WO2014125935A1 - Procédé de production d'un filtre couleur, filtre couleur produit de cette façon, élément d'imagerie à l'état solide et dispositif d'affichage à cristaux liquides - Google Patents

Procédé de production d'un filtre couleur, filtre couleur produit de cette façon, élément d'imagerie à l'état solide et dispositif d'affichage à cristaux liquides Download PDF

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WO2014125935A1
WO2014125935A1 PCT/JP2014/052153 JP2014052153W WO2014125935A1 WO 2014125935 A1 WO2014125935 A1 WO 2014125935A1 JP 2014052153 W JP2014052153 W JP 2014052153W WO 2014125935 A1 WO2014125935 A1 WO 2014125935A1
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Prior art keywords
color filter
exposure
pattern
present
colored layer
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PCT/JP2014/052153
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English (en)
Japanese (ja)
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光司 吉林
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富士フイルム株式会社
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters

Definitions

  • the present invention relates to a method of manufacturing a color filter that can be used for coating on peripheral equipment, exposure, patterning using development, and the like.
  • the present invention also relates to a color filter used for liquid crystal display devices, solid-state imaging devices and the like.
  • a manufacturing method of a color filter used for a liquid crystal display or a solid-state imaging device after applying a photosensitive coloring composition on a substrate, it irradiates with ultraviolet rays by an exposure process via a predetermined mask pattern, and develops with an alkaline solution after that Is generally used to obtain a pattern image.
  • a color filter in which organic pixels of plural colors such as red pixels, green pixels and blue pixels are two-dimensionally arrayed is provided on a support such as a semiconductor substrate.
  • Patent Document 1 describes a method of forming a color filter pattern in which an exposure method is devised from the viewpoint of forming a small opening in a color filter while suppressing residues.
  • Patent Document 2 describes a scanning exposure type pattern drawing apparatus which draws a regular pattern on the surface of a substrate such as a color filter substrate.
  • Patent Document 3 describes a color filter having a patterned substrate in which only a black matrix is formed by a photolithographic method.
  • a Bayer pattern or the like suitable for forming a color filter tends to be difficult to form a finer pattern than an island pattern or a line and space pattern or the like, and tends to be easily crushed when the exposure amount becomes excessive. From such a point of view, even if the color filter pattern becomes finer or the exposure dose becomes excessive, the exposure latitude (EL; mask followability) is excellent, the rectangularity of the pattern is good, and the depth of focus (Depth It is desired to develop a method of manufacturing a color filter which is excellent in the likelihood of of focus (DOF) and has a good throughput (processing speed).
  • DOE likelihood of of focus
  • the present invention has been made in view of the above problems, and an object thereof is to set the likelihood of exposure latitude (EL; mask followability) and depth of focus (DOF) without deteriorating throughput (processing speed).
  • EL exposure latitude
  • DOF depth of focus
  • a method of manufacturing a color filter that can be improved and the rectangularity of the color filter pixel array pattern can also be improved by the improvement of the mask followability, a color filter manufactured using the same, a solid-state imaging device, and To provide a liquid crystal display device.
  • a method for producing a color filter comprising the step of forming an array pattern, wherein the exposure is carried out continuously at the same coordinates and divided into plural times.
  • [4] The method for producing a color filter according to any one of [1] to [3], wherein the exposure divided in the plurality of times has a smaller exposure amount in the first exposure than in the second exposure.
  • [5] The method for producing a color filter according to any one of [1] to [4], wherein the color filter pixel array pattern is a Bayer pattern.
  • [6] The method for producing a color filter according to any one of [1] to [5], wherein the photosensitive colored layer contains a coloring material which is an organic compound.
  • [7] The manufacturing method of the color filter as described in [6] whose coloring material which is the said organic compound is an organic pigment.
  • the likelihood of EL (mask tracking) and DOF can be improved without loss of throughput, and the rectangularity of the color filter pixel array pattern is also improved by the improvement of the mask following. It is possible to provide a method of manufacturing a color filter that can be used, and a color filter, a solid-state imaging device, and a liquid crystal display device manufactured using the same.
  • a pixel having a pixel size of particularly less than 1.2 ⁇ m in a color filter for solid-state imaging device red, green, blue, CMY (cyan, magenta, yellow), transparency, etc.
  • EL mask followability
  • DOF the rectangularity of the color filter pattern that can be observed from the top surface and the cross section can be improved.
  • the notations not describing substitution and non-substitution include those having no substituent and those having a substituent.
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
  • the total solid content refers to the total mass of the components excluding the solvent from the total composition of the coloring composition.
  • “(meth) acrylate” represents acrylate and methacrylate
  • “(meth) acrylic” represents acrylic and methacrylic
  • “(meth) acryloyl” represents acryloyl and methacryloyl.
  • “monomer” and “monomer” are synonymous.
  • the monomer in the present invention is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of less than 2,000.
  • the polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer.
  • the polymerizable group refers to a group involved in the polymerization reaction.
  • radiation as used in the present invention means one including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.
  • the method for producing a color filter of the present invention is Exposing a photosensitive colored layer containing a radically polymerizable monomer and a photoradical polymerization initiator using a photomask for a color filter pixel array; and developing the photosensitive colored layer after the exposure to form a color filter pixel. It has the process of forming an array pattern, and the above-mentioned exposure is divided into a plurality of times continuously with the same coordinates, and is performed.
  • the color filter means a color filter for color separation in the visible range (400 nm to 700 nm). This includes transparent materials in the visible range (95% or more) and grays such as semi-transmission. It does not include a black resist intended to block light in the visible range.
  • a photomask for a color filter pixel array means a photomask for color separation applications such as an image sensor light receiving unit such as red, green, blue, CMY, or transparent, a liquid crystal display device, and the like. A photomask for pattern formation intended to shield light is not included.
  • a photomask for the color filter pixel array a known one can be used as a photomask for the color filter pixel array, and a photomask for multiple exposure is not required.
  • “same coordinate” means that the relative position (x coordinate, y coordinate) between the photo mask for the color filter pixel array and the photosensitive colored layer (or substrate) is not changed.
  • each step in the step & repeat method (known as a so-called stepper method in which exposure of one section is exposed and then exposure of the next section is sequentially repeated) is known.
  • Means exposure in the In the present invention “continuously” means that the non-exposure time (hereinafter, also simply referred to as "delay time”) between divided exposures is 1000 msec or less.
  • the non-exposure time (delay time) between divided exposures is preferably 10 to 1000 ms, more preferably 15 to 300 ms, and still more preferably 20 to 100 ms.
  • the method for producing a color filter according to the present invention is preferable in the case of using a photosensitive colored layer having a high transmittance of exposure light with an exposure wavelength of 365 nm, from the viewpoint of suppressing diffusion of radicals due to scattering of exposure light by color materials. is there.
  • the Bayer pattern or the hole pattern tends to be easily crushed when it becomes a fine pattern or when the exposure amount becomes excessive, as compared with the island pattern, the line and space pattern, and the like.
  • the effect of the EL improvement by the color filter manufacturing method of the present invention and the accompanying pattern shape improvement is suitable for processing the shape of a color filter pixel array pattern such as a Bayer pattern or a hole pattern.
  • the separation ability of the color filter pixel array pattern of these Bayer pattern or hole pattern can be dramatically improved, and in particular, the pattern separation ability of the Bayer pattern is dramatically improved.
  • the resolution of a color filter pixel array pattern such as an island pattern can be sufficiently improved.
  • the likelihood of EL (mask followability) and DOF can be improved without loss of throughput, and the improvement of the mask followability improves the color filter pixel array pattern.
  • the reason why the rectangularity can also be improved is not clear but is estimated as follows.
  • the exposure amount per divided exposure (for example, for each of the first exposure, the second exposure, and the third exposure) is reduced by dividing the exposure, the lateral radical diffusion in the photosensitive colored layer is suppressed. It is thought that it can do.
  • the radicals in the vicinity of the center of the photosensitive colored layer in the exposed area are kept by exposure residual heat or inactivated by oxygen by further performing additional exposure (second exposure, third exposure, etc.) at time intervals.
  • radical diffusion toward the substrate is promoted, which is considered to contribute to the improvement of the adhesion to the substrate.
  • radicals generated in the first exposure are considered to be inactivated by oxygen in the photosensitive colored layer and the surface of the layer, and lateral diffusion is suppressed.
  • the same phenomenon is considered to occur also in the second exposure, so that lateral thickening (such as thickening in the line width when the exposure amount is large, thickening in the line width when the focus is shifted, etc.) is suppressed. It is considered to be a thing.
  • the likelihood of EL (mask follow-up ability) and DOF can be improved without deteriorating the throughput, and the above-mentioned mask follow-up ability improves the color filter pixel array. It is estimated that the rectangularity of the pattern can also be improved.
  • the photosensitive colored layer containing a radical polymerizable monomer and a photo radical polymerization initiator is pattern-exposed through a photomask for a color filter pixel array using an exposure apparatus such as a stepper, for example. obtain.
  • an exposure apparatus such as a stepper, for example.
  • ultraviolet rays such as g-line and i-line are preferably used (particularly preferably i-line).
  • divided and irradiated (exposure) has been dose preferably 30 ⁇ 1500mJ / cm 2 as the sum of (exposure), more preferably 50 ⁇ 1000mJ / cm 2, most 80 ⁇ 500mJ / cm 2 preferable.
  • the exposure divided into a plurality of times is preferably an exposure divided into two or more times, and more preferably an exposure divided into three or more times. In the exposure divided into a plurality of times, it is preferable that the exposure amount in the first exposure be smaller than the exposure amount in the second exposure.
  • the present invention includes the step of developing the photosensitive colored layer after the exposure to form a color filter pixel array pattern.
  • the development is preferably alkali development.
  • the photosensitive colored layer in the light non-irradiated part in the exposing step is eluted in an alkaline aqueous solution, and only the photocured part remains.
  • Negative type color filter pixel array pattern Can be formed.
  • As the developing solution an organic alkaline developing solution which does not cause damage to the underlying imaging element or circuit is desirable.
  • the development time may be from 20 seconds to 90 seconds, but in recent years it may be carried out from 120 seconds to 180 seconds in order to remove more residue. Furthermore, in order to further improve the residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.
  • alkaline agent used for the developer examples include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4, 0] -7-an alkaline aqueous solution obtained by diluting such alkaline agents with pure water to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, including organic alkaline compounds such as undecene Is preferably used as a developer.
  • An inorganic alkali may be used for the developer, and as the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium borate, sodium metaborate and the like are preferable.
  • the developing solution which consists of such alkaline aqueous solution, generally it wash
  • the method for producing a color filter of the present invention may, if necessary, have a step known as a method for producing a color filter as a step other than the exposure step and the developing step.
  • a step known as a method for producing a color filter as a step other than the exposure step and the developing step.
  • the photosensitive colored layer forming step for example, forming a photosensitive colored layer in the present invention by providing a negative photosensitive colored composition containing a radically polymerizable monomer and a photoradical polymerization initiator on a substrate.
  • the substrate in the present invention is not particularly limited, for example, soda glass, borosilicate glass, quartz glass used for liquid crystal display elements etc., those obtained by attaching a transparent conductive film to these, photoelectrics used for imaging elements etc.
  • a conversion element substrate such as a silicon substrate, an oxide film, silicon nitride and the like can be mentioned.
  • the color filter pixel array pattern in the present invention may be formed on the imaging element forming surface side (front surface) of a substrate such as a substrate for a solid-state imaging element, or formed on the imaging element non-forming surface side (rear surface). May be A light shielding film may be provided between each imaging device on a substrate such as a substrate for a solid-state imaging device or on the back surface of the substrate for a solid-state imaging device.
  • a base layer may be provided on the substrate, as necessary, to improve the adhesion with the upper layer, to prevent the diffusion of substances, or to planarize the surface of the substrate.
  • various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied.
  • the thickness of the photosensitive colored layer is preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 0.2 ⁇ m to 5 ⁇ m, and still more preferably 0.2 ⁇ m to 3 ⁇ m.
  • Drying (pre-baking) of the photosensitive colored layer applied on the substrate can be carried out at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds by a hot plate, an oven or the like.
  • Post-baking is a heat treatment after development to complete the curing, and a heat curing treatment is usually performed at 100 ° C. to 240 ° C., preferably 200 ° C. to 240 ° C.
  • This post-baking treatment is carried out continuously or batchwise using a heating means such as a hot plate, convection oven (hot air circulation dryer), high frequency heater or the like so that the coated film after development is under the above conditions. be able to.
  • the photosensitive colored layer according to the present invention when used, for example, clogging of the nozzle and piping of the discharge unit of the coating device, contamination of the photosensitive colored layer and pigment in the coating device due to adhesion, sedimentation and drying occur. There is a case. Therefore, in order to efficiently clean the contamination caused by the photosensitive coloring composition of the present invention, it is preferable to use a solvent for the present composition described later as a cleaning solution. Also, Japanese Patent Application Laid-Open Nos. 7-128867, 7-146562, 8-278637, 2000-273370, 2006-85140, 2006-291191, and the like.
  • the cleaning solution described in JP2007-2101A, JP2007-2102A, JP2007-281523A and the like can also be suitably used as the cleaning and removal of the photosensitive coloring composition according to the present invention.
  • alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferable.
  • These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group.
  • the mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 80/20.
  • the surfactant related to the composition described above may be added to the cleaning solution.
  • the negative-working photosensitive coloring composition in the present invention contains a radically polymerizable monomer.
  • the radically polymerizable monomer can make up the photosensitive coloring composition in a negative type.
  • the radically polymerizable monomer is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds.
  • the radically polymerizable monomers in the present invention may be used singly or in combination of two or more.
  • examples of the monomer include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid etc.) and esters thereof, amides, and large amounts of these.
  • examples thereof include an ester of unsaturated carboxylic acid and aliphatic polyhydric alcohol compound, and an amide of unsaturated carboxylic acid and aliphatic polyhydric amine compound, and multimers thereof.
  • addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group etc.
  • radical polymerizable monomer a compound having at least one addition polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or more under normal pressure is also preferable.
  • monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, etc .; (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri
  • Polyfunctional (meth) acrylate obtained by reacting a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group with a polyfunctional carboxylic acid can also be mentioned.
  • a radically polymerizable monomer it has a fluorene ring described in JP-A 2010-160418, JP-A 2010-129825, Japanese Patent No. 4364216, etc., and it has an ethylenic polymerizable group. It is also possible to use a compound having two or more functions, a cardo resin.
  • radically polymerizable monomers represented by formulas (MO-1) to (MO-5) described in paragraphs 0297 to 0300 of JP-A-2012-215806 can also be suitably used.
  • radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-5) compounds described in paragraph No. 0248 to paragraph No. 0251 of JP-A-2007-269779 can be mentioned. It can also be suitably used in the present invention.
  • radically polymerizable monomers RP 1040 (manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol triacrylate (commercially available product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available product As KAYARAD D-320; Nippon Kayaku Co., Ltd.
  • dipentaerythritol penta (meth) acrylate commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.
  • dipentaerythritol hexa (meth) acrylate commercially available As a product, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and a structure in which these (meth) acryloyl groups are interposed between ethylene glycol and propylene glycol residues are preferable.
  • KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.
  • a structure in which these (meth) acryloyl groups are interposed between ethylene glycol and propylene glycol residues are preferable.
  • These oligomer types can also be used.
  • the radically polymerizable monomer is a polyfunctional monomer, and may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is, but if necessary, the hydroxyl of the ethylenic compound described above A nonaromatic carboxylic acid anhydride may be reacted with the group to introduce an acid group.
  • non-aromatic carboxylic acid anhydrides include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydride Maleic acid is mentioned.
  • the monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a nonaromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
  • Polyfunctional monomers having an acid group are preferred, and particularly preferred in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.
  • Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • One of these monomers may be used alone, or two or more of these monomers may be mixed and used because it is difficult to use a single compound in production.
  • a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as monomers.
  • the acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40 mg-KOH / g, particularly preferably 5 to 30 mg-KOH / g.
  • a polyfunctional monomer having a caprolactone structure described in paragraphs 0306 to 0313 of JP 2012-215806 A can also be used.
  • multifunctional monomers having such a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and include DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc. It can be mentioned.
  • polyfunctional monomers having a caprolactone structure can be used alone or in combination of two or more.
  • SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmar, Nippon Kayaku Co., Ltd.
  • examples include DPCA-60, which is a hexafunctional acrylate having six pentylene oxy chains manufactured by a company, and TPA-330, which is a trifunctional acrylate having three isobutylene oxy chains.
  • radical polymerizable monomers urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765, and Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417 and JP-B-62-39418 are also suitable.
  • polymerizable compounds addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 can be used.
  • the curable composition excellent in very high photosensitive speed can be obtained.
  • ethylenically unsaturated compounds having an acid group are also suitable.
  • Ethylenically unsaturated compounds having an acid group can be formed by (meth) acrylate forming a hydroxy group of a part of the polyfunctional alcohol, and adding an acid anhydride to the remaining hydroxy group to form a carboxy group, etc. can get.
  • Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • a polyfunctional thiol compound having two or more mercapto (SH) groups in the same molecule described in paragraphs 0216 to 0220 of JP 2012-150468 A can also be used.
  • a polymerizable compound having a trifunctional or higher functional group and having a different ethylene oxide chain length in combination, since the developability of the photosensitive coloring composition can be controlled and excellent pattern forming ability can be obtained.
  • the selection and selection of the polymerizable compound may be made for compatibility and dispersibility with other components (for example, a photopolymerization initiator, a coloring material (pigment), a binder polymer, etc.) contained in the photosensitive coloring composition.
  • the method of use is an important factor, and it may be possible to improve the compatibility, for example, by the use of a low purity compound or a combination of two or more.
  • a specific structure may be selected from the viewpoint of improving the adhesion to a hard surface such as a support.
  • the content of the radically polymerizable monomer in the photosensitive coloring composition of the present invention is preferably 0.1% by mass to 90% by mass, and more preferably 1.0% by mass to the solid content in the photosensitive coloring composition. 80% by mass is more preferable, and 2.0% by mass to 70% by mass is particularly preferable.
  • the negative-working photosensitive coloring composition in the present invention contains a radical photopolymerization initiator.
  • the radical photopolymerization initiator can impart photosensitivity to the polymerizable composition to form a photosensitive composition, and can be suitably used for a color resist or the like.
  • a radical photopolymerization initiator what is known as a photoinitiator mentioned below can be used.
  • the photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators, for example, visible from the ultraviolet region Those having photosensitivity to light rays are preferable, and they may be active agents that produce an active radical by causing an action with a photoexcited sensitizer.
  • the photopolymerization initiator preferably contains at least one component having a molecular absorption coefficient of at least about 50 in the range of about 300 to 800 nm (more preferably 330 to 500 nm).
  • Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), an acylphosphine compound such as an acylphosphine oxide, hexaarylbiimidazole, oxime
  • Examples include oxime compounds such as derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone and the like.
  • halogenated hydrocarbon compound having a triazine skeleton examples include, for example, 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, an F. compound. C. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-58241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, specification of U.S. Pat. No. 4,129,976 Compounds described in the book, and the like.
  • Examples of the compounds described in the aforementioned US Pat. No. 4,129,976 include compounds having an oxadiazole skeleton (eg, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) ) -1,3,4-oxadiazole,
  • polyhalogen compounds for example, acridine derivatives (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, etc.
  • ketone compound examples include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-Ethoxycarbonylbenzoluphenone, benzophenonetetracarboxylic acid or its tetramethyl ester, 4,4'-bis (dialkylamino) benzophenones (eg, 4,4'-bis (dimethylamino) benzophenone, 4,4'- Bisdicyclohexylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4'-dimethylamime Benzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone
  • a hydroxyacetophenone compound, an aminoacetophenone compound, and an acyl phosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine oxide initiator described in Japanese Patent No. 4225898 can also be used.
  • a hydroxyacetophenone type initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade name: all manufactured by BASF Corp.) can be used.
  • aminoacetophenone initiators commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF AG) can be used.
  • aminoacetophenone initiator a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long wave light source such as 365 nm or 405 nm can also be used.
  • an acyl phosphine type initiator IRGACURE-819 and DAROCUR-TPO (brand name: all made by BASF Corporation) which are commercial items can be used.
  • an oxime type compound is mentioned.
  • compounds described in JP-A-2001-233842 compounds described in JP-A-2000-80068, and compounds described in JP-A-2006-342166 can be used.
  • oxime ester compounds other than those described above compounds described in JP-T-2009-519904, in which an oxime is linked to the carbazole N-position, compounds described in US Pat. No. 7,626,957, in which a hetero substituent is introduced in the benzophenone moiety
  • compounds described in JP-A-2010-15025 and U.S. Patent Publication 2009-292039 in which a nitro group is introduced at the site, a ketoxime compound according to WO2009-131189, and containing a triazine skeleton and an oxime skeleton in the same molecule
  • the compound described in US Pat. No. 7,556,910, the compound described in JP-A 2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source may be used.
  • the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A can also be suitably used.
  • cyclic oxime compounds cyclic oxime compounds fused to a carbazole dye described in JP-A-2010-32985 and JP-A-2010-185072 are particularly preferable from the viewpoint of high light absorption and high light absorption.
  • the compound described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can also be suitably used because high sensitivity can be achieved by regenerating the active radical from the polymerization inactive radical. .
  • an oxime compound having a specific substituent described in JP-A-2007-269779 and an oxime compound having a thioaryl group disclosed in JP-A-2009-191061 can be mentioned.
  • the radical photopolymerization initiators used in the present invention may be used in combination of two or more, if necessary.
  • the content (total content in the case of two or more types) of the radical photopolymerization initiator in the photosensitive coloring composition is 0.1 to 20% by mass with respect to the total solid content of the photosensitive coloring composition
  • the range 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 patternability can be obtained.
  • the negative-working photosensitive coloring composition preferably contains a colorant.
  • the colorants that can be used in the present invention are not particularly limited, and various conventionally known dyes and pigments (organic pigments, inorganic pigments, etc.) can be used alone or in combination.
  • the colorant is preferably an organic compound, and more preferably an organic pigment.
  • a pigment which can be used for this invention various inorganic pigments or organic pigments conventionally known can be mentioned.
  • a pigment whose average particle diameter is as small as possible, and also considering the handling property it is preferable to use a pigment whose average particle diameter is as small as possible, and also considering the handling property, the average particle diameter of the pigment is 0.01 ⁇ m to 0.1 ⁇ m is preferable, and 0.01 ⁇ m to 0.05 ⁇ m is more preferable.
  • organic pigment which can be preferably used in the present invention.
  • present invention is not limited to these.
  • C.I. I. Pigment green 36 (hereinafter, also simply referred to as PG 36) is preferable.
  • C.I. I. Pigment yellow 139 may be referred to as PY 139
  • C.I. I. Pigment green 7 may be referred to as PG7.
  • the coloring material when the coloring material is a dye, it can be uniformly dissolved in the composition.
  • the dye which can be used as a coloring material which comprises the composition in this invention does not have a restriction
  • the chemical structure includes pyrazole azo type, anilino azo type, triphenylmethane type, anthraquinone type, anthrapyridone type, benzylidene type, oxonol type, pyrazolotriazole azo type, pyridone azo type, cyanine type, phenothiazine type, pyrrolopyrazole azomethine type, Dyes of xyatin type, phthalocyanine type, benzopyran type, indigo type can be used.
  • an inorganic pigment which can be used as a coloring material metal compounds represented by metal oxides, metal complex salts and the like can be mentioned, and specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, Mention may be made of metal oxides such as magnesium, chromium, zinc, antimony and silver, and composite oxides of the aforementioned metals.
  • metal oxides such as magnesium, chromium, zinc, antimony and silver, and composite oxides of the aforementioned metals.
  • a nitride of titanium, a silver-tin compound, a silver compound, and the like can also be used.
  • Particularly preferred inorganic pigments include carbon black, titanium black and titanium white.
  • inorganic pigments and organic pigments can be used in combination.
  • the content of the colorant in the total solid content of the photosensitive coloring composition in the invention is preferably 40% by mass or more, more preferably 50% by mass or more and less than 100% by mass, and more preferably 55% by mass or more and 90% % Or less is more preferable.
  • the content ratio by mass of the coloring material to the polymerizable monomer in the photosensitive coloring composition of the present invention is preferably 1: 2 to 20: 1, and preferably 1: 1 to 10: 1. It is more preferable that
  • the photosensitive coloring composition according to the present invention may contain various additives, for example, binders, solvents, surfactants, adhesion promoters, antioxidants, and ultraviolet absorbers, as needed, as long as the effects of the present invention are not impaired.
  • An agent, an anticoagulant, a dispersant and the like can be blended.
  • Binder ⁇ The binder is often added at the time of preparation of the pigment dispersion, and it may be soluble in an organic solvent and capable of maintaining dispersion stability and curability.
  • the binder is preferably a linear organic high molecular weight polymer which is soluble in an organic solvent.
  • linear organic high molecular weight polymers polymers having a carboxylic acid in the side chain, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54- No. 25957, JP-A-59-53836, JP-A-59-71048, such as methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid co-polymer
  • a polymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, etc. may be mentioned, and similarly, an acidic cellulose derivative having a carboxylic acid in its side chain is useful.
  • polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins and acrylic / acrylamide copolymer resins are preferable from the viewpoint of heat resistance, and from the viewpoint of control of developability, Acrylic resins, acrylamide resins and acrylic / acrylamide copolymer resins are preferred.
  • acrylic resin a copolymer comprising a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide and the like, such as benzyl methacrylate / methacrylic acid,
  • benzyl methacrylate / methacrylic acid a copolymer comprising a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide and the like, such as benzyl methacrylate / methacrylic acid,
  • KS Resist-106 manufactured by Osaka Organic Chemical Industry Co., Ltd.
  • Cyclomer P series manufactured by Daicel Chemical Industries, Ltd.
  • Resins having a polymerizable group in the side chain described in JP-A-2008-189747, paragraphs 0021 to 0108, JP-A-2009-216913, paragraphs 0062 to 0220 can also be preferably used as a binder in the present invention. Moreover, such a resin can be suitably used also as a below-mentioned dispersing agent. By dispersing the coloring material at a high concentration in these binders, adhesion to the lower layer can be imparted, and these also contribute to the spin-coated surface.
  • the dispersant can be added to improve the dispersibility of the pigment.
  • a well-known thing can be selected suitably and can be used as said dispersing agent, For example, a cationic surfactant, a fluorine-type surfactant, a polymer dispersing agent etc. are mentioned.
  • pigment dispersants examples include polymer dispersants [for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate (Meth) acrylic copolymers, naphthalenesulfonic acid formalin condensates], and surfactants such as polyoxyethylene alkyl phosphates, polyoxyethylene alkyl amines, alkanolamines, pigment derivatives, etc. Can. Polymer dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers according to their structures.
  • terminal-modified polymers having an anchor site on the pigment surface include polymers having a phosphoric acid group at the terminals described in JP-A-3-112929 and JP-A-2003-533455, etc., JP-A-2002 Examples thereof include polymers having a sulfonic acid group at the terminal as described in JP-273191A and the like, and polymers having a partial skeleton of an organic dye and a heterocycle described in JP-A-9-77994 and the like.
  • polymers described in JP-A-2007-277514 in which two or more anchor sites (acid group, basic group, partial skeleton of organic dye, heterocyclic ring, etc.) are introduced at the polymer end are also available. It is excellent in dispersion stability and preferable.
  • graft polymers having anchor sites on the pigment surface include poly (lower alkyleneimines) described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668 and the like. And the reaction product of polyarylamine and polyester described in JP-A-9-169821 and the like, and the macromonomer described in JP-A-10-339949 and JP-A-2004-37986 and the like. Copolymers with nitrogen atom monomers, graft polymers having a partial skeleton or a heterocyclic ring of the organic dye described in JP-A-2003-238837, JP-A 2008-9426, JP-A 2008-81732, etc.
  • amphoteric dispersion resin having a basic group and an acidic group described in JP-A-2009-203462 exhibits the dispersibility of the pigment dispersion, the dispersion stability, and the colored curable composition using the pigment dispersion. Particularly preferred from the viewpoint of developability.
  • a known macromonomer can be used as a macromonomer to be used when producing a graft type polymer having an anchor site to a pigment surface by radical polymerization, and a macromonomer AA-6 (terminally manufactured by Toagosei Co., Ltd.) Poly (methyl methacrylate) in which the group is methacryloyl, AS-6 (polystyrene in which the terminal is methacryloyl), AN-6S (copolymer of styrene and acrylonitrile in which the terminal is methacryloyl), AB-6 Butyl acrylate having a methacryloyl group as the terminal group, Plaxel FM5 ( ⁇ -caprolactone 5-mole equivalent adduct of 2-hydroxyethyl methacrylate) manufactured by Daicel Chemical Industries, Ltd., FA 10 L (2-hydroxyethyl acrylate) ⁇ -caprolactone (10 molar equivalent adduct), and JP-A-2-272 Examples
  • polyester macromonomers which are particularly excellent in flexibility and lipophilicity are particularly preferred from the viewpoint of the dispersibility of the pigment dispersion, the dispersion stability, and the developability of the colored curable composition using the pigment dispersion.
  • a polyester-based macromonomer represented by a polyester-based macromonomer described in JP-A-2-272009 is most preferable.
  • block type polymer having an anchor site to the pigment surface block type polymers described in JP-A 2003-49110, JP-A 2009-52010, etc. are preferable.
  • the pigment dispersant that can be used in the present invention is also available as a commercial product, and as such specific examples, "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (by carboxylic acid), BYK Chemie Copolymer containing acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) "," BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ), EFKA 4047, 4050 to 4010 to 4165 (polyurethane type), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylic acid) manufactured by EFKA Salt), 6220 (fatty acid polyester), 674 (Phthalocyanine derivative), 6750 (Azo pigment derivative) "," Adispar
  • "W001: cationic surfactant” polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl
  • Nonionic surfactants such as ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017”, fluorine surfactants such as Megafac F781 (manufactured by DIC) Surfactant, Morishita Sangyo Co., Ltd.
  • pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.
  • the pigment dispersant of the present invention may be used in combination with an alkali-soluble resin together with a terminal-modified polymer having an anchor site on the pigment surface, a graft polymer, and a block polymer.
  • (meth) acrylic acid copolymer As the alkali-soluble resin, (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain
  • denatured the acid anhydride to the polymer which has a hydroxyl group are mentioned, Especially a (meth) acrylic acid copolymer is preferable.
  • the resin described in JP-A-2010-106268 is also preferable, and particularly, from the viewpoint of dispersibility, a polymer dispersant having a polyester chain in a side chain is preferable, and an acid group and a polyester chain The resin which has and can also be mentioned suitably.
  • resin examples include those described in paragraphs 0078 to 0111 of JP-A-2010-106268.
  • the dispersants may be used alone or in combination of two or more.
  • the amount of the dispersant added to the photosensitive coloring composition in the present invention is usually preferably about 0.1 to 50 parts by mass with respect to 100 parts by mass of the pigment.
  • the photosensitive coloring composition may contain a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and lengthening the photosensitive wavelength.
  • a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and lengthening the photosensitive wavelength.
  • the sensitizer that can be used in the present invention those capable of sensitizing the above-described photoradical polymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable.
  • Examples of the sensitizer used in the photosensitive coloring composition include compounds described in Paragraph Nos. [0101] to [0154] of JP-A-2008-32803.
  • the content of the sensitizer in the photosensitive coloring 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 initiation decomposition efficiency, More preferably, 5% by mass to 15% by mass.
  • the sensitizers may be used alone or in combination of two or more.
  • the photosensitive coloring composition of the present invention can generally be constituted using an organic solvent.
  • the organic solvent is basically not particularly limited as long as the solubility of each component and the coating property of the photosensitive coloring composition are satisfied, but it is selected in particular in consideration of the solubility, the coating property and the safety of the binder. Is preferred.
  • organic solvents examples 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 etc.), alkyl 3-hydroxypropionate Esters (eg methyl 3-oxypropionate, ethyl 3-oxypropionate etc.
  • esters such as ethyl acetate, n-butyl acetate, is
  • Alkyl oxypropionates eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.
  • ether for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolv
  • methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl are particularly preferable in this case.
  • the content of the organic solvent in the photosensitive coloring composition is preferably such that the total solid concentration of the composition is 5 to 80% by mass, and more preferably 5 to 60% by mass. And 10 to 50% by mass are particularly preferable.
  • additives can be further added to the photosensitive coloring composition in the present invention as required.
  • various additives for example, various additives described in the above-mentioned JP-A-2005-326453 can be mentioned.
  • the method for producing a color filter according to the present invention requires, for example, a minute size having a thickness of 0.7 ⁇ m or less and / or a pixel pattern size (one side in a square pattern) of 2 ⁇ m or less (eg, 0.5 to 2.0 ⁇ m) It is effective in producing a color filter for solid-state imaging devices.
  • the present invention also relates to a color filter produced by the method for producing a color filter of the present invention.
  • the color filter of the present invention is manufactured by the method of manufacturing a color filter of the present invention, the likelihood of exposure latitude (mask followability) and depth of focus is manufactured without loss of throughput, and color filter pixel array pattern Rectangularity is also improved.
  • the color filter of the present invention can be suitably used for solid-state imaging devices such as CCDs and CMOSs, and is particularly suitable for high-resolution CCDs and CMOSs having one million pixels or more.
  • the color filter of the present invention can be used, for example, as a color filter disposed between the light receiving portion of each pixel constituting a CCD or CMOS and a microlens for collecting light.
  • color filter of the present invention for example, a form of a multicolor color filter in which the red pattern and other colored patterns are combined (for example, 3 having at least the red pattern, blue pattern, and green pattern) Color filters of colors or more are preferred.
  • a film thickness of the coloring pattern in a color filter 2.0 micrometers or less are preferable, and 1.0 micrometer or less is more preferable.
  • a size (pattern width) of a coloring pattern 2.0 micrometers or less are preferable, and 1.7 micrometers or less are more preferable.
  • the solid-state imaging device of the present invention includes the color filter of the present invention described above.
  • the configuration of the solid-state imaging device according to the present invention is a configuration provided with the color filter according to the present invention, and is not particularly limited as long as it functions as a solid-state imaging device. .
  • a plurality of photodiodes constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicon and the like are provided.
  • the device has a light shielding film made of tungsten or the like opened only at the light receiving portion of the diode, and has a device protective film made of silicon nitride or the like formed on the light shielding film to cover the entire light shielding film and the photodiode light receiving portion It is a structure which has a color filter of this invention on a protective film.
  • a configuration having a condensing means for example, a micro lens etc. hereinafter the same
  • the device protective layer and under the color filter (closer to the support), or a constitution having a condensing means on the color filter Or the like.
  • the solid-state imaging device is briefly described with reference to FIG. 1 as an example.
  • the solid-state imaging device 10 includes a light receiving element (photodiode) 42 provided on a silicon substrate, a color filter 13, a flattening layer (underlayer) 14, a micro lens 15 and the like.
  • the planarization layer 14 is not necessarily required.
  • the mutual thickness and the ratio of the width are disregarded and it exaggerates and displays it in part.
  • the support is not particularly limited as long as it is used for a color filter other than a silicon substrate.
  • a color filter other than a silicon substrate For example, soda glass, borosilicate glass, quartz glass used for liquid crystal display elements and the like, and transparent conductive films are attached thereto Or a photoelectric conversion element substrate used for a solid-state imaging device or the like, such as an oxide film or silicon nitride.
  • an interlayer or the like may be provided between the support and the color filter 13 as long as the present invention is not impaired.
  • a P well 41 is provided on a silicon substrate, and a photodiode 42 is provided on part of the surface of the P well.
  • the photodiode 42 is formed by performing heat treatment after ion-implanting an N-type impurity such as P or As into a part of the surface of the P well.
  • an impurity diffusion layer 43 having a higher N-type impurity concentration than the photodiode 42 is provided on the surface of the P well 41 of the silicon substrate and in a region different from the part.
  • the impurity diffusion layer 43 is formed by performing heat treatment after ion implantation of an N-type impurity such as P or As, and the role of the floating diffusion layer for transferring the charge generated by the photodiode 42 receiving the incident light. Play.
  • the well 41 as a P-type impurity layer and the photodiode 42 and the impurity diffusion layer 43 as an N-type impurity layer
  • the well 41 as an N-type impurity layer and the photodiode 42 and the impurity diffusion layer 43 as a P-type impurity layer.
  • An insulating film 47 such as SiO 2 or SiO 2 / SiN / SiO 2 is provided on the P well 41, the photodiode 42, and the impurity diffusion layer 43, and poly Si, tungsten, or the like is provided on the insulating film 47.
  • An electrode 44 made of tungsten silicide, Al, Cu or the like is provided.
  • the electrode 44 plays a role of the gate of the gate MOS transistor, and can play a role of a transfer gate for transferring the charge generated in the photodiode 42 to the impurity diffusion layer 43.
  • a wiring layer 45 is formed above the electrode 44. Above the wiring layer 45, a BPSG film 46 and a P-SiN film 48 are provided.
  • the interface between the BPSG film 46 and the P-SiN film 48 is formed to be curved downward above the photodiode 42 and serves as an intralayer lens for efficiently guiding incident light to the photodiode 42. Play.
  • a planarization layer (underlayer) 49 is formed on the BPSG film 46 in order to planarize the surface of the P-SiN film 48 or the uneven portion other than the pixel region.
  • the color filter 13 is formed on the planarizing layer (base layer) 49.
  • the colored film (so-called solid film) formed on the silicon substrate without dividing the area is referred to as a “colored (colored radiation-sensitive) layer”, and the area is divided into a pattern.
  • the colored film (for example, a film patterned in a stripe shape) is called a "colored pattern”.
  • a coloring pattern (for example, a coloring pattern patterned in a square or a rectangle, etc.) which is an element constituting the color filter 13 is referred to as "coloring (red, green, blue) pixel”.
  • the color filter 13 is composed of a plurality of two-dimensionally arranged green pixels (first color pixels) 20G, red pixels (second color pixels) 20R, and blue pixels (third color pixels) 20B.
  • the colored pixels 20R, 20G, and 20B are formed above the light receiving element 42, respectively.
  • the green pixels 20G are formed in a checkered pattern, and the blue pixels 20B and the red pixels 20R are formed between the green pixels 20G.
  • each colored pixel 20R, 20G, 20B is arranged and displayed on 1 row.
  • the planarization layer 14 is formed to cover the upper surface of the color filter 13 and planarizes the color filter surface.
  • the microlens 15 is a condensing lens disposed with the convex surface upward, and is provided above the planarization layer 14 (in the case where the planarization film is not provided, the color filter) and above the light receiving element 42. Each microlens 15 efficiently guides the light from the subject to each light receiving element 42.
  • the color filter of the present invention is also suitable as a color filter for liquid crystal display devices.
  • a liquid crystal display device provided with such a color filter can display a high quality image having a good display color and excellent display characteristics.
  • the color filter of the present invention is useful for a color TFT liquid crystal display device.
  • the color TFT liquid crystal display device is described, for example, in “Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., published in 1996)”.
  • the present invention is applied to a liquid crystal display device with a wide viewing angle such as IPS or other horizontal electric field drive method, MVA or other pixel division method, STN, TN, VA, OCS, FFS, R-OCB, etc. it can.
  • the color filter of the present invention can also be used for a bright and high-definition color-filter on array (COA) system.
  • COA color-filter on array
  • the colored layer formed by the COA method has a rectangular shape with a side length of about 1 to 15 ⁇ m in order to electrically connect the ITO electrode disposed on the colored layer and the terminal of the driving substrate below the colored layer. It is necessary to form a conductive path such as a through hole or a U-shaped recess, and it is preferable to make the size of the conductive path (that is, the length of one side) particularly 5 ⁇ m or less. It is also possible to form a conduction path of 5 ⁇ m or less.
  • the liquid crystal display device of the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle ensuring film, and the like, in addition to the color filter of the present invention.
  • the color filter of the present invention can be applied to a liquid crystal display element composed of these known members.
  • these members for example, “'94 Liquid crystal display peripheral materials and chemicals market (Kentaro Shima, Inc., CMSC Co., Ltd. 1994 issue),” “Present state and future prospect of liquid crystal related market in 2003 (second volume) (Yoshikichi Co., Ltd. Fuji Chimera Research Institute, published in 2003).
  • For backlight see SID meeting Digest 1380 (2005) (A. Konno et. Al), pages 18 to 24 of Monthly Display December 2005 (Yasuhiro Shima), pages 25 to 30 (Takaaki Yagi), etc. Have been described.
  • the color filter of the present invention When the color filter of the present invention is used in a liquid crystal display, high contrast can be realized when it is combined with a conventionally known cold cathode three-wavelength tube, but red, green and blue LED light sources (RGB-LED) By using as a backlight, it is possible to provide a liquid crystal display device having high luminance and high color purity and good color reproducibility.
  • RGB-LED red, green and blue LED light sources
  • ⁇ Color filter manufacturing test conditions> A transparent flattening layer (transparent foundation layer) was formed on a silicon substrate using the following base agent, and a Bayer pattern was formed thereon with a 1.0 ⁇ m pattern using the photosensitive green composition prepared above.
  • Photosensitive green composition • Film thickness of photosensitive green layer: 0.6 ⁇ m (after pre-baking) Pre-bake: 100 ° C.
  • Exposure wavelength 356 nm
  • Exposure apparatus Canon Inc.
  • Development conditions Substrate temperature: 23 ° C Development: CD-2000 (Fujifilm Electronics Materials Co., Ltd.) 60% diluted product Straight nozzle 100 ml discharge, 60 seconds paddle processing, with shaking
  • Liquid temperature: 23 ° C Rinse Use a straight nozzle and fix the nozzle at the center of the top of the wafer.
  • Example 1-1 The delay time between each exposure was 35 msec for the two-division exposure and the three-division exposure.
  • the total of the irradiation amount (exposure amount) was performed within the range of 100 to 500 mJ / cm 2 for all of the division non-division, 2-division exposure and 3-division exposure.
  • the exposure amount was equally divided for the two-part exposure and the three-part exposure.
  • the EL, DOF and rectangularity by the above-mentioned divided exposure were evaluated. Evaluation criteria are as follows.
  • the EL evaluation criteria The EL was evaluated by measuring the underexposure margin.
  • the underexposure margin refers to the line width of the mask pattern and the line width of the actual pattern after development from the lowest exposure amount where the adhesion between the pattern and the substrate is weak and the phenomenon of pattern peeling-off does not occur. It means the exposure amount range up to the matching optimum exposure amount (Eopt).
  • Eopt optimum exposure amount
  • 2 The pattern appeared, and the underexposure margin was improved by 5% or more over the evaluation standard 1.
  • 3 The pattern appeared, and the underexposure margin was further improved by 5% or more over the evaluation standard 2.
  • 4 The pattern appeared, and the underexposure margin was further improved by 5% or more than the evaluation criteria 3.
  • 5 The pattern was developed, and the underexposure margin was further improved by 5% or more than the evaluation standard 4.
  • DOF evaluation criteria The DOF margin was evaluated with a CD (Critical Dimension) value ⁇ 10% as an allowable value. That is, in the DOF margin, the exposure amount at which the line width of the mask pattern matches the line width of the obtained pattern at the best focus is the optimum exposure amount (Eopt), and the depth of focus is the best focus at the optimum exposure amount (Eopt). It means the depth of focus range where the line width fluctuation falls within ⁇ 10% when shifted from.
  • the rectangularity of the 1.0 ⁇ m square pattern observed from above was evaluated by the line width ratio in the lateral direction and the line width in the diagonal direction.
  • 2: The line width ratio in the diagonal direction / lateral direction was 1.1 or more and less than 1.13.
  • Example 4 The line width ratio in the diagonal direction / lateral direction was 1.16 or more and less than 1.20.
  • 5 The line width ratio in the diagonal direction / lateral direction was 1.20 or more.
  • the results are shown in the following table. [Examples 1-2 to 1-5] The EL, DOF, and rectangularity by division exposure were evaluated in the same manner as in Example 1-1 except that the radically polymerizable monomer and the photoradical polymerization initiator were changed to the compounds shown in the following table, respectively. The results are shown in the following table.
  • the radically polymerizable monomers and the photoradical polymerization initiator used in the above table are as follows.
  • Example 2 In the same manner as in Example 1-1, the radical polymerizable monomer and the photo radical polymerization initiator were evaluated as EL and throughput by changing the delay time at the time of 2-division exposure as A-1 and B-2, respectively.
  • the total dose (exposure dose) was in the range of 100 to 500 mJ / cm 2 , and the exposure dose was equally divided.
  • EL evaluation criteria The EL was evaluated by measuring the underexposure margin. 1: The pattern appeared but the underexposure margin was narrow. 2: The pattern appeared, and the underexposure margin was improved by 5% or more over the evaluation standard 1. 3: The pattern appeared, and the underexposure margin was further improved by 5% or more over the evaluation standard 2.
  • the EL and the throughput decrease as the delay time is increased. Therefore, it is understood that shortening the delay time as much as possible is suitable for improving the EL.
  • the reason why the EL decreases as the delay time becomes longer is presumed to be that the adhesion failure between the obtained pattern and the substrate occurs in the low exposure region.
  • Example 3 As in Example 1-1, the radically polymerizable monomer and the photoradical polymerization initiator are respectively divided into two portions as A-1 and B-2 and the respective exposures at the time of three division exposure (first exposure, second exposure, The EL due to the change of the exposure amount in the third exposure) was evaluated. The delay time between each exposure was 35 msec for the two-division exposure and the three-division exposure. In addition, the total of the irradiation amount (exposure amount) was performed within the range of 100 to 500 mJ / cm 2 for all of the division non-division, 2-division exposure and 3-division exposure. Evaluation criteria are as follows. 1: The pattern appeared but the EL margin was narrow.
  • the ratio of the exposure amount in the divided exposure is such that the smaller the exposure amount of the first exposure and the higher the number of divisions, the better the EL.
  • This is presumed to be because when the exposure amount of the first exposure is larger than the exposure amount of the second exposure, the diffusion of radicals in the first exposure is large and the contribution of the second exposure is small. That is, it is considered that as a result, it becomes close to the exposure which is not divided.
  • the number of divisions is large, even if the total exposure amount is the same, since the exposure amount of unit exposure such as the first exposure and the second exposure is small, it is possible to move in the lateral direction (contributing to the line width) by exposure.
  • the EL is improved because the radical diffusion of the compound is inactivated by oxygen inhibition.
  • the deactivation toward the substrate is considered to be delayed compared to the deactivation of radicals in the lateral direction, it is presumed that the deterioration of the adhesion between the obtained pattern and the substrate does not increase.
  • the method for producing a color filter of the present invention can be applied to a liquid crystal display element or a solid-state imaging element, and is particularly suitable for a high resolution CCD element or CMOS having a size of more than one million pixels. In particular, it is suitable at the time of manufacture of the color filter of a pixel size of 1.0 micrometer or less.
  • the present invention it is possible to improve the likelihood of EL and DOF without deteriorating the throughput, and improve the rectangularity of the color filter pixel array pattern by improving the mask followability.
  • a manufacturing method, and a color filter, a solid-state imaging device, and a liquid crystal display manufactured using the same can be provided.
  • a pixel having a pixel size of particularly less than 1.2 ⁇ m in a color filter for solid-state imaging device red, green, blue, CMY (cyan, magenta, yellow), transparency, etc.
  • EL mask followability
  • DOF the rectangularity of the color filter pattern that can be observed from the top surface and the cross section can be improved.
  • solid-state imaging device 13 color filter 14 flattening layer 15 micro lens 20 G green pixel (first color pixel) 20R red pixel (second color pixel) 20B blue pixel (third color pixel) 41 P well 42 light receiving element (photodiode) 43 impurity diffusion layer 44 electrode 45 wiring layer 46 BPSG film 47 insulating film 48 P-SiN film 49 planarizing layer

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Abstract

La présente invention concerne : un procédé destiné à produire un filtre couleur et qui peut augmenter la rectangularité d'un motif de réseau de pixels de filtre couleur au moyen d'une augmentation du traçage de masque et qui peut augmenter la probabilité de latitude d'exposition (suivi de masque) et de profondeur focale sans perte de débit ; un filtre couleur produit à l'aide de celui-ci ; un élément d'imagerie à l'état solide ; et un dispositif d'affichage à cristaux liquides. Le procédé de production d'un filtre couleur passe par les étapes suivantes : une étape d'exposition d'une couche colorée photosensible, qui contient un monomère polymérisable par voie radicalaire et un initiateur photo-radicalaire qui utilise un masque photographique pour un réseau de pixels de filtre couleur ; et une étape de formation du motif de réseau de pixels de filtre couleur au moyen de développement de la couche colorée photosensible post-exposition. L'exposition est réalisée de manière divisée en une pluralité d'instances qui se suivent aux mêmes coordonnées.
PCT/JP2014/052153 2013-02-18 2014-01-30 Procédé de production d'un filtre couleur, filtre couleur produit de cette façon, élément d'imagerie à l'état solide et dispositif d'affichage à cristaux liquides WO2014125935A1 (fr)

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WO2023234095A1 (fr) * 2022-06-01 2023-12-07 富士フイルム株式会社 Élément de photodétection, capteur d'image et procédé de fabrication d'élément de photodétection
WO2023234094A1 (fr) * 2022-06-01 2023-12-07 富士フイルム株式会社 Élément photodétecteur, capteur d'image et procédé de fabrication d'élément photodétecteur

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JP2008287213A (ja) * 2007-01-12 2008-11-27 Toyo Ink Mfg Co Ltd 着色組成物およびカラーフィルタの製造方法
JP2009169413A (ja) * 2007-12-19 2009-07-30 Toppan Printing Co Ltd カラーフィルタの製造方法およびカラーフィルタ
JP2010085600A (ja) * 2008-09-30 2010-04-15 Fujifilm Corp 着色硬化性組成物、カラーフィルタ及びその製造方法、並びに固体撮像素子

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008287213A (ja) * 2007-01-12 2008-11-27 Toyo Ink Mfg Co Ltd 着色組成物およびカラーフィルタの製造方法
JP2009169413A (ja) * 2007-12-19 2009-07-30 Toppan Printing Co Ltd カラーフィルタの製造方法およびカラーフィルタ
JP2010085600A (ja) * 2008-09-30 2010-04-15 Fujifilm Corp 着色硬化性組成物、カラーフィルタ及びその製造方法、並びに固体撮像素子

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