JPH02175897A - Formation of multistage thin film - Google Patents

Abstract

PURPOSE:To easily form plural films of a hydrophobic material without need for three-dimensional wiring, etc., by forming a thin film on an electrode, then removing the unnecessary electrode takeout part, and then securing the selective connection of the electrode takeout part to be coated with a thin film to the takeout electrode at the time of forming a multistage thin film utilizing a micelle forming agent. CONSTITUTION:A board is obtained by connecting a takeout electrode 5 such as a platinum wire to an electrode A of the longest pattern. The left side of the electrode A is dipped in a micelle soln. 6 obtained by solubilizing a hydrophobic material such as dyestuff, and electrolyzed by micelle electrolysis to form a thin film only on the hatched part. The board is then inverted, the right side of the electrode A is dipped in a liq. etchant 7, the takeout electrode 5 is connected to the left part, and electrolytic etching is applied to remove the right dipped part. The same process is repeatedly applied to electrodes B-E to continuously form plural thin films of a hydrophobic material, and the short circuit between the takeout parts of the electrodes A-E is prevented without need for special wiring such as three-dimensional wiring.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a multi-stage thin film forming method, and more specifically, a hydrophobic substance is solubilized using a micelle agent, and an electrochemical method is used to solubilize a hydrophobic substance. , optical materials such as color filters, photosensitive materials,
The present invention relates to a multi-stage film forming method that can easily and efficiently produce electrodes having thin films made of multiple types of hydrophobic substances that can be used as electronic materials and the like.

[Conventional technology]

Known methods for producing color filters include dyeing methods, printing methods, color resist methods, polymer electrodeposition methods, and micelle electrolysis methods. Among these, micellar electrolysis is a film-forming method that has recently attracted attention, and refers to a method in which a micelle solution of a hydrophobic substance such as a dye is electrolytically treated to form a thin film on the electrode surface (Japanese Patent Laid-Open No. 63 (Refer to Publication No.-243298). This method has the feature that it is possible to form a thin film in an aqueous solution, and the obtained thin film has conductivity in an aqueous solution, and is expected to be developed as a method for forming thin films.

However, by applying this thin film formation method to color filters, three colors of ROB (R: red, C:
In cases where thin films of multiple colors such as green and blue (B) are continuously formed, complicated special wiring such as three-dimensional wiring as shown in FIG. 2 is required.

FIG. 2 is an explanatory plan view showing three-dimensional wiring in the case of forming three-color dye films of R and GSB on an insulating substrate with ITO electrodes, in which the wirings to each electrode cross each other. At this intersection, it is necessary to coat each wiring with an insulating film such as SiO□ or AlzCh, so manufacturing is not easy.

[Problems to be Solved by the Invention] The present invention has been made based on the above-mentioned circumstances, and its purpose is to easily and efficiently solve multiple hydrophobic It is an object of the present invention to provide a multi-stage thin film forming method capable of forming a film of a substance.

(Means for Solving the Problems) As a result of extensive research in order to solve the above problems, the present inventors focused on the fact that the formed thin film has conductivity, and formed a thin film on an electrode. After that, the unnecessary electrode extraction portion is removed together with the thin film by electrolytic etching, and the above object is achieved by not interfering with the selective connection between the electrode extraction portion and the extraction electrode that will then form the thin film. Based on this finding, we have completed the present invention.

That is, the present invention provides a method for applying a plurality of hydrophobic substances by micelle electrolysis to the surface of a plurality of electrodes that are patterned on an insulating substrate into a shape having a plurality of sets of take-out portions with different take-out positions for each set. When forming a thin film, the extraction part of one set of electrodes is connected to the extraction electrode, a thin film of a hydrophobic substance is formed on the electrode by micelle electrolysis, and then the extraction part of the other set of electrodes is connected to the extraction electrode. In order to prevent a short circuit when the electrodes are connected, the lead-out part of the set of electrodes on which a thin film has been formed is selectively removed by electrolytic etching, and then the lead-out part of the other set of electrodes is connected to the lead-out electrode. A thin film of another hydrophobic substance is formed on another set of electrodes by a micelle electrolysis method, and by continuing this operation a necessary number of times, a plurality of thin films of a hydrophobic substance are formed on the plurality of sets of electrodes. The present invention provides a multi-stage film forming method for thin films.

In the method of the present invention, the micellar electrolysis method refers to adding a micellar agent made of a ferrocene derivative and a hydrophobic substance to an aqueous medium whose electrical conductivity has been adjusted by adding a supporting electrolyte as necessary to water and thoroughly mixing the mixture. By stirring and dispersing,
A micelle solution containing a hydrophobic substance inside the micelle,
This is a method in which particles of a hydrophobic substance are deposited on an anode by electrolysis to form a thin film. In the micelle electrolysis method, micelles are attracted to the anode by electrolytic treatment, and the ferrocene derivatives in the micelles lose electrons on the anode, and the micelles collapse and the hydrophobic substances inside are deposited on the anode. On the other hand, the oxidized ferrocene derivative is attracted to the cathode, receives and receives electrons, forms micelles again, and takes the hydrophobic substance inside. In the process of repeating the formation and collapse of micelles, particles of the hydrophobic substance are deposited on the anode to form a thin film. By further subjecting the thin film thus formed to a heat treatment, a stable thin film that is not redissolved in the micelle solution can be obtained.

The present invention uses the above-mentioned micelle electrolysis method to simply and efficiently provide a plurality of sets of thin films of a hydrophobic substance on a plurality of sets of electrodes.The present invention will be described in detail below with reference to the drawings.

FIG. 1 shows a substrate consisting of ITO electrodes provided on an insulating substrate 1, in which five pairs of ITO electrodes A to E are patterned with their extraction portions slightly shifted. This 5
When a thin film of a hydrophobic substance of 5 & Il is provided on a set of electrodes, the central part β in the figure becomes the effective part of the electrode on which the thin film is formed. In the figure, the electrodes are provided linearly and in parallel in this effective part, but they may also include dots or diagonal wiring.

To explain the film forming procedure, first, as shown in Fig. 3, a take-out electrode 5 made of platinum wire, conductive rubber, silver paste, etc. is attached to electrode A so that only the longest pattern of electrode A is energized. Connect.

When this substrate is immersed on the left side of the electrode A in a micelle solution 6 in which a hydrophobic substance such as a dye is solubilized and subjected to electrolytic treatment using the micelle electrolysis method, a thin film is formed on the electrode only in the shaded area in the figure. .

■ Next, turn the substrate upside down, immerse the right side of electrode A in etching solution 7 as shown in Fig. 4, and connect the extraction electrode 5 to the left extraction part of electrode A formed in step (■). When electrolytic etching is performed, the portion of electrode A immersed in the etching solution is removed together with the thin film. As a result, the connection between the next extraction portion of electrode B and the extraction electrode can be made extremely easily without fear of short circuiting to electrode A.

■Next, as shown in Figure 5, return the top and bottom of the board to their original positions.
When the left side of electrode B is immersed in micelle solution 8 in which a hydrophobic substance has been solubilized, the extraction part of electrode B is connected to the extraction electrode, and electrolytic treatment is performed using the micelle electrolysis method, only the shaded area of electrode B in the figure is A thin film is formed on the surface.

(2) Next, in the same manner as in (2), the etching solution immersed part of the electrode B is removed to facilitate the connection between the next extraction part of the electrode C and the extraction electrode.

By repeating the above operations as necessary, it becomes possible to continuously form thin films of a plurality of hydrophobic substances.

Therefore, the multi-stage film forming method of the present invention is an extremely effective film forming method for manufacturing color filters that require the formation of thin films of three colors of dyes on electrodes.

Note that in the above explanation, the multi-stage film forming method of the present invention will be described as the first
We have explained the case where micellar electrolysis and electrolytic etching are applied alternately to the substrate shown in the figure, but film formation is performed continuously from both sides of the substrate, and then electrolytic etching is performed to remove unnecessary film-formed electrode parts. Good too.

The micellizing agent used in the micelle electrolysis method is made of a ferrocene derivative. There are various types of ferrocene derivatives, such as the following (1) and (2).
, (3).

First, a ferrocene compound (ferrocene or a suitable alkyl or a substituent such as an acetyl group).

Here, if the number of carbon atoms in the main chain is small, micelles will not be formed, and if the number of carbon atoms is too large, it will not dissolve in water.

There are various ways in which the ferrocene compound is bonded to the surfactant, and can be roughly divided into those bonded to the end of the main chain of the surfactant, those bonded directly or through an alkyl group in the middle of the main chain, and those bonded in the main chain. Examples include those incorporated into.

Ammonium type ferrocene derivatives such as 2 have the general formula (wherein R1 and R2 are each hydrogen or carbon It~4
(however, it does not exceed the integer m described below) represents an alkyl group,
2+ and Z2 each represent hydrogen or a substituent (such as a methyl group, ethyl group, methoxy group or carbomethoxy group), and X represents a halogen. Also, m and n are m≧0, n≧0
and represents an integer satisfying 4≦m+n≦16. )
, General formula General formula (wherein R1, R1, k is h≧0, j≧0
, k≧1, and indicates an integer satisfying 3≦hfj10 and ≦15, and P indicates an integer satisfying 0≦p≦−1. )
, (where RIXRl, x, z' and Z2 are the same as above (however, the number of carbon atoms in R' and "does not exceed the integer r described below), and r, s and t are r≧0 .s≧0, t
Indicates an integer that is ≧1 and satisfies 4≦r+s+t≦16. ), or the general formula (wherein, R1, χ Zl, Zt, r, s, and t are the same as above).

Specific examples of ferrocene derivatives as micellizing agents include:

Next, (2) other types of ferrocene derivatives are represented by the general formula and the average value of the numbers. Furthermore, Y in the above general formula is oxygen (-0-) or oxycarbonyl group (
-0-Co-) or an ether type ferrocene derivative represented by. Here, a represents an integer from 2 to 18, and b is 2.0
~50.0 real number. Since a is an integer from 2 to 18 as described above, there is an ethylene group between the ring member carbon atom and Y,
An alkylene group having 2 to 18 carbon atoms such as a propylene group is present. Furthermore, the alkylene group may be branched or may contain a phenyl group. Alternatively, hydrogen in an alkylene group may be substituted with a halogen atom, a methyl group, or a methoxy group. Also, b is 2
．． It means not only an integer between 0 and 50.0 but also a real number including these, and this refers to the repetition of the oxyethylene group (-CHtCH!0-) constituting the ferrocene derivative (hydrogen or substituted Indicates the group.

Furthermore, (3) other types of ferrocene derivatives include pyridinium-type ferrocene derivatives represented by the general formula. In this formula, Zl, Z! , X is the same as above, R3 is an alkyl group having 1 to 4 carbon atoms, and
4 alkoxy group, carbalkoxy group having 1 to 5 carbon atoms, hydroxyl group, carboxyl group, sulfonic acid group, etc.
Further, C-Hz- represents a straight chain or branched alkylene group having 1 to 16 carbon atoms. Specifically, CJ is a polymethylene group (C)+2) such as a tetramethylene group, a pentamethylene group, an octamethylene group, an undecamethylene group, a dodecamethylene group, and a hexadecamethylene group. Examples include straight chain alkylene groups such as ', and branched alkylene groups such as 2-methylundecamethylene and 4-ethylundecamethylene groups.

As the micellizing agent used in the method of the present invention, the above-mentioned (
The ferrocene derivatives 1), (2), or (3) are preferably used.

On the other hand, the hydrophobic substance that is the raw material for the thin film produced by the method of the present invention is one that is insoluble or slightly soluble in water, and whose particles can be incorporated into micelles (i.e., particles that are soluble in micelles). Various types of materials can be used, and there are no particular restrictions. e.g. organic and inorganic pigments,
Various materials such as paints, photosensitive materials, organic conductive materials, and electrically insulating materials can be used.

Specifically, phthalocyanine, chlorophthalocyanine,
Metal complexes of copper, zinc, iron, cobalt, aluminum, magnesium, etc. of phthalocyanine m-1 phthalocyanine such as methyl phthalocyanine or phthalocyanine derivatives, perylene pigments, anthraquinone pigments, lake pigments (Ca
, Ba, SrSMn), disazo pigments, benzopyran pigments, cadmium sulfide pigments, Fe(nl) oxide pigments, titanium oxide, tungsten oxide, zirconia oxide, naphthalocyanine, naphthalocyanine derivatives, naphthalocyanine metal complexes, In addition to optical memory dyes and organic dyes such as metal complexes of naphthalocyanine derivatives, porphyrins, porphyrin derivatives (such as tetraphenylporphyrin), metal complexes of porphyrins, and metal complexes of porphyrin derivatives, 1.1'-dihebutyl-4.4' Biviridinium dibromide, l,1'-didodecyl-4
, 4'-bipyridinium bromide and other electrochromic materials, and photosensitive materials such as 6-nitro-1°3,3-trimethylspiro-(2'H-1'-benzopyran-2,2'-indoline) (commonly known as spiropyran). (photochromic materials), optical sensor materials, liquid crystal display pigments such as p-azoxyanisole, etc. , organic conductive materials and gas sensor materials such as a 1:1 complex of 7,8.8-tetracyanoquinone dimethane (TCNQ) and tetrathiafulvalene (TTF), photocurable paints such as pentaerythritol diacrylate, and stearin. Insulating materials such as acids,
Examples include diazo type photosensitive materials such as 1-phenylazo-2-naphthol and paints. Furthermore,
Polymers that are insoluble in water, such as polycarbonate, polystyrene, polyethylene, polypropylene, polyamide,
Polyphenylene polysulfide (PPS), polyphenylene oxide (PPO), polyacrylonitrile (
General-purpose polymers such as PAN), polyphenylene,
Mention may be made of polypyrrole, polyaniline, polythiophene, acetylcellulose, polyvinyl acetate, polyvinyl butyral, as well as various polymers (such as polyvinylpyridine) or copolymers (such as a copolymer of methyl methacrylate and methacrylic acid).

In the method of the present invention, the above-mentioned micellizing agent and hydrophobic substance are added to water or an aqueous medium mainly composed of water to solubilize the hydrophobic substance. Add supporting salts (supporting electrolytes) as necessary for adjustment. The amount of supporting salt added may be within a range that does not interfere with the precipitation of the solubilized hydrophobic substance, and is usually at a concentration of about 0 to 300 times that of the micelle agent, preferably 50 to 2 times.
Aim for a concentration of about 00 times. Although electrolysis can be carried out without adding this supporting salt, in this case a highly pure thin film containing no supporting salt can be obtained. In addition, when using a supporting salt, there are no particular restrictions on the type of supporting salt as long as it can adjust the electrical conductivity of the aqueous medium without interfering with the formation of micelles or the precipitation of the hydrophobic substance onto the electrode. do not have.

Specifically, sulfates (lithium, potassium, sodium, rubidium,
salts such as aluminum), acetates (salts such as lithium, potassium, sodium, rubidium, beryllium, magnesium, calcium, strontium, barium, aluminum, etc.), halide salts (salts such as lithium, potassium,
Sodium, rubidium, calcium, magnesium,
salts such as aluminum), water-soluble oxide salts (lithium,
salts of potassium, sodium, rubidium, calcium, magnesium, aluminum, etc.) are preferred.

Further, the material of the electrode used in the micelle electrolysis method of the present invention may be any metal or conductor that has a higher oxidation potential than ferrocene (+0.15 to 0.26 V vs. saturated electrode).

Specific examples include ITO (mixed oxide of indium oxide and tin oxide), tin dioxide, platinum, gold, silver, grady carbon, conductive metal oxides, conductive polymer films, and the like.

In the micelle electrolysis method, first, a micellar agent made of the above-mentioned ferrocene derivative, a hydrophobic substance, and a supporting salt as necessary are added to an aqueous medium, and the micelles are sufficiently dispersed using ultrasonic waves, a homogenizer, a stirrer, etc. to form. Preferably, the dispersion is carried out using ultrasonic waves for usually 0 to 1 hour, preferably 1 to 20 minutes, and then usually 1 hour to 10 minutes.
Stirring is carried out for days, preferably from 2 hours to 4 days. Thereafter, if necessary, excess hydrophobic substances are removed, and the resulting micelle solution is subjected to electrolytic treatment using the above-mentioned electrode while standing still or with slight stirring. The concentration of the micelle forming agent at this time may be at least the critical micelle concentration, specifically at least about 0.1 mM. On the other hand, the concentration of the hydrophobic substance may be at least the saturation concentration. The electrolytic conditions may be selected appropriately depending on various situations, but usually the liquid temperature is 0 to 70°C, preferably 5 to 40°C, and the voltage is the oxidation-reduction potential of the ferrocene derivative that is the micelle agent. With the above, the voltage is set to be less than the hydrogen generation potential, specifically, 0.05 to 1.5 cm, preferably 0.1 to 0.9 cm, and the current density is 10 mA.
/ crM or less, preferably 50 to 300 μA/C1
Let it be a. Electrolysis time is usually 30 minutes to 2 hours.

Through such electrolytic treatment, a thin film (functional thin film) of 300 to 900 particles of the desired hydrophobic substance is formed on the anode.

Next, the electrolytic etching performed in the present invention is not particularly limited as long as it is a method that can remove the lead-out portion of the electrode on which the thin film of hydrophobic substance is formed by applying electricity to the electrode on which the thin film of hydrophobic substance is formed.

For example, as an etching solution, use MCI of 0.1 to 6N and 0.1 to 6N.
1 to IOM FeC]: Using a solution consisting of + solution, usually -0.1 to -10V, preferably -0.5 to -
Etching is carried out at 1.5 V, typically for 1-120 minutes, until the IT○ electrode is etched.

In the present invention, since the thin film formed by micelle electrolysis has conductivity, electrolytic etching is possible, and unnecessary electrode extraction parts can be selectively removed, making it easier to form the next thin film. Multi-stage film formation becomes possible.

[Examples] Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited thereto.

Example 1 Add a nonionic micelle agent to 100cc of water and use the general formula 190μ of was added and stirred to obtain a homogeneous micellar solution.

Lake pigment (
BASF product name K3700), PcCuCl5
Brs (manufactured by BASF, product name 9360),
Copper phthalocyanine (BASF product name K6902)
0.2 g was added and dispersed and solubilized to prepare three sets of pigment solutions of three colors, R, G, and B. These solutions were each stirred for 10 minutes and then stirred for 3 days using a stirrer. A supporting salt LiBr was added to each of the obtained dispersed micelle solutions to a concentration of 0.1 M. Each of these solutions was made into an electrolyte solution R.
1 electrolyte G and electrolyte B.

Next, MCI was added to 100 Fnf water to make it 1 normal, and FeCl was further added to make IM, and this solution was used as an etching solution.

FIG. 7 is a plan view of an insulating substrate with BirO electrodes used in this example for multi-stage film formation. IT to form a thin film of pigment
The O electrode 2 is patterned in parallel to the insulating substrate l-h with the position of the lead-out portion being shifted. In this case, since there are three types of pigments forming the thin film, the patterning is performed so as to have three sets of extraction positions.

When performing micelle electrolysis and electrolytic etching on the ITO electrode, conductive rubber was used as the extraction electrode, parallel electrodes were connected in a skewed manner, and electrolysis and etching were performed.

The procedures of micelle electrolysis and etching will be explained below. This method is an example in which the multi-stage manufacturing and removing method of the present invention is applied from both sides of an ITO electrode.

■ As shown in Figure 8, the insulator substrate with ITO is immersed with the left side down in the micellar electrolyte R of No. 9, and the right side of the first set of electrodes is formed from the right side of the ITO electrode to form the first set of R films. The extraction part and the extraction electrode 5 are connected, and a platinum plate is used as a counter electrode.
Using a saturated 4↑kou electrode as a reference electrode, the potential is +0.7■
Constant potential electrolysis was performed for 30 minutes to form a thin film of R on the electrode. Thereafter, this thin film was dried and baked at 250°C for 1 hour.

■ Next, as shown in Figure 9, the right side of the insulator substrate with ITO obtained in step (■) above is immersed in 10 micellar electrolyte B with the right side facing down, and the Connect the left take-out part of the second set of ITO electrodes forming one set of B films to the take-out electrode, use a platinum plate as a counter electrode and a saturated white electrode as a reference electrode, and apply a voltage of +0.7 V to 30
Constant potential electrolysis was performed for one minute to form a thin film of B on the electrode. Thereafter, this thin film was dried and baked at 250°C for 1 hour.

■ Next, the insulator substrate with ITO obtained in the above
As shown in the figure, the ITo electrode was immersed with the right side facing down in the etching solution No. 11, and the left take-out part of the ITo electrode on which the R film and B film were formed was connected to the take-out electrode. When electrolytic etching is performed for a minute, a current flows through the R-circumferential electrode and the daily-use electrode, and the portions of the R-circumferential electrode and the daily-use electrode that are immersed in the etching solution are removed by etching, and no current flows through the G-circumferential electrode. Since there is no, it will remain as is.

■ Next, as shown in Figure 11, 12 micellar electrolyte G
The right side of the ITO-coated insulator substrate obtained in step ① above was immersed in the liquid, and the right-side extraction portion of the third set of ITO electrodes forming the first & Il G films from the left side of the ITO electrode and the extraction electrode were immersed. Using a platinum plate as a counter electrode and a saturable copper electrode as a reference electrode, constant potential electrolysis was performed at a potential of +0.7 μ for 30 minutes to form a G thin film on the electrode. Thereafter, this thin film was dried and baked at 250°C for 1 hour.

In this way, R, B, and G thin films could be obtained on the electrodes.

(Effects of the Invention) According to the method of the present invention, films of multiple hydrophobic substances can be easily and efficiently formed without special wiring such as three-dimensional wiring. It can be suitably used in the production of color filters that require the formation of thin films.

[Brief explanation of the drawing]

FIG. 1 is a plan view of an insulator substrate with electrodes to which the multi-stage film forming method of the present invention is applied. FIG. 2 is an explanatory diagram illustrating a conventional multi-stage film forming method. 3 to 6 are explanatory diagrams for explaining the multi-stage film forming method of the present invention. FIG. 7 is a plan view of an insulator substrate with electrodes to which the multi-stage film forming method of the present invention is applied. 8th
11 are explanatory diagrams for explaining an embodiment of the multi-stage film forming method of the present invention. Micellar solution electric scraping effective part 8, 9. 10゜11゜ Symbol explanation 2, electrode 5, extraction electrode 12, micellar electrolyte/notching liquid curtain f diagram

Claims (1)

[Claims] 1. Using micelle electrolysis, multiple thin films of hydrophobic substances are formed on the surfaces of multiple electrodes that are patterned on an insulating substrate into a shape that has multiple sets of extraction parts with different extraction positions for each set. At this time, the extraction part of one set of electrodes is connected to the extraction electrode, a thin film of a hydrophobic substance is formed on the electrode by micelle electrolysis, and then the extraction part of the other set of electrodes is connected to the extraction electrode. In order to prevent short circuits when the electrodes are removed, the lead-out portions of the electrodes of the set with a thin film formed thereon are selectively removed by electrolytic etching, and then the lead-out parts of the other sets of electrodes are connected to the lead-out electrodes using micelle electrolysis. A multi-layered thin film characterized in that a thin film of another hydrophobic substance is formed on another set of electrodes, and by continuing this operation a necessary number of times, a plurality of thin films of a hydrophobic substance are formed on the plurality of sets of electrodes. Film forming method.