JPH02200797A - Production of organic thin film - Google Patents

Abstract

PURPOSE:To form a thin film of a hydrophobic org. substance in a molecularly dispersed state by mixing a soln. of the hydrophobic org. substance in a nonaq. solvent with an aq. medium and a ferrocene deriv. as a micelle forming agent and supplying electric current to form a thin film of the hydrophobic org. substance on an electrode. CONSTITUTION:A ferrocene deriv. as a micelle forming agent is put in an aq. medium such as water to prepare a micelle soln. having about 0.5-5mM concn. of the micelle forming agent. A hydrophobic org. substance such as porphyrin is dissolved in a nonaq. solvent such as ethanol to proper concn. The micelle soln. is mixed with the resulting soln. of the hydrophobic org. substance and electric current is supplied to the mixed soln. at about 0-70 deg.C and about 0.03-1.5V voltage for about 30min-2hr to form a thin film of the hydrophobic org. substance on an electrode. The hydrophobic org. substance forms the thin film in a molecularly dispersed state and the thin film is useful as the material of an optical disk, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing an organic thin film, and more particularly, it uses a specific micellar agent and a mixture of a non-aqueous solvent and an aqueous medium. The present invention also relates to a method for efficiently producing organic thin films that can be used for optical memory materials, photosensitive materials, electronic materials, coating materials, etc. by using electrochemical techniques.

[Problems to be solved by conventional techniques and inventions] In recent years, various methods have been developed for forming organic thin films. For materials, vacuum evaporation methods and thermal CVD methods are generally used.

The thin film is made by a plasma CVD method, an ultra-high vacuum (ion beam, molecular beam epitaxy) method, an LB method, a casting method, or the like. More recently, a thin film forming technology called micelle electrolysis has been developed (Japanese Patent Application Laid-Open No. 63-243).
(Refer to Publication No. 298), it has become easier to form a thin film of the above-mentioned hydrophobic organic substance, and at the same time, the homogenization of the thin film, the Y4 thickness, etc. have been further improved, and it has become possible to form a high-quality thin film. . This micelle electrolysis method is characterized in that it can form a film while maintaining the shape of the primary particles or secondary particles of a hydrophobic organic substance.

However, although the above-mentioned micelle electrolysis method can form a film while maintaining the shape of the primary particles and secondary particles, it has not been possible to form a thin film in which the particles are dispersed in molecular form.

Therefore, the inventors of the present invention conducted extensive research in order to develop a method for forming a thin film in which molecules are dispersed, which could not be achieved using the micelle electrolysis method described above.

As a result, a hydrophobic organic substance was dispersed in a conventional micelle solution.
Instead of solubilizing, the non-aqueous solvent C,7 hydrophobic organic substance is dissolved, and the solution is mixed with a micellar agent and an aqueous medium, and each time the mixture is subjected to electrical treatment, the desired 1.]
We found that the target can be achieved. The present invention was completed based on this knowledge.

[Means to solve the problem]

That is, the present invention provides (a) a solution of a hydrophobic organic substance dissolved in an aqueous solvent, (1,,) an aqueous medium, and (c)
-, mixing a micellar agent consisting of a 7-z locene derivative,
The present invention provides a method for producing an organic thin film, characterized in that the resulting mixed solution is subjected to electrical current treatment to form a thin film of the hydrophobic organic substance on an electrolyte.

Various hydrophobic organic substances can be used in the method of the present invention, including perylene.

Gold@complexes of perylene and their derivatives, Re:t#
1, metal complexes of phthalocyanine, phthalocyanine green, 12), metal complexes of phthalocyanine, phthalocyanine, phthalocyanine, and derivatives thereof; Porphyrins, metal complexes of porphyrins and their derivatives, anthraquinones, azo dyes, quinacridone-9, bio-11gen, sudan and other photomemory dyes and organic dyes, as well as 1.1"-dihebdyl-4,4"-biviridinium di Bromide 1.1”-didodecyl-4,4
- Bibily; engineered 1/cuta chromic materials such as chromium dibromonide;
Photosensitive materials (photosensitive materials) such as (=-indoline) (commonly known as spiropyran), optical sensor materials, dyes for liquid crystal display such as P-azo-4-cyanisole, and also "Color Gemmical Encyclopedia 1 CMC Co., Ltd., 1983-313 281] Issue No. 542, page 71'1 lists the techniques listed on page 71'1: dyes for chromism, 5 for recording, dyes for environmental chromism, 1 for photography, dyes for energy use, dyes for biomedical use, 1 food, Examples include hydrophobic compounds among cosmetic pigments, dyes, pigments, and special coloring pigments.

In addition, 7,7,8,8-tetracyanoquinone dimethane (
TCNQ) and Tetrasia Full Bare = / (TTF)]
: 1. Organic conductive materials such as SR bodies, gas cell materials, photocurable paints such as bentaerythritol diacrylate, insulating materials such as phosphoric acid, etc.
Examples include photosensitive materials and paints based on di7zotypes such as -phenylazo-2-naphthol.

Next, the above-mentioned hydrophobic organic substance is dissolved in a non-aqueous solvent.
...Aliphatic hydrocarbons such as butane, tetrahydrofuran (
cyclic ethers such as 1'HF), methane-ru.

Alcohol such as ethanol and propatool, acetone,
Ketones such as methyl ethyl getone, ethers such as ethyl acetate, aromatic hydrocarbons such as benzene, toluene, and xylene, as well as dimethylborumamide (DMF),
Suitable examples include nitrile sulfoxide 5-acetate, nitrile 5-methylene chloride, and nitrile 0-naphthalene. In any case, any organic solvent can be used as long as it dissolves the above-mentioned hydrophobic organic substances (t)) regardless of whether it is compatible with the aqueous medium or not.

In the method of the present invention, component (a) is a solution in which the above hydrophobic organic substance is dissolved in well water solvent, and (1)) an aqueous medium and (c) a micellar agent are mixed therein. α)) The aqueous medium includes various water-based media such as water, a mixture of water and alcohol, and a mixture of water and acetone.

On the other hand, the micelle forming agent used as component (c) is composed of a 7°rocene derivative. Here, there are various ferrocene derivatives that can be used.
Ether-type soap 1 sen f shown in specification No. 718
f11 form, [[s 3-52696 specification pyridinium-type ferrocene derivatives, and Japanese Patent Application No. 1983
: l-233798 specification, 63-248600
There are various types of ferrocene derivatives shown in the specification of No. 63-248601 and the like.

In the method of the present invention, a liquid mixture obtained by mixing the components (a), 0)) and (c) is used. This mixed solution is (a
) If the non-aqueous solvent in the component & the aqueous medium as the component (b) are insoluble, the solution (component (a)) in which the hydrophobic substance is dissolved in the non-aqueous solvent G (component (a)) is Emulsified L'? in an aqueous medium containing a micelle-forming agent: At the same time as becoming an emuldigon, the hydrophobic organic substance '6 is mixed with the micelle-forming agent 1,
It is thought that the -. part dissolves in the aqueous medium (molecule ik). Also, what if the non-aqueous solvent and water 11 medium are compatible? , Koha1. T'? It is thought that the hydrophobic organic substance n that forms the fusion is dispersed throughout the system by the micelle-forming agent and incorporated into the micelle-forming agent. In any case of IF5, the hydrophobic organic substance is dispersed or solubilized in molecular form (θ), and by subsequent IJ]1 electrolysis treatment, it becomes a thin film formed by being dispersed in molecular form.

The energization process performed by the method of the present invention includes (a) described in -1-,
(11)) and (c) components are used (as a result of this, a thin layer of hydrophobic organic material is applied to the electrode
A film is formed.

Various aspects of the operating procedure of the method of the present invention can be considered, examples of which are as follows.

That is, first, a micelle-forming agent made of a nocorocene derivative is placed in an aqueous medium to prepare a micelle solution.

The concentration of the micelle agent at this time is not particularly limited, but is usually higher than the limit micelle concentration, specifically 10 μM.
~IM, preferably in the range of 0.5 to 5rnM. It is also effective to add a supporting salt to the micelle solution of τ, if desired. When adding a supporting salt, the type of supporting salt should be one that can adjust the electrical conductivity of the aqueous medium without interfering with the progress of solubilization of the hydrophobic organic substance or the precipitation of the electrode. There are no particular restrictions. Specifically, various sulfates, acetates, halides, water-soluble acids, salts, etc. are absorbed at 1 V, and the amount of supporting salt added is 0 to 300 times that of the micellar agent described in the standard. The standard concentration is approximately 10 to 200 times higher. .

On the other hand, a hydrophobic organic substance is dissolved in the non-aqueous solvent at an appropriate temperature, usually at a concentration above the saturation level, and this solution of the hydrophobic organic substance is mixed with the cell solution described above. During this mixing, in step 7, thoroughly mix and stir using 2 ultrasonic waves, a homogenizer, a stirrer, etc., then remove the excess hydrophobic organic substance of j as necessary, and leave the resulting mixture still. Electrification treatment is carried out using an electrode while the mixture is being heated or while being slightly stirred.Also, during the 1 lll electrification treatment, a solution of the hydrophobic organic substance 4 dissolved in a non-aqueous solvent may be added to the mixed solution, Alternatively, the mixed liquid near the anode can be moved out of the system 51, and the mixed liquid that has been drawn out can be frozen.
A solution prepared by electrolyzing a hydrophobic 41 substance in a non-aqueous solvent) is added and thoroughly mixed. 7. After t7, r; 2. Return this solution to the vicinity of the cathode. 34, yes. The energizing conditions at this time can be selected as appropriate depending on various situations.
However, the liquid temperature is usually 0 to 70°C, preferably 20 to 30°C.
°C, voltage 0°03 to 1.5■, preferably 0.1
Set in the range of 0.5■. In addition, the energization time varies depending on the situation, but in general, it is 30 minutes ~ 2
About an hour is enough.

Note that the electrodes used at this time are micellar agent C, y
, if it is a metal or conductor that has a higher oxidation potential than the oxidation potential of the locene derivative (+0.10 to 0.30v vs. p sum electrode), it is 1, specifically 1TO (indium oxide and tin oxide). platinum, gold, if.

Examples include grady carbon, conductive metal oxides, and organic polymer conductors.

In this way, the mixture consisting of the components (a), (b) and (c) is energized? By increasing P and 1°, a thin film in which molecular G of a hydrophobic organic substance is dispersed is formed. This thin film has hydrophobic fi@f obtained by conventional micelle electrolysis method.
The microstructure is significantly different from the thin film formed by dispersing the J-Prize particles.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 A saturated dye solution was prepared by dissolving tetraph 4)-diluporphyrin in ethanol. The optical absorption spectrum of this saturated dye/8 solution is shown in the first concave (marked A).

On the other hand, add 100+fi of water to make 2 volumes of 2mM micelles, add 3 cc of the saturated dye solution to 25 ee of this micelle electrolyte, and stir with a stirrer for 1 hour to obtain a mixed solution (micelle mixed solution). . Furthermore, lithium Q chloride was added as a supporting salt to the mixed micelle solution to a concentration of 0.1 M to prepare a micellar electrolyte. The absorption spectrum of this micelle electrolyte is shown in Figure 1. (Not shown in mark B).

This micellar electrolyte was subjected to constant potential electrolysis at an applied voltage of 0.5 V using an ITO transparent glass electrode 1 as an anode, platinum as a cathode, and a saturated sweet electrode as a reference electrode.
Ta. The current density at this time is 6.87! A/e+fl
The energization time was 30 minutes and the energization amount was 0601 cu.1.con (c).

As a result, a dye thin film was obtained on the I'l'O transparent glass electrode. The visible spectrum of this thin film is shown in Figure 1 (mark C). Compared to the visible absorption spectrum of the thin film produced in Comparative Example 1 (described below) (Fig. 1 (mark D)), it shows a spectrum close to that of a saturated dye solution, indicating that it has a structure close to that of a dissolved (monomolecular dispersion). .

From the above, in Example 1, a thin film in which molecules were dispersed could be obtained.

Comparative Example 1 A thin film was produced in the same manner as in Example 1, except that 0.1 g of tetraphenylporphyry (tetraphenylporphyry) was not dissolved and was directly dispersed and solubilized into 2 volumes of micelles overnight.

As a result, a dye thin film was obtained on the ITO transparent electrode.

The visible absorption spectrum of this thin film is shown in FIG. 1 (marked D'').

Example 2 Dissolving tetraphenylporphyrin in toluene)
A saturated dye solution was prepared. The visible absorption spectrum of this saturated dye solution is shown in FIG. 2 (mark A).

On the other hand, 1. , Add to O O ml of water to make a micelle solution of ζ2rriM, add 3 cc of the above saturated dye) electrolytic solution to 25 cc of this micelle solution, stir for 1 hour with a stirrer, and mix with Mihir)': 4 liquids. And so.

In step C, add brominated cam as a supporting salt to this micelle mixture solution to a concentration of O.i.M.
・It was made into a liquid. Micelle electrolysis: The visible absorption spectrum at night is shown in Figure 2 (EIIB).

A micellar electrolyte of 25'C. Applied voltage Q. Perform constant potential electrolysis at 5V,
Ta. At this time, the current density was 11.5 μm, 17 cm, 30 minutes per energization time, and 0.1 μm current density. It was 0.02C.

the result,! A dye thin film was obtained on the TO transparent gas electrode 1-.2 The optical absorption spectrum of this thin film is shown in Figure 2 (
Mark C)4. :show. Compared to the visible spectrum of the dye produced in Comparative Example 1 (Fig. 1 (rJ]D)), it exhibits a spectrum close to that of a saturated dye solution and has a structure close to that of a dissolved (monomolecular dispersion). I understand that.

From the above. In Example 2, it was attempted to obtain a molecularly dispersed thin film.

Example 3 A saturated dye solution was prepared by dissolving a tetraphenylporphyrin zinc complex in 1 ethanol. The visible absorption spectrum of this saturated dye solution is shown in Figure 13.

On the other hand, add 100d of water and get 2rr+! vi, and 25 cc of this Mihill solution. Add 3 cc of the saturated dye solution to
was added and stirred for 1 hour under a starburst, followed by mixing with the micelle mixed solution and C7.

Furthermore, 1 tium bromide was added as a supporting salt to this micelle mixed solution at 0.1%. M was added to the solution to obtain a micellar electrolyte solution. The visible absorption spectrum of this micellar electrolyte is
It is shown in the figure (marked B).

This micellar electrolyte was subjected to constant potential electrolysis using an ITO transparent glass electrode as an anode, platinum as a cathode, and a saturated 41゛ copper electrode as a reference electrode at an applied voltage of 0.5㎜.The current at this time was The density was 15.671 A/c, the current application time was 30 minutes, and the current flow amount was 0.0250.

(As a result, a dye thin film was obtained on the ITO transparent glass electrode.

The visible absorption spectrum of this thin film is shown in FIG. 3 (mark C). Compared to the visible absorption spectrum of the thin film produced in Comparative Example 2 (described later) (Fig. 3 (mark D)), it shows a spectrum close to that of a saturated dye solution7, indicating that it has a structure close to dissolution (monomolecular dispersion). illull.

From the above, in Example 3, a thin film in which molecules were dispersed could be obtained.

Comparative Example 2 A thin film was produced in the same manner as in Example 3, except that 0.1 g of the te)-raphenylborphyline zinc complex was dissolved in ethanol and 0.1 g thereof was directly dispersed and solubilized in the micelle solution. Ta.

As a result, a thin dye film C,' was obtained on the ITO transparent electrode.

The visible absorption spectrum of this thin film is shown in Figure 3 (mark D).

Example 4 A saturated dye solution was prepared by dissolving phthalocyanine in chloro-nophthalene. The visible absorption spectrum of this saturated dye solution is shown in FIG. 4 (mark A).

On the other hand, FPEG was added to 100-ml water to make a 2mM micelle solution, and 25cc of this micelle solution was added to the saturated dye solution 3.
ee was added and stirred with a stirrer for 1 hour to obtain a micelle mixed solution. Furthermore, lithium bromide was added as a supporting salt to this micelle mixed solution to a concentration of 0.1 h,
It was made into a micellar electrolyte.

The visible absorption spectrum of this micellar electrolyte is shown in Figure 4 (marked!
3).

This micellar electrolyte was subjected to constant potential electrolysis at 25°C2 with an applied voltage of 0.5μ using an ITO transparent glass electrode as the anode, platinum as the cathode, and a saturated 1 [co·′) electrode as the reference electrode. . The current density at this time is 8.6μA/ +=ffl
, energization time is 30 minutes 1 time 0.015 C
Thank you very much.

As a result, a dye thin film was obtained on the [TO transparent glass electrode].

The visible absorption spectrum of this thin film is shown in Figure 4 (mark C). Compared to the visible absorption spectrum of the thin film produced in Comparative Example 3 (described later) (Fig. 4 (marked I)), it shows a spectrum close to that of a saturated dye solution and has a structure close to that of a dissolved (monomolecular dispersion).
I know that there is.

As described above, in Example 4, a thin film in which molecules were dispersed could be obtained.

Comparative Example 3 Phthalocyanine in chloronaphthalene? Without electrolysis, 0.1 g of it was directly dispersed in micelles).

A thin film was produced in the same manner as in Example 4 except for solubilization.

Result 1. A dye thin film was obtained on the ITO transparent electrode.

The visual absorption spectrum of this thin film is shown in FIG. 4 (mark D).

Example 5 Magnesium ivy τ' cyanine was dissolved in ethanol to prepare a saturated dye solution. The visible absorption spectrum of this saturated dye solution is shown in Figure 5 (mark A).
3 cc of the saturated dye solution was added to 25 cc of this micelle solution, and the mixture was stirred with a stirrer for 1 hour to obtain a mixed micelle solution. Furthermore, lithium bromide was added as a supporting salt to the micelle mixed solution to a concentration of 0.1M to obtain a micelle electrolyte. The visible absorption spectrum of this micellar electrolyte is shown in FIG. 5 (marked B).

Using this micellar electrolyte, an ITO transparent glass electrode as an anode, platinum as a cathode, and a saturated white electrode as a reference electrode,
Constant potential electrolysis was performed at 25°C and an applied voltage of 0.5V. At this time, the current density was 9.111 A/cd, the current application time was 30 minutes, and it was 0.015 C.

As a result, a thin film of C dye was obtained on the BJ0 transparent glass electrode. Figure 215 shows the visible absorption spectrum of this thin film (mark C).
Shown below. Compared to the visible absorption spectrum of the thin film produced in Comparative Example 4 (described later) (Fig. 5 (mark 1)), it shows a spectrum close to that of a saturated dye solution, indicating that it has a structure close to that of a dissolved dye (monomolecular dispersion). I understand.

From the following F, in Example 5, it was possible to obtain a thin film in which heptad molecules were dispersed.

Comparative Example 4 A thin film was produced in the same manner as in Example 5, except that the magnesium phthalocyanine was not dissolved in ethanol and 0.1 g thereof was directly dispersed and solubilized in a micelle solution.

As a result, a dye thin film was obtained on the ITO transparent electrode.

The visible absorption spectrum of this W film is shown in Fig. 5 (marked I).

(Effects of the Invention) As described above, according to the method of the present invention, thin films made of various hydrophobic organic substances can be made extremely thick, thin, and dispersed in molecular form (that is, monomolecular dispersion). It can be formed in the form of a cane.

Therefore,. The organic thin film produced by the method of the present invention has a high optical response and can be used as an optical disk material, an optical memory material, etc.
Photo hole burning (PHB) memory materials, photosensitive materials, photochromic materials.

It is expected to be effectively used as color filters, solar cells, electronic materials, coating materials, etc.

[Brief explanation of the drawing]

Figures 1 to 5 show Examples 1 to 5 and Comparative Examples i to 4, respectively.
Saturated dye solution obtained in micellar electrolyte. The iii visual absorption spectrum of the thin film is shown. Patent Applicant: Idemitsu Kosan Co., Ltd. [7th Patent Attorney] Tamotsu Tani! G:・-,・130
0" No. 9
”'r--+-1--!-1l--T-'-t-'1-
1'--ゝrU"-"'+"""-1-"-'11-
--1600 7α'I
'i' 8 C) invasion (nrh) -51,,3-

Claims (1)

[Claims] (1) Mix (a) a solution of a hydrophobic organic substance in a non-aqueous solvent, (b) an aqueous medium, and (c) a micelle agent made of a ferrocene derivative, and apply current to the resulting mixture to form an electrode. A method for producing an organic thin film, comprising forming a thin film of the hydrophobic organic substance thereon.