JP2003096574A - Method for producing oxide ceramic patterned film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing oxide ceramic patterned film which is such a method that a patterned self-organization film is made a template and an oxide ceramic is selectively grown thereon. SOLUTION: The patterned self-organization film formed by the surface functional groups by which the catalyst metal is easily attached to an organic silane film formed on a substrate and the surface functional groups by which the catalyst metal is hardly attached to the same is made the template. Therein, the oxide ceramic patterned film is produced by depositing the metal oxide film on the surface functional group part to which the catalyst metal is easily attached by using an electroless deposition method based on nitric acid ion reduction using a borane amine complex. Otherwise, a hydroxide film is deposited in stead of the oxide film and is heated in an oxidizing environment and, thereby, the oxide ceramic patterned film may be produced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an oxide ceramics patterned film useful as an electronic material (transparent electrode or dielectric), magnetic material, optical material (fluorescent material, etc.).

[0002]

2. Description of the Related Art Usually, patterning of a ceramic film is performed by selective etching. That is, after synthesizing the ceramic thin film, an organic resist material is applied, and thereafter, light is applied through a photomask to selectively cure the resist material.
Next, the part not exposed to light is melted and peeled off. Then, the ceramic film is partially melted by performing treatment in a ceramic etchant in the wet process and etching in plasma in the dry process. Finally, the resist material is peeled off.

However, such a manufacturing method has complicated steps as described above, and the selection of an etching agent and
There is a problem that it is difficult to find suitable etching conditions such as processing time, temperature and concentration. Further, there is a problem that the etching of the ceramic film is exceeded and the underlying substrate is also etched.

A patterning method using a lift-off process is also used. First, an organic resist material is applied, and then light is applied through a photomask to selectively cure it. Next, the part not exposed to light is melted and peeled off. A ceramic thin film is synthesized on it. Thereafter, when the resist material is treated in a solvent, the resist material is dissolved and peeled off together with the ceramics thereon.

However, in this method, since a uniform thin film is partially broken to be peeled off, there are many problems such as peeling off a portion to be left and a limit of resolution of pattern boundary.

Therefore, attempts have been made to pattern the ceramic film by using the patterned self-assembled film as a template. However, it may be necessary to peel it off by using the difference in adhesive force after film formation on the whole surface,
It had the same problems as the lift-off process described above.

As a method for forming oxide ceramics,
Various methods have been proposed so far, including a sputtering method, a chemical vapor deposition (CVD) method, a spray method, and an electrochemical deposition method. By these methods, even if the oxide ceramics is formed on the substrate on which the patterned self-assembled film is formed, since the self-assembled film is an organic film, high temperature conditions,
In an environment that synthesizes by energizing, it breaks and cannot function. Therefore, regardless of the pattern of the self-assembled film, the film is entirely deposited, and it is not possible to form the oxide ceramic pattern film by selective precipitation.

[0008]

SUMMARY OF THE INVENTION The present invention is to develop a method for producing an oxide ceramics pattern film by using a patterned self-assembled film as a template and selectively growing oxide ceramics on the template. With the goal.

[0009]

The present invention has been achieved as a result of searching for a method of utilizing a patterned self-assembled monolayer formed on a substrate in order to achieve the object, and the nitrate ion of borane amine complex is reached. The method is characterized in that a patterned film is produced by an electroless deposition method of a metal oxide or a hydroxide by reduction.

That is, according to the present invention, a borane amine complex is formed by using a patterned self-organizing film formed by a surface functional group to which a catalytic metal is often attached and a surface functional group which is difficult to be attached to an organosilane film formed on a substrate as a template. A method for producing an oxide ceramics patterned film, which comprises depositing an oxide film of a metal on a surface functional group portion to which a catalyst metal often adheres by an electroless deposition method using nitrate ion reduction used.

Further, according to the present invention, a borane amine complex is formed by using a patterned self-organizing film formed by a surface functional group to which a catalytic metal is often attached and a surface functional group which is not easily attached to an organosilane film formed on a substrate as a template. Oxide ceramics patterning characterized by depositing a metal hydroxide film on the surface functional group part where the catalyst metal adheres well by the electroless deposition method using nitrate ion reduction and heating it in an oxidizing atmosphere It is a manufacturing method of a film.

The patterned self-assembled film is obtained by patterning the surface functional groups of the self-assembled film on the substrate, and the adhesive force of the catalytic metal such as palladium coated on the surface functional group of the self-assembled film is Depends on Therefore, by combining a surface functional group that adheres well and a surface functional group that does not easily adhere, it becomes possible to selectively adhere a catalytic metal such as palladium.

The surface functional group to which the catalyst metal adheres well has an aromatic hydrocarbon group, an amino group or a vinyl group, and the surface functional group to which the catalyst metal hardly adheres has a hydroxyl group or an alkyl group. However, it is not particularly limited.

The present invention is characterized by using an electroless deposition method of nitrate ion reduction of borane amine complex for synthesizing oxide ceramics. This method is a soft method that can be synthesized at a low temperature of 100 ° C. or lower. Because of the chemical method, the action as a template can be fully utilized without destroying the self-organizing film. In addition, since this reaction is strongly promoted by catalytic metals such as palladium, metal hydroxide or oxide can be deposited only on the catalyst selectively adhered to the substrate, and patterning of oxide ceramics is possible. Becomes

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION
First, a self-assembled film is prepared, but a method of dissolving the film substance in an organic solvent and immersing the substrate in this solution or vapor deposition of the film substance is performed. An oxide, a metal having an oxide film on its surface, or a semiconductor is used for the substrate.

As the membrane substance for the self-assembled membrane, chlorine group,
Organosilanes having 1 to 3 halogen groups such as bromine groups or alkoxy groups such as methoxy groups and ethoxy groups, and 1 to 3 organic functional groups are used. As the organic functional group, a terminal group such as a phenyl group, an alkyl group or an amino group is used.

The patterning of the self-assembled film is performed by forming a self-assembled film on the entire surface of the substrate and then irradiating it with ultraviolet light through a photomask, drawing with an ultraviolet laser, an electron beam or an ion beam, or using a microchip. A method such as partially changing the surface functional groups of the self-organizing film by drawing by scratching is used.

A method of partially forming a self-organizing film on a substrate using a micro stamp is also used. In addition, after patterning by these treatments, it is also possible to change the surface functional group by producing another self-organizing film on the portion where the self-organizing film is not attached or changed. Alternatively, a patterned substrate obtained by combining two or more types of self-assembled films may be used as a template.

As the metal catalyst to be applied to the substrate, palladium, platinum, silver or the like which is used when forming a metal electroless plating film is used. As a method of applying a catalyst, a method similar to that for electroless plating of metal is used, and a method such as a sensitizing / activating method or a colloid / accelerator method is used. However, the purpose is that the metal catalyst is adsorbed on the substrate, and the method is not limited. Also, the same effect can be obtained by using an organic silane used for forming the self-assembled film with a metal such as palladium.

In addition to the above-mentioned metals, a coexisting catalyst such as tin oxide for improving the adhesion effect is also effective. Further, as the form of the catalyst metal, even if it is not a metal,
Either a metal ion or a surface metal oxide may be used. However, it is effective to acidify and metallize it for activation.

The kind of metal of the oxide ceramics to be produced by the present invention is a metal oxide or hydroxide film deposited on the surface functional group portion to which the catalyst metal is often attached by the electroless deposition method by nitrate ion reduction. Any type of metal can be used, and the type of metal is not limited. Group 1A metals do not take the form of hydroxides and oxides, while Group 2A metals such as Mg take the form of hydroxides, but the precipitation pH is too high at 10 or higher, so it is not powdered on the substrate, but powder. It is not suitable because it forms as a precipitate. Further, noble metals are not suitable because it is difficult to prepare an aqueous solution. For example, a first transition metal such as iron or zinc, indium, or tin is preferable because an oxide or hydroxide film can be easily formed.

It is possible to use these oxides or hydroxides to which additives have been added or complex oxides. The additives and oxides to be complexed here are limited to those which can be coprecipitated under the film forming conditions of the base substance.

When borane amine complex is added to an aqueous solution containing a metal ion capable of forming an oxide or hydroxide film and a nitrate ion to reduce the nitrate ion to a nitrite ion, the pH of the aqueous solution rises and metal hydroxide is added. The precipitation of an object or an oxide can occur. The reduction reaction of this nitrate ion to nitrite ion is strongly promoted by a metal catalyst such as palladium, so that the metal hydroxide or oxide can be deposited only on the catalyst selectively adhered to the substrate. It enables selective film formation of oxide ceramics.

The chemical species of the compound of the metal ion source in the aqueous solution used in the present invention is not particularly limited, and examples thereof include nitrates, sulfates, chlorides, carbonates and the like. The nitrate ion source is also not particularly limited, and metal nitrate, ammonium nitrate, sodium nitrate, potassium nitrate and the like can be used. The concentration of metal ions and nitrate ions is
If it is too low, the amount of precipitation becomes extremely small and a ceramic film cannot be obtained. Also, if it is too high, the deposition rate will increase,
A film with good film quality cannot be obtained. The concentration is 0.0001 mol /
L to 1 mol / l is suitable, and about 0.01 mol / l is preferable.

Borane amine complex is used as a reducing agent for reducing nitrate ions to nitrite ions. The borane amine complex may be any water-soluble compound, and examples thereof include dimethylamine borane and trimethylamine borane. The concentration is not particularly limited, but if it is low, the deposition rate of the film becomes slow and it is difficult to obtain a ceramic film. On the other hand, if it is too high, powdery precipitation will occur, which is not suitable for film formation. Therefore, 0.001 mol / liter to 0.5 mol / liter
L is preferred.

To form the oxide ceramics film, the substrate is immersed in an aqueous solution containing metal ions, nitrate ions and borane amine complex and heated. Liquid temperature is 40 ℃ to 100 ℃
Is preferred. Below this, the reaction rate is low and it is difficult to obtain a film. Further, if it is higher than this, it is difficult to maintain the concentration of the solution, which is not preferable.

The pH of the aqueous solution is not particularly limited, but if the pH is low, the film forming rate will be low and it will be difficult to obtain a film. If the pH is too high, powdery precipitation will occur, which is not suitable for film formation. Therefore, the solution
The pH is preferably about 3 to 8.

Further, depending on the substance, it may be precipitated as hydroxide instead of oxide. At this time, it can be obtained as an oxide by heating in an oxidizing atmosphere. The heating temperature is not limited, but 150 ° C to 800 ° C is suitable.

[0029]

EXAMPLES Example 1: A phenyltrichlorosilane self-assembled film was formed on a silicon substrate having a natural oxide film to form a phenyl group on the surface, and then ultraviolet light of a mercury lamp was emitted through a photomask. After irradiation for a while, it was partially converted into hydroxyl groups to form a patterned self-assembled film. Next, a catalyst was applied using a palladium / tin colloidal solution (manufactured by Shipley). The substrate was immersed in an aqueous solution of 0.05 mol / liter of zinc nitrate and 0.05 mol / liter of dimethylamine borane to deposit zinc oxide. The reaction was performed at 60 ° C. Zinc oxide begins to precipitate only in the phenyl group portion in 5 minutes,
A patterned zinc oxide film was obtained.

Example 2: In Example 1, 0.01 mol /
The substrate was immersed in an aqueous solution of iron (III) nitrate and 0.03 mol / liter of dimethylamine borane. As a result, iron oxide was deposited on the phenyl group self-assembled film portion, and an iron oxide pattern was obtained.

Example 3: In Example 1, 0.05 mol /
The substrate was immersed in an aqueous solution of tin (II) chloride, 0.05 mol / liter of potassium nitrate, and 0.05 mol / liter of trimethylamine borane. As a result, tin oxide was deposited on the phenyl group self-assembled film portion and a pattern was obtained.

Example 4: In Example 1, glass was used as the substrate, trimethoxysilylethylpyridine was used as the self-assembling film substance, and palladium colloid synthesized using sodium palladium chloride was used as the catalyst, and 0.1 mol / liter was used. The substrate was immersed in an aqueous solution of indium nitrate of 0.05 mol / liter of trimethylamine borane. As a result, indium hydroxide was deposited on the self-assembled film portion terminated with pyridine. Then, it heated at 200 degreeC and obtained the indium oxide pattern.

Comparative Example 1: Using the patterned self-assembled film substrate used in Example 1, a zinc oxide film was formed by a sputtering method. The spatter has an output of 100 W and a pressure of 1 Pa.
In an Ar gas atmosphere at room temperature. However, there is little difference in the deposition rate between the hydroxyl group and the phenyl group,
The entire surface was deposited, and a pattern film could not be obtained.

Comparative Example 2: In Example 1, 0.05 mol /
The substrate was immersed by setting liter of magnesium nitrate and 0.05 mol / liter of dimethylamine borane aqueous solution to pH 8. However, a magnesium oxide film was not obtained.

[0035]

The functional oxide ceramic patterning technique of the present invention is useful for integration in device fabrication. Further, in the case of a fluorescent material, it is also useful for high resolution displays and the like.

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Claims (2)

[Claims] 1. A nitrate ion using a borane amine complex, using a patterned self-assembled film formed by a surface functional group to which a catalytic metal is often attached and a surface functional group which is difficult to be attached to an organosilane film formed on a substrate as a template. A method for producing an oxide ceramics patterned film, which comprises depositing an oxide film of a metal on a surface functional group portion to which a catalyst metal often adheres by an electroless deposition method by reduction. 2. A nitrate ion using a borane amine complex with a patterned self-assembled film formed by a surface functional group to which a catalytic metal is often adhered and a surface functional group which is difficult to adhere to an organosilane film formed on a substrate as a template. A method for producing an oxide ceramics patterned film, which comprises depositing a metal hydroxide film on a surface functional group portion to which a catalyst metal adheres well by an electroless deposition method by reduction and heating the film in an oxidizing atmosphere. .