Patent Description:
In general solid-state imaging elements having a photodiode within a semiconductor substrate, the pixel size reaches the limits of miniaturization, and an enhancement of performance such as sensitivity is becoming difficult. Then, there is proposed a stack type solid-state imaging element with high sensitivity in which a photoelectric conversion layer is provided above a semiconductor substrate, so as to enable one to achieve <NUM> % of an aperture ratio (see <CIT>).

The stack type solid-state imaging element described in <CIT> has a configuration in which plural pixel electrodes are arranged and formed above a semiconductor substrate, an organic material-containing light receiving layer (including at least a photoelectric conversion layer) is formed above the plural pixel electrodes, and a counter electrode is formed above this light receiving layer. In such a stack type solid-state imaging element, a bias voltage is impressed to the counter electrode, so as to add an electric field to the light receiving layer; a charge generated within the light receiving layer is transferred into the pixel electrodes; and a signal in response to the charge is read out by a read-out circuit connected to the pixel electrodes.

In the stack type solid-state imaging element, there may be the case where after forming the pixel electrodes, the light receiving layer and the counter electrode, for example, a protective film for blocking the outside air (e.g., water or oxygen), a color filter and other functional film, and so on are formed above the stack. In such case regarding a color filter, for example, the light receiving layer is coated with chemicals for the protective film, the color filter and other functional film, and also subjected to a heating step of heating generally at a temperature of about <NUM> for achieving curing.

Also, on the occasion of wire bonding for electrically connecting a substrate circuit and a package to each other and on the occasion of die bonding of chips to a package or solder reflow for connecting a package to an IC substrate, and the like, the heating step is performed. Furthermore, for achieving the wire bonding, it is necessary to provide a PAD opening in the chip circumferences and the like. On that occasion, resist pattern formation and etching are performed, and the substrate having the light receiving layer formed thereon goes through the heating step in each of the resist pattern formation step and the etching step.

In the light of the above, in the case where it is intended to fabricate a solid-state imaging element using an organic material-containing light receiving layer, when a processing method which is used for usual silicon devices is utilized, a high-temperature heating step is necessary, and the light receiving layer is required to endure such a heating step.

As a technique for enhancing the heat resistance of the light receiving layer, the use of a material having a small thermal change (for example, a material having a high glass transition temperature Tg) is generally applied. However, since the light receiving layer is required to have not only heat resistance but characteristics such as high photoelectric conversion efficiency and low dark current, it is necessary to select a material capable of satisfying these characteristics and heat resistance. In consequence, a width of selection of material of the light receiving layer is narrowed.

As described above, as the technique for enhancing the heat resistance of the light receiving layer, many techniques for improving the light receiving layer itself are proposed. However, any technique for enhancing the heat resistance while paying attention to constituent elements other than the light receiving layer has not been known yet.

Incidentally, even in not only the solid-state imaging element but other devices such as solar cells using a light receiving layer, so far as those prepared through the heating step after the formation of a light receiving layer are concerned, such a problem regarding the heat resistance is similarly generated.

<CIT>, <CIT>, and <CIT> describe a manufacturing method of a photoelectric conversion element in which ITO is film-formed on a glass substrate by means of sputtering and then subjected to patterning to form pixel electrodes, the substrate is heat dried at <NUM>, and thereafter, a light receiving layer and a counter electrode are formed.

However, in this manufacturing method, only heating is performed at <NUM> for drying the ITO pixel electrodes, but an enhancement of the heat resistance is not aimed. Also, a specific configuration for enhancing the heat resistance is not described.

Also, <CIT> and <CIT> describe that pixel electrodes are formed by a CVD method. Specifically, <CIT> describes a photoelectric conversion element having a first electrode made of titanium oxide. However, these patent documents do not describe a specific configuration for enhancing the heat resistance. <NPL> discloses TiNxOy thin-film coatings for infrared focal-plane array applications. It was found that the amount of oxygen in the films controls both its electrical and optical properties. The films are formed by sputtering.

It is also known to form films of TiNxOy by chemical vapor deposition, for example from <NPL>.

Also, <CIT> describes a manufacturing method in which pixel electrodes are formed and then heated at <NUM> or higher. However, this patent document does not describe a specific configuration for enhancing the heat resistance.

In view of the foregoing circumstances, the invention has been made, and an object thereof is to provide an electrode structure for a photoelectric conversion element, the photoelectric conversion element including an organic material-containing light receiving layer, which is able to enhance heat resistance regardless of the material of the light receiving layer. Also, another object of the invention is to provide a method for manufacturing this photoelectric conversion element, a method for manufacturing a solid-state imaging element equipped with this photoelectric conversion element, and an imaging apparatus equipped with a solid-state imaging element, which has been obtained by the respective method.

As described herein, a photoelectric conversion element includes an insulating film, a first electrode, a light receiving layer, and a second electrode. The insulating film is formed on a substrate and is made of an oxide film. The first electrode is formed on the insulating film. The light receiving layer is formed on the first electrode and includes an organic material. The second electrode is formed on the light receiving layer. The first electrode is made of titanium oxynitride. A composition of the first electrode just before forming the light receiving layer meets (<NUM>) a requirement that an amount of oxygen contained in the whole of the first electrode is <NUM> at% or more of an amount of titanium, or (<NUM>) a requirement that in a range of from the substrate side of the first electrode to <NUM> or a range of from the substrate side of the first electrode to <NUM>/<NUM> of the thickness of the first electrode, an amount of oxygen is <NUM> at% or more of an amount of titanium. In addition, , a composition of the first electrode just before forming the light receiving layer further meets (<NUM>) a requirement that an amount of nitrogen contained in the whole of the first electrodes is <NUM> at% to <NUM> at% of an amount of titanium, or (<NUM>) a requirement that in a range of from the substrate side of the first electrode to <NUM> or a range of from the substrate side of the first electrode to <NUM>/<NUM> of the thickness of the first electrode, an amount of nitrogen is <NUM> at% to <NUM> at% of an amount of titanium.

Subject-matter of the present invention is an electrode structure as claimed in claim <NUM>, a method for manufacturing a photoelectric conversion element as claimed in claim <NUM>, a method for manufacturing a solid-state imaging element as claimed in claim <NUM>, and an imaging apparatus as claimed in claim <NUM>. Embodiments of the method of claim <NUM> are claimed in dependent claims <NUM> and <NUM>.

According to the invention, it is possible to provide an electrode structure for a photoelectric conversion element including an organic material-containing light receiving layer, which is able to enhance heat resistance regardless of the material of the light receiving layer. Also, the electrode structure allows to provide a solid-state imaging element equipped with this photoelectric conversion element, and an imaging apparatus equipped with this solid-state imaging element. According to the invention, it is also possible to provide a method for manufacturing this photoelectric conversion element.

Embodiments of the invention are hereunder described by reference to the accompanying drawings.

In a photoelectric conversion element in which an insulating film constituted of an oxide film is formed on a substrate and which includes pixel electrodes formed on the insulating film, an organic material-containing light receiving layer formed on the pixel electrodes and a counter electrode formed on the light receiving layer, the present inventors made investigation on how to enhance the heat resistance. As a result, it has been found that in the case where each of the pixel electrodes is constituted of titanium oxynitride (TiON), even when the same light receiving layer is used, the heat resistance of the photoelectric conversion element is different depending upon a ratio of at least one of oxygen and nitrogen to titanium in the pixel electrode.

Specifically, when a composition of the pixel electrode just before forming the light receiving layer meets (<NUM>) a requirement that an amount of oxygen contained in the whole of pixel electrodes is <NUM> at% or more (preferably <NUM> at% or more, and more preferably <NUM> at% or more) of an amount of titanium, or (<NUM>) a requirement that in a range of from the substrate side of the pixel electrode to <NUM> or a range of from the substrate side of the pixel electrode to <NUM>/<NUM> of the whole thickness, an amount of oxygen is <NUM> at% or more (preferably <NUM> at% or more, and more preferably <NUM> at% or more) of an amount of titanium, the heat resistance of the light receiving layer to be formed thereon is enhanced. When an oxygen ratio within the pixel electrode is excessively high, electric conductivity is lowered, and hence, it is preferable that the amount of oxygen is <NUM> at% or less relative to the amount of titanium in all of the requirements (<NUM>) and (<NUM>).

Alternatively, when a composition of the pixel electrode just before forming the light receiving layer meets (<NUM>) a requirement that an amount of nitrogen contained in the whole of pixel electrodes is <NUM> at% or less (preferably <NUM> at% or less, and more preferably <NUM> at% or less) of an amount of titanium, or (<NUM>) a requirement that in a range of from the substrate side of the pixel electrode to <NUM> or a range of from the substrate side of the pixel electrode to <NUM>/<NUM> of the whole thickness, an amount of nitrogen is <NUM> at% or less (preferably <NUM> at% or less, and more preferably <NUM> at% or less) of an amount of titanium, the heat resistance of the light receiving layer to be formed thereon is enhanced.

According to the present invention, a requirement (<NUM>) or (<NUM>), and further a requirement (<NUM>) or (<NUM>) are met. According to requirement (<NUM>) of the present invention, the amount of nitrogen is <NUM> at% to <NUM> at% of an amount of titanium, and according to requirement (<NUM>) of the present invention, the amount of nitrogen is <NUM> at% to <NUM> at% of an amount of titanium.

Although the reasons why the heat resistance is enhanced by the present prescriptions are not elucidated yet, it may be considered that when a light receiving layer is formed relative to a substrate in which TiON having different conditions from those described above is formed, change of the state of the pixel electrode, for example, one acting on the light receiving layer, is caused in a heating step to be performed later on the photoelectric conversion element, whereby the performance is deteriorated due to that action.

Incidentally, the heating step to be performed later on the photoelectric conversion element, as referred to herein, means a high-temperature heating treatment which is performed in, for example, curing of a color filter, wire bonding, die bonding, solder reflow, formation of a PAD opening, or the like (in general, a heating treatment at <NUM> or higher), which are performed after the formation of a counter electrode.

It may be considered that by the heating step to be performed later on the photoelectric conversion element, oxygen is incorporated into the pixel electrodes from an oxide film (for example, an SiO2 film) existing beneath the pixel electrodes, and as a result, for example, a very small amount of a gas spouts to act on the light receiving layer, thereby possibly producing a process of deteriorating the performance.

Although the kind of a volatilized gas is not certain, in view of the facts that deterioration of the performance of the light receiving layer is inhibited by controlling an amount of nitrogen in the pixel electrodes to a fixed amount or less; and that a ratio of nitrogen to titanium decreases after heating the pixel electrodes as compared with that before heating, it may be assumed that a nitrogen-containing gas volatilizes. For that reason, it may be considered that it is preferable to control the amount of nitrogen in the pixel electrodes to a fixed amount or less. In consequence, it may be considered that it is effective to meet the foregoing requirement (<NUM>), i.e. an amount of nitrogen contained in the whole of the first electrode is <NUM> at% to <NUM> at% of an amount of titanium.

Also, it may be considered that volatilization of a nitrogen-containing gas component following at the time of the heating step to be performed later on the photoelectric conversion element is caused due to incorporation of oxygen from the oxide film on the substrate surface. For that reason, there may be taken an embodiment in which the ratio of nitrogen is small in not only the whole of pixel electrodes but the neighborhood of the substrate surface. In consequence, it may be considered that it is also effective to meet the foregoing requirement (<NUM>) in place of the foregoing requirement (<NUM>), i.e. in a range of from the substrate side of the first electrode to <NUM> or a range of from the substrate side of the first electrode to <NUM>/<NUM> of the thickness of the first electrode, an amount of nitrogen is <NUM> at% to <NUM> at% of an amount of titanium.

Also, it may be considered that volatilization of a nitrogen-containing gas component following at the time of the heating step to be performed later on the photoelectric conversion element is caused due to incorporation of oxygen from the oxide film on the substrate surface. For that reason, in order that a large quantity of oxygen may not penetrate into the pixel electrodes after the heating step, it may be considered to be effective that a composition of the pixel electrode just before forming the light receiving layer meets the foregoing requirement (<NUM>).

Also, since there may be the case where the penetration of oxygen is caused due to incorporation of oxygen into the pixel electrodes from the oxide film of the substrate surface, there may be taken an embodiment in which the ratio of oxygen is large in not only the whole of pixel electrodes but the neighborhood of the substrate surface. In consequence, it may also be considered to be effective to meet the foregoing requirement (<NUM>) in place of the foregoing requirement (<NUM>).

For enhancing the heat resistance, according to the invention, both the foregoing requirement (<NUM>) or (<NUM>) and the foregoing requirement (<NUM>) or (<NUM>) are met, because it may be considered that the incorporation of oxygen and the volatilization of a gas is effectively prevented from occurring.

As a method of allowing at least one of the foregoing requirements (<NUM>) to (<NUM>) to be met, the following method is exemplified.

First of all, an oxide film (for example, silicon oxide) is formed on a substrate such as silicon and glass; thereafter, titanium oxynitride is film-formed thereon by means of sputtering; and this titanium oxynitride is subjected to patterning by means of photolithography and etching, thereby forming plural pixel electrodes. Subsequently, the plural pixel electrodes are heated, and thereafter, a light receiving layer and a counter electrode are successively formed on the plural pixel electrodes, thereby accomplishing a photoelectric conversion element.

In heating the plural pixel electrodes, when heating is performed at a temperature higher than a heating temperature in a step where the heating temperature is highest in the heating step of heating the substrate to be performed on the photoelectric conversion element after forming the counter electrode (preferably a temperature of at least <NUM> higher than the subject heating temperature, and more preferably a temperature of at least <NUM> higher than the subject heating temperature), at least one of the foregoing requirements (<NUM>) to (<NUM>) can be met. Incidentally, a temperature in heating the plural pixel electrodes is <NUM> or higher. When the temperature exceeds <NUM>, in case where oxygen exist in the environment of the heating step, oxygen react with the pixel electrode and the pixel electrode becomes an insulator, and hence, the temperature in heating the plural pixel electrodes is preferably not higher than <NUM>.

In this way, it may be considered that when heating is performed at a temperature higher than the heating temperature in the subsequent heating step after forming the pixel electrodes and before forming the light receiving layer (a temperature to an extent that the composition of the pixel electrode does not substantially change in the subsequent heating step), a sufficient amount of oxygen is incorporated into the pixel electrodes, and nitrogen thoroughly volatilizes. As a result, at least one of the requirements (<NUM>) to (<NUM>) under which the heat resistance can be enhanced can be met.

When at least one the requirements (<NUM>) to (<NUM>) is met, even in the case of performing the heating step after forming the counter electrode, incorporation of oxygen into the pixel electrodes does not occur so much; volatilization of nitrogen does not generate so much; and change of the state of the pixel electrode, for example, one acting on the light receiving layer, is not caused, whereby the heat resistance is enhanced. In the present invention, requirement (<NUM>) or (<NUM>) and further requirement (<NUM>) or (<NUM>) are met.

As another method of allowing at least one of the foregoing requirements (<NUM>) to (<NUM>) to be met, the following method is exemplified.

An oxide film (for example, silicon oxide) is formed on a substrate such as silicon and glass; thereafter, titanium oxynitride is film-formed thereon by means of a CVD method; and this titanium oxynitride is subjected to patterning by means of photolithography and etching, thereby forming plural pixel electrodes. Subsequently, a light receiving layer and a counter electrode are successively formed on the plural pixel electrodes, thereby accomplishing a photoelectric conversion element. According to this method, at least one of the requirements (<NUM>) to (<NUM>) is met without performing heating after forming the pixel electrodes.

Incidentally, the foregoing explanation is made on a premise that plural pixel electrodes are formed. However, even in a photoelectric conversion element including a single pixel electrode, a light receiving layer disposed on the pixel electrode and a counter electrode disposed on the light receiving layer, by heating the pixel electrode or forming the pixel electrode by means a CVD method as described above, at least one of the requirements (<NUM>) to (<NUM>) can be met. In the present invention, requirement (<NUM>) or (<NUM>) and further requirement (<NUM>) or (<NUM>) are met.

An embodiment of a solid-stage imaging element using a photoelectric conversion element including an organic material-containing light receiving layer is hereunder described.

<FIG> is a sectional schematic view showing a diagrammatic configuration of a solid-state imaging element for explaining one embodiment of the invention. This solid-state imaging element is used upon being mounted on an imaging apparatus such as a digital camera, a digital video camera, an electronic endoscope apparatus, and a camera-equipped mobile phone.

A solid-state imaging element <NUM> shown in <FIG> is equipped with a substrate <NUM>, an insulating layer <NUM>, a connection electrode <NUM>, a pixel electrode <NUM>, a connection part <NUM>, a connection part <NUM>, a light receiving layer <NUM>, a counter electrode <NUM>, a buffer layer <NUM>, a sealing layer <NUM>, a color filter <NUM>, a partition wall <NUM>, a light shielding layer <NUM>, a protective layer <NUM>, a counter electrode voltage supply part <NUM>, and a read-out circuit <NUM>.

The substrate <NUM> is a glass substrate or a semiconductor substrate made of silicon or the like. The insulating layer <NUM> made of silicon oxide is formed on the substrate <NUM>. A plurality of the pixel electrodes <NUM> are arranged and formed on the surface of the insulating layer <NUM>, and the connection electrodes <NUM> are formed corresponding to the pixel electrodes <NUM> within the insulating layer <NUM>.

The light receiving layer <NUM> is an organic material-containing layer and is configured to include at least a photoelectric conversion layer. The photoelectric conversion layer is one for generating a charge in response to the received light. The light receiving layer <NUM> is provided on the plural pixel electrodes <NUM> to cover the plural pixel electrodes <NUM>. Although the light receiving layer <NUM> has a fixed film thickness on the pixel electrodes <NUM>, there is no problem even when the film thickness of the light receiving layer <NUM> changes in parts other than the pixel part (outside an effective pixel region). Details of the light receiving layer <NUM> are described later. Incidentally, the light receiving layer <NUM> includes not only one configured of a layer which is composed only of an organic material but a configuration in which a part of layers contains an inorganic material.

The counter electrode <NUM> is an electrode counter to to the pixel electrodes <NUM> and is provided on the light receiving layer <NUM> to cover the light receiving layer <NUM>. The counter electrode <NUM> is formed extending over the connection electrodes <NUM> disposed outside the light receiving layer <NUM> and electrically connected to the connection electrodes <NUM>.

For the purpose of making light incident into the light receiving layer <NUM> including a photoelectric conversion layer, the counter electrode <NUM> is preferably constituted of a transparent electrically conductive film, and examples of a material constituting the counter electrode <NUM> include metals, metal oxides, metal nitrides, metal borides, organic electrically conductive compounds, and mixtures thereof.

Specific examples thereof include electrically conductive metal oxides such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), indium tungsten oxide (IWO), and titanium oxide; metal nitrides such as TiN; metals such as gold (Au), platinum (Pt), silver (Ag), chromium (Cr), nickel (Ni), and aluminum (Al); mixtures or stacks of such metal and electrically conductive metal oxide; organic electrically conductive compounds such as polyaniline, polythiophene, and polypyrrole; and stacks of such an organic electrically conductive compound and ITO.

Any one of materials of ITO, IZO, tin oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), zinc oxide, antimony-doped zinc oxide (AZO), and gallium-doped zinc oxide (GZO) is especially preferable as the material of the transparent electrically conductive film.

The connection part <NUM> is embedded in the insulating layer <NUM> and is a plug for electrically connecting the connection electrode <NUM> and the counter electrode voltage supply part <NUM> to each other, or the like.

The counter electrode voltage supply part <NUM> is formed in the substrate <NUM> and impresses a prescribed voltage to the counter electrode <NUM> via the connection part <NUM> and the connection electrode <NUM>.

In the case where a voltage to be impressed to the counter electrode <NUM> is higher than a power supply voltage of the solid-state imaging element <NUM>, the foregoing prescribed voltage is supplied by boosting the power supply voltage by a charge pump boosting circuit or the like.

The pixel electrode <NUM> is a charge collecting electrode for collecting a charge generated within the light receiving layer <NUM> existing between the pixel electrode <NUM> and the counter electrode <NUM> counter to the pixel electrode <NUM>.

The pixel electrode <NUM> is constituted of titanium oxynitride (TiON). A composition of the pixel electrode <NUM> just before forming the light receiving layer <NUM> meets both of the foregoing requirement (<NUM>) or (<NUM>) and the foregoing requirement (<NUM>) or (<NUM>).

The read-out circuit <NUM> is provided in the substrate <NUM> corresponding to each of the plural pixel electrodes <NUM> and reads out a signal in response to a charge collected by the corresponding pixel electrode <NUM>.

The read-out circuit <NUM> is configured of, for example, CCD, an MOS circuit, a TFT circuit, or the like and shielded from light by a non-illustrated light shielding layer disposed within the insulting layer <NUM>.

The buffer layer <NUM> is formed on the counter electrode <NUM> to cover the counter electrode <NUM>.

The sealing layer <NUM> is formed on the buffer layer <NUM> to cover the butter layer <NUM>.

The color filter <NUM> is formed on the sealing layer <NUM> at a position counter to each of the pixel electrodes <NUM>.

The partition wall <NUM> is provided between the color filters <NUM> each other and is one for enhancing light transmission efficiency of the color filter <NUM>.

The light shielding layer <NUM> is formed on the sealing layer <NUM> in other regions than those in which the color filters <NUM> and the partition walls <NUM> are provided and prevents light from incidence into the light receiving layer <NUM> formed in other region than the effective pixel region.

The protective layer <NUM> is formed on the color filters <NUM>, the partition walls <NUM> and the light shielding layers <NUM> and protects the whole of the solid-state imaging element <NUM>.

Incidentally, in the example of <FIG>, although the mode in which the pixel electrodes <NUM> and the connection electrodes <NUM> are embedded in the surface part of the insulating layer <NUM> is taken, a mode in which these electrodes <NUM> and connection electrodes <NUM> are formed on the insulating layer <NUM> may also be taken.

Also, a plural number of a set of the connection electrode <NUM>, the connection part <NUM> and the counter electrode voltage supply part <NUM> is provided. However, only one set may also be provided. As seen in the example of <FIG>, by supplying a voltage to the counter electrode <NUM> from the both ends of the counter electrode <NUM>, a voltage drop in the counter electrode <NUM> can be inhibited. The number of this set may be properly increased or decreased taking into consideration a chip area of the element.

A preferred configuration of the light receiving layer <NUM> is hereunder described.

<FIG> is a section showing an example of the configuration of the light receiving layer <NUM>. As shown in <FIG>, the light receiving layer <NUM> includes a charge blocking layer 107b provided on the side of the pixel electrode <NUM> and a photoelectric conversion layer 107a provided on the charge blocking layer 107b. A positional relation between the charge blocking layer 107b and the photoelectric conversion layer 107a may be reversed.

The charge blocking layer 107b has a function to inhibit a dark current. The charge blocking layer may be configured of plural layers. By configuring the charge blocking layer 107b of plural layers, an interface between the plural charge blocking layers is formed, and discontinuity is generated in an intermediate level existing in each of the layers, whereby a charge carrier hardly transfers via the intermediate level, and a dark current can be strongly inhibited.

The photoelectric conversion layer 107a includes a p-type organic semiconductor and an n-type organic semiconductor. By joining the p-type organic semiconductor and the n-type organic semiconductor to form a donor/acceptor interface, exciton dissociation efficiency can be increased. For that reason, the photoelectric conversion layer 107a having a configuration in which the p-type organic semiconductor and the n-type organic semiconductor are joined reveals high photoelectric conversion efficiency. In particular, the photoelectric conversion layer 107a in which the p-type organic semiconductor and the n-type organic semiconductor are mixed is preferable because a joined interface increases, whereby the photoelectric conversion efficiency is enhanced.

The p-type organic semiconductor (compound) is an organic semiconductor with donor properties and means an organic compound which is represented chiefly by hole transporting organic compounds and which has properties of easily donating an electron. In more detail, the p-type organic semiconductor refers to an organic compound having a smaller ionization potential when two organic materials are brought into contact with each other. In consequence, as for the organic compound with donor properties, any organic compound can be used so far as it is an organic compound having electron donating properties. Examples of the compound which can be used include 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, indole compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds (for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives, etc.), and metal complexes having a nitrogen-containing heterocyclic compound as a ligand. Incidentally, the compound is not limited to those described above, and an organic compound may be used as the organic semiconductor with donor properties so far as it has an ionization potential smaller than that of an organic compound used as the n-type (with acceptor properties) compound.

The n-type organic semiconductor (compound) is an organic semiconductor with acceptor properties and means an organic compound which is represented chiefly by electron transporting organic compounds and which has properties of easily accepting an electron. In more detail, the n-type organic semiconductor refers to an organic compound having a larger electron affinity when two organic materials are brought into contact with each other. In consequence, as for the organic compound with acceptor properties, any organic compound can be used so far as it is an organic compound having electron accepting properties. Examples of the compound which can be used include condensed aromatic carbocyclic compounds (for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives, etc.), <NUM>-membered to <NUM>-membered heterocyclic compounds containing a nitrogen atom, an oxygen atom or a sulfur atom (for example, 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, oxadiazole, imidazopyridiene, pyrazine, pyrrolopyridine, thiadiazolopyridine, dibenzazepine, tribenzazepine, etc.), polyarylene compounds, fluorenone compounds, cyclopentadiene compounds, silyl compounds, and metal complexes having a nitrogen-containing heterocyclic compound as a ligand. Incidentally, the compound is not limited to those described above, and an organic compound may be used as the organic semiconductor with acceptor properties so far as it has an electron affinity larger than that of an organic compound used as the p-type (with donor properties) compound.

As the p-type organic semiconductor or n-type organic semiconductor, any organic dye may be used. Preferred examples thereof include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zero-methine merocyanine (simple merocyanine)), trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, complex cyanine dyes, complex merocyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarium dyes, croconium dyes, azamethine dyes, coumarin dyes, allylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, spiro compounds, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, perinone dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, acridinone dyes, diphenylamine dyes, quinacridone dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, diketopyrropyrrole dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, metal complex dyes, and condensed aromatic carbocyclic dyes (for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives, etc.).

It is especially preferable to use, as the n-type organic semiconductor, a fullerene or a fullerene derivative having excellent electron transport properties. The fullerene as referred to herein expresses fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C80, fullerene C82, fullerene C84, fullerene C90, fullerene C96, fullerene C240, fullerene C540, a mixed fullerene, or a fullerene nanotube; and the fullerene derivative as referred to herein expresses a compound in which a substituent is added such a fullerene.

When the photoelectric conversion layer 107a contains a fullerene or a fullerene derivative, an electron generated due to photoelectric conversion can be fast transported into the pixel electrode <NUM> or the counter electrode <NUM> via a fullerene molecule or a fullerene derivative molecule. When a path of electrons is formed in a state where fullerene molecules or fullerene derivative molecules are in a line, the electron transport properties are enhanced, thereby enabling one to realize high-speed responsibility of the photoelectric conversion element. In order to achieve this, it is preferable that the fullerene or the fullerene derivative is contained in a content of <NUM> % or more in the photoelectric conversion layer 107a. Indeed, the content of the fullerene or the fullerene derivative is excessively high, the content of the p-type organic semiconductor decreases, and the joined interface becomes small, so that the exciton dissociation efficiency is lowered.

Use of a triarylamine compound described in <CIT> or the like as the p-type organic semiconductor which is mixed together with the fullerene or the fullerene derivative in the photoelectric conversion layer 107a is especially preferable because it becomes possible to reveal a high SN ratio of the photoelectric conversion element. When the ratio of the fullerene or the fullerene derivative in the photoelectric conversion layer 107a is excessively large, the content of the triarylamine compound becomes small, so that the absorption amount of incident light is lowered. According to this, the photoelectric conversion efficiency decreases. Therefore, a composition in which the content of the fullerene or the fullerene derivative to be contained in the photoelectric conversion layer 107a is not more than <NUM> % is preferable.

It is preferable to use a compound represented by the following general formula (<NUM>) as the p-type organic semiconductor which is used in the photoelectric conversion layer 107a.

In the formula, each of L2 and L3 represents a methine group. n represents an integer of from <NUM> to <NUM>. Ar1 represents a divalent substituted arylene group or unsubstituted arylene group. Each of Ar2 and Ar3 independently represents a substituted aryl group, an unsubstituted aryl group, a substituted alkyl group, an unsubstituted alkyl group, a substituted heteroaryl group, or an unsubstituted heteroaryl group. Also, each of R1 to R6 independently represents a hydrogen atom, a substituted alkyl group, an unsubstituted alkyl group, a substituted aryl group, an unsubstituted aryl group, a substituted heteroaryl group, or an unsubstituted heteroaryl group, and adjoining groups may be bonded to each other to form a ring.

The arylene group represented by Ar1 is preferably an arylene group having from <NUM> to <NUM> carbon atoms, and more preferably an arylene group having from <NUM> to <NUM> carbon atoms. The arylene group may have a substituent and is preferably an arylene having from <NUM> to <NUM> carbon atoms which may have an alkyl group having from <NUM> to <NUM> carbon atoms. Examples of the arylene group represented by Ar1 include a phenylene group, a naphthylene group, a methylphenylene group, and a dimethylphenylene group. Of these, a phenylene group or a naphthylene group is preferable, with a phenylene group being more preferable.

Each of the aryl groups represented by Ar2 and Ar3 is independently preferably an aryl group having from <NUM> to <NUM> carbon atoms, and more preferably an aryl group having from <NUM> to <NUM> carbon atoms. The aryl group may have a substituent and is preferably an aryl group having from <NUM> to <NUM> carbon atoms which may have an alkyl group having from <NUM> to <NUM> carbon atoms or an aryl group having from <NUM> to <NUM> carbon atoms. Examples of each of the aryl groups represented by Ar2 and Ar3 include a phenyl group, a naphthyl group, a tolyl group, an anthryl group, a dimethylphenyl group, and a biphenyl group. Of these, a phenyl group or a naphthyl group is preferable, with a phenyl group being more preferable. n is preferably <NUM> or <NUM>.

The alkyl group represented by each of Ar2 and Ar3 is preferably an alkyl group having from <NUM> to <NUM> carbon atoms, and more preferably an alkyl group having from <NUM> to <NUM> carbon atoms. Examples of the alkyl groups represented by each of Ar2 and Ar3 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. Of these, a methyl group or an ethyl group is preferable, with a methyl group being more preferable.

Each of the heteroaryl groups represented by Ar2 and Ar3 is independently preferably a heteroaryl group having from <NUM> to <NUM> carbon atoms, and more preferably a heteroaryl group having from <NUM> to <NUM> carbon atoms. The heteroaryl group may have a substituent and is preferably a heteroaryl group having from <NUM> to <NUM> carbon atoms which may have an alkyl group having from <NUM> to <NUM> carbon atoms or an aryl group having from <NUM> to <NUM> carbon atoms. Also, the heteroaryl group represented by each of Ar2 and Ar3 may be a condensed ring structure. The condensed ring structure is preferably one composed of a combination of rings (the rings may be the same as each other) selected among a furan ring, a thiophene ring, a selenophene ring, silole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, an oxazole ring, a thiazole ring, a triazole ring, an oxadiazole ring, and a thiadiazole ring. Of these, a quinoline ring, an isoquinoline ring, a benzothiophene ring, a dibenzothiophene ring, a thienothiophene ring, a bithienobenzene ring, a bithienothiophene ring is preferable.

The alkyl group represented by each of R1 to R6 is preferably an alkyl group having from <NUM> to <NUM> carbon atoms, and more preferably an alkyl group having from <NUM> to <NUM> carbon atoms. Examples of the alkyl group represented by each of R1 to R6 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. Each of R1 to R6 is preferably a methyl group or an ethyl group, and more preferably a methyl group. n is preferably o or <NUM>.

Each of the heteroaryl groups represented by R1 to R6 is independently preferably a heteroaryl group having from <NUM> to <NUM> carbon atoms, and more preferably a heteroaryl group having from <NUM> to <NUM> carbon atoms. The heteroaryl group may have a substituent and is preferably a heteroaryl group having from <NUM> to <NUM> carbon atoms which may have an alkyl group having from <NUM> to <NUM> carbon atoms or an aryl group having from <NUM> to <NUM> carbon atoms. Also, the heteroaryl group represented by each of R1 to R6 is preferably a heteroaryl group composed of a <NUM>-membered, <NUM>-membered or <NUM>-membered ring or a condensed ring thereof. Examples of the hetero atom which is contained in the heteroaryl group include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the ring constituting the heteroaryl group include a furan ring, a thiophene ring, a pyrrole ring, a pyrroline ring, a pyrrolidine group, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an imidazoline ring, an imidazolidine ring, a pyrazole ring, a pyrazoline ring, a pyrazolidine group, a triazole ring, a furazane ring, a tetrazole ring, a pyran ring, a thyine ring, a pyridine ring, a piperidine ring, an oxazine ring, a morpholine ring, a thiazine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperazine ring, and a triazine ring.

Examples of the condensed ring include a benzofuran ring, an isobenzofuran ring, a benzothiophene ring, an indole ring, an indoline ring, an isoindole ring, a benzoxazole ring, a benzothiazole ring, an indazole ring, a benzoimidazole ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a phthalazine ring, a quinazoline ring, a quinoxaline ring, a dibenzofuran ring, a carbazole ring, a xanthene ring, an acridine ring, a phenanthridine ring, a phenanthroline ring, a phenazine ring, a phenoxazine ring, a thianthrene ring, a thienothiophene ring, an indolizine ring, a quinolidine ring, a quinuclidine ring, a naphthridine ring, a purine ring, and a pteridine ring.

Each of the aryl groups represented by R1 to R6 is independently preferably an aryl group having from <NUM> to <NUM> carbon atoms, and more preferably an aryl group having from <NUM> to <NUM> carbon atoms. The aryl group may have a substituent and is preferably an aryl group having from <NUM> to <NUM> carbon atoms which may have an alkyl group having from <NUM> to <NUM> carbon atoms or an aryl group having from <NUM> to <NUM> carbon atoms. Examples of the aryl group represented by each of R1 to R6 include a phenyl group, a naphthyl group, an anthracenyl group, a pyrenyl group, a phenanthrenyl group, a methylphenyl group, a dimethylphenyl group, and a biphenyl group. Of these, a phenyl group, a naphthyl group, or anthracenyl group is preferable.

Adjoining substituents among Ar1, Ar2, Ar3, and R1 to R6 may be connected to each other to form a ring. Preferred examples of the ring which is formed include a cyclohexene ring, a cyclopentene ring, a benzene ring, a naphthalene ring, a thiophene ring, and a pyran ring.

In the case where each of Ar2, Ar3, and R1 to R6 has a substituent, examples of the substituent include a halogen atom, an alkyl group (including a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, a cycloalkyl group, a bicycloalkyl group, and tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group (may also be called a hetero ring group), a cyano group, a hydroxyl group, a nitro group, a carboxy group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group (including an aniline group), an ammonio group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl- or arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkyl- or arylsulfinyl group, an alkyl- or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a phosphono group, a silyl group, a hydrazino group, a ureido group, a boronic acid group (-B(OH)<NUM>), a phosphato group (-OPO(OH)<NUM>), a sulfato group (-OSO3H), and other known substituents.

Specific examples of the compound represented by the general formula (<NUM>) are hereunder shown, but it should not be construed that the invention is limited thereto. <CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

For the charge blocking layer 107b, an electron donating organic material can be used. Specifically, examples of a low molecular weight material which can be used include aromatic diamine compounds such as N,N'-bis(<NUM>-methylphenyl)-(<NUM>,<NUM>'-biphenyl)-<NUM>,<NUM>'-diamine (TPD) and <NUM>,<NUM>'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl (□-NPD), oxazole, oxadiazole, triazole, imidazole, imidazolone, stilbene derivatives, pyrazoline derivatives, tetrahydroimidazole, polyarylalkanes, butadiene, <NUM>,<NUM>',<NUM>"-tris(N-(<NUM>-methylphenyl)N-phenylamino)triphenylamine (m-MTDATA), porphyrin compounds such as porphine, tetraphenylporphine copper, phthalocyanine, copper phthalocyanine, and titanium phthalocyanine oxide, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, and silazane derivatives. Examples of a polymer material which can be used include polymers of, for example, phenylenevinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene or the like, and derivatives of these polymers. It is also possible to use even a compound which is not an electron donating compound but has sufficient hole transporting properties.

It is also possible to use an inorganic material as the charge blocking layer 107b. Since an inorganic material is in general larger in dielectric constant than an organic material, in the case of using an inorganic material in the charge blocking layer 107b, a large voltage is applied to the photoelectric conversion layer 107a, thereby enabling one to enhance the photoelectric conversion efficiency. Examples of a material which can be formed into the charge blocking layer 107b include calcium oxide, chromium oxide, copper chromium oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium oxide, copper strontium oxide, niobium oxide, molybdenum oxide, copper indium oxide, silver indium oxide, and iridium oxide.

In the charge blocking layer 107b composed of plural layers, it is preferable that in the plural a layers, the layer adjacent to the photoelectric conversion layer 107a is a layer made of the same material as the p-type organic semiconductor which is contained in the photoelectric conversion layer 107a. By using the same p-type organic semiconductor in the charge blocking layer 107b, the formation of an intermediate level at an interface of the layer adjacent to the photoelectric conversion layer 107a is inhibited, so that a dark current can be more inhibited.

In the case where the charge blocking layer 107b is a single layer, the layer can be a layer made of an inorganic material. In the case where the charge blocking layer 107b is composed of plural layers, one or two or more layers can be a layer made of an inorganic material.

It is preferable to use a compound represented by the following general formula (<NUM>-A1) or general formula (<NUM>-A2) as the material which is used in the charge blocking layer 107b. <CHM>
<CHM>.

In the general formulae (<NUM>-A1) and (<NUM>-A2), each of R1 and R2 independently represents a heterocyclic group which may be substituted with an alkyl group. Each of X1 and X2 independently represents a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a silicon atom, each of which may further have a substituent. L represents a single bond, an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group, a cycloalkylene group, a cycloalkenylene group, an arylene group, a divalent heterocyclic group, or an imino group, each of which may further have a substituent. Each of n1 and n2 independently represents an integer of from <NUM> to <NUM>.

The heterocyclic group represented by each of R1 and R2 may contain a condensed ring composed of from <NUM> to <NUM> single rings. Also, the heterocyclic group has preferably from <NUM> to <NUM> carbon atoms, and more preferably from <NUM> to <NUM> carbon atoms.

Also, the alkyl group which may substitutes on the heterocyclic group is preferably an alkyl group having from <NUM> to <NUM> carbon atoms. The alkyl group may be a linear or branched alkyl group or a cyclic alkyl group (cycloalkyl group), and plural alkyl groups may be bonded to each other to form a ring (for example, a benzene ring). The alkyl group is preferably a branched alkyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and a neopentyl group.

L represents a single bond, an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group, a cycloalkylene group, a cycloalkenylene group, an arylene group, a divalent heterocyclic group, or an imino group. L is preferably a single bond, an alkylene group having from <NUM> to <NUM> carbon atoms, an alkenylene group having from <NUM> to <NUM> carbon atoms (for example, -CH=CH-), an arylene group (for example, a <NUM>,<NUM>-phenylene group or a <NUM>,<NUM>-naphthylene group), a heterocyclic group having from <NUM> to <NUM> carbon atoms, an oxygen atom, a sulfur atom, or an imino group having a hydrocarbon group having from <NUM> to <NUM> carbon atoms (preferably, an aryl group or an alkyl group) (for example, a phenylimino group, a methylimino group, or a t-butylimino group); more preferably a single bond, an alkylene group having from <NUM> to <NUM> carbon atoms (for example, a methylene group, a <NUM>,<NUM>-ethylene group, or a <NUM>,<NUM>-dimethylmethylene group), an oxygen atom, a sulfur atom, or an imino group having from <NUM> to <NUM> carbon atoms; and especially preferably a single bond or an alkylene group having from <NUM> to <NUM> carbon atoms.

When L represents an alkylene group, an alkenylene group, a cycloalkylene group, a cycloalkenylene group, an arylene group, a divalent heterocyclic group, or an imino group, such a group may further have a substituent. Examples of the further substituent include an alkyl group, a halogen atom, an aryl group, and a heterocyclic group.

Examples of the heterocyclic group which may be substituted with an alkyl group, as represented by each of R1 and R2, include the following N1 to N15. Of these, N13 is preferable.

The substituent which each of X1 and X2 has is preferably an alkyl group or an aryl group.

The alkyl group is preferably an alkyl group having from <NUM> to <NUM> carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a t-butyl group. Of these, a methyl group is more preferable.

The aryl group is preferably an aryl group having from <NUM> to <NUM> carbon atoms. The aryl group may have an alkyl group and is preferably an aryl group having from <NUM> to <NUM> carbon atoms, which may have an alkyl group having from <NUM> to <NUM> carbon atoms. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a <NUM>-dimethylfluorenyl group, a methylphenyl group, and a dimethylphenyl group. Of these, a phenyl group, a naphthyl group, an anthracenyl group, or a <NUM>-dimethylfluorenyl group is preferable.

Compounds represented by the following formulae are especially preferable as the material of the electron blocking layer. <CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

The solid-state imaging element <NUM> having the foregoing configuration is manufactured in the following manner.

First of all, the substrate <NUM> in which the insulating layer <NUM> including the connection parts <NUM> and <NUM> shown in <FIG> is prepared, and TiON is film-formed on the insulating layer <NUM> of this substrate <NUM> by means of a sputtering method.

Subsequently, the TiON film is subjected to patterning by means of photolithography and etching in such a manner that the TiON film remains on the connection pats <NUM> and <NUM>, thereby forming a plurality of the pixel electrodes <NUM> and a plurality of the connection electrodes <NUM>. Incidentally, it is preferable to perform this patterning under vacuum taking into consideration prevention adhesion of a deterioration factor of the light receiving layer to the substrate from occurring.

After forming a plurality of the pixel electrodes <NUM> and a plurality of the connection electrodes <NUM>, an insulating film is formed thereon and then flattened, thereby accomplishing the insulating layer <NUM> having the configuration shown in <FIG>.

Subsequently, the substrate <NUM> is heated at a temperature higher than a heating temperature in a step where the heating temperature is highest in the heating step to be performed after forming the counter electrode <NUM>. According to the invention, the substrate is heated at <NUM> or higher. At that time, the heating temperature and the heating time are set up so as to meet at least two of the foregoing requirements (<NUM>) to (<NUM>), i.e. (<NUM>) or (<NUM>) and further (<NUM>) or (<NUM>).

After completion of heating of the substrate <NUM>, the light receiving layer <NUM>, the counter electrode <NUM>, the buffer layer <NUM>, the sealing layer <NUM>, the color filters <NUM>, and the protective layer <NUM> are successively formed, thereby accomplishing the solid-state imaging element <NUM>.

According to such a manufacturing method, denaturation of the pixel electrode <NUM> is prevented in the heating step to be performed after forming the photoelectric conversion element, whereby the heat resistance of the solid-state imaging element <NUM> can be enhanced.

Incidentally, the solid-state imaging element <NUM> may also be manufactured in the following manner.

First all, the substrate <NUM> in which the insulating layer <NUM> including the connection parts <NUM> and <NUM> shown in <FIG> is prepared, and TiON is film-formed on the insulating layer <NUM> of this substrate <NUM> by means of a CVD method. At that time, the condition of CVD is set up so as to meet at least two of the foregoing requirements (<NUM>) to (<NUM>), i.e. (<NUM>) or (<NUM>) and further (<NUM>) or (<NUM>).

Subsequently, the TiON film is subjected to patterning by means of photolithography and etching in such a manner that the TiON film remains on the connection pats <NUM> and <NUM>, thereby forming a plurality of the pixel electrodes <NUM> and a plurality of the connection electrodes <NUM>.

After forming a plurality of the pixel electrodes <NUM> and a plurality of the connection electrodes <NUM>, an insulating film is formed thereon and then flattened, thereby accomplishing the insulating layer having the configuration shown in <FIG>.

Subsequently, the light receiving layer <NUM>, the counter electrode <NUM>, the buffer layer <NUM>, the sealing layer <NUM>, the color filters <NUM>, and the protective layer <NUM> are successively formed without performing a treatment of heating the substrate <NUM>, thereby accomplishing the solid-state imaging element <NUM>.

Even according to such a manufacturing method, denaturation of the pixel electrode <NUM> is prevented in the heating step to be performed after forming the photoelectric conversion element, whereby the heat resistance of the solid-state imaging element <NUM> can be enhanced.

The effects of the invention are hereunder described by reference to the Examples.

On a CMOS substrate having a signal read-out circuit, in which an insulating film (including a connection part) made of SiO2 was formed on the surface thereof, titanium oxynitride (TiON) was film-formed in a thickness of <NUM> by means of a sputtering method, and this film was subjected to patterning by means of photolithography and dry etching method, thereby forming pixel electrodes. Incidentally, the pixel electrodes are electrically connected to the signal read-out circuit within the substrate through connection parts within the insulating film. Thereafter, this substrate was heated in the air at <NUM> for <NUM> minutes.

Thereafter, the following Compound <NUM> was film-formed in a thickness of <NUM> by means of a vacuum thermal vapor deposition method, thereby forming an electron blocking layer. Thereafter, the following Compound <NUM> and C60 were film-formed in a ratio of <NUM> : <NUM> as reduced into a single film by means of a vapor co-deposition method, thereby forming a light receiving layer.

Thereafter, ITO was film-formed in a thickness of <NUM> by means of a sputtering method, thereby forming a counter electrode; alumina was film-formed in a thickness of <NUM> thereon by means of an ALCVD method, thereby forming a buffer layer; and a silicon oxynitride film was film-formed in a thickness of <NUM> thereon by means of a sputtering method, thereby forming a sealing layer. There was thus fabricated a solid-state imaging element having up to the sealing layer shown in <FIG>.

Solid-state image elements were fabricated in the same manner as that in Example <NUM>, except for changing the material of the electron blocking layer, the material of the photoelectric conversion layer and the substrate heating temperature in the heating treatment of pixel electrodes before forming the light receiving layer as shown in Table <NUM>. As for an expression "**/***" shown in the column of "Light receiving layer configuration" in Table <NUM>, "**" shows an electron blocking layer, and "***" shows a photoelectric conversion layer.

On a CMOS substrate the same as that used in Example <NUM>, titanium oxynitride (TiON) was film-formed in a thickness of <NUM> by means of a CVD method, and this film was subjected to patterning by means of photolithography and dry etching method, thereby forming pixel electrodes. Incidentally, the pixel electrodes are electrically connected to the signal read-out circuit within the substrate through connection parts within the insulating film.

Thereafter, the following Compound <NUM> was film-formed in a thickness of <NUM> on the substrate by means of a vacuum thermal vapor deposition method, thereby forming an electron blocking layer. Thereafter, a photoelectric conversion layer, et seq. were formed in the same manner as that in Example <NUM>. There was thus fabricated a solid-state imaging element having up to the sealing layer shown in <FIG>.

Solid-state imaging elements were fabricated in the same manner as that in Example <NUM>, except for changing the film forming method of titanium oxynitride to a sputtering method and changing the materials of the electron blocking layer and the photoelectric conversion layer to those described in Table <NUM>.

A solid-state imaging element was fabricated in the same manner as that in Example <NUM>, except for changing the substrate heating temperature in the heat treatment of the pixel electrodes before forming the light receiving layer to <NUM>.

As for the solid-state imaging elements of Examples <NUM>, <NUM> and <NUM> to <NUM> and Comparative Examples <NUM> and <NUM>, the composition of the pixel electrode before and after heating prior to the formation of the light receiving layer was measured; and as for other solid-state imaging elements, the composition of the pixel electrode prior to the formation of the light receiving layer was measured. The results are shown in Table <NUM>. Also, as for all of the fabricated solid-state imaging elements, in the case of impressing an electric field of <NUM> × <NUM> <NUM>V/cm to a minus direction on the pixel electrode side, the dark current density was measured after completion of the fabrication of the solid-state imaging element and after heating the solid-state imaging element at <NUM> of the same temperature in the heating step to be performed in a post- step for <NUM> minutes, respectively, and the measurement result after heating is shown as a relative value to the measurement result before heating.

As shown in Table <NUM>, the dark current in the Comparative Examples <NUM> to <NUM> which do not meet any of the foregoing requirements (<NUM>) to (<NUM>) is significantly increased by the heating step at <NUM> for <NUM> minutes. On the other hand, all of the solid-state imaging elements of Examples <NUM>, <NUM> and <NUM> to <NUM> meet any one of the foregoing requirements (<NUM>) to (<NUM>) and it was noted that the dark current does not increase even after the heating step, and the heat resistance is enhanced.

Also, as compared with Comparative Example <NUM> in which the pixel electrode is heated at <NUM>, in Example <NUM> in which the pixel electrode is heated at <NUM>, the dark current greatly decreases. In view of this fact, it was noted that in the case of heating the pixel electrode at a temperature of <NUM> or higher, an effect for enhancing the heat resistance is obtained.

Incidentally, the manufacturing methods of <CIT>, <CIT>, and <CIT> are concerned with the working examples in which the pixel electrode is ITO, a premise of which is significantly different from that of the present application in which the pixel electrode is constituted of TiON. In consequence, it is not easy to obtain the pixel electrode having a composition specified in the present invention from the inventions described in <CIT>, <CIT>, and <CIT>. Also, the temperature for heating the substrate is a temperature necessary for drying, and a relation with the maximum temperature in the subsequent heating step is not considered.

Also, <CIT> and <CIT> describe that the pixel electrode (including TiO2) is formed by means of a CVD method. However, these patent documents do not describe TiON. Also, in TiO2, although there is a possibility of incorporation of oxygen from the insulating film by the heating step, there is no possibility that the nitrogen gas volatilizes dues to this incorporation.

For that reason, in the pixel electrodes of <CIT> and <CIT>, it is not necessary to specify the oxygen content or nitrogen content, and it is not easy to accomplish the present invention from the inventions described in these patent documents.

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

The disclosed photoelectric conversion element is a photoelectric conversion element comprising a substrate having thereon an insulating film constituted of an oxide film, a first electrode formed on the insulating film, an organic material-containing light receiving layer formed on the first electrode, and a second electrode formed on the light receiving layer, wherein the first electrode is constituted of titanium oxynitride, and a composition of the first electrode just before forming the light receiving layer meets (<NUM>) a requirement that an amount of oxygen contained in the whole of the first electrode is <NUM> at% or more of an amount of titanium, or (<NUM>) a requirement that in a range of from the substrate side of the first electrode to <NUM> or a range of from the substrate side of the first electrode to <NUM>/<NUM> of the thickness of the first electrode, an amount of oxygen is <NUM> at% or more of an amount of titanium. In addition,
a composition of the first electrode just before forming the light receiving layer further meets (<NUM>) a requirement that an amount of nitrogen contained in the whole of the first electrodes is <NUM> at% to <NUM> at% of an amount of titanium, or (<NUM>) a requirement that in a range of from the substrate side of the first electrode to <NUM> or a range of from the substrate side of the first electrode to <NUM>/<NUM> of the thickness of the first electrode, an amount of nitrogen is <NUM> at% <NUM> at% of an amount of titanium.

The disclosed photoelectric conversion element is one in which a plurality of the first electrodes are arranged and formed on the insulating film, and the light receiving layer is formed to cover the plural first electrodes.

The disclosed photoelectric conversion element is one in which the light receiving layer includes an organic material-containing charge blocking layer and an organic material-containing photoelectric conversion layer.

The disclosed solid-state imaging element is one comprising the foregoing photoelectric conversion element and a signal read-out circuit formed on the substrate, which reads out a signal in response to a charge amount of charge generated within the light receiving layer and collected by the first electrode.

The disclosed imaging apparatus is one comprising the foregoing solid-state imaging element.

The disclosed manufacturing method of a photoelectric conversion element is a method for manufacturing a photoelectric conversion element including a substrate having thereon an insulating film constituted of an oxide film, a first electrode formed on the insulating film, an organic material-containing light receiving layer formed on the first electrode, and a second electrode formed on the light receiving layer, which comprises a first step of forming the first electrode on the insulating film; a second step of forming the light receiving layer on the first electrode; and a third step of forming the second electrode on the light receiving layer, wherein in the first step, after completion of the first step, the first electrode is formed so as to meet (<NUM>) a requirement that an amount of oxygen contained in the whole of the first electrode is <NUM> at% or more of an amount of titanium, or (<NUM>) a requirement that in a range of from the substrate side of the first electrode to <NUM> or a range of from the substrate side of the first electrode to <NUM>/<NUM> of the thickness of the first electrode, an amount of oxygen is <NUM> at% or more of an amount of titanium. In addition, in the first step, the first electrode is formed so as to further meet (<NUM>) a requirement that an amount of nitrogen contained in the whole of the first electrodes is <NUM> at% to <NUM> at% of an amount of titanium, or (<NUM>) a requirement that in a range of from the substrate side of the first electrode to <NUM> or a range of from the substrate side of the first electrode to <NUM>/<NUM> of the thickness of the first electrode, an amount of nitrogen is <NUM> at% to <NUM> at% of an amount of titanium.

Further, the first step is constituted of a step of film-forming the titanium oxynitride on the insulating film by a sputtering method, a step of patterning a film of the film-formed titanium oxynitride, and a step of after patterning, heating the substrate at <NUM> or higher, or
the first step is constituted of a step of film-forming the titanium oxynitride on the insulating film by a CVD (chemical vapor deposition) method and a step of patterning a film of the film-formed titanium oxynitride.

Claim 1:
An electrode structure for a photoelectric conversion element, the electrode structure comprising:
a substrate;
an insulating film that is formed on the substrate and is made of an oxide film; and
a first electrode that is formed on the insulating film;
wherein the first electrode is made of titanium oxynitride, and
a composition of the first electrode meets
(<NUM>) a requirement that an amount of oxygen contained in the whole of the first electrode is <NUM> at% or more of an amount of titanium, or
(<NUM>) a requirement that in a range of from the substrate side of the first electrode to <NUM> or a range of from the substrate side of the first electrode to <NUM>/<NUM> of the thickness of the first electrode, an amount of oxygen is <NUM> at% or more of an amount of titanium, characterised in that the composition of the first electrode further meets
(<NUM>) a requirement that an amount of nitrogen contained in the whole of the first electrodes is <NUM> at% to <NUM> at% of an amount of titanium, or
(<NUM>) a requirement that in a range of from the substrate side of the first electrode to <NUM> or a range of from the substrate side of the first electrode to <NUM>/<NUM> of the thickness of the first electrode, an amount of nitrogen is <NUM> at% to <NUM> at% of an amount of titanium.