JPH0427161A - Color solid-state image sensor and manufacture thereof - Google Patents
Color solid-state image sensor and manufacture thereofInfo
- Publication number
- JPH0427161A JPH0427161A JP2131284A JP13128490A JPH0427161A JP H0427161 A JPH0427161 A JP H0427161A JP 2131284 A JP2131284 A JP 2131284A JP 13128490 A JP13128490 A JP 13128490A JP H0427161 A JPH0427161 A JP H0427161A
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- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 229920001721 polyimide Polymers 0.000 claims abstract description 81
- 239000004642 Polyimide Substances 0.000 claims abstract description 71
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- 239000002243 precursor Substances 0.000 claims abstract description 45
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- -1 methoxy, ethoxy, propoxy, butoxy Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000003384 imaging method Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 44
- 230000000694 effects Effects 0.000 abstract description 11
- 230000003595 spectral effect Effects 0.000 abstract description 9
- 239000002966 varnish Substances 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 50
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 239000009719 polyimide resin Substances 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 229920002189 poly(glycerol 1-O-monomethacrylate) polymer Polymers 0.000 description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000000740 bleeding effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013007 heat curing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- YLHUPYSUKYAIBW-UHFFFAOYSA-N 1-acetylpyrrolidin-2-one Chemical compound CC(=O)N1CCCC1=O YLHUPYSUKYAIBW-UHFFFAOYSA-N 0.000 description 1
- LVUQCTGSDJLWCE-UHFFFAOYSA-N 1-benzylpyrrolidin-2-one Chemical compound O=C1CCCN1CC1=CC=CC=C1 LVUQCTGSDJLWCE-UHFFFAOYSA-N 0.000 description 1
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QISSLHPKTCLLDL-UHFFFAOYSA-N N-Acetylcaprolactam Chemical compound CC(=O)N1CCCCCC1=O QISSLHPKTCLLDL-UHFFFAOYSA-N 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Solid State Image Pick-Up Elements (AREA)
- Optical Filters (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、カラー固体撮像素子及びその製造方法に係り
、特に固体撮像素子基板上にカラーフィルタ形成の下地
平坦化層としてポリイミド樹脂を使用するに好適なカラ
ー固体撮像素子及びその製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a color solid-state image sensor and a method for manufacturing the same, and in particular uses a polyimide resin as a base flattening layer for forming a color filter on a solid-state image sensor substrate. The present invention relates to a color solid-state image sensor suitable for use in a color solid-state image sensor and a method for manufacturing the same.
半導体基板上に、パッシベーション膜で覆われた光電変
換を行う受光部及びこの受光部で発生した電気信号を取
り出す走査部が形成されているＣＣＤ（チャージ・カッ
プルド・デバイス）やＭＩＤ（モス・イメージ・デバイ
ス）等の固体撮像素子において、前記撮像素子の受光部
上にカラーフィルタを一体的に形成するカラー固体撮像
素子が製造されている。CCD (Charge Coupled Device) and MID (Moss Image) have a light-receiving section covered with a passivation film that performs photoelectric conversion and a scanning section that extracts the electrical signals generated in the light-receiving section on a semiconductor substrate. A color solid-state image sensor is manufactured in which a color filter is integrally formed on the light receiving section of the image sensor.
従来のカラーフィルタを形成する方法としては、例えば
テレビジョン学会誌（第３７巻、第７号、第５５３〜５
５８頁、１９８３年）に記載されているように、固体撮
像素子表面の保護及び凹凸を低減するために下地膜とし
て先ずＰＧＭＡ （ポリグリシジルメタクリレート）膜
を形成し、この膜を介して固体撮像素子基板上にカラー
フィルタを形成する方法が知られている。Conventional methods for forming color filters include, for example, the Journal of the Society of Television Engineers (Volume 37, No. 7, Nos. 553-5).
58, 1983), a PGMA (polyglycidyl methacrylate) film is first formed as a base film to protect the surface of the solid-state image sensor and reduce unevenness, and then the solid-state image sensor is coated through this film. A method of forming a color filter on a substrate is known.
また、特開昭５６−８７３８２号公報に記載されている
ように、固体撮像素子表面の保護及び凹凸を埋め且つ表
面を平坦にする膜、例えばポリイミド樹脂系よりなる膜
、を介して撮像素子上にカラーフィルタを形成する方法
が知られている。In addition, as described in Japanese Patent Application Laid-open No. 56-87382, a film that protects the surface of the solid-state image sensor, fills in irregularities, and flattens the surface, such as a film made of polyimide resin, is placed on the image sensor. A method of forming a color filter is known.
上記従来技術でＰＧＭＡ膜をフィルタの下地平坦化層と
して用いる場合、Ｐ Ｇ Ｍ Ａ膜の平坦化効果につい
ての配慮がなされていない。この平坦化層による固体撮
像素子表面の凹凸の平坦化が不十分な場合、平坦化層上
に形成されるカラーフィルタにおいてこの凹凸によりク
ラック、段切れ、剥離などの欠陥が発生するとか、フィ
ルタ膜厚にバラツキが生じることにより分光特性のバラ
ツキが生じるとか、フィルタをパターニングする際にパ
ターン精度が悪くなり９色のにじみが生じる等の問題が
あった。When using the PGMA film as the underlying planarization layer of the filter in the above-mentioned conventional technology, no consideration is given to the planarization effect of the PGMA film. If the flattening layer does not sufficiently flatten the unevenness on the surface of the solid-state image sensor, the unevenness may cause defects such as cracks, breaks, and peeling in the color filter formed on the flattening layer, or the filter film may There were problems such as variations in spectral characteristics due to variations in thickness, and poor pattern accuracy and bleeding of nine colors when patterning the filter.
また、ポリイミド樹脂系膜を平坦化層として用いる場合
、平坦化層の膜厚と平坦化効果についての考慮がなされ
ていない。通常、ポリイミド樹脂系膜は膜厚が厚いと平
坦化効果が良好である。しかし、カラー固体撮像素子に
おいて平坦化層が厚いと素子基板上の受光面とフィルタ
面との距離が大きくなり、入射光が平坦化層内で拡散、
減衰して分光特性が悪くなるという問題があった。Further, when a polyimide resin film is used as a planarization layer, no consideration is given to the thickness of the planarization layer and the planarization effect. Generally, the thicker the polyimide resin film, the better the planarization effect. However, if the flattening layer in a color solid-state image sensor is thick, the distance between the light-receiving surface on the element substrate and the filter surface becomes large, and the incident light is diffused within the flattening layer.
There was a problem that the spectral characteristics deteriorated due to attenuation.
したがって９本発明の目的は、上記従来の問題点を解消
することにあり、その第１の目的は、平坦化効果に優れ
た平坦化層を形成し、カラーフィルタに欠陥がなく、か
つ分光特性や感度が優れたカラー固体撮像素子を、また
、第２の目的は、そのようなカラー固体撮像素子の製造
方法を、それぞれ提供することにある。Therefore, it is an object of the present invention to solve the above-mentioned conventional problems, and the first object is to form a flattening layer with an excellent flattening effect, have no defects in the color filter, and have spectral characteristics. A second object of the present invention is to provide a color solid-state image sensor with excellent sensitivity and sensitivity, and a method of manufacturing such a color solid-state image sensor.
上記第１の目的は、
（１）固体撮像素子基板上に、その表面を平坦化する平
坦化層と、前記平坦化層上に形成されたフィルタ層とを
積層してなるカラー固体撮像素子において、前記平坦化
層が分子末端がエンドキャップされたポリイミド前駆体
からつくられたポリイミド層から成るカラー固体撮像素
子により、達成される。The above first object is as follows: (1) In a color solid-state image sensor in which a flattening layer for flattening the surface of the solid-state image sensor substrate and a filter layer formed on the flattening layer are laminated on a solid-state image sensor substrate. , is achieved by a color solid-state imaging device in which the planarization layer consists of a polyimide layer made from a polyimide precursor end-capped at the molecular ends.
そして、さらに好ましい本発明の具体的な目的達成手段
は、
（２）上記ポリイミド層が、下記の一般式（Ｉ）で表さ
れるポリイミド前駆体からつくられたポリイミド層から
成る上記（１）記載のカラー固体撮像素子。Further, a more preferable specific means for achieving the object of the present invention is as follows: (2) The polyimide layer described in the above (1) is composed of a polyimide layer made from a polyimide precursor represented by the following general formula (I). color solid-state image sensor.
〔ただし、上記一般式（Ｉ）中のＡｒ’及びＡｒ２は共
に可視光領域で透光性を阻害しない有機基で、Ａｒ１は
４個以上の炭素を含む４価の有機基を、Ａｒ”は２価の
有機基を表し、Ｒ’ はメチル、エチル、プロピル、ブ
チルもしくはフェニル基であり、Ｒ２はメチル、エチル
、ブチル、フェニル、メトキシ、エトキシ、プロポキシ
、ブトキシもしくはフェノキシ基であり、Ｒ’ はメチ
レン、エチレン、プロピレン、ブチレンもしくはフェニ
レン基であり、ｍはＯまたは１〜３の整数であり、ｎは
１〜１００の整数である〕により、また、（３）上記ポ
リイミド層が、下記の−・般式（ＩＩ）で表されるポリ
イミド前駆体からつくられたボリイミド層から成る上記
（１）記載のカラー固体撮像素子。[However, Ar' and Ar2 in the above general formula (I) are both organic groups that do not inhibit translucency in the visible light region, Ar1 is a tetravalent organic group containing 4 or more carbons, and Ar'' is Represents a divalent organic group, R' is methyl, ethyl, propyl, butyl or phenyl group, R2 is methyl, ethyl, butyl, phenyl, methoxy, ethoxy, propoxy, butoxy or phenoxy group, R' is methylene, ethylene, propylene, butylene or phenylene group, m is O or an integer of 1 to 3, and n is an integer of 1 to 100], and (3) the polyimide layer has the following - - The color solid-state image sensing device according to the above (1), comprising a polyimide layer made from a polyimide precursor represented by the general formula (II).
一般式
〔ただし、上記一般式（ＩＩ）中のＡｒ”及びＡｒ”は
共に可視光領域で透光性を阻害しない有機基で、Ａｒ’
は４個以上の炭素を含む４価の有機基を、Ａｒ”は２価
の有機基をそれぞれ表し、Ｒ４は次の６つの構造式のう
ちの何れか１種の基であり、ｎは１〜１００
の整数である〕
（４）上記ポリイミド層が、下記の一般式（ＤＩ）で表
されるポリイミド前駆体からつくられたポリイミド層か
ら成る上記（１）記載のカラー固体撮像素子。General formula [However, Ar'' and Ar'' in the above general formula (II) are both organic groups that do not inhibit light transmission in the visible light region, and Ar'
represents a tetravalent organic group containing 4 or more carbon atoms, Ar'' represents a divalent organic group, R4 is any one of the following six structural formulas, and n is 1 -100] (4) The color solid-state imaging device according to (1) above, wherein the polyimide layer is a polyimide layer made from a polyimide precursor represented by the following general formula (DI).
〔ただし、上記一般式（ＩＩＩ）中のＡｒ”及びＡｒ”
は共に可視光領域で透光性を阻害しない有機基で、Ａｒ
”は４個以上の炭素を含む４価の有機基を、Ａｒ”は２
価の有機基を、Ｒ５は１価の有機基をそれぞれ表し、ｎ
は１〜１００の整数である〕そして、上記第２の目的は
、
（１）固体撮像素子基板上に平坦化層を形成する工程と
、その上にフィルタを形成する工程とを有して成るカラ
ー固体撮像素子の製造方法において、前記平坦化層を形
成する工程として分子末端がエンドキャップされたポリ
イミド前駆体を塗布する工程と、前記ポリイミド前駆体
を硬化してポリイミド平坦化層を形成する工程とを有し
て成るカラー固体撮像素子の製造方法により、達成され
る。[However, Ar" and Ar" in the above general formula (III)
Both are organic groups that do not inhibit translucency in the visible light region, and Ar
"Ar" means a tetravalent organic group containing 4 or more carbons, and Ar means 2
R5 represents a monovalent organic group, and n
is an integer from 1 to 100] The second object comprises the steps of: (1) forming a flattening layer on the solid-state image sensor substrate; and forming a filter thereon. In the method for manufacturing a color solid-state image sensor, the step of forming the flattening layer includes a step of applying a polyimide precursor whose molecular terminals are end-capped, and a step of curing the polyimide precursor to form a polyimide flattening layer. This is achieved by a method of manufacturing a color solid-state image sensor comprising:
そして、さらに好ましい本発明の具体的な目的達成手段
は。Further, what are the more preferable specific means for achieving the object of the present invention?
（２）上記ポリイミド前駆体が下記の一般式（Ｉ）で表
せる化合物から成る上記（１）記載のカラー固体撮像素
子の製造方法により、また、〔ただし、上記一般式（Ｉ
）中のＡｒ１及びＡｒ”は共に可視光領域で透光性を阻
害しない有機基で、Ａｒ’は４個以上の炭素を含む４価
の有機基を、Ａｒ”は２価の有機基を表し、Ｒ″はメチ
ル、エチル、プロピル、ブチルもしくはフェニル基であ
り Ｒ２はメチル、エチル、ブチル、フェニル、メトキ
シ、エトキシ、プロポキシ、メトキシもしくはフェノキ
シ基であり、Ｒ３はメチレン、エチレン、プロピレン、
ブチレンもしくはフェニレン基であり、ｍはＯまたは１
〜３の整数であり、ｎは１〜１００の整数である〕
（３）上記ポリイミド前駆体が下記の一般式（ｎ）で表
せる化合物から成る上記（１）記載のカラー固体撮像素
子の製造方法により、また、一般式
【ただし、上記一般式（ＩＩ）中のＡｒ’及びＡｒ”は
共に可視光領域で透光性を阻害しない有機基で、Ａｒ１
は４個以上の炭素を含む４価の有機基を、Ａｒ”は２価
の有機基をそれぞれ表し、Ｒ４は次の６つの構造式のう
ちの何れか１種の基であり。(2) By the method for producing a color solid-state image sensor according to the above (1), wherein the polyimide precursor is a compound represented by the following general formula (I), [provided that the above general formula (I)
) Ar1 and Ar'' in ) are both organic groups that do not inhibit translucency in the visible light region, Ar' is a tetravalent organic group containing 4 or more carbons, and Ar'' is a divalent organic group. , R'' is a methyl, ethyl, propyl, butyl or phenyl group; R2 is a methyl, ethyl, butyl, phenyl, methoxy, ethoxy, propoxy, methoxy or phenoxy group; R3 is methylene, ethylene, propylene,
is a butylene or phenylene group, m is O or 1
3, and n is an integer of 1 to 100.] (3) The method for producing a color solid-state image sensor according to (1) above, wherein the polyimide precursor is a compound represented by the following general formula (n). According to the general formula [However, Ar' and Ar'' in the above general formula (II) are both organic groups that do not inhibit light transmission in the visible light region, and Ar1
represents a tetravalent organic group containing 4 or more carbon atoms, Ar'' represents a divalent organic group, and R4 represents any one of the following six structural formulas.
ｎは１〜１００の整数である〕
（４）上記ポリイミド前駆体が下記の一般式（ＩＩＩ）
で表せる化合物から成る上記（１）記載のカラー固体撮
像素子の製造方法により、そしてまた。n is an integer of 1 to 100.] (4) The polyimide precursor has the following general formula (III)
According to the method for manufacturing a color solid-state image sensing device according to the above (1), which comprises a compound represented by: and also.
〔ただし、上記一般式（Ｉ）中のＡｒ”及びＡｒ”は共
に可視光領域で透光性を阻害しない有機基で、Ａｒ”は
４個以上の炭素を含む４価の有機基を、Ａｒ２は２価の
有機基を、ＲＳは１価の有機基咎それぞれ表し、ｎは１
〜１００の整数である〕（５）上記ポリイミド前駆体を
硬化してポリイミド平坦化層を形成する工程として、前
記ポリイミド前駆体を１２０〜４００℃にて加熱硬化し
て成る上記（１）乃至（４）何れか記載のカラー固体撮
像素子の製造方法により、達成される。[However, Ar'' and Ar'' in the above general formula (I) are both organic groups that do not inhibit light transmission in the visible light region, and Ar'' is a tetravalent organic group containing 4 or more carbons, Ar2 represents a divalent organic group, RS represents a monovalent organic group, and n is 1
- an integer of 100] (5) The step of curing the polyimide precursor to form a polyimide flattening layer includes heating and curing the polyimide precursor at 120 to 400°C. 4) Achieved by any of the methods for manufacturing a color solid-state image sensor.
以下、本発明のカラー固体撮像素子における平坦化層に
つき、さらに詳述する。Hereinafter, the planarization layer in the color solid-state image sensor of the present invention will be explained in more detail.
上記一般式（Ｉ）〜（ＩＩ［）で表せるポリイミド前駆
体を加熱硬化してなるポリイミド平坦化層は、可視光領
域で透明（光透過率が９０％以上）であるものが良い、
そして上記一般式（Ｉ）〜（ＩＩＩ）における好ましい
有機基Ａｒ’及び有機基Ａｒ”としては、それぞれ下記
の構造式で表せる少なくとも１種の有機基が望ましい。The polyimide flattening layer formed by heating and curing the polyimide precursor represented by the above general formulas (I) to (II[) is preferably transparent in the visible light region (light transmittance of 90% or more).
In the general formulas (I) to (III), the organic group Ar' and the organic group Ar'' are each preferably at least one kind of organic group represented by the following structural formula.
有機基Ａｒ”としては。As the organic group Ar''.
〔ただし、 ｋ。〔however, k.
Ｑ、ｍは０〜１０の整数。Q and m are integers from 0 to 10.
ｐは１〜 １０の整数、 ＲＳ。p is 1~ 10 integers, R.S.
Ｒ７は低級アルキル基を表す〕 等 有機基Ａｒ”としては、 〔ただし、 ｔはＯ〜５の整数、 Ｒ１、 Ｒ”。R7 represents a lower alkyl group] etc As the organic group Ar”, 〔however, t is an integer from 0 to 5, R1, R”.
Ｒ” 【ただし。R” 【however.
ｐは１〜ｌＯの整数。p is an integer from 1 to IO.
Ｒｏは低級アルキ ル基〕 等であり。Ro is lower alki group] etc.
さらに好ましくは。More preferably.
〔ただし。〔however.
ｔは０〜５の整数。t is an integer from 0 to 5.
Ｐは１〜ｌＯの整数。P is an integer from 1 to lO.
ｑは２〜ｌＯの整数。q is an integer from 2 to 1O.
Ｒ１、 Ｒ１゜ Ｒ１・、 Ｒｏは水素。R1, R1゜ R1・, Ro is hydrogen.
−ＳＯ，−３ であり。-SO, -3 Yes.
特に好ましくは。Especially preferably.
一４Ｃ）（） −（Ｃ）１．〜 −（ＣＨキ （（：Ｈ，八。14C) () -(C)1. ~ -(CH Ki ((:H, 8.
等である。etc.
また、上記一般式（Ｉ［Ｉ）
中の好ましいＲ“とし
＋（Ｈ，ＣＨ，０）ｖ−ＣＨ，Ｃ’ｒ”＋ｇツ
【ただし、ｐは１〜１０の整数、ｑは２〜１０の整数、
ｔは０〜５の整数、Ｒｍ、 Ｒ１，ＲＬ＠、 Ｒ口は水
素もしくは低級アルキル基、Ｙは一〇−１−Ｓ−Ｒ”は
低級アルキル基、
Ｐ゛は０〜ｌＯの整数〕
で
等である。In addition, preferred R in the general formula (I [I) + (H, CH, 0) v-CH, C'r] + g [where p is an integer of 1 to 10, and q is 2 to 10] an integer of
t is an integer of 0 to 5, Rm, R1, RL@, R is hydrogen or a lower alkyl group, Y is 10-1-SR'' is a lower alkyl group, P is an integer of 0 to 1O] etc.
上記一般式で示したポリイミド前駆体は、所定の有機溶
剤に溶解した溶液状態で用いるが、この場合に用いる溶
剤としては溶解性の観点から非プロトン性極性溶媒が望
ましく、Ｎ−メチル−２−ピロリドン、Ｎ−アセチル−
２−ピロリドン、Ｎ−ベンジル−２−ピロリドン、Ｎ、
Ｎ−ジメチルホルムアミド、Ｎ、Ｎ−ジメチルアセトア
ミド、ジメチルスルホキシド、ヘキサメチルホスホルト
リアミド、Ｎ−アセチル−ε−カプロラクタム、ジメチ
ルイミダゾリジノン、１，２−ジメトキシエタン、１，
２−ジェトキシエタン、１−アセトキシ−２−メトキシ
エタン、ジエチレングリコールジメチルエーテル、トリ
エチレングリコールジメチルエーテルなどが例として挙
げられる。これらは、単独でも良いし、混合して用いる
ことも可能である。The polyimide precursor represented by the above general formula is used in the form of a solution dissolved in a predetermined organic solvent, but the solvent used in this case is preferably an aprotic polar solvent from the viewpoint of solubility, and N-methyl-2- Pyrrolidone, N-acetyl-
2-pyrrolidone, N-benzyl-2-pyrrolidone, N,
N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, N-acetyl-ε-caprolactam, dimethylimidazolidinone, 1,2-dimethoxyethane, 1,
Examples include 2-jethoxyethane, 1-acetoxy-2-methoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and the like. These may be used alone or in combination.
また、上記ポリイミド前駆体溶液の固形成分重量比は
１〜５０ ｗｔ％の範囲が望ましい。固形成分重量比が
これ以下であると、十分な平坦化層厚みが得られにくく
、またこれ以上であると溶液がゲル化し易くなり、ポッ
トライフが短くなる。In addition, the solid component weight ratio of the polyimide precursor solution is
A range of 1 to 50 wt% is desirable. If the solid component weight ratio is less than this, it is difficult to obtain a sufficient thickness of the flattened layer, and if it is more than this, the solution tends to gel, resulting in a short pot life.
固体撮像素子基板への上記ポリイミド前駆体溶液の塗布
には、スピンナを用いた回転塗布、浸漬、噴霧印刷など
の手段が可能であり、適宜選択することができる。塗布
膜厚は、塗布手段、溶液の固形分濃度、粘度等によって
調節可能である。The polyimide precursor solution can be applied to the solid-state image sensor substrate by means such as spin coating using a spinner, dipping, and spray printing, which can be selected as appropriate. The coating film thickness can be adjusted by the coating means, the solid content concentration of the solution, the viscosity, etc.
さらにまた、分子末端がエンドキャップされたポリイミ
ド前駆体を加熱硬化してポリイミド樹脂から成る平坦化
層を形成するに際しては、上記加熱硬化時の加熱温度を
１４０〜４００℃、好ましくは２００〜４００℃、加熱
時間を５〜１８０分、好ましくは１０〜１２０分とする
ことが望ましい。雰囲気は、Ａｒ、Ｎ２等の不活性ガス
中か、もしくは圧力０．１ｐａ以下の減圧状態であるこ
とが望ましい。Furthermore, when forming a flattened layer made of polyimide resin by heating and curing a polyimide precursor whose molecular terminals are end-capped, the heating temperature at the time of heating and curing is set at 140 to 400°C, preferably 200 to 400°C. It is desirable that the heating time be 5 to 180 minutes, preferably 10 to 120 minutes. The atmosphere is preferably an inert gas such as Ar or N2, or a reduced pressure state of 0.1 pa or less.
本発明の特徴である分子末端がエンドキャップされたポ
リイミド前駆体を用いることにより、分子量の制御が確
実にでき、硬化時の樹脂の流動性を高め、平坦化層の平
坦化効果を顕著に向上させることができる。したがって
、この平坦化層上に形成されるカラーフィルタは、段差
による段切れ。By using a polyimide precursor with end-capped molecular ends, which is a feature of the present invention, molecular weight can be reliably controlled, the fluidity of the resin during curing is increased, and the flattening effect of the flattening layer is significantly improved. can be done. Therefore, the color filter formed on this flattening layer is broken due to the step difference.
剥離等の欠陥がなく、しかもフィルタ膜厚のバラツキを
低減し、フィルタのパターン精度を向上させることがで
きるため従来に例を見ない分光特性や感度に優れたカラ
ー固体撮像素子を実現することを可能とした。We aim to create a color solid-state image sensor with unprecedented spectral characteristics and sensitivity, as it is free from defects such as peeling, reduces variations in filter film thickness, and improves filter pattern accuracy. made possible.
実施例１゜
以下１本発明の一実施例を第１図の工程図を用いて説明
する。Example 1 Below 1 An example of the present invention will be explained using the process diagram of FIG.
第１図（ａ）に示すように、下地の凹凸段差が２．１−
ある固体撮像素子基板１上に、下記の構造式で示される
樹脂分濃度が２（ｈｔ％のＮ、Ｎ−ジメチルアセトアミ
ド溶剤のポリイミド前駆体ワニスを塗布し、窒素雰囲気
中で２００℃、３０分間、続いて３００℃で３０分間加
熱して１．０ｐ厚さの高透明のポリイミド平坦化層２を
形成した。この時、平坦化層２表面の凹凸段差を０．５
−以下にまで平坦化することができた。As shown in Fig. 1(a), the uneven level difference of the base is 2.1-
A polyimide precursor varnish of N,N-dimethylacetamide solvent with a resin concentration of 2 (ht%) represented by the following structural formula was applied onto a certain solid-state image sensor substrate 1, and the mixture was heated at 200°C for 30 minutes in a nitrogen atmosphere. Subsequently, heating was performed at 300°C for 30 minutes to form a highly transparent polyimide flattening layer 2 with a thickness of 1.0p.At this time, the unevenness level difference on the surface of the flattening layer 2 was reduced to 0.5.
-It was possible to flatten the surface to below.
ポリイミド前駆体の構造：
ｍ＝ｏ、ｎを１０〜５０としたもので、具体的には、次
ぎの構造式で表せる。Structure of polyimide precursor: m=o and n is 10 to 50, and specifically, it can be represented by the following structural formula.
次ぎに第１図（ｂ）に示すように、平坦化層２上に重ク
ロム酸アンモニウムを感光剤として加えたゼラチンのネ
ガ型感光性可染性フィルタ母材を０．５−厚さで成膜し
、露光、現像して所望の位置にフィルタ母材のパターン
３を形成した。続いて染色液に浸漬してシアン（Ｃｙ）
染色を施し、第１層目のカラーフィルタを形成した。Next, as shown in FIG. 1(b), a negative-type photosensitive dyeable gelatin filter base material containing ammonium dichromate as a photosensitizer is formed on the planarization layer 2 to a thickness of 0.5. A film was formed, exposed, and developed to form a pattern 3 of the filter base material at a desired position. Then, it is immersed in a dyeing solution to dye cyan (Cy).
Dyeing was performed to form a first layer color filter.
次ぎに第１図（ｃ）に示すように、混色防止のためにＰ
ＧＭＡ （ポリグリシジルメタクリレート）の保護膜４
で第１色目のカラーフィルタを覆った。Next, as shown in Figure 1(c), P
GMA (polyglycidyl methacrylate) protective film 4
The first color filter was covered with .
次いで、第１図（ｄ）に示すように、上記工程を繰り返
して、黄色から成る第２色目のカラーフィルタ５及びＰ
ＧＭＡ保護層６を形成してカラー固体撮像素子を得た。Next, as shown in FIG. 1(d), the above steps are repeated to form the second color filter 5 and P of yellow.
A GMA protective layer 6 was formed to obtain a color solid-state image sensor.
このとき、フィルタの下地となる平坦化層２の平坦度が
良好なため、フィルタのパターン精度を向上させること
ができた。At this time, since the flatness of the flattening layer 2 serving as the base of the filter was good, the pattern accuracy of the filter could be improved.
なお、比較例１として、平坦化層２を形成する材料を従
来のＰＧＭＡとして前記実施例１と同様に固体撮像素子
基板上に１．０．成膜した。この時、ＰＧＭＡ膜表面の
凹凸段差は１．０−以上あり、実施例１（凹凸段差、
Ｏ，Ｓ、以下）に比較してＰＧＭＡ膜は平坦化効果が著
しく劣っていた。As Comparative Example 1, a material of 1.0. A film was formed. At this time, the level difference in the unevenness on the surface of the PGMA film was 1.0- or more.
The planarization effect of the PGMA film was significantly inferior to that of O, S, below).
続いて、実施例１と同様にＰＧＭＡ平坦化膜上にカラー
フィルタを形成し、カラー固体撮像素子を得た。この時
、フィルタパターン精度が悪く。Subsequently, a color filter was formed on the PGMA flattening film in the same manner as in Example 1 to obtain a color solid-state image sensor. At this time, the filter pattern accuracy is poor.
色のにじみが生じ、分光特性が良くなかった。Color bleeding occurred and the spectral characteristics were poor.
実施例２゜
実施例１と同様の固体撮像素子基板１上に、下記の構造
式で示される樹脂分濃度が２０ｗｔ％のＮ。Example 2 A solid-state image sensor substrate 1 similar to that of Example 1 was coated with N having a resin concentration of 20 wt% represented by the following structural formula.
Ｎ−ジメチルアセトアミドとＮ−メチル−２−ピロリド
ンとの混合溶剤系のポリアミド前駆体ワニスを塗布し、
窒素雰囲気中で２００℃、３０分間、続いて３００℃で
３０分間加熱して２．０４厚さの高透明のポリイミド平
坦化層２を形成した。この時、平坦化層表面の凹凸段差
を０．２−以下にまで平坦化することができた。Applying a polyamide precursor varnish based on a mixed solvent of N-dimethylacetamide and N-methyl-2-pyrrolidone,
A highly transparent polyimide flattening layer 2 having a thickness of 2.04 cm was formed by heating in a nitrogen atmosphere at 200° C. for 30 minutes and then at 300° C. for 30 minutes. At this time, it was possible to flatten the unevenness level difference on the surface of the flattening layer to 0.2- or less.
ポリイミド前駆体の構造：
ここで用いたポリイミド前駆体の構造は、式次ぎの構造
式で表せる。Structure of polyimide precursor: The structure of the polyimide precursor used here can be represented by the following structural formula.
上記平坦化層上に実施例１と同様にしてカラーフィルタ
層とＰＧＭＡ保護層を形成し、カラー固体撮像素子を得
た。この時、ポリイミド平坦化層により十分に素子表面
の凹凸を平坦にすることができ、平坦化層上に形成した
カラーフィルタのパターン精度を向上させ、カラー固体
撮像素子の分光特性を向上させることができた。A color filter layer and a PGMA protective layer were formed on the planarization layer in the same manner as in Example 1 to obtain a color solid-state image sensor. At this time, the polyimide flattening layer can sufficiently flatten the unevenness on the device surface, improving the pattern accuracy of the color filter formed on the flattening layer, and improving the spectral characteristics of the color solid-state image sensor. did it.
なお、比較例２として、平坦化層２を形成する樹脂材料
を下記の構造式で示される分子の末端がエンドキャップ
されない従来のポリイミド樹脂を用い、この樹脂分濃度
１５ｗｔ％のＮ、Ｎ−ジメチルアセトアミドとＮ−メチ
ル−２−ピロリドンとの混合溶剤系のポリアミド前駆体
ワニスを塗布し、窒素雰囲気中で２００℃、３０分間、
続いて３００’Ｃで３０分間加熱して２．０．厚さのポ
リイミド膜を形成した。この時、ポリイミド膜の凹凸段
差は１．０−以上あり、実施例２に比べて平坦化効果が
著しく劣ることがわかった。As Comparative Example 2, the resin material forming the flattening layer 2 was a conventional polyimide resin in which the ends of the molecules shown by the structural formula below are not end-capped, and N,N-dimethyl with a resin concentration of 15 wt% was used. A polyamide precursor varnish based on a mixed solvent of acetamide and N-methyl-2-pyrrolidone was applied and heated at 200°C for 30 minutes in a nitrogen atmosphere.
Subsequently, heat at 300'C for 30 minutes to give a temperature of 2.0. A thick polyimide film was formed. At this time, the unevenness level difference of the polyimide film was 1.0 or more, and it was found that the flattening effect was significantly inferior to that of Example 2.
続いて実施例２と同様にしてカラーフィルタを形成し、
カラー固体撮像素子を得た。この時、フィルタのパター
ン精度が悪く１色のにじみが生じ、分光特性が悪かった
。Subsequently, a color filter was formed in the same manner as in Example 2,
A color solid-state image sensor was obtained. At this time, the pattern accuracy of the filter was poor, and bleeding of one color occurred, resulting in poor spectral characteristics.
ポリイミド前駆体の構造（比較例２）：ここで用いたポ
リイミド前駆体の構造は、式（Ｉｆ）の〔〕外に示した
末端基な有しない従来のポリイミド前駆体で、ｎは１０
０以上のものである。Structure of polyimide precursor (Comparative Example 2): The structure of the polyimide precursor used here is a conventional polyimide precursor that does not have any terminal groups shown outside [] of formula (If), and n is 10.
It is 0 or more.
実施例３〜２８゜
第１表に示すポリイミド前駆体〔一般式（Ｉ）に関連〕
の２０ｗｔ％Ｎ、Ｎ−ジメチルアセトアミド溶剤ワニス
を用いて、他は全て実施例２と同様にしてカラー固体撮
像素子を得た。この時、ポリイミド平坦化層表面での凹
凸段差は、いずれも０．４−以下にまで平坦にすること
ができた。Examples 3 to 28 Polyimide precursors shown in Table 1 [Related to general formula (I)]
A color solid-state image sensor was obtained in the same manner as in Example 2 except that a 20 wt % N,N-dimethylacetamide solvent varnish was used. At this time, all unevenness levels on the surface of the polyimide flattening layer could be flattened to 0.4- or less.
以下余白
実施例２９〜４９゜
第２表に示すポリイミド前駆体〔一般式（ＩＩ）に関連
〕の２０ｖｔ％Ｎ、Ｎ−ジメチルアセトアミドとＮ−メ
チル−２−ピロリドンとの混合溶剤ワニスを用いて、他
は全て実施例２と同様にしてカラー固体撮像素子を得た
。この時、ポリイミド平坦化層表面での凹凸段差は、い
ずれも０．４．以下にまで平坦にすることができた。The following blank examples 29 to 49 were prepared using a mixed solvent varnish of 20vt% N, N-dimethylacetamide and N-methyl-2-pyrrolidone of the polyimide precursor [related to general formula (II)] shown in Table 2. A color solid-state image sensor was obtained in the same manner as in Example 2 in all other respects. At this time, the unevenness level difference on the surface of the polyimide flattening layer was 0.4. I was able to flatten it to below.
第２表（その１）
第２表（その２）
第２表
（その３）
実施例５０〜５８゜
第３表に示すポリイミド前駆体〔一般式（Ｉ［ｌ）に関
連〕の２０ｗｔ％Ｎ、Ｎ−ジメチルアセトアミドとＮ−
メチル−２−ピロリドンとの混合溶剤ワニスを用いて、
他は全て実施例２と同様にしてカラー固体撮像素子を得
た。この時、ポリイミド平坦化層表面での凹凸段差は、
いずれも０．４−以下にまで平坦にすることができた。Table 2 (Part 1) Table 2 (Part 2) Table 2 (Part 3) Examples 50 to 58゜20wt%N of the polyimide precursor [related to general formula (I[l]]) shown in Table 3 , N-dimethylacetamide and N-
Using a mixed solvent varnish with methyl-2-pyrrolidone,
A color solid-state image sensor was obtained in the same manner as in Example 2 in all other respects. At this time, the uneven steps on the surface of the polyimide flattening layer are
In both cases, it was possible to flatten the surface to 0.4 or less.
第３表
以上、一般式（１）〜（Ｉｌｌ）で表示できる種々のポ
リイミド前駆体を固体撮像素子基板上に塗布、加熱硬化
して、ポリイミド樹脂からなる平坦化層をカラーフィル
タの下地層としてカラー固体撮像素子を形成した実施例
につき説明した。As shown in Table 3 and above, various polyimide precursors represented by general formulas (1) to (Ill) are applied onto a solid-state image sensor substrate and cured by heating to form a flattening layer made of polyimide resin as a base layer of a color filter. An example in which a color solid-state image sensor is formed has been described.
この加熱硬化したポリイミド樹脂は、下記の一般式（工
゛）〜（Ｉｏ）に表示するように、本発明の特徴である
分子の末端がエンドキャップされたポリイミド前駆体の
末端基は、それぞれ反応して形は多少変形しているが、
基本的な骨格は保持されている。In this heat-cured polyimide resin, as shown in the following general formulas (Io) to (Io), the end groups of the polyimide precursor whose molecular ends are end-capped, which is a feature of the present invention, are reacted. Although the shape is slightly deformed,
The basic skeleton is retained.
一般式（Ｉ）の加熱硬化後の構造式ニ
一般式
の加熱硬化後の構造式：
一般式
（Ｉ）
の加熱硬化後の構造式：
〔発明の効果〕
本発明は１以上説明したように構成されているので以下
に記載されるような効果を奏する。Structural formula after heat curing of general formula (I) Structural formula after heat curing of general formula (I): Structural formula after heat curing of general formula (I): [Effects of the Invention] The present invention has the following properties as described above. Because of this structure, the following effects can be achieved.
即ち、平坦化効果に優れた高透明のポリイミドを平坦化
層にとしても用いることにより、平坦化層上に形成され
るカラーフィルタのクラック、段切れ、剥離等の欠陥を
なくし、フィルタ膜厚のバラツキを低減し、フィルタの
パターン精度を向上させ、分光特性や感度に優れたカラ
ー固体撮像素子を得ることができる。In other words, by using highly transparent polyimide with excellent flattening effects as the flattening layer, defects such as cracks, breakage, and peeling of the color filter formed on the flattening layer can be eliminated, and the filter film thickness can be reduced. It is possible to reduce variations, improve filter pattern accuracy, and obtain a color solid-state image sensor with excellent spectral characteristics and sensitivity.
第１図は、本発明のカラー固体撮像素子及びその製造工
程を示す素子断面図である。
〈符号の説明〉
１・・・固体撮像素子基板、
２・・・ポリイミド平坦化層、
３．５・・・カラーフィルタ。FIG. 1 is a cross-sectional view of the color solid-state image sensor of the present invention and its manufacturing process. <Explanation of symbols> 1... Solid-state image sensor substrate, 2... Polyimide flattening layer, 3.5... Color filter.
Claims (1)
化層と、前記平坦化層上に形成されたフィルタ層とを積
層してなるカラー固体撮像素子において、前記平坦化層
が分子末端がエンドキャップされたポリイミド前駆体か
らつくられたポリイミド層から成るカラー固体撮像素子
。 ２、上記ポリイミド層が、下記の一般式（ I ）で表さ
れるポリイミド前駆体からつくられたポリイミド層から
成る請求項１記載のカラー固体撮像素子。 ▲数式、化学式、表等があります▼・・・・・・（ I
） 〔ただし、上記一般式（ I ）中のＡｒ＾１及びＡｒ＾
２は共に可視光領域で透光性を阻害しない有機基で、Ａ
ｒ＾１は４個以上の炭素を含む４価の有機基を、Ａｒ＾
２は２価の有機基を表し、Ｒ＾１はメチル、エチル、プ
ロピル、ブチルもしくはフェニル基であり、Ｒ＾２はメ
チル、エチル、ブチル、フェニル、メトキシ、エトキシ
、プロポキシ、ブトキシもしくはフェノキシ基であり、
Ｒ＾３はメチレン、エチレン、プロピレン、ブチレンも
しくはフェニレン基であり、ｍは０または１〜３の整数
であり、ｎは１〜１００の整数である〕 ３、上記ポリイミド層が、下記の一般式（II）で表され
るポリイミド前駆体からつくられたポリイミド層から成
る請求項１記載のカラー固体撮像素子。 一般式 ▲数式、化学式、表等があります▼・・・・・・（II） 〔ただし、上記一般式（II）中のＡｒ＾１及びＡｒ＾２
は共に可視光領域で透光性を阻害しない有機基で、Ａｒ
＾１は４個以上の炭素を含む４価の有機基を、Ａｒ＾２
は２価の有機基をそれぞれ表し、Ｒ＾４は次の６つの構
造式のうちの何れか１種の基であり、▲数式、化学式、
表等があります▼、▲数式、化学式、表等があります▼
、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、▲数式、化学式、表等があります▼
、▲数式、化学式、表等があります▼、 ｎは１〜１００の整数である〕 ４、上記ポリイミド層が、下記の一般式（III）で表さ
れるポリイミド前駆体からつくられたポリイミド層から
成る請求項１記載のカラー固体撮像素子。 一般式 ▲数式、化学式、表等があります▼・・・・・・（III
） 〔ただし、上記一般式（III）中のＡｒ＾１及びＡｒ＾
２は共に可視光領域で透光性を阻害しない有機基で、Ａ
ｒ＾１は４個以上の炭素を含む４価の有機基を、Ａｒ＾
２は２価の有機基を、Ｒ＾５は１価の有機基をそれぞれ
表し、ｎは１〜１００の整数である〕 ５、上記有機基Ａｒ＾１及び有機基Ａｒ＾２が、それぞ
れ下記の構造式で表せる有機基から成る請求項２、３も
しくは４記載のカラー固体撮像素子。 有機基Ａｒ＾１は、次ぎの構造式の少なくとも１種から
選択される。 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、▲数式、化学式、表等があります▼
、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼ 〔ただし、ｋ、ｌ、ｍは０〜１０の整数、ｐは１〜１０
の整数、Ｒ＾６及びＲ＾７は低級アルキル基を表す〕そ
して、 有機基Ａｒ＾２は、次ぎの構造式の少なくとも１種から
選択される。 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼ （ただしｐは１〜１０の整数、ｑは２〜１０の整数〕▲
数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼ 〔ただし、ｔは０〜５の整数、Ｒ＾８、Ｒ＾９、Ｒ＾１
＾０基、Ｙは−Ｏ−、−Ｓ−、−ＣＯ−、▲数式、化学
式、表等があります▼、▲数式、化学式、表等がありま
す▼、もしくは−ＳＯ＿２−を表す〕 ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼ 〔ただし、ｐは１〜１０の整数、Ｒ＾１＾２は低級アル
キル基を表す〕。 ６、固体撮像素子基板上に平坦化層を形成する工程と、
その上にフィルタを形成する工程とを有して成るカラー
固体撮像素子の製造方法において、前記平坦化層を形成
する工程として分子末端がエンドキャップされたポリイ
ミド前駆体を塗布する工程と、前記ポリイミド前駆体を
硬化させてポリイミド平坦化層を形成する工程とを有し
て成るカラー固体撮像素子の製造方法。 ７、上記ポリイミド前駆体が下記の一般式（ I ）で表
せる化合物から成る請求項６記載のカラー固体撮像素子
の製造方法。 一般式 ▲数式、化学式、表等があります▼・・・・・・（ I
） 〔ただし、上記一般式（ I ）中のＡｒ＾１及びＡｒ＾
２は共に可視光領域で透光性を阻害しない有機基で、Ａ
ｒ＾１は４個以上の炭素を含む４価の有機基を、Ａｒ＾
２は２価の有機基を表し、Ｒ＾１はメチル、エチル、プ
ロピル、ブチルもしくはフェニル基であり、Ｒ＾２はメ
チル、エチル、ブチル、フェニル、メトキシ、エトキシ
、プロポキシ、ブトキシもしくはフェノキシ基であり、
Ｒ＾３はメチレン、エチレン、プロピレン、ブチレンも
しくはフェニレン基であり、ｍは０または１〜３の整数
であり、ｎは１〜１００の整数である〕 ８、上記ポリイミド前駆体が下記の一般式（II）で表せ
る化合物から成る請求項６記載のカラー固体撮像素子の
製造方法。 一般式 ▲数式、化学式、表等があります▼・・・・・・（II） 〔ただし、上記一般式（II）中のＡｒ＾１及びＡｒ＾２
は共に可視光領域で透光性を阻害しない有機基で、Ａｒ
＾１は４個以上の炭素を含む４価の有機基を、Ａｒ＾２
は２価の有機基をそれぞれ表し、Ｒ＾４は次の６つの構
造式のうちの何れか１種の基であり、▲数式、化学式、
表等があります▼、▲数式、化学式、表等があります▼
、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、▲数式、化学式、表等があります▼
、▲数式、化学式、表等があります▼ ｎは１〜１００の整数である〕 ９、上記ポリイミド前駆体が下記の一般式（III）で表
せる化合物から成る請求項６記載のカラー固体撮像素子
の製造方法。 一般式 ▲数式、化学式、表等があります▼・・・・・・（III
） 〔ただし、上記一般式（III）中のＡｒ＾１及びＡｒ＾
２は共に可視光領域で透光性を阻害しない有機基で、Ａ
ｒ＾１は４個以上の炭素を含む４価の有機基を、Ａｒ＾
２は２価の有機基を、Ｒ＾５は１価の有機基をそれぞれ
表し、ｎは１〜１００の整数である〕 １０、上記ポリイミド前駆体を硬化してポリイミド平坦
化層を形成する工程として、前記ポリイミド前駆体を１
２０〜４００℃に加熱硬化して成る請求項６乃至９何れ
か記載のカラー固体撮像素子の製造方法。[Scope of Claims] 1. A color solid-state image sensor comprising a solid-state image sensor substrate, a flattening layer for flattening the surface thereof, and a filter layer formed on the flattening layer, which are laminated on a solid-state image sensor substrate. A color solid-state imaging device in which the flattening layer is made of a polyimide layer made from a polyimide precursor with end-capped molecular ends. 2. The color solid-state imaging device according to claim 1, wherein the polyimide layer is a polyimide layer made from a polyimide precursor represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・( I
) [However, Ar^1 and Ar^ in the above general formula (I)
2 are both organic groups that do not inhibit translucency in the visible light region, and A
r^1 is a tetravalent organic group containing 4 or more carbons, Ar^
2 represents a divalent organic group, R^1 is methyl, ethyl, propyl, butyl or phenyl group, and R^2 is methyl, ethyl, butyl, phenyl, methoxy, ethoxy, propoxy, butoxy or phenoxy group. can be,
R^3 is a methylene, ethylene, propylene, butylene or phenylene group, m is 0 or an integer of 1 to 3, and n is an integer of 1 to 100.] 3. The polyimide layer has the following general formula: 2. The color solid-state image sensor according to claim 1, comprising a polyimide layer made from a polyimide precursor represented by (II). General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) [However, Ar^1 and Ar^2 in the above general formula (II)
Both are organic groups that do not inhibit translucency in the visible light region, and Ar
^1 is a tetravalent organic group containing 4 or more carbons, Ar^2
each represents a divalent organic group, and R^4 is any one of the following six structural formulas, ▲ mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, n is an integer from 1 to 100] 4. The above polyimide layer is made from a polyimide layer made from a polyimide precursor represented by the following general formula (III). The color solid-state image sensor according to claim 1. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) [However, Ar^1 and Ar^ in the above general formula (III)
2 are both organic groups that do not inhibit translucency in the visible light region, and A
r^1 is a tetravalent organic group containing 4 or more carbons, Ar^
2 represents a divalent organic group, R^5 represents a monovalent organic group, and n is an integer from 1 to 100] 5. The above organic group Ar^1 and organic group Ar^2 are each the following: 5. The color solid-state image sensing device according to claim 2, comprising an organic group represented by the structural formula: The organic group Ar^1 is selected from at least one of the following structural formulas. ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ [However, k, l, m are integers from 0 to 10, and p is from 1 to 10.
and R^6 and R^7 represent lower alkyl groups] and the organic group Ar^2 is selected from at least one of the following structural formulas. ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc.▼ (where p is an integer between 1 and 10, and q is an integer between 2 and 10)]▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables etc. ▼ [However, t is an integer from 0 to 5, R^8, R^9, R^1
＾0 group, Y represents -O-, -S-, -CO-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or -SO_2-] ▲Mathematical formulas, There are chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, p is an integer from 1 to 10, and R^1^2 represents a lower alkyl group]. 6. Forming a flattening layer on the solid-state image sensor substrate;
forming a filter thereon; the step of forming the flattening layer includes applying a polyimide precursor whose molecular terminals are end-capped; A method for manufacturing a color solid-state image sensor, comprising the steps of: curing a precursor to form a polyimide flattening layer. 7. The method for manufacturing a color solid-state image sensing device according to claim 6, wherein the polyimide precursor comprises a compound represented by the following general formula (I). General formulas▲Mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
) [However, Ar^1 and Ar^ in the above general formula (I)
2 are both organic groups that do not inhibit translucency in the visible light region, and A
r^1 is a tetravalent organic group containing 4 or more carbons, Ar^
2 represents a divalent organic group, R^1 is a methyl, ethyl, propyl, butyl or phenyl group, and R^2 is a methyl, ethyl, butyl, phenyl, methoxy, ethoxy, propoxy, butoxy or phenoxy group. can be,
R^3 is a methylene, ethylene, propylene, butylene or phenylene group, m is 0 or an integer of 1 to 3, and n is an integer of 1 to 100.] 8. The polyimide precursor has the following general formula 7. The method for manufacturing a color solid-state image sensor according to claim 6, which comprises a compound represented by (II). General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) [However, Ar^1 and Ar^2 in the above general formula (II)
Both are organic groups that do not inhibit translucency in the visible light region, and Ar
^1 is a tetravalent organic group containing 4 or more carbons, Ar^2
each represents a divalent organic group, and R^4 is any one of the following six structural formulas, ▲ mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ Numerical formulas, chemical formulas, tables, etc. ▼ n is an integer from 1 to 100] 9. The color solid-state imaging device according to claim 6, wherein the polyimide precursor is composed of a compound represented by the following general formula (III). Production method. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) [However, Ar^1 and Ar^ in the above general formula (III)
2 are both organic groups that do not inhibit translucency in the visible light region, and A
r^1 is a tetravalent organic group containing 4 or more carbons, Ar^
2 represents a divalent organic group, R^5 represents a monovalent organic group, and n is an integer of 1 to 100.] 10. Step of curing the polyimide precursor to form a polyimide flattening layer. As, the polyimide precursor is 1
The method for manufacturing a color solid-state image sensor according to any one of claims 6 to 9, wherein the color solid-state imaging device is cured by heating at 20 to 400°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2131284A JPH0427161A (en) | 1990-05-23 | 1990-05-23 | Color solid-state image sensor and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2131284A JPH0427161A (en) | 1990-05-23 | 1990-05-23 | Color solid-state image sensor and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0427161A true JPH0427161A (en) | 1992-01-30 |
Family
ID=15054355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2131284A Pending JPH0427161A (en) | 1990-05-23 | 1990-05-23 | Color solid-state image sensor and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0427161A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7476476B2 (en) * | 2003-06-02 | 2009-01-13 | Toray Industries, Inc. | Photosensitive resin composition, electronic component using the same, and display unit using the same |
-
1990
- 1990-05-23 JP JP2131284A patent/JPH0427161A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7476476B2 (en) * | 2003-06-02 | 2009-01-13 | Toray Industries, Inc. | Photosensitive resin composition, electronic component using the same, and display unit using the same |
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