JPH0527117A - Color solid-state image pickup element and its production - Google Patents

Abstract

PURPOSE:To decrease variation of film thickness and to improve spectral characteristics and sensitivity by forming an org. film of a transparent material from a photosetting compsn. comprising org. polymer material or org. silicon material and an oxygen producing agent. CONSTITUTION:A substrate for a solid-state image pickup element consists of a semiconductor substrate component of a photodetector to effect photo-electric conversion, a scanning part to pickup electric signals produced in the photodetector, a passivation film to protect the photodetector and the scanning part. A flattening layer comprising a transparent material is provided thereon, and further, on the flattening layer corresponding to the photodetector on the substrate, a color filter pattern protected with an org. film of transparent material is provided. In this case, the org. film of the transparent material consists of a photosetting compsn. comprising org. polymer material or org. silicon material and an oxygen producing agent. Thereby, flatness of the film can be improved since fluidity of the material can be improved by heat during the film formation, and thereby, an extremely flat film can be formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color solid-state image pickup device and a method for manufacturing the same, and more particularly, to a protective film layer excellent in flatness using a photocurable protective film made of a material containing an acid generator. The present invention relates to a color solid-state imaging device suitable for forming and a manufacturing method thereof.

[0002]

2. Description of the Related Art A semiconductor substrate is provided with a light receiving portion for photoelectric conversion covered by a passivation film, and a scanning portion for taking out an electric signal generated in the light receiving portion.
In the light receiving part of the solid-state image sensor such as D (charge coupled device) or MID (mos image device),
There is known a color solid-state image sensor in which a color filter is integrally formed.

Conventionally, various protective films are formed on this type of color filter. For example, Journal of Television Society (Vol. 37, No. 7, pp. 553 to 558, 1
983), in order to protect the surface of the solid-state image sensor and reduce the unevenness, PG is first used as a base film.
There are known a method of forming an MA (polyglycidyl methacrylate) film and forming a color filter on the solid-state image sensor substrate through this film, and a method of using the PGMA film as a protective film between filter layers.

Further, as described in JP-A-60-60755, there is also known a method of manufacturing a solid-state image pickup device with a microlens in which a minute lens is provided for each pixel in the solid-state image pickup device.

[0005]

[Problems to be Solved] The PGMA film is a transparent material which has thermosetting properties and also serves as a positive type Deep UV resist. As described above, the PGMA film has conventionally been used to form a flattening film under the filter layer, a protective film between the filter layers, or a protective film on the filter layer in the case of a solid-state imaging device with a microlens. However, since the PGMA film is formed of a thermosetting material, it has poor thermal fluidity and insufficient flatness. Therefore, there are various problems as described below.

(1) In the case of forming a base flattening film in order to eliminate uneven steps on the surface of the solid-state image pickup device substrate,
Since the flattening effect is insufficient, the color filters formed on the flattening layer have a film thickness difference, and the spectral characteristics of the color filters vary.

(2) Since the flattening effect of the protective film between the color filter layers or the protective film formed on the filter layer in the case of a solid-state image pickup device with a microlens is insufficient in any case, each pixel is Due to the difference in the thickness of the provided microlens and the height from the light receiving portion of the element, the condensing effect of the microlens changes for each pixel, and the sensitivity varies for each pixel.

Therefore, an object of the present invention is to solve the above-mentioned conventional problems, and the first object thereof is to provide a filter base film having a high flatness, a protective film between filter layers, or a solid body with a microlens. In the case of an image pickup device, a color solid-state image pickup device in which a protective film is formed on a filter layer having high flatness is provided, and a second purpose thereof is to provide an improved manufacturing method for forming such a color solid-state image pickup device. To do.

[0009]

A first object of the present invention is to provide a light receiving portion for performing photoelectric conversion, a scanning portion for taking out an electric signal generated in the light receiving portion, and a passivation film for protecting the light receiving portion and the scanning portion. A flattening layer made of a transparent material is provided on a solid-state image sensor substrate made of a semiconductor substrate on which a transparent material is made on the flattening layer at a position corresponding to a light receiving portion on the solid-state image sensor substrate. In a color solid-state imaging device having a color filter pattern protected by an organic film, an organic film made of the transparent material is used as a photocurable composition made of an organic polymer material or an organic silicon material and an acid generator. This is achieved by the color solid-state image sensor formed by.

Further, the first object is to form a light receiving portion for performing photoelectric conversion, a scanning portion for taking out an electric signal generated in the light receiving portion, and a passivation film for protecting the light receiving portion and the scanning portion. A flattening layer made of a transparent material is provided on a solid-state imaging device substrate made of a semiconductor substrate, and an organic film made of a transparent material protects the flattening layer at a position corresponding to the light receiving portion on the solid-state imaging device substrate. In the color solid-state imaging device in which the convex color microlenses are formed on the uppermost layer of the color filter layer through the organic protective film, the organic protective film of the uppermost layer of the color filter layer is This is achieved by a color solid-state imaging device formed of a photocurable composition containing a polymer material or an organic silicon material and an acid generator.

It is preferable that the flattening layer and the microlenses made of the transparent material are formed of a photocurable composition containing an organic polymer material or an organic silicon material and an acid generator, respectively. It is also preferable that the flattening layer made of the transparent material is made of a transparent polyimide formed by curing a polyimide precursor having an end-capped molecular end.

The acid generator is preferably a substance having a property of generating a proton (hydrogen cation) when exposed to light, for example, the following general formulas (1) and (2).
Alternatively, an onium salt represented by (3), tri (methanesulfonyl-oxy) benzene, or a mixture of the onium salt and tri (methanesulfonyl-oxy) benzene is preferable.

[0013]

[Chemical 7]

[0014]

[Chemical 8]

[0015]

[Chemical 9]

However, in the above general formula, X is, for example, BF ₄ ~, SbF ₆ ~, AsF ₆ ~, PF ₆ ~, CF ₃ SO ₃ ~.
Represents an anion such as Ar ^{1 to} Ar ⁶ is, for example, an aromatic ring,
R represents an organic group such as an aliphatic group.

Specific examples of more preferable acid generators are shown in Tables 1 to 4 below.

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

[Table 3]

[0021]

[Table 4]

In the photocurable composition comprising the organic polymer material and the acid generator, preferred organic polymer materials include, for example, phenol resin, novolac resin,
Examples thereof include a cresol resin or an epoxy resin, or a resin having an olefin-based, lactone-based, or lactam-based structure.

Further, the preferable mixing ratio of the photocurable composition comprising the organic polymer material or the organic silicon material and the acid generator is 100 parts by weight of the solid content of the organic polymer material or the organic silicon material. On the other hand, the amount of the acid generator is 0.01 to 30 parts by weight.

A second object is a semiconductor having a light receiving portion for performing photoelectric conversion, a scanning portion for taking out an electric signal generated in the light receiving portion, and a passivation film for protecting the light receiving portion and the scanning portion. A step of forming a flattening layer made of a transparent material on a solid-state image sensor substrate made of a substrate; a step of forming a color filter layer on the flattening layer; and an organic polymer material or an organic material on the color filter layer. The method has a step of forming an organic protective film from a photocurable composition comprising a silicon-based material and an acid generator, and a step of forming convex microlenses on the organic protective film on the color filter layer. A method of manufacturing a color solid-state imaging device comprising the step of forming an organic protective film from a photocurable composition comprising the organic polymer material or organosilicon material and an acid generator. It has a step of applying a photocurable composition comprising a polymer material or an organosilicon material and an acid generator, a step of heating this coating film, and a step of exposing the entire surface of the film with ultraviolet light. And a method of manufacturing a color solid-state imaging device.

Further, the second object is to form a light receiving portion for performing photoelectric conversion, a scanning portion for taking out an electric signal generated in the light receiving portion, and a passivation film for protecting the light receiving portion and the scanning portion. A step of forming a flattening layer made of a transparent material on a solid-state imaging device substrate made of a semiconductor substrate; and an organic film made of a transparent material on the flattening layer at a position corresponding to a light receiving portion on the solid-state imaging device substrate And a step of forming a color filter layer protected by the step of forming a color filter layer protected by an organic film made of the transparent material (that is, a color The step of forming the organic protective film of the filter) is a step of applying a photocurable composition comprising an organic polymer material or an organic silicon material and an acid generator, and then applying this coating film. And a step of exposing the entire surface of the film with ultraviolet light, the method for manufacturing a color solid-state imaging device comprising a step of repeating these steps as many times as necessary in accordance with the configuration of the color filter, To be achieved.

Preferably, both the step of forming the flattening layer made of the transparent material and the step of forming the convex microlenses are performed using an organic polymer material or an organic silicon material and an acid generator. It is desirable to include a step of applying the photocurable composition described above, a step of heating this coating film, and a step of exposing the entire surface of the film with ultraviolet light. More preferably, it is desirable to add a heating step after the step of exposing the entire surface of the film with these ultraviolet rays.

The step of forming the flattening layer made of the transparent material is composed of a step of applying a polyimide precursor having end caps of molecular ends and a step of forming a transparent polyimide film by heat curing. Is also preferable.

Further, the organic polymer material, the organic silicon material and the acid generator constituting the photocurable composition are all the same as those described in the means for achieving the first object. The material of can be used. Furthermore, the same applies to the preferable mixing ratio of the organic polymer material or the organic silicon material and the acid generator.

The structure of the color solid-state image pickup device of the present invention will be described in more detail below. In the color solid-state imaging device of the present invention, a light receiving portion for performing photoelectric conversion, a scanning portion for taking out an electric signal generated in the light receiving portion, a passivation film for protecting the light receiving portion and the scanning portion, etc. are previously formed on the main surface of the semiconductor substrate. A solid-state imaging device, a flattening layer formed thereon using a transparent material, a color filter layer of a plurality of colors disposed on the flattening layer at a position corresponding to the light receiving portion, and the color filter layer The protective film is made of a transparent material, and a convex microlens is disposed on the uppermost layer of the color filter via an organic protective film at a position corresponding to the light receiving portion.

Next, an example of one process for manufacturing the color solid-state image pickup device of the present invention will be described. First, on a solid-state imaging device substrate on which a light receiving portion for performing photoelectric conversion on a main surface of a semiconductor substrate in advance, a scanning portion for taking out an electric signal generated in the light receiving portion, a passivation film for protecting the light receiving portion and the scanning portion, and the like are formed. Then, a flattening layer made of a transparent material is formed. Next, a color filter pattern is formed and a filter protective film made of a transparent material is formed. Next, a photocurable composition comprising an organic polymer material or an organic silicon material and an acid generator is applied to the uppermost layer of the color filter layer, then heated and fluidized and dried, and the entire surface of the film is exposed to ultraviolet light. After curing, an organic protective film is formed on the uppermost layer of the color filter layer. Next, a convex microlens is formed at a position corresponding to the light receiving section to obtain a color solid-state image sensor.

[0031]

In the color solid-state image pickup device of the present invention, a photocurable organic protective film containing an acid generator is used as a flattening layer under the color filter layer, a protective film between color filter layers, or a flattening layer for microlenses. When it is used as a protective film on the color filter layer to be formed, the fluidity due to heating is increased during film formation, the flatness of the film is improved, and an extremely flat film can be formed. Therefore, it is possible to reduce the variation in the thickness of the color filter pattern or the variation in the thickness and height of the microlens. This makes it possible to obtain a color solid-state imaging device having excellent spectral characteristics and sensitivity.

[0032]

EXAMPLES Examples of the present invention will be described below. <Embodiment 1> A resin content is formed on a solid-state imaging device substrate in which a light receiving portion and a scanning portion are formed in advance in a semiconductor substrate, and the surface is covered with a passivation film and has a surface step difference of 2.5 μm at maximum. 12 wt%, viscosity 30 cP, molecular weight about 300,000 polyglycidyl methacrylate (hereinafter, PG
MA resin) solution as a thermal crosslinking agent 2,2 ', 4,
A composition obtained by adding 1.0 wt% of 4'-tetrahydroxybenzophenone to the resin weight (hereinafter referred to as thermosetting composition 1) is applied.

This coating film was heated to 200 using a hot plate.
After baking at 10 ° C. for 10 minutes, an element flattening film underlying the filter layer was formed to a thickness of 2 μm. Then, a negative type photosensitive dyeable filter base material of casein was formed on the element flattening film in an amount of 0.
A film having a thickness of 5 μm was formed, exposed and developed to form a pattern of the filter base material at a desired position on the light receiving portion. Then, it was immersed in a dyeing solution and dyed with cyan (Cy) to form a cyan filter of the first color.

Next, in order to prevent color mixing, the above-mentioned PGMA resin composition containing a thermal crosslinking agent (thermosetting composition 1) is applied,
The film was baked at 200 ° C. for 10 minutes using a hot plate to form a 0.8 μm-thick film, and the cyan filter pattern was covered. Then, the above steps were repeated to form a yellow filter, a magenta filter, and a color mixing prevention film for the same.

Next, the molecular weight 3 represented by the following formula (4)
Sample N of Table 2 was used as an acid generator in a solution of 200,000 poly (isopropenylphenyl glycidyl ether) (hereinafter abbreviated as PIPGE resin) having a resin content of 20 wt%.
o. 2.0 wt% of triphenylsulfonium trifluoromethanesulfonate shown in 15 to the resin weight
The added composition (hereinafter referred to as photocurable composition 4) was applied and baked at 200 ° C. for 10 minutes using a hot plate to form a film having a thickness of 1 μm.

[0036]

[Chemical 10]

Next, the entire surface was exposed with Deep UV light and baked at 100 ° C. for 5 minutes using a hot plate to form a protective film on the filter layer. At this time, the exposure amount of Deep UV light was 200 mJ when measured at 254 nm. Next, a deep UV resist was applied on the protective film on the filter layer and baked at 90 ° C. for 30 minutes. Then, after forming the lens pattern by well-known photolithography technology,
It was baked at 180 ° C. for 30 minutes, heated and flowed to form convex microlenses, and a color solid-state imaging device with microlenses was obtained.

At this time, the unevenness of the surface of the protective film on the filter layer formed from the photocurable composition 4 is about 0.1 μm, and the flatness of the surface is good. It was possible to suppress variations in thickness and height. As a comparative example, when the protective film was formed by the conventional thermosetting composition 1, the unevenness was about 0.4 μm, and the effectiveness of the present invention was confirmed.

Example 2 After forming a filter layer in the same manner as in Example 1, poly (vinylphenyltetrahydropyranyl ether) having a molecular weight of 200,000 to 300,000 represented by the following formula (5) (hereinafter referred to as PVTPE A composition obtained by adding 1.5 wt% of triphenylsulfonium trifluoromethanesulfonate as an acid generator to a resin content of 20 wt% of the resin content (hereinafter referred to as photocurable composition 5). (Note) was applied and baked at 200 ° C. for 10 minutes using a hot plate to form a film having a thickness of 1 μm.

[0040]

[Chemical 11]

Next, the entire surface was exposed with Deep UV light and baked at 100 ° C. for 5 minutes using a hot plate to form a protective film on the filter layer. At this time, the exposure amount of Deep UV light was 200 mJ when measured at 254 nm. next,
By the same steps as in Example 1, convex microlenses were formed on the protective film on the filter layer to obtain a color solid-state imaging device with microlenses.

At this time, the unevenness of the surface of the protective film on the filter layer formed from the photocurable composition 5 was about 0.05 μm, and the flatness of the surface was good. I was able to suppress the height variation.

<Example 3> On the same substrate as in Example 1,
The photo-curable composition 4 is applied, baked at 200 ° C. for 10 minutes using a hot plate, and then exposed on the entire surface at an exposure amount of 200 mJ measured by Deep UV light at 254 nm,
Then, using a hot plate, baking was performed at 100 ° C. for 10 minutes to form an element flattening film as the filter lowermost layer with a thickness of 1.0 μm. Then, the same steps as above were repeated to further form a device flattening film having a thickness of 1 μm. Then, a negative type photosensitive dyeable filter base material of casein having a thickness of 0.5 μm is formed on the element flattening film, exposed and developed to form a pattern of the filter base material at a desired position on the light receiving portion. Formed. Then, it was immersed in a dyeing solution and dyed with cyan (Cy) to form a cyan filter of the first color.

Next, in order to prevent color mixture, the above-mentioned thermosetting composition 1 was applied, and the mixture was applied at 200 ° C. for 1 hour using a hot plate.
The film was baked for 0 minutes to form a film having a thickness of 0.8 μm and covered the cyan filter pattern. Then, the above steps were repeated to form a yellow filter, a magenta filter, and a color mixing prevention film for the same.

Next, the photocurable composition 4 was applied onto the uppermost filter layer, and the photocurable composition 4 was applied at 10 ° C. at 10 ° C. using a hot plate.
A minute baking was performed to form a film having a thickness of 1 μm. Then Deep
The whole surface is exposed with UV light at an exposure dose of 100 mJ measured at 254 nm, and then 5 hours at 100 ° C. using a hot plate.
After baking for a minute, a protective film was formed on the filter layer.

Next, by the same steps as in Example 1, a convex microlens was formed on the protective film on the filter layer to obtain a color solid-state image pickup device with a microlens.

In the case of this example, the unevenness on the surface of the protective film was smaller than that in Example 1, and good surface flatness was obtained.

Example 4 On the same substrate as in Example 1,
The photo-curable composition 5 is applied, baked at 200 ° C. for 10 minutes using a hot plate, and then exposed to the entire surface at an exposure amount of 100 mJ measured by Deep UV light at 254 nm,
Then, using a hot plate, baking was performed at 100 ° C. for 5 minutes to form an element flattening film as the filter lowermost layer with a thickness of 1.0 μm. Then, the same steps as above are repeated, and further 1
An element flattening film having a thickness of μm was formed.

Then, a negative type photosensitive dyeable filter base material of casein having a thickness of 0.5 μm is formed on the element flattening film, exposed and developed to form a filter base at a desired position on the light receiving portion. A pattern of material was formed. Then, it was immersed in a dyeing solution and dyed with cyan (Cy) to form a cyan filter of the first color. Next, in order to prevent color mixing, the above-mentioned thermosetting composition 1 was applied, and a hot plate was used for 10 minutes at 200 ° C.
A minute baking was performed to form a 0.8 μm thick film to cover the cyan filter pattern. Then, the above steps were repeated to form a yellow filter, a magenta filter, and a color mixing prevention film for the same.

Next, the photocurable composition 5 was applied onto the uppermost filter layer, and the photocurable composition 5 was applied at 10 ° C. at 10 ° C. using a hot plate.
A minute baking was performed to form a film having a thickness of 1 μm. Then Deep
The whole surface is exposed with UV light at an exposure dose of 100 mJ measured at 254 nm, and then 5 hours at 100 ° C. using a hot plate.
After baking for a minute, a protective film was formed on the filter layer.

Next, by the same steps as in Example 1, convex microlenses were formed on the protective film on the filter layer to obtain a color solid-state image pickup device with microlenses.

In the case of this embodiment, the unevenness of the surface of the protective film was smaller than that of the embodiment 2, and good surface flatness was obtained.

<Embodiment 5> A photo-curable type is formed on a solid-state image pickup device substrate having a light receiving portion and a scanning portion formed in advance in a semiconductor substrate and having a surface step covered by a passivation film with a maximum of 2.5 μm. Composition 4 was applied. This coating film was baked on a hot plate at 200 ° C. for 10 minutes to give D
eep UV light exposure at 200mJ with 254nm measurement, whole surface exposure, then 1 at 100 ° C using hot plate
After baking for 0 minutes, the element flattening film underlying the filter layer is 1.
It was formed to a thickness of 5 μm.

Next, a negative type photosensitive dyeable filter base material of gelatin is formed on the element flattening film to a thickness of 0.5 μm, exposed and developed to form a filter base material at a desired position on the light receiving portion. Pattern was formed. Then, it was immersed in a dyeing solution and dyed with cyan (Cy) to form a cyan filter of the first color.

Next, in order to prevent color mixture, the photocurable composition 4 was applied and baked at 200 ° C. for 10 minutes using a hot plate to form a film having a thickness of 0.8 μm, and a cyan filter pattern was formed. Covered. Then, the above steps were repeated to form a yellow filter, a magenta filter, and a color mixing prevention film for the same.

Next, the photocurable composition 4 was applied and baked at 200 ° C. for 10 minutes using a hot plate to form a film having a thickness of 1 μm. Next, the whole surface was exposed with Deep UV light at an exposure amount of 100 mJ measured at 254 nm, and baked at 100 ° C. for 5 minutes using a hot plate to form a protective film on the filter layer.

Next, on the protective film on the filter layer, Deep
A UV resist was applied and baked at 90 ° C. for 30 minutes.
Subsequently, a lens pattern was formed by a well-known photolithography technique, followed by baking at 180 ° C. for 30 minutes, heating and flowing to form a convex microlens, and a color solid-state imaging device with a microlens was obtained.

In the case of this example, the unevenness of the surface of the protective film was smaller than that in Example 3, and good surface flatness was obtained.

<Embodiment 6> A photo-curable type is formed on a solid-state image pickup device substrate having a surface step with a maximum of 2.5 μm in which a light receiving portion and a scanning portion are formed in advance in a semiconductor substrate and the surfaces thereof are covered with a passivation film. Composition 5 was applied. This coating film was baked on a hot plate at 200 ° C. for 10 minutes to give D
eep UV light exposure at 200mJ with 254nm measurement, whole surface exposure, then 1 at 100 ° C using hot plate
After baking for 0 minutes, the element flattening film underlying the filter layer is 1.
It was formed to a thickness of 5 μm.

Next, a negative photosensitive dyeable filter base material of gelatin is formed on the element flattening film to a thickness of 0.5 μm, exposed and developed to form a filter base material at a desired position on the light receiving portion. Pattern was formed. Then, it was immersed in a dyeing solution and dyed with cyan (Cy) to form a cyan filter of the first color. Next, in order to prevent color mixture, the photocurable composition 5 was applied, and baked at 200 ° C. for 10 minutes using a hot plate to form a film having a thickness of 0.8 μm and covering the cyan filter pattern. Then, the above steps were repeated to form a yellow filter, a magenta filter, and a color mixing prevention film for the same.

Next, the photocurable composition 5 was applied and baked at 200 ° C. for 10 minutes using a hot plate to form a film having a thickness of 1 μm. Next, the entire surface was exposed to Deep UV light and baked at 100 ° C. for 5 minutes using a hot plate to form a protective film on the filter layer. At this time, Deep
The exposure amount of UV light was 100 mJ when measured at 254 nm.

Then, on the protective film on the filter layer, Deep
A UV resist was applied and baked at 90 ° C. for 30 minutes.
Subsequently, a lens pattern was formed by a well-known photolithography technique, followed by baking at 180 ° C. for 30 minutes, heating and flowing to form a convex microlens, and a color solid-state imaging device with a microlens was obtained.

In the case of this example, the unevenness on the surface of the protective film was smaller than that in Example 4, and good surface flatness was obtained.

<Embodiment 7> After forming a filter layer in the same manner as in Embodiment 1, a molecular weight of 20 represented by the following formula (6) is obtained.
~ Resin content of 300,000 polyvinyl cinnamate 20
A composition obtained by adding 2.0 wt% of triphenylsulfonium trifluoromethanesulfonate as an acid generator to the resin weight (hereinafter referred to as photocurable composition 6) was applied to the wt% solution, and a hot plate was applied. Use at 200 ℃ 1
The film was baked for 0 minutes to form a film having a thickness of 1 μm.

Next, the entire surface was exposed with Deep UV light at an exposure amount of 200 mJ measured at 254 nm, and then baked at 100 ° C. for 10 minutes using a hot plate to form a protective film on the filter layer. Next, by the same steps as in Example 1, convex microlenses were formed on the protective film on the filter layer to obtain a color solid-state imaging device with microlenses. In this way, good surface flatness comparable to that of Example 1 was obtained.

[0066]

[Chemical 12]

<Embodiment 8> On the same substrate as in Embodiment 1,
The photocurable composition 6 is applied, baked at 200 ° C. for 10 minutes using a hot plate, and then exposed to the entire surface at an exposure amount of 200 mJ measured by Deep UV light at 254 nm,
Then, using a hot plate, baking was performed at 100 ° C. for 5 minutes to form an element flattening film as the filter lowermost layer with a thickness of 1.5 μm.

Next, a negative type photosensitive dyeable filter base material of casein having a thickness of 0.5 μm is formed on the element flattening film, exposed and developed to form a filter base material at a desired position on the light receiving portion. Pattern was formed. Then, it was immersed in a dyeing solution and dyed with cyan (Cy) to form a cyan filter of the first color. Next, in order to prevent color mixing, the above-mentioned thermosetting composition 1 was applied, and a hot plate was used for 10 minutes at 200 ° C.
A minute baking was performed to form a 0.8 μm thick film to cover the cyan filter pattern. Then, the above steps were repeated to form a yellow filter, a magenta filter, and a color mixing prevention film for the same.

Next, the photocurable composition 6 was applied on the uppermost filter layer, and the photocurable composition 6 was applied at 10 ° C. at 10 ° C. using a hot plate.
A minute baking was performed to form a film having a thickness of 1 μm. Then Deep
The whole surface is exposed with UV light at an exposure dose of 100 mJ measured at 254 nm, and then 5 hours at 100 ° C. using a hot plate.
After baking for a minute, a protective film was formed on the filter layer.

Then, by the same steps as in Example 1, convex microlenses were formed on the protective film on the filter layer to obtain a color solid-state image pickup device with microlenses. In this way, good surface flatness substantially equal to that of Example 3 was obtained.

<Embodiment 9> A photo-curable type is formed on a solid-state imaging device substrate having a light receiving portion and a scanning portion formed in advance in a semiconductor substrate, the surface of which is covered with a passivation film and having a surface step of maximum 2.5 μm. Composition 6 was applied. This coating film was baked on a hot plate at 200 ° C. for 10 minutes to give D
eep UV light exposure at 200mJ with 254nm measurement, whole surface exposure, then 1 at 100 ° C using hot plate
After baking for 0 minutes, the element flattening film underlying the filter layer is 1.
It was formed to a thickness of 5 μm.

Next, a negative photosensitive dyeable filter base material of gelatin is formed in a thickness of 0.5 μm on the element flattening film, exposed and developed to form a filter base material at a desired position on the light receiving portion. Pattern was formed. Then, it was immersed in a dyeing solution and dyed with cyan (Cy) to form a cyan filter of the first color.

Next, in order to prevent color mixture, the photocurable composition 6
Is applied and baked at 200 ° C. for 10 minutes using a hot plate and 100 mJ when measured with Deep UV light at 254 nm.
Then, the whole surface was exposed with an exposure amount of 100 ° C. and then baked at 100 ° C. for 10 minutes using a hot plate to form a film having a thickness of 0.8 μm to cover the cyan filter pattern. Then, the above steps were repeated to form a yellow filter, a magenta filter, and a color mixing prevention film for the same.

Next, the photocurable composition 6 was applied and baked at 200 ° C. for 10 minutes using a hot plate to form a film having a thickness of 1 μm. Next, the whole surface was exposed with Deep UV light at an exposure amount of 100 mJ measured at 254 nm, and baked at 100 ° C. for 5 minutes using a hot plate to form a protective film on the filter layer.

Then, on the protective film on the filter layer, Deep
A UV resist was applied and baked at 90 ° C. for 30 minutes.
Subsequently, a lens pattern was formed by a well-known photolithography technique, followed by baking at 180 ° C. for 30 minutes, heating and flowing to form a convex microlens, and a color solid-state imaging device with a microlens was obtained. In this way
Good surface flatness, which was substantially the same as that of Example 5, was obtained.

Example 10 After forming the filter layer in the same manner as in Example 1, the molecular weight 2 represented by the following formula (7) was obtained.
2.0 wt% of triphenylsulfonium trifluoromethanesulfonate as an acid generator is added to a 20 wt% resin content solution of poly (cinnamic acid-β-vinyloxyethyl ester) of 0 to 300,000 with respect to the resin weight. The added composition (hereinafter, referred to as photocurable composition 7) was applied and baked at 200 ° C. for 10 minutes using a hot plate to form a film having a thickness of 1 μm. Next, the whole surface was exposed with Deep UV light at an exposure amount of 200 mJ measured at 254 nm, and then baked at 100 ° C. for 10 minutes using a hot plate to form a protective film on the filter layer. Next, by the same steps as in Example 1, convex microlenses were formed on the protective film on the filter layer to obtain a color solid-state imaging device with microlenses. In this way, good surface flatness almost equal to that of Example 1 was obtained.

[0077]

[Chemical 13]

Example 11 The same photocurable composition 7 was applied onto the same substrate as in Example 1, baked at 200 ° C. for 10 minutes using a hot plate, and then Deep U.
The entire surface was exposed with V light at an exposure amount of 200 mJ measured at 254 nm, and then baked at 100 ° C. for 5 minutes using a hot plate to form an element flattening film as a filter lowermost layer with a thickness of 1.5 μm.

Then, a negative type photosensitive dyeable filter base material of casein having a thickness of 0.5 μm is formed on the element flattening film, exposed and developed to form a filter base material at a desired position on the light receiving portion. Pattern was formed. Then, it was immersed in a dyeing solution and dyed with cyan (Cy) to form a cyan filter of the first color.

Next, in order to prevent color mixture, the above thermosetting composition 1 was applied, and the mixture was applied at 200 ° C. for 1 hour using a hot plate.
The film was baked for 0 minutes to form a film having a thickness of 0.8 μm and covered the cyan filter pattern. Then, the above steps were repeated to form a yellow filter, a magenta filter, and a color mixing prevention film for the same.

Next, the photocurable composition 7 was applied on the filter layer and baked at 200 ° C. for 10 minutes using a hot plate to form a film having a thickness of 1 μm. Then Deep UV
The entire surface was exposed to light with an exposure amount of 100 mJ measured at 254 nm, and then baked at 100 ° C. for 5 minutes using a hot plate to form a protective film on the filter layer.

Next, by the same steps as in Example 1, convex microlenses were formed on the protective film on the filter layer to obtain a color solid-state image pickup device with microlenses. In this way, a protective film having substantially the same flatness as in Example 1 could be realized.

<Embodiment 12> A photo-curable type is formed on a solid-state imaging device substrate having a light receiving portion and a scanning portion formed in advance in a semiconductor substrate and having a surface step covered by a passivation film with a maximum surface difference of 2.5 μm. Composition 7 was applied. Baking this coating film at 200 ° C. for 10 minutes using a hot plate,
The entire surface was exposed with Deep UV light at an exposure amount of 200 mJ measured at 254 nm, and then baked at 100 ° C. for 10 minutes using a hot plate to form an element flattening film of 1.5 μm thickness as a filter layer base.

Next, a negative-working photosensitive dyeable filter base material of gelatin having a thickness of 0.5 μm is formed on the element flattening film, exposed and developed to form a filter base material at a desired position on the light receiving portion. Pattern was formed. Then, it was immersed in a dyeing solution and dyed with cyan (Cy) to form a cyan filter of the first color.

Next, in order to prevent color mixture, the photocurable composition 7
Was applied and baked at 200 ° C. for 10 minutes using a hot plate to form a film having a thickness of 0.8 μm to cover the cyan filter pattern. Then, the above steps were repeated to form a yellow filter, a magenta filter, and a color mixing prevention film for the same.

Next, the photocurable composition 7 was applied and baked at 200 ° C. for 10 minutes using a hot plate to form a film having a thickness of 1 μm. Next, the whole surface was exposed with Deep UV light at an exposure amount of 100 mJ measured at 254 nm, and baked at 100 ° C. for 5 minutes using a hot plate to form a protective film on the filter layer.

Next, Deep is formed on the protective film on the filter layer.
A UV resist was applied and baked at 90 ° C. for 30 minutes.
Subsequently, a lens pattern was formed by a well-known photolithography technique, followed by baking at 180 ° C. for 30 minutes, heating and flowing to form a convex microlens, and a color solid-state imaging device with a microlens was obtained. In this way
A protective film having substantially the same flatness as in Example 5 could be realized.

<Examples 13 to 23> As a resin component, for each of the polymers (Sample Nos. 1 to 11) shown in Tables 5, 6 and 7, triphenyl as an acid generator was added to a solution containing 20 wt% of resin content. A color solid-state imaging device with a microlens was obtained in the same manner as in Example 1 except that the photocurable composition containing 1.5 wt% of sulfonium trifluoromethanesulfonate was added to the resin weight. In this way, it was possible to realize a protective film having a flatness substantially equal to that of Example 1.

[0089]

[Table 5]

[0090]

[Table 6]

[0091]

[Table 7]

<Examples 24 to 34> As the resin component, for each of the polymers (Sample Nos. 1 to 11) shown in Tables 5, 6 and 7, a solution containing 20 wt% of the resin component was added with triphenyl as an acid generator. A color solid-state imaging device with a microlens was obtained in the same manner as in Example 3 except that the photocurable composition containing 1.5 wt% of sulfonium trifluoromethanesulfonate was added to the resin weight. In this way, it was possible to realize a protective film having a flatness substantially equal to that of Example 3.

<Examples 35 to 45> As a resin component, for each of the polymers (Sample Nos. 1 to 11) shown in Tables 5, 6 and 7, triphenyl was used as an acid generator in a 20 wt% resin content solution. A color solid-state imaging device with a microlens was obtained in the same manner as in Example 4 except that the photo-curable composition containing 1.5 wt% of sulfonium trifluoromethanesulfonate was added to the resin weight. In this way, a protective film having substantially the same flatness as that of Example 4 could be realized.

<Examples 45 to 47> A solution of polyvinyl alcohol having a resin content of 15 wt% was prepared by adding 10 wt% of N-methylolacrylamide to the resin weight and triphenylsulfonium trifluoromethanesulfonate as an acid generator. Examples 1 and 3 except that the photocurable composition was added in an amount of 1.5 wt% with respect to the weight, and the baking temperature of the photocurable composition by the hot plate before the whole surface exposure with Deep UV light was 150 ° C. Similar to 4,
A color solid-state imaging device with a microlens was obtained. In this way, it was possible to realize a protective film having substantially the same flatness as in Examples 1, 3, and 4.

<Examples 48 to 50> A solution containing 15 wt% of a resin component of polyvinylphenol, 10 wt% of N-methylolacrylamide based on the weight of the resin, and triphenylsulfonium trifluoromethanesulfonate as an acid generator were added to the resin. Examples 1 and 3 except that the photocurable composition was added in an amount of 1.5 wt% with respect to the weight, and the baking temperature of the photocurable composition by the hot plate before the whole surface exposure with Deep UV light was 150 ° C. Similar to 4,
A color solid-state imaging device with a microlens was obtained. In this way, it was possible to realize a protective film having substantially the same flatness as in Examples 1, 3, and 4.

<Examples 51 to 65> In place of the triphenylsulfonium trifluoromethanesulfonate used in Example 1, sample No. 6 in Table 8 was used as an acid generator. Phenacyl tetramethylene sulfonium trifluoromethane sulfonate shown in 12 is used, and polyglycidyl methacrylate, poly (isopropenylphenyl glycidyl ether), poly (vinylphenyl tetrahydropyranyl ether), polyvinyl cinnamate, poly (cinnamon skin) are used as the resin. Acid-β-vinyloxyethyl ester), Table 5,
Using the polymers (Sample Nos. 1 to 11) shown in Tables 6 and 7, a photocurable type in which the above-mentioned acid generator was added to the solution containing 15 wt% of the resin content in an amount of 1.5 wt% based on the weight of the resin Using the composition, a color solid-state imaging device with a microlens was obtained in the same manner as in Example 1. In this way, it was possible to realize a protective film having a flatness substantially equal to that of Example 1.

[0097]

[Table 8]

<Examples 66 to 80> Using the photocurable compositions used in Examples 51 to 65, color solid-state image pickup devices with microlenses were obtained in the same manner as in Example 3. In this way, it was possible to realize a color solid-state image sensor having a protective film having a flatness substantially equal to that of Example 3.

<Examples 81 to 95> Using the photocurable compositions used in Examples 51 to 65, color solid-state image pickup devices with microlenses were obtained in the same manner as in Example 4. In this way, it was possible to realize a color solid-state image pickup device having a protective film having substantially the same flatness as in Example 4.

<Examples 96 to 98> A solution of polyvinyl alcohol having a resin content of 15 wt% was used, 10 wt% of N-methylolacrylamide was added to the resin, and phenacyltetramethylenesulfonium trifluoromethanesulfone was used as an acid generator. 1.5 to acid salt
Examples 1 to 3 except that the baking temperature of the photocurable composition by the hot plate before the whole surface exposure with Deep UV light is 150 ° C. using the photocurable composition added by wt%.
A color solid-state imaging device with a microlens was obtained in the same manner as in. In this way, it was possible to realize a color solid-state image pickup device having a protective film having substantially the same flatness as in Examples 1, 3, and 4.

Examples 99 to 101 A solution of polyvinylphenol in a resin content of 15% by weight was used, 10% by weight of N-methylolacrylamide based on the weight of the resin, and phenacyltetramethylenesulfonium trifluoromethanesulfone as an acid generator. The acid salt is 1.
Using the photocurable composition added at 5 wt%, Examples 1 and 3 except that the baking temperature of the photocurable composition by the hot plate before the whole surface exposure with Deep UV light is 150 ° C.
A color solid-state imaging device with a microlens was obtained in the same manner as in 4. In this way, all of Examples 1, 3, 4
It was possible to realize a color solid-state image pickup device having a protective film having a flatness substantially equal to the above.

<Examples 102 to 116> In place of the triphenylsulfonium trifluoromethanesulfonate used in Example 1, sample No. 3 in Table 8 was used as an acid generator. 1
Phenylphenacyl tetramethylene sulfonium trifluoromethanesulfonate shown in 3 is used, and polyglycidyl methacrylate, poly (isopropenylphenyl glycidyl ether), poly (vinylphenyl tetrahydropyranyl ether), polyvinyl cinnamate, poly (silica) is used as a resin. Cinic acid-β-vinyloxyethyl ester), polymers shown in Table 5, Table 6 and Table 7 (Sample Nos. 1 to 1)
11), the resin content of 15
The above acid generator in a wt% solution is 1.5w with respect to the resin weight.
A color solid-state imaging device with a microlens was obtained in the same manner as in Example 1 using the photocurable composition added with t%. In this way, it was possible to realize a color solid-state image sensor having a protective film having a flatness substantially equal to that of Example 1.

<Examples 117-131> Example 102-
Using the photocurable composition used in Example 116, a color solid-state imaging device with a microlens was obtained in the same manner as in Example 3. In this way, it was possible to realize a color solid-state image sensor having a protective film having a flatness substantially equal to that of Example 3.

<Examples 132 to 146> Example 102 to
Using the photocurable composition used in Example 116, a color solid-state imaging device with a microlens was obtained in the same manner as in Example 4. In this way, it was possible to realize a color solid-state image pickup device having a protective film having substantially the same flatness as in Example 4.

Examples 147 to 149 A solution of polyvinyl alcohol having a resin content of 15 wt% was used, 10 wt% of N-methylolacrylamide was added to the resin weight, and phenylphenacyltetramethylenesulfonium trifluoromethane as an acid generator. Using a photocurable composition in which a sulfonate is added in an amount of 1.5 wt% with respect to the resin weight, D
A color solid-state imaging device with a microlens was obtained in the same manner as in Examples 1, 3, and 4 except that the baking temperature of the photocurable composition on the hot plate before the entire surface exposure with eep UV light was 150 ° C. In this way, it was possible to realize a color solid-state image pickup device having a protective film having substantially the same flatness as in Examples 1, 3, and 4.

<Examples 150 to 152> A solution of polyvinylphenol having a resin content of 15% by weight was used, 10% by weight of N-methylolacrylamide based on the weight of the resin, and phenylphenacyltetramethylenesulfonium trifluoromethane as an acid generator. Using a photocurable composition in which a sulfonate is added in an amount of 1.5 wt% with respect to the resin weight, D
eep A color solid-state imaging device with a microlens was obtained in the same manner as in Examples 1, 3, and 4 except that the baking temperature of the photocurable composition on the hot plate before exposure on the entire surface by UV light was 150 ° C. In this way, it was possible to realize a color solid-state image pickup device having a protective film having substantially the same flatness as in Examples 1, 3, and 4.

<Examples 153 to 167> Instead of the triphenylsulfonium trifluoromethanesulfonate salt used in Example 1, the sample No. 3 of Table 8 was used as an acid generator. 1
Using the acenaphthyltetramethylene sulfonium trifluoromethanesulfonate shown in 4 as a resin, polyglycidyl methacrylate, poly (isopropenylphenyl glycidyl ether), poly (vinylphenyl tetrahydropyranyl ether), polyvinyl cinnamate, poly (cinnamon bark) Acid-β-vinyloxyethyl ester), polymers shown in Table 5, Table 6 and Table 7 (Sample Nos. 1 to 1)
11), the resin content of 15
The above acid generator in a wt% solution is 1.5w with respect to the resin weight.
A color solid-state imaging device with a microlens was obtained in the same manner as in Example 1 using the photocurable composition added with t%. In this way, it was possible to realize a color solid-state image sensor having a protective film having a flatness substantially equal to that of Example 1.

<Examples 168 to 182> Examples 153 to 153
A color solid-state imaging device with a microlens was obtained in the same manner as in Example 3 using the photocurable composition used in 167. In this way, it was possible to realize a color solid-state image sensor having a protective film having a flatness substantially equal to that of Example 3.

<Examples 183-197> Examples 153-
A color solid-state imaging device with a microlens was obtained in the same manner as in Example 4 using the photocurable composition used in 167. In this way, it was possible to realize a color solid-state image pickup device having a protective film having substantially the same flatness as in Example 4.

<Examples 198 to 200> A solution of polyvinyl alcohol having a resin content of 15% by weight was used, 10% by weight of N-methylolacrylamide based on the weight of the resin, and acenaphthyltetramethylenesulfonium trifluoromethanesulfone as an acid generator. Using a photocurable composition in which an acid salt is added in an amount of 1.5 wt% with respect to the resin weight, Deep U
Example 1, except that the baking temperature of the photocurable composition on the hot plate before the entire surface exposure with V light was 150 ° C.
A color solid-state imaging device with a microlens was obtained in the same manner as 3 and 4. In this way, in each case, Example 1,
It was possible to realize a color solid-state image pickup device having a protective film having substantially the same flatness as that of Nos. 3 and 4.

<Examples 201 to 203> A solution of polyvinylphenol having a resin content of 15% by weight was used, 10% by weight of N-methylolacrylamide based on the weight of the resin, and acenaphthyltetramethylenesulfonium trifluoromethanesulfone as an acid generator. Using a photocurable composition in which an acid salt is added in an amount of 1.5 wt% with respect to the resin weight, Deep U
Example 1, except that the baking temperature of the photocurable composition on the hot plate before the entire surface exposure with V light was 150 ° C.
A color solid-state imaging device with a microlens was obtained in the same manner as 3 and 4. In this way, in each case, Example 1,
It was possible to realize a color solid-state image pickup device having a protective film having substantially the same flatness as that of Nos. 3 and 4.

[0112]

EFFECTS OF THE INVENTION An underlying flattening film is formed by forming a filter underlying flattening film having high flatness, a filter interlayer protective film, or in the case of a solid-state imaging device with a microlens, a protective film on the filter layer having high flatness. By reducing the variation in film thickness of the color filter pattern formed above and the variation in thickness and height of the microlenses formed on the protective film on the filter layer, a color solid with excellent spectral characteristics and sensitivity is obtained. An image sensor is obtained.

Continued front page    (72) Inventor Akiya Izumi             Hitachi, Ltd. 3300 Hayano, Mobara-shi, Chiba             Mobara Factory (72) Inventor Tatsuo Hamamoto             Hitachi, Ltd. 3300 Hayano, Mobara-shi, Chiba             Mobara Factory (72) Inventor Takumi Kuji             Hitachi, Ltd. 3300 Hayano, Mobara-shi, Chiba             Mobara Factory (72) Inventor Toshio Nakano             Hitachi Device, 3681 Hayano, Mobara-shi, Chiba             Engineering Co., Ltd. (72) Inventor Takashi Isoda             Hitachi Device, 3681 Hayano, Mobara-shi, Chiba             Engineering Co., Ltd.

Claims (19)

[Claims] 1. A solid-state imaging device comprising a semiconductor substrate having a light receiving portion for performing photoelectric conversion, a scanning portion for taking out an electric signal generated in the light receiving portion, and a passivation film for protecting the light receiving portion and the scanning portion. A flattening layer made of a transparent material is provided on the substrate, and a color filter pattern protected by an organic film made of a transparent material is arranged on the flattening layer at a position corresponding to the light receiving portion on the solid-state imaging device substrate. In the color solid-state image sensor, the organic film made of the transparent material is formed by a photocurable composition made of an organic polymer material or an organic silicon material and an acid generator. 2. A solid-state image pickup device comprising a semiconductor substrate having a light receiving portion for performing photoelectric conversion, a scanning portion for taking out an electric signal generated in the light receiving portion, and a passivation film for protecting the light receiving portion and the scanning portion. A flattening layer made of a transparent material is provided on the substrate, and a color filter pattern protected by an organic film made of a transparent material is arranged on the flattening layer at a position corresponding to the light receiving portion on the solid-state imaging device substrate. Then, in the color solid-state imaging device in which a convex microlens is formed on the uppermost layer of the color filter layer through an organic protective film, the uppermost organic protective film of the color filter layer is formed of an organic polymer material or an organic silicon. A color solid-state image sensor formed of a photocurable composition comprising a base material and an acid generator. 3. The color solid according to claim 1, wherein the planarizing layer made of the transparent material is formed of a photocurable composition containing an organic polymer material or an organic silicon material and an acid generator. Image sensor. 4. The color solid-state image pickup device according to claim 2, wherein the microlenses are formed of a photocurable composition comprising an organic polymer material or an organic silicon material and an acid generator. 5. The acid generator is represented by the following general formula (1):
The onium salt represented by (2) or (3), tri (methanesulfonyl-oxy) benzene, or a mixture of the onium salt and tri (methanesulfonyl-oxy) benzene. The color solid-state imaging device described. [Chemical 1] [Chemical 2] [Chemical 3] However, in the above general formula, X ~ is BF ₄ ~, SbF
₆ ~, AsF ₆ ~, PF ₆ ~, or CF ₃ SO ₃ ~ anion, and Ar ^{1 to} Ar ⁶ and R represent organic groups. 6. The organic polymer material is a phenol resin,
5. The color solid-state image pickup device according to claim 1, wherein the color solid-state image pickup device is made of any one of a novolac resin, a cresol resin, and an epoxy resin, or a resin having any one of an olefin type, a lactone type, and a lactam type structure. 7. The color solid-state image pickup device according to claim 1, wherein the organosilicon material is composed of a resin containing a silanol compound. 8. The color solid-state image pickup device according to claim 1, wherein the flattening layer made of the transparent material is made of a transparent polyimide formed by curing a polyimide precursor having an end-capped molecular end. . 9. A photocurable composition comprising the organic polymer material or organic silicon material and an acid generator is added to generate an acid with respect to 100 parts by weight of the solid content of the organic polymer material or the organic silicon material. 5. The color solid-state image pickup device according to claim 1, which is composed of a composition containing 0.01 to 30 parts by weight of an agent. 10. A solid-state imaging device comprising a semiconductor substrate having a light receiving portion for performing photoelectric conversion, a scanning portion for taking out an electric signal generated in the light receiving portion, and a passivation film for protecting the light receiving portion and the scanning portion. A step of forming a flattening layer made of a transparent material on a substrate, a step of forming a color filter layer on the flattening layer, an organic polymer material or an organic silicon material and acid generation on the color filter layer. Of a color solid-state imaging device, which comprises a step of forming an organic protective film from a photocurable composition comprising an agent and a step of forming convex microlenses on the organic protective film on the color filter layer. In the manufacturing method, the step of forming the organic protective film comprises a step of applying a photocurable composition comprising an organic polymer material or an organic silicon material and an acid generator, Process and method for producing a color solid-state imaging device comprising and a step of exposing the film over the entire surface by ultraviolet light to heat the film. 11. A solid-state imaging device comprising a semiconductor substrate on which a light receiving portion for performing photoelectric conversion, a scanning portion for taking out an electric signal generated in the light receiving portion, and a passivation film for protecting the light receiving portion and the scanning portion are formed. A step of forming a flattening layer made of a transparent material on a substrate, and a color filter layer protected by an organic film made of a transparent material on the flattening layer at a position corresponding to a light receiving portion on the solid-state imaging device substrate And a step of forming an organic film for protecting the color filter, the method comprising the steps of forming an organic polymer material or an organic silicon-based material and an acid generator. The step of applying the photo-curable composition, and the step of heating this coating film, and the step of exposing the entire surface of the film with ultraviolet light are repeated as many times as necessary according to the configuration of the color filter. Method for producing a color solid-state imaging device comprising and a step. 12. A step of forming a planarizing layer made of the transparent material, a step of applying a photocurable composition made of an organic polymer material or an organic silicon material and an acid generator,
Next, it comprises a step of heating the coating film and a step of exposing the entire surface of the film with ultraviolet light.
1. The method for manufacturing the color solid-state image sensor according to 1. 13. After the step of exposing the entire surface of the film with ultraviolet light in the step of forming the convex microlenses,
The method for manufacturing a color solid-state image pickup device according to claim 10, which further comprises a step of heating. 14. A step of applying a photocurable composition comprising the above organic polymer material or organosilicon material and an acid generator, then a step of heating this coating film, and exposing the entire surface of the film to ultraviolet light. 14. The method for manufacturing a color solid-state imaging device according to claim 10, further comprising a step of heating after the step of exposing in the protective film forming step including the step of. 15. The step of forming a flattening layer made of the transparent material includes a step of applying a polyimide precursor having end caps of molecular ends and a step of forming a transparent polyimide film by heat curing. Claim 10 or 1 which consists of
1. The method for manufacturing the color solid-state image sensor according to 1. 16. The acid generator as an onium salt represented by the following general formula (1), (2) or (3), tri (methanesulfonyl-oxy) benzene, or the onium salt and tri (methanesulfonyl). -Oxy) benzene as a mixture.
3. The method for manufacturing a color solid-state image sensor according to any one of 3). [Chemical 4] [Chemical 5] [Chemical 6] However, in the above general formula, X ~ is BF ₄ ~, SbF
₆ ~, AsF ₆ ~, PF ₆ ~, or CF ₃ SO ₃ ~ anion, and Ar ^{1 to} Ar ⁶ and R represent organic groups. 17. The organic polymer material comprises a resin having any one of a phenol resin, a novolac resin, a cresol resin, and an epoxy resin, or an olefin resin, a lactone resin, or a lactam resin. 14. The method for manufacturing a color solid-state image sensor according to any one of 13 to 13. 18. A material containing a silanol compound is used as the organosilicon material.
A method for manufacturing the color solid-state imaging device according to any one of claims. 19. A photocurable composition comprising the organic polymer material or organosilicon material and an acid generator, wherein the organic polymer material or organosilicon material has a solid content of 100.
14. The method for manufacturing a color solid-state image pickup device according to claim 10, wherein a composition containing 0.01 to 30 parts by weight of an acid generator is used with respect to parts by weight.