KR20160034345A - Image sensor and method for manufacturing same - Google Patents

Abstract

A method of manufacturing an image sensor having (a) a pixel of a color filter, (b) an inorganic protective layer, (c) an organic photoelectric conversion portion, and (d) an inorganic photoelectric conversion portion, wherein the inorganic protective layer (b) (C). ≪ / RTI >

Description

[0001] IMAGE SENSOR AND METHOD FOR MANUFACTURING SAME [0002]

The present invention relates to an image sensor and a method of manufacturing the same.

Conventional color image sensors generally form a color filter in which three color pixels of red (R), green (G), and blue (B) are two-dimensionally arranged and spatially color-separated. On the other hand, with the miniaturization and the multi-image reduction of the image sensor, the cell size of one pixel has recently been reduced to 2.0 mu m or less per square. Thus, the area and the volume per pixel are reduced. As a result, the saturation signal amount and sensitivity are lowered, resulting in deterioration of image quality. There has been a demand for a technique of maintaining a spatial luminance and a resolution of a chroma while keeping a certain amount of sensitivity and a saturated signal amount without reducing a cell.

On the other hand, recently, an image sensor using an organic photoelectric conversion film has been devised (for example, see Patent Document 1). According to this, by using the organic photoelectric conversion film of a specific color, signals of the other two colors in R / G / B can be received through the color filter. The number of pixels is simply two, and a space of 1/3 can be reduced.

Patent Document 1: JP-A-2008-258474

However, the organic photoelectric conversion film is weak in temperature and humidity because it is an organic material. On the other hand, it is inevitable that heat is applied to the organic photoelectric conversion film due to baking at the time of molding, for example, when a pixel of a color filter is placed on the upper side. If the baking temperature is simply set to a low temperature, the curing becomes insufficient. When the pixels of the two color tones of the color filter are coated, lithographically, and developed, some of the pixels of the one color tone are partially melted, So that the spectral intensity of the pixel of the one-color tone is deteriorated.

SUMMARY OF THE INVENTION Accordingly, the present invention is directed to an image sensor capable of suppressing damage to an organic photoelectric conversion film suitably at the time of heat treatment such as post-baking of a pixel of a color filter and obtaining a good pixel (hardened portion) .

The above problem has been solved by the following means.

[1] A manufacturing method of an image sensor having a pixel of a color filter, an inorganic protective layer, an organic photoelectric conversion portion, and an inorganic photoelectric conversion portion, characterized by comprising: a step of forming an inorganic protective layer on the organic photoelectric conversion portion Way.

[2] The method of manufacturing an image sensor according to [1], further comprising a step of providing a pixel of the color filter on the inorganic protective layer.

[3] A method of manufacturing an image sensor according to [2], wherein the temperature at the time of forming the pixel of the color filter is 200 占 폚 or less.

[4] A method for manufacturing an image sensor according to [2], wherein the oxygen concentration of the atmosphere at the time of forming the pixel of the color filter is 19% or less.

[5] A method of manufacturing an image sensor according to any one of [2] to [4], wherein the pixels of the color filter are cured by UV irradiation.

[6] The method of manufacturing an image sensor according to any one of [1] to [5], wherein the inorganic protective layer is composed of two or more layers.

[7] wherein the inorganic protective layer Al ₂ O _3, SiO _2, and the lower layer and the upper side containing at least one selected from TiO _2, is selected from SiON, SiO _2, Al ₂ O _3, and SiN A method for manufacturing an image sensor according to [6], comprising an upper layer containing at least one species.

[8] The method for manufacturing an image sensor according to any one of [1] to [7], wherein the inorganic protective layer has a surface roughness Ra of 1 nm or more and 100 nm or less.

[9] An image sensor having a pixel of a color filter, an inorganic protective layer, an organic photoelectric conversion portion, and an inorganic photoelectric conversion portion, wherein the inorganic protective layer is provided on the organic photoelectric conversion portion.

[10] An image sensor according to [9], wherein the pixel of the color filter is made of a UV curable resin.

[11] The image sensor according to [9] or [10], wherein the inorganic protective layer is composed of two or more layers.

[12] The method according to any one of [1] to [10], wherein the inorganic protective layer comprises a lower layer containing at least one selected from Al ₂ O ₃ , SiO ₂ , and TiO ₂ and a lower layer selected from SiON, SiO ₂ , Al ₂ O ₃ , and SiN The image sensor according to [11], comprising an upper layer containing at least one species.

[13] An image sensor according to any one of [9] to [12], wherein the inorganic protective layer has a surface roughness Ra of 1 nm or more and 100 nm or less.

[14] A laminate comprising a pixel of a color filter, an inorganic protective layer, an organic photoelectric conversion portion, and an image sensor having an inorganic photoelectric conversion portion, wherein the inorganic protective layer is provided on the organic photoelectric conversion portion.

In the present invention means to be arranged on the upper side or the lower side of the target portion and means to be arranged on the upper side or the lower side via another member or material. However, the term "providing" is not meant to limit the order of formation, but the target portion may be formed as a base portion, or the target portion may be formed by forming the arranged portion. Specifically, the organic photoelectric conversion portion may be formed first, or the protective layer may be formed first.

According to the image sensor and the manufacturing method thereof of the present invention, damage to the organic photoelectric conversion film is suitably suppressed during heat treatment such as post-baking of the color filter, and a good pixel (hardened portion) can be obtained.

These and other features and advantages of the present invention will become more apparent from the following description and the accompanying drawings.

1 is a partial cross-sectional view of an image sensor according to a preferred embodiment of the present invention.

One embodiment of the image sensor (solid-state image pickup device) of the present invention will be described with reference to Fig. 1 shows a part of the entire surface opening type CMOS image sensor 10. 1, the image sensor 10 is provided with an organic photoelectric conversion film 6 on the inorganic photoelectric conversion portions 4 and 5 and further includes a protective layer 3 (an upper layer 31, (Pixel electrode 32) of the color filter are formed. The pixels 1 and 2 of the color filter are formed in correspondence with the photoelectric conversion units 4 and 5. For example, in order to extract blue and red, pixels 1 and 2 of the color filter in the interiors, And the pixels 1 of the color filter of FIG. On the pixels of each color filter, a condenser lens for condensing the incident light to each photoelectric conversion unit may be formed. In this embodiment, the inorganic photoelectric conversion portion 4 is red (R) and the inorganic photoelectric conversion portion 5 is a light receiving portion of blue (B).

The active layer formed of the semiconductor substrate includes, for example, an inorganic photoelectric conversion portion (for example, photodiodes) 4 and 5 for converting incident light into an electric signal, a transistor group such as a transfer transistor, And a plurality of pixel portions having a plurality of pixel regions are formed. As the semiconductor substrate, for example, a silicon substrate is used. Further, a signal processing section for processing the signal charges read from the respective photoelectric conversion sections is formed. In Fig. 1, it is assumed that there are various embodiments, and the members below the inorganic photoelectric conversion units 4 and 5 are not shown.

A wiring layer may be formed on the surface side of the semiconductor substrate on which the photoelectric conversion section is formed. This wiring layer is composed of an insulating film which covers wirings and wirings. A support substrate is formed on the wiring layer. This supporting substrate is made of, for example, a silicon substrate.

The image sensor 10 takes out a signal from the organic photoelectric conversion film 6 with green and extracts blue and red in combination with pixels of the cyan and yellow color filters as described above. The color combination and combination of these colors is not limited to the above example but may be a combination of B (blue), G (green), R (red), Cy (cyan), M (magenta) Type image sensor.

Although the image sensor of the structure shown in FIG. 1 has been described above, the present invention is not limited thereto. As a modification thereof, for example, the organic photoelectric conversion film may be arranged above the color filter (the arrangement layer of the pixels of the color filter) (light incidence side). At this time, the protective layer may be sandwiched between the organic photoelectric conversion film and the color filter, or may be disposed on the upper side (light incidence side) of the organic photoelectric conversion film. In the present invention, it is preferable that the protective layer and the organic photoelectric conversion film are disposed in direct contact with each other. Here, direct contact means that in addition to the form in which both layers are in contact with each other without any intervening material, the intervening material or thin layer may be interposed within the range of the effect of the present invention.

In the present specification, the light incident side (upper drawing) of the image sensor is referred to as "upper" and the opposite side (lower side of the drawing) is referred to as "lower".

[Protective layer]

The protective layer 3 preferably includes an inorganic layer made of an inorganic material formed by an ALCVD method. The ALCVD method is an atomic layer CVD method and can form a dense inorganic layer and can be an effective protective layer of the organic photoelectric conversion layer 6. [ The ALCVD method is also known as the ALE method or the ALD method. The inorganic layer formed by the ALCVD method is preferably composed of Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , MgO, HfO ₂ and Ta ₂ O ₅ , more preferably Al ₂ O ₃ , SiO ₂ , and most preferably Al ₂ O ₃ .

The thickness of the protective layer is preferably 50 nm or more, more preferably 150 nm or more, from the viewpoint that the effect of the present invention can be suitably obtained. The upper limit is preferably 500 nm or less, more preferably 300 nm or less.

The protective layer 3 is preferably composed of two or more layers than the single layer. By making the protective layer two or more layers, it is possible to prevent moisture from entering the photoelectric conversion film and to prevent deterioration of the photoelectric conversion film in the post-baking process when a color filter or the like is disposed in a subsequent process. When the protective layer has three or more layers, the above effect can be further increased, but it is preferable to use two layers from the viewpoint of productivity.

When the protective layer 3 is formed of two or more layers, it is preferable to use different materials for the first and second layers. Specifically, it is preferable to select a layer of Al ₂ O ₃ , SiO ₂ , TiO ₂ or the like in the first layer (lower layer 32). Among them, a layer of Al ₂ O ₃ is particularly preferable. After the second layer (upper layer 31), it is preferable to select layers such as SiON, SiO ₂ , Al ₂ O ₃ , and SiN. Among them, it is preferable to use SiON. Further, in the range showing the effect of the present invention, another layer may be interposed between the first layer (lower layer) and the second layer (upper layer), and another layer may exist on the upper side or the lower side thereof.

When the protective layer is two or more layers, the thickness of the first layer is preferably 5 to 200 nm, more preferably 10 to 100 nm, and most preferably 15 to 50 nm. The total thickness after the second layer is preferably 50 to 400 nm, more preferably 100 to 300 nm, and most preferably 150 to 250 nm.

The surface roughness Ra after the formation of the protective layer 3 is preferably 1 to 100 nm, more preferably 1 to 80 nm, still more preferably 1 to 60 nm, still more preferably 1 to 40 nm, More preferably from 1 to 15 nm, and particularly preferably from 1 to 10 nm. By setting the surface roughness of the protective layer within this range, the transmittance of the color filter of the two-color tone when the color filter is formed in the subsequent process is increased. The surface roughness Ra of the inorganic protective layer can be measured by AFM (Atomic Force Microscope) Dimension 3100 manufactured by Veeco Co., Ltd. Ra of the present application is measured by the above apparatus. The surface roughness Ra of the inorganic protective layer is defined in accordance with the definition of JIS B0601 (2013).

The surface roughness of the inorganic protective layer can be changed by appropriately adjusting the conditions in the formation of the uppermost layer (uppermost layer). As the ALCVD method, reference can be made, for example, to [0078] to [0081] of Japanese Laid-Open Patent Publication No. 2011-71483. That is, the thin film is formed by alternately repeating the adsorption / reaction of the thin film material on the substrate surface and decomposition of the unreacted group contained therein. When the SiON layer or the like is provided by the CVD method, the surface roughness can be changed by appropriately controlling the temperature and the deposition rate in accordance with a known method.

[Organic photoelectric conversion portion]

The organic photoelectric conversion portion absorbs green light, for example, so that the following inorganic photoelectric conversion portion can easily separate the blue light and the red light. The organic photoelectric conversion portion preferably has a maximum absorption wavelength in the range of 510 to 560 nm. And more preferably in the range of 520 to 550 nm. Here, the maximum absorption wavelength means an absorption wavelength with the highest absorption rate of light. The absorption rate at the maximum absorption wavelength, that is, the maximum absorption rate is preferably 80% or more and 100% or less. More preferably, it is 90% or more and 100% or less. Preferably, the half value width of the absorption ratio is 50 nm or more and 100 nm or less. More preferably 60 nm or more and 90 nm or less. Herein, the half-width of the absorption rate means the width of the absorption wavelength at the half-maximum absorption rate.

The organic layer as the organic photoelectric conversion film is formed by superimposing or mixing a portion for absorbing electromagnetic waves, a photoelectric conversion portion, an electron transport portion, a hole transport portion, an electron blocking portion, a hole blocking portion, a crystallization prevention portion, do. The organic layer preferably contains an organic p-type compound or an organic n-type compound.

Organic p-type semiconductors (compounds) are donor organic semiconductors (compounds), usually represented by hole-transporting organic compounds, and have the property of donating electrons. More specifically, it refers to an organic compound having a small ionization potential when two organic materials are used in contact with each other. Therefore, the donor organic compound is preferably an organic compound having an electron donor, and any organic compound can be used. Examples of the compound include triarylamine compounds, benzidine compounds, pyrazoline compounds, styrylamine compounds, hydrazone compounds, triphenylmethane compounds, carbazole compounds, polysilane compounds, thiophene compounds, phthalocyanine compounds Anthracene derivatives, phenanthrene derivatives, tetracene derivatives, phenanthrene derivatives, phenanthrene derivatives, phenanthrene derivatives, phenanthrene derivatives, phenanthrene derivatives, phenanthrene derivatives, Derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives), metal complexes having a nitrogen-containing heterocyclic compound as a ligand, and the like can be used. Further, as described above, the organic compound is preferably an organic compound having an ionization potential smaller than that of the organic compound used as the n-type (acceptor) compound, and may be used as a donor organic semiconductor.

Organic n-type semiconductors (compounds) are acceptor organic semiconductors (compounds), and are mainly represented by electron-transporting organic compounds, and have organic properties that are easy to accept electrons. More specifically, it refers to an organic compound having a larger electron affinity when two organic compounds are used in contact with each other. Therefore, the acceptor organic compound is preferably an organic compound having electron acceptability, and any organic compound can be used. For example, a condensed aromatic cyclic compound (a naphthalene derivative, an anthracene derivative, a phenanthrene derivative, a tetracene derivative, a pyrene derivative, a perylene derivative, a fluoranthene derivative), a nitrogen atom, an oxygen atom, 7-membered heterocyclic compounds such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, phthyridine, acridine, Benzothiazole, benzooxazole, benzazole, carbazole, purine, triazalopyridazine, benzothiazole, benzothiazole, benzothiazole, benzothiazole, , Triazalopyrimidines, tetrazenes, oxadiazoles, imidazopyridines, pyrrolidines, pyrrolopyridines, thiadiazolopyridines, dibenzazepines, tribenzazepines, etc.), polyarylene compounds, Fluorenation A silane compound, a metal complex having a nitrogen-containing heterocyclic compound as a ligand, and the like. Further, as described above, the organic compound is preferably an organic compound having a larger electron affinity than the organic compound used as the donor organic compound, and may be used as an acceptor organic semiconductor.

As the p-type organic dye or the n-type organic dye, any of a cyanine dye, a styryl dye, a hemicyanine dye, a merocyanine dye (merometaine (merocyanine And the like), 3-core merocyanine dye, 4-nuclear merocyanine dye, rhodacyanine dye, complex thymine dye, complex merocyanine dye, allopara dye, oxolin dye, hemioxanol dye, An azo dye, an azo dye, an azomethine dye, a spiro compound, a metallocene dye, a fluorescene dye, an azo dye, an azo dye, an aziridine dye, an anthraquinone dye, a triphenylmethane dye, A dyes, a dyes, a dyes, a dyes, an acridine dyes, an acridine dyes, dyes, pigments, dyes, pigments, (Naphthalene derivative, naphthalene derivative, naphthalene derivative, naphthalene derivative, naphthalene derivative, naphthalene derivative, naphthalene derivative, naphthalene derivative, naphthalene derivative, naphthalene derivative, Anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives).

Next, the metal complex compound will be described. The metal complex compound is preferably a metal complex having at least one nitrogen atom or a ligand having an oxygen atom or a sulfur atom coordinating to the metal. The metal ion in the metal complex is not particularly limited and preferably beryllium ion, magnesium ion, aluminum ion, gallium ion, zinc ion, indium ion or tin ion, more preferably beryllium ion, Or a zinc ion, more preferably an aluminum ion or a zinc ion. As the ligand contained in the metal complex, there are various known ligands. For example, in H. Yersin, "Photochemistry and Photophysics of Coordination Compounds" Springer-Verlag, published in 1987 by Akio Yamamoto, Application - "Shokabosa, published in 1982 and the like.

As the ligand, 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, may be a monodentate ligand or a ligand of two or more) Preferably a bidentate ligand, such as a pyridine ligand, a bipyridyl ligand, a quinolinol ligand, a hydroxyphenylzole ligand (a hydroxyphenylbenzimidazole, a hydroxyphenylbenzoxazole ligand, a hydroxyphenylimidazole An alkoxy ligand (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, (Preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl (meth) acrylate, 2-naphthyloxy, 2,4,6-trimethylphenyloxy, 4-biphenyloxy and the like), a heteroaryloxy ligand (preferably having 1 to 30 carbon atoms, more preferably 1 to 30 carbon atoms, Preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.), an alkylthio ligand Preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio), an arylthio ligand Preferably 6 to 20 carbon atoms, more preferably 6 to 20 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenylthio), a heterocyclic substituted thio ligand More preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, Benzoxazolylthio, 2-benzthiazolylthio, etc.), or a siloxy ligand (preferably having 1 to 30 carbon atoms, more preferably 1 to 30 carbon atoms) More preferably 3 to 25 carbon atoms, and particularly preferably 6 to 20 carbon atoms, and examples thereof include a triphenylsiloxy group, a triethoxysiloxy group, and a triisopropylsiloxy group), and more preferably, An aryloxy ligand, a heteroaryloxy group, or a siloxy ligand, more preferably a nitrogen-containing heterocyclic ligand, an aryloxy ligand, or a siloxyl ligand.

In the present embodiment, a p-type semiconductor layer and an n-type semiconductor layer are formed between a pair of electrodes, at least one of the p-type semiconductor and the n-type semiconductor is an organic semiconductor, And a photoelectric conversion film (photosensitive layer) having, as an intermediate layer, a bulk heterojunction structure layer containing the p-type semiconductor and the n-type semiconductor. In such a case, by containing a bulk heterojunction structure in the organic layer in the photoelectric conversion film, the carrier diffusion length of the organic layer can be compensated for short defects, and the photoelectric conversion efficiency can be improved. The bulk heterojunction structure is described in detail in Japanese Patent Application No. 2004-080639.

In this embodiment, a photoelectric conversion film having a structure having two or more repeating structures (tandem structures) of a pn junction layer formed of a p-type semiconductor layer and a n-type semiconductor layer between a pair of electrodes ), And more preferably, a thin layer of a conductive material is inserted between the repeating structures. The number of the repeating structure (tandem structure) of the pn junction layer may be any number, and is preferably 2 to 50, more preferably 2 to 30, and particularly preferably 2 or 10 in order to increase the photoelectric conversion efficiency . As the conductive material, silver or gold is preferable, and silver is most preferable. The tandem structure is described in detail in Japanese Patent Application No. 2004-079930.

A photoelectric conversion film having a p-type semiconductor layer and an n-type semiconductor layer (preferably a mixed / dispersed (bulk heterojunction structure) layer) between a pair of electrodes is provided on at least one of a p- The case of the photoelectric conversion film containing the orientation-controlled organic compound is preferable, and more preferably, the organic compound containing orientation-controlled (possible) is contained in both the p-type semiconductor and the n-type semiconductor. As the organic compound used in the organic layer of the photoelectric conversion film, it is preferable to use π-conjugated electrons. It is preferable that the π-electron plane is oriented not at right angles to the substrate (electrode substrate) . The angle with respect to the substrate is preferably not less than 0 ° and not more than 80 °, more preferably not less than 0 ° and not more than 60 °, more preferably not less than 0 ° and not more than 40 °, more preferably not less than 0 ° and not more than 20 ° , Particularly preferably 0 DEG to 10 DEG, and most preferably 0 DEG (i.e., parallel to the substrate). As described above, the orientation-controlled layer of the organic compound may include at least a part of the whole organic layer. Preferably, the ratio of the orientation-controlled portion to the entire organic layer is 10% or more, 30% or more, more preferably 50% or more, more preferably 70% or more, particularly preferably 90% or more, and most preferably 100%. This state is to improve the photoelectric conversion efficiency by compensating short defects in the carrier diffusion length of the organic layer by controlling the orientation of the organic compound in the organic layer in the photoelectric conversion film.

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 preferable that the heterojunction plane be aligned at an angle close to the vertical rather than parallel to the substrate (electrode substrate). The angle with respect to the substrate is preferably from 10 to 90, more preferably from 30 to 90, more preferably from 50 to 90, Particularly preferably not less than 80 ° and not more than 90 °, and most preferably 90 ° (that is, perpendicular to the substrate). The layer of the organic compound whose heterojunction surface is controlled as described above may include a part of the entire organic layer. Preferably, the proportion of the portion in which the orientation of the organic layer is controlled is 10% or more, more preferably 30% or more, more preferably 50% or more, still more preferably 70% or more, 90% or more, and most preferably 100%. In this case, the area of the heterojunction surface in the organic layer is increased, and the amount of carriers such as electrons, holes, and electron hole pairs generated at the interface is increased, and the photoelectric conversion efficiency can be improved. In the above photoelectric conversion film in which the orientation of both the heterojunction plane of the organic compound and the? Electron plane is controlled, the photoelectric conversion efficiency can be improved in particular. Such a state is described in detail in Japanese Patent Application No. 2004-079931.

From the viewpoint of light absorption, it is preferable that the film thickness of the organic dye layer is larger, but considering the ratio not contributing to charge separation, the film thickness of the organic dye layer in this embodiment is preferably 30 nm or more and 300 nm or less Preferably 50 nm or more and 250 nm or less, and particularly preferably 80 nm or more and 200 nm or less.

These layers containing an organic compound are formed by a dry film forming method or a wet film forming method. Specific examples of the dry film forming method include a physical vapor phase growth method such as a vacuum vapor deposition method, a sputtering method, an ion plating method and an MBE method, or a CVD method such as plasma polymerization. As the wet film formation method, a cast method, a spin coat method, a dipping method, an LB method, or the like is used.

When a polymer compound is used as at least one of a p-type semiconductor (compound) and an n-type semiconductor (compound), it is preferable that the film is formed by a wet film forming method that is easy to manufacture. In the case of using a dry film forming method such as vapor deposition, it is difficult to use a polymer because there is a risk of decomposition, and the oligomer can be preferably used instead. On the other hand, in the present embodiment, when a small molecule is used, a dry film forming method is preferably used, and in particular, a vacuum vapor deposition method is preferably used. The vacuum deposition method is a basic parameter such as a method of heating a compound such as a resistance heating deposition method or an electron beam heating deposition method, a shape of an evaporation source such as a crucible or a boat, a vacuum degree, a deposition temperature, a substrate temperature and a deposition rate. It is desirable to rotate and deposit the substrate to enable uniform deposition. The vacuum degree is preferably as high as possible, and vacuum deposition is performed at 10 ^-4 Torr or less, preferably 10 ^-6 Torr or less, particularly preferably 10 ^-8 Torr or less. It is preferable that all the steps at the time of 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-mentioned conditions of the vacuum deposition affect the crystallinity, amorphousness, density, compactness and the like of the organic film, and therefore strict control is required. It is preferable to control the deposition rate by PI or PID using a film thickness monitor such as a crystal oscillator or an interferometer. When two or more compounds are simultaneously deposited, a co-deposition method, a flash deposition method, or the like can be preferably used.

[Inorganic photoelectric conversion portion]

The inorganic photoelectric conversion portion preferably performs photoelectric conversion of a specific color set in relation to the organic photoelectric conversion portion. Particularly, it is preferable that the inorganic photoelectric conversion portion is made of a silicon semiconductor, and photoelectric conversion is carried out by separating at least blue light and red light in the depth direction of the silicon semiconductor. For example, the inorganic photoelectric conversion portion is a silicon p-type substrate and has an n-type well, a p-type well, and an n-type well. Photoelectric conversion is performed by each pn junction, signals of at least blue light are collected by the n-type well, and signals of at least red light are collected by the n-type well. The color discrimination in the depth direction using the difference in the absorption coefficient of silicon is described in the above-mentioned known examples. The signal can be read by the signal wiring. The inorganic photoelectric conversion portion is preferably a silicon semiconductor having a CMOS structure. A horizontal shift register, a vertical shift register, a noise suppressing circuit, and the like related to signal readout are omitted in FIG.

The light passing through the organic layer in the upper layer is photoelectrically converted into the inorganic layer. As the inorganic layer, pn junction or pin junction of a compound semiconductor such as crystal silicon, amorphous silicon or GaAs is generally used. As a laminated structure, a method disclosed in U.S. Patent No. 5,965,875 can be employed. That is, the wavelength dependence of the absorption coefficient of silicon is used to form a laminated light-receiving portion, and color separation is performed in the depth direction. In this case, since the color separation is performed at the light entry depth of silicon, the spectral range to be detected by each of the light receiving units stacked is widened. However, by using the above-described organic layer in the upper layer, that is, by detecting light transmitted through the organic layer in the depth direction of the silicon, the color separation is remarkably improved. Particularly, when the G layer is disposed in the organic layer, the light passing through the organic layer becomes B light and R light, so that the light in the depth direction in the silicon becomes only the BR light so that color separation is improved. When the organic layer is the B layer or the R layer, the color separation is remarkably improved by appropriately selecting the electromagnetic wave absorption / photoelectric conversion sites of the silicon in the depth direction. When the organic layer has two layers, the function as the electromagnetic wave absorption / photoelectric conversion region in silicon may basically be 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 for emitting color signals corresponding to signal charges generated in the respective photodiodes by the light absorbed by the plurality of photodiodes Shipment is structure. Preferably, the plurality of photodiodes include at least one of a first photodiode provided at a depth for absorbing the B light and a second photodiode provided at a depth for absorbing the R light, And a color signal reading circuit for reading a color signal corresponding to the signal charge generated in each of the diodes. With this configuration, color separation can be performed without using a color filter. Further, in some cases, since light of the sub-sensitivity component can be detected, color imaging with good color reproducibility can be performed. The junction of the first photodiode is formed to a depth of about 0.2 mu m from the surface of the semiconductor substrate and the junction of the second photodiode is formed to a depth of about 2 mu m from the surface of the semiconductor substrate.

The inorganic layer will be described in more detail. Examples of preferred structures of the inorganic layer include photodetectors, p-n junctions, Schottky junctions, PIN junctions, MSM (metal-semiconductor-metal) light receiving elements and phototransistor type light receiving elements. In this embodiment, a plurality of regions of a first conductivity type and regions of a second conductivity type opposite to the first conductivity type are alternately stacked in a single semiconductor substrate, and the first conductivity type and the second It is preferable to use a light receiving element in which each junction surface of the conductive type region is formed at a suitable depth for mainly photoelectric conversion of light of a plurality of different wavelength bands. As a single semiconductor substrate, monocrystalline silicon is preferable, and color separation can be performed using the absorption wavelength characteristic 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 may be used. The n-GaN-based inorganic semiconductor is adjusted so as to have a maximum absorption value within the wavelength range of blue by appropriately changing the composition of In. That is, the composition is InxGa1-xN (0? X <1). Such compound semiconductors are produced using an organic metal vapor phase epitaxy (MOCVD) method. The InAlN system of the nitride semiconductor using Al as the Group 13 raw material of Ga can be used as the short wavelength light receiving unit similarly to the InGaN system. It is also possible to use InAlP or InGaAlP lattice-matched to a GaAs substrate.

The inorganic semiconductor may have a buried structure. The buried structure means a structure in which both ends of the short wavelength light receiving portion are covered with a semiconductor different from the short wavelength light receiving portion. The semiconductor covering both ends is preferably a semiconductor having a band gap wavelength shorter than or equal to the band gap wavelength of the short wavelength light receiving portion. The organic layer and the inorganic layer may be bonded in any form. It is preferable to provide an insulating layer between the organic layer and the inorganic layer in order to electrically insulate the organic layer from the inorganic layer. It is preferable that the junction is made of npn or pnpn from the light incidence side. Particularly, since a p-layer is provided on the surface to increase the potential of the surface, holes and dark current generated in the vicinity of the surface can be trapped and the dark current can be reduced, so that the pnpn junction is more preferable.

[Color Filter]

Each pixel of the color filter according to the preferred embodiment of the present invention is preferably formed by curing the following colored and radiation-sensitive composition. (B) a polymer having no polymerizable group, (c) a monomer having an ethylenically unsaturated double bond (preferably three or more), (d) an acrylic polymer having a polymerizable group, ) Polymerization initiator, and (e) a colorant.

Specific acrylic polymers having a polymerizable group

As the polymerizable group of a specific acrylic polymer, an ethylenically unsaturated bonding group is exemplified, and a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is more preferable. The acrylic polymer is preferably a vinyl polymer having a repeating unit derived from at least one of (meth) acrylic acid, (meth) acrylic acid ester and (meth) acrylamide. In the present specification, (meth) acryl or (meth) acryloyl is meant to include acrylic or acryloyl and methacryloyl or methacryloyl.

The proportion of the polymerizable group contained in a specific acrylic polymer is preferably from 5 to 50, and more preferably from 10 to 40. By setting this range, compatibility between hardenability and developability can be more effectively achieved. Here, the ratio of the polymerizable group means a molar copolymerization ratio. As another structural unit, a structural unit containing an acid group is exemplified. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and a carboxyl group is preferable. The acid value of the specific acrylic polymer is preferably 10 to 200 mgKOH / g, more preferably 20 to 150 mgKOH / g. By setting this range, it becomes possible to enhance the solubility of the unexposed portion at the time of pattern formation. Acid value refers to a value obtained by neutralization titration with a potassium hydroxide solution.

Specific examples of the acrylic polymer include a glycidyl group-containing unsaturated compound such as glycidyl (meth) acrylate and allyl glycidyl ether, allyl alcohol, 2-hydroxyacrylate, 2- A resin obtained by reacting an unsaturated carboxylic acid group-containing unsaturated compound and an unsaturated acid anhydride with a carboxyl group-containing resin having a hydroxyl group, a resin obtained by reacting an unsaturated carboxylic acid with an epoxy resin and an unsaturated carboxylic acid, A resin reacted with a polybasic acid anhydride, a resin obtained by reacting an addition reaction product of a conjugated diene copolymer and an unsaturated dicarboxylic acid anhydride with a polyfunctional monomer containing a hydroxyl group, a specific functional group giving a unsaturated group by a cleavage reaction Is synthesized, and the resin is subjected to a base treatment to produce an unsaturated group And the like can be given as typical resins.

The specific acrylic polymer is preferably a resin containing at least one kind selected from structural units (specific structural units) represented by any one of the following formulas (1) to (3).

[Chemical Formula 1]

A ¹ , A ² and A ³ each represent an oxygen atom, a sulfur atom, or -N (R ²¹ ) -, and R ²¹ represents an alkyl group. G ¹ , G ² and G ³ each represent a divalent organic group. X, Y and Z each represent a single bond, an oxygen atom, a sulfur atom, a phenylene group or -N (R ²² ) -, and R ²² represents an alkyl group or a hydrogen atom. Each of R ¹ to R ²⁰ independently represents a hydrogen atom or a monovalent organic group.

G ¹ , G ² and G ^{3 each} represent a divalent organic group, preferably an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof, More preferably a group consisting of a straight or branched alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a combination thereof, and is preferably a linear or branched alkylene group having 1 to 10 carbon atoms , A cycloalkylene group having 3 to 10 carbon atoms, and a group formed by a combination thereof are particularly preferable. These groups may further have a substituent, and the substituent is preferably a hydroxyl group. More preferred examples of G ¹ , G ² and G ³ are - (CH ₂ ) _n - (a cycloalkylene group which may have a substituent) - (CH ₂ ) _n -, n is an integer of 0 to 2 , The cycloalkylene group is a 5-membered ring or a 6-membered ring (more preferably a 6-membered ring).

Each of R ¹ to R ⁴ , R ⁷ to R ¹⁰ and R ¹³ to R ¹⁸ represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ¹ and R ² are more preferably a hydrogen atom, and R ³ is more preferably a hydrogen atom or a methyl group.

^{R 5, R 6, R 11} , R 12, R 19, R 20 are each a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group, an aryl group, an alkoxy group , An aryloxy group, an alkylsulfonyl group and an arylsulfonyl group are exemplified, and a hydrogen atom, an alkoxycarbonyl group, an alkyl group and an aryl group are preferable, a hydrogen atom or a methyl group is more preferable, and a hydrogen atom is particularly preferable.

The synthesis of the polymer compound having a specific structural unit can be carried out based on the synthesis method described in Japanese Patent Laid-Open Publication No. 2003-262958, paragraphs 0027 to 0057. Of these, the synthesis method 1) in the same publication is preferable. Specific examples of the compound of the polymer having a specific structural unit include the following compounds. Needless to say, the present invention is not limited to these compounds.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

The specific acrylic polymer (a) is preferably 1 to 40% by mass, more preferably 1 to 20% by mass, and further preferably 1 to 10% by mass in the composition. By setting this range, it is possible to form a colored layer with less film shrinkage, excellent pattern formation property and less surface roughness when cured to form a colored layer. The specific acrylic polymer (a) is preferably 10 to 50 mass%, more preferably 20 to 40 mass%, based on the total solid content.

The weight average molecular weight (Mw) of the specific acrylic polymer (a) is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 7,000 to 20,000.

In the present specification, the molecular weight of the polymer is defined as the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC) unless otherwise specified. As a measurement method, a column in which three TOSOH TSK gel Super AWM-Hs are connected, and 10 mM LiBr / N-methylpyrrolidone is used as an eluent, or TOSOH TSK gel Super HZM-H, TOSOH TSK gel Super HZ4000, TOSOH TSK gel HZ2000, and using tetrahydrofuran as an eluent. The flow rate of the eluent was 1.0 ml / min, and the column temperature was 40 占 폚. However, depending on the type of polymer, an appropriate column and eluent may be selected and used.

Polymers not having a polymerizable group

Examples of the polymer having no polymerizable group include an alkali-soluble resin, a dispersant, and a dispersion resin other than an alkali-soluble resin used as a dispersed resin or a further added resin. Further, even when the resin is an alkali-soluble resin, the specific acrylic polymer corresponds to a specific acrylic polymer (a). As the polymer (b), it is preferable to include an acrylic polymer having no polymerizable group, and a preferable example thereof is an alkali-soluble resin.

Alkali-soluble resin

As the alkali-soluble resin, a linear organic polymer can be appropriately selected from an alkali-soluble resin having at least one group capable of promoting alkali solubility in a molecule (preferably an acrylic copolymer, a styrene-based copolymer as a main chain) . From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin and an acryl / acrylamide copolymer resin are preferable. From the viewpoint of development control, an acrylic resin, an acrylamide resin , An acrylic / acrylamide copolymer resin is preferable. Examples of the group capable of accelerating the alkali solubility (hereinafter also referred to as acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group and the like, preferably soluble in a solvent and developable by a weakly alkaline aqueous solution , And (meth) acrylic acid are particularly preferable. These acid groups may be one kind or two or more kinds.

Examples of the monomer capable of imparting an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, monomers having an epoxy group such as glycidyl (meth) acrylate, And isocyanatoethyl (meth) acrylate; and the like. The monomers for introducing these acid groups may be one kind or two or more kinds. In order to introduce an acid group into an alkali soluble binder, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter also referred to as " monomer for introducing an acid group ") may be used as a monomer component .

When an acid group is introduced as a monomer component capable of imparting an acid group after polymerization, a treatment for imparting an acid group as described later, for example, is required after polymerization.

For the production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as the temperature, pressure, kind and amount of the radical initiator and the type of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, have.

As the linear organic polymer used as an alkali-soluble resin, a polymer having a carboxylic acid in its side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, Maleic acid copolymer, and alkali-soluble phenol resin such as novolak resin, and acidic cellulose derivatives having a carboxylic acid in the side chain, and acid anhydride added to a polymer having a hydroxyl group. Particularly, a copolymer of (meth) acrylic acid and other monomers copolymerizable therewith is suitable as an alkali-soluble resin.

As the alkali-soluble resin, a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid copolymer and benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl methacrylate is particularly suitable. Examples of other monomers in this case include 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy- 3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer , 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, and the like.

As the alkali-soluble resin, the following are also preferable.

The alkali-soluble resin of the present embodiment is a linear organic polymer which is a polymer having at least one group capable of promoting alkali solubility in an alkali-soluble resin having molecules (preferably, an acrylic copolymer, a styrene-based copolymer as a main chain) It can be selected appropriately. From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin and an acryl / acrylamide copolymer resin are preferable. From the viewpoint of development control, an acrylic resin, an acrylamide resin , An acrylic / acrylamide copolymer resin is preferable.

Examples of the group capable of promoting alkali solubility (hereinafter also referred to as acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group and the like, which are soluble in an organic solvent and can be developed by a weakly alkaline aqueous solution And (meth) acrylic acid is particularly preferable. These acid groups may be one kind or two or more kinds.

Examples of the monomer capable of imparting an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, monomers having an epoxy group such as glycidyl (meth) acrylate, And isocyanatoethyl (meth) acrylate; and the like. The monomers for introducing these acid groups may be one kind or two or more kinds. In order to introduce an acid group into an alkali soluble binder, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter also referred to as " monomer for introducing an acid group ") may be used as a monomer component . When an acid group is introduced as a monomer component capable of imparting an acid group after polymerization, a treatment for imparting an acid group as described later, for example, is required after polymerization.

For the production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as the temperature, pressure, kind and amount of the radical initiator and the kind of solvent at the time of producing the alkali-soluble resin by the radical polymerization method can be easily set by those skilled in the art, have.

As the linear organic polymer used as an alkali-soluble resin, a polymer having a carboxylic acid in its side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, Maleic acid copolymer, and alkali-soluble phenol resin such as novolak resin, and acidic cellulose derivatives having a carboxylic acid in the side chain, and acid anhydride added to a polymer having a hydroxyl group. Particularly, a copolymer of (meth) acrylic acid and other monomers copolymerizable therewith is suitable as an alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hexyl (meth) (Meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. Examples of the vinyl compound include styrene, Vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate As there may be mentioned monomers, etc., as the above N-substituted maleimide monomers described in Japanese Kokai Publication Hei-10-300922 call, jN--phenyl maleimide, N- cyclohexyl maleimide and the like.

The other monomer copolymerizable with (meth) acrylic acid is preferably a repeating unit represented by the following formula (A1).

[Chemical Formula 6]

Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 or 3 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and n represents an integer of 1 to 15 Lt; / RTI &gt; The repeating unit represented by the formula (A1) has good adsorption and / or orientation to the pigment surface due to the effect of the pi electrons of the benzene ring present in the side chain. Particularly, when the side chain moiety has an ethylene oxide or propylene oxide structure of para-cumylphenol, its stereoscopic effect is also added, and a more favorable adsorption and / or orientation plane can be formed on the pigment, desirable. R ³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and is preferably an alkyl group having 1 to 20 carbon atoms. When R ³ is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ³ is an alkyl group having a carbon number of 1 to 10, the alkyl group is hindered to inhibit the resin from approaching to promote adsorption to the pigment and / or orientation. When the number of carbon atoms is more than 10, So that adsorption and / or orientation of the benzene ring to the pigment surface may be disturbed. This phenomenon becomes remarkable as the chain length of the alkyl group of R ³ becomes longer. When the number of carbon atoms exceeds 20, the adsorption and / or orientation of the benzene ring is extremely lowered. As a result, the alkyl group represented by R ³ has a carbon number of 1 to 20. As the alkyl group represented by R ³ , an unsubstituted alkyl group or an alkyl group substituted with a phenyl group is preferable.

R ² in the formula (A1) is preferably an alkylene group having 2 carbon atoms from the viewpoint of developability.

Further, n in the formula (A1) is preferably in the range of 1 to 12 from the viewpoint of developability.

The repeating unit represented by the formula (A1) can be introduced into the alkali-soluble resin using the ethylenically unsaturated monomer represented by the following formula (A2).

(7)

In the formula ^{(i), R 1, R} 2, R 3, and n, and ^{R 1, R 2, R 3} , and n and copper in the formula (A2), preferred examples are the same.

The acid value of the alkali-soluble resin is preferably 30 to 200 mgKOH / g, more preferably 50 to 150 mgKOH / g, and even more preferably 70 to 120 mgKOH / g. Such a range allows the development residue of the unexposed portion to be effectively reduced.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 7,000 to 20,000.

The content of the alkali-soluble resin is preferably from 10 to 50% by mass, more preferably from 15 to 40% by mass, and particularly preferably from 20 to 35% by mass, based on the total solid content of the composition.

Dispersant

Examples of the dispersing agent include polymer dispersing agents such as polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, Acrylic copolymer, naphthalenesulfonic acid-formalin condensate), polyoxyethylene alkylphosphoric acid ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative and the like.

The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer based on the structure.

The polymer dispersant adsorbs on the surface of the pigment and acts to prevent re-aggregation. Accordingly, a terminal modified polymer, graft-type polymer, and block-type polymer having an anchor site to the pigment surface are preferable structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

Specific examples of the pigment dispersant usable in the present embodiment include Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161 , BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), BYK2001 ", EFKA manufactured by EFKA 4047, 4050, 4010, 4165 (polyurethane copolymer)," 162, 163, 164, 165, 166, (Modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (phthalocyanine), EFKA4330, 4340 (block copolymer), 4400, (Azole pigment oligomer), 6750 (azo pigment derivative) manufactured by Ajinomoto Fine Techno Co., Ltd., Ajisper PB821 and PB822 manufactured by Ajinomoto Fine Techno Co., Ltd., Floren TG-710 , No. 300 (acrylic copolymer) ", Dysparon KS-860, 873SN, 874, # 2150 (product of Kusumoto Chemical Industry Co., ), # 7004 (polyetherester), DA-703-50, DA-705, DA-725 ", Daemol RN, N (naphthalene sulfonic acid-formaldehyde polycondensate) (Aromatic sulfonic acid-formalin polycondensate) "," homogenol L-18 (high molecular polycarboxylic acid) "," EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ", 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 (macromolecule having function at the terminal part), " stearyl amine acetate " , NIKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemicals, etc. .

These dispersants may be used alone or in combination of two or more. In the present embodiment, it is particularly preferable to use a combination of a pigment derivative and a polymeric dispersant.

The content of the dispersant is preferably from 1 to 100 parts by mass, more preferably from 3 to 100 parts by mass, and still more preferably from 5 to 80 parts by mass, per part of the colorant (pigment). Further, it is preferably 10 to 30% by mass relative to the total solid content of the composition.

Monomers having an ethylenically unsaturated double bond

The monomer having an ethylenically unsaturated double bond (hereinafter sometimes referred to as "specific monomer") can be used without particular limitation, and is preferably a multifunctional monomer. The specific monomers may be used alone or in combination of two or more. Specific monomers are preferably (meth) acrylate monomers. As specific compounds of these compounds, compounds described in paragraphs 0095 to 0108 of JP-A No. 2009-288705 can be suitably used in this embodiment.

In the present embodiment, radically polymerizable monomers represented by the following formulas (MO-1) to (MO-6) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

[Chemical Formula 8]

Wherein n is 0 to 14 and m is 1 to 8, respectively. The plurality of R, T and Z present in one molecule may be the same or different. When T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R. At least three of R's are polymerizable groups.

n is preferably 0 to 5, more preferably 1 to 3.

m is preferably from 1 to 5, more preferably from 1 to 3.

Specific examples of the radically polymerizable monomer represented by the above formulas (MO-1) to (MO-6) include compounds described in paragraphs 0248 to 0251 of JP-A No. 2007-269779 And can be suitably used.

Of these, dipentaerythritol triacrylate (KAYARAD D-330 manufactured by Nippon Kayaku K.K.) and dipentaerythritol tetraacrylate (KAYARAD D-320 manufactured by Nippon Kayaku Co., Ltd.) are commercially available as polymerizable monomers, (Trade name: KAYARAD D-310, manufactured by Nippon Kayaku K.K.), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA; (Meth) acryloyl group interposed between ethylene glycol and propylene glycol moieties, and a structure in which diglycerin EO (ethylene oxide) modified (meth) acrylate ( As a commercial product, M-460 (Toagosei Co., Ltd.) is preferable. These oligomer types can also be used.

The specific monomer is particularly preferably at least one selected from the compound represented by the following formula (i) and the compound represented by the formula (ii).

[Chemical Formula 9]

In the formula, E, _{respectively, - ((CH 2) y} CH 2 O) -, or _{- ((CH 2) y CH} (CH 3) O) - represents _{the, - ((CH 2) y} CH 2 O) - is preferred.

y each represent an integer of 1 to 10, preferably an integer of 1 to 5, more preferably 1 to 3.

X represents a hydrogen atom, an acryloyl group, a methacryloyl group or a carboxyl group, respectively.

In the formula (i), the total of the acryloyl group and the methacryloyl group is 3 or 4, preferably 4.

m each represents an integer of 0 to 10, preferably 1 to 5; The sum of each m is an integer of 1 to 40, preferably 4 to 20.

In the formula (ii), the total of the acryloyl group and the methacryloyl group is 5 or 6, preferably 6.

n each represent an integer of 0 to 10, preferably 1 to 5; The sum of n is an integer of 1 to 60, preferably 4 to 30.

The specific monomer may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Therefore, it is preferable that the ethylenic compound has an unreacted carboxyl group as in the case of the mixture as described above, and it can be used as it is. However, if necessary, a nonaromatic carboxylic acid anhydride may be added to the hydroxyl group of the above- And then an acid group may be introduced. In this case, specific examples of the non-aromatic carboxylic acid anhydrides to be used include anhydrous tetrahydrophthalic acid, alkylated anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, alkylated anhydrous hexahydrophthalic acid, succinic anhydride, and maleic anhydride.

The monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid and a polyfunctional monomer having an acid group by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride, Particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Commercially available products include, for example, M-305, M-510 and M-520 of Aronix series, which are polybasic acid-modified acrylic oligomers made by Toagosei Co.,

The preferred acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg KOH / g, particularly preferably 5 to 30 mg KOH / g.

The details of the structure, the single use, the combination use, the amount of addition, etc. of these multifunctional monomers can be arbitrarily set according to the final performance design of the composition. In this embodiment, a method of controlling both sensitivity and strength by using a combination of different functional water and / or different polymerizable groups (for example, acrylic acid ester, methacrylic ester, styrene-based compound, vinylether-based compound) Is also available. In addition, it is preferable to use a specific monomer having three or more functionalities and eight or less functional groups and having different ethylene oxide chain lengths from the viewpoint that the developability of the composition can be controlled and excellent pattern forming ability can be obtained. The compatibility and dispersibility with other components (for example, a polymerization initiator, a colorant (pigment), a resin, etc.) contained in the composition is also an important factor for selecting and using specific monomers. For example, The compatibility may be improved by the use of the compound or by the combined use of two or more compounds. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a substrate.

The specific monomer is preferably smaller in molecular weight than the specific acrylic polymer. The molecular weight of the specific monomer is not particularly limited, but is preferably 300 or more and 1500 or less, and more preferably 400 or more and 700 or less.

The concentration (blending ratio) of the specific monomer is preferably 1% by mass or more, more preferably 5% by mass or more, of the total solid content in the coloring and radiation-sensitive composition. The upper limit is not particularly limited, but is preferably 50 mass% or less, and more preferably 40 mass% or less.

· Polymerization initiator

The polymerization initiator is preferably one having an ability to initiate polymerization of the specific monomer, and is not particularly limited and may be appropriately selected from known polymerization initiators. For example, it is preferable to have a photosensitivity to a light ray (particularly visible light from an ultraviolet ray region), and it may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, Or an initiator that initiates cationic polymerization. The polymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

Examples of the polymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton and the like), acylphosphine compounds such as acylphosphine oxide, Oxime compounds such as benzimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.

As the halogenated hydrocarbon compound having a triazine skeleton, for example, see Wakabayashi et al., Bull. Chem. Soc. Compounds described in GB-A-5313428, compounds described in German Patent Publication No. 3337024, compounds described in J. Org., &Lt; RTI ID = 0.0 &gt; . Chem .; 29, 1527 (1964), compounds described in Japanese Laid-Open Patent Publication No. 62-58241, compounds described in Japanese Laid-Open Patent Publication No. 5-281728, compounds described in Japanese Laid-Open Patent Publication No. 5-34920, Compounds described in Japanese Patent Publication No. 4212976, and the like.

Examples of the compound described in the above-mentioned US Patent Publication No. 4212976 include compounds having an oxadiazole skeleton, JP-A-53-133428, JP-A-57-1819, JP-A-57-6096 And the compounds described in U.S. Patent No. 3615455. [

As the polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, for example, the aminoacetophenone-based initiator disclosed in Japanese Patent Application Laid-Open No. 10-291969 or the acylphosphine oxide-based initiator disclosed in Japanese Patent Publication No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long-wavelength light source such as 365 nm or 405 nm can be used. Commercially available acylphosphine initiators include IRGACURE-819 and DAROCUR-TPO (all trade names, manufactured by BASF).

As the polymerization initiator, oxime compounds are more preferable. As specific examples of the oxime-based compounds, the compounds described in Japanese Laid-Open Patent Publication No. 2001-233842, the compounds described in Japanese Laid-Open Patent Publication No. 2000-80068, and the compounds described in Japanese Laid-Open Patent Publication No. 2006-342166 can be used.

Examples of the oxime compounds such as oxime derivatives that are suitably used as the polymerization initiator in the present embodiment include 3-benzoyloxyiminobutain-2-one, 3-acetoxyiminobutain-2- 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane- 1-one, 3- (4-toluenesulfonyloxy) iminobutain-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one.

Specifically, the oxime-based polymerization initiator is preferably a compound represented by the following formula (1). Further, the N-O bond of the oxime may be an oxime compound of the (E) form, an oxime compound of the (Z) form, or a mixture of the form (E) and the form (Z).

[Chemical formula 10]

(In the formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.)

The monovalent substituent represented by R is preferably a monovalent nonmetal atomic group. Examples of the monovalent non-metallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. The substituent described above may be substituted with another substituent. Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

The monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified. The substituent described above may be substituted with another substituent. Among them, particularly preferred is the structure shown below. Y, X, and n in the following structures are synonymous with Y, X, and n in the formula (2), respectively, and preferred examples are also the same.

(11)

Examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group, and an alkynylene group. These groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified. The substituent described above may be substituted with another substituent.

Among them, A is preferably an alkylene group substituted by an unsubstituted alkylene group, an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group or a dodecyl group) An alkylene group substituted with an alkenyl group (e.g., a vinyl group or an allyl group), an aryl group (e.g., a phenyl group, a p-tolyl group, a xylyl group, a cumene group, a naphthyl group, , Styryl group) is preferable.

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent. The substituent may be the same as the substituent introduced into the substituted aryl group as a specific example of the aryl group which may have a substituent.

Among them, a substituted or unsubstituted phenyl group is preferable in that the sensitivity is increased and coloration due to heating over time is suppressed.

In the formula (1), the structure of "SAr" formed from S adjacent to Ar is preferable from the viewpoint of sensitivity in the following structure. Me represents a methyl group, and Et represents an ethyl group.

[Chemical Formula 12]

The oxime compound is preferably a compound represented by the following formula (2).

[Chemical Formula 13]

In the formulas, R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents an integer of 0 to 5. R, A, and Ar in the formula correspond to R, A, and Ar in the formula (1), and preferable examples are also the same. Examples of the monovalent substituent represented by X include alkyl, aryl, alkoxy, aryloxy, acyloxy, acyl, alkoxycarbonyl, amino, heterocyclic and halogen atoms. These groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified. The substituent described above may be substituted with another substituent. Of these, X is preferably an alkyl group in view of solvent solubility and improvement of absorption efficiency in a long wavelength region. In the formula (2), n represents an integer of 0 to 5, preferably an integer of 0 to 2.

Examples of the divalent organic group represented by Y include the following structures. In the following groups, * represents a bonding position between Y and adjacent carbon atoms in the formula (2).

[Chemical Formula 14]

Specific examples (C-4) to (C-13) of the oxime compounds suitably used are shown below, but the present invention is not limited thereto.

[Chemical Formula 15]

The oxime compound has a maximum absorption wavelength in a wavelength range of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength range of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 455 nm.

The molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000 from the viewpoint of sensitivity.

Specifically, the molar extinction coefficient of the compound can be measured by using an ultraviolet visible spectrophotometer (Carry-5 spactrophotometer manufactured by Varian) with an ethyl acetate solvent at a concentration of 0.01 g / L .

The polymerization initiator may be used in combination of two or more as necessary. The content (the total content in the case of two or more kinds) of the polymerization initiator in the coloring and radiation-sensitive composition is preferably in the range of 0.1 to 20 mass%, more preferably in the range of 0.5 to 20 mass%, based on the total solid content of the radiation- 10% by mass, particularly preferably 1 to 8% by mass. Within this range, good sensitivity and pattern formability can be obtained.

For the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the wavelength of the photosensitive wavelength, a sensitizer may be contained. As the sensitizer usable in the present embodiment, it is preferable to increase or decrease the amount of the polymerization initiator by an electron transfer mechanism or an energy transfer mechanism.

As the sensitizer, for example, compounds described in paragraphs 0101 to 0154 of JP-A No. 2008-32803 can be mentioned.

The content of the sensitizer in the composition is preferably from 0.1% by mass to 20% by mass, more preferably from 0.5% by mass to 20% by mass, in terms of solid content, from the viewpoint of the light absorption efficiency into the deep portion and the decomposition efficiency at the start, To 15% by mass is more preferable.

The sensitizer may be used alone, or two or more may be used in combination.

·coloring agent

The coloring agent is not particularly limited, and various dyes and pigments known in the art can be used singly or in combination of two or more, and they are appropriately selected according to the use of the composition of the present embodiment. It is preferable that the composition of the present embodiment is used for the production of a color filter. It is preferably a coloring agent (chromatic coloring agent) of a luster color system such as red, magenta, yellow, blue, Any of the black coloring agents (black coloring agents) generally used for forming a black matrix may be used. In the present embodiment, the colorant is preferably at least one selected from red, magenta, yellow, blue, cyan, and green.

Hereinafter, the colorant will be described in detail as an example of a colorant suitable for color filter use.

As the pigments of the raindrop series, various conventionally known inorganic pigments or organic pigments can be used. In view of the fact that a high transmittance is preferable for both the inorganic pigment and the organic pigment, it is preferable to use a finely small one. Considering the handling property, the average primary particle size of the pigment is preferably 0.01 탆 to 0.1 탆 , And more preferably 0.01 mu m to 0.05 mu m.

Examples of the inorganic pigments include metallic compounds represented by metal oxides and metal complex salts and specifically include metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, Oxides, and composite oxides of the above metals. Nitrides of titanium, silver tin compounds, silver compounds, and the like can also be used.

When the coloring agent is a dye, a colored composition in a uniformly dissolved state in the composition can be obtained.

The dye that can be used as the colorant contained in the coloring and radiation-sensitive composition is not particularly limited, and known dyes for color filters can be used. Examples of the compound include pyrazolone compounds, anilino compounds, triphenylmethane compounds, anthraquinone compounds, anthrapyridone compounds, benzylidene compounds, oxolin compounds, pyrazolotriazole compounds, Dyes such as dyestuffs, pyrrolopyrazolesulfonate, dyestuffs, phthalocyanine dyes, benzopyran dyes, indigo dyes, and pyromethene dyes can be used. It is also possible to use a multimer of these dyes.

In the case of carrying out water or alkali development, the acid dye and / or its derivative may be suitably used from the viewpoint of completely removing the binder and / or the dye of the non-irradiated portion by the development.

In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azo dyes, disperse dyes, useful dyes, food dyes, and / or derivatives thereof may also be usefully used.

Acid dyes, azothenes, phthalocyanine dyes other than the above are also preferable, and C. I. Solvent Blue 44, 38; C. I. Solvent orange 45; Rhodamine B and Rhodamine 110, and derivatives of these dyes are also preferably used.

Among them, colorants include triarylmethane, anthraquinone, azomethine, benzilidene, oxonol, cyan, phenothiazine, pyrrolopyrazole, trimethyin, zanthene, phthalocyanine It is preferable that the colorant is a colorant selected from the group consisting of benzopyran, indigo, pyrazole, anilino azo, pyrazolotriazoazo, pyridino azo, anthrapyridone and pyromethene.

A pigment and a dye may be used in combination. Particularly, C. I. Pigment Red 122 and C. I. Pigment Yellow 185 are preferred.

The coloring agent that can be used in the coloring and radiation-sensitive composition is preferably a dye or a pigment. Particularly, a pigment satisfying an average particle diameter (r) of 20 nm? R? 300 nm, preferably 125 nm? R? 250 nm, particularly preferably 30 nm? R? By using such a pigment having an average particle diameter, a pixel having a high contrast ratio and a high light transmittance can be obtained. The term "average particle size" as used herein means an average particle size of secondary particles aggregated by primary particles (single crystals) of the pigment. The average primary particle diameter can be determined by observing with SEM or TEM, measuring 100 particle sizes in the portion where particles are not aggregated, and calculating an average value.

(Hereinafter simply referred to as "particle size distribution") of the secondary particles of the pigment is preferably 70% by mass or more, more preferably 80% by mass or more, of the total of the secondary particles contained in the (average particle diameter ± 100) . The particle size distribution was measured using the scattering intensity distribution.

The pigment having an average particle size and a particle size distribution is obtained by mixing a commercially available pigment with a pigment mixture mixed with a dispersant and a solvent, together with other pigments (average particle diameter usually exceeds 300 nm) For example, by pulverizing using a pulverizer such as a bead mill or a roll mill. The pigment thus obtained usually takes the form of a pigment dispersion.

The content (concentration) of the colorant contained in the coloring and radiation-sensitive composition is preferably 10% by mass or more, more preferably 15% by mass or more, and more preferably 20% by mass or more, of the total solid content of the coloring and radiation- Do. The upper limit is not particularly limited, but is preferably 45% by mass or less.

When the content of the coloring agent is within the above range, an appropriate chromaticity can be obtained when the color filter is produced by the coloring and radiation-sensitive composition. In addition, since the photo-curing can sufficiently proceed and the strength as a film can be maintained, it is possible to prevent the development latitude at the time of alkali development from being narrowed.

The coloring and radiation-sensitive composition may contain other components. Examples of the other components include a solvent, a surfactant, a UV absorber, a polymerization inhibitor, and an adhesion improver.

·solvent

The coloring and radiation-sensitive composition can be generally constituted by using a solvent. The solvent is not particularly limited so long as it satisfies the solubility of each component and the coatability of the coloring and radiation-sensitive composition, but is preferably selected in consideration of the solubility, coatability and reliability of the ultraviolet absorber and binder resin. In preparing the coloring and radiation-sensitive composition, it is preferable to include at least two kinds of solvents.

Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, , Methyl lactate, ethyl lactate, alkyloxyacetate (such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, Ethoxyacetic acid ethyl, etc.), 3-oxypropionic acid alkyl esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Ethoxypropionate, ethyl 3-ethoxypropionate), 2-oxypropionic acid alkyl esters (e.g., methyl 2-oxypropionate, 2-oxypropionate Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate) Methyl 2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy- , Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers such as diethylene glycol dimethyl ether, tetra Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, Ether, diethyl Diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol For example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like, and aromatic hydrocarbon such as xylene, for example, Can be suitably selected.

The content of the solvent in the coloring and radiation-sensitive composition is preferably such that the total solid concentration of the composition is 5 to 80% by mass, more preferably 5 to 60% by mass, Particularly preferably 50% by mass.

· Other additives

Surfactants

To the composition, various surfactants may be added in order to further improve the applicability. As the surfactant, various surfactants such as a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used. The amount of the surfactant to be added is preferably from 0.001 mass% to 2.0 mass%, more preferably from 0.005 mass% to 1.0 mass%, based on the total mass of the composition.

Polymerization inhibitor

It is preferable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the specific monomer during or during the preparation of the composition. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, o-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'- Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine cerium salt . Further, the radiation sensitive composition may contain a notarizing agent for the purpose of further improving the sensitivity to the actinic radiation of the sensitizing dye or initiator, or inhibiting the polymerization inhibition of the specific monomer by oxygen. In order to improve the physical properties of the cured coating, known additives such as a diluent, a plasticizer and a sensitizer may be added as needed. When the polymerization inhibitor is used, the addition amount is preferably in the range of 0.001 mass% to 0.015 mass%, more preferably 0.03 mass% to 0.09 mass%, of the total solid content in the colored photosensitive resin composition.

Adhesion improver

When the adhesion improver is used, the addition amount is preferably in the range of 0.1% by mass to 5.0% by mass, more preferably 0.2% by mass to 3.0% by mass, in the total solid content in the colored radiation sensitive resin composition.

Ultraviolet absorber

The composition may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate, benzophenone, benzotriazole, substituted acrylonitrile and triazine ultraviolet absorbers can be used. When the ultraviolet absorber is contained, the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.1% by mass or less based on the mass of the total solid content.

Preparation of color sensitive radiation-sensitive compositions

The preparation of the coloring and radiolucent composition is not particularly limited, but can be prepared by mixing, for example, essential ingredients and various additives used in combination according to purposes.

The coloring and radiation-sensitive composition is preferably filtered with a filter for the purpose of eliminating foreign matter or reducing defects. It is preferably used for filtration applications and the like, and can be used without particular limitation.

The above-mentioned "method of adjusting the turbidity to be 30 ppm or less by filtration of the filter ", in other words, is a method of producing a polymerization solution containing a dye having turbidity of 30 ppm or less by filtering a polymerization solution containing a dye. In this method, the aggregate of the pigment is removed from the polymerization solution so that the turbidity of the polymerization solution becomes 30 ppm or less.

This method has an advantage that the selection of the solvent for the dye is wide.

As the filter used for filtering the filter, it is preferable to use a filter which has been conventionally used for filtration or the like, and can be used without any particular limitation.

Examples of the material of the filter include fluororesins such as PTFE (polytetrafluoroethylene); Polyamide based resins such as nylon-6, nylon-6,6 and the like; Polyolefin resins (including high density, ultra high molecular weight) such as polyethylene and polypropylene (PP); And the like. Of these materials, polypropylene (including high-density polypropylene) is preferable.

Cured film and method for producing the same -

The cured film according to the preferred embodiment of the present invention has a high color purity, a thin layer, and a high extinction coefficient, and has a satisfactory fastness (particularly, heat resistance and light resistance). The production method of the cured film includes a step of applying the coloring and radiation-sensitive composition onto a substrate and a step of exposing the coloring and radiation-sensitive composition. Specifically, when a cured film is formed on an arbitrary substrate or substrate, a coloring and radiation-sensitive composition is applied, or a substrate or the like is immersed in a coloring and radiation-sensitive composition to form a coloring and radiation-sensitive composition layer, . In the case of forming a patterned cured film, a known printing method such as printing or offset printing may be applied on the substrate by an ink-jet recording method, but from the viewpoint of forming a high-definition pattern, A method of forming a coloring and radiation-sensitive composition layer on a substrate, exposing it to a pattern, and then developing it to remove the unexposed portion of the coloring and radiation-sensitive composition layer.

The film thickness of the cured film may be, for example, 0.5 to 1.5 占 퐉.

Color filter and manufacturing method thereof:

The manufacturing method of the color filter includes a step of applying the coloring and radiation-sensitive composition onto a substrate and a step of pattern-exposing the coloring and radiation-sensitive composition. Specifically, a step of forming a coloring and radiation-sensitive composition layer by applying the above-described coloring and radiation-sensitive composition on a support (hereinafter also referred to as a "step of forming a coloring and radiation-sensitive composition layer"), (Hereinafter, also referred to as an " exposure step ") of developing a coloring radiation-sensitive composition layer after exposure, and a step of forming a coloring pattern (Hereinafter also referred to as "development process").

Coloration Sensitization Radiation Composition Layer Formation Process

In the step of forming a coloring and radiation-sensitive composition layer, a coloring and radiation-sensitive composition is applied on a support to form a coloring and radiation-sensitive composition layer.

As a support which can be used in the present step, for example, a solid substrate (e.g., a silicon substrate) provided with an imaging element (light receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) A substrate for an imaging device can be used.

The coloring pattern may be formed on the imaging element formation surface side (front surface) of the substrate for the solid-state imaging element or on the imaging element non-formation surface side (back surface).

A light shielding film may be provided between each imaging element in the substrate for the solid-state imaging element or on the back surface of the substrate for the solid-state imaging element.

If necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or planarizing the surface of the substrate.

As a method of applying the coloring and radiation-sensitive composition onto a support, various coating methods such as slit coating, ink-jetting, spin coating, flexible coating, roll coating, screen printing and the like can be applied.

The film thickness of the coloring and radiation-sensitive composition layer is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and further preferably 0.2 to 3 μm.

Drying (prebaking) of the coloring and radiation-sensitive composition layer applied on the support can be carried out at a temperature of 50 to 140 캜 for 10 to 300 seconds in a hot plate, an oven or the like.

· Exposure process

In the exposure step, the coloring and radiation-sensitive composition layer formed in the step of forming the coloring and radiation-sensitive composition layer is subjected to pattern exposure through a mask having a predetermined mask pattern, for example, using an exposure apparatus such as a stepper. As the radiation (light) usable at the time of exposure, ultraviolet rays such as g-line and i-line are preferably used (particularly preferably i-line). Irradiation dose (exposure dose) is 30 ~ 1500mJ / cm ² are preferred, and 50 ~ 1000mJ / cm ² is more preferably, 80 ~ 500mJ / cm ² is most preferred.

· Development process

Subsequently, development such as alkali developing treatment is carried out, whereby the coloring and radiation-sensitive composition layer of the unexamined portion in the exposure step is eluted into the aqueous alkaline solution, leaving only the light-cured portion. As the developing solution, an organic alkali developing solution which does not cause damage to the imaging element, circuit, etc. on the ground (base) is preferable. The development temperature is usually 20 ° C to 30 ° C, and the development time is 20 seconds to 90 seconds, for example. In order to remove residues more, it is sometimes performed 120 seconds to 180 seconds recently. Further, in order to further improve the removability of the residue, the step of removing the developing solution every 60 seconds and supplying a new developing solution may be repeated a number of times.

· Post-baking

Subsequently, it is preferable to carry out a heat treatment (post-baking) after drying. It is preferable to form a multicolor colored pattern, and the above process can be repeated for each color in order to produce a cured film. As a result, a color filter is obtained. The post-baking is post-development heat treatment to make the curing complete. The heating temperature is preferably 240 占 폚 or lower, more preferably 220 占 폚 or lower, more preferably 200 占 폚 or lower, and particularly preferably 190 占 폚 or lower, from the viewpoint of suppressing damage to the organic photoelectric conversion portion. Although there is no particular lower limit, it is preferable to carry out the heat curing treatment at 50 캜 or higher, more preferably 100 캜 or higher, in consideration of efficient and effective treatment.

(Low oxygen low bake)

In the present invention, in post-baking under low oxygen, the lower the post-baking temperature is, the better the rectangularity of the pixel becomes. The post-baking temperature is preferably 150 占 폚 or lower, more preferably 140 占 폚 or lower, even more preferably 130 占 폚 or lower, and particularly preferably 100 占 폚 or lower. The lower limit is preferably 70 DEG C or higher.

The post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot-air circulation type drier), a high-frequency heater or the like so as to achieve the above-

In the present invention, the post-baking by heating may be changed to cure the pixels of the color filter by UV (ultraviolet) irradiation. At this time, it is preferable that the UV curing agent can be cured at a wavelength shorter than 365 nm, which is the exposure wavelength of the initiator added for the lithography process by ordinary I-line exposure.

For UV curing, it is more preferable to add a second initiator in addition to the first initiator for lithography of the color filter.

As the second initiator, it is preferable that absorption at 365 nm is small.

Here, the absorption at 365 nm is defined as Absorbance (ABS) when absorption of 0.01% by mass in acetonitrile is measured. ABS is preferably 0.10 or less, more preferably 0.07 or less, and most preferably 0.05 or less desirable.

As the UV curing agent, for example, Zibair Cure 2959 (trade name) can be mentioned. As the specific wavelength of the UV irradiation light, it is preferable to use a material which hardens at 340 nm or less. The lower limit of the wavelength is not particularly limited, but is generally 220 nm or more. The exposure dose of UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and even more preferably 800 to 3500 mJ. The UV curing process is preferably performed after the lithography process in order to more effectively perform low-temperature curing. It is preferable to use an ozone mercury lamp as the exposure light source.

In the present invention, post-baking of the above radiation sensitive composition is preferably performed in an atmosphere of a low oxygen concentration. The oxygen concentration is preferably not more than 19% (volumetric basis), more preferably not more than 15% (volumetric basis), more preferably not more than 10% (volumetric basis), more preferably not more than 7% , And particularly preferably not more than 3% (volumetric basis). There is no lower limit, but more than 10 ppm (volume basis) is practical.

The film thickness of the colored pattern (colored pixel) in the color filter is preferably 2 占 퐉 or less, and more preferably 1 占 퐉 or less. The size (pattern width) of the coloring pattern (coloring pixel) is preferably 2.5 占 퐉 or less, more preferably 2 占 퐉 or less, and particularly preferably 1.7 占 퐉 or less.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it is beyond the ordinary knowledge. Unless otherwise stated, "part" and "%" are based on mass.

Fabrication of organic photoelectric conversion part (layer)

A vapor-deposited film of quinacridone was prepared. Details were in accordance with known documents. Specifically, in accordance with Japanese Patent Application Laid-Open No. 2010-103457 [0341], amorphous ITO 30 nm was formed on a glass substrate by a sputtering method. Then, quinacridone was deposited thereon by vacuum evaporation deposition to have a thickness of 100 nm, thereby forming a layer corresponding to the photoelectric conversion layer. Amorphous ITO was deposited to a thickness of 5 nm as a top electrode by a sputtering method to obtain a transparent electrode.

Formation of inorganic protective layer

The inorganic protective layer was produced in accordance with Japanese Patent Application Laid-Open No. 2010-103457 [0341]. Specifically, an Al ₂ O ₃ layer was formed to a thickness of 30 nm on the organic photoelectric conversion portion by ALCVD as a protective layer. Further, a SiON layer was formed to a thickness of 200 nm by CVD (the thickness of the inorganic film was 230 nm). Vacuum deposition was performed at a vacuum degree of 4 x 10 &lt; ~ ⁴ &gt; The surface roughness Ra of this protective film 1 was measured by AFM (atomic force microscope) Dimension 3100 manufactured by Veeco Co. The Ra was 25 nm.

Protective layers 2 to 4 having a surface roughness Ra of not more than 2 were prepared by changing the formation conditions of the SiON layer of the second layer.

[Table A]

Formation of organic passivation layer (comparative example)

An aqueous solution in which 10 mass% of PVA (polyvinyl alcohol) was dissolved was prepared. This was coated on the organic photoelectric conversion portion (layer) with a spin coat. Thereafter, it was dried to obtain an organic protective film of 230 nm.

[Preparation of Pigment Dispersion]

The mixed liquid of the following composition was mixed and dispersed for 3 hours with a bead mill (high pressure disperser NANO-3000-10 (manufactured by Nippon Express Co., Ltd.) with a pressure reducing mechanism) using 0.3 mm diameter zirconia beads, To prepare a pigment dispersion.

(Pigment dispersion Y)

C. I. Pigment Yellow 185 18.0 parts

· Dispersant 1.8 part

· Resin 1 9.9 part

·solvent 70.3 parts

(Pigment dispersion Cy)

C. I. Pigment Blue 15: 6 7.4

Aluminum phthalocyanine 10.6 part

· Dispersant 1.8 part

· Resin 1 9.9 part

·solvent 70.3 parts

[Preparation of coloring and radiation-sensitive composition]

The following components were mixed to prepare a coloring and radiation-sensitive composition.

(Color Sensitive Radiation Composition Y)

Pigment dispersion Y 36.1 part

· Specific acrylic polymer 0.6 part

· Resin 1 4.5 parts

Polymerizable compound 1 2.0 parts

Polymerizable compound 2 6.0 parts

Polymerization initiator 1 1.2 part

·solvent 49.6 parts

[Color Sensitive Radiation Composition Cy]

Pigment dispersion Cy 27.8 parts

· Specific acrylic polymer 0.6 part

· Resin 1 6.8 part

Polymerizable compound 1 6.3 parts

Polymerizable compound 2 2.1 part

Polymerization initiator 1 1.0 part

·solvent 55.4 parts

Dispersant: (b) Polymer having no polymerizable group Manufactured by BYK BYK-2001

Resin 1: (b) Polymer having no polymerizable group

        Benzyl methacrylate / methacrylic acid copolymer

        (= 70/30 mole ratio, Mw: 30000,

                     Acid value: 110 mgKOH / g)

Specific acrylic polymer:

        (a) Acrylic polymer having a polymerizable group

        Manufactured by Daicel Chemical Industries, Ltd. Cyclomer P

Polymerizable compound 1: Dipentaerythritol hexaacrylate

                (Manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA)

Polymerizable compound 2: pentaerythritol ethylene oxide

                Modified tetraacrylate (RP-1040, trade name, manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator 1: IRGACURE-OXE01 manufactured by BASF

Solvent: Propylene glycol methyl ether acetate

Each of the coloring and radiation-sensitive compositions obtained was used to evaluate spectroscopic characteristics. The results are shown in the following table.

[Single spectral characteristics]

Each coloring and radiation-sensitive composition was spin-coated on a glass substrate so as to have a film thickness of 1.0 mu m after post-baking, dried with a hot plate at 100 DEG C for 120 seconds, (Post-baking) for 300 seconds.

[Production of color filter]

CF1 Hue

Cy was coated on the protective layer of the organic photoelectric conversion film obtained above using a spin coater so as to have a film thickness of 1.0 mu m after drying and heat treatment for 120 seconds using a hot plate at 100 DEG C Pre-baking) was performed.

Subsequently, the pattern exposure was carried out at a total of 399 patterns of patterns arranged in a matrix of 21 rows x 19 columns using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.). In this case, the 21 rows in the matrix are conditions in which the minimum exposure amount is 500 J / m ² and the exposure amount is increased every 500 rows from 500 J / m ² to 500 J / m ² , And the focal length was changed at intervals of 0.1 mu m centering on the optimum distance (Foucus 0.0 mu m). That is, a photomask in which a square pixel pattern with a square of 3.0 탆 is arranged within a range of 4 mm x 3 mm is used as a condition that the center line is an optimum focal length distance and the focal length is changed for each column.

Thereafter, the substrate on which the exposed coating film was formed was placed on a horizontal rotation table of a spin shower developing machine (DW-30 type, manufactured by KEMITRONICS Co., Ltd.), and CD-2060 (manufactured by Fuji Film Electronics Materials Co., Paddle development was performed at 23 DEG C for 60 seconds to form a colored pattern on the substrate.

The substrate on which the colored pattern was formed was rinsed with pure water, and then spray-dried.

Further, a heat treatment (post-baking) was performed for 300 seconds using a hot plate at the temperature shown in Table 1 to obtain a substrate having colored pixels corresponding to the coloring agent. The oxygen concentration in the atmosphere at this time was as shown in Table 1.

In Test 108, 1.2 parts of Irgacure 2959 (ABS 0.03 at 365 nm in 0.01% by weight of acetonitrile) was added to the coloring and radiation-sensitive composition Y in addition. The postbake was irradiated by an ozone gas mercury lamp at 300 mW for 10 seconds by using an ultraviolet irradiation device UMA-802-HC552 manufactured by Ushio DENKI, not by heating. A coloring pattern was formed in the same manner as above except that the evaluation test was carried out.

CF2 Hue

Y was further subjected to spray drying under the same conditions as in the above Cy. The spectral change at this time was performed in the same manner as the color filter 1.

(Assessment Methods)

A coating film (protective film) in a single layer together with an organic photoelectric conversion film and a color filter was prepared and used as a reference. And the sequence was given a size based on the spectral change of the maximum transmittance (between 450 nm and 700 nm) when laminated as shown in FIG. This measurement was carried out at room temperature (25 占 폚).

[Table B]

[Table 1]

Temperature: Process temperature

Oxygen concentration: process oxygen concentration

Spectroscopic change: Evaluation result of spectroscopic change

Conventional lithography: according to the process employed in the production of CF1

From the above results, it can be seen that a good CMOS image sensor can be manufactured by the manufacturing method of the present invention. In particular, the quality of the organic photoelectric conversion film is maintained, and a high-quality image sensor can be obtained.

(Additional evaluation)

(Change of CF2 to single layer spectroscopy)

CF2 (YELLOW color filter) was coated on the glass substrate in a single layer in the same manner as described in the above < CF2 color tones >, and the maximum spectral transmittance was measured (Tmax). Next, the protective film shown in the following table was applied, a color filter of Cy was formed on the photoelectric conversion film, a process process was performed, and a color filter of CF2 was formed.

The spectral transmittance after formation is measured, and the maximum spectral transmittance is Ty. Ty and Tmax were compared for each sample, and rank classification by the difference was performed in the following table to evaluate the change of CF2 with respect to single layer spectroscopy. Test 201 is an example in which the protective layer is a single layer of Al ₂ O ₃ .

[Table C]

(Rectangularity of CF1)

CF1 is ideally a square pattern of 3.0 microns. The length of one side of CF1 after forming CF2 was measured, and it was evaluated whether or not a square pattern deviated by several percent at 3.0 mu m was obtained, and rank classification was performed.

[Table D]

[Table 2]

While the present invention has been described in conjunction with the embodiments thereof, it is to be understood that the invention is not to be limited to any details of the description thereof except as specifically set forth and that the invention is broadly construed and interpreted without departing from the spirit and scope of the invention as set forth in the appended claims. .

The present application claims priority based on Japanese Patent Application No. 2013-149797, filed on July 18, 2013, which is incorporated herein by reference in its entirety.

1 Color Filter Pixel (Y)
2 color filter pixel (Cy)
3 protective layer
4 inorganic photoelectric conversion unit (R)
5 inorganic photoelectric conversion portion (B)
6 Organic photoelectric conversion unit (G)
10 CMOS image sensor

Claims (14)

A manufacturing method of an image sensor having pixels of a color filter, an inorganic protective layer, an organic photoelectric conversion portion, and an inorganic photoelectric conversion portion, the method comprising: providing the inorganic protective layer on the organic photoelectric conversion portion. The method according to claim 1,
Further comprising the step of providing a pixel of the color filter on the inorganic protective layer. The method of claim 2,
Wherein the temperature at the time of forming the pixels of the color filter is 200 占 폚 or less. The method of claim 2,
Wherein the oxygen concentration of the atmosphere at the time of forming the pixel of the color filter is set to 19% or less. The method according to any one of claims 2 to 4,
And the pixels of the color filter are cured by UV irradiation. The method according to any one of claims 1 to 5,
Wherein the inorganic protective layer comprises two or more layers. The method of claim 6,
The lower layer and the upper side containing at least one said inorganic protective layer is selected from Al ₂ O _3, SiO _2, and TiO _2, at least one selected from SiON, SiO _2, Al ₂ O _3, and SiN species &Lt; / RTI &gt; The method according to any one of claims 1 to 7,
Wherein the inorganic protective layer has a surface roughness Ra of 1 nm or more and 100 nm or less. An image sensor comprising pixels of a color filter, an inorganic protective layer, an organic photoelectric conversion portion, and an inorganic photoelectric conversion portion, wherein the inorganic protective layer is provided on the organic photoelectric conversion portion. The method of claim 9,
And the pixel of the color filter is made of a UV curable resin. The method according to claim 9 or 10,
Wherein the inorganic protective layer comprises two or more layers. The method of claim 11,
The lower layer and the upper side containing at least one said inorganic protective layer is selected from Al ₂ O _3, SiO _2, and TiO _2, at least one selected from SiON, SiO _2, Al ₂ O _3, and SiN species And an upper layer containing the first layer and the second layer. The method according to any one of claims 9 to 12,
Wherein the inorganic protective layer has a surface roughness Ra of 1 nm or more and 100 nm or less. A laminate comprising pixels of a color filter, an inorganic protective layer, an organic photoelectric conversion portion, and an image sensor having an inorganic photoelectric conversion portion, wherein the inorganic protective layer is provided on the organic photoelectric conversion portion.

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