JPH02298294A - Production of thin film - Google Patents

Abstract

PURPOSE:To efficiently produce a stable thin film sticking firmly on the cathode by dispersing or solubilizing a hydrophobic substance in an aq. medium with a ferrocene deriv. as a micelle forming agent and supplying electric current to the resulting dispersion or soln. CONSTITUTION:A hydrophobic substance is dispersed or solubilized in an aq. medium with a ferrocene deriv. as a micelle forming agent. Perylene, lake pigment or anthraquinone may be used as the hydrophobic substance. The dispersion or solubilization is carried out through an ultrasonic generator, a homogenizer, a stirrer, etc., and sulfate or other supporting salt is used as required. Electric current is supplied to the resulting dispersion or soln. under continuous required to form a thin film of the hydrophobic substance on the cathode. A base metal such as Al is suitable for use as the cathode. A stable thin film sticking firmly on the cathode is efficiently formed at relatively low voltage without causing flocculation in the soln.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Application of the Invention) The present invention relates to a method for manufacturing a thin film, and more particularly to a method for extremely efficiently manufacturing a thin film firmly adhered to a cathode using a base metal such as aluminum.

[Prior art and problems to be solved by the invention] Hitherto, a method has been known in which a micelle solution of a hydrophobic substance is electrolytically controlled to form a thin film on the electrode surface, the so-called micelle electrolysis method (Japanese Patent Application Laid-Open No. 63 243298, etc.), and the thin films produced in this way are expected to be developed into various uses such as color filters and photoelectric conversion materials.

However, although it is possible to form a thin film on an anode according to the method disclosed herein, it is extremely difficult to form a film on a base metal that is easily dissolved by anodic polarization.

On the other hand, in the field of photosensitive materials, there is a desire to form films on base metal substrates such as aluminum, and there are expectations for the development of a method for forming thin films firmly attached to base metals.

[Means to solve the problem]

Therefore, the present inventor conducted extensive research in order to develop a method for forming a thin film that is uniform and firmly adhered to base metals. As a result, by using a micellizing agent made of a ferrocene derivative and conducting an electrical treatment under specific conditions,
It was discovered that the desired thin film could be produced.The present invention was completed based on this knowledge.

That is, the present invention provides a dispersion or solution obtained by dispersing or solubilizing a hydrophobic substance in an aqueous medium using a micellizing agent made of a ferrocene derivative under conditions that produce a thin film of the hydrophobic substance on the cathode. Below, a method for manufacturing a thin film is provided, which is characterized by carrying out an energization treatment.

The hydrophobic substance used in the method of the present invention includes various substances that can be solubilized or dispersed in an aqueous medium using a ferrocene derivative. For example, perylene
Optical memory such as lake pigments, phthalocyanine blue, phthalocyanine green, anthraquinone, phthalocyanine, metal complexes of phthalocyanine and their derivatives, naphthalocyanine, metal complexes of naphthalocyanine and their derivatives, porphyrin, metal complexes of porphyrin and their derivatives. 6- Nitro-1,3,3-1-lynchyl spiro (
2°H-1'-benzopyran-2,2°-indoline)
Photosensitive materials (photochromic materials) such as (commonly known as spiropyran), optical sensor materials, pigments for liquid crystal displays such as p-azoxyanisole, and "Color Chemical Encyclopedia" CMC Co., Ltd., No. 54, published March 28, 1988.
Electronics dyes, recording dyes, environmental chromism dyes, photographic dyes, energy dyes, biomedical dyes 1 Food and cosmetic dyes, dyes listed on pages 2 to 717.

Examples include hydrophobic compounds of pigments and special coloring dyes. Additionally, 7,7,8.8-tetracyanoquinone dimethane (TCNQ) and tetrathiafulvalene (TTF
), organic conductive materials and gas sensor materials such as 1:1 complex with etc. can be given. Furthermore, water-insoluble polymers such as polycarbonate polystyrene, polyethylene, polypropylene, polyamide, polyphenylene sulfide (PPS), polyphenylene oxide (
General-purpose polymers such as PPO), polyacrylonitrile (PAN), as well as polyphenylene, polypyrrole, and polyaniline.

Examples include polythiophene, acetylcellulose, polyvinyl acetate, polyvinyl butyral, and various other polymers (such as polyvinylpyridine) or copolymers (such as copolymers of methyl methacrylate and methacrylic acid).

Various types of ferrocene derivatives can be used to solubilize or disperse such hydrophobic substances. The following alkoxy groups, amino groups, dimethylamino groups, hydroxyl groups, acetylamino groups, carboxyl groups, and methoxycarbonyl groups.

Indicates an acetoxy group, an aldehyde group or a halogen,
R3 represents hydrogen or a linear or branched alkyl group or alkenyl group having 4 to 18 carbon atoms, and R4 and R5 each represent hydrogen or a methyl group. Y represents oxygen or an oxycarbonyl group, a represents an integer of 0 to 4, b represents an integer of O to 4, 1m represents an integer of 1 to 18, and n represents a real number of 2.0 to 70.0. ] The ferrocene derivative represented by is a typical example. Here, each symbol in general formula (1) is as described above. In other words, International Publication WO
3B10753B, WO39101939゜Patent Application 1986
-233797 and others, R1 and R1 are each an alkyl group (methyl group) having 6 or less carbon atoms.
CH, ethyl group (C! Hs), etc.), alkoxy group (
methoxy group (OCH3), ethoxy group (OC!H2), etc.), amino group (NH,).

Dimethylamino group (N(C1(s)g)), hydroxyl group (
OH).

Acetylamino group (NHCOCH,), carboxyl group (COOH), 7-cetoxy group (OCOCH,).

Methoxycarbonyl group (COOCH), aldehyde group (CHO) or halogen (chlorine, bromine).

fluorine, iodine, etc.). R1 and R1 may be the same or different, and even if a plurality of R1 and Rz each exist in the five-membered ring of ferrocene, the plurality of substituents may be the same or different, respectively. . Further, R3 represents hydrogen or a linear or branched alkyl group or alkenyl group having 4 to 18 carbon atoms.

Furthermore, Y is oxygen (-0-) or oxycarbonyl group (-
C-0-), and R4 and R11 are hydrogen or a methyl group (
CH,). Therefore, −0(CH2CH2O), I
H.

-0(CHICHO), )I, -〇(CHCH,O)
, HI3 CHs CH5 -C-0 (CH2CHtO), IH or the like.

Moreover, m represents an integer of 1 to 18. Therefore, an alkylene group having 1 to 18 carbon atoms, such as an ethylene group or a propylene group, is interposed between the ring carbon atom and the oxygen or oxycarbonyl group. Furthermore, n indicates the number of repeats of the oxyalkylene group such as the above oxyethylene group,
It means not only integers from 2.0 to 7060 but also real numbers including these, and indicates the average number of repeats (ffi) of oxyalkylene groups, etc.

The ferrocene derivative in the present invention has the above general formula [1]
In addition to those represented by , there are various other types, such as ammonium type, pyridine type
7538, etc.), Japanese Patent Application No. 63-233797, No. 63-233798, No. 63-248
No. 600, No. 63-248601, Japanese Patent Application No. 1-45370, No. 1-54956, No. 1-70680, No. 1-70681, No. 1- No. 76498 and No. 1-76499
Examples include the ferrocene derivatives described in the patent specification.

These ferrocene derivatives can very efficiently solubilize or disperse hydrophobic substances in an aqueous medium.

In the present invention, there are various methods for preparing a micelle solution or dispersion, but specifically, in an aqueous medium,
Various ferrocene derivatives (micelle forming agents), including the ferrocene derivative of the general formula (1), are adjusted to a concentration higher than the limit micelle concentration, a supporting salt is added as necessary, and a hydrophobic organic substance is added, and the mixture is subjected to ultrasonic waves. The mixture may be sufficiently dispersed using a homogenizer or a stirrer to form micelles. Further, from the thus obtained hydrophobic organic substance solubilized solution (micelle solution, aqueous solution, or dispersion), excess hydrophobic organic substance is then removed as necessary.

Specifically, the supporting salts that are added as needed include sulfates (salts of lithium, potassium, sodium, rubidium, aluminum, etc.) and acetates (salts of lithium, potassium, sodium, etc.), which are generally widely used as supporting salts. , rubidium, beryllium, magnesium, calcium, strontium, barium, aluminum, etc.], halide salts (lithium, pentapotassium, sodium, etc.).

salts of rubidium, calcium, magnesium, aluminum, etc.), water-soluble oxide salts (lithium.

Potassium, sodium, rubidium, calcium.

salts of magnesium, aluminum, etc.) are preferred.

The concentration of these supporting salts is not particularly limited and may be any concentration that does not hinder the precipitation of solubilized substances or dispersed substances, but it is usually 10 to 300 times the concentration of the overcellifying agent, preferably 50
~200 times.

In the micelle solution or dispersion thus produced, a thin film is produced by applying current to the micelle electrolysis method under conditions that produce a thin film on the cathode.

There are various types of electrodes used in the present invention, but
Oxidation potential of ferrocene derivatives (+0.15v to +0.3
A metal or conductor with higher resistance (0 V vs. saturated electrode) is preferable. Specifically, as an anode, ITO (mixed oxide of indium oxide and tin oxide), platinum, gold, silver, gladi-carbon, conductive Examples include metal oxides and organic polymer conductors. In addition, aluminum and iron can be used as the cathode.

Base metals such as zinc, cobalt, and tin, as well as copper.

Stainless steel, gold, platinum, silver, gray carbon.

Examples include conductive metal oxides, conductive polymers, ITO, and the like.

This energization treatment is usually performed while stirring.

Alternatively, the hydrophobic organic substance may be supplemented and added to the micelle solution during the energization process, 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. , a circulation circuit may be provided for returning this liquid to the vicinity of the cathode.

The current treatment at this time is performed under conditions such that the solubilized substance or the dispersed substance forms a thin film on the cathode. Such conditions include a liquid temperature of 0 to 70°C, preferably 5 to 40°C, and a cathode potential of -0.03 to -5.00V,
Preferably it is -0.05 to -2.00V. Further, the current density is set to less than -10 mA/clI", preferably -50 to 300 μA/cm".

When current is applied under these conditions, the pH environment near the cathode changes significantly, and as a result, the micelles become unstable and become dispersed. As the micelles disperse, the solubilized hydrophobic substance is precipitated onto the cathode, forming a uniform thin film firmly attached to the cathode.

〔Example〕

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

Example 1 A ferrocene derivative micellar agent represented by structural formula 1 was added to 100 cc of water to make a 2 mM solution, and this micelle solution 20
0.1 gm of phthalocyanine in cc, 10 gm in t with ultrasound
The mixture was stirred for 1 minute to disperse and solubilize.

Furthermore, after stirring for two days and nights using Starcy, the obtained dispersed and solubilized micelle solution was centrifuged at 2000 rpa+ for 30 minutes. From the visible absorption spectrum of this supernatant, it was confirmed that phthalocyanine was dispersed.

Add 0.1M lithium bromide to this dispersed and solubilized micelle solution.
and stirred with Starcy for 10 minutes. Using this solution as an electrolyte, a platinum plate is used as the anode, and an I plate is used as the cathode.
Using a TO glass electrode and a saturated material copper electrode as a reference electrode, constant potential electrolysis was performed at 25"C with an applied voltage of -0.5V.The current density at this time was -11.0μA/cd, and the current application time was The amount of current applied for 30 minutes was 0.02 coulombs (C).

As a result, a thin film of phthalocyanine was obtained on the ITO transparent glass electrode. Since the absorption spectrum of the best phthalocyanine in this ITO transparent glass and the absorption spectrum of the dispersed and solubilized micelle solution match, the thin film on the ITO transparent glass electrode is phthalocyanine, and the film thickness is 0.6 μm based on its absorbance. It turns out.

Example 2 A ferrocene derivative micellar agent represented by structural formula 2 was added to 100 cc of water to make a 2 mM solution, and this micelle solution 20
Perylene pigment (K3580) (manufactured by BASF) in cc
0.1 g was added and stirred with ultrasonic waves for 10 minutes to disperse and solubilize. Furthermore, after stirring for two days and nights using Starcy, the obtained dispersed and solubilized micelle solution was centrifuged at 2000 rpm for 30 minutes. From the visible absorption spectrum of this supernatant, it was confirmed that K3580 was dispersed.

Add 0.1M lithium bromide to this dispersed and solubilized micelle solution.
and stirred with Starcy for 10 minutes. Using this solution as an electrolyte, constant potential electrolysis was performed at 25° C. and an applied voltage of −0.8 V using a platinum plate as an anode, an aluminum electrode as a cathode, and a saturated copper electrode as a reference electrode. At this time, the current density was -22.0 μA/cd, the current application time was 30 minutes, and the current application amount was 0.03C.

As a result, a thin film of K3580 was obtained on the aluminum electrode. Since the reflection spectrum of 3580 on this aluminum electrode and the peak wavelength of the absorption spectrum of the dispersed solubilized micelle solution match, the thin film on the aluminum electrode is 3580, and the film thickness is 0.4 μm from the tomographic electron micrograph. It turned out to be.

Example 3 A ferrocene derivative micellar agent represented by structural formula 3 was added to 100 cc of water to make a 2 mM solution, and this micelle solution 20
0.1 g of copper phthalocyanine (manufactured by Dainichiseika Chemical Co., Ltd.) was added to the cc and stirred with ultrasonic waves for 10 minutes to disperse and solubilize. Furthermore, after stirring for two days and nights using Starcy, the obtained dispersed and solubilized micelle solution was centrifuged at 2000 rpm for 30 minutes. From the visible absorption spectrum of this supernatant,
It was confirmed that copper phthalocyanine was dispersed.

Add lithium bromide to this dispersed solubilized micelle solution at 0°IM.
and stirred with Starcy for 10 minutes. Using this solution as an electrolyte, constant potential electrolysis was carried out at 25 DEG C. and an applied voltage of -0.3 mm using a platinum plate as an anode, an aluminum electrode as a cathode, and a saturated copper electrode as a reference electrode. The current density at this time was -7.6 μA/d, the current application time was 30 minutes, and the current application amount was 0.015C.

As a result, a thin film of copper phthalocyanine was obtained on the aluminum electrode. The peak wavelength of the reflection spectrum of the copper phthalocyanine on the aluminum electrode and the absorption spectrum of the dispersed solubilized micelle solution is clearly the same, indicating that the thin film on the aluminum electrode is copper phthalocyanine, and the thickness of the film is 0.5 mm from the tomographic electron micrograph. It was found to be 25 μm.

Example 4 A ferrocene derivative micellar agent represented by structural formula 4 was added to 100 cc of water to make a 2 mM solution, and this micelle solution 20
Add 0.1g of viologen to cc and apply ultrasound for 10 minutes.
It was stirred to disperse and solubilize. Furthermore, after stirring for two days and nights with Starcy, the obtained dispersed and solubilized micelle solution was
Centrifugation was performed at 000 rpm for 30 minutes. From the visible absorption spectrum of this supernatant, it was confirmed that viologen was dispersed.

Add 0,1 lithium bromide to this dispersed and solubilized micelle solution.
The mixture was added to a concentration of M and stirred with Starcy for 10 minutes. Using this solution as an electrolyte, a platinum plate as an anode, a copper electrode as a cathode, and a saturated copper electrode as a reference electrode, the temperature was 25°C.
Constant potential electrolysis was performed at an applied voltage of -0.7 cm. At this time, the current density was -17.6 μA/cd, the current application time was 30 minutes, and the current application amount was 0.030.

As a result, a thin film of viologen was obtained on the copper electrode. Since the peak wavelength of the reflection spectrum of viologen on this copper electrode and the absorption spectrum of the dispersed solubilized micelle solution match, the thin film on the copper electrode is viologen, and the film thickness is 0.65 μm from the tomographic electron micrograph. It turned out that.

Example 5 A ferrocene derivative micellar agent represented by structural formula 5 was added to 100 cc of water to make a 2 mM solution, and this micelle solution 20
CuPcClmBra (L 9361) (B
0.1 g of ASF (manufactured by ASF) was added and stirred for 10 minutes using ultrasonic waves to disperse and solubilize. Furthermore, after stirring with a stirrer for two days and nights, the obtained dispersed solubilized micelle solution was
Centrifugation was performed at Orpm for 30 minutes. From the visible absorption spectrum of this supernatant, it was confirmed that L9361 was dispersed.

Add 0 to 1 M of lithium bromide to this dispersed and solubilized micelle solution.
and stirred with a stirrer for 10 minutes. Using this solution as an electrolyte, constant potential electrolysis was performed at 25° C. and an applied voltage of −0.7 V using a platinum plate as an anode, a polyaniline/ITO electrode as a cathode, and a saturated material copper electrode as a reference electrode. The current density at this time is -11.3 μA /
cd, the current application time was 30 minutes, and the current application amount was 0.02C.

As a result, a thin film of L9361 was obtained on the polyaniline/ITO electrode. L on this polyaniline/ITO electrode
Since the peak wavelengths of the reflection spectrum of 9361 and the absorption spectrum of the dispersed solubilized micelle solution matched, it was determined that the thin film on the polyaniline/ITO electrode was L9361, and the film thickness was 0.6 μm from the tomographic electron micrograph. Ta.

Structural formula 5 Add the ferrocene derivative micelle agent represented by structural formula 6 to 100 cc of water to make a 2 mM solution, and make a 2 mM solution of this micelle solution.
0.1 g of Sudan 1 was added to the cc and stirred with ultrasonic waves for 10 minutes to disperse and solubilize. Furthermore, after stirring with a stirrer for two days and nights, the obtained dispersed solubilized micelle solution was
Centrifugation was performed at 0 rpa+ for 30 minutes. From the visible absorption spectrum of this supernatant, it was confirmed that Sudan I was dispersed.

To this dispersed solubilized micelle solution, lithium bromide was added at 0 and 1
The mixture was added to a concentration of M and stirred with a stirrer for 10 minutes. Using this solution as an electrolyte, constant potential electrolysis was performed at 25° C. and an applied voltage of −0.5 V using a platinum plate as an anode, a stainless steel electrode as a cathode, and a saturated copper electrode as a reference electrode. The current density at this time is -8.6μA/cii! The energization time was 30 minutes, and the energization amount was oic.

As a result, a thin film of Sudan 2 was obtained on the stainless steel electrode. Since the peak wavelength of the reflection spectrum of Sudan R on this stainless steel electrode and the absorption spectrum of the dispersed solubilized micelle solution match, the thin film on the stainless steel electrode is Sudan I, and the film thickness is 0.2 μm from the tomographic electron micrograph. It turned out to be.

Example 7 A ferrocene derivative micellar agent represented by structural formula 7 was added to 100 cc of water to make a 2 mM solution, and this micelle solution 20
Tetraphenylporphyrin zinc complex (Zn-T
PP) was added and stirred for 10 minutes using ultrasonic waves to disperse and solubilize. Furthermore, after stirring for two days and nights with a stirrer, the obtained dispersed solubilized micelle solution was heated at 200 rpm.
Centrifugation was performed at + for 30 minutes. From the visible absorption spectrum of this supernatant, it was confirmed that Zn-TPP was dispersed.

Add 0.1M lithium bromide to this dispersed and solubilized micelle solution.
and stirred with a stirrer for 10 minutes. Using this solution as an electrolyte, using a platinum plate as an anode, a platinum electrode as a cathode, and a saturated material electrode as a reference electrode,
Constant potential electrolysis was performed at °C and an applied voltage of -0, 6V. The current density at this time was -17.2μA/cd, and the current application time was 3
The amount of current applied was 0.03C for 0 minutes.

As a result, a thin film of Zn-TPP was obtained on the platinum electrode. Since the peak wavelengths of the reflection spectrum of Zn-TPP on this platinum electrode and the absorption spectrum of the dispersed solubilized micelle solution match, the thin film on the platinum electrode is Zn-TPP, and the film thickness is 0 from the tomographic electron micrograph. It was found to be .18 μm.

Structural formula 7 A ferrocene derivative micellar agent represented by structural formula 8 is added to 100 cc of water to make a 2 mM solution, and this micelle solution 20
Add 0.1g of triphenylamine to cc and 1
The mixture was stirred for 0 minutes to disperse and solubilize. Furthermore, after stirring for two days and nights using Starcy, the obtained dispersed and solubilized micelle solution was centrifuged at 200 rpm for 30 minutes. From the visible absorption spectrum of this supernatant, it was determined that triphenylamine was dispersed.

Add 0, 1 lithium bromide to this dispersed and solubilized micelle solution.
The mixture was added to a concentration of M and stirred with Starcy for 10 minutes. Using this solution as an electrolytic solution, constant potential electrolysis was performed at 25° C. and an applied voltage of -0.9 V using a platinum plate as an anode, an aluminum electrode as a cathode, and a saturated copper electrode as a reference electrode. The current density at this time is -25.3μA/cff
1, the current application time was 30 minutes, and the current application amount was 0.04C.

As a result, a thin film of triphenylamine was obtained on the aluminum electrode. The reflection spectrum of triphenylamine on the aluminum electrode and the peak wavelength of the absorption spectrum of the dispersed solubilized micelle solution are completely different, so the thin film on the aluminum electrode is triphenylamine. It was found to be 0.45 μm.

Structural Formula 8 Example 9 A ferrocene derivative micelle forming agent represented by Structural Formula 9 was added to 100 cc of water to make a 2 mM solution, and this micelle solution 20
Add 0 lake pigment (K3700) (manufactured by BASF) to cc.
．． 1 g was added and stirred using ultrasound for 10 minutes to disperse and solubilize. Furthermore, after stirring for two days and nights with Starcy,
The obtained dispersed solubilized micelle solution was heated at 200 rpm for 30 min.
Centrifugation was performed for minutes. From the visible absorption spectrum of this supernatant, it was confirmed that K3700 was dispersed.

Add 0, 1 lithium bromide to this dispersed and solubilized micelle solution.
The mixture was added to a concentration of M and stirred with Starcy for 10 minutes. Using this solution as an electrolyte, constant potential electrolysis was carried out at 25°C and an applied voltage of -0, 8V using a platinum plate as an anode, a grady carbon (GC) electrode as a cathode, and a saturated sweet electrode as a reference electrode. Ta. The current density at this time is -12.8μA
/ cd, energizing time is 30 minutes, energizing amount is 0.25
It was C.

As a result, a thin film of K3700 was obtained on the GC electrode.

Since the reflection spectrum of 3700 on this GC electrode and the peak wavelength of the absorption spectrum of the dispersed solubilized micelle solution match, the thin film on the GC electrode is 3700, and the film thickness is 0.4 μm from the tomographic electron micrograph. It turned out to be.

Structural Formula 9 Add the ferrocene derivative micelle agent represented by Structural Formula 10 to 100 cc of water to make a 2mM solution, and make this micelle solution 2.
Add 0.1g of naphthol As to 0cc and 10
The mixture was stirred for 1 minute to disperse and solubilize. Furthermore, after stirring for two days and nights using Starcy, the obtained dispersed and solubilized micelle solution was centrifuged at 200 rpm for 30 minutes. From the visible absorption spectrum of this supernatant, it was confirmed that naphthol AS was dispersed.

Add 0.1M lithium bromide to this dispersed and solubilized micelle solution.
and stirred with Starcy for 10 minutes. Using this solution as an electrolyte, a platinum plate is used as the anode, and an I plate is used as the cathode.
Constant potential electrolysis was performed at 25° C. and an applied voltage of -0.5 μm using a TO glass electrode and a saturated sweetened electrode as a reference electrode. At this time, the current density was -5.5 μA/cd, the current application time was 30 minutes, and the current application amount was 0.0 IC.

As a result, a thin film of naphthol As was obtained on the ITO glass electrode. Naphthol As on this ITO glass electrode
The peak wavelength of the absorption spectrum of the dispersion-solubilized micelle solution coincided with that of the absorption spectrum of the dispersed solubilized micelle solution, and it was determined that the thin film on the ITO glass electrode was naphthol As, and the thickness of the film was 0.4 μm from the tomographic electron micrograph. .

〔Effect of the invention〕

As described above, according to the method of the present invention, a thin film can be efficiently formed on a cathode made of a base metal or the like at a relatively low voltage without causing aggregation of the solution. Furthermore, the obtained thin film is firmly attached to the cathode and is stable.

As described above, since the method of the present invention can produce useful thin films with high productivity, it is expected to be used in fields such as electrophotographic photoreceptors and color filters.

Claims (2)

[Claims] (1) A dispersion or solution obtained by dispersing or solubilizing a hydrophobic substance in an aqueous medium using a micellizing agent made of a ferrocene derivative is prepared under conditions such that a thin film of the hydrophobic substance is formed on the cathode. , a method for producing a thin film, characterized by carrying out an energization treatment. (2) The method for producing a thin film according to claim 1, wherein the cathode is a base metal.