JPH0541635B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel ferrocene derivative, a surfactant containing the same, and a method for producing an organic thin film using the same. and a surfactant containing the ferrocene derivative and capable of solubilizing various hydrophobic organic substances such as dyes such as phthalocyanine and water-insoluble polymers, and a surfactant (micellar agent) containing the ferrocene derivative.
This invention relates to a method for efficiently producing organic thin films that can be used as electronic materials, coating materials, etc. by using an electrochemical method.

[Problems to be solved by conventional technology and invention]

Generally, dyes such as phthalocyanine or its derivatives are insoluble in water, and are soluble in organic solvents such as dimethylformamide (DMF) and tetrahydrofuran (THF), but the amount of solubilized is small; It has a solubility of only a few mg.

Although surfactants for dissolving phthalocyanine and the like in water have been researched for some time, no satisfactory product has yet been developed. It has been reported that functional group-substituted phthalocyanine derivatives can be slightly dissolved in water using sulfonic surfactants, but their solubility is not always sufficiently high, and unsubstituted phthalocyanine cannot be dissolved at all.

Furthermore, with respect to water-insoluble polymers, surfactants for dissolving them in water are being researched in the same way as described above, but at present, sufficient results have not yet been obtained.

The present inventors have conducted extensive research in order to develop a surfactant that can solubilize pigments such as phthalocyanine and its derivatives, or water-insoluble polymers.

[Means to solve the problem]

In the course of this research, we found that ferrocene derivatives are promising as surfactants with the above-mentioned properties. The present inventors continued their research based on these findings and found that a new ferrocene derivative, in which a specific substituent containing a pyridinium ion was introduced into ferrocene or its derivatives, could achieve the objective. I discovered that. Furthermore, we have also discovered that water-insoluble (hydrophobic) organic thin films can be efficiently produced by applying an electrochemical method using this ferrocene derivative.

The present invention was completed through such a research process. That is, the present invention has the general formula [In the formula, R ¹ , R ² and R ³ each represent hydrogen, a methyl group, an ethyl group, a methoxy group or a carbomethoxy group, and X represents a halogen. Also,
C _o H _2o represents a straight or branched alkylene group having 4 to 16 carbon atoms. The present invention provides a novel ferrocene derivative represented by the following formula, and also provides a surfactant containing the novel ferrocene derivative represented by the above general formula [].
Furthermore, the present invention solubilizes a hydrophobic organic substance in an aqueous medium with a surfactant (micelle-forming agent) made of a novel ferrocene derivative of the above general formula [], electrolyzes the resulting micelle solution, and applies it to an electrode. The present invention also provides a method for producing an organic thin film, which comprises forming a thin film of the hydrophobic organic substance on a substrate.

The ferrocene derivative of the present invention is represented by the general formula [], in which R ¹ , R ² and R ³ each represent hydrogen, a methyl group, an ethyl group, a methoxy group or a carbomethoxy group, and X represents a halogen group. , that is, chlorine, bromine, iodine, etc. Also, C _o
H _2o represents a straight or branched alkylene group having 4 to 16 carbon atoms (that is, n is an integer of 4 to 16), specifically a tetramethylene group, a pentamethylene group, an octamethylene group, an undecamethylene group, Linear alkylene groups including polymethylene groups (CH ₂ ) _o such as dodecamethylene group and hexadecamethylene group, and branched chain alkylene groups such as 2-methylundecamethylene group and 4-ethylundecamethylene group. be able to.

The ferrocene derivative represented by the general formula [] can be produced by various methods, but for example, the ferrocene derivative represented by the general formula [] [In the formula, R ¹ , R ² , X and C _o H _2o are the same as above. ] The halogen-containing ferrocene derivative represented by
general formula [In the formula, R ³ is the same as above. ] It can be produced by adding a pyridine compound represented by the following and reacting for about 1 to 5 hours at a temperature of 20 to 70° C. with sufficient stirring in an atmosphere of an inert gas such as nitrogen gas. After that, the product is washed with diethyl ether, etc., dried, and further dissolved in a polar solvent such as acetone, methanol, ethanol, tetrahydrofuran, etc., and the solution is poured into diethyl ether, etc. to precipitate, and this operation is repeated several times. If the mixture is then filtered, the ferrocene derivative of the general formula [] can be obtained with high purity.

The ferrocene derivative of the present invention having the general formula [] obtained by the above method is effective as a surfactant, particularly as a surfactant (micellar agent) for solubilizing hydrophobic organic substances in water or an aqueous medium. Can be used.

The surfactant of the present invention contains a ferrocene derivative of the above general formula [] as a main component,
Other various additives can also be added as appropriate.

There are various hydrophobic organic substances that can be solubilized in water or an aqueous medium by the surfactant of the present invention, including organic dyes such as phthalocyanine and metal complexes of phthalocyanine, 1,1'-diheptyl-4, Electrochromic materials such as 4'-bipyridinium dibromide, 1,1'-didodecyl-4,4'-bipyridinium dibromide, 6-nitro-1,3,3-trimethylspiro-(2'H-1'- Photosensitive materials (photochromic materials) such as benzopyran-2,2'-indoline (commonly known as spiropyran), liquid crystal display dyes such as p-azoxyanisole, and 7,7,8,8-tetracyanoquinone dimethane (TCNQ). Organic conductive materials such as a 1:1 complex of and tetrathiafulvalene (TTF), photocurable paints such as pentaerythritol diacrylate, insulating materials such as stearic acid, and diazo-type photosensitive materials such as 1-phenylazo-2-naphthol. You can list materials, paints, etc. Furthermore, general-purpose polymers such as water-insoluble polymers such as polycarbonate, polystyrene, polyethylene, polypropylene, polyamide, polyphenylene sulfide (PPS), polyphenylene oxide (PPO), and polyacrylonitrile (PAN), as well as polyphenylene, Examples include 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).

There are various ways to use the ferrocene derivative of the present invention as a surfactant. For example, if it is used as a surfactant (micellar agent) in the production method of the present invention described above, A thin film of organic material can be formed.

To explain in detail the method for producing an organic thin film of the present invention, first, in the method of the present invention, the above-mentioned surfactant (micellar agent) and hydrophobic organic substance are added to water or an aqueous medium mainly composed of water. If necessary, a supporting salt (supporting electrolyte) may be added to this aqueous medium to adjust its electrical conductivity.
Add. The amount of supporting salt added is usually about 10 to 300 times the concentration of the above surfactant, preferably 50 to 300 times.
Aim for a concentration of about 200 times. The type of supporting salt is not particularly limited 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 organic substance onto the electrode.

Specifically, sulfates (lithium, potassium, sodium,
Preferred are salts of rubidium, aluminum, etc.), acetates (salts of lithium, potassium, sodium, rubidium, beryllium, magnesium, calcium, strontium, barium, aluminum, etc.).

Further, the electrode used in the method of the present invention may be any metal or conductor that is nobler than the oxidation potential of ferrocene (+0.15 V vs. saturated red electrode). Specific examples include ITO (mixed oxide of indium oxide and tin oxide), platinum, gold, silver, glassy carbon, conductive metal oxides, and organic polymer conductors.

In the method of the present invention, first, the above-mentioned surfactant, supporting salt, and hydrophobic organic substance are added to an aqueous medium and sufficiently dispersed using an ultrasonic wave, a homogenizer, a stirrer, etc. to form micelles, and then, as necessary, to remove excess hydrophobic organic substances,
The obtained micelle solution is electrolytically treated using the above-mentioned electrode while it is left standing or with some stirring. Additionally, the hydrophobic organic substance may be supplemented and added to the micelle solution during the electrocage treatment, or the micelle solution near the anode is extracted from the system, the hydrophobic organic substance is added to the extracted micelle solution, and the mixture is thoroughly mixed and stirred. However, a circulation circuit may be provided for returning this liquid to the vicinity of the cathode. The electrolysis conditions at this time may be selected appropriately depending on various situations, but usually the liquid temperature is 0.
~70℃, preferably 20~30℃, voltage 0.03~1.5V,
Preferably 0.1 to 0.5V, current density 10mA/cm ²
Hereinafter, it is preferably 50 to 300 μA/cm ² .

When this electrolytic treatment is performed, the reaction as shown in FIG. 8 proceeds as described above. Focusing on the behavior of Fe ions in ferrocene derivatives, the Fe ²⁺ of ferrocene becomes Fe ³⁺ at the anode, the micelles collapse, and hydrophobic organic particles (about 600 to 900 Å) are deposited on the anode. Precipitate. On the other hand, at the cathode, Fe ³⁺ oxidized at the anode is reduced to Fe ²⁺ and returns to the original micelles, so the film forming operation can be performed repeatedly using the same solution.

Through such electrolytic treatment, a thin film of particles of about 600 to 900 Å of the desired hydrophobic organic substance is formed on the anode.

〔Example〕

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

Example 1 (Synthesis of ferrocene derivative) Preparation of 1-ferrocenyl-11-bromide undecanoic acid 11-bromide undecanoic acid chloride synthesized from 50.0 g of 11-bromide undecanoic acid and 90.0 g of thionyl chloride and 37.6 g of anhydride Aluminum chloride and 35.0
3 g of ferrocene in methylene chloride at 5°C.
Allowed time to react. After the reaction was completed, the mixture was treated with the desired acid and extracted with a solvent to obtain 10-decanylbromide ferrocenyl ketone.

Then, in the presence of an amalgam prepared with 65.4 g of zinc and 27.2 g of mercuric chloride, the 10-decanyl bromide ferrocenyl ketone prepared as above was added.
56.9 g was refluxed for 6 hours in a mixed solvent of concentrated hydrochloric acid and ethanol to react. After the reaction was completed, extraction was performed with a solvent to obtain 1-ferrocenyl-11-undecane bromide.

Preparation of ferrocene derivative 0.5 g of 1-ferrocenyl-11-bromide undecane obtained above and 0.1 ml of pyridine were mixed,
The reaction was carried out in a nitrogen atmosphere for 120 hours while heating at 60°C in a water bath. This reaction was completed by more than 95% in the first 4 hours, and the reaction solution solidified as the reaction progressed, and finally solidified. 10 ml of dimethyl ether was added to this solid powder and it was thoroughly washed. After washing, the powder was separated by filtration. After sufficiently drying, 10 ml of acetone was added to the powder to dissolve it. Add 10 dimethyl ether to this solution.
ml was added to obtain a precipitate. Repeat this operation three times,
After drying, 0.22 g (yield: 38%) of purified product was obtained.

The elemental analysis values of this substance were as follows. The measurement results of the proton nuclear magnetic resonance ( ^1H -NMR) spectrum (CDCl ₃ , TMS standard) are shown in Figure 1, and the measurement results of the infrared (IR) absorption spectrum (KBr tablet method, 25℃) are shown in Figure 1. The results were as shown in Figure 2, and the measurement results of the ultraviolet-visible (UV-VIS) absorption spectrum were as shown in Figure 3.

Elemental analysis value (%) Carbon Hydrogen Nitrogen Calculated value 62.53 7.28 2.81 Measured value 62.08 7.65 2.73 From the above results, the above substance has the formula It was found that it is a ferrocene derivative represented by

Example 2 To 100 ml of water were added 99.6 mg of the ferrocene derivative obtained in Example 1 as a surfactant (micellar agent) and 2.56 g of lithium sulfate as a supporting salt, and to this was added 10 mg of 1-phenylazo-2-naphthol. was added and irradiated with ultrasound for 10 minutes to disperse and dissolve.
Furthermore, after stirring with a stirrer for two days and nights, the obtained micelle solution was centrifuged at 2000 rpm for 1 hour. The UV-VIS absorption spectrum of this supernatant liquid is shown in FIG. 4 (marked). From this, 1-
It was confirmed that phenylazo-2-naphthol was solubilized in the micelle solution. Furthermore, the solubility is
It was a 59μM/2mM micellar agent solution. For reference, a solution containing only a surfactant was prepared without adding 1-phenylazo-2-naphthol, and this UV-
The VIS absorption spectrum is shown in Figure 4 (marked).

Comparative example 1 In 100ml of water, add the formula Add 95.6 mg of the ferrocene derivative represented by as a surfactant (micelle agent) and 2.56 g of lithium sulfate as a supporting salt, add 10 mg of 1-phenylazo-2-naphthol, and irradiate with ultrasound for 10 minutes. Disperse and dissolve. Furthermore, after stirring with a stirrer for two days and nights, the obtained micelle solution was
Centrifugation was performed at 2000 rpm for 1 hour. The UV-VIS absorption spectrum of this supernatant liquid is shown in Figure 4 (marked).
Shown below. The solubility of this 1-phenylazo-2-naphthol was 38 μM/2 mM micellar agent solution.

This shows that when the micellar agent of Example 1 is used, 1-phenylazo-2-naphthol is dissolved about 1.5 times as compared to the micellar agent of Comparative Example 1.

Example 3 Adding lithium sulfate as a supporting salt to 100ml of water
0.02 mol was dissolved, and 0.2 mmol of the ferrocene derivative obtained in Example 1 was added thereto as a micellizing agent, and the mixture was dispersed by ultrasonic waves to form micelles. Next, a dye (1-phenylazo-2-naphthol), which is a hydrophobic organic substance, is added to this micelle solution.
After adding 0.2 mmol, the dye was incorporated into the micelles using ultrasound. After stirring for two days and nights, excess dye was removed by centrifugation to obtain a micelle solution. This micelle solution is used as an electrolyte and applied to the anode.
Using ITO, platinum as the cathode, and a saturated sweet electrode as the reference electrode, temperature 25℃, applied voltage 0.3V, current density
Electrolytic treatment was performed under the condition of 36 μA/cm ² . After 60 minutes,
A dye thin film with primary particles with an average particle size of 700-1000 Å was obtained on ITO.

Scanning electron microscopy (SEM) of the produced dye thin film
A photograph (35,000x magnification, JSM-T220 manufactured by JEOL Ltd.) is shown in Figure 5. The curve in Figure 6 shows the UV absorption spectrum of this thin film dissolved in ethanol. The UV absorption spectrum of the above dye simply dissolved in ethanol is shown in the curve in Figure 6, and since the absorption peaks match the curve, it can be concluded that the thin film on ITO is made of the above dye. I understand.

The amount of this thin film deposited was 18 nanomol/cm ² .

In addition, after solubilizing a substance corresponding to n=11 of this general formula [1] (0.1 g in 100 c.c. of 10 mM surfactant solution)
(state when copper phthalocyanine is dispersed) is uniformly dispersed, HLB = 2.8, average particle size (evaluated by dynamic light scattering, using Otsuka Electronics' ELS-800) is 83 nm, and the formed thin film is It was transparent and uniform.

Comparative example 2 Add lithium sulfate as a supporting salt to 100ml of water.
0.02 mol was dissolved, and 0.2 mmol of the ferrocene derivative used in Comparative Example 1 was added thereto as a micellizing agent, and dispersed by ultrasonic waves to form micelles. Next, a dye (1-phenylazo-2-naphthol), which is a hydrophobic organic substance, is added to this micelle solution.
After adding 0.2 mmol, the dye was incorporated into the micelles using ultrasound. After stirring for two days and nights, excess dye was removed by centrifugation to obtain a micelle solution. This micelle solution is used as an electrolyte and applied to the anode.
Using ITO, platinum as the cathode, and a saturated sweet electrode as the reference electrode, temperature 25℃, applied voltage 0.3V, current density
Electrolytic treatment was performed under the condition of 35 μA/cm ² . After 60 minutes,
A dye thin film with primary particles with an average particle size of 700 Å is ITO
Got on top.

Scanning electron microscopy (SEM) of the produced dye thin film
A photograph (35,000x magnification, JSM-T220 manufactured by JEOL Ltd.) is shown in Figure 7. The curve in Figure 6 shows the UV absorption spectrum of this thin film dissolved in ethanol. The UV absorption spectrum of the above dye simply dissolved in ethanol is shown in the curve in Figure 6, and since the absorption peaks match the curve, it can be concluded that the thin film on ITO is made of the above dye. I understand.

The amount of this thin film deposited was 12 nanomol/cm ² .

From this, it can be seen that when the micellar agent of Example 1 is used, the amount of adhesion is approximately 1.5 times that of the micellar agent used in Comparative Example 2.

Comparative Example 3 Preparation of 1-ferrocenyl-3-bromide propane 3-bromide propionic acid chloride synthesized from 28.8 g of 3-bromide propionic acid and 90.0 g of thionyl chloride, 37.6 g of anhydrous aluminum chloride, and 35.0 g of 3-bromide propionic acid chloride.
3 g of ferrocene in methylene chloride at 5°C.
Allowed time to react. After the reaction was completed, the mixture was treated with dilute hydrochloric acid and extracted with a solvent to obtain 2-ethyl ferrocenyl ketone bromide.

Then, in the presence of an amalgam prepared with 65.4 g of zinc and 27.2 g of mercuric chloride, the 2-ethylferrocenyl ketone bromide prepared as above was added.
40.2 g was refluxed for 6 hours in a mixed solvent of concentrated hydrochloric acid and ethanol to react. After the reaction was completed, extraction was performed with a solvent to obtain 1-ferrocenyl-3-bromide propane.

Preparation of ferrocene derivative 1-ferrocenyl-11-undecane bromide 0.5 g
Except that 0.36 g of 1-ferrocenyl-3-bromide propane obtained above was used instead of
The same reaction as in Example 1 was carried out. As a result, the yield of the purified product was 0.11 g (yield 24%), and the proton nuclear magnetic resonance ( ¹ H-NMR) spectrum (CDCl ₃ ,
The measurement results (TMS standard) were as shown in Figure 9.
The elemental analysis values of this substance were as follows.

Carbon Hydrogen Nitrogen Calculated value 55.84 5.22 3.61 Measured value 55.64 5.65 3.52 The substance obtained in the above reaction is a substance corresponding to n = 3 in the general formula [1], and the solubilization ability is non-uniform dispersion and HLB = 6.6. Furthermore, the formed thin film was rough and opaque.

Example 4 Preparation of 1-ferrocenyl-4-bromidebutane 3-bromobutyric acid chloride synthesized from 31.5 g of 3-bromobutyric acid and 90.0 g of thionyl chloride, 37.6 g of anhydrous aluminum chloride, and 35.0 g of ferrocene , and reacted in methylene chloride at 5° C. for 3 hours. After the reaction was completed, the mixture was treated with dilute hydrochloric acid and extracted with a solvent to obtain 3-propenylbromide ferrocenyl ketone.

Next, in the presence of an amalgam prepared with 65.4 g of zinc and 27.2 g of mercuric chloride, 39.0 g of 3-propenyl bromide ferrocenyl ketone prepared as described above was added in a mixed solvent of concentrated hydrochloric acid and ethanol. The mixture was refluxed for an hour to react. After the reaction was completed, extraction was performed with a solvent to obtain 1-ferrocenyl-4-bromide butane.

Preparation of ferrocene derivative 1-ferrocenyl-11-undecane bromide 0.5 g
The same reaction as in Example 1 was carried out, except that 0.38 g of 1-ferrocenyl-4-bromide butane obtained above was used instead. As a result, the yield of the purified product was 0.14 g (yield 30%), and the proton nuclear magnetic resonance ( ¹ H-NMR) spectrum (CDCl ₃ , TMS
The measurement results for the standard) were as shown in Figure 10. The elemental analysis values of this substance were as follows.

Carbon Hydrogen Nitrogen Calculated value 56.88 5.53 3.49 Measured value 55.92 5.48 3.23 The substance obtained in the above reaction is a substance corresponding to n = 4 in the general formula [1] in the present invention, and the solubilization ability is uniformly dispersed and HLB = 6.1, and the average particle size (evaluated by the above-mentioned dynamic light scattering) was 83 nm, and the formed thin film was transparent and uniform.

Example 5 Preparation of 1-ferrocenyl-15-bromide pentadecane 60.5 g of 15-bromide pentadecanoic acid (which is 15-
15-Bropentadecanoic acid chloride synthesized from 90.0 g of thionyl chloride, 37.6 g of anhydrous aluminum chloride, and 35.0 g of ferrocene were mixed in methylene chloride at 5°C. The mixture was reacted for 3 hours. After the reaction is completed, it is treated with dilute hydrochloric acid and then extracted with a solvent.
Tetradecanyl ferrocenyl bromide ketone was obtained.

Next, in the presence of an amalgam purified with 65.4 g of zinc and 27.2 g of mercuric chloride, 54.2 g of 14-tetradecanyl bromide ferrocenyl ketone produced as described above was added to a mixed solvent of concentrated hydrochloric acid and ethanol. The mixture was refluxed for 6 hours to react. After the reaction was completed, extraction was performed with a solvent to obtain 1-ferrocenyl-15-pentadecane bromide.

Preparation of ferrocene derivative 1-ferrocenyl-11-undecane bromide 0.5 g
The same reaction as in Example 1 was carried out, except that 0.57 g of 1-ferrocenyl-15-bromide pentadecane obtained above was used instead. As a result, the yield of the purified product was 0.18 g (yield 27%), and the measurement results of proton nuclear magnetic resonance ( ¹ H-NMR) spectrum (CDCl ₃ , TMS standard) were as shown in FIG. The elemental analysis values of this substance were as follows.

Carbon Hydrogen Nitrogen Calculated value 64.86 8.00 2.52 Measured value 65.05 8.20 2.62 The substance obtained in the above reaction is a substance corresponding to n = 15 of the general formula [1] in the present invention, and the solubilization ability is uniformly dispersed and HLB = 0.9, and the average particle size (as evaluated by the above-mentioned dynamic light scattering) was 96 nm, and the formed thin film was transparent and uniform.

Comparative Example 4 Ferrocenylmethylpyridinium bromide,
That is, the solubilization ability and thin film forming ability of the substance corresponding to n=1 in general formula [1] were measured. As a result, the solubilization ability was unevenly dispersed, HLB=7.5, and the formed thin film was transparent and uniform.

〔Effect of the invention〕

The ferrocene derivative of the present invention is an unprecedented new compound and can be used for various purposes such as a surfactant (micellar agent), a catalyst, a combustion improver, a flotation agent, and a dispersant. In particular, when this ferrocene derivative is used as a surfactant (micelle forming agent), micelles are formed in an aqueous solution system, and dyes such as phthalocyanine, which have a wide range of applications, and water-insoluble polymers can be solubilized. In addition, by adding this surfactant (micelle forming agent) and utilizing aggregation and dispersion of micelles by aqueous electrolysis, it is possible to form an extremely thin organic film.

[Brief explanation of the drawing]

Figure 1 shows the ¹ H-NMR spectrum of the ferrocene derivative obtained in Example 1, and Figure 2 shows the 1H-NMR spectrum of the ferrocene derivative obtained in Example 1.
The IR spectrum is shown, and FIG. 3 shows its UV-VIS spectrum. Moreover, FIG. 4 shows the UV-VIS spectrum of the supernatant liquid obtained in Example 2 and Comparative Example 1, and FIG. 5 is an electron micrograph showing the surface structure of the thin film formed in Example 3. FIG. 6 shows the UV spectrum of the ethanol solution of the thin film formed in Example 3 and Comparative Example 2, FIG. 7 is an electron micrograph showing the surface structure of the thin film formed in Comparative Example 2, and FIG. The figure is an explanatory diagram schematically showing the principle of the method of the present invention. Figure 9 shows comparative example 3.
FIG ^. 10 shows the ¹ H-NMR spectrum of the ferrocene derivative obtained in Example 4,
FIG. 11 shows the ¹ H-NMR spectrum of the ferrocene derivative obtained in Example 5. In addition, in FIG. 8, 1 is a ferrocene derivative, 2 is a hydrophobic organic substance, 3 is a micelle, 4 is an oxidized ferrocene derivative, 5 is an anode, 6 is a cathode,
Fc indicates ferrocene, and e ^- indicates electron.

Claims (1)

[Claims] 1. General formula [In the formula, R ¹ , R ² and R ³ each represent hydrogen, a methyl group, an ethyl group, a methoxy group or a carbomethoxy group, and X represents a halogen. Also,
C _o H _2o represents a straight or branched alkylene group having 4 to 16 carbon atoms. ] A novel ferrocene derivative represented by 2. A surfactant containing the novel ferrocene derivative according to claim 1. 3. Solubilizing a hydrophobic organic substance in an aqueous medium with a surfactant comprising the novel ferrocene derivative according to claim 1, and electrolyzing the resulting micellar solution to form a thin film of the hydrophobic organic substance on an electrode. A method for producing an organic thin film characterized by: