JPH08260159A - Metal oxide thin film pattern forming composition, its production, metal oxide thin film pattern forming method and production of electronic parts and optical parts - Google Patents

Abstract

PURPOSE: To efficiently form a metal oxide thin film pattern with photoirradiation of low energy at the time of forming the pattern by a sol-gel method. CONSTITUTION: This metal oxide thin film pattern forming composition contains 0.05-6mols of a nitrobenzyl alcohol derivative and/or a nitrobenzaldehyde derivative per mol of a metal alkoxide. The composition is applied on a substrate, irradiated with light and patterned by utilizing the solubility difference between the light-irradiated part due to the photolysis reaction of the irradiated part and the unirradiated part. The nitrobenzyl alcohol derivative or nitrobenzaldehyde derivative reacts easily with the metal alkoxide to form a metallic compd. high in photochemical reactivity. The metallic compd. decomposes easily on absorbing light to form a metallic compd. with the solubility greatly different from that of the original metal alkoxide, and hence a large solubility difference is obtained with a small amt. of irradiation energy.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composition for forming a metal oxide thin film pattern containing a metal alkoxide by a sol-gel method, a method for producing the same, a method for forming a metal oxide thin film pattern, and an electronic component and an optical component. The method, in particular, to enhance the photoreactivity of the metal alkoxide,
Composition for forming metal oxide thin film pattern capable of greatly reducing required light irradiation energy, method for producing the same, method for forming metal oxide thin film pattern using the composition, and method for producing electronic component and optical component Regarding

[0002]

2. Description of the Related Art A metal oxide thin film is used in various devices as a capacitor film, an optical waveguide, an optical element, etc. due to its electrical and optical properties. When a metal oxide thin film is used in a device, it is generally necessary to pattern the metal oxide thin film so as to form a predetermined circuit.

Conventionally, a metal oxide thin film pattern is formed by CVD.
After forming a thin film of a metal oxide on the substrate by a sputtering method or a sputtering method, wet etching using a resist or dry etching such as RIE is performed and patterning is performed.

Further, a method for forming a metal oxide thin film pattern by the sol-gel method, that is, a general alkoxide such as metal methoxide, ethoxide and isopropoxide, or an additive for stabilizing the metal oxide if necessary. There is also known a method of forming a pattern by irradiating a gel film formed by applying a solution containing a metal alkoxide, which has been partially substituted by adding to a substrate, with ultraviolet rays to cause a reaction, and performing etching. Further, an example in which an acid generator is mixed is also known (Japanese Patent Laid-Open No. 5-116454).

[0005]

The patterning by wet etching or dry etching has many drawbacks such as many steps and high cost. The film to which an acid generator is added to increase the sensitivity can process the film with low energy, but has a drawback that impurity elements such as sulfur are likely to remain and the electric properties are deteriorated.

On the other hand, the processing by ultraviolet irradiation of the sol-gel method has an advantage that the number of steps is relatively small, but on the other hand, since the metal alkoxide used in the coating solution has weak photoreactivity,
There is a drawback that the light irradiation energy needs to be considerably large. In addition, since the metal compound in the solution has hydrolysis reactivity in addition to photoreactivity, a stable pattern can be formed when it is left on the substrate for a long time after application or when the humidity of the working atmosphere is high. In some cases it was not possible to do so.

The present invention solves the above problems of the prior art, and in forming a metal oxide thin film pattern by the sol-gel method, a metal oxide thin film pattern of high characteristics can be efficiently formed by light irradiation with a small amount of energy. COMPOSITION FOR FORMING METAL OXIDE THIN FILM PATTERN AND METHOD FOR MANUFACTURING THE SAME, METHOD FOR FORMING METAL OXIDE THIN FILM PATTERN USING THIS COMPOSITION, AND METHOD FOR PRODUCING ELECTRONIC COMPONENT AND OPTICAL COMPONENT HAVING SUCH METAL OXIDE THIN FILM PATTERN The purpose is to provide.

[0008]

The metal oxide thin film pattern forming composition of the present invention is a metal oxide thin film pattern forming composition containing a metal alkoxide, wherein the composition is a nitrobenzyl alcohol derivative and / or nitrobenzaldehyde. It is characterized by containing a derivative.

When the composition for forming a metal oxide thin film pattern of the present invention is applied to a substrate and irradiated with light according to a predetermined pattern, the photo-reacted portion due to the light irradiation has a small irradiation energy amount to a non-irradiated portion (that is, The solubility in the solvent changes dramatically with respect to the unreacted part).

The details of the mechanism by which the large change in solubility is caused by the composition for forming a metal oxide thin film pattern of the present invention are not clear, but it is presumed as follows.

That is, the nitrobenzyl alcohol derivative contained in the metal oxide thin film pattern forming composition of the present invention can be easily alcohol-exchanged or distributed with the metal alkoxide in the composition, for example, according to the following formula (I). It undergoes a ligand exchange reaction to produce a metal compound (A) having high photoreactivity. Since this metal compound (A) has a high photoreactivity, even if light with a small irradiation energy amount is absorbed, the ligand is easily decomposed according to the following formula (II), and the original metal A metal compound (RO) ₃ M—O whose solubility in a solvent is greatly different from that of the alkoxide M (OR) _4.
Generate H. Therefore, according to the present invention, it is estimated that a large difference in solubility can be obtained with a small amount of irradiation energy.

[0012]

Embedded image

Even when the composition for forming a metal oxide thin film pattern contains a nitrobenzaldehyde derivative, a metal compound having a very different solubility in a solvent from the original metal alkoxide is produced by the same reaction as described above. It is estimated that

In the composition for forming a metal oxide thin film pattern of the present invention, a nitrobenzyl alcohol derivative and / or
Alternatively, the nitrobenzaldehyde derivative is preferably contained in an amount of 0.05 to 6 times, especially 0.3 to 2 times the mol of the metal alkoxide.

In the present invention, the nitrobenzyl alcohol derivative is preferably 2-nitrobenzyl alcohol, and the nitrobenzaldehyde derivative is preferably 2-nitrobenzaldehyde or 2,4-dinitrobenzaldehyde.

The composition for forming a metal oxide thin film pattern of the present invention preferably further contains a stabilizer for metal alkoxide which does not exhibit strong absorption in the wavelength region of irradiation light. Moisture resistance and stability over time are improved, and stable pattern formation is possible.

That is, in the composition for forming a metal oxide thin film pattern of the present invention, it is considered that a photoreactive substituent is introduced into a metal alkoxide to form a highly photoreactive compound as described above. However, since the remaining functional group (alkoxy group) has high hydrolyzability, the metal compound in the solution has hydrolyzability in addition to photoreactivity. Therefore, if left on the substrate for a long time after coating,
Alternatively, if the humidity of the working atmosphere is high, it may not be possible to form a pattern stably, but by adding a stabilizer for hydrolysis resistance, it is possible to form a film in the air or in a high humidity atmosphere after forming the film. The pattern can be stably formed even after being left inside for a long time.

The stabilizer is preferably one or more selected from ethanolamines, β-diketones, β-ketoesters, carboxylic acids, glycols and glycol esters.

Further, in the present invention, it is advantageous that the metal alkoxide and the nitro group-containing compound are dissolved in a solvent and heated under reflux to form a complex of the metal alkoxide and the nitro group-containing compound. Is.

That is, in order to significantly reduce the required light irradiation energy (improve the sensitivity), it is necessary to increase the amount of the above-mentioned highly photoreactive metal compound produced. For this reason,
By reacting the metal alkoxide and the nitro group-containing compound under reflux in a solvent to form a complex of the metal alkoxide and the nitro group-containing compound in advance, a small amount of the nitro group-containing compound can be added to improve the photosensitivity. The composition for forming a highly sensitive photosensitive oxide thin film pattern can be obtained.

The metal oxide thin film pattern forming composition of the present invention is particularly suitable when it contains two or more metal alkoxides, and in this case, the two or more metal alkoxides are contained as a composite alkoxide. Is preferable in terms of stabilization of patterning. Further, in order to prevent the complex alkoxide once formed from returning to a simple substance by a reverse reaction, a method of removing organic substances generated during complexation is also effective.

The composition for forming a metal oxide thin film pattern of the present invention forms a complex of a metal alkoxide and a nitro group-containing compound in advance by heating and refluxing the metal alkoxide and the nitro group-containing compound in a solvent. After that, it is preferable to add the stabilizer and other components to manufacture.

When two or more metal alkoxides are contained, the two or more metal alkoxides are heated under reflux in a solvent to form a complex alkoxide in advance, and then a stabilizer and other components are added. It is preferable to manufacture it.

The nitro group-containing compound is preferably compounded with the compound alkoxide as described above. When the metal alkoxide or the composite metal alkoxide and the nitro group-containing compound are compounded, a method of removing the generated organic matter is also effective in order to prevent a reverse reaction.

The method for forming a metal oxide thin film pattern of the present invention comprises applying the composition for forming a metal oxide thin film pattern of the present invention onto a substrate, irradiating the obtained coating film with light according to a predetermined pattern, and then irradiating the same. It is characterized in that the coating film is patterned by utilizing the solubility difference in the solvent between the light-irradiated part and the non-irradiated part caused by the photoreaction of the part.

The method of manufacturing an electronic component of the present invention is characterized by manufacturing an electronic component having a metal oxide thin film pattern according to the above method.

The method for producing an optical component of the present invention is characterized by producing an optical component having a metal oxide thin film pattern according to the above method.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

In the present invention, the nitrobenzyl alcohol derivative contained in the composition for forming a metal oxide thin film pattern together with the metal alkoxide includes 2-nitrobenzyl alcohol, 3-nitrobenzyl alcohol, and 4
-Nitrobenzyl alcohol, 2-nitro-3-methylbenzyl alcohol, 2-nitro-4-methylbenzyl alcohol, 2-nitro-5-methylbenzyl alcohol, 2-nitro-6-methylbenzyl alcohol, 2,
Examples thereof include 3-dinitrobenzyl alcohol, 2,4-dinitrobenzyl alcohol, 2,5-dinitrobenzyl alcohol and 2,6-dinitrobenzyl alcohol. Further, as the nitrobenzaldehyde derivative, 2
-Nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 2-nitro-3-methylbenzaldehyde, 2-nitro-4-methylbenzaldehyde, 2-
Nitro-5-methylbenzaldehyde, 2-nitro-6
-Methylbenzaldehyde, 2,3-dinitrobenzaldehyde, 2,5-dinitrobenzaldehyde, 2,6
-Dinitrobenzaldehyde and the like.

In the present invention, particularly, 2-nitrobenzyl alcohol is used as the nitrobenzyl alcohol derivative, and 2 is used as the nitrobenzaldehyde derivative.
Preference is given to using -nitrobenzaldehyde or 2,4-dinitrobenzaldehyde.

Even if these derivatives are used alone,
You may use 2 or more types together.

The content ratio of these nitrobenzyl alcohol derivative and / or nitrobenzaldehyde derivative in the composition for forming a metal oxide thin film pattern of the present invention (2
When more than one kind is used, the total content ratio thereof is 0.05 to 6 times mol of the content of the metal alkoxide (the total content when two or more kinds of metal alkoxides are contained in the composition). In particular, it is preferable that the molar amount is 0.3 to 2 times. If this ratio is less than 0.05 times by mole, the irradiation energy reducing effect of the present invention due to the inclusion of these derivatives cannot be sufficiently obtained, and practical sensitivity can be obtained by adding at least 0.3 times by mole. . Further, there is no difference in the improvement effect even if it exceeds 2 times the mole, and if it exceeds 6 times the mole, problems such as solubility in a solution and residual organic matters in the film after heat treatment occur, which is not preferable.

In the present invention, the metal alkoxide is a raw material for the metal oxide, and therefore, a lower alkoxide such as ethoxide, propoxide, isopropoxide, butoxide, isobutoxide of the metal of the metal oxide to be formed is preferable. Is.

The metal oxide thin film pattern forming composition of the present invention may contain, as a metal oxide raw material, such a metal alkoxide, a metal acetylacetonate complex or a metal carboxylate. In this case, the metal carboxylate is preferably a lower fatty acid salt such as acetate or propionate, but is not limited thereto.

There is no particular limitation on the combination of these metal oxide raw materials and the usage ratio thereof, and a metal oxide raw material corresponding to the intended metal oxide thin film may be selected.

In the present invention, in addition to the metal alkoxide and the nitro group-containing compound, in order to improve moisture resistance and stability over time, a stabilizer which does not show strong absorption in the wavelength region of irradiation light, that is, It is desirable to contain a hydrolysis inhibitor for the alkoxy group.

Examples of such stabilizers include ethanolamines such as ethanolamine, diethanolamine and triethanolamine, β-diketones such as acetylacetone, benzoylacetone and dibenzoylmethane, and 3
-Β-ketoesters such as ethyl oxobutanoate, 2-
Carboxylic acids such as ethylhexanoic acid, 2-ethylbutyric acid, butyric acid, valeric acid, 1,3-butylene glycol, 2,4-
One or more selected from glycols such as amylene glycol and glycol esters can be used.

The amount of such a stabilizer added varies depending on the type of metal alkoxide used, the amount of the nitro group-containing compound added, the required moisture resistance, stability over time, etc. The amount is preferably 5 times or less, particularly preferably 0.5 to 2 times the mol of the metal alkoxide.
If the proportion of this stabilizer exceeds 5 times the molar amount of the metal alkoxide, the sensitivity of the stabilizer that is more likely to bond to the metal than the nitro group-containing compound will decrease the photosensitivity, which is not preferable.

The compositions and methods of the present invention include lead zirconate titanate (PZT), lanthanum-containing lead zirconate titanate (PLZT), strontium titanate (STO), barium titanate (BTO), and barium strontium titanate (PZT). BSTO), bismuth titanate (Bi ₄ Ti ₃
O _12), tantalum oxide (Ta ₂ O _5), titanium dioxide (TiO _2), lead oxide (PbO), zirconium dioxide (ZrO _2), alumina (Al ₂ O _3), tin dioxide (SnO _2), ruthenium dioxide It can be suitably used for forming a thin film pattern of a metal oxide (including both a composite metal oxide and a single metal oxide) such as (RuO ₂ ). As a matter of course, to form a thin film of these metal oxides, a metal oxide raw material containing a metal alkoxide of these metal oxides is used.

The present invention is particularly suitable for those containing two or more kinds of metal alkoxides. For example, Sr alkoxide Sr (OR) ₂ (R: alkyl group) and Bi alkoxide Bi (OR) ₃ are used as metal alkoxide. , Ta alkoxide Ta (OR) ₅ and / or Nb alkoxide Nb (OR) ₅ and the composition formula SrBi ₂ (Ta _x
Nb _2−x ) O ₉ Bi layered oxide thin film pattern forming composition, or in this composition, Bi alkoxide is replaced by bismuth carboxylate, bismuth nitrate, bismuth chloride and bismuth sulfate Examples include one or two or more selected from the group.

In the composition for forming a metal oxide thin film pattern of the present invention, a metal oxide raw material containing a metal alkoxide is used as a suitable organic solvent (eg, ethanol, isopropanol, 2-
Alcohols such as methoxyethanol; lower aliphatic carboxylic acids such as acetic acid and propionic acid), and then a predetermined amount of nitro group-containing compound, that is, nitrobenzyl alcohol derivative and / or nitrobenzaldehyde derivative, in the resulting solution. Can be prepared by adding. However, it is desirable to heat and reflux the metal alkoxide and the nitro group-containing compound in a solvent to form a complex of the metal alkoxide and the nitro group-containing compound in advance, and then add other components such as a stabilizer. It is preferable to add them, which can improve the photosensitivity and reduce the amount of the nitro group-containing compound used. Further, in order to prevent the reverse reaction of complexation, a method of removing the produced organic matter is also effective.

When the target is a complex oxide thin film pattern, two or more kinds of metal oxide raw materials are used in proportions corresponding to the abundance ratio of each metal in the target.
When two or more metal alkoxides are contained, the
It is preferable to heat and reflux one or more metal alkoxides in a solvent to form a complex alkoxide in advance, and then add other additives such as a stabilizer. Also in this case, it is desirable that the nitro group-containing compound is heated under reflux in a solvent together with the complex alkoxide to form a complex. In this case as well, in order to prevent the reverse reaction of complexation, the method of removing the produced organic matter is also effective.

The concentration of the metal oxide raw material in the composition is preferably in the range of 1 to 20% by weight.

The coating of this composition on the substrate is not particularly limited as long as it is a coating method capable of forming a coating film having a uniform film thickness, but a spin coating method is often employed industrially. If necessary, the coating operation can be repeated after the coating film has gelated to obtain a desired coating film thickness. In the present invention, since the exposure can be performed with a small irradiation energy by adding the nitrobenzyl alcohol derivative and / or the nitrobenzaldehyde derivative, the coating film can be thickened. Generally, the film thickness of the metal oxide thin film formed using the composition of the present invention is preferably in the range of 300 to 1000Å.

The coating film obtained loses its fluidity after being left for a short time and can be exposed. The standing time may be determined so that the coating film is dried (the fluidity is lost) to the extent that light irradiation for image formation is possible, and is usually in the range of several seconds to several minutes.

Next, image formation exposure is performed by irradiating light to form an image corresponding to the desired pattern. Ultraviolet light is generally used as the light for irradiation. The ultraviolet ray source may be, for example, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, an excimer laser, or the like. The image-forming exposure can be performed by a conventional method of irradiating light through a mask or a direct writing method of irradiating patterned laser light when the light source is a laser. The irradiation energy amount is not particularly limited and varies depending on the film thickness and the kind of the metal oxide raw material, but according to the present invention, it is usually 0.5 to 2 J by addition of the nitrobenzyl alcohol derivative and / or the nitrobenzaldehyde derivative. The energy amount can be as low as / cm ² .

In particular, when the metal alkoxide and the nitro group-containing compound are compounded in advance, the energy amount can be lowered to 0.1 to ² J / cm ² by improving the photosensitivity. .

By the irradiation of light, the exposed portion is cured by the photoreaction of the metal alkoxide, etc., as described in the section of the action described later, and the solubility in the solvent such as alcohol is lowered. In the present invention, since the nitrobenzyl alcohol derivative and / or the nitrobenzaldehyde derivative are preferably present as a complex with a metal alkoxide,
The photoreaction of the metal alkoxide in the exposed area can be selectively promoted with a small amount of light irradiation energy. for that reason,
Even with ultraviolet rays having a low energy density, the purpose of irradiation can be sufficiently achieved in a short time.

If desired, after this irradiation, the temperature may be 1 to 40 to 100 ° C. in a dry inert gas (N ₂ , Ar, etc.) atmosphere.
It may be left for about 10 minutes. By thus blocking the water content in the air and maintaining the temperature, the curing reaction of the coating film in the exposed area can be selectively promoted while suppressing the hydrolysis of the coating film components in the unexposed area. The difference in solubility between the exposed area and the unexposed area is further increased.

After the irradiation, the coating film may be dried by heating the entire surface of the substrate, if necessary. As a result, the water and organic solvent remaining in the exposed portion that remains as a pattern are removed. This total heating is, for example,
It may be carried out at 100 to 150 ° C. for about 5 to 10 minutes.

After that, by developing with an appropriate solvent to remove the uncured coating film in the unexposed area, a negative pattern consisting of the exposed area is formed on the substrate.
The solvent used as the developer may be any solvent that can dissolve the material in the unexposed area and has low solubility in the cured film in the exposed area. Generally, water or alcohol is preferably used. Suitable alcohols include alkoxy alcohols such as 2-methoxyethanol, 2-ethoxyethanol. In this case, if the dissolving power is too high and dissolution of the exposed portion may occur, the dissolving power can be adjusted by adding an alkyl alcohol such as ethyl alcohol or isopropyl alcohol (IPA) to the above alcohol.

Development is carried out, for example, in a solvent at room temperature for 10 seconds to 1 second.
It can be carried out by soaking for about 0 minutes. The developing conditions are set so that the unexposed portion is completely removed and the exposed portion is not substantially removed. Therefore, the development conditions vary depending on the light irradiation amount, the presence or absence of subsequent heat treatment, and the type of solvent used for development.

After development, that is, after pulling up the coating film sample from the developing solution, in order to prevent the residual film portion from being dissolved by the developing solution adhering to the coating film and to completely stop the development, a rinsing solution is added as necessary. It is also possible to carry out an operation of immersing in the developer and washing away the developing solution. As the rinsing solution, a solution having a weak film-dissolving power and easily mixed with a developing solution is preferable, and it is generally preferable to use a lower alcohol. Suitable alcohols include ethyl alcohol and isopropyl alcohol.

In this way, a negative type coating film pattern in which the exposed portion remains is formed on the substrate. Then, the substrate is heat-treated to completely convert the metal compound in the coating film into a metal oxide, whereby a thin film pattern made of a metal oxide having a desired composition is obtained. This heat treatment is usually 300-80 in the air.
It is preferable to perform firing at 0 ° C. for 1 second to 2 hours.

If necessary, a different kind or the same kind of metal oxide thin film pattern may be formed on the metal oxide thin film pattern thus formed by the same method.

Examples of electronic components manufactured by such a method include DRAM, nonvolatile ferroelectric thin film memory, bipolar memory, semiconductor memory such as GaAs IC, liquid crystal element, and capacitor array.

The optical components include an optical waveguide, a thin film type optical isolator, a Fresnel lens and the like.

[0058]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist.

Example 1 Lead acetate trihydrate 11.
65 g was added and dissolved by heating, and dehydrated as an azeotropic mixture to obtain an anhydrous lead acetate solution. To this, 6.12 g of zirconium tetra-normal butoxide and 4.19 g of titanium tetraisopropoxide were added, and the total amount was adjusted to 100 g with 2-methoxyethanol for weight adjustment, and 10% by weight of P was added.
A bZr _0.52 Ti _0.48 O ₃ (PZT) solution was obtained, and 2-nitrobenzyl alcohol was added to this solution at the ratios shown in Table 1 to obtain a PZT thin film pattern forming composition.

Each of the obtained compositions was applied on a silicon substrate by a spin coating method so as to have a film thickness of 500 Å, and then the applied film was irradiated with ultraviolet rays having an energy amount shown in Table 1 through a photomask, Then, it was developed by immersing it in a mixed solvent of 2-methoxyethanol and isopropyl alcohol at a volume ratio of 1: 1 for 10 seconds. Table 1 shows whether patterning is possible (∘) or not (x).

[0061]

[Table 1]

Example 2 32.96 g of a 5 wt% Ba solution prepared from barium octylate and isoamyl acetate, and a 5 wt% Sr solution prepared from strontium octylate and isoamyl acetate 21.
03 g and titanium tetraisopropoxide 6.82
g and mix with isoamyl acetate to bring the total amount to 100 g.
A _0.5 wt% Ba _0.5 Sr _0.5 TiO ₃ (BST) solution was obtained, and 2-nitrobenzyl alcohol was added to this solution at the ratios shown in Table 2 to obtain a BST thin film pattern forming composition.

Using the composition thus obtained, exposure and development were carried out in the same manner as in Example 1, and Table 2 shows whether patterning is possible (◯) or not (X).

[0064]

[Table 2]

Example 3 8.68 g of 5 wt% Sr solution prepared from strontium octylate and isoamyl acetate, 51.2 wt% Bi solution prepared from bismuth octylate and isoamyl acetate 41.2 g
1 g and 4.02 g of tantalum pentaethoxide were mixed, and isoamyl acetate and 2-methoxyethanol were mixed at a ratio of 1: 1.
(Volume ratio) The total amount was adjusted to 100 g with a mixed solvent to obtain a 5 wt% SrBi ₂ Ta ₂ O ₉ solution, and 2-nitrobenzyl alcohol was added to this solution at the ratios shown in Table 3, respectively.
The composition was used for forming a Bi ₂ Ta ₂ O ₉ thin film pattern.

Using the composition thus obtained, exposure and development were carried out in the same manner as in Example 1, and Table 3 shows whether patterning is possible (◯) or not (x).

[0067]

[Table 3]

Example 4 1.76 g of lithium ethoxide, 10.76 g of niobium pentaethoxide and 87.48 of 2-methoxyethanol.
g was mixed to obtain a 5 wt% LiNbO ₃ solution, and 2-nitrobenzyl alcohol was added to this solution at the ratios shown in Table 4, to obtain a LiNbO ₃ thin film pattern forming composition.

Using the composition thus obtained, exposure and development were carried out in the same manner as in Example 1, and Table 4 shows whether patterning is possible (◯) or not (x).

[0070]

[Table 4]

Example 5 71.26 g of a 5 wt% Bi solution prepared from bismuth octylate and isoamyl acetate was mixed with 3.65 g of titanium tetraisopropoxide, and isoamyl acetate and 2-
A 1: 1 (volume ratio) mixed solution of methoxyethanol was added to 100 g to obtain a 5 wt% Bi ₄ Ti ₃ O ₁₂ solution, and 2-nitrobenzyl alcohol was added to this solution at the ratios shown in Table 5, respectively. The composition was used for forming a Bi ₄ Ti ₃ O ₁₂ thin film pattern.

Using the composition thus obtained, exposure and development were carried out in the same manner as in Example 1, and Table 5 shows whether patterning is possible (◯) or not (x).

[0073]

[Table 5]

Example 6 In place of 2-nitrobenzyl alcohol, 2-nitrobenzaldehyde was added in the ratio shown in Table 6, except that
A composition for forming a PZT thin film pattern was obtained in the same manner as in Example 1, and similarly exposed and developed, and Table 6 shows whether patterning is possible (◯) or not (x).

[0075]

[Table 6]

Example 7 2-Nitrobenzaldehyde was added in place of 2-nitrobenzyl alcohol in the proportions shown in Table 7, except that
A BST thin film pattern-forming composition was obtained in the same manner as in Example 2, and similarly exposed and developed, and Table 7 shows whether patterning is possible (◯) or not (x).

[0077]

[Table 7]

Example 8 Except that 2-nitrobenzaldehyde was added in the ratio shown in Table 8 instead of 2-nitrobenzyl alcohol.
A composition for forming a SrBi ₂ Ta ₂ O ₉ thin film pattern was obtained in the same manner as in Example 3, and similarly exposed and developed, and Table 8 shows whether patterning is possible (◯) or not (x).

[0079]

[Table 8]

Example 9 2-Nitrobenzaldehyde was added in place of 2-nitrobenzyl alcohol in the proportions shown in Table 9, except that
A composition for forming a LiNbO ₃ thin film pattern was obtained in the same manner as in Example 4, and similarly exposed and developed, and Table 9 shows whether patterning is possible (◯) or not (x).

[0081]

[Table 9]

Example 10 A composition for forming a Bi ₄ Ti ₃ O ₁₂ thin film pattern in the same manner as in Example 5 except that 2-nitrobenzaldehyde was added in the proportion shown in Table 10 instead of 2-nitrobenzyl alcohol. Then, exposure and development were performed in the same manner, and whether patterning is possible (◯) or not (X) is shown in Table 10.

[0083]

[Table 10]

Example 11 A PZT thin film pattern forming composition was obtained in the same manner as in Example 1 except that 2,4-dinitrobenzaldehyde was added in the proportion shown in Table 11 instead of 2-nitrobenzyl alcohol. Similarly, exposure and development were performed, and the patternability (◯) and non-patternability (X) are shown in Table 11.

[0085]

[Table 11]

Example 12 A BST thin film pattern forming composition was obtained in the same manner as in Example 2 except that 2,4-dinitrobenzaldehyde was added in the proportion shown in Table 12 instead of 2-nitrobenzyl alcohol. Similarly, exposure and development were carried out, and whether patterning is possible (◯) or not (x) is shown in Table 12.

[0087]

[Table 12]

Example 13 For forming a SrBi ₂ Ta ₂ O ₉ thin film pattern as in Example 3, except that 2,4-dinitrobenzaldehyde was added in the proportion shown in Table 13 instead of 2-nitrobenzyl alcohol. The composition is obtained, similarly exposed and developed,
Table 13 shows whether patterning is possible (◯) or not (x).

[0089]

[Table 13]

Example 14 A composition for forming a LiNbO ₃ thin film pattern was obtained in the same manner as in Example 4 except that 2,4-dinitrobenzaldehyde was added in the ratio shown in Table 14 instead of 2-nitrobenzyl alcohol. In the same manner, exposure and development were performed, and whether patterning is possible (◯) or not (x) is shown in Table 14.

[0091]

[Table 14]

Example 15 For forming a Bi ₄ Ti ₃ O ₁₂ thin film pattern as in Example 5, except that 2,4-dinitrobenzaldehyde was added in the proportion shown in Table 15 instead of 2-nitrobenzyl alcohol. The composition was obtained, and similarly exposed and developed, and whether patterning is possible (◯) or not (X) is shown in Table 15.

[0093]

[Table 15]

It is clear from Tables 1 to 15 that the amount of irradiation energy required for exposure can be significantly reduced by adding a predetermined ratio of the nitrobenzyl alcohol derivative and / or the nitrobenzaldehyde derivative.

Example 16 In Example 1, after adding 2-nitrobenzyl alcohol in an equimolar amount to the metal alkoxide, Table 16 was further added.
A PZT thin film pattern forming composition was prepared in the same manner except that the stabilizer shown in 1 was added in an amount of 1.5 times the mol of the metal alkoxide.

Each of the obtained compositions was applied on a silicon substrate by a spin coating method so as to have a film thickness of 500 Å. 2J / cm ² through this coating film through a photomask
After irradiating with the ultraviolet rays of the above, it was left in a constant temperature and humidity room at room temperature of 25 ° C. and a humidity of 70% for the time period shown in Table 16, and thereafter, it was placed in a mixed solvent of 2-methoxyethanol and isopropyl alcohol in a ratio of 1: 2 (volume ratio). After dipping for 2 seconds to develop, stability with time in a high humidity atmosphere was examined depending on whether patterning was performed or not. The results are shown in Table 16. In Table 16, the symbol “◯” indicates that patterning was possible, and the symbol “x” indicates that the light non-irradiated portion was insolubilized because it was hydrolyzed by moisture in the air and could not be patterned.

[0097]

[Table 16]

Example 17 In Example 2, instead of 2-nitrobenzyl alcohol, 2-nitrobenzaldehyde was added in an equimolar amount to the metal alkoxide, and the stabilizer shown in Table 17 was added to the metal alkoxide in an amount of 1. A BST thin film pattern forming composition was prepared in the same manner except that a 5-fold molar amount was added.

The compositions obtained were each tested in Example 1.
In the same manner as in No. 6, coating, light irradiation, leaving and development were performed to examine the stability over time, and the results are shown in Table 17.

[0100]

[Table 17]

Example 18 In Example 1, 2,4-dinitrobenzaldehyde was added in an equimolar amount to the metal alkoxide instead of 2-nitrobenzyl alcohol, and then the stabilizer shown in Table 18 was added to the metal alkoxide. A composition for forming a PZT thin film pattern was prepared in the same manner except that 1.5 times mol was added.

The compositions obtained are each tested in Example 1.
In the same manner as in No. 6, coating, light irradiation, leaving and development were performed to examine the stability over time, and the results are shown in Table 18.

[0103]

[Table 18]

Example 19 2-MethoxyethoxyBa 5 wt% Ba solution prepared by dissolving Ba metal in 2-methoxyethanol 32.
96 g, 21.03 g of a 5 wt% Sr solution of 2-methoxyethoxy Sr prepared by dissolving Sr metal in 2-methoxyethanol, and 6.82 g of titanium tetraisopropoxide were mixed, and the total amount was adjusted with 2-methoxyethanol. To 100 g and 5 wt% of Ba _0.5 Sr _0.5 TiO
₃ (BST) solution was obtained, and 2-nitrobenzaldehyde was added to this solution in an equimolar amount to the metal alkoxide, and the stabilizer shown in Table 19 was further added to the metal alkoxide in a 1.5-fold molar amount to prepare a BST thin film pattern A forming composition was prepared.

The compositions obtained were each tested in Example 1.
In the same manner as in No. 6, coating, light irradiation, leaving and development were performed to examine stability over time, and the results are shown in Table 19.

[0106]

[Table 19]

Example 20 Tetra tert-butoxy tin Sn (Ot-Bu) ₄
12.28 g and tributoxy antimony Sb (OBu)
₃ 1.05 g was dissolved in 2-methoxyethanol 86.67 g to obtain a 5 wt% ATO solution. 2-Nitrobenzaldehyde was added to this solution with a metal alkoxide (Sn and Sb).
2 times the total number of moles) of the metal alkoxide, and the stabilizer shown in Table 20 is further added in an amount of 1.5 times the mole of the metal alkoxide.
A composition for forming a TO thin film pattern was prepared.

[0108] The obtained compositions were each prepared in Example 1
In the same manner as in No. 6, coating, light irradiation, leaving and development were carried out to examine stability over time, and the results are shown in Table 20.

[0109]

[Table 20]

From Tables 16 to 20, it is clear that the use of the stabilizer improves the temporal stability of the metal oxide thin film pattern forming composition in a high humidity environment.

Example 21 The metal alkoxide shown in Table 21 was dissolved in 2-methoxyethanol, and 2-nitrobenzyl alcohol was added to the solution in an amount (molar ratio) shown in Table 21 and heated under reflux for 5 hours to carry out metal alkoxide. And a 2-nitrobenzyl alcohol complex was formed. This solution was applied onto a silicon substrate by spin coating so that the film thickness would be 500 Å. This coating film is irradiated with ultraviolet rays of 0.05 J / cm ² through a photomask, and then developed by immersing in a mixed solvent of 2-methoxyethanol and isopropyl alcohol (volume ratio) for 10 seconds for patterning. Table 21 shows whether or not (◯) and not (x).

[0112]

[Table 21]

Example 22 Formation of a complex, coating, irradiation with light and development were carried out in the same manner as in Example 21 except that 2-nitrobenzaldehyde was used in place of 2-nitrobenzyl alcohol to perform patterning ( ◯) and no (x) were examined, and the results are shown in Table 22.

[0114]

[Table 22]

Example 23 Formation of a complex, coating, irradiation with light and development were carried out in the same manner as in Example 21 except that 2,4-dinitrobenzaldehyde was used in place of 2-nitrobenzyl alcohol to perform patterning. Possibility (◯) and failure (x) were examined, and the results are shown in Table 23.

[0116]

[Table 23]

As is clear from Tables 21 to 23, by compounding a metal alkoxide and a nitro group-containing compound, it is possible to perform patterning with low energy irradiation even if the addition amount of the nitro group-containing compound is small.

Example 24 9.3 g of bismuth-t-pentoxite, 8.71 g of tantalum ethoxide and 9.95% by weight strontium-
To the Bi ₂ SrTa ₂ composite alkoxide formed by heating and refluxing a mixture of 8.03 g of a 2-methoxyethanol solution, the ratio of 2-nitrobenzaldehyde shown in Table 24 was added to form a complex, and the remaining complex alkoxide was added. By adding 2.3 g of 2-methylbutyric acid in order to suppress the high hydrolyzability of the functional group and stabilize the solution, and finally preparing with 2-methoxyethanol, 10 wt% Bi
₂ Sr ₁ Ta ₂ O ₉ thin film pattern forming composition 100 g
I got

Each of the obtained compositions was applied on a silicon substrate by a spin coating method so as to have a film thickness of 800 Å, and then the applied film was irradiated with ultraviolet rays having an energy amount shown in Table 24 through a photomask. It was developed by immersing it in an isopropyl alcohol solvent for 10 seconds. Table 24 shows whether patterning is possible (◯) or not (x).

[0120]

[Table 24]

Example 25 For forming a 10% by weight Bi ₂ Sr ₁ Ta ₂ O ₉ thin film pattern in the same manner as in Example 24 except that 6.17 g of ethoxydiethylbismuth was used instead of Bi-t-pentoxite. The composition was prepared, and similarly exposed and developed, and whether patterning is possible (◯) or not (x) is shown in Table 25.

[0122]

[Table 25]

Example 26 Except that 2-nitrobenzyl alcohol was added in the ratio shown in Table 26 instead of 2-nitrobenzaldehyde.
10 wt% Bi ₂ Sr ₁ Ta _{2 in the same} manner as in Example 24
The composition for forming an O ₉ thin film pattern was obtained, and similarly exposed and developed to determine whether patterning was possible (◯) or not (X).
It was shown to.

[0124]

[Table 26]

Example 27 For forming a 10% by weight Bi ₂ Sr ₁ Ta ₂ O ₉ thin film pattern in the same manner as in Example 24 except that 2-ethylhexanoic acid was added as a stabilizer instead of 2-ethylbutyric acid. The composition was obtained, and similarly exposed and developed, and whether patterning is possible (◯) or not (x) is shown in Table 27.

[0126]

[Table 27]

Example 28 10.19 g of bismuth-t-pentoxite, 9.54 g of strontium alkoxide, 4.4 g of tantalum ethoxide, and 3.45 g of niobium ethoxide were added to the solution at the ratio of 2 shown in Table 28. -Nitrobenzaldehyde was added, 2-ethylbutyric acid was further added, and finally adjusted to 100 g with 2-methoxyethanol to prepare 10 wt% B.
A composition for forming an i ₂ Sr ₁ Ta ₂ O ₉ thin film pattern was prepared, exposed and developed in the same manner as in Example 24, and Table 28 shows whether patterning is possible (◯) or not (x).

[0128]

[Table 28]

EXAMPLE 29 A mixture of 27.1 g of tantalum ethoxide and 29.4 g of a 9.95 wt% strontium-2-methoxyethanol solution was heated to reflux to form a 15 wt% SrTa prepared with 2-methoxyethanol. ₂ compound alkoxide 10
2-Methylbutyric acid was added to 0 g to stabilize the solution by suppressing the high hydrolyzability of the remaining functional groups of this complex alkoxide by adding 2-nitrobenzaldehyde in the ratio shown in Table 29 to form a complex. 8 g was added, and to this solution was added 9.63% by weight bismuth 2-ethylhexanoate using isoamyl acetate as a solvent, and finally prepared with 2-methoxyethanol to obtain 10% by weight Bi ₂ Sr _1.
A composition for forming a Ta ₂ O ₉ thin film pattern was obtained.

Using the composition thus obtained, exposure and development were carried out in the same manner as in Example 24, and Table 29 shows whether patterning is possible (◯) or not (x).

[0131]

[Table 29]

Example 30 Except that 2-nitrobenzyl alcohol was added in place of 2-nitrobenzaldehyde in the ratio shown in Table 30,
10 wt% Bi ₂ Sr ₁ Ta ₂ as in Example 29
A composition for forming an O ₉ thin film pattern was obtained, and similarly exposed and developed to show whether patterning was possible (◯) or not (x).
It was shown to.

[0133]

[Table 30]

Example 31 10 was carried out in the same manner as in Example 29 except that 2-ethylhexanoic acid was used as a stabilizer instead of 2-ethylbutyric acid.
A composition (% by weight) of Bi ₂ Sr ₁ Ta ₂ O ₉ thin film pattern formation was obtained, and similarly exposed and developed, and whether patterning is possible (◯) or not (x) is shown in Table 31.

[0135]

[Table 31]

Example 32 A 10% by weight Bi ₂ Sr ₁ Ta ₂ O ₉ thin film pattern forming composition was obtained in the same manner as in Example 29 except that the bismuth raw material was a solution of bismuth 2-ethylbutyrate in isoamyl acetate. Similarly, exposure and development are performed, and the patternability (◯) and the patternability (×) are shown in Table 32.

[0137]

[Table 32]

Example 33 The bismuth raw material used in Example 29 was 2-bismuth nitrate.
A 10% by weight Bi ₂ Sr ₁ Ta ₂ O ₉ thin film pattern forming composition was obtained in the same manner except that the solution was changed to a methoxyethanol solution. ×) is shown in Table 33.

[0139]

[Table 33]

Example 34 The bismuth raw material used in Example 29 was 2-bismuth sulfate.
A 10% by weight Bi ₂ Sr ₁ Ta ₂ O ₉ thin film pattern forming composition was obtained in the same manner except that the solution was changed to a methoxyethanol solution. ×) is shown in Table 34.

[0141]

[Table 34]

From Tables 24 to 34, it is clear that even better results can be obtained by forming a composite alkoxide of a metal alkoxide and further adding a nitro group-containing compound to form a composite.

[0143]

As described in detail above, according to the composition for forming a metal oxide thin film pattern, the method for producing the same, and the method for forming a metal oxide thin film pattern of the present invention, the number of manufacturing steps is small, and the cost is low and the efficiency is high. By the sol-gel method capable of effective patterning, the characteristics of the formed metal oxide thin film pattern are not deteriorated, and the irradiation energy is small. Therefore, the patterning time and the patterning cost are reduced, and the efficiency is further improved. Patterning can be performed.

Therefore, according to the method of manufacturing the electronic component and the optical component of the present invention, the electronic component and the optical component having high characteristics can be easily, efficiently and inexpensively manufactured by such a method.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsumi Ogi 1-297 Kitabukuro-cho, Omiya-shi, Saitama Mitsubishi Materials Corporation

Claims (18)

[Claims] 1. A composition containing a metal alkoxide for forming a metal oxide thin film pattern by irradiation with light, which contains a nitro group-containing compound consisting of a nitrobenzyl alcohol derivative and / or a nitrobenzaldehyde derivative. A composition for forming a metal oxide thin film pattern, which comprises: 2. The composition for forming a metal oxide thin film pattern according to claim 1, wherein the nitro group-containing compound is contained in an amount of 0.05 to 6 times the mole of the metal alkoxide. 3. The composition for forming a metal oxide thin film pattern according to claim 2, wherein the nitro group-containing compound is contained in a molar amount of 0.3 to 2 times that of the metal alkoxide. 4. The composition for forming a metal oxide thin film pattern according to any one of claims 1 to 3, wherein the nitrobenzyl alcohol derivative is 2-nitrobenzyl alcohol. 5. The composition for forming a metal oxide thin film pattern according to any one of claims 1 to 3, wherein the nitrobenzaldehyde derivative is 2-nitrobenzaldehyde. 6. The composition according to claim 1, wherein the nitrobenzaldehyde derivative is 2,4-
A composition for forming a metal oxide thin film pattern, which is dinitrobenzaldehyde. 7. The composition according to claim 1, further comprising a metal alkoxide stabilizer which does not exhibit strong absorption in the wavelength region of irradiation light. Composition for forming thin film pattern. 8. The composition of claim 7, wherein the stabilizer is one or more selected from ethanolamines, β-diketones, β-ketoesters, carboxylic acids, glycols and glycol esters. A composition for forming a metal oxide thin film pattern, which comprises: 9. The composition according to claim 1, wherein the metal alkoxide and the nitro group-containing compound are formed by dissolving the metal alkoxide and the nitro group-containing compound in a solvent and heating under reflux. A composition for forming a metal oxide thin film pattern, which comprises a complex with 10. The composition for forming a metal oxide thin film pattern according to claim 1, which contains two or more kinds of metal alkoxides. 11. The composition for forming a metal oxide thin film pattern according to claim 10, wherein two or more kinds of metal alkoxides are contained as a composite alkoxide. 12. A method for producing the composition according to any one of claims 1 to 11, wherein the metal alkoxide and the nitro group-containing compound are heated and refluxed in a solvent to previously prepare the metal alkoxide. A method for producing a composition for forming a metal oxide thin film pattern, which comprises adding a component after forming a complex of the compound with a nitro group-containing compound. 13. A method for producing the composition according to any one of claims 7 to 11, wherein the metal alkoxide and the nitro group-containing compound are heated and refluxed in a solvent to previously prepare the metal alkoxide. A method for producing a composition for forming a metal oxide thin film pattern, which comprises adding a stabilizer after forming a complex of the compound with a nitro group-containing compound. 14. A method for producing the composition according to claim 10 or 11, wherein two or more kinds of metal alkoxides are heated under reflux in a solvent to form a complex alkoxide, and then other components are added. A method for producing a composition for forming a metal oxide thin film pattern, which comprises: 15. A method for producing the composition according to claim 10 or 11, wherein two or more kinds of metal alkoxides are heated and refluxed in a solvent to form a complex alkoxide, and the nitro group-containing compound is added. Then, the mixture is heated and refluxed to form a complex of the complex alkoxide and the nitro group-containing compound, and then a stabilizer is added to the method for producing a composition for forming a metal oxide thin film pattern. 16. A composition for forming a metal oxide thin film pattern according to any one of claims 1 to 11 is applied to a substrate, and then the obtained coating film is irradiated with light according to a predetermined pattern, and an irradiation part is provided. A method for forming a metal oxide thin film pattern, which comprises patterning the coating film by utilizing a solubility difference in a solvent between a light-irradiated portion and a non-irradiated portion caused by the photoreaction. 17. A method of manufacturing an electronic component, which comprises manufacturing an electronic component having a metal oxide thin film pattern according to the method of claim 16. 18. A method of manufacturing an optical component, which comprises manufacturing an optical component having a metal oxide thin film pattern according to the method of claim 16.