JP5520647B2 - Manufacturing method of organic photoelectric conversion element - Google Patents

Description

The present invention relates to a method for producing an organic photoelectric conversion element .

  An organic photoelectric conversion element having a pair of electrodes and a photoelectric conversion layer using an organic material provided between the pair of electrodes is known. Until now, various efforts have been made to improve the characteristics of organic photoelectric conversion elements. For example, Patent Document 1 discloses that the photoelectric conversion layer includes a fullerene or a fullerene derivative so that the SN ( A method for improving the photoelectric conversion efficiency / dark current) is disclosed.

  In recent years, the sensitivity of image pickup devices has been increased, and in order to apply an organic photoelectric conversion device to this, further improvement in SN of the organic photoelectric conversion device is required.

JP 2007-123707 A

This invention is made | formed in view of the said situation, and it aims at providing the manufacturing method of the organic photoelectric conversion element which can improve SN.

The method for producing an organic photoelectric conversion element of the present invention is formed between a first electrode, a second electrode formed above the first electrode, and the first electrode and the second electrode. A method for producing an organic photoelectric conversion element, comprising: a photoelectric conversion layer containing an organic material; and the first electrode, the second electrode, and a sealing layer for sealing the photoelectric conversion layer. A second step of forming the photoelectric conversion layer above the first electrode, and a third step of forming the second electrode above the photoelectric conversion layer. A step, a fourth step of forming the sealing layer above the second electrode, between the second step and the third step, and between the third step and the fourth step. Do not add any structure to the organic photoelectric conversion element in the process of preparation, either or both during the process. And a fifth step of at least 30 minutes under an inert atmosphere, in the second step, and the compound and the fullerene represented by the general formula (1) were co-deposited by vacuum heating deposition the compound The photoelectric conversion layer composed of a mixed layer with fullerene is formed .

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the organic photoelectric conversion element which can improve SN can be provided.

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

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

  FIG. 1 is a schematic cross-sectional view showing a schematic configuration of an organic photoelectric conversion element for explaining an embodiment of the present invention. An organic photoelectric conversion element 10 shown in FIG. 1 includes a substrate 1, an electrode 2 formed on the substrate 1, an electron blocking layer 3 formed on the electrode 2, and a photoelectric conversion formed on the electron blocking layer 3. A layer 4, an electrode 5 formed on the photoelectric conversion layer 4, and a sealing layer 6 formed on the electrode 5 are provided.

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

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

  The photoelectric conversion layer 4 receives light and generates an electric charge according to the amount of light, and includes an organic photoelectric conversion material. Specifically, the photoelectric conversion layer 4 is a layer having a bulk hetero structure in which a p-type organic semiconductor (p-type organic compound) and a fullerene or a fullerene derivative that is an n-type organic semiconductor are mixed.

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

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

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

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

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

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

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

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

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

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

  In this manufacturing method, in each process of the formation process of the electrode 2, the formation process of the electron blocking layer 3, the formation process of the photoelectric conversion layer 4, the formation process of the electrode 5, and the formation process of the sealing layer 6, In addition, in order to prevent deterioration factors of the film such as water and oxygen from being mixed into the film, the respective processes are performed under vacuum. As a result of intensive studies, the inventor has a period in which no configuration is added to the organic photoelectric conversion element 10 in the process of manufacturing between the processes between the process of forming the photoelectric conversion layer 4 and the process of forming the sealing layer 6. It has been found that the performance of the organic photoelectric conversion element 10 is improved by providing a period of 30 minutes or longer (ideally 3 hours or longer) (hereinafter, referred to as a leaving period).

  Here, the leaving period is not limited to a vacuum, and may be provided under a non-vacuum. Under non-vacuum means a space with a higher pressure than under vacuum when each step is performed. Specifically, non-vacuum refers to an air atmosphere or an inert atmosphere. The inert atmosphere indicates that both oxygen and water are 10 ppm or less (ideally 0.5 ppm or less) in a space at atmospheric pressure.

  The leaving period is, for example, between the process of forming the photoelectric conversion layer 4 and the process of forming the electrode 5 (first period), and between the process of forming the electrode 5 and the process of forming the sealing layer 6 (second process). (Period).

  In the case where a standing period is provided in a non-vacuum state, from the device for forming the electrode 5 and the transport path of the organic photoelectric conversion element in the process of production from the device for forming the photoelectric conversion layer 4 to the device for forming the electrode 5. It is not necessary to make the conveyance path of the organic photoelectric conversion element in the middle of production leading to the device for forming the sealing layer 6 into a vacuum state. As a result, the manufacturing facility for the organic photoelectric conversion element 10 can be simplified, and the manufacturing cost can be reduced.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Also in the manufacturing method of the image pickup device 100, the image pickup device 100 in the process of being manufactured for 30 minutes or more between the formation process of the photoelectric conversion layer included in the organic layer 107 and the formation step of the sealing layer 110 is vacuum or non-vacuum. By adding a step to be placed below, it is possible to prevent the performance deterioration of the plurality of organic photoelectric conversion elements. By adding this step, it is possible to suppress the manufacturing cost while preventing the performance degradation of the image sensor 100.

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

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

  Any organic dye may be used as the p-type organic semiconductor, but preferred are a cyanine dye, a styryl dye, a hemicyanine dye, a merocyanine dye (including zero methine merocyanine (simple merocyanine)), a trinuclear merocyanine dye, 4 Nuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol dye, hemioxonol dye, squalium dye, croconium dye, azamethine dye, coumarin dye, arylidene dye, anthraquinone dye, triphenylmethane dye, azo Dye, azomethine dye, spiro compound, metallocene dye, fluorenone dye, fulgide dye, perylene dye, perinone dye, phenazine dye, phenothiazine dye, quinone color , Diphenylmethane dye, polyene dye, acridine dye, acridinone dye, diphenylamine dye, quinacridone dye, quinophthalone dye, phenoxazine dye, phthaloperylene dye, diketopyrrolopyrrole dye, dioxane dye, porphyrin dye, chlorophyll dye, phthalocyanine dye, metal complex dye And condensed aromatic carbocyclic dyes (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives).

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

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

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

In the photoelectric conversion layer 4, when a triarylamine compound described in Japanese Patent No. 4213832 is used as a p-type organic semiconductor mixed with fullerene or a fullerene derivative, a high SN ratio of the organic photoelectric conversion element can be expressed. Is particularly preferred. When the ratio of fullerene or fullerene derivative in the photoelectric conversion layer 4 is too large, the amount of the triarylamine compound is reduced and the amount of incident light absorbed is reduced. As a result, the photoelectric conversion efficiency is reduced. Therefore, the fullerene or fullerene derivative contained in the photoelectric conversion layer 4 preferably has a composition of 85% or less.
The p-type organic semiconductor is preferably a compound represented by the following general formula (1).

(In the formula, L ₂ and L ₃ each represent a 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 each independently represents 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, and R _{1 to} R ₆ are each independently Represents a hydrogen atom, a substituted alkyl group, an unsubstituted alkyl group, a substituted aryl group, an unsubstituted aryl group, a substituted heteroaryl group, or an unsubstituted heteroaryl group, and adjacent ones may be bonded to each other to form a ring. Good.)

The arylene group represented by Ar ₁ is preferably an arylene group having 6 to 30 carbon atoms, and more preferably an arylene group having 6 to 18 carbon atoms. The arylene group may have a substituent, and is preferably an arylene group having 6 to 18 carbon atoms which may have an alkyl group having 1 to 4 carbon atoms. For example, a phenylene group, a naphthylene group, a methylphenylene group, a dimethylphenylene group and the like can be mentioned. A phenylene group or a naphthylene group is preferable, and a phenylene group is more preferable.
The aryl groups represented by Ar ₂ and Ar ₃ are each independently preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 18 carbon atoms. The aryl group may have a substituent, preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 18 carbon atoms which may have an aryl group having 6 to 18 carbon atoms. is there. For example, a phenyl group, a naphthyl group, a tolyl group, an anthryl group, a dimethylphenyl group, a biphenyl group etc. are mentioned, A phenyl group or a naphthyl group is preferable and a phenyl group is more preferable. n is preferably 0 or 1.

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

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

The alkyl group represented by R _{1 to} R ₆ is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. R _{1 to} R ₆ are preferably a methyl group or an ethyl group, and more preferably a methyl group.
n is preferably 0 or 1.

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

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

Ar ₂ , Ar ₃ , R _{1 to} R ₆ may be adjacent to each other to form a ring, and the ring to be formed is preferably a cyclohexene ring, a cyclopentene ring, a benzene ring, a naphthalene ring, a thiophene ring, A pyran ring etc. are mentioned.

When Ar ₂ , Ar ₃ , R _{1 to} R ₆ have a substituent, the substituent includes a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (cycloalkenyl group). , Alkynyl group, aryl group, heterocyclic group (may be referred to as heterocyclic group), cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, Heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino Group, sulfamoylamino group, Alkyl and arylsulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfamoyl groups, sulfo groups, alkyl and arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups Carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (-B (OH) ₂ ), phosphato group (—OPO (OH) ₂ ), sulfato group (—OSO ₃ H), and other known substituents.

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

[Electronic blocking layer]
An electron-donating organic material can be used for the electron blocking layer 3. Specifically, in a low molecular material, N, N′-bis (3-methylphenyl)-(1,1′-biphenyl) -4,4′-diamine (TPD) or 4,4′-bis [N Aromatic diamine compounds such as-(naphthyl) -N-phenyl-amino] biphenyl (α-NPD), oxazole, oxadiazole, triazole, imidazole, imidazolone, stilbene derivative, pyrazoline derivative, tetrahydroimidazole, polyarylalkane, butadiene 4,4 ′, 4 ″ -tris (N- (3-methylphenyl) N-phenylamino) triphenylamine (m-MTDATA), porphine, tetraphenylporphine copper, phthalocyanine, copper phthalocyanine, titanium phthalocyanine oxide, etc. Porphyrin compounds, triazole derivatives, oxazizazo Derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, annealing amine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, silazane derivatives, etc. In the polymer material, a polymer such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene, or a derivative thereof can be used. Any compound having sufficient hole transportability can be used.

  Specifically, for example, it is preferable to use the following compounds described in JP-A-2008-72090. The following Ea represents the electron affinity of the material, and Ip represents the ionization potential of the material. “EB” in EB-1, 2,... Stands for “electronic blocking”.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The first sealing layer preferably has a thickness of 0.05 μm or more and 0.2 μm or less. The first sealing layer preferably contains any of aluminum oxide, silicon oxide, and titanium oxide.

Hereinafter, the effect of providing the standing period of 30 minutes or more will be described in Examples.

Example 1
An image sensor provided with an organic photoelectric conversion element was produced. The procedure is as follows. First, an amorphous ITO film is formed by sputtering on a CMOS substrate on which a readout circuit composed of a CMOS circuit and a connection electrode connected thereto are formed, and this is patterned, and a pixel electrode is formed on each connection electrode. Formed. Next, an electron blocking layer was formed on the plurality of pixel electrodes by depositing a material indicated by EB-3 with a thickness of 100 nm by vacuum heating deposition. Next, Compound 1 and fullerene (C ₆₀ ) were co-deposited by vacuum heating deposition on the electron blocking layer to form a photoelectric conversion layer having a thickness of 400 nm. In this deposition, an organic material deposition cell “Thermo Ball Cell (manufactured by Choshu Sangyo Co., Ltd.)” was used. Next, after the imaging device in the process of being produced was placed in an air atmosphere for 30 minutes, this imaging device was set in an apparatus for forming a counter electrode, and amorphous ITO with a thickness of 10 nm was formed on the photoelectric conversion layer by sputtering. A counter electrode was formed by film formation. The counter electrode was formed under vacuum. Next, after the imaging device in the middle of production was placed in an air atmosphere for 30 minutes, this imaging device was set in an apparatus for forming a sealing layer, and a silicon oxide film was formed on the counter electrode by heat evaporation. An aluminum oxide film was formed thereon by ALCVD to form a sealing layer. The sealing layer was formed under vacuum.

(Example 2)
Except for 30 minutes between the formation process of the photoelectric conversion layer and the formation process of the counter electrode, and between the formation process of the counter electrode and the formation process of the sealing layer, in the inert atmosphere for 30 minutes, An image sensor was manufactured in the same manner as in Example 1.

(Example 3)
Except that the imaging device in the process of preparation was placed under vacuum for 30 minutes between the photoelectric conversion layer forming step and the counter electrode forming step and between the counter electrode forming step and the sealing layer forming step. An image sensor was produced in the same manner as in Example 1.

Example 4
An imaging device in the middle of fabrication is placed under vacuum for 3 minutes between the photoelectric conversion layer forming step and the counter electrode forming step, and an imaging device in the middle of fabrication between the counter electrode forming step and the sealing layer forming step. Was prepared in the same manner as in Example 1 except that was placed in an air atmosphere for 48 hours.

(Comparative Example 1)
Except that the imaging element in the process of being produced was placed in the atmospheric atmosphere for 3 minutes between the photoelectric conversion layer forming step and the counter electrode forming step, and between the counter electrode forming step and the sealing layer forming step, An image sensor was manufactured in the same manner as in Example 1.

(Comparative Example 2)
Except that the imaging element in the process of preparation was placed in an inert atmosphere for 3 minutes between the photoelectric conversion layer forming step and the counter electrode forming step, and between the counter electrode forming step and the sealing layer forming step, An image sensor was manufactured in the same manner as in Example 1.

(Comparative Example 3)
Except that the imaging device in the process of production was placed under vacuum for 3 minutes between the photoelectric conversion layer forming step and the counter electrode forming step, and between the counter electrode forming step and the sealing layer forming step. An image sensor was produced in the same manner as in Example 1.

FIG. 3 shows the measurement results of the external quantum efficiency (relative value when the numerical value of Comparative Example 3 is set to 100) at the maximum sensitivity wavelength when the dark current is 400 pA / cm ² of each organic photoelectric conversion element in Examples and Comparative Examples. Show. Note that the value of the external quantum efficiency was a value when a positive bias was applied to the counter electrode of the fabricated element, light was incident from the counter electrode side, and holes were extracted from the pixel electrode.

  Comparing Examples 1 to 3 with Comparative Examples 1 to 3, it can be seen that the external quantum efficiency is increased by nearly 10% by providing a standing period of 30 minutes. In addition, comparing Examples 1 to 3 with Example 4, it can be seen that the external quantum efficiency increases without decreasing even if the leaving period is longer than 30 minutes. From this result, it was found that device performance can be improved by providing a standing period of 30 minutes or more in any or all of the steps from the photoelectric conversion layer formation step to the sealing layer formation step. .

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

  The disclosed method for producing an organic photoelectric conversion element is formed between a first electrode, a second electrode formed above the first electrode, and the first electrode and the second electrode. A method for producing an organic photoelectric conversion element, comprising: a photoelectric conversion layer containing an organic material; and the first electrode, the second electrode, and a sealing layer for sealing the photoelectric conversion layer. A second step of forming the photoelectric conversion layer above the first electrode, and a third step of forming the second electrode above the photoelectric conversion layer. And a fourth step of forming the sealing layer above the second electrode, and between each step between the second step and the fourth step, A fifth step is provided in which a leaving period in which no configuration is added to the photoelectric conversion element is provided for 30 minutes or more.

  The disclosed method for producing an organic photoelectric conversion element is to carry out the fifth step under vacuum or non-vacuum.

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

  In the disclosed method for producing an organic photoelectric conversion element, the fifth step is performed between the second step and the third step, and between the third step and the fourth step. It is what is implemented in.

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

  In the disclosed method for producing an organic photoelectric conversion element, the photoelectric conversion layer is composed of a mixed layer of fullerene or a fullerene derivative and a p-type organic semiconductor.

  The manufacturing method of the disclosed organic photoelectric conversion element is a method in which in the second step, the compound represented by the general formula (1) and fullerene are co-evaporated by vacuum heating evaporation to form the photoelectric conversion layer. is there.

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

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

  The disclosed imaging device is a circuit board on which a plurality of the organic photoelectric conversion elements and a signal readout circuit that reads a signal corresponding to the charge generated in the photoelectric conversion layer of each organic photoelectric conversion element are formed, And a circuit board formed below the plurality of organic photoelectric conversion elements.

  The disclosed imaging device includes the imaging device.

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

Claims (3)

A first electrode; a second electrode formed above the first electrode; a photoelectric conversion layer including an organic material formed between the first electrode and the second electrode; A method for producing an organic photoelectric conversion element, comprising: a second electrode; and a sealing layer that seals the photoelectric conversion layer,
A first step of forming the first electrode;
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;
Do not add any configuration to the organic photoelectric conversion element in the process of production in one or both of the second process and the third process and between the third process and the fourth process. A fifth step of leaving for 30 minutes or more in a vacuum or an air atmosphere or an inert atmosphere,
In said 2nd process, the organic photoelectric conversion which co-deposits the compound represented by following General formula (1), and fullerene by vacuum heating vapor deposition and forms the said photoelectric converting layer which consists of a mixed layer of this compound and fullerene Device manufacturing method.

(In the formula, L2 and L3 each represent a methine group. N represents an integer of 0 to 2. Ar1 represents a divalent substituted arylene group or an unsubstituted arylene group. Ar2 and Ar3 are each independent. Represents 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, and R1 to R6 each independently represent a hydrogen atom or a substituted alkyl group. Represents an unsubstituted alkyl group, a substituted aryl group, an unsubstituted aryl group, a substituted heteroaryl group, or an unsubstituted heteroaryl group, and adjacent groups may be bonded to each other to form a ring.) It is a manufacturing method of the organic photoelectric conversion element according to claim 1,
The manufacturing method of the organic photoelectric conversion element which implements the said 5th process under non-vacuum under an atmospheric condition or an inert atmosphere. It is a manufacturing method of the organic photoelectric conversion element of Claim 1 or 2,
The manufacturing method of the organic photoelectric conversion element which implements said 5th process both between said 2nd process and said 3rd process, and between said 3rd process and said 4th process.

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