KR101846975B1 - Method of manufacturing organic photo-electric conversion device, organic photo-electric conversion device, imaging device, and imaging apparatus - Google Patents

Abstract

A manufacturing method of an organic photoelectric conversion element capable of preventing deterioration of device performance and increase in cost is provided.
An electrode 5 formed above the electrode 2 and the electrode 2 and a photoelectric conversion layer 4 including an organic material formed between the electrode 2 and the electrode 5 and the electrode 2, And a sealing layer (6) sealing the photoelectric conversion layer (4), wherein the photoelectric conversion layer (4) comprises a mixed layer of fullerene or a fullerene derivative and a p-type organic semiconductor A first step of forming an electrode 2 above the substrate 1, a second step of forming a photoelectric conversion layer 4 above the electrode 2, a second step of forming a photoelectric conversion layer 4, And a fourth step of forming a sealing layer 6 above the electrode 5, wherein each step of the second step to the fourth step is carried out under vacuum And a fifth step of placing the organic photoelectric conversion element under production in a non-vacuum state between each step between the second step and the fourth step.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic photoelectric conversion device, an organic photoelectric conversion device, an organic photoelectric conversion device, an organic electroluminescence device, an organic electroluminescent device, an organic electroluminescent device,

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

An organic photoelectric conversion element having a pair of electrodes and a photoelectric conversion layer using an organic material formed between the pair of electrodes is known. Patent Document 1 discloses an organic photoelectric conversion device using a mixed layer of a p-type organic semiconductor and a fullerene or fullerene derivative (layer in which two materials are deposited together) as a photoelectric conversion layer for the purpose of improving photoelectric conversion efficiency.

In general, it is known that an organic material is affected by moisture or oxygen and its characteristics are changed. Therefore, when manufacturing the organic photoelectric conversion element, it has been considered as common sense that it is preferable to perform all the steps in a vacuum state.

On the other hand, there is a concern that if the vacuum coherent process is to be realized, the manufacturing facility becomes large-scale and the cost is increased. Thus, a method of obtaining an organic photoelectric conversion element without deterioration in performance while suppressing the manufacturing cost has been desired.

Patent Document 2 discloses that all the manufacturing steps of the organic photoelectric conversion element are not performed in a vacuum consistently. Patent Document 2 discloses an organic solar cell in which electrodes, fullerene, p-type organic semiconductors and electrodes are stacked in this order, fullerene and p-type organic semiconductors are sequentially formed on the electrode by vacuum evaporation, And thereafter the electrode is formed by vacuum deposition. However, this method can not prevent deterioration of device characteristics.

In addition, in the organic EL device which is not an organic photoelectric conversion element but an element using the same organic material, the one which is manufactured by the vacuum unified process is described in Patent Document 3. In order to stabilize the performance, The production method is described in Patent Documents 4 and 5.

Japanese Patent Application Laid-Open No. 2007-123707 Japanese Patent Application Laid-Open No. 09-74216 Japanese Unexamined Patent Application Publication No. 10-335061 Japanese Patent Application Laid-Open No. 2009-231278 Japanese Patent Application Laid-Open No. 09-330790

The present invention relates to an organic photoelectric conversion device having a photoelectric conversion layer including a mixed layer of a fullerene or a fullerene derivative and a p-type organic semiconductor, which can prevent deterioration of the device performance and an increase in cost, And an object of the present invention is to provide an organic photoelectric conversion element manufactured by this manufacturing method, an image pickup element having the organic photoelectric conversion element, and an image pickup apparatus having the image pickup element.

A method of manufacturing an organic photoelectric conversion device according to the present invention includes 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, And a sealing layer that seals the first electrode, the second electrode, and the photoelectric conversion layer, wherein the photoelectric conversion layer includes a mixed layer of a fullerene or a fullerene derivative and a p-type organic semiconductor A second step of forming the photoelectric conversion layer above the first electrode; and a second step of forming a second electrode on the photoelectric conversion layer, And a fourth step of forming the sealing layer above the second electrode, wherein each step of the second step to the fourth step is performed under vacuum, and the step After termination of the second step to the fifth step includes placing the organic photoelectric conversion element manufactured by the way between the start of the fourth step under non-vacuum.

According to this manufacturing method, since the fifth step is formed after the end of the second step to the start of the fourth step, a non-luminescent photoelectric conversion layer containing a mixed layer of fullerene or a fullerene derivative and a p-type organic semiconductor is provided It is possible to prevent performance deterioration and increase in cost of an organic photoelectric conversion element. Patent Documents 4 and 5 are inventions related to a light emitting device and are completely different from the method of manufacturing an organic photoelectric conversion device having a non-luminescent photoelectric conversion layer. Patent Document 2 does not describe the formation of the photoelectric conversion layer as a mixed layer. In addition, as described in the comparative example described later, in the structure in which the photoelectric conversion layer is formed not in the mixed layer but in the laminated structure, deterioration of the device performance can not be prevented even if the fifth step is formed. In view of this, the inventions described in Patent Documents 1 to 5 can not solve the problems of the present invention, but this problem can be solved by the present manufacturing method.

The organic photoelectric conversion device of the present invention is manufactured by the above-described manufacturing method.

An image pickup device of the present invention includes a circuit board on which a plurality of the organic photoelectric conversion elements and a signal reading circuit for reading a signal corresponding to the charge generated in the photoelectric conversion layer of each organic photoelectric conversion element are formed.

The image pickup apparatus of the present invention includes the image pickup element.

(Effects of the Invention)

According to the present invention, there is provided a method of manufacturing 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, which can prevent degradation of device performance and increase in cost, , An organic photoelectric conversion element manufactured by this manufacturing method, an image pickup element having the organic photoelectric conversion element, and an image pickup apparatus having the image pickup element.

1 is a schematic cross-sectional view showing a schematic structure of an organic photoelectric conversion element for explaining an embodiment of the present invention.
2 is a schematic cross-sectional view showing a schematic configuration of an image pickup device for explaining an embodiment of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to the drawings.

1 is a schematic cross-sectional view showing a schematic structure of an organic photoelectric conversion element for explaining an embodiment of the present invention. The organic photoelectric conversion element 10 shown in Fig. 1 comprises a substrate 1, electrodes 2 formed on the substrate 1, an electron blocking layer 3 formed on the electrode 2, an electron blocking layer The electrode 5 formed on the photoelectric conversion layer 4 and the sealing layer 6 formed on the electrode 5. The photoelectric conversion layer 4 is formed on the photoelectric conversion layer 3, 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 containing 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 trapping holes in the charge 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 electric charges corresponding 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 an n-type organic semiconductor, fullerene or fullerene derivative, are mixed. The mixed layer refers to a layer in which a plurality of materials are mixed or dispersed, for example, a layer formed by co-depositing a plurality of materials together. Or a layer formed by mixing and mixing a plurality of materials in a solvent and applying the same. By incorporating such a mixed layer in the photoelectric conversion layer 4, it is possible to improve the photoelectric conversion efficiency of the photoelectric conversion layer by compensating for the drawback that the carrier diffusion length of the photoelectric conversion layer is short.

The photoelectric conversion layer 4 is a non-luminescent layer having characteristics different from the luminescent layer of the organic EL (the layer converting the electric signal into light). The non-luminescent layer has a luminescence quantum efficiency of 1% or less, preferably 0.5% or less, more preferably 0.1% or less in a visible light region (wavelength 400 nm to 730 nm). The reason why the photoelectric conversion layer 4 is a non-luminescent layer is that when the organic photovoltaic device is used as an image pickup device, the light emission quantum efficiency exceeds 1%, the image pickup 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 forming method is preferable in that uniform film formation is easy and impurities are difficult to be incorporated, and also because it is easy to control film thickness or to laminate different materials.

Specific examples of the dry film forming method include a physical vapor phase growth method such as a vacuum vapor deposition method, a sputtering method, an ion plating method and an MBE method, or a CVD method such as plasma polymerization. The vacuum deposition method is preferably used, and in the case of forming the film by the vacuum deposition method, the manufacturing conditions such as the degree of vacuum and the deposition temperature can be set according to a normal method. In the case of forming the light-receiving layer by a vapor deposition method, the larger the decomposition temperature than the deposition-possible temperature, the more preferable the thermal decomposition at the time of vapor deposition can be suppressed.

In the case of forming the light receiving layer by a dry film forming method, a degree of vacuum at the time of forming it is considering to prevent the deterioration of device characteristics at the time of forming the light receiving layer 1 × 10 ^-3 Pa or less, preferably, 4 × 10 ^-4 Pa or less More preferably 1 x 10 <" ⁴ > Pa or less.

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. When it is 10 nm or more, a desirable dark current suppressing effect is obtained, and when it is 1000 nm or less, a preferable photoelectric conversion efficiency is obtained.

The electron blocking layer 3 included in the light receiving layer suppresses injection of electrons from the electrode 2 into the photoelectric conversion layer 4 and prevents electrons generated in the photoelectric conversion layer 4 from flowing toward the electrode 2 . The electron blocking layer 3 is composed of an organic material or an inorganic material or both.

The electrode 5 is an electrode that collects electrons in the charge generated in the photoelectric conversion layer 4. The electrode 5 uses a conductive material (for example, ITO) which is sufficiently transparent with respect to light having a sensitivity of the photoelectric conversion layer 4 in order to cause light to enter the photoelectric conversion layer 4. It is possible to move holes in the charge generated in the photoelectric conversion layer 4 to the electrode 2 and electrons to the electrode 5 by applying a bias voltage between the electrode 5 and the electrode 2. [

The sealing layer 6 is a layer for preventing a factor that deteriorates an organic material such as water or oxygen from intruding into a light-receiving layer containing an organic material. The sealing layer 6 is formed so as to cover the electrode 2, the electron blocking layer 3, the photoelectric conversion layer 4, and the electrode 5.

In the organic photoelectric conversion device 10 constructed as described above, the electrode 5 is an electrode on the light incidence side, and when light is incident from above the electrode 5, the light passes through the electrode 5 to form the photoelectric conversion layer 4 , And charges are generated there. The holes in the generated charges move to the electrode 2. The light that has moved to the electrode 2 is converted into a voltage signal in accordance with the amount of the voltage, and the light is converted into a voltage signal to be drawn out.

The electron blocking layer 3 may be composed of a plurality of layers. By doing so, an interface is formed between the respective layers constituting the electron blocking layer 3, and discontinuity occurs in the intermediate level existing in each layer. As a result, the electron blocking effect can be enhanced because the movement of the charge through the intermediate level or the like becomes difficult. However, if the layers constituting the electron blocking layer 3 are made of the same material, the intermediate levels present in each layer may be completely the same. Therefore, in order to further enhance the electron blocking effect, .

Alternatively, a bias voltage may be applied so as to collect electrons in the electrode 2 and collect holes in the electrode 5. In this case, a hole blocking layer may be formed instead of the electron blocking layer 3. The hole blocking layer is a layer composed of an organic material for inhibiting the injection of holes from the electrode 2 into the photoelectric conversion layer 4 and preventing the holes generated in the photoelectric conversion layer 4 from flowing toward the electrode 2 . By forming a plurality of the hole blocking layers, the hole blocking effect can be enhanced.

Further, the electrons or holes collected by the electrode 5 may be converted into a voltage signal corresponding to the amount of the electrons or holes and may be taken out to the outside. In this case, an electron blocking layer or a hole blocking layer may be formed 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, a method of manufacturing the organic photoelectric conversion element 10 will be described.

First, for example, ITO is formed on the substrate 1 by the sputtering method to form the electrode 2. Subsequently, an electromagnetic blocking material is deposited on the electrode 2 by, for example, vapor deposition to form the electromagnetic blocking layer 3. Then,

Subsequently, a p-type organic semiconductor and a fullerene or a fullerene derivative are deposited together, for example, on the electron blocking layer 3 to form the photoelectric conversion layer 4. Then, for example, ITO is formed on the photoelectric conversion layer 4 by a sputtering method to form the electrode 5. Subsequently, silicon oxide is deposited on the electrode 5 and the substrate 1 by, for example, vapor deposition to form the sealing layer 6.

In the present manufacturing method, the step of forming the electrode 2, the step of forming the electron blocking layer 3, the step of forming the photoelectric conversion layer 4, the step of forming the electrode 5, and the step of forming the sealing layer 6 The respective steps are performed under vacuum in order to prevent deterioration factors of the film such as water and oxygen from being mixed into the film during film formation in each step and deteriorate the properties of the film. As a result of intensive studies, the present inventors have found that a period during which the organic photoelectric conversion element 10 during fabrication is placed under the non-vacuum condition after the formation of the photoelectric conversion layer 4 to the start of the formation process of the sealing layer 6 (Hereinafter, referred to as a non-vacuum period), the performance of the organic photoelectric conversion element 10 is not deteriorated.

Here, it refers to a space having a pressure higher than that under vacuum when each step for non-vacuuming is carried out. Concretely, it refers to an atmosphere under non-vacuum atmosphere or under an inert atmosphere. The inert atmosphere indicates that both oxygen and water in the space of atmospheric pressure are all 100 ppm or less (preferably 10 ppm or less, ideally 0.5 ppm or less).

Examples of the inert gas species under the inert atmosphere include rare gases such as nitrogen gas and argon, and incombustible gases, and a combination of a plurality of these inert gases may be used. Preferably, nitrogen gas is used.

The non-vacuum period may be, for example, a period between the step of forming the photoelectric conversion layer 4 and the step of forming the electrode 5 (the first period) and the step of forming the electrode 5 and the step of forming the sealing layer 6 (The second period).

Until now, the formation of the photoelectric conversion layer 4 including the organic material and the formation of the sealing layer 6 for preventing penetration of deterioration factors of organic materials such as water and oxygen, It has been considered that if the conversion element 10 is placed under a non-vacuum state, the organic material is deteriorated by moisture or oxygen, and the performance of the organic photoelectric conversion element is deteriorated. In fact, in the organic photoelectric conversion device 10 in which the photoelectric conversion layer 4 is formed using only the compound 1 described in the comparative example to be described later, it is found that the device performance deteriorates when the non-vacuum period is set.

However, in the organic photoelectric conversion device 10 using a mixed layer of a p-type organic semiconductor and a fullerene or a fullerene derivative as the photoelectric conversion layer 4, the formation of the photoelectric conversion layer 4 and the formation of the sealing layer 6 The inventors have found that the device performance is not deteriorated even when the organic photoelectric conversion element 10 under production is placed under a non-vacuum state. Further, the present inventors have 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 set in the first period and the second period. Therefore, the organic photoelectric conversion element transport path from the apparatus for forming the photoelectric conversion layer 4 to the apparatus for forming the electrode 5 and the transport path of the organic photoelectric conversion element from the apparatus for forming the electrode 5 to the sealing layer 6, It is not necessary to set the transport path of the organic photoelectric conversion element in the vacuum state to the apparatus for forming the organic photoelectric conversion element. As a result, the manufacturing facility of the organic photoelectric conversion element 10 can be simplified, and the manufacturing cost can be reduced.

Further, there is no difference in the effect due to the difference in the direction in which the photoelectric conversion layer 4 is held in the non-vacuum period. Further, the atmosphere between the step of forming the electron blocking layer 3 and the step of forming the photoelectric conversion layer 4, and the step of placing the element under preparation in the atmosphere or the step of forming the photoelectric conversion layer 4 in the non- The presence or absence of light irradiation is not particularly limited as long as the effect of the present invention is not significantly impaired.

In the case where the non-vacuum period is set in either the first period or the second period, the apparatus may be designed so that the transport path of the element in the period in which the non-vacuum period is not set is in the vacuum state. When the non-vacuum period is set in both of the first period and the second period, the cost of the equipment can be drastically reduced.

Next, a structural example of an image pickup device using the organic photoelectric conversion element 10 will be described.

2 is a schematic cross-sectional view showing a schematic configuration of an image pickup device for explaining an embodiment of the present invention. The 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.

The image pickup element has a plurality of organic photoelectric conversion elements of the structure shown in Fig. 1 and a circuit board on which a readout circuit for reading 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 plane.

2 includes a substrate 101, an insulating layer 102, a connecting electrode 103, a pixel electrode 104, a connecting portion 105, a connecting portion 106, A protective layer 109, a sealing layer 110, a color filter (CF) 111, a barrier rib 112, a light shielding layer 113, a protection layer Layer 114, counter electrode voltage supply section 115, and 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 structure as the light-receiving layer formed 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. A part of the counter electrode 108 facing the pixel electrode 104 and a light receiving layer 107 sandwiched between these electrodes and a buffer layer 109 opposed to the pixel electrode 104 and a part of the sealing layer 110 Constitute an organic photoelectric conversion element.

The substrate 101 is a glass substrate or a semiconductor substrate such as Si. On the substrate 101, an insulating layer 102 is formed. 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 formed on the plurality of pixel electrodes 104 so as to cover them.

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

The connection portion 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 portion 115. [ The counter electrode voltage supply unit 115 is formed on the substrate 101 and applies a predetermined voltage to the counter electrode 108 through 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 pickup device, the power supply voltage is boosted by a boosting circuit such as a charge pump to supply the predetermined voltage.

The reading circuit 116 is formed on the substrate 101 in correspondence with each of the plurality of pixel electrodes 104 and reads signals corresponding to the charges collected by the corresponding pixel electrodes 104. [ The reading circuit 116 is composed of, for example, a CCD, a MOS circuit, or a TFT circuit, and is shielded by a shielding layer (not shown) disposed in the insulating layer 102. The reading circuit 116 is electrically connected to the pixel electrode 104 corresponding thereto via the connecting portion 105. [

The buffer layer 109 is formed so as to cover the counter electrode 108 on 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 barrier ribs 112 are formed between the color filters 111 to improve the light transmission efficiency of the color filters 111.

The light shielding layer 113 is formed in a region other than the region where the color filter 111 and the barrier rib 112 are formed on the sealing layer 110 and prevents light from being incident on the light receiving layer 107 formed outside the effective pixel region. The protective layer 114 is formed on the color filter 111, the partition wall 112 and the light shielding layer 113 to protect the entire image pickup device 100.

In the image pickup device 100 constructed as described above, when light is incident, the light enters the light-receiving layer 107, and charges are generated there. The generated positive holes are collected by the pixel electrode 104, and a voltage signal corresponding to the amount is output to the outside of the image pickup device 100 by the readout circuit 116.

A method of manufacturing the image pickup device 100 is as follows.

The connection portions 105 and 106, the plurality of connection electrodes 103, the plurality of the pixel electrodes 104 and the insulating layer 102 are formed on the circuit board on which the counter electrode voltage supplying portion 115 and the reading circuit 116 are formed . The plurality of pixel electrodes 104 are arranged on the surface of the insulating layer 102, for example, in a tetragonal lattice pattern.

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

In the manufacturing method of the imaging element 100, a step of placing the imaging element 100 under production in a non-vacuum state 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 It is possible to prevent performance deterioration of a plurality of organic photoelectric conversion elements. By adding this step, deterioration of the performance of the image pickup device 100 can be prevented, and the manufacturing cost can be suppressed.

Details of the components (the electron blocking layer 3, the hole blocking layer, the photoelectric conversion layer 4, the electrode 2, the electrode 5, and the sealing layer 6) of the organic photoelectric conversion element described above Explain.

[Photoelectric conversion layer]

The p-type organic semiconductor (compound) constituting the photoelectric conversion layer 4 is a donor organic semiconductor (compound), which is represented by a hole-transporting organic compound and has an easy property of donating electrons. More specifically, it refers to an organic compound having a small ionization potential when the two organic materials are used in contact with each other. Therefore, any organic compound can be used as long as the donor organic compound is an organic compound having an electron donor. Examples of the compound include triarylamine compounds, pyran compounds, quinacridone compounds, benzidine compounds, pyrazoline compounds, styrylamine compounds, hydrazone compounds, triphenylmethane compounds, carbazole compounds, polysilane compounds, thiophene compounds, The present invention relates to a method for producing a curable resin composition comprising a curing agent, a curing agent, a curing agent, a curing agent, a curing agent, a curing accelerator, a phthalocyanine compound, cyanine compound, merocyanine compound, oxolone compound, polyamine compound, indole compound, pyrrole compound, pyrazole compound, Phenylene derivatives, perylene derivatives, fluoranthene derivatives), metal complexes having a nitrogen-containing heterocyclic compound as a ligand, and the like can be used. Further, the present invention is not limited to this, and an organic compound having an ionization potential lower than that of the organic compound used as the n-type organic semiconductor may be used as the donor organic semiconductor.

Of these, triarylamine compounds, pyran compounds, quinacridone compounds, pyrrole compounds, phthalocyanine compounds, merocyanine compounds and condensed aromatic carbocyclic compounds are preferable.

As the p-type organic semiconductor, any organic dye may be used, and preferred examples thereof include a cyanine dye, a styryl dye, a hemicyanine dye, a merocyanine dye (including zeromethine merocyanine (simple merocyanine)), A complex cyanine dye, a complex merocyanine dye, a complex dye, an arofora dye, an oxolin dye, a hemioxolin dye, a squarylium dye, a croconium dye, a quinone merocyanine dye, Azo dye, azomethine dye, coumarin dye, arylidene dye, anthraquinone dye, triphenylmethane dye, azo dye, azomethine dye, spiro compound, metallocene dye, fluorolenone dye, unwashed dye, perylene dye, A quinacridone coloring matter, a quinacridone coloring matter, a quinacridone coloring matter, a quinacridone coloring matter, a quinacridone coloring matter, a quinacridone coloring matter, a quinacridone coloring matter, a quinacridone coloring matter, The present invention relates to a colorant, a pigment, a phenoxyphoto pigment, a phthalopyrrole pigment, a diketopyrrolopyrrole pigment, a dioxane pigment, a porphyrin pigment, a chlorophyll pigment, a phthalocyanine pigment, a metal complex pigment, a condensed aromatic carbon ring dye (naphthalene derivatives, Derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives). Specific p-type organic semiconductors (compounds) are illustrated below, but the present invention is not limited to the following examples.

The fullerenes constituting the photoelectric conversion layer 4 are 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 C ₅₄₀ , mixed fullerene, fullerene nanotubes, and the fullerene derivative represents a compound to which a substituent is added.

The substituent of the fullerene derivative is preferably an alkyl group, an aryl group or a heterocyclic group. The alkyl group is more preferably an alkyl group having 1 to 12 carbon atoms. The aryl group and the heterocyclic group are preferably a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a triphenylene ring, a naphthacene ring, A thiazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, An isoquinoline ring, a carbazole ring, a phenanthrene ring, an imidazopyridine ring, an imidazopyridine ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, Anthracene ring, thianthrene ring, chromane ring, xanthane ring, phenoxathiine ring, phenothiazine ring or phenazine ring, more preferably a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring , Pyridine ring, imidazole ring, oxazole ring or thiazole And, in particular ring preferably a benzene ring, naphthalene ring or pyridine. These may also have a substituent, and the substituent may be bonded as far as possible to form a ring. Furthermore, they may have a plurality of substituents, and they may or may not be the same. The plurality of substituents may be bonded to each other to form a ring as much as possible.

The photoelectric conversion layer 4 includes fullerene or a fullerene derivative so that charge generated by photoelectric conversion via the fullerene molecule or the fullerene derivative molecule can be quickly transported to the electrode 2 or the electrode 5. [ When fullerene molecules or fullerene derivative molecules are in a continuous state and an electron path is formed, the electron transportability is improved and high-speed responsiveness of the organic photoelectric conversion element can be realized. For this purpose, it is preferable that fullerene or a fullerene derivative is contained in the photoelectric conversion layer 4 in an amount of 40% or more. However, if the amount of the fullerene or fullerene derivative is too large, the p-type organic semiconductor becomes less and the bonding interface becomes small, and the exciton dissociation efficiency is lowered.

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

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

(Wherein 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 group, Ar ₂ , Ar ₃ are each independently a substituted aryl group, an unsubstituted aryl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted heteroaryl represents an aryl group or an unsubstituted heteroaryl group. Ar _1, Ar _2, It is adjacent of Ar ₃ to connect to each other L ₁ represents an unsubstituted methine group or a substituted methine group bonded to the following general formula (2), or a group represented by the following general formula (3).

In the formula, Z ₁ represents a condensed ring containing at least any one of a 5-membered ring, a 6-membered ring, a 5-membered ring and a 6-membered ring including a carbon atom bonded to L ₁ and a carbonyl group adjacent to the carbon atom. X represents a hetero atom. Z ₂ represents a condensed ring containing at least one of a 5-membered ring, a 6-membered ring, a 7-membered ring, or a 5-membered ring, a 6-membered ring and a 7-membered ring. L _{4 to} L ₆ each independently represent an unsubstituted methine group or a substituted methine group. R ₆ and R ₇ each independently represent a hydrogen atom or a substituent, and adjacent atoms may be bonded to each other to form a ring. and k represents an integer of 0 to 2. * In the general formula (2) represents a bonding position to be bonded to L ₁ , and * in the general formula (3) represents L ₂ Or a bonding position to be bonded to Ar < _{1 &} gt ;.

Z ₁ in the general formula (2) means a condensed ring containing at least any one of a 5-membered ring, a 6-membered ring, a 5-membered ring and a 6-membered ring including two carbon atoms. As such ring, it is usually preferable to use it as an acid nucleus with merocyanine dye, and specific examples thereof include, for example, the following.

(a) 1,3-dicarbonyl nucleus: 1,3-indanedione nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3- Dioxane-4,6-dione and the like.

(b) pyrazolinone nuclei: for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl- ) -3-methyl-2-pyrazolin-5-one.

(c) isoxazoline nucleus: for example, 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one and the like.

(d) Oxyindole nucleus: for example, 1-alkyl-2,3-dihydro-2-oxyindole and the like.

(e) 2,4,6-Tricetohexahydropyrimidine nucleus: for example, barbituric acid or 2-thiobarbituric acid and derivatives thereof. Examples of the derivative include 1-alkyl such as 1-methyl and 1-ethyl, 1,3-dialkyl such as 1,3-dimethyl, 1,3-diethyl and 1,3- Diaryls such as 3-diphenyl, 1,3-di (p-chlorophenyl) and 1,3-di (p-ethoxycarbonylphenyl) 1-alkyl-1-aryl, 1,3-di (2-pyridyl), and the like.

(f) 2-thio-2,4-thiazolidinedione nucleus: for example, rhodanine and derivatives thereof. Examples of the derivative include 3-alkyl rhodanines such as 3-methyl rhodanine, 3-ethyl rhodanine and 3-aryl rhodanine, 3-aryl rhodanines such as 3-phenyl rhodanine, 3- 3-position heterocyclic substituted rhodanine such as rhodanine, and the like.

(g) 2-thio-2,4-oxazolidinedione (2-thio-2,4- (3H, 5H) -oxazolone nucleus: - oxazolidinedione and the like.

(h) Thianaphthene nuclei: For example, 3 (2H) -thianaphthene-1,1-dioxide.

(i) 2-thio-2,5-thiazolidinedione nucleus: for example, 3-ethyl-2-thio-2,5-thiazolidinedione.

(j) 2,4-thiazolidinedione nucleus: for example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidine Dion and others.

(k) Thiazolin-4-one nuclei: for example, 4-thiazolinone, 2-ethyl-4-thiazolinone and the like.

(l) 2,4-imidazolidinedione (hydantoin) nucleus: 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, and the like.

(m) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus: for example, 2-thio-2,4-imidazolidinedione, 3-ethyl- -2,4-imidazolidinedione and the like.

(n) 2-Imidazoline-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 nuclei: 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, 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-tricetohexahydropyrimidine nucleus (including thioketone, for example, 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-imidazolidinedione nucleus, 2-thio-2,4-imidazolidinedione nucleus, 2-imidazoline- 5-pyrazolidinedione nucleus, benzothiophen-3-one nucleus and indanone nucleus, more preferably 1,3-dicarbonyl nucleus, 2,4,6-tricetohexahydropyrimidine nucleus (thio Pyrazolidinedione nucleus, benzothiophene-3-one nucleus, indanone nucleus, and more preferably 1 < RTI ID = 0.0 > , 3-dicarbonyl nucleus, 2,4,6-tricetohexahydropyrimidine nucleus (including thioketones, G is barbie acid nucleus, 2-thio barbie acid nucleus), and particularly preferably 1, 3-indan-dione nucleus, barbie acid nucleus, 2-thio barbie nuclear acid and their derivatives.

Preferred as the ring represented by Z < ₁ > is represented by the following formula.

Z ³ represents a condensed ring containing at least any one of a 5-membered ring, a 6-membered ring, a 5-membered ring and a 6-membered ring, including a carbon atom bonded to L ₁ and two carbonyl groups adjacent to the carbon atom. * Represents a bonding position to be bonded to L < ₁ >. Z ³ can be selected from the ring represented by Z ₁ , and is preferably 1,3-dicarbonyl nucleus, 2,4,6-tricetohexahydropyrimidine nucleus (including thioketone) Preferred are 1,3-indanedione nucleus, barbituric acid nucleus, 2-thiobarbituric acid nucleus and derivatives thereof.

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

In the formula, R ₂ to R ₅ each independently represent a hydrogen atom or a substituent, and adjacent groups may be bonded to each other to form a ring. * Represents a bonding position to be bonded to L < ₁ >.

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 NR < _{10 &} gt ;. Preferred as the ring represented by Z ₂ is represented by the following formula (6).

In the formula, X represents O, S or NR 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 groups may be bonded to each other to form a ring. m represents an integer of 1 to 3; When m is 2 or more, plural R _{1 s} may or may not be the same. * L ₂ Or a bonding position to be bonded to Ar < _{1 &} gt ;.

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 thereof include a phenylene group, a naphthylene group, a methylphenylene group and a dimethylphenylene group, and a phenylene group and a naphthylene group are preferable.

Each of the aryl groups represented by Ar ₂ and Ar ₃ is independently preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms. The aryl group may have a substituent, and is preferably an aryl group having 6 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. For example, a phenyl group, a naphthyl group, a tolyl group, an anthryl group, a dimethylphenyl group, and a biphenyl group are exemplified, and 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, more preferably an alkyl group having 1 to 4 carbon atoms. For example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group are exemplified and a methyl group or an ethyl group is preferable and a methyl group is more preferable.

Each of the heteroaryl groups represented by Ar ₂ and Ar ₃ is independently preferably a heteroaryl group having 3 to 30 carbon atoms, more preferably a heteroaryl group having 3 to 18 carbon atoms. The heteroaryl group may have a substituent, and is preferably a heteroaryl group 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. The heteroaryl group represented by Ar ₂ and Ar ₃ may be a cyclic structure or a fused ring structure such as a furan ring, a thiophene ring, a selenopentane ring, a silole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, an oxazole ring, a thiazole ring, Oxadiazole ring, and thiadiazole ring is preferable, and a ring structure of a ring selected from a quinoline ring, an isoquinoline ring, a benzothiophene ring, a dibenzothiophene ring, a thienothiophene ring, A ring, and a bithienothiophen ring.

Ar ₁ , Ar ₂ , Ar ₃ , R ₁ , R ₂ to R ₇ , R ₁₀ May be connected to each other to form a ring. The ring is preferably a ring formed by a hetero atom, an alkylene group, an aromatic ring, or the like. For example, when two of an aryl group (for example, Ar ₁ , Ar ₂ and Ar ₃ in the general formula (1)) are connected to each other through a single bond or a linking group, a nitrogen atom (N in the general formula (1) And the like. Examples of the linking group include a group formed by a hetero atom (e.g., -O-, -S-, etc.), an alkylene group (e.g., a methylene group or an ethylene group), or a combination thereof, Group is preferable. The nitrogen atom (for example, by the general formula (1) N), alkylene (e.g., methylene group) and an aryl group (for example, Ar ₁ in the formula (1), Ar ₂ Or Ar < ₃ >) is preferable.

The ring may also 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), and a plurality of the substituents may be connected to each other to form a ring (for example, Benzene ring or the like) may be formed.

It is also preferable that R ₃ and R ₄ are connected to each other to form a ring, and the ring is preferably a benzene ring.

Further, in the case of a plurality of R _{1 s} (m is 2 or more), adjacent ones of the plurality of R _{1 s} may be connected to each other to form a ring, and the ring is preferably a benzene ring.

Examples of the substituent group when Ar ₁ , Ar ₂ and Ar ₃ have a substituent and the substituent of R ₁ , R ₂ to R ₇ and R ₁₀ include a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group) , A substituted alkyl group, an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a substituted aryl group, a heterocyclic group (which may be a heterocyclic group), a cyano group, a hydroxy group, An alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group (including an anilino group), an ammonio group, An amino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, An acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl and a heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group, a phosphine group, a phosphine group, (-OH (OH) ₂ ), phosphato group (-OPO (OH) ₂ ), sulfato group (-OSO), phosphino group, phosphino group, silyl group, hydrazino group, ureido group, ₃ H), and other known substituents. R ₁ , R ₂ to R ₇ , The substituent of R ₁₀ is preferably an alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, cyano, nitro, alkoxy, aryloxy, amino, alkylthio, alkenyl or halogen atom.

When Ar ₁ , Ar ₂ and Ar ₃ have a substituent, they are each independently a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, a nitro group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, An arylthio group, an alkenyl group, a cyano group or a heterocyclic thio group is preferable.

R ₁ is more preferably an alkyl group or an aryl group. As R ₆ and R _{7, a} cyano group is more preferable.

Examples of the substituent of the substituted alkyl group and the substituted aryl group include the above-exemplified substituents, an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group), an aryl group (an aryl group having 6 to 18 carbon atoms, More preferably a phenyl group) is preferable.

_{L 1, L 2, L 3} , L 4, L 5, L 6 each independently indicate an unsubstituted methine group or a substituted methine, the substituents of the substituted methine group include an alkyl group, an aryl group, a heterocyclic group, an alkenyl group, An alkoxy group or an aryloxy group, and the substituents may be bonded to each other to form a ring. The ring may be a 6-membered ring (for example, a benzene ring). In addition, L ₁ Or the substituents of L < _{3 >} and Ar < ₁ > may be bonded to each other to form a ring. The substituents of L < ₆ > and R < ₇ > may be bonded to each other to form a ring.

The alkyl group represented by R ₁ , R ₂ to R ₇ and R ₁₀ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. As R ₂ to R ₇ , a methyl group or an ethyl group is preferable, and a methyl group is more preferable. As R ₁ , a methyl group, an ethyl group or a t-butyl group is preferable, and a methyl group or a t-butyl group is more preferable.

n is preferably 0 or 1.

Each of the aryl groups represented by R ₁ , R ₂ to R ₇ and R ₁₀ is independently preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms. The aryl group may have a substituent, and is preferably an aryl group having 6 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. For example, a phenyl group, a naphthyl group, an anthracenyl group, a pyrenyl group, a phenanthrenyl group, a methylphenyl group, a dimethylphenyl group, and a biphenyl group are exemplified, and a phenyl group, a naphthyl group or an anthracenyl group is preferable.

Each of the heteroaryl groups represented by R ₁ , R ₂ to R ₇ and R ₁₀ is independently preferably a heteroaryl group having 3 to 30 carbon atoms, more preferably a heteroaryl group having 3 to 18 carbon atoms. The heteroaryl group may have a substituent, and is preferably a heteroaryl group 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. The heteroaryl group represented by R ₁ and R ₂ to R ₇ is preferably a heteroaryl group comprising 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 furan ring, thiophene ring, pyrrole ring, pyrrole ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, A heterocyclic ring, a thiazine ring, a thiazine ring, a tetrazole ring, a pyran ring, a pyran ring, a thiazine ring, a pyridine ring, a piperidine ring, a oxazine ring, a morpholine ring, Pyrimidine ring, pyrazine ring, piperazine ring, triazine ring and the like.

Examples of the condensed rings include benzofuran ring, isobenzofuran ring, benzothiophen ring, indole ring, indolin ring, isoindole ring, benzoxazole ring, benzothiazole ring, indazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, A phenanthrene ring, a phenanthrene ring, a thianthrene ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring, a thianthrene ring, , Thienothiophen ring, indolizine ring, quinolizine ring, quinuclidine ring, naphthyridine ring, purine ring, phthalidine ring and the like.

m represents an integer of 1 to 3, preferably 1 or 2, 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 the case of a low-molecular material, N, N'-bis (3-methylphenyl) - (1,1'-biphenyl) -4,4'- diamine (TPD) or 4,4'- ) -N-phenylamino] biphenyl (? -NPD), and aromatic diamine compounds such as oxazole, oxadiazole, triazole, imidazole, imidazolone, stilbene derivatives, pyrazoline derivatives, tetrahydroimidazole, (M-MTDATA), porphine, tetraphenylporphine copper, phthalocyanine, copper phthalocyanine (N-methylphenylamino) , And titanium phthalocyanine oxide, triazole derivatives, oxadiazolyl derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, para-zolone derivatives, phenylenediamine derivatives, arylamine derivatives, fluorene derivatives, amino substitution Chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorolenone derivatives, A polymer or a derivative thereof such as phenylenevinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene and the like can be used as the polymer material. It is possible to use a compound having sufficient hole transportability even if it is not an electron donor compound.

Specifically, for example, the following compounds described in Japanese Patent Application Laid-Open No. 2008-72090 are shown, but the present invention is not limited thereto. In the following, Ea represents the electron affinity of the material, and Ip represents the ionization potential of the material. EB-1, 2, ... Quot; EB " is an abbreviation of " electronic blocking ".

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

It is preferable that a layer adjacent to the photoelectric conversion layer 4 in a plurality of layers of the electron blocking layer 3 made of a plurality of layers is a layer made of the same material as the p-type organic semiconductor included in the photoelectric conversion layer 4. [ By using the same p-type organic semiconductor in the electron blocking layer 3, formation of the intermediate level at the interface between the photoelectric conversion layer 4 and the adjacent layer can be suppressed, and the dark current can be further suppressed.

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

[Hole blocking layer]

An electron-accepting organic material can be used for the hole blocking layer. Examples of the electron-accepting material include oxadiazole derivatives such as 1,3-bis (4-tert-butylphenyl-1,3,4-oxadiazolyl) phenylene (OXD-7), anthraquinodimethane derivatives, (8-hydroxyquinolinate) aluminum complex, bis (4-methyl-8-quinolinate) aluminum complex, distyryl compound, tris An arylene derivative, a silole compound and the like can be used. Further, even if it is not an electron-accepting organic material, it can be used as a material having sufficient electron-transporting ability. A styryl compound such as a porphyrin compound or DCM (4-dicyanomethylene-2-methyl-6- (4- (dimethylaminostyryl)) -4H pyran) or a 4H pyran compound may be used.

[Pixel electrode]

Examples of the material of the electrode 2 (the pixel electrode 104) include metals, metal oxides, metal nitrides, metal borides, organic conductive compounds, and mixtures thereof. Specific examples thereof include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), indium tungsten oxide (IWO) and titanium oxide, metal nitrides such as TiN, A metal such as platinum (Pt), silver (Ag), chromium (Cr), nickel (Ni) and aluminum (Al), or a mixture or laminate of these metals and a conductive metal oxide, polyaniline, polythiophene, , A laminate of ITO and the like, and the like. Particularly preferable materials for the transparent conductive film are ITO, IZO, tin oxide, antimony doped tin oxide (ATO), fluorine doped tin oxide (FTO), zinc oxide, antimony doped zinc oxide (AZO), and gallium doped zinc oxide It is one of the materials.

A step corresponding to the film thickness of the electrode 2 at the end of the electrode 2 is steep or a remarkable irregularity is present on the surface of the electrode 2 or a minute dust Or the layer on the electrode 2 becomes thinner or cracked than the desired film thickness. If the electrode 5 (counter electrode 108) is formed on the layer in such a state, the contact of the electrode 2 and the electrode 5 in the defective portion and the increase of the dark current due to the electric field concentration, Pixel defect occurs. In addition, the above-described defects may lower the adhesion between the electrode 2 and the layer thereon and the heat resistance of the organic photoelectric conversion element 10.

In order to prevent the above defects and improve the reliability of the device, 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 irregularities of the surface, and the better the surface flatness is. 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 in order to remove particles on the electrode 2. [

[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 thereof include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), indium tungsten oxide (IWO) and titanium oxide, metal nitrides such as TiN, A metal such as platinum (Pt), silver (Ag), chromium (Cr), nickel (Ni) and aluminum (Al), or a mixture or laminate of these metals and a conductive metal oxide, polyaniline, polythiophene, , A laminate of ITO and the like, and the like. Particularly preferable materials for the transparent conductive film are ITO, IZO, tin oxide, antimony doped tin oxide (ATO), fluorine doped tin oxide (FTO), zinc oxide, antimony doped zinc oxide (AZO), and gallium doped zinc oxide It is one of the materials.

[Sealing layer]

As the sealing layer 6 (sealing layer 110), the following conditions are required.

Firstly, the photoelectric conversion layer is protected by inhibiting the penetration of a factor which deteriorates the organic photoelectric conversion material contained in solution, plasma or the like in each manufacturing process of the device.

Secondly, after the device is manufactured, the penetration of a factor that deteriorates 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.

Thirdly, when the sealing layer 6 is formed, the already formed photoelectric conversion layer is not deteriorated.

Fourth, since the incident light reaches the photoelectric conversion layer 4 through the sealing layer 6, the sealing layer 6 must be transparent to the light of the wavelength detected by the photoelectric conversion layer 4.

The sealing layer 6 may be made of a thin film made of a single material, but it is possible to form a multilayer structure and to impart functions to the respective layers to relieve stresses of the entire sealing layer 6, Suppressing the occurrence of defects such as cracks and pinholes, and facilitating optimization of material development can be expected. For example, the sealing layer 6 may be formed on the layer that achieves the original purpose of preventing the permeation of deterioration factors such as water molecules or the like, by providing a " sealing auxiliary layer " 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 considering the manufacturing cost.

[Formation of Sealing Layer 6 by Atomic Layer Deposition Method]

The performance of the organic photoelectric conversion material is markedly deteriorated by the presence of deterioration factors such as water molecules. Therefore, it is necessary to seal the entire photoelectric conversion layer with ceramics such as dense metal oxides, metal nitrides, metal nitrides, or the like, which do not permeate water molecules, or diamond-like carbon (DLC). Conventionally, aluminum oxide, silicon oxide, silicon nitride, silicon nitride oxide or a stacked structure of them and a stacked structure of them and an organic polymer are formed by various vacuum film forming techniques as sealing layers. However, since these conventional sealing layers are difficult to grow the thin film (step difference becomes shaded) in the step due to the structure of the surface of the substrate, micro-defects on the surface of the substrate, particles adhered to the surface of the substrate, Is remarkably thinned. As a result, the step portion becomes a path through which the degradation factor penetrates. In order to completely cover the stepped portion with the sealing layer, it is necessary to form the film so as to have a film thickness of 1 mu m or more in the flat portion, and to thicken the entire sealing layer. The degree of vacuum at the time of forming the sealing layer is preferably 1 x 10 ³ Pa or less, more preferably 5 x 10 ² Pa or less.

When the distance between the color filter 111 and the photoelectric conversion layer, that is, the film thickness of the sealing layer 110, is large in the imaging element 100 having a pixel size of less than 2 占 퐉, particularly about 1 占 퐉, Diffraction / divergence occurs and color mixing occurs. Therefore, the imaging element 100 having a pixel size of about 1 mu m requires a sealing layer material / manufacturing method in which the device performance is not degraded 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 in which the adsorption / reaction of organic metal compound molecules, metal halide molecules, and metal hydride molecules to be a thin film material on the substrate surface and the decomposition of unreacted To form a thin film repeatedly. When the thin film material reaches the surface of the substrate, the thin film can grow even if there is a very small space into which small molecules can enter due to the low molecular state. Therefore, the step portion which is difficult to achieve by the conventional thin film forming 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 good. Therefore, the step difference due to the structure of the substrate surface, the micro-defects of the substrate surface, the particles adhered to the substrate surface, and the like can be completely covered, so that such a stepped portion does not become a penetration path of the deterioration factor of the photoelectric conversion material. When the formation of the sealing layer 6 is performed by the atomic layer deposition method, it is possible to thin the thickness of the sealing layer which is more effectively required than in the prior art.

In the case of forming the sealing layer 6 by the atomic layer deposition method, a material suitable for the ceramics suitable for the sealing layer 6 can be appropriately selected. However, since the photoelectric conversion layer of the present invention uses an organic photoelectric conversion material, the photoelectric conversion layer is limited to a material capable of film growth at a relatively low temperature at which the organic photoelectric conversion material does not deteriorate. According to the atomic layer deposition method using an alkyl aluminum or a halogenated aluminum material, a dense aluminum oxide thin film can be formed at a temperature lower than 200 占 폚 at which the organic photoelectric conversion material does not deteriorate. Particularly, when trimethyl aluminum is used, an aluminum oxide thin film can be formed even at about 100 ° C, which is preferable. Silicon oxide or titanium oxide is also preferable because a dense thin film can be formed at a temperature of less than 200 占 폚 like aluminum oxide by appropriately selecting a material.

[Sealing auxiliary layer]

The thin film formed by the atomic layer deposition method can achieve unprecedented thin film formation at low temperatures in view of step coverage and compactness. However, the physical properties of the thin film material may be deteriorated by the chemicals used in the photolithography process. For example, since the aluminum oxide thin film formed by the atomic layer deposition method is amorphous, the surface is eroded by an alkaline solution such as a developer or a peeling liquid. 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, the sealing auxiliary layer which becomes the functional layer for protecting the sealing layer 6 is required.

On the other hand, a thin film formed by a CVD method such as an atomic layer deposition method has many tensile stresses having a very large internal stress. In a semiconductor manufacturing process, a process in which intermittent heating and cooling are repeated or a process in which a long period of high temperature / Deterioration in which cracks are generated in the thin film itself may occur due to storage / use.

In order to overcome the problems of the sealing layer 6 formed by the atomic layer deposition method, for example, metal oxides, metal nitrides, metal nitrides, and the like, which are excellent in chemical resistance and formed by a physical vapor deposition (PVD) method such as a sputtering method Or the like, is preferably formed on the surface of the substrate. Here, the one formed by the atomic layer deposition method is referred to as a first sealing layer, the one formed by the PVD method on the first sealing layer and containing any one of a metal oxide, a metal nitride, and a metal nitride oxide is referred to as a second sealing layer . In this way, it is easy to improve the chemical resistance of the entire sealing layer 6. The ceramics formed by the PVD method such as the sputtering method often have a large compressive stress and can cancel the tensile stress of the first sealing layer formed by the atomic layer deposition method. Therefore, not only the stress of the entire sealing layer 6 is relaxed, the reliability of the sealing layer 6 itself is enhanced, but also the stress of the sealing layer 6 deteriorates the performance of the photoelectric conversion layer, Can be remarkably suppressed.

In particular, it is preferable that the second sealing layer has a structure comprising a first sealing layer containing any one of aluminum oxide, silicon oxide, silicon nitride, and silicon nitride oxide formed by a sputtering method.

It is preferable that the film thickness of the first sealing layer is 0.05 탆 or more and 0.5 탆 or less. Further, it is preferable that the first sealing layer includes any one of aluminum oxide, silicon oxide, and titanium oxide.

Hereinafter, an effect of forming a non-vacuum period will be described in an embodiment.

Example

(Example 1)

And an organic electroluminescent device. The order is as follows. First, amorphous ITO was formed on a CMOS substrate formed with a readout circuit made of a CMOS circuit and a connection electrode connected to the readout circuit by a sputtering method, and this was patterned to form a pixel electrode on each connection electrode. Subsequently, a material represented by EB-3 was deposited on the plurality of pixel electrodes by vacuum evaporation deposition to a thickness of 100 nm to form an electron blocking layer. Subsequently, Compound 1 and fullerene (C ₆₀ ) were vapor-deposited on the electron blocking layer by vacuum heating deposition (at a ratio of 1: 3) to form a photoelectric conversion layer having a film thickness of 400 nm. In this deposition, an organic material vapor deposition cell "Thermo VOLCEL (manufactured by Chosho Sangyo Kogyo Co., Ltd.)" was used. Vacuum deposition of the electron blocking layer and the photoelectric conversion layer was performed at a vacuum degree of 4 x 10 < ~ ⁴ > Subsequently, the image pickup element in the middle of production was placed in an air atmosphere for 3 minutes. The image pickup element was set on the apparatus for forming the counter electrode, and amorphous ITO was deposited on the photoelectric conversion layer to a thickness of 10 nm by sputtering An opposite electrode was formed. The counter electrode was formed under vacuum. Subsequently, the image pickup element in production was placed in an air atmosphere for 3 minutes, the image pickup element was set in an apparatus for forming a sealing layer, silicon oxide was formed on the counter electrode by thermal evaporation, Aluminum was deposited 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)

The image pickup element was manufactured in the same manner as in Example 1 except that the image pickup element during manufacture was placed between the step of forming the photoelectric conversion layer and the step of forming the counter electrode and the step of forming the counter electrode and the step of forming the seal layer, . In addition, the time for placing the imaging element in the atmosphere of nitrogen gas during the production was 3 minutes.

(Example 4)

An imaging device was produced in the same manner as in Example 1 except that the time for holding the imaging element in the atmosphere under production was 30 minutes.

(Example 5)

An image pickup device was produced in the same manner as in Example 3 except that the time for holding the image pickup device in the atmosphere of nitrogen gas during production was 30 minutes.

(Example 6)

An imaging device was produced in the same manner as in Example 1, except that the time for placing the imaging device in the atmosphere under production was 1 minute.

(Example 7)

An imaging device was manufactured in the same manner as in Example 3 except that the time for holding the imaging device in the atmosphere of nitrogen gas during production was 1 minute.

(Example 8)

Between the step of forming the photoelectric conversion layer and the step of forming the counter electrode, the image pickup element in the middle of production is kept under vacuum for 3 minutes, and the image pickup element in the middle of the production process of the counter electrode and the step of forming the seal layer is placed An image pickup device was produced in the same manner as in Example 1 except that it was left 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)

Between the step of forming the photoelectric conversion layer and the step of forming the counter electrode, and the step of forming the counter electrode and the step of forming the sealing layer, the image pickup element under production is left under vacuum for 3 minutes, , An image pickup device was produced in the same manner as in Example 1. [

(Comparative Example 2)

Between the step of forming the photoelectric conversion layer and the step of forming the counter electrode, and the step of forming the counter electrode and the step of forming the sealing layer, the image pickup element under production is left under vacuum for 3 minutes, An imaging device was produced in the same manner as in Example 2. [

(Comparative Example 3)

Compound 1 was formed into a photoelectric conversion layer by vacuum evaporation deposition to a thickness of 100 nm to form a photoelectric conversion layer between the step of forming the photoelectric conversion layer and the step of forming the counter electrode and the step of forming the counter electrode and the step of forming the sealing layer An imaging device was produced in the same manner as in Example 1 except that the imaging device in the middle was placed under vacuum for 3 minutes and then set in the apparatus for performing the next process.

(Comparative Example 4)

Between the step of forming the photoelectric conversion layer and the step of forming the counter electrode, and the step of forming the counter electrode and the step of forming the sealing layer, the image pickup element in the middle of production is placed under the atmosphere for 3 minutes, An imaging device was produced in the same manner as in Comparative Example 3. [

(Comparative Example 5)

Compound 1 was deposited by vacuum evaporation to a thickness of 100 nm and then fullerene (C ₆₀ ) was deposited on Compound 1 to a thickness of 100 nm to form a photoelectric conversion layer having a thickness of 200 nm, Between the step of forming the counter electrode and the step of forming the counter electrode and the step of forming the sealing layer, the image pickup element in the middle of the production was left under vacuum for 3 minutes and then the apparatus was set in the apparatus for performing the next step. 1, an image pickup device was manufactured.

(Comparative Example 6)

The image pickup element was manufactured in the same manner as in Comparative Example 5 except that the image pickup element in the middle of the production was placed in the atmosphere between the step of forming the photoelectric conversion layer and the step of forming the counter electrode and the step of forming the counter electrode and the step of forming the sealing layer. .

(Comparative Example 7)

Between the step of forming the photoelectric conversion layer and the step of forming the counter electrode, and the step of forming the counter electrode and the step of forming the sealing layer, the image pickup element under production is left under vacuum for 3 minutes, An imaging device was produced in the same manner as in Example 9. [

The external quantum efficiency (the relative value when the numerical value of Comparative Example 1 was taken as 100) at the maximum sensitivity wavelength when the organic photoelectric conversion elements in Examples and Comparative Examples were applied at an electric field of 2 x 10 ⁵ V / ) Are shown in Table 1. The value of the external quantum efficiency was a value obtained when a positive bias was applied to the opposite electrode of the fabricated device, light was incident from the opposite electrode side, and holes were drawn out from the pixel electrode.

Comparing Comparative Example 3 and Comparative Example 4, it can be seen that when the photoelectric conversion layer is formed of one material, the external quantum efficiency is reduced by half by setting the non-vacuum period. Compared with the comparative example 5 and the comparative example 6, in the case where the photoelectric conversion layer has the laminated structure of the compound 1 and the C ₆₀ , the external quantum efficiency is lowered by about 20% by setting the non-vacuum period.

On the other hand, in the case where the photoelectric conversion layer is a mixed layer of the compound 1 and the C _60, the external quantum efficiency is not deteriorated even if the non-vacuum period is set, . In contrast, in the case where the photoelectric conversion layer is a mixed layer of the compound 9 and the C _60, the external quantum efficiency does not deteriorate even if the non-vacuum period is set. In comparison between Example 7 and Examples 9 and 10, when the photoelectric conversion layer is made of a mixed layer of the compound 7 and the C _60, the external quantum efficiency is not deteriorated even when the non-vacuum period is set. In Example 8, a vacuum period and a non-vacuum period are set. However, in this case as well, as in Comparative Example 1, the external quantum efficiency was found to be higher than that in the case where no non-vacuum period was set.

When the photoelectric conversion layer is formed of a mixed layer of a p-type organic semiconductor and a fullerene or a fullerene derivative, the photoelectric conversion layer can be formed in any part or all of the steps from the step of forming the photoelectric conversion layer to the step of forming the sealing layer. The device performance was not deteriorated even when the period was set.

In Examples 4 and 5, the external quantum efficiency is increased by about 1% as compared with Examples 1, 3, 6 and 7. [ In Example 8, the external quantum efficiency is about 1% higher than in Examples 1, 3, 6, and 7. [ From these results, it was found that the device performance can be further improved by setting the non-vacuum period to 30 minutes or more.

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

As described above, in the present specification, the following matters are disclosed.

A manufacturing method of an organic photoelectric conversion device includes a photoelectric conversion layer including a first electrode, a second electrode formed above the first electrode, and an organic material formed between the first electrode and the second electrode, A method for manufacturing an organic photoelectric conversion element comprising a first electrode, a second electrode, and a sealing layer sealing the photoelectric conversion layer, wherein the photoelectric conversion layer is made of a non-luminescent material including a mixed layer of fullerene or a fullerene derivative and a p- A second step of forming the photoelectric conversion layer above the first electrode; a second step of forming the second electrode above the photoelectric conversion layer; And a fourth step of forming the sealing layer above the second electrode, wherein each step of the second step to the fourth step is performed under vacuum, and the second step And a fifth step of placing the organic photoelectric conversion element under the non-vacuum state during the period from the end of the process to the start of the fourth process.

The manufacturing method of the disclosed organic photoelectric conversion element is that under the non-vacuum state in the fifth step is in an air atmosphere or an inert atmosphere.

The disclosed method of manufacturing an organic photoelectric conversion element is performed between the second step and the third step and between the third step and the fourth step.

The manufacturing method of the disclosed organic photoelectric conversion element is the fifth step performed between the second step and the third step or between the third step and the fourth step.

The disclosed method for manufacturing an organic photoelectric conversion element is one wherein the photoelectric conversion layer is formed by a dry film formation method in the second step.

In the method of manufacturing an organic photoelectric conversion device, the fullerene or the fullerene derivative and the p-type organic semiconductor are vapor-deposited together by vacuum evaporation deposition to form the mixed layer in the second step.

In the disclosed method for producing an organic photoelectric conversion element, the p-type organic semiconductor includes a compound represented by the general formula (1).

In the manufacturing method of the organic photoelectric conversion element disclosed in the fifth step, the organic photoelectric conversion element during manufacture is placed under the non-vacuum for 1 minute or more.

The method of manufacturing an organic photoelectric conversion device according to claim 1, wherein the organic photoelectric conversion element includes an electron blocking layer formed between the first electrode and the photoelectric conversion layer, and after the first process, before the second process, Is formed.

The disclosed method of manufacturing an organic photoelectric conversion device includes a sixth step of forming an electron blocking layer represented by EB-3 on the first electrode between the first step and the second step.

The disclosed organic photoelectric conversion device is manufactured by the above-described method of manufacturing an organic photoelectric conversion device.

The disclosed image pickup device includes a circuit substrate on which a plurality of the organic photoelectric conversion elements and a signal reading circuit for reading signals corresponding to charge generated in the photoelectric conversion layers of the organic photoelectric conversion elements are formed.

The disclosed imaging device includes the imaging device.

1: substrate 2, 5: electrode
3: electron blocking layer 4: photoelectric conversion layer
6: sealing layer 10: organic photoelectric conversion element

Claims (13)

A photoelectric conversion layer including a first electrode, a second electrode formed above the first electrode, and an organic material formed between the first electrode and the second electrode, and a second electrode formed on the first electrode, A method of manufacturing an organic photoelectric conversion element comprising a sealing layer that seals a photoelectric conversion layer, comprising:
The photoelectric conversion layer is a non-luminescent layer including a mixed layer of a fullerene or a fullerene derivative and a p-type organic semiconductor;
A first step of forming the first electrode above a 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,
And a fourth step of forming the sealing layer above the second electrode;
Performing the respective steps of the second step to the fourth step under vacuum;
And a fifth step of placing the organic photoelectric conversion element under production in a non-vacuum state between the end of the second step and the start of the fourth step,
Wherein the p-type organic semiconductor is a compound represented by the following general formula (1).

[Wherein L ₂ and L ₃ each independently represent an unsubstituted methine group or a substituted methine group. and n represents an integer of 0 to 2. Ar ₁ represents a divalent substituted arylene group or an unsubstituted arylene group. Ar ₂ and Ar ₃ each independently represent a substituted aryl group, an unsubstituted aryl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted heteroaryl group or an unsubstituted heteroaryl group. Ar ₁ , Ar ₂ and Ar _{3 may} be adjacent to each other to form a ring. L ₁ represents an unsubstituted methine group or a substituted methine group bonded to the following general formula (2)

[Wherein Z ₁ represents a condensed ring containing at least one of a 5-membered ring, a 6-membered ring, or a 5-membered ring and a 6-membered ring including a carbon atom bonded to L ₁ and a carbonyl group adjacent to the carbon atom , And the ring represented by Z ₁ is represented by the following general formula (4). * In the general formula (2) represents a bonding position to be bonded to L ₁ .

[Wherein Z ³ represents a condensed ring containing at least any one of a 5-membered ring, a 6-membered ring, a 5-membered ring and a 6-membered ring, including a carbon atom bonded to L ₁ and two carbonyl groups adjacent to the carbon atom . * Represents a bonding position to be bonded to L < ₁ >. The method according to claim 1,
Wherein said organic photoelectric conversion element is in an atmospheric air atmosphere or an inert atmosphere in said non-vacuum state in said fifth step. 3. The method according to claim 1 or 2,
Wherein the fifth step is performed between the second step and the third step and between the third step and the fourth step. 3. The method according to claim 1 or 2,
Wherein the fifth step is performed between the second step and the third step or between the third step and the fourth step. 3. The method according to claim 1 or 2,
Wherein the photoelectric conversion layer is formed by a dry film formation method in the second step. 6. The method of claim 5,
Wherein the fullerene or fullerene derivative and the p-type organic semiconductor are vapor-deposited together by vacuum evaporation deposition to form the mixed layer in the second step. delete 3. The method according to claim 1 or 2,
Wherein in the fifth step, the organic photoelectric conversion element during the production is placed under the non-vacuum for 1 minute or more. 3. The method according to claim 1 or 2,
Wherein the organic photoelectric conversion element includes an electron blocking layer formed between the first electrode and the photoelectric conversion layer;
And a step of forming the electron blocking layer before the second step after the first step. An organic photoelectric conversion element characterized by being manufactured by the method for manufacturing an organic photoelectric conversion element according to any one of claims 1 to 3. A plurality of organic photoelectric conversion elements according to claim 10; And
And a signal reading circuit for reading a signal corresponding to the charge generated in the photoelectric conversion layer of each organic photoelectric conversion element. An image pickup apparatus comprising the image pickup device according to claim 11.

3. The method according to claim 1 or 2,
Wherein in the fifth step, the organic photoelectric conversion element during manufacture is placed under the non-vacuum for 3 hours or more.

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