JPH045631A - Formation of thin film and thin film and application thereof - Google Patents

Abstract

PURPOSE:To obtain thin films of desired patterns by exposing the photosensitive material layer of a transparent substrate through opaque patterns as a mask from the opposite side thereof to partially expose the photosensitive material layer and subjecting the layer to development processing. CONSTITUTION:The photosensitive material layer 3 is formed on the transparent substrate 1. This material layer 3 is partially exposed and is subjected to the development processing, by which the thin films 2 of the desired patterns are formed. A photosensitive mixture composed of at least one kind among an org. Ti compd., org. In compd. and org. Zr compd. and an org. Si compd. is used as the photosensitive material. The opaque patterns 2 are formed of the desired patterns on the transparent substrate 1 and the photosensitive material layer 3 is formed thereon. The photosensitive material layer 3 is partially exposed by exposing the same from the rear side of the transparent substrate 1 and is subjected to the development processing, by which the thin films 4 of the desired patterns are formed. The thin films 4 having the desired patterns are obtd. with good productivity at a uniform film thickness.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for forming a thin film based on at least one of Ti(h, In1Oi, and ZrL and SiO□), a thin film formed thereby, and a method for forming a thin film using the same. This relates to the liquid crystal display element used.

[Prior Art] Conventionally, when forming a thin film having a desired pattern, a printing method or a photolithography method is usually used.

Screen printing methods, flexographic printing methods, offset printing methods, etc. are used as printing methods.

When directly patterning using this printing method, the problem is that the ink builds up at the edge of the pattern, and the film thickness varies depending on the thread width, area, etc., making it difficult to obtain a uniform film thickness. It has l and S.

FIG. 2 shows a cross-sectional view of a thin film formed by a printing method.

In FIG. 2, the thin film 14 formed by printing on the substrate 11 had a tendency to bulge at its edges, making it difficult to obtain a uniform film thickness.

On the other hand, in the photolithography method, after forming a thin film with a uniform thickness, a photosensitive resist is applied on top of the thin film, a mask with the desired pattern is layered, exposed to ultraviolet rays, developed, and etched to form the desired pattern. A patterned thin film was obtained. Thin films formed by this method are less likely to have the drawbacks of printing methods in terms of definition, shape, and film thickness, but they do have problems such as a complicated formation process, poor productivity, and high costs. .

[Problem to be Solved by the Invention 1] On the other hand, in a liquid crystal display element, etc., unevenness of color filters and electrodes becomes a step, and the thickness d of the liquid crystal layer of the liquid crystal display element becomes non-uniform, resulting in an increase in the refractive index anisotropy of the liquid crystal. Since this appears as a difference between the product Δn·d and n, there is a problem in that the appearance of the liquid crystal element deteriorates.

Further, in touch switches and the like, the pattern of the transparent electrode is visible, which tends to deteriorate the appearance.

In addition, with other glass substrates with thin films, etc., when a conductive film is formed thereon, disconnection may occur due to a step at the edge of the thin film.

For this reason, it has been desired to use a printing method or a similar method with a simple formation process, and to obtain high definition, accurate shape accuracy, and uniform film thickness.

[Means for Solving the Problems 1] The present invention has been made to solve the above-mentioned problems, and includes forming a photosensitive material layer on a transparent substrate and partially exposing the photosensitive material layer to light. , a method for forming a thin film in which a thin film with a desired pattern is formed by development treatment, in which a photosensitive mixture of at least one of an organic titanium compound, an organic indium compound, an organic zirconium compound and an organic silicon compound is used as a photosensitive material. , forming an opaque pattern in a desired pattern on a transparent substrate, forming the photosensitive material layer thereon, exposing the transparent substrate from the back side to partially expose the photosensitive material layer, and developing. A thin film forming method characterized in that a thin film with a desired pattern is formed by A thin film forming method characterized by using a photosensitive mixture of an organotitanium compound and an organosilicon compound, and using a transparent substrate having a patterned second thin film as a transparent substrate thereof, forming an opaque pattern on the thin film pattern, forming the photosensitive material layer thereon, exposing the transparent substrate to light from the back side to partially expose the photosensitive material particle layer, and developing. A thin film forming method characterized by forming a thin film on a portion other than a portion corresponding to an opaque pattern, and a substrate with electrodes characterized in that a transparent substrate having patterned electrodes is used as the transparent substrate. A thin film formed by exposing, developing, and heating using these thin film forming methods, the main components being at least one of Ti0z, In2L, and Zr0z and SiO□. and a thin film characterized in that the thin film has TiO2 and 5if2 as main components, and a transparent substrate having a thin film formed by such a thin film forming method. The present invention provides a liquid crystal element with characteristics.

In the present invention, a photosensitive mixture of at least one of an organic titanium compound, an organic indium compound, and an organic zirconium compound and an organic silicon compound is used, and this photosensitive mixture is applied to a substrate on which an opaque pattern is formed by a printing method or the like. By supplying it to a substrate, exposing it to light from the back side of the transparent substrate, and turning it, a thin film with a uniform thickness can be obtained with good productivity.

In particular, an opaque pattern is formed on a second thin film pattern formed on a transparent substrate, the photosensitive material layer is formed thereon, and the photosensitive material layer is exposed from the back side of the transparent substrate. By partially exposing and developing, a thin film can be easily formed in areas other than those corresponding to the opaque pattern. This second thin film may be a conductive film, a color filter, a light shielding film, or the like.

Specifically, by covering the space between the color filters of a transparent substrate on which color filters are formed, with the thin film of the present invention,
The difference in level of the color filter is reduced, and when a conductive film is provided on top of the color filter and patterned, disconnection due to the difference in level becomes less likely to occur. In addition, by covering the patterned electrodes with the thin film of the present invention, unevenness caused by the electrodes is eliminated, electrode jaggedness is less likely to occur, and when used as a liquid crystal device, the thickness of the liquid crystal layer becomes constant and the appearance is good.

The photosensitive mixture for forming the photosensitive material layer used in the present invention includes an organic titanium compound, an organic indium compound,
A photosensitive solution containing at least one organic zirconium compound and an organic silicon compound can be used.

As this organic titanium compound, organic titanium compounds that form a photosensitive mixture can be used, and specifically, titanium octylene glycolate (TOG), tetrabutyl titanate (TBT), and tetraethyl titanate, which generate photosensitivity with a chelating agent, can be used. Typical examples include tetraalkyl titanates shown below, such as titanate, tetraisopropyl titanate, and dimethyldibentyltitanate, and oligomers thereof.

R, , R2, R3, and R4 are each an alkyl group having 1 to 10 carbon atoms, and n is preferably a natural number of 1O or less.

Furthermore, alkyltrialkoxytitanium in which the alkoxy group of the above compound is substituted with an alkyl group can also be used.

These organic titanium compounds may be those that mainly form TiO□ upon exposure to light, development, and heating.

In addition, as this organic indium compound, organic indium compounds that form a photosensitive mixture like organic titanium compounds can be used, and specifically, trialkoxyindium that becomes photosensitized by a chelating agent and oligomers thereof are representative examples. It is mentioned as something like that.

These organic indium compounds may be those that mainly form In20i upon exposure to light, development, and heating.

In addition, as this organic zirconium compound, organic zirconium compounds that form a photosensitive mixture like organic titanium compounds can be used, and specifically, tetraalkoxyzirconium that becomes photosensitive due to a chelating agent and oligomers thereof are representative examples. It is mentioned as something like that. In addition, alkyltrialkoxyzirconium can also be used.

These organic zirconium compounds may be those that mainly form Zr0z upon exposure to light, development, and heating.

In the present invention, at least one of these organic titanium compounds, organic indium compounds, and organic zirconium compounds that produce photosensitivity is used.

Which of these compounds to use or a mixture thereof and the proportions thereof may be determined depending on the intended use of the thin film.

However, among these, organic titanium compounds have high productivity and
This is preferable in view of the ease of obtaining the compound.

Typical examples of the organosilicon compound include the following tetraalcodixylane such as tetraethyl silicate and tetrabutyl silicate, as well as oligomers thereof, as well as organotitanium compounds.

R6, R6, R1, and R8 are each an alkyl group having 1 to 10 carbon atoms, and n is preferably a natural number of 1O or less.

Furthermore, alkyltrialkoxysilanes in which the alkoxy groups of the above compounds are substituted with alkyl groups can also be used.

These organosilicon compounds may be those that mainly form 5iOa upon exposure to light, development, and heating.

The mixing ratio of the organic titanium compound, organic indium compound, and organic zirconium compound with the organic silicon compound depends on its refractive index optically, its dielectric constant electrically, its semiconductor properties, and its mechanical properties. In other words, it may be determined by considering hardness, etc.

Ketones can generally be used as chelating agents to impart photosensitivity to organic titanium compounds, organic indium compounds, and organic zirconium compounds, and a typical example is acetylacetone. be.

For example, up to four oxygen atoms in a ketone coordinate with the titanium atom in an organic titanium compound, so one titanium atom
The theoretical value is that the number of ketones is 4 per unit, but since it is sometimes used in the form of a solution, it is sufficient to mix the number to about 2 to 6.

Specifically, in the combination of tetrabutyl titanate and acetylacetone, since acetylacetone has two ketone groups, about 1 to 3 moles of acetylacetone may be mixed with respect to 1 mole of tetrabutyl titanate.

The solvent is the organic titanium compound, organic indium compound, organic zirconium compound, organic silicon compound,
Any material that dissolves the chelating agent etc. can be used. Specifically, there are alcohol-based, glycol-based, cellosolve-based, carpitol-based, etc.

In the present invention, a necessary catalyst is added in order to hydrolyze and react these organic titanium compounds, organic indium compounds, organic zirconium compounds, and organic silicon compounds. Specifically, nitric acid, acetic acid, sulfonic acid, etc. can be used.

In the present invention, at least one of these organic titanium compounds, organic indium compounds, and organic zirconium compounds is mixed with an organic silicon compound, and other necessary components are added to form a photosensitive mixture.

In the present invention, a photosensitive material layer is formed on a transparent substrate on which an opaque pattern is formed in a desired pattern, and the photosensitive material layer is partially exposed to light by exposing from the back side of the transparent substrate,
It is used for development processing.

This opaque pattern may be formed by a printing method such as offset printing or screen printing, or may be patterned using a photoresist. In particular, it is preferable to use photoresist because the pattern becomes more precise. Among these, preferred is a positive type photoresist, which is mainly composed of a novolac resin, a photosensitizer, and a dye, and is soluble in an alkaline aqueous solution.

Further, in the case where a second thin film is formed, if the thin film itself is opaque to the exposure source itself, the second thin film itself may be used as an opaque pattern.

A specific example of this is that when a red color filter is used as the second thin film, if this red color filter is opaque to ultraviolet rays, the red color filter itself can be used as an opaque pattern to separate the A thin film with a desired pattern can be formed without forming an opaque pattern. Similarly, if the second thin film itself has an opaque pattern, such as a light-shielding film or a metal electrode, a thin film with a desired pattern can be formed without forming a separate opaque pattern.

If the second thin film is transparent, an opaque pattern is formed thereon. As mentioned above, if the purpose is to eliminate the step difference in the second thin film, the opaque pattern may basically be the same pattern as the second thin film. However, in consideration of over-etching, under-etching, etc. during etching, the opaque pattern may be adjusted to be slightly larger or smaller than the second thin film.

Furthermore, if the pattern of the thin film to be formed is unrelated to the pattern of the second thin film, an opaque pattern may be formed in a portion other than the desired thin film pattern.

Hereinafter, the steps will be explained step by step with reference to the drawings. FIGS. 1A, 1B, and 1C are cross-sectional views showing the basic steps of the thin film forming method of the present invention.

FIG. 1(A) shows that an opaque pattern 2 is formed on a transparent substrate 1.

Next, as shown in FIG. 1(B), a photosensitive material layer 3 is formed by supplying the photosensitive material of the present invention thereon.

That is, this photosensitive material is supplied onto a transparent substrate l on which an opaque pattern 2 has been formed using a spin coater roll coater 1 printing machine or the like, or it is immersed in a transparent substrate liquid to coat an organic titanium compound, Forms a photosensitive material layer containing a small amount of an organic indium compound, an organic zirconium compound, and an organic silicon compound.Usually, it is dried to the extent that it does not stick when heated to a certain degree. .

Next, from the back side of the photosensitive material layer 3, that is, in FIG.
) from the underside, the photosensitive material layer 3 is partially exposed using the opaque pattern 2 as a mask. This exposure has
Usually, ultraviolet light is used, and low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, etc. are used.

As a result of this exposure to light, the organic chains in the compound are decomposed where the light hits, forming bonds such as 5L-0-3i and Ti-0-Ti. This causes a difference in the solubility of the photosensitive material layer between areas exposed to light and areas not exposed to light.

Next, as shown in FIG. 1C, by developing with alcohol, alkaline aqueous solution, etc., the unexposed portion corresponding to the opaque pattern can be removed, and a thin film with a desired pattern can be formed. At this time, by using a photoresist that can be dissolved in an alkaline aqueous solution as described above for the opaque pattern, there is an advantage that the opaque pattern can also be removed at the same time.

Further, this is heated to a desired temperature to oxidize the photosensitive material layer, thereby producing a thin film 4 whose main components are at least one of TiO□, In, Oa, and ZrO□ and SiO□.

The heating temperature and time may be determined in consideration of the characteristics of the thin film to be produced. Normally, the temperature is about 150 to 650℃,
It is sufficient to bake it for about 60 minutes.

In this way, according to the present invention, it is possible to easily produce an oxide thin film having a specific pattern and having desired reflective properties, insulation properties, etc.

The thickness of this thin film varies depending on the application and required properties, but it can be used as long as it is within the range of about 0.005 to 10 μm. This means that at a thickness of less than 0.005 μm,
It is not preferable (,
This is because if the thickness exceeds 10 μm, cracks are likely to occur during film formation.

FIGS. 3(A), 3(B), and 3(C) are cross-sectional views showing the steps of a thin film forming method using a transparent substrate on which a second thin film is formed.

FIG. 3(A) shows a transparent substrate 21 having a second thin film 25.
Above, an opaque pattern 22 is shown formed using the same pattern.

Next, as shown in FIG. 3(B), a photosensitive material layer 23 is formed by supplying the photosensitive material of the present invention thereon.

Next, from the bottom of FIG. 3(B), the opaque pattern 22
The photosensitive material layer 23 is partially exposed using the mask as a mask.

Next, as shown in FIG. 3(C), the unexposed portion corresponding to the opaque pattern can be removed by developing with alcohol, alkaline aqueous solution, etc., and a thin film with a desired pattern can be formed.

According to this example, a thin film pattern made of the photosensitive material can be formed in a portion where there is no second thin film pattern, and the thickness can be made uniform (thereby, the level difference on the surface of the transparent substrate can be almost eliminated).

As mentioned above, the second thin film includes a color filter, a conductive film (electrode), a light shielding film, etc., and the parts without these are
Covering with a thin film made of a photosensitive material, it can be used to eliminate or slightly reduce the level difference to prevent the electrode pattern from being visible or to prevent electrode disconnection. It is possible to prevent deterioration in appearance due to unevenness.

The transparent substrate forming the thin film of the present invention can be used as long as it has transparency that allows exposure from the back side and can withstand subsequent heating. Usually, it is suitable for transparent glass substrates, but it is also applicable to transparent plastic substrates and transparent glass ceramic substrates. Furthermore, ITO (
In203-3n02), transparent electrodes such as SnO□,
Metal films such as A1, Cr, N1, Au, Cu, MgF2
, Al2O3, Sin□ and other inorganic material films, polyimide,
An organic material film such as silicone resin or the like may be provided.

[Function] In the thin film forming method of the present invention, an opaque pattern is formed in advance using a photosensitive mixture of at least one of an organic titanium compound, an organic indium compound, and an organic zirconium compound and an organic silicon compound as a photosensitive material. A photosensitive material layer is formed on the transparent substrate.

Then, using the opaque pattern as a mask, the photosensitive material layer is exposed to ultraviolet light or the like from the side opposite to the side on which the photosensitive material layer is provided, thereby partially exposing the photosensitive material layer. Due to this exposure to light, the organic chains in the film are decomposed at the portions of the photosensitive material layer that are exposed to the light, and bonds such as 5i-OSi and Ti-0-Ti are formed.

In particular, this reaction is promoted if titanium atoms and the like are chelated with a chelating agent. This results in
There is a difference in the solubility and scratch resistance of the photosensitive material layer between areas exposed to light and areas not exposed to light.

Therefore, by developing with alcohol, alkaline aqueous solution, etc., the unexposed portions can be removed and a desired pattern can be formed. At this time, by using a photoresist or the like that forms the opaque pattern that can be removed with alcohol, alkaline aqueous solution, etc., the opaque pattern can be removed in the same process.

Further, this is heated to a desired temperature to oxidize the photosensitive material layer to obtain a material having desired reflective properties and insulation properties mainly composed of at least one of TiO□, InzOs, and ZrO□ and 5i (h). A thin film is produced.

For example, the thin film forming method of the present invention can be applied to a transparent glass substrate having irregularities caused by transparent electrodes, and the recesses between the electrode patterns can be filled with a thin film. A polyimide film is provided on the surface of this transparent glass substrate with a transparent electrode having a flat surface, and two polyimide films are rubbed and oriented, and spacer particles are scattered so that the oriented surfaces face each other. A liquid crystal cell can be formed by arranging and sealing the periphery with a sealing material to form an empty cell, injecting nematic liquid crystal through an injection port, and sealing the injection port.

A pair of polarizing films may be placed on both sides of the liquid crystal cell manufactured in this manner to form a TN (twisted nematic) type liquid crystal element.

In addition, the thin film forming method of the present invention may be used to correct the unevenness of a color filter or a light-shielding film to construct a liquid crystal cell instead of correcting the unevenness of a transparent electrode.

Furthermore, we have developed a 5TN (super twisted nematic) type liquid crystal element, which is different from a TN type liquid crystal element, and a G
It can also be applied to H (guest host) type liquid crystal elements, ferroelectric liquid crystal elements using smectic liquid crystal, etc.

[Example 1 Example 1] By applying a positive photoresist (mainly composed of novolak resin and soluble in an alkaline aqueous solution) onto a transparent glass substrate, exposing it to light using a mask, and developing it. , an opaque pattern as shown in FIG. 1(A) was formed.

The composition shown below was used as a photosensitive material.

Ethyl silicate 0.90 parts by weight Tetrabutyl titanate 13.62 parts by weight Acetylacetone 4.00 parts by weight Nitric acid
13.62 parts by weight hexylene glycol 3
5.67 parts by weight A solution of the above photosensitive material was supplied onto the transparent glass substrate on which the opaque pattern was formed by a spinner method to form a photosensitive material layer over the entire surface, and heated at 60°C.
The photosensitive material was dried for 10 minutes to the extent that the photosensitive material did not stick to the finger even when touched with the finger.

Next, 7500 mJ of ultraviolet rays are applied to the side of the transparent glass substrate on which the photosensitive material layer is not formed using high-pressure mercury or the like.
/ Cm2 irradiation. Next, development was performed using ethyl alcohol to remove the unirradiated portions of the photosensitive material layer.

Furthermore, the photoresist on which the opaque pattern was formed was removed using an alkaline aqueous solution.

Then, by baking this layer at 600°C for 10 minutes, the film thickness distribution is uniform, as shown in Figure 1 (C).
A thin film with the desired pattern was obtained.

Example 2 The transparent glass substrate of Example 1 was made into a transparent glass substrate with transparent electrodes patterned with ITO transparent electrodes, and the transparent glass substrate with transparent electrodes was prepared as shown in Fig. 3 (A
), an opaque pattern was formed in the same pattern as this transparent electrode, and a thin film was formed in the same manner as in Example 1.

This thin film is formed exactly where there is no transparent electrode,
As shown in FIG. 3(C), a flat transparent glass substrate with transparent electrodes having almost no unevenness caused by the transparent electrodes was obtained.

A polyimide film is provided on the surface of this transparent glass substrate with transparent electrodes, and two sheets are rubbed and oriented, then spacer particles are scattered and the oriented surfaces are placed facing each other to seal the periphery. An empty cell was formed by sealing with a material, and nematic liquid crystal was injected through the injection port, and the injection port was sealed to form a liquid crystal cell. A pair of polarizing films was placed on both sides of this liquid crystal cell to produce a liquid crystal element.

Since this liquid crystal element had almost no irregularities due to the transparent electrode, the thickness of the liquid crystal layer was uniform within the cell, and color unevenness did not occur (and the appearance was high).

In this case, rather than forming the opaque pattern separately,
By leaving the photoresist used to pattern the transparent electrode as it is on the transparent electrode and using that photoresist as an opaque pattern, the process of forming the opaque pattern is not necessary, improving productivity. , which is preferable because it does not easily cause pattern deviation.

Example 3 A thin film was formed in the same manner as in Example 1, using the transparent glass substrate of Example 1 as a transparent glass substrate with a reflective electrode patterned with a reflective electrode (opaque), and using the reflective electrode itself as an opaque pattern. .

This thin film is formed exactly where there is no reflective electrode,
As shown in FIG. 3(C), a flat transparent glass substrate with a reflective electrode having almost no unevenness caused by the reflective electrode was obtained.

A polyimide film was provided on the surface of this transparent glass substrate with a reflective electrode and the transparent glass substrate with a transparent electrode of Example 2, which had been subjected to alignment treatment by rubbing, and spacer particles were scattered thereon to form an alignment treatment surface. The cells are arranged so that they face each other and the periphery is sealed with a sealing material to form an empty cell. A dichroic dye nematic liquid crystal is injected through the injection port, the injection port is sealed, and the liquid crystal cell is completed. Formed. A polarizing film was placed on the front side of this liquid crystal cell to produce a liquid crystal element.

This liquid crystal element has almost no irregularities caused by electrodes, so
The thickness of the liquid crystal layer was uniform within the cell, and color unevenness did not occur (and the appearance was high).

Furthermore, since the reflective electrode itself is used as an opaque pattern, a separate process for forming an opaque pattern is not necessary, improving productivity and preventing pattern shift.

Example 4 Instead of the transparent glass substrate with transparent electrodes on which the ITO transparent electrodes of Example 2 were patterned, a transparent glass substrate on which patterned color filters were formed was used, as shown in FIG. 3(A). An opaque pattern was formed in the same pattern as this color filter, and a thin film was formed in the same manner as in Example 2, except that ultraviolet irradiation was used, the firing temperature was lowered to below the heat-resistant temperature of the color filter, and the firing time was increased. was formed.

This thin film was formed exactly on the area where there was no color filter, and as shown in FIG. 3(C), a flat transparent glass substrate with a color filter having almost no unevenness caused by the color filter was obtained.

Furthermore, since the color filter itself is used as the opaque pattern, there is no need for a separate step to form an opaque pattern, resulting in good productivity (and no pattern shift occurs).

Examples 5 to 8 Thin films were obtained in the same manner as in Example 1, except that solutions of the photosensitive materials of Examples 1 to 4 were supplied onto glass substrates by flexographic printing to form photosensitive material layers. . This thin film also had a uniform film thickness distribution and a desired pattern as in Examples 1 to 4.

Examples 9-12 Composition component 13 of tetrabutyl titanate of Examples 1-4
．． Example 1 was prepared using a liquid composition in which a part of 62 parts by weight was replaced with triethoxyindium and the weight ratio of tetrabutyl titanate and triethoxyindium was 4:1.3:2.2:3.1:4. A thin film was prepared in the same manner as in 4. These thin films also had a uniform film thickness distribution and a desired pattern as in Example 1.

Examples 13-16 Composition component 13 of tetrabutyl titanate of Examples 1-4
．． Example 1 was prepared by replacing part of 62 parts by weight with tetraethoxyzirconium and using liquid compositions in which the weight ratios of tetrabutyl titanate and tetraethoxyzirconium were 4:l, 3:2.2:3, and l:4, respectively. A thin film was prepared in the same manner as in 4. These thin films also had a uniform film thickness distribution and a desired pattern as in Examples 1 to 4.

[Effects of the Invention] As explained above, in the present invention, an opaque pattern is formed on a transparent substrate, a photosensitive material layer is formed thereon,
A thin film with a desired pattern is formed by exposing the transparent substrate to light using an opaque pattern as a mask from the opposite side of the photosensitive material layer, exposing the photosensitive material layer partially to light, and developing it. Organic titanium compound as material,
By using a photosensitive mixture of at least one of an organic indium compound and an organic zirconylum compound and an organic silicon compound, a thin film having a desired pattern can be obtained with a uniform thickness.

In addition, a reflective electrode formed on a transparent substrate in advance,
A new opaque pattern is created by using the photoresist remaining on the transparent electrode after patterning the light-shielding film, color filter, and transparent electrode (the photoresist remains on the transparent electrode after etching) as an opaque pattern. Thin film patterning can be easily performed without any problems.

By patterning using the second thin film previously formed on the transparent substrate, the second
A thin film can be easily and accurately formed on areas where there is no thin film without pattern deviation.

In addition, unlike thin films patterned using conventional printing methods, it is less prone to problems such as raised edges and uneven film thickness, making it easier to pattern accurately than with printing methods. .

When a liquid crystal element is manufactured using a flattened transparent glass substrate using this thin film, the thickness of the liquid crystal layer becomes uniform and △
Since nd is constant, color unevenness does not occur and the appearance is improved.

In particular, the combined use of a chelating agent improves photosensitivity and allows photosensitization to be achieved with short-time irradiation.

The present invention can be applied in various ways in the future without detracting from the effects of the present invention, and has a desired pattern,
Films and insulating films having various reflective properties can be easily obtained.

[Brief explanation of drawings]

FIGS. 1(A), 1(B), and 1(C) are cross-sectional views showing the method for forming a thin film according to the present invention in the order of steps. FIG. 2 is a cross-sectional view of a thin film formed by a conventional printing method. FIGS. 3(A), 3(B), and 3(C) are cross-sectional views showing another method of forming a thin film according to the present invention in the order of steps. Transparent substrate: 1.21 Opaque pattern = 2.22 Photosensitive material layer: 3.23 Thin film: 4.24 Second thin film: 25 figure

Claims (8)

[Claims] (1) In a thin film forming method in which a photosensitive material layer is formed on a transparent substrate, the photosensitive material layer is partially exposed to light, and developed to form a thin film with a desired pattern, an organic material is used as the photosensitive material. A photosensitive mixture of at least one of a titanium compound, an organic indium compound, and an organic zirconium compound and an organic silicon compound is used to form an opaque pattern in a desired pattern on a transparent substrate, and the photosensitive material layer is placed on top of the opaque pattern. 1. A method for forming a thin film, which comprises forming a thin film in a desired pattern by exposing the transparent substrate to light from the back side to partially expose the photosensitive material layer, and performing a development process. (2) A method for forming a thin film, characterized in that the photosensitive mixture according to claim 1 contains a chelating agent. (3) A method for forming a thin film, characterized in that the photosensitive mixture according to claim 1 or 2 is a photosensitive mixture of an organic titanium compound and an organic silicon compound. (4) As the transparent substrate according to any one of claims 1 to 3,
using a transparent substrate having a patterned second thin film;
forming an opaque pattern on the second thin film pattern;
The photosensitive material layer is formed thereon, and the photosensitive material layer is partially exposed to light by exposure from the back side of the transparent substrate, and developed to form a thin film in areas other than those corresponding to the opaque pattern. A thin film forming method characterized by: (5) As the transparent substrate according to any one of claims 1 to 4,
A method for forming a thin film on a substrate with electrodes, the method comprising using a transparent substrate having patterned electrodes. (6) TiO_2, In_2O formed by exposing, developing, and heating the thin film forming method according to any one of claims 1 to 5.
_3. A thin film characterized by containing at least one kind of ZrO_2 and SiO_2 as generated components. (7) A thin film according to claim 6, characterized in that the thin film has TiO_2 and SiO_2 as main components. (8) A liquid crystal device characterized in that a transparent substrate having a thin film formed by the thin film forming method according to any one of claims 1 to 5 is used for at least one of the substrates.