JP3120701B2 - Composition for forming metal oxide thin film pattern, method for manufacturing the same, method for forming metal oxide thin film pattern, and method for manufacturing electronic components and optical components - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composition for forming a metal oxide thin film pattern by a sol-gel method, comprising a metal alkoxide, a method for producing the same, a method for forming a metal oxide thin film pattern, and production of electronic components and optical components. According to the method, in particular, to enhance the photoreactivity of the metal alkoxide,
Composition for forming metal oxide thin film pattern capable of significantly reducing required light irradiation energy, method for producing the same, method for forming metal oxide thin film pattern using this composition, and method for producing electronic components and optical components About.

[0002]

2. Description of the Related Art Metal oxide thin films are used in various devices as capacitor films, optical waveguides, optical elements, etc. due to their electrical and optical properties. When a metal oxide thin film is used for a device, it is generally necessary to form a pattern of the metal oxide thin film so as to form a predetermined circuit.

Conventionally, metal oxide thin film patterns have been formed by CVD.
It is formed by forming a metal oxide thin film on a substrate by a sputtering method or a sputtering method, and then performing wet etching using a resist or dry etching such as RIE and patterning.

Further, a method of forming a metal oxide thin film pattern by a sol-gel method, that is, a general alkoxide such as a metal methoxide, ethoxide, or isopropoxide, or, if necessary, an additive for stabilization. A method is also known in which a gel film formed by applying a solution containing a metal alkoxide which has been partially replaced by adding a metal to a substrate is irradiated with ultraviolet rays to cause a reaction, followed by etching to form a pattern. Furthermore, an example in which an acid generator is mixed is also known (JP-A-5-116454).

[0005]

[0005] Patterning by wet etching or dry etching has the disadvantage that it involves many steps and is costly.

On the other hand, the processing by ultraviolet irradiation in the sol-gel method has the advantage that the number of steps is relatively small, but the photoreactivity of the metal alkoxide used in the coating solution is weak.
There is a disadvantage that the light irradiation energy needs to be considerably increased. When an acid generator is added to increase the sensitivity, processing of the film can be performed with low energy, but there is a disadvantage that impurity elements such as sulfur are likely to remain and electrical characteristics are inferior. In addition, since the metal compound in the solution has hydrolytic reactivity in addition to photoreactivity, a pattern is formed stably when 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.

The present invention solves the above-mentioned conventional problems and, when forming a metal oxide thin film pattern by the sol-gel method, efficiently forms a high-performance metal oxide thin film pattern by irradiating a small amount of energy with light. COMPOSITION FOR FORMING METAL OXIDE THIN FILM PATTERN AND METHOD FOR PRODUCING THE SAME, METHOD FOR FORMING METAL OXIDE THIN FILM PATTERN USING THE COMPOSITION, AND METHOD FOR MANUFACTURING ELECTRONIC COMPONENTS AND OPTICAL COMPONENTS HAVING SUCH METAL OXIDE THIN PATTERN The purpose is to provide.

[0008]

The composition for forming a metal oxide thin film pattern of the present invention is a composition for forming a metal oxide thin film pattern containing a metal alkoxide, characterized in that it contains a nitrofuran derivative. And

When the composition for forming a metal oxide thin film pattern of the present invention is applied to a substrate and irradiated with light in accordance with a predetermined pattern, a portion which has been photoreacted by the light irradiation has a non-irradiated portion (ie, a non-irradiated portion with a small irradiation energy amount). The solubility in the solvent changes dramatically with respect to the unreacted portion).

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

That is, the nitrofuran derivative contained in the composition for forming a metal oxide thin film pattern of the present invention easily undergoes a ligand exchange reaction with a metal alkoxide in the composition, resulting in high photoreactivity. Produces metal compounds. Since this metal compound has high photoreactivity, even if light with a small irradiation energy amount is absorbed, the ligand is easily decomposed, and the solubility in a solvent is significantly different from that of the original metal alkoxide. Produces metal compounds. For this reason, according to the present invention, it is estimated that a large solubility difference can be obtained with a small irradiation energy amount.

In the composition for forming a metal oxide thin film pattern according to the present invention, the nitrofuran derivative is preferably contained in an amount of 0.05 to 6 times, particularly 0.3 to 2 times, the mole of the metal alkoxide.

In the present invention, the nitrofuran derivative may be 2-nitrofuran, anti-5-nitro-2-furaldoxime, 5-nitro-2-furanoic acid, or 5-nitrofuran.
Nitro-2-furaldehyde is preferred.

The composition for forming a metal oxide thin film pattern of the present invention preferably further contains a metal alkoxide stabilizer which does not show strong absorption in the wavelength region of irradiation light. And the stability over time can be improved, and a stable pattern can be formed.

That is, in the composition for forming a metal oxide thin film pattern of the present invention, it is considered that a compound having high photoreactivity is formed by introducing a photoreactive substituent into the metal alkoxide as described above. However, since the remaining functional groups (alkoxy groups) have high hydrolyzability, the metal compound in the solution has hydrolyzability other than photoreactivity. For this reason, if left for a long time after coating on the substrate,
Alternatively, when the humidity of the working atmosphere is high, a pattern cannot be stably formed in some cases. However, by adding a stabilizer for hydrolysis resistance, it is possible to form a pattern in air or in a high-humidity atmosphere after forming a coating film. Even after being left inside for a long time, the pattern can be formed stably.

As the stabilizer, one or more selected from ethanolamines, β-diketones, β-ketoesters, carboxylic acids, glycols and glycol esters are preferred.

Further, in the present invention, it is advantageous to form a complex of the metal alkoxide and the nitrofuran derivative by dissolving the metal alkoxide and the nitrofuran derivative in a solvent and heating and refluxing the solution. .

That is, in order to greatly reduce the required light irradiation energy (improve the sensitivity), it is necessary to increase the amount of the metal compound having high photoreactivity. For this reason,
By reacting the metal alkoxide and the nitrofuran derivative under reflux in a solvent to form a complex of the metal alkoxide and the nitrofuran derivative in advance, the photosensitivity is very high with a small amount of the nitrofuran derivative added. It can be a composition for forming a photosensitive oxide thin film pattern.

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

The composition for forming a metal oxide thin film pattern according to the present invention is obtained by forming a complex of a metal alkoxide and a nitrofuran derivative in advance by heating and refluxing the metal alkoxide and the nitrofuran derivative in a solvent. It is preferable to add a stabilizer and other components.

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

It is preferable that the nitrofuran derivative is complexed with the complex alkoxide as described above. When a metal alkoxide or a composite metal alkoxide is combined with a nitrofuran derivative, a method of removing generated organic substances is also effective in order to prevent a reverse reaction.

In the method for forming a metal oxide thin film pattern according to the present invention, the composition for forming a metal oxide thin film pattern according to the present invention is applied to a substrate, and the obtained coating film is irradiated with light according to a predetermined pattern. The coating film is patterned by utilizing a difference in solubility in a solvent between a light-irradiated portion and a non-irradiated portion caused by a photoreaction of the portion.

According to the method of manufacturing an electronic component of the present invention, an electronic component having a metal oxide thin film pattern is manufactured according to the above method.

According to the method of manufacturing an optical component of the present invention, an optical component having a metal oxide thin film pattern is manufactured according to the above method.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

In the present invention, the nitrofuran derivatives to be contained together with the metal alkoxide in the composition for forming a metal oxide thin film pattern include 2-nitrofuran, anti-5-nitro-2-furaldoxime, 5-nitro-2-nitrofuran.
Furanic acid, 5-nitro-2-furaldehyde, 5-nitro-2-furaldehyde diacetate, 5-nitro-2
Nitrofuran-based compounds such as -furaldehyde semicarbazone and 5-nitro-2-fluanacrolein.

In the present invention, 2-nitrofuran, anti-5-nitro-2-furaldoxime, 5-nitro-
Preference is given to using 2-furonic acid or 5-nitro-2-furaldehyde.

[0029]

Embedded image

These derivatives may be used alone or
Two or more kinds may be used in combination.

The content of these nitrofuran derivatives 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 thereof is 0.05 to 6 times mol of the content of the metal alkoxide (when two or more kinds of metal alkoxide are contained in the composition, the total content), In particular, it is preferably from 0.3 to 2 moles. If this ratio is less than 0.05 mole, the irradiation energy reduction effect of the present invention cannot be sufficiently obtained by including these derivatives, and practical sensitivity can be obtained by adding 0.3 mole or more. . There is no difference in the improvement effect even when the molar ratio exceeds 2 times, and when the molar ratio exceeds 6 times, problems such as solubility in the solution and residual organic matter in the film after the heat treatment occur.

In the present invention, the metal alkoxide is a raw material of the metal oxide. Therefore, lower alkoxides such as ethoxide, propoxide, isopropoxide, butoxide, and isobutoxide of the metal of the metal oxide to be formed are preferable. It is.

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

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

In the present invention, in addition to the metal alkoxide and the nitrofuran derivative, 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, It is desirable to include a group hydrolysis inhibitor.

Examples of such a stabilizer include ethanolamines such as ethanolamine, diethanolamine, and triethanolamine; β-diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane;
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 varies depending on the type of the metal alkoxide used, the amount of the nitrofuran derivative, the required moisture resistance, the stability over time, and the like. It is preferably 5 times or less, particularly preferably 0.5 to 2 times, the mole of the alkoxide.
If the ratio of the stabilizer exceeds 5 times the molar amount of the metal alkoxide, the photosensitivity of a stabilizer that is more easily bonded to a metal than a nitrofuran derivative is undesirably reduced.

The composition and the method of the present invention comprise 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 such as (RuO ₂ ) (including both a composite metal oxide and a single metal oxide). Naturally, to form a thin film of these metal oxides, a metal oxide raw material containing an alkoxide of a metal of these metal oxides is used.

The present invention is particularly suitable for those containing two or more metal alkoxides. For example, Sr alkoxide Sr (OR) ₂ (R: alkyl group), Bi alkoxide Bi (OR) ₃ , A Ta alkoxide Ta (OR) ₅ and / or a Nb alkoxide Nb (OR) ₅ containing SrBi ₂ (Ta _x
The composition for forming a Bi layered oxide-based thin film pattern represented by Nb _2-x ) O ₉ or, in this composition, bismuth carboxylate, bismuth nitrate, bismuth chloride and bismuth sulfate instead of Bi alkoxide Those containing one or more selected from the group are mentioned.

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 mixed with 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 adding a predetermined amount of a nitrofuran derivative to the resulting solution. By heating and refluxing the and the nitrofuran derivative in a solvent to form a complex of the metal alkoxide and the nitrofuran derivative in advance, it is preferable to add another component such as a stabilizer, It is possible to improve the light sensitivity and reduce the amount of the nitrofuran derivative used. In order to prevent the reverse reaction of complexation, a method of removing the generated organic matter is also effective.

When the target is a composite oxide thin film pattern, two or more kinds of metal oxide raw materials are used in proportions corresponding to the abundance of each metal in the target.
When two or more metal alkoxides are contained,
It is preferable to heat and reflux at least one kind of metal alkoxide in a solvent to form a composite alkoxide in advance, and then add another additive such as a stabilizer. Also in this case, it is desirable that the nitrofuran derivative is heated and refluxed in a solvent together with the complex alkoxide to form a complex. In this case as well, a method of removing the generated organic matter is also effective to prevent the reverse reaction of complexation.

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

The application of this composition to a substrate is not particularly limited as long as it is a coating method capable of forming a coating film having a uniform thickness, but a spin coating method is often employed industrially. If necessary, after the coating film has gelled, the coating operation can be repeated 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 nitrofuran derivative, the coating film can be thickened. Generally, the thickness of the metal oxide thin film formed using the composition of the present invention is preferably in the range of 300 to 1000 °.

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

Next, in order to form an image corresponding to a desired pattern, light is irradiated to perform image forming exposure. As the light to be irradiated, ultraviolet light is generally used. The ultraviolet source may be, for example, an ultra-high pressure mercury lamp, a low pressure mercury lamp, an excimer laser, or the like. The image forming exposure can be carried out by a conventional method by irradiating light through a mask or, when the light source is a laser, by a direct drawing method of irradiating patterned laser light. The irradiation energy amount is not particularly limited and varies depending on the film thickness and the kind of the metal oxide raw material. However, according to the present invention, the addition of the nitrofuran derivative usually results in a low energy amount of 0.5 to ² J / cm ^2. It can be.

In particular, when the metal alkoxide and the nitrofuran derivative are previously compounded, the energy can be further reduced to 0.1 to ² J / cm ² by improving the photosensitivity.

By the irradiation of the light, the exposed portion is hardened by the photoreaction of the metal alkoxide in the exposed portion, as described later, and the solubility in a solvent such as alcohol is reduced. In the present invention, since the nitrofuran derivative is preferably present as a complex with a metal alkoxide,
The photoreaction of the metal alkoxide in the exposed part can be selectively promoted with a small light irradiation energy. for that reason,
Irradiation can be sufficiently achieved in a short time even with ultraviolet rays having low energy density.

If desired, after this irradiation, the temperature is raised to 40 to 100 ° C. in a dry inert gas (N ₂ , Ar, etc.) atmosphere.
It may be left for about 10 minutes. By blocking the moisture in the air and maintaining the temperature in this manner, the curing reaction of the coating film on the exposed portion can be selectively further advanced while suppressing the hydrolysis of the coating film component on the unexposed portion. The solubility difference between the part and the unexposed part is further increased.

After the irradiation, the coating may be dried by heating the entire surface of the substrate, if necessary. As a result, the moisture and the organic solvent remaining in the exposed portion remaining as a pattern are removed. This overall heating is, for example,
What is necessary is just to perform at 100-150 degreeC for about 5 to 10 minutes.

Thereafter, the uncured coating film in the unexposed portions is removed by developing with an appropriate solvent, and a negative pattern composed of the exposed portions is formed on the substrate.
The solvent used as the developer only needs to be a solvent that can dissolve the material in the unexposed portion and has low solubility in the cured film in the exposed portion. In general, it is preferable to use water or alcohols. Suitable alcohols include alkoxy alcohols such as 2-methoxyethanol and 2-ethoxyethanol. In this case, when the dissolving power is too high and dissolution of the exposed portion can occur, the dissolving power can be adjusted by adding an alkyl alcohol such as ethyl alcohol or isopropyl alcohol (IPA) to the alcohol.

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

After the development, that is, after pulling up the coating film sample from the developing solution, if necessary, in order to prevent the remaining film portion from being dissolved by the developing solution attached to the coating film and to completely stop the development, a rinsing solution may be used. May be performed by immersing the developing solution in the developing solution. As the rinsing liquid, a solvent which has a low dissolving power of the film and is easily mixed with the developing solution is preferable. In general, lower alcohols are preferably used. Suitable alcohols include ethyl alcohol and isopropyl alcohol.

In this way, a negative-type coating film pattern with the exposed portions remaining is formed on the substrate. Thereafter, when the substrate is heat-treated to completely convert the metal compound in the coating film into a metal oxide, a thin film pattern composed of a metal oxide having a desired composition is obtained. This heat treatment is usually performed in an air atmosphere at 300 to 80.
It is preferable to perform baking 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.

The electronic components manufactured according to such a method include DRAM, nonvolatile ferroelectric thin film memory, bipolar memory, semiconductor memory such as GaAsIC, 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.

[0057]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 Lead acetate trihydrate in 75 g of 2-methoxyethanol
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 tetranormal butoxide and 4.19 g of titanium tetraisopropoxide were added, and the total amount was adjusted to 100 g with 2-methoxyethanol to adjust the weight.
bZr _0.52 Ti _0.48 O ₃ (PZT) solution was obtained, and 2-nitrofuran was added to this solution at the ratio shown in Table 1 to obtain a PZT solution.
This was a composition for forming a T thin film pattern.

Each of the obtained compositions is applied on a silicon substrate by a spin coating method so as to have a film thickness of 500 °, and the applied film is irradiated with ultraviolet rays having an energy amount shown in Table 1 through a photomask. And immersion in a mixed solvent of 1: 2 (volume ratio) of 2-methoxyethanol and isopropyl alcohol for 10 seconds for development. Table 1 shows whether patterning is possible (O) or not (X).

[0060]

[Table 1]

Example 2 32.96 g of a 5 wt% Ba solution prepared from barium octylate and isoamyl acetate, a 5 wt% Sr solution prepared from strontium octylate and isoamyl acetate 21.
03g and titanium tetraisopropoxide 6.82
g and mixed with isoamyl acetate to make the total amount 100 g.
Obtain the weight percent of _{Ba 0.5 Sr 0.5 TiO 3 (BST} ) solution was added at a rate that indicates the 2-nitro-furan To this solution to each table 2, and a BST thin film pattern forming composition.

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

[0063]

[Table 2]

Example 3 8.68 g of a 5 wt% Sr solution prepared from strontium octylate and isoamyl acetate, 41.2 wt% Bi solution prepared from bismuth octylate and isoamyl acetate
1 g of tantalum pentaethoxide and 4.01 g of tantalum pentaethoxide, and 1: 1 of isoamyl acetate and 2-methoxyethanol.
(Volume ratio) The total amount was made 100 g with a mixed solvent to obtain a 5% by weight SrBi ₂ Ta ₂ O ₉ solution. To this solution, 2-nitrofuran was added in the proportions shown in Table 3 to obtain SrBi ₂ Ta _2.
This was a composition for forming an O ₉ thin film pattern.

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

[0066]

[Table 3]

Example 4 1.76 g of lithium ethoxide, 10.76 g of niobium pentaethoxide and 87.48 of 2-methoxyethanol
g of LiNbO ₃ solution to obtain a 5% by weight LiNbO ₃ solution.
The composition for forming an iNbO ₃ thin film pattern was used.

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

[0069]

[Table 4]

Example 5 71.26 g of a 5% by weight Bi solution prepared from bismuth octylate and isoamyl acetate and 3.65 g of titanium tetraisopropoxide were mixed, and isoamyl acetate and 2-amyl acetate were mixed.
The total amount was made 100 g with a 1: 1 (volume ratio) mixed solution of methoxyethanol to obtain a 5 wt% Bi ₄ Ti ₃ O ₁₂ solution, and 2-nitrofuran was added to this solution at the ratio shown in Table 5 to obtain a Bi ₂ Ti ₃ O 2 solution. _A composition for forming a ₄ Ti ₃ O ₁₂ thin film pattern was obtained.

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

[0072]

[Table 5]

Example 6 Instead of 2-nitrofuran, anti-5-nitro-2-
Except that furaldoxime was added in the proportions shown in Table 6.
A composition for forming a PZT thin film pattern was obtained in the same manner as in Example 1. Exposure and development were performed in the same manner, and Table 6 shows whether patterning was possible (O) or not (X).

[0074]

[Table 6]

Example 7 Instead of 2-nitrofuran, anti-5-nitro-2-
Except that furaldoxime was added in the proportions shown in Table 7.
A composition for forming a BST thin film pattern was obtained in the same manner as in Example 2. Exposure and development were performed in the same manner, and Table 7 shows whether patterning was possible (O) or not (X).

[0076]

[Table 7]

Example 8 Instead of 2-nitrofuran, anti-5-nitro-2-
Except that furaldoxime was added in the proportions shown in Table 8,
A composition for forming a SrBi ₂ Ta ₂ O ₉ thin film pattern was obtained in the same manner as in Example 3. Exposure and development were carried out in the same manner.

[0078]

[Table 8]

Example 9 Instead of 2-nitrofuran, anti-5-nitro-2-
Except that furaldoxime was added in the proportions shown in Table 9.
A composition for forming a LiNbO ₃ thin film pattern was obtained in the same manner as in Example 4. Exposure and development were performed in the same manner, and Table 9 shows whether patterning was possible (O) or not (X).

[0080]

[Table 9]

Example 10 In place of 2-nitrofuran, anti-5-nitro-2-
Except that furaldoxime was added at the ratio shown in Table 10, a composition for forming a Bi ₄ Ti ₃ O ₁₂ thin film pattern was obtained in the same manner as in Example 5, and exposure and development were performed in the same manner to allow patterning (可). , No (X) are shown in Table 10.

[0082]

[Table 10]

Example 11 A PZT thin film pattern forming composition was obtained in the same manner as in Example 1 except that 5-nitro-2-furanoic acid was added in place of 2-nitrofuran at the ratio shown in Table 11. Exposure and development are performed in the same manner, and patterning is possible (○), not possible (×)
Are shown in Table 11.

[0084]

[Table 11]

Example 12 A composition for forming a BST thin film pattern was obtained in the same manner as in Example 2 except that 5-nitro-2-furanoic acid was added in place of 2-nitrofuran at the ratio shown in Table 12. Exposure and development are performed in the same manner, and patterning is possible (○), not possible (×)
Are shown in Table 12.

[0086]

[Table 12]

Example 13 A SrBi ₂ Ta ₂ O ₉ thin film pattern was formed in the same manner as in Example 3 except that 5-nitro-2-furonic acid was added in place of 2-nitrofuran at the ratio shown in Table 13. The composition for use was obtained, exposed and developed in the same manner, and Table 13 shows whether patterning was possible (O) or not (X).

[0088]

[Table 13]

Example 14 A composition for forming a LiNbO ₃ thin film pattern was prepared in the same manner as in Example 4 except that 5-nitro-2-furanic acid was added in place of 2-nitrofuran at the ratio shown in Table 14. Then, exposure and development were performed in the same manner, and Table 14 shows whether patterning was possible (O) or not (X).

[0090]

[Table 14]

Example 15 A Bi ₄ Ti ₃ O ₁₂ thin film pattern was formed in the same manner as in Example 5 except that 5-nitro-2-furanoic acid was added in place of 2-nitrofuran at the ratio shown in Table 15. A composition for
Exposure and development are performed in the same way to enable patterning (○),
Table 15 shows the results of failure (x).

[0092]

[Table 15]

Example 16 A PZT thin film pattern forming composition was obtained in the same manner as in Example 1 except that 5-nitro-2-furaldehyde was added in place of 2-nitrofuran at the ratio shown in Table 16. In the same manner, exposure and development were performed, and patternability (O) and failure (X) are shown in Table 16.

[0094]

[Table 16]

Example 17 A composition for forming a BST thin film pattern was obtained in the same manner as in Example 2 except that 5-nitro-2-furaldehyde was added in place of 2-nitrofuran at the ratio shown in Table 17. In the same manner, exposure and development were performed, and patternability (O) and failure (X) were shown in Table 17.

[0096]

[Table 17]

Example 18 A SrBi ₂ Ta ₂ O ₉ thin film pattern was formed in the same manner as in Example 3 except that 5-nitro-2-furaldehyde was added in place of 2-nitrofuran at the ratio shown in Table 18. The composition for exposure was obtained and exposed and developed in the same manner. Table 18 shows whether patterning was possible (O) or not (X).

[0098]

[Table 18]

Example 19 The composition for forming a LiNbO ₃ thin film pattern was prepared in the same manner as in Example 4 except that 5-nitro-2-furaldehyde was added in place of 2-nitrofuran at the ratio shown in Table 19. Then, exposure and development were performed in the same manner, and Table 19 shows whether patterning was possible (O) or not (X).

[0100]

[Table 19]

Example 20 A Bi ₄ Ti ₃ O ₁₂ thin film pattern was formed in the same manner as in Example 5 except that 5-nitro-2-furaldehyde was added in place of 2-nitrofuran at the ratio shown in Table 20. The composition for use was obtained, exposed and developed in the same manner, and Table 20 shows whether patterning was possible (O) or not (X).

[0102]

[Table 20]

From Tables 1 to 20, it is clear that the addition of a predetermined ratio of the nitrofuran derivative can significantly reduce the irradiation energy required for exposure.

Example 21 In Example 1, 2-nitrofuran was added in an equimolar amount to the metal alkoxide, and then a stabilizer shown in Table 21 was further added in a 1.5-fold molar amount to the metal alkoxide. Except for the above, a composition for forming a PZT thin film pattern was prepared in the same manner.

Each of the obtained compositions was applied on a silicon substrate by spin coating so as to have a thickness of 500 °. ² J / cm ² through a photomask through this coating film
And then left in a constant temperature / humidity room at a room temperature of 25 ° C. and a humidity of 70% for the time shown in Table 21. Thereafter, the mixture was placed in a 1: 2 (volume ratio) mixed solvent of 2-methoxyethanol and isopropyl alcohol. It was immersed for 2 seconds and developed, and the stability over time in a high humidity atmosphere was examined depending on whether or not patterning was possible. The results are shown in Table 21. In Table 21, the mark “○” indicates that the pattern was formed, and the mark “X” indicates that the non-light-irradiated portion was insolubilized due to hydrolysis in the moisture in the air and could not be patterned.

[0106]

[Table 21]

Example 22 In Example 2, anti-nitrofuran was used instead of 2-nitrofuran.
5-nitro-2-furaldoxime was added in an equimolar amount to the metal alkoxide, and the stabilizer shown in Table 22 was added in a 1.5-fold molar amount to the metal alkoxide in the same manner as described above for forming a BST thin film pattern. A composition was prepared.

Each of the obtained compositions was prepared in Example 2
In the same manner as in Example 1, coating, light irradiation, standing, and development were performed, and the stability over time was examined. The results are shown in Table 22.

[0109]

[Table 22]

Example 23 In Example 1, 5-nitro-2-furonic acid was added in an equimolar amount to the metal alkoxide in place of 2-nitrofuran, and then a stabilizer shown in Table 23 was added to the metal alkoxide. In the same manner as above except that
A composition for forming a ZT thin film pattern was prepared.

Each of the obtained compositions was prepared in Example 2.
Coating, light irradiation, standing, and development were performed in the same manner as in Example 1 to examine the stability with time. The results are shown in Table 23.

[0112]

[Table 23]

Example 24 A 5 wt% Ba solution of 2-methoxyethoxy Ba prepared by dissolving Ba metal in 2-methoxyethanol
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 mixed with 2-methoxyethanol. 100 g, 5% by weight of Ba _0.5 Sr _0.5 TiO
₃ (BST) solution was obtained, and 2-nitro-2-furaldehyde was added to this solution in an equimolar amount to the metal alkoxide.
Further, a stabilizer shown in Table 24 was added in a 1.5-fold molar amount to the metal alkoxide to prepare a composition for forming a BST thin film pattern.

Each of the obtained compositions was prepared in Example 2.
Coating, light irradiation, standing, and development were performed in the same manner as in Example 1 to examine the stability over time. The results are shown in Table 24.

[0115]

[Table 24]

Example 25 Tetra-tert-butoxytin Sn (Ot-Bu) ₄
12.28 g and tributoxyantimony Sb (OBu)
₃ 1.05 g was dissolved in 86.67 g of 2-methoxyethanol to obtain a 5% by weight ATO solution. To this solution, 2-nitro-2-furaldehyde was added twice as much as the metal alkoxide (total number of moles of Sn and Sb), and the stabilizer shown in Table 25 was added 1.5 times as much as the metal alkoxide. Thus, a composition for forming an ATO thin film pattern was prepared.

Each of the obtained compositions was prepared in Example 2
In the same manner as in Example 1, coating, light irradiation, standing, and development were performed, and the stability over time was examined. The results are shown in Table 25.

[0118]

[Table 25]

From Tables 21 to 25, it is clear that the use of a stabilizer improves the temporal stability of the composition for forming a metal oxide thin film pattern under a high humidity environment.

Example 26 A metal alkoxide shown in Table 26 was dissolved in 2-methoxyethanol, and 2-nitrofuran was added to the solution in the amount (molar ratio) shown in Table 26. A complex of 2-nitrofuran was formed. This solution is spin-coated on a silicon substrate to a thickness of 500
Å was applied. This coating film is irradiated with 0.1 J / cm ² ultraviolet light through a photomask,
-Methoxyethanol and isopropyl alcohol 1:
Table 2 shows whether patterning was possible (浸漬) or not (混合).

[0121]

[Table 26]

Example 27 A complex was formed, coated, irradiated with light and developed in the same manner as in Example 26 except that anti-5-nitro-2-furaldoxime was used instead of 2-nitrofuran. Whether patterning was possible (O) or not (X) was examined, and the results are shown in Table 27.

[0123]

[Table 27]

Example 28 A composite was formed, coated, irradiated with light and developed in the same manner as in Example 26 except that 5-nitro-2-furanoic acid was used instead of 2-nitrofuran, and patterning was carried out. The results were shown in Table 28.

[0125]

[Table 28]

Example 29 A composite was formed, coated, irradiated with light, and developed in the same manner as in Example 26 except that 5-nitro-2-furaldehyde was used instead of 2-nitrofuran. (OK) and NO (X) were checked, and the results are shown in Table 29.

[0127]

[Table 29]

As is clear from Tables 26 to 29, by complexing a metal alkoxide with a nitrofuran derivative, patterning with low energy irradiation becomes possible even when the amount of the nitrofuran derivative added is small.

Example 30 9.3 g of bismuth-t-pentoxite, 8.71 g of tantalum ethoxide and 9.95% by weight of strontium-
Mixture of 2-methoxyethanol solution 8.03g to Bi ₂ SrTa ₂ complex alkoxide formed by heating to reflux was added 2-nitro-furan ratio shown in Table 24 to form a complex, still remaining in the composite alkoxide 2.3 g of 2-methylbutyric acid is added to suppress the high hydrolyzability of the functional group and stabilize the solution, and finally prepared with 2-methoxyethanol to obtain 10% by weight of Bi ₂ Sr ₁ T.
100 g of a ₂ O ₉ thin film pattern forming composition was obtained.

Each of the obtained compositions was applied on a silicon substrate by spin coating so as to have a film thickness of 800 °, and the applied film was irradiated with ultraviolet rays having an energy amount shown in Table 30 through a photomask. And immersed in an isopropyl alcohol solvent for 10 seconds for development. Table 30 shows whether patterning is possible (O) or not (X).

[0131]

[Table 30]

Example 31 Except that anti-5-nitro-2-furaldoxime was added in place of 2-nitrofuran in the proportions shown in Table 31,
10% by weight Bi ₂ Sr ₁ Ta ₂ as in Example 30
The composition for forming an O ₉ thin film pattern was obtained and exposed and developed in the same manner to determine whether patterning was possible (○) or not (×).
It was shown to.

[0133]

[Table 31]

Example 32 A mixture of 27.1 g of tantalum ethoxide and 29.4 g of a 9.95% by weight strontium-2-methoxyethanol solution was formed by heating under reflux, and 15% by weight SrTa prepared with 2-methoxyethanol was prepared. ₂ complex alkoxide 10
0 g of 2-nitrofuran in the proportions shown in Table 32 was added to form a complex.
It was added methyl butyrate 7.8 g, further the solution 9.63 wt% bismuth 2-ethylhexanoate were isoamyl acetate as a solvent was added to 2- 10% by weight methoxy ethanol by finally preparing Bi ₂ Sr ₁ Ta ₂ O ₉
A composition for forming a thin film pattern was obtained.

Using the obtained composition, exposure and development were carried out in the same manner as in Example 30. Table 32 shows whether patterning was possible (O) or not (X).

[0136]

[Table 32]

Example 33 Except that anti-5-nitro-2-furaldoxime was added in place of 2-nitrofuran in the proportions shown in Table 33,
10% by weight Bi ₂ Sr ₁ Ta ₂ as in Example 32
The composition for forming an O ₉ thin film pattern was obtained and exposed and developed in the same manner. Table 3 shows whether patterning was possible (可) or not (×).

[0138]

[Table 33]

Example 34 In Example 32, the bismuth raw material was replaced with bismuth nitrate 2-
1 in the same manner except that a methoxyethanol solution was used.
A composition for forming a 0% by weight Bi ₂ Sr ₁ Ta ₂ O ₉ thin film pattern was obtained, and exposed and developed in the same manner. Table 34 shows whether patterning was possible (O) or not (X).

[0140]

[Table 34]

From Tables 26 to 33, it is clear that better results can be obtained by forming a composite alkoxide of a metal alkoxide and further adding a nitrofuran derivative to form a composite.

[0142]

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 production steps is small, the cost is low, and the efficiency is low. By the sol-gel method capable of efficient patterning, it is possible to further reduce the patterning time and the patterning cost without causing deterioration in the characteristics of the metal oxide thin film pattern to be formed, thereby reducing the patterning time and the patterning cost. Patterning can be performed.
Therefore, according to the method for manufacturing an electronic component and an optical component of the present invention, an electronic component and an optical component having high characteristics can be easily, efficiently, and inexpensively manufactured by such a method.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Katsumi Ogi 1-297 Kitabukuro-cho, Omiya City, Saitama Prefecture, Mitsubishi Materials Research Institute (56) References JP-A-7-187669 (JP, A) JP-A-7-268637 (JP, A) JP-A-6-166501 (JP, A) JP-A-1-313329 (JP, A) JP-A-5-116454 (JP, A) JP-A-6-172068 (JP) , A) JP-A-60-243279 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C23C 18/14 C01B 13/32 H01L 21/316 C01G 1/02 G03F 7/004 502

Claims (19)

(57) [Claims] Claims: 1. A composition for forming a metal oxide thin film pattern by light irradiation, comprising a metal alkoxide, comprising a nitrofuran derivative. . 2. The composition for forming a metal oxide thin film pattern according to claim 1, wherein the nitrofuran derivative is contained in a molar amount of 0.05 to 6 times the amount of the metal alkoxide. 3. The composition for forming a metal oxide thin film pattern according to claim 2, wherein the nitrofuran derivative is contained in a molar amount of 0.3 to 2 times the amount of the metal alkoxide. 4. The composition for forming a metal oxide thin film pattern according to claim 1, wherein the nitrofuran derivative is 2-nitrofuran. 5. The composition for forming a metal oxide thin film pattern according to claim 1, wherein the nitrofuran derivative is anti-5-nitro-2-furaldoxime. 6. The composition for forming a metal oxide thin film pattern according to claim 1, wherein the nitrofuran derivative is 5-nitro-2-furonic acid. 7. The composition for forming a metal oxide thin film pattern according to claim 1, wherein the nitrofuran derivative is 5-nitro-2-furaldehyde. 8. The composition according to claim 1, further comprising a metal alkoxide stabilizer which does not show strong absorption in the wavelength region of the irradiation light. Composition for forming thin film patterns. 9. The composition according to 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. 10. The composition according to claim 1, wherein the metal alkoxide and the nitrofuran derivative are dissolved in a solvent and heated to reflux to form a mixture of the metal alkoxide and the nitrofuran derivative. A composition for forming a metal oxide thin film pattern, comprising a composite. 11. The composition for forming a metal oxide thin film pattern according to claim 1, which comprises two or more metal alkoxides. 12. The composition for forming a metal oxide thin film pattern according to claim 10, wherein two or more metal alkoxides are contained as a composite alkoxide. 13. The method for producing a composition according to claim 1, wherein the metal alkoxide and the nitrofuran derivative are heated and refluxed in a solvent to thereby form the metal alkoxide and the metal alkoxide in advance. A method for producing a composition for forming a metal oxide thin film pattern, which comprises adding a component after forming a complex with a nitrofuran derivative. 14. A method for producing the composition according to claim 7, wherein the metal alkoxide and the nitrofuran derivative are heated and refluxed in a solvent to thereby form the metal alkoxide and the metal alkoxide in advance. After forming a complex with a nitrofuran derivative, the above-mentioned nitrofuran derivative is added and heated under reflux to form a complex of a complex alkoxide and a nitrofuran derivative, and then a stabilizer is added. For producing a composition for forming a metal oxide thin film pattern. 15. A method for producing the composition according to claim 10, wherein two or more metal alkoxides are heated and refluxed in a solvent to form a composite alkoxide in advance, and then other components are added. A method for producing a composition for forming a metal oxide thin film pattern, characterized by comprising: 16. A method for producing the composition according to claim 10, wherein two or more metal alkoxides are heated to reflux in a solvent to form a composite alkoxide in advance, and then a stabilizer is added. A method for producing a composition for forming a metal oxide thin film pattern, characterized by comprising: 17. After applying the composition for forming a metal oxide thin film pattern according to any one of claims 1 to 12 to a substrate, irradiating the obtained coating film with light according to a predetermined pattern. Forming a metal oxide thin film pattern by patterning the coating film using a difference in solubility of a light-irradiated portion and a non-irradiated portion in a solvent caused by the photoreaction. 18. A method for manufacturing an electronic component, comprising: manufacturing an electronic component having a metal oxide thin film pattern according to the method according to claim 17. 19. A method for manufacturing an optical component, comprising: manufacturing an optical component having a metal oxide thin film pattern according to the method according to claim 17.