JP2015038979A - Image sensor and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image sensor and a method for manufacturing the same, capable of suitably suppressing damage to an organic photoelectric conversion film and obtaining excellent pixels (hardened part) when performing heating treatment such as post-bake of color filter pixels.SOLUTION: A method for manufacturing an image sensor 10 comprising color filter pixels 1 and 2, an inorganic protective layer 3, an organic photoelectric conversion unit 6, and inorganic photoelectric conversion units 4 and 5 includes a step of providing the inorganic protective layer on the organic photoelectric conversion unit.

Description

  The present invention relates to an image sensor and a manufacturing method thereof.

  Conventional color image sensors are generally spatially separated by forming a color filter in which pixels of the three colors red (R), green (G), and blue (B) are two-dimensionally arranged. It is. On the other hand, with the downsizing of image sensors and the increase in the number of pixels, the cell size of one pixel has recently been reduced to 2.0 μm square or less. Accordingly, the area and volume per pixel are reduced. As a result, the saturation signal amount and sensitivity are reduced, and the image quality is lowered. There has been a demand for a technique for maintaining spatial luminance and chroma resolution while maintaining a certain amount of sensitivity and saturation signal amount without reducing the cell size.

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

JP 2008-258474 A

However, since the organic photoelectric conversion film is an organic material, it is vulnerable to temperature and humidity. On the other hand, it is inevitable that the organic photoelectric conversion film is heated by baking at the time of molding, such as when a pixel of a color filter is placed on the upper part. If the baking temperature is simply lowered, curing will be insufficient, and when the second color pixel is applied, lithographically and developed, part of the first color pixel will melt or part of the second color pixel will It remains in the pixel of the first color, and the spectrum of the pixel of the first color also deteriorates.
Accordingly, the present invention provides an image sensor capable of suitably suppressing damage to the organic photoelectric conversion film and obtaining a good pixel (cured portion) in the heat treatment such as post-baking of the pixel of the color filter, and the production thereof. The purpose is to provide a method.

The above problem has been solved by the following means.
[1] A method for manufacturing an image sensor having a pixel of a color filter, an inorganic protective layer, an organic photoelectric conversion unit, and an inorganic photoelectric conversion unit, the image sensor comprising a step of providing the inorganic protective layer on the organic photoelectric conversion unit Sensor manufacturing method.
[2] The method for producing an image sensor according to [1], further comprising a step of providing pixels of the color filter on the inorganic protective layer.
[3] The method for manufacturing an image sensor according to [2], wherein the temperature at the time of creating the pixel of the color filter is 200 ° C. or lower.
[4] The method for manufacturing an image sensor according to [2], wherein the oxygen concentration of the atmosphere at the time of creating the pixel of the color filter is 19% or less.
[5] The method for producing 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 for producing an image sensor according to any one of [1] to [5], wherein the inorganic protective layer is composed of two or more layers.
[7] and the lower the inorganic protective layer contains at least one selected from _Al 2 _O 3, SiO _2, and TiO _2, on its upper side, selected _{SiON, SiO 2, Al 2 O} 3, and from SiN The method for producing an image sensor according to [6], including an upper layer containing at least one kind.
[8] The method for producing an image sensor according to any one of [1] to [7], wherein the inorganic protective layer has a surface roughness Ra of 1 nm to 100 nm.
[9] An image sensor having a color filter pixel, an inorganic protective layer, an organic photoelectric conversion unit, and an inorganic photoelectric conversion unit, wherein the inorganic protective layer is provided on the organic photoelectric conversion unit.
[10] The image sensor according to [9], wherein the pixels of the color filter are 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] and a lower layer containing at least one inorganic protective layer is selected from _Al 2 _O 3, SiO _2, and TiO _2, on its upper side, selected _{SiON, SiO 2, Al 2 O} 3, and from SiN The image sensor according to [11], including an upper layer containing at least one kind.
[13] The image sensor according to any one of [9] to [12], wherein the inorganic protective layer has a surface roughness Ra of 1 nm to 100 nm.
[14] A laminate comprising an image sensor having a color filter pixel, 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. .
In the present invention, “provided on” means to be arranged on the upper side or lower side of the target portion, and means to be arranged on the upper side or the lower side through another member or substance. However, “providing” does not mean that the order of formation is limited, and the arrangement portion may be formed on the target portion as a base, or the arrangement portion may be formed to form the target portion. . Specifically, it means that the organic photoelectric conversion part 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, it is possible to suitably suppress the damage of the organic photoelectric conversion film and obtain a good pixel (cured portion) during the heat treatment such as post-baking of the color filter. .

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

  An embodiment of an image sensor (solid-state imaging device) of the present invention will be described with reference to FIG. In FIG. 1, a part of the entire surface opening type CMOS image sensor 10 is shown. As shown in FIG. 1, in the image sensor 10, an organic photoelectric conversion film 6 is formed on the inorganic photoelectric conversion units 4 and 5, and further, the pixel 1 of the color filter via the protective layer 3 (upper layer 31 and lower layer 32). 2 is formed. The color filter pixels 1 and 2 are formed so as to correspond to the photoelectric conversion units 4 and 5. For example, in order to extract blue and red, a cyan color filter pixel 2 and a yellow color filter pixel 1 are used. It consists of things arranged in a checkered pattern. A condensing lens for condensing incident light on each photoelectric conversion unit may be formed on each color filter pixel. In this embodiment, the inorganic photoelectric conversion unit 4 is a red (R) light receiving portion, and the inorganic photoelectric conversion unit 5 is a blue (B) light receiving portion.

  The active layer formed of a semiconductor substrate includes, for example, a plurality of transistor groups such as inorganic photoelectric conversion units (for example, photodiodes) 4 and 5 that convert incident light into electric signals, transfer transistors, amplification transistors, reset transistors, and the like. The pixel portion is formed. For example, a silicon substrate is used as the semiconductor substrate. Further, a signal processing unit for processing signal charges read from each photoelectric conversion unit is formed. In FIG. 1, the members below the inorganic photoelectric conversion units 4 and 5 are not illustrated on the assumption that there are various embodiments.

  A wiring layer may be formed on the surface side of the semiconductor substrate on which the photoelectric conversion portion is formed. The wiring layer is made of a wiring and an insulating film covering the wiring. A support substrate is formed on the wiring layer. The support substrate is made of, for example, a silicon substrate.

  The image sensor 10 takes out a signal of green from the organic photoelectric conversion film 6 and takes out blue and red in combination with pixels of cyan and yellow color filters as described above. The color schemes and combinations of these colors are not limited to the above example, and a desired combination of B (blue), G (green), R (red), Cy (cyan), M (magenta), and Y (yellow) It can be an image sensor of a form.

Although the image sensor having the structure shown in FIG. 1 has been described above, the present invention is not construed as being limited thereto. As a modification thereof, for example, the organic photoelectric conversion film may be disposed above (light incident side) above the color filter (color filter pixel array layer). In this case, the protective layer may be interposed between the organic photoelectric conversion film and the color filter, or may be disposed on the upper side (light incident side) of the organic photoelectric conversion film. In the present invention, the protective layer and the organic photoelectric conversion film are preferably arranged in direct contact with each other. Here, “directly contacting” means not only the form in which both layers are in contact with each other without any substance, but also the inclusion of a substance or a thin layer within the range where the effects of the present invention are exhibited.
In this specification, the upper and lower sides of the image sensor are referred to as “upper” on the light incident side (upper side of the drawing) and “lower” on the opposite side (lower side of the drawing).

[Protective layer]
The protective layer 3 preferably includes an inorganic layer made of an inorganic material formed by the ALCVD method. The ALCVD method is an atomic layer CVD method, can form a dense inorganic layer, and can be an effective protective layer for the organic photoelectric conversion layer 6. The ALCVD method is also known as the ALE method or ALD method. The inorganic layer formed by the ALCVD method is preferably made of Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , MgO, HfO ₂ , Ta ₂ O ₅ , more preferably made of Al ₂ O ₃ , SiO ₂ , Most preferably, it consists of Al ₂ O ₃ .
The thickness of the protective layer is preferably 50 nm or more, and more preferably 150 nm or more, from the viewpoint of suitably obtaining the effects of the present invention. As an upper limit, it is preferable that it is 500 nm or less, and it is more preferable that it is 300 nm or less.

The protective layer 3 is preferably composed of two or more layers rather than a single layer. By making the protective layer into two or more layers, moisture can be prevented from entering the photoelectric conversion film, and alteration of the photoelectric conversion film can be prevented in the post-baking process when a color filter or the like is disposed in a subsequent process. The above effect can be further increased if the protective layer has three or more layers, but two layers are preferable from the viewpoint of productivity.
When the protective layer 3 has two or more layers, it is preferable to use different materials for the first layer and the second and subsequent layers. Specifically, it is preferable to select a layer of Al ₂ O ₃ , SiO ₂ , TiO ₂ or the like for the first layer (lower layer 32). Of these, an Al ₂ O ₃ layer is particularly preferable. The second layer (upper layer 31) and _later, SiON, it is preferable to select a layer of _{SiO 2, Al 2 O 3,} SiN or the like. Among these, it is preferable to use SiON. It should be noted that other layers may be interposed between the first layer (lower layer) and the second layer (upper layer) within the range where the effects of the present invention are exhibited, and there are other layers on the upper or lower side. May be.
When the protective layer has 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 of the second and subsequent layers is preferably 50 to 400 nm, more preferably 100 to 300 nm, and most preferably 150 to 250 nm.

  Moreover, about surface roughness Ra after forming the protective layer 3, 1-100 nm is preferable, 1-80 nm is more preferable, 1-60 nm is more preferable, 1-40 nm is further more preferable, 1-20 nm is further more preferable. 1 to 15 nm is more preferable, and 1 to 10 nm is particularly preferable. By setting the surface roughness of the protective layer within this range, the transmittance of the color filter for the second color when the color filter is formed in the subsequent process is increased. The surface roughness Ra of the inorganic protective layer can be measured with an AFM (Atomic Force Microscope) Dimension 3100 manufactured by Veeco. Ra of this application is measured with the said apparatus. Note that the surface roughness Ra of the inorganic protective layer conforms to 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 (outermost layer). As the ALCVD method, for example, reference can be made to [0078] to [0081] of JP-A-2011-71483. That is, the thin film is formed by alternately repeating adsorption / reaction of the thin film material on the substrate surface and decomposition of unreacted groups contained therein. When the SiON layer or the like is formed 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 part]
When the organic photoelectric conversion unit absorbs green light, for example, the following inorganic photoelectric conversion unit can easily separate blue light and red light. The organic photoelectric conversion part preferably has a maximum absorption wavelength in the range of 510 to 560 nm. More preferably, it exists in the range of 520-550 nm. Here, the maximum absorption wavelength means an absorption wavelength having the highest light absorptance. 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 absorptance half width is 50 nm or more and 100 nm or less. More preferably, it is 60 nm or more and 90 nm or less. Here, the absorptance half-value width means the width of the absorption wavelength at the absorptance half of the maximum absorptance.

  The organic layer as an organic photoelectric conversion film is a part that absorbs electromagnetic waves, a photoelectric conversion part, an electron transport part, a hole transport part, an electron blocking part, a hole blocking part, a crystallization prevention part, an electrode, an interlayer contact improvement part, etc. Formed from stacking or mixing. The organic layer preferably contains an organic p-type compound or an organic n-type compound.

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

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

  Any p-type organic dye or n-type organic dye may be used, but preferably a cyanine dye, a styryl dye, a hemicyanine dye, a merocyanine dye (including zero methine merocyanine (simple merocyanine)), Trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol dye, hemioxonol dye, squalium dye, croconium dye, azamethine dye, coumarin dye, arylidene dye, anthraquinone dye, Triphenylmethane dye, azo dye, azomethine dye, spiro compound, metallocene dye, fluorenone dye, fulgide dye, perylene dye, phenazine dye, phenothiazine dye, quinone dye, in Pigment dye, diphenylmethane dye, polyene dye, acridine dye, acridinone dye, diphenylamine dye, quinacridone dye, quinophthalone dye, phenoxazine dye, phthaloperylene dye, porphyrin dye, chlorophyll dye, phthalocyanine dye, metal complex dye, condensed aromatic carbocyclic system And dyes (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives).

  Next, the metal complex compound will be described. The metal complex compound is preferably a metal complex having a ligand having at least one nitrogen atom, oxygen atom or sulfur atom coordinated to the metal. The metal ion in the metal complex is not particularly limited, but is preferably beryllium ion, magnesium ion, aluminum ion, gallium ion, zinc ion, indium ion, or tin ion, more preferably beryllium ion, aluminum ion, gallium ion, Or it is a zinc ion, More preferably, it is an aluminum ion or a zinc ion. As the ligand contained in the metal complex, there are various known ligands. Yersin's “Photochemistry and Photophysics of Coordination Compounds” Springer-Verlag, published in 1987, Yamamoto Akio, “Organic Metal Chemistry-Fundamentals and Applications”, listed in Soukabo, 1982, etc. .

  The above ligand is preferably a nitrogen-containing heterocyclic ligand (preferably having 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, and is a monodentate ligand. Or a bidentate or higher ligand, preferably a bidentate ligand such as a pyridine ligand, a bipyridyl ligand, a quinolinol ligand, a hydroxyphenylazole ligand (hydroxyphenyl) Benzimidazole, hydroxyphenylbenzoxazole ligand, hydroxyphenylimidazole ligand)), alkoxy ligand (preferably 1-30 carbon atoms, more preferably 1-20 carbon atoms, particularly preferably carbon 1-10, for example, methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc.), aryloxy ligands Preferably it has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy, 2,4,6-trimethylphenyl Oxy, 4-biphenyloxy, etc.), heteroaryloxy ligands (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridyl. Oxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.), alkylthio ligands (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio, Ethylthio, etc.), arylthio ligands (preferably having 6 to 30 carbon atoms, more preferred) Has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), a heterocyclic substituted thio ligand (preferably 1 to 30 carbon atoms, more preferably 1 to carbon atoms). 20, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like, or siloxy ligand (preferably Has 1 to 30 carbon atoms, more preferably 3 to 25 carbon atoms, particularly preferably 6 to 20 carbon atoms, and examples thereof include a triphenylsiloxy group, a triethoxysiloxy group, and a triisopropylsiloxy group. More preferably a nitrogen-containing heterocyclic ligand, an aryloxy ligand, a heteroaryloxy group, or a siloxy ligand, Preferably, a nitrogen-containing heterocyclic ligand, an aryloxy ligand, or a siloxy ligand is used.

  In the present embodiment, a p-type semiconductor layer and an n-type semiconductor layer are provided between a pair of electrodes, and at least one of the p-type semiconductor and the n-type semiconductor is an organic semiconductor, and these semiconductors It is preferable that a photoelectric conversion film (photosensitive layer) having a bulk heterojunction structure layer including the p-type semiconductor and the n-type semiconductor as an intermediate layer is included between the layers. In such a case, in the photoelectric conversion film, by incorporating a bulk heterojunction structure in the organic layer, the disadvantage that the carrier diffusion length of the organic layer is short can be compensated, and the photoelectric conversion efficiency can be improved. The bulk heterojunction structure is described in detail in Japanese Patent Application No. 2004-080639.

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

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

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

In terms of light absorption, the thickness of the organic dye layer is preferably as large as possible. However, considering the ratio that does not contribute to charge separation, the film thickness of the organic dye layer in the present embodiment is preferably 30 nm to 300 nm, and more preferably 50 nm. It is not less than 250 nm and particularly preferably not less than 80 nm and not more than 200 nm.
The layer containing these organic compounds is formed by a dry film formation method or a wet film formation method. Specific examples of the dry film forming method include a vacuum vapor deposition method, a sputtering method, an ion plating method, a physical vapor deposition method such as an MBE method, or a CVD method such as plasma polymerization. As the wet film forming method, a casting method, a spin coating method, a dipping method, an LB method, or the like is used.

In the case of using a polymer compound as at least one of the p-type semiconductor (compound) and the n-type semiconductor (compound), it is preferable to form the film by a wet film forming method that is easy to create. When a dry film formation method such as vapor deposition is used, it is difficult to use a polymer because it may be decomposed, and an oligomer thereof can be preferably used instead. On the other hand, in the present embodiment, when a low molecule is used, a dry film forming method is preferably used, and a vacuum deposition method is particularly preferably used. The basic parameters of the vacuum deposition method are the heating method of the compound such as resistance heating deposition method and electron beam heating deposition method, the shape of the deposition source such as crucible and boat, vacuum degree, deposition temperature, substrate temperature, deposition rate, etc. is there. In order to enable uniform deposition, it is preferable to perform deposition by rotating the substrate. The degree of vacuum is preferably higher, 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 steps during the vapor deposition are performed in a vacuum, and basically the compound is not directly in contact with oxygen and moisture in the outside air. The above-described conditions for vacuum deposition need to be strictly controlled because they affect the crystallinity, amorphousness, density, density, etc. of the organic film. It is preferable to use PI or PID control of the deposition rate using a film thickness monitor such as a quartz crystal resonator or an interferometer. When two or more kinds of compounds are vapor-deposited simultaneously, a co-evaporation method, a flash vapor deposition method, or the like can be preferably used.

[Inorganic photoelectric conversion part]
The inorganic photoelectric conversion unit is preferably one that performs photoelectric conversion of a specific color set in relation to the organic photoelectric conversion unit. In particular, it is preferable that the inorganic photoelectric conversion part is made of a silicon semiconductor, and at least blue light and red light are separated in the depth direction of the silicon semiconductor for photoelectric conversion. For example, the inorganic photoelectric conversion unit is a silicon p-type substrate, and has an n-type well, a p-type well, and an n-type well. There is one that performs photoelectric conversion by each pn junction, collects at least a blue light signal in the n-type well, and collects at least a red light signal in the n-type well. The color discrimination in the depth direction using the difference in absorption coefficient of silicon is described in the above-mentioned known examples. The signal can be read out by signal wiring. The inorganic photoelectric conversion part is preferably a silicon semiconductor having a CMOS structure. A horizontal shift register, a vertical shift register, a noise suppression circuit, and the like related to signal reading are omitted in FIG.

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

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

  The inorganic layer will be described in more detail. As a preferable configuration of the inorganic layer, a photoconductive type, a pn junction type, a Schottky junction type, a PIN junction type, an MSM (metal-semiconductor-metal) type light receiving element or a phototransistor type light receiving element can be given. In the present embodiment, a plurality of first conductivity type regions and second conductivity type regions having a conductivity type opposite to the first conductivity type are alternately stacked in a single semiconductor substrate. It is preferable to use a light receiving element in which each joint surface of the conductive type region and the second conductive type region is formed at a depth suitable for mainly photoelectrically converting light in a plurality of different wavelength bands. As the single semiconductor substrate, single crystal silicon is preferable, and color separation can be performed using absorption wavelength characteristics depending on the depth direction of the silicon substrate.

  As the inorganic semiconductor, an InGaN-based, InAlN-based, InAlP-based, or InGaAlP-based inorganic semiconductor can also be used. The nGaN-based inorganic semiconductor is adjusted so as to have a maximum absorption value in the blue wavelength range by appropriately changing the composition of In. That is, the composition is InxGa1-xN (0 ≦ X <1). Such a compound semiconductor is manufactured using a metal organic chemical vapor deposition method (MOCVD method). A nitride semiconductor InAlN system using Al, which is the same group 13 raw material as Ga, can also be used as a short wavelength light receiving section in the same manner as the InGaN system. InAlP or InGaAlP lattice-matched to the GaAs substrate can also be used.

  The inorganic semiconductor may have a buried structure. The embedded structure means a structure in which both ends of the short wavelength light receiving part are covered with a semiconductor different from the short wavelength light receiving part. The semiconductor covering both ends is preferably a semiconductor having a band gap wavelength shorter than or equivalent to the band gap wavelength of the short wavelength light receiving part. The organic layer and the inorganic layer may be combined in any form. In addition, it is preferable to provide an insulating layer between the organic layer and the inorganic layer in order to electrically insulate. The junction is preferably npn or pnpn from the light incident side. In particular, by providing a p layer on the surface and increasing the surface potential, holes generated in the vicinity of the surface and dark current can be trapped and dark current can be reduced. preferable.

[Color filter]
Each pixel of the color filter according to a preferred embodiment of the present invention is preferably formed by curing the following colored radiation-sensitive composition. The colored radiation-sensitive composition comprises (a) an acrylic polymer having a polymerizable group, (b) a polymer having no polymerizable group, (c) an ethylenically unsaturated double bond (preferably 3 or more). A monomer having (d) a polymerization initiator, and (e) a colorant.

-Specific acrylic polymer having a polymerizable group Examples of the polymerizable group possessed by the specific acrylic polymer include an ethylenically unsaturated bond group, preferably a (meth) acryloyl group and a vinyl group, and a (meth) acryloyl group. Further preferred. The acrylic polymer is preferably a vinyl polymer having a repeating unit derived from one or more of (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylamide. In this specification, the term “(meth) acrylic” or “(meth) acryloyl” means that acrylic or acryloyl and methacrylic or methacryloyl are included.

  The ratio of the polymerizable group contained in the specific acrylic polymer is preferably 5 to 50, and more preferably 10 to 40. By setting it as such a range, coexistence of hardening, property, and developability is achieved more effectively. Here, the ratio of a polymerizable group means a molar copolymerization ratio. As another structural unit, the structural unit containing an acid group is illustrated. Examples of the acid group include a carboxyl group, a phosphate 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, and more preferably 20 to 150 mgKOH / g. By setting it as such a range, it becomes possible to improve the solubility of the unexposed part at the time of pattern formation. The acid value refers to a value obtained by neutralization titration with a potassium hydroxide solution.

  Specific acrylic polymers include, for example, carboxyl group-containing resins such as glycidyl group-containing unsaturated compounds such as glycidyl (meth) acrylate and allyl glycidyl ether, and unsaturated alcohols such as allyl alcohol, 2-hydroxy acrylate, and 2-hydroxy methacrylate. Resin reacted, carboxyl group-containing resin having hydroxyl group, free isocyanate group-containing unsaturated compound, resin reacted with unsaturated acid anhydride, addition reaction product of epoxy resin and unsaturated carboxylic acid polybasic acid anhydride , A resin obtained by reacting a hydroxyl group-containing polyfunctional monomer with an addition reaction product of a conjugated diene copolymer and an unsaturated dicarboxylic acid anhydride, and a base treatment to cause an elimination reaction to give an unsaturated group By synthesizing a resin having a functional group and applying a base treatment to the resin Resins to produce a saturated group can be cited as typical resins.

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

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. R ^{1 to} R ²⁰ each independently represents a hydrogen atom or a monovalent organic group.

G ¹ , G ² , and G ³ represent a divalent organic group, 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, and combinations thereof A group consisting of a linear 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 and a combination thereof, is more preferable. A group consisting of a linear or branched alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, and a combination thereof is particularly preferable. These groups may further have a substituent, and the substituent is preferably a hydroxyl group. More preferable embodiments of G ¹ , G ² , and G ³ are — (CH ₂ ) _n — (cycloalkylene group that may have a substituent) — (CH ₂ ) _n —, and each n is 0. And an cycloalkylene group is a 5-membered ring or a 6-membered ring (more preferably a 6-membered ring).

R ^{1 to} R ⁴ , R ^{7 to} R ¹⁰ , and R ^{13 to} R ¹⁸ each represent a hydrogen atom or a monovalent organic group, and 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 aryl group. Examples include an oxy group, an alkylsulfonyl group, and an arylsulfonyl group, preferably a hydrogen atom, an alkoxycarbonyl group, an alkyl group, and an aryl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

  The synthesis of the polymer compound having the specific structural unit can be performed based on the synthesis method described in paragraph Nos. 0027 to 0057 of JP-A No. 2003-262958. Of these, the synthesis method 1) in the publication is preferred. Specific examples of the polymer compound having the specific structural unit include the following compounds. It goes without saying that the present invention is not limited to these compounds.

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 it within this range, when the cured colored layer is cured, film shrinkage hardly occurs, and a colored layer having excellent pattern formability and less surface roughness can be formed. The specific acrylic polymer (a) is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass with respect to 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, unless otherwise specified, the molecular weight of the polymer is the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC). As a measuring method, a column to which three TOSOH TSKgel Super AWM-Hs are connected is used, and 10 mM LiBr / N-methylpyrrolidone is used as an eluent, or TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel HSK4000 TOSGu SSKgel HSK4000. Using a connected column, measurement is performed by a method using tetrahydrofuran as an eluent. The flow rate of the eluent was 1.0 ml / min, and the column temperature was 40 ° C. However, an appropriate column and eluent may be selected and used depending on the polymer type.

・ Polymer having no polymerizable group Examples of the polymer having no polymerizable group include alkali-soluble resins, dispersants, and dispersion resins other than alkali-soluble resins used as dispersion resins and additional resins. The In addition, even if it is alkali-soluble resin, a specific acrylic polymer corresponds to a specific acrylic polymer (a). The polymer (b) preferably includes an acrylic polymer having no polymerizable group, and a preferable example thereof is an alkali-soluble resin.

Alkali-soluble resin The alkali-soluble resin is a linear organic high-molecular polymer having at least one alkali-soluble polymer in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group that promotes. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred. Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, but are soluble in a solvent and can be developed with a weak alkaline aqueous solution. Of these, (meth) acrylic acid is particularly preferred. These acid groups may be used alone or in combination of two or more.
Examples of the monomer capable of imparting an acid group after the polymerization include, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types. 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 sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component.
In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and experimental conditions are determined. It can also be done.

  As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolak resins, etc., acid cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group. Can be mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.

  As the alkali-soluble resin, in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer or a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl methacrylate is suitable. . Other monomers in this case include 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl described in JP-A-7-140654. 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 / A methacrylic acid copolymer etc. are mentioned.

The alkali-soluble resin is also preferably the following.
The alkali-soluble resin of the present embodiment is a linear organic high-molecular polymer and has at least one alkali-soluble polymer in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group that promotes. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. The group is soluble in an organic solvent and developed with a weak alkaline aqueous solution. Possible are preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.
Examples of the monomer capable of imparting an acid group after the polymerization include, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types. 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 sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component. In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolak resins, etc., acid cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group. Can be mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (iso) pentyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) ) Acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and other vinyl compounds include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile , Vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like, as N-substituted maleimide monomers described in JP-A-10-300922, jN-phenylmaleimide, N-cyclohexyl A maleimide etc. can be mentioned.
The other monomer copolymerizable with (meth) acrylic acid is preferably a repeating unit represented by the following formula (A1).

In the above formula (A1), 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, n Represents an integer of 1 to 15. The repeating unit represented by the above formula (A1) has good adsorption and / or orientation on the pigment surface due to the effect of π electrons of the benzene ring present in the side chain. In particular, when this side chain portion has an ethylene oxide or propylene oxide structure of paracumylphenol, its steric effect is added, and a better adsorption and / or orientation plane can be formed on the pigment. Therefore, it is more effective and preferable. 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. In addition, when R ³ is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. This is because when R ³ is an alkyl group having 1 to 10 carbon atoms, this alkyl group becomes an obstacle and suppresses the approach between resins to promote adsorption and / or orientation to the pigment. This is because the steric hindrance effect of the alkyl group is increased and the adsorption and / or orientation of the benzene ring on the pigment surface may be hindered. This phenomenon becomes more prominent as the chain length of the alkyl group of R ³ becomes longer. When the carbon number exceeds 20, the adsorption and / or orientation of the benzene ring is extremely lowered. Therefore, the alkyl group represented by R ³ has a range of 1 to 20 carbon atoms. The alkyl group represented by R ³ is preferably an unsubstituted alkyl group or an alkyl group substituted with a phenyl group.

R ² in formula (A1) is preferably an alkylene group having 2 carbon atoms from the viewpoint of developability.
Furthermore, 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 by using an ethylenically unsaturated monomer represented by the following formula (A2).

式中、Ｒ^１、Ｒ^２、Ｒ^３、及びｎは、上記式（Ａ１）におけるＲ^１、Ｒ^２、Ｒ^３、及びｎと同義であり、好ましい例も同様である。

^{Wherein, R 1, R 2, R} 3, and ^{n, R 1, R 2, R} 3 in the formula (A1), and have the same meanings as n, and preferred examples thereof are also the same.

The acid value of the alkali-soluble resin is preferably 30 to 200 mgKOH / g, more preferably 50 to 150 mgKOH / g, still more preferably 70 to 120 mgKOH / g. By setting it as such a range, the image development residue of an unexposed part can be reduced effectively.
Further, 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.
As content of alkali-soluble resin, 10-50 mass% is preferable with respect to the total solid of the said composition, More preferably, it is 15-40 mass%, Most preferably, it is 20-35 mass%.

Dispersants Dispersants include polymer dispersants (for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) Acrylic copolymer, naphthalenesulfonic acid formalin condensate), polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, 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 from the structure thereof.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred 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 that can be used in the present embodiment include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group)”, 130 (manufactured by BYK Chemie). Polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), BYK2001 ”,“ EFKA4047, manufactured by EFKA, 4050, 4010, 4165 (polyurethane), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester) , 6745 (Phthalocyanine invitation Body), 6750 (azo pigment derivative) "," Ajispur PB821, PB822 "manufactured by Ajinomoto Fan Techno Co.," Floren TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co.," Polyflow No. 50E, No. 300 (acrylic type). Copolymer) ”, manufactured by Enomoto Kasei Co., Ltd.“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA -725 "," Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L-18 (polymeric polycondensate) " Carboxylic acid) ”,“ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) Tel) "," Acetamine 86 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (functional part at the end part) 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical Co., Ltd., etc. Is mentioned.

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

  As content of a dispersing agent, it is preferable that it is 1-100 mass parts with respect to 1 part of coloring agents (pigment), 3-100 mass parts is more preferable, and 5-80 mass parts is more preferable. Moreover, it is preferable that it is 10-30 mass% with respect to the total solid of a composition.

-Monomers having ethylenically unsaturated double bonds Monomers having ethylenically unsaturated double bonds (hereinafter sometimes referred to as "specific monomers") can be used without any particular limitation and are polyfunctional monomers. It is preferable. A specific monomer may be used individually by 1 type, and may use 2 or more types together. The specific monomer is preferably a (meth) acrylate monomer. As these specific compounds, the compounds described in JP-A 2009-288705, paragraphs 0095 to 0108 can also be suitably used in this embodiment.

  In the present embodiment, radical 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.

式中、ｎは、それぞれ、０〜１４であり、ｍは、それぞれ、１〜８である。一分子内に複数存在するＲ、ＴおよびＺは、それぞれ、同一であっても、異なっていてもよい。Ｔがオキシアルキレン基の場合には、炭素原子側の末端がＲに結合する。Ｒのうち少なくとも３つは、重合性基である。

In the formula, n is 0 to 14 respectively, and m is 1 to 8 respectively. A 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 are polymerizable groups.

n is preferably 0 to 5, and more preferably 1 to 3.
m is preferably 1 to 5, and more preferably 1 to 3.
Specific examples of the radically polymerizable monomer represented by the above formulas (MO-1) to (MO-6) include compounds described in paragraph numbers 0248 to 0251 of JP-A-2007-26979. This embodiment can also be used favorably.

  Among them, as a polymerizable monomer, dipentaerythritol triacrylate (KAYARAD D-330 as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320; Nippon Kayaku) Dipentaerythritol penta (meth) acrylate (manufactured by K.K.) and dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; Nippon Kayaku Co., Ltd.) Company-made), and the structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available product is M-460; Etsu Chemical Co., Ltd.) is preferable. These oligomer types can also be used.

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

In the above formulae, E represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) —, and — ((CH ₂ ) _y CH ₂ O)-is preferred.
y represents the integer of 1-10, respectively, the integer of 1-5 is preferable and 1-3 are more preferable.
X represents a hydrogen atom, an acryloyl group, a methacryloyl group, or a carboxyl group, respectively.
In the formula (i), the total of acryloyl group and methacryloyl group is 3 or 4, and 4 is preferable.
m represents the integer of 0-10, respectively, and 1-5 are preferable. The total of each m is an integer of 1-40, and 4-20 pieces are preferable.
In the formula (ii), the total number of acryloyl groups and methacryloyl groups is 5 or 6, with 6 being preferred.
n represents the integer of 0-10, respectively, and 1-5 are preferable. The total of n is an integer of 1-60, respectively, and 4-30 are preferable.

  As a specific monomer, you may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Therefore, it is preferable that the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, and this can be used as it is. The hydroxyl group may be reacted with a non-aromatic carboxylic anhydride to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

The monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. The polyfunctional monomer provided is preferred, and particularly preferably in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix series M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.

About these polyfunctional monomers, the detail of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of a composition. In the present embodiment, a method of adjusting both sensitivity and strength by using different functional numbers and / or different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). Is also effective. Further, it is preferable to use a specific monomer having an ethylene oxide chain length of 3 or more and 8 or less in that the developability of the composition can be adjusted and an excellent pattern forming ability can be obtained. Also, the selection and use of specific monomers is an important factor for compatibility and dispersibility with other components (eg, polymerization initiators, colorants (pigments), resins, etc.) contained in the composition. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. 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 preferably has a molecular weight smaller than that of 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 (mixing ratio) of the specific monomer is preferably 1% by mass or more, and preferably 5% by mass or more, based on the total solid content in the colored radiation-sensitive composition. Although there is no restriction | limiting in particular about an upper limit, It is preferable that it is 50 mass% or less, and it is more preferable that it is 40 mass% or less.

-Polymerization initiator The polymerization initiator preferably has the ability to initiate the polymerization of the specific monomer, and is not particularly limited and can be appropriately selected from known polymerization initiators. For example, those having photosensitivity to light (especially, visible light from the ultraviolet region) are preferable, and may be an activator that generates an active radical by generating some action with a photoexcited sensitizer. Depending on the type, an initiator that initiates cationic polymerization may be used. 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, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives. Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Examples of the compounds described in the above U.S. Pat. No. 4,221,976 include compounds having an oxadiazole skeleton, JP-A-53-133428, JP-B-57-1819, and JP-A-57-6096. And compounds described in US Pat. No. 3,615,455.

As the polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used. As the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

  More preferred examples of the polymerization initiator include oxime compounds. Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.

Examples of oxime compounds such as oxime derivatives that are preferably used as a polymerization initiator in the present embodiment include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
Specifically, the oxime polymerization initiator is preferably a compound represented by the following formula (1). The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

（式（１）中、Ｒ及びＢは各々独立に一価の置換基を表し、Ａは二価の有機基を表し、Ａｒはアリール基を表す。）

(In 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 nonmetallic atomic group. Examples of the monovalent nonmetallic 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. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by 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. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent. Of these, the structures shown below are particularly preferred. In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (2) described later, and preferred examples are also the same.

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. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent. Examples of the substituent include the same substituents as those introduced into the substituted aryl group mentioned above as specific examples of the aryl group which may have a substituent.
Among these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the formula (1), it is preferable from the viewpoint of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure. Me represents a methyl group, and Et represents an ethyl group.

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

  In the formula, 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 is an integer of 0 to 5. R, A, and Ar in the formula are synonymous with R, A, and Ar in the formula (1), and preferred examples are also the same. Examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic group, and a halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent. Among these, X is preferably an alkyl group from the viewpoints of solvent solubility and improvement in absorption efficiency in the long wavelength region. Moreover, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

  Examples of the divalent organic group represented by Y include the structures shown below. In the group shown below, * represents a bonding position between Y and an adjacent carbon atom in the above formula (2).

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

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

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
For the molar extinction coefficient of the compound, a known method can be used. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Vary Inc., Carry-5 spectrphotometer) using an ethyl acetate solvent is used. It is preferable to measure at a concentration of / L.

  You may use a polymerization initiator in combination of 2 or more type as needed. The content of the polymerization initiator in the colored radiation-sensitive composition (the total content in the case of two or more) is in the range of 0.1 to 20% by mass with respect to the total solid content of the radiation-sensitive composition. Is preferable, more preferably in the range of 0.5 to 10% by mass, and particularly preferably in the range of 1 to 8% by mass. Within this range, good sensitivity and pattern formability can be obtained.

  A sensitizer may be contained for the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the photosensitive wavelength. As a sensitizer that can be used in this embodiment, a sensitizer that sensitizes a polymerization initiator by an electron transfer mechanism or an energy transfer mechanism is preferable.

Examples of the sensitizer include compounds described in paragraph numbers 0101 to 0154 of JP-A-2008-32803.
When blended, the content of the sensitizer in the composition is preferably 0.1% by mass to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency to the deep part and starting decomposition efficiency. 0.5 mass% to 15 mass% is more preferable.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

Colorant The colorant is not particularly limited, and various conventionally known dyes and pigments can be used singly or in combination of two or more, depending on the use of the composition of the present embodiment. It is selected appropriately. It is preferable that the composition of the present embodiment is used for producing a color filter, and chromatic colorants such as red, magenta, yellow, blue, cyan, and green that form color pixels of the color filter (existing) (Coloring colorant) and a black colorant (black colorant) generally used for forming a black matrix can 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 using a colorant suitable for a color filter application as an example.
As the chromatic pigment, various conventionally known inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a finer one as much as possible, and considering the handling properties, the average primary particle diameter of the pigment is 0.01 μm. -0.1 micrometer is preferable and 0.01 micrometer -0.05 m are more preferable.

  Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, Examples thereof include metal oxides such as silver and complex oxides of the above metals. Titanium nitrides, silver tin compounds, silver compounds, and the like can also be used.

When the colorant is a dye, a colored composition in a state of being uniformly dissolved in the composition can be obtained.
The dye that can be used as the colorant contained in the colored radiation-sensitive composition is not particularly limited, and conventionally known dyes for color filters can be used. For example, pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, Dyes such as phthalocyanine, benzopyran, indigo, and pyromethene can be used. Moreover, you may use the multimer of these dyes.

Moreover, when performing water or alkali image development, an acidic dye and / or its derivative may be used suitably from a viewpoint that the binder and / or dye of a light non-irradiation part are removed completely by image development.
In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.

  Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Solvent orange 45; Rhodamine B, Rhodamine 110 and other acid dyes and derivatives of these dyes are also preferably used.

Among them, as the colorant, triarylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazole azo It is preferable that the colorant is selected from a series, anilinoazo, pyrazolotriazole azo, pyridone azo, and anthrapyridone pyromethene.
Further, pigments and dyes may be used in combination. In particular, C.I. I. Pigment red 122, C.I. I. Pigment Yellow 185 is preferable.

The colorant that can be used in the colored radiation-sensitive composition is preferably a dye or a pigment. In particular, a pigment having an average particle size (r) of 20 nm ≦ r ≦ 300 nm, preferably 125 nm ≦ r ≦ 250 nm, particularly preferably 30 nm ≦ r ≦ 200 nm is desirable. By using a pigment having such an average particle diameter, a pixel having a high contrast ratio and a high light transmittance can be obtained. Here, the “average particle size” means the average particle size of secondary particles in which primary particles (single crystallites) of the pigment are aggregated. The average primary particle diameter can be obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.
The particle size distribution of the secondary particles of the pigment (hereinafter, simply referred to as “particle size distribution”) is 70% by mass or more, preferably 80% by mass or more of the total secondary particles entering (average particle size ± 100) nm. It is desirable that The particle size distribution was measured using a scattering intensity distribution.

  The pigment having the above average particle size and particle size distribution is preferably a pigment obtained by mixing a commercially available pigment with other pigments to be used (the average particle size is usually more than 300 nm), preferably mixed with a dispersant and a solvent. As a liquid mixture, it can prepare by mixing and disperse | distributing, grind | pulverizing, for example using grinders, such as a bead mill and a roll mill. The pigment thus obtained is usually in the form of a pigment dispersion.

The content (concentration) of the colorant contained in the colored radiation-sensitive composition is preferably 10% by mass or more, more preferably 15% by mass or more, based on the total solid content of the colored radiation-sensitive composition. More preferably 20% by mass or more. Although there is no restriction | limiting in particular about an upper limit, Preferably it is 45 mass% or less.
By setting the content of the colorant in the above range, an appropriate chromaticity can be obtained when a color filter is produced from the colored radiation-sensitive composition. Further, since photocuring sufficiently proceeds and the strength as a film can be maintained, it is possible to prevent the development latitude during alkali development from becoming narrow.

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

-Solvent The colored radiation-sensitive composition can generally be constituted using a solvent. The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coating property of the colored radiation-sensitive composition, but particularly considers the solubility, coating property, and reliability of the ultraviolet absorber and binder resin. Is preferably selected. Moreover, when preparing a colored radiation-sensitive composition, it is preferable to contain at least two types 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, butyl butyrate, methyl lactate, ethyl lactate, Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate (Eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)) ), 2-Oki Propionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropion) Propyl acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, 2-methoxy-2-methyl Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. And examples of ethers Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like, and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. Suitable examples of aromatic hydrocarbons include xylene.

  The content of the solvent in the colored 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, from the viewpoint of applicability. 10 to 50% by mass is particularly preferable.

-Other additives Surfactant Various surfactants may be added to the above composition from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. When blended, the additive amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass, based on the total mass of the composition. .

Polymerization inhibitor It is desirable to add a small amount of polymerization inhibitor in order to prevent unnecessary thermal polymerization of a specific monomer during the production or storage 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′-thiobis (3-methyl-6- t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like. Further, the radiation-sensitive composition may contain a co-sensitizer for the purpose of further improving the sensitivity of the sensitizing dye or initiator to active radiation or suppressing the inhibition of polymerization of a specific monomer by oxygen. . Moreover, in order to improve the physical property of a cured film, you may add well-known additives, such as a diluent, a plasticizer, a fat-sensitizing agent, as needed. In the case of using a polymerization inhibitor, the addition amount is preferably in the range of 0.001% by mass to 0.015% by mass in the total solid content in the colored photosensitive resin composition, preferably 0.03% by mass to 0.09 mass% is more preferable.

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 in the total solid content in the colored radiation-sensitive resin composition. 2 mass%-3.0 mass% is more preferable.

Ultraviolet Absorber The composition may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. When the ultraviolet absorber is included, the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, and 0.01% by mass or more and 0.1% by mass with respect to the total solid mass. The following is more preferable.

-Preparation of colored radiation-sensitive composition The preparation mode of the colored radiation-sensitive composition is not particularly limited, but for example, it can be prepared by mixing essential components and various additives used together as desired. .

The colored radiation-sensitive composition is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. It is preferable that it is conventionally used for the filtration use etc., It can use without being specifically limited.
The above-mentioned “method of adjusting the turbidity to be 30 ppm or less by filter filtration” is, in other words, producing a polymerization solution containing a dye having a turbidity of 30 ppm or less by filtering the polymer solution containing the dye. It is a method to do. In this method, pigment aggregates are removed from the polymerization solution to such an extent that the turbidity of the polymerization solution is 30 ppm or less.
This method has the advantage that the choice of solvent for the dye is wide.

As a filter used for filter filtration, it is preferable that it is a filter conventionally used for the filtration use etc., It can use without being specifically limited.
Examples of the filter material include: a fluororesin such as PTFE (polytetrafluoroethylene); a polyamide resin such as nylon-6 and nylon-6, 6; a polyolefin resin such as polyethylene and polypropylene (PP) (high density, Including ultra high molecular weight); Among these materials, polypropylene (including high density polypropylene) is preferable.

Cured film and method for producing the same:
The cured film according to a preferred embodiment of the present invention has high color purity, a high absorption coefficient in a thin layer, and good fastness (especially heat resistance and light resistance). The manufacturing method of a cured film includes the process of applying a colored radiation sensitive composition on a board | substrate, and the process of exposing the said colored radiation sensitive composition. Specifically, when forming a cured film on an arbitrary substrate or substrate, a colored radiation-sensitive composition is applied, or the substrate or the like is immersed in the colored radiation-sensitive composition to give a colored feeling. A radiation composition layer may be formed and cured. Further, when forming a patterned cured film, it may be applied on a substrate by an inkjet recording method, or a known printing method such as textile printing or offset printing may be applied, but a high-definition pattern is formed. From the viewpoint of being able to be obtained, a method of forming a colored radiation-sensitive composition layer on a substrate, which will be described later, and exposing to a pattern, and developing to remove an unexposed portion of the colored radiation-sensitive composition layer is preferable. .
The film thickness of the cured film can be, for example, 0.5 to 1.5 μm.

Color filter and manufacturing method thereof:
The manufacturing method of a color filter includes the process of applying a colored radiation sensitive composition on a board | substrate, and the process of carrying out pattern exposure of the said colored radiation sensitive composition. Specifically, a step of forming a colored radiation-sensitive composition layer by applying the above-described colored radiation-sensitive composition on a support (hereinafter also referred to as “colored radiation-sensitive composition layer forming step”). ), A step of pattern exposure of the colored radiation-sensitive composition layer through a mask (hereinafter also referred to as “exposure step”), and development of the colored radiation-sensitive composition layer after exposure to develop a colored pattern (hereinafter referred to as “exposure step”). , (Also referred to as “colored pixels”) (hereinafter also referred to as “development process”).

-Colored radiation sensitive composition layer formation process In a colored radiation sensitive composition layer formation process, a colored radiation sensitive composition layer is formed on a support by applying a colored radiation sensitive composition.
As a support that can be used in this step, for example, a solid-state imaging in which an imaging element (light-receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate). An element substrate can be used.
The coloring pattern may be formed on the imaging element forming surface side (front surface) of the solid-state imaging element substrate, or may be formed on the imaging element non-forming surface side (back surface).
A light-shielding film may be provided between the image sensors on the solid-state image sensor substrate or on the back surface of the solid-state image sensor substrate.
Further, if necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.

  As a method for applying the colored radiation-sensitive composition on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied.

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

  The colored radiation-sensitive composition layer coated on the support can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, oven, or the like.

-Exposure step In the exposure step, the colored radiation-sensitive composition layer formed in the colored radiation-sensitive composition layer forming step is patterned through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper, for example. Exposure. As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferable (particularly preferably i-line). Irradiation dose (exposure amount) is more preferably preferably ^{50~1000mJ / cm 2 30~1500mJ / cm 2} , 80~500mJ / cm 2 being most preferred.

-Development process Next, by performing development such as an alkali development treatment, the colored radiation-sensitive composition layer of the non-light-irradiated part in the exposure process is eluted in the alkaline aqueous solution, and only the photocured part remains. The developer is preferably an organic alkali developer that does not cause damage to the underlying image sensor or circuit. The development temperature is usually 20 ° C. to 30 ° C., and the development time is, for example, 20 seconds to 90 seconds. In order to remove the residue more, in recent years, it may be carried out for 120 seconds to 180 seconds. Furthermore, in order to further improve residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.

-Post-baking Next, it is preferable to perform heat processing (post-baking) after drying. It is preferable to form a multicolored pattern, and a cured film can be produced by sequentially repeating the above steps for each color. Thereby, a color filter is obtained. Post-baking is a heat treatment after development for complete curing. The heating temperature is preferably 240 ° C. or lower, more preferably 220 ° C. or lower, further preferably 200 ° C. or lower, and particularly preferably 190 ° C. or lower from the viewpoint of suppressing damage to the organic photoelectric conversion part. Although there is no particular lower limit, in view of an efficient and effective treatment, it is preferable to perform a thermosetting treatment of 50 ° C. or higher, and more preferably 100 ° C. or higher.

(Low oxygen bake)
In the present invention, when post-baking is performed under low oxygen, the lower the post-baking temperature, the better the pixel rectangularity, which is preferable. The post-baking temperature is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, further preferably 130 ° C. or lower, and particularly preferably 100 ° C. or lower. The lower limit is preferably 70 ° C. or higher.

  This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

In the present invention, the pixel of the color filter may be cured by UV (ultraviolet) irradiation instead of the post-baking by heating. At this time, the UV curing agent is preferably one that can be cured at a wavelength of a single wave from 365 nm which is an exposure wavelength of an initiator added for a lithography process by normal I-line exposure.
For UV curing, it is more preferable to add a second initiator in addition to the first initiator for color filter lithography.
As the second initiator, those having little absorption at 365 nm are preferable.
Absorption at 365 nm here is defined by Absorbance (ABS) when measuring 0.01% by mass of absorption in acetonitrile. ABS is preferably 0.10 or less, more preferably 0.07 or less, and 0 .05 or less is most preferable.
Examples of the UV curing agent include Ciba-Iru Gacure 2959 (trade name). The specific wavelength of the UV irradiation light is preferably a material that cures at 340 nm or less. Although there is no lower limit of wavelength, it is generally 220 nm or more. Moreover, the exposure amount of UV irradiation is preferably 100 to 5000 mJ, preferably 300 to 4000 mJ, and more preferably 800 to 3500 mJ. This UV curing step is preferably performed after the lithography step in order to perform low-temperature curing more effectively. The exposure light source is preferably an ozoneless mercury lamp.

  In the present invention, the post-baking of the radiation-sensitive composition is preferably performed in an atmosphere having a low oxygen concentration. The oxygen concentration is preferably 19% (volume basis) or less, more preferably 15% (volume basis) or less, further preferably 10% (volume basis) or less, and 7% (volume basis). (Standard) or less, more preferably 3% (volume basis) or less. There is no particular lower limit, but 10 ppm (volume basis) or more is practical.

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

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

Preparation of organic photoelectric conversion part (layer) A vapor deposited film of quinacrine was prepared. Details were based on known literature. Specifically, in conformity with [0341] of JP 2010-103457, an amorphous ITO 30 nm film was formed on a glass substrate by a sputtering method. Further, quinacridone was formed into a layer corresponding to the photoelectric conversion layer by vacuum heating vapor deposition so as to have a thickness of 100 nm. Furthermore, an amorphous ITO film having a thickness of 5 nm was formed as an upper electrode by a sputtering method to form a transparent electrode.

Formation of Inorganic Protective Layer The inorganic protective layer was produced according to [0341] of JP2010-103457A. Specifically, an Al ₂ O ₃ layer having a thickness of 30 nm was formed as a protective layer on the organic photoelectric conversion portion by ALCVD. Furthermore, the SiON layer was formed with a thickness of 200 nm by the CVD method (the thickness of the inorganic film was 230 nm). All the vacuum depositions were performed at a vacuum degree of 4 × 10 ⁻⁴ Pa or less. When the surface roughness Ra of the protective film 1 was measured by AFM (Atomic Force Microscope) Dimension 3100 manufactured by Veeco, Ra was 25 nm.
Furthermore, the formation conditions of the 2nd SiON layer were changed, and the surface roughness Ra created the protective layers 2-4 below.

Formation of organic protective film layer (comparative example)
An aqueous solution in which PVA (polyvinyl alcohol) was dissolved at 10% by mass was prepared. This was applied onto the organic photoelectric conversion part (layer) by spin coating. Thereafter, it was dried to obtain an organic protective film having a thickness of 230 nm.

(Preparation of pigment dispersion)
Using a zirconia bead having a diameter of 0.3 mm, a mixed solution having the following composition was mixed and dispersed for 3 hours in a bead mill (high pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.)). Thus, each pigment dispersion was prepared.
(Pigment dispersion Y)
・ C. I. Pigment Yellow 185 18.0 parts, Dispersant 1.8 parts, Resin 1 9.9 parts, Solvent: 70.3 parts (Pigment dispersion Cy)
・ C. I. Pigment Blue 15: 6 7.4 parts, Aluminum phthalocyanine 10.6 parts, Dispersant 1.8 parts, Resin 1 9.9 parts, Solvent: 70.3 parts

(Preparation of colored radiation-sensitive composition)
The following components were mixed to prepare a colored radiation-sensitive composition.
(Colored radiation-sensitive composition Y)
-Pigment dispersion Y 36.1 parts-Specific acrylic polymer 0.6 parts-Resin 1 4.5 parts-Polymerizable compound 1 2.0 parts-Polymerizable compound 2 6.0 parts-Polymerization initiator 1 2 parts, solvent 49.6 parts

[Colored radiation-sensitive composition Cy]
-Pigment dispersion Cy 27.8 parts-Specific acrylic polymer 0.6 parts-Resin 1 6.8 parts-Polymerizable compound 1 6.3 parts-Polymerizable compound 2 2.1 parts-Polymerization initiator 1 0 parts, solvent 55.4 parts

Dispersant: (b) Polymer having no polymerizable group: BYK-2001 manufactured by BYK
Resin 1: (b) Polymer having no polymerizable group
Benzyl methacrylate / methacrylic acid copolymer
(= 70/30 molar ratio, Mw: 30000,
Acid value: 110 mg KOH / g)
Specific acrylic polymer:
(A) Acrylic polymer having a polymerizable group
Product name Cyclomer P manufactured by Daicel Chemical Industries
Polymerizable compound 1: Dipentaerythritol hexaacrylate
(Product name Kayalad DPHA manufactured by Nippon Kayaku Co., Ltd.)
Polymerizable compound 2: pentaerythritol ethylene oxide
Modified tetraacrylate (trade name RP-1040 manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator 1: manufactured by BASF, IRGACURE-OXE01
Solvent: Propylene glycol methyl ether acetate

Spectral characteristics were evaluated using each of the obtained colored radiation-sensitive compositions. The results are shown in the table below.
[Single spectral characteristics]
Each colored radiation-sensitive composition was spin-coated on a glass substrate, applied so that the film thickness after post-baking was (1.0) μm, dried on a hot plate at 100 ° C. for 120 seconds, and dried. Thereafter, heat treatment (post-baking) was further performed for 300 seconds using a 200 ° C. hot plate.

[Production of color filters]
The colored radiation-sensitive composition of CF 1st color Cy was applied on the protective layer of the organic photoelectric conversion film obtained above by using a spin coater so that the film thickness after drying was 1.0 μm. Heat treatment (pre-baking) was performed for 120 seconds using a plate.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), pattern exposure was performed at a total of 399 locations in a pattern arranged in a matrix of 21 rows × 19 columns. At this time, the above-mentioned 21 rows of the matrix are under the condition that the minimum exposure amount is 500 J / m ² and the exposure amount is increased for each row at intervals of 500 J / m ² to 500 J / m ^2. In the above 19th column, the focal length is changed at intervals of 0.1 μm with the focal length optimum value (Focus 0.0 μm) as the center. That is, the photo is formed so that a square pixel pattern of 3.0 μm square is arranged within a range of 4 mm × 3 mm under the condition that the central one row is the optimum focal length and the focal length is changed for each row. A mask was used.
Thereafter, the substrate on which the exposed coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2060 (Fuji Film Electronics Material). Paddle development was performed at 23 ° 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.
Furthermore, heat treatment (post-baking) was performed for 300 seconds using a hot plate having a temperature shown in Table 1 to obtain a substrate having colored pixels corresponding to the colorant. The oxygen concentration in the atmosphere at this time was as shown in Table 1.

  In Test 108, Irgacure 2959 (ABS 0.03 at 365 nm with 0.01% by weight of acetonitrile) was further added to the colored radiation-sensitive composition Y in an additional 1.2 parts. The post-baking was not performed by heating, but using an ultraviolet irradiation device UMA-802-HC552 manufactured by USHIO ELECTRIC CO., LTD., 300 mW for 10 seconds was performed by an ozone-less mercury lamp. A colored pattern was prepared in the same manner as above, and an evaluation test was performed.

The colored radiation-sensitive composition of CF 2nd color Y was further subjected to spray drying under the same conditions as the above Cy. The spectral change at this time was performed in the same manner as the color filter 1.

(Evaluation method)
A single-layer coating film (protective film) was prepared together with the organic photoelectric conversion film and the color filter and used as a reference. Based on the spectral change of the maximum transmittance (between 450 nm and 700 nm) when this is laminated as shown in FIG. This measurement was performed at room temperature (25 ° C.).

温度：プロセス温度
酸素濃度：プロセス酸素濃度
分光変化：分光変化の評価結果
通常のリソグラフィー：上記ＣＦ１の作製で採用した工程による

Temperature: Process temperature Oxygen concentration: Process oxygen concentration Spectral change: Evaluation result of spectral change Normal lithography: According to the process adopted in the production of CF1

  From the above results, it can be seen that a good CMOS image sensor can be manufactured according to 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 with respect to single-layer spectroscopy)
CF2 (YELLOW color filter) was applied as a single layer on the glass substrate in the same manner as described in the above <CF2 color>, and the maximum spectral transmittance was measured (Tmax). Next, a protective film shown in the following table was applied, a Cy color filter was formed on the photoelectric conversion film, and after processing, a CF2 color filter was formed.
The spectral transmittance after the formation is measured, and the maximum spectral transmittance is defined as Ty. Ty and Tmax were compared for each sample, and the difference was ranked according to the difference in the following table to evaluate the change of CF2 with respect to the single-layer spectroscopy. Test 201 is an example in which the protective layer is a single layer of Al ₂ O ₃ .

(Rectangularity of CF1)
CF1 ideally has a square pattern of 3.0 μm. The length of one side of CF1 after the formation of CF2 was measured, and the percentage of the square pattern shifted from 3.0 μm was evaluated and ranked.

1 Color filter pixel (Y)
2 Color filter pixels (Cy)
3 Protective layer 4 Inorganic photoelectric conversion part (R)
5 Inorganic photoelectric conversion part (B)
6 Organic photoelectric conversion part (G)
10 CMOS image sensor

Claims (14)

  A method of manufacturing an image sensor having a pixel of a color filter, an inorganic protective layer, an organic photoelectric conversion unit, and an inorganic photoelectric conversion unit, the method comprising: providing the inorganic protective layer on the organic photoelectric conversion unit Method.   The method of manufacturing an image sensor according to claim 1, further comprising a step of providing pixels of the color filter on the inorganic protective layer.   The method for manufacturing an image sensor according to claim 2, wherein a temperature at the time of forming the pixel of the color filter is set to 200 ° C. or less.   The method of manufacturing an image sensor according to claim 2, wherein an oxygen concentration in an atmosphere at the time of creating the pixel of the color filter is 19% or less.   The image sensor manufacturing method according to claim 2, wherein the pixels of the color filter are cured by UV irradiation.   The method for manufacturing an image sensor according to claim 1, wherein the inorganic protective layer is composed of two or more layers. A lower layer containing at least one inorganic protective layer is selected from _Al 2 _O 3, SiO _2, and TiO _2, on its upper _{side, SiON, SiO 2, Al 2} O 3, and at least one selected from SiN The method for producing an image sensor according to claim 6, comprising an upper layer containing   The method for manufacturing an image sensor according to claim 1, wherein the inorganic protective layer has a surface roughness Ra of 1 nm to 100 nm.   An image sensor having a color filter pixel, an inorganic protective layer, an organic photoelectric conversion unit, and an inorganic photoelectric conversion unit, wherein the inorganic protective layer is provided on the organic photoelectric conversion unit.   The image sensor according to claim 9, wherein the pixel of the color filter is made of a UV curable resin.   The image sensor according to claim 9 or 10, wherein the inorganic protective layer is composed of two or more layers. A lower layer containing at least one inorganic protective layer is selected from _Al 2 _O 3, SiO _2, and TiO _2, on its upper _{side, SiON, SiO 2, Al 2} O 3, and at least one selected from SiN The image sensor according to claim 11, comprising an upper layer containing   The image sensor according to any one of claims 9 to 12, wherein the inorganic protective layer has a surface roughness Ra of 1 nm to 100 nm.   A laminate comprising an image sensor having a color filter pixel, an inorganic protective layer, an organic photoelectric conversion part, and an inorganic photoelectric conversion part, wherein the inorganic protective layer is provided on the organic photoelectric conversion part.

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