JPH01111892A - Patternized electrolytically oxidized film and its formation - Google Patents

Abstract

PURPOSE:To form the above stable patternized electrolytically oxidized film by forming an aromatic compd. monomer film on the electrode substrate in the shape of a pattern, and then electrolytically oxidizing the film. CONSTITUTION:The aromatic compd. monomer film 3 is formed by sputtering, vapor deposition, etc., on the electrically conductive part 2 of the electrode substrate 1 in the shape of a pattern by using a metal mask, etc. The electrode substrate 1 is dipped in the electrolytic soln. 5 contg. an electrolyte along with a counter electrode 4. A DC voltage is impressed with the electrode substrate 1 as an anode and the counter electrode 4 as a cathode to form a patternized electrolytically oxidized film. As a result, a smooth, good-quality, and patternized electrolytically oxidized film can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an improved patterned electrolytic oxide film and a method for producing the same.

[Conventional technology and problems]

In recent years, digital display devices such as liquid crystal displays,
There is a rapid increase in demand for touch pen type handwriting input devices, facsimile machines, etc.

The display parts of these in-home devices, such as liquid crystal display devices and chromic display devices, connection of electrode extraction parts, touch ben input, image sensor output extraction for facsimile, etc. In contrast, there is a demand for an inexpensive film that has high conductivity in an arbitrary pattern. In addition, sensor elements are becoming smaller and more solid-state year by year, and for example, in the case of ion sensors, it is now possible to create a homogeneous film with conductivity and redox properties in any desired pattern for minute electrode parts. requested.

Conventionally, 3# conductive polymer films have been produced by mixing various thermoplastic resins with conductive fillers and molding them into films, by vapor-depositing conductive materials on the surface of polymer films, etc. Spray coating or plating have been used. With any of these films, it is easy to obtain a uniformly conductive film, but in order to obtain a film that has conductivity only in the desired pattern, it is necessary to perform some pattern forming process on the film. .

On the other hand, unlike such composite systems of metals or carbon and various resins, conductive polymer materials in which the polymer material itself is electrically conductive are attracting attention because of their high electrical conductivity. That is, a certain type of aromatic compound can be dissolved in a solvent containing an electrolyte and electrolytically oxidized to form a conductive polymer film on an electrode substrate. As such aromatic compounds, polycyclic compounds such as vinyl compounds and thiophenes, and polycyclic aromatic compounds such as azulene, pyrene, and triphenylene are known [for example, J, bourbon (J , Bar!1ion), S, Hohmand, R,J, Walt+++an,
113M Journal of Re5
Search & Development) No. 27
See Vol. 4, p. 330 (1983)]. In addition to exhibiting electrical conductivity, these polymers have reversible redox properties and electrochromism, and are attracting attention as materials for batteries, displays, and sensors.

However, in the method of forming a polymer film by electrolytic oxidation on an electrode substrate, the monomers that can be used are limited due to the solubility of the formed polymer, and the homogeneity of the formed film is low. There are various problems, such as the amount of chlorine used is large compared to the amount of membrane to be used, and the electrolytic solvent is significantly contaminated. Furthermore, the resulting conductive polymer film is generally brittle and difficult to mold, so no technology has been established for patterning it. Furthermore, in electro-S polymerization from such a seven-mer solution, the monomer in the solution diffuses to the electrode surface and polymerizes, but on the electrode surface, the diffusion state of the seven-mer is different between the center and the periphery, so the polymerization rate is slow. However, it is difficult to obtain a homogeneous polymeric film at each location on the electrode. When a patterned electrode is used, the diffusion state of the seven-layer compound becomes complicated depending on the size of the pattern and the density of the pattern, so a uniform film cannot be obtained and it is difficult to control polymerization.

Recently, a method has been discovered in which a general-purpose polymer such as polyvinyl chloride is coated on a substrate having a patterned conductive site, and this is used as an electrode for electrolytic oxidation in a monomer solution. However, in the patterned conductive polymer film obtained by this method, the conductive polymer is dispersed in a general-purpose polymer, and the conductivity is extremely low, the redox rate is also low, and the electroconductive polymer is dispersed in a general-purpose polymer. Chromism and sensitivity as a sensor are also reduced. In addition, the polymerization itself is dependent on the diffusion of heptamers in general-purpose polymers, and the problem of nonuniformity of polymerization associated with this has not been solved at all.

The present invention has been made to eliminate the above-mentioned conventional drawbacks, and its purpose is to provide patterned polymer (electrolytic oxidation) films with high homogeneity and an efficient method for producing them. .

[Means for solving problems]

To summarize the present invention, the first invention of the present invention is an invention of a patterned electrolytic oxide film, in which an aromatic compound monomer film is formed in a pattern on an electronic substrate, and this aromatic compound monomer is It is characterized by being electrolytically oxidized. - Also, the second invention of the present invention is an invention of a method for producing a patterned hidden wII film, which includes a step of producing an aromatic compound monomer film in a pattern on an electrode substrate, and a step of producing a patterned aromatic compound monomer film on an electrode substrate; It is characterized by including the steps of electrolytically oxidizing the monomer.

As mentioned above, the conventional fabrication of patterned polymer films involves mixing or laminating a polymer material and a conductive material, or electrolytically polymerizing a solution of an aromatic compound monomer. It is accompanied by many problems such as pattern processing, complicated pattern forming process on the produced film, limitations on usable monomers due to solubility, and contamination of electrolytic solvents.

In contrast, in the present invention, on a conductive substrate in advance,
A smooth aromatic compound monomer film is formed in a pattern by applying ordinary film forming techniques such as vacuum evaporation and sputtering. Next, the substrate having the patterned aromatic compound monomer film is immersed in an electrolytic solution together with a counter electrode, and a suitable DC current voltage is applied with the electrode substrate as the positive electrode and the counter electrode as the negative electrode, thereby obtaining a patterned electrolytic oxide film. It is something.

The inventors of the present invention have discovered that the electrolytic oxidation reaction proceeds even on an electrode substrate having such a patterned aromatic compound monomer film, and that monomers that are difficult to fabricate from conventional homogeneous solution systems. We have found that a stable patterned electrolytic oxide film can be fabricated on an electrode substrate even when using . In addition,
The term "polymer" used in the present invention refers to a state in which two or more monomers are bonded together.

Hereinafter, the patterned electrolytic oxide film of the present invention and the method for producing the same will be explained in more detail.

The aromatic compound monomer necessary for producing the patterned electrolytic oxide film of the present invention is not particularly limited as long as it can be electrolytically oxidized, but for example, Bifkoji/lz, p-1-
Phenyl, 〇-terphenyl, p-quarterphenyl,
Monomers used in ordinary polymerization by electrolytic oxidation, such as 2-hydroxybiphenyl and N-vinylcarbazole, and derivatives and oligomers of these monomers can be used.

Normally liquid monomers can be used as long as they can be made into a solid film in the form of derivatives or oligomers.

The patterned aromatic compound nitrate film on the electrode substrate only needs to be adhered to the substrate with sufficient adhesion to prevent it from peeling off during electrolytic oxidation. It can be produced by attaching a metal mask having openings in a desired pattern shape thereon or fixing it at an appropriate distance, and then vacuum-depositing or sputtering an aromatic compound monomer. That is, in the present invention, the method for producing the aromatic compound monomer film is not limited.

The electrode substrate is not particularly limited as long as it has a conductive portion and is not corroded by the electrolytic reaction solution. Examples include glass, plastic films, ceramics, paper, minerals coated with metals or metal oxides, or metals themselves.

The electrode and substrate having the aromatic compound monomer film prepared by the above method are immersed together with the counter electrode in an electrolytic reaction solution containing the electrolyte necessary for energization, and the electrode substrate is used as the positive electrode and the counter electrode is used as the negative electrode. By applying a direct current voltage, a patterned electrolytic oxide film can be obtained.

As the electrolyte necessary for energization, for example, alkali metal halides, tetraalkylammonium fluoroborate, barchlorate, sulfate, sulfquaternate, etc. can be used.

A representative example of the method of the present invention is shown in FIG. That is, the first
The figure is a schematic diagram showing a part of the manufacturing process of a typical example of the present invention, where 1 is an electrode substrate, 2 is a conductive part of the electrode substrate, and 3 is a pattern that becomes a patterned electrolytic oxide film by applying a voltage. 4 is a counter electrode, 5 is an aromatic compound monomer film of
means electrolytic reaction solution.

The patterned electrolytic oxide film obtained in this way is a polymerized patterned seven-layer film without pinholes or irregularities produced on the electrode substrate, and is similar to the original monomer film. It maintains its good quality shape and structure.

In addition, the raw material monomers necessary for the electrolytic reaction are only those present on the surface of the electrode substrate, and furthermore, aromatic compound monomers do not disappear during the electrolytic reaction unlike in conventional homogeneous solution systems. . Therefore, it is also possible to set the amount, thickness, etc. of the electrolytic oxide film to be formed on the electrode V plate F in advance.

The reason why such a smooth and high-quality patterned electrolytic oxide film can be obtained is that the electrolyte in the solution diffuses into the patterned aromatic compound 7-layer film, thereby preventing the interface between the 7-layer film and the electrode substrate. This is presumed to be because a conductive portion is formed on the electrode substrate, the electrolytic oxidation reaction progresses, and an electrolytic oxide film is formed from the electrode substrate side.

Therefore, a uniform patterned electrolytic oxide film can be obtained by selecting a seven-layer membrane in which the electrolyte can diffuse and a composition of the electrolytic reaction solution.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited thereto.

(Example 1) A patterned pyrene thin film having a thickness of 0.5 μm was prepared by vacuum evaporating pyrene while closely adhering a metal mask having a one-dimensional grid of 1# bits onto a Nesa glass substrate.

The Nesa glass substrate having the pyrene thin film was immersed in an electrolytic solution together with a mesh-shaped counter electrode made of platinum, and electrolytic oxidation of pyrene was carried out at a constant voltage of 2.5 μm with the Nesa glass substrate as the positive electrode and the counter electrode as the negative electrode. The electrolytic solution was prepared by dissolving 0.1 M of electrolytic salt (tetra-1-thylammonium perchlorate) in a water/acetonitrile mixed solvent. By applying voltage for about 1 minute, the patterned pyrene thin film was gradually polymerized. After thoroughly washing this film with water and drying it overnight, microscopic observation revealed that a patterned electrolytically oxidized pyrene film was formed that was much more homogeneous than that obtained using the conventional solution method. It was confirmed that

(Examples 2 to 10) A metal mask similar to that used in Example 1 was tightly attached onto a conductive substrate, and carbazole (Example 2), isothianaphthene (Example 3), and azulene were deposited by vacuum evaporation. (
Example 4), methyl azulene (Example 5), N-phenylpyrrole (Example 6), naphthalene (Example 7), triphenylene (Example 8), biphenyl (Example 9), N-vinylcarbazole ( A patterned thin film of Example 10) was produced. The 1FFI substrate having these patterned thin films was immersed in an electrode solution together with the counter electrode, and electrolytic oxidation was performed in the same manner as in Example 1 using the conductive yuzu board as the positive electrode and the counter electric bridge as the negative electrode. After applying a voltage for about 1 minute, these membranes were thoroughly washed with water, dried overnight, and then observed under a microscope. As a result, it was confirmed that a patterned electrolytic oxide film with extremely superior homogeneity was formed compared to the conventional solution method. The implementation conditions are shown in Table 1.

(Example 11) A carbazole film (II!a thickness: 0115 μTrL) was formed in a one-dimensional lattice shape with a pitch of 1 on 11 m of base glass by screen printing. The NESA glass substrate having this carbazole film was immersed in an electrolytic solution together with a mesh-like counter electrode made of platinum, and carbazole was electrolytically oxidized at a constant voltage of 2.5 V with the NEN glass substrate as a positive electrode and the counter electrode as a negative electrode. The electrolytic solution is a water/acetonitrile mixed solvent with an electrolytic salt (
Tetraethylammonium perchlorate (0.1 M) was dissolved and zested.

By applying voltage for about 5 minutes, the patterned carbazole film gradually turned dark green. Wash this membrane thoroughly with water,
- After drying at night, microscopic observation was performed, and it was confirmed that a patterned electro-wI oxidized carbazole film was formed which was much more homogeneous than that obtained by the conventional solution method.

〔Effect of the invention〕

As explained above, by producing a patterned aromatic compound monomer film on an electrode substrate according to the present invention and electrolytically oxidizing this film in an electrolytic solution, a patterned electrolytic oxide film with excellent homogeneity can be obtained. A particularly remarkable effect can be achieved in that it can be easily produced. The resulting patterned electrolytic oxide film has improved conductivity, redox properties, and electrochromic properties, similar to films obtained by ordinary electrolytic polymerization. Therefore, secondary batteries, especially? It is useful as monolayer batteries, sensors, and display materials.

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view showing a part of the manufacturing process of a typical example of the present invention. 1... Electrode substrate, 2... Conductive portion of electrode substrate, 3...
A patterned aromatic compound monomer film which becomes a patterned W4 oxide film upon voltage application, 4... Counter electrode, 5... Electrolytic reaction solution. Applicant Nippon Telegraph and Telephone Corporation

Claims (2)

[Claims] (1) A patterned electrolytic oxide film, characterized in that an aromatic compound monomer film is formed in a pattern on an electrode substrate, and the aromatic compound monomer is electrolytically oxidized. (2) A patterned electrolytic oxide film comprising the following steps: forming an aromatic compound monomer film in a pattern on an electrode substrate, and electrolytically oxidizing the aromatic compound monomer. How to make