JPH01209405A - Color solid-state image pickup element - Google Patents

Abstract

PURPOSE:To improve the reliability of environmental resistance, etc., by combining and arranging color filters which have picture elements of red, green, and blue containing specific photosensitive resin and pigments on a substrate in a three-color separated state. CONSTITUTION:Photodetecting elements 2 and peripheral circuits 3 which operate those elements are incorporated on the substrate 1, and the color filters 4 consisting of picture elements of red (R), green (G), and blue (B) containing the photosensitive resin and pigments are combined and arranged on the substrate 1 in a three-color separated state. This photosensitive resin consists of a multifunctional acrylate monomer, an organic polymer binder, and a photopolymerization initiator made of a trihalomethyl-s-triazine compound. Consequently, the high-reliability solid-state image pickup element is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is applicable to a color solid-state image sensor device used in a color camera or the like.

Conventional color solid-state imaging devices generally have a structure in which the solid-state imaging device and color filter are manufactured separately in the early stages of development, and then they are aligned and bonded together using an optical adhesive or the like.

In recent years, color filters have been mounted directly on the light detection section of solid-state imaging devices in order to improve the workability of manufacturing. In this case, color filters are often formed by a dyeing method or a printing method.

Problems to be Solved by the Invention Color filters using the dyeing method are created by dyeing a dyed base material with a natural photosensitive resin such as gelatin or a photosensitive synthetic resin such as amine-modified polyvinyl alcohol with a dye such as an acid dye. There are problems with reliability such as light resistance, heat resistance, and moisture resistance. Furthermore, the printing method is created using an ink containing a pigment dispersed in a thermosetting resin or an ultraviolet curable resin, but there are problems in creating a high-definition pattern and in surface smoothness.

In addition, anthraquinone, as a photopolymerization initiator for photosensitive resin,
Polycyclic quinone compounds such as naphthoquinone have been used in the past, but because their sensitivity wavelength is relatively short, it takes a long time to form pixels by light irradiation, especially when pigments are included. there were.

Furthermore, when the pigment concentration is increased to obtain good color reproducibility, it is not possible to obtain a sufficient polymerized product by light irradiation alone, resulting in poor adhesion and poor image formation through development, and environmental resistance. Reliability, such as gender, was also an issue.

Next, when dispersing the pigment, it is difficult to finely disperse the pigment due to aggregation or association, and even if the pigment is dispersed, reaggregation occurs, resulting in a stability problem.

Means for Solving the Problem A plurality of photodetecting elements and a peripheral circuit for operating them are installed on the upper part of the substrate.
It is characterized by a photosensitive resin whose composition is a photopolymerization initiator made of a triazine compound, and a color filter having red, green, and blue pixels containing a pigment, which are arranged in combination so that three colors can be separated. Create a color solid-state image sensor.

A color solid-state imaging device is obtained which has a high-definition pattern with good surface smoothness made of a functional photosensitive resin and a color filter with good environmental resistance made of a pigment.

Example FIG. 1 shows a cross-sectional view of a color solid-state image sensing device of the present invention.

1 is a board in which a plurality of photodetecting elements 2 and a peripheral circuit 3 for operating them are incorporated; 4 is this board 1;
red, green, containing photosensitive resin particles and pigments formed on top;
This is a color filter made up of blue pixels.

Next, an example of the material of the color filter used in the present invention will be shown. Photosensitive resins include polyfunctional acrylate monomers such as ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate, as well as heat-resistant and resistant resins. The basic composition consists of an organic polymer binder and a photopolymerization initiator consisting of a trihalomethyl-s-triazine compound to impart chemical properties such as drug properties and mechanical properties such as surface hardness and volume shrinkage.

As the organic polymer binder, unsaturated organic acid compounds such as acrylic acid and methacrylic acid that are compatible with acrylate monomers and vinyl group-containing compounds such as methyl acrylate, ethyl methacrylate, and benzyl methacrylate are used.
[Copolymers using ester as a monomer may be mentioned.] Having an acidic group such as a carboxyl group enables water-soluble development, which is more economical and safer than organic solvent development. Photopolymerization initiators for trihalomethyl-8-triazine compounds include 2-phenyl-4,6-bis(trichloromethyl)-S-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl )-S-triazine, 2-(p-tolyl)-4,6-bis-(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis-(trichloromethyl)
-s-) riazine, 2-(2',4'-dichlorophenyl)-4,6-bis-(trichloromethyl)-S-) riazine, and the like.

As the red pigment, anthraquinone pigments and perylene pigments may be used alone, or a mixture thereof, or a mixture with a disazo yellow pigment or an isoindoline yellow pigment may be used. For example, as an anthraquinone pigment, C0
! , Pigment Red 177, Perylene pigments include C01, Pigment Red 155, and in terms of color reproducibility, C01, Pigment Yellow-83 or C0
1. Mixing with Pigment Yellow-139 was good.

As the green pigment, a halogenated phthalocinine pigment alone or a mixture with a disazo yellow pigment or an isoindoline yellow pigment is used, such as C01, Pigment Gerinf, 36.37 and C01, Pigment Yellow 83 or C01, Mixing with Pigment Yellow-139 was good.

The blue pigment is a phthalocyanine pigment alone or
A mixture with a dioxazine-based purple pigment is used, for example, C0
1, Pigment Blue 15:3 and C01, Pigment Violet 23 were mixed well.

Furthermore, the above pigments are mixed with acrylic resin, maleic acid resin,
A pigment-containing photosensitive resin with good dispersibility and dispersion stability was obtained by using a powdered processed pigment finely dispersed in either a chlorinated vinyl vinegar picopolymer or an ethyl cellulose resin. In particular, processed pigments using acrylic resin and ethyl cellulose resin were optimal in terms of transparency and dispersion stability.

In addition, the pigment particle system has visible light wavelengths (from 400 to 700 r).
un) with a smaller average particle size, more preferably l/
Sample No. 2 had better light transmittance. This will be explained below using examples.

(Example 1) A color filter is formed using the pigment-dispersed photosensitive resin of the present invention shown below on a substrate in which a plurality of light detection elements and peripheral circuits for operating them are incorporated, and a color solid state is formed. An image sensor was created.

Red photosensitive resin product name: Color Mosaic Red (CM-R) (manufactured by Fuji Hunt Electro Technology) Green photosensitive resin product name: Color Mosaic Green (CM-C;) (manufactured by Fuji Hunt Electro Technology) Blue photosensitive resin product name: Color Mosaic Blue (CM-B) (Fuji Hunt Electro Technology) Next, each coating condition and exposure condition are shown.

The pre-baking temperature was 80° C. for 15 minutes, and the development was carried out using a sodium carbonate (1wtχ) aqueous solution. The coating order of each color was the order of red, green, and blue pixels. Each thickness is shown below.

FIG. 3 shows the spectral sensitivity characteristics of the color solid-state imaging device produced under the above conditions.

(Comparative Example 1) As in Example 1, 15 parts by weight of low molecular weight gelatin (average molecular @IO,000), 2 parts by weight of ammonium dichromate, 1 part by weight of 0.5 parts of chromium alum, and 82 parts by weight of water were placed on a substrate in the same manner as in Example 1. ．．
Using a photosensitive dyeing base material consisting of 5 layers and 1 part, red 24P (manufactured by Nippon Kayaku), green IP, blue 5C1 black C,1,1 were used as dyes.
It was stained with 10.

The pre-bake temperature was 60℃ for 5 minutes, and the pixels were red, green,
I created a color filter in the order of blue.

Thickness: red 2.0μm, green 2.0μm1 blue 2.0μm
It was set as m.

(Example 2) The color filters of Example 1 and Comparative Example 1 were subjected to a light resistance test using a xenon fade meter (FAL-25AX-HC model manufactured by Suga Test Instruments Co., Ltd.), and the results after 1000 hours and further heat resistance were determined. The results of the sex test (170°C, 10 hours) were
It is shown below as ΔE due to b.

Effects of the Invention According to the present invention, a highly reliable color solid-state image sensor can be obtained.

[Brief explanation of the drawing]

FIG. 1 is a sectional view of a color solid-state image sensing device of the present invention, and FIG. 2 is a spectral sensitivity characteristic diagram. l...Substrate, 2...Photodetection element, 3...Peripheral circuit, 4...Color filter.

Claims (1)

[Claims] A photopolymerization initiator consisting of a polyfunctional acrylate monomer, an organic polymer binder, and a trihalomethyl-s-triazine compound is placed on the top of the substrate in which a plurality of photodetecting elements and peripheral circuits for operating the same are incorporated. 1. A color solid-state image sensor, characterized in that a color filter having red, green, and blue pixels containing a photosensitive resin and a pigment is arranged in combination so as to be able to separate three colors.