JP5651507B2 - Manufacturing method of organic photoelectric conversion element, organic photoelectric conversion element, imaging element, imaging apparatus - Google Patents

Description

  The present invention relates to a method for manufacturing an organic photoelectric conversion element, an organic photoelectric conversion element, an imaging element, and an imaging apparatus.

  An organic photoelectric conversion element having a pair of electrodes and a photoelectric conversion layer using an organic material provided between the pair of electrodes is known. Patent Document 1 discloses an organic photoelectric conversion element using a mixed layer of p-type organic semiconductor and fullerene or a fullerene derivative (a layer obtained by co-evaporation of two materials) as a photoelectric conversion layer for the purpose of improving photoelectric conversion efficiency. Is disclosed.

  In general, it is known that characteristics of organic materials change due to the influence of moisture and oxygen. For this reason, when manufacturing an organic photoelectric conversion element, it has been considered as common sense that it is desirable to perform all the processes in a consistent vacuum.

  On the other hand, if an integrated vacuum process is to be realized, there is a concern that the manufacturing equipment becomes large and the cost increases. Therefore, a method for obtaining an organic photoelectric conversion element free from performance deterioration while suppressing the manufacturing cost is desired.

  In an organic photoelectric conversion element, there is one described in Patent Document 2 as a process in which all manufacturing steps are not performed in a consistent vacuum. In Patent Document 2, in an organic solar cell in which electrodes, fullerenes, p-type organic semiconductors, and electrodes are stacked in this order, fullerenes and p-type organic semiconductors are sequentially formed on the electrodes by vacuum deposition, and then the device is temporarily turned to air. A method is described for exposing and then forming the electrode by vacuum evaporation. However, this method cannot prevent deterioration of element characteristics.

  In addition, although it is not an organic photoelectric conversion element, in the organic EL element which is an element using the same organic material, there exists what was described in patent document 3 as what is manufactured in a vacuum consistent process, in order to stabilize a performance. In addition, there are methods described in Patent Documents 4 and 5 as manufacturing methods in which all the steps are not consistent in vacuum.

JP 2007-123707 A JP 09-74216 A JP-A-10-335061 JP 2009-231278 A JP 09-330790 A

  The present invention is an organic photoelectric conversion element having a photoelectric conversion layer including a mixed layer of fullerene or a fullerene derivative and a p-type organic semiconductor, and capable of preventing deterioration in element performance and increase in cost. An object of the present invention is to provide a manufacturing method, an organic photoelectric conversion element manufactured by the manufacturing method, an imaging element including the organic photoelectric conversion element, and an imaging apparatus including the imaging element.

The method for producing an organic photoelectric conversion element of the present invention is formed between a first electrode, a second electrode formed above the first electrode, and the first electrode and the second electrode. A method for producing an organic photoelectric conversion element, comprising: a photoelectric conversion layer containing an organic material; and the first electrode, the second electrode, and a sealing layer for sealing the photoelectric conversion layer. The layer is a non-light-emitting layer including a mixed layer of fullerene or a fullerene derivative and a p-type organic semiconductor, and a first step of forming the first electrode above the substrate, and above the first electrode A second step of forming the photoelectric conversion layer, a third step of forming the second electrode above the photoelectric conversion layer, and a second step of forming the sealing layer above the second electrode. Four steps, and each step of the second step to the fourth step is performed under vacuum, Between after completion of the second step to the start of the fourth step comprises a fifth step of placing said organic photoelectric conversion element of the process of manufacturing under non-vacuum, the p-type organic semiconductor of the general formula It is a compound represented by (1).

  According to this manufacturing method, since the fifth step is provided between the end of the second step and the start of the fourth step, a mixed layer of fullerene or a fullerene derivative and a p-type organic semiconductor is included. It is possible to prevent performance deterioration and cost increase of the organic photoelectric conversion element including the non-light emitting photoelectric conversion layer. Patent Documents 4 and 5 are inventions related to light-emitting elements, which are completely different from the method for producing an organic photoelectric conversion element having a non-light-emitting photoelectric conversion layer. Moreover, patent document 2 is not described about forming a photoelectric converting layer as a mixed layer. In addition, as described in a comparative example described later, in the configuration in which the photoelectric conversion layer has a laminated structure instead of a mixed layer, deterioration of element performance cannot be prevented even if the fifth step is provided. For these reasons, the inventions described in Patent Documents 1 to 5 cannot solve the problem of the present invention, but according to the present manufacturing method, this problem can be solved.

  The organic photoelectric conversion element of this invention is manufactured by the said manufacturing method.

  The imaging device of the present invention includes a plurality of the organic photoelectric conversion elements, and a circuit board on which a signal readout circuit for reading a signal corresponding to the charge generated in the photoelectric conversion layer of each organic photoelectric conversion element is formed. It is.

  The imaging device of the present invention includes the imaging element.

  ADVANTAGE OF THE INVENTION According to this invention, it is an organic photoelectric conversion element which has a photoelectric converting layer containing the mixed layer of fullerene or a fullerene derivative, and a p-type organic semiconductor, Comprising: Organic photoelectric conversion which can prevent deterioration of element performance and increase in cost A conversion element manufacturing method, an organic photoelectric conversion element manufactured by this manufacturing method, an image pickup element including the organic photoelectric conversion element, and an image pickup apparatus including the image pickup element can be provided.

Sectional schematic diagram which shows schematic structure of the organic photoelectric conversion element for describing one Embodiment of this invention 1 is a schematic cross-sectional view showing a schematic configuration of an image sensor for explaining an embodiment of the present invention.

  Embodiments of the present invention will be described below with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view showing a schematic configuration of an organic photoelectric conversion element for explaining an embodiment of the present invention. An organic photoelectric conversion element 10 shown in FIG. 1 includes a substrate 1, an electrode 2 formed on the substrate 1, an electron blocking layer 3 formed on the electrode 2, and a photoelectric conversion formed on the electron blocking layer 3. A layer 4, an electrode 5 formed on the photoelectric conversion layer 4, and a sealing layer 6 formed on the electrode 5 are provided. A light receiving layer is formed by the electron blocking layer 3 and the photoelectric conversion layer 4. The light receiving layer may be a layer including at least the photoelectric conversion layer 4 and may be a layer including a layer other than the electron blocking layer 3 (for example, a hole blocking layer).

  The substrate 1 is a silicon substrate, a glass substrate, or the like.

  The electrode 2 is an electrode for collecting holes out of charges generated in the photoelectric conversion layer 4. The electrode 2 is made of a conductive material such as ITO (indium tin oxide).

  The photoelectric conversion layer 4 receives light and generates an electric charge according to the amount of light, and includes an organic photoelectric conversion material. Specifically, the photoelectric conversion layer 4 includes at least a mixed layer in which a p-type organic semiconductor (p-type organic compound) and a fullerene or a fullerene derivative that is an n-type organic semiconductor are mixed. The mixed layer refers to a layer in which a plurality of materials are mixed or dispersed. For example, the mixed layer is a layer formed by co-evaporating a plurality of materials. Alternatively, it may be a layer formed by mixing a plurality of materials in a solvent and coating them. When the photoelectric conversion layer 4 includes such a mixed layer, it is possible to compensate for the shortcoming of the short carrier diffusion length of the photoelectric conversion layer and to improve the photoelectric conversion efficiency of the photoelectric conversion layer.

  The photoelectric conversion layer 4 is a non-light-emitting layer having characteristics different from those of an organic EL light-emitting layer (a layer that converts an electric signal into light). The non-light-emitting layer is a case where the emission quantum efficiency is 1% or less in the visible light region (wavelength 400 nm to 730 nm), preferably 0.5% or less, more preferably 0.1% or less. The reason for making the photoelectric conversion layer 4 a non-light-emitting layer is that when an organic photoelectric conversion element is used as an imaging element application, if the emission quantum efficiency exceeds 1%, the imaging performance is affected.

  The light receiving layer can be formed by a dry film forming method or a wet film forming method. The dry film formation method is preferable in that a uniform film formation is easy and impurities are not easily mixed, and that film thickness control and lamination on different materials are easy.

  Specific examples of the dry film forming method include a vacuum vapor deposition method, a sputtering method, an ion plating method, a physical vapor deposition method such as an MBE method, or a CVD method such as plasma polymerization. A vacuum deposition method is preferred, and in the case of forming a film by the vacuum deposition method, the production conditions such as the degree of vacuum and the deposition temperature can be set according to conventional methods. When the light receiving layer is formed by vapor deposition, it is preferable that the decomposition temperature is higher than the vapor deposition possible temperature because thermal decomposition during vapor deposition can be suppressed.

When forming the light receiving layer by a dry film forming method, degree of vacuum during formation, considering possible to prevent deterioration of the device characteristics during the absorption layer formation, it is preferably not more than ^{1 × 10 -3 Pa, 4 ×} 10 - ⁴ Pa or less is more preferable, and 1 × 10 ⁻⁴ Pa or less is particularly preferable.

  The thickness of the light receiving layer is preferably 10 nm or more and 1000 nm or less, more preferably 50 nm or more and 800 nm or less, and particularly preferably 100 nm or more and 600 nm or less. By setting it to 10 nm or more, a suitable dark current suppressing effect is obtained, and by setting it to 1000 nm or less, suitable photoelectric conversion efficiency is obtained.

  The electron blocking layer 3 included in the light receiving layer is a layer for suppressing the injection of electrons from the electrode 2 to the photoelectric conversion layer 4 and preventing the electrons generated in the photoelectric conversion layer 4 from flowing to the electrode 2 side. It is. The electron blocking layer 3 includes an organic material, an inorganic material, or both.

  The electrode 5 is an electrode that collects electrons out of the charges generated in the photoelectric conversion layer 4. The electrode 5 uses a conductive material (for example, ITO) that is sufficiently transparent to light having a wavelength with which the photoelectric conversion layer 4 has sensitivity in order to make light incident on the photoelectric conversion layer 4. By applying a bias voltage between the electrode 5 and the electrode 2, among the charges generated in the photoelectric conversion layer 4, holes can be moved to the electrode 2 and electrons can be moved to the electrode 5.

  The sealing layer 6 is a layer for preventing factors that degrade the organic material such as water and oxygen from entering the light receiving layer containing the organic material. The sealing layer 6 is formed to cover the electrode 2, the electron blocking layer 3, the photoelectric conversion layer 4, and the electrode 5.

  In the organic photoelectric conversion element 10 configured as described above, the electrode 5 is used as an electrode on the light incident side, and when light enters from above the electrode 5, the light passes through the electrode 5 and enters the photoelectric conversion layer 4. Here, charge is generated. Of the generated charges, holes move to the electrode 2. By converting the holes moved to the electrode 2 into a voltage signal corresponding to the amount of the holes and reading out the light, the light can be converted into a voltage signal and extracted.

  The electron blocking layer 3 may be composed of a plurality of layers. By doing in this way, an interface is formed between each layer which comprises the electron blocking layer 3, and a discontinuity arises in the intermediate level which exists in each layer. As a result, it becomes difficult for the charge to move through the intermediate level, and the electron blocking effect can be enhanced. However, if the layers constituting the electron blocking layer 3 are made of the same material, the intermediate levels existing in the layers may be exactly the same. Therefore, in order to further enhance the electron blocking effect, the materials constituting the layers are different. It is preferable to make it.

  Further, a bias voltage may be applied so as to collect electrons at the electrode 2 and collect holes at the electrode 5. In this case, a hole blocking layer may be provided instead of the electron blocking layer 3. The hole blocking layer suppresses injection of holes from the electrode 2 into the photoelectric conversion layer 4, and an organic material for inhibiting holes generated in the photoelectric conversion layer 4 from flowing to the electrode 2 side. It may be a layer composed of By making the hole blocking layer into a plurality of layers, the hole blocking effect can be enhanced.

  Further, electrons or holes collected by the electrode 5 may be converted into a voltage signal corresponding to the amount and taken out to the outside. In this case, an electron blocking layer or a hole blocking layer may be provided between the electrode 5 and the photoelectric conversion layer 4. In either case, the portion sandwiched between the electrode 2 and the electrode 5 becomes the light receiving layer.

  Next, the manufacturing method of the organic photoelectric conversion element 10 is demonstrated.

  First, an electrode 2 is formed by depositing, for example, ITO on the substrate 1 by sputtering. Next, an electron blocking material is formed on the electrode 2 by vapor deposition, for example, to form the electron blocking layer 3.

  Next, a p-type organic semiconductor and fullerene or a fullerene derivative are co-evaporated on the electron blocking layer 3 to form the photoelectric conversion layer 4. Next, an electrode 5 is formed on the photoelectric conversion layer 4 by, for example, depositing ITO by sputtering. Next, a silicon oxide film is formed on the electrode 5 and the substrate 1 by, for example, vapor deposition to form the sealing layer 6.

  In this manufacturing method, in each process of the formation process of the electrode 2, the formation process of the electron blocking layer 3, the formation process of the photoelectric conversion layer 4, the formation process of the electrode 5, and the formation process of the sealing layer 6, In addition, in order to prevent deterioration factors of the film such as water and oxygen from being mixed into the film, the respective processes are performed under vacuum. As a result of intensive studies, the present inventor puts the organic photoelectric conversion element 10 in the process of non-vacuum during the period from the end of the formation process of the photoelectric conversion layer 4 to the start of the formation process of the sealing layer 6. It has been found that the performance of the organic photoelectric conversion element 10 does not deteriorate even when provided (hereinafter referred to as a non-vacuum period).

  Here, under non-vacuum means a space having a higher pressure than under vacuum when each step is performed. Specifically, non-vacuum refers to an air atmosphere or an inert atmosphere. The inert atmosphere indicates that oxygen and water are both 100 ppm or less (preferably 10 ppm or less, ideally 0.5 ppm or less) in a space at atmospheric pressure.

  Inert gas species under an inert atmosphere include noble gases such as nitrogen gas and argon, and incombustible gases, and a combination of a plurality of these inert gases may be used. Nitrogen gas is preferable.

  The non-vacuum period is, for example, between the formation process of the photoelectric conversion layer 4 and the formation process of the electrode 5 (first period), and between the formation process of the electrode 5 and the formation process of the sealing layer 6 (second In at least one of the periods).

  Up to now, the organic photoelectric conversion in the process of being formed after the photoelectric conversion layer 4 containing the organic material is formed and before the sealing layer 6 for preventing the intrusion of the deterioration factors of the organic material such as water and oxygen is formed. When the element 10 is placed in a non-vacuum state, it has been considered that the organic material deteriorates due to moisture, oxygen, etc., and the performance of the organic photoelectric conversion element deteriorates. In fact, in the organic photoelectric conversion element 10 in which the photoelectric conversion layer 4 is formed using only the compound 1 described in a comparative example described later, it is known that the element performance deteriorates when a non-vacuum period is provided.

  However, in the organic photoelectric conversion element 10 using a mixed layer of a p-type organic semiconductor and fullerene or a fullerene derivative as the photoelectric conversion layer 4, between the formation process of the photoelectric conversion layer 4 and the formation process of the sealing layer 6. The present inventors have found that the device performance is not deteriorated even when the organic photoelectric conversion device 10 in the process of production is not vacuumed. Furthermore, the present inventor has also found that the performance of the organic photoelectric conversion element 10 can be further improved by setting the length of the non-vacuum period to 30 minutes or longer (ideally 3 hours or longer).

  In this manufacturing method, a non-vacuum period can be provided in the first period and the second period. For this reason, from the apparatus which forms the photoelectric converting layer 4 to the apparatus which forms the electrode 5, the conveyance path | route of the organic photoelectric conversion element in the middle of preparation, and the apparatus from which the electrode 5 is formed to the apparatus which forms the sealing layer 6 It is not necessary to make the transport path of the organic photoelectric conversion element in the middle of the production to be in a vacuum state. As a result, the manufacturing facility for the organic photoelectric conversion element 10 can be simplified, and the manufacturing cost can be reduced.

  In the non-vacuum period, there is no difference in effect due to the difference in the direction in which the photoelectric conversion layer 4 is held. In addition, the atmosphere between the step of forming the electron blocking layer 3 and the step of forming the photoelectric conversion layer 4 and the time during which the device in the process of preparation is placed in the atmosphere or the light irradiation of the organic photoelectric conversion element 10 in the non-vacuum period The presence or absence is not particularly limited as long as the effects of the present invention are not significantly impaired.

  If a non-vacuum period is provided in either the first period or the second period, the equipment should be designed so that the element transport path in the non-vacuum period is in a vacuum state. Good. When the non-vacuum period is provided in both the first period and the second period, the cost of the facility can be significantly reduced.

  Next, a configuration example of an imaging element using the organic photoelectric conversion element 10 will be described.

  FIG. 2 is a schematic cross-sectional view showing a schematic configuration of an image sensor for explaining an embodiment of the present invention. This imaging device is used by being mounted on an imaging device such as a digital camera or a digital video camera, an imaging module such as an electronic endoscope or a mobile phone, or the like.

  The image pickup device includes a plurality of organic photoelectric conversion elements configured as shown in FIG. 1, a circuit board on which a readout circuit that reads a signal corresponding to the charge generated in the photoelectric conversion layer of each organic photoelectric conversion element is formed, And a plurality of organic photoelectric conversion elements are arranged one-dimensionally or two-dimensionally on the same surface above the circuit board.

  2 includes a substrate 101, an insulating layer 102, a connection electrode 103, a pixel electrode 104, a connection portion 105, a connection portion 106, a light receiving layer 107, a counter electrode 108, and a buffer layer. 109, a sealing layer 110, a color filter (CF) 111, a partition 112, a light shielding layer 113, a protective layer 114, a counter electrode voltage supply unit 115, and a readout circuit 116.

  The pixel electrode 104 has the same function as the electrode 2 of the organic photoelectric conversion element 10 shown in FIG. The counter electrode 108 has the same function as the electrode 5 of the organic photoelectric conversion element 10 shown in FIG. The light receiving layer 107 has the same configuration as the light receiving layer provided between the electrode 2 and the electrode 5 of the organic photoelectric conversion element 10 shown in FIG. The sealing layer 110 has the same function as the sealing layer 6 of the organic photoelectric conversion element 10 shown in FIG. The pixel electrode 104, a part of the counter electrode 108 facing the pixel electrode 104, the light receiving layer 107 sandwiched between the electrodes, and the buffer layer 109 and the part of the sealing layer 110 facing the pixel electrode 104 are subjected to organic photoelectric conversion. The element is configured.

  The substrate 101 is a glass substrate or a semiconductor substrate such as Si. An insulating layer 102 is formed on the substrate 101. A plurality of pixel electrodes 104 and a plurality of connection electrodes 103 are formed on the surface of the insulating layer 102.

  The light receiving layer 107 is a layer common to all the organic photoelectric conversion elements provided on the plurality of pixel electrodes 104 so as to cover them.

  The counter electrode 108 is one electrode provided on the light receiving layer 107 and common to all organic photoelectric conversion elements. The counter electrode 108 is formed up to the connection electrode 103 disposed outside the light receiving layer 107 and is electrically connected to the connection electrode 103.

  The connection part 106 is embedded in the insulating layer 102 and is a plug or the like for electrically connecting the connection electrode 103 and the counter electrode voltage supply part 115. The counter electrode voltage supply unit 115 is formed on the substrate 101 and applies a predetermined voltage to the counter electrode 108 via the connection unit 106 and the connection electrode 103. When the voltage to be applied to the counter electrode 108 is higher than the power supply voltage of the image sensor, the power supply voltage is boosted by a booster circuit such as a charge pump to supply the predetermined voltage.

  The readout circuit 116 is provided on the substrate 101 corresponding to each of the plurality of pixel electrodes 104, and reads out a signal corresponding to the charge collected by the corresponding pixel electrode 104. The reading circuit 116 is configured by, for example, a CCD, a MOS circuit, or a TFT circuit, and is shielded from light by a light shielding layer (not shown) disposed in the insulating layer 102. The readout circuit 116 is electrically connected to the corresponding pixel electrode 104 via the connection unit 105.

  The buffer layer 109 is formed on the counter electrode 108 so as to cover the counter electrode 108. The sealing layer 110 is formed on the buffer layer 109 so as to cover the buffer layer 109. The color filter 111 is formed at a position facing each pixel electrode 104 on the sealing layer 110. The partition wall 112 is provided between the color filters 111 and is for improving the light transmission efficiency of the color filter 111.

  The light shielding layer 113 is formed in a region other than the region where the color filter 111 and the partition 112 on the sealing layer 110 are provided, and prevents light from entering the light receiving layer 107 formed outside the effective pixel region. The protective layer 114 is formed on the color filter 111, the partition 112, and the light shielding layer 113, and protects the entire image sensor 100.

  In the imaging device 100 configured as described above, when light is incident, the light is incident on the light receiving layer 107, and charges are generated here. Holes in the generated charges are collected by the pixel electrode 104, and a voltage signal corresponding to the amount is output to the outside of the image sensor 100 by the readout circuit 116.

  The manufacturing method of the image sensor 100 is as follows.

  On the circuit substrate on which the common electrode voltage supply unit 115 and the readout circuit 116 are formed, the connection units 105 and 106, the plurality of connection electrodes 103, the plurality of pixel electrodes 104, and the insulating layer 102 are formed. The plurality of pixel electrodes 104 are arranged on the surface of the insulating layer 102 in a square lattice pattern, for example.

  Next, the light receiving layer 107 is formed on the plurality of pixel electrodes 104 by, for example, a vacuum heating vapor deposition method. Next, the counter electrode 108 is formed on the light receiving layer 107 under a vacuum, for example, by sputtering. Next, the buffer layer 109 and the sealing layer 110 are sequentially formed on the counter electrode 108 by, for example, a vacuum heating deposition method. Next, after forming the color filter 111, the partition 112, and the light shielding layer 113, the protective layer 114 is formed, and the imaging element 100 is completed.

  Also in the manufacturing method of the image pickup device 100, a step of placing the image pickup device 100 being manufactured under non-vacuum is added between the step of forming the photoelectric conversion layer included in the light receiving layer 107 and the step of forming the sealing layer 110. Thereby, performance degradation of a plurality of organic photoelectric conversion elements can be prevented. By adding this step, it is possible to suppress the manufacturing cost while preventing the performance degradation of the image sensor 100.

  Below, the detail of the component (the electron blocking layer 3, the hole blocking layer, the photoelectric converting layer 4, the electrode 2, the electrode 5, the sealing layer 6) of the organic photoelectric conversion element mentioned above is demonstrated.

[Photoelectric conversion layer]
The p-type organic semiconductor (compound) constituting the photoelectric conversion layer 4 is a donor-type organic semiconductor (compound), which is mainly represented by a hole-transporting organic compound and refers to an organic compound having a property of easily donating electrons. . More specifically, an organic compound having a smaller ionization potential when two organic materials are used in contact with each other. Therefore, any organic compound can be used as the donor organic compound as long as it is an electron-donating organic compound. For example, triarylamine compounds, pyran compounds, quinacridone compounds, benzidine compounds, pyrazoline compounds, styrylamine compounds, hydrazone compounds, triphenylmethane compounds, carbazole compounds, polysilane compounds, thiophene compounds, phthalocyanine compounds, cyanine compounds, merocyanine compounds, oxonol Compound, polyamine compound, indole compound, pyrrole compound, pyrazole compound, polyarylene compound, condensed aromatic carbocyclic compound (naphthalene derivative, anthracene derivative, phenanthrene derivative, tetracene derivative, pyrene derivative, perylene derivative, fluoranthene derivative), nitrogen-containing hetero A metal complex having a ring compound as a ligand can be used. However, the present invention is not limited thereto, and any organic compound having an ionization potential smaller than that of the organic compound used as the n-type organic semiconductor may be used as the donor organic semiconductor.
Among the above, preferred are triarylamine compounds, pyran compounds, quinacridone compounds, pyrrole compounds, phthalocyanine compounds, merocyanine compounds, and condensed aromatic carbocyclic compounds.

  Any organic dye may be used as the p-type organic semiconductor, but preferred are a cyanine dye, a styryl dye, a hemicyanine dye, a merocyanine dye (including zero methine merocyanine (simple merocyanine)), a trinuclear merocyanine dye, 4 Nuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol dye, hemioxonol dye, squalium dye, croconium dye, azamethine dye, coumarin dye, arylidene dye, anthraquinone dye, triphenylmethane dye, azo Dye, azomethine dye, spiro compound, metallocene dye, fluorenone dye, fulgide dye, perylene dye, perinone dye, phenazine dye, phenothiazine dye, quinone color , Diphenylmethane dye, polyene dye, acridine dye, acridinone dye, diphenylamine dye, quinacridone dye, quinophthalone dye, phenoxazine dye, phthaloperylene dye, diketopyrrolopyrrole dye, dioxane dye, porphyrin dye, chlorophyll dye, phthalocyanine dye, metal complex dye And condensed aromatic carbocyclic dyes (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives). Specific p-type organic semiconductors (compounds) are exemplified below, but the present invention is not limited to the compounds listed below.

The fullerene constituting the photoelectric conversion layer 4 is fullerene C ₆₀ , fullerene C ₇₀ , fullerene C ₇₆ , fullerene C ₇₈ , fullerene C ₈₀ , fullerene C ₈₂ , fullerene C ₈₄ , fullerene C ₉₀ , fullerene C ₉₆ , fullerene C _240. , Fullerene ₅₄₀ , mixed fullerene, and fullerene nanotubes, and the fullerene derivative means a compound having a substituent added thereto.

  The substituent for the fullerene derivative is preferably an alkyl group, an aryl group, or a heterocyclic group. More preferably, the alkyl group is an alkyl group having 1 to 12 carbon atoms, and the aryl group and the heterocyclic group are preferably a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring. , Biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran Ring, benzimidazole ring, imidazopyridine ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline , Thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, or phenazine ring, more preferably a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyridine ring, imidazole ring, oxazole ring, or A thiazole ring, particularly preferably a benzene ring, a naphthalene ring, or a pyridine ring. These may further have a substituent, and the substituents may be bonded as much as possible to form a ring. In addition, you may have a some substituent and they may be the same or different. A plurality of substituents may be combined as much as possible to form a ring.

  When the photoelectric conversion layer 4 contains fullerene or a fullerene derivative, charges generated by photoelectric conversion can be quickly transported to the electrode 2 or the electrode 5 via the fullerene molecule or the fullerene derivative molecule. When fullerene molecules or fullerene derivative molecules are connected to form an electron path, the electron transport property is improved, and the high-speed response of the organic photoelectric conversion element can be realized. For this purpose, it is preferable that 40% or more of fullerene or fullerene derivative is contained in the photoelectric conversion layer 4. However, when there are too many fullerenes or fullerene derivatives, the p-type organic semiconductor is reduced, the junction interface is reduced, and the exciton dissociation efficiency is lowered.

  In the photoelectric conversion layer 4, when a triarylamine compound described in Japanese Patent No. 4213832 is used as a p-type organic semiconductor mixed with fullerene or a fullerene derivative, a high SN ratio of the organic photoelectric conversion element can be expressed. Is particularly preferred. When the ratio of fullerene or fullerene derivative in the photoelectric conversion layer 4 is too large, the amount of the triarylamine compound is reduced and the amount of incident light absorbed is reduced. As a result, the photoelectric conversion efficiency is reduced. Therefore, the fullerene or fullerene derivative contained in the photoelectric conversion layer 4 preferably has a composition of 85% or less.

  In order to express the effect of the present invention remarkably, the p-type organic semiconductor is preferably a compound represented by the following general formula (1).

(In the formula, L ₂ and L ₃ each independently represent an unsubstituted methine group or a substituted methine group. N represents an integer of 0 to 2. Ar ₁ represents a divalent substituted arylene group or an unsubstituted arylene. .Ar _2, Ar ₃ represents a group independently represents a substituted aryl group, an unsubstituted aryl group, a substituted alkyl group, an unsubstituted alkyl group, .Ar ₁ representing a heteroaryl group, or an unsubstituted heteroaryl group into substituted, Adjacent ones of Ar ₂ and Ar ₃ may be linked to each other to form a ring, L ₁ is an unsubstituted methine group or a substituted methine group bonded to the following general formula (2), or the following general formula The group represented by (3) is represented.

式中、Ｚ_１は、無置換メチン基若しくは置換メチン基と結合する炭素原子と該炭素原子に隣接するカルボニル基を含む環であって、５員環、６員環、又は、５員環及び６員環の少なくともいずれかを含む縮合環を表す。Ｘはヘテロ原子を表す。Ｚ_２は、Ｘを含む環であって、５員環、６員環、７員環、又は、５員環及び６員環及び７員環の少なくともいずれかを含む縮合環を表す。Ｌ_４〜Ｌ_６は、それぞれ独立に無置換メチン基若しくは置換メチン基を表す。Ｒ_６、Ｒ_７はそれぞれ独立に、水素原子又は置換基を表し、隣接するものが互いに結合して環を形成してもよい。ｋは０〜２の整数を表す。一般式（２）中の＊は無置換メチン基若しくは置換メチン基に結合する結合位置を表し、一般式（３）中の＊はＬ_２又はＡｒ_１に結合する結合位置を表す。
一般式（２）のＺ_１は、２つの炭素原子を含む環であって、５員環、６員環、又は、５員環及び６員環の少なくともいずれかを含む縮合環を表す。このような環としては、通常メロシアニン色素で酸性核として用いられるものが好ましく、その具体例としては例えば以下のものが挙げられる。

In the formula, Z ₁ is a ring containing a carbon atom bonded to an unsubstituted methine group or a substituted methine group and a carbonyl group adjacent to the carbon atom, and is a 5-membered ring, 6-membered ring, or 5-membered ring; A condensed ring containing at least one of 6-membered rings is represented. X represents a hetero atom. Z ₂ is a ring containing X, and represents a 5-membered ring, a 6-membered ring, a 7-membered ring, or a condensed ring containing at least one of a 5-membered ring, a 6-membered ring and a 7-membered ring. L _{4 to} L ₆ each independently represents an unsubstituted methine group or a substituted methine group. R ₆ and R ₇ each independently represents a hydrogen atom or a substituent, and adjacent ones may be bonded to each other to form a ring. k represents an integer of 0-2. Formula (2) in the * represents a bonding position for coupling to an unsubstituted methine group or a substituted methine group, the general formula (3) in the * represents a bonding position for coupling to the L ₂ or Ar _1.
Z _{1 in the} general formula (2) is a ring containing two carbon atoms and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. As such a ring, what is normally used as an acidic nucleus with a merocyanine dye is preferable, and specific examples thereof include the following.

(A) 1,3-dicarbonyl nucleus: For example, 1,3-indandione nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dioxane-4,6- Zeon etc.
(B) pyrazolinone nucleus: for example 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1- (2-benzothiazoyl) -3-methyl-2 -Pyrazolin-5-one and the like.
(C) Isoxazolinone nucleus: For example, 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one and the like.
(D) Oxindole nucleus: For example, 1-alkyl-2,3-dihydro-2-oxindole and the like.
(E) 2,4,6-triketohexahydropyrimidine nucleus: for example, barbituric acid or 2-thiobarbituric acid and its derivatives. Examples of the derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl, 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl and 1,3-dibutyl, 1,3-diphenyl, 1,3-diaryl compounds such as 1,3-di (p-chlorophenyl) and 1,3-di (p-ethoxycarbonylphenyl), 1-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl, Examples include 1,3-di (2-pyridyl) 1,3-diheterocyclic substituents and the like.
(F) 2-thio-2,4-thiazolidinedione nucleus: for example, rhodanine and derivatives thereof. Examples of the derivatives include 3-alkylrhodanine such as 3-methylrhodanine, 3-ethylrhodanine and 3-allylrhodanine, 3-arylrhodanine such as 3-phenylrhodanine, and 3- (2-pyridyl) rhodanine. And the like.

(G) 2-thio-2,4-oxazolidinedione (2-thio-2,4- (3H, 5H) -oxazoledione nucleus: for example, 3-ethyl-2-thio-2,4-oxazolidinedione and the like.
(H) Tianaphthenone nucleus: For example, 3 (2H) -thianaphthenone-1,1-dioxide and the like.
(I) 2-thio-2,5-thiazolidinedione nucleus: for example, 3-ethyl-2-thio-2,5-thiazolidinedione and the like.
(J) 2,4-thiazolidinedione nucleus: For example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione, and the like.
(K) Thiazolin-4-one nucleus: For example, 4-thiazolinone, 2-ethyl-4-thiazolinone and the like.
(L) 2,4-imidazolidinedione (hydantoin) nucleus: for example, 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, etc.
(M) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus: for example, 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione etc.
(N) 2-imidazolin-5-one nucleus: For example, 2-propylmercapto-2-imidazolin-5-one and the like.
(O) 3,5-pyrazolidinedione nucleus: for example, 1,2-diphenyl-3,5-pyrazolidinedione, 1,2-dimethyl-3,5-pyrazolidinedione and the like.
(P) Benzothiophen-3-one nucleus: for example, benzothiophen-3-one, oxobenzothiophen-3-one, dioxobenzothiophen-3-one and the like.
(Q) Indanone nucleus: For example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, 3,3-dimethyl-1-indanone and the like.

The ring represented by Z ₁ is preferably a 1,3-dicarbonyl nucleus, a pyrazolinone nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone body, for example, a barbituric acid nucleus, a 2-thiobarbituric acid nucleus ), 2-thio-2,4-thiazolidinedione nucleus, 2-thio-2,4-oxazolidinedione nucleus, 2-thio-2,5-thiazolidinedione nucleus, 2,4-thiazolidinedione nucleus, 2,4- An imidazolidinedione nucleus, a 2-thio-2,4-imidazolidinedione nucleus, a 2-imidazolin-5-one nucleus, a 3,5-pyrazolidinedione nucleus, a benzothiophen-3-one nucleus, an indanone nucleus, More preferably, a 1,3-dicarbonyl nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone body, for example, a barbituric acid nucleus, 2-thiobarbitu Nucleoside), 3,5-pyrazolidinedione nucleus, benzothiophen-3-one nucleus, indanone nucleus, more preferably 1,3-dicarbonyl nucleus, 2,4,6-triketohexahydropyrimidine Nuclei (including thioketone bodies, such as barbituric acid nuclei, 2-thiobarbituric acid nuclei), particularly preferably 1,3-indandione nuclei, barbituric acid nuclei, 2-thiobarbituric acid nuclei and their derivatives. is there.

What is preferable as a ring represented by Z ₁ is represented by the following formula.

In the formula, Z ³ is a ring containing a carbon atom bonded to L ₁ and two carbonyl groups adjacent to the carbon atom, and is a 5-membered ring, a 6-membered ring, or a 5-membered ring and a 6-membered ring. A condensed ring containing at least one of them is represented. * Represents a bonding position for coupling with L _1. Z ³ can be selected from the ring represented by Z ₁ above, preferably 1,3-dicarbonyl nucleus, 2,4,6-triketohexahydropyrimidine nucleus (including thioketone body), particularly preferably Are 1,3-indandione nucleus, barbituric acid nucleus, 2-thiobarbituric acid nucleus and derivatives thereof.

When the ring represented by Z ₁ is a 1,3-indandione nucleus, it is preferably a group represented by the following general formula (5).

式中、Ｒ_２〜Ｒ_５はそれぞれ独立に、水素原子又は置換基を表し、隣接するものが互いに結合して環を形成してもよい。＊は無置換メチン基若しくは置換メチン基と結合する結合位置を示す。

In the formula, R _{2 to} R ₅ each independently represents a hydrogen atom or a substituent, and adjacent ones may be bonded to each other to form a ring. * Indicates a binding position for binding to an unsubstituted methine group or a substituted methine group .

K in the general formula (3) represents an integer of 0 to 2, preferably 0 or 1, more preferably 0. X is preferably O, S, or N—R ₁₀ . A preferable ring represented by Z ₂ is represented by the following formula (6).

式中、ＸはＯ、Ｓ、Ｎ−Ｒ_１０を表す。Ｒ_１０は水素原子又は置換基を表す。式中、Ｒ_１、Ｒ_６、Ｒ_７はそれぞれ独立に、水素原子又は置換基を表し、隣接するものが互いに結合して環を形成してもよい。ｍは１〜３の整数を表す。ｍが２以上のとき複数のＲ_１は同じでも異なっていてもよい。＊はＬ_２又はＡｒ_１に結合する結合位置を表す。

In the formula, X represents O, S, or N—R ₁₀ . R ₁₀ represents a hydrogen atom or a substituent. In the formula, R ₁ , R ₆ and R ₇ each independently represent a hydrogen atom or a substituent, and adjacent ones may be bonded to each other to form a ring. m represents an integer of 1 to 3. When m is 2 or more, the plurality of R ₁ may be the same or different. * Represents a bonding position bonded to L ₂ or Ar ₁ .

The arylene group represented by Ar ₁ is preferably an arylene group having 6 to 30 carbon atoms, and more preferably an arylene group having 6 to 18 carbon atoms. The arylene group may have a substituent, and is preferably an arylene group having 6 to 18 carbon atoms which may have an alkyl group having 1 to 4 carbon atoms. Examples include a phenylene group, a naphthylene group, a methylphenylene group, a dimethylphenylene group, and the like, and a phenylene group and a naphthylene group are preferable.

The aryl groups represented by Ar ₂ and Ar ₃ are each independently preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 18 carbon atoms. The aryl group may have a substituent, preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 18 carbon atoms which may have an aryl group having 6 to 18 carbon atoms. is there. For example, a phenyl group, a naphthyl group, a tolyl group, an anthryl group, a dimethylphenyl group, a biphenyl group etc. are mentioned, A phenyl group and a naphthyl group are preferable.

The alkyl group represented by Ar ₂ and Ar ₃ is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. A methyl group or an ethyl group is preferable, and a methyl group is more preferable.

The heteroaryl groups represented by Ar ₂ and Ar ₃ are preferably each independently a heteroaryl group having 3 to 30 carbon atoms, and more preferably a heteroaryl group having 3 to 18 carbon atoms. The heteroaryl group may have a substituent, and preferably a heteroaryl having 3 to 18 carbon atoms which may have an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 18 carbon atoms. It is a group. The heteroaryl group represented by Ar ₂ or Ar ₃ may have a condensed ring structure, such as a furan ring, a thiophene ring, a selenophene ring, a silole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, an oxazole ring, a thiazole ring, or a triazole. A condensed ring structure of a ring combination selected from a ring, an oxadiazole ring, and a thiadiazole ring (which may be the same) is preferable. A bithienothiophene ring is preferred.

Ar ₁ , Ar ₂ , Ar ₃ , R ₁ , R _{2 to} R ₇ and R ₁₀ may be adjacent to each other to form a ring. Furthermore, the ring is preferably a ring formed of a hetero atom, an alkylene group, an aromatic ring, or the like. For example, an aryl group (for example, Ar ₁ , Ar ₂ , Ar _{3 in the} general formula (1)) is linked via a single bond or a linking group, so that together with a nitrogen atom (N in the general formula (1)) Examples include the ring that is formed. Examples of the linking group include heteroatoms (for example, —O—, —S—, etc.), alkylene groups (for example, methylene group, ethylene group, etc.), and groups comprising a combination thereof, —S—, A methylene group is preferred. A ring formed by a nitrogen atom (for example, N in the general formula (1)), an alkylene group (for example, a methylene group) and an aryl group (for example, Ar ₁ , Ar ₂ or Ar _{3 in} the general formula (1)) is preferable. .
The ring may further have a substituent, and examples of the substituent include an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group). They may be connected to each other to further form a ring (for example, a benzene ring).
R ₃ and R ₄ are preferably connected to each other to form a ring, and the ring is preferably a benzene ring.
Furthermore, when there are a plurality of R ₁ (m is 2 or more), adjacent ones of the plurality of R ₁ can be connected to each other to form a ring, and the ring is preferably a benzene ring.

In the case where Ar ₁ , Ar ₂ , Ar ₃ has a substituent, and the substituents of R ₁ , R _{2 to} R ₇ , R ₁₀ include a halogen atom, an alkyl group (a cycloalkyl group, a bicycloalkyl group) , Including tricycloalkyl groups), substituted alkyl groups, alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, substituted aryl groups, and heterocyclic groups (may be referred to as heterocyclic groups) Cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group (anilino group) ), Ammonio group, acylamino group, aminocarbonylamino group, alkoxy group Bonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and Arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, Examples include silyl groups, hydrazino groups, ureido groups, boronic acid groups (—B (OH) ₂ ), phosphato groups (—OPO (OH) ₂ ), sulfato groups (—OSO ₃ H), and other known substituents. . As the substituent for R ₁ , R _{2 to} R ₇ , R ₁₀ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heteroaryl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, amino Group, an alkylthio group, an alkenyl group, or a halogen atom is preferred.

When Ar ₁ , Ar ₂ , Ar ₃ have a substituent, each independently a halogen atom, alkyl group, aryl group, heterocyclic group, hydroxy group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, amino Group, alkylthio group, arylthio group, alkenyl group, cyano group or heterocyclic thio group is preferred.
R ₁ is more preferably an alkyl group or an aryl group. R ₆ and R ₇ are more preferably a cyano group.
Examples of the substituent of the substituted alkyl group or the substituted aryl group include the substituents listed above. An alkyl group (preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group) or an aryl group (carbon). An aryl group of formula 6-18, more preferably a phenyl group, is preferred.
When L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , and L ₆ each independently represent an unsubstituted methine group or a substituted methine group, the substituent of the substituted methine group is an alkyl group, an aryl group, or a heterocyclic ring Represents a group, an alkenyl group, an alkoxy group or an aryloxy group, and the substituents may be bonded to each other to form a ring. A 6-membered ring (for example, benzene ring etc.) is mentioned as a ring. Moreover, the substituents of L ₁ or L ₃ and Ar ₁ may be bonded to form a ring. Further, the substituents of L ₆ and R ₇ may be bonded to each other to form a ring.

As an alkyl group which R < ₁ >, R < ₂ > -R < ₇ >, R < ₁₀ > represents, Preferably it is a C1-C6 alkyl group, More preferably, it is a C1-C4 alkyl group. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. R _{2 to} R ₇ are preferably a methyl group or an ethyl group, and more preferably a methyl group. R ₁ is preferably a methyl group, an ethyl group or a t-butyl group, more preferably a methyl group or a t-butyl group.
n is preferably 0 or 1.

The aryl groups represented by R ₁ , R _{2 to} R ₇ , and R ₁₀ are each independently preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 18 carbon atoms. The aryl group may have a substituent, preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 18 carbon atoms which may have an aryl group having 6 to 18 carbon atoms. is there. Examples include a phenyl group, a naphthyl group, an anthracenyl group, a pyrenyl group, a phenanthrenyl group, a methylphenyl group, a dimethylphenyl group, a biphenyl group, and the like, and a phenyl group, a naphthyl group, or an anthracenyl group is preferable.

The heteroaryl groups represented by R ₁ , R _{2 to} R ₇ and R ₁₀ are each independently preferably a heteroaryl group having 3 to 30 carbon atoms, more preferably a heteroaryl group having 3 to 18 carbon atoms. is there. The heteroaryl group may have a substituent, and preferably a heteroaryl having 3 to 18 carbon atoms which may have an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 18 carbon atoms. It is a group. In addition, the heteroaryl group represented by R ₁ , R _{2 to} R ₇ is preferably a heteroaryl group composed of a 5-membered, 6-membered or 7-membered ring or a condensed ring thereof. Examples of the hetero atom contained in the heteroaryl group include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the ring constituting the heteroaryl group include a furan ring, a thiophene ring, a pyrrole ring, a pyrroline ring, a pyrrolidine ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an imidazoline ring, and an imidazolidine. Ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiine ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, Examples include a piperazine ring and a triazine ring.
As the condensed ring, benzofuran ring, isobenzofuran ring, benzothiophene ring, indole ring, indoline ring, isoindole ring, benzoxazole ring, benzothiazole ring, indazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, cinnoline ring, Phthalazine ring, quinazoline ring, quinoxaline ring, dibenzofuran ring, carbazole ring, xanthene ring, acridine ring, phenanthridine ring, phenanthroline ring, phenazine ring, phenoxazine ring, thianthrene ring, thienothiophene ring, indolizine ring, quinolidine ring, A quinuclidine ring, a naphthyridine ring, a purine ring, a pteridine ring, etc. are mentioned.

  m represents an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

  Among the compounds represented by the general formula (1), the following compounds are particularly preferable.

[Electronic blocking layer]
An electron-donating organic material can be used for the electron blocking layer 3. Specifically, in a low molecular material, N, N′-bis (3-methylphenyl)-(1,1′-biphenyl) -4,4′-diamine (TPD) or 4,4′-bis [N Aromatic diamine compounds such as-(naphthyl) -N-phenyl-amino] biphenyl (α-NPD), oxazole, oxadiazole, triazole, imidazole, imidazolone, stilbene derivative, pyrazoline derivative, tetrahydroimidazole, polyarylalkane, butadiene 4,4 ′, 4 ″ -tris (N- (3-methylphenyl) N-phenylamino) triphenylamine (m-MTDATA), porphine, tetraphenylporphine copper, phthalocyanine, copper phthalocyanine, titanium phthalocyanine oxide, etc. Porphyrin compounds, triazole derivatives, oxazizazo Derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, fluorene derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, silazane derivatives, etc. As the polymer material, polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene, and derivatives thereof can be used. Even if it is not, it is possible to use a compound having sufficient hole transportability.

  Specifically, for example, the following compounds described in JP-A-2008-72090 are shown, but the present invention is not limited thereto. The following Ea represents the electron affinity of the material, and Ip represents the ionization potential of the material. “EB” in EB-1, 2,... Stands for “electronic blocking”.

  An inorganic material can also be used as the electron blocking layer 3. In general, since an inorganic material has a dielectric constant larger than that of an organic material, when it is used for the electron blocking layer 3, a large voltage is applied to the photoelectric conversion layer 4, and the photoelectric conversion efficiency can be increased. Materials that can be the electron blocking layer 3 include calcium oxide, chromium oxide, chromium oxide copper, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, indium copper oxide, Examples include indium silver oxide and iridium oxide.

  In the electron blocking layer 3 composed of a plurality of layers, the layer adjacent to the photoelectric conversion layer 4 among the plurality of layers is preferably a layer made of the same material as the p-type organic semiconductor contained in the photoelectric conversion layer 4. By using the same p-type organic semiconductor for the electron blocking layer 3, it is possible to suppress the formation of intermediate levels at the interface between the photoelectric conversion layer 4 and the adjacent layer, and to further suppress the dark current.

  When the electron blocking layer 3 is a single layer, the layer can be a layer made of an inorganic material, or in the case of a plurality of layers, one or more layers can be a layer made of an inorganic material. it can.

[Hole blocking layer]
An electron-accepting organic material can be used for the hole blocking layer. Examples of the electron-accepting material include 1,3-bis (4-tert-butylphenyl-1,3,4-oxadiazolyl) phenylene (OXD-7) and other oxadiazole derivatives, anthraquinodimethane derivatives, and diphenylquinone derivatives. , Bathocuproine, bathophenanthroline, and derivatives thereof, triazole compounds, tris (8-hydroxyquinolinato) aluminum complexes, bis (4-methyl-8-quinolinato) aluminum complexes, distyrylarylene derivatives, silole compounds, etc. Can do. Moreover, even if it is not an electron-accepting organic material, it can be used if it is a material which has sufficient electron transport property. A porphyrin-based compound or a styryl-based compound such as DCM (4-dicyanomethylene-2-methyl-6- (4- (dimethylaminostyryl))-4H pyran) or a 4H pyran-based compound can be used.

[Pixel electrode]
Examples of the material of the electrode 2 (pixel electrode 104) include metals, metal oxides, metal nitrides, metal borides, organic conductive compounds, and mixtures thereof. Specific examples include tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), indium tungsten oxide (IWO), conductive metal oxides such as titanium oxide, and metal nitrides such as TiN. Metal, gold (Au), platinum (Pt), silver (Ag), chromium (Cr), nickel (Ni), aluminum (Al), etc., and a mixture or laminate of these metals and conductive metal oxides Products, organic conductive compounds such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO. As the material for the transparent conductive film, ITO, IZO, tin oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), zinc oxide, antimony-doped zinc oxide (AZO), gallium-doped zinc oxide ( GZO).

  A step corresponding to the film thickness of the electrode 2 is steep at the end of the electrode 2, there are conspicuous irregularities on the surface of the electrode 2, or minute dust (particles) adhere to the electrode 2 Then, the layer on the electrode 2 becomes thinner than a desired film thickness or cracks are generated. When the electrode 5 (counter electrode 108) is formed on the layer in such a state, a pixel defect such as an increase in dark current or a short circuit occurs due to contact or electric field concentration between the electrode 2 and the electrode 5 in the defective portion. . Furthermore, the above-described defects may reduce the adhesion between the electrode 2 and the layer above it and the heat resistance of the organic photoelectric conversion element 10.

  In order to prevent the above defects and improve the reliability of the element, the surface roughness Ra of the electrode 2 is preferably 0.6 nm or less. The smaller the surface roughness Ra of the electrode 2, the smaller the surface unevenness, and the better the surface flatness. Further, in order to remove particles on the electrode 2, it is particularly preferable to clean the substrate by a general cleaning technique used in a semiconductor manufacturing process before forming the electron blocking layer 3.

[Counter electrode]
Examples of the material of the electrode 5 (counter electrode 108) include metals, metal oxides, metal nitrides, metal borides, organic conductive compounds, and mixtures thereof. Specific examples include tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), indium tungsten oxide (IWO), conductive metal oxides such as titanium oxide, and metal nitrides such as TiN. Metal, gold (Au), platinum (Pt), silver (Ag), chromium (Cr), nickel (Ni), aluminum (Al), etc., and a mixture or laminate of these metals and conductive metal oxides Products, organic conductive compounds such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO. As the material for the transparent conductive film, ITO, IZO, tin oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), zinc oxide, antimony-doped zinc oxide (AZO), gallium-doped zinc oxide ( GZO).

[Sealing layer]
The following conditions are required for the sealing layer 6 (sealing layer 110).
First, it is possible to protect the photoelectric conversion layer by preventing intrusion of factors that degrade the organic photoelectric conversion material contained in the solution, plasma, and the like in each manufacturing process of the device.
Secondly, after the device is manufactured, the penetration of factors that degrade the organic photoelectric conversion material, such as water molecules, is prevented, and deterioration of the photoelectric conversion layer 4 is prevented over a long period of storage / use.
Third, when forming the sealing layer 6, the already formed photoelectric conversion layer is not deteriorated.
Fourth, since incident light reaches the photoelectric conversion layer 4 through the sealing layer 6, the sealing layer 6 must be transparent to light having a wavelength detected by the photoelectric conversion layer 4.

  The sealing layer 6 can be composed of a thin film made of a single material. However, by providing a different function for each layer in a multi-layer structure, the stress of the entire sealing layer 6 is reduced, and dust is generated during the manufacturing process. Such effects as the suppression of defects such as cracks and pinholes caused by the above, and the optimization of material development can be expected. For example, the sealing layer 6 is formed by laminating a “sealing auxiliary layer” that has a function that is difficult to achieve on the layer that serves the original purpose of preventing the penetration of deterioration factors such as water molecules. A two-layer structure can be formed. Although it is possible to have three or more layers, it is preferable that the number of layers is as small as possible in consideration of manufacturing costs.

[Formation of sealing layer 6 by atomic layer deposition]
The performance of organic photoelectric conversion materials is significantly deteriorated due to the presence of deterioration factors such as water molecules. Therefore, it is necessary to cover and seal the entire photoelectric conversion layer with ceramics such as dense metal oxide / metal nitride / metal nitride oxide that does not allow water molecules to permeate, diamond-like carbon (DLC), or the like. Conventionally, aluminum oxide, silicon oxide, silicon nitride, silicon nitride oxide, a laminated structure thereof, a laminated structure of them and an organic polymer, or the like is used as a sealing layer by various vacuum film forming techniques. However, since these conventional sealing layers are difficult to grow in a step due to structures on the substrate surface, minute defects on the substrate surface, particles adhering to the substrate surface, etc. (because the step becomes a shadow), In comparison, the film thickness is significantly reduced. For this reason, the step portion becomes a path through which the deterioration factor penetrates. In order to completely cover the step with the sealing layer, it is necessary to form the film so as to have a film thickness of 1 μm or more in the flat portion, and to increase the thickness of the entire sealing layer. The degree of vacuum when forming the sealing layer is preferably 1 × 10 ³ Pa or less, and more preferably 5 × 10 ² Pa or less.

  In the image sensor 100 having a pixel size of less than 2 μm, particularly about 1 μm, if the distance between the color filter 111 and the photoelectric conversion layer, that is, the film thickness of the sealing layer 110 is large, incident light is diffracted / diverged in the sealing layer 110. As a result, color mixing occurs. For this reason, the imaging element 100 with a pixel size of about 1 μm requires a sealing layer material / manufacturing method that does not deteriorate the element performance even if the film thickness of the entire sealing layer 110 is reduced.

  The atomic layer deposition (ALD) method is a kind of CVD method, and adsorption / reaction of organometallic compound molecules, metal halide molecules, and metal hydride molecules, which are thin film materials, onto the substrate surface and unreacted groups contained therein. Is a technique for forming a thin film by alternately repeating decomposition. When the thin film material reaches the substrate surface, it is in the above-mentioned low molecular state, so that the thin film can be grown in a very small space where the low molecule can enter. For this reason, the step portion, which was difficult with the conventional thin film formation method, is completely covered (the thickness of the thin film grown on the step portion is the same as the thickness of the thin film grown on the flat portion), that is, the step coverage is very high. Excellent. For this reason, steps due to structures on the substrate surface, minute defects on the substrate surface, particles adhering to the substrate surface, and the like can be completely covered, and such a step portion does not become an intrusion path for a deterioration factor of the photoelectric conversion material. When the sealing layer 6 is formed by the atomic layer deposition method, the required sealing layer thickness can be effectively reduced as compared with the prior art.

  In the case of forming the sealing layer 6 by the atomic layer deposition method, a material corresponding to the ceramics preferable for the sealing layer 6 described above can be appropriately selected. However, since the photoelectric conversion layer of the present invention uses an organic photoelectric conversion material, it is limited to a material capable of growing a thin film at a relatively low temperature so that the organic photoelectric conversion material does not deteriorate. According to the atomic layer deposition method using alkyl aluminum or aluminum halide as the material, a dense aluminum oxide thin film can be formed at less than 200 ° C. at which the organic photoelectric conversion material does not deteriorate. In particular, when trimethylaluminum is used, an aluminum oxide thin film can be formed even at about 100 ° C. Silicon oxide and titanium oxide are also preferable because a dense thin film can be formed at less than 200 ° C., similarly to aluminum oxide, by appropriately selecting materials.

[Sealing auxiliary layer]
The thin film formed by the atomic layer deposition method can achieve a high-quality thin film formation at a low temperature that is unmatched from the viewpoint of step coverage and denseness. However, the physical properties of the thin film material may be deteriorated by chemicals used in the photolithography process. For example, since an aluminum oxide thin film formed by atomic layer deposition is amorphous, the surface is eroded by an alkaline solution such as a developer or a stripping solution. In this case, a thin film having excellent chemical resistance must be formed on the aluminum oxide thin film formed by the atomic layer deposition method, that is, a sealing auxiliary layer serving as a functional layer for protecting the sealing layer 6 is provided. I need it.

  On the other hand, a thin film formed by a CVD method such as an atomic layer deposition method has many examples in which internal stress has a very large tensile stress, and a process in which intermittent heating and cooling are repeated like a semiconductor manufacturing process, The storage / use in a high-temperature / high-humidity atmosphere for a long time may cause deterioration of the thin film itself with cracks.

  In order to overcome the problems of the sealing layer 6 formed by the atomic layer deposition method as described above, for example, a metal having excellent chemical resistance formed by a physical vapor deposition (PVD) method such as a sputtering method. A configuration in which a sealing auxiliary layer including any one of ceramics such as oxide, metal nitride, and metal nitride oxide is provided is preferable. Here, the first sealing layer is formed by the atomic layer deposition method, and is formed on the first sealing layer by the PVD method and is any one of metal oxide, metal nitride, and metal nitride oxide. One containing one is defined as a second sealing layer. If it carries out like this, it will become easy to improve the chemical resistance of the sealing layer 6 whole. Furthermore, ceramics formed by PVD methods such as sputtering often have a large compressive stress, and can cancel the tensile stress of the first sealing layer formed by atomic layer deposition. Therefore, not only the stress of the sealing layer 6 is alleviated and the reliability of the sealing layer 6 itself is increased, but the stress of the sealing layer 6 deteriorates or destroys the performance of the photoelectric conversion layer or the like. Occurrence can be remarkably suppressed.

  In particular, the first sealing layer preferably includes a second sealing layer formed by sputtering and containing any one of aluminum oxide, silicon oxide, silicon nitride, and silicon nitride oxide. .

  The first sealing layer preferably has a thickness of 0.05 μm or more and 0.5 μm or less. The first sealing layer preferably contains any of aluminum oxide, silicon oxide, and titanium oxide.

  Hereinafter, the effect of providing the non-vacuum period will be described in Examples.

Example 1
An image sensor provided with an organic photoelectric conversion element was produced. The procedure is as follows. First, an amorphous ITO film is formed by sputtering on a CMOS substrate on which a readout circuit composed of a CMOS circuit and a connection electrode connected thereto are formed, and this is patterned, and a pixel electrode is formed on each connection electrode. Formed. Next, an electron blocking layer was formed on the plurality of pixel electrodes by depositing the material indicated by EB-3 to a thickness of 100 nm by vacuum heating deposition. Next, Compound 1 and fullerene (C ₆₀ ) were co-deposited on the electron blocking layer by vacuum heating deposition (in a ratio of 1: 3) to form a photoelectric conversion layer having a thickness of 400 nm. In this deposition, an organic material deposition cell “Thermo Ball Cell (manufactured by Choshu Sangyo Co., Ltd.)” was used. The vacuum deposition of the electron blocking layer and the photoelectric conversion layer was all performed at a vacuum degree of 4 × 10 ⁻⁴ Pa or less. Next, after the imaging device in the process of being produced was placed in an air atmosphere for 3 minutes, this imaging device was set in a device for forming a counter electrode, and amorphous ITO with a thickness of 10 nm was formed on the photoelectric conversion layer by sputtering. A counter electrode was formed by film formation. The counter electrode was formed under vacuum. Next, after placing the imaging element in the process of being in an air atmosphere for 3 minutes, this imaging element was set in an apparatus for forming a sealing layer, and a silicon oxide film was formed on the counter electrode by heat evaporation. An aluminum oxide film was formed thereon by the ALD method to form a sealing layer. The counter electrode and the sealing layer were formed under vacuum.

(Example 2)
An imaging device was produced in the same manner as in Example 1 except that Compound 1 was changed to Compound 9.

Example 3
Except that the imaging device in the process of production was placed in a nitrogen gas atmosphere between the photoelectric conversion layer forming step and the counter electrode forming step and between the counter electrode forming step and the sealing layer forming step. In the same manner as in Example 1, an image sensor was produced. It should be noted that the time for placing the imaging element in the middle of the production in a nitrogen gas atmosphere was 3 minutes.

Example 4
An image pickup device was manufactured in the same manner as in Example 1 except that the time during which the image pickup device in the process of preparation was kept in the atmosphere was 30 minutes.

(Example 5)
An image pickup device was manufactured in the same manner as in Example 3 except that the time during which the image pickup device in the process of preparation was placed in a nitrogen gas atmosphere was 30 minutes.

(Example 6)
An image pickup device was manufactured in the same manner as in Example 1 except that the time during which the image pickup device in the process of preparation was kept in the atmosphere was 1 minute.

(Example 7)
An image pickup device was manufactured in the same manner as in Example 3 except that the time during which the image pickup device in the process of preparation was placed in a nitrogen gas atmosphere was 1 minute.

(Example 8)
An imaging device in the middle of fabrication is placed under vacuum for 3 minutes between the photoelectric conversion layer forming step and the counter electrode forming step, and an imaging device in the middle of fabrication between the counter electrode forming step and the sealing layer forming step. Was prepared in the same manner as in Example 1 except that was placed in an air atmosphere for 48 hours.

Example 9
An imaging device was produced in the same manner as in Example 1 except that Compound 1 was changed to Compound 7.

(Example 10)
An imaging device was produced in the same manner as in Example 3 except that Compound 1 was changed to Compound 7.

(Comparative Example 1)
After the photoelectric conversion layer forming step and the counter electrode forming step, and between the counter electrode forming step and the sealing layer forming step, the imaging device being fabricated was placed under vacuum for 3 minutes, An image pickup device was manufactured in the same manner as in Example 1 except that it was set in an apparatus for performing the next step.

(Comparative Example 2)
After the photoelectric conversion layer forming step and the counter electrode forming step, and between the counter electrode forming step and the sealing layer forming step, the imaging device being fabricated was placed under vacuum for 3 minutes, An imaging device was manufactured in the same manner as in Example 2 except that the imaging device was set in an apparatus for performing the next step.

(Comparative Example 3)
Compound 1 is formed into a photoelectric conversion layer by vacuum heating vapor deposition with a thickness of 100 nm, between the photoelectric conversion layer forming step and the counter electrode forming step, and between the counter electrode forming step and the sealing layer forming step. Then, an imaging device was fabricated in the same manner as in Example 1 except that the imaging device in the middle of production was placed under vacuum for 3 minutes and then set in an apparatus for performing the next step.

(Comparative Example 4)
The imaging element being fabricated was placed in the atmosphere for 3 minutes between the photoelectric conversion layer forming step and the counter electrode forming step, and between the counter electrode forming step and the sealing layer forming step. An imaging device was manufactured in the same manner as in Comparative Example 3 except that it was set in an apparatus for performing the next step.

(Comparative Example 5)
Compound 1 was formed into a film with a thickness of 100 nm by vacuum heating vapor deposition, and then fullerene (C ₆₀ ) was formed with a thickness of 100 nm on compound 1 to form a photoelectric conversion layer with a thickness of 200 nm. The imaging device being fabricated was placed under vacuum for 3 minutes between the layer forming step and the counter electrode forming step, and between the counter electrode forming step and the sealing layer forming step. An image pickup device was manufactured in the same manner as in Example 1 except that it was set in an apparatus for performing the process.

(Comparative Example 6)
Comparative Example 5 except that the imaging element being produced was placed in an air atmosphere between the photoelectric conversion layer forming step and the counter electrode forming step, and between the counter electrode forming step and the sealing layer forming step. In the same manner as described above, an image sensor was manufactured.

(Comparative Example 7)
After the photoelectric conversion layer forming step and the counter electrode forming step, and between the counter electrode forming step and the sealing layer forming step, the imaging device being fabricated was placed under vacuum for 3 minutes, An image pickup device was manufactured in the same manner as in Example 9 except that it was set in an apparatus for performing the next step.

The external quantum efficiency (relative value when the numerical value of Comparative Example 1 is set to 100) at the maximum sensitivity wavelength when applied with an electric field of 2 × 10 ⁵ V / cm of each organic photoelectric conversion element in Examples and Comparative Examples The measurement results are shown in Table 1. Note that the value of the external quantum efficiency was a value when a positive bias was applied to the counter electrode of the fabricated element, light was incident from the counter electrode side, and holes were extracted from the pixel electrode.

Comparing Comparative Example 3 and Comparative Example 4, it can be seen that the external quantum efficiency is halved by providing a non-vacuum period when the photoelectric conversion layer is formed of one material. When comparing the Comparative Examples 5 and 6, in the case where the photoelectric conversion layer in the laminated structure of compound 1 and C _60, by providing a non-vacuum period, it can be seen that the external quantum efficiency is reduced nearly 20%.

On the other hand, when comparing the Comparative Example 1 and Example 1, 3, 6, 7, in the case where a photoelectric conversion layer and a mixed layer of compound 1 and C _60, the external quantum efficiency is provided a non-vacuum period not deteriorate Rather, it can be seen that it rises slightly. Further, comparing Comparative Example 2 and Example 2, it can be seen that when the photoelectric conversion layer is a mixed layer of Compound 9 and _C60 , the external quantum efficiency does not deteriorate even if a non-vacuum period is provided. Further, comparing Comparative Example 7 with Examples 9 and 10, it can be seen that when the photoelectric conversion layer is a mixed layer of Compound 7 and _C60 , the external quantum efficiency does not deteriorate even if a non-vacuum period is provided. In Example 8, a vacuum period and a non-vacuum period are provided, but even in this case, the external quantum efficiency is increased as compared with the case where no non-vacuum period is provided as in Comparative Example 1. I understood.

  From this result, when the photoelectric conversion layer is a mixed layer of a p-type organic semiconductor and fullerene or a fullerene derivative, any of the steps from the photoelectric conversion layer formation step to the sealing layer formation step is performed. Alternatively, it has been found that the device performance does not deteriorate even when a non-vacuum period is provided in all.

  In Examples 4 and 5, the external quantum efficiency is increased by nearly 10% compared to Examples 1, 3, 6 and 7. In Example 8, the external quantum efficiency is increased by nearly 10% compared to Examples 1, 3, 6, and 7. From this result, it was also found that the device performance can be further improved by setting the non-vacuum period to 30 minutes or more.

  Even when the photoelectric conversion layer was formed directly on the pixel electrode without forming the electron blocking layer, the same results as shown in Table 1 were obtained.

  As described above, the following items are disclosed in this specification.

  The disclosed method for producing an organic photoelectric conversion element is formed between a first electrode, a second electrode formed above the first electrode, and the first electrode and the second electrode. A method for producing an organic photoelectric conversion element, comprising: a photoelectric conversion layer containing an organic material; and the first electrode, the second electrode, and a sealing layer for sealing the photoelectric conversion layer. The layer is a non-light-emitting layer including a mixed layer of fullerene or a fullerene derivative and a p-type organic semiconductor, and a first step of forming the first electrode above the substrate, and above the first electrode A second step of forming the photoelectric conversion layer, a third step of forming the second electrode above the photoelectric conversion layer, and a second step of forming the sealing layer above the second electrode. Four steps, and each step of the second step to the fourth step is performed under vacuum, During the serial after completion of the second step to the start of the fourth step, those comprising a fifth step of placing said organic photoelectric conversion element of the process of manufacturing under non-vacuum.

  In the disclosed method for producing an organic photoelectric conversion element, the non-vacuum state in the fifth step is an air atmosphere or an inert atmosphere.

  In the disclosed method for producing an organic photoelectric conversion element, the fifth step is performed between the second step and the third step, and between the third step and the fourth step. This is what you do.

  In the disclosed method for producing an organic photoelectric conversion element, the fifth step is performed between the second step and the third step, or between the third step and the fourth step. Is.

  In the disclosed method for producing an organic photoelectric conversion element, the photoelectric conversion layer is formed by a dry film forming method in the second step.

  In the disclosed method for producing an organic photoelectric conversion element, in the second step, the fullerene or fullerene derivative and the p-type organic semiconductor are co-evaporated by vacuum heating vapor deposition to form the mixed layer.

  The manufacturing method of the disclosed organic photoelectric conversion element contains what the said p-type organic semiconductor is a compound represented by General formula (1).

  In the fifth method, the disclosed method for producing an organic photoelectric conversion element is to place the organic photoelectric conversion element in the process of production in the non-vacuum for 1 minute or longer.

  In the disclosed method for producing an organic photoelectric conversion element, the organic photoelectric conversion element includes an electron blocking layer provided between the first electrode and the photoelectric conversion layer, and after the first step, the first A step of forming the electron blocking layer before the second step.

  The manufacturing method of the disclosed organic photoelectric conversion element is a sixth step of forming an electron blocking layer indicated by EB-3 on the first electrode between the first step and the second step. Is provided.

  The disclosed organic photoelectric conversion element is manufactured by the manufacturing method of the organic photoelectric conversion element.

  The disclosed imaging device includes a plurality of the organic photoelectric conversion elements and a circuit board on which a signal readout circuit for reading a signal corresponding to the charge generated in the photoelectric conversion layer of each organic photoelectric conversion element is formed. It is.

  The disclosed imaging device includes the imaging device.

DESCRIPTION OF SYMBOLS 1 Substrate 2, 5 Electrode 3 Electron blocking layer 4 Photoelectric conversion layer 6 Sealing layer 10 Organic photoelectric conversion element

Claims (8)

A first electrode; a second electrode formed above the first electrode; a photoelectric conversion layer including an organic material formed between the first electrode and the second electrode; A method for producing an organic photoelectric conversion element, comprising: a second electrode; and a sealing layer that seals the photoelectric conversion layer,
The photoelectric conversion layer is a non-light-emitting layer including a mixed layer of fullerene or a fullerene derivative and a p-type organic semiconductor,
A first step of forming the first electrode above the substrate;
A second step of forming the photoelectric conversion layer above the first electrode;
A third step of forming the second electrode above the photoelectric conversion layer;
A fourth step of forming the sealing layer above the second electrode,
Perform each step of the second step to the fourth step under vacuum,
Between the end of the second step and the start of the fourth step, comprising a fifth step of placing the organic photoelectric conversion element in the middle of production under non-vacuum,
The said p-type organic semiconductor is a manufacturing method of the organic photoelectric conversion element which is a compound represented by following General formula (1).

(In the formula, L ₂ and L ₃ each independently represent an unsubstituted methine group or a substituted methine group. N represents an integer of 0 to 2. Ar ₁ represents a divalent substituted arylene group or an unsubstituted arylene. .Ar _2, Ar ₃ represents a group independently represents a substituted aryl group, an unsubstituted aryl group, a substituted alkyl group, an unsubstituted alkyl group, .Ar ₁ representing a heteroaryl group, or an unsubstituted heteroaryl group into substituted, Adjacent ones of Ar ₂ and Ar ₃ may be linked to each other to form a ring, L ₁ is an unsubstituted methine group or a substituted methine group bonded to the following general formula (2), or the following general formula The group represented by (3) is represented.

(In the formula, Z ₁ is a ring containing a carbon atom bonded to an unsubstituted methine group or a substituted methine group and a carbonyl group adjacent to the carbon atom, and is a 5-membered ring, a 6-membered ring, or a 5-membered ring. And a condensed ring containing at least one of 6-membered ring, X represents a hetero atom, Z ₂ is a ring containing X, and is a 5-membered ring, 6-membered ring, 7-membered ring, or 5-membered A condensed ring containing at least one of a ring, a 6-membered ring and a 7-membered ring, L _{4 to} L ₆ each independently represents an unsubstituted methine group or a substituted methine group, and R ₆ and R ₇ each independently Represents a hydrogen atom or a substituent, and adjacent ones may be bonded to each other to form a ring, k represents an integer of 0 to 2. * in the general formula (2) is an unsubstituted methine group or a substituted group Represents the position of binding to the methine group , and * in the general formula (3) binds to L ₂ or Ar ₁ Represents the bond position. It is a manufacturing method of the organic photoelectric conversion element according to claim 1,
The non-vacuum under the fifth step is an organic photoelectric conversion element manufacturing method in an air atmosphere or an inert atmosphere. It is a manufacturing method of the organic photoelectric conversion element of Claim 1 or 2,
The manufacturing method of the organic photoelectric conversion element which performs a said 5th process in both between said 2nd process and said 3rd process, and between said 3rd process and said 4th process. It is a manufacturing method of the organic photoelectric conversion element of Claim 1 or 2,
The manufacturing method of the organic photoelectric conversion element which performs said 5th process between said 2nd process and said 3rd process or between said 3rd process and said 4th process. It is a manufacturing method of the organic photoelectric conversion element given in any 1 paragraph of Claims 1-4,
In the second step, a method for producing an organic photoelectric conversion element, wherein the photoelectric conversion layer is formed by a dry film forming method. It is a manufacturing method of the organic photoelectric conversion element according to claim 5,
In the second step, the fullerene or fullerene derivative and the p-type organic semiconductor are co-evaporated by vacuum heating deposition to form the mixed layer. It is a manufacturing method of the organic photoelectric conversion element given in any 1 paragraph of Claims 1-6,
In the fifth step, the method for producing an organic photoelectric conversion element in which the organic photoelectric conversion element being produced is placed in the non-vacuum for 1 minute or longer. It is a manufacturing method of the organic photoelectric conversion element given in any 1 paragraph of Claims 1-7,
The organic photoelectric conversion element includes an electron blocking layer provided between the first electrode and the photoelectric conversion layer,
The manufacturing method of the organic photoelectric conversion element which has the process of forming the said electron blocking layer after said 1st process and before said 2nd process.

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