JPS5970092A - Solid state color image pickup element - Google Patents

Abstract

PURPOSE:To prevent danger of pollution due to such as alkali metal by coloring a resin film of a micro-color filter with a coloring matter containing cations consisting of plural nonmetallic atoms at a prescribed ratio. CONSTITUTION:A coloring matter expressed by a general formula D-(SO3HmXn)p is used for a part or all of the coloring matter of the color resin film of the micro-color filter formed on the surface of a photodetecting part of a solid state image pickup element. In said formula, D is a coloring matter part, X is cations consisting of plural metallic atoms, m and n are values of more than 0 and less than 1 and m+n=1, and p is an integer selected from 1-6. Thus, the danger of pollution due to alkali metal of the solid state color image pickup element can be extremely prevented.

Description

[Detailed description of the invention] The present invention relates to a color solid-state image sensor.

For example, in VTR cameras and the like, color imaging devices in which a light receiving section is provided with a micro color filter have been commonly used in order to extract color signals corresponding to color images. These color image pickup tubes are typified by types of image pickup tubes called sachicon, vidicon, etc.

On the other hand, recently various solid-state image sensors such as CCD, BBD, and MOS have been developed as devices to replace image pickup tubes. The practical application of a color solid-state image sensor combining a color filter and a micro color filter is being studied, and some have already been put into practical use.

A color solid-state image sensor is generally made up of microscopic photoelectric conversion elements called pixels and a flat image sensor integrated circuit ('jC) that integrates a scanning circuit. It consists of a micro color filter in which several types of minute color separation filter elements (colored resin films) such as red, green, blue, cyan, magenta, and yellow are combined in a mosaic or stripe pattern. It is something.

The color solid-state image sensor is manufactured by a method called "bonding method" or "on-wafer method" in 6M.

Among these methods, the bonding method involves forming a color separation filter element corresponding to each pixel of a solid-state image sensor on a transparent support such as glass to produce a micro color filter, and then bonding this to the surface of the solid-state image sensor. This method is used to create a color solid-state image sensor. Therefore, in this method, when adhering independently manufactured micro color filters to the surface of a solid-state image sensor, strict control is required so that each color separation filter element accurately corresponds to each pixel of the solid-state image sensor. operation is required.

On the other hand, the on-wafer method is a method in which a micro color filter is formed directly on a solid-state image sensor. Therefore, this on-wafer method can be incorporated into the manufacturing process of a solid-state image sensor, and has the advantage of facilitating the manufacture of a color solid-state image sensor.

Note that the on-wafer method involves simultaneously manufacturing a large number of color solid-state image sensors by forming color separation filter elements corresponding to each pixel of each solid-state image sensor on a wafer on which a large number of solid-state image sensors are arranged. A single color solid-state image sensor is manufactured by cutting out a single solid-state image sensor (chip) from a wafer in which a large number of solid-state image sensors are arranged, and forming a color separation filter element on each chip. Although several methods (on-chip methods) are known, in this specification, any of these methods are included in the on-wafer method.

As mentioned above, a solid-state image sensor consists of a flat IC in which a photoelectric conversion element and a scanning circuit are highly integrated.For this reason, a solid-state image sensor is susceptible to dirt, dust, alkali metals, etc. 11j dyeing caused by impurities is extremely disliked. Solid-state imaging devices contaminated with such impurities often fail to exhibit predetermined characteristics, which directly leads to a reduction in product yield. Therefore, even in the process of attaching a micro color filter to a solid-state image sensor, great care is taken to avoid contamination with such impurities as much as possible.

Based on the above-mentioned technical background, the present invention colors a colored resin film of a micro color filter attached to a solid-state image sensor using a dye that does not contain an alkali metal and is represented by a specific general formula. Accordingly, it is an object of the present invention to provide a color solid-state image sensor that can prevent the risk of alkali metal contamination of the solid-state image sensor as much as possible.

That is, one aspect of the present invention is colored resin II for micro color filters! 2 is the general formula (■): D (S03HmXn
)p (I) (D is a dye moiety, This is a color solid-state image sensor characterized by being colored with a dye represented by (an integer of ).

Next, the present invention will be explained in detail.

In the present invention, when preparing a colored resin film of a micro color filter formed on the surface of a light-receiving part of a solid-state image sensor, instead of various alkali metal-containing pigments that have been conventionally used as the pigment, a part or All represented by the general formula (I) ・D (SOa HmXn)p
By using the dye represented by (I), the present invention provides a color solid-state imaging device which is designed to minimize the risk of contamination caused by alkali metals, etc. of the color solid-state imaging device.

In the above general formula (I), D is a dye moiety (3), X is a cation consisting of a plurality of nonmetallic atoms, m and n are each a numerical value of 0 or more and less than 1, provided that m+n=1, and p is 1 to 1. You can choose from 6 integers. However, it is preferable that n be a numerical value (larger than m);
It is preferable that the power is more than twice that of

The dye of general formula (I) used in the present invention may be composed of a wide range of dyes, or may be a combination of a plurality of dyes. I will elaborate on this point next.

The dye of general formula (I) used in the present invention may be composed of a single dye if there are a plurality of sulfonic acid groups, that is, 2 to 6 sulfonic acid groups in the molecular structure of the dye. be. For example, when there are two sulfonic acid groups in the molecular structure of a dye, one is a sulfonic acid group in the form of ML free acid [-(502)1) ], and the other is in the form of a salt. It can be a sulfonic acid group [-(S03X)], in this dye m=n=0.5 and p=2. Alternatively, if there are four sulfonic acid groups in the molecular structure of the dye, such as ordinary phthalocyanine dyes, one of them is a sulfonic acid group in the form of free a-acid [~(SO3H)] , and the other four can be sulfonic acid groups [-(SO3X)] in salt form, in this dye m=0.25, r, = 0
, 75, and p-4.

In addition, when the dye of general formula (I) is a mixture of multiple dyes, for example, 2
sulfonic acid groups in the form of Ml acid [-(S.

A case can be mentioned in which a dye having only 3H)] and a dye having only a sulfonic acid group [(SO3X)] in the form of a salt are combined to form a dye mixture. If this dye mixture is a mixture of 1 for the former and 4 for the latter, then m=0.2, n=0.8, and p=
It is 2.

Alternatively, in the case where there are four sulfonic acid groups in the molecular structure of the dye as in the case of ordinary phthalocyanine dyes, sulfonic acid M in the form of M+'a+l: M'A
A dye having only [-(so3H)] and a dye having only sulfonic acid group [-(so3x)'' in the form of a salt may be mixed, resulting in a tetrapod combination of dyes. In this dye mixture, when the mixing ratio of the former and the latter is 1:9, m=0.1, n=0.9, and p=4.

Furthermore, the dye of general formula (I) used in the present invention is 1l
A dye containing both a sulfonic acid group in the form of an IJk acid [(SO3H)] and a sulfonic acid group [-(SO3X)] in the form of a salt, and a sulfonic acid group in the form of either of them. It may also be a mixture with a dye having only one.

In addition, when there is only one sulfonic acid group in the molecular structure of the dye, the dye of O'U formula (I) necessarily contains the sulfonic acid group [-(SOaH)] in the form of a free acid.
dyes with only sulfonic acid groups [(
A dye mixture is obtained in which dyes having only SC)3X)] are mixed. In that case, m and n correspond to the mixing ratio, and p is l.

Preferred examples of the dye corresponding to the dye moiety D include azo dyes, bisazo dyes, and phthalocyanine dyes.

As an azo dye, general formula (■): A-N=N-B (III) (however,
A is a group derived from a coupling component, and B is a group derived from an azo component, and the sulfonic acid group in any of the above forms is bonded to both A and B, or to either one of them. It is preferable to use Here, examples of coupling components include phenol, naphthol, 5-pyrazolone, pyridinol, aniline, naphthylamine, 5-aminopyrazole, and aminopyridine (all of which may have a substituent). can be mentioned. Furthermore, examples of the azo component include aniline, naphthylamine, and aromatic heterocyclic amine (all of which may have a substituent).

As the bisazo dye, general formula (IV): AN=
N-B'-N=N-A' (IV) (where A and A' may each be the same or different and represent a group derived from a camping component, and B' is an azo It is a group derived from a component, and the sulfonic acid group in any of the above forms is preferably one represented by (one or more sulfonic acid groups bonded to all or any one of A, A' and B) . Here, examples of coupling components include phenol, naphthol, 5
-Pyrazolone, pyridinol, aniline, naphthylamine, 5-aminopyrazole, and aminopyridine (all of which may have a substituent). Examples of B' derived from an azo component include (each of these groups may have a substituent).

Examples of phthalocyanine dyes include copper phthalocyanine dyes.

In the above general formula (I), examples of the cation consisting of a plurality of nonmetallic atoms represented by A cation derived from an aromatic heterocyclic base, and the general formula (■): (R5) (R2) (R3) (R')N"
, (II) (Hl, R2, R3 and R4 may be the same or different and each represents a hydrogen atom, an aliphatic group or an aromatic group).

In addition, at least one of R1, R2, R3 and R4 in the above general formula (II) is a hydrogen atom, and the others are a lower alkyl group having 1 to 6 carbon atoms or a phenyl group (carbon (optionally substituted with a lower alkyl group having 1 to 6 carbon atoms or a lower alkoxyl group having 1 to 6 carbon atoms) is preferable.

Next, examples of dyes represented by the above general formula (I) and preferably used in the present invention are listed. For convenience of display, the sulfonic acid group of each dye is [-3o3Y]
is displayed. That is, here Y is H or the above-mentioned X
(Unless otherwise noted, it represents a pyridinium cation).

Dye-1 (Yellow) Dye-2 (Yellow) OY 1'-4 Dye-7 (Yellow) Dye-8 (Yellow) Dye-1O (Yellow) Color Dye-13 (Yellow Dye-16 (Yellow) Dye -17 (yellow) Dye -19 (yellow) Dye -21 (yellow) Dye -22 (yellow) A dye having the formula of dye 21, which is Y or (02H5)3NH+ Dye -23 (yellow) Having the formula of dye 21 R5 means H, and R6 means C(CH3)3.

Dye-2'' (magenta) has dye 28, R5 has R2, and R has dye 28, R5 or Hl, and in R or dye 28, R and R
A dye that is both C2H5.

Goi-32 (magenta) R7 means H and R means C(CH3)3.

Dye-33 (Magenta) A dye having Dye-32, where R is Hl and R is.

Dye-34 (Magenta) A dye having dye 32, where R is Hl, and in dye 32, both R and R are CH25.

Dye-36 (cyan) (Cu P'c) (S O3Hm X'n)
a [(Cu P c) means copper phthalocyanine nucleus.

Taste. And preferably, okm≦0.3.1
> n≧0.7. Phthalocyanine dye-37 (cyan) Phthalocyanine dye-38 (cyan) which has the formula of dye 36 and where Y is (C2H5)3NH+ Phthalocyanine dye-39 (cyan) which has the formula of dye 36 and where Y is CXNHA Cyan) Dye 36 (7) Formula = L, YcH3oONH
Phthalocyanine dye Dye-40 (cyan) which is A Phthalocyanine dye Dye-41 (cyan) which has the formula of Dye 36 and Y is NH: It has the formula of Dye 36 and Y is C)13N)13 Phthalocyanine dye dye-42 (cyan) Phthalocyanine dye dye-43 (cyan) has the formula of dye 36 and Y is C2H3N) Phthalocyanine dye dye-43 (cyan) has the formula of dye 36 and Y is (C2H→2NH"2) Phthalocyanine dye Dye-46 (cyan), which is a phthalocyanine dye, has the formula Dye 36, and Y is (CH) 'N)I'' 5
3 Phthalocyanine dye dye-47 (yellow) Color index (C, 1,) Assynt yellow 14
The sulfonic acid group of 1 is represented by -(S○3HmXn) [however, preferred is 0 m≦0.3.
1 > n≧0.7].

The dye of general formula (I) used in the present invention is, for example, general formula (V).

D-(SO3M)p (V)(D and p
represents the above-mentioned meaning, and M is an alkali metal ion.
After obtaining a compound represented by p (VI) (D and p have the above-mentioned meanings, and Hal is a halogen atom), an organic base consisting of a plurality of nonmetallic atoms or ammonia, and a suitable It can be produced by reacting with a large amount of a proton source (preferably water or alcohol).

In addition, a compound in which D is a phthalocyanine dye moiety in general formula (Vl) can also be obtained by reacting phthalocyanine with chlorosulfonic acid.

Alternatively, the general formula (Vl) D (S O2Hal
) A proton source is applied to the compound P in advance to form D-
After preparing the sulfonic acid represented by (SO3M)p, it may be treated with a 41 base or ammonia in an amount corresponding to n.

Alternatively, general formula (VI) D (S 02 Hal
) The compound p may be reacted in advance with an organic base or ammonia to form an organic base or ammonia salt of a sulfonic acid represented by D (S03X)p, and then an appropriate amount of a proton source may be reacted thereon.

Examples of halogenating agents used in the above production method include phosphorus oxychloride, phosphorus pentachloride, chlorosulfonic acid,
Mention may be made of rolating agents such as thionyl chloride.

Examples of the proton source include water and alcohols such as methyl alcohol, ethyl alcohol, 2-propyl alcohol, and 2-methoxyethyl alcohol. Further, in this reaction operation, an appropriate amount of protic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, etc. may be used in combination.

As a method of attaching a colored resin film containing a dye represented by the general formula CI) of the present invention to a solid-state image sensor to obtain a color solid-state image sensor equipped with a micro color filter, the following method is generally used. I can do it.

A photocurable resin solution such as dichromate gelatin is applied to the light receiving area of the solid-state image sensor to form a photocurable resin layer, and the surface of the photocurable resin layer is irradiated with light that has passed through an exposure pattern to form a photocurable resin layer. Once a mosaic or stripe-shaped cured portion is generated, this resin layer is then washed with an appropriate solvent to dissolve and remove the uncured portion to obtain a mosaic or stripe-shaped cured resin layer, Next, this hard resin layer is dyed with a type of dye such as red, green, blue, cyan, macenta, or yellow represented by the general formula CI) to form a color separation filter element (colored resin film). I
form.

Next, a color contamination prevention layer was formed on the color separation filter element thus formed, and a photocurable resin layer was further formed thereon in the same manner, and another jW light pattern was passed through the surface thereof. The resin layer is irradiated with light to form another mosaic or stripe-like hardened portion. and,
In the same manner, the uncured resin portion is removed, and the cured resin layer is dyed with another dye (it is preferable to use a dye represented by the general formula (I)) to form a color separation filter element (colored resin film). Form. Further, if necessary, the operation for forming the color separation filter elements is repeated to form a desired group of color separation filters, and finally, a surface coating layer is formed to complete the formation of the micro color filter.

Furthermore, during or before and after each of the operations described in 2.
Although operations such as exposing the honding butt portion necessary for circuit formation may also be included, these operations are not directly related to the present invention, and therefore their explanations will be omitted.

Further, by subjecting each colored resin film to a surface modification treatment for preventing color staining, it is possible to omit the above-mentioned color stain preventing layer.

The color solid-state image sensor of the present invention is provided with a micro color filter made of a colored resin film colored with the dye represented by the general formula (I), in which the solid-state image sensor portion is formed of a conventionally used alkali film. Compared to the case of using metal-containing dyes, this method provides much more effective protection from contamination by harmful alkali metal components, and the risk that the resulting color solid-state image sensor will no longer exhibit the desired characteristics is significantly reduced. It becomes a color solid-state image sensor that is suitable for practical use.

Further, in the present invention, a microcolorf is attached to the solid-state image sensor.・Since the coloring of Luther's colored resin film is carried out using a dye that does not contain an alkali metal and is expressed by the above general formula (1), even if a micro color filter installation process is incorporated into the solid-state image sensor manufacturing line, there will be no alkali metal-containing dye. No contamination problems arise.

Next, examples of the present invention will be shown.

In addition, Dye-47 used in the following examples was manufactured by the method described in the following [Manufacturing Example 1], and corresponds to the above-mentioned Dye-47.

Moreover, dyes-1 to dye-35 can also be produced by the same method.

[Production Example 1] Color index (C,1,) acid yellow t4i (24g) was mixed with N,N-dimethylacetamide 48
48 ml of phosphorus oxychloride was added dropwise to this solution over 30 minutes at a temperature of 40 to 50°C. After stirring this mixture at room temperature for 1 hour, approximately 500 mM
into ice water. The precipitated crystals were collected by filtration, washed with water, and dried. In this way, sulfonyl chloride (5.5 g
) was obtained. This compound was determined by mass spectrometry.
It was found to have a molecular weight of 900 and two sulfonyl chloride groups.

The above sulfonyl chloride (5, Og) was added to N.

Dissolve in 25 m of N-dimethylacetamide, and add a methanol solution of 0.15 g of pyridine (25 m) to this solution.
was added dropwise while stirring. Then, the mixture was stirred at room temperature for 2 hours. Add 40ml of water and 35% salt to this reaction solution (40ml
m sentence) were added dropwise in sequence.

The precipitated crystals were collected by filtration, washed with dilute hydrochloric acid, and then dried in the air. This way) and Color Intex (C
, 1, > - Partial pyridinium salt of Acid Yellow 141 (- has two sulfonic acid groups in the molecule, and about 17% of the sulfonic acid groups are pyridinium salts) 2.5
I got g.

According to the measurement results of atomic absorption spectroscopy, the Na content of this dye-47 is 0.06% by weight, and the content of Na in 4 is 0.06% by weight.
It was less than 0.04% by weight.

Further, Dye-36 was produced by the method described in the following [Production Example 2], and corresponds to the above-mentioned Dye-36. Moreover, dyes-37 to dye-46 can also be produced by the same method.

[Production Example 2] After adding 10 g of copper phthalocyanine into 130 g of chlorosulfonic acid in portions at a temperature of 50°C or less, reaction 4 was carried out.
The mixture was stirred at 130°C for 4 hours.

After stirring, the reaction mixture was cooled to 35°C and heated to 80°C.
The mixture was poured into 0 ml of ice water. The precipitated crystals were collected by filtration, washed with water, and dried. In this way, copper phthalocyanine tetrasulfonyl chloride (13 g) was obtained.

The above copper phthalocyanine tetrasulfonyl chloride (1
3 g) was dissolved in 200 mJ1 of methanol and refluxed for 1 hour while stirring. After cooling this solution, 3.7 g of pyridine
was added dropwise while stirring. This solution was then diluted with 1
Refluxed for an hour. After 15 minutes of flow, the reaction solution was cooled,
The precipitated crystals were collected by filtration, washed with methanol, and then dried. Thus the formula: %Formula %) (where Pc represents a phthalocyanine, PyH represents a pyridinium cation, m is 0.125, and n is 0.
Dye-36 (cyan) 12 represented by 875)
I got g. According to the results of atomic absorption spectroscopy,
The Na content of this dye-36 was 0.02% by weight, and the K content was 0.02% by weight or less.

[Example 1] On the undercoat layer of a CCD type solid-state image sensor (the surface of which is provided with a protective layer made of phosphosilicate glass and an undercoat layer made of a transparent organic polymer compound) A dichromate gelatin photocurable resin layer was provided, and a mask (exposure pattern) consisting of a mosaic pattern was placed on this layer to perform contact light writing. Next, the exposed resin layer was washed with hot water to elute and remove the uncured portions of the resin, leaving a cured resin layer consisting of mosaic-like convex portions.

This cured resin layer was dyed with dye-47 to prepare a colored (yellow) resin film I.

Next, on the colored resin film thus formed, a color stain prevention layer was formed using ethyl p-phenylene diacrylate-1,4-bis(β-hydroxyethoxy)cyclohexane, and a layer for preventing color staining was further formed on top of the colored resin film. A photocurable resin layer was formed, and the surface of the photocurable resin layer was irradiated with light that had passed through another exposure pattern to generate another mosaic-shaped cured portion in the resin layer. Then, remove the uncured resin part in the same way, dye the cured resin layer with dye-36, and color (cyan) the resin film.
was prepared.

Finally, a part of the micro color filter was formed by forming a surface coating layer using ethyl p-phenylene diacrylate-1,4-bis(β-hydroxyethoxy)cyclohexane, and a color solid-state image sensor was obtained. .

[Examples 2 to 15] Color solid-state imaging devices were obtained in the same manner except that the dyes for dyeing the colored resin film and the colored resin film (1) were changed to the dyes listed in Table 1, respectively.

In addition, each dye used in the following examples corresponds to the dye number mentioned above. Table 1 Example Colored resin film Colored resin film ■2
Dye 1 Dye 363 Dye 4
Same as above 4 Dye 5 Same as above 5 Dye 6 Same as above 6
Dye 8 Same as above 7 Dye 9
Same as above 8 Dye 10 Same as above 9
Dye 11 Same as above 10 Dye 15 Same as above 11 Dye 21
Same as above 12 Dye 22 Same as above 1
3 Dye 24 Same as above 14
Dye 25 Same as above 15 Dye 27
Note as above: Each of the above dyes is used in Production Example 1 above.
The sulfonic acid group in each dye is pL-type sulfonic acid group [303H] and the salt form sulfonic acid group [5o3X (however, dye 22, pL-type sulfonic acid group [5o3X)]
．． 25 and other than 27, X is a pyridinium cation, that is, the ratio of the general formula (I
) is as shown in Table 2 below.

Table 2

Claims (1)

[Claims] The colored resin film of the 10 micro color filter has the general formula (
I): D (S O3Hm X n ) p (1
) (where, D is a dye moiety, X is a cation consisting of multiple nonmetal atoms, m and n are each a numerical value of 0 or more and less than 1, provided that m + n = 1, and p is an integer of 1 to 6 1. A color solid-state image sensor, characterized in that it is colored with a dye represented by 2゜Claim 1, characterized in that X in general formula (I) is a cation derived from an aromatic heterocyclic base
The color solid-state image sensor described in . 3. The color solid-state imaging device according to claim 2, wherein X in the general formula (I) is a pyridinium cation which may include a substituent. 4. The color solid-state imaging device according to claim 2, wherein X in the general formula (I) is a quinolinium cation which may include a substituent. 5゜X in general formula (I) is general formula (■): (R') (R
2) (R3) (R4) N+ (ff) (Tatashi, R
”, R2, R3 and R4 may be the same or different and each represents a hydrogen atom, an aliphatic group or an aromatic group). 6. The color solid-state imaging device according to any one of claims 1 to 5, characterized in that D in the general formula (I) is a dye moiety.7. D in general formula (I) of the color solid-state imaging device according to any one of claims 1 to 5, wherein D in I) is a binuane dye moiety.
The color solid-state imaging device according to any one of claims 1 to 5, wherein is a phthalocyanine dye moiety. 9. The color solid-state image sensor according to claim 1, wherein n in formula (I) is larger than m. 10. The color solid-state imaging device according to claim 9, wherein n in the general formula (I) is twice or more m.