conversion element that selectively absorbs blue light having a wavelength greater than or equal to 400 nm and less than 450 nm. The red photoelectric conversion element 3R is an organic photoelectric conversion element that selectively absorbs red light having a wavelength greater than or equal to 600 nm.

[0074] Therefore, in the solid-state image sensor 1 according to the embodiment of the present disclosure, each photoelectric conversion element can selectively absorb light corresponding to a specific wavelength band of red, green or blue. For this reason, in the solid-state image sensor 1 according to the embodiment of the present disclosure, it is not necessary to set a filter for separating the incident light into each color, and all the incident light can be used for photoelectric conversion. Therefore, since the solid-state image sensor 1 according to the embodiment of the present disclosure can increase the light used for photoelectric conversion to about 3 times that of the solid-state image sensor 5 according to the comparative example, the detection sensitivity of each color can be further increased.

[0075] In addition, in the solid-state image sensor 1 according to the embodiment of the present disclosure, the blue photoelectric conversion element 3B and the red photoelectric conversion element 3R can be silicon photodiodes that perform photoelectric conversion on light of a wide band (specifically, for example, 190nm to 1100nm). In this case, the blue photoelectric conversion element 3B and the red photoelectric conversion element 3R use the difference in the penetration depth of light of each wavelength relative to the solid-state image sensor 1 to separate the colors into blue light 2B and red light 2R. Specifically, because the red light 2R has a longer wavelength and is less likely to scatter than the blue light 2B, the red light 2R penetrates to a depth far from the incident surface. On the other hand, because the blue light 2B has a shorter wavelength and is more likely to scatter than the red light 2R, the blue light 2B penetrates only to a depth close to the incident surface. Therefore, when the red photoelectric conversion element 3R is configured at a position far from the incident surface of the solid-state image sensor 1, the red light 2R and the blue light 2B can be detected separately. Therefore, even when silicon photodiodes are used as the blue photoelectric conversion element 3B and the red photoelectric conversion element 3R, the blue light 2B and the red light 2R can be separated using the difference in penetration depth of light, and signals of each color can be extracted.

[0076] Therefore, in the photoelectric conversion elements 3G, 3B, and 3R included in the solid-state image sensor 1 according to the embodiment of the present disclosure, it is necessary to selectively absorb light of a specific wavelength band corresponding to red, green, or blue and transmit light having a wavelength other than the absorption wavelength. In particular, the green photoelectric conversion element 3G closest to the incident surface has an absorption spectrum showing a steep peak in a green band (for example, a band of 450 nm to 600 nm), and it is necessary to reduce absorption in a band less than 450 nm and a band greater than 600 nm.

[0077] In view of the above situation, the inventors of the present disclosure have extensively studied a photoelectric conversion film suitable for a solid-state image sensor and completed the technology according to the present disclosure. When the photoelectric conversion film according to the embodiment of the present disclosure includes a compound to be described in the following embodiment, it can selectively absorb light in a specific wavelength band and have suitable spectral characteristics as a photoelectric conversion film for a solid-state image sensor. Therefore, when the photoelectric conversion film according to the embodiment of the present disclosure is used, the sensitivity and resolution of the solid-state image sensor can be increased.

[0078] Hereinafter, the photoelectric conversion films according to the first and second embodiments of the present disclosure will be described. Furthermore, the photoelectric conversion element according to the third embodiment of the present disclosure having a suitable configuration as a photoelectric conversion element of a solid-state image sensor will be described.

[0079] 2. First Implementation Method

[0080] (2.1. Configuration of Photoelectric Conversion Film According to First Embodiment)

[0081] First, a photoelectric conversion film according to a first embodiment of the present disclosure will be described. The photoelectric conversion film according to the first embodiment of the present disclosure is a photoelectric conversion film including a quinacridone derivative represented by the following general formula (1) and a subphthalocyanine derivative represented by the following general formula (2) and absorbing green light.

[0082] [Chemical formula 4]

[0083]

[0084] In the above general formula (1), R1 to R 10 Each independently represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl, or R1 to R2 are substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl. 10 Any at least two adjacent ones of are condensed to form an aryl or heteroaryl group.

[0085] [Chemical formula 5]

[0086]

[0087] In the above general formula (2), R 11 ~R 16 each independently represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl, X represents any substituent selected from halogen, hydroxy, mercapto, imido, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkylthio and substituted or unsubstituted arylthio, and R 11 ~R 16 At least one of represents fluorine.

[0088] Here, the photoelectric conversion film according to the first embodiment of the present disclosure can be formed as a bulk heterogeneous hybrid film. In this case, since the quinacridone derivative represented by the general formula (1) is used as a p-type photoelectric conversion material and the subphthalocyanine derivative represented by the general formula (2) is used as an n-type photoelectric conversion material, a bulk heterojunction is formed by these derivatives.

[0089] For example, a bulk heterogeneous hybrid film is a film having a microstructure in which one of the p-type photoelectric conversion material and the n-type photoelectric conversion material forming the film is in a crystalline particle state and the other is in an amorphous state, and the amorphous layer uniformly covers the surface of the crystalline particles. In such a bulk heterogeneous hybrid film, since the area of ​​the pn junction that induces charge separation is increased by the microstructure, charge separation can be more effectively induced and the photoelectric conversion efficiency can be increased. Alternatively, the bulk heterogeneous hybrid film can be a film having a microstructure in which both the p-type photoelectric conversion material and the n-type photoelectric conversion material forming the film are in a microcrystalline state and mixed.

[0090] On the other hand, the spectral characteristics of such a bulk heterogeneous hybrid film are affected by the spectral characteristics of the p-type photoelectric conversion material and the n-type photoelectric conversion material to be mixed. For this reason, when the spectral characteristics of the p-type photoelectric conversion material and the n-type photoelectric conversion material forming the bulk heterogeneous hybrid film do not match, the absorption wavelength of light of the bulk heterogeneous hybrid film may become broadened. Therefore, the photoelectric conversion film formed as a bulk heterogeneous hybrid film may not obtain suitable spectral characteristics as a photoelectric conversion film in a solid-state image sensor.

[0091] When the photoelectric conversion film according to the first embodiment of the present disclosure contains a quinacridone derivative and a subphthalocyanine derivative having spectral characteristics matching those of the quinacridone derivative, it can have appropriate spectral characteristics as a photoelectric conversion film for green light in a solid-state image sensor.

[0092] Specifically, in the subphthalocyanine derivative included in the photoelectric conversion film according to the first embodiment of the present disclosure, R 11 ~R 16 At least one of them is fluorine, so the spectral characteristics match those of quinacridone derivatives. Specifically, R 11 ~R 16 The subphthalocyanine derivative in which at least one of the subphthalocyanines is fluorine reduces the maximum value of the absorption wavelength to a shorter wavelength, thereby reducing the absorption of light having a wavelength greater than or equal to 600 nm. Therefore, since the photoelectric conversion film according to the first embodiment of the present disclosure has an absorption spectrum showing a steep peak in the green band (a band of 450 nm to 600 nm), it is possible to achieve suitable spectral characteristics as a photoelectric conversion film for green light in a solid-state image sensor.

[0093] In addition, in the process of manufacturing the photoelectric conversion element and the solid-state image sensor, a treatment accompanied by heating (e.g., annealing treatment) may be performed. When the photoelectric conversion material contained in the photoelectric conversion film has low heat resistance, the photoelectric conversion material migrates and the spectral characteristics may change due to the heat in such a heating treatment. In particular, since general subphthalocyanine derivatives have low heat resistance, when the photoelectric conversion film containing the general subphthalocyanine derivative is subjected to a treatment accompanied by heating, the absorbance decreases significantly.

[0094] In the subphthalocyanine derivative included in the photoelectric conversion film according to the first embodiment of the present disclosure, since R 11 ~R 16 At least one of the fluorine is fluorine, so the heat resistance is significantly increased. Therefore, in the photoelectric conversion film according to the first embodiment of the present disclosure, because the included photoelectric conversion material has high heat resistance, the change of spectral characteristics can be suppressed during the heating process. Therefore, in the photoelectric conversion film according to the first embodiment of the present disclosure, the degree of freedom in the process of manufacturing the photoelectric conversion element and the solid-state image sensor can be increased.

[0095] In the subphthalocyanine derivative represented by the general formula (2), R 11 ~R 16 and have symmetry (line symmetry or point symmetry), or R can be replaced by fluorine 11 ~R 16 It does not have symmetry.

[0096] Furthermore, in the subphthalocyanine derivative represented by the general formula (2), X may be any substituent as long as the substituent can bind to boron. However, it is more preferred that X is selected from halogen, hydroxyl, substituted or unsubstituted alkoxy and substituted or unsubstituted aryloxy.

[0097] Here, in the subphthalocyanine derivative included in the photoelectric conversion film according to the first embodiment of the present disclosure, preferably, R 11 ~R 16 All are fluorine. Specifically, as will be demonstrated in the following examples, in R 11 ~R 16 In the subphthalocyanine derivatives containing all fluorine, the maximum absorption wavelength can be further reduced to a shorter wavelength. Therefore, since the subphthalocyanine derivative represented by the general formula (2) can further reduce the absorption of 600 nm or more, it can more selectively absorb green light.

[0098] Furthermore, in the subphthalocyanine derivative represented by the general formula (2), preferably, the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are energy levels that can smoothly perform a photoelectric conversion mechanism on the quinacridone derivative.

[0099] Specifically, when the subphthalocyanine derivative represented by the general formula (2) is used as an n-type photoelectric conversion material and the quinacridone derivative represented by the general formula (1) is used as a p-type photoelectric conversion material, preferably, the LUMO energy level of the subphthalocyanine derivative is deeper than the LUMO energy level of the quinacridone derivative. In other words, preferably, the absolute value of the LUMO energy level of the subphthalocyanine derivative is greater than the absolute value of the LUMO energy level of the quinacridone derivative.

[0100] Here, as the photoelectric conversion mechanism of the photoelectric conversion film according to the first embodiment of the present disclosure, the following two mechanisms are considered.

[0101] A photoelectric conversion mechanism is a mechanism in which a quinacridone derivative used as a p-type photoelectric conversion material is excited by light and the excited electrons move from the quinacridone derivative to a subphthalocyanine derivative used as an n-type photoelectric conversion material. In this case, it is preferred that the LUMO energy level of the subphthalocyanine derivative is an energy level at which the excited electrons excited in the quinacridone derivative can smoothly move to the subphthalocyanine derivative. Specifically, it is preferred that the difference between the LUMO energy level of the subphthalocyanine derivative represented by the general formula (2) and the LUMO energy level of the quinacridone derivative represented by the general formula (1) is greater than or equal to 0.1 eV and less than or equal to 1.0 eV. More specifically, it is preferred that the LUMO energy level of the subphthalocyanine derivative is greater than or equal to -4.8 eV and less than or equal to -3.5 eV, and more preferably, greater than or equal to -4.5 eV and less than or equal to -3.8 eV.

[0102] In addition, another photoelectric conversion mechanism is a mechanism in which a subphthalocyanine derivative used as an n-type photoelectric conversion material is excited by light and the excited electrons move to the LUMO energy level of the subphthalocyanine derivative. Therefore, holes can move from the quinacridone derivative used as a p-type photoelectric conversion material to the subphthalocyanine derivative. In this case, preferably, the HOMO energy level of the subphthalocyanine derivative is an energy level at which holes can smoothly move from the quinacridone derivative to the subphthalocyanine derivative. Specifically, preferably, the HOMO energy level of the subphthalocyanine derivative is greater than or equal to -7.0 eV and less than or equal to -5.5 eV, more preferably, greater than or equal to -6.7 eV and less than or equal to -5.8 eV.

[0103] In addition, when the purpose of the photoelectric conversion film is to extract an electromotive force, for example, in a solar cell, in order to increase the open end voltage, it is necessary to increase the difference by reducing the HOMO energy level of the p-type photoelectric conversion material and increasing the LUMO energy level of the n-type photoelectric conversion material. On the other hand, the purpose of the solid-state image sensor in which the photoelectric conversion film according to the first embodiment of the present disclosure is used is to extract a signal of light of a specific wavelength. To this end, in the photoelectric conversion film according to the first embodiment of the present disclosure, preferably, the LUMO energy level of the subphthalocyanine derivative (n-type photoelectric conversion material) is set based on the relationship with the LUMO energy level of the quinacridone derivative (p-type photoelectric conversion material) rather than the HOMO energy level. Specifically, as described above, it is preferred that the difference between the LUMO energy level of the subphthalocyanine derivative and the LUMO energy level of the quinacridone derivative is greater than or equal to 0.1 eV and less than or equal to 1.0 eV.

[0104] Here, specific examples of the subphthalocyanine derivative represented by the general formula (2) are represented by the following compounds 1 to 9. However, the subphthalocyanine derivative contained in the photoelectric conversion film according to the first embodiment of the present disclosure is not limited to the following compounds.

[0105] [Chemical formula 6]

[0106]

[0107] As described above, since the photoelectric conversion film according to the first embodiment of the present disclosure contains the quinacridone derivative represented by the general formula (1) and the subphthalocyanine derivative represented by the general formula (2), green light (for example, light having a wavelength greater than or equal to 450 nm and less than 600 nm) can be selectively absorbed. In addition, in the photoelectric conversion film according to the first embodiment of the present disclosure, since the quinacridone derivative and the subphthalocyanine derivative contained therein have high heat resistance, changes in spectral characteristics can be suppressed during the process of manufacturing a photoelectric conversion element and a solid-state image sensor. Therefore, since the photoelectric conversion film according to the first embodiment of the present disclosure can be suitably used for a green photoelectric conversion element in a solid-state image sensor, the sensitivity of the solid-state image sensor can be increased.

[0108] (2.2. Configuration of Photoelectric Conversion Element According to First Embodiment)

[0109] Next, we will refer to Figure 2 A photoelectric conversion element according to a first embodiment of the present disclosure is described. Figure 2 is a schematic diagram illustrating an exemplary photoelectric conversion element according to the first embodiment of the present disclosure.

[0110] like Figure 2As shown, the photoelectric conversion element 100 according to the first embodiment of the present disclosure includes a substrate 102, a lower electrode 104 arranged on the substrate 102, an electron blocking layer 106 arranged on the lower electrode 104, a photoelectric conversion layer 108 arranged on the electron blocking layer 106, a hole blocking layer 110 arranged on the photoelectric conversion layer 108, and an upper electrode 112 arranged on the hole blocking layer 110.

[0111] However, Figure 2 The structure of the photoelectric conversion element 100 shown in FIG. 1 is only an example. The structure of the photoelectric conversion element 100 according to the first embodiment of the present disclosure is not limited to Figure 2 For example, one or both of the electron blocking layer 106 and the hole blocking layer 110 may not be provided.

[0112] The substrate 102 is a support body in which the layers of the photoelectric conversion element 100 are stacked. As the substrate 102, a substrate used in a general photoelectric conversion element can be used. For example, the substrate 102 can be various types of glass substrates (e.g., high strain point glass substrates, soda glass substrates, and borosilicate glass substrates), quartz substrates, semiconductor substrates, and plastic substrates (e.g., polymethyl methacrylate, polyvinyl alcohol, polyimide, or polycarbonate substrates). In addition, when incident light is transmitted and the transmitted incident light is received again in another photoelectric conversion element, preferably, the substrate 102 is made of a transparent material.

[0113] The lower electrode 104 and the upper electrode 112 are made of a conductive material, and at least one of them is made of a transparent conductive material. Specifically, the lower electrode 104 and the upper electrode 112 can be made of indium tin oxide (In2O3-SnO2: ITO), indium zinc oxide (In2O3-ZnO: IZO), etc. In addition, when incident light is transmitted and the transmitted incident light is received again in another photoelectric conversion element, preferably, the lower electrode 104 and the upper electrode 112 are made of a transparent conductive material such as ITO.

[0114] Here, a bias voltage is applied to the lower electrode 104 and the upper electrode 112. For example, the bias voltage is applied to set polarity so that electrons among charges generated in the photoelectric conversion layer 108 move to the upper electrode 112 and holes move to the lower electrode 104.

[0115] Furthermore, it is needless to say that a bias voltage is applied to set polarity so that holes among charges generated in the photoelectric conversion layer 108 move to the upper electrode 112 and electrons move to the lower electrode 104. In this case, Figure 2 In the photoelectric conversion element 100 shown, the positions of the electron blocking layer 106 and the hole blocking layer 110 can be switched.

[0116] The electron blocking layer 106 is a layer that suppresses the increase of dark current caused by the injection of electrons from the lower electrode 104 to the photoelectric conversion layer 108 when a bias voltage is applied. Specifically, the electron blocking layer 106 can be made of an electron-donating material, such as arylamine, oxazole, oxadiazole, triazole, imidazole, distilbene, polyarylalkane, porphyrin, anthracene, fluorenone and hydrazine. For example, the electron blocking layer 106 can be made of N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (α-NPD), 4,4',4"-tris(N-(3-methylphenyl)N-phenylamino)triphenylamine (m-MTDATA), tetraphenylporphyrin copper, phthalocyanine or copper phthalocyanine.

[0117] The photoelectric conversion layer 108 is a layer that selectively absorbs light of a specific wavelength and performs photoelectric conversion on the absorbed light. Specifically, the photoelectric conversion layer 108 is formed by the photoelectric conversion film described above (2.1. Composition of the photoelectric conversion film according to the first embodiment). Therefore, the photoelectric conversion layer 108 can selectively absorb green light (for example, light with a wavelength greater than or equal to 450nm and less than 600nm).

[0118] The hole blocking layer 110 is a layer that can suppress the increase of dark current caused by the injection of holes from the upper electrode 112 into the photoelectric conversion layer 108 when a bias voltage is applied. Specifically, the hole blocking layer 110 can be made of an electron accepting material, for example, fullerene, carbon nanotube, oxadiazole, triazole compound, anthraquinone dimethane, diphenylquinone, distyryl and silole compound. For example, the hole blocking layer 110 can be made of 1,3-bis (4-tert-butylphenyl-1,3,4-oxadiazolyl) phenylene (OXD-7), bathocuproin, bathophenanthroline or tris (8-hydroxyquinoline) aluminum (Alq3).

[0119] In addition, Figure 2 In the structure of the photoelectric conversion element 100 shown, the materials forming each layer other than the photoelectric conversion layer 108 are not particularly limited, and known materials used for photoelectric conversion elements can be used.

[0120] Here, each layer in the above-described photoelectric conversion element 100 according to the first embodiment of the present disclosure can be formed by an appropriate film-forming method selected according to the material, for example, a deposition method, a sputtering method, and various coating methods.

[0121] For example, in the various layers forming the photoelectric conversion element 100 according to the first embodiment of the present disclosure, the lower electrode 104 and the upper electrode 112 can be formed by a deposition method including an electron beam deposition method, a hot wire deposition method, and a vacuum deposition method, a sputtering method, a chemical vapor deposition method (CVD method), a combination of an ion plating method and an etching method, various types of printing methods such as a screen printing method, an inkjet printing method, and a metal mask printing method, a plating method (electroplating method and chemical plating method), and the like.

[0122] In addition, in the various layers forming the photoelectric conversion element 100 according to the first embodiment of the present disclosure, for example, organic layers such as the electron blocking layer 106, the photoelectric conversion layer 108 and the hole blocking layer 110 can be formed by a deposition method such as a vacuum deposition method, a printing method such as a screen printing method and an inkjet printing method, a laser transfer method, or a coating method such as a spin coating method.

[0123] In the above, the exemplary configuration of the photoelectric conversion element 100 according to the first embodiment of the present disclosure has been described.

[0124] (2.3. Example according to the first embodiment)

[0125] Hereinafter, the photoelectric conversion film and the photoelectric conversion element according to the first embodiment of the present disclosure will be described in detail with reference to Examples and Comparative Examples. However, the following Examples are only examples, and the photoelectric conversion film and the photoelectric conversion element according to the first embodiment of the present disclosure are not limited to the following Examples.

[0126] (Simulation Analysis)

[0127] First, the spectral characteristics of the subphthalocyanine derivative according to the first embodiment of the present disclosure are evaluated by simulation analysis. Specifically, the subphthalocyanine derivative represented by the following structural formula is simulated and analyzed, and the HOMO and LUMO energy levels and the maximum absorption wavelength λ are calculated. max .

[0128] Here, "F6-SubPc-Cl", "F3(C3)-SubPc-Cl" and "F3(C1)-SubPc-Cl" are subphthalocyanine derivatives according to the first embodiment of the present disclosure (Examples 1 to 3). "Bay-F6-SubPc-Cl", "F12-SubPc-Cl", "Cl6-SubPc-Cl", "Bay-Cl6-SubPc-Cl" and "Cl12-SubPc-Cl" are subphthalocyanine derivatives not included in the first embodiment of the present disclosure (Comparative Examples 1 to 5).

[0129] [Chemical formula 7]

[0130]

[0131] Furthermore, in the simulation analysis, calculations were performed according to density functional theory (DFT), Gaussian 09 was used as a calculation program, and calculations were performed at the level of "B3LYP / 6-31+G**".

[0132] Table 1 shows the HOMO and LUMO energy levels and the maximum absorption wavelength λ of each subphthalocyanine derivative calculated by simulation analysis. max In addition, since the HOMO and LUMO energy levels and the maximum absorption wavelength λ of the subphthalocyanine derivatives shown in Table 1 max These are the results of simulation analysis in a single molecule, so the absolute values ​​do not strictly match the actual measured values ​​of the thin film to be described.

[0133] [Table 1]

[0134] HOMO(eV) LUMO(eV) <![CDATA[λ max (nm)]]> Example 1 F6-SubPc-Cl -6.18 -3.44 492.76 Example 2 F3-Cl-SubPc-Cl -5.89 -3.19 497.38 Example 3 F3-C3-SubPc-Cl -5.89 -3.22 491.27 Comparative Example 1 Bay-F6-SubPc-Cl -5.99 -3.14 520.39 Comparative Example 2 F12-SubPc-Cl -6.51 -3.9 513.96 Comparative Example 3 Cl6-SubPc-Cl -6.15 -3.49 510.02 Comparative Example 4 Bay-C16-SubPc-Cl -5.98 -3.39 525.73 Comparative Example 5 Cl12-SubPc-Cl -6.33 -3.76 533.21

[0135] As shown in Table 1, it can be understood that the maximum absorption wavelength λ of the subphthalocyanine derivatives according to Examples 1 to 3 is max The maximum absorption wavelength λ of the subphthalocyanine derivatives according to Comparative Examples 1 to 5 is max short.

[0136] Specifically, in the subphthalocyanine derivatives according to Examples 1 to 3, at least one of the β positions (R 11 ~R 16 ). Therefore, the maximum absorption wavelength λ max In addition, in the subphthalocyanine derivative according to Example 1, it can be understood that because the β position (R 11 ~R 16 ) are all replaced by fluorine, so the maximum absorption wavelength λ max becomes shorter than the maximum absorption wavelength λ of the subphthalocyanine derivatives according to Examples 2 and 3 in which the β position is partially substituted with fluorine. max Short wavelength.

[0137] On the other hand, in the subphthalocyanine derivatives according to Comparative Examples 1 and 2, since the α-position of the subphthalocyanine skeleton is substituted with fluorine, the maximum absorption wavelength λ is 2.37 W·m-1·K-1 compared with the subphthalocyanine derivatives according to Examples 1 to 3. max In addition, in the subphthalocyanine derivative according to Comparative Example 2, the β position (R 11 ~R 16 ) are all substituted with fluorine, but the α position is also substituted with fluorine. Therefore, compared with the subphthalocyanine derivatives according to Examples 1 to 3, the maximum absorption wavelength λ max Become longer.

[0138] The change in spectral characteristics according to the position of the substituent is considered to be caused by the presence of molecular orbitals of the HOMO level and the LUMO level that affect the spectral characteristics of subphthalocyanine at the α-position and the β-position of the subphthalocyanine skeleton. Therefore, in the subphthalocyanine derivative according to the first embodiment of the present disclosure, the α-position of the subphthalocyanine skeleton is all hydrogen and at least any one of the β-positions (R 11 ~R 16 ) substitution with fluorine is believed to be important.

[0139] In addition, in the subphthalocyanine derivatives according to Comparative Examples 3 to 5, the α-position or β-position of the subphthalocyanine skeleton is substituted with chlorine. Therefore, compared with the subphthalocyanine derivatives according to Examples 1 to 3, the maximum absorption wavelength λ max Therefore, in the subphthalocyanine derivative according to the first embodiment of the present disclosure, it is considered important that the substituent for substituting the subphthalocyanine skeleton is fluorine.

[0140] (Synthesis of Subphthalocyanine Derivatives)

[0141] Next, the synthesis method of the subphthalocyanine derivative according to the first embodiment of the present disclosure will be described. Specifically, the above-mentioned compound 2 (F6-SubPc-Cl) and compound 9 (F6-SubPc-OC6F5) are synthesized by the following synthesis method. Using nuclear magnetic resonance ( 1 HNMR) and field desorption-mass spectrometry (FD-MS) were used to identify the synthesized subphthalocyanine derivative. However, the synthesis method to be described below is only an example, and the synthesis method of the subphthalocyanine derivative according to the first embodiment of the present disclosure is not limited to the following example.

[0142] Synthesis of F6-SubPc-Cl

[0143] F6-SubPc-Cl used as the subphthalocyanine derivative according to the first embodiment of the present disclosure is synthesized by the following Reaction Formula 1.

[0144] [Chemical formula 8]

[0145] Reaction (1)

[0146]

[0147] Difluorophthalonitrile (30 g, 183 mmol) was added to 1-chloronaphthalene (150 ml) dissolved with BCl3 (14 g, 120 mmol), and the mixture was heated to reflux under a nitrogen atmosphere. After cooling, the mixture was separated and purified by silica chromatography, and then the product was purified by sublimation purification to obtain F6-SubPc-Cl (11 g, yield 34%).

[0148] Synthesis of F6-SubPc-OC6F5

[0149] F6-SubPc-OC6F5 used as the subphthalocyanine derivative according to the first embodiment of the present disclosure is synthesized by the following reaction formula 2.

[0150] [Chemical formula 9]

[0151] Reaction (2)

[0152]

[0153] Pentafluorophenol (13 g, 10 mmol) was added to chlorobenzene (100 ml) in which F6-SubPc-Cl (10 g, 2.3 mmol) synthesized by the above synthesis method was dissolved, and the mixture was heated to reflux. After cooling, the mixture was separated and purified by silica chromatography, and then the product was purified by sublimation purification to obtain F6-SubPc-OC6F5 (5.9 g, yield 60%).

[0154] (Evaluation of spectral characteristics)

[0155] Subsequently, the spectral characteristics of the subphthalocyanine derivative according to the first embodiment of the present disclosure were evaluated. Specifically, an evaluation sample containing the subphthalocyanine derivative according to the first embodiment of the present disclosure was produced, and changes in spectral characteristics before and after annealing were measured.

[0156] (Example 4)

[0157] First, the glass substrate with the ITO electrode was cleaned by UV / ozone treatment. In addition, the film thickness of the ITO film in the glass substrate was 50 nm. Next, the glass substrate was placed in an organic deposition device and the surface was less than or equal to 1×10 -5 The synthesized F6-SubPc-Cl was deposited at a deposition rate of 0.1 nm / sec by a resistance heating method while rotating the substrate holder in a vacuum of 1.5 Pa. The film thickness of the deposited F6-SubPc-Cl was 50 nm. In addition, in order to cover the organic layer, an ITO film with a film thickness of 50 nm was formed by a sputtering method, thereby manufacturing a sample for evaluating spectral characteristics.

[0158] (Comparative Example 6)

[0159] A spectrum characteristic evaluation sample was manufactured by the same method as in Example 4, except that F12-SubPc-Cl, which will be described in the following synthesis method, was used instead of F6-SubPc-Cl used in Example 4.

[0160] In addition, F12-SubPc-Cl used in Comparative Example 6 was synthesized by the following Reaction Formula 3. In addition, the synthesized F12-SubPc-Cl was identified using NMR and FD-MS.

[0161] [Chemical formula 10]

[0162] Reaction (3)

[0163]

[0164] Tetrafluorophthalonitrile (37 g, 183 mmol) was added to 1-chloronaphthalene (150 ml) dissolved with BCl3 (14 g, 120 mmol), and the mixture was heated to reflux under a nitrogen atmosphere. After cooling, the mixture was separated and purified by silica chromatography, and then the product was purified by sublimation purification to obtain F12-SubPc-Cl (5.3 g, yield 64%).

[0165] (Comparative Example 7)

[0166] A spectrum characteristic evaluation sample was manufactured by the same method as in Example 4, except that SubPc-OC6F5, which will be described in the following synthesis method, was used instead of F6-SubPc-Cl used in Example 4.

[0167] In addition, SubPc-OC6F5 used in Comparative Example 7 was synthesized by the following Reaction Formula 4. In addition, the synthesized SubPc-OC6F5 was identified using NMR and FD-MS.

[0168] [Chemical formula 11]

[0169] Reaction (4)

[0170]

[0171] Pentafluorophenol (13 g, 10 mmol) was added to 1,2-chlorobenzene (100 ml) in which sublimation-purified subphthalocyanine (manufactured by Tokyo Chemical Industry Co., Ltd.) (10 g, 2.3 mmol) was dissolved, and the mixture was heated to reflux. After cooling, the mixture was separated and purified by silica gel column chromatography, and then the product was purified by sublimation purification to obtain SubPc-OC6F5 (6.5 g, yield 65%).

[0172] (Comparative Example 8)

[0173] A sample for evaluating spectral characteristics was prepared by the same method as in Example 4, except that subphthalocyanine chloride (SubPc-Cl) represented by the following structural formula was used instead of F6-SubPc-Cl used in Example 4. In addition, as the subphthalocyanine chloride, a sublimation-purified product purchased from Tokyo Chemical Industry Co., Ltd. was used.

[0174] [Chemical formula 12]

[0175]

[0176] (Reference example)

[0177] A sample for evaluating spectral characteristics was prepared by the same method as in Example 4, except that quinacridone (QD) represented by the following structural formula was used instead of F6-SubPc-Cl used in Example 4. In addition, as quinacridone, a sublimation-purified product purchased from Tokyo Chemical Industry Co., Ltd. was used.

[0178] [Chemical formula 13]

[0179]

[0180] Using an ultraviolet visible spectrophotometer, the spectral characteristics of Example 4, Comparative Examples 7 to 9, and Reference Example prepared were evaluated for changes in spectral characteristics before and after annealing. Specifically, the spectral characteristics of Example 4, Comparative Examples 7 to 9, and Reference Example were measured before annealing, after annealing at 160° C. for 60 minutes, and after annealing at 160° C. for 210 minutes. Figure 3A to Figure 3E The evaluation results of the changes in spectral characteristics are shown in FIG.

[0181] here, Figure 3A The graphs showing the evaluation results of the changes in the spectral characteristics of Example 4 (F6-SubPc-Cl) are shown. Figure 3B A graph showing the evaluation results of changes in spectral characteristics of Comparative Example 7 (F12-SubPc-Cl). Figure 3C A graph showing the evaluation results of changes in spectral characteristics of Comparative Example 8 (SubPc-OC6F5). Figure 3D The graph showing the evaluation results of the spectral characteristic changes of Comparative Example 9 (SubPc-Cl) is shown. Figure 3E A graph showing the evaluation results of changes in spectral characteristics of a reference example (QD).

[0182] Reference Figure 3A In Example 4, it can be understood that the absorption of red light having a wavelength greater than or equal to 600 nm is low and green light can be selectively absorbed. In addition, in Example 4, it can be understood that the absorption coefficient has almost no change before and after annealing and the heat resistance is high.

[0183] On the other hand, Figure 3C to Figure 3E As shown, in Comparative Example 7 (F12-SubPc-Cl), Comparative Example 8 (SubPc-OC6F5) and Comparative Example 9 (SubPc-Cl), it can be understood that the absorption of red light with a wavelength greater than or equal to 600nm is high and red light can be absorbed. In addition, in Comparative Examples 7 to 9, it can be understood that the absorption coefficient changes greatly before and after annealing and the heat resistance is still low.

[0184] In addition, it can be understood that Example 4 has Figure 3E Therefore, it can be understood that when the subphthalocyanine derivative according to the first embodiment of the present disclosure forms a bulk heterogeneous mixed film together with the quinacridone derivative, the wavelength band of the light to be absorbed will not be widened, and a photoelectric conversion film having a steep absorption peak in the green band can be formed.

[0185] Based on the above results, it can be understood that since the subphthalocyanine derivative according to the first embodiment of the present disclosure can selectively absorb green light, it is suitable as a material for a green photoelectric conversion film of a solid-state image sensor.

[0186] (Evaluation of Photoelectric Conversion Element)

[0187] In addition, the photoelectric conversion element according to the first embodiment of the present disclosure is produced by the following manufacturing method. However, the structure and manufacturing method of the photoelectric conversion element to be described below are just examples. The structure and manufacturing method of the photoelectric conversion element according to the first embodiment of the present disclosure are not limited to the following examples.

[0188] Here, in the following examples, F6-SubPc-Cl, F6-SubPc-OC6F5, F12-SubPc-Cl and SubPc-OC6F5 were synthesized, sublimation purified and used by the above method. In addition, as SubPc-Cl, quinacridone and N,N'-dimethylquinacridone, sublimation purified products purchased from Tokyo Chemical Industry Co., Ltd. were used.

[0189] (Example 5)

[0190] First, the glass substrate with the ITO electrode was cleaned by UV / ozone treatment. In addition, the film thickness of the ITO film corresponding to the lower electrode in the glass substrate was 50 nm. Next, the glass substrate was placed in an organic deposition device and the pressure was reduced to less than or equal to 1×10 -5 Pa, and while rotating the substrate holder, F6-SubPc-Cl and quinacridone were deposited by a resistance heating method. Further, deposition was performed at a deposition rate of 0.1 nm / sec so that the ratio of F6-SubPc-Cl and quinacridone became 1:1, and a total of 100 nm of film was formed to form a photoelectric conversion layer.

[0191] Furthermore, an AlSiCu film with a film thickness of 100 nm was formed on the photoelectric conversion layer by a deposition method to form an upper electrode. Using the above manufacturing method, a photoelectric conversion element with a photoelectric conversion area of ​​1 mm×1 mm was manufactured.

[0192] (Example 6)

[0193] A photoelectric conversion element was produced by the same method as in Example 5, except that F6-SubPc-OC6F5 was used instead of F6-SubPc-Cl used in Example 5.

[0194] (Example 7)

[0195] A photoelectric conversion element was produced by the same method as in Example 5, except that N,N′-dimethylquinacridone (DMQD) represented by the following structural formula was used instead of the quinacridone used in Example 5.

[0196] [Chemical formula 14]

[0197]

[0198] (Comparative Example 10)

[0199] A photoelectric conversion element was produced by the same method as in Example 5, except that SubPc-Cl was used instead of F6-SubPc-Cl used in Example 5.

[0200] (Comparative Example 11)

[0201] A photoelectric conversion element was produced by the same method as in Example 5, except that SubPc-OC6F5 was used instead of F6-SubPc-Cl used in Example 5.

[0202] (Comparative Example 12)

[0203] A photoelectric conversion element was produced by the same method as in Example 5, except that F12-SubPc-Cl was used instead of F6-SubPc-Cl used in Example 5.

[0204] (Comparative Example 13)

[0205] A photoelectric conversion element was produced by the same method as in Example 5, except that N,N′-dimethylquinacridone and SubPc—Cl were used instead of quinacridone and F6-SubPc—Cl used in Example 5.

[0206] (Comparative Example 14)

[0207] A photoelectric conversion element was produced by the same method as in Example 5, except that N,N′-dimethylquinacridone and SubPc-OC6F5 were used instead of quinacridone and F6-SubPc-Cl used in Example 5.

[0208] (Comparative Example 15)

[0209] A photoelectric conversion element was produced by the same method as in Example 5, except that SubPc—Cl was used instead of quinacridone used in Example 5.

[0210] (Evaluation results)

[0211] First, the photoelectric conversion efficiency and spectral characteristics of the photoelectric conversion elements according to Examples 5 to 7 and Comparative Examples 10 to 15 manufactured as described above were evaluated.

[0212] The photoelectric conversion efficiency was evaluated by measuring the external quantum efficiency using a semiconductor parameter analyzer. Specifically, the intensity was 1.62 μW / cm 2 Light from the light source passes through the filter and irradiates the photoelectric conversion element, and the external quantum efficiency is calculated from the bright current value and the dark current value when the bias voltage applied between the electrodes is set to -1 V. The external quantum efficiency before and after annealing at 160°C for 210 minutes is measured, and the external quantum efficiency after annealing is divided by the external quantum efficiency before annealing to calculate the annealing resistance.

[0213] In addition, the spectral characteristics were evaluated using an ultraviolet-visible spectrophotometer. The absorption coefficient at 600 nm was divided by the maximum absorption wavelength λ max The absorbance ratio at 600 nm was calculated using the absorbance coefficient at 400 nm.

[0214] The results of the above evaluation are shown in the following Table 2. In Table 2, "QD" represents quinacridone, and "DMQD" represents N,N'-dimethylquinacridone.

[0215] [Table 2]

[0216]

[0217]

[0218] As shown in the results in Table 2, it can be understood that Examples 5 to 7 including the photoelectric conversion element according to the first embodiment of the present disclosure have lower absorbance ratios at 600 nm and higher annealing resistance than Comparative Examples 10 to 15. In addition, it can be understood that Examples 5 to 7 have generally higher external quantum efficiencies after annealing than Comparative Examples 10 to 15.

[0219] Specifically, it can be understood that Examples 5 to 7 contain the subphthalocyanine derivative and the quinacridone derivative according to the first embodiment of the present disclosure, and therefore Examples 5 to 7 have lower absorbance ratios at 600 nm and higher annealing resistance than Comparative Examples 11 to 15. In addition, since Comparative Example 10 has high annealing resistance but also has a high absorbance ratio at 600 nm, Comparative Example 10 is not preferred.

[0220] Subsequently, in Examples 5 to 7 and Comparative Examples 10 to 15, the HOMO level and the LUMO level of the subphthalocyanine derivative and the quinacridone derivative used in the photoelectric conversion layer were measured.

[0221] In addition, in order to measure the HOMO level, a sample in which each organic material was formed into a 20 nm film by a deposition method on a silicon substrate that had been treated with UV / ozone was used. The HOMO level of the sample in which each organic material was formed into a film was calculated using an ultraviolet photoelectron spectroscopy (UPS) method.

[0222] In addition, in order to measure the LUMO energy level, a sample in which each organic material is formed into a 50 nm film by a deposition method on a quartz substrate that has been treated with UV / ozone is used. First, the transmittance and reflectance of the sample are measured using a spectrophotometer (JASCO V-570), and the absorption coefficient α relative to the wavelength is calculated. Next, the absorption end of the visible light region of the calculated absorption coefficient α is calculated as the HOMO-LUMO energy gap, and the HOMO-LUMO energy gap is subtracted from the HOMO energy level to calculate the LUMO energy level.

[0223] The measured HOMO energy level, LUMO energy level and maximum absorption wavelength λ of the subphthalocyanine derivative and quinacridone derivative are shown in Table 3 below. max In Table 3, "QD" represents quinacridone, and "DMQD" represents N,N'-dimethylquinacridone.

[0224] [Table 3]

[0225]

[0226]

[0227] As shown in the results in Table 3, it can be understood that “F6-SubPc-Cl” used as the subphthalocyanine derivative according to the first embodiment of the present disclosure has a shorter maximum absorption wavelength λ than “SubPc-Cl”, “SubPc-OC6F5”, and “F12-SubPc-Cl” used as the subphthalocyanine derivative according to the comparative example even in a thin film. max .

[0228] In addition, it can be understood that in the "F6-SubPc-Cl" used as the subphthalocyanine derivative according to the first embodiment of the present disclosure, the LUMO energy level difference between the "QD" and the "DMQD" forming the bulk heterogeneous hybrid film in Example 5 or 7 is included in the preferred range of the first embodiment of the present disclosure (greater than or equal to 0.1eV and less than or equal to 1.0eV).

[0229] As can be understood from the above results, when the photoelectric conversion film according to the first embodiment of the present disclosure contains the quinacridone derivative represented by the general formula (1) and the subphthalocyanine derivative represented by the general formula (2), the heat resistance can be increased and green light can be selectively absorbed. Therefore, since the photoelectric conversion film according to the first embodiment of the present disclosure can be suitably used as a green photoelectric conversion film in a solid-state image sensor, the sensitivity of the solid-state image sensor can be increased.

[0230] 3. Second Implementation Method

[0231] (3.1. Configuration of Photoelectric Conversion Film According to Second Embodiment)

[0232] Next, a photoelectric conversion film according to a second embodiment of the present disclosure will be described. The photoelectric conversion film according to the second embodiment of the present disclosure is a photoelectric conversion film including a transparent compound represented by the following general formula (3) or (4) and not absorbing visible light.

[0233] [Chemical formula 15]

[0234]

[0235]

[0236] In the above general formula (3), R 21 ~R 32 Each independently represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl, or R 21 ~R 32 Any at least two adjacent ones of are condensed to form an aryl or heteroaryl group.

[0237] In the above general formula (4), R 41 ~R 48 Each independently represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, acylimido, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl, or R 41 ~R 48Any at least two adjacent ones of the groups are condensed to form an aryl group or a heteroaryl group, and Ar1 to Ar4 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

[0238] Here, the photoelectric conversion film according to the second embodiment of the present disclosure may also include an organic dye compound, and similar to the first embodiment, may be formed as a bulk heterogeneous mixed film. In this case, for example, because the organic dye compound is used as a p-type photoelectric conversion material and the transparent compound represented by the general formula (3) or (4) is used as an n-type photoelectric conversion material, a bulk heterojunction is formed therebetween.

[0239] Here, as explained in the first embodiment of the present disclosure, in the bulk heterogeneous mixed film, the spectral characteristics are affected by both the spectral characteristics of the mixed p-type photoelectric conversion material and the n-type photoelectric conversion material. Therefore, when the spectral characteristics of the p-type photoelectric conversion material and the n-type photoelectric conversion material do not match, the photoelectric conversion film formed as the bulk heterogeneous mixed film has a wide band of light to be absorbed, and may not obtain suitable spectral characteristics as a photoelectric conversion film in a solid-state image sensor.

[0240] In the photoelectric conversion film according to the second embodiment of the present disclosure, when a transparent compound that does not absorb visible light and is represented by the general formula (3) or (4) is used, the photoelectric conversion film can be prevented from widening the wavelength band of light to be absorbed in the photoelectric conversion film. Specifically, in the photoelectric conversion film according to the second embodiment of the present disclosure, since the transparent compound represented by the general formula (3) or (4) does not absorb visible light, it can have spectral characteristics that reflect the spectral characteristics of the organic dye compound contained therein.

[0241] As the organic dye compound contained in the photoelectric conversion film according to the second embodiment of the present disclosure, any one can be used. For example, as the organic dye compound, cyanine dyes, styryl dyes, semi-cyanine dyes, merocyanine dyes (including zero-methine merocyanine and simple merocyanine), trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodanine dyes, composite cyanine dyes, composite merocyanine dyes, heteropolar dyes, oxonol dyes, semi-oxonol dyes, aromatic acid cyanine dyes, keto acid dyes, azamethine dyes, coumarin dyes, arylide dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, spiro compounds, metallocene dyes, fluorenone dyes, Fulginate dye, perylene dye, pyrinone dye, phenazine dye, phenothiazine dye, quinone dye, diphenylmethane dye, polyene dye, acridine dye, acridone dye, diphenylamine dye, quinacridone dye, quinophthalone dye, phenoxazine dye, phthalic perylene dye, dione pyrrolopyrrole dye, dioxane dye, porphyrin dye, chlorophyll dye, phthalocyanine dye, metal complex dye or condensed aromatic carbocyclic dye (for example, naphthalene derivative, anthracene derivative, phenanthrene derivative, tetraphenyl derivative, pyrene derivative, perylene derivative and fluoranthene derivative). In addition, in the second embodiment of the present disclosure, as the organic dye compound, quinacridone derivative is more preferably used.

[0242] For example, when the photoelectric conversion film according to the second embodiment of the present disclosure includes a quinacridone derivative represented by the general formula (1), it can have a spectral characteristic in which the spectral characteristic of the quinacridone derivative represented by the general formula (1) is reflected. In this case, since the photoelectric conversion film according to the second embodiment of the present disclosure can selectively absorb green light similar to the quinacridone derivative represented by the general formula (1), it is possible to achieve a suitable spectral characteristic as a photoelectric conversion film for green light in a solid-state image sensor.

[0243] In addition, the transparent compound represented by the general formula (3) or (4) can form a bulk heterogeneous mixed layer including crystalline particles of a size suitable for charge separation from the quinacridone derivative represented by the general formula (1). Therefore, in the photoelectric conversion film according to the second embodiment of the present disclosure, the charge separation of the excitons generated when the quinacridone derivative absorbs light can be carried out quickly at each interface. In particular, because the transparent compound represented by the general formula (3) or (4) has electron accepting ability and has high electron mobility, charge separation can be efficiently carried out on the bulk heterogeneous mixed film, and the photoelectric conversion efficiency of the photoelectric conversion film can be increased.

[0244] In the photoelectric conversion film according to the second embodiment of the present disclosure, the mixing ratio of the transparent compound represented by the general formula (3) or (4) and the organic dye compound can be any ratio, but, for example, transparent compound: organic dye compound = 10:90 or 90:10 (volume ratio) is preferred, and 20:80 to 50:50 (volume ratio) is more preferred. On the other hand, when the absolute amount of the organic dye compound contained in the photoelectric conversion film is too small, it is not preferred because there may be insufficient absorption of incident light by the dye. In addition, when the absolute amount of the transparent compound contained in the photoelectric conversion film is too small, it is not preferred because a conductive path between the transparent compound and the organic dye compound required for the generated carriers (i.e., electrons and holes) to smoothly move to the corresponding electrode is not formed.

[0245] Here, in the general formula (3), R 21 ~R 32 is hydrogen or any substituent, preferably, R 21 , R 24 , R 25 , R 28 , R 29 and R 32 It may be all hydrogen.

[0246] For example, as specific examples of the transparent compound represented by the general formula (3), compounds represented by the following structural formulas can be cited. However, the transparent compound represented by the general formula (3) according to the second embodiment of the present disclosure is not limited to the following exemplary compounds.

[0247] [Chemical formula 16]

[0248]

[0249] In addition, in the general formula (4), R 41 ~R 48 Each independently represents hydrogen or any substituent, and Ar1 to Ar4 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

[0250] As the aryl group that can be obtained from Ar1 to Ar4, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl and indenyl are exemplified. In addition, as the heteroaryl group that can be obtained from Ar1 to Ar4, thienyl, furanyl, pyrrolyl, thiazolyl, thiadiazolyl, imidazolyl, oxazolyl, oxadiazolyl, pyridyl and pyrimidyl are exemplified.

[0251] In addition, Ar1 to Ar4 may be aryl or heteroaryl groups having a substituent. As the substituents of Ar1 to Ar4, halogen, hydroxyl, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino and alkoxycarbonyl are exemplified.

[0252] In the general formula (4), preferably, the substituents of Ar1 to Ar4 and R 41 ~R 48 At least one of them is an electron-withdrawing group. In other words, preferably, the transparent compound represented by the general formula (4) has at least one electron-withdrawing group as a substituent. In this case, in the transparent compound represented by the general formula (4), since the LUMO energy level becomes deeper (the absolute value increases) and becomes a LUMO energy level that can effectively perform charge separation with the organic dye compound, the photoelectric conversion efficiency can be increased.

[0253] In addition, in order to set the LUMO energy level of the transparent compound represented by the general formula (4) to a more suitable value, preferably, the transparent compound represented by the general formula (4) includes a plurality of electron-withdrawing groups, and preferably, the included substituent has a higher electron-withdrawing ability. In addition, when Ar1 to Ar4 include an electron-withdrawing group as a substituent, the substitution position of the electron-withdrawing group is preferably a para position relative to the binding position of Ar1 to Ar4 and the triazine ring. In this case, because the transparent compound represented by the general formula (4) has a LUMO energy level that can more effectively perform charge separation with the organic dye compound, the photoelectric conversion efficiency of the photoelectric conversion film can be increased.

[0254] In the above description, the electron withdrawing group may be, for example, halogen, cyano, nitro, sulfonyl, arylsulfonyl, alkylsulfonyl, acyl, acylamino, acyloxy, acylimido, carboxyl, formylamino, alkoxycarbonyl, halogenated alkyl and halogenated aryl.

[0255] As a preferred specific example of the transparent compound represented by the general formula (4), there can be cited the compound represented by the following structural formula. However, the transparent compound represented by the general formula (4) according to the second embodiment of the present disclosure is not limited to the following exemplary compounds. In addition, referring to the following exemplary compounds, it can be understood that when Ar1 to Ar4 are heteroaryl groups serving as electron donors, R 41 ~R 48 Preferred are electron withdrawing groups which function as electron acceptors.

[0256] [Chemical formula 17]

[0257]

[0258]

[0259] Furthermore, it is preferred that the HOMO and LUMO energy levels of the transparent compound represented by the general formula (3) or (4) are energy levels that can smoothly perform a photoelectric conversion mechanism on the organic dye compound.

[0260] Specifically, in order that the transparent compound represented by the general formula (3) or (4) can be used as an n-type photoelectric conversion material and the organic dye compound can be used as a p-type photoelectric conversion material, preferably, the LUMO energy level of the transparent compound represented by the general formula (3) or (4) is lower than the LUMO energy level of the organic dye compound.

[0261] Here, as the photoelectric conversion mechanism of the photoelectric conversion film according to the second embodiment of the present disclosure, the following mechanism can be specifically considered. That is, when the organic dye compound used as a p-type photoelectric conversion material absorbs light and is excited and the excited electrons move to the transparent compound used as an n-type photoelectric conversion material and represented by the general formula (3) or (4), charge separation is performed. In this case, preferably, the LUMO energy level of the transparent compound represented by the general formula (3) or (4) is an energy level at which the excited electrons in the organic dye compound can smoothly move to the transparent compound represented by the general formula (3) or (4).

[0262] Specifically, preferably, the difference between the LUMO level of the transparent compound represented by the general formula (3) or (4) and the LUMO level of the organic dye compound represented by the general formula (1) is greater than or equal to 0.1 eV and less than or equal to 1.0 eV.

[0263] For example, when the quinacridone derivative represented by the above general formula (1) is used as an organic dye compound, considering the LUMO energy level of the quinacridone derivative, preferably, the LUMO energy level of the transparent compound represented by the general formula (3) or (4) is greater than or equal to -4.8 eV and less than or equal to -3.5 eV, more preferably, greater than or equal to -4.5 eV and less than or equal to -3.8 eV.

[0264] In addition, preferably, the HOMO level of the transparent compound represented by the general formula (3) or (4) is, for example, greater than or equal to -7.8 eV and less than or equal to -6.5 eV, more preferably greater than or equal to -7.5 eV and less than or equal to -6.8 eV.

[0265] Here, as a compound having the same hexaazatriphenylene skeleton as the transparent compound represented by the general formula (3), for example, hexaazatriphenylene-hexacarbonitrile (HAT-CN) represented by the following structural formula can be exemplified.

[0266] [Chemical formula 18]

[0267]

[0268] For example, HAT-CN is a compound used as a charge transport material in an organic electroluminescent element. However, since the LUMO energy level of HAT-CN is about -5.58 eV, it is very different from the LUMO energy level of the organic dye compound forming the bulk heterogeneous mixed film in the photoelectric conversion film. Therefore, in the photoelectric conversion film, when HAT-CN is used as an n-type photoelectric conversion material, it is difficult to smoothly move excited electrons at the interface between HAT-CN and the organic dye compound.

[0269] Therefore, among the transparent compounds included in the photoelectric conversion film according to the second embodiment of the present disclosure, among the compounds having a structure represented by the general formula (3) or (4), a compound having a LUMO energy level relatively close to that of the organic dye compound forming the bulk heterogeneous mixed film is preferred. Specifically, it is preferred that the transparent compound represented by the general formula (3) or (4) has a structure in which the difference in LUMO energy level with the organic dye compound is greater than or equal to 0.1 eV and less than or equal to 1.0 eV.

[0270] As described above, when the photoelectric conversion film according to the second embodiment of the present disclosure includes an organic dye compound and a transparent compound represented by the general formula (3) or (4), light absorbed by the organic dye compound can be selectively photoelectrically converted. For example, when a quinacridone derivative represented by the general formula (1) is used as an organic dye compound, the photoelectric conversion film according to the second embodiment of the present disclosure can selectively photoelectrically convert green light (e.g., light having a wavelength greater than or equal to 450 nm and less than 600 nm).

[0271] In addition, since the transparent compound represented by the general formula (3) or (4) has high electron mobility and can form a bulk heterogeneous mixed film with a high charge separation efficiency together with the organic dye compound, the photoelectric conversion efficiency of the photoelectric conversion film can be increased. Therefore, the photoelectric conversion film according to the second embodiment of the present disclosure can be suitably used for the photoelectric conversion film in the solid-state image sensor, and the sensitivity of the solid-state image sensor can be increased.

[0272] (3.2. Configuration of Photoelectric Conversion Element According to Second Embodiment)

[0273] Since the configuration of the photoelectric conversion element according to the second embodiment of the present disclosure is substantially the same as the configuration described in the first embodiment of the present disclosure, their detailed description will be omitted.

[0274] That is, the photoelectric conversion element according to the second embodiment of the present disclosure is different from that of the first embodiment in that the photoelectric conversion layer 108 is configured as a photoelectric conversion film containing a transparent compound represented by the general formula (3) or (4).

[0275] (3.3. Example according to the second embodiment)

[0276] Hereinafter, the photoelectric conversion element according to the second embodiment of the present disclosure will be described in detail with reference to Examples and Comparative Examples. However, the following Examples are just examples, and the photoelectric conversion element according to the second embodiment of the present disclosure is not limited to the following Examples.

[0277] (Fabrication of Photoelectric Conversion Element)

[0278] In addition, the photoelectric conversion element according to the second embodiment of the present disclosure is produced by the following manufacturing method. However, the structure and manufacturing method of the photoelectric conversion element to be described below are just examples. The structure and manufacturing method of the photoelectric conversion element according to the second embodiment of the present disclosure are not limited to the following examples.

[0279] (Example 8)

[0280] First, the glass substrate with the ITO electrode was cleaned by UV / ozone treatment. In addition, the film thickness of the ITO film corresponding to the lower electrode in the glass substrate was 50 nm. Next, the glass substrate was placed in an organic deposition device and the pressure was reduced to less than or equal to 1×10 -4 Pa, and while rotating the substrate holder, 5,6,11,12,17,18-hexaazatrinaphthylene (HATNA) and quinacridone represented by the following structural formula were deposited by a resistance heating method. Furthermore, deposition was performed at a deposition rate of 0.1 nm / sec so that the ratio of HATNA to quinacridone became 1:1, and a film of 100 nm in total was formed to form a photoelectric conversion layer. HATNA is a transparent compound having a structure represented by general formula (3).

[0281] Furthermore, an AlSiCu film with a film thickness of 100 nm was formed on the photoelectric conversion layer by a deposition method to form an upper electrode. Using the above manufacturing method, a photoelectric conversion element with a photoelectric conversion area of ​​1 mm×1 mm was manufactured.

[0282] [Chemical formula 19]

[0283]

[0284] (Example 9)

[0285] A photoelectric conversion element was prepared by the same method as in Example 8, except that 2,3,8,9,14,15-hexachloro-5,6,11,12,17,18-hexaazatrinaphthylene (Cl6-HATNA) represented by the following structural formula was used instead of HATNA used in Example 8. Cl6-HATNA is a transparent compound having a structure represented by the general formula (3).

[0286] [Chemical formula 20]

[0287]

[0288] (Example 10)

[0289] A photoelectric conversion element was prepared by the same method as in Example 8, except that 4,4'-bis(4,6-diphenyl-1,3,5-triazine-2-yl)biphenyl (BTB) represented by the following structural formula was used instead of HATNA used in Example 8. BTB is a transparent compound having a structure represented by the general formula (4).

[0290] [Chemical formula 21]

[0291]

[0292] (Comparative Example 16)

[0293] A photoelectric conversion element was produced by the same method as in Example 8, except that only quinacridone was used instead of HATNA and quinacridone used in Example 8 to form a photoelectric conversion layer with a film thickness of 100 nm.

[0294] (Comparative Example 17)

[0295] A photoelectric conversion element was prepared by the same method as in Example 8, except that 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine (B4PyMPM) represented by the following structural formula was used instead of HATNA used in Example 8. In addition, B4PyMPM is a transparent compound having a LUMO energy level value close to that of HATNA.

[0296] [Chemical formula 22]

[0297]

[0298] (Comparative Example 18)

[0299] A photoelectric conversion element was prepared by the same method as in Example 8, except that only subphthalocyanine chloride (SubPc-Cl) represented by the following structural formula was used instead of HATNA and quinacridone used in Example 8 to form a photoelectric conversion layer with a film thickness of 100 nm. In addition, SubPc-Cl is a transparent compound having a LUMO energy level value close to that of HATNA but absorbing light in the visible light band.

[0300] [Chemical formula 23]

[0301]

[0302] (Comparative Example 19)

[0303] A photoelectric conversion element was produced by the same method as in Example 8, except that SubPc-Cl was used instead of HATNA used in Example 8.

[0304] In the above examples, quinacridone and SubPc-Cl were purified by sublimation purchased from Tokyo Chemical Industry Co., Ltd. In addition, HATNA, Cl6-HATNA and BTB were purified by sublimation purchased from Lumtec Corp. (Taiwan).

[0305] (Evaluation of optical conversion characteristics)

[0306] First, the photoelectric conversion efficiency and spectral characteristics will be evaluated for the photoelectric conversion elements according to Examples 8 to 10 and Comparative Examples 16 to 19 manufactured above.

[0307] Here, the photoelectric conversion efficiency was evaluated by measuring the external quantum efficiency using a semiconductor parameter analyzer. Specifically, the intensity was 1.62 μW / cm 2 , light with a wavelength of 565nm is irradiated from the light source through the filter to the photoelectric conversion element, and when the bias voltage applied between the electrodes is set to -1V, the external quantum efficiency is calculated from the bright current value and the dark current value.

[0308] In addition, the spectral characteristics were evaluated using an incident photon to current conversion efficiency (IPCE) measurement device to measure the change rate of the external quantum efficiency with respect to the wavelength and calculate the half maximum full width of the peak. Specifically, 1.62 μW / cm 2 Light from the light source passes through the filter and irradiates the photoelectric conversion element, and when the bias voltage applied between the electrodes is set to -1 V, the external quantum efficiency is calculated from the bright current value and the dark current value. In addition, the above external quantum efficiency is calculated for each wavelength, and the half maximum full width of the peak is calculated.

[0309] The above evaluation results are shown in Table 4 below. Figure 4 The IPCE measurement results of Example 8 and Comparative Example 19 are shown in Table 4. In Table 4, "QD" indicates quinacridone, and "-" indicates that the corresponding material is not added. Figure 4 A graph showing the IPCE measurement results of Example 8 and Comparative Example 19 is shown, with the solid line representing Example 8 and the dotted line representing Comparative Example 19.

[0310] [Table 4]

[0311]

[0312] As shown in the results in Table 4, it can be understood that Examples 8 to 10 serving as the photoelectric conversion element according to the second embodiment of the present disclosure have much higher external quantum efficiencies than Comparative Examples 16 to 18.

[0313] Here, similar to Examples 8 to 10, Comparative Example 19 has high external quantum efficiency, but SubPc-Cl that absorbs visible light is used as an n-type photoelectric conversion material. For this reason, since the half maximum full width of the peak measured by IPCE in Comparative Example 19 is wider than that of Examples 8 to 10, this is not preferred. Specifically, as Figure 4 As shown, since the distribution peak of the external quantum efficiency in Comparative Example 19 is wider than that of Example 8 relative to the wavelength, and red light with a wavelength greater than or equal to 600nm or blue light with a wavelength less than 450nm can also be absorbed, this is not preferred.

[0314] On the other hand, Figure 4 As shown, it can be understood that the distribution peak of the external quantum efficiency of Example 8 with respect to the wavelength is steeper than that of Comparative Example 19, and that green light with a wavelength greater than or equal to 450 nm and less than 600 nm can be more selectively absorbed and photoelectric conversion can be performed. Therefore, it can be understood that because Example 8 has a higher selectivity of the wavelength of the absorbed light than Comparative Example 19, Example 8 is suitable for a photoelectric conversion element in a solid-state image sensor.

[0315] Subsequently, in Examples 8 to 10 and Comparative Examples 16 to 19, the HOMO energy level and the LUMO energy level of the p-type photoelectric conversion material and the n-type photoelectric conversion material used in the photoelectric conversion layer were measured.

[0316] Furthermore, to measure the HOMO level, a sample in which each organic material was formed into a 20 nm film by a deposition method on a silicon substrate that had been treated with UV / ozone was used. The HOMO level was calculated for the sample in which each organic material was formed into a film using the UPS method.

[0317] In addition, in order to measure the LUMO energy level, a sample in which each organic material is formed into a 50 nm film by a deposition method on a quartz substrate that has been treated with UV / ozone is used. First, the transmittance and reflectance of the sample are measured, and the absorption coefficient α relative to the wavelength is calculated. Then, the absorption end of the visible light region of the calculated absorption coefficient α is calculated as the HOMO-LUMO energy gap, and the HOMO-LUMO energy gap is subtracted from the HOMO energy level to calculate the LUMO energy level.

[0318] The measured HOMO energy levels and LUMO energy levels of the p-type photoelectric conversion material and the n-type photoelectric conversion material are shown in the following Table 5. In Table 5, "QD" means quinacridone.

[0319] [Table 5]

[0320] HOMO(eV) LUMO(eV) HATNA -6.9 -3.8 Cl6-HATNA -7.8 -5.1 BTB -6.9 -3.6 B4PyMPM -7.6 -4.05 SubPc-Cl -5.7 -3.7 QD -5.55 -3.55

[0321] As shown in the results in Table 5, the LUMO energy level difference between "HATNA" and "QD" used in Example 8 is 0.25 eV. The LUMO energy level difference between "Cl6-HATNA" and "QD" used in Example 9 is 1.55 eV. The LUMO energy level difference between "BTB" and "QD" used in Example 10 is 0.05 eV. As shown in the results in Table 4, it can be understood that Example 8 has a LUMO energy level difference included in the preferred range of the second embodiment of the present disclosure (greater than or equal to 0.1 eV and less than or equal to 1.0 eV), and the external quantum efficiency of Example 8 is higher than the external quantum efficiency of Examples 9 and 10 whose LUMO energy level differences are outside the preferred range.

[0322] In addition, "B4PyMPM" used in Comparative Example 17 is a transparent compound having a LUMO level close to the LUMO level of "HATNA" used as a transparent material according to the second embodiment of the present disclosure. However, Comparative Example 17 has an external quantum efficiency much lower than that of Examples 8 to 10. Therefore, it can be understood that in the photoelectric conversion film according to the second embodiment of the present disclosure, in order to increase the external quantum efficiency, it is important that the transparent compound has a structure represented by the general formula (3) or (4).

[0323] Specifically, when the transparent compound represented by the general formula (3) or (4) forms a bulk heterogeneous mixed film together with the organic dye compound, crystalline particles having a size suitable for charge separation can be formed. Therefore, the external quantum efficiency is considered to be increased in the photoelectric conversion film using the transparent compound represented by the general formula (3) or (4). On the other hand, because the "B4PyMPM" having a structure not represented by the general formula (3) or (4) cannot form crystalline particles having a size suitable for charge separation, it is considered difficult to increase the external quantum efficiency.

[0324] (Detailed Examination of the Transparent Compound Represented by General Formula (4))

[0325] Next, more preferred structures of the transparent compound represented by the general formula (4) will be examined.

[0326] (Synthesis of the Transparent Compound Represented by General Formula (4))

[0327] First, a method for synthesizing BTB-1 to BTB-6, which are transparent compounds represented by the general formula (4) and represented by the following structures, will be described. The purity of the synthesized BTB-1 to BTB-6 was checked using high performance liquid chromatography (HPLC), and 1 HNMR and matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOFMS) were used for identification. However, the following synthesis method to be described is only an example, and the synthesis method of the transparent compound represented by the general formula (4) is not limited to the following example.

[0328] [Chemical formula 24]

[0329]

[0330]

[0331] Synthesis of BTB-1

[0332] BTB-1 was synthesized by the following reaction formula 5.

[0333] [Chemical formula 25]

[0334] Reaction (5)

[0335]

[0336] Under argon (Ar) atmosphere, biphenyl dicarbonyl chloride (28.8 g, 103 mmol), thionyl chloride (SOCl2) (8.43 g, 70.9 mmol), o-dichlorobenzene (405 mL), aluminum chloride (30.6 g, 230 mmol) and benzonitrile (61.1 g, 444 mmol) were added to a four-necked flask. The mixture was stirred well and then heated and stirred at 150° C. for 30 minutes. Subsequently, the temperature was lowered to 120° C., ammonium chloride (23.1 g, 432 mmol) was added, and the mixture was heated and stirred again at 170° C. for 4 hours.

[0337] After the temperature was cooled to room temperature, the reaction solution was mixed with a solution in which 28% ammonia water (400 mL) and methanol (3 L) were mixed, and the precipitated solid was filtered and extracted. The precipitated solid was suspended and washed with pure water (1 L), and suspended and washed again with methanol (1 L) to obtain a gray solid. In addition, the obtained gray solid was sublimated and purified twice to obtain BTB-1 (11.4 g, yield 18%) as the target compound.

[0338] Synthesis of BTB-2

[0339] BTB-2 was synthesized by the same method as in Reaction Scheme 5 above, except that 4-fluoro-benzonitrile was used instead of benzonitrile.

[0340] Synthesis of BTB-3

[0341] BTB-3 was synthesized by the same method as in the above reaction formula 5, except that 4-trifluoromethylbenzonitrile was used instead of benzonitrile.

[0342] Synthesis of BTB-4

[0343] BTB-4 was synthesized by the same method as in Reaction Scheme 5 above, except that 4-chloro-benzonitrile was used instead of benzonitrile.

[0344] Synthesis of BTB-5

[0345] BTB-5 was synthesized by the same method as in the above reaction formula 5, except that tetrafluorodiphenylphosgene was used instead of diphenylphosgene.

[0346] Synthesis of BTB-6

[0347] BTB-6 was synthesized by the same method as in Reaction Scheme 5 above, except that tetrafluorodiphenylphosgene was used instead of diphenylphosgene and 4-chloro-benzonitrile was used instead of benzonitrile.

[0348] (Evaluation of Spectral Characteristics of the Transparent Compound Represented by General Formula (4))

[0349] Next, a single-layer film sample of the transparent compound represented by the general formula (4) was prepared, and the spectral characteristics of the transparent compound represented by the general formula (4) were identified.

[0350] Specifically, samples were prepared by forming each organic material (BTB-1 to BTB-6) into a 50 nm film at a deposition rate of 0.05 nm / sec on a quartz substrate that had been treated with UV / ozone. Then, the transmittance and reflectance of the prepared samples were measured using a spectrophotometer (JASCO V-570), and the absorption coefficient α relative to the wavelength was calculated. Figure 5 The measurement results of the absorption coefficient α are shown in FIG. Figure 5 The graphs of the absorption coefficients α of BTB-1 to BTB-6 in the range of 300 nm to 800 nm are shown.

[0351] like Figure 5 As shown, it can be understood that all BTB-1 to BTB-6 in the transparent compound represented by the general formula (4) have a low absorption coefficient in the wavelength range of 400 nm to 800 nm. In other words, it can be understood that BTB-1 to BTB-6 in the transparent compound represented by the general formula (4) are transparent compounds that do not absorb light in the visible light band.

[0352] (Evaluation of electrical properties of the transparent compound represented by the general formula (4))

[0353] Subsequently, a photoelectric conversion element was produced using the transparent compound represented by the general formula (4), and the electrical characteristics of the photoelectric conversion element were evaluated.

[0354] (Example 11)

[0355] First, the glass substrate with the ITO electrode was cleaned by UV / ozone treatment. In addition, the film thickness of the ITO film corresponding to the lower electrode in the glass substrate was 50 nm. Next, the glass substrate was placed in an organic deposition device and the pressure was reduced to less than or equal to 1×10 -5 Pa, and while rotating the substrate holder, the above-synthesized BTB-1 and quinacridone (a product after sublimation purification manufactured by Tokyo Chemical Industry Co., Ltd.) were deposited by a resistance heating method. In addition, deposition was performed at deposition rates of 0.03 nm / sec and 0.07 nm / sec, respectively, so that the ratio of BTB-1 to quinacridone became 3:7, and a film of 120 nm in total was formed to form a photoelectric conversion layer.

[0356] Subsequently, a 0.5 nm LiF film was deposited at 0.002 nm / sec on the photoelectric conversion layer, and a 100 nm thick AlSiCu film was further formed by deposition to form an upper electrode. Using the above method, a photoelectric conversion element including a photoelectric conversion area of ​​1 mm×1 mm was manufactured.

[0357] (Examples 12 to 16)

[0358] A photoelectric conversion element was produced by the same method as in Example 11, except that BTB-2 to BTB-6 were used instead of BTB-1 used in Example 11.

[0359] (Comparative Example 20)

[0360] A photoelectric conversion element was produced by the same method as in Example 11, except that quinacridone was used instead of BTB-1 used in Example 11 and only quinacridone was used to form the photoelectric conversion layer.

[0361] The photoelectric conversion efficiency was evaluated for the photoelectric conversion elements according to Examples 11 to 16 and Comparative Example 20 manufactured above. Here, the photoelectric conversion efficiency was evaluated by measuring the external quantum efficiency using a semiconductor parameter analyzer. Specifically, the intensity was 1.62 μW / cm 2 Light from the light source is irradiated to the photoelectric conversion element through the optical filter, and when the bias voltage applied between the electrodes is set to -1 V, the external quantum efficiency is calculated from the bright current value and the dark current value.

[0362] The evaluation results are shown in the following Table 6. In Table 6, "QD" indicates quinacridone, and "-" indicates that the corresponding material was not added.

[0363] In addition, the external quantum efficiency before and after the annealing treatment was evaluated. The annealing treatment was performed by heating the photoelectric conversion element using a hot plate in a glove box. Here, the heating temperature was 160° C. and the heating time was 210 minutes.

[0364] [Table 6]

[0365]

[0366] As shown in the results in Table 6, it can be understood that Examples 11 to 16 have higher external quantum efficiencies than Comparative Example 20. In addition, it can be understood that BTB-1 to BTB-6 among the transparent compounds represented by the general formula (4) have high heat resistance because the external quantum efficiencies of Examples 11 to 16 are not significantly reduced before and after annealing.

[0367] In addition, by comparing Example 11 with Examples 12 to 16, it can be understood that Examples 12 to 16 using BTB-2 to BTB-6 including an electron-withdrawing group as a substituent have higher external quantum efficiencies than Example 11 using BTB-1 not including an electron-withdrawing group as a substituent. Therefore, it can be understood that the transparent compound represented by the general formula (4) preferably includes an electron-withdrawing group as a substituent. Specifically, in the general formula (4), it can be understood that the substituents of Ar1 to Ar4 and R 41 ~R 48 At least one of the groups is preferably an electron withdrawing group.

[0368] As can be understood from the above results, when the photoelectric conversion element according to the second embodiment of the present disclosure contains the transparent compound represented by the general formula (3) or (4), the photoelectric conversion efficiency can be increased while selectively absorbing light of a specific wavelength. Therefore, since the photoelectric conversion element according to the second embodiment of the present disclosure can be used as a photoelectric conversion element in a solid-state image sensor, the sensitivity of the solid-state image sensor can be increased.

[0369] 4. Third Implementation Method

[0370] (4.1. Configuration of Photoelectric Conversion Element According to Third Embodiment)

[0371] Next, a photoelectric conversion element according to a third embodiment of the present disclosure will be described. The photoelectric conversion element according to the third embodiment of the present disclosure is a photoelectric conversion element including a hole blocking layer and having a difference between an ionization potential of the hole blocking layer and a work function of an electrode adjacent to the hole blocking layer of greater than or equal to 2.3 eV.

[0372] Specifically, like the first embodiment of the present disclosure, the photoelectric conversion element according to the third embodiment of the present disclosure includes a substrate 102, a lower electrode 104 disposed on the substrate 102, an electron blocking layer 106 disposed on the lower electrode 104, a photoelectric conversion layer 108 disposed on the electron blocking layer 106, a hole blocking layer 110 disposed on the photoelectric conversion layer 108, and an upper electrode 112 disposed on the hole blocking layer 110. In addition, in the photoelectric conversion element according to the third embodiment of the present disclosure, the difference between the ionization potential of the hole blocking layer 110 and the work function of the upper electrode 112 is greater than or equal to 2.3 eV. In addition, the ionization potential of the hole blocking layer 110 corresponds to the absolute value of the energy of the HOMO level of the compound forming the hole blocking layer 110.

[0373] Generally, in the photoelectric conversion element used in the solid-state image sensor, in many cases, in order to increase the sensitivity, a voltage is applied from the outside to increase the photoelectric conversion efficiency and the response speed. However, when a voltage is applied from the outside to the photoelectric conversion element, because the number of holes and electrons injected from the electrode due to the external electric field increases, the dark current flowing increases regardless of the incidence of light. In the photoelectric conversion element used in the solid-state image sensor, in order to extract the difference between the dark current when no light is incident and the bright current when light is incident as a signal, when the dark current increases, the S / N ratio may decrease.

[0374] In particular, when the temperature of the use environment is high (for example, greater than or equal to 50° C.), since the dark current flowing in the photoelectric conversion element increases as the temperature rises, it is necessary to suppress the dark current.

[0375] In the photoelectric conversion element according to the third embodiment of the present disclosure, dark current can be suppressed by using a hole blocking layer whose ionization potential is greater than or equal to 2.3 eV compared to the work function of the adjacent electrode. In particular, in the photoelectric conversion element according to the third embodiment of the present disclosure, dark current can be suppressed from increasing even in a high temperature environment (e.g., greater than or equal to 50°C).

[0376] In addition, preferably, the energy difference between the ionization potential of the hole blocking layer 110 (i.e., the absolute value of the HOMO energy level of the compound forming the hole blocking layer 110) and the work function of the adjacent electrode is higher. Therefore, the upper limit of the energy difference between the ionization potential of the hole blocking layer 110 and the work function of the adjacent electrode is not particularly limited, but may be, for example, less than or equal to 3.0 eV.

[0377] For example, when the upper electrode 112 adjacent to the hole blocking layer 110 is formed of indium tin oxide (ITO) as a transparent conductive material, because the work function of indium tin oxide is 4.8 eV, preferably, the HOMO energy level of the compound forming the hole blocking layer 110 is less than or equal to -6.8 eV, more preferably, less than or equal to -7.1 eV.

[0378] In addition, the upper electrode 112 adjacent to the hole blocking layer 110 may be formed of a conductive material, but the material forming the upper electrode 112 is not limited to the above indium tin oxide. For example, the upper electrode 112 may be formed of a transparent conductive material and may be formed of indium zinc oxide (IZO), a graphene transparent electrode, etc.

[0379] In addition, it is preferred that the LUMO energy level of the compound forming the hole blocking layer 110 is the same as or shallower (smaller in absolute value) than the LUMO energy level of the n-type photoelectric conversion material of the adjacent photoelectric conversion layer 108. In this case, the hole blocking layer 110 can effectively move the electrons generated in the photoelectric conversion layer 108 due to photoelectric conversion to the upper electrode 112. In addition, in order to more effectively move the electrons generated in the photoelectric conversion layer 108 to the upper electrode 112, it is preferred that the difference between the LUMO energy level of the compound forming the hole blocking layer 110 and the LUMO energy level of the n-type photoelectric conversion material of the adjacent photoelectric conversion layer 108 is smaller.

[0380] For example, when the n-type photoelectric conversion material contained in the photoelectric conversion layer 108 is a subphthalocyanine derivative, preferably, the LUMO energy level of the compound forming the hole blocking layer 110 is greater than or equal to -5.5 eV and less than or equal to -3.3 eV, more preferably, greater than or equal to -5.0 eV and less than or equal to -3.5 eV.

[0381] In addition, preferably, the film thickness of the hole blocking layer 110 is greater than or equal to 1 nm and less than or equal to 50 nm, more preferably, greater than or equal to 2 nm and less than or equal to 30 nm, and most preferably, greater than or equal to 5 nm and less than or equal to 10 nm. When the film thickness of the hole blocking layer 110 is within the above range, the hole blocking layer 110 can effectively move electrons from the photoelectric conversion layer 108 to the upper electrode 112 while suppressing hole injection from the upper electrode 112.

[0382] Here, it is preferred that the hole blocking layer 110 contains a compound represented by the following general formula (5).

[0383] [Chemical formula 26]

[0384]

[0385] In the above general formula (5), R 50 It represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl, and Ar5 to Ar8 represent substituted or unsubstituted heteroaryl.

[0386] The compound represented by the general formula (5) above has a deep HOMO level (the absolute value of the energy of the HOMO level is high) and a high ionization potential. Therefore, in the compound represented by the general formula (5), the difference between the ionization potential of the hole blocking layer 110 and the work function of the adjacent upper electrode 112 can be set to be greater than or equal to 2.3 eV. Therefore, the hole blocking layer 110 can suppress the injection of holes from the upper electrode 112 due to the external electric field, and can suppress dark current even in a high temperature environment.

[0387] In the general formula (5), it is preferred that the substituents of Ar5 to Ar8 and R 50 At least one substituent in is an electron-withdrawing group. In other words, the compound represented by the general formula (5) preferably has at least one electron-withdrawing group as a substituent. In this case, in the compound represented by the general formula (5), because the HOMO energy level becomes deeper (the absolute value increases) and the ionization potential increases, the difference in work function with the adjacent upper electrode 112 becomes larger. Because the hole blocking layer 110 including the compound represented by the general formula (5) can further suppress the injection of holes from the upper electrode 112, the dark current can be further suppressed.

[0388] In addition, in order to set the HOMO energy level of the compound represented by the general formula (5) to a deeper value, it is preferred that the compound represented by the general formula (5) includes more electron-withdrawing groups, and preferably, the electron-withdrawing ability of the included substituent is set to be higher. In this case, since the compound represented by the general formula (5) can further suppress the injection of holes from the upper electrode 112, the dark current can be further suppressed.

[0389] In the above description, the electron withdrawing group may be, for example, halogen, cyano, nitro, sulfonyl, arylsulfonyl, alkylsulfonyl, acyl, acylamino, acyloxy, acylimido, carboxyl, formylamino, alkoxycarbonyl, halogenated alkyl, and halogenated aryl.

[0390] As preferred specific examples of the compound represented by the above general formula (5), there can be exemplified compounds represented by the following structural formulas. However, the compound represented by the general formula (5) according to the third embodiment of the present disclosure is not limited to the following exemplary compounds.

[0391] [Chemical formula 27]

[0392]

[0393] In addition, in the photoelectric conversion element according to the third embodiment of the present disclosure, since the constitutions of the substrate 102, the lower electrode 104, the electron blocking layer 106, the photoelectric conversion layer 108, and the upper electrode 112 are substantially the same as those of the first embodiment, their detailed description will be omitted. However, preferably, the photoelectric conversion layer 108 is formed in the above-mentioned photoelectric conversion film according to the first embodiment and the second embodiment.

[0394] As described above, when a hole blocking layer having an ionization potential that is greater than or equal to 2.3 eV different from the work function of an adjacent electrode is used, the photoelectric conversion element according to the third embodiment of the present disclosure can suppress dark current. In particular, in the photoelectric conversion element according to the third embodiment of the present disclosure, even in a high temperature environment (e.g., greater than or equal to 50° C.), the increase in dark current can be suppressed.

[0395] In addition, in the photoelectric conversion element according to the third embodiment of the present disclosure, when the compound represented by the general formula (5) is used in the hole blocking layer, the energy difference between the ionization potential of the hole blocking layer and the work function of the adjacent electrode can be set to be greater than or equal to 2.3 eV. Therefore, in the photoelectric conversion element according to the third embodiment of the present disclosure, dark current can be suppressed while maintaining high photoelectric conversion efficiency.

[0396] (4.2. Example according to the third embodiment)

[0397] Hereinafter, the photoelectric conversion element according to the third embodiment of the present disclosure will be described in detail with reference to Examples and Comparative Examples. However, the following Examples are just examples, and the photoelectric conversion element according to the third embodiment of the present disclosure is not limited to the following Examples.

[0398] (Synthesis of the compound represented by the general formula (5))

[0399] First, the synthesis method of the compound represented by the general formula (5) will be described. Specifically, B4PyMPM and B3PyMPM represented by the following structural formulas were synthesized. 1 HNMR and FD-MS were used to identify the synthesized B4PyMPM and B3PyMPM. However, the synthesis method to be described below is only an example, and the synthesis method of the compound represented by the general formula (5) is not limited to the following example.

[0400] [Chemical formula 28]

[0401]

[0402] Synthesis of B4PyMPM

[0403] B4PyMPM was synthesized by the following reaction formulas 6 and 7.

[0404] [Chemical formula 29]

[0405] Reaction (6)

[0406]

[0407] Reaction (7)

[0408]

[0409] First, under a nitrogen atmosphere, 4,6-dichloro-2-methyl-pyrimidine (5.0 g, 30.7 mmol), 3,5-dichlorophenylboric acid (12.9 g, 67.7 mmol), dichlorobis(triphenylphosphine)palladium(II) (PdCl2(PPh3)2) (1.07 g, 0.96 mmol) and an aqueous sodium carbonate solution (1.0 mol / L, 150 ml) were added to a three-necked flask, and the mixture was stirred for 10 minutes in an acetonitrile (500 ml) solvent. The reaction solution was mixed with water, and the precipitated solid was extracted by filtration. The precipitated solid was suspended and washed with pure water to obtain a white solid. In addition, the obtained white solid was recrystallized to obtain intermediate compound A (11.8 g, yield 72%).

[0410] Next, under a nitrogen atmosphere, intermediate compound A (4.6 g, 11.9 mmol), 4-pyridineboronic acid pinacol ester (10.8 g, 52.6 mmol), tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3) (0.43 g, 0.48 mmol), tricyclohexylphosphine (PCy3) (0.322 g, 1.15 mmol) and potassium phosphate aqueous solution (1.35 mol / L, 138 ml) were added to a three-necked flask, and the mixture was stirred in dioxane (440 ml) solvent for 24 hours. The reaction solution was mixed with water, and the precipitated solid was extracted by filtration. The precipitated solid was suspended and washed with pure water to obtain a white solid. In addition, the obtained white solid was sublimated and purified to obtain B4PyMPM (6.67 g, yield 77%) as the target compound.

[0411] Synthesis of B3PyMPM

[0412] In Reaction Scheme 7, B3PyMPM is synthesized by the same method as Reaction Scheme 6 or 7, except that 3-pyridineboronic acid pinacol ester is used instead of 4-pyridineboronic acid pinacol ester.

[0413] (Evaluation of Photoelectric Conversion Element)

[0414] In addition, the photoelectric conversion element according to the third embodiment of the present disclosure is produced by the following manufacturing method. However, the structure and manufacturing method of the photoelectric conversion element to be described below are just examples. The structure and manufacturing method of the photoelectric conversion element according to the third embodiment of the present disclosure are not limited to the following examples.

[0415] (Example 17)

[0416] First, the Si substrate with the ITO electrode was cleaned by UV / ozone treatment. In addition, the film thickness of the ITO film corresponding to the lower electrode in the Si substrate was 100 nm. Next, the Si substrate was placed in an organic deposition device and the pressure was reduced to less than or equal to 1×10 -5 Pa, and while rotating the substrate holder, F6-SubPc-Cl (a product after sublimation purification manufactured by Tokyo Chemical Industry Co., Ltd.) and tert-butylquinacridone (a product after sublimation purification manufactured by Tokyo Chemical Industry Co., Ltd.) were deposited by a resistance heating method. In addition, the deposition was performed at a deposition rate of 0.05 nm / sec so that the ratio of F6-SubPc-Cl and tert-butylquinacridone (BQD) became 1:1, and a film of 120 nm in total was formed to form a photoelectric conversion layer.

[0417] Next, the B4PyMPM synthesized above was deposited on the photoelectric conversion layer by a resistance heating method. The deposition rate was 0.05nm / sec, and a 5nm film was formed to form a hole blocking layer. Subsequently, an ITO film with a film thickness of 50nm was deposited on the hole blocking layer by a sputtering method to form an upper electrode. In addition, the lower electrode and the upper electrode were formed to have a photoelectric conversion area of ​​0.5mm×0.5mm. In addition, the heat treatment of the element forming the upper electrode was carried out on a hot plate in a glove box replaced with nitrogen at 160°C for 3.5 hours to make a photoelectric conversion element. Below, the structural formulas of F6-SubPc-Cl and tert-butylquinacridone (BQD) used in the photoelectric conversion layer are shown.

[0418] [Chemical formula 30]

[0419]

[0420] (Example 18)

[0421] A photoelectric conversion element was produced by the same method as in Example 17, except that the hole blocking layer was formed into a film of 10 nm.

[0422] (Example 19)

[0423] A photoelectric conversion element was produced by the same method as in Example 17, except that the hole blocking layer was formed into a film of 20 nm.

[0424] (Example 20)

[0425] A photoelectric conversion element was produced by the same method as in Example 17, except that B3PyMPM was used instead of B4PyMPM to form the hole blocking layer.

[0426] (Comparative Example 21)

[0427] A photoelectric conversion element was produced by the same method as in Example 17, except that HATNA represented by the following structural formula was used instead of B4PyMPM to form the hole blocking layer.

[0428] (Comparative Example 22)

[0429] A photoelectric conversion element was produced by the same method as in Example 17, except that Me6-HATNA represented by the following structural formula was used instead of B4PyMPM to form the hole blocking layer.

[0430] [Chemical formula 31]

[0431]

[0432] (Comparative Example 23)

[0433] A photoelectric conversion element was produced by the same method as in Example 17, except that the hole blocking layer was not formed.

[0434] (Evaluation results)

[0435] First, the HOMO level and LUMO level of the compounds (B4PyMPM, B3PyMPM, HATNA, Me6-HATNA, F6-SubPc-Cl, and BQD) used in each layer of the photoelectric conversion elements according to Examples 17 to 20 and Comparative Examples 21 to 23 were measured.

[0436] In addition, in order to measure the HOMO level, a sample in which each compound was formed into a 20 nm film by a deposition method on a silicon substrate that had been treated with UV / ozone was used. The HOMO level of the sample in which each compound was formed into a film was calculated using the UPS method.

[0437] In addition, in order to measure the LUMO energy level, a sample in which each organic material is formed into a 50 nm film by a deposition method on a quartz substrate that has been treated with UV / ozone is used. First, the transmittance and reflectance of the sample are measured, and the absorption coefficient α with respect to the wavelength is calculated. Then, the absorption end of the visible light region of the calculated absorption coefficient α is calculated as the HOMO-LUMO energy gap, and the HOMO-LUMO energy gap is subtracted from the HOMO energy level to calculate the LUMO energy level.

[0438] The measured HOMO energy level and LUMO energy level of each compound are shown in the following Table 7. In addition, the work function of ITO used in the upper electrode is 4.8 eV.

[0439] [Table 7]

[0440] (Table 7)

[0441]

[0442] As shown in the results in Table 7, it can be understood that the difference between the ionization potential (absolute value of HOMO level) of B4PyMPM used in the hole blocking layer of Examples 17 to 19 and the work function of the upper electrode (ITO) is 2.8 eV, and is included in the preferred range of the third embodiment of the present disclosure. In addition, it can be understood that the difference between the ionization potential of B3PyMPM used in the hole blocking layer of Example 20 and the work function of the upper electrode is 2.4 eV, and is included in the preferred range of the third embodiment of the present disclosure.

[0443] On the other hand, it is understood that the difference between the ionization potential of HATNA used in the hole blocking layer of Comparative Example 21 and the work function of the upper electrode is 2.1 eV, which is outside the preferred range of the third embodiment of the present disclosure. In addition, it is understood that the difference between the ionization potential of Me6-HATNA used in the hole blocking layer of Comparative Example 22 and the work function of the upper electrode is 1.5 eV, which is outside the preferred range of the third embodiment of the present disclosure.

[0444] Furthermore, the photoelectric conversion efficiency was evaluated for the photoelectric conversion elements according to Examples 17 to 20 and Comparative Examples 21 to 23 manufactured above. Furthermore, all evaluations of the photoelectric conversion elements according to Examples 17 to 20 and Comparative Examples 21 to 23 were performed in a high temperature environment of 60°C.

[0445] The photoelectric conversion efficiency was evaluated by measuring the external quantum efficiency using a semiconductor parameter analyzer. Specifically, the intensity was 1.62 μW / cm 2 , light with a wavelength of 565nm is irradiated from the light source through the filter to the photoelectric conversion element, and when the bias voltage applied between the electrodes is set to -1 V or -5 V, the external quantum efficiency is calculated from the bright current value and the dark current value. Here, the condition that the bias voltage applied between the electrodes is set to -5 V can increase the external quantum efficiency and also increase the dark current.

[0446] The above evaluation results are shown in the following Table 8. In Table 8, "-" indicates that the corresponding layer is not formed. In addition, "energy difference" represents the energy difference between the ionization potential of the hole blocking layer and the work function of the upper electrode, and is calculated by obtaining the difference between the absolute value of the HOMO energy level of each compound forming the hole blocking layer and the work function (4.8 eV) of the upper electrode (ITO) formed of ITO.

[0447] [Table 8]

[0448]

[0449] As shown in the results in Tables 7 and 8, it can be understood that in Examples 17 to 20 according to the third embodiment of the present disclosure, the dark current can be reduced at bias voltages of -1V and -5V compared to Comparative Example 23 in which the hole blocking layer is not provided. In addition, it can be understood that Examples 17 to 20 can increase the external quantum efficiency to the same degree or greater than that of Comparative Example 23 at bias voltages of -1V and -5V. However, Example 19 in which the hole blocking layer is formed as a 20nm film can reduce the dark current more than Examples 17 and 18, but has the same external quantum efficiency as Comparative Example 23 in which the hole blocking layer is not provided. Therefore, it can be understood that the preferred film thickness of the hole blocking layer that can reduce the dark current and increase the external quantum efficiency is less than or equal to 20nm.

[0450] In addition, it can be understood that in Comparative Examples 21 and 22, because the energy difference between the ionization potential of the hole blocking layer and the work function of the upper electrode is outside the preferred range according to the third embodiment of the present disclosure, the dark current at a bias voltage of -5 V increases compared to Examples 17 to 20, so this is not preferred.

[0451] In addition, comparing Example 17 and Example 20, it can be understood that Example 17 can increase the external quantum efficiency. The LUMO energy level of B4PyMPM used in the hole blocking layer of Example 17 is considered to be more preferred than the LUMO energy level of B3PyMPM used in the hole blocking layer of Example 20. Specifically, because the LUMO energy level of B4PyMPM (-4.05eV) is closer to the LUMO energy level of F6-SubPc-Cl (-4.2eV) of the n-type photoelectric conversion material used as the photoelectric conversion layer than the LUMO energy level of B3PyMPM (-3.65eV), the electrons generated by photoelectric conversion are considered to be more efficiently moved to the electrode. Therefore, it should be understood that the LUMO energy level of the compound used in the hole blocking layer is shallower (smaller in absolute value) than the LUMO energy level of the n-type photoelectric conversion material of the photoelectric conversion layer, and preferably, the difference between the LUMO energy level of the compound used in the hole blocking layer and the LUMO energy level of the n-type photoelectric conversion material is very small.

[0452] As can be understood from the above results, in the photoelectric conversion element according to the third embodiment of the present disclosure, when a hole blocking layer having an ionization potential and a work function of an adjacent electrode having a difference of greater than or equal to 2.3 eV is provided, dark current can be suppressed. In particular, the photoelectric conversion element according to the third embodiment of the present disclosure can suppress the increase of dark current under conditions of high temperature (e.g., greater than or equal to 50° C.) and high bias voltage.

[0453] 5. Application Examples of the Photoelectric Conversion Element According to the Embodiments of the Present Disclosure

[0454] Below, we will refer to Figure 6 to Figure 8 Application examples of a photoelectric conversion element including a photoelectric conversion film according to an embodiment of the present disclosure are described.

[0455] (5.1. Structure of solid-state image sensor)

[0456] First, refer to Figure 6 and Figure 7 The configuration of a solid-state image sensor to which the photoelectric conversion element according to an embodiment of the present disclosure is applied is described. Figure 6 : is a schematic diagram showing the structure of a solid-state image sensor to which the photoelectric conversion element according to the embodiment of the present disclosure is applied.

[0457] Here, in Figure 6 , pixel regions 201, 211, and 231 are regions where photoelectric conversion elements including photoelectric conversion films according to embodiments of the present disclosure are provided. In addition, control circuits 202, 212, and 242 are operation processing circuits configured to control each component in the solid-state image sensor. Logic circuits 203, 223, and 243 are signal processing circuits configured to process signals obtained by photoelectric conversion of the photoelectric conversion elements in the pixel regions.

[0458] For example, Figure 6 As shown in (A) in FIG. 8 , in a solid-state image sensor to which the photoelectric conversion element according to the embodiment of the present disclosure is applied, a pixel region 201 , a control circuit 202 , and a logic circuit 203 can be formed within one semiconductor chip 200 .

[0459] In addition, if Figure 6 As shown in (B) in FIG. 1 , a solid-state image sensor using a photoelectric conversion element according to an embodiment of the present disclosure may be a stacked solid-state image sensor in which a pixel region 211 and a control circuit 212 are formed in a first semiconductor chip 210 and a logic circuit 223 is formed in a second semiconductor chip 220 .

[0460] In addition, if Figure 6 As shown in (C) in FIG. 1 , a solid-state image sensor using a photoelectric conversion element according to an embodiment of the present disclosure may be a stacked solid-state image sensor in which a pixel region 231 is formed in a first semiconductor chip 230 and a control circuit 242 and a logic circuit 243 are formed in a second semiconductor chip 240 .

[0461] exist Figure 6 In the solid-state image sensors shown in (B) and (C) of FIG. 1 , at least one of the control circuit and the logic circuit is formed in a semiconductor chip separate from a semiconductor chip in which a pixel region is formed. Figure 6 The solid-state image sensors shown in (B) and (C) can extend the pixel area by more than Figure 6 The solid-state image sensor shown in (A) in FIG. 1 is large, so the number of pixels accommodated in the pixel area increases. Therefore, the plane resolution can be increased. For this reason, it is more preferable that the solid-state image sensor using the photoelectric conversion element according to the embodiment of the present disclosure is Figure 6 The stacked solid-state image sensor shown in (B) and (C) in FIG.

[0462] Then, refer to Figure 7 A specific structure of a solid-state image sensor to which the photoelectric conversion element according to an embodiment of the present disclosure is applied is described. Figure 7 is a cross-sectional view showing an outline of a unit pixel in a solid-state image sensor to which a photoelectric conversion element according to an embodiment of the present disclosure is applied. Figure 7 The solid-state image sensor 300 shown in FIG. 1 is a back-illuminated solid-state image sensor in which light is incident from a surface opposite to a surface on which pixel transistors and the like are formed. Figure 7 In the figure, the upper side is a light receiving surface, and the lower side is a circuit forming surface on which pixel transistors and peripheral circuits are formed.

[0463] like Figure 7 As shown, the solid-state image sensor 300 has the following structure: in the photoelectric conversion region 320, a photoelectric conversion element including a first photodiode PD1 formed in a semiconductor substrate 330, a photoelectric conversion element including a second photodiode PD2 formed in the semiconductor substrate 330, and a photoelectric conversion element including an organic photoelectric conversion film 310 formed on the back side of the semiconductor substrate 330 are stacked in the incident direction of light.

[0464] The first photodiode PD1 and the second photodiode PD2 are formed in a well region 331 which is a first conductive type (eg, p-type) semiconductor region of a semiconductor substrate 330 made of silicon.

[0465] The first photodiode PD1 includes an n-type semiconductor region 332 depending on a second conductive type (e.g., n-type) impurity formed on the light receiving surface side of the semiconductor substrate 330 and an extension portion 332a formed by extending a portion to reach the surface side of the semiconductor substrate 330. A high-concentration p-type semiconductor region 334 serving as a charge accumulation layer is formed on the surface of the extension portion 332a. In addition, the extension portion 332a is formed as an extraction layer for extracting signal charges accumulated in the n-type semiconductor region 332 of the first photodiode PD1 to the surface side of the semiconductor substrate 330.

[0466] The second photodiode PD2 includes an n-type semiconductor region 336 formed on the light receiving face side of the semiconductor substrate 330 and a high-concentration p-type semiconductor region 338 formed on the surface side of the semiconductor substrate 330 and serving as a charge accumulation layer.

[0467] In the first photodiode PD1 and the second photodiode PD2 , when a p-type semiconductor region is formed at the interface of the semiconductor substrate 330 , dark current generated at the interface of the semiconductor substrate 330 can be suppressed.

[0468] Here, for example, the second photodiode PD2 formed in the area farthest from the light receiving surface is a red photoelectric conversion element that absorbs red light and performs photoelectric conversion. In addition, for example, the first photodiode PD1 formed closer to the light receiving surface side than the second photodiode PD2 is a blue photoelectric conversion element that absorbs blue light and performs photoelectric conversion.

[0469] An organic photoelectric conversion film 310 is formed on the back side of the semiconductor substrate 330 via an anti-reflection film 302 and an insulating film 306. In addition, the organic photoelectric conversion film 310 is sandwiched between an upper electrode 312 and a lower electrode 308 to form a photoelectric conversion element. Here, for example, the organic photoelectric conversion film 310 is an organic film that absorbs green light and performs photoelectric conversion, and is formed as the above-mentioned photoelectric conversion film according to the embodiment of the present disclosure. In addition, for example, the upper electrode 312 and the lower electrode 308 are made of a transparent conductive material such as indium tin oxide and indium zinc oxide.

[0470] In addition, the lower electrode 308 is connected to a vertical transfer path 348 formed from the back side of the semiconductor substrate 330 to the surface side via a contact plug 304 penetrating the anti-reflection film 302. The vertical transfer path 348 is formed to have a structure in which a connection portion 340, a barrier layer 342, a charge accumulation layer 344, and a p-type semiconductor region 346 are stacked from the back side of the semiconductor substrate 330.

[0471] The connection portion 340 includes an n-type impurity region with a high impurity concentration formed on the back side of the semiconductor substrate 330 and is formed to be in ohmic contact with the contact plug 304. The barrier layer 342 includes a p-type impurity region with a low concentration and forms a barrier between the connection portion 340 and the charge accumulation layer 344. The charge accumulation layer 344 accumulates signal charges transmitted from the organic photoelectric conversion film 310 and is formed in an n-type impurity region with a lower concentration than the connection portion 340. In addition, a p-type semiconductor region 346 with a high concentration is formed on the surface of the semiconductor substrate 330. With the p-type semiconductor region 346, dark current generated at the interface of the semiconductor substrate 330 can be suppressed.

[0472] Here, on the surface side of the semiconductor substrate 330, a multilayer wiring layer 350 including wirings 358 stacked in multiple layers is formed via an interlayer insulating layer 351. In addition, near the surface of the semiconductor substrate 330, readout circuits 352, 354, and 356 corresponding to the first photodiode PD1, the second photodiode PD2, and the organic photoelectric conversion film 310 are formed. The readout circuits 352, 354, and 356 read the signals output from each photoelectric conversion element and transmit the signals to a logic circuit (not shown). In addition, a support substrate 360 ​​is formed on the surface of the multilayer wiring layer 350.

[0473] On the other hand, on the light receiving surface side of the upper electrode 312, a light shielding film 316 is formed to shield the extension 332a of the first photodiode PD1 and the vertical transfer path 348. Here, the spaced region between the light shielding films 316 is the photoelectric conversion region 320. In addition, an on-chip lens 318 is formed on the light shielding film 316 via the planarization film 314.

[0474] The solid-state image sensor 300 to which the photoelectric conversion element according to the embodiment of the present disclosure is applied has been described above. In addition, in the solid-state image sensor 300 to which the photoelectric conversion element according to the embodiment of the present disclosure is applied, since the unit pixel is color-separated in the longitudinal direction, a filter or the like is not required.

[0475] (5.2. Composition of electronic equipment)

[0476] Next, we will refer to Figure 8 The configuration of an electronic device to which the photoelectric conversion element according to an embodiment of the present disclosure is applied is described. Figure 8 : is a block diagram showing the configuration of an electronic device to which a photoelectric conversion element according to an embodiment of the present disclosure is applied.

[0477] like Figure 8 As shown, the electronic device 400 includes an optical system 402, a solid-state image sensor 404, a digital signal processor (DSP) circuit 406, a control unit 408, an output unit 412, an input unit 414, a frame memory 416, a recording unit 418 and a power supply unit 420.

[0478] Here, the DSP circuit 406 , the control unit 408 , the output unit 412 , the input unit 414 , the frame memory 416 , the recording unit 418 , and the power supply unit 420 are connected to one another via a bus 410 .

[0479] The optical system 402 obtains incident light from the subject and forms an image on the imaging surface of the solid-state image sensor 404. In addition, the solid-state image sensor 404 includes a photoelectric conversion element according to an embodiment of the present disclosure, converts the intensity of the incident light focused on the imaging surface through the optical system 402 into an electrical signal in units of pixels, and outputs the result as a pixel signal.

[0480] The DSP circuit 406 processes the pixel signal transmitted from the solid-state image sensor 404 and outputs the result to the output unit 412, the frame memory 416, the recording unit 418, etc. In addition, the control unit 408 includes an arithmetic processing circuit, for example, and controls the operation of each component in the electronic device 400.

[0481] For example, the output unit 412 is a panel type display device such as a liquid crystal display and an organic electroluminescent display, and displays a video or a still image imaged by the solid-state image sensor 404. Here, the output unit 412 may also include a sound output device such as a speaker and a headphone. Here, for example, the input unit 414 is a device for inputting a user's operation such as a touch panel and a button, and issues operation instructions for various functions of the electronic device 400 according to the user's operation.

[0482] The frame memory 416 temporarily stores video, still images, etc. imaged by the solid-state image sensor 404. In addition, the recording unit 418 stores video, still images, etc. imaged by the solid-state image sensor 404 in a removable storage medium such as a magnetic disk, an optical disk, a magneto-optical disk, and a semiconductor memory.

[0483] The power supply unit 420 appropriately supplies various types of power used as operation power sources for the DSP circuit 406 , the control unit 408 , the output unit 412 , the input unit 414 , the frame memory 416 , and the recording unit 418 to these supply targets.

[0484] The electronic device 400 to which the photoelectric conversion element according to the embodiment of the present disclosure is applied has been described above. For example, the electronic device 400 to which the photoelectric conversion element according to the embodiment of the present disclosure is applied may be an imaging device.

[0485] 6. Summary

[0486] As described above, when the photoelectric conversion film according to the embodiment of the present disclosure includes the above-mentioned compound, light of a specific wavelength band can be selectively absorbed. Therefore, since the photoelectric conversion element including the photoelectric conversion film according to the embodiment of the present disclosure has suitable spectral characteristics as a photoelectric conversion element in a solid-state image sensor, the sensitivity and resolution of the solid-state image sensor can be increased.

[0487] The photoelectric conversion film according to the first embodiment of the present disclosure comprises a quinacridone derivative represented by the above general formula (1) and a subphthalocyanine derivative represented by the above general formula (2). The subphthalocyanine derivative represented by the above general formula (2) has high heat resistance, selectively absorbs green light and has a spectral characteristic matching that of the quinacridone derivative. Therefore, the photoelectric conversion film according to the first embodiment of the present disclosure has a steep spectral characteristic of absorbing green light. Therefore, since the photoelectric conversion film according to the first embodiment of the present disclosure can selectively absorb green light, it is suitable for a green photoelectric conversion element in a solid-state image sensor. Therefore, the sensitivity and resolution of the solid-state image sensor can be increased.

[0488] In addition, the photoelectric conversion film according to the second embodiment of the present disclosure includes a transparent compound that does not absorb visible light and is represented by the general formula (3) or (4) above. Because the transparent compound that does not absorb visible light represented by the general formula (3) or (4) above does not have an absorption band of visible light, it has no effect on the spectral characteristics of the photoelectric conversion film. Therefore, the photoelectric conversion film formed to include a transparent compound represented by the general formula (3) or (4) and an organic dye compound can have the same spectral characteristics as the organic dye compound. Therefore, since the photoelectric conversion film according to the second embodiment of the present disclosure can selectively absorb the light absorbed by the organic dye compound, it is suitable for the photoelectric conversion element in the solid-state image sensor. Therefore, the sensitivity and resolution of the solid-state image sensor can be increased.

[0489] In addition, the photoelectric conversion element according to the third embodiment of the present disclosure includes a hole blocking layer whose difference between the ionization potential and the work function of the adjacent electrode is greater than or equal to 2.3 eV. Because such a hole blocking layer can suppress the injection of holes from the electrode due to the external electric field, the dark current can be reduced. Therefore, since the photoelectric conversion element according to the third embodiment of the present disclosure can suppress the dark current, it is suitable for a solid-state image sensor. The sensitivity and resolution of the solid-state image sensor can be increased.

[0490] It should be understood by those skilled in the art that various modifications, combinations, sub-combinations and alterations may occur depending on design requirements and other factors insofar as they are within the scope of the appended claims or the equivalents thereof.

[0491] In addition, the effects described in this specification are merely illustrative and exemplary, and are not restrictive. In other words, together with or instead of the effects based on this specification, the technology according to the present disclosure can exhibit other effects that are obvious to those skilled in the art.

[0492] Furthermore, the present disclosure may also be configured as follows.

[0493] (1) A photoelectric conversion film comprising:

[0494] A quinacridone derivative represented by the following general formula (1); and

[0495] A subphthalocyanine derivative represented by the following general formula (2),

[0496] [Chemical formula 32]

[0497]

[0498] In the general formula (1),

[0499] R1~R 10Each independently represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl, or R1 to R2 are substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl. 10 Any at least two adjacent condensed aryl or heteroaryl groups, and

[0500] [Chemical formula 33]

[0501]

[0502] In general formula (2),

[0503] R 11 ~R 16 each independently represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl,

[0504] X represents any substituent selected from halogen, hydroxyl, mercapto, imido, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkylthio and substituted or unsubstituted arylthio, and

[0505] R 11 ~R 16 At least one of represents fluorine.

[0506] (2) The photoelectric conversion film according to (1), wherein R 11 ~R 16 Represents fluorine.

[0507] (3) The photoelectric conversion film according to (1) or (2), wherein X represents any substituent selected from halogen, hydroxyl, substituted or unsubstituted alkoxy and substituted or unsubstituted aryloxy.

[0508] (4) A photoelectric conversion film according to any one of (1) to (3), wherein the lowest unoccupied molecular orbital (LUMO) energy level of the subphthalocyanine derivative is deeper than the LUMO energy level of the quinacridone derivative, and the difference between the LUMO energy level of the subphthalocyanine derivative and the LUMO energy level of the quinacridone derivative is greater than or equal to 0.1 eV and less than or equal to 1.0 eV.

[0509] (5) The photoelectric conversion film according to any one of (1) to (4), wherein the quinacridone derivative and the subphthalocyanine derivative form a bulk heterogeneous film.

[0510] (6) A photoelectric conversion film comprising:

[0511] A transparent compound which does not absorb visible light and is represented by the general formula (3) or (4),

[0512] [Chemical formula 34]

[0513]

[0514]

[0515] In general formula (3),

[0516] R 21 ~R 32 Each independently represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl, or R 21 ~R 32 Any at least two adjacent condensed aryl or heteroaryl groups, and

[0517] In general formula (4),

[0518] R 41 ~R 48 Each independently represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, acylimido, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl, or R 41 ~R 48Any at least two adjacent condensed aryl or heteroaryl groups, and

[0519] Ar1 to Ar4 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

[0520] (7) The photoelectric conversion film according to (6), wherein R in the general formula (3) 21 , R 24 , R 25 , R 28 , R 29 and R 32 Represents hydrogen.

[0521] (8) The photoelectric conversion film according to (6), wherein the substituents of Ar1 to Ar4 in the general formula (4) and R 41 ~R 48 At least one of them is an electron withdrawing group.

[0522] (9) A photoelectric conversion film according to (8), wherein the electron-withdrawing group is any substituent selected from halogen, cyano, nitro, sulfonyl, arylsulfonyl, alkylsulfonyl, acyl, acylamino, acyloxy, acylimide, carboxyl, formylamino, alkoxycarbonyl, halogenated alkyl and halogenated aryl.

[0523] (10) The photoelectric conversion film according to any one of (6) to (9), further comprising:

[0524] Organic dye compounds,

[0525] The organic dye compound and the compound represented by the general formula (3) or the general formula (4) form a bulk heterogeneous film.

[0526] (11) The photoelectric conversion film according to (10), wherein the organic dye compound is a compound that absorbs green light in a wavelength band of about 450 nm or more and about 600 nm or less.

[0527] (12) The photoelectric conversion film according to (10) or (11), wherein the organic dye compound is a quinacridone derivative represented by the following general formula (1):

[0528] [Chemical formula 35]

[0529]

[0530] In the general formula (1),

[0531] R1~R 10Each independently represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl, or R1 to R2 are substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl. 10 Any at least two adjacent ones of are condensed to form an aryl or heteroaryl group.

[0532] (13) A photoelectric conversion film according to (12), wherein the LUMO energy level of the compound represented by the general formula (3) or (4) is deeper than the LUMO energy level of the quinacridone derivative, and the difference between the LUMO energy level of the compound represented by the general formula (3) or (4) and the LUMO energy level of the quinacridone derivative is greater than or equal to 0.1 eV and less than or equal to 1.0 eV.

[0533] (14) A photoelectric conversion element comprising:

[0534] Photoelectric conversion film;

[0535] a pair of electrodes disposed on both sides of the photoelectric conversion film with the photoelectric conversion film sandwiched therebetween; and

[0536] a hole blocking layer disposed between the photoelectric conversion film and an electrode,

[0537] The difference between the ionization potential of the hole blocking layer and the work function of an electrode adjacent to the hole blocking layer is greater than or equal to 2.3 eV.

[0538] (15) The photoelectric conversion element according to (14), wherein the hole blocking layer contains a compound represented by the following general formula (5),

[0539] [Chemical formula 36]

[0540]

[0541] In general formula (5),

[0542] R 50 represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl, and

[0543] Ar5 to Ar8 represent substituted or unsubstituted heteroaryl groups.

[0544] (16) The photoelectric conversion element according to (15), wherein the substituents of Ar5 to Ar8 and R 50 At least one of them is an electron withdrawing group.

[0545] (17) A photoelectric conversion element according to (16), wherein the electron-withdrawing group is any substituent selected from halogen, cyano, nitro, sulfonyl, arylsulfonyl, alkylsulfonyl, acyl, acylamino, acyloxy, acylamino, carboxyl, formylamino, alkoxycarbonyl, halogenated alkyl and halogenated aryl.

[0546] (18) The photoelectric conversion element according to (15), wherein the compound represented by the general formula (5) is a compound represented by any one of the following structural formulas.

[0547] [Chemical formula 37]

[0548]

[0549] (19) The photoelectric conversion element according to any one of (14) to (18), wherein the thickness of the hole blocking layer is greater than or equal to 5 nm and less than or equal to 20 nm.

[0550] (20) The photoelectric conversion element according to any one of (14) to (19), wherein the adjacent one electrode is a transparent electrode.

[0551] (21) The photoelectric conversion element according to (20), wherein the adjacent one electrode contains at least one of indium tin oxide and indium zinc oxide.

[0552] (22) A solid-state image sensor comprising a photoelectric conversion film comprising a quinacridone derivative represented by the following general formula (1) and a subphthalocyanine derivative represented by the following general formula (2),

[0553] [Chemical formula 38]

[0554]

[0555] In the general formula (1),

[0556] R1~R 10Each independently represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl, or R1 to R2 are substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl. 10 Any at least two adjacent condensed aryl or heteroaryl groups, and

[0557] [Chemical formula 39]

[0558]

[0559] In general formula (2),

[0560] R 11 ~R 16 each independently represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl,

[0561] X represents any substituent selected from halogen, hydroxyl, mercapto, imido, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkylthio and substituted or unsubstituted arylthio, and

[0562] R 11 ~R 16 At least one of represents fluorine.

[0563] (23) A solid-state image sensor comprising a photoelectric conversion film containing a transparent compound represented by the following general formula (3) or (4) and not absorbing visible light,

[0564] [Chemical formula 40]

[0565]

[0566] In general formula (3),

[0567] R 21 ~R 32Each independently represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl, or R 21 ~R 32 Any at least two adjacent condensed aryl or heteroaryl groups, and

[0568] In general formula (4),

[0569] R 41 ~R 48 Each independently represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, acylimido, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl, or R 41 ~R 48 Any at least two adjacent condensed aryl or heteroaryl groups, and

[0570] Ar1 to Ar4 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

[0571] (24) A solid-state image sensor comprising:

[0572] A photoelectric conversion element, the photoelectric conversion element comprising:

[0573] Photoelectric conversion film,

[0574] a pair of electrodes disposed on both sides of the photoelectric conversion film, with the photoelectric conversion film sandwiched therebetween, and

[0575] a hole blocking layer disposed between the photoelectric conversion film and an electrode,

[0576] Wherein, the difference between the ionization potential of the hole blocking layer and the work function of an adjacent electrode is greater than or equal to 2.3 eV.

[0577] (25) A solid-state image sensor according to any one of (22) to (24), wherein the photoelectric conversion film contains an organic dye compound that absorbs green light in a wavelength band greater than or equal to 450 nm and less than or equal to 600 nm and performs photoelectric conversion on the absorbed green light.

[0578] (26) A solid-state image sensor according to any one of (22) to (24), which is constructed as a stacked solid-state image sensor, including a first chip formed with a photoelectric conversion film and a second chip stacked on the first chip, which has a signal processing circuit configured to process a signal obtained by photoelectric conversion of the photoelectric conversion film.

[0579] (27) An electronic device comprising:

[0580] A solid-state image sensor comprising a photoelectric conversion film having a quinacridone derivative represented by the following general formula (1) and a subphthalocyanine derivative represented by the following general formula (2);

[0581] an optical system configured to direct incident light to the solid-state image sensor; and

[0582] an arithmetic processing circuit configured to perform arithmetic processing on a signal output from the solid-state image sensor,

[0583] [Chemical formula 41]

[0584]

[0585] In the general formula (1),

[0586] R1~R 10 Each independently represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl, or R1 to R2 are substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl. 10 Any at least two adjacent condensed aryl or heteroaryl groups, and

[0587] [Chemical formula 42]

[0588]

[0589] In general formula (2),

[0590] R 11 ~R 16each independently represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl,

[0591] X represents any substituent selected from halogen, hydroxyl, mercapto, imido, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkylthio and substituted or unsubstituted arylthio, and

[0592] R 11 ~R 16 At least one of represents fluorine.

[0593] (28) An electronic device comprising:

[0594] A solid-state image sensor comprising a photoelectric conversion film including a transparent compound represented by the following general formula (3) or (4) and not absorbing visible light;

[0595] an optical system configured to direct incident light to the solid-state image sensor; and

[0596] an arithmetic processing circuit configured to perform arithmetic processing on a signal output from the solid-state image sensor,

[0597] [Chemical formula 43]

[0598]

[0599] In general formula (3),

[0600] R 21 ~R 32 Each independently represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl, or R 21 ~R 32 Any at least two adjacent condensed aryl or heteroaryl groups, and

[0601] In general formula (4),

[0602] R41 ~R 48 Each independently represents any substituent selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, acylimido, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl, or R 41 ~R 48 Any at least two adjacent condensed aryl or heteroaryl groups, and

[0603] Ar1 to Ar4 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

[0604] (29) An electronic device comprising:

[0605] A solid-state image sensor, the solid-state image sensor comprising a photoelectric conversion element, the photoelectric conversion element comprising: a photoelectric conversion film; a pair of electrodes arranged on both sides of the photoelectric conversion film, the photoelectric conversion film being sandwiched therebetween; and a hole blocking layer arranged between the photoelectric conversion film and one of the electrodes, wherein the difference between the ionization potential of the hole blocking layer and the work function of an adjacent electrode is greater than or equal to 2.3 eV;

[0606] an optical system configured to direct incident light to the solid-state image sensor; and

[0607] An arithmetic processing circuit configured to perform arithmetic processing on a signal output from the solid-state image sensor.

[0608] (30) A photoelectric conversion film comprising:

[0609] Quinacridone derivatives represented by the general formula (1):

[0610] [Chemical formula 44]

[0611] and

[0612] Subphthalocyanine derivatives represented by the general formula (2):

[0613] [Chemical formula 45]

[0614]

[0615] In the general formula (1), R1 to R 10Each is independently selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and R1 to R2 10 At least two adjacent groups in are condensed to form an aryl or heteroaryl group,

[0616] In the general formula (2), R 11 ~R 16 each is independently selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl,

[0617] wherein X is selected from halogen, hydroxyl, mercapto, imido, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkylthio and substituted or unsubstituted arylthio, and

[0618] Among them, R 11 ~R 16 At least one of represents fluorine.

[0619] (31) The photoelectric conversion film according to (30), wherein R 11 ~R 16 Each one is fluorine.

[0620] (32) The photoelectric conversion film according to (30) or (31), wherein X is selected from a halogen, a hydroxyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryloxy group.

[0621] (33) A photoelectric conversion film according to any one of (30) to (32), wherein the lowest unoccupied molecular orbital (LUMO) energy level of the subphthalocyanine derivative is deeper than the LUMO energy level of the quinacridone derivative, and the difference between the LUMO energy level of the subphthalocyanine derivative and the LUMO energy level of the quinacridone derivative is greater than or equal to 0.1 eV and less than or equal to 1.0 eV.

[0622] (34) The photoelectric conversion film according to any one of (30) to (33), wherein the quinacridone derivative and the subphthalocyanine derivative are a bulk heterogeneous film.

[0623] (35) A photoelectric conversion film comprising:

[0624] A transparent compound that does not absorb visible light and is represented by at least one of the general formula (3) and the general formula (4):

[0625] [Chemical formula 46]

[0626]

[0627] In general formula (3), R 21 ~R 32 Each is independently selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and R 21 ~R 32 At least two adjacent groups in are condensed to form an aryl or heteroaryl group, and

[0628] In general formula (4), R 41 ~R 48 Each is independently selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, imido, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and R 41 ~R 48 At least two adjacent groups in are condensed to form an aryl or heteroaryl group, and

[0629] wherein Ar1 to Ar4 are each independently one of a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group.

[0630] (36) The photoelectric conversion film according to (35), wherein the transparent compound is represented by at least the general formula (3), and R in the general formula (3) 21 , R 24 , R 25 , R 28 , R 29 and R 32 All are hydrogen.

[0631] (37) The photoelectric conversion film according to (35) or (36), wherein the transparent compound is represented by at least the general formula (4), and Ar1 to Ar4 and R 41 ~R 48 At least one of them is an electron withdrawing group.

[0632] (38) A photoelectric conversion film according to any one of (35) to (37), wherein the electron-withdrawing group is selected from halogen, cyano, nitro, sulfonyl, arylsulfonyl, alkylsulfonyl, acyl, acylamino, acyloxy, acylamino, carboxyl, formylamino, alkoxycarbonyl, halogenated alkyl and halogenated aryl.

[0633] (39) The photoelectric conversion film according to any one of (35) to (38), further comprising:

[0634] An organic dye compound, wherein the organic dye compound and the compound represented by at least one of the general formula (3) and the general formula (4) are a bulk heterogeneous film.

[0635] (40) The photoelectric conversion film according to any one of (35) to (39), wherein the organic dye compound absorbs green light in a wavelength band greater than or equal to about 450 nm and less than or equal to about 600 nm.

[0636] (41) The photoelectric conversion film according to any one of (35) to (40), wherein the organic dye compound is a quinacridone derivative represented by the general formula (1):

[0637] [Chemical formula 47]

[0638]

[0639] In the general formula (1), R1 to R 10 Each is independently selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and R1 to R2 10 At least two adjacent groups in the aryl or heteroaryl groups are condensed to form an aryl or heteroaryl group.

[0640] (42) A photoelectric conversion film according to any one of (35) to (41), wherein the LUMO energy level of at least one of the general formulas (3) and (4) is deeper than the LUMO energy level of the quinacridone derivative, and the difference between the LUMO energy level of at least one of the general formulas (3) and (4) and the LUMO energy level of the quinacridone derivative is greater than or equal to 0.1 eV and less than or equal to 1.0 eV.

[0641] (43) A photoelectric conversion element comprising:

[0642] Photoelectric conversion film;

[0643] a pair of electrodes disposed on both sides of the photoelectric conversion film with the photoelectric conversion film sandwiched therebetween; and

[0644] a hole blocking layer disposed between the photoelectric conversion film and an electrode,

[0645] Wherein, the difference between the ionization potential of the hole blocking layer and the work function of one electrode is greater than or equal to 2.3 eV.

[0646] (44) The photoelectric conversion element according to (43), wherein the hole blocking layer contains a compound represented by the general formula (5):

[0647] [Chemical formula 48]

[0648]

[0649] In general formula (5), R 50 is selected from the group consisting of hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, and

[0650] wherein Ar5 to Ar8 each represent a substituted or unsubstituted heteroaryl group.

[0651] (45) The photoelectric conversion element according to (43) or (44), wherein Ar5 to Ar8 and R 50 At least one of them is an electron withdrawing group.

[0652] (46) A photoelectric conversion element according to any one of (43) to (45), wherein the electron-withdrawing group is selected from halogen, cyano, nitro, sulfonyl, arylsulfonyl, alkylsulfonyl, acyl, acylamino, acyloxy, acylamino, carboxyl, formylamino, alkoxycarbonyl, halogenated alkyl and halogenated aryl.

[0653] (47) The photoelectric conversion element according to any one of (43) to (46), wherein the general formula (5) is any one of the following structural formulas:

[0654] [Chemical formula 49]

[0655]

[0656]

[0657] (48) The photoelectric conversion element according to any one of (43) to (47), wherein the thickness of the hole blocking layer is greater than or equal to about 5 nm and less than or equal to about 20 nm.

[0658] (49) An electronic device comprising:

[0659] A photoelectric conversion film, the photoelectric conversion film comprising:

[0660] Quinacridone derivatives represented by the general formula (1):

[0661] [Chemical formula 50]

[0662] and

[0663] Subphthalocyanine derivatives represented by the general formula (2):

[0664] [Chemical formula 51]

[0665]

[0666] In the general formula (1), R1 to R 10 Each is independently selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and R1 to R2 10 The adjacent to each other

[0667] at least two aryl or heteroaryl groups formed by condensation;

[0668] In general formula (2), R 11 ~R 16 each is independently selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;

[0669] wherein X is selected from halogen, hydroxyl, mercapto, imido, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkylthio and substituted or unsubstituted arylthio; and

[0670] Among them, R 11 ~R 16 At least one of represents fluorine.

[0671] Reference numerals list

[0672] 100 Photoelectric conversion element

[0673] 102 substrate

[0674] 104 Lower electrode

[0675] 106 Electron blocking layer

[0676] 108 Photoelectric conversion layer

[0677] 110 Hole blocking layer

[0678] 112 Upper electrode

Claims

1. A photoelectric conversion film, comprising: Transparent compounds that do not absorb visible light; and An organic dye compound, wherein the organic dye compound absorbs green light in a wavelength band greater than or equal to 450 nm and less than or equal to 600 nm, in, The transparent compound and the organic dye compound are a bulk heterogeneous mixed film, wherein the bulk heterogeneous mixed film is a film having a microstructure in which one of the transparent compound and the organic dye compound is in a crystalline particle state and the other is in an amorphous state, or the bulk heterogeneous mixed film is a film having a microstructure in which both the transparent compound and the organic dye compound are in a microcrystalline state, Wherein, the transparent compound is represented by at least one of the general formula (3) and the general formula (4): In general formula (3), R 21 ~R 32 Each is independently selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and R 21 ~R 32 At least two adjacent groups in are condensed to form an aryl or heteroaryl group, and In general formula (4), R 41 ~R 48 Each is independently selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, imido, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and R 41 ~R 48 At least two adjacent groups in are condensed to form an aryl or heteroaryl group, and wherein Ar1 to Ar4 are each independently one of a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group, Wherein, the organic dye compound is a quinacridone derivative represented by the general formula (1): In the general formula (1), R1 to R 10 Each is independently selected from hydrogen, halogen, hydroxy, alkoxy, cyano, nitro, silyl, silyloxy, arylsilyl, thioalkyl, thioaryl, sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxyl, formylamino, alkoxycarbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and R1 to R2 10 At least two adjacent groups in are condensed to form an aryl or heteroaryl group, and The photoelectric conversion film has a half maximum width of a distribution peak of external quantum efficiency with respect to wavelength of 130 nm.

2. The photoelectric conversion film according to claim 1, wherein The photoelectric conversion film selectively photoelectrically converts green light having a wavelength greater than or equal to 450 nm and less than or equal to 600 nm.

3. The photoelectric conversion film according to claim 1, wherein The transparent compound is represented by at least the general formula (3), and R in the general formula (3) 21 , R 24 , R 25 , R 28 , R 29 and R 32 All are hydrogen.

4. The photoelectric conversion film according to claim 1, wherein The transparent compound is at least represented by the general formula (4), and Ar1 to Ar4 and R in the general formula (4) 41 ~R 48 At least one of them is an electron withdrawing group.

5. The photoelectric conversion film according to claim 4, wherein The electron withdrawing group is selected from halogen, cyano, nitro, sulfonyl, arylsulfonyl, alkylsulfonyl, acyl, acylamino, acyloxy, acylimido, carboxyl, formylamino, alkoxycarbonyl, halogenated alkyl and halogenated aryl.

6. The photoelectric conversion film according to claim 1, wherein The lowest unoccupied molecular orbital energy level of the transparent compound is deeper than the lowest unoccupied molecular orbital energy level of the quinacridone derivative, and the difference between the lowest unoccupied molecular orbital energy level of the transparent compound and the lowest unoccupied molecular orbital energy level of the quinacridone derivative is greater than or equal to 0.1 eV and less than or equal to 1.0 eV.

7. The photoelectric conversion film according to claim 1, wherein The transparent compound serves as an n-type photoelectric conversion material and the organic dye compound serves as a p-type photoelectric conversion material. 8 . An electronic device comprising the photoelectric conversion film according to claim 1 .

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