KR20110104910A - Method of manufacturing organic photo-electric conversion device, organic photo-electric conversion device, imaging device, and imaging apparatus - Google Patents

Abstract

Provided is a method of manufacturing an organic photoelectric conversion element that can prevent deterioration of device performance and increase in cost.
An electrode 2 and an electrode 5 formed above the electrode 2, a photoelectric conversion layer 4 including an organic material formed between the electrode 2 and the electrode 5, an electrode 2, and an electrode ( 5) and the manufacturing method of the organic photoelectric conversion element 10 including the sealing layer 6 which seals the photoelectric conversion layer 4, the photoelectric conversion layer 4 is a mixed layer of fullerene or fullerene derivative and p-type organic semiconductor. A first step of forming the electrode 2 above the substrate 1, a second step of forming the photoelectric conversion layer 4 above the electrode 2, and a photoelectric conversion layer 4. And a fourth step of forming the electrode 5 above the second electrode, and a fourth step of forming the sealing layer 6 above the electrode 5, wherein the respective steps of the second to fourth steps are carried out under vacuum. And a fifth step of placing the organic photoelectric conversion element during the production under non-vacuum between the steps between the second step and the fourth step.

Description

TECHNICAL FIELD OF MANUFACTURING ORGANIC PHOTO-ELECTRIC CONVERSION DEVICE, ORGANIC PHOTO-ELECTRIC CONVERSION DEVICE, IMAGING DEVICE, AND IMAGING APPARATUS

TECHNICAL FIELD This invention relates to the manufacturing method of an organic photoelectric conversion element, an organic photoelectric conversion element, an imaging element, and an imaging device.

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

In general, it is known that organic materials change their properties under 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 preferable to perform all the processes consistently in a vacuum.

On the other hand, when the vacuum integrated process is to be realized, there is a concern that the cost increases because the manufacturing equipment becomes large. Therefore, there is a demand for a method for obtaining an organic photoelectric conversion element without deteriorating performance while suppressing manufacturing cost.

There exists a thing of patent document 2 as what does not perform all manufacturing processes in a vacuum consistently in an organic photoelectric conversion element. Patent Literature 2 discloses an electrode, a fullerene, a p-type organic semiconductor, and an organic solar cell laminated in the order of the electrodes, in which a fullerene and a p-type organic semiconductor are sequentially formed on the electrode by vacuum deposition, and then the device is exposed to air once. Thereafter, a method of forming the electrode by vacuum deposition is described. However, this method cannot prevent deterioration of device characteristics.

In addition, what is manufactured by the vacuum coherence process in the organic electroluminescent element which is not an organic photoelectric conversion element but the element using the same organic material is what was described in patent document 3, and in order to stabilize performance, all processes are not made vacuum uniform. As a manufacturing method, there exist some described in patent documents 4 and 5.

Japanese Patent Publication No. 2007-123707 Japanese Patent Laid-Open No. 09-74216 Japanese Patent Laid-Open No. 10-335061 Japanese Patent Publication No. 2009-231278 Japanese Patent 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, the method of manufacturing an organic photoelectric conversion device capable of preventing deterioration of device performance and increase in cost; It aims at providing the organic photoelectric conversion element manufactured by this manufacturing method, the imaging element provided with this organic photoelectric conversion element, and the imaging device provided with this imaging element.

The manufacturing method of the organic photoelectric conversion element of the present invention includes a photoelectric conversion layer comprising a first electrode, a second electrode formed above the first electrode, an organic material formed between the first electrode and the second electrode, A method of manufacturing an organic photoelectric conversion device including a sealing layer for sealing 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 first step of forming the first electrode above the substrate, a second step of forming the photoelectric conversion layer above the first electrode, and the second electrode above the photoelectric conversion layer. And a fourth step of forming the sealing layer above the second electrode, and performing each step of the second step to the fourth step under vacuum. 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 between the end of the second step and the start of the fourth step, a non-light-emitting photoelectric conversion layer including a mixed layer of fullerene or fullerene derivative and p-type organic semiconductor is provided. It is possible to prevent deterioration of performance and increase in cost of an organic photoelectric conversion element. Patent documents 4 and 5 are inventions regarding a light emitting element, and are completely different from the manufacturing method of the organic photoelectric conversion element which has a non-luminescent photoelectric conversion layer. Moreover, patent document 2 is not described about forming a photoelectric conversion layer as a mixed layer. In addition, as described in Comparative Examples described later, in the configuration in which the photoelectric conversion layer is not a mixed layer but a laminated structure, deterioration of device performance cannot be prevented even when the fifth step is formed. In this regard, the invention described in Patent Documents 1 to 5 cannot solve the problem of the present invention, but according to the present production method, this problem can be solved.

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

An imaging device of the present invention includes a plurality of the organic photoelectric conversion elements and a circuit board on which a signal reading circuit for reading signals corresponding to charges generated in the photoelectric conversion layers of the respective organic photoelectric conversion elements is formed.

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

(Effects of the Invention)

According to the present invention, there is provided 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, and a method for manufacturing an organic photoelectric conversion device capable of preventing deterioration of device performance and increase in cost; The organic photoelectric conversion element manufactured by this manufacturing method, the imaging element provided with this organic photoelectric conversion element, and the imaging device provided with this imaging element can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows schematic structure of the organic photoelectric conversion element for demonstrating one Embodiment of this invention.
It is a cross-sectional schematic diagram which shows schematic structure of the imaging element for demonstrating one Embodiment of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described with reference to drawings.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows schematic structure of the organic photoelectric conversion element for demonstrating one Embodiment of this invention. The 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 an electron blocking layer ( The photoelectric conversion layer 4 formed on 3), the electrode 5 formed on the photoelectric conversion layer 4, and the sealing layer 6 formed on the electrode 5 are provided. The light receiving layer is formed of 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 (for example, a hole blocking layer) other than the electron blocking layer 3.

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

The electrode 2 is an electrode for collecting 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 is composed of an organic photoelectric conversion material. Specifically, the photoelectric conversion layer 4 contains at least the mixed layer which mixed the p-type organic semiconductor (p-type organic compound) and the fullerene or fullerene derivative which is n-type organic semiconductor. A mixed layer refers to a layer in which a plurality of materials are mixed or dispersed, and is a layer formed by depositing a plurality of materials together, for example. Alternatively, a plurality of materials may be placed in a solvent to be mixed, and a layer formed by applying the same may be used. When the photoelectric conversion layer 4 includes such a mixed layer, the shortcoming of the carrier diffusion length of the photoelectric conversion layer can be compensated for, and the photoelectric conversion efficiency of the photoelectric conversion layer can be improved.

The photoelectric conversion layer 4 is a non-light emitting layer having a different characteristic from the light emitting layer of the organic EL (layer for converting an electrical signal to light). The non-luminescent layer is a case where the luminescence quantum efficiency is 1% or less in the visible light region (wavelength 400 nm to 730 nm), preferably 0.5% or less, and more preferably 0.1% or less. The reason why the photoelectric conversion layer 4 is used as a non-light emitting layer is that when the organic photoelectric conversion element is used as the imaging element, when the light emission quantum efficiency exceeds 1%, the imaging performance is affected.

The light receiving layer can be formed by a dry film formation method or a wet film formation method. The dry film forming method is preferable in that uniform film formation is easy, impurities are difficult to be mixed, and film thickness control or lamination to different materials is easy.

As a specific example of a dry film-forming method, physical vapor deposition methods, such as a vacuum vapor deposition method, sputtering method, an ion plating method, MBE method, or CVD methods, such as plasma polymerization, are mentioned. Preferably, it is a vacuum vapor deposition method, and when it forms into a film by the vacuum vapor deposition method, manufacturing conditions, such as a vacuum degree and vapor deposition temperature, can be set according to a conventional method. In the case where the light receiving layer is formed by the vapor deposition method, the decomposition temperature is higher than the depositionable temperature, so that thermal decomposition during deposition can be suppressed.

In the case where the light receiving layer is formed by the dry film forming method, the degree of vacuum during formation is preferably 1 × 10 ^-3 Pa or less, in consideration of preventing deterioration of device characteristics during the formation of the light receiving layer, and 4 × 10 ^-4 Pa or less Is more preferable and 1 * 10 <^-4> Pa or less is especially 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, particularly preferably 100 nm or more and 600 nm or less. By setting it as 10 nm or more, a preferable dark current suppression effect is obtained, and by setting it as 1000 nm or less, preferable photoelectric conversion efficiency is obtained.

The electron blocking layer 3 included in the light receiving layer suppresses the injection of electrons from the electrode 2 into the photoelectric conversion layer 4 and prevents the electrons generated in the photoelectric conversion layer 4 from flowing to the electrode 2 side. It is a layer for doing so. The electron blocking layer 3 is comprised including the organic material, the inorganic material, or both.

The electrode 5 is an electrode which collects electrons among charges generated in the photoelectric conversion layer 4. The electrode 5 uses a conductive material (for example, ITO) that is sufficiently transparent with respect to light having a wavelength at which the photoelectric conversion layer 4 has sensitivity to inject light into the photoelectric conversion layer 4. By applying a bias voltage between the electrode 5 and the electrode 2, holes in the charge generated in the photoelectric conversion layer 4 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 the factor which degrades organic materials, such as water and oxygen, from invading into the light receiving layer containing an organic material. The sealing layer 6 covers the electrode 2, the electron blocking layer 3, the photoelectric conversion layer 4, and the electrode 5, and is formed.

In the organic photoelectric conversion element 10 configured as described above, the electrode 5 is used as the electrode on the light incidence side. When light is incident from above the electrode 5, the light penetrates the electrode 5 and the photoelectric conversion layer 4 ), And electric charges are generated therein. Holes generated in the charge move to the electrode 2. By converting and reading the hole moved to the electrode 2 into a voltage signal corresponding to the quantity, light can be converted into a voltage signal and drawn out.

In addition, the electron blocking layer 3 may be comprised from multiple layers. By doing in this way, an interface will arise between each layer which comprises the electron blocking layer 3, and discontinuity will arise in the intermediate level which exists in each layer. As a result, since the transfer of charges through the intermediate level or the like becomes difficult, the electron blocking effect can be enhanced. However, if each layer constituting the electron blocking layer 3 is the same material, the intermediate level present in each layer may be completely the same, so that the material constituting each layer may be different in order to further enhance the electron blocking effect. It is preferable to make it.

In addition, a bias voltage may be applied to collect electrons in the electrode 2 and to collect holes in the electrode 5. In this case, the hole blocking layer may be formed in place of the electron blocking layer 3. The hole blocking layer is a layer made of an organic material for suppressing the injection of holes from the electrode 2 into the photoelectric conversion layer 4 and for preventing the holes generated in the photoelectric conversion layer 4 from flowing out to the electrode 2 side. You can do it. The hole blocking effect can be improved by using a plurality of hole blocking layers as well.

In addition, the electrons or holes collected by the electrode 5 may be converted into a voltage signal corresponding to the amount thereof and drawn 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 any case, the part sandwiched between the electrode 2 and the electrode 5 becomes a light receiving layer.

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

First, ITO is formed into a film by the sputtering method, for example on the board | substrate 1, and the electrode 2 is formed. Subsequently, an electron blocking material is formed into a film by vapor deposition, for example on the electrode 2, and the electron blocking layer 3 is formed.

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

In this manufacturing method, 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 each step, the above steps are carried out under vacuum in order to prevent the deterioration factors of the film such as water and oxygen from being mixed into the film and deteriorating the properties of the film during film formation. MEANS TO SOLVE THE PROBLEM As a result of earnest examination, this inventor puts the organic photoelectric conversion element 10 in a non-vacuum period after manufacture of the formation process of the photoelectric conversion layer 4 to the start of the formation process of the sealing layer 6 under vacuum. It has been found that the performance of the organic photoelectric conversion element 10 does not deteriorate even after setting (hereinafter referred to as a non-vacuum period).

Here, the space where a pressure is higher than a vacuum under each non-vacuum process is performed. Specifically, it refers to a non-vacuum atmospheric atmosphere or an inert atmosphere. Inner atmosphere shows that oxygen and water are 100 ppm or less (preferably 10 ppm or less, ideally 0.5 ppm or less) in the space of atmospheric pressure.

As an inert gas species in an inert atmosphere, there exist rare gases, such as nitrogen gas and argon, and incombustible gas, and what combined multiple of these inert gases may be sufficient. Preferably 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 the formation process of the electrode 5 and the formation process of the sealing layer 6. It can set in at least one of (2nd period).

Until now, after forming the photoelectric conversion layer 4 containing an organic material, and forming the sealing layer 6 which prevents the invasion of the deterioration factor of organic materials, such as water and oxygen, organic photovoltaic during manufacture When the conversion element 10 is placed under non-vacuum, it is considered that the organic material deteriorates due to moisture, oxygen, or the like, 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 Comparative Example described later, it can be seen that the device performance deteriorates when the non-vacuum period is set.

However, in the organic photoelectric conversion element 10 using the p-type organic semiconductor and the mixed layer of fullerene or fullerene derivative as the photoelectric conversion layer 4, between the formation process of the photoelectric conversion layer 4 and the formation of the sealing layer 6. The inventors have found that the device performance does not deteriorate even when the organic photoelectric conversion element 10 during fabrication is placed under non-vacuum. The present inventors 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 more (ideally 3 hours or more).

In this manufacturing method, a non-vacuum period can be set in a 1st period and a 2nd period. For this reason, the conveyance path | route of the organic photoelectric conversion element during manufacture from the apparatus which forms the photoelectric conversion layer 4 to the apparatus which forms the electrode 5, and the sealing layer 6 from the apparatus which forms the electrode 5 is carried out. It is not necessary to make the conveyance path | route of the organic photoelectric conversion element in the middle of manufacture to the apparatus which forms into a vacuum state. As a result, the manufacturing equipment of the organic photoelectric conversion element 10 can be simplified, and manufacturing cost can be reduced.

In addition, there is no difference in the effect by the difference in the direction in which the photoelectric conversion layer 4 is maintained in the non-vacuum period. In addition, the atmosphere between the formation process of the electron blocking layer 3 and the formation process of the photoelectric conversion layer 4 and the organic photoelectric conversion element 10 in the time or non-vacuum period of placing the device in the atmosphere under the above atmosphere. The presence or absence of light irradiation is not particularly limited as long as the effects of the present invention are not impaired remarkably.

When the non-vacuum period is set in any of the first period and the second period, the facility may be designed so that the transportation path of the element in the period in which the non-vacuum period is not set is in a vacuum state. When the non-vacuum period is set in both the first period and the second period, the cost of the facility can be significantly reduced.

Next, the structural example of the image pick-up element using the organic photoelectric conversion element 10 is demonstrated.

It is a cross-sectional schematic diagram which shows schematic structure of the imaging element for demonstrating one Embodiment of this invention. This imaging element is mounted on an imaging device such as a digital camera, a digital video camera, an electronic endoscope, a mobile phone or the like and used.

This imaging element has a circuit board in which the some organic photoelectric conversion element of the structure shown in FIG. 1, and the read circuit which reads the signal according to the electric charge which generate | occur | produced in the photoelectric conversion layer of each organic photoelectric conversion element are formed, A plurality of organic photoelectric conversion elements are arranged on the same surface in one or two dimensions.

The imaging device 100 shown in FIG. 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, and light receiving. The layer 107, the counter electrode 108, the buffer layer 109, the sealing layer 110, the color filter (CF) 111, the partition wall 112, the light shielding layer 113, and the protection A layer 114, a counter electrode voltage supply 115, and a read circuit 116 are provided.

The pixel electrode 104 has the same function as the electrode 2 of the organic photoelectric conversion element 10 shown in FIG. 1. The counter electrode 108 has the same function as the electrode 5 of the organic photoelectric conversion element 10 shown in FIG. 1. 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. 1. The sealing layer 110 has the same function as the sealing layer 6 of the organic photoelectric conversion element 10 shown in FIG. 1. A portion of the pixel electrode 104 and a counter electrode 108 facing the pixel electrode, a light receiving layer 107 sandwiched by these electrodes, and a portion of the buffer layer 109 and the sealing layer 110 facing the pixel electrode 104. Constitutes an organic photoelectric conversion element.

The substrate 101 is a glass substrate or a semiconductor substrate such as Si. An insulating layer 102 is formed on the substrate 101. The plurality of pixel electrodes 104 and the 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 organic photoelectric conversion elements formed by covering them on the plurality of pixel electrodes 104.

The counter electrode 108 is one electrode common to all organic photoelectric conversion elements formed on the light receiving layer 107. The counter electrode 108 is formed even on the connection electrode 103 arrange | positioned outside the light receiving layer 107, and is electrically connected with the connection electrode 103. As shown in FIG.

The connection part 106 is embedded in the insulating layer 102 and is a plug etc. 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 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 imaging device, 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 formed on the substrate 101 corresponding to each of the plurality of pixel electrodes 104, and reads a signal corresponding to the charges collected by the corresponding pixel electrode 104. The read circuit 116 is composed of, for example, a CCD, a MOS circuit, a TFT circuit, and the like, and is shielded by a light blocking layer (not shown) disposed in the insulating layer 102. The read circuit 116 is electrically connected to the pixel electrode 104 corresponding to it through the connection portion 105.

The buffer layer 109 is formed by covering the counter electrode 108 on the counter electrode 108. The sealing layer 110 is formed by covering the buffer layer 109 on the buffer layer 109. The color filter 111 is formed at a position facing the pixel electrode 104 on the sealing layer 110. The partition 112 is formed 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 in which the color filter 111 and the partition wall 112 are formed on the sealing layer 110, and prevents light from entering the light receiving layer 107 formed in addition to 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 whole imaging element 100.

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

The manufacturing method of the imaging device 100 is as follows.

The connecting portions 105 and 106, the plurality of connecting electrodes 103, the plurality of pixel electrodes 104, and the insulating layer 102 are formed on the circuit board on which the counter electrode voltage supply 115 and the readout circuit 116 are formed. . The plurality of pixel electrodes 104 are arranged on the surface of the insulating layer 102 in a square lattice, for example.

Subsequently, the light receiving layer 107 is formed on the plurality of pixel electrodes 104 by, for example, vacuum heating deposition. Next, the counter electrode 108 is formed on the light receiving layer 107 under vacuum by, for example, sputtering. Subsequently, the buffer layer 109 and the sealing layer 110 are sequentially formed on the counter electrode 108 by, for example, vacuum heating deposition. Subsequently, 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 pick-up element 100, the process of putting the image pick-up element 100 under manufacture non-vacuum between the formation process of the photoelectric conversion layer contained in the light receiving layer 107, and the formation process of the sealing layer 110 is carried out. By adding, the performance deterioration of several organic photoelectric conversion element can be prevented. By adding this step, the manufacturing cost can be suppressed while preventing performance deterioration of the imaging device 100.

Hereinafter, the details of the components (electron blocking layer 3, hole blocking layer, photoelectric conversion layer 4, electrode 2, electrode 5, 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) and is mainly represented by a hole transporting organic compound, and refers to an organic compound having a property of easily donating electrons. In more detail, when the two organic materials are contacted and used, the organic compound with the smaller ionization potential is mentioned. Therefore, any organic compound can be used as long as a donor organic compound is an organic compound which has an electron donation. 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 compound, cyanine compound, merocyanine compound, oxonol compound, polyamine compound, indole compound, pyrrole compound, pyrazole compound, polyarylene compound, condensed aromatic carbocyclic compound (naphthalene derivative, anthracene derivative, phenanthrene derivative, tetra Sen derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives), and metal complexes having a nitrogen-containing heterocyclic compound as a ligand. In addition, it is not limited to this, If it is an organic compound whose ionization potential is smaller than the organic compound used as an n type organic semiconductor, it can be used as a donor organic semiconductor.

Among these, preferable are a triarylamine compound, a pyran compound, a quinacridone compound, a pyrrole compound, a phthalocyanine compound, a merocyanine compound, and a condensed aromatic carbocyclic compound.

As the p-type organic semiconductor, any organic dye may be used, but preferred examples thereof include cyanine dye, styryl dye, hemicyanine dye, and merocyanine dye (including zero methine merocyanine (simple merocyanine)), 3 Nuclear merocyanine pigments, tetranuclear merocyanine pigments, rhodicyanine pigments, complex cyanine pigments, complex merocyanine pigments, arophora pigments, oxonol pigments, hemioxonol pigments, squarylium pigments, croconium pigments, Azamethine pigments, coumarin pigments, arylidene pigments, anthraquinone pigments, triphenylmethane pigments, azo pigments, azomethine pigments, spiro compounds, metallocene pigments, fluorenone pigments, fulle pigments, perylene pigments, Perry Non pigment, phenazine pigment, phenothiazine pigment, quinone pigment, diphenylmethane pigment, polyene pigment, acridine pigment, acridinone pigment, diphenylamine pigment, quinacridone pigment, quinophthal Pigments, phenoxazine pigments, phthaloperylene pigments, diketopyrrolopyrrole pigments, dioxane pigments, porphyrin pigments, chlorophyll pigments, phthalocyanine pigments, metal complex pigments, condensed aromatic carbocyclic pigments (naphthalene derivatives, anthracene derivatives, phenanthrene Derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives). Although a specific p-type organic semiconductor (compound) is illustrated below, the present invention is not limited to the compounds exemplified below.

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 C ₅₄₀ , mixed fullerene, and fullerene nanotube, and a fullerene derivative represents a compound to which a substituent is added thereto.

As a substituent of a fullerene derivative, Preferably, they are an alkyl group, an aryl group, or a heterocyclic group. As an alkyl group, More preferably, they are a C1-C12 alkyl group, As an aryl group and a heterocyclic group, Preferably they are a benzene ring, a naphthalene ring, anthracene ring, a phenanthrene ring, a fluorene ring, a triphenylene ring, a naphthacene ring, a biphenyl Ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indoliazine ring, indole ring, benzofuran ring, benzothiophene Ring, isobenzofuran ring, benzimidazole ring, imidazopyridine ring, quinolysin ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenan Tridine ring, acridine ring, phenanthroline ring, thianthrene ring, chroman ring, xanthene ring, phenoxatiin ring, phenothiazine ring or phenazine ring, more preferably benzene ring, naphthalene ring, anthracene ring, 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 combine as much as possible and form a ring. Moreover, you may have several substituent and they may be the same or they may not be the same. In addition, several substituents may combine as much as possible and form a ring.

Since the photoelectric conversion layer 4 contains a fullerene or a fullerene derivative, the charge generated by the photoelectric conversion can be quickly transferred 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 in a continuous state and electron paths are formed, electron transportability is improved, and 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 a fullerene derivative is contained in the photoelectric conversion layer 4. However, when there are too many fullerenes or fullerene derivatives, there will be less p-type organic semiconductor, and a junction interface will become small, and excitation dissociation efficiency will fall.

When the 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, which is particularly preferable. . When the ratio of fullerene or fullerene derivative in the photoelectric conversion layer 4 is too big | large, the said triarylamine compound will become small and the absorption amount of incident light will fall. Since the photoelectric conversion efficiency is reduced by this, it is preferable that the fullerene or fullerene derivative contained in the photoelectric conversion layer 4 is 85% or less of composition.

In order to express the effect of this invention remarkably, it is preferable that a p-type organic semiconductor is a compound represented by 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 the unsubstituted methine group or substituted methine group couple | bonded with following General formula (2), or group represented by following General formula (3).

In formula, Z <_1> is a ring containing the carbon atom couple | bonded with L <_1>, and the carbonyl group adjacent to the said carbon atom, and 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. X represents a hetero atom. Z ₂ is a ring containing X, and represents a condensed ring including 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 groups may combine with each other to form a ring. k represents the integer of 0-2. In general formula (2), * represents the coupling | bonding position couple | bonded with L <_1> , and * in general formula (3) represents L <_2>. Or a bonding position that binds to Ar ₁ .

Z ₁ in General Formula (2) means a condensed ring including at least one of a 5-membered ring, a 6-membered ring, or a 5-membered ring and a 6-membered ring as a ring containing two carbon atoms. As such a ring, what is normally used as an acidic nucleus with a merocyanine pigment | dye is preferable, As the specific example, the following are mentioned, for example.

(a) 1,3-dicarbonyl nucleus: for example, 1,3-indane dione nucleus, 1,3-cyclohexane dione, 5,5-dimethyl-1,3-cyclohexane dione, 1,3- Dioxane-4,6-dione and the like.

(b) Pyrazolinone nuclei: 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) isoxazoline nucleus: for example, 3-phenyl-2-isooxazolin-5-one, 3-methyl-2-isooxazolin-5-one and the like.

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

(e) 2,4,6-triketohexahydropyrimidine nuclei: for example barbituric acid or 2-thiobarbituric acid and derivatives thereof and the like. As a derivative, 1, 3- dialkyl bodies, such as 1-alkyl bodies, such as 1-methyl and 1-ethyl, 1, 3- dimethyl, 1, 3- diethyl, and 1, 3- dibutyl, 1 1,3-diaryl, such as 1,3-diphenyl, 1,3-di (p-chlorophenyl), 1,3-di (p-ethoxycarbonylphenyl), and 1-ethyl-3-phenyl And 1,3-position diheterocyclic substituents such as 1-alkyl-1-aryl and 1,3-di (2-pyridyl).

(f) 2-thio-2,4-thiazolidine dione nucleus: for example, rhodanine and its derivatives and the like. As the derivative, for example, 3-alkyl rhodanine such as 3-methyl rhodanine, 3-ethyl rhodanine, 3-aryl rhodanine, 3-aryl rhodanine, such as 3-phenyl rhodanine, 3- (2-pyri) 3-position heterocyclic substituted rhodanine, such as dill) rhodanine, etc. are mentioned.

(g) 2-thio-2,4-oxazolidine dione (2-thio-2,4- (3H, 5H) -oxazole dione nucleus: for example, 3-ethyl-2-thio-2,4 Oxazolidine dione and the like.

(h) thianaphthenic nuclei: for example 3 (2H) -thianaphthene-1,1-dioxide and the like.

(i) 2-thio-2,5-thiazolidine dione nucleus: for example, 3-ethyl-2-thio-2,5-thiazolidine dione and the like.

(j) 2,4-thiazolidine dione nuclei: for example 2,4-thiazolidine dione, 3-ethyl-2,4-thiazolidine dione, 3-phenyl-2,4-thiazolidine Dion etc.

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

(l) 2,4-imidazolidine dione (hydantoin) nucleus: for example, 2,4-imidazolidine dione, 3-ethyl-2,4-imidazolidine dione and the like.

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

(n) 2-imidazolin-5-one nucleus: for example, 2-propylmercapto-2-imidazolin-5-one and the like.

(o) 3,5-pyrazolidine dione nuclei: for example 1,2-diphenyl-3,5-pyrazolidine dione, 1,2-dimethyl-3,5-pyrazolidine dione and the like.

(p) Benzothiophen-3-one nucleus: For example, benzothiophen-3-one, oxobenzothiophen-3-one, dioxobenzothiophen-3-one, etc.

(q) indanone nucleus: for example, 1-indanon, 3-phenyl-1-indanon, 3-methyl-1-indanon, 3,3-diphenyl-1-indanon, 3,3- Dimethyl-1-indanon 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, 2-thiobarbituric acid nucleus), 2-thio-2,4-thiazolidine dione nucleus, 2-thio-2,4-oxazolidine dione nucleus, 2-thio-2,5-thiazolidine dione nucleus , 2,4-thiazolidine dione nucleus, 2,4-imidazolidine dione nucleus, 2-thio-2,4-imidazolidine dione nucleus, 2-imidazoline-5-one nucleus, 3, 5-pyrazolidine dione nucleus, benzothiophen-3-one nucleus, indanone nucleus, more preferably 1,3-dicarbonyl nucleus, 2,4,6-triketohexahydropyrimidine nucleus (thio Ketone bodies are also included, for example barbituric acid nucleus, 2-thiobarbituric acid nucleus), 3,5-pyrazolidine dione nucleus, benzothiophen-3-one nucleus, indanone nucleus, and more preferably 1 , 3-dicarbonyl nucleus, 2,4,6-triketo hexahydropyrimidine nucleus (including thioketone bodies, eg 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.

Preferable 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 represents a condensed ring including at least one of a 5-membered ring, a 6-membered ring, a 5-membered ring, and a 6-membered ring. * Represents a bonding position to bond with L ₁ . Z ³ can be selected from the ring represented by Z ₁ , preferably a 1,3-dicarbonyl nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including thioketone bodies), and in particular Preferred are 1,3-indane dione nuclei, barbituric acid nuclei, 2-thiobarbituric acid nuclei and derivatives thereof.

When the ring which Z <_1> represents is a ₁ , 3- indan dione nucleus, the case where it is group represented by following General formula (5) is preferable.

In the formula, each of R ₂ to R ₅ independently represents a hydrogen atom or a substituent, and adjacent groups may combine with each other to form a ring. * Represents a bonding position to bond with L ₁ .

X in general formula (3) represents the integer of 0-2, Preferably it is 0 or 1, More preferably, it is zero. X is preferably O, S, or NR ₁₀ . Preferable examples of the ring represented by Z ₂ are represented by the following formula (6).

In the formula, X represents O, S, and NR ₁₀ . R ₁₀ represents a hydrogen atom or a substituent. In formula, R <_1> , R <_6> , R <_7> may respectively independently represent a hydrogen atom or a substituent, and the adjacent one may combine with each other and form a ring. m represents the integer of 1-3. When m is two or more, some R <_1> may be same or not same. ＊ L ₂ Or a bonding position that binds to 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 said arylene group may have a substituent, Preferably it is a C6-C18 arylene group which may have a C1-C4 alkyl group. For example, a phenylene group, a naphthylene group, a methylphenylene group, a dimethylphenylene group, etc. are mentioned, A phenylene group and a naphthylene group are preferable.

As an aryl group which Ar <_2> and Ar <_3> represent respectively, Preferably they are a C6-C30 aryl group, More preferably, they are a C6-C18 aryl group. The said aryl group may have a substituent, Preferably it is a C6-C18 aryl group which may have a C1-C4 alkyl group or a C6-C18 aryl group. For example, a phenyl group, a naphthyl group, a tolyl group, anthryl group, a dimethylphenyl group, a biphenyl group, etc. are mentioned, A phenyl group and a naphthyl group are preferable.

As an alkyl group which Ar <_2> and Ar <_3> represent, Preferably they are a C1-C6 alkyl group, More preferably, they are a C1-C4 alkyl group. For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group is mentioned, 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 each independently preferably a heteroaryl group having 3 to 30 carbon atoms, and more preferably a heteroaryl group having 3 to 18 carbon atoms. The said heteroaryl group may have a substituent, Preferably it is a C3-C18 heteroaryl group which may have a C1-C4 alkyl group or a C6-C18 aryl group. The heteroaryl group represented by Ar ₂ and Ar ₃ may have a condensed ring structure, a furan ring, a thiophene ring, a selenophene ring, a silol ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, an oxazole ring, a thiazole ring, a triazole ring, A condensed ring structure of a combination (which may be the same) of a ring selected from an oxadiazole ring and a thiadiazole ring is preferable, and a quinoline ring, an isoquinoline ring, a benzothiophene ring, a dibenzothiophene ring, a thienothiophene ring, and a bithienobenzene Rings and bithienothiophene rings are preferable.

Ar ₁ , Ar ₂ , Ar ₃ , R ₁ , R ₂ to R ₇ , R ₁₀ Adjacent ones may be connected to each other to form a ring. In addition, the ring is preferably a ring formed of a hetero atom, an alkylene group, an aromatic ring, or the like. For example, two of an aryl group (for example, Ar ₁ , Ar ₂ , Ar ₃ of Formula (1)) are connected through a single bond or a linking group together with a nitrogen atom (N of Formula (1)). The ring formed is mentioned. Examples of the linking group include a group consisting of a hetero atom (e.g., -O-, -S-, etc.), an alkylene group (e.g., methylene group, ethylene group, etc.) and a combination thereof, and -S-, methylene Group is preferred. Nitrogen atoms (e.g., N in general formula (1)), alkylene groups (e.g., methylene group) and aryl groups (e.g., Ar ₁ and Ar _{2 in} general formula (1) Or a ring formed of Ar ₃ ).

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), and a plurality of the substituents are linked to each other and further include a ring (for example, Benzene ring, etc.) may be formed.

Moreover, it is also preferable that R <_3> and R <_4> mutually connect and form the ring, and a benzene ring is preferable as said ring.

When there are a plurality of R ₁ (m is 2 or more), adjacent ones of the plurality of R ₁ may be connected to each other to form a ring, and as the ring, a benzene ring is preferable.

As said substituent in the case where Ar <_1> , Ar <_2> , Ar <_3> has a substituent, and a substituent of R <_1> , R <_2> -R <_7> , R <_10> , a halogen atom and an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group) , Substituted alkyl group, alkenyl group (including cycloalkenyl group, bicycloalkenyl group), alkynyl group, aryl group, substituted aryl group, heterocyclic group (may be called heterocyclic group), cyano group, hydroxy group, nitro group, carboxyl group, Alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group (including an alinino group), ammonia group, acylamino group, aminocarbonyl Amino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thi group, sulfamo Diary, sulfo, alkyl and arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imido groups, phosphino groups, phosphinyl groups, phosphines Neyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (-B (OH) ₂ ), phosphate group (-OPO (OH) ₂ ), sulfato group (-OSO ₃ H), it can be a substituent other known. R ₁ , R ₂ to R ₇ , As the substituent for 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, an amino group, an alkylthio group, an alkenyl group or a halogen atom is particularly preferable.

When Ar ₁ , Ar ₂ , Ar ₃ each independently have 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 amino group, an alkylthio group, An arylthio group, alkenyl group, cyano group, or heterocyclic thi group is preferable.

As R ₁ , an alkyl group and an aryl group are more preferable. As R <_6> and R <_{7>, a} cyano group is more preferable.

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

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 may be an alkyl group, an aryl group, a heterocyclic group, an alkenyl group, An alkoxy group or an aryloxy group may be shown and substituents may combine and form a ring. As a ring, a 6-membered ring (for example, a benzene ring etc.) is mentioned. In addition, L ₁ Alternatively, substituents of L ₃ and Ar ₁ may be bonded to each other to form a ring. In addition, 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> and R <_10> represent, Preferably they are a C1-C6 alkyl group, More preferably, they are a C1-C4 alkyl group. For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group is mentioned. As R <_2> -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 t-butyl group is preferable, and a methyl group or t-butyl group is more preferable.

n is preferably 0 or 1.

As an aryl group which R <_1> , R <_2> -R <_7> and R <_10> represent, they are each independently a C6-C30 aryl group, More preferably, they are a C6-C18 aryl group. The said aryl group may have a substituent, Preferably it is a C6-C18 aryl group which may have a C1-C4 alkyl group or a C6-C18 aryl group. For example, a phenyl group, naphthyl group, anthracenyl group, pyrenyl group, phenanthrenyl group, methylphenyl group, dimethylphenyl group, biphenyl group, etc. are mentioned, A phenyl group, a naphthyl group, or anthracenyl group is preferable.

As a heteroaryl group which R <_1> , R <_2> -R <_7> and R <_10> represent, each independently, It is a C3-C30 heteroaryl group, More preferably, it is a C3-C18 heteroaryl group. The said heteroaryl group may have a substituent, Preferably it is a C3-C18 heteroaryl group which may have a C1-C4 alkyl group or a C6-C18 aryl group. Moreover, the heteroaryl group which the heteroaryl group which R <_1> , R <_2> -R <_7> represents represents 5-membered, 6-membered or 7-membered ring, or its condensed ring is preferable. As a hetero atom contained in a heteroaryl group, an oxygen atom, a sulfur atom, and a nitrogen atom are mentioned. 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 imida. Zolidine ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, A pyrimidine ring, a pyrazine ring, a piperazine ring, a triazine ring, etc. are mentioned.

As the condensed ring, a benzofuran ring, isobenzofuran ring, benzothiophene ring, indole ring, indolin 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 , A thienothiophene ring, an indolijin ring, a quinoligin ring, a quinuclidin ring, a naphthyridine ring, a purine ring, a putridine ring, and the like.

m represents the integer of 1-3, Preferably it is 1 or 2, More preferably, it is 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 low molecular weight materials, N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine (TPD) or 4,4'-bis [N- (naphthyl) Aromatic diamine compounds such as) -N-phenylamino] 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, tetraphenylporpin copper, phthalocyanine, copper phthalocyanine , Porphyrin compounds such as titanium phthalocyanine oxide, triazole derivatives, oxadiazolyl derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, parazolone derivatives, phenylenediamine derivatives, aryl amine derivatives, fluorene derivatives, amino substitutions Chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluolenone derivatives, Dragan derivatives, silazane derivatives and the like can be used, and polymer materials such as phenylenevinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene, and derivatives thereof Even if it is not an electron donating compound, if it is a compound which has sufficient hole transport property, it can be used.

Specifically, for example, the following compounds described in JP-A-2008-72090A are shown, but the present invention is not limited thereto. In addition, Ea below shows the electron affinity of the material, and Ip shows the ionization potential of the material. EB-1, 2,... "EB" is an abbreviation of "electronic blocking."

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

In the electron blocking layer 3 which consists of multiple layers, it is preferable that the layer adjacent to the photoelectric conversion layer 4 among the multiple layers is a layer which consists of the same material as the p-type organic semiconductor contained in the said photoelectric conversion layer 4. By using the same p-type organic semiconductor for the electron blocking layer 3, the 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.

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

[Hole blocking layer]

An electron-accepting organic material can be used for the hole blocking layer. Examples of electron-accepting materials include oxadiazole derivatives such as 1,3-bis (4-tert-butylphenyl-1,3,4-oxadiazolyl) phenylene (OXD-7), anthraquinodimethane derivatives, and diphenylquinones. Derivatives, vasocuproin, vasophenanthroline and derivatives thereof, triazole compounds, tris (8-hydroxyquinolinate) aluminum complex, bis (4-methyl-8-quinolinate) aluminum complex, distyryl Arylene derivatives, silol compounds and the like. Moreover, even if it is not an electron accepting organic material, if it is a material which has sufficient electron transport property, it can be used. A styryl type compound, such as a porphyrin type compound, DCM (4-dicyano methylene-2-methyl-6- (4- (dimethylamino styryl))-4H pyran), and a 4H pyran type compound can be used.

[Pixel electrode]

As a material of the electrode 2 (pixel electrode 104), a metal, a metal oxide, a metal nitride, a metal boride, an organic conductive compound, a mixture thereof, etc. are mentioned, for example. 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, and gold (Au) , Metals such as platinum (Pt), silver (Ag), chromium (Cr), nickel (Ni), aluminum (Al), and mixtures or laminates of these metals with conductive metal oxides, polyanilines, polythiophenes, polypyrroles Organic conductive compounds such as these, laminates of these and ITO, and the like. Particularly preferred as 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 (GZO). Either material.

At the end of the electrode 2, a step corresponding to the film thickness of the electrode 2 is steep, a significant unevenness is present on the surface of the electrode 2, or a fine dust (particle) on the electrode 2 is formed. When attached, the layer on the electrode 2 becomes thinner than the desired film thickness or cracks occur. When the electrode 5 (counter electrode 108) is formed on the layer in such a state, the dark current is increased or shorted due to the contact of the electrode 2 and the electrode 5 at the defective portion or concentration of an electric field. Pixel defects occur. Moreover, the said defect may reduce the adhesiveness of the electrode 2 and the layer on it, and the heat resistance of the organic photoelectric conversion element 10.

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

Counter electrode

As a material of the electrode 5 (counter electrode 108), a metal, a metal oxide, a metal nitride, a metal boride, an organic conductive compound, a mixture thereof, etc. are mentioned, for example. 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, and gold (Au) , Metals such as platinum (Pt), silver (Ag), chromium (Cr), nickel (Ni), aluminum (Al), and mixtures or laminates of these metals with conductive metal oxides, polyanilines, polythiophenes, polypyrroles Organic conductive compounds such as these, laminates of these and ITO, and the like. Particularly preferred as 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 (GZO). Either material.

[Sealing layer]

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

First, in each manufacturing process of an element, the photoelectric conversion layer is protected by preventing the invasion of the factor which degrades the organic photoelectric conversion material contained in a solution, a plasma, etc.

Secondly, after the device is manufactured, intrusion of a factor that degrades organic photoelectric conversion materials 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 photoelectric conversion layer already formed is not degraded.

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.

Although the sealing layer 6 can also be comprised from the thin film which consists of a single material, by providing each function to each layer as a multilayered structure, by the stress relaxation of the whole sealing layer 6, oscillation in a manufacturing process, etc. Effects such as suppressing defects such as cracks and pinholes and optimizing material development can be expected. For example, the sealing layer 6 is formed by laminating a "sealing auxiliary layer" having a function that is difficult to achieve in the layer on a layer that achieves an original purpose of preventing penetration of deterioration factors such as water molecules. Layer configurations can be formed. Although the structure of three or more layers is also possible, it is preferable that the number of layers is small so that manufacturing cost may be considered.

[Formation of sealing layer 6 by atomic layer deposition method]

The performance of the organic photoelectric conversion material is remarkably degraded due to the presence of deterioration factors such as water molecules. Therefore, it is necessary to coat and seal the whole photoelectric conversion layer with ceramics, diamond-like carbon (DLC), etc., such as dense metal oxide, metal nitride, and metal nitride oxide which do not penetrate water molecules. Background Art Conventionally, aluminum oxide, silicon oxide, silicon nitride, silicon nitride oxide, their laminated constitutions, lamination constitutions of them and organic polymers, and the like are formed by various vacuum film forming techniques as sealing layers. However, these conventional sealing layers are difficult to grow a thin film in the step due to the structure of the substrate surface, micro-defects on the substrate surface, particles adhered to the substrate surface, etc. (because the step becomes a shadow), compared with the flat portion. Becomes significantly thinner. For this reason, the stepped portion becomes a path through which the deterioration factor penetrates. In order to completely cover this step | step with a sealing layer, it is necessary to form into a film | membrane so that it may become 1 micrometer or more in a flat part, and to thicken the whole sealing layer. 1 x 10 ³ Pa or less is preferable and, as for the vacuum degree at the time of sealing layer formation, 5 x 10 ² Pa or less is more preferable.

In the imaging device 100 having a pixel dimension of less than 2 μm, particularly about 1 μm, 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, incident light in the sealing layer 110 is caused. This diffraction / divergence produces mixed color. For this reason, the imaging element 100 which has a pixel dimension of about 1 micrometer requires the sealing layer material / manufacturing method which does not deteriorate element performance even if the film thickness of the whole sealing layer 110 is reduced.

The atomic layer deposition (ALD) method is a kind of CVD method that alternates the adsorption / reaction of the organometallic compound molecules, metal halide molecules, and metal hydride molecules that become thin film materials to the substrate surface and decomposition of unreacted groups contained in them. It is a technique to form a thin film repeatedly. When the thin film material reaches the surface of the substrate, the low molecular state allows the thin film to grow as long as there is a very small space in which the low molecules can enter. Therefore, the stepped portion, which was difficult in the conventional thin film forming method, is completely covered (the thickness of the thin film grown on the stepped 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 level difference can be completely covered by the structure of the substrate surface, minute defects on the surface of the substrate, particles attached to the surface of the substrate, and the like, so that the level difference portion does not become an intrusion path of the deterioration factor of the photoelectric conversion material. When formation of the sealing layer 6 is carried out by the atomic layer deposition method, it becomes possible to make the sealing layer film thickness required more effective than the prior art.

When forming the sealing layer 6 by the atomic layer deposition method, the material corresponding to the ceramics suitable for the sealing layer 6 mentioned above can be selected suitably. 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 formation at a relatively low temperature at which the organic photoelectric conversion material is not degraded. According to the atomic layer deposition method using alkyl aluminum or aluminum halide, a dense aluminum oxide thin film can be formed at less than 200 ° C. where the organic photoelectric conversion material is not degraded. In particular, when trimethyl aluminum is used, the aluminum oxide thin film can be formed even at about 100 ° C, which is preferable. Silicon oxide and titanium oxide are also preferable because they can form a dense thin film at less than 200 ° C. like aluminum oxide by appropriately selecting a material.

[Sealing auxiliary layer]

The thin film formed by the atomic layer deposition method can achieve high quality thin film formation at a low temperature, which is unprecedented from the viewpoint of step coverage and compactness. However, the physical properties of the thin film material may deteriorate with the chemicals used in the photolithography step. For example, since the 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 excellent in chemical resistance must be formed on the aluminum oxide thin film formed by atomic layer deposition, that is, a sealing auxiliary layer serving as a functional layer for protecting the sealing layer 6 is required.

On the other hand, thin films formed by CVD methods such as atomic layer deposition have many cases where the internal stress has a very high tensile stress, and in the process of repeated intermittent heating and cooling, such as a semiconductor manufacturing process, or in a long-term high temperature / high humidity atmosphere. Deterioration that a crack occurs in the thin film itself may occur by 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, and metal nitride oxides having excellent chemical resistance formed by physical vapor deposition (PVD) methods such as sputtering. The structure which forms the sealing auxiliary layer containing any of ceramics, such as these, is preferable. Here, what was formed by the atomic layer deposition method is called a 1st sealing layer, The 2nd sealing layer formed by the PVD method on the said 1st sealing layer and containing any one of a metal oxide, a metal nitride, and a metal nitride oxide is mentioned. It is called. In this way, it becomes easy to improve the chemical resistance of the whole sealing layer 6. In addition, ceramics formed by PVD methods such as sputtering often have large compressive stress, and the tensile stress of the first sealing layer formed by atomic layer deposition can be canceled out. Therefore, the stress of the whole sealing layer 6 is alleviated, and the reliability of the sealing layer 6 itself becomes high, and the defect which the stress of the sealing layer 6 worsens or destroys the performance of a photoelectric conversion layer, etc. arises. It is possible to significantly suppress.

It is preferable to set it as the structure which has a 2nd sealing layer especially containing any one of aluminum oxide, silicon oxide, silicon nitride, and silicon nitride oxide formed on the 1st sealing layer by sputtering method.

It is preferable that a 1st sealing layer has a film thickness of 0.05 micrometer or more and 0.5 micrometer or less. Moreover, it is preferable that a 1st sealing layer contains any one of aluminum oxide, silicon oxide, and titanium oxide.

Hereinafter, the effect by having formed the non-vacuum period is demonstrated in an Example.

Example

(Example 1)

The imaging element provided with an organic photoelectric conversion element was produced. The order is as follows: First, amorphous ITO was formed into a film by sputtering on the CMOS substrate in which the readout circuit which consists of a CMOS circuit and the connection electrode connected to this was formed, and this patterned and the pixel electrode was formed on each connection electrode. Subsequently, the material represented by said EB-3 was formed into a film by thickness of 100 nm by vacuum heating vapor deposition on the some pixel electrode, and the electron blocking layer was formed. Then, electron blocking layer of a compound 1 and fullerene (C ₆₀₎ by a vacuum heating deposition to: to form a photoelectric conversion layer of the film thickness (1 to 3 ratio) deposited by film formation with, and 400㎚. In this evaporation, the cell "Thermobolcell (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. Subsequently, the imaging element in the middle of the production is placed in an air atmosphere for 3 minutes, and then the imaging element is set in an apparatus for forming the counter electrode, and amorphous ITO is deposited on the photoelectric conversion layer by a thickness of 10 nm by sputtering. The counter electrode was formed. In addition, formation of the counter electrode was performed under vacuum. Subsequently, the imaging device in the middle of the production is placed in an air atmosphere for 3 minutes, and then the imaging device is set in a device for forming a sealing layer, and silicon oxide is deposited on the counter electrode by heat deposition, followed by oxidation by the ALD method. Aluminum was formed into a film and the sealing layer was formed. The counter electrode and the sealing layer were formed under vacuum.

(Example 2)

Except having changed the compound 1 into the compound 9, it carried out similarly to Example 1, and produced the imaging element.

(Example 3)

An imaging device is carried out in the same manner as in Example 1 except that the imaging device in the middle of production is placed under a nitrogen gas atmosphere between the photoelectric conversion layer forming step and the counter electrode forming step, and the counter electrode forming step and the sealing layer forming step. Made. In addition, the time which leaves the imaging element in the middle of manufacture in nitrogen gas atmosphere was made into 3 minutes.

(Example 4)

An imaging device was manufactured in the same manner as in Example 1 except that the time for setting the imaging device in the middle of the production in the air atmosphere was 30 minutes.

(Example 5)

An imaging device was produced in the same manner as in Example 3, except that the time of placing the imaging device in the middle of the production in a nitrogen gas atmosphere was 30 minutes.

(Example 6)

An imaging device was manufactured in the same manner as in Example 1 except that the time for setting the imaging device in the middle of the production in the atmospheric atmosphere was 1 minute.

(Example 7)

An imaging device was manufactured in the same manner as in Example 3, except that the time of placing the imaging device in the middle of the production in a nitrogen gas atmosphere was 1 minute.

(Example 8)

Between the formation process of a photoelectric conversion layer and the formation process of a counter electrode, the imaging element in manufacture is put under vacuum for 3 minutes, and between the formation process of a counter electrode and the formation process of a sealing layer, the imaging element in preparation is produced under an atmospheric atmosphere. Except for 48 hours, an image pickup device was manufactured in the same manner as in Example 1.

(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 manufactured in the same manner as in Example 3 except that Compound 1 was changed to Compound 7.

(Comparative Example 1)

Between the process of forming the photoelectric conversion layer and the process of forming the counter electrode, and the process of forming the counter electrode and the process of forming the sealing layer, the imaging element in the middle of manufacturing is placed under vacuum for 3 minutes and then set in an apparatus for carrying out the next process. An imaging device was produced in the same manner as in Example 1 except for the above.

(Comparative Example 2)

Between the process of forming the photoelectric conversion layer and the process of forming the counter electrode, and the process of forming the counter electrode and the process of forming the sealing layer, the imaging element in the middle of manufacturing is placed under vacuum for 3 minutes and then set in an apparatus for carrying out the next process. An imaging device was manufactured in the same manner as in Example 2 except for the above.

(Comparative Example 3)

Compound 1 was deposited to a thickness of 100 nm by vacuum heating deposition to form a photoelectric conversion layer, which was prepared between the formation process of the photoelectric conversion layer and the formation of the counter electrode, the formation process of the counter electrode and the formation of the sealing layer. An imaging device was manufactured in the same manner as in Example 1 except that the intermediate imaging device was placed under vacuum for 3 minutes and then this was set in the apparatus for carrying out the following step.

(Comparative Example 4)

Between the process of forming the photoelectric conversion layer and the process of forming the counter electrode, and the process of forming the counter electrode and the process of forming the sealing layer, the imaging element in the middle of production is placed in the air for 3 minutes and then set in the apparatus for carrying out the next process. An imaging device was produced in the same manner as in Comparative Example 3 except for the above.

(Comparative Example 5)

Compound 1 was formed by vacuum heating evaporation to a thickness of 100 nm, and then fullerene (C ₆₀ ) was formed into a film by thickness of 100 nm on compound 1 to form a photoelectric conversion layer having a thickness of 200 nm. Except for setting the imaging element under manufacture for 3 minutes under vacuum for three minutes between the step of forming the counter electrode and the step of forming the counter electrode, and the step of forming the counter electrode, and setting it in an apparatus for carrying out the next step. An imaging device was manufactured in the same manner as in 1.

(Comparative Example 6)

An imaging device is constructed in the same manner as in Comparative Example 5 except that the imaging device in the middle of production is placed in an atmospheric atmosphere between the photoelectric conversion layer forming step and the counter electrode forming step, and the counter electrode forming step and the sealing layer forming step. Made.

(Comparative Example 7)

Between the process of forming the photoelectric conversion layer and the process of forming the counter electrode, and the process of forming the counter electrode and the process of forming the sealing layer, the imaging element in the middle of manufacturing is placed under vacuum for 3 minutes and then set in an apparatus for carrying out the next process. An imaging device was manufactured in the same manner as in the ninth example except for the above.

External quantum efficiency (relative value when the numerical value of Comparative Example 1 is 100) at the maximum sensitivity wavelength when applied at 2 × 10 ⁵ V / cm electric field of each organic photoelectric conversion element in Examples and Comparative Examples Table 1 shows the measurement results. In addition, the value of an external quantum efficiency was made into the value in the case where positive bias is applied to the counter electrode of the produced element, light is incident from the counter electrode side, and the hole is taken out from a pixel electrode.

In comparison with 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 halved by setting the non-vacuum period. In comparison with Comparative Example 5 and Comparative Example 6, when the photoelectric conversion layer is a laminated structure of Compound 1 and C ₆₀ , it can be seen that the external quantum efficiency is reduced by almost 20% by setting the non-vacuum period.

On the other hand, in comparison with Comparative Example 1 and Examples 1, 3, 6, and 7, when the photoelectric conversion layer is a mixed layer of Compound 1 and C _60, the external quantum efficiency does not deteriorate even if a non-vacuum period is set, but rather rises slightly. I can see that. In addition, in comparison with Comparative Example 2 and Example 2, it can be seen that the external quantum efficiency does not deteriorate even when the non-vacuum period is set when the photoelectric conversion layer is a mixed layer of compounds 9 and C ₆₀ . In addition, when Example 7 is compared with Examples 9 and 10, it can be seen that when the photoelectric conversion layer is a mixed layer of Compound 7 and C _60, the external quantum efficiency does not deteriorate even if the non-vacuum period is set. In Example 8, although the vacuum period and the non-vacuum period were set, it was found that the external quantum efficiency also increased in this case as compared with the case where the non-vacuum period was not set as in Comparative Example 1.

From this result, when the photoelectric conversion layer is a mixed layer of a p-type organic semiconductor and fullerene or fullerene derivative, it is non-vacuum in any part or all of the steps between the formation process of the photoelectric conversion layer and the formation process of the sealing layer. It was found that the device performance did not deteriorate even if the period was set.

In Examples 4 and 5, the external quantum efficiency is increased by about 10% compared with Examples 1, 3, 6 and 7. In Example 8, the external quantum efficiency is increased by about 10% compared with Examples 1, 3, 6, and 7. From this result, 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 mentioned above, the following is disclosed in this specification.

The disclosed method for manufacturing an organic photoelectric conversion element includes a photoelectric conversion layer comprising a first electrode, a second electrode formed above the first electrode, an organic material formed between the first electrode and the second electrode, and the first electrode. A method of manufacturing an organic photoelectric conversion element comprising a sealing layer for sealing a first electrode, the second electrode, and the photoelectric conversion layer, wherein the photoelectric conversion layer includes a non-luminescent layer comprising 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 the substrate, a second step of forming the photoelectric conversion layer above the first electrode, and 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 is performed. Between the end of a process and the start of a said 4th process, the 5th process of putting the said organic photoelectric conversion element in the middle of manufacture under non-vacuum is provided.

The manufacturing method of the disclosed organic photoelectric conversion element is one in which the non-vacuum in the fifth step is under an atmospheric atmosphere or an inert atmosphere.

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

The manufacturing method of the disclosed organic photoelectric conversion element is to form the photoelectric conversion layer by a dry film forming method in the second step.

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

The manufacturing method of the disclosed organic photoelectric conversion element includes that the X-type organic semiconductor is a compound represented by the general formula (1).

The disclosed method for manufacturing an organic photoelectric conversion element is to leave the organic photoelectric conversion element during the production under the non-vacuum for at least one minute in the fifth step.

The disclosed method for manufacturing an organic photoelectric conversion element includes an electron blocking layer in which the organic photoelectric conversion element is formed between the first electrode and the photoelectric conversion layer, and after the first process and before the second process, the electron blocking layer. It has a process of forming a.

The disclosed method for manufacturing an organic photoelectric conversion element 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 method for producing the organic photoelectric conversion device.

The disclosed image pickup device includes a plurality of the organic photoelectric conversion elements and a circuit board on which signal reading circuits for reading signals corresponding to charges generated in the photoelectric conversion layers of the respective 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 (12)

A photoelectric conversion layer comprising a first electrode, a second electrode formed above the first electrode, an organic material formed between the first electrode and the second electrode, the first electrode, the second electrode, and the As a manufacturing method of the organic photoelectric conversion element containing the sealing layer which seals a photoelectric conversion layer:
The photoelectric conversion layer is a non-luminescent layer comprising 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 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;
Each step of the second step to the fourth step is performed under vacuum;
And a fifth step of placing the organic photoelectric conversion element during the production under non-vacuum between the end of the second step and the start of the fourth step. The method of claim 1,
It is under the said non-vacuum atmospheric | air atmosphere or an inert atmosphere in a said 5th process, The manufacturing method of the organic photoelectric conversion element characterized by the above-mentioned. The method according to claim 1 or 2,
The fifth step is performed between the second step and the third step and between the third step and the fourth step. The method according to claim 1 or 2,
The fifth process is performed between the second process and the third process, or between the third process and the fourth process. The method according to any one of claims 1 to 4,
In the second step, the photoelectric conversion layer is formed by a dry film forming method. The method of claim 5, wherein
In the second step, the fullerene or the fullerene derivative and the X-type organic semiconductor are deposited together by vacuum heating evaporation to form the mixed layer. The method according to any one of claims 1 to 6,
Said X type organic semiconductor is a compound represented by following General formula (1), The manufacturing method of the organic photoelectric conversion element characterized by the above-mentioned.

[Wherein, L ₂ and L ₃ each independently represent an unsubstituted methine group or a substituted methine group. n represents the integer of 0-2. 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. Adjacent ones of Ar ₁ , Ar ₂ , and Ar ₃ may be bonded 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), or a group represented by the following General Formula (3).]

[Wherein Z ₁ is a ring containing a carbon atom bonded to L ₁ and a carbonyl group adjacent to the carbon atom, and represents a condensed ring including at least one of a 5-membered ring, a 6-membered ring, or a 5-membered ring and a 6-membered ring; . X represents a hetero atom. Z ₂ is a ring containing X, and represents a 5-membered ring, 6-membered ring, 7-membered ring, or a condensed ring including one or more of 5-membered ring, 6-membered ring, and 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 groups may combine with each other to form a ring. k represents the integer of 0-2. In general formula (2), * represents the coupling | bonding position couple | bonded with L <_1> , and * in general formula (3) represents the coupling | bonding position couple | bonded with L <_2> or Ar <_1> .] The method according to any one of claims 1 to 7,
In the fifth step, the organic photoelectric conversion element during the production is kept under the non-vacuum for at least 1 minute. The method according to any one of claims 1 to 8,
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 after the first step and before the second step. The organic photoelectric conversion element manufactured by the manufacturing method of the organic photoelectric conversion element in any one of Claims 1-9. A plurality of organic photoelectric conversion elements according to claim 10; And
And a circuit board on which a signal reading circuit for reading a signal according to the charge generated in the photoelectric conversion layer of each of the organic photoelectric conversion elements is formed. An imaging device comprising the image pickup device according to claim 11.

Images