WO2017057105A1 - 高分子化合物、樹脂組成物、膜、固体撮像素子、高分子化合物の製造方法、固体撮像素子の製造方法、および光学デバイス - Google Patents

高分子化合物、樹脂組成物、膜、固体撮像素子、高分子化合物の製造方法、固体撮像素子の製造方法、および光学デバイス Download PDF

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WO2017057105A1
WO2017057105A1 PCT/JP2016/077727 JP2016077727W WO2017057105A1 WO 2017057105 A1 WO2017057105 A1 WO 2017057105A1 JP 2016077727 W JP2016077727 W JP 2016077727W WO 2017057105 A1 WO2017057105 A1 WO 2017057105A1
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polymer compound
general formula
film
solid
photoelectric conversion
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PCT/JP2016/077727
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English (en)
French (fr)
Japanese (ja)
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陽平 此島
利保 日比野
諏訪　充史
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東レ株式会社
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Priority to KR1020187005555A priority Critical patent/KR20180059751A/ko
Priority to JP2016560932A priority patent/JP6790826B2/ja
Priority to CN201680051409.3A priority patent/CN108026253B/zh
Publication of WO2017057105A1 publication Critical patent/WO2017057105A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation

Definitions

  • the present invention relates to a polymer compound, a resin composition, a film, a solid-state image sensor, a method for producing a polymer compound, a method for producing a solid-state image sensor, and an optical device.
  • the mainstream method for fabricating microlenses, waveguides, and white pixels is to process the applied resin by dry etching.
  • high refractive index materials obtained by combining a metal oxide such as titanium oxide or zirconium oxide with a siloxane resin or an acrylic resin have been studied (for example, see Patent Documents 1 to 3).
  • the present invention has a high surface roughness after dry etching, a high refractive index, a polymer compound that gives a highly transparent film, a resin composition and a solid-state imaging device using the same, a method for producing a polymer compound,
  • An object of the present invention is to provide a method for manufacturing a solid-state imaging device and an optical device.
  • the present invention provides at least (A) a compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group, and (B) a heterocyclic aromatic compound containing two or more structures of the general formula (1).
  • A a compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group
  • B a heterocyclic aromatic compound containing two or more structures of the general formula (1).
  • R 1 represents a hydrogen atom or an organic group having 1 to 6 carbon atoms.
  • the present invention it is possible to obtain a polymer material having a good surface roughness after dry etching and capable of forming a film having a high refractive index and a high transparency.
  • a highly transparent film containing the polymer material of the present invention as a microlens, a small and high-definition optical device can be manufactured.
  • the polymer compound of the present invention comprises (A) a compound having at least two polycyclic aromatic groups having a hydroxyl group or an alkoxy group, and (B) a heterocyclic fragrance containing two or more structures of the general formula (1).
  • a group compound is polycondensed.
  • R 1 represents a hydrogen atom or an organic group having 1 to 6 carbon atoms.
  • the polycyclic aromatic group is, for example, a naphthyl group Fluorene group, phenanthrene group, anthracene group, pyrene group, acenaphthene group, acenaphthylene group, fluoranthene group, chrysene group and the like.
  • a naphthyl group and a fluorene group are preferable from the viewpoint of transparency of the polymer compound, and a naphthyl group is particularly preferable from the viewpoint of a high refractive index.
  • Examples of the compound having a naphthyl group include compounds represented by the general formula (2).
  • n 1 and n 2 , k 1 and k 2 each independently represents an integer of 1 to 4.
  • m represents an integer of 0 to 1.
  • n 1 and n 2 , k 1 and k 2 mean the number of substituents OR 2 or R 3 bonded to the naphthyl group.
  • m means the number of consecutive groups X.
  • X is selected from the group consisting of oxygen atoms, sulfur atoms, methylene groups, and combinations thereof.
  • R 2 is a hydrogen atom or an organic group having 1 to 6 carbon atoms.
  • R 3 is a hydrogen atom or an organic group having 1 to 6 carbon atoms.
  • R 2 and R 3 may be the same or different.
  • a combination of an oxygen atom, a sulfur atom and a methylene group as an option for X is, for example, — (CH 2 ) j —, —O— (CH 2 ) j —, — And groups represented by S— (CH 2 ) j —, — (CH 2 ) j —O— (CH 2 ) 1 —, — (CH 2 ) j —S— (CH 2 ) 1 —, and the like.
  • j and l are each an integer of 1 or more, preferably an integer of 1 to 4, more preferably an integer of 1 to 2.
  • X is preferably an oxygen atom, a sulfur atom or a methylene group.
  • n 1 and n 2 , k 1 and k 2 are 1, m is 0, and R 2 is a hydrogen atom or an organic group having 1 or 2 carbon atoms.
  • R 3 is a functional group represented by a hydrogen atom or an organic group having 1 or 2 carbon atoms is preferable.
  • Examples of the compound of the polycyclic aromatic group having (A) a hydroxyl group or an alkoxy group having 2 or more, k 1 and k 2 are 0, compounds represented by the following general formula (5) is preferable.
  • n 1 and n 2 each independently represents an integer of 1 to 4.
  • m represents an integer of 0 to 1.
  • X is selected from the group consisting of oxygen atoms, sulfur atoms, methylene groups, and combinations thereof.
  • R 2 is a hydrogen atom or an organic group having 1 to 6 carbon atoms.
  • R 3 is a hydrogen atom or an organic group having 1 to 6 carbon atoms.
  • R 2 and R 3 may be the same or different.
  • More preferable compounds represented by the general formula (5) are those in which n 1 and n 2 are 1 and m is 0. Particularly preferred is a 1,1′-bi (2-hydroxy) naphthyl structure. By using this structure, the aromatic density in the constituent components of the film is improved, and a film having a higher refractive index can be formed.
  • the charging ratio of the compound (A) having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group used for polymerization is preferably 50% by mass or more, and 60% by mass with respect to the constituent components in the polymer compound. The above is more preferable.
  • the charging ratio of the compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group is 50% by mass or more because the refractive index of the film can be further improved.
  • the charging ratio of the compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group is preferably 90% by mass or less, more preferably 80% by mass or less, with respect to the constituent components in the polymer compound. More preferred. When it is 90% by mass or less, the crosslinking density in the film can be improved, and the strength of the film is further improved.
  • Examples of the compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group include, but are not limited to, the following compounds.
  • the compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group used for polymerization may be a single type or a plurality of types, and those shown in the present specification may be used alone or in combination. It can be used as a compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group.
  • (A) the compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group is a compound represented by the general formula (5), and contains at least a structure in which m is 0. Is preferable from the viewpoint of increasing the refractive index. A refractive index improves, so that there is much content of an aromatic component in the structural component of a film
  • R 1 is a hydrogen atom, methyl Group, ethyl group, propyl group, butyl group, etc.
  • Examples of the heterocyclic aromatic compound containing two or more structures of the general formula (1) include a triazine group, a pyrrole group, a furan group, a thiophene group, a pyridine group, an imidazole group, a pyrazole group, and a thiazole group. From the viewpoint of transparency, a triazine group, a pyrrole group and a furan group are preferable, and from the viewpoint of versatility, a compound having a triazine group represented by the general formula (3) is more preferable.
  • R 4 is an organic group having 1 to 12 carbon atoms or a functional group represented by the following general formula (4).
  • R 5 and R 6 are functional groups represented by the following general formula (4).
  • R 5 and R 6 may be the same or different.
  • X 1 and X 2 are a hydrogen atom or a functional group represented by General Formula (1). However, at least one of X 1 and X 2 is a functional group represented by the general formula (1).
  • R 4 is preferably an organic group having 1 to 12 carbon atoms.
  • R 4 is preferably an organic group having 1 to 12 carbon atoms.
  • phenyl group for example, phenyl group, tolyl group, styryl.
  • aromatic group such as a naphthyl group.
  • Particularly preferred are a phenyl group and a naphthyl group. If the ratio of the aromatic group in the constituent components of the film increases, the refractive index also increases accordingly.
  • R 4 is preferably a functional group represented by the general formula (4).
  • A a compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group
  • B a structure represented by the general formula (1) by a nitrogen atom in the functional group represented by the general formula (4). Since the number of polycondensation reaction points with one or more heterocyclic aromatic compounds is increased, the crosslinking density is improved and the hardness of the film is improved.
  • the functional group represented by the general formula (1) may be referred to as a methylol functional group.
  • heterocyclic aromatic compound containing two or more structures of the general formula (1) examples include, but are not limited to, the following compounds.
  • the heterocyclic aromatic compound containing two or more structures of the general formula (1) used in the polymerization may be a single type or a plurality of types, and those shown in the present specification may be used alone or in combination ( B) It can be used as a heterocyclic aromatic compound containing two or more structures of the general formula (1).
  • a solvent is added to (A) a compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group, and (B) a heterocyclic aromatic compound containing two or more structures of the general formula (1), followed by stirring. And dissolve. Thereafter, an appropriate catalyst is added and the mixture is further stirred for 20 minutes to 3 hours to obtain the target polymer compound.
  • (B) The methylol functional group in the heterocyclic aromatic compound containing two or more structures of the general formula (1) is hydrolyzed, reacts with protons in the system and dehydrates to generate a carbocation.
  • (A) In a compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group by a reaction of (A) a compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group. A methylene bond is formed between the adjacent site of the hydroxy group and the nitrogen atom in the functional group represented by the general formula (1). As this reaction occurs sequentially, the polymerization proceeds and a polymer compound is obtained.
  • A a compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group by 1 H, 13 C and 15 N NMR analysis, mass spectrometry, gel permeation chromatography (GPC) measurement, and the like
  • B Presence of a polymer compound containing a component derived from a heterocyclic aromatic compound containing two or more structures of the general formula (1) can be estimated.
  • the weight average molecular weight of the polymer compound of the present invention is a value obtained as a polystyrene converted value by GPC measurement.
  • the lower limit of the weight average molecular weight of the polymer compound is preferably 10,000 or more.
  • 100,000 or less is preferable and 50,000 or less is more preferable.
  • ⁇ Membrane> A method for forming a film using the polymer compound of the present invention will be described with examples.
  • the polymer compound of the present invention is dissolved in a suitable solvent and applied on a base substrate by a known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating or slit coating, and then hot plate. Or it prebakes with heating apparatuses, such as oven, and forms a film
  • the solvent is preferably an alcoholic compound, an ester compound, a ketone compound or an ether compound in order to uniformly dissolve the polymer compound and other additives.
  • propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, diacetone alcohol, ethylene glycol mononormal butyl ether, 2-ethoxyethyl acetate, 1-methoxypropyl-2-acetate, 3-methoxy-3-methylbutanol, 3-methoxy -3-methylbutanol acetate, 3-methoxybutyl acetate, 1,3-butylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, ethyl acetoacetate, cyclobutanone, cyclopenta Non, cyclohexanone, cycloheptanone or ⁇ -butyrolactone
  • the film is thermally cured at 120 to 280 ° C. for about 3 minutes to 1 hour using a heating device such as a hot plate or oven to obtain a film.
  • the film thickness of the film obtained by thermosetting is not particularly limited, but it is preferably prepared in the range of 0.1 to 10 ⁇ m depending on the application.
  • the film according to the present invention obtained by the above-described method has a refractive index of 1.65 to 1.85 at 633 nm from the viewpoint of imparting suitable performance as a microlens, waveguide, or white pixel material. preferable. Moreover, it is preferable that the transmittance
  • the film according to the present invention needs to transmit visible light sufficiently in order to give a suitable performance as a solid-state imaging device such as an image sensor.
  • the light is transmitted in the entire wavelength range of 400 to 800 nm.
  • the rate is preferably 80% or more per 1 ⁇ m of film thickness.
  • the solution of the polymer compound for forming the film may contain a thermal cross-linking agent for improving chemical resistance.
  • the thermal crosslinking agent preferably has a crosslinking reaction temperature lower than 250 ° C. This is because even when baked at a low temperature of 250 ° C. or lower, a film having sufficient chemical resistance can be obtained.
  • a compound having a methylol functional group represented by —CH 2 OR 7 is preferred.
  • ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, ML-TBC having one methylol functional group DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, etc.
  • DML-PCHP DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML- PFP, DML-PSBP, DML-MB25, DML-MTrisPC, D L-Bis25X-34XL, DML-Bis25X-PCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nicalak MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl- TriML-P, TriML-35XL, TriML-TrisCR-HAP (and more) have three such as 4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co
  • R 7 in the methylol functional group is a hydrogen atom or an organic group having 1 to 6 carbon atoms, and is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, or the like. Is particularly preferred.
  • thermal crosslinking agent used in the polymer compound of the present invention those containing 2 to 4 methylol functional groups represented by —CH 2 OR 7 are preferred, and those having two are particularly preferred.
  • 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML- EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nicarax MX-290 (trade name, Sansei Co., Ltd.) (Wa Chemical), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol TriML-P and TriML-35XL (trade name, manufactured by Honshu Chemical Industry Co., Ltd.
  • the compounds having the group represented by —CH 2 OR 5 are DML-PC, DML-PTBP, Nicalak MX-270, Nicalak MX-280 (above, trade name, Sanwa Chemical Co., Ltd.) Manufactured) and the like.
  • the thermal cross-linking agent When the thermal cross-linking agent is mixed with an unsubstituted one or a large amount, the cross-linking of the polymer compound may not sufficiently proceed. For this reason, it is preferable that the purity of the thermal crosslinking agent of this invention is 80% or more, and it is more preferable in it being 95% or more. If the purity is 80% or more, the polymer compound can be sufficiently cross-linked to reduce the number of unreacted groups that are water-absorbing groups, so that the water absorption of the polymer compound can be reduced. In order to obtain a high-purity thermal crosslinking agent, a method of collecting only the target product by recrystallization, distillation or the like can be mentioned. The purity of the thermal crosslinking agent can be determined by a liquid chromatography method.
  • the polymer compound solution for forming the film may contain a thermal acid generator in addition to the thermal crosslinking agent in order to improve the crosslinking rate of the film.
  • the thermal acid generator preferably has a thermal decomposition starting temperature lower than 220 ° C. This is because even when baked at a low temperature of 250 ° C. or lower, particularly 220 ° C. or lower, acid is easily generated, so that the cross-linking ratio of the resulting film is improved and sublimation of the compound can be suppressed.
  • thermal acid generator examples include 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate, 4-methoxycarbonyloxyphenyldimethylsulfonium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, and 2-methylbenzyl.
  • the polymer compound solution for forming the film may contain a surfactant.
  • the surfactant include silicone surfactants, silicon surfactants such as organopolysiloxanes, fluorine surfactants, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenyl ether.
  • Nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate or polyethylene glycol distearate, polyalkylene oxide surfactants, poly (meth) acrylate surfactants, acrylic or methacrylic surfactants
  • a surfactant made of a polymer is exemplified.
  • surfactants examples include “Megafac” (registered trademark) F142D, F172, F173, F183, F445, F470, F475 or F477 (all manufactured by Dainippon Ink & Chemicals, Inc.) or NBX- 15 or FTX-218 (both manufactured by Neos Co., Ltd.) and other fluorine-based surfactants, BYK-352, BYK-333, BYK-301, BYK-331, BYK-345 or BYK-307 (all of which are Big Chemie Acrylic surfactants such as silicone surfactants such as Japan Flow), polyflow 50E, polyflow 50EHF, polyflow 54N, polyflow 75, polyflow 77, polyflow 90, polyflow 95, polyflow 99C (all manufactured by Kyoeisha Chemical). Agents.
  • the polymer solution for forming a film may contain an additive such as a stabilizer or an antifoaming agent, if necessary.
  • the total solid content concentration including the polymer compound and other components may be appropriately determined according to the coating method and the like, but should be 1 to 50% by mass. Is preferred.
  • the film having the polymer compound of the present invention has a constant etching rate in processes such as dry etching and ashing, and can exhibit good roughness after these processes.
  • the film containing the polymer compound of the present invention having the above characteristics can be suitably used for a solid-state imaging device in an optical device such as a digital camera or a smartphone camera.
  • a solid-state image sensor it can be used for a microlens, a white pixel, a waveguide, etc., for example.
  • it can be suitably used as a microlens for a solid-state imaging device by utilizing a high refractive index and transmittance.
  • a first embodiment of a solid-state imaging device to which a film having a polymer compound of the present invention can be applied includes at least a photoelectric conversion unit, a color filter provided above a light receiving surface of the photoelectric conversion unit, and the above-described high And a microlens containing a molecular compound.
  • the solid-state imaging device further planarizes the waveguide provided between the light receiving surface of the photoelectric conversion unit and the color filter and / or the upper surface of the color filter as necessary. You may have.
  • the film having the polymer compound of the present invention has a high refractive index and high transparency, in the present embodiment including the microlens containing the polymer compound, the light collection efficiency is increased and the sensitivity of the captured image is increased. Can be improved.
  • the above-described polymer compound only needs to be included in at least the microlens, and may also be included in a waveguide provided as necessary.
  • the color filter may have a white pixel, and the above-described polymer compound may be included in the white pixel.
  • the step of forming the solid-state imaging device of the present embodiment includes the step of forming a film containing the above-described polymer compound on the color filter or the planarizing layer provided as necessary, as the forming step of the microlens. And heating the film.
  • the second embodiment of the solid-state imaging device to which the film having the polymer compound of the present invention can be applied includes at least a photoelectric conversion unit and a light receiving surface of the photoelectric conversion unit, and includes the above-described polymer compound. It has a color filter having white pixels and a microlens.
  • the solid-state imaging device further planarizes the waveguide provided between the light receiving surface of the photoelectric conversion unit and the color filter and / or the upper surface of the color filter as necessary. You may have.
  • the film having the polymer compound of the present invention has a high refractive index and high transparency, in this embodiment including a color filter having a white pixel containing the polymer compound, the effect of preventing color mixing is enhanced.
  • the sensitivity of the captured image can be improved.
  • the above-described polymer compound may be included in at least a white pixel, and may be further included in a microlens or a waveguide provided as necessary.
  • the step of forming the solid-state imaging device of this embodiment is a step of patterning the film containing the above-described polymer compound on the photoelectric conversion unit or the waveguide provided as necessary, as the white pixel forming step. And heating the film.
  • the third embodiment of the solid-state imaging device to which the film having the polymer compound of the present invention can be applied includes at least a photoelectric conversion unit and a light receiving surface of the photoelectric conversion unit, and includes the above-described polymer compound. It has a waveguide, a color filter, and a microlens.
  • membrane which has a high molecular compound of this invention has a high refractive index and high transparency, in this embodiment, a condensing efficiency can be improved and the sensitivity of a captured image can be improved.
  • the above-described polymer compound only needs to be included in at least the waveguide, and may also be included in the microlens.
  • the color filter may have a white pixel, and the above-described polymer compound may be included in the white pixel.
  • the step of forming the solid-state imaging device of the present embodiment includes a step of forming a film containing the above-described polymer compound on the photoelectric conversion unit and a step of heating the film as the step of forming the waveguide. .
  • FIG. 1 is a partial cross-sectional view showing an embodiment of a solid-state imaging device to which the present invention can be applied.
  • An electrode 12 and a photoelectric conversion unit 13 are provided on the semiconductor substrate 11.
  • a waveguide 14 is provided on the photoelectric conversion unit 13, and a color filter 16 and a planarizing layer 15 are provided on the waveguide 14.
  • the color filter 16 is further provided with a white pixel 17 which is a white pixel in FIG. 1, but it is sufficient if at least pixels corresponding to red (R), green (G) and blue (B) are provided. Further, the planarizing layer 15 may not be provided.
  • the side on which these are provided is the light receiving surface of the photoelectric conversion unit 13 and has a microlens 18 above it. Note that the configuration between the photoelectric conversion unit 13 and the microlens 18, the configuration between the photoelectric conversion unit 13 and the waveguide 14, or the configuration between the photoelectric conversion unit 13 and the white pixel 17 is not limited to this form. .
  • FIG. 2 is a partial cross-sectional view showing another embodiment of the solid-state imaging device to which the present invention can be applied.
  • An electrode 12 and a photoelectric conversion unit 13 are provided on the semiconductor substrate 11.
  • a color filter 16, a white pixel 17, and a planarization layer 15 are provided on the photoelectric conversion unit 13.
  • the side where these are provided is the light-receiving surface of the photoelectric conversion unit 13, and has a microlens 18 above it.
  • the configuration between the photoelectric conversion unit 13 and the microlens 18 or the configuration between the photoelectric conversion unit 13 and the white pixel 17 is not limited to this form. Also in this embodiment, whether or not the white pixel 17 and the flattening layer 15 are provided is arbitrary.
  • the manufacturing method of the solid-state image sensor of this invention includes the process of forming the film
  • the method for manufacturing a solid-state imaging device of the present invention includes a step of providing an electrode on a semiconductor substrate, a step of providing a color filter, and the like, and these can use known methods. .
  • the film can be formed by applying a solution containing the above-described polymer compound.
  • the coating method is not particularly limited, and known methods such as a spin coating method, a spray coating method, a slit coating method, and a dip coating method can be exemplified, but the spin coating method is preferable.
  • a known heating method such as a hot plate or an oven is used.
  • the first-stage baking at 80 to 130 ° C. and the second-stage baking at 180 to 300 ° C., which can suppress cracks and voids. If the solvent in the film is substantially volatilized during the spin coating, the subsequent baking does not cause bumping of the solvent, and repelling or cloudiness can be suppressed.
  • a mask layer made of a KrF resist film or an i-line resist film is formed in a predetermined shape on the upper layer of the film.
  • the mask layer is formed into a predetermined shape by, for example, forming a mask layer, patterning by a photolithography process, etc., and developing to process into a predetermined shape.
  • Etching is performed on the film structure thus formed. That is, by simultaneously etching the mask layer and the film, the shape of the mask layer is transferred to the film. Later, by removing the mask layer, a pattern having a predetermined shape is formed.
  • MW-100LM and BX-4000 correspond to (B) heterocyclic aromatic compounds containing two or more structures of the general formula (1) used in the present invention.
  • Synthesis Example 1 Synthesis of Polymer Compound (X1) 26.01 g (0.09 mol) of 1,1′-binaphthol (manufactured by Tokyo Chemical Industry) and 8.87 g (0.02 mol) of MW-100LM (Sanwa Chemical) 15 g of CP (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the product and stirred at 40 ° C. for 1 hour in an oil bath. Next, 0.174 g of phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.) is added, the temperature of the oil bath is set to 160 ° C., and after stirring for 30 minutes, the oil bath is set to 180 ° C. and stirred for 30 minutes. Heating was stopped to complete the reaction. After completion of the reaction, the resulting product was ice-cooled and cooled to room temperature to obtain a polymer compound (X1). The obtained polymer compound (X1) had a weight average molecular weight of 46,000.
  • Synthesis Example 2 Synthesis of Polymer Compound (X2) 20.89 g (0.06 mol) of 1,1′-binaphthol (manufactured by Tokyo Chemical Industry) and 13.99 g (0.03 mol) of BX-4000 (Sanwa Chemical) 15 g of CP (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the product, and the mixture was stirred in an oil bath at 40 ° C. for 1 hour. Next, 0.174 g of phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.) is added, the temperature of the oil bath is set to 160 ° C., and after stirring for 30 minutes, the oil bath is set to 180 ° C. and stirred for 30 minutes. Heating was stopped to complete the reaction. After completion of the reaction, the resulting product was ice-cooled and cooled to room temperature to obtain a polymer compound (X2). The weight average molecular weight of the obtained polymer compound (X2) was 20,000.
  • Synthesis Example 3 Synthesis of Polymer Compound (X3) 20.68 g (0.07 mol) of 1,1′-thiobis (2-naphthol) (manufactured by Tokyo Chemical Industry) and 6.34 g (0.02 mol) of MW— To 100LM (manufactured by Sanwa Chemical Co., Ltd.), 15 g of CP (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at 40 ° C. for 1 hour in an oil bath.
  • phosphoric acid manufactured by Wako Pure Chemical Industries, Ltd.
  • the temperature of the oil bath was set to 160 ° C.
  • the oil bath was set to 180 ° C. and stirred for 30 minutes. Heating was stopped to complete the reaction.
  • the resulting product was ice-cooled and cooled to room temperature to obtain a polymer compound (X3).
  • the weight average molecular weight of the obtained polymer compound was 45,000.
  • Synthesis Example 5 Synthesis of Polymer Compound (X5) 27.28 g (0.10 mol) of 1,1′-binaphthol (manufactured by Tokyo Chemical Industry) and 14.08 g (0.05 mol) of MX-290 (Sanwa Chemical) 15 g of CP (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the product, and the mixture was stirred in an oil bath at 40 ° C. for 1 hour. Next, 0.174 g of phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.) is added, the temperature of the oil bath is set to 160 ° C., and after stirring for 30 minutes, the oil bath is set to 180 ° C. and stirred for 30 minutes. Heating was stopped to complete the reaction. After completion of the reaction, the resulting product was ice-cooled and cooled to room temperature to obtain a polymer compound (X5). The weight average molecular weight of the obtained polymer compound was 12,000.
  • Synthesis Example 6 Synthesis of Polymer Compound (X6) 26.50 g (0.09 mol) of 1,1′-binaphthol (manufactured by Tokyo Chemical Industry) and 8.38 g (0.05 mol) of 2,6-bis (hydroxy) 15 g of CP (manufactured by Wako Pure Chemical Industries, Ltd.) was added to methyl) paracresol (manufactured by Wako Pure Chemical Industries, Ltd.), and stirred at 40 ° C. for 1 hour in an oil bath.
  • Synthesis Example 7 Preparation of Titanium Oxide Dispersion 21.51 g of methyltrimethoxysilane (KBM-13; manufactured by Shin-Etsu Chemical Co., Ltd.), 73.07 g of phenyltrimethoxysilane (KBM-103; Shin-Etsu Chemical Co., Ltd.) Product), phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.) 0.473 g and purified water (manufactured by Wako Pure Chemical Industries, Ltd.) 28.43 g were charged and stirred in an oil bath at 40 ° C. for 1 hour.
  • the temperature of the oil bath was set to 70 ° C., and a mixture of 253 g of titanium oxide nanoparticles (“OPTRAIK” TR-527; manufactured by Catalytic Chemical Co., Ltd.) and 165 g of PGMEA was added dropwise over about 30 minutes.
  • the temperature of the oil bath was set to 120 ° C., and after the temperature in the flask reached 100 ° C., the mixture was stirred for 3 hours, and then the heating was stopped to complete the reaction.
  • the flask was cooled with ice and cooled to room temperature, and an anion and a cation exchange resin were added and stirred for 10 hours. Finally, the ion exchange resin was removed by filtration to obtain a titanium oxide dispersion (Y1).
  • Synthesis Example 8 Synthesis of Polymer Compound (X7) 20.68 g (0.07 mol) of 2,2′-dimethoxy-1,1′-binaphthyl (manufactured by Tokyo Chemical Industry) and 6.34 g (0.02 mol) of MW To -100LM (manufactured by Sanwa Chemical Co., Ltd.), 15 g of CP (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred in an oil bath at 40 ° C. for 1 hour.
  • phosphoric acid manufactured by Wako Pure Chemical Industries, Ltd.
  • the temperature of the oil bath was set to 160 ° C.
  • the oil bath was set to 180 ° C. and stirred for 30 minutes. Heating was stopped to complete the reaction.
  • the resulting product was ice-cooled and cooled to room temperature to obtain a polymer compound (X7).
  • the weight average molecular weight of the obtained polymer compound was 25,000.
  • Example 1 1.999 g of the polymer compound (X1) was diluted with 7.901 g of CP, and 0.100 g of a surfactant (Polyflow 77 CP1 mass% solution (corresponding to a concentration of 100 ppm)) was added and stirred. Next, it filtered with the 0.45 micrometer filter and obtained the dilution liquid of the high molecular compound. About the obtained high molecular compound, the transmittance
  • the composition was spin-coated on a 5 cm square Tempax glass substrate (manufactured by AGC Techno Glass Co., Ltd.) using a spin coater and then hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) was used. Prebaking was performed at 100 ° C. for 3 minutes to prepare a prebaked film having a thickness of 1.0 ⁇ m. The obtained pre-baked film was baked for 5 minutes at 220 ° C. in air on a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) to prepare a film having a thickness of 0.7 ⁇ m. The obtained film was evaluated by measuring the transmittance at 400 to 800 nm using an ultraviolet-visible spectrophotometer (UV-260; manufactured by Shimadzu Corporation), and taking the lowest value as the transmittance during this period. .
  • UV-260 ultraviolet-visible spectrophotometer
  • a film having a thickness of 0.7 ⁇ m was produced by the same method as the evaluation of transmittance.
  • the obtained film was measured for the refractive index at 633 nm (using a He—Ne laser) at 22 ° C. using a prism coupler MODEL 2010 (manufactured by Metricon).
  • Example 2 to Example 3 A composition containing a polymer compound was obtained in the same manner as in Example 1 except that the polymer compound was changed to X2 or X3, and the same evaluation as in Example 1 was performed. Table 1 shows the composition and evaluation results of the composition containing the obtained polymer compound.
  • Examples 4 to 5 1.960 g of the polymer compound (X1) and 0.039 g of 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate or 2-methylbenzyl-4-methoxycarbonyloxyphenylmethylsulfonium trifluoromethanesulfonate Diluted with 901 g of CP, 0.100 g of a surfactant (Polyflow 77 CP 1% by mass solution (corresponding to a concentration of 100 ppm)) was added and stirred. Evaluation similar to Example 1 was performed. Table 1 shows the composition and evaluation results of the composition containing the obtained polymer compound.
  • a surfactant Polyflow 77 CP 1% by mass solution (corresponding to a concentration of 100 ppm)
  • Examples 6 to 7 Dilute 1.764 g of polymer compound (X1), 0.039 g of 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate and 0.196 g of MW-100LM or BX-4000 with 7.901 g of CP Then, 0.100 g of a surfactant (Polyflow 77 CP 1% by mass solution (corresponding to a concentration of 100 ppm)) was added and stirred. Evaluation similar to Example 1 was performed. Table 1 shows the composition and evaluation results of the composition containing the obtained polymer compound.
  • a surfactant Polyflow 77 CP 1% by mass solution (corresponding to a concentration of 100 ppm)
  • Example 8> A composition containing a polymer compound was obtained in the same manner as in Example 1 except that the polymer compound was changed to X7, and the same evaluation as in Example 1 was performed. Table 1 shows the composition and evaluation results of the composition containing the obtained polymer compound.
  • Example 1 A composition containing a polymer compound was obtained in the same manner as in Example 1 except that the polymer compound was changed to X4 to X6, and the same evaluation as in Example 1 was performed.
  • Table 2 shows the composition and evaluation results of the composition containing the obtained polymer compound.
  • the film obtained from the composition containing the polymer compound of Comparative Example 1 has an insufficient refractive index, and Comparative Examples 2 to 3 have an insufficient crosslinking rate. The film sublimated, and no satisfactory film could be formed.
  • Example 4 A composition containing a titanium oxide dispersion was obtained in the same manner as in Example 1 except that the polymer compound was changed to the titanium oxide dispersion Y1, and the same evaluation as in Example 1 was performed. Table 2 shows the composition and evaluation results of the obtained composition. As apparent from the results in Table 2, the dry etching property of the obtained film was poor in roughness due to the difference in etching rate between the metal oxide and the resin, and a satisfactory film could not be formed.

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PCT/JP2016/077727 2015-09-28 2016-09-20 高分子化合物、樹脂組成物、膜、固体撮像素子、高分子化合物の製造方法、固体撮像素子の製造方法、および光学デバイス WO2017057105A1 (ja)

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