JPS62108204A - Color filter - Google Patents

Abstract

PURPOSE:To obtain the titled filter having a deposited red coloring layer which has excellent properties of spectral characteristics, thermal resistance, and solvent resistance by patternwisely forming the layer contg. a red coloring matter deposited a specific magenta and yellow coloring matters on a substrate. CONSTITUTION:The resist pattern 2 is formed on the substrate 1 to form a mask. The coloring matter layer 3 is formed by depositing the magenta coloring matter of quinacridone type and the yellow coloring matter of isoindolinone type or the magenta coloring matter of quinacridone type and the yellow coloring matter of an anthraquinone type using said mask. The layer 4 contg. the red coloring matter of the stripe pattern type is formed by removing the resist pattern 2 and the layer 3 thereon, by dipping said substrate in a solvent which does not dissolve the coloring matter to obtain the titled filter. The titled filter may be provided with a protective layer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a color filter, and particularly to a CCn filter.
(charge, coupled, device), BBD (packet, bricate, device), CID C charge, injection, device), BASIS (base, store type, image sensor), color image sensors, color sensors, color displays, etc. This invention relates to a color filter for fine color separation.

[Conventional technology]

Traditionally, color filters have been made using gelatin,
A dyed color filter is known in which a mordant layer made of a hydrophilic polymer material such as casein, gris, or polyvinyl alcohol is provided, and the mordant layer is dyed with a dye to form a colored layer.

In this dyeing method, many dyes can be used, and it is relatively easy to meet the spectral characteristics required for filters. It uses a dipping method that is difficult to control, and also has the disadvantage of poor yields because it involves a complicated process of providing an interlayer for resist dyeing for each color. In addition, the heat resistance of the dyes that can be used is 1
The temperature is relatively low at about 50 to 160°C, making it difficult to use in processes requiring thermal treatment.

On the other hand, a vapor deposition method is known in which a thin film of dye or pigment is formed as a colored layer by a vapor deposition method such as vapor deposition (Japanese Unexamined Patent Publication No. 55-14840θ, etc.).

According to this method, the colored layer can be formed from the dye itself, so the colored layer can be formed thinner than in the dyeing method, and the color filter can be made thinner. Also, since it is a non-aqueous process, the management and control of the process is easy. Additionally, the vapor-deposited dye layer generally has good heat resistance due to the characteristics of the vapor-depositable dye.

Furthermore, it also has the advantage that a photolithography process can be directly applied as one of the methods for patterning the colored layer. However, the vapor deposition method has not been widely used so far because it is not easy to select available dyes suitable for vapor deposition.

By the way, when looking at color filters from the perspective of dyes, dyes for color filters are required to have the following characteristics. First of all, it must have appropriate spectral characteristics as a color separation filter.

In addition, from a manufacturing method point of view, even if the spectral characteristics are good, dyes lack manufacturing stability or require special processing steps, leading to a decrease in yield, making them unsuitable for color filters. Put it away.

Therefore, as a dye for color filters, it is necessary to select an optimal dye that is well-balanced in terms of both spectral characteristics and manufacturing.

In particular, the vapor deposition method has strong manufacturing constraints as it must be heat resistant, easy to evaporate, and withstand solvent treatment in the photolithography process, and the dyes that can be used are limited. Although thinly coated color filters have various advantages over dyeing methods, they have not become widespread.

By the way, the characteristics required of the dye used in vapor-deposited filters are that it can be vapor-deposited as mentioned above, that it can withstand solvents and heat treatment in the photolithography process using the resist after vapor-deposition, and
In addition, it has well-balanced spectral characteristics as a filter, and quinacridone-based magenta dyes are known as dyes that relatively satisfies these characteristics.

However, although the quinacridone-based magenta dye has excellent vapor deposition properties and solvent resistance, its spectral characteristics include a blue spectral component, and it is not necessarily satisfactory as a dye for forming a red colored layer.

[Problem that the invention seeks to solve]

The present invention has been made in view of these problems, and the main objects of the present invention are to solve the problems of the red spectral characteristics of the quinacridone magenta dye, and to The object of the present invention is to provide a vapor-deposited color filter having a red colored layer that has excellent spectral characteristics and also has excellent heat resistance and solvent resistance by utilizing the excellent vapor deposition properties and solvent resistance.

[Means for solving problems]

To achieve the above object, the present invention provides a color characterized by having a red dye layer formed by vapor-depositing a quinacridone magenta dye and an isoindolinone yellow dye, or a quinacridone magenta dye and an anthraquinone strong color dye. It's a filter.

In other words, the color filter of the present invention utilizes a quinacridone magenta dye with excellent heat resistance and solvent resistance, and also uses an isoindolinone yellow dye or anthraquinone yellow dye to improve the color of the quinacridone magenta dye. It has a colored layer that cuts blue spectral components and exhibits excellent spectral characteristics as a red color.

The red dye layer of the color filter of the present invention is usually formed by successively depositing a quinacridone magenta dye and an isoindolinone yellow dye, or by sequentially depositing a quinacridone magenta dye and an anthraquinone dye. . However, mixing or simultaneous vapor deposition of quinacridone magenta dye and isoindolinone yellow dye,
Alternatively, a quinacridone magenta dye and an anthraquinone dye may be mixed and dispersed by mixing or co-evaporating a quinacridone magenta dye and an isoindolinone yellow dye or anthraquinone dye.

The film thickness or deposition amount of such a red dye layer is appropriately determined depending on the desired spectral characteristics of the color filter.

In the case of a laminated structure, the film thickness is usually 500~
l0QOOA is appropriate. Of course, in the case of mixing and dispersing, the object of the present invention can be fully achieved with a single layer structure, but if desired, two or more layers with different dispersion ratios may be sequentially laminated. In this case as well, the film thickness is
500-100OOA is appropriate for each.

The quinacridone magenta dye used in the present invention is
It has a basic skeleton represented by the following formula CI) and also includes derivatives thereof.

Examples of the derivative include the following, and these may be used alone or as a mixture thereof.

Specific examples of such quinacridone-based magenta dyes include commercially available ones (product names) such as Lionogen Recdo 2B (manufactured by Toyo Ink), Lionogen Magenta R (manufactured by Toyo Ink), and First Gain Super Magenta R, RS. Examples include Syncasia Red BRT (manufactured by Dainippon Ink), YRT (manufactured by DuPont), and Syncasia Violet BRT (manufactured by DuPont).

Quinacridone-based magenta dyes are thermally stable and do not decompose at high temperatures, but they easily evaporate when the temperature exceeds a certain level, making it extremely difficult to form a thin dye film by vapor deposition. suitable.

The thin film of quinacridone magenta dye formed by vapor deposition is not a loose film as is often seen in organic films, but is extremely dense and adheres strongly to the surface of inorganic materials such as glass, and has excellent physical properties as a vapor deposited film. It is something.

However, as mentioned above, in order to exhibit the excellent spectral characteristics of the red color, it is necessary to cut the blue spectral component, that is, perform color correction using a coloring dye.

The dye used for color correction of such a quinacridone-based magenta dye must be a yellow dye that can cut most of the blue spectral components, and since it is formed by a vapor deposition method, it must have vapor deposition properties comparable to quinacridone-based magenta dyes. Although it is necessary to have solvent resistance, the isoindolinone-based or anthraquinone-based yellow dye used in the present invention satisfies all of these properties, and in combination with the quinacridone-based magenta dye, it is an excellent vapor-deposited dye. This makes it possible to form a red colored layer.

The isoindolinone yellow pigment, which is one of the yellow pigments used in the present invention, has an aromatic condensed polysensitive structure containing a petro atom, and is basically represented by the following formula (II). be able to.

(However, R represents a divalent organic group.) 4.5. Ef,
Although those in which the 7-position is not substituted with chlorine may also be included, substituted types are preferred in terms of light resistance and solvent resistance.

An example of a typical isoindolinone yellow pigment is the formula (
R in II) is listed as follows.

CH3CH3 However, the isoindolinone yellow pigment in the present invention is
It is not necessarily limited to these.

Specific examples of such isoindolinone yellow pigments include commercially available products (trade names).

Irgazin yellow 2aRt, at, tE, 2aLri
1 (manufactured by Ciba Geigy) Lionogen Yellow 3GX (manufactured by Toyo Ink) First Gen Super Yellow GR, GRO, GROH (manufactured by Dainippon Ink) Irgazine Yellow 2RLT, 3RLT, 3RLTN (manufactured by Dainippon Ink)
(manufactured by Ciba Geigy) Lionogen Yellow RX (manufactured by Toyo Ink) Resol Fast Yellow 1840 (manufactured by BASF) Kayaset Yellow E-2RL, E-3RL17B (manufactured by Nippon Kayaku) Cromophthal Orange 2G (manufactured by Ciba Geigy), etc. .

Another yellow pigment used in the present invention, an anthraquinone yellow pigment, has, for example, a structural formula as exemplified below.

However, the anthraquinone yellow pigment in the present invention is not necessarily limited to these.

Specific examples of such anthraquinone yellow pigments include commercially available products (trade names).

Kuromonotaru Yellow A2R (manufactured by Ciba Geigy) C, 1, No, 70800
Helio First Yellow E3R (manufactured by Bayer) Paliogen Yellow L15ElO (manufactured by BASF) C,1,? to, 88
420 Kaya Set Yellow To R (Nippon Kayaku) C:, 1. No. 85049
Chromophthal Yellow AGR (manufactured by Ciba Geigy) Pipelast Yellow E2G (manufactured by Bayer) Nihonthrene Yellow GCN (manufactured by Sumitomo Chemical) C, 1, No, 67300 Mikethrene Yellow GK (manufactured by Mitsui Toatsu) (:, 1. No, 81725
Indanthrene Printing Yellow GOK (manufactured by Hoechst) C, 1, No, 59100 Anthrazole Yellow V (manufactured by Hoechst) C, 1, No, 80531 Mikethrene Solicoble Yellow 12G (manufactured by Mitsui Toatsu) C, 1, No, 80805 Mikethren Yellow CF (manufactured by Mitsui Toatsu) C, 1, No, 88510 Nihon Thren Yellow GCF (manufactured by Sumitomo Chemical) C, 1, No, [f5430
Indanthrene Yellow 3G (manufactured by Bayer) C, 1, No, 85405 Dihonthrene Yellow 4GL (manufactured by Sumitomo Chemical) Indanthrene Yellow 5GK (manufactured by Bayer) C, 1, No, 85410 Paranthrene Yellow PGA (manufactured by BASF) C, 1, No. 884
00 Cibanon Yellow 2G (manufactured by Ciba Geigy) Indanthrene Yellow F2GC (manufactured by Hoechst) Anthrazole Yellow ICG (manufactured by Hoechst) Indanthrene Yellow 5CF (manufactured by BASF) Mikethrene Yellow 3GL (manufactured by Mitsui Toatsu) Indanthrene Yellow LGF (manufactured by BASF) Monolite Yellow FR (manufactured by Tar), Kayaset Yellow E-AR (manufactured by Nippon Kayaku), etc.

The isoindolinone-based yellow pigments and anthraquinone-based yellow pigments are extremely stable thermally due to their basic skeleton, which is an aromatic condensed polycyclic structure, and do not decompose even when heated, and do not decompose when heated to a certain temperature or higher. It has the property of being easily evaporated, and like the quinacridone magenta dye described above, it is extremely suitable for forming a thin dye film by vapor deposition.

In addition, the thin film of isoindolinone-based fungal color dye or anthraquinone-based yellow dye formed by M-adhesion is not a loose film often seen in organic films, but is extremely dense and glassy, similar to that of quinacridone-based magenta dye. It also adheres strongly to the surface of inorganic materials such as
It has excellent physical properties as a deposited film.

Furthermore, the vapor-deposited films of these quinacridone magenta dyes, isoindolinone yellow dyes, and anthraquinone yellow dyes have excellent resistance to organic solvents, as well as poor solvents such as alcohols, ketones, esters,
It hardly dissolves in good solvents such as ether alcohols and halogen solvents, and does not cause any change in spectral characteristics.
τj, there is no problem at all even when development is performed, and the fine processing of the dye layer can also be carried out easily.

It is extremely suitable for manufacturing fine color filters, etc.

As mentioned above, the red dye layer of the color filter of the present invention uses the above-mentioned quinacridone magenta dye and an isoindolinone yellow dye or an anthrahonone yellow dye, and usually a quinacridone magenta dye and an isoindolinone yellow dye. It is formed by sequentially depositing an indolinone yellow dye or a quinacridone magenta color and an anthraquinone dye, but mixing or simultaneous vapor deposition of a quinacridone magenta dye and an isoindolinone yellow dye,
Alternatively, a mixture or simultaneous vapor deposition of a quinacridone magenta dye and an anthraquinone dye may be used.

Next, patterning of the basic dye layer when forming the color filter of the present invention will be explained.

One typical patterning technique for the M dye layer is:
There are dry etching method and lift-off method.

In the dry etching method, a resist pattern with a shape corresponding to the pattern to be formed is provided on a vapor-deposited dye layer provided on a substrate such as glass, and the vapor-deposited dye layer is etched using plasma or ion etching using the resist pattern as a mask. A dye pattern is formed by removing parts of the substrate other than those covered by the mask. (Unexamined Japanese Patent Publication No. 58
-349E11, etc.), this method does not require the formation of an intermediate layer as in the dyeing method, but instead a resist mask remains on the dye pattern, and furthermore, this mask can be removed without causing any damage to the dye layer. Since it is extremely difficult to do so, the result is a two-layer structure in which a substantially optically unnecessary resist mask is laminated on the dye layer.

On the other hand, in the lift-off method, for example, a resist pattern having a shape corresponding to the pattern to be formed is first provided on a substrate using a substance that can be dissolved in a developer, such as a resist, and then this resist pattern is A dye layer is deposited onto the provided substrate. In this way, a resist pattern is formed on the substrate below the dye layer to be removed.Next, this substrate is treated with a developer, during which the resist pattern is dissolved or peeled off. removed from the substrate. that time.

Together with the resist pattern, the dye layer located on this resist pattern is also removed from the substrate.
The colored layer is patterned on the substrate (the portion directly laminated on the substrate is left on the substrate). Therefore, according to the lift-off method, unnecessary portions of the colored dye layer can be physically removed from the substrate without any direct effect on the vapor-deposited dye layer on the substrate.

The resist used for patterning by the lift-off method of the dye layer can be either negative or positive type, as long as it can be peeled off or dissolved from the substrate when removed from the substrate using a developer later. In general, crosslinking progresses when exposed to radiation, and a solvent with strong dissolving power is required to dissolve it.

Therefore, it is not preferable because it tends to damage or dissolve the dye layer.

In this regard, with positive type resists, especially if the entire surface is irradiated with radiation after the resist pattern is formed, the resist becomes soluble in the developer, so compared to negative type resists, it is possible to select a solvent that is less likely to dissolve the dye, making it suitable for lift-off. It is. In addition, positive resists have a wide variety of resin components, and the solvents used for coating and development also vary. - As an example, a positive resist mainly composed of fluorine-containing methacrylate shown in the following structure as the t-position can be cited as a preferable example. This resist dissolves well not only in good solvents with high solubility such as esters, aromatics, and halogenated hydrocarbons, but also in poor solvents with low solubility such as alcohols, which affects the dye film. This is because less solvent can be used.

Such resists include FPM 210. FBM
llo and FBM 120 (both trade names manufactured by Daikin 1 Gyo).

(2) Here, R1 and R2 are hydrogen or an alkyl group, and R3 is an alkyl group in which at least one fluorine is bonded to each carbon.

Examples of typical combinations of R2, R2 and R3 include the following.

As other resists, various types of resists commercially available under the following trade names can be used as appropriate.

AZ series: 111, 119A, 120, 340,
1350B, 135QJ.

1370.1375, 1450, 1450J, 147G
, 1475, 2400, 2415° (manufactured by Shipley) Waycoat: HPR-204
, HPR-205°HPR-206, HPR-207,
)IPR-1182, Waycoat: MPR(
(Manufactured by Hunt) Kodak Micro Positive Resist (Nioda
k Micro Po5itive Re5ist)
8H (manufactured by Kodak) Isofin Positive Resist (Isofin)
e Po5itive Re5ist) (manufactured by Micro Image Technology) P (: 129,129SF
(manufactured by Polychrome) OFPRII: 7
7.78,8000EBR: 1000,1010.1
0300DUR: 1000,1001,1010,1
013.1014 (manufactured by Tokyo Ohkasha) EBR: 1, 9 (manufactured by Toshi) F
MR: Eloo, EIOI (Fuji Pharmaceutical Co., Ltd.) Jenis R Positive Photoresist (JSRPo5itive Photoresis)
t) PFR3003 (manufactured by Nippon Gosei Rubber Co., Ltd.) Selectilux P (manufactured by Merck & Co., Ltd.) The vapor-deposited dye layer is patterned by the patterning process as explained above, and the vapor-deposited dye layer is formed for each color of the color filter. After repeating this patterning process to form a patterned dye layer of multiple predetermined colors, it is desirable to provide a protective film on these dye layers. This is to prevent this and protect the dye layer from various environmental conditions. Various commonly known methods can be used to form this protective film.

Preserves the pigment layer! Examples of materials that can form a film include polyurethane, polycarbonate, silicon,
Organic resins such as acrylic polyparaxylylene, Si3
N, ,5i02, Sin, Al2O3, Ta2O
Inorganic films such as No. 3 are listed, and materials selected from these are spin-coded and de-impeded.

A protective layer can be formed on the vapor-deposited dye layer by a coating method such as a roll coater or a vapor deposition method. For forming this protective layer, it is also possible to use various photosensitive resins, such as various resists.

The patterning of the vapor-deposited dye layer as described below can be carried out on a suitable substrate, and the substrate used can be one on which one dye can be vapor-deposited, and the formed color filter has a predetermined function. However, it is not particularly limited.

For example, specifically, the following can be used as a substrate. A glass plate, an optical resin plate, a resin film or plate such as gelatin, polyvinyl alcohol, hydroxyethyl cellulose, methyl methacrylate, polyester, butyral, polyamide, or a patterned dye layer is formed integrally with the one applied as a color filter. It is also possible. Examples of substrates in this case include the display surface of a cathode ray tube and the light receiving surface of an image pickup tube.

Examples include wafers on which solid-state imaging devices such as CGD, BBD, CIO, and BASIS are formed, liquid crystal display surfaces of contact type image sensors using thin film semiconductors, photoreceptors for color electrophotography, and the like.

If it is necessary to further increase the adhesion between the vapor-deposited dye layer and the underlying substrate, such as glass, apply a thin layer of polyurethane resin, polycarbonate resin, silane coupling agent, etc. to the glass substrate before applying the vapor-deposited dye. Forming a layer is even more effective.

Hereinafter, a typical method for forming a color filter of the present invention will be described with reference to the drawings, taking as an example the case of forming a red stripe filter.

First, a positive resist is spin-coated onto a desired substrate using a spinner. After drying, the resist layer is prebaked under appropriate temperature conditions. Next, the resist layer is exposed to light or electron beam having resist sensitivity through a mask having a predetermined pattern shape corresponding to the pattern to be formed (stripe pattern), and this is further developed.

Form a resist pattern. If necessary, pretreatment for the purpose of alleviating distortion of the resist film may be performed before development, and rinsing treatment may be performed after development to suppress moisture on the film. If so-called scum cannot be removed, it can be removed by plasma ashing.

By the above step 1, the resist pattern 2 shown in FIG. 1 is formed on the substrate 11:. Next, as shown in FIG. 2, the entire surface of the resist pattern 2 is irradiated with light or an electron beam having resist sensitivity. This is to facilitate the subsequent dissolution and removal of the resist pattern by cutting and decomposing the t-chain of the resist, but it can be omitted.

If it is omitted, it is necessary to use a solvent with stronger solubility.

Next, as shown in FIG. 3, a dye layer 3 is formed on the resist pattern 2.
is formed by a vacuum evaporation method. When laminating a quinacridone magenta dye and an isoindolinone yellow dye or anthraquinone color dye, vapor deposition is repeated.6 The thickness of the dye layer 3 is determined depending on the desired spectral characteristics, but is usually 500 to 10,000. It is about eight.

Next, the plate on which the dye layer 3 is provided is removed by dissolving only the resist pattern or removing it from the substrate without dissolving the dye and without damaging the spectral characteristics in order to remove the resist pattern 2 under the dye layer. Immerse in solvent to remove.

Removal of the resist pattern simultaneously removes the overlying dye layer, and it is also effective to apply ultrasonic energy during dipping to assist in this removal. In this way, the red dye layer 4 in a striped pattern as shown in FIG. 4 can be formed, and the color filter of the present invention can be obtained.

In addition, when forming the color filter of the present invention consisting of two or more colors, the color filter may be further adjusted as necessary, that is, depending on the number of colors of the filter used.

The steps from Fig. 1 to Fig. 4 are repeated using the pigments corresponding to each color.1 For example, colored layers of different colors as shown in Fig. 5 4. A color consisting of three colors 5 and 6. A filter can be formed.

Furthermore, the color filter of the present invention may have a protective layer 7 formed from the above-mentioned materials on the former part of the filter, as shown in FIG.

〔Example〕

Examples of the present invention are shown below.

Example 1 A positive resist FPM210 (trade name: manufactured by Daikin Industries) was coated on a glass substrate using a spinner coating method.
, the resist layer was coated to a film thickness of 180℃, 3
After blebbing for 0 minutes, this resist layer was further exposed to deep ultraviolet light through a pattern mask corresponding to the shape of the pattern to be formed. After the exposure, the resist layer of substrate-F was treated with a resist developer and a special rinse solution, and a resist pattern was formed on the substrate. Next, the entire surface of this resist pattern was irradiated with deep ultraviolet light so that it would be easily dissolved in a developer during lift-off treatment using a developer to be performed later.

Next, a glass substrate on which a resist pattern was formed and 1 Lionogen Red 2B (trade name: manufactured by Toyo Ink Co., Ltd., C, 1, N) which is a quinacridone magenta dye according to the present invention.
A molybdenum evaporation port filled with molybdenum evaporation port 48,500) was placed at a predetermined position in the vacuum chamber of the vacuum shoulder device, and the inside of the vacuum chamber was evacuated. At a vacuum level of to-5 to 104 torr, the deposition boat is heated to 400 to 500°C to about 200O
A vapor deposited layer of Lionogen Red 2B was formed to a thickness of A on a substrate E on which a resist pattern was formed.

By the same method as above, Fast Gain Super Yellow GROH (trade name, manufactured by Nippon Ink Co., Ltd.) as an isoindolinone-based yellow pigment was vapor-deposited to a thickness of about 4000 mm on the vapor-deposited layer of Lionogen Red 2B.

Finally, the glass substrate after vapor deposition is immersed in the previously used resist developer and stirred to dissolve the resist pattern while removing unnecessary portions of the vapor-deposited dye layer from the substrate. A red dye layer on a substrate made of an indolinone yellow dye was patterned into stripes to obtain a color filter of the present invention.

Even through these series of steps, the vapor-deposited dye layer on the substrate-1 was not damaged in any way, and almost no deterioration in the spectral characteristics of the vapor-deposited dye layer was observed.

The spectral characteristics of the obtained red dye layer are shown in the curve 1O in FIG. The red dye layer of the color filter of the present invention has excellent red characteristics that cut the blue component in the spectral characteristics (curve 8) of Lionogen Red 2B, a quinacridone-based magenta dye, and make the most of the red component. was recognized as doing so.

Examples 2 to 8 Colors of the present invention were produced in the same manner as in Example 1, except that the dyes shown in Table 1 were used in combination as the quinacridone magenta dye, isoindolinone yellow dye, and anthraquinone yellow dye. The red dye layer of the filter was formed.

In each case, patterned red dye layers with improved spectral characteristics were obtained as in Example 1.

Example 9 First, a green stripe pattern was formed on a glass substrate as the first color, and copper octave 4.5- was used as the dye for forming the vapor-deposited dye layer.
It was formed at a predetermined position according to the method of Example 1 using phenyl phthalocyanine. This copper octave 4,5-7
The vapor deposition layer made of enyl phthalocyanine was formed by setting the degree of vacuum in the vacuum chamber to 10'5-10' torr and heating the vapor deposition boat to 450 to 550° C. so that the layer thickness was about 3000.

Next, on the glass substrate on which the green stripe pattern was formed, a resist layer was exposed as a second color using a pattern mask corresponding to the shape of the blue stripe pattern, and Cu phthalocyanine was further used as a dye for forming a vapor-deposited dye layer. A blue stripe pattern was formed at a predetermined position on the substrate in the same manner as in Example 1 except that a blue stripe pattern was used.

Note that the formation of the vapor deposited layer consisting of Cu phthalocyanine is as follows:
The vacuum degree of the vacuum chamber was set to 10'S-10' torr, the vapor deposition port was heated to 450-550°C, and the layer thickness was approximately 40°C.
It was carried out so that it became 00A.

Further, on the substrate on which the green and blue stripe patterns have been formed in this way, a resist is exposed as a third color using a pattern mask corresponding to the shape of the red stripe pattern, and in the same manner as in Example 1. A red stripe pattern is formed at a predetermined position on the substrate, and R
A colored pattern of three color stripes of (red), G (green), and B (blue) was obtained.

In the process of forming the colored pattern described above, not only the green and blue dye layers but also the red dye layer do not dissolve at all during the development process, and even during the heat treatment process, these dye layers do not crack, peel, or deteriorate. There was no damage to the spectral characteristics.

Finally, commercially available negative resist O is used as a protective film for rubber resin.
[lUR110WR (trade name, manufactured by Tokyo Ohka) tt is coated on the three-color stripe colored pattern formed as described above, and is cured by pre-baking and full-surface exposure to complete the three-color stripe color filter of the present invention. Ta.

The spectral characteristics of the three-color filter thus formed are shown in FIG.

Example 10 A color liquid crystal display element was manufactured in the following manner using a thin film transistor as a substrate and forming the color filter of the present invention on the substrate.

First, as shown in FIG. 9(a), a glass substrate (product name:
7059. (manufactured by Corning) 807 with a layer thickness of 100OA. After forming the T,0 pixel electrode 81 into a desired pattern by a photolithography process, 100% of A1 is further formed on this surface.
A gate electrode 92 as shown in FIG. 9(b) was formed by vacuum evaporating to a thickness of OA and patterning this evaporated layer into a desired shape by a photolithography process.

Next, photosensitive polyimide (product name: Semicofine,
Toshisha Co., Ltd.) is coated on the surface of the substrate 90 on which the electrodes are provided to form an insulating layer 83, and through pattern exposure and development are performed to form through holes 84 that form the contact portion between the drain electrode 98 and the pixel electrode 91. It was formed as shown in FIG. 9(c).

Here, the substrate θ0 is set at a predetermined position in the deposition tank,
S i H4 diluted with H2 is introduced into the deposition tank, and a-9i with a layer thickness of 200 OA is applied to the entire substrate 90 on which the electrodes 91 and 92 and the insulating layer 93 are provided by a glow discharge method in a vacuum. Photoconductive layer (intrinsic layer) consisting of
After depositing the photoconductive layer 95, a ninth n1 layer 8B having a thickness of too thick is deposited on the photoconductive layer 95 by the same operation.
They were laminated as shown in Figure (d). This substrate 90 was taken out from the deposition bath, and the N1 layer 96 and the photoconductive layer 95 were each patterned in the desired shape by dry etching in this order as shown in FIG. 9(e).

Next, on the substrate surface on which the photoconductive layer 95 and the n+ layer 86 are provided, AI is vacuum-deposited to a thickness of IGOOA, and then this AI-deposited layer is patterned into a desired shape by a photolithography process. Thus, a source electrode 97 and a drain electrode 98 as shown in FIG. 9m were formed.

Finally, three colored patterns of red, blue and green are formed in the same manner as in Example 9 to correspond to each of the pixel electrodes 81 as shown in FIG. 9(g), and then the substrate surface is A polyimide resin serving as an insulating film 99 with an orientation function sealed was applied to a thickness of 120 OA over the entire surface, and the resin was cured by heat treatment at 250° C. for 1 hour to produce a thin film transistor with an integrated color filter. .

A color liquid crystal display element was further formed using the thus produced thin film transistor with a color filter.

That is, 1000A was applied to the negative side of a glass substrate (trade name: 7059, manufactured by Corning Inc.) in the same manner as described above.
1. A T,0 electrode layer was formed, and an insulating layer of 1200A thick made of polyimide resin with an alignment function was formed on the electrode layer, and between this substrate and the previously formed thin film transistor with color filter. Liquid crystal was sealed and the whole was fixed to obtain a color liquid crystal display element.

The color liquid crystal display element thus formed had good functionality, and the same effects as in Examples 1 and 9 were obtained in forming the color filter.

Example I! Instead of installing a three-color filter on the pixel electrode,
A color liquid crystal display element having a color filter of the present invention was obtained in the same manner as in Example 10 except that it was provided on the counter electrode.

The color liquid crystal display element thus formed had good functionality, and the same effects as in Examples 1 and 9 were obtained in forming the color filter.

Example 12 A wafer on which a ccn (charge, coupled, device) was formed was used as a substrate, and three-color stripes were formed so that each colored pattern of a color filter was arranged corresponding to each light-receiving cell of a CCD. A color solid-state imaging device having a color filter of the present invention was formed in the same manner as in Example 9 except that the color filter was formed.

The color solid-state imaging device thus formed had good functionality, and the same effects as in Examples 1 and 9 were obtained in forming the color filter.

Example 13 The color filters formed in Example 9 were placed on a wafer on which a CCD (charge, coupled, device) was formed, corresponding to each light receiving cell of the CC[l].
The color filters were aligned and adhered so that each colored pattern of the color filter was arranged, thereby forming a color solid-state image sensor.

The color solid-state imaging device thus formed had good functionality, and the same effects as in Examples 1 and 9 were obtained in forming the color filter.

Example 14 A color photosensor array having a color filter of the present invention as shown in the partial plan view of FIG. 1θ was formed as described below according to the steps shown in FIG.

First, a photoconductive layer (intrinsic layer) II+ consisting of an a-3i (amorphous silicon) layer is formed by a glow discharge method on a glass substrate (trade name: 7059, manufactured by Corning Inc.) 110, as shown in FIG. 11(a). It was set up like this.

i.e. S i 84 diluted to 10% by volume with H2
gas pressure 0.50 Torr, RF (Radio Fr.
equenc7) Power 10W, ) f, board temperature 25
0.7μ by depositing on the substrate for 2 hours at 0°C.
A photoconductive layer 111 having a film thickness of s was obtained.

Subsequently, an n+ layer 112 was provided on this photoconductive layer 111 by a glow discharge method as shown in FIG. 11(b).

That is, 5in4 diluted to 10% by volume with H7,
H2 Te 100 PP layer dilution sample PH3 To'Ft 1
:1G Te mixed gas is used as the raw material, and the others are as follows:
The photoconductive layer is deposited under the same conditions as the previous photoconductive layer! 11
Subsequently, an n+ layer 112 having a layer thickness of 0.1- was provided.

Next, as shown in FIG. 11(c), AI was deposited on the n 4P layer 112 to a thickness of 0.3 by electron beam evaporation to form a conductive layer 113. Next, Figure 11(d)
As shown in FIG. 2, a portion of the conductive layer 113 corresponding to a portion that will become a light conversion portion was removed.

That is, positive type Microposit 1300-27 (
After forming a photoresist pattern in a desired shape using a photoresist (product name 1.5 manufactured by Hipley),
Exposed areas (areas without a resist pattern) were etched using an etching solution prepared by mixing phosphorus # (85% by volume aqueous solution), nitric acid (SO), ice aqueous solution, glacial acetic acid and water in a ratio of 18:1:2:1. ) was removed from the substrate to form a common electrode 115 and individual electrodes 114.

Next, the part of the n1 layer 112 that will become the light conversion part is shown in FIG.
It was removed as shown in e).

That is, after peeling off the Microposit 1300-27 photoresist from the substrate, it was etched by RF using a plasma etching method (also known as reactive ion etching method) using a parallel plate type plasma etching device EX-451 (manufactured by Nikkei Anelva Co., Ltd.). Power 120W, gas pressure 0.1T
Dry etching with CF4 gas was performed for 5 minutes at the
A portion of the surface layer of No. 11 was removed from the substrate.

In this example, in order to prevent implantation of the cathode material in the etching device, a polysilicon sputtering target (8 inches, purity 99.999%) was placed on the cathode, and the sample was placed on top of it. The portion where the SUS of the cathode material was exposed was etched using a Teflon sheet cut out in the shape of a donut with a force of -L, and the SUS surface was hardly exposed to plasma. Thereafter, heat treatment was performed at 200° C. for 60 minutes in an oven in which nitrogen was flowed at a rate of 3 J/+win.

A protective layer was first formed on the surface of the photosensor array thus prepared in the following manner.

That is, a silicon nitride layer 11B as a protective layer was formed on the photosensor array by a glow discharge method.

That is, SiH4 diluted to 10% by volume with H2 and 1
Silicon nitride (a-Si) with a layer thickness of 0.5- Si
The NH) layer was formed as shown in FIG. 11(r).

Furthermore, using this protective layer 118 as a substrate, a color filter consisting of a colored pattern of three colors, blue 5, green 4, and red 6, was formed in the same manner as in Example 9, as shown in FIG. 1O.
A color photosensor array was formed in which colored filters were placed on each photosensor.

In the color photosensor array formed in this example, the same effect as in Examples 1 and 9 can be obtained during color film formation, and the color filter has excellent spectral characteristics. - A color photo sensor can be obtained. Therefore, the reading accuracy of the color photo sensor is improved, and since it has excellent heat resistance and solvent resistance, the occurrence of bit defects is reduced and the yield is improved.

Example 15 Example! The color filter formed in Example 9 was prepared using an adhesive. A color photosensor array was formed by pasting it on the photosensor array formed in step 4.

The color photosensor formed in this example was also similar to that formed in Example 14.

It had good functionality.

〔Effect of the invention〕

As explained below, according to the invention, the problem of the red spectral characteristics of the quinacridone magenta dye can be solved, and the excellent vapor deposition properties and solvent resistance of the quinacridone magenta dye can be utilized. It has excellent spectral properties.

It has now become possible to provide a color filter having a red colored layer that also has excellent heat resistance and solvent resistance.

Furthermore, in the reading sensor having the color filter of the present invention, the reading accuracy is greatly improved because the color filter has excellent characteristics. Furthermore, since the color filter of the present invention has excellent heat resistance and solvent resistance, when the color filter of the present invention is provided in an element that handles a large number of bits (e.g., photosensor, thin film transistor, CCD, etc.), bit defects can be prevented. occurrence is reduced and yield is improved.

[Brief explanation of drawings]

Figures 1 to 6 are process diagrams for explaining the manufacturing method of the color filter of the present invention, and Figure 7 is the spectral transmission of the red dye layer of the color filter of the present invention obtained in Example 1. 8 is a graph showing the spectral transmittance of the dye layer of the color filter of the present invention obtained in Example 9, and FIG. 9(a) to (h) are graphs showing the spectral transmittance of the color filter of the present invention FIG. 1 θ is a manufacturing process diagram of a color liquid crystal display element having a filter, and FIG.
FIGS. 1(a) to 1(g) are process diagrams for forming the color photosensor array shown in FIG. 10. 1, 90.110: Substrate 2 Resist pattern 3: Dye layer 4, 5, 8: Patterned dye layer 7: Protective layer l! :Spectral characteristics of red dye layer 12
: Spectral properties of green dye layer 13: Spectral properties of blue dye layer 95.111 : Photoconductive layer θB, 112: n+
Layer 113: Conductive layer 114: Individual electrode 115: Common electrode 116: Protective layer 91: Pixel electrode 9
2: Gate electrodes 93, 99: Insulating layer 94 Ni through hole 87: Source electrode 88 Ni drain electrode. Patent applicant Canon Co., Ltd. Agent Tadashi Wakabayashi Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 400 500 eoo 700 losses
Technique (nm) Fig. 7 400 500 600 7CO He Long
(nm) Figure 8 Figure 9 Figure 10

Claims (6)

[Claims] (1) A color filter characterized by having a red dye layer formed by vapor-depositing a quinacridone magenta dye and an isoindolinone yellow dye, or a quinacridone magenta dye and an anthraquinone yellow dye. (2) The color filter according to claim 1, wherein the red dye layer is a patterned red dye layer provided on a substrate. (3) The red dye layer is formed by depositing the quinacridone magenta dye and isoindolinone yellow dye, or the quinacridone magenta dye and anthraquinone yellow dye on a substrate having a resist pattern, and then depositing the red dye layer on the resist pattern of the dye vapor deposited layer. 3. The color filter according to claim 2, which is a patterned red dye layer formed by removing a portion provided on the pattern from the substrate together with the resist pattern. (4) The color filter according to claim 2 or 3, wherein the substrate is a display section of a display device. (5) The color filter according to claim 2 or 3, wherein the substrate is a solid-state image sensor. (6) In a color photosensor array provided with a color filter consisting of a colored pattern having a red dye layer on the photosensor array, the red dye layer is a quinacridone-based magenta dye, an isoindolinone-based yellow dye, or a quinacridone-based magenta dye. and a color photosensor array formed by vapor-depositing an anthraquinone-based yellow pigment.