JP6790826B2 - Polymer compound, resin composition, film, solid-state image sensor, method for manufacturing polymer compound, method for manufacturing solid-state image sensor, and optical device - Google Patents

Description

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.

In recent years, with the rapid development of digital cameras, smartphones, and the like, there is a demand for smaller size and higher pixel count of solid-state image sensors. Since the miniaturization of the solid-state image sensor causes a decrease in sensitivity, the internal lens is placed between the light receiving part and the color filter, the microlens is placed above the color filter, and the waveguide is formed between the light receiving part and the color filter. , By forming white pixels between color filters, etc., light is efficiently condensed and the decrease in sensitivity is prevented. Since these microlenses, waveguides, and white pixels can generally achieve high sensitivity by using high refractive index materials, development and research of high refractive index materials are being actively conducted.

As a method for producing a microlens, a waveguide, and a white pixel, a method of processing the applied resin by dry etching is currently the mainstream. As a material for that purpose, a high refractive index material obtained by combining a metal oxide such as titanium oxide or zirconium oxide with a siloxane resin or an acrylic resin has been studied (see, for example, Patent Documents 1 to 3).

JP-A-2007-246877 Japanese Unexamined Patent Publication No. 2011-127906 Japanese Unexamined Patent Publication No. 2008-156390

However, in the composite material of the metal oxide and the resin, since the properties of the metal oxide and the resin are significantly different, the difference in etching rate between the two is large, and it is difficult to process the composite material while maintaining good roughness. Therefore, according to the present invention, a polymer compound which has good surface roughness after dry etching and gives a high refractive index and a highly transparent film, a resin composition and a solid-state image sensor using the same, and a method for producing a polymer compound. An object of the present invention is to provide a method for manufacturing a solid-state image sensor and an optical device.

That is, the present invention comprises (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). , Is a polymer compound obtained by polycondensing.

一般式（１）中、Ｒ^１は水素原子または炭素数１〜６の有機基を示す。

In the general formula (1), R ¹ represents a hydrogen atom or an organic group having 1 to 6 carbon atoms.

According to the present invention, it is possible to obtain a polymer material having good surface roughness after dry etching and capable of forming a film having a high refractive index and a high transparency. By applying a highly transparent film containing the polymer material of the present invention as a microlens, it is possible to manufacture a compact and high-definition optical device.

It is a partial cross-sectional view which shows one Example of the solid-state image sensor by this invention. It is a partial cross-sectional view which shows one Example of the solid-state image sensor by this invention.

The polymer compound of the present invention is a heterocyclic aromatic compound containing at least (A) a compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group and (B) two or more structures of the general formula (1). It is made by polycondensing group compounds.

一般式（１）中、Ｒ^１は水素原子または炭素数１〜６の有機基を示す。

In the general formula (1), R ¹ represents a hydrogen atom or an organic group having 1 to 6 carbon atoms.

<(A) Compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group>
In the compound having two or more polycyclic aromatic groups having (A) a hydroxyl group or an alkoxy group, which is one of the compounds for producing the polymer compound of the present invention, the polycyclic aromatic group is, for example, a naphthylene 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 high refractive index. Examples of the compound having a naphthyl group include a compound represented by the general formula (2).

一般式（２）中、ｎ^１及びｎ^２、ｋ^１及びｋ^２はそれぞれ独立に１〜４の整数を表す。ｍは０〜１の整数を示す。ｎ^１及びｎ^２、ｋ^１及びｋ^２は、ナフチル基に結合する置換基ＯＲ^２またはＲ^３の個数を意味している。ｍは、基Ｘの連続する個数を意味している。Ｘは酸素原子、硫黄原子、メチレン基およびこれらの組み合わせからなる群より選ばれる。Ｒ^２は水素原子または炭素数１〜６の有機基である。Ｒ^３は水素原子または炭素数１〜６の有機基である。Ｒ^２およびＲ^３はそれぞれ同じあっても異なっていても良い。

In the general formula (2), n ¹ and n ² , k ¹ and k ² each independently represent 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 attached 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.

In the compound represented by the general formula (2), the combination of the oxygen atom, the sulfur atom and the methylene group as X options is, for example, − (CH ₂ ) _j −, −O− (CH ₂ ) _j −, −. Examples thereof include groups represented by S- (CH ₂ ) _j -,-(CH ₂ ) _j- O- (CH ₂ ) _l -,-(CH ₂ ) _j -S- (CH ₂ ) _l- . Here, j and l are each an integer of 1 or more, preferably an integer of 1 to 4, and more preferably an integer of 1 to 2. Among these, X is preferably an oxygen atom, a sulfur atom or a methylene group.

As the compound represented by the general formula (2), n ¹ and n ² , k ¹ and k ² are 1, m is 0, and R ² is represented by a hydrogen atom or an organic group having 1 or 2 carbon atoms. that functional group, R ³ is the compound is a functional group represented by hydrogen or C 1 or 2 organic groups preferably having a carbon.

一般式（５）中、ｎ^１及びｎ^２はそれぞれ独立に１〜４の整数を表す。ｍは０〜１の整数を示す。Ｘは酸素原子、硫黄原子、メチレン基およびこれらの組み合わせからなる群より選ばれる。Ｒ^２は水素原子または炭素数１〜６の有機基である。Ｒ^３は水素原子または炭素数１〜６の有機基である。Ｒ^２およびＲ^３はそれぞれ同じあっても異なっていても良い。Further, as the compound (A) having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group, a compound represented by the following general formula (5) in which k ¹ and k ² are 0 is preferable.

In the general formula (5), n ¹ and n ² independently represent integers 1 to 4, respectively. 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 constituents of the film is improved, and a film having a higher refractive index can be formed.

The charging ratio of the compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group (A) used for polymerization to the constituent components in the polymer compound is preferably 50% by mass or more, preferably 60% by mass. The above is more preferable. (A) It is preferable that 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.

Further, the charging ratio of the compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group (A) is preferably 90% by mass or less, preferably 80% by mass or less, based on the constituent components in the polymer compound. More preferred. When it is 90% by mass or less, the crosslink density in the film can be improved, and the strength of the film is further improved.

(A) 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 (A) used for polymerization and having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group may be a single type or a plurality of types, and those shown in the present specification may be used alone or in combination to form (A). It can be used as a compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group. Among them, (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. The higher the content of aromatic components in the constituents of the film, the higher the refractive index.

<(B) Heterocyclic aromatic compound containing two or more structures of the general formula (1)>
In the heterocyclic aromatic compound containing two or more of the structures of (B) general formula (1), which is one of the compounds for producing the polymer compound of the present invention, R ¹ is a hydrogen atom or methyl. Examples thereof include a group, an ethyl group, a propyl group and a butyl group. (A) A highly reactive hydrogen atom from the viewpoint of reactivity with a compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group. , Methyl group and ethyl group are preferable, and methyl group and ethyl group are particularly preferable from the viewpoint of easy control of reactivity.

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.

一般式（３）中、Ｒ^４は炭素数１〜１２の有機基または下記一般式（４）で表される官能基である。Ｒ^５およびＲ^６は下記一般式（４）で表される官能基である。Ｒ^５およびＲ^６は同じでも異なっても良い。

In the general formula (3), 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.

一般式（４）中、Ｘ^１およびＸ^２は水素原子または一般式（１）で表される官能基である。但し、Ｘ^１およびＸ^２の少なくとも１つは、一般式（１）で表される官能基である。

In the general formula (4), X ¹ and X ² are hydrogen atoms or functional groups represented by the general formula (1). However, at least one of X ¹ and X ² is a functional group represented by the general formula (1).

In the compounds having a triazine group represented by the general formula (3), it is preferred that R ⁴ is an organic group having 1 to 12 carbon atoms, from the viewpoint of high refractive index, for example, a phenyl group, a tolyl group, a styryl It is preferably an aromatic group such as a group or a naphthyl group. Particularly preferred are a phenyl group and a naphthyl group. As the proportion of aromatic groups in the constituents of the film increases, the refractive index also improves accordingly.

Further, in the compound having a triazine group represented by the general formula (3), it is also preferable that R ⁴ is a functional group represented by the general formula (4). The structure of (A) a compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group and (B) the structure of the general formula (1) are formed by the nitrogen atom in the functional group represented by the general formula (4). Since the polycondensation reaction point with the heterocyclic aromatic compound contained at least one is increased, the crosslink density is improved and the hardness of the film is improved.
In the following description, the functional group represented by the general formula (1) may be referred to as a methylol-based functional group.

(B) Examples of the heterocyclic aromatic compound containing two or more structures of the general formula (1) include, but are not limited to, the following compounds.

The heterocyclic aromatic compound containing two or more of the structures of the general formula (1) used in the polymerization may be a single type or a plurality of types, and the ones shown in the present specification may be used alone or in combination (1). B) It can be used as 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 and (B) a heterocyclic aromatic compound containing two or more structures of the general formula (1) are polycondensed. Polymer compounds>
The following methods are exemplified as typical methods for producing the polymer compound of the present invention. 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), and the mixture is stirred. And dissolve. Then, an appropriate catalyst is added, and the mixture is further stirred for 20 minutes to 3 hours to obtain the desired polymer compound.

At this time, the polycondensation of (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) is , It is considered that the process proceeds as follows. (A) 1,1'-bi-2-naphthol as a compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group, and (B) a heterocycle containing two or more structures of the general formula (1). MW-100LM (manufactured by Sanwa Chemical Co., Ltd.) will be described below as an example of the formula aromatic compound.

(B) The methylol-based functional group in the heterocyclic aromatic compound containing two or more of the structures of the general formula (1) is hydrolyzed and reacted with the protons in the system to dehydrate to generate a carbocation. By reacting this carbocation with a compound having two or more polycyclic aromatic groups having (A) a hydroxyl group or an alkoxy group, the compound having two or more polycyclic aromatic groups having (A) a hydroxyl group or an alkoxy group A methylene bond is formed between the site adjacent to the hydroxy group and the nitrogen atom in the functional group represented by the general formula (1). When this reaction occurs in sequence, the polymerization proceeds and a polymer compound is obtained.

¹ H, ¹³ C and ¹⁵ N NMR analysis, mass analysis, gel permeation chromatography (GPC) measurement, etc. (A) Compounds having two or more polycyclic aromatic groups having hydroxyl groups or alkoxy groups and ( B) It is possible to infer the existence of a polymer compound containing a component derived from a heterocyclic aromatic compound containing two or more structures of the general formula (1).

The weight average molecular weight of the polymer compound of the present invention is a value obtained as a polystyrene-equivalent value by GPC measurement. The weight average molecular weight of the polymer compound is preferably 10,000 or more as the lower limit. The upper limit is preferably 100,000 or less, more preferably 50,000 or less.

<Membrane>
A method for forming a film using the polymer compound of the present invention will be described with reference to an example. The polymer compound of the present invention is dissolved in an appropriate solvent and applied onto a base substrate by a known method such as microgravia coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating or slit coating, and then applied to a hot plate. Alternatively, it is prebaked with a heating device such as an oven to form a film. The prebaking is preferably performed at 50 to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after prebaking is preferably 0.1 to 10 μm.

As the solvent, an alcohol compound, an ester compound, a ketone compound or an ether compound is preferable because the polymer compound and other additives are uniformly dissolved. For example, 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 γ-butyrolactone can be mentioned.

After prebaking, the film is obtained by thermosetting the film at 120 to 280 ° C. for about 3 minutes to 1 hour using a heating device such as a hot plate or an oven.

The film thickness obtained by thermosetting is not particularly limited, but it is preferably prepared in the range of 0.1 to 10 μm depending on the application.

The film according to the present invention obtained by the above method has a refractive index of 1.65 to 1.85 at 633 nm from the viewpoint of imparting suitable performance as a microlens, a waveguide, and a white pixel material. preferable. Further, it is preferable that the transmittance of light at a wavelength of 400 nm when the film thickness is 1.0 μm is 90% or more.

The film according to the present invention needs to sufficiently transmit visible light in order to impart suitable performance as a solid-state image sensor such as an image sensor. In that case, the film transmits light in the entire region having a wavelength of 400 to 800 nm. The ratio is preferably 80% or more per 1 μm of the film thickness.

<Other ingredients to be added to the membrane>
The solution of the polymer compound for forming the film may contain a thermal cross-linking agent in order to improve chemical resistance. The heat cross-linking agent preferably has a cross-linking reaction temperature lower than 250 ° C. This is because a film having sufficient chemical resistance can be obtained even when fired at a low temperature of 250 ° C. or lower.

As the thermal cross-linking agent used in the present invention, a compound having a methylol-based functional group as represented by −CH ₂ OR ⁷ is preferable. For example, ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, ML-TBC (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as having one methylol-based functional group. DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP (trade name, manufactured by Asahi Organic Materials Industry 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, DML-Bis25X-34XL, DML-Bis25X-PCHP (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), Nicarac MX-290 (trade name, Co., Ltd.) ) Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc. -P, TriML-35XL, TriML-TrisCR-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), etc. TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.) ), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (above, trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), Nikalac MX-280, Nikalac MX-270 (above, HML-TPPHBA, HML-TPHAP (above, trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.) can be mentioned as having six such as trade name and Sanwa Chemical Co., Ltd. Here, R ⁷ in the methylol-based functional group is a hydrogen atom or an organic group having 1 to 6 carbon atoms, preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group and the like, and a methyl group and an ethyl group. Is particularly preferable.

Of these, as the thermal cross-linking agent used in the polymer compound of the present invention, those containing 2 to 4 methylol-based functional groups represented by −CH ₂ OR ⁷ are preferable, and those having two are particularly preferable. 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Industry 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.), Nicarac MX-290 (trade name, San Co., Ltd.) (Made by Japanese Chemicals), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc., TriML-P as having three , TriML-35XL (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), TML-pp-BPF, TML as having four -BPA, TMOM-BP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nicarac MX-280, Nicarac MX-270 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.). Further, more preferably, DML-PC, DML-PTBP, Nicarac MX-270, Nicarac MX-280 (above, trade name, Sanwa Chemical Co., Ltd.), which are compounds having a group represented by -CH ₂ OR ⁵ , above. Made) and the like.

If an unsubstituted or a large amount of the heat-crosslinking agent is mixed, the cross-linking of the polymer compound may not proceed sufficiently. Therefore, the purity of the thermal cross-linking agent of the present invention is preferably 80% or more, and more preferably 95% or more. When the purity is 80% or more, the cross-linking reaction of the polymer compound can be sufficiently carried out and the number of unreacted groups which are water-absorbing groups can be reduced, so that the water absorption of the polymer compound can be reduced. In order to obtain a high-purity thermal cross-linking agent, a method of collecting only the target product by recrystallization, distillation or the like can be mentioned. The purity of the thermal cross-linking agent can be determined by a liquid chromatography method.

In order to improve the cross-linking rate of the film, the solution of the polymer compound for forming the film may contain a thermo-acid generator in addition to the heat-crosslinking agent. The thermal acid generator preferably has a thermal decomposition start temperature lower than 220 ° C. This is because the acid is easily generated even when the compound is fired at a low temperature of 250 ° C. or lower, particularly 220 ° C. or lower, so that the cross-linking rate of the obtained film is improved and the sublimation of the compound can be suppressed.

Examples of the thermoacid generator include 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate, 4-methoxycarbonyloxyphenyldimethylsulfonium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, and 2-methylbenzyl. -4-Hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 2-methylbenzyl-4-methoxycarbonyloxyphenylmethylsulfonium trifluoromethanesulfonate or 2-methylbenzyl-4-acetoxyphenylmethylsulfonium trifluoromethanesulfonate (above, Sanshin) (Made by Chemical Industry Co., Ltd.) and the like.

A surfactant may be contained in the solution of the polymer compound for forming the film. Examples of the surfactant include silicone-based surfactants, silicon-based surfactants such as organopolysiloxane, fluorine-based surfactants, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenyl ether. , Polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurylate or polyethylene glycol distearate, etc. Nonionic surfactants Polyalkylene oxide surfactants, poly (meth) acrylate surfactants or acrylic or methacrylic surfactants Examples include surfactants composed of polymers. Examples of commercially available surfactants include "Megafuck" (registered trademark) F142D, F172, F173, F183, F445, F470, F475 or F477 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.) or NBX-. Fluorosurfactants such as 15 or FTX-218 (all manufactured by Neos Co., Ltd.), BYK-352, BYK-333, BYK-301, BYK-331, BYK-345 or BYK-307 (all by Big Chemie. Silicone surfactants such as Japan Co., Ltd., polyflow 50E, polyflow 50EHF, polyflow 54N, polyflow 75, polyflow 77, polyflow 90, polyflow 95, polyflow 99C (all manufactured by Kyoeisha Chemical Co., Ltd.) and other acrylic surfactants. Agents can be mentioned.

The solution of the polymer compound for forming the film may contain an additive such as a stabilizer or an antifoaming agent, if necessary.

In the solution of the polymer compound for forming the film, 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 preferable.

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 those processes.

The film having the polymer compound of the present invention having the above characteristics can be suitably used for a solid-state image sensor in an optical device such as a digital camera or a camera of a smartphone. In a solid-state image sensor, it can be used, for example, in a microlens, a white pixel, a waveguide, or the like. In particular, it can be suitably used as a microlens for a solid-state image sensor by taking advantage of its high refractive index and transmittance.

<Solid image sensor>
(Embodiment 1)
A first embodiment of a solid-state image sensor 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-mentioned high height. It has a microlens containing a molecular compound. In this embodiment, the solid-state image sensor further flattens 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, if necessary. It does not matter if it has.

Since the film containing the polymer compound of the present invention has a high refractive index and high transparency, in the present embodiment including a microlens containing the polymer compound, the focusing efficiency is increased and the sensitivity of the captured image is increased. Can be improved.

In the present embodiment, the above-mentioned polymer compound may be contained at least in the microlens, and may be further contained in the waveguide provided as needed. Further, the color filter may have white pixels, and the above-mentioned polymer compound may be contained in the white pixels.
The step of forming the solid-state image sensor of the present embodiment is a step of forming the film containing the above-mentioned polymer compound on the color filter or the flattening layer provided as needed, as a step of forming the microlens. , Including the step of heating the film.

(Embodiment 2)
A second embodiment of a solid-state image sensor to which a film having a polymer compound of the present invention can be applied is provided at least above a photoelectric conversion unit and a light receiving surface of the photoelectric conversion unit, and includes the above-mentioned polymer compound. It has a color filter having white pixels and a microlens. In this embodiment, the solid-state image sensor further flattens 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, if necessary. It does not matter if it has.

Since the film containing the polymer compound of the present invention has a high refractive index and high transparency, in the present embodiment including a color filter having white pixels containing the polymer compound, the effect of preventing color mixing is enhanced. The sensitivity of the captured image can be improved.

In the present embodiment, the above-mentioned polymer compound may be contained in at least white pixels, and may be further contained in a microlens or a waveguide provided as needed.

The step of forming the solid-state image sensor of the present embodiment is a step of forming a pattern of a film containing the above-mentioned polymer compound on the photoelectric conversion unit or, if necessary, the waveguide provided as the white pixel forming step. And the step of heating the film.

(Embodiment 3)
A third embodiment of a solid-state image sensor to which a film having a polymer compound of the present invention can be applied is provided at least above a photoelectric conversion unit and a light receiving surface of the photoelectric conversion unit, and includes the above-mentioned polymer compound. It has a waveguide, a color filter, and a microlens.

Since the film containing the polymer compound of the present invention has a high refractive index and high transparency, in the present embodiment, it is possible to increase the light collection efficiency and the sensitivity of the captured image.
In the present embodiment, the above-mentioned polymer compound may be contained at least in the waveguide, and may be further contained in the microlens. Further, the color filter may have white pixels, and the above-mentioned polymer compound may be contained in the white pixels.

The step of forming the solid-state image sensor of the present embodiment includes a step of forming a film containing the above-mentioned polymer compound on the photoelectric conversion unit and a step of heating the film as the step of forming the waveguide. ..

The solid-state image sensor included in these embodiments will be described in more detail. FIG. 1 is a partial cross-sectional view showing an embodiment of a solid-state image sensor to which the present invention can be applied. The semiconductor substrate 11 is provided with an electrode 12 and a photoelectric conversion unit 13. A waveguide 14 is provided above the photoelectric conversion unit 13, and a color filter 16 and a flattening layer 15 are provided above the waveguide 14. Regarding the color filter 16, although the white pixel 17 which is a white pixel is further provided in FIG. 1, it is sufficient if the color filter 16 is provided with at least pixels corresponding to red (R), green (G), and blue (B). Further, the flattening 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 the microlens 18 is provided above the light receiving surface. 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 a solid-state image sensor to which the present invention can be applied. The semiconductor substrate 11 is provided with an electrode 12 and a photoelectric conversion unit 13. Further, a color filter 16, a white pixel 17, and a flattening layer 15 are provided above the photoelectric conversion unit 13. The side on which these are provided is the light receiving surface of the photoelectric conversion unit 13, and the microlens 18 is provided above the light receiving surface. 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. Further, also in this embodiment, it is arbitrary whether or not the white pixel 17 and the flattening layer 15 are provided.

<Manufacturing method of solid-state image sensor>
The method for manufacturing a solid-state image sensor of the present invention includes a step of forming a film containing the above-mentioned polymer compound at a predetermined position and a step of heating the film. The method for manufacturing the solid-state image sensor of the present invention includes, in addition to the above steps, a step of providing an electrode on a semiconductor substrate, a step of providing a color filter, and the like, and known methods can be used for these steps. ..

The film can be formed by applying a solution containing the above-mentioned 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 mentioned, but the spin coating method is preferable.

In the step of heating the film after coating, a known heating method such as a hot plate or an oven is used. At this time, it is preferable to perform the first-stage baking at 80 to 130 ° C. and the second-stage baking at 180 to 300 ° C., whereby cracks and voids can be suppressed. Further, if the solvent in the film is substantially volatilized during spin coating, the solvent does not suddenly boil in the subsequent baking, and repellent and cloudiness can be suppressed.

As a pattern forming method when pattern forming is required such as white pixels, for example, 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. As a step of forming the mask layer into a predetermined shape, specifically, for example, after forming the mask layer, patterning is performed by a photolithography step or the like, and then the mask layer is developed and processed into a predetermined shape. The film structure thus formed is subjected to an etching process. That is, the shape of the mask layer is transferred to the film by simultaneously etching the mask layer and the film. Later, by removing the mask layer, a pattern having a predetermined shape is formed.

Examples and comparative examples are shown below, and the present invention will be described in more detail, but the present invention is not limited to these ranges.

The abbreviations of the solvents used are as follows.
CP: Cyclopentanone PGMEA: Propylene glycol monomethyl ether acetate NMP: N-methylpyrrolidone DAA: Diacetone alcohol

The compounds used as the compounds containing two or more of the structures of the general formula (1) are as follows. MW-100LM and BX-4000 correspond to the heterocyclic aromatic compound containing two or more of the structures of (B) general formula (1) used in the present invention.

[Measurement of molecular weight]
Gel permeation chromatography (GPC) system Waters 2690 (manufactured by Waters), TSK-GEL α-4000, α-2500 (manufactured by Tosoh), measured at 40 ° C using NMP as a solvent, converted to polystyrene. As a value, the weight average molecular weight was determined.

<Synthesis Example 1> Synthesis of Polymer Compound (X1) 26.01 g (0.09 mol) of 1,1'-binaphthol (manufactured by Tokyo Kasei) 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 thereto, 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.) was added, the temperature of the oil bath was set to 160 ° C., and after stirring for 30 minutes, the oil bath was set to 180 ° C. and stirred for 30 minutes. The heating was stopped and the reaction was terminated. After completion of the reaction, the obtained product was ice-cooled and cooled to room temperature to obtain a polymer compound (X1). The weight average molecular weight of the obtained polymer compound (X1) was 46,000.

<Synthesis Example 2> Synthesis of polymer compound (X2) 20.89 g (0.06 mol) of 1,1'-binaphthol (manufactured by Tokyo Kasei) 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 (manufactured by Wako Junyaku Co., Ltd.), 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.) was added, the temperature of the oil bath was set to 160 ° C., and after stirring for 30 minutes, the oil bath was set to 180 ° C. and stirred for 30 minutes. The heating was stopped and the reaction was terminated. After completion of the reaction, the obtained 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 Kasei) and 6.34 g (0.02 mol) of MW- 15 g of CP (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 100 LM (manufactured by Sanwa Chemical Co., Ltd.), and the mixture was stirred in an oil bath at 40 ° C. for 1 hour. Next, 0.135 g of phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added, the temperature of the oil bath was set to 160 ° C., and after stirring for 30 minutes, the oil bath was set to 180 ° C. and stirred for 30 minutes. The heating was stopped and the reaction was terminated. After completion of the reaction, the obtained 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 4> Synthesis of Polymer Compound (X4) 20.80 g (0.08 mol) of 2-naphthol (manufactured by Tokyo Kasei) and 14.08 g (0.02 mol) of MW-100LM (manufactured by Sanwa Chemical Co., Ltd.) 15 g of CP (manufactured by Wako Pure Chemical Industries, Ltd.) was added, 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.) was added, the temperature of the oil bath was set to 160 ° C., and after stirring for 30 minutes, the oil bath was set to 180 ° C. and stirred for 30 minutes. The heating was stopped and the reaction was terminated. After completion of the reaction, the obtained product was ice-cooled and cooled to room temperature to obtain a polymer compound (X4). The weight average molecular weight of the obtained polymer compound was 13,000.

<Synthesis Example 5> Synthesis of Polymer Compound (X5) 27.28 g (0.10 mol) of 1,1'-binaphthol (manufactured by Tokyo Kasei) 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 (manufactured by Wako Pure Chemical Industries, Ltd.), 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.) was added, the temperature of the oil bath was set to 160 ° C., and after stirring for 30 minutes, the oil bath was set to 180 ° C. and stirred for 30 minutes. The heating was stopped and the reaction was terminated. After completion of the reaction, the obtained 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 Kasei) and 8.38 g (0.05 mol) of 2,6-bis (hydroxy) 15 g of CP (manufactured by Wako Junyaku Co., Ltd.) was added to methyl) paracresol (manufactured by Wako Junyaku Co., Ltd.), 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.) was added, the temperature of the oil bath was set to 160 ° C., and after stirring for 30 minutes, the oil bath was set to 180 ° C. and stirred for 30 minutes. The heating was stopped and the reaction was terminated. After completion of the reaction, the obtained product was ice-cooled and cooled to room temperature to obtain a polymer compound (X6). The weight average molecular weight of the obtained polymer compound was 15,000.

<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.) , 0.473 g of phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 28.43 g of purified water (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred at 40 ° C. for 1 hour in an oil bath. Next, the temperature of the oil bath was set to 70 ° C., and a mixture of 253 g of titanium oxide nanoparticles (“Optreak” TR-527; manufactured by Catalysis Chemical Co., Ltd.) and 165 g of PGMEA was added dropwise over about 30 minutes. One hour after the completion of the dropping, 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 end the reaction. After completion of the reaction, the flask was ice-cooled to cool to room temperature, an anion exchange resin and a cation exchange resin were added, and the mixture was stirred for 10 hours. Finally, the ion exchange resin was filtered off 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 Kasei) and 6.34 g (0.02 mol) of MW 15 g of CP (manufactured by Wako Pure Chemical Industries, Ltd.) was added to -100 LM (manufactured by Sanwa Chemical Co., Ltd.), and the mixture was stirred in an oil bath at 40 ° C. for 1 hour. Next, 0.135 g of phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added, the temperature of the oil bath was set to 160 ° C., and after stirring for 30 minutes, the oil bath was set to 180 ° C. and stirred for 30 minutes. The heating was stopped and the reaction was terminated. After completion of the reaction, the obtained 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, 0.100 g of a surfactant (Polyflow 77 CP1 mass% solution (corresponding to a concentration of 100 ppm)) was added, and the mixture was stirred. Next, filtration was performed with a 0.45 μm filter to obtain a diluted solution of the polymer compound. The obtained polymer compound was evaluated for transmittance, refractive index, shrinkage rate and dry etching property by the following methods. Table 1 shows the composition of the composition (1) containing the obtained polymer compound and the results of each evaluation. Of the values in parentheses in Table 1, those without a unit indicate the mass part.

[Evaluation of transmittance]
The composition was spin-coated on a 5 cm square Tempax glass substrate (manufactured by AGC Technoglass Co., Ltd.) using a spin coater, and then using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). Prebaking was performed at 100 ° C. for 3 minutes to prepare a prebaked film having a film thickness of 1.0 μm. The obtained pre-baked film was baked on a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) at 220 ° C. in the air for 5 minutes to prepare a film having a film thickness of 0.7 μm.
The obtained film was evaluated with a transmittance of 400 to 800 nm using an ultraviolet-visible spectrophotometer (UV-260; manufactured by Shimadzu Corporation), and the lowest value during this period was defined as the transmittance. ..

[Evaluation of refractive index]
A film having a film thickness of 0.7 μm was prepared in the same manner as in the evaluation of the transmittance. With respect to the obtained film, the refractive index at 633 nm (using a He-Ne laser) at 22 ° C. was measured using a prism coupler MODEL2010 (manufactured by Metrocon Co., Ltd.).

[Evaluation of shrinkage rate]
A pre-baked film was prepared on a 6-inch silicon wafer in the same manner as in the evaluation of transmittance, and the thickness of the pre-baked film was measured using Lambda Ace STM-602 (trade name, manufactured by Dainippon Screen). With respect to this prebaked film, the shrinkage rate can be obtained by the following formula by producing a film by the same method as the evaluation of the transmittance and measuring the thickness.
Shrinkage rate (%) = 100 x (pre-bake film thickness-film thickness) / pre-bake film thickness

[Evaluation of dry etching properties]
A film was formed on a 6-inch silicon wafer in the same manner as the evaluation of transmittance, and the roughness of the surface was measured by an atomic force microscope (AFM). A dry etching experiment was performed on this film under the following conditions.
Etching conditions ・ RIE-10N (trade name, manufactured by SAMCO)
-Gas flow rate: Ar / O2 = 24/6 sccm
・ Bias: 200W
・ Pressure: 0.09 torr
・ Etching time: 120 sec
After that, the surface roughness was measured again with an atomic force microscope (AFM), and the dry etching property was evaluated according to the following criteria.
Good (○): Roughness change before and after dry etching is less than 10 nm Defective (×): Roughness change before and after dry etching is 10 nm or more.

<Examples 2 to 3>
The polymer compound was changed to X2 or X3, and compositions containing the polymer compound were obtained by the same method as in Example 1, 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 high molecular compound (X1) and 0.039 g of 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate or 2-methylbenzyl-4-methoxycarbonyloxyphenylmethylsulfonium trifluoromethanesulfonate 7 It was diluted with 901 g of CP, 0.100 g of a surfactant (1% by mass solution of polyflow 77 in CP (corresponding to a concentration of 100 ppm)) was added, and the mixture was stirred. 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 6 to 7>
1.764 g of polymeric compound (X1), 0.039 g of 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate and 0.196 g of MW-100LM or BX-4000 diluted with 7.901 g of CP Then, 0.100 g of a surfactant (CP1 mass% solution of Polyflow 77 (corresponding to a concentration of 100 ppm)) was added, and the mixture was stirred. 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 8>
The polymer compound was changed to X7, and compositions containing the polymer compound were obtained in the same manner as in Example 1 and evaluated in the same manner as in Example 1. Table 1 shows the composition and evaluation results of the composition containing the obtained polymer compound.

<Comparative Examples 1 to 3>
The polymer compounds were changed to X4 to X6, and compositions containing the polymer compounds were obtained in the same manner as in Example 1 and evaluated in the same manner as in Example 1. Table 2 shows the composition and evaluation results of the composition containing the obtained polymer compound.
As is clear from the results in Table 2, the film obtained from the composition containing the polymer compound of Comparative Example 1 has an insufficient refractive index, and the cross-linking ratio is insufficient in Comparative Examples 2 and 3. , Sublimated, and none of them could form a satisfactory film.

<Comparative example 4>
The polymer compound was changed to the titanium oxide dispersion Y1 to obtain a composition containing the titanium oxide dispersion by the same method as in Example 1, and the same evaluation as in Example 1 was performed. The composition of the obtained composition and the evaluation results are shown in Table 2.
As is clear from the results in Table 2, the dry etching properties of the obtained film were 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.

11 Semiconductor substrate 12 Electrode 13 Photoelectric conversion unit 14 waveguide 15 Flattening layer 16 Color filter 17 White pixel 18 Microlens

Claims (14)

A compound having at least two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group represented by the general formula (2) , and a heterocyclic aromatic compound represented by the general formula ( 3 ) (B). , A polymer compound obtained by polycondensation.

(In the general formula (2), n ¹ and n ² , k ¹ and k ² each independently represent an integer of 1 to 4. m represents an integer of 0 to 1. X represents an oxygen atom, a sulfur atom and methylene. Selected from the group consisting of 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.)

(In the general formula (3), 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 represented by the following general formula (4). R ⁵ and R ⁶ may be the same or different.)

(In the general formula (4), X ¹ and X ² are hydrogen atoms or functional groups represented by the following general formula (1). However, at least one of X ¹ and X ² is the general formula (1). It is a functional group represented by.)

(In the general formula (1), R ¹ represents a hydrogen atom or an organic group having 1 to 6 carbon atoms.) The compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group represented by the general formula (2) (A) is at least a compound represented by the general formula (2) in which m is 0. The polymer compound according to claim 1 . A resin composition containing the polymer compound according to claim 1 or 2 . A film containing the polymer compound according to claim 1 or 2 , having a refractive index of 1.65 to 1.85 at a wavelength of light of 633 nm. The film according to claim 4 , wherein the transmittance in the entire region having a wavelength of light of 400 to 800 nm is 80% or more per 1 μm of the film thickness. A solid-state imaging device comprising the film according to claim 4 or 5 . A solid-state image sensor having at least a photoelectric conversion unit, a color filter provided above the light receiving surface of the photoelectric conversion unit, and a microlens containing the polymer compound according to claim 1 or 2 . A solid-state image sensor having at least a photoelectric conversion unit, a color filter provided above the light receiving surface of the photoelectric conversion unit and having white pixels containing the polymer compound according to claim 1 or 2 , and a microlens. Solid-state imaging having at least a photoelectric conversion unit, a waveguide provided above the light receiving surface of the photoelectric conversion unit and containing the polymer compound according to claim 1 or 2 , a color filter, and a microlens. element. A compound having two or more polycyclic aromatic groups having a hydroxyl group or an alkoxy group represented by (A) the general formula (2) according to claim 1 or 2 and (B) represented by the general formula ( 3 ). A method for producing a polymer compound in which a heterocyclic aromatic compound is polycondensed. It has at least a photoelectric conversion unit, a color filter provided above the light receiving surface of the photoelectric conversion unit, and a microlens, and is further provided between the light receiving surface of the photoelectric conversion unit and the color filter, if necessary. A method for manufacturing a solid-state image sensor having a waveguide and / or a flattening layer that flattens the upper surface of the color filter.
As a step of forming the microlens,
A step of forming a film containing the polymer compound according to claim 1 or 2 on the color filter or the flattening layer provided as needed.
A method for manufacturing a solid-state image sensor, which comprises a step of heating the film. It has at least a photoelectric conversion unit, a color filter provided above the light receiving surface of the photoelectric conversion unit, and a microlens, and the color filter has white pixels, and if necessary, further of the photoelectric conversion unit. A method for manufacturing a solid-state image sensor having a waveguide provided between a light receiving surface and the color filter and / or a flattening layer for flattening the upper surface of the color filter.
As the process of forming the white pixel,
A step of forming a pattern of a film containing the polymer compound according to claim 1 or 2 on the photoelectric conversion unit or the waveguide provided as needed.
A method for manufacturing a solid-state image sensor, which comprises a step of heating the film. A flattening unit having at least a photoelectric conversion unit, a waveguide provided above the light receiving surface of the photoelectric conversion unit, a color filter, and a microlens, and further flattening the upper surface of the color filter as needed. A method for manufacturing a solid-state image sensor having a layer.
As a step of forming the waveguide,
A step of forming a film containing the polymer compound according to claim 1 or 2 on the photoelectric conversion unit, and
A method for manufacturing a solid-state image sensor, which comprises a step of heating the film. An optical device including the solid-state image sensor according to any one of claims 6 to 9 .

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