JP2007088440A - Photoelectric conversion device and imaging device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoelectric conversion device with improved sensitivity and noise level that facilitates the film forming method of a clear electrode to be used in the device. <P>SOLUTION: This photoelectric conversion device is composed of the lamination of a conductive thin film, photoelectric conversion film and transparent conductive thin film stacked on the above sequence. The main feature of the photoelectric conversion device is that the thickness of the transparent conductive thin film is no more than a fifth (1/5) that of the photoelectric conversion film. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a solid-state imaging device having a transparent electrode above a photoelectric conversion layer, and provides a solid-state imaging device with high sensitivity, low noise, and high yield.

In a photoelectric conversion element in which a transparent electrode is formed on a photoelectric conversion unit, in order to increase the absolute amount of light incident on the photoelectric conversion unit and increase the efficiency of carrier reading after photoelectric conversion, A higher transmittance has been demanded. In view of such high transmittance and low resistance value, it is generally considered that a transparent conductive oxide (TCO) thin film is preferable. The TCO transparent electrode is generally formed by a sputtering method or the like. In that case, compared with an Al electrode or the like, an increase in leakage current, which is thought to be caused by an increase in the short-circuited portion, easily occurs, and the S / N deteriorates. There arises problems such as variations in performance, and in some cases, DC short-circuiting occurs and the device does not drive.
Normally, when a transparent conductive oxide thin film is formed on an organic film by sputtering or the like, a metal layer or a specific organic layer is thinly laminated on the organic film as a protective layer in order to reduce damage to the organic film. The method of making it known is known. This may reduce the increase in leakage current, but the introduction of such a protective layer may cause other performance degradation of the device.
Japanese Patent Laid-Open No. 5-299682 relates to a photovoltaic device, but only there is a description that the preferred thickness of the transparent electrode is 1 to 1000 nm. There is no description about the ratio. Japanese Patent Application Laid-Open No. 2003-332551 relates to a stacked solid-state imaging device, and an example of an Ag electrode of 80 nm is described as a light incident side electrode formed on a photoelectric conversion film on a substrate. In this case, the light transmittance of the film itself is low and it cannot be said that it is a transparent electrode. Light is incident by providing an opening, and a photoelectric conversion film and a transparent conductive film capable of entering light laminated on the photoelectric conversion film are formed. There is no description about thickness and ratio.

  For a solid-state imaging device having an upper transparent electrode, an increase in dark current, deterioration in yield, and variation in device performance are improved.

The present invention has been solved by the following means.
(1) In a photoelectric conversion element in which a conductive thin film, a photoelectric conversion film, and a transparent conductive thin film are laminated in this order on a substrate, the thickness of the transparent conductive thin film is 1/5 or less of the thickness of the photoelectric conversion film. The photoelectric conversion element characterized by the above-mentioned.
(2) The photoelectric conversion element according to (1), wherein the thickness of the transparent conductive thin film is 1/10 or less of the thickness of the photoelectric conversion film.
(3) In a photoelectric conversion element in which a conductive thin film, a photoelectric conversion film, and a transparent conductive thin film are laminated in this order on a substrate, the thickness of the transparent conductive thin film is 5 nm to 30 nm. Conversion element.
(4) The photoelectric conversion element according to any one of (1) to (3), wherein the photoelectric conversion film has a thickness of 350 nm or less.
(5) The photoelectric conversion element according to any one of (1) to (4), wherein the transparent conductive thin film is made of a transparent conductive oxide.
(6) The photoelectric conversion element according to any one of (1) to (5), wherein the light transmittance of the transparent conductive thin film is 75% or more in a light wavelength range of 400 to 700 nm.
(7) The photoelectric conversion element according to any one of (1) to (6), wherein a sheet resistance of the transparent conductive thin film is 100Ω / □ or more and 10000Ω / □ or less.
(8) The photoelectric conversion element according to any one of (1) to (7), wherein the transparent conductive thin film is formed by a plasma-free method.
(9) The photoelectric conversion element according to any one of (1) to (8), wherein the photoelectric conversion film includes a pigment-based material layer.
(10) The photoelectric conversion element according to (9), wherein the thickness of the pigment-based material layer is 75 nm or more.
(11) The photoelectric conversion element according to (9) or (10), wherein the thickness of the pigment-based material layer is 100 nm or more.
(12) A photoelectric conversion element comprising an inorganic photoelectric conversion film in a semiconductor substrate, and the photoelectric conversion film according to any one of (1) to (11) laminated on the inorganic photoelectric conversion film.
(13) An imaging device having the photoelectric conversion device according to any one of (1) to (12).

  According to the present invention, the photoelectric conversion element can be made highly sensitive and have low noise, and the yield of the element can be increased.

In a photoelectric conversion element in which a conductive thin film, a photoelectric conversion film, and a transparent conductive thin film are laminated on a substrate in this order, the thickness of the transparent conductive thin film is 1/5 or less, preferably 1/10 or less of the thickness of the photoelectric conversion film. Such a photoelectric conversion element is a feature of the present invention.
In the present invention, the photoelectric conversion film includes an n-type semiconductor, a layer made of a semiconductor such as a p-type semiconductor, and a charge transport layer, and a counter electrode (preferably a transparent conductive thin film) and a pixel electrode (preferably a conductive thin film). It means a film sandwiched between. The film thickness of the photoelectric conversion film of the present invention is preferably 350 nm or less, more preferably 300 nm or less, and more preferably 200 nm or less.

  One of the causes of increase in leakage current that occurs when a transparent conductive thin film such as a transparent conductive oxide (TCO) is laminated on the photoelectric conversion film is that fine cracks introduced into the photoelectric conversion film are caused by TCO or the like. This is considered to be due to coverage with the dense film and increased conduction between the conductive thin film on the opposite side. For this reason, in the case of an electrode having a poor film quality such as Al, an increase in leakage current hardly occurs. In the present invention, based on the above phenomena and considerations, the increase in leakage current is greatly increased by controlling the film thickness of the transparent conductive thin film with respect to the film thickness of the photoelectric conversion film (that is, the crack depth). It was found that it can be suppressed. The thickness of the transparent conductive thin film is desirably 1/5 or less, preferably 1/10 or less (preferably 1/100 or more) of the thickness of the photoelectric conversion film.

Usually, when the conductive thin film is made thinner than a certain range, the resistance value is rapidly increased. However, in the photoelectric conversion element of the present invention, the sheet resistance is preferably 100Ω / □ or more and 10000Ω / □ or less, and the film thickness is reduced. The degree of freedom in the range of film thickness that can be produced is large. Further, the thinner the transparent conductive thin film is, the less light is absorbed, and the light transmittance is generally increased. The increase in light transmittance is very preferable because it increases the light absorption in the photoelectric conversion film and increases the photoelectric conversion ability. In consideration of the suppression of leakage current, the increase in the resistance value of the thin film, and the increase in transmittance due to the thinning, the thickness of the transparent conductive thin film is 5 nm or more and 30 nm or less, preferably 5 nm or more and 15 nm m or less. Things are desirable.
The light transmittance of the transparent conductive thin film is preferably 75% or more in the light wavelength range of 400 to 700 nm, more preferably 80% or more, still more preferably 90% or more, particularly preferably 95% or more. It is.
The effect of the present invention is noticeable when a denser film is applied as a transparent conductive thin film. As the transparent conductive thin film, a transparent conductive oxide (TCO) is preferably considered because of its high transmittance and low resistivity. Generally, the transparent conductive oxide (TCO) film is a metal thin film such as Al. On the other hand, since a dense film is formed, the effect of the present invention is remarkably exhibited.

The effect of the present invention is particularly remarkable for a photoelectric conversion film including a crystalline film (that is, a film including a layer having a grain boundary) that is easily cracked. When an organic thin film is applied as the photoelectric conversion film, the effect of the present invention is great if a pigment-based material is included in the photoelectric conversion film. Further, since the non-uniformity of the film increases, the effect of the present invention is further enhanced when the film thickness of the pigment-based material is increased. In order to have light absorption and sufficient photoelectric conversion performance, the film thickness of the pigment-based material should be thick within a certain range, preferably 75 nm or more, more preferably 100 nm or more (preferably 1000 nm or less). Grain boundaries can be confirmed with an electron microscope or the like.
Examples of the pigment-based material include ordinary pigments, that is, organic pigments and inorganic pigments, which are substances that are almost insoluble in water and organic solvents. In the present invention, a material that forms a crystalline film as described above is used. means. In addition, even a substance that dissolves in water or an organic solvent includes a material that is used in a solid state to form a crystalline film. As the pigment-based material, an organic pigment is preferable, and as the organic pigment, a pigment described later, that is, a p-type organic dye or an n-type organic dye is preferably used.

When an organic film is assumed as the photoelectric conversion film, if the transparent conductive thin film is formed by a normal sputtering method or the like, the performance of the photoelectric conversion layer may be deteriorated due to plasma damage. For this reason, it is preferable that the transparent conductive thin film is formed by a plasma-free method. Here, plasma free means that no plasma is generated during the formation of the transparent electrode film, or the distance from the plasma generation source to the substrate is 2 cm or more, preferably 10 cm or more, more preferably 20 cm or more. It means a state in which the plasma that reaches is reduced.
Examples of an apparatus that does not generate plasma during the formation of the transparent electrode film include an electron beam vapor deposition apparatus (EB vapor deposition apparatus) and a pulse laser vapor deposition apparatus. Regarding EB deposition equipment or pulse laser deposition equipment, “Surveillance of Transparent Conductive Films” supervised by Yutaka Sawada (published by CMC, 1999), “New Development of Transparent Conductive Films II” supervised by Yutaka Sawada (published by CMC, 2002) ), "Transparent conductive film technology" by the Japan Society for the Promotion of Science (Ohm Co., 1999), and the references attached thereto, etc. can be used. Hereinafter, a method of forming a transparent electrode film using an EB vapor deposition apparatus is referred to as an EB vapor deposition method, and a method of forming a transparent electrode film using a pulse laser vapor deposition apparatus is referred to as a pulse laser vapor deposition method.

  For an apparatus that can realize a state in which the distance from the plasma generation source to the substrate is 2 cm or more and the arrival of plasma to the substrate is reduced (hereinafter referred to as a plasma-free film forming apparatus), for example, an opposed target sputtering Equipment, arc plasma deposition, etc. are considered, and these are supervised by Yutaka Sawada "New development of transparent conductive film" (published by CMC, 1999), and supervised by Yutaka Sawada "New development of transparent conductive film II" (published by CMC) 2002), “Transparent conductive film technology” (Ohm Co., 1999) by the Japan Society for the Promotion of Science, and references and the like attached thereto can be used.

  The substrate temperature during the formation of the conductive thin film and the transparent conductive thin film is preferably 500 ° C. or lower, more preferably 300 ° C. or lower, still more preferably 200 ° C. or lower, and further preferably 150 ° C. or lower.

The material of the conductive thin film and the transparent conductive thin film satisfying the present invention is a conductive metal oxide such as tin oxide, zinc oxide, indium oxide and indium tin oxide (ITO), or a metal such as gold, silver, chromium and nickel. Furthermore, mixtures or laminates of these metals and conductive metal oxides, transparent conductive oxides (TCO) such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene and polypyrrole, silicon compounds and A laminate of these and ITO can be mentioned, preferably a conductive metal oxide, more preferably an In ₂ O ₃ -based material or a ZnO-based material, especially productivity, high conductivity, transparent From the viewpoint of properties, ITO or IZO is preferable.

(Photoelectric conversion element)
The photoelectric conversion element of the present invention will be described below.
The photoelectric conversion element of the present invention comprises an electromagnetic wave absorption / photoelectric conversion site (including a conductive thin film, a photoelectric conversion film, and a transparent conductive thin film) and a charge accumulation / transfer / readout site for charges generated by photoelectric conversion.
In the present invention, the electromagnetic wave absorption / photoelectric conversion site has a laminated structure of at least two layers capable of absorbing and photoelectrically converting at least blue light, green light, and red light. The blue light absorbing layer (B) can absorb light of at least 400 nm or more and 500 nm or less, and preferably the peak wavelength absorptance in the wavelength region is 50% or more. The green light absorbing layer (G) can absorb light of at least 500 nm to 600 nm, and preferably the peak wavelength absorptance in the wavelength region is 50% or more. The red light absorbing layer (R) can absorb light of at least 600 nm or more and 700 nm or less, and preferably has an absorptance of a peak wavelength in the wavelength region of 50% or more. The order of these layers may be any order, and in the case of a three-layer stacked structure, the order of BGR, BRG, GBR, GRB, RBG, and RGB is possible from the upper layer (light incident side). Preferably, the uppermost layer is G. In the case of a two-layer structure, when the upper layer is the R layer, the lower layer is the same BG layer, when the upper layer is the B layer, the lower layer is the same planar GR layer, and when the upper layer is the G layer, the lower layer is the same A BR layer is formed in a planar shape. Preferably, the upper layer is a G layer and the lower layer is a BR layer on the same plane. Thus, when two light absorption layers are provided on the same plane of the lower layer, it is preferable to provide, for example, a mosaic layer on the upper layer or a filter layer capable of color separation between the upper layer and the lower layer. In some cases, it is possible to provide a fourth layer or more as a new layer or in the same plane.

In the present invention, the charge accumulation / transfer / readout part is provided under the electromagnetic wave absorption / photoelectric conversion part. It is preferable that the electromagnetic wave absorption / photoelectric conversion site in the lower layer also serves as a charge storage / transfer / readout site.
In the present invention, the electromagnetic wave absorption / photoelectric conversion site is composed of an organic layer, an inorganic layer, or a mixture of an organic layer and an inorganic layer. The organic layer may form a B / G / R layer, or the inorganic layer may form a B / G / R layer. A mixture of an organic layer and an inorganic layer is preferred. In this case, basically, when the organic layer is one layer, the inorganic layer is one or two layers, and when the organic layer is two layers, the inorganic layer is one layer. When the organic layer and the inorganic layer are one layer, the inorganic layer forms electromagnetic wave absorption / photoelectric conversion sites of two or more colors on the same plane. Preferably, the upper layer is an organic layer and is a G layer, and the lower layer is an inorganic layer and is an order of B layer and R layer from the top. In some cases, it is possible to provide a fourth layer or more as a new layer or in the same plane. In the case where the organic layer forms a B / G / R layer, a charge accumulation / transfer / readout portion is provided thereunder. When an inorganic layer is used as the electromagnetic wave absorption / photoelectric conversion site, this inorganic layer also serves as a charge accumulation / transfer / readout site.

(Organic layer)
In the present invention, the organic layer will be described. The electromagnetic wave absorption / photoelectric conversion site comprising the organic layer of the present invention comprises an organic layer sandwiched between a pair of electrodes. The organic layer is formed by stacking or mixing parts that absorb electromagnetic waves, photoelectric conversion parts, electron transport parts, hole transport parts, electron blocking parts, hole blocking parts, crystallization prevention parts, electrodes and interlayer contact improvement parts, etc. The The organic layer preferably contains an organic p-type compound or an organic n-type compound. 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”, Springer-Verlag H. Examples include the ligands described in Yersin's 1987 issue, “Organometallic Chemistry-Fundamentals and Applications”, Akio Yamamoto's 1982 issue.

  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. Or a bidentate or higher ligand, preferably a bidentate ligand such as a pyridine ligand, a bipyridyl ligand, a quinolinol ligand, a hydroxyphenylazole ligand (hydroxyphenyl) Benzimidazole, hydroxyphenylbenzoxazole ligand, hydroxyphenylimidazole ligand)), alkoxy ligand (preferably 1-30 carbon atoms, more preferably 1-20 carbon atoms, particularly preferably carbon 1-10, for example, methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc.), aryloxy ligands Preferably it has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as 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.), arylthio ligands (preferably having 6 to 30 carbon atoms, more preferred) Has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), a heterocyclic substituted thio ligand (preferably 1 to 30 carbon atoms, more preferably 1 to carbon atoms). 20, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like, or siloxy ligand (preferably Has 1 to 30 carbon atoms, more preferably 3 to 25 carbon atoms, particularly preferably 6 to 20 carbon atoms, and examples thereof include a triphenylsiloxy group, a triethoxysiloxy group, and a triisopropylsiloxy group. More preferably a nitrogen-containing heterocyclic ligand, an aryloxy ligand, a heteroaryloxy group, or a siloxy ligand, Preferably, a nitrogen-containing heterocyclic ligand, an aryloxy ligand, or a siloxy ligand is used.

In the present invention, a p-type semiconductor layer and an n-type semiconductor layer are provided between a pair of electrodes, and at least one of the p-type semiconductor and the n-type semiconductor is an organic semiconductor, and these semiconductor layers It is preferable to contain a photoelectric conversion film (photosensitive layer) having a bulk heterojunction structure layer containing the p-type semiconductor and the n-type semiconductor as an intermediate layer. In such a case, in the photoelectric conversion film, by incorporating a bulk heterojunction structure in the organic layer, the disadvantage that the carrier diffusion length of the organic layer is short can be compensated, and the photoelectric conversion efficiency can be improved. The bulk heterojunction structure is described in detail in Japanese Patent Application No. 2004-080639.
In the present invention, a photoelectric conversion film (photosensitive layer) having a structure having two or more repeating structures (tandem structures) of a pn junction layer formed of a p-type semiconductor layer and an n-type semiconductor layer between a pair of electrodes ) Is preferable, and more preferably, a thin layer of a conductive material is inserted between the repetitive structures. The number of repeating structures (tandem structures) of the pn junction layer may be any number, but is preferably 2 to 50, more preferably 2 to 30, and particularly preferably 2 to 10 in order to increase the photoelectric conversion efficiency. It is. Silver or gold is preferable as the conductive material, and silver is most preferable. The tandem structure is described in detail in Japanese Patent Application No. 2004-079930.

  In a photoelectric conversion film having a p-type semiconductor layer, an n-type semiconductor layer (preferably a mixed / dispersed (bulk heterojunction structure) layer) between a pair of electrodes, at least one of the p-type semiconductor and the n-type semiconductor In the case of a photoelectric conversion film characterized in that it includes an organic compound whose orientation is controlled in the direction, more preferably in the case where an organic compound whose orientation is controlled is included in both the p-type semiconductor and the n-type semiconductor. It is. As the organic compound used in the organic layer of the photoelectric conversion film, one having π-conjugated electrons is preferably used, but this π-electron plane is not perpendicular to the substrate (electrode substrate) but oriented at an angle close to parallel. The better it is. The angle with respect to the substrate is preferably 0 ° or more and 80 ° or less, more preferably 0 ° or more and 60 ° or less, further preferably 0 ° or more and 40 ° or less, and further preferably 0 ° or more and 20 ° or less. Particularly preferably, it is 0 ° or more and 10 ° or less, and most preferably 0 ° (that is, parallel to the substrate). As described above, the organic compound layer whose orientation is controlled may be partially included in the entire organic layer, but preferably the proportion of the portion whose orientation is controlled with respect to the entire organic layer is 10% or more. More preferably, it is 30% or more, more preferably 50% or more, further preferably 70% or more, particularly preferably 90% or more, and most preferably 100%. Such a state compensates for the shortcoming of the short carrier diffusion length of the organic layer by controlling the orientation of the organic compound in the organic layer in the photoelectric conversion film, and improves the photoelectric conversion efficiency.

In the case where the orientation of the organic compound is controlled, it is more preferable that the heterojunction plane (for example, the pn junction plane) is not parallel to the substrate. It is more preferable that the heterojunction plane is oriented not at a parallel to the substrate (electrode substrate) but at an angle close to the vertical. The angle with respect to the substrate is preferably 10 ° or more and 90 ° or less, more preferably 30 ° or more and 90 ° or less, further preferably 50 ° or more and 90 ° or less, and further preferably 70 ° or more and 90 ° or less. Particularly preferably, it is 80 ° or more and 90 ° or less, and most preferably 90 ° (that is, perpendicular to the substrate). The organic compound layer whose heterojunction surface is controlled as described above may be partially included in the entire organic layer. Preferably, the proportion of the portion where the orientation is controlled with respect to the entire organic layer is 10% or more, more preferably 30% or more, more preferably 50% or more, further preferably 70% or more, and particularly preferably 90%. Above, most preferably 100%. In such a case, the area of the heterojunction surface in the organic layer increases, the amount of carriers of electrons, holes, electron-hole pairs, etc. generated at the interface increases, and the photoelectric conversion efficiency can be improved. In the above-described photoelectric conversion film (photoelectric conversion film) in which the orientation of both the heterojunction plane and the π-electron plane of the organic compound is controlled, the photoelectric conversion efficiency can be particularly improved. These states are described in detail in Japanese Patent Application No. 2004-079931.
In terms of light absorption, the larger the thickness of the organic dye layer is, the more preferable, but considering the ratio that does not contribute to charge separation, the thickness of the organic dye layer in the present invention is preferably 30 nm to 300 nm, more preferably 50 nm or more. It is 250 nm or less, and particularly preferably 80 nm or more and 200 nm or less.

(Formation method of organic layer)
The layer containing these organic compounds is formed by a dry film formation method or a wet film formation method. Specific examples of the dry film forming method include a vacuum vapor deposition method, a sputtering method, an ion plating method, a physical vapor deposition method such as an MBE method, or a CVD method such as plasma polymerization. As the wet film forming method, a casting method, a spin coating method, a dipping method, an LB method, or the like is used.
In the case of using a polymer compound as at least one of the p-type semiconductor (compound) or the n-type semiconductor (compound), it is preferable to form the film by a wet film forming method that is easy to create. When a dry film formation method such as vapor deposition is used, it is difficult to use a polymer because it may be decomposed, and an oligomer thereof can be preferably used instead. On the other hand, in the present invention, when a low molecule is used, a dry film forming method is preferably used, and a vacuum deposition method is particularly preferably used. The vacuum deposition method is basically based on the method of heating compounds such as resistance heating deposition method and electron beam heating deposition method, shape of deposition source such as crucible and boat, degree of vacuum, deposition temperature, base temperature, deposition rate, etc. It is a parameter. In order to make uniform deposition possible, it is preferable to perform deposition by rotating the substrate. The higher the degree of vacuum is, preferably 10 ⁻⁴ Torr (1.33 × 10 ⁻² Pa) or less, preferably 10 ⁻⁶ Torr (1.33 × 10 ⁻⁴ Pa) or less, particularly preferably 10 ⁻⁸ Torr (1 .33 × 10 ⁻⁶ Pa) or less, vacuum deposition is performed. It is preferable that all steps during the vapor deposition are performed in a vacuum, and basically the compound is not directly in contact with oxygen and moisture in the outside air. The above-described conditions for vacuum deposition need to be strictly controlled because they affect the crystallinity, amorphousness, density, density, etc. of the organic film. It is preferable to use PI or PID control of the deposition rate using a film thickness monitor such as a quartz crystal resonator or an interferometer. When two or more kinds of compounds are vapor-deposited simultaneously, a co-evaporation method, a flash vapor deposition method, or the like can be preferably used.

(electrode)
The electromagnetic wave absorption / photoelectric conversion site made of the organic layer of the present invention is sandwiched between a pair of electrodes, each of which forms a pixel electrode and a counter electrode. The lower layer is preferably a pixel electrode.
The counter electrode preferably takes out holes from the hole transporting photoelectric conversion film or the hole transport layer.
As a material of the counter electrode other than the present invention, a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. The pixel electrode (including the conductive thin film of the present invention) preferably takes out electrons from the electron-transporting photoelectric conversion layer or the electron-transporting layer, and has adhesion with adjacent layers such as the electron-transporting photoelectric conversion layer and the electron-transporting layer. And electron affinity, ionization potential, stability, etc. Specific examples of these include conductive metal oxides such as tin oxide, zinc oxide, indium oxide and indium tin oxide (ITO), or metals such as gold, silver, chromium and nickel, and these metals and conductive metal oxides. Inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene and polypyrrole, silicon compounds and laminates of these with ITO, etc. In particular, ITO or IZO is preferable from the viewpoint of productivity, high conductivity, transparency, and the like. Although the thickness of the pixel electrode can be appropriately selected depending on the material, it is usually preferably in the range of 10 nm to 1 μm, more preferably 20 nm to 500 nm, and still more preferably 30 nm to 300 nm. Various methods are used for manufacturing the pixel electrode and the counter electrode other than the present invention depending on the material. For example, in the case of ITO, an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method, etc.), oxidation, etc. A film is formed by a method such as application of a dispersion of indium tin. In the case of ITO, UV-ozone treatment, plasma treatment, etc. can be performed.

It is preferable that the transparent electrode film other than the present invention is also produced without plasma. By creating a transparent electrode film free from plasma, the influence of plasma on the substrate can be reduced, and the photoelectric conversion characteristics can be improved. Here, plasma free means that no plasma is generated during the formation of the transparent electrode film, or the distance from the plasma generation source to the substrate is 2 cm or more, preferably 10 cm or more, more preferably 20 cm or more. It means a state in which the plasma that reaches is reduced.
As an apparatus in which plasma is not generated during the formation of the transparent electrode film, the same apparatus and method as described above can be applied.

The electrode of the organic electromagnetic wave absorption / photoelectric conversion site of the present invention will be described in more detail. The photoelectric conversion film of the organic layer is sandwiched between the pixel electrode film and the counter electrode film, and can include an interelectrode material or the like. The pixel electrode film is an electrode film formed above the substrate on which the charge accumulation / transfer / read-out site is formed, and is usually divided for each pixel. This is to obtain an image by reading out the signal charges converted by the photoelectric conversion film on a charge storage / transfer / signal readout circuit substrate for each pixel.
The counter electrode film has a function of discharging a signal charge having a polarity opposite to that of the signal charge by sandwiching the photoelectric conversion film together with the pixel electrode film. Since the discharge of the signal charge does not need to be divided between the pixels, the counter electrode film can be commonly used between the pixels. Therefore, it may be called a common electrode film (common electrode film).
The photoelectric conversion film is located between the pixel electrode film and the counter electrode film. The photoelectric conversion function functions by the photoelectric conversion film, the pixel electrode film, and the counter electrode film.
As a configuration example of the photoelectric conversion film stacking, first, in the case where there is one organic layer stacked on the substrate, the pixel electrode film (basically a transparent electrode film, equivalent to the conductive thin film of the present invention) from the substrate, photoelectric conversion Although the structure which laminated | stacked the film | membrane (equivalent to the photoelectric converting film of this invention) and the counter electrode film | membrane (transparent electrode film | membrane, equivalent to the transparent conductive thin film of this invention) in order is mentioned, it is not limited to this.
Further, when there are two organic layers stacked on the substrate, for example, from the substrate to the pixel electrode film (basically a transparent electrode film), a photoelectric conversion film, a counter electrode film (transparent electrode film), an interlayer insulating film, a pixel electrode A configuration in which a film (basically a transparent electrode film), a photoelectric conversion film, and a counter electrode film (transparent electrode film) are stacked in order.

  As the material of the transparent electrode film other than the present invention constituting the photoelectric conversion site, the same material as the material of the transparent conductive thin film of the present invention is used.

Particularly preferred as the material for the transparent electrode film are ITO, IZO, SnO ₂ , ATO (antimony-doped tin oxide), ZnO, AZO (Al-doped zinc oxide), GZO (gallium-doped zinc oxide), TiO ₂ , FTO (fluorine). Doped tin oxide). The light transmittance of the transparent electrode film is preferably 60% or more, more preferably 80% or more, more preferably, in the photoelectric conversion light absorption peak wavelength of the photoelectric conversion film included in the photoelectric conversion element including the transparent electrode film. It is 90% or more, more preferably 95% or more. The preferred range of the surface resistance of the transparent electrode film varies depending on whether it is a pixel electrode or a counter electrode, and whether the charge storage / transfer / read-out site is a CCD structure or a CMOS structure. When it is used for the counter electrode and the charge storage / transfer / readout part has a CMOS structure, it is preferably 10000Ω / □ or less, more preferably 1000Ω / □ or less. When it is used for the counter electrode and the charge storage / transfer / readout part has a CCD structure, it is preferably 1000Ω / □ or less, more preferably 100Ω / □ or less. When used for a pixel electrode, it is preferably 1000000 Ω / □ or less, more preferably 100000 Ω / □ or less.

  The conditions at the time of forming the transparent electrode film other than the present invention will be described. The substrate temperature at the time of forming the transparent electrode film is preferably 500 ° C. or lower, more preferably 300 ° C. or lower, further preferably 200 ° C. or lower, and further preferably 150 ° C. or lower. Further, a gas may be introduced during the formation of the transparent electrode film, and basically the gas species is not limited, but Ar, He, oxygen, nitrogen and the like can be used. Further, a mixed gas of these gases may be used. In particular, in the case of an oxide material, oxygen defects are often introduced, so that oxygen is preferably used.

When a voltage is applied to the photoelectric conversion film of the present invention, it is preferable in terms of improving the photoelectric conversion efficiency. The applied voltage may be any voltage, but the required voltage varies depending on the film thickness of the photoelectric conversion film. That is, the photoelectric conversion efficiency improves as the electric field applied to the photoelectric conversion film increases, but the applied electric field increases as the film thickness of the photoelectric conversion film decreases even at the same applied voltage. Therefore, when the photoelectric conversion film is thin, the applied voltage may be relatively small. The electric field applied to the photoelectric conversion film is preferably 10 V / m or more, more preferably 1 × 10 ³ V / m or more, further preferably 1 × 10 ⁵ V / m or more, and particularly preferably 1 × 10 ⁶ V / m. m or more, most preferably 1 × 10 ⁷ V / m or more. There is no particular upper limit, but if an electric field is applied too much, an electric current flows even in a dark place, which is not preferable, and is preferably 1 × 10 ¹² V / m or less, and more preferably 1 × 10 ⁹ V / m or less.

(Inorganic layer)
The inorganic layer as the electromagnetic wave absorption / photoelectric conversion site will be described. In this case, light passing through the upper organic layer is photoelectrically converted by the inorganic layer. As the inorganic layer, a pn junction or a pin junction of a compound semiconductor such as crystalline silicon, amorphous silicon, or GaAs is generally used. The method disclosed in US Pat. No. 5,965,875 can be adopted as the laminated structure. In other words, a stacked light receiving portion is formed using the wavelength dependence of the absorption coefficient of silicon, and color separation is performed in the depth direction. In this case, since color separation is performed based on the light penetration depth of silicon, the spectral range detected by each stacked light receiving unit is broad. However, color separation is remarkably improved by using the above-described organic layer as an upper layer, that is, by detecting light transmitted through the organic layer in the depth direction of silicon. In particular, when the G layer is disposed in the organic layer, the light transmitted through the organic layer becomes B light and R light, so that the separation of light in the depth direction in silicon becomes only BR light, and color separation is improved. Even when the organic layer is a B layer or an R layer, color separation is remarkably improved by appropriately selecting the electromagnetic wave absorption / photoelectric conversion site of silicon in the depth direction. When the organic layer has two layers, the function as an electromagnetic wave absorption / photoelectric conversion site in silicon may be basically one color, and preferable color separation can be achieved.

  The inorganic layer is preferably formed by stacking a plurality of photodiodes for each pixel in the depth direction in the semiconductor substrate, and a color signal corresponding to a signal charge generated in each photodiode by light absorbed by the plurality of photodiodes. It is a structure that reads out to the outside. Preferably, the plurality of photodiodes include a first photodiode provided at a depth that absorbs B light and at least one of a second photodiode provided at a depth that absorbs R light, It is preferable to include a color signal readout circuit that reads out a color signal corresponding to the signal charge generated in each of the plurality of photodiodes. With this configuration, color separation can be performed without using a color filter. In some cases, light of a negative sensitivity component can also be detected, so that color imaging with good color reproducibility is possible. In the present invention, the junction portion of the first photodiode is formed to a depth of about 0.2 μm from the surface of the semiconductor substrate, and the junction portion of the second photodiode is the surface of the semiconductor substrate. To a depth of about 2 μm.

The inorganic layer will be described in more detail. As a preferable configuration of the inorganic layer, a photoconductive type, a pn junction type, a Schottky junction type, a PIN junction type, an MSM (metal-semiconductor-metal) type light receiving element or a phototransistor type light receiving element can be given. In the present invention, a plurality of first conductivity type regions and second conductivity type regions opposite to the first conductivity type are alternately stacked in a single semiconductor substrate, and the first conductivity type is stacked. It is preferable to use a light receiving element in which each joint surface of the region of the mold and the second conductivity type is formed to a depth suitable for mainly photoelectrically converting light in a plurality of different wavelength bands. As the single semiconductor substrate, single crystal silicon is preferable, and color separation can be performed using absorption wavelength characteristics depending on the depth direction of the silicon substrate.
As the inorganic semiconductor, an InGaN-based, InAlN-based, InAlP-based, or InGaAlP-based inorganic semiconductor can also be used. The nGaN-based inorganic semiconductor is adjusted so as to have a maximum absorption value in the blue wavelength range by appropriately changing the composition of In. That is, the composition is In _x Ga _1-x N (0 <X <1). Such a compound semiconductor is manufactured using a metal organic chemical vapor deposition method (MOCVD method). A nitride semiconductor InAlN system using Al, which is the same group 13 source material as InGa, can also be used as a short wavelength light receiving section in the same manner as the InGaN system. InAlP or InGaAlP lattice-matched to the GaAs substrate can also be used.

The inorganic semiconductor may have a buried structure. The embedded structure means a structure in which both ends of the short wavelength light receiving part are covered with a semiconductor different from the short wavelength light receiving part. The semiconductor covering both ends is preferably a semiconductor having a band gap wavelength shorter than or equivalent to the band gap wavelength of the short wavelength light receiving part.
The organic layer and the inorganic layer may be combined in any form. In addition, it is preferable to provide an insulating layer between the organic layer and the inorganic layer in order to electrically insulate.
The junction is preferably npn or pnpn from the light incident side. In particular, by providing a p layer on the surface and increasing the surface potential, holes generated in the vicinity of the surface and dark current can be trapped and dark current can be reduced. preferable.
In such a photodiode, an n-type layer, a p-type layer, an n-type layer, and a p-type layer that are sequentially diffused from the surface of the p-type silicon substrate are formed deeply in this order, so that the pn junction diode has a silicon depth. Four layers of pnpn are formed in the direction. The light incident on the diode from the surface side penetrates deeper as the wavelength is longer, and the incident wavelength and attenuation coefficient show values specific to silicon, so that the depth of the pn junction surface covers each wavelength band of visible light. design. Similarly, an n-type layer, a p-type layer, and an n-type layer are formed in this order to obtain a npn three-layer junction diode. Here, an optical signal is taken out from the n-type layer, and the p-type layer is connected to the ground.
Further, when an extraction electrode is provided in each region and a predetermined reset potential is applied, each region is depleted, and the capacitance of each junction becomes an extremely small value. Thereby, the capacity | capacitance produced in a joint surface can be made very small.

(Auxiliary layer)
In the present invention, it is preferable to have an ultraviolet absorption layer and / or an infrared absorption layer in the uppermost layer of the electromagnetic wave absorption / photoelectric conversion site. The ultraviolet absorbing layer can absorb or reflect at least light of 400 nm or less, and preferably has an absorptance of 50% or more in a wavelength region of 400 nm or less. The infrared absorbing layer can absorb or reflect light of at least 700 nm or more, and preferably has an absorptance of 50% or more in a wavelength region of 700 nm or more.

These ultraviolet absorbing layer and infrared absorbing layer can be formed by a conventionally known method. For example, a method of forming a colored layer by providing a mordanting layer made of a hydrophilic polymer material such as gelatin, casein, mulled or polyvinyl alcohol on a substrate and adding or dyeing a dye having a desired absorption wavelength to the mordanting layer. Are known. Furthermore, a method using a colored resin in which a certain kind of coloring material is dispersed in a transparent resin is known. For example, JP-A-58-46325, JP-A-60-78401, JP-A-60-184202, JP-A-60-184203, JP-A-60-184204, JP-A-60-184204 As shown in Japanese Patent Application Laid-Open No. 60-184205 and the like, a colored resin film obtained by mixing a colorant with a polyamino resin can be used. A colorant using a polyimide resin having photosensitivity is also possible.
Dispersing a coloring material in an aromatic polyamide resin having a photosensitivity group described in JP-B-7-113685 in the molecule and capable of obtaining a cured film at 200 ° C. or lower, JP-B-7-69486 It is also possible to use dispersed colored resins with the stated content.

In the present invention, a dielectric multilayer film is preferably used. The dielectric multilayer film is preferably used because the wavelength dependency of light transmission is sharp.
Each electromagnetic wave absorption / photoelectric conversion site is preferably separated by an insulating layer. The insulating layer can be formed using a transparent insulating material such as glass, polyethylene, polyethylene terephthalate, polyethersulfone, and polypropylene. Silicon nitride, silicon oxide and the like are also preferably used. Silicon nitride formed by plasma CVD is preferably used because it has high density and good transparency.
A protective layer or a sealing layer can be provided for the purpose of preventing contact with oxygen or moisture. Examples of protective layers include diamond thin films, inorganic material films such as metal oxides and metal nitrides, polymer films such as fluororesins, polyparaxylene, polyethylene, silicon resins, and polystyrene resins, and photocurable resins. Can be mentioned. Further, the element portion can be covered with glass, gas-impermeable plastic, metal, etc., and the element itself can be packaged with an appropriate sealing resin. In this case, a substance having high water absorption can be present in the packaging.
Furthermore, since the light collection efficiency can be improved by forming the microlens array on the light receiving element, such an embodiment is also preferable.

(Charge accumulation / transfer / readout part)
Regarding the charge transfer / readout part, reference can be made to JP-A-58-103166, JP-A-58-103165, JP-A-2003-332551 and the like. A configuration in which a MOS transistor is formed in each pixel unit on a semiconductor substrate or a configuration having a CCD as an element can be appropriately employed. For example, in the case of a photoelectric conversion element using a MOS transistor, charges are generated in the photoconductive film by incident light transmitted through the electrodes, and the charges are generated by an electric field generated between the electrodes by applying a voltage to the electrodes. It travels to the electrode through the photoconductive film, and further moves to the charge storage part of the MOS transistor, and charges are stored in the charge storage part. The charge accumulated in the charge accumulation unit moves to the charge readout unit by switching of the MOS transistor, and is further output as an electric signal. Thereby, a full-color image signal is input to the solid-state imaging device including the signal processing unit.

It is possible to inject a certain amount of bias charge into the storage diode (refresh mode) and store the constant charge (photoelectric conversion mode), and then read out the signal charge. The light receiving element itself can be used as a storage diode, or a storage diode can be additionally provided.
The signal readout will be described in more detail. An ordinary color readout circuit can be used for signal readout. The signal charge or signal current optically / electrically converted by the light receiving unit is stored in the light receiving unit itself or an attached capacitor. The stored charge is read out together with the selection of the pixel position by a technique of a MOS type image pickup device (so-called CMOS sensor) using an XY address method. In addition, as an address selection method, there is a method in which each pixel is sequentially selected by a multiplexer switch and a digital shift register and read as a signal voltage (or charge) to a common output line. An image sensor for XY address operation that is two-dimensionally arrayed is known as a CMOS sensor. This is because a switch connected to a pixel connected to the intersection of XY is connected to a vertical shift register, and when a switch is turned on by a voltage from the vertical scanning shift register, it is read from a pixel placed in the same row. The signal is read out to the output line in the column direction. This signal is sequentially read from the output through a switch driven by a horizontal scanning shift register.
For reading out the output signal, a floating diffusion detector or a floating gate detector can be used. Further, the S / N can be improved by providing a signal amplification circuit in the pixel portion or a correlated double sampling technique.
For signal processing, gamma correction by an ADC circuit, digitization by an AD converter, luminance signal processing, and color signal processing can be performed. Examples of the color signal processing include white balance processing, color separation processing, and color matrix processing. When used for NTSC signals, RGB signals can be converted to YIQ signals.
The charge transfer / readout site needs to have a charge mobility of 100 cm ² / volt · sec or more, and this mobility is selected from a group IV, III-V, or II-VI group semiconductor. Can be obtained. Of these, silicon semiconductors (also referred to as Si semiconductors) are preferable because miniaturization technology is advanced and the cost is low. Many methods of charge transfer / charge reading have been proposed, but any method may be used. A particularly preferred method is a CMOS type or CCD type device. Furthermore, in the case of the present invention, the CMOS type is often preferable in terms of high-speed readout, pixel addition, partial readout, power consumption, and the like.

(Connection)
A plurality of contact parts for connecting the electromagnetic wave absorption / photoelectric conversion part and the charge transfer / reading part may be connected by any metal, but preferably selected from copper, aluminum, silver, gold, chromium, and tungsten. In particular, copper is preferred. In accordance with a plurality of electromagnetic wave absorption / photoelectric conversion sites, it is necessary to install each contact site between the charge transfer / readout site. When a laminated structure of a plurality of photosensitive units of blue, green, and red light is adopted, between the blue light extraction electrode and the charge transfer / readout portion, between the green light extraction electrode and the charge transfer / readout portion, and the red light extraction electrode; It is necessary to connect between the charge transfer / readout portions.

(process)
The laminated photoelectric conversion device of the present invention can be manufactured according to a so-called microfabrication process used for manufacturing a known integrated circuit or the like. Basically, this method uses pattern exposure by active light or electron beam (mercury i, g emission line, excimer laser, X-ray, electron beam), pattern formation by development and / or burning, element formation material By repeated operations of arrangement (coating, vapor deposition, sputtering, CV, etc.) and removal of non-patterned material (heat treatment, dissolution treatment, etc.).

(Use)
The chip size of the device can be selected from brownie size, 135 size, APS size, 1 / 1.8 inch, and even smaller size. The pixel size of the laminated photoelectric conversion element of the present invention is represented by a circle-equivalent diameter corresponding to the maximum area of a plurality of electromagnetic wave absorption / photoelectric conversion sites. Any pixel size may be used, but a pixel size of 2 to 20 microns is preferable. More preferably, it is 2 to 10 microns, but 3 to 8 microns is particularly preferable.
When the pixel size exceeds 20 microns, the resolving power decreases, and even if the pixel size is smaller than 2 microns, the resolving power decreases due to radio wave interference between the sizes.

The photoelectric conversion element of the present invention can be used for a digital still camera. It is also preferable to use it for a TV camera. Other applications include digital video cameras, surveillance cameras for the following applications (office buildings, parking lots, financial institutions and unmanned contractors, shopping centers, convenience stores, outlet malls, department stores, pachinko halls, karaoke boxes, game centers, Hospital), various other sensors (TV door phone, personal authentication sensor, factory automation sensor, home robot, industrial robot, piping inspection system), medical sensor (endoscope, fundus camera), video conference system, It can be used for applications such as videophones, mobile phones with cameras, safe driving systems for vehicles (back guide monitors, collision prediction, lane keeping systems), and video game sensors.
Especially, the photoelectric conversion element of this invention is suitable also for a television camera use. This is because a television camera can be reduced in size and weight because no color separation optical system is required. Further, since it has high sensitivity and high resolution, it is particularly preferable for a television camera for high-definition broadcasting. In this case, the high-definition broadcast television camera includes a digital high-definition broadcast camera.
Furthermore, the photoelectric conversion element of the present invention is preferable in that an optical low-pass filter can be omitted, and higher sensitivity and higher resolution can be expected.

Furthermore, in the photoelectric conversion element of the present invention, it is possible to reduce the thickness and eliminate the need for a color separation optical system, so that "an environment with different brightness such as daytime and nighttime" For shooting scenes that require different sensitivities, such as `` subjects that are moving and subjects that are moving, '' and other shooting scenes that require different spectral sensitivity and color reproducibility, replace the photoelectric conversion element of the present invention and shoot. A single camera can meet a variety of shooting needs, and it is not necessary to carry multiple cameras at the same time, reducing the burden on the photographer. As the photoelectric conversion element to be exchanged, an exchange photoelectric conversion element can be prepared for infrared light photography, black-and-white photography, and dynamic range change in addition to the above.
The TV camera of the present invention can be obtained by referring to the description in Chapter 2 of the TV Information Technology Society, Television Camera Design Technology (August 20, 1999, Corona, ISBN 4-339-00714-5). Fig. 2.1 The television camera can be manufactured by replacing the part of the color separation optical system and the imaging device in the basic configuration with the photoelectric conversion element of the present invention. The above-described stacked light receiving elements can be used not only as an image pickup element by arranging them but also as a light sensor such as a biosensor or a chemical sensor or a color light receiving element as a single unit.

(Preferred photoelectric conversion element of the present invention)
A preferred photoelectric conversion element of the present invention will be described with reference to FIG. Reference numeral 113 denotes a silicon single crystal substrate, which serves as an electromagnetic wave absorption / photoelectric conversion site for B light and R light and a charge accumulation / transfer / readout site for charges generated by photoelectric conversion. Usually, a p-type silicon substrate is used. Reference numerals 121, 122, and 123 respectively denote an n layer, a p layer, and an n layer provided in the silicon substrate. The n layer 121 is an R light signal charge accumulating unit that accumulates R light signal charges photoelectrically converted by a pn junction. The accumulated electric charge is connected to the signal readout pad 127 through the transistor indicated by 126 through the metal wiring 119. The n layer 123 is a B light signal charge accumulating unit that accumulates the B light signal charge photoelectrically converted by the pn junction. The accumulated charge is connected to the signal readout pad 127 through a transistor similar to 126 and 119 metal wiring. Here, the p layer, the n layer, the transistor, the metal wiring, and the like are schematically shown. However, as described in detail in the previous discussion, an optimal structure is appropriately selected. Since B light and R light are separated according to the depth of the silicon substrate, selection of the depth from the silicon substrate such as a pn junction and the doping concentration is important. Reference numeral 112 denotes a layer including metal wiring, which is a layer mainly composed of silicon oxide, silicon nitride, or the like. The thickness of the layer 112 is preferably as small as possible, and is 5 μm or less, preferably 3 μm or less, and more preferably 2 μm or less. Similarly, 111 is a layer mainly composed of silicon oxide, silicon nitride or the like. 111 and 112 layers are provided with plugs for sending G light signal charges to the silicon substrate. The plug is connected by 116 pads between the 111 and 112 layers. The plug is preferably made mainly of tungsten. A pad mainly composed of aluminum is preferably used. It is preferable that a barrier layer is provided including the metal wiring described above. The signal charges of G light transmitted through the plugs 115 are accumulated in the n layer indicated by 125 in the silicon substrate. The n layer shown at 125 is separated by the p layer shown at 124. The accumulated charge is connected to the signal readout pad 127 through a transistor similar to 126 and 119 metal wiring. Since photoelectric conversion by the pn junctions 124 and 125 becomes noise, the light shielding film 117 is provided in the 111 layer. As the light shielding film, a film mainly composed of tungsten, aluminum or the like is usually used. The thickness of the layer 112 is preferably as small as possible, but is 3 μm or less, preferably 2 μm or less, more preferably 1 μm or less. The signal readout pad 127 is preferably provided for each of the B, G, and R signals. The above process can be prepared by a conventionally known process, a so-called CMOS process.

The electromagnetic wave absorption / photoelectric conversion site of G light is indicated by 105, 106, 107, 108, 109, 110, 114. Reference numerals 105 and 114 denote transparent electrodes, which correspond to a counter electrode and a pixel electrode, respectively. The pixel electrode 114 is a transparent electrode, but in many cases, a portion such as aluminum or molybdenum is required for the connection portion in order to make an electrical connection with the plug 115. A bias is applied between these transparent electrodes through wiring from 118 connection electrodes and 120 counter electrode pads. A structure in which electrons can be accumulated in 125 by applying a positive bias to the pixel electrode 114 with respect to the counter electrode 105 is preferable. In this case, 107 is an electron blocking layer, 108 is a p layer, 109 is an n layer, and 110 is a hole blocking layer, showing a typical organic layer structure. 106 is a buffer layer, and the total thickness of the organic layer composed of 107, 108, 109, 110 is preferably 0.5 μm or less, more preferably 0.35 μm or less, still more preferably 0.3 μm or less, particularly preferably 0. .2 μm or less. The thicknesses of the transparent counter electrode 105 and the transparent pixel electrode 114 are particularly preferably 0.2 μm or less. Reference numerals 103 and 104 denote protective films mainly composed of silicon nitride or the like. These protective films facilitate the manufacturing process of the layer including the organic layer. In particular, these layers can reduce damage to the organic layer at the time of forming a resist pattern at the time of forming a connection electrode such as 118, and at the time of etching. Further, in order to avoid the formation of a resist pattern, etching, etc., it is possible to manufacture with a mask. The thicknesses of the protective films 103 and 104 are preferably 0.5 μm or less as long as the above-described conditions are satisfied.
Reference numeral 103 denotes a protective film for 118 connection electrodes. Reference numeral 102 denotes a laminated film of an infrared cut dielectric multilayer film and an ultraviolet cut layer. Reference numeral 101 denotes an antireflection film. The total thickness of the layers 101, 102 and 103 is preferably 1 μm or less.
The photoelectric conversion element described with reference to FIG. 1 has a configuration in which the G pixel is 4 pixels and the B pixel and the R pixel are 1 pixel. The G pixel may be configured with one B pixel and the R pixel for one pixel, or the G pixel may be configured with one pixel for the B pixel and the R pixel for three pixels. In addition, the B pixel and the R pixel may be configured as one pixel with respect to the G pixel as two pixels. Furthermore, arbitrary combinations may be used. Although the above shows the preferable aspect of this invention, it is not limited to this.

[Example]
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

In the preferable photoelectric conversion element structure, the transparent pixel electrode 114 of the present invention and the comparative example used ITO, and its film thickness was 100 nm. The transparent electrode 105 of the present invention and the comparative example used ITO, and the film thickness was 10 nm for the present invention and 50 nm for the comparative example. The transparent pixel electrode was formed by using the rf magnetron sputtering method (distance between TS: 10 cm), the amount of introduced O ₂ was 0%, and the temperature during film formation was 25 ° C. The transparent electrode of the present invention was formed using the rf magnetron method (distance between TS: 10 cm), the amount of introduced O ₂ was 0%, the temperature during film formation was 25 ° C., and the film formation time was 4 minutes and 50 seconds. On the other hand, the transparent electrode of the comparative example was formed using the rf magnetron sputtering method (distance between TS of 10 cm), the amount of introduced O ₂ was 0%, the temperature during film formation was 25 ° C., and the film formation time was 23 minutes 30 seconds. did. Instead of the organic layers 107 to 110 of the preferable photoelectric conversion element, films of tris-8-hydroxyquinoline aluminum (Alq) and 2-9-dimethylquinacridone were formed from 50 to 100 nm by heating evaporation from the substrate side, respectively. When a negative voltage of 1 V was applied to the transparent electrode 105 side and the dark current value of the comparative example was 1, it decreased to 0.001 in the present invention.
According to the present invention, an element having a good S / N ratio could be produced.

  The photoelectric conversion element of the present invention can be applied to imaging elements such as digital cameras, video cameras, facsimile machines, scanners, and copying machines. It can also be used as an optical sensor such as a bio or chemical sensor.

It is typical sectional drawing of the photoelectric conversion element of the preferable aspect of this invention.

Explanation of symbols

101 Antireflection film 102 Infrared cut dielectric multilayer film 103, 104 Protective film 105 Transparent counter electrode 106 Buffer layer 107 Electron blocking layer 108 P layer 109 n layer 110 Hole blocking layer 111, 112 Layer 113 including metal wiring Silicon single Crystal substrate 114 Transparent pixel electrode 115 Plug 116 Pad 117 Light shielding film 118 Connection electrode 119 Metal wiring 120 Counter electrode pad 121 n layer 122 p layer 123 n layer 124 p layer 125 n layer 126 Transistor 127 Signal readout pad

Claims (13)

  A photoelectric conversion element in which a conductive thin film, a photoelectric conversion film, and a transparent conductive thin film are laminated in this order on a substrate, wherein the thickness of the transparent conductive thin film is 1/5 or less of the thickness of the photoelectric conversion film A photoelectric conversion element.   2. The photoelectric conversion element according to claim 1, wherein the thickness of the transparent conductive thin film is 1/10 or less of the thickness of the photoelectric conversion film.   A photoelectric conversion element in which a conductive thin film, a photoelectric conversion film, and a transparent conductive thin film are laminated in this order on a substrate, wherein the transparent conductive thin film has a thickness of 5 nm to 30 nm.   The film thickness of the said photoelectric conversion film is 350 nm or less, The photoelectric conversion element in any one of Claims 1-3 characterized by the above-mentioned.   The photoelectric conversion element according to claim 1, wherein the transparent conductive thin film is made of a transparent conductive oxide.   The photoelectric conversion element according to claim 1, wherein the light transmittance of the transparent conductive thin film is 75% or more in a light wavelength range of 400 to 700 nm.   The sheet resistance of the said transparent conductive thin film is 100 ohms / square or more and 10000 ohms / square or less, The photoelectric conversion element in any one of Claims 1-6 characterized by the above-mentioned.   The photoelectric conversion element according to claim 1, wherein the transparent conductive thin film is formed by a plasma-free method.   The photoelectric conversion element according to claim 1, wherein the photoelectric conversion film includes a pigment-based material layer.   The film thickness of the said pigment-type material layer is 75 nm or more, The photoelectric conversion element of Claim 9 characterized by the above-mentioned.   The film thickness of the said pigment-type material layer is 100 nm or more, The photoelectric conversion element of Claim 9 or 10 characterized by the above-mentioned.   The photoelectric conversion element which has an inorganic photoelectric conversion film in a semiconductor substrate, and laminates | stacks the photoelectric conversion film in any one of Claims 1-11 above this inorganic photoelectric conversion film.   The image pick-up element which has a photoelectric conversion element in any one of Claims 1-12.

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