JP2009252903A - Photoelectric conversion element, its manufacturing method, and imaging element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoelectric conversion element and a solid-state imaging element with a low dark current and a high photoelectric conversion efficiency, which can be responded at high speed. <P>SOLUTION: There are provided: a pair of electrodes 101, 104; a photoelectric conversion layer 102 arranged between the pair of electrodes 101, 104; and electric charge blocking layers 105, 103 provided between at least one of the pair of electrodes 101, 104 and the photoelectric conversion layer 102, wherein the electric charge blocking layers 105, 103 contain a hydrogenation inorganic oxide. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photoelectric conversion element provided between a pair of electrodes and having a photoelectric change layer that generates an electron carrier and a hole carrier by applying an electric field, and an imaging element including the photoelectric conversion element.

  Currently, a photoelectric conversion element is used as an imaging element such as an optical sensor mounted on an imaging apparatus such as a digital camera. The photoelectric conversion element has a photoelectric conversion layer that generates an electric charge by applying an electric field. For example, the photoelectric conversion layer has a configuration in which the photoelectric conversion layer is disposed between a pair of electrodes. In this configuration, by applying an electric field between the pair of electrodes, charges are generated by electron carriers and hole carriers generated in the photoelectric conversion layer, and the charges are read as signals. As described above, in the photoelectric conversion element, a voltage is often applied from the outside in order to maximize the photoelectric conversion efficiency and improve the photoelectric conversion efficiency and the response speed.

  When the photoelectric conversion layer is composed of an organic photoelectric conversion film, a charge blocking layer may be provided between the electrode and the organic photoelectric conversion film in order to improve the photoelectric conversion rate without increasing the dark current. It is valid. For example, Patent Document 1 below describes an image reading element having a configuration using silicon oxide as a charge blocking layer.

JP-A-5-129576 JP 2007-273945 A

  By the way, in the said patent document 1, in order to suppress a dark current, although silicon oxide was used as a positive hole blocking layer, when such a structure is used as a photoelectric conversion element, several rises and falls of a photocurrent are mentioned. It takes ms time. For this reason, in an imaging device using silicon oxide as a hole blocking layer, high-speed response could not be sufficiently performed.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a photoelectric conversion element capable of suppressing a dark current increase and capable of high-speed response, a method for manufacturing the photoelectric conversion element, and an imaging element. It is in.

The above object of the present invention is achieved by the following configurations.
(1) a pair of electrodes;
A photoelectric conversion layer disposed between the pair of electrodes;
A charge blocking layer provided between at least one of the pair of electrodes and the photoelectric conversion layer;
The photoelectric conversion element, wherein the charge blocking layer contains a hydrogenated inorganic oxide.
(2) The photoelectric conversion element according to (1), wherein an organic charge transport layer is provided between the photoelectric conversion layer and the hydrogenated inorganic oxide.
(3) The photoelectric conversion element according to the above (1) or (2), wherein the hydrogenated inorganic oxide is formed by a vapor phase growth method.
(4) The photoelectric conversion element according to any one of (1) to (3), wherein the hydrogenated inorganic oxide is hydrogenated silicon oxide or hydrogenated titanium oxide.
(5) An imaging device comprising the photoelectric conversion device according to any one of (1) to (4) above.
(6) a pair of electrodes;
A photoelectric conversion layer disposed between the pair of electrodes;
A method for producing a photoelectric conversion element comprising a charge blocking layer between at least one of the pair of electrodes and the photoelectric conversion layer,
A method for producing a photoelectric conversion element, wherein the charge blocking layer is formed by supplying cracked hydrogen while heating and depositing an inorganic oxide.
(7) a pair of electrodes;
A photoelectric conversion layer disposed between the pair of electrodes;
A method for producing a photoelectric conversion element comprising a charge blocking layer between at least one of the pair of electrodes and the photoelectric conversion layer,
A method for producing a photoelectric conversion element, wherein the charge blocking layer is formed by sputtering an inorganic oxide using a mixed gas of argon (Ar) and hydrogen (H ₂ ).

The photoelectric conversion element according to the present invention includes a charge blocking layer between a pair of electrodes and a photoelectric conversion layer, and the charge blocking layer is made of a hydrogenated inorganic oxide. In general, an oxide (semiconductor) can increase charge mobility by generating oxygen vacancies. Actually, silicon oxide (SiO ₂ ) is an insulator, but SiOx (x <2) has the property of becoming an n-type semiconductor due to oxygen defects and causing charge transfer ability (conductivity). For this reason, silicon oxide can be used as a (hole) blocking layer which is an n-type semiconductor. At this time, since oxygen is deficient, dangling bonds are generated, and the dangling bonds have high activity and act as charge traps to hinder charge transfer. Therefore, charge trapping can be avoided by reducing the activity by terminating the dangling bonds of silicon oxide with hydrogen. Thus, since the photoelectric conversion element concerning this invention can suppress that a charge is trapped by a charge blocking layer, it can improve high-speed responsiveness.

  According to the present invention, it is possible to provide a photoelectric conversion element and an imaging element capable of high-speed response with low dark current and high photoelectric conversion efficiency.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing a configuration of an embodiment of a photoelectric conversion element according to the present invention.
A photoelectric conversion element 10 shown in FIG. 1 includes a substrate S, a lower electrode (pixel electrode) 101 formed on the substrate S, an electron blocking layer 103 formed on the lower electrode 101, and an electron blocking layer 103. And a hole blocking layer 105 formed on the photoelectric conversion layer 102, and an upper electrode (counter electrode) 104 formed on the hole blocking layer 105. In the following description, the electron blocking layer 103 and the hole blocking layer 105 are collectively referred to as a charge blocking layer. The charge blocking layer may be provided between at least one of the pair of electrodes of the lower electrode 101 and the upper electrode 104 and the photoelectric conversion layer 102.

  The photoelectric conversion element 10 is assumed to receive light from above the upper electrode 104. In addition, among the charges (holes and electrons) generated in the photoelectric conversion layer 102, a bias is applied between the lower electrode 101 and the upper electrode 104 so that electrons move to the upper electrode 104 and holes move to the lower electrode 101. It is assumed that a voltage is applied. That is, the upper electrode 104 is an electron collecting electrode and the lower electrode 101 is a hole collecting electrode.

  For the lower electrode 101 and the upper electrode 104, the upper electrode 104 can be formed with a thickness of 5 to 20 nm by sputtering ITO.

  The electron blocking layer 103 is formed by forming an organic compound with a thickness of 100 nm by a vacuum deposition method.

  The photoelectric conversion layer 102 is formed by forming an organic compound with a thickness of 100 nm by a vacuum deposition method.

  The hole blocking layer 104 is formed using an organic compound with a thickness of 50 nm by a vacuum deposition method.

  The photoelectric conversion layer 102 includes an organic material having a photoelectric conversion function. As the organic material, for example, various organic semiconductor materials such as those used in electrophotographic photosensitive materials can be used. Among these, from the viewpoint of having high photoelectric conversion performance, excellent color separation at the time of spectroscopy, high durability against long-time light irradiation, easy vacuum deposition, etc., the merocyanine skeleton is Particularly preferred are materials containing and organic materials containing a phthalocyanine skeleton.

  When a merocyanine compound represented by the following formula is used as the photoelectric conversion layer 102, the photoelectric conversion layer 102 can absorb light in the green wavelength region and generate a charge corresponding to the light.

  When zinc phthalocyanine represented by the following formula is used as the photoelectric conversion layer 102, the photoelectric conversion layer 102 can absorb light in the red wavelength region and generate a charge corresponding to the light.

  Moreover, it is preferable that the organic material which comprises the photoelectric converting layer 102 contains at least one of an organic p-type semiconductor and an organic n-type semiconductor. In order to increase the photoelectric conversion efficiency and increase the carrier transport capability, a layer in which an organic p semiconductor and an organic n-type semiconductor are mixed can be used as the photoelectric conversion layer. As the organic p-type semiconductor and the organic n-type semiconductor, any of merocyanine compounds, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives can be particularly preferably used.

  The organic p-type semiconductor (compound) is a donor-type organic semiconductor (compound), which is mainly represented by a hole-transporting organic compound and refers to an organic compound having a property of easily donating electrons. More specifically, an organic compound having a smaller ionization potential when two organic materials are used in contact with each other. Therefore, any organic compound can be used as the donor organic compound as long as it is an electron-donating organic compound. For example, triarylamine compounds, benzidine compounds, pyrazoline compounds, styrylamine compounds, hydrazone compounds, triphenylmethane compounds, carbazole compounds, polysilane compounds, thiophene compounds, phthalocyanine compounds, cyanine compounds, merocyanine compounds, oxonol compounds, polyamine compounds, indoles 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. Not limited to this, as described above, any organic compound having an ionization potential smaller than that of the organic compound used as the n-type (acceptor property) compound may be used as the donor organic semiconductor.

  Organic n-type semiconductors (compounds) are acceptor organic semiconductors (compounds), which are mainly represented by electron-transporting organic compounds and refer to organic compounds that easily accept electrons. More specifically, the organic compound having the higher electron affinity when two organic compounds are used in contact with each other. Therefore, as the acceptor organic compound, any organic compound can be used as long as it is an electron-accepting organic compound. For example, condensed aromatic carbocyclic compounds (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives), 5- to 7-membered heterocyclic compounds containing nitrogen atoms, oxygen atoms, and sulfur atoms (E.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, indazole, benzimidazole, benzotriazole, Benzoxazole, benzothiazole, carbazole, purine, triazolopyridazine, triazolopyrimidine, tetrazaindene, o Metal complexes having ligands such as saziazole, imidazopyridine, pyralidine, pyrrolopyridine, thiadiazolopyridine, dibenzazepine, tribenzazepine), polyarylene compounds, fluorene compounds, cyclopentadiene compounds, silyl compounds, and nitrogen-containing heterocyclic compounds. Etc. Note that the present invention is not limited thereto, and as described above, any organic compound having an electron affinity higher than that of the organic compound used as the donor organic compound may be used as the acceptor organic semiconductor.

  Any p-type organic dye or n-type organic dye may be used, but preferably a cyanine dye, styryl dye, hemicyanine dye, merocyanine dye (including zero methine merocyanine (simple merocyanine)), three nucleus 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, triphenyl Methane dye, azo dye, azomethine dye, spiro compound, metallocene dye, fluorenone dye, fulgide dye, perylene dye, phenazine dye, phenothiazine dye, quinone dye, indigo Dye, diphenylmethane dye, polyene dye, acridine dye, acridinone dye, diphenylamine dye, quinacridone dye, quinophthalone dye, phenoxazine dye, phthaloperylene dye, porphyrin dye, chlorophyll dye, phthalocyanine dye, metal complex dye, condensed aromatic carbocyclic dye (Naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives).

  Next, the metal complex compound will be described. The metal complex compound is a metal complex having a ligand having at least one nitrogen atom or oxygen atom or sulfur atom coordinated to the metal, and the metal ion in the metal complex is not particularly limited, but preferably beryllium ion, magnesium Ion, aluminum ion, gallium ion, zinc ion, indium ion, or tin ion, more preferably beryllium ion, aluminum ion, gallium ion, or zinc ion, and still more preferably aluminum ion or zinc ion. There are various known ligands contained in the metal complex. For example, “Photochemistry and Photophysics of Coordination Compounds” published by Springer-Verlag H. Yersin in 1987, “Organometallic Chemistry— Examples of the ligands described in “Basics and Applications—” published by Akio Yamamoto, 1982, etc.

  The ligand is preferably a nitrogen-containing heterocyclic ligand (preferably having 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, and a monodentate ligand. May also be a bidentate or higher ligand, preferably a bidentate ligand, such as a pyridine ligand, bipyridyl ligand, quinolinol ligand, hydroxyphenylazole ligand (hydroxyphenylbenz). Imidazole, hydroxyphenylbenzoxazole ligand, hydroxyphenylimidazole ligand)), alkoxy ligand (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably carbon number). 1 to 10, for example, methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc.), aryloxy ligand (preferably Alternatively, it has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms. For example, phenyloxy, 1-naphthyloxy, 2-naphthyloxy, 2,4,6-trimethylphenyl Oxy, 4-biphenyloxy, etc.), heteroaryloxy ligands (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridyl. Oxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.), alkylthio ligands (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio, Ethylthio etc.), an arylthio ligand (preferably having 6 to 30 carbon atoms, more preferably A prime number of 6 to 20, particularly preferably 6 to 12 carbon atoms, such as phenylthio, and the like, a heterocyclic substituted thio ligand (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, Particularly preferably, it has 1 to 12 carbon atoms, and examples thereof include pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like, or siloxy ligand (preferably carbon 1-30, more preferably 3-25 carbon atoms, particularly preferably 6-20 carbon atoms, and examples thereof include triphenylsiloxy group, triethoxysiloxy group, triisopropylsiloxy group, and the like. Preferred are nitrogen-containing heterocyclic ligands, aryloxy ligands, heteroaryloxy groups, or siloxy ligands, and more preferred. Examples thereof include a nitrogen-containing heterocyclic ligand, an aryloxy ligand, and a siloxy ligand.

  In the present embodiment, the charge blocking layer of the hole blocking layer 105 includes a hydrogenated inorganic oxide. Hydrogenated silicon oxide can be used as the hydrogenated inorganic oxide.

  The hydrogenated inorganic oxide can be formed by a vapor phase growth method.

  In the photoelectric conversion element of this embodiment, an organic charge transport layer may be provided between the photoelectric conversion layer and the hydrogenated inorganic oxide.

The photoelectric conversion element of this embodiment is provided with a charge blocking layer between a pair of electrodes and a photoelectric conversion layer, and the charge blocking layer is composed of a hydrogenated inorganic oxide. In general, an oxide (semiconductor) can increase charge mobility by generating oxygen vacancies. Although silicon oxide (SiO ₂ ) used as an inorganic oxide in this embodiment is an insulator, SiO x (x <2) has the property that it becomes an n-type semiconductor due to oxygen defects and generates charge transferability (conductivity). is there. For this reason, silicon oxide can be used as a (hole) blocking layer which is an n-type semiconductor. At this time, since oxygen is deficient, dangling bonds are generated, and the dangling bonds have high activity and act as charge traps to hinder charge transfer. Therefore, charge trapping can be avoided by reducing the activity by terminating the dangling bonds of silicon oxide with hydrogen. Thus, since the photoelectric conversion element of this embodiment can suppress a charge being trapped by the charge blocking layer, the high-speed response can be improved.

As a manufacturing procedure of the charge blocking layer of the photoelectric conversion element, it can be formed by supplying cracked hydrogen while heating and depositing an inorganic oxide. Alternatively, the inorganic oxide can be formed by sputtering using a mixed gas of argon (Ar) and hydrogen (H ₂ ).

(Example)
Next, the optical response time was measured for the photoelectric conversion elements shown in the following examples.

(Example 1)
The photoelectric conversion element of Example 1 is composed of a lower electrode, an electron blocking layer, a photoelectric conversion layer, an inorganic blocking layer, and an upper electrode. Here, the electron blocking layer, the photoelectric conversion layer, the inorganic blocking layer, and the upper electrode are formed in this order. The lower electrode is ITO. The electron blocking layer is formed by depositing an organic compound represented by the following compound 1 with a film thickness of 100 nm by vacuum deposition. The photoelectric conversion layer is formed by forming an organic compound represented by the following compound 2 with a film thickness of 100 nm by vacuum deposition. The inorganic blocking layer forms silicon hydride with a thickness of 30 nm by simultaneously supplying silicon monoxide sublimated by heating and hydrogen (0.1 to 10 sccm) cracked by a cracking cell. The upper electrode is made of ITO with a film thickness of 5 to 20 nm by high frequency magnetron sputtering.

(Example 2)
The photoelectric conversion element of Example 2 is composed of a lower electrode, an electron blocking layer, a photoelectric conversion layer, an organic hole blocking layer, an inorganic blocking layer, and an upper electrode. Here, an electron blocking layer, a photoelectric conversion layer, an organic hole blocking layer, an inorganic blocking layer, and an upper electrode are formed in this order. The lower electrode is ITO. The electron blocking layer is formed by depositing an organic compound represented by Compound 1 with a thickness of 100 nm by vacuum deposition. The photoelectric conversion layer is formed by forming an organic compound represented by Compound 2 with a film thickness of 100 nm by vacuum deposition. The organic hole blocking layer is formed by depositing an organic compound represented by the following compound 3 with a film thickness of 50 nm by vacuum deposition. The inorganic blocking layer forms silicon hydride with a thickness of 30 nm by simultaneously supplying silicon monoxide sublimated by heating and hydrogen (0.1 to 10 sccm) cracked by a cracking cell. The upper electrode is made of ITO with a film thickness of 5 to 20 nm by high frequency magnetron sputtering.

(Comparative Example 1)
The photoelectric conversion element of Comparative Example 1 includes a lower electrode, an electron blocking layer, a photoelectric conversion layer, an inorganic blocking layer, and an upper electrode. Here, the electron blocking layer, the photoelectric conversion layer, the inorganic blocking layer, and the upper electrode are formed in this order. The lower electrode is ITO. The electron blocking layer is formed by depositing an organic compound represented by Compound 1 with a thickness of 100 nm by vacuum deposition. The photoelectric conversion layer is formed by forming an organic compound represented by Compound 2 with a film thickness of 100 nm by vacuum deposition. The inorganic blocking layer is formed of silicon monoxide with a film thickness of 30 nm by a vacuum deposition method. The upper electrode is made of ITO with a film thickness of 5 to 20 nm by high frequency magnetron sputtering.

(Comparative Example 2)
The photoelectric conversion element of Comparative Example 2 includes a lower electrode, an electron blocking layer, a photoelectric conversion layer, an organic hole blocking layer, and an upper electrode. Here, the electron blocking layer, the photoelectric conversion layer, and the upper electrode are formed in this order. The lower electrode is ITO. The electron blocking layer is formed by depositing an organic compound represented by Compound 1 with a thickness of 100 nm by vacuum deposition. The photoelectric conversion layer is formed by forming an organic compound represented by Compound 2 with a film thickness of 100 nm by vacuum deposition. The organic hole blocking layer is formed by depositing an organic compound represented by Compound 3 with a film thickness of 50 nm by vacuum deposition. The upper electrode is made of ITO with a film thickness of 5 to 20 nm by high frequency magnetron sputtering.

Table 1 shows the photoelectric conversion efficiency and dark current when a positive bias of 5.0 × 10E + 5 V / cm is applied to the upper electrode side of the organic photoelectric conversion elements of Examples 1 and 2 and Comparative Examples 1 and 2. Shows the afterimage time. The afterimage time is a time until the photocurrent does not flow when the organic photoelectric conversion element is shielded from the light incident state. Table 1 shows the relative values when the photoelectric conversion efficiency and dark current of Example 1 are set to 1.
As in the configurations of the photoelectric conversion elements of Examples 1 and 2, it was found that the dark current was reduced as compared with Comparative Example 2 by introducing an inorganic blocking layer. When Example 1, Example 2 and Comparative Example 1 were compared, it was found that in Comparative Example 1, the afterimage time was significantly increased. In Comparative Example 2, it was found that the dark current increased although the afterimage time could be shortened.

(Example 3)
The photoelectric conversion element of Example 3 is composed of a lower electrode, an inorganic blocking layer, a photoelectric conversion layer, an electron blocking layer, and an upper electrode. Here, the inorganic blocking layer, the photoelectric conversion layer, the electron blocking layer, and the upper electrode are laminated in this order. The lower electrode is ITO. The inorganic blocking layer is formed by forming a TiO target with a thickness of 30 nm by high-frequency magnetron sputtering using argon (Ar) and hydrogen (H ₂ ) gas. The photoelectric conversion layer is formed by forming an organic compound represented by Compound 2 with a film thickness of 100 nm by vacuum deposition. The electron blocking layer is formed by depositing an organic compound represented by the following compound 4 with a film thickness of 100 nm by a vacuum deposition method. The upper electrode is made of ITO with a film thickness of 5 to 20 nm by high frequency magnetron sputtering.

(Comparative Example 3)
The photoelectric conversion element of Comparative Example 3 includes a lower electrode, an inorganic blocking layer, a photoelectric conversion layer, an electron blocking layer, and an upper electrode. Here, the inorganic blocking layer, the photoelectric conversion layer, the electron blocking layer, and the upper electrode are laminated in this order. The lower electrode is ITO. For the inorganic blocking layer, a TiO target is formed by high frequency magnetron sputtering using Ar, and titanium oxide is formed with a thickness of 30 nm. The photoelectric conversion layer is formed by forming an organic compound represented by Compound 2 with a film thickness of 100 nm by vacuum deposition. The electron blocking layer is formed by depositing an organic compound represented by Compound 4 with a film thickness of 100 nm by vacuum deposition. The upper electrode is made of ITO with a film thickness of 5 to 20 nm by high frequency magnetron sputtering.

(Comparative Example 4)
The photoelectric conversion element of Comparative Example 4 includes a lower electrode, a photoelectric conversion layer, an electron blocking layer, and an upper electrode. Here, the photoelectric conversion layer, the electron blocking layer, and the upper electrode are laminated in this order. The lower electrode is ITO. For the photoelectric conversion layer, an organic compound represented by Compound 2 is formed with a film thickness of 100 nm by a vacuum deposition method. The electron blocking layer is formed by forming an organic compound represented by Compound 4 with a film thickness of 100 nm by a vacuum deposition method. The upper electrode is made of ITO with a film thickness of 5 to 20 nm by high frequency magnetron sputtering.

Table 2 shows the photoelectric conversion efficiency and dark current when a negative bias of 5.0 × 10E + 5 V / cm is applied to the upper electrode side of the organic photoelectric conversion elements of Examples 3 and 4 and Comparative Examples 3 and 4. Shows the afterimage time. Table 2 shows the relative values when the photoelectric conversion efficiency and dark current of Example 3 are set to 1.
In the structure of the photoelectric conversion element shown in Examples 3 and 4, it was found that the dark current was lower than that of Comparative Example 2 by introducing the inorganic blocking layer. When Example 3 and Comparative Example 3 are compared, in Comparative Example 3, the afterimage time is significantly increased. In Comparative Example 4, it was found that although the afterimage time can be shortened, the dark current increases.

In addition, this invention is not limited to embodiment mentioned above, A suitable deformation | transformation, improvement, etc. are possible.
For example, the photoelectric conversion element of the above embodiment can be applied to an image sensor such as an optical sensor mounted on an image pickup apparatus such as a digital camera. High-speed response can be realized with conversion efficiency.

It is a cross-sectional schematic diagram which shows the structure of one Embodiment of the photoelectric conversion element concerning this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Photoelectric conversion element 101 Pixel electrode 102 Photoelectric conversion layer 103 Electron blocking layer 104 Counter electrode 105 Hole blocking layer

Claims (7)

A pair of electrodes;
A photoelectric conversion layer disposed between the pair of electrodes;
A charge blocking layer provided between at least one of the pair of electrodes and the photoelectric conversion layer;
The photoelectric conversion element, wherein the charge blocking layer contains a hydrogenated inorganic oxide.   The photoelectric conversion element according to claim 1, wherein an organic charge transport layer is provided between the photoelectric conversion layer and the hydrogenated inorganic oxide.   The photoelectric conversion element according to claim 1, wherein the hydrogenated inorganic oxide is formed by a vapor phase growth method.   The photoelectric conversion element according to any one of claims 1 to 3, wherein the hydrogenated inorganic oxide is hydrogenated silicon oxide or hydrogenated titanium oxide.   The image pick-up element provided with the photoelectric conversion element as described in any one of the said Claim 1 to 4. A pair of electrodes;
A photoelectric conversion layer disposed between the pair of electrodes;
A method for producing a photoelectric conversion element comprising a charge blocking layer between at least one of the pair of electrodes and the photoelectric conversion layer,
A method for producing a photoelectric conversion element, wherein the charge blocking layer is formed by supplying cracked hydrogen while heating and depositing an inorganic oxide. A pair of electrodes;
A photoelectric conversion layer disposed between the pair of electrodes;
A method for producing a photoelectric conversion element comprising a charge blocking layer between at least one of the pair of electrodes and the photoelectric conversion layer,
A method for producing a photoelectric conversion element, wherein the charge blocking layer is formed by sputtering an inorganic oxide using a mixed gas of argon (Ar) and hydrogen (H ₂ ).

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