JPS61105507A - Production of color filter - Google Patents

Abstract

PURPOSE:To obtain a highly durable color filter by forming a protective layer by plasma polymn. on a dye layer. CONSTITUTION:Three kinds of dye patterns 4, 5, 6 are formed on a substrate then the protective film 7 by the plasma polymn. is formed on the dye patterns. The protective film 7 to be formed by the plasma polymn. is formed by discharging electricity in a gaseous atmosphere of >=1 kinds of hydrocarbons such as CH4 or compds. such as Si(CH3)4 called organosilane to deposit said hydrocarbon or compd. on the substrate. A hydrocarbon polymer is deposited when gaseous hydrocarbon is used and a carbon-silane-hydrogen polymer is deposited when gaseous organosilane is used. A glow discharge decomposition method is preferably suited for the plasma polymn. method to be used.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to a CCD (charge coupled device) B
BD (valid bridge device), CID
(charge injection device), BASI
It relates to color filters used for color solid-state image sensors such as S (paste store type image sensors), contact type image sensors, and color displays, and is particularly concerned with the formation of a protective layer on a dye film formed by vapor phase deposition. Regarding color filters.

[Conventional technology]

Conventionally, a method has been proposed in which a dye layer is formed by a thin film of vapor-deposited dye by vacuum vapor deposition in the manufacturing method of minute colored patterns such as color filters (for example, Japanese Patent Laid-Open No. 55-146
Publication No. 406).

According to this method, a colored layer can be formed from the dye itself, and a mordant layer in the dyeing method is not required, resulting in an extremely thin film, and the dye layer can be formed by a non-aqueous process.

In addition, as a method for patterning such a dye layer, there is a technique in which a resist pattern is created on the dye film, and this is used as a mask to form a dye pattern by dry etching such as plasma or ion etching (Japanese Patent Application Laid-Open No.
8-34961, etc.).

However, in this method, a resist mask remains on the patterned dye layer.

Furthermore, since it is extremely difficult to remove this mask without causing any damage to the dye layer, the result is a two-layer structure in which the resist mask is laminated on the dye layer.

The remaining resist mask not only causes a decrease in optical performance due to light loss at the interface between the resist and the dye layer (it also has the drawback of easily leading to a decrease in reliability of various physical properties including heat resistance). ing.

On the other hand, a resist mask (hereinafter referred to as an undermask) is provided below the dye layer in the portion to be removed, and by removing the lower undermask from the substrate, the dye layer above it is also physically removed at the same time. There is a pattern Jung method based on a so-called reverse etching method (or lift-off method). In this method, after an undermask is formed using a substance that can later be dissolved, a vapor-deposited dye layer is provided thereon, and then the undermask is dissolved to form a desired pattern. According to the reverse etching method, a pattern is formed by removing the undermask itself, so the structure is simple, with only a dye layer and no mask remaining, and all the drawbacks of the dry etching method are improved.

After the color filter colored layers of multiple colors are formed through the above patterning process, dust is removed.

It is desirable to provide a protective film on the colored layer to prevent defects such as scratches and protect it from various environmental conditions.

As a protective film, an inorganic film such as alumina, titanium oxide,
Metal oxides such as tantalum pentoxide and silicon compounds such as silicon nitride and silicon dioxide are deposited, sputtered,
Formed by glow discharge decomposition method, etc., or organic film 1
For example, polyurethane resin, polycarbonate resin, silicone resin, glass resin, epoxy resin, and polyparaxylene resin have been formed by coating methods such as spin cord, dipping, and roll coater.

Among these protective films, the inorganic film has physical properties (particularly the coefficient of thermal expansion) that are significantly different from those of the organic vapor-deposited dye layer filter, and has the disadvantage that defects such as cracks and peeling are likely to occur.

In addition, in the case of an organic film, the physical properties are very similar to that of an organic vapor-deposited dye layer filter, and the matching with the dye layer is better than that of an inorganic film, but there is no resin that has excellent durability (in terms of appearance, cracks occur, In terms of optical properties, there was a drawback in that a significant change in spectral transmittance occurred.

[Problem that the invention seeks to solve]

The present invention was made in view of the above-mentioned drawbacks of the conventional technology, and provides a highly durable color filter by protecting the dye layer with a protective film that has excellent matching with the dye layer and is also durable. The purpose is to

[Means for solving problems]

The structure of the present invention is a method for producing a color filter having a dye layer formed by vapor deposition, which is characterized in that a protective layer is formed on the dye layer by plasma polymerization.

Hereinafter, an example of the method of the present invention will be explained in detail based on the drawings. In Fig. 1, a spinner is used on the desired substrate 1 (
・Rotate and apply resist. After drying, prebaking is performed under appropriate temperature conditions. Then, it is exposed and developed in a predetermined pattern shape with light or electron beam having resist sensitivity.

Through the above steps, the resist pattern 2 shown in FIG. 1 is formed on the substrate 1. Then, as shown in FIG. 2, a dye layer 8 is formed on the resist pattern by vacuum evaporation.

Next, in order to remove the resist pattern under the dye layer,
It is immersed in a liquid that dissolves or peels only the resist pattern from the substrate without dissolving the dye layer or damaging the spectral characteristics.

Removal of the resist mask simultaneously removes the overlying dye layer, and to assist this,
It is also effective to apply ultrasonic energy during immersion.

In this way, the first dye pattern 4 is formed as shown in FIG. If a different dye pattern is to be formed on the same substrate, the position of the resist mask may be shifted according to the pattern and the above steps may be repeated.
FIG. 4 shows the state in which three types of dye patterns 4, 5 and 6 obtained in this manner are formed on a substrate.

A protective film 7 is then formed on this dye pattern by plasma polymerization as shown in FIG.

The protective film 7 formed by plasma polymerization is CH4°C2
H4, Ca Hs・C2H,, C, H4・(CH3)2
Hydrocarbons such as S! (”H3) 4 + S
L (0”2 H!l )4 * S l (OC2
It is formed by depositing one or more compounds called organosilanes, such as H5)2.(CH3)2, on a substrate by discharging in a gas atmosphere. When a hydrocarbon gas is used, a hydrocarbon polymer is deposited, and when an organosilane gas is used, a carbon-silane-hydrogen polymer is deposited. At this time, other raw material gas such as SiH
4, S 12H6, S i, H3, S i4H,. Silicon hydrides such as S tF49 S 12F6
+ S I C14+ By using a mixed gas mixed with a silicon halide such as 5IBr4 and appropriately controlling the mixing ratio and other manufacturing conditions, a desired concentration of carbon atoms can be halogenated with a hydrocarbon gas in the deposited layer. It may be mixed with silicon, or may be mixed by replacing the above hydrocarbon gas with organosilane gas.

For example, the effect of mixing CH4 and 81-, Si(CH3)4 and SiH4, etc. is that the concentration of carbon atoms in the deposited layer can be changed by the mixing ratio of the two types of gases mentioned above, and the spectral transmittance of the film can be changed. It is possible to do so.

The plasma polymerization method used in the present invention can form a deposited layer of the organic film 7 on the dye layer by causing discharge in the above-mentioned gas atmosphere. As the discharge used in this case, a discharge phenomenon such as a direct current glow discharge method, a high frequency discharge method, a microwave discharge method, etc. can be used.

In preferred embodiments of the invention, it is suitable to use glow discharge decomposition methods. FIG. 6 shows a manufacturing apparatus using the glow discharge decomposition method.

A gas cylinder 602 in the figure is sealed with a raw material gas for forming a deposited layer of a hydrocarbon polymer on a substrate on which a dye pattern is formed. It is. Although not shown in the drawings, it is possible to add cylinders of desired gas types in addition to these as needed.

In order to flow these gases into the reaction chamber 60゛l, the pulp 603 and leakage nozzle 604 of the gas cylinder 602 are
Make sure that the inlet valve 60 is closed and that the inlet valve 60 is closed.
5'. After confirming that the outflow pulp 606 and the auxiliary nozzle 607 are open, first open the main valve 608 to exhaust the reaction chamber 601 and the gas piping. Next, when the reading on the vacuum gauge 609 reaches approximately 5 x 10 torr, close the auxiliary valve 607 and the outflow pulp 606. Next, the C2H4 gas is supplied from the gas cylinder 602 to the pulp 603 by opening the outlet pressure gauge 610. The pressure is adjusted and the inflow valve 605 is gradually opened to allow the flow into the mass flow controller 611. Continuing to leak Nokuru 6
06 and the auxiliary pulp 607 are gradually opened to allow the respective gases to flow into the reaction chamber 601. At this time, the opening of the main valve 608 is adjusted while checking the reading on the vacuum gauge 609 so that the pressure in the reaction chamber reaches a desired value. A deposited layer of hydrocarbon polymer is formed on the dye-patterned substrate 618 by setting the power supply 612 to a desired power to generate a glow discharge in the reaction chamber 601 .

The protective film formed in this manner is suitably formed to have a thickness of about 50A to 2μ, preferably about 100K to 1μ. The protective film formed by the above method has sufficient durability even when formed at a thinner film thickness than the inorganic film obtained by the vacuum evaporation method conventionally used for this type of purpose or the organic film formed by the coating method. can have.

Further, the dye material used in the present invention is a dye or pigment that can be sublimated or vapor deposited, such as a phthalonanine pigment, an isoindolinone pigment, a polycyclic pigment, or a naphthol pigment.

Indathrene dyes, oil-soluble dyes, monodispersed dyes, and the like are used.

Further, the resist used for creating the resist pattern may be either negative or positive type as long as it can be dissolved later.

However, positive resists are preferred, such as product names [FPM 210, FBM 11].
0゜FBM120J l'Ikin Kogyo) ``Az series: 111.119A, 120, 340, 1850B
, 1850J, 1370°1375.1450.145
0J, 1470.1475, 100.2415°248
0j (manufactured by Nprey) [Waycoat HPR-
204゜205.206.207,1182J "W
aycoat MPRJ (manufactured by Hunt) "Koda
k Micro Po5itive Re5ist J
(manufactured by Kodak) [l5ofine Po5itive
Re5ist J (made by Micro Image Technology) “PC129°129sFJ (made by Polychrome) [
0FPR? ? , 78°800J [0EBR1000
,1010,lol J [0DUR1000゜10
01.1010.1013.1014J (manufactured by Tokyo Ohka) rEBRl, 9J (manufactured by Toshi) "FMRE
loo, Elol J (manufactured by Fuji Pharmaceutical Co., Ltd.) “JSR
Po5itive pHotoresist PFR80
03J (made by Japan Synthetic Rubber) “5erectilu
x PJ (manufactured by Merck) and the like.

The substrate used in the present invention is not particularly limited as long as it can be coated with a resin. Specifically, the following can be used. For example, glass plates; optical resin plates; gelatin; polyvinyl alcohol, hydroquine ether cellulose, polymethyl methacrylate, polyester, polyvinyl butyral.

Resin films such as polyamide. It is also possible to integrally form a substrate with a material to which a patterned dye layer can be applied as a color filter.

Examples of substrates in this case include cathode ray tube display surfaces, image pickup tube light receiving surfaces, CCDs, BBDs, CIDs, and BASIS.
A wafer on which a solid-state image sensor is formed, a contact type image sensor using a thin film semiconductor-1 liquid crystal die blade surface,
Examples include photoreceptors for color electrophotography.

The present invention will be explained in more detail below based on examples.
According to the steps shown in FIG. 5, a positive resist (product name: 0FPR8) is applied onto the glass substrate 1 by a spinner coating method.
00, manufactured by Tokyo Ohka Co., Ltd.) was applied to a film thickness of 800 OA.

After pre-baking at 90°C for 80 minutes, mask exposure was performed with ultraviolet light, immersion in 0FPR exclusive developer for 1 minute,
Similarly, a resist mask 2 was formed by immersing it in a dedicated rinsing liquid for 1 minute. Next, the glass substrate 1 on which the resist mask was formed and the copper phthalocyanine packed in the MO boat were placed in a vacuum chamber, and the Mo
The boat was heated to 450-550°C to perform vapor deposition of copper phthalonanine. The film thickness was 4000A. Thereafter, the blue dye pattern 4 was formed by immersing and stirring in a developer exclusively for 0FPR and removing unnecessary portions of the deposited film while dissolving the resist mask.

Subsequently, 0FPR800 was coated in the same process on the glass substrate on which the patterned blue dye layer was formed, exposed and developed to form a resist mask corresponding to the next patterned green dye. This is installed in a vacuum evaporation machine, and this time pb
Softanine is vapor-deposited at 450-550℃ and 3000
Film A was obtained.

Thereafter, it was immersed in a developer and stirred to form a green dye pattern 5. Furthermore, a red pigment was produced using the same process using Irgazin Red BPT (trade name: Teva Geigy C).
I NcL71127) at 400 to 500℃ about a
ooo X was deposited and treated with a developer to obtain a red dye pattern 6.

Next, on the glass substrate on which this dye layer was formed, an ethylene plasma polymerized film 7 was formed by glow discharge of 13.56 MH2 under the following film forming conditions. Ethylene was used as the monomer, the pressure was 1 torr, the discharge time was 10 minutes,
Monomer gas flow rate was 20 SCCM.

The discharge power was 50W.

Under these conditions, a plasma polymerized film of ethylene was formed to a thickness of about 1 μm. The color filter thus produced had no defects in appearance such as cracks and peeling. In addition, to check the durability of this color filter, the temperature was 85°.
C9 relative humidity 85%.

A 500-hour durability test was conducted, but there were no changes in appearance such as cracks or peeling, and regarding changes in spectral characteristics, the change in peak transmittance was less than 0 to 2%.

The peak wavelength change was less than 18 nm from 0 to Z nm.

Example 2 The color filter created in Example 1 was used as a solid-state image sensor (
For example, Charge Coupled Device
(CCD)Base 5tore Type Ima
ge 5 sensor (BASIS), etc.) was bonded onto a wafer on which a sensor was formed.

The color solid-state image sensor thus produced had excellent durability and good color reproducibility.

Example 8 Solid-state image sensor (for example, Charge Coupled
Device (CCD), Ba5e 5tore
Type Image 5 sensor (BASIS
) etc.) A color filter was formed on the wafer substrate in the same process as in Example 1 to obtain a color solid-state image sensor.

The color solid-state image sensor thus produced had excellent durability and good color reproducibility.

Example 4 FIG. 7 is a schematic cross-sectional view for explaining a preferred embodiment of the color photosensor manufacturing method according to the present invention, and FIG. 8 is a color photosensor array obtained by the manufacturing method of the present invention. FIG. Also, Fig. 9 shows A-
It is a cross-sectional schematic diagram at B.

First, a photoconductive layer consisting of an a-8i layer (
Intrinsic@)9 was established. That is, SiH4 diluted to 10 volumes with H2 was heated to a gas pressure of 0.50 Torr.
A photoconductive layer 9 with a thickness of 0.7 μm was obtained by depositing the photoconductive layer 9 on the substrate for 2 hours at a low RF (Radio Frequency) power and a substrate temperature of 250° C. Similarly, an n layer 10 was provided using the glow discharge method. That is, H
Sin diluted to 10 volumes with 2, and 10 with H2
A gas prepared by mixing PH8 diluted to 0 ppm with a mixing ratio of 10 was used as a raw material, and the other conditions were the same as those for the photoconductive layer 9, so that a layer of 0.1 μm was continuously deposited on the photoconductive layer 9.
A layer 1o of thickness n was provided. Next, A
I! A conductive layer 11 was formed by depositing 0.3 μm thick. Subsequently, the portion of the conductive layer 11 that would become the photoelectric 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: 5hlplayy), phosphoric acid (85 volume water solution), nitric acid (60 volume water solution?rjL), glacial acetic acid, and water were added at 16:1. Using an etching solution mixed in a volume ratio of 1:2:1, the conductive layer 11 in the exposed portion (the portion where the resist pattern is not provided) is removed;
After forming the common electrode 12 and the individual electrodes 13, the n-layer 10 in the portion that would become the photoelectric conversion section was removed from the substrate. That is, after peeling off the Microposit 1300-27 photoresist, a parallel plate plasma etching apparatus (
R etching was performed using plasma etching method (also known as reactive ion etching method) using Nichiden Anelpa Dx-451).
F power 120W, gas pressure 0. Dry etching using CF and gas was performed at ITorr for 5 minutes to remove exposed portions of the + n layer 10 and the surface layer of the photoconductive layer 9 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 exposed portion of the SUS cathode material was covered with a Teflon sheet cut out in a donut shape, and etching was performed with the SUS surface hardly exposed to plasma.

After that, it was heated in an open chamber with a nitrogen flow of 81/min.
Heat treatment was performed at 00°C for 60 minutes. Prior to forming the dye layer, a protective layer was formed on the surface of the photosensor array thus produced in the following steps.

That is, a silicon nitride layer 14 was formed on the photosensor array by a glow discharge method.

That is, SiH4 diluted to 10 volumes with H2 and 100
A silicon nitride (a-8iNH) layer 14 having a thickness of 0.5 μm was formed using a gas mixed with %NH3 at a flow rate ratio of 1:4, but under the same conditions as for forming the a-8i layer.

Next, using this protective layer 14 as a substrate, a blue dye pattern 15 is formed in the same process as in Example 1. Green dye pattern 16. A red dye pattern 17 was formed.

Next, on the photosensor array on which this dye layer was formed, xylene was applied as a layer, and 13.56 embryos glowed under the film-forming conditions of a pressure of 1 torr, a discharge time of 20 minutes, a monomer gas flow rate of 203 CCM, and a discharge power of 50 W. A protective layer 18 of a plasma heavy metal film having a thickness of 1 μm was formed by electric discharge.

The color photosensor array thus produced had excellent durability and good color reproducibility.

Example 5 As another embodiment of Example 4, as shown in FIGS. 10 and 11, a dye layer was formed directly on the photosensor array without forming the protective layer 14, and then the same process as in Example 4 was performed. A protective layer 18 made of a plasma polymerized film was formed using the following method.

The color photosenner array produced in this manner was excellent in durability and had good color reproducibility.

Example 6 The color filter created in Example 1 was used in Example 4 or 5.
A color photosensor array was formed by laminating it on the photosensor array prepared in .

The color photocentiarray thus produced had excellent durability and good color reproducibility.

Example 7 A thin film transistor array was formed on a glass substrate, and a dye pattern and a protective layer were formed on pixel electrodes by the same process as in Example 1.

Next, liquid crystal was injected between this substrate and the substrate on which the counter electrode was formed, to create a color liquid crystal display element.

It should be noted that the dye pattern and the protective layer formed thereon are applied not only to the substrate on which the thin film transistor is formed, but also to the opposite side.
It is also possible to form the TO electrode corresponding to the pixel electrode on the substrate on which the TO electrode is formed.

The color liquid crystal display element thus formed was a color display with excellent durability and color fidelity.

〔Effect of the invention〕

The effects of the present invention include that the protective layer formed by plasma polymerization is free from film distortion, cracks, and pinholes compared to inorganic films formed by vacuum evaporation, and is more effective than organic films formed by coating. Since the dye layer is not damaged by the solvent contained therein, there is almost no change in the spectral characteristics of the filter. In addition, it is a thinner film and has better durability than the above-mentioned organic films, and various protective films can be obtained by appropriately selecting a mixed gas.

[Brief explanation of drawings]

Figures 1 to 5 are diagrams showing the color filter production process for explaining the present invention in detail, Figure 6 is a schematic diagram of a manufacturing apparatus using the glow discharge method, and Figure 7 is a detailed explanation of the present invention. 8 is a plan view of the color photosensor array, FIG. 9 is an A-B sectional view of the color photosensor array, and FIG. 10 is a cross-sectional view of the color photosensor array. A plan view showing another embodiment, FIG. 11 is a C-
It is a D sectional view. 1...Substrate, 2...Resist mask. 3...Dye Ii, 4.5.6...Dye pattern. 7.18...Protective film, 8...Glass substrate. 9... photoconductive layer, 10... n layer. 11... Conductive layer, 12... Common electrode. 13...pcs%1□electrode, 14...
...Silicon nitride layer. 15.16.17...Dye pattern. 601...Reaction chamber, 602...
gas cylinder. 603...Pal 7", 604...
・Leak pulp. 605... Inflow pulp, 606... Outflow pulp. 607... Auxiliary pulp, 608... Main pulp. 609... Vacuum gauge, 610...
Outlet pressure gauge. 611... Mass flow controller. 612...Power supply. b Figure 8 Figure 10

Claims (1)

[Claims] A method for producing a color filter having a dye layer formed by vapor deposition, the method comprising forming a protective layer on the dye layer by plasma polymerization.