JP2544915B2 - Color filter, manufacturing method thereof and device using the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a color filter, a method for manufacturing the same, and an element using the same, and particularly for fine color separation such as a color image pickup element, a color sensor, and a color display. The present invention relates to a suitable color filter, a method for producing the same, and an element using the same.

[Prior Art] Conventionally, as a color filter, a mordant layer made of a hydrophilic polymer such as gelatin, casein, mulberry or polyvinyl alcohol is provided on a substrate, and the mordant layer is dyed with a dye to form a colored layer. A dyeing color filter that does is known.

With such a dyeing method, it is relatively easy to deal with the spectral characteristics required as a filter because many dyes can be used, but in the dyeing process of the mordant layer, the mordant layer is dissolved in the dye bath. It employs a wet process that is difficult to control, such as dipping, and it has a drawback that the yield is poor because it has a complicated process such as providing an intermediate layer for dye protection for each color. In addition, the heat resistance of dyeable dyes
It is relatively low at about 150 ° C or less, and when the filter requires thermal treatment, it is difficult to use and also has a drawback that the dyeing film itself has poor reliability such as heat resistance and light resistance. ing.

On the other hand, conventionally, a color filter using a colored resin in which a certain kind of coloring material is dispersed in a transparent resin is known.

For example, JP-A-58-46325, JP-A-60-78401, JP-A-60-184202, JP-A-60-184203,
As described in JP-A-60-184204 and JP-A-60-184205, a color filter characterized by a colored resin film in which a coloring material is mixed with a polyamino resin is used. The resin itself is excellent in properties such as heat resistance and light resistance, but since it is a non-photosensitive resin, the pattern formation of the color filter is performed by a method which is disadvantageous to the fine pattern or on the colored resin film. It was necessary to adopt a complicated method of the manufacturing process in which the colored resin film was etched after the resist mask was provided on the substrate.

In recent years, a colorant using a photosensitive polyimide resin has been known, but this resin is a polyimide precursor type, and usually requires thermosetting at 300 ° C. or higher for imidization.

On the other hand, as disclosed in JP-A-55-134807, JP-A-57-16407, JP-A-57-74707, JP-A-60-129707, etc. According to a color filter characterized by a colored resin film mixed with a coloring material, a fine pattern can be formed only by a photolithography process which is common for a color filter manufacturing method, and the process can be simplified. The resin generally used has not been sufficiently satisfactory in its complicatedness, which must be prepared by mixing a resin film material and a photosensitive curing agent, and in its properties such as heat resistance and light resistance.

Further, even if a photosensitive resin having excellent performance is used, the colorant contained in the photosensitive resin absorbs light, so that the photosensitive characteristics of the photosensitive resin are inferior.
Specifically, a photosensitive resin mixed with a coloring material generally requires a double or more exposure amount as compared with an uncolored photosensitive resin, and even a method of forming a color filter is originally simple in process. It was inferior in productivity.

[Problems to be Solved by the Invention] An object of the present invention is to eliminate the drawbacks of the above-mentioned conventional examples, to form a fine pattern by a simple manufacturing process, and to use a photosensitive resin containing a colorant. To improve the productivity of the exposure process due to the sensitivity decrease of
Another object of the present invention is to provide a color filter having excellent properties such as mechanical properties, heat resistance, light resistance, solvent resistance, etc., a method for producing the same, and an element using the same.

[Means for Solving Problems] and [Function] That is, the first invention of the present invention comprises a coloring material dispersed in a low temperature curable polyamino resin having a photosensitive group in its molecule. In a color filter having a patterned colored resin layer formed by a photolithography process of a colored resin, the color filter has a resist layer having a higher sensitivity than the colored resin on each of the patterned colored resin layers, The color filter is characterized in that the resist layer is dissolved in the developing solution of the colored resin before curing and is not dissolved in the developing solution of the colored resin after curing.

A second invention of the present invention is, on a substrate, a colored resin film comprising a colored resin in which a coloring material is dispersed in a low-temperature-curable polyamino resin having a photosensitive group in the molecule, and the colored resin. A resist film that is more sensitive and that dissolves in the developing solution of the colored resin before curing and that does not dissolve in the developing solution of the colored resin after curing is sequentially formed by coating, and then the resist is passed through a predetermined mask. The exposed portion of the resist film is cured by exposing it to a light amount necessary for photocuring the film, and then the uncured portion of the resist film and the colored resin film underneath are simultaneously developed and removed, and then the colored resin film is removed. A method of manufacturing a color filter, comprising forming a resist layer on a patterned colored resin layer by exposing the entire surface with a light amount required for photocuring.

The third invention of the present invention is a patterned colored resin layer formed by a photolithography process of a colored resin in which a colored material is dispersed in a low temperature curable polyamino resin having a photosensitive group in the molecule. A resist layer having a higher sensitivity than the colored resin, which is dissolved in the developing solution of the colored resin before curing and is not dissolved in the developing solution of the colored resin after curing, on each of the patterned colored resin layers. A liquid crystal element including a color filter and a liquid crystal.

The fourth invention of the present invention is a patterned colored resin layer formed by a photolithography process of a colored resin in which a coloring material is dispersed in a low temperature curable polyamino resin having a photosensitive group in the molecule. A resist layer having a higher sensitivity than the colored resin, which is dissolved in the developing solution of the colored resin before curing and is not dissolved in the developing solution of the colored resin after curing, on each of the patterned colored resin layers. It is a solid-state image sensor having a color filter provided with.

A fifth invention of the present invention is a patterned colored resin layer formed by a photolithography process of a colored resin in which a coloring material is dispersed in a low temperature curable polyamino resin having a photosensitive group in its molecule. A resist layer having a higher sensitivity than the colored resin, which is dissolved in the developing solution of the colored resin before curing and is not dissolved in the developing solution of the colored resin after curing, on each of the patterned colored resin layers. An image sensor element having a color filter provided with.

That is, the color filter of the present invention is excellent in reliability because it is formed from a colored resin layer using a resin system and a coloring material having good durability such as mechanical properties, heat resistance, light resistance, and solvent resistance. It is possible to easily design a color filter having the above-mentioned characteristics and further having a desired spectral characteristic, and to form a fine pattern by a simple method of only a general photolithography process.

In addition, a resist that is generally more sensitive than the colored resin after the colored resin layer is formed, and that is not dissolved in the developing solution of the colored resin after curing, with respect to the reduction in the productivity of the exposure process that generally occurs due to the decreased sensitivity of the photosensitive resin containing the coloring material. When forming a layer and patterning, first, only the light amount required to cure the resist layer is exposed, then the resist layer in the final-exposed portion is developed together with the lower colored resin layer, and then the entire surface is exposed. Therefore, the exposure process time using the aligner can be shortened.

The low-temperature curable polyamino resin having a photosensitive group in the molecule forming the colored resin layer of the color filter of the present invention (hereinafter referred to as photosensitive polyamino resin) is a cured film at 200 ° C. or lower. What you get, eg 1
A cured film can be formed by heat at 50 ° C for about 30 minutes, for example, aromatic polyamide resins and polyimide resins having a photosensitive group in the molecule, especially in the visible light wavelength range (400 to 700 nm)
And those having no specific light absorption characteristics (light transmittance of about 90% or more) are preferable. In this respect, an aromatic polyamide resin is particularly preferable.

The photosensitive group in the present invention may be any aromatic chain having a photosensitive hydrocarbon unsaturated group as shown below, for example: (1) benzoic esters (In the formula, R ₁ is CHX = CY-COO-Z-, X is -H or -C ₆ H ₅ ,
Y is -H or -CH _3, Z is - or an ethyl group or a glycidyl group) (2) Benzyl acrylate (In the formula, Y represents -H or CH ₃ ) (3) Diphenyl ethers (Wherein R ₂ is _{CHX = CY-CONH-, CH 2} = CY-COO- (CH 2) 2 -O
CO or CH ₂ = containing one or more CY-COO-CH _2- , X and Y have the above meanings) (4) Chalcones and other compound chains (Wherein R ₃ represents H-, an alkyl group or an alkoxy group) Etc.

Specific examples of aromatic polyamide resins and polyimide resins having these groups in the molecule are lysocoat PA-1.
000 (produced by Ube Industries, Ltd.), Lithocoat PI-400 (produced by Ube Industries, Ltd.) and the like.

In general, the photosensitive resin used in the photolithography process varies depending on its chemical structure, but few of them have excellent durability such as heat resistance, light resistance and solvent resistance as well as mechanical properties. On the other hand, the above-mentioned photosensitive polyamino resin of the present invention is a resin system having excellent durability in terms of chemical structure as well, and the color filter formed by using them also has very good durability. Becomes

The coloring material forming the colored resin layer of the color filter of the present invention is not particularly limited as long as it can obtain desired spectral characteristics among organic pigments, inorganic pigments, dyes and the like. In this case, each material can be used alone or as a mixture of some of them. However, when a dye is used, the performance of the color filter is governed by the durability of the dye itself. However, when the resin system of the present invention is used, the performance is superior to that of an ordinary dyed color filter. Can be formed. Therefore, an organic pigment is most preferable as the coloring material in consideration of the color characteristics and various performances of the color filter.

Organic pigments include azo pigments such as soluble azo pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, and indigo pigments, anthraquinone pigments, perylene pigments, perinone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments. A condensed polycyclic pigment containing a pigment, a phthalone pigment, a methine / azomethine pigment, a metal complex pigment, or a mixture of some of these pigments is used.

In the present invention, the colored resin used to form the colored resin layer is prepared by blending the photosensitive polyamino resin solution with the coloring material having the desired spectral characteristics in a proportion of about 10 to 50% by ultrasonic waves or After sufficiently dispersing with a three-roll mill or the like, it is preferably prepared by removing the one having a large particle size with a filter of about 1 μm.

The colored resin layer of the color filter of the present invention, the colored resin is applied onto the substrate by a coating device such as a spinner or a roll coater, and the layer thickness thereof is determined according to the desired spectral characteristics. About 0.5 to 5 μm, preferably about 1 to 2 μm is desirable.

As the photosensitive material for forming the resist layer of the present invention,
Aromatic photosensitive polyamide resin and photosensitive polyimide resin, which are the same as those that make up the colored resin layer, have excellent transparency among photosensitive acrylic resins (specific light absorption in the visible light wavelength range of 400 nm to 700 nm). Light transmittance of 90 without characteristics
% Or more), which have higher sensitivity characteristics than the photosensitive coloring resin used in the present invention and which are insoluble in the developing solution of the coloring resin after photocuring.

Further, since the resist layer is usually formed as it is on the color filter and also plays a role of a protective layer on the colored resin, a resin having good durability such as heat resistance, light resistance and solvent resistance in addition to mechanical properties. From this point of view, the same aromatic photosensitive polyamide resin as that constituting the colored resin layer is preferable.

The resist layer of the present invention, on the colored resin layer formed by coating on the substrate, the photosensitive resin is applied by a coating device such as a spinner or a roll coater, and usually has a film thickness of about 0.5 to 3.0 μm, preferably 0.5. It is applied with a film thickness of about 1.0 μm.

Then, the resist layer is exposed through a predetermined pattern mask only with an exposure amount required for photo-curing. Then, desirably, the exposed resist layer is developed with the same developer as that for the colored resin layer, and the unexposed resist portion and the colored resin layer as the lower layer are patterned at the same time.

Then, the entire surface is exposed to light, and the colored resin pattern is also photo-cured, and then heat-cured to form a colored resin pattern having a transparent protective layer on the top.

Incidentally, the colored resin layer constituting the resist layer on the upper portion of the color filter of the present invention is itself composed of a good material having sufficient durability, but in some cases, from various environmental conditions, In order to protect the colored resin layer, polyamide, polyimide,
Polyurethane, polycarbonate, silicon-based organic resin or inorganic film such as Si ₃ N ₄ , SiO ₂ , SiO, Al ₂ O ₃ , Ta ₂ O ₃ can be applied by spin coating, roll coating, or vapor deposition. It can be provided as a protective layer. Furthermore, after forming the above-mentioned protective layer, depending on the material, it may be applied to a device using liquid crystal by subjecting itself to an alignment treatment.

The sensitivity of the high-sensitivity resist layer used in the present invention is generally 1000 mJ / cm ² or less, preferably 500 mJ / cm ² or less, and the sensitivity of the colored resin layer is 500 mJ / cm ² or more, preferably 100.
It is 0 mJ / cm ² or more. Further, the sensitivity of the high-sensitivity resist layer to the sensitivity of the colored resin layer is preferably twice or more. The smaller the numerical value, the higher the sensitivity.

The color filter having the colored resin layer forming the resist layer thereon as described above can be formed on an appropriate substrate. For example, a glass plate, a transparent resin plate, a resin film, or a cathode ray tube display surface, a light receiving surface of an image pickup tube, a wafer on which a solid-state image pickup device such as CCD, BBD, CID, or BASIS is formed, or a contact image sensor using a thin film semiconductor. , A liquid crystal display substrate surface using a thin film semiconductor, a ferroelectric liquid crystal display substrate surface, a photoconductor for color electrophotography, and the like.

If it is necessary to further increase the adhesiveness between the colored resin layer and the underlying substrate, a colored resin pattern may be formed on the substrate in advance with a thin coating with a silane coupling agent or the like, or the colored resin pattern may be formed in advance. It is more effective to form a color filter by using a mixture of a small amount of a silane coupling agent and the like.

Hereinafter, a typical method for forming a color filter of the present invention will be described with reference to the drawings.

FIG. 1 is a process diagram illustrating a method for forming a color filter of the present invention. First, as shown in FIG. 1A, a colored resin film 2 of a first color is formed on a predetermined substrate 1 by using a polyamino resin solution (NMP solution) in which a predetermined amount of a coloring material having a desired spectral characteristic is mixed. A spinner is used to apply and form a predetermined film thickness, and prebaking is performed under an appropriate temperature condition.

Then, on the colored resin film 2, a polyamino resin liquid similar to that for forming the coloring material is applied and formed to have a predetermined film thickness using a spinner, and prebaked under an appropriate temperature condition, A transparent resist film 7 is formed.

Then, as shown in FIG. 1 (b), the pattern to be formed is treated with light having the sensitivity of the resist film (for example, a high-pressure mercury lamp) and with an exposure amount required for photo-curing the resist film. The resist film is exposed through the photomask 3 having the predetermined pattern shape, and the pattern portion is photocured.

Then, as shown in FIG. 1 (c), the resist film 7 having the photo-cured portion 7a is formed by using a solvent that dissolves only the unexposed portion and the colored resin (for example, an N-methyl-2-pyrrolidone-based solvent as a main component). Of the resist pattern film and the colored resin film therebelow are formed, and rinse treatment (for example, 1,1,1, trichloroethane or the like) is performed. After that, the entire surface is exposed to perform photo-curing of the colored resin pattern portion, and post-baking treatment is performed to obtain the resist layer of the present invention as shown in FIG.
The patterned colored resin layer 4 having 7b as the upper layer can be obtained.

In the case of forming the color filter of the present invention having two or more colors, further depending on the need, that is, depending on the number of colors of the filter used, FIG. 1 (a) to FIG. 1 (d) The steps up to are repeated by using the colored resin liquids in which the coloring materials corresponding to the respective colors are dispersed, and for example, pattern coloring having resist layers of different colors as shown in FIG. 1 (e). It is possible to form a color filter having three colors of the resin layers 4, 5 and 6.

Further, the color filter of the present invention may have a protective layer 8 formed of the above-mentioned materials on the upper part of the filter as shown in FIG. 1 (f).

[Examples] Examples of the present invention will be shown below. The “sensitivity” in the following examples is the exposure amount (mJ / cm ² ) of the high-pressure mercury lamp required for the residual film after development to have a thickness of 0.5 μm when a photosensitive layer having a thickness of 1.0 μm is formed. Represent.

Example 1 A blue colored resin material [Heliogen Blu (Heliogen Blu) capable of obtaining desired spectral characteristics] on a glass substrate.
e) L7080 (trade name, manufactured by BASF, CI No. 74160) is PA-1000C
(Product name, manufactured by Ube Industries, polymer content 10%, solvent = N-
Methyl-2-pyrrolidone, pigment: polymer = 1: 2 blended)
The photosensitive colored resin material prepared by being dispersed in [1] was applied to a film thickness of 1.5 μm by a spinner application method. Next, after pre-baking the colored resin layer at 80 ° C. for 30 minutes, a resist material PA-1000C (trade name, manufactured by Ube Industries, Ltd.) was applied to the colored resin layer by a spinner coating method to a film thickness of 0.5 μm. Applied. Next, prebaking was performed at 80 ° C. for 30 minutes. Then, it was exposed with a high-pressure mercury lamp at an exposure amount required for photocuring PA-1000C through a pattern mask corresponding to the pattern shape to be formed. At this time, the sensitivity of the colored resin layer is 15
It was 00 mJ / cm ² . The sensitivity of the non-colored resin layer at this time was 380 mJ / cm ² .

After completion of the exposure, a dedicated developing solution (N-methyl-2) for dissolving the unexposed portion of the resist film and the colored resin film underlying the resist film is formed.
-Development solution containing pyrrolidone as the main component) using ultrasonic waves and processing with a special rinse solution (rinse solution containing 1,1,1, trichloroethane as the main component), then at 150 ° C for 30 minutes Was post-baked to form a blue colored resin film having a pattern shape and a resist film on the top.

Then, a green colored resin material [Lionol Green 6YK (trade name, manufactured by Toyo Ink Co., Ltd., C.
I.No.74265) was dispersed in PA-1000C (trade name, Ube Industries, Ltd., polymer content 10%, solvent = N-methyl-2-pyrrolidone, pigment: polymer = 1: 2) In the same manner as above, except that the colored resin material of No. 1] was used, a green colored pattern having a resist layer on the upper portion was formed at a predetermined position on the substrate.

Furthermore, as a third color, a red colored resin material [Irgazin Red BPT (trade name, manufactured by Ciba-Geigy Co., CINo. .71127) to PA-10
00C (Product name, Ube Industries, Polymer content 10%, solvent =
N-methyl-2-pyrrolidone, a pigment: polymer = 1: 2 blended) and prepared in the same manner as above except that a photosensitive colored resin material] is used. 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.

The obtained color filter has excellent heat resistance and can withstand a temperature of 250 ° C. or higher, which makes it possible to form ITO on CF by sputtering.

In addition, even when the CF is configured to contact the spacer in the liquid crystal cell with high hardness and excellent mechanical properties, it is
Will not be damaged. Further, it has excellent solvent resistance, is strong against each solvent after curing, does not change during each production process step, and has excellent light resistance.

Furthermore, since the obtained color filters have the same film thickness, there are few steps on the surface, and they are useful for ferroelectric liquid crystal elements that can lead to alignment defects even with slight steps. is there.

Example 2 A thin film transistor was used as a substrate, and a color liquid crystal display device in which the color filter of the present invention was formed on the substrate was manufactured as follows.

First, as shown in Fig. 2 (a), ITO having a layer thickness of 1000Å is formed on a glass substrate (trade name: 7059, manufactured by Corning).
After the pixel electrode 11 is formed into a desired pattern by a photolithography process, Al is further vacuum-deposited to a layer thickness of 1000Å on this surface, and the deposited layer is patterned into a desired shape by the photolithography process, as shown in FIG. ) Gate electrode
12 formed.

Subsequently, a photosensitive polyimide (trade name: Semicofine, manufactured by Toray) is coated on the surface of the substrate 1 on which the electrodes are provided to form an insulating layer 13, and the drain electrode 18 and the pixel electrode are formed by pattern exposure and development treatment. A through hole 14 forming a contact portion with 11 was formed as shown in FIG. 2 (c).

Here, the substrate 1 is set at a predetermined position in the deposition tank,
SiH ₄ diluted with H ₂ was introduced into the deposition tank, and a glow discharge method was used in vacuum to form a layer of 2000 Å a-Si on the entire surface of the substrate 1 on which the electrodes 11 and 12 and the insulating layer 13 were provided. After depositing a photoconductive layer (intrinsic layer) 15 formed on the photoconductive layer 15 by the same operation as described above, an n ⁺ layer having a layer thickness of 1000 Å is formed.
Layer 16 was laminated as shown in Figure 2 (d). The substrate 1 was taken out of the deposition tank, and each of the n ⁺ layer 16 and the photoconductive layer 15 was patterned in this order into a desired shape by a dry etching method as shown in FIG. 2 (e).

Then, on the surface of the substrate on which the photoconductive layer 15 and the n ⁺ layer 16 are provided in this manner, Al is vacuum-deposited with a layer thickness of 1000 Å, and then this Al deposition layer is patterned into a desired shape by a photolithography process. Then, a source electrode 17 and a drain electrode 18 as shown in FIG. 2 (f) were formed.

Finally, in the same manner as in Example 1, corresponding to each of the pixel electrodes 11, a colored pattern of three colors of red, blue and green having a resist layer on the upper part thereof is shown in FIG. 2 (g). Then, as shown in FIG. 2 (h), a polyimide resin as an insulating film 22 having an orientation function is applied to the entire surface of the substrate in a layer thickness of 1200 Å, and the resin is heated by heating at 250 ° C. for 1 hour. Curing was performed to produce a thin film transistor in which a color filter was integrated.

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

That is, on one side of a glass substrate (trade name: 7059, manufactured by Corning Co., Ltd.), in the same manner as the above-mentioned method, 1000 liters of ITO
An electrode layer is formed, and an insulating layer having a layer thickness of 1200 Å made of a polyimide resin having an orientation function is further formed on the electrode layer,
A liquid crystal was enclosed between this substrate and the thin film transistor with a color filter formed earlier and the whole was fixed to obtain a color liquid crystal display element.

The color liquid crystal display element thus formed is
It had a good function.

Example 3 In the same manner as in Example 2 except that the three-color filter is provided on the counter electrode instead of on the pixel electrode,
A color liquid crystal display device having the color filter of the invention was obtained.

The color liquid crystal display element thus formed is
It has a good function.

Example 4 A color liquid crystal display device having a color filter of the present invention was obtained in the same manner as in Example 2 except that a three-color color filter was first formed on a counter substrate and then a counter electrode was provided.

The color liquid crystal display element thus formed had a good function.

Example 5 A three-color filter was first formed in the same manner as in Example 1, and then, as shown in FIG. 3, ITO was formed into a film with a thickness of 500Å by a sputtering method to form a transparent electrode 35. As the orientation control film 37, a polyimide forming solution (Hitachi Chemical Co., Ltd. “PIQ”) was applied by a spinner rotating at 3000 rpm and heated at 150 ° C. for 30 minutes to form a 2000 Å polyimide film. Then, the surface of this polyimide coating film was rubbed.

The color filter substrate thus formed and the opposing substrate 33 were bonded together to form a cell assembly, and the ferroelectric liquid crystal was injected and sealed to obtain a liquid crystal element.

The color ferroelectric liquid crystal element thus formed had a good function.

Example 6 A wafer having a CCD (charge, coupled, device) formed thereon is used as a substrate, and three-color stripes are arranged so that each colored pattern of a color filter is arranged corresponding to each light receiving cell of the CCD. A color solid-state imaging device having the color filter of the present invention was formed in the same manner as in Example 1 except that the color filter was formed.

The color solid-state image sensor formed in this manner had a good function.

Example 7 The color filter formed in Example 1 is formed on a wafer on which CCDs (charge, coupled, device) are formed, and the colored patterns of the color filters are formed in correspondence with the light receiving cells of the CCD. The color solid-state imaging device was formed by aligning and adhering so as to be arranged.

The color solid-state image sensor formed in this manner had a good function.

Example 8 A color photosensor array having a color filter of the present invention as shown in the partial schematic plan view of FIG. 4 was formed according to the steps shown in FIG. 5 as follows.

First, a glass substrate (product name: 7059, manufactured by Corning)
A photoconductive layer (intrinsic layer) 15 composed of an a-Si (amorphous silicon) layer was provided on the substrate 1 by the glow discharge method as shown in FIG. 5 (a).

That is, SiH ₄ diluted to 10% by volume with H ₂ has a gas pressure of 0.
50Torr, RF (Radio Frequency) power 10W, substrate temperature 25
A photoconductive layer 15 having a film thickness of 0.7 μm was obtained by depositing it on the substrate at 0 ° C. for 2 hours.

Then, a fifth layer is formed on the photoconductive layer 15 by a glow discharge method.
An n ⁺ layer 16 was provided as shown in FIG.

That is, the SiH ₄ diluted with H ₂ to 10 volume%, with H ₂ 10
A gas in which PH ₃ diluted to 0 ppm was mixed at a ratio of 1:10 was used as a raw material, and other conditions were the same as the previous photoconductive layer deposition conditions. An n ⁺ layer 16 was provided.

Next, as shown in FIG. 5 (c), the electron beam evaporation method is used.
Al was deposited to a thickness of 0.3 μm on the n ⁺ layer 16 to form a conductive layer 19
Was deposited. Then, as shown in FIG.
The part corresponding to the part to be the light conversion part of 19 was removed.

That is, after forming a photoresist pattern in a desired shape using a positive type Microposit 1300-27 (trade name, manufactured by Shipley) photoresist, phosphoric acid (85% by volume aqueous solution), nitric acid (60% by volume aqueous solution) ), Glacial acetic acid and water are mixed in a ratio of 16: 1: 2: 1 to remove the conductive layer 19 on the exposed portion (the portion where the resist pattern is not provided) from the substrate, and the common electrode 21 And individual electrode 20
Was formed.

Next, as shown in FIG. 5 (e), the n ⁺ layer 16 in the portion to be the light conversion portion was removed.

That is, after peeling off the above Microposit 1300-27 photoresist from the substrate, RF power of 120 W is applied by a plasma etching method (also known as reactive ion etching method) using a parallel plate type plasma etching apparatus DEM-451 (manufactured by Nichiden Anelva). Then, dry etching with CF ₄ gas was performed for 5 minutes at a gas pressure of 0.1 Torr to remove a part of the exposed surface of the n ⁺ layer 16 and the photoconductive layer 15 from the substrate.

In this example, in order to prevent the implantation of the cathode material of the etching apparatus, a sputtering target of polysilicon (8 inches, purity 99.999%) was placed on the cathode, and the sample was placed on the target, The exposed portion of SUS was covered with a Teflon sheet cut out in a donut shape, and etching was performed while the SUS surface was barely exposed to plasma. Then, heat treatment was performed at 20 ° C. for 60 minutes in an oven in which nitrogen was flown at a rate of 3 l / min.

Next, a protective layer was formed on the surface of the photosensor array thus produced as follows.

That is, a silicon nitride layer as the protective layer 8 was formed on the photosensor array by the glow discharge method.

That is, SiH ₄ and 100% NH ₃ diluted to 10% by volume with H _2.
Is used in the same ratio as the previous a-Si layer, except that the mixed gas is mixed at a flow rate ratio of 1: 4, and the protection consists of a silicon nitride (a-SiNH) layer with a layer thickness of 0.5 μm. Layer 8 was formed as shown in Figure 5 (f).

Further, using this protective layer 8 as a substrate, in the same manner as in Example 1, a resist layer 7b was formed on the upper part of the blue 5, green 4,
A color filter composed of three colored patterns of red 6 was formed, and as shown in FIG. 4, a color photosensor array was formed in which the colored filters were arranged on the respective photosensors.

The color photosensor array formed in this example also had a good function.

Example 9 A color photosensor array was formed by sticking the color filter formed in Example 1 onto the photosensor array formed in Example 8 using an adhesive.

The color photosensor formed in this example also had a good function as in the case of forming the color photosensor in Example 8.

Example 10 Instead of the non-colored photosensitive resin layer used in Example 1, a polyimide photosensitive resin “Photo Nice UR36” manufactured by Toray Industries, Inc. was used.
Film thickness 10 formed with "00 (trade name)" (sensitivity 50 mJ / cm ² or less)
The same results as in Example 1 were obtained when the film was prepared by the completely same method except that the 00Å coating was used.

EFFECTS OF THE INVENTION According to the present invention, a coloring resin material obtained by dispersing a coloring material in a polyamino resin having a photosensitive group in its molecule is used, and the photosensitivity which has been a problem in patterning the same. Since the non-colored resist layer is provided on the colored resin film against the deterioration of the sensitivity of the resin, the following effects can be obtained.

That is, since the exposure time by the aligner is determined by the exposure amount required for the highly sensitive non-colored resist layer,
The aligner exposure step can be carried out in a short time, and the method is excellent in productivity.

Further, the non-colored resist layer has a dual function of serving as a mask during the development of the colored resin layer in the step of forming the color filter, and at the same time serving as a surface protective layer after the formation of the color filter.

Furthermore, according to the present invention, the mechanical strength is also excellent, and
A color filter having a fine pattern excellent in various properties such as heat resistance, light resistance, and solvent resistance can be manufactured by a simple manufacturing process. Therefore, it is possible to apply to a wide range of various devices that require a color filter with good performance, and it is possible to manufacture a color device with excellent characteristics.

According to the present invention, desired spectral characteristics can be easily designed by controlling the type and concentration of the coloring material in the colored resin and the thickness of the colored resin layer.

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 (a) to (f) are process drawings for explaining a method for forming a color filter of the present invention, and FIGS. 2 (a) to (h) are color filters of the present invention. 3 is a sectional view of a ferroelectric liquid crystal device for color having a color filter of the present invention, and FIG. 4 is a photosensor for color having a color filter of the present invention. Schematic plan partial view of the array, FIG. 5 (a)-
7G is a process drawing of the color photosensor array shown in FIG. 4. FIG. 1,33 …… Substrate 2 …… Colored resin film 3 …… Photomask 4,5,6 …… Patterned colored resin layer 7 …… Resist film 7a …… Photocured part 7b …… Resist layer 8 …… Protective layer 11 …… Pixel electrode 12 …… Gate electrode 13 …… Insulating layer 14 …… Through hole 15 …… Photoconductive layer 16 …… n ⁺ layer 17 …… Source electrode 18 …… Drain electrode 19 …… Conductive layer 20 …… Individual Electrode 21 …… Common electrode 22 …… Insulation film 31 …… Ferroelectric liquid crystal element 34 …… Ferroelectric liquid crystal 35,36 …… Transparent electrode 37,38 …… Alignment control film

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tatsuo Murata 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Nobuyuki Sekimura 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. Incorporated (72) Inventor Toru Takahashi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (9)

(57) [Claims] 1. A color filter having a patterned colored resin layer formed by a photolithography process of a colored resin obtained by dispersing a colored material in a low temperature curable polyamino resin having a photosensitive group in the molecule. The color filter has a resist layer having a higher sensitivity than the colored resin on each of the patterned colored resin layers, the resist layer is dissolved in a developing solution of the colored resin before curing, and after curing, A color filter which is insoluble in a developer of the colored resin. 2. The color filter according to claim 1, wherein the resist layer is made of the same low temperature curable polyamino resin as the low temperature curable polyamino resin constituting the colored resin. 3. The aromatic polyamide resin or the polyimide resin, wherein the polyamino resin has a photosensitive group in the molecule and a cured film can be obtained at 200 ° C. or lower. Alternatively, the color filter according to item 2. 4. A colored resin film made of a colored resin in which a coloring material is dispersed in a low-temperature-curable polyamino resin having a photosensitive group in its molecule on a substrate, and with higher sensitivity than the colored resin. , And dissolves in the developer of the colored resin before curing,
After curing, a resist film that does not dissolve in the developing solution of the colored resin is sequentially applied and formed, and then the exposed portion of the resist film is cured by exposing through a predetermined mask with the amount of light necessary for photocuring the resist film. Then, the uncured portion of the resist film and the colored resin film underneath are simultaneously developed and removed, and then the entire surface is exposed with the light amount required for photocuring the colored resin film to form a pattern on the colored resin layer. A method for producing a color filter, which comprises forming a resist layer on. 5. The method according to claim 4, wherein the resist layer is made of the same low temperature curable polyamino resin as the low temperature curable polyamino resin constituting the colored resin. 6. The aromatic polyamide resin or the polyimide resin, wherein the polyamino resin has a photosensitive group in the molecule and a cured film can be obtained at 200 ° C. or lower. Alternatively, the manufacturing method according to item 5. 7. A patterned colored resin layer formed by a photolithography process of a colored resin comprising a coloring material dispersed in a low temperature curable polyamino resin having a photosensitive group in its molecule, A resist layer, which has a higher sensitivity than the colored resin and is dissolved in the developing solution of the colored resin before curing and is insoluble in the developing solution of the colored resin after curing, is provided on each patterned colored resin layer. A liquid crystal device including a color filter and a liquid crystal. 8. A colored resin layer having a pattern formed by a photolithography process of a colored resin in which a colored material is dispersed in a low temperature curable polyamino resin having a photosensitive group in the molecule, A resist layer, which has a higher sensitivity than the colored resin and is dissolved in the developing solution of the colored resin before curing and is insoluble in the developing solution of the colored resin after curing, is provided on each patterned colored resin layer. Solid-state image sensor with color filter. 9. A pattern-shaped colored resin layer formed by a photolithography process of a colored resin comprising a coloring material dispersed in a low-temperature-curable polyamino resin having a photosensitive group in its molecule. A resist layer, which has a higher sensitivity than the colored resin and is dissolved in the developing solution of the colored resin before curing and is insoluble in the developing solution of the colored resin after curing, is provided on each patterned colored resin layer. Image sensor device with color filter.