JP2020096168A - Flattened film formation resin composition for solid-state imaging element - Google Patents
Flattened film formation resin composition for solid-state imaging element Download PDFInfo
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- JP2020096168A JP2020096168A JP2019160342A JP2019160342A JP2020096168A JP 2020096168 A JP2020096168 A JP 2020096168A JP 2019160342 A JP2019160342 A JP 2019160342A JP 2019160342 A JP2019160342 A JP 2019160342A JP 2020096168 A JP2020096168 A JP 2020096168A
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- state imaging
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- 239000011342 resin composition Substances 0.000 title claims abstract description 64
- 238000003384 imaging method Methods 0.000 title claims abstract description 41
- 230000015572 biosynthetic process Effects 0.000 title abstract 3
- -1 silane compound Chemical class 0.000 claims abstract description 114
- 229910000077 silane Inorganic materials 0.000 claims abstract description 40
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 8
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 239000007859 condensation product Substances 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 16
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 29
- 230000007062 hydrolysis Effects 0.000 description 17
- 238000006460 hydrolysis reaction Methods 0.000 description 17
- 150000001450 anions Chemical class 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 6
- 150000007942 carboxylates Chemical class 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 150000004703 alkoxides Chemical class 0.000 description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 125000005372 silanol group Chemical group 0.000 description 5
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 5
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 150000001350 alkyl halides Chemical class 0.000 description 4
- 150000001502 aryl halides Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 229940116333 ethyl lactate Drugs 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229940102396 methyl bromide Drugs 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 2
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 2
- FZXRXKLUIMKDEL-UHFFFAOYSA-N 2-Methylpropyl propanoate Chemical compound CCC(=O)OCC(C)C FZXRXKLUIMKDEL-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- GFUIDHWFLMPAGY-UHFFFAOYSA-N ethyl 2-hydroxy-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)O GFUIDHWFLMPAGY-UHFFFAOYSA-N 0.000 description 2
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 2
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- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Solid State Image Pick-Up Elements (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
本発明は固体撮像素子用平坦化膜形成樹脂組成物、及び当該樹脂組成物を用いた平坦化膜の作製方法に関するものである。 The present invention relates to a flattening film forming resin composition for a solid-state imaging device, and a method for producing a flattening film using the resin composition.
ＣＣＤイメージセンサー、ＣＭＯＳイメージセンサー等の固体撮像素子は、その製造工程において、溶剤、又は酸、アルカリ溶液等の薬液に曝される処理や、スパッタリング、ドライエッチング、半田リフロー等の高温に曝される処理が行われる。このような処理によって固体撮像素子が劣化又は損傷することを防止するために、前記高温に曝される処理に対して耐性を有する硬化膜を、固体撮像素子上に形成することが行われている。前記硬化膜には、耐薬品性、高透明性、耐熱性等が要求される。 A solid-state image sensor such as a CCD image sensor or a CMOS image sensor is exposed to a solvent, a chemical solution such as an acid or an alkaline solution, or a high temperature such as sputtering, dry etching, or solder reflow in its manufacturing process. Processing is performed. In order to prevent the solid-state image sensor from being deteriorated or damaged by such a process, a cured film having resistance to the process exposed to the high temperature is formed on the solid-state image sensor. .. The cured film is required to have chemical resistance, high transparency, heat resistance and the like.
前記固体撮像素子には、例えば、マイクロレンズ、カラーフィルター、回路配線部、遮光膜又はインナーレンズ（内部レンズ）に起因する凹凸が存在する。そのため、固体撮像素子製造時のプロセスマージンの確保、デバイス特性の均一性の確保等の観点から、前記硬化膜には段差平坦化性も要求される（特許文献１乃至特許文献４）。 The solid-state imaging device has irregularities due to, for example, a microlens, a color filter, a circuit wiring portion, a light shielding film, or an inner lens (inner lens). Therefore, from the viewpoint of ensuring a process margin at the time of manufacturing a solid-state imaging device, ensuring uniformity of device characteristics, and the like, the cured film is also required to have a step flattening property (Patent Documents 1 to 4).
本発明は、前記の事情に基づいてなされたものであり、その目的は、優れた耐薬品性、耐熱性、透明性及び平坦化性を有する平坦化膜を形成できる、固体撮像素子用平坦化膜形成樹脂組成物を提供することである。また、本発明の他の目的は、優れた耐薬品性、耐熱性、透明性及び平坦化性を有する平坦化膜を提供することである。 The present invention has been made based on the above circumstances, and an object thereof is to form a flattening film having excellent chemical resistance, heat resistance, transparency, and flattening property, which is a flattening for a solid-state imaging device. A film forming resin composition is provided. Another object of the present invention is to provide a flattening film having excellent chemical resistance, heat resistance, transparency and flattening property.
本発明者らは、前記の課題を解決するべく鋭意検討を行った結果、本発明を完成するに至った。すなわち、本発明の第１態様は、下記式（１）で表されるシラン化合物を含む加水分解性シランの加水分解縮合物、及び溶剤を含有し、該溶剤を除いた固形分の含有割合が１質量％乃至５０質量％である、固体撮像素子用平坦化膜形成樹脂組成物である。
前記加水分解縮合物が、例えば、前記式（１）で表されるシラン化合物を１００モル％乃至５０モル％、及び下記式（２）で表されるシラン化合物を０モル％乃至５０モル％となる割合で含む加水分解性シランの加水分解縮合物である。
前記加水分解縮合物が、例えば下記式（３）で表される構造単位を有するポリシロキサンである。
前記加水分解縮合物が、例えば、ランダム構造、ラダー型構造、完全かご型構造、又は不完全かご型構造を持つ。 The hydrolysis-condensation product has, for example, a random structure, a ladder type structure, a complete cage type structure, or an incomplete cage type structure.
本発明の固体撮像素子用平坦化膜形成樹脂組成物は、さらに硬化触媒を含有してもよい。 The flattening film forming resin composition for a solid-state imaging device of the present invention may further contain a curing catalyst.
前記硬化触媒は、例えば、下記式（４）で表されるシラン化合物、又はアンモニウム塩である。
前記硬化触媒は、前記固形分中の含有量に基づいて、例えば０．１質量％乃至１０質量％含まれる。 The curing catalyst is contained in an amount of, for example, 0.1% by mass to 10% by mass based on the content in the solid content.
前記加水分解縮合物の重量平均分子量は、例えば１，０００乃至５０，０００である。 The weight average molecular weight of the hydrolysis-condensation product is, for example, 1,000 to 50,000.
本発明の第２態様は、本発明の第１態様の固体撮像素子用平坦化膜形成樹脂組成物を、凹凸面を有する基板上に塗布後、加熱手段を用いて前記樹脂組成物を８０℃乃至２６０℃でベークすることによる平坦化膜の作製方法である。 According to a second aspect of the present invention, the flattening film forming resin composition for a solid-state imaging device according to the first aspect of the present invention is applied onto a substrate having an uneven surface, and then the resin composition is heated to 80° C. using a heating means. It is a method for producing a planarizing film by baking at to 260° C.
本発明の固体撮像素子用平坦化膜形成樹脂組成物から作製される平坦化膜は、優れた耐薬品性、耐熱性、透明性及び平坦化性を有する。これにより、前記平坦化膜は、その作製工程、又は配線等の周辺装置の形成工程において、溶剤、又は酸、アルカリ溶液等の薬液に曝される処理や、スパッタリング、ドライエッチング、半田リフロー等の高温に曝される処理が行われる場合に、固体撮像素子が劣化又は損傷する可能性を著しく減少できる。また、例えば、マイクロレンズ、カラーフィルター、回路配線部、遮光膜又はインナーレンズに起因する凹凸が存在する基板上に、本発明の固体撮像素子用平坦化膜形成樹脂組成物を用いて平坦化膜を作製する場合、固体撮像素子製造時のプロセスマージンの確保、及びデバイス特性の均一性の確保が可能となる。 The flattening film produced from the flattening film forming resin composition for a solid-state imaging device of the present invention has excellent chemical resistance, heat resistance, transparency and flattening property. As a result, the flattening film is exposed to a chemical solution such as a solvent or an acid or alkali solution in a manufacturing process of the flattening film or a process of forming a peripheral device such as wiring, sputtering, dry etching, or solder reflow. It is possible to significantly reduce the possibility that the solid-state image pickup device is deteriorated or damaged when the process exposed to high temperature is performed. In addition, for example, a flattening film using the flattening film forming resin composition for a solid-state image pickup device of the present invention on a substrate having irregularities caused by a microlens, a color filter, a circuit wiring portion, a light-shielding film, or an inner lens. In the case of manufacturing, it is possible to secure a process margin at the time of manufacturing a solid-state image sensor and to ensure uniformity of device characteristics.
本発明は、特定の加水分解性シランを含む加水分解性シランの加水分解縮合物、及び溶剤を含有する固体撮像素子用平坦化膜形成樹脂組成物である。以下、各成分の詳細を説明する。本発明の固体撮像素子用平坦化膜形成樹脂組成物から溶剤を除いた固形分は通常、１質量％乃至５０質量％である。前記固形分の濃度が５０質量％を超えると、本発明の固体撮像素子用平坦化膜形成樹脂組成物の保存性が悪化する場合がある。 The present invention is a flattening film forming resin composition for a solid-state imaging device, which contains a hydrolysis-condensation product of a hydrolyzable silane containing a specific hydrolyzable silane, and a solvent. The details of each component will be described below. The solid content obtained by removing the solvent from the flattening film forming resin composition for a solid-state imaging device of the present invention is usually 1% by mass to 50% by mass. When the concentration of the solid content exceeds 50% by mass, the storage stability of the flattening film forming resin composition for a solid-state imaging device of the present invention may be deteriorated.
＜加水分解縮合物＞
本発明の固体撮像素子用平坦化膜形成樹脂組成物に含まれる、前記式（１）で表されるシラン化合物を含む加水分解性シランの加水分解縮合物は、Ｓｉ原子に対し、シラノール基を２０モル％以下の割合で含むものである。シラノール基の割合は、例えば５モル％乃至２０モル％、又は１０モル％乃至２０モル％とすることができる。前記加水分解縮合物中のシラノール基比率は１Ｈ ＮＭＲにて算出できる。さらに前記加水分解縮合物は、末端にアルコキシ基、例えばメトキシ基及びエトキシ基を有してもよい。前記加水分解縮合物は、シラノール基又はアルコキシ基を有することにより、加熱処理により容易に脱水縮合又は脱アルコール縮合が進行し、その結果、高分子量の硬化膜を形成することができる。
<Hydrolysis condensate>
The hydrolysis-condensation product of the hydrolyzable silane containing the silane compound represented by the formula (1) contained in the flattening film forming resin composition for a solid-state imaging device of the present invention has a silanol group for a Si atom. It is contained at a ratio of 20 mol% or less. The proportion of silanol groups can be, for example, 5 mol% to 20 mol%, or 10 mol% to 20 mol%. The silanol group ratio in the hydrolysis-condensation product can be calculated by 1 H NMR. Further, the hydrolysis-condensation product may have an alkoxy group, for example, a methoxy group and an ethoxy group at the terminal. Since the hydrolysis-condensation product has a silanol group or an alkoxy group, dehydration condensation or dealcoholization condensation can easily proceed by heat treatment, and as a result, a cured film having a high molecular weight can be formed.
前記加水分解縮合物の重量平均分子量は、例えば１，０００乃至５０，０００であり、好ましくは１，２００乃至２０，０００または１，０００乃至１０，０００である。前記加水分解縮合物は、重量平均分子量が小さいほど溶剤への溶解性が優れる。 The weight average molecular weight of the hydrolyzed condensate is, for example, 1,000 to 50,000, preferably 1,200 to 20,000 or 1,000 to 10,000. The smaller the weight average molecular weight of the hydrolysis-condensation product, the better the solubility in a solvent.
前記加水分解縮合物は、前記式（１）で表されるシラン化合物を１００モル％乃至５０モル％、及び前記式（２）で表されるシラン化合物を０モル％乃至５０モル％となる割合で含む加水分解性シランの加水分解縮合物が好ましい。さらに好ましくは、前記式（１）で表されるシラン化合物を１００モル％乃至７０モル％及び、前記式（２）で表されるシラン化合物を０モル％乃至３０モル％となる割合で含む加水分解性シランの加水分解縮合物である。 The hydrolysis-condensation product is such that the silane compound represented by the formula (1) is 100 mol% to 50 mol% and the silane compound represented by the formula (2) is 0 mol% to 50 mol%. The hydrolysis-condensation product of the hydrolyzable silane contained in 1) is preferable. More preferably, the silane compound represented by the formula (1) is added in an amount of 100 mol% to 70 mol% and the silane compound represented by the formula (2) is added in an amount of 0 mol% to 30 mol%. It is a hydrolytic condensate of decomposable silane.
本発明の固体撮像素子用平坦化膜形成樹脂組成物は、前記加水分解縮合物の原料である加水分解性シラン、又は該加水分解性シランの加水分解物を、該加水分解縮合物と共に含有してもよい。本発明の固体撮像素子用平坦化膜形成樹脂組成物はまた、前記加水分解縮合物を得る際に加水分解が完全に完了しない部分加水分解物、及び前記加水分解性シランを、該加水分解縮合物と共に含有することもできる。前記加水分解縮合物は、シロキサン構造を有するポリマーである。 The flattening film forming resin composition for a solid-state imaging device of the present invention contains a hydrolyzable silane that is a raw material of the hydrolyzed condensate or a hydrolyzate of the hydrolyzable silane together with the hydrolyzed condensate. May be. The flattening film-forming resin composition for a solid-state imaging device of the present invention also comprises a partial hydrolyzate, which is not completely hydrolyzed when the hydrolytic condensate is obtained, and the hydrolyzable silane. It can also be included with the product. The hydrolysis-condensation product is a polymer having a siloxane structure.
前記式（１）及び式（２）のＲ１が炭素原子数１乃至３のアルキル基を表す場合、該アルキル基は直鎖又は分岐を有する炭素原子数１乃至３のアルキル基であり、例えばメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基が挙げられる。また前記アルキル基として、環状アルキル基を用いることもでき、炭素原子数３の環状アルキル基として、シクロプロピル基が挙げられる。 When R 1 in the above formulas (1) and (2) represents an alkyl group having 1 to 3 carbon atoms, the alkyl group is a linear or branched alkyl group having 1 to 3 carbon atoms, for example, Examples thereof include a methyl group, an ethyl group, an n-propyl group and an i-propyl group. A cyclic alkyl group may be used as the alkyl group, and a cyclopropyl group may be mentioned as the cyclic alkyl group having 3 carbon atoms.
前記式（１）及び式（２）のＲ１が炭素原子数１乃至３のアルケニル基を表す場合、該アルケニル基として、例えばビニル基及びアリル基が挙げられる。 When R 1 in the formulas (1) and (2) represents an alkenyl group having 1 to 3 carbon atoms, examples of the alkenyl group include a vinyl group and an allyl group.
前記式（１）及び式（２）のＲ２がアルコキシ基を表す場合、該アルコキシ基として、例えば炭素原子数１乃至２０の直鎖状、分岐状、又は環状のアルキル部分を有するアルコキシ基が挙げられる。前記直鎖状又は分岐状のアルキル部分を有するアルコキシ基として、例えば、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｎ−ブトキシ基、ｉ−ブトキシ基、ｓ−ブトキシ基、ｔ−ブトキシ基、ｎ−ペンチロキシ基、１−メチル−ｎ−ブトキシ基、２−メチル−ｎ−ブトキシ基、３−メチル−ｎ−ブトキシ基、１，１−ジメチル−ｎ−プロポキシ基、１，２−ジメチル−ｎ−プロポキシ基、２，２−ジメチル−ｎ−プロポキシ基、１−エチル−ｎ−プロポキシ基、ｎ−ヘキシロキシ基、１−メチル−ｎ−ペンチロキシ基、２−メチル−ｎ−ペンチロキシ基、３−メチル−ｎ−ペンチロキシ基、４−メチル−ｎ−ペンチロキシ基、１，１−ジメチル−ｎ−ブトキシ基、１，２−ジメチル−ｎ−ブトキシ基、１，３−ジメチル−ｎ−ブトキシ基、２，２−ジメチル−ｎ−ブトキシ基、２，３−ジメチル−ｎ−ブトキシ基、３，３−ジメチル−ｎ−ブトキシ基、１−エチル−ｎ−ブトキシ基、２−エチル−ｎ−ブトキシ基、１，１，２−トリメチル−ｎ−プロポキシ基、１，２，２−トリメチル−ｎ−プロポキシ基、１−エチル−１−メチル−ｎ−プロポキシ基及び１−エチル−２−メチル−ｎ−プロポキシ基が挙げられる。前記環状のアルキル部分を有するアルコキシ基として、シクロプロポキシ基、シクロブトキシ基、１−メチル−シクロプロポキシ基、２−メチル−シクロプロポキシ基、シクロペンチロキシ基、１−メチル−シクロブトキシ基、２−メチル−シクロブトキシ基、３−メチル−シクロブトキシ基、１，２−ジメチル−シクロプロポキシ基、２，３−ジメチル−シクロプロポキシ基、１−エチル−シクロプロポキシ基、２−エチル−シクロプロポキシ基、シクロヘキシロキシ基、１−メチル−シクロペンチロキシ基、２−メチル−シクロペンチロキシ基、３−メチル−シクロペンチロキシ基、１−エチル−シクロブトキシ基、２−エチル−シクロブトキシ基、３−エチル−シクロブトキシ基、１，２−ジメチル−シクロブトキシ基、１，３−ジメチル−シクロブトキシ基、２，２−ジメチル−シクロブトキシ基、２，３−ジメチル−シクロブトキシ基、２，４−ジメチル−シクロブトキシ基、３，３−ジメチル−シクロブトキシ基、１−ｎ−プロピル−シクロプロポキシ基、２−ｎ−プロピル−シクロプロポキシ基、１−ｉ−プロピル−シクロプロポキシ基、２−ｉ−プロピル−シクロプロポキシ基、１，２，２−トリメチル−シクロプロポキシ基、１，２，３−トリメチル−シクロプロポキシ基、２，２，３−トリメチル−シクロプロポキシ基、１−エチル−２−メチル−シクロプロポキシ基、２−エチル−１−メチル−シクロプロポキシ基、２−エチル−２−メチル−シクロプロポキシ基、及び２−エチル−３−メチル−シクロプロポキシ基が挙げられる。 When R 2 in the formulas (1) and (2) represents an alkoxy group, the alkoxy group is, for example, an alkoxy group having a linear, branched or cyclic alkyl moiety having 1 to 20 carbon atoms. Can be mentioned. Examples of the alkoxy group having a linear or branched alkyl moiety include, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t -Butoxy group, n-pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2 -Dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group , 3-methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group Group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n- Butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group and 1-ethyl-2-methyl- An n-propoxy group is mentioned. As the alkoxy group having a cyclic alkyl moiety, a cyclopropoxy group, a cyclobutoxy group, a 1-methyl-cyclopropoxy group, a 2-methyl-cyclopropoxy group, a cyclopentyloxy group, a 1-methyl-cyclobutoxy group, 2- Methyl-cyclobutoxy group, 3-methyl-cyclobutoxy group, 1,2-dimethyl-cyclopropoxy group, 2,3-dimethyl-cyclopropoxy group, 1-ethyl-cyclopropoxy group, 2-ethyl-cyclopropoxy group, Cyclohexyloxy group, 1-methyl-cyclopentyloxy group, 2-methyl-cyclopentyloxy group, 3-methyl-cyclopentyloxy group, 1-ethyl-cyclobutoxy group, 2-ethyl-cyclobutoxy group, 3-ethyl -Cyclobutoxy group, 1,2-dimethyl-cyclobutoxy group, 1,3-dimethyl-cyclobutoxy group, 2,2-dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group, 2,4-dimethyl -Cyclobutoxy group, 3,3-dimethyl-cyclobutoxy group, 1-n-propyl-cyclopropoxy group, 2-n-propyl-cyclopropoxy group, 1-i-propyl-cyclopropoxy group, 2-i-propyl -Cyclopropoxy group, 1,2,2-trimethyl-cyclopropoxy group, 1,2,3-trimethyl-cyclopropoxy group, 2,2,3-trimethyl-cyclopropoxy group, 1-ethyl-2-methyl-cyclo Examples thereof include a propoxy group, a 2-ethyl-1-methyl-cyclopropoxy group, a 2-ethyl-2-methyl-cyclopropoxy group, and a 2-ethyl-3-methyl-cyclopropoxy group.
前記式（１）及び式（２）のＲ２がハロゲノ基を表す場合、該ハロゲノ基として、例えばフルオロ基、クロロ基、ブロモ基、ヨード基が挙げられる。以上に記載した置換基の例は、後述する、ハロゲン化アルキル、ハロゲン化アリール、ハロゲン化シリル及びアルコキシシリルにおける、アルキル基、アルコキシ基及びハロゲノ基の部分にも適用される。 When R 2 in the formulas (1) and (2) represents a halogeno group, examples of the halogeno group include a fluoro group, a chloro group, a bromo group, and an iodo group. The examples of the substituents described above are also applied to the alkyl group, the alkoxy group and the halogeno group in the alkyl halide, aryl halide, silyl halide and alkoxysilyl described below.
本発明の固体撮像素子用平坦化膜形成樹脂組成物に用いられる加水分解縮合物の具体例として、下記式（１−１）乃至式（１−５）で表される構造単位を有するポリシロキサンが挙げられる。
前記加水分解縮合物の重量平均分子量は、ＧＰＣ分析によるポリスチレン換算で得られる。ＧＰＣは、ゲル浸透クロマトグラフィーの略称である。ＧＰＣの測定条件は、例えばＧＰＣ装置（日本分光（株）製ＧＰＣシステム）、カラム（昭和電工製Ｓｈｏｄｅｘ〔登録商標〕ＫＦ−８０４Ｌ及びＫＦ−８０３Ｌ）、カラム温度は４０℃、溶離液（溶出溶媒）はテトラヒドロフラン、流量（流速）は１．０ｍｌ／分、標準試料はポリスチレン（昭和電工（株）製）を用いて行うことができる。 The weight average molecular weight of the hydrolysis-condensation product is obtained in terms of polystyrene by GPC analysis. GPC is an abbreviation for gel permeation chromatography. The measurement conditions of GPC are, for example, a GPC device (GPC system manufactured by JASCO Corporation), a column (Shodex [registered trademark] KF-804L and KF-803L manufactured by Showa Denko), a column temperature of 40° C., an eluent (elution solvent). ) Is tetrahydrofuran, the flow rate (flow rate) is 1.0 ml/min, and the standard sample is polystyrene (Showa Denko KK).
前記加水分解性シランの加水分解性基であるアルコキシシリル基又はハロゲン化シリル基の加水分解には、該加水分解性基１モル当たり、０．５モル乃至１００モル、好ましくは１モル乃至１０モルの水を用いる。前記加水分解は、加水分解触媒を用いて行うことができるが、加水分解触媒を用いずに行うこともできる。加水分解触媒を用いる場合は、前記加水分解性基１モル当たり０．００１モル乃至１０モル、好ましくは０．００１モル乃至１モルの加水分解触媒を用いることができる。加水分解及び縮合を行う際の反応温度は、通常２０℃乃至１１０℃である。前記加水分解は、完全に加水分解を行うことも、部分加水分解することでもよい。即ち、加水分解縮合物中に加水分解物やモノマーが残存していてもよい。 For the hydrolysis of the alkoxysilyl group or silyl halide group which is the hydrolyzable group of the hydrolyzable silane, 0.5 mol to 100 mol, preferably 1 mol to 10 mol, per 1 mol of the hydrolyzable group. Use water. The hydrolysis can be performed using a hydrolysis catalyst, but can also be performed without using a hydrolysis catalyst. When a hydrolysis catalyst is used, 0.001 mol to 10 mol, preferably 0.001 mol to 1 mol of the hydrolysis catalyst can be used per 1 mol of the hydrolyzable group. The reaction temperature during the hydrolysis and condensation is usually 20°C to 110°C. The hydrolysis may be complete hydrolysis or partial hydrolysis. That is, the hydrolyzate or the monomer may remain in the hydrolyzed condensate.
前記加水分解触媒としては、酸又は塩基を用いることができる。該加水分解触媒として、例えば、金属キレート化合物、有機酸、無機酸、有機塩基、及び無機塩基を挙げることができる。 An acid or a base can be used as the hydrolysis catalyst. Examples of the hydrolysis catalyst include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.
＜溶剤＞
本発明の固体撮像素子用平坦化膜形成樹脂組成物に使用される溶剤としては、前記の固形分を溶解できる溶剤であれば、特に制限なく使用することができる。そのような溶剤としては、例えば、メチルセロソルブアセテート、エチルセロソルブアセテート、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、メチルイソブチルカルビノール、プロピレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエテルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、２−ヒドロキシプロピオン酸エチル、２−ヒドロキシ−２−メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２−ヒドロキシ−３−メチルブタン酸メチル、３−メトキシプロピオン酸メチル、３−メトキシプロピオン酸エチル、３−エトキシプロピオン酸エチル、３−エトキシプロピオン酸メチル、ピルビン酸メチル、ピルビン酸エチル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノプロピルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテルプロピレングリコールモノメチルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールジプロピルエーテル、プロピレングリコールジブチルエーテル、乳酸エチル、乳酸プロピル、乳酸イソプロピル、乳酸ブチル、乳酸イソブチル、ギ酸メチル、ギ酸エチル、ギ酸プロピル、ギ酸イソプロピル、ギ酸ブチル、ギ酸イソブチル、ギ酸アミル、ギ酸イソアミル、酢酸メチル、酢酸エチル、酢酸ｎ−プロピル、酢酸アミル、酢酸イソアミル、酢酸ヘキシル、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸プロピル、プロピオン酸イソプロピル、プロピオン酸ブチル、プロピオン酸イソブチル、酪酸メチル、酪酸エチル、酪酸プロピル、酪酸イソプロピル、酪酸ブチル、酪酸イソブチル、ヒドロキシ酢酸エチル、２−ヒドロキシ−２−メチルプロピオン酸エチル、３−メトキシ−２−メチルプロピオン酸メチル、２−ヒドロキシ−３−メチル酪酸メチル、メトキシ酢酸エチル、エトキシ酢酸エチル、３−メトキシプロピオン酸メチル、３−エトキシプロピオン酸エチル、３−メトキシプロピオン酸エチル、３−メトキシブチルアセテート、３−メトキシプロピルアセテート、３−メチル−３−メトキシブチルアセテート、３−メチル−３−メトキシブチルプロピオネート、３−メチル−３−メトキシブチルブチレート、アセト酢酸メチル、トルエン、キシレン、メチルエチルケトン、メチルプロピルケトン、メチルブチルケトン、２−ヘプタノン、３−ヘプタノン、４−ヘプタノン、シクロヘキサノン、Ｎ、Ｎ−ジメチルホルムアミド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン、４−メチル−２−ペンタノール、及びγ−ブチロラクトンを挙げることができる。これらの溶剤は１種単独で、または２種以上の組み合わせで使用することができる。
<Solvent>
As the solvent used in the resin composition for forming a flattening film for a solid-state imaging device of the present invention, any solvent can be used without particular limitation as long as it can dissolve the above-mentioned solid content. Examples of such a solvent include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether. Ether ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate , Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate , Isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, n-propyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, propionic acid Methyl, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyrate Isopropyl acetate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethoxy Ethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl- 3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone , N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone. These solvents can be used alone or in combination of two or more.
本発明の固体撮像素子用平坦化膜形成用樹脂組成物は、例えば、前記加水分解縮合物及び後述するその他の成分を前記溶剤に溶解させることによって調製でき、均一な溶液状態で用いられる。調製した樹脂組成物は、フィルター等を用いてろ過した後、使用するのが好ましい。 The resin composition for forming a flattening film for a solid-state imaging device of the present invention can be prepared, for example, by dissolving the hydrolysis condensate and other components described below in the solvent, and is used in a uniform solution state. The prepared resin composition is preferably used after being filtered using a filter or the like.
＜その他の成分＞
本発明の固体撮像素子用平坦化膜形成樹脂組成物に含まれていてもよい、その他の成分について以下に説明する。
<Other ingredients>
Other components that may be contained in the flattening film forming resin composition for a solid-state imaging device of the present invention will be described below.
本発明の固体撮像素子用平坦化膜形成樹脂組成物は、硬化触媒を含有することができる。該硬化触媒は、加水分解縮合物を含有する塗布膜を加熱し硬化させる時に触媒の働きをする。該硬化触媒としては、例えば、前記式（４）で表されるシラン化合物、及びアンモニウム塩を用いることができる。該硬化触媒の含有量は、前記加水分解縮合物１００質量部に対して、０．０１質量部乃至１０質量部、または０．１質量部乃至１０質量部、または０．０１質量部乃至５質量部、または０．０１質量部乃至３質量部である。 The flattening film forming resin composition for a solid-state imaging device of the present invention can contain a curing catalyst. The curing catalyst acts as a catalyst when the coating film containing the hydrolyzed condensate is heated and cured. As the curing catalyst, for example, a silane compound represented by the above formula (4) and an ammonium salt can be used. The content of the curing catalyst is 0.01 parts by mass to 10 parts by mass, or 0.1 parts by mass to 10 parts by mass, or 0.01 parts by mass to 5 parts by mass with respect to 100 parts by mass of the hydrolysis-condensation product. Parts, or 0.01 parts by mass to 3 parts by mass.
前記式（４）で表されるシラン化合物として、例えばＮ−（３−トリエトキシシリルプロピル）−４，５−ジヒドロイミダゾール等のイミダゾール環含有シラン化合物が挙げられる。 Examples of the silane compound represented by the above formula (4) include imidazole ring-containing silane compounds such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.
前記アンモニウム塩としては、下記式（５−１）：
下記式（５−２）：
下記式（５−３）：
下記式（５−４）：
下記式（５−５）：
下記式（５−６）：
Formula (5-2) below:
Formula (5-3) below:
Formula (5-4) below:
Formula (5-5) below:
前記式（５−１）で表される構造を有する第４級アンモニウム塩は、アミンから誘導される第４級アンモニウム塩である。該第４級アンモニウム塩のＲ４は、例えば、炭素原子数１乃至１８、好ましくは炭素原子数２乃至１０のアルキル基又はアリール基を表し、エチル基、プロピル基、ブチル基等の直鎖アルキル基、ベンジル基、シクロヘキシル基、シクロヘキシルメチル基、及びジシクロペンタジエニル基が挙げられる。該第４級アンモニウム塩の陰イオン（Ｙ−）は、例えば、塩素イオン（Ｃｌ−）、臭素イオン（Ｂｒ−）、ヨウ素イオン（Ｉ−）等のハロゲンイオン、及びカルボキシラート（−ＣＯＯ−）、スルホナト（−ＳＯ３ −）、アルコキシド（−Ｏ−）等の酸基を挙げることができる。 The quaternary ammonium salt having the structure represented by the formula (5-1) is a quaternary ammonium salt derived from an amine. R 4 of the quaternary ammonium salt represents, for example, an alkyl group or an aryl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and a linear alkyl group such as an ethyl group, a propyl group or a butyl group. Group, benzyl group, cyclohexyl group, cyclohexylmethyl group, and dicyclopentadienyl group. The anion (Y − ) of the quaternary ammonium salt is, for example, a chlorine ion (Cl − ), a bromide ion (Br − ), a halogen ion such as an iodine ion (I − ), or a carboxylate (—COO − ). And acid groups such as sulfonato (—SO 3 − ) and alkoxide (—O − ).
前記式（５−２）で表される第４級アンモニウム塩のＲ５、Ｒ６、Ｒ７、及びＲ８は、例えば、炭素原子数１乃至１８のアルキル基又はアリール基を表す。該第４級アンモニウム塩の陰イオン（Ｙ−）は、塩素イオン（Ｃｌ−）、臭素イオン（Ｂｒ−）、ヨウ素イオン（Ｉ−）等のハロゲンイオン、及びカルボキシラート（−ＣＯＯ−）、スルホナト（−ＳＯ３ −）、アルコキシド（−Ｏ−）等の酸基を挙げることができる。該第４級アンモニウム塩は、市販品を入手することが可能であり、例えば、テトラメチルアンモニウムアセテート、テトラブチルアンモニウムアセテート、塩化トリエチルベンジルアンモニウム、臭化トリエチルベンジルアンモニウム、塩化トリオクチルメチルアンモニウム、塩化トリブチルベンジルアンモニウム、及び塩化トリメチルベンジルアンモニウムが挙げられる。 R 5 , R 6 , R 7 , and R 8 of the quaternary ammonium salt represented by the formula (5-2) represent, for example, an alkyl group or an aryl group having 1 to 18 carbon atoms. The anion (Y − ) of the quaternary ammonium salt is a halogen ion such as chlorine ion (Cl − ), bromine ion (Br − ), iodine ion (I − ), carboxylate (—COO − ), sulfonato. Examples thereof include acid groups such as (—SO 3 − ) and alkoxide (—O − ). The quaternary ammonium salt can be obtained as a commercially available product, and examples thereof include tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride and tributyl chloride. Benzyl ammonium, and trimethyl benzyl ammonium chloride are mentioned.
前記式（５−３）で表される構造を有する第４級アンモニウム塩は、１−置換イミダゾールから誘導される第４級アンモニウム塩である。該第４級アンモニウム塩のＲ９及びＲ１０は、例えば、炭素原子数１乃至１８のアルキル基又はアリール基を表し、Ｒ９及びＲ１０の炭素原子数の総和が７以上であることが好ましい。該第４級アンモニウム塩のＲ９は、例えば、メチル基、エチル基、プロピル基、フェニル基、ベンジル基が挙げられ、Ｒ１０は、例えば、ベンジル基、オクチル基、オクタデシル基が挙げられる。該第４級アンモニウム塩の陰イオン（Ｙ−）は、塩素イオン（Ｃｌ−）、臭素イオン（Ｂｒ−）、ヨウ素イオン（Ｉ−）等のハロゲンイオン、及びカルボキシラート（−ＣＯＯ−）、スルホナト（−ＳＯ３ −）、アルコキシド（−Ｏ−）等の酸基を挙げることができる。該第４級アンモニウム塩は、市販品を入手することもできるが、例えば、１−メチルイミダゾール、１−ベンジルイミダゾール等のイミダゾール系化合物と、臭化ベンジル、臭化メチル等のハロゲン化アルキル又はハロゲン化アリールとを反応させて製造することもできる。 The quaternary ammonium salt having the structure represented by the formula (5-3) is a quaternary ammonium salt derived from 1-substituted imidazole. R 9 and R 10 of the quaternary ammonium salt represent, for example, an alkyl group or an aryl group having 1 to 18 carbon atoms, and the total number of carbon atoms of R 9 and R 10 is preferably 7 or more. .. Examples of R 9 of the quaternary ammonium salt include a methyl group, ethyl group, propyl group, phenyl group and benzyl group, and examples of R 10 include a benzyl group, an octyl group and an octadecyl group. The anion (Y − ) of the quaternary ammonium salt is a halogen ion such as chlorine ion (Cl − ), bromine ion (Br − ), iodine ion (I − ), carboxylate (—COO − ), sulfonato. Examples thereof include acid groups such as (—SO 3 − ) and alkoxide (—O − ). As the quaternary ammonium salt, a commercially available product can be obtained. For example, imidazole compounds such as 1-methylimidazole and 1-benzylimidazole, and alkyl halides or halogens such as benzyl bromide and methyl bromide. It can also be produced by reacting with an aryl halide.
前記式（５−４）で表される構造を有する第４級アンモニウム塩は、ピリジンから誘導される第４級アンモニウム塩である。該第４級アンモニウム塩のＲ１１は、例えば、炭素原子数１乃至１８、好ましくは炭素原子数４乃至１８のアルキル基又はアリール基を表し、ブチル基、オクチル基、ベンジル基、及びラウリル基が挙げられる。該第４級アンモニウム塩の陰イオン（Ｙ−）は、塩素イオン（Ｃｌ−）、臭素イオン（Ｂｒ−）、ヨウ素イオン（Ｉ−）等のハロゲンイオン、及びカルボキシラート（−ＣＯＯ−）、スルホナト（−ＳＯ３ −）、アルコキシド（−Ｏ−）等の酸基を挙げることができる。該第４級アンモニウム塩は、市販品を入手することもできるが、例えばピリジンと、塩化ラウリル、塩化ベンジル、臭化ベンジル、臭化メチル、臭化オクチル等のハロゲン化アルキル又はハロゲン化アリールとを反応させて製造することができる。該第４級アンモニウム塩は、例えば、塩化Ｎ−ラウリルピリジニウム、臭化Ｎ−ベンジルピリジニウムを挙げられる。 The quaternary ammonium salt having the structure represented by the formula (5-4) is a quaternary ammonium salt derived from pyridine. R 11 of the quaternary ammonium salt represents, for example, an alkyl group or an aryl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, and is a butyl group, an octyl group, a benzyl group, and a lauryl group. Can be mentioned. The anion (Y − ) of the quaternary ammonium salt is a halogen ion such as chlorine ion (Cl − ), bromine ion (Br − ), iodine ion (I − ), carboxylate (—COO − ), sulfonato. Examples thereof include acid groups such as (—SO 3 − ) and alkoxide (—O − ). As the quaternary ammonium salt, a commercially available product can be obtained, but for example, pyridine and an alkyl halide or aryl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide and octyl bromide can be used. It can be produced by reacting. Examples of the quaternary ammonium salt include N-laurylpyridinium chloride and N-benzylpyridinium bromide.
前記式（５−５）で表される構造を有する第４級アンモニウム塩は、ピコリン（メチルピリジン）に代表される置換ピリジンから誘導される第４級アンモニウム塩である。該第４級アンモニウム塩のＲ１２は、例えば、炭素原子数１乃至１８、好ましくは炭素原子数４乃至１８のアルキル基又はアリール基を表し、メチル基、オクチル基、ラウリル基、及びベンジル基が挙げられる。Ｒ１３は、例えば、炭素原子数１乃至１８のアルキル基又はアリール基であり、例えばピコリンから誘導される第４級アンモニウムである場合はＲ１３はメチル基である。該第４級アンモニウム塩の陰イオン（Ｙ−）は、塩素イオン（Ｃｌ−）、臭素イオン（Ｂｒ−）、ヨウ素イオン（Ｉ−）等のハロゲンイオン、及びカルボキシラート（−ＣＯＯ−）、スルホナト（−ＳＯ３ −）、アルコラート（−Ｏ−）等の酸基を挙げることができる。該第４級アンモニウム塩は市販品を入手することもできるが、例えばピコリン等の置換ピリジンと、臭化メチル、臭化オクチル、塩化ラウリル、塩化ベンジル、臭化ベンジル等のハロゲン化アルキル、又はハロゲン化アリールを反応させて製造することができる。該第４級アンモニウム塩は、例えば、Ｎ−ベンジルピコリニウムクロライド、Ｎ−ベンジルピコリニウムブロマイド、Ｎ−ラウリルピコリニウムクロライドを挙げることができる。 The quaternary ammonium salt having the structure represented by the formula (5-5) is a quaternary ammonium salt derived from a substituted pyridine represented by picoline (methylpyridine). R 12 of the quaternary ammonium salt represents, for example, an alkyl group or an aryl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, and is represented by a methyl group, an octyl group, a lauryl group, and a benzyl group. Can be mentioned. R 13 is, for example, an alkyl group or an aryl group having 1 to 18 carbon atoms, and when it is, for example, a quaternary ammonium derived from picoline, R 13 is a methyl group. The anion (Y − ) of the quaternary ammonium salt is a halogen ion such as chlorine ion (Cl − ), bromine ion (Br − ), iodine ion (I − ), carboxylate (—COO − ), sulfonato. Examples thereof include acid groups such as (—SO 3 − ) and alcoholate (—O − ). The quaternary ammonium salt may be commercially available, for example, a substituted pyridine such as picoline, an alkyl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride or benzyl bromide, or a halogen. It can be produced by reacting an aryl halide. Examples of the quaternary ammonium salt include N-benzylpicolinium chloride, N-benzylpicolinium bromide, and N-laurylpicolinium chloride.
前記式（５−６）で表される構造を有する第３級アンモニウム塩は、アミンから誘導される第３級アンモニウム塩である。該第３級アンモニウム塩の陰イオン（Ｙ−）は、塩素イオン（Ｃｌ−）、臭素イオン（Ｂｒ−）、ヨウ素イオン（Ｉ−）等のハロゲンイオン、及びカルボキシラート（−ＣＯＯ−）、スルホナト（−ＳＯ３ −）、アルコキシド（−Ｏ−）等の酸基を挙げることができる。該第３級アンモニウム塩は、例えば、アミンと、カルボン酸、フェノール等の弱酸との反応によって製造することができる。該カルボン酸としてはギ酸及び酢酸が挙げられ、ギ酸を使用した場合は、陰イオン（Ｙ−）は（ＨＣＯＯ−）であり、酢酸を使用した場合は、陰イオン（Ｙ−）は（ＣＨ３ＣＯＯ−）である。また弱酸としてフェノールを使用した場合は、陰イオン（Ｙ−）は（Ｃ６Ｈ５Ｏ−）である。 The tertiary ammonium salt having the structure represented by the formula (5-6) is a tertiary ammonium salt derived from an amine. The anion (Y − ) of the tertiary ammonium salt is a halogen ion such as a chlorine ion (Cl − ), a bromine ion (Br − ), an iodine ion (I − ), a carboxylate (—COO − ), a sulfonate. Examples thereof include acid groups such as (—SO 3 − ) and alkoxide (—O − ). The tertiary ammonium salt can be produced, for example, by reacting an amine with a weak acid such as carboxylic acid or phenol. Examples of the carboxylic acid include formic acid and acetic acid. When formic acid is used, the anion (Y − ) is (HCOO − ), and when acetic acid is used, the anion (Y − ) is (CH 3 ). COO − ). When phenol is used as the weak acid, the anion (Y − ) is (C 6 H 5 O − ).
加水分解性シランを溶媒中で加水分解触媒を用いて加水分解し縮合し、得られた加水分解縮合物（ポリマー）は、減圧蒸留等により、副生成物のアルコール、用いた加水分解触媒及び水を同時に除去することができる。また、加水分解触媒に用いた酸又は塩基を、中和又はイオン交換により取り除くことができる。そして本発明の固体撮像素子用平坦化膜形成樹脂組成物には、該樹脂組成物の安定化のために、有機酸、水、アルコール、又はそれらの組み合わせを添加することができる。 The hydrolysis-condensation product (polymer) obtained by hydrolyzing and condensing a hydrolyzable silane in a solvent by using a hydrolysis catalyst, the resulting hydrolysis-condensation product (polymer) is subjected to distillation under reduced pressure and the like, by-product alcohol, the used hydrolysis catalyst and water. Can be removed at the same time. Further, the acid or base used for the hydrolysis catalyst can be removed by neutralization or ion exchange. Then, an organic acid, water, alcohol, or a combination thereof can be added to the resin composition for forming a flattening film for a solid-state imaging device of the present invention in order to stabilize the resin composition.
前記有機酸としては、例えば、シュウ酸、マロン酸、メチルマロン酸、コハク酸、マレイン酸、リンゴ酸、酒石酸、フタル酸、クエン酸、グルタル酸、クエン酸、乳酸、及びサリチル酸が挙げられる。これらの中でも、シュウ酸及びマレイン酸が好ましい。前記有機酸の添加量は、前記加水分解縮合物（ポリオルガノシロキサン）１００質量部に対して、例えば０．１質量部乃至５．０質量部である。また前記水としては、例えば、純水、超純水、及びイオン交換水が挙げられ、その添加量は、本発明の固体撮像素子用平坦化膜形成樹脂組成物１００質量部に対して、１質量部乃至２０質量部とすることができる。また前記アルコールとしては、該樹脂組成物を塗布後、加熱により飛散しやすいものが好ましく、例えばメタノール、エタノール、プロパノール、イソプロパノール、及びブタノールが挙げられる。前記アルコールの添加量は、該樹脂組成物１００質量部に対して、例えば１質量部乃至２０質量部とすることができる。 Examples of the organic acid include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, citric acid, lactic acid, and salicylic acid. Among these, oxalic acid and maleic acid are preferable. The addition amount of the organic acid is, for example, 0.1 parts by mass to 5.0 parts by mass with respect to 100 parts by mass of the hydrolysis-condensation product (polyorganosiloxane). Examples of the water include pure water, ultrapure water, and ion-exchanged water, and the addition amount thereof is 1 part with respect to 100 parts by mass of the flattening film forming resin composition for a solid-state image pickup device of the present invention. It may be from 20 to 20 parts by weight. The alcohol is preferably one that is easily scattered by heating after applying the resin composition, and examples thereof include methanol, ethanol, propanol, isopropanol, and butanol. The amount of the alcohol added may be, for example, 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the resin composition.
従って、本発明の固体撮像素子用平坦化膜形成樹脂組成物は、水、アルコール、有機酸、及び硬化触媒からなる群から選ばれた１つ以上を含むことができる。本発明の固体撮像素子用平坦化膜形成樹脂組成物は、前記の成分の他、必要に応じて、有機ポリマー化合物、光酸発生剤、及び界面活性剤からなる群から選ばれた１つ以上をさらに含むことができる。 Therefore, the flattening film forming resin composition for a solid-state imaging device of the present invention may include one or more selected from the group consisting of water, alcohol, organic acid, and a curing catalyst. The flattening film forming resin composition for a solid-state image pickup device of the present invention is, in addition to the above components, one or more selected from the group consisting of an organic polymer compound, a photoacid generator, and a surfactant, if necessary. Can be further included.
前記光酸発生剤としては、例えば、オニウム塩化合物、スルホンイミド化合物、及びジスルホニルジアゾメタン化合物が挙げられる。前記オニウム塩化合物としては、ジフェニルヨードニウムヘキサフルオロホスフエート、ジフェニルヨードニウムトリフルオロメタンスルホネート、ジフェニルヨードニウムノナフルオロノルマルブタンスルホネート、ジフェニルヨードニウムパーフルオロノルマルオクタンスルホネート、ジフェニルヨードニウムカンファースルホネート、ビス（４−ｔｅｒｔ−ブチルフェニル）ヨードニウムカンファースルホネート、ビス（４−ｔｅｒｔ−ブチルフェニル）ヨードニウムトリフルオロメタンスルホネート等のヨードニウム塩化合物、及びトリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムノナフルオロノルマルブタンスルホネート、トリフェニルスルホニウムカンファースルホネート、トリフェニルスルホニウムトリフルオロメタンスルホネート等のスルホニウム塩化合物が挙げられる。 Examples of the photoacid generator include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds. Examples of the onium salt compound include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butane sulfonate, diphenyliodonium perfluoronormal octane sulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl). Iodonium salt compounds such as iodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butane sulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium Examples thereof include sulfonium salt compounds such as trifluoromethanesulfonate.
前記スルホンイミド化合物としては、例えば、Ｎ−（トリフルオロメタンスルホニルオキシ）スクシンイミド、Ｎ−（ノナフルオロノルマルブタンスルホニルオキシ）スクシンイミド、Ｎ−（カンファースルホニルオキシ）スクシンイミド、及びＮ−（トリフルオロメタンスルホニルオキシ）ナフタルイミドが挙げられる。 Examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)na. Examples include phthalimide.
前記ジスルホニルジアゾメタン化合物としては、例えば、ビス（トリフルオロメチルスルホニル）ジアゾメタン、ビス（シクロヘキシルスルホニル）ジアゾメタン、ビス（フェニルスルホニル）ジアゾメタン、ビス（ｐ−トルエンスルホニル）ジアゾメタン、ビス（２，４−ジメチルベンゼンスルホニル）ジアゾメタン、及びメチルスルホニル−ｐ−トルエンスルホニルジアゾメタンが挙げられる。 Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzene). Sulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.
前記光酸発生剤は１種のみを使用することができ、又は２種以上を組み合わせて使用することができる。本発明の固体撮像素子用平坦化膜形成樹脂組成物が光酸発生剤を含む場合、その含有割合としては、前記加水分解縮合物１００質量部に対して、例えば、０．０１質量部乃至１５質量部、または０．１質量部乃至１０質量部、または０．５質量部乃至１質量部である。 The photo-acid generator may be used alone or in combination of two or more. When the flattening film forming resin composition for a solid-state imaging device of the present invention contains a photo-acid generator, the content ratio thereof is, for example, 0.01 parts by mass to 15 parts by mass with respect to 100 parts by mass of the hydrolysis-condensation product. Parts by mass, or 0.1 to 10 parts by mass, or 0.5 to 1 part by mass.
前記界面活性剤は、本発明の固体撮像素子用平坦化膜形成樹脂組成物を基板に塗布した際に、ピンホール、ストレーション（ｓｔｒｉａｔｉｏｎ）等の発生を抑制するのに有効である。本発明の平坦化用組成物に含まれる界面活性剤としては、例えば、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー類、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタントリステアレート等のソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリオレエート、ポリオキシエチレンソルビタントリステアレート等のポリオキシエチレンソルビタン脂肪酸エステル類等のノニオン系界面活性剤、エフトップ〔登録商標〕ＥＦ３０１、同ＥＦ３０３、同ＥＦ３５２（以上、三菱マテリアル電子化成（株）製）、メガファック〔登録商標〕Ｆ−１７１、同Ｆ−１７３、同Ｒ−３０、同Ｒ−４０、同Ｒ−４０−ＬＭ（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１（以上、スリーエムジャパン（株）製）、アサヒガード〔登録商標〕ＡＧ７１０、サーフロン〔登録商標〕Ｓ−３８２、同ＳＣ１０１、同ＳＣ１０２、同ＳＣ１０３、同ＳＣ１０４、同ＳＣ１０５、同ＳＣ１０６（ＡＧＣ（株）製）、ＦＴＸ−２０６Ｄ、ＦＴＸ−２１２Ｄ、ＦＴＸ−２１８、ＦＴＸ−２２０Ｄ、ＦＴＸ−２３０Ｄ、ＦＴＸ−２４０Ｄ、ＦＴＸ−２１２Ｐ、ＦＴＸ−２２０Ｐ、ＦＴＸ−２２８Ｐ、ＦＴＸ−２４０Ｇ、ＤＦＸ−１８等のフタージェントシリーズ（（株）ネオス製）等のフッ素系界面活性剤、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）を挙げることができる。 The surfactant is effective in suppressing the occurrence of pinholes, streaks, etc. when the flattening film forming resin composition for a solid-state imaging device of the present invention is applied to a substrate. Examples of the surfactant contained in the planarizing composition of the present invention include, for example, polyoxyethylene alkyl such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether. Polyoxyethylene alkylaryl ethers such as ethers, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostea Sorbitan monooleate, sorbitan trioleate, sorbitan tristearate and other sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as trioleate and polyoxyethylene sorbitan tristearate, Ftop [registered trademark] EF301, EF303, EF352 (above, Mitsubishi Materials Denshi Kasei Co., Ltd.) Manufactured by MEGAFACK [registered trademark] F-171, F-173, R-30, R-40, R-40-LM (above, manufactured by DIC Corporation), Fluorard FC430, FC431 ( As above, 3M Japan Co., Ltd.), Asahi Guard [registered trademark] AG710, Surflon [registered trademark] S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC) ), FTX-206D, FTX-212D, FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G, DFX-18 etc. Fluorosurfactants such as (manufactured by Neos) and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned.
前記界面活性剤は、１種単独で使用しても、２種以上を組み合わせて使用してもよい。本発明の固体撮像素子用平坦化膜形成樹脂組成物が界面活性剤を含む場合、その含有割合としては、前記加水分解縮合物１００質量部に対して、例えば、０．０００１質量部乃至５質量部、または０．００１質量部乃至１質量部、または０．０１質量部乃至１質量部である。 The surfactants may be used alone or in combination of two or more. When the flattening film forming resin composition for a solid-state imaging device of the present invention contains a surfactant, the content ratio thereof is, for example, 0.0001 parts by mass to 5 parts by mass with respect to 100 parts by mass of the hydrolysis-condensation product. Parts, or 0.001 to 1 parts by mass, or 0.01 to 1 parts by mass.
＜平坦化膜の作製方法＞
本発明の固体撮像素子用平坦化膜形成樹脂組成物を用いた平坦化膜の作製方法について説明する。基板（例えば、半導体基板、ガラス基板、石英基板、シリコンウエハー及びこれらの表面に各種金属膜、複数のマイクロレンズが配列したマイクロレンズアレイ、カラーフィルター等が形成された基板）上に、スピナー、コーター等の適当な塗布方法により本発明の固体撮像素子用平坦化膜形成樹脂組成物を塗布後、ホットプレート、オーブン等の加熱手段を用いてベークして硬化させて、平坦化膜を作製する。ベーク条件は、ベーク温度８０℃乃至３００℃、好ましくは８０℃乃至２６０℃、より好ましくは８０℃乃至２３０℃、ベーク時間０．５分乃至６０分間の中から適宜選択される。前記ベーク温度範囲内の異なる温度で２ステップ以上ベーク処理してもよい。また、本発明の固体撮像素子用平坦化膜形成樹脂組成物から作製される平坦化膜の膜厚としては、例えば０．００１μｍ乃至１，０００μｍであり、好ましくは０．０１μｍ乃至１００μｍであり、より好ましくは０．１μｍ乃至１０μｍである。
<Method for producing flattening film>
A method for producing a flattening film using the flattening film forming resin composition for a solid-state imaging device of the present invention will be described. Spinner, coater on a substrate (for example, a semiconductor substrate, a glass substrate, a quartz substrate, a silicon wafer and a substrate on which various metal films, a microlens array in which a plurality of microlenses are arranged, a color filter, etc. are formed) After applying the flattening film forming resin composition for a solid-state imaging device of the present invention by a suitable coating method such as the above, the flattening film is prepared by baking and curing using a heating means such as a hot plate or an oven. The baking conditions are appropriately selected from a baking temperature of 80° C. to 300° C., preferably 80° C. to 260° C., more preferably 80° C. to 230° C., and a baking time of 0.5 minutes to 60 minutes. Baking may be performed in two or more steps at different temperatures within the baking temperature range. The thickness of the flattening film produced from the flattening film forming resin composition for a solid-state imaging device of the present invention is, for example, 0.001 μm to 1,000 μm, preferably 0.01 μm to 100 μm, More preferably, it is 0.1 μm to 10 μm.
以下に実施例及び比較例に基づいて本発明をより詳細に説明するが、本発明はこれら実施例に限定されるものでない。
［固体撮像素子用平坦化膜形成樹脂組成物の調製］
＜実施例１＞
加水分解性シランの加水分解縮合物としてポリメチルシルセスキオキサン（ＳＲ−１３Ｈ（小西化学工業（株）製）、シラノール基比率：１０モル％）７．０ｇ、及び界面活性剤としてＤＦＸ−１８（（株）ネオス製）０．００２ｇを、酢酸ｎ−プロピル９．２ｇ、プロピレングリコールモノメチルエーテル２１．６ｇ、及び乳酸エチル２０．５ｇに溶解させて溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過して、樹脂組成物を調製した。前記ポリメチルシルセスキオキサンは、前記式（１）で表されるシラン化合物を含む加水分解性シランの加水分解縮合物である。本実施例で調製した樹脂組成物は、硬化触媒を含有しない。
Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to these Examples.
[Preparation of flattening film forming resin composition for solid-state imaging device]
<Example 1>
7.0 g of polymethylsilsesquioxane (SR-13H (manufactured by Konishi Chemical Industry Co., Ltd., silanol group ratio: 10 mol %)) as a hydrolyzed condensate of hydrolyzable silane, and DFX-18 as a surfactant. 0.002 g (manufactured by Neos Co., Ltd.) was dissolved in 9.2 g of n-propyl acetate, 21.6 g of propylene glycol monomethyl ether, and 20.5 g of ethyl lactate to obtain a solution. Then, it filtered using the polyethylene micro filter with a pore size of 0.10 micrometer, and prepared the resin composition. The polymethylsilsesquioxane is a hydrolytic condensate of a hydrolyzable silane containing the silane compound represented by the formula (1). The resin composition prepared in this example does not contain a curing catalyst.
＜実施例２＞
加水分解性シランの加水分解縮合物として実施例１で用いたポリメチルシルセスキオキサン（ＳＲ−１３Ｈ（小西化学工業（株）製））７．０ｇ、硬化触媒としてＮ−（３−トリエトキシシリルプロピル）−４，５−ジヒドロイミダゾール０．０４ｇ、及び界面活性剤としてＤＦＸ−１８（（株）ネオス製）０．００２ｇを、酢酸ｎ−プロピル９．３ｇ、プロピレングリコールモノメチルエーテル２１．７ｇ、及び乳酸エチル２０．６ｇに溶解させて溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過して、樹脂組成物を調製した。
<Example 2>
7.0 g of polymethylsilsesquioxane (SR-13H (manufactured by Konishi Chemical Industry Co., Ltd.)) used in Example 1 as a hydrolysis-condensation product of hydrolyzable silane, N-(3-triethoxy) as a curing catalyst. Silylpropyl)-4,5-dihydroimidazole 0.04 g, and DFX-18 (manufactured by Neos Co., Ltd.) 0.002 g as a surfactant, n-propyl acetate 9.3 g, propylene glycol monomethyl ether 21.7 g, And 20.6 g of ethyl lactate to make a solution. Then, it filtered using the polyethylene micro filter with a pore size of 0.10 micrometer, and prepared the resin composition.
＜実施例３＞
加水分解性シランの加水分解縮合物として実施例１で用いたポリメチルシルセスキオキサン（ＳＲ−１３Ｈ（小西化学工業（株）製））７．０ｇ、硬化触媒として塩化トリエチルベンジルアンモニウム０．０４ｇ、及び界面活性剤としてＤＦＸ−１８（（株）ネオス製）０．００２ｇを、酢酸ｎ−プロピル９．３ｇ、プロピレングリコールモノメチルエーテル２１．７ｇ、及び乳酸エチル２０．６ｇに溶解させて溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過して、樹脂組成物を調製した。
<Example 3>
7.0 g of polymethylsilsesquioxane (SR-13H (manufactured by Konishi Chemical Industry Co., Ltd.)) used in Example 1 as a hydrolysis-condensation product of hydrolyzable silane, and 0.04 g of triethylbenzylammonium chloride as a curing catalyst. , And DFX-18 (manufactured by Neos Co., Ltd.) 0.002 g as a surfactant were dissolved in n-propyl acetate 9.3 g, propylene glycol monomethyl ether 21.7 g, and ethyl lactate 20.6 g to give a solution. .. Then, it filtered using the polyethylene micro filter with a pore size of 0.10 micrometer, and prepared the resin composition.
＜比較例１＞
加水分解性シランの加水分解縮合物としてポリフェニルシルセスキオキサン（ＳＲ−２１（小西化学工業（株）製））を用いた以外は、前記実施例１と同じ条件で樹脂組成物を調製した。前記ポリフェニルシルセスキオキサンは、前記式（１）で表されるシラン化合物を含む加水分解性シランの加水分解縮合物に該当しない。
<Comparative Example 1>
A resin composition was prepared under the same conditions as in Example 1 except that polyphenylsilsesquioxane (SR-21 (manufactured by Konishi Chemical Industry Co., Ltd.)) was used as the hydrolyzed condensate of the hydrolyzable silane. .. The polyphenylsilsesquioxane does not correspond to a hydrolytic condensate of a hydrolyzable silane containing the silane compound represented by the formula (1).
＜比較例２＞
加水分解性シランの加水分解縮合物として比較例１で用いたポリフェニルシルセスキオキサン（ＳＲ−２１（小西化学工業（株）製））を用いた以外は、前記実施例２と同じ条件で樹脂組成物を調製した。
<Comparative example 2>
Under the same conditions as in Example 2, except that the polyphenylsilsesquioxane (SR-21 (manufactured by Konishi Chemical Industry Co., Ltd.)) used in Comparative Example 1 was used as the hydrolyzable condensate of the hydrolyzable silane. A resin composition was prepared.
［耐薬品性試験］
実施例１乃至実施例３並びに比較例１及び比較例２で調製した樹脂組成物を、それぞれ、シリコンウエハー上にスピンコーターを用いて塗布し、その後ホットプレート上において１００℃で１分間、さらに２００℃で１０分間ベークを行い、膜厚０．５μｍの硬化膜を形成した。これらの硬化膜に対して、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、メチルイソブチルケトン、２−プロパノール及び２．３８質量％濃度の水酸化テトラメチルアンモニウム水溶液に、それぞれ２３℃の温度条件下、５分間浸漬する試験を行った。浸漬試験前及び浸漬試験後それぞれの硬化膜の膜厚を測定し、膜厚変化を算出した。前記浸漬試験に使用した溶剤のうち１つでも、浸漬試験前の膜厚に対して５％以上の膜厚増減があった場合は“×”、前記浸漬試験に使用した全ての溶剤について、浸漬試験前の膜厚に対する膜厚増減が５％未満であった場合は“○”として、耐薬品性を評価した。評価結果を表１に示す。
[Chemical resistance test]
Each of the resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was applied onto a silicon wafer by using a spin coater, and then applied on a hot plate at 100° C. for 1 minute and then 200 times. Baking was performed at 10° C. for 10 minutes to form a cured film having a film thickness of 0.5 μm. For these cured films, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, 2-propanol, and a 2.38 mass% concentration tetramethylammonium hydroxide aqueous solution, respectively, at a temperature of 23° C., A test of soaking for 5 minutes was performed. The film thickness of each cured film was measured before and after the immersion test, and the change in film thickness was calculated. If at least one of the solvents used in the immersion test had a film thickness increase or decrease of 5% or more with respect to the film thickness before the immersion test, “x” was applied, and all the solvents used in the immersion test were immersed. When the change in film thickness with respect to the film thickness before the test was less than 5%, the chemical resistance was evaluated as “◯”. The evaluation results are shown in Table 1.
［透過率測定］
実施例１乃至実施例３並びに比較例１及び比較例２で調製した樹脂組成物を、それぞれ、石英基板上にスピンコーターを用いて塗布し、その後ホットプレート上において１００℃で１分間、さらに２００℃で１０分間ベークを行い、膜厚０．５μｍの硬化膜を形成した。これらの硬化膜に対して、紫外線可視分光光度計ＵＶ−２６００（（株）島津製作所製）を用いて、波長４００ｎｍ〜８００ｎｍの範囲で波長を２ｎｍずつ変化させて透過率を測定した。さらにこれらの硬化膜を２６０℃で５分間加熱した後、再び波長４００ｎｍ〜８００ｎｍの範囲で波長を２ｎｍずつ変化させて透過率を測定した。２６０℃で５分間加熱する前及び後での、波長４００ｎｍ〜８００ｎｍの範囲で測定された最低透過率の値を表１に示す。
[Measurement of transmittance]
Each of the resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was applied on a quartz substrate by using a spin coater, and then on a hot plate at 100° C. for 1 minute, and further 200 times. Baking was performed at 10° C. for 10 minutes to form a cured film having a film thickness of 0.5 μm. The transmittance of these cured films was measured by using an ultraviolet-visible spectrophotometer UV-2600 (manufactured by Shimadzu Corporation) while changing the wavelength by 2 nm in the wavelength range of 400 nm to 800 nm. Further, these cured films were heated at 260° C. for 5 minutes, and then the wavelength was changed again by 2 nm in the wavelength range of 400 nm to 800 nm, and the transmittance was measured. Table 1 shows the minimum transmittance values measured in the wavelength range of 400 nm to 800 nm before and after heating at 260° C. for 5 minutes.
［段差平坦化性］
実施例１乃至実施例３並びに比較例１及び比較例２で調製した樹脂組成物を、それぞれ、高さ０．３μｍ、ライン幅１０μｍ、ライン間スペース１０μｍの段差基板（図１参照）上にスピンコーターを用いて塗布し、その後ホットプレート上において１００℃で１分間、さらに２００℃で１０分間ベークを行い、膜厚０．５μｍの硬化膜を形成した。図１の段差基板１に示すｈ１（段差基板の段差）とｈ２（硬化膜の段差、即ちライン上の硬化膜の高さとスペース上の硬化膜の高さとの高低差）の値から、“式：（１−（ｈ２／ｈ１））×１００”を用いて平坦化率を求めた。評価結果を表１に示す。
[Step flattenability]
The resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were spun on a stepped substrate (see FIG. 1) having a height of 0.3 μm, a line width of 10 μm, and a space between lines of 10 μm. It was applied using a coater, and then baked on a hot plate at 100° C. for 1 minute and then at 200° C. for 10 minutes to form a cured film having a film thickness of 0.5 μm. From the values of h1 (step of the stepped substrate) and h2 (step of the cured film, that is, the height difference between the height of the cured film on the line and the height of the cured film on the space) shown in the stepped substrate 1 of FIG. The flattening rate was obtained using (1-(h2/h1))×100″. The evaluation results are shown in Table 1.
［屈折率測定］
実施例１乃至実施例３並びに比較例１及び比較例２で調製した樹脂組成物を、それぞれ、シリコンウエハー上にスピンコーターを用いて塗布し、その後ホットプレート上において１００℃で１分間、さらに２００℃で１０分間ベークを行い、膜厚０．５μｍの硬化膜を形成した。これらの硬化膜に対して、高速分光エリプソメーターＭ−２０００（（株）ジェー・エー・ウーラム・ジャパン製）を用いて波長６３３ｎｍの屈折率を測定した。評価結果を表１に示す。
[Refractive index measurement]
Each of the resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was applied onto a silicon wafer by using a spin coater, and then applied on a hot plate at 100° C. for 1 minute and then 200 times. Baking was performed at 10° C. for 10 minutes to form a cured film having a film thickness of 0.5 μm. The refractive index at a wavelength of 633 nm was measured for these cured films using a high-speed spectroscopic ellipsometer M-2000 (manufactured by JA Woollam Japan Co., Ltd.). The evaluation results are shown in Table 1.
表１に示す結果から、本発明の固体撮像素子用平坦化膜形成樹脂組成物から作製された硬化膜は、高耐薬品性を有すると共に、波長４００ｎｍ〜８００ｎｍの範囲で高透明性を有するものであった。また、本発明の固体撮像素子用平坦化膜形成樹脂組成物から作製された硬化膜は、平坦化率７０％を超える高い段差平坦化性を有するものであり、平坦化膜として好適であることが示された。さらに、マイクロレンズ上に形成される平坦化膜は、その屈折率が、該マイクロレンズの屈折率（例えば１．５４〜１．５８）よりも低い程、反射防止効果が高くなる。したがって、該マイクロレンズ上の平坦化膜の屈折率は、具体的には１．５０以下が好ましい。本発明の固体撮像素子用平坦化膜形成樹脂組成物から作製された硬化膜は、１．４０という低屈折率を有するため、マイクロレンズ上の平坦化膜として好適であることが示された。 From the results shown in Table 1, a cured film prepared from the resin composition for forming a flattening film for a solid-state image pickup device of the present invention has high chemical resistance and high transparency in a wavelength range of 400 nm to 800 nm. Met. Further, the cured film produced from the resin composition for forming a flattening film for a solid-state imaging device of the present invention has a high step flattening property exceeding a flattening rate of 70% and is suitable as a flattening film. It has been shown. Furthermore, the lower the refractive index of the flattening film formed on the microlens is than the refractive index of the microlens (for example, 1.54 to 1.58), the higher the antireflection effect is. Therefore, specifically, the refractive index of the flattening film on the microlens is preferably 1.50 or less. The cured film produced from the resin composition for forming a flattening film for a solid-state imaging device of the present invention has a low refractive index of 1.40, and thus it was shown to be suitable as a flattening film on a microlens.
一方、比較例１及び比較例２で調製した樹脂組成物から作製された硬化膜は、波長４００ｎｍ〜８００ｎｍの範囲で高透明性であるものの、耐薬品性は低く、かつ平坦化率７０％未満であり段差平坦化性に乏しいため、平坦化膜として不適であることが分かった。また、比較例１及び比較例２で調製した樹脂組成物から作製された硬化膜は、屈折率が１．５６であるため、該硬化膜をマイクロレンズ上に形成しても、反射防止効果は期待できない。 On the other hand, the cured films prepared from the resin compositions prepared in Comparative Examples 1 and 2 have high transparency in the wavelength range of 400 nm to 800 nm, but have low chemical resistance and a flattening ratio of less than 70%. Therefore, it was found that it is unsuitable as a flattening film because the step flattening property is poor. Further, since the cured films prepared from the resin compositions prepared in Comparative Examples 1 and 2 have a refractive index of 1.56, even if the cured film is formed on the microlens, the antireflection effect is not obtained. I can't expect.
１：段差基板
２：硬化膜
３：ライン幅
４：ライン間スペース
ｈ１：段差基板の段差
ｈ２：硬化膜の段差
1: stepped substrate 2: cured film 3: line width 4: interline space h1: stepped substrate step h2: cured film stepped
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