JPS5944005A - Solid-state color image pickup element - Google Patents

Abstract

PURPOSE:To eliminate danger of alkali metal contamination from a solid-state image pickup element, by using a dye represented by a specified general formula to prepare the colored resin film of a microcolor-filter attached to this element. CONSTITUTION:To prepare the colored resin film of a microcolor-filter, a dye represented by the following general formula: D-(SO3H)m ( I ) is used for said coloring with or without another dye. In said formula ( I ), D is the moiety of dye, and (m) is an integer of 1-6. As the dye corresponding to the moiety of D, azo dyes, bisazo dyes, phthalocyanine dyes, etc. are usable.

Description

[Detailed description of the invention] 7. The present invention relates to a color solid-state image sensor.

For example, in a VTR camera or the like, in order to extract a color signal that corresponds to a color image, light reception t";
Color photography 1t with micro color filter installed on H
'i'i・or more commonly used. These colors 1 and 1'&'i'i are represented by, for example, 4Φ type imaging called Sachicon, Himicon, etc./'1.

On the other hand, recently, as a device to replace the image pickup tube, for example,
As various solid-state imaging 1ψ elements such as CCD, BBD, and MOS have been developed, small-sized devices such as the V'r RI11 camera described in "L" have been developed. With the main purpose of achieving 11 colors, tests are being conducted on the practical application of a color solid-state image sensor that combines a solid-state image sensor and a micro color filter, and δ-I has already been put into practical use.

A color solid-state image sensor is a solid-state image sensor that consists of a photoelectric conversion element that has minus-sized pixels and Ilf, and a flat image sensor integrated circuit (IC) that integrates a scanning circuit. 5111, green, l' corresponding to each pixel
1, Noan, macenta, and yellow microscopic color separation filters; +3? ' + color resin 11ζ or mosaic or stripe shape with several 4Φ 1'h4IJt
Is this a white micro color filter or is it an old one?
It consists of 4 IX 11 components.

1 ton of color solid-state photography! The device is manufactured by a single person, which is referred to as ``one person bonding'' or ``one person on wafer''.

Among these methods, the bonding method forms micro color filter V by forming color-separate filter elements, .
Manufactured and attached to the surface of the solid-state image sensor! 1 to form a color solid-state image sensor. Therefore, in this method, when adhering independently manufactured micro color filters to the surface of the solid-state imaging device, each color separation filter element is attached to each pixel of the solid-state imaging device in a single density so that each pixel corresponds accurately to each pixel of the solid-state imaging device. Control operations are required.

On the other hand, the on-wafer method is a method in which a surface microcolor filter is formed on a solid-state image sensor. Therefore, this on-uni/\- method can be incorporated into the manufacturing process of solid-state imaging devices, and has the advantage of facilitating the manufacturing of color solid-state imaging devices.

Note that in the off-wafer method, a wafer 1. By forming a color separation filter element corresponding to each pixel of each solid-state imaging element, a large number of color solid-state imaging devices can be used. A method for manufacturing 44-1 is shown in FIG. A method of manufacturing a color solid-state image sensor (on-chip method) is known, but in the Mizuhiki IfIII document, any of these methods' is included in the on-wafer method.

As mentioned above, solid-state image sensors consist of a plate-shaped IC in which a photoelectric conversion element and a scanning circuit are highly integrated, and for this reason, solid-state image sensors are free from dirt, dust, alkali metals, etc. Contamination by representative impurities is extremely f
It is something that is in. A solid-state imaging device contaminated with such a blunt object often does not retain the predetermined characteristics. This is directly linked to a decrease in the yield of A-product. Therefore, even in the 1° culm where a micro color filter is installed in the solid-state imaging hole, a high degree of resistance is taken to avoid contamination with such impurities as much as possible.

Based on the technical background as described in 1 above, the present invention is based on the technical background described in 1. The object of the present invention is to provide a color solid-state imaging device that can minimize the risk of alkali metal staining of the solid-state imaging device by using a dye that does not contain the dye.

That is, the present invention provides that the alcoholic resin film of the micro color filter has the following formula (I): Q (SOa H)m (I) (however,
D is a dye portion, and m is an integer from 1 to 6).

Next, the present invention will be explained in detail.

In the present invention, when preparing a stone Buddha resin film of a micro color filter formed on the surface of the light receiving part of a solid-state imaging element, a part of the pigment is used instead of various alkali metal-containing pigments that have been conventionally used as the pigment. Or a pot of pot”
By using a dye represented by the formula (■): D-(503H)m (I), r,! 71
An object of the present invention is to provide a color solid-state imaging device in which the risk of contamination of the body imaging device with alkali metals is prevented as much as possible.

In the general formula (I) shown below, D represents a dye moiety, and m represents an integer of 1 to 6.

Preferred examples of the dye corresponding to the dye moiety D include:
Mention may be made of azo dyes, bisazo dyes, and phthalocyanine dyes.

As an azo dye, the general formula (■): A-N=N-B (n) (tatashi, no)
are derived from Camplink components and are 0, I, 1. ,
Therefore, B is derived from the an component i^, (and, ``River, 5self's -(S Oa H)□ becomes, (is, A
Preferably, it is expressed as and (combined with both forces of iB, or with one of the forces). Here, examples of power and link components include phenol, nano-1-l, 5
- pyranhone, pyricinol, aniline 4-naphthylamine, 5-aminopyrasol, and aminopyridine (all of which may be substituted)
can be listed.

Further, as examples of 7-I&min, aniline, naphthylamine, and aromatic heterocyclic amine (all of which may have a substituent) can be mentioned.

The general formula (■) = A-N = N-B
'-N=N-A' (III) (], A and A'' may be the same or different, and from the campliner component, 1f5z9 represents ノ, (,
B'' is induced by the azo component)1(, and the above -(SOaH)m), (is all or any of A, A', and B, or any one of them or It is preferable to use a compound represented by the following formula (in which a plurality of particles are tied together). Here, examples of the force and link components include phenol and naphthol.

5-pyrasolone, viridinol, aniline, naphthylamine, 5-aminopyrazole, and aminopyridine (
These can include (all may have substitutions) and (may have). Further, examples of Bo which is 119 from the azo component include (these names) 1 (both are substituted) and (even if 1 is substituted).

As an example of fucrocyanine inclusion, mention may be made of copper phthalocyanine dyes.

Next, an example of the color J, which is represented by the n-bag formula (1) of No. 1111 and is preferably used in Mokukomei, will be given.

oH 11--, -3 (yellow) Bo3)+ Color, (, -6 ((two rows) Dye-9 (yellow) o　H o　H Dye-12-(: (yellow) S03H803H Dye-14 (yellow) Colored egg 2” 6 (yellow) S03H80311 R5 means H and R6 means C(CH3)3.

Dye-23 (magenta) - Dye 22 is I1, R5 or Hl, and R6 is Dye 22.
In this case, both R and R are C2H5.

Dye-Color"-(Eshijidoichimetsu-) R7 means H, and R8 means C(C)I3)3.

Dye-17 (Magenta) has dye 26, R7 is Hl and R8 is color 7 east 26
A dye in which R is R2 and R<=color (in 926, R and R) (C2H5)2.

l-30 (cyan) (cuPc)-(503-H+)a [(CuPc) tastes copper phthalocyanine nucleus] Pigment-31〈:f yellow) Color inch 5. Cus (C, 1,) An-, I. Ieroni 141 sulfone brew.

For the dye 1 of the formula 111λ used in the present invention, for example, the general formula (m: D C3Oa M) m (IV) (]D
represents the G taste described in +iii, and Mlf is an alkali metal ion).
Hal ) m (V) (D represents the above-mentioned meaning, and Hal is a halogen atom) is obtained, and then it can be produced by refluxing it with an alcohol. Alternatively, by ion-exchanging the compound represented by general formula (IV), -
It can also be converted into a dye of formula (I).

Examples of halogenating agents used in the production method described above include phosphorus oxychloride, phosphorus pentachloride, chlorosulfonic acid,
Mention may be made of rolating agents such as thionyl 94ide.

As a way to make a color solid-state image sensor equipped with a micro color filter by installing a colored resin film containing a dye represented by the general formula (I) of the present invention on a solid-state image sensor, the following method can be used. method can be used.

A photocurable resin layer is formed by coating the light-receiving part of the solid-state image sensor with a photocurable resin solution such as a weight roll or anti-gelatin.
The surface is irradiated with light that has passed through the exposure pattern, and +
A mosaic or strip-like cured portion i1B is generated on the AI fat layer. Next, this resin layer is
By washing with a suitable solvent, the unsaturated resin layer is dissolved and removed, leaving a mosaic-like or slender curved cured resin layer, and then this cured phase is removed. 11ti layer,
is dyed with a red, green, magenta, or yellow pigment represented by the general formula (I) to form a color separation filter AI element (71-color resin film). .

Next, one of the color separation filter loess formed in this way is
1 layer of color 7 colored μ horn is formed on -1; The passed light is ij (Qj
Then, another mosaic-like or stripe-like hardened portion is generated in the tree layer. Then, in the same manner as in 1-1, remove the uncured resin part, dye the cured resin layer with another dye (preferably a dye represented by general formula (I)), and dye the color separation filter ocher (six-color resin film). )■ form. Roughly speaking, if necessary, this operation for forming color separation filter elements is repeated to form a group of nine color separation filters, and finally, a surface coating layer is formed to form a micro color filter. Complete.

In addition, during or before and after each operation in 1-,
The process may also include an operation to expose the bonding band portion necessary for circuit formation, and since these operations are not directly related to the present invention, their explanation will be omitted.

Another person! By subjecting the color resin 11 to a surface modification treatment to prevent color staining, the provision of the color stain prevention layer described above can be omitted.

The color solid-state image sensor of the present invention is provided with a micro color filter 4-J made of a colored resin 11 colored with the dye represented by the general formula (I). Compared to the case where an alkali metal base is used, it is much more effectively protected from contamination by harmful alkali metal components, and there is a risk that the color solid-state image sensor will not exhibit the specified characteristics. As the name suggests, it has a low r, making it an excellent color solid-state imaging device for practical use.

Mayu, 74-In Jyoake, fixed camera whale 7th 8th mouth 1 set-4-67□fri a force-Filkuno 2'i village +
AI 1 piece 11 patterns 071 colors or 7 colors expressed by the general formula (1) of 111, since it is carried out using a pigment that does not contain sigma, fixed-shooting whale JS r3. Even if a micro color filter and a single filtration filter are installed in a JI-in, the problems caused by alkali metals will not occur.

/'A: 7+ indicates an embodiment of the invention.

/j: O, the color used in the following example, L, -31 is the color described in 14-made Chichinomata, 11, by the method described in the following [Kesha Good Example 1], L- This corresponds to No. 31.

Yo/2 Dye-1 to IQ-29 were constructed using the same method, and are in parallel to the above-mentioned color numbers.

[A,′! ] Ancient example 1] Color・r-ntex (C, 1,)・reed・)・1ζ・
Add r Yellow 141 (24 g) to this solution with 48 m of N,N-dimethylacetamide.
Oxy 11 conversion 748 m SL over 30 minutes 40
-50°C? I, dripped at A degree. This mixture
After stirring for 1 hour at room temperature, the mixture was poured into about 500 m of ice water. The precipitated crystals were collected by filtration, washed with water, and dried.

In this way, sulfonyl chloride (5.5 g) was purified.

Add 2 sulfonyl chloride (5.0 g) of methanol to
It was dissolved in 00m and boiled. Pour this solution under pressure for half a hour.
After adding 1 amount of agricultural shrinkage to J, add 1 amount of agricultural shrinkage solution to a box of hydrochloric acid (35%'
JAM 5 m St/water 100 mF).

The AJi crystals were collected by filtration, washed with kondanbutai, and then dried in the air. In this way, 1.5 g of dye-31 (yellow) was prepared.

According to the A11 constant results of absorption spectroscopy, the Na content of this dye-31 is 0.05 73i%, and (the content is 0,03% Tii%). Ta.

In addition, Dye-30 was produced by the method described in the following [Manufacturing Example 2], and corresponds to the above-mentioned Dye-30. After being charged in portions into Northulfone liquor at a temperature of 509C or less, the mixture of Aki and I1 was IW stirred at 130C for 4 hours.

11.2 After the end of stirring, the reaction mixture was cooled to 35°C and poured into an 800 m tube in water. The precipitated crystals are 1
It was taken care of, washed with water, and kept dry. In this way, copper phthalonanoanineteIrasulfonyl chloride (13 g) and l!
Copper phthalocyanine tetrasulfonyl chloride F (1)
Dissolve 3g) in 200m methanol and heat it. 6L
did. After crystallization, the reaction solution was drained, one core of the precipitated crystals was collected, and the crystals were washed with methanol and dried. Thus, the formula (CuPc)-(
SO3H+) 4 (CuPc represents copper phthalocyanine) 8g of J-30 (cyan), a color expressed as 4, was removed.

J! According to the 4111 constant results of IC r-absorption spectroscopy,
The Na content of this dye-30 is 0.05 weight I11%,
And, K-kaiiai,i, was 0.02 fold hY% or less.

[Example 1] CCD type solid-state image sensor (transparent image sensor with the purpose of increasing the damage to the solid-state image sensor f on the solid-state image sensor with a protective layer consisting of a ring and a glass on the surface and a micro color filter) A 0.7 micron thick rotary acid gelatin photocurable resin layer is provided on the undercoat resin layer (1) of the undercoat resin layer made of a high-density A compound, and this 1- is covered with a mosaic. A mask consisting of a pattern (ν■ light pattern) was placed and exposure was carried out for 11 days. Next, the exposed 10M resin layer was washed with warm 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-31 to prepare a colored (yellow) resin film (2).

Next, p-phenylene diacrylate ethyl-1,4-bis(β
- Form a colored dye-proof layer using (hydroxyethoxy)cyclohexane, then form a photocurable resin layer on top of it in the same manner, and irradiate the surface with light that has passed through another light-changing pattern. This produced another mosaic-like cured portion in the resin layer. Then, remove the uncured resin part in the same way, and dye the cured resin layer with dye-30 to color it (cyan).
Tree 11'n114', II was prepared and P-
A part of the macro color filter is formed by forming a surface coating layer using ethyl phenylene diacrylate-1,4-his(β-H-roxy-I-xy)cyclohexane, and a color solid-state imaging film is formed by forming a surface coating layer using ethyl phenylene diacrylate. I started r.

[Examples 2 to 15] The dyes for dyeing A° 5 Color Resin ++2 I and Colored Resin 11 G Color solid-state image sensors are finished.

In addition, each dye used in the following examples corresponds to the dye number mentioned above. -Colored resin film ■ Soft color resin 1 pattern ■ 2
Dye 1 Dye 303 Dye 4 Same-L4 Color, also 5
Same] ;5 Dye 6 Same as above 6 Dye 8 Same as above 1-17
Dye 9 Same 1-8 Dye 10.
Same 1=9 Dye 11
Same as above lO dye 15 Same'2

Claims (1)

[Claims] The colored resin film of the 10 micro color filter has the 11Q formula (I): D-(So,H) m (I) (where D
is a dye portion, and m is an integer from 1 to 6). 44. The color solid-state imaging device according to claim 1, wherein D in the general formula (I) is 41f01 representing an azo dye moiety. 3. The color solid-state imaging device according to claim 1, wherein D in formula (I) of 3°11'A is a bisazo dye moiety. 4. The color solid-state imaging device according to claim 1, wherein D in the general formula (I) is a phthalocyanine dye moiety, which is a #Jf symbol.