JP6581772B2 - Amorphous compound gel, method for producing amorphous compound gel, method for producing oxide crystal, method for producing metal crystal, oxide crystal, and metal crystal - Google Patents

Description

  The present invention relates to an amorphous compound gel, a method for producing an amorphous compound gel, a method for producing an oxide crystal, a method for producing a metal crystal, a method for producing a transparent conductor, an oxide crystal, and a metal crystal.

  The manufacturing method of metal film formation has expanded the range of processes from patterning using a sputtering method to application of printing technology using metal nanoparticles. In particular, in the case of forming an electrode of a thin film semiconductor (TFT), etc., formation of source, drain and gate electrodes using an ink jet method is in progress. In addition, as a formation method by liquid phase coating of metal-containing thin films, there is a technique for forming a metal or semiconductor film by applying a solution in which an amorphous material containing a metal is dissolved instead of metal or inorganic nanoparticles and irradiating energy. It is disclosed (see Patent Document 1).

  In oxide semiconductors, IGZO (In—Ga—Zn—O) and the like have been put into practical use, and these include vapor phase methods such as direct current magnetron sputtering (see Patent Document 2). . In this case, steps such as preparation of an oxide target material, patterning by sputtering, and annealing are required.

  In Patent Document 3, an aqueous solution of a metal salt of aluminum, titanium, and zirconium and an aqueous solution of a neutralizing agent are simultaneously added to water in which a carboxylic acid compound is dispersed or dissolved, and a hydroxide or water is added. Disclosed is a method for producing fine particulate metal oxides that can be used for fine particles of Japanese products, firing the obtained fine particles, fillers such as plastics, paints, and adhesives, abrasives for precision processing, etc. .

On the other hand, in Non-Patent Document 1, the product obtained from the reaction solution consisting of copper sulfate, glycerin and sodium hydroxide is repeatedly decanted with an aqueous glycerin solution, then washed with dilute hydrochloric acid, and then dispersed in glycerin. Furthermore, a method for synthesizing amorphous copper hydroxide that is washed with distilled water and then dried is disclosed.
Non-Patent Document 2 discloses a method of forming a conductor pattern by light irradiation from an amorphous thin film of copper hexanoate hydrate.

US Pat. No. 5,534,312 International Publication No. 2009/084537 Japanese Patent Laying-Open No. 2005-081501

Journal of Colloid and Interface Science, 215, 23-27 (1999) Journal of the American Chemical Society, 118, 237-238 (1996)

In the method for forming a metal-containing thin film disclosed in Patent Document 1 by liquid phase coating, a reducing atmosphere such as a hydrogen gas atmosphere is required for firing the amorphous material, and it has not been put into practical use.
In the case of forming the thin film type semiconductor electrode, the thickness accuracy and flatness depend on the shape and dispersibility of the metal nanoparticles in the formation of the source, drain and gate electrodes using the inkjet method. There are restrictions on the use for forming fine TFTs. In the method for manufacturing an oxide semiconductor disclosed in Patent Document 2, many steps such as preparation of an oxide target material, patterning by sputtering, and annealing are required, and among these, about 400 ° C. is applied when the temperature is applied in the annealing process. Therefore, fine control of the annealing atmosphere is necessary because there is a concern that oxygen defects disappear and mobility decreases. Patent Document 3 discloses a method for producing fine particles of hydroxide or hydrate having a particle size of about 50 to 200 nm suitable for the above-mentioned use, but does not disclose a method for producing an amorphous compound. Further, in both of Non-Patent Document 1 and Non-Patent Document 2, a method for easily manufacturing an amorphous compound gel that can be used for manufacturing an oxide crystal, a metal crystal, and the like by electrolytic reduction, and an oxide crystal The composition of a solvent suitable for the production of a metal crystal or the like is not disclosed.

  This invention solves the said subject and provides an amorphous compound obtained by carrying out the electrolytic reduction of the electrolytic reaction solution containing a metal ion on specific conditions. Another object of the present invention is to provide an oxide crystal, a metal crystal or the like formed by irradiating and / or heating the amorphous compound.

  In the present invention, in view of the above prior art, by making an electrolytic reaction solution containing a metal ion into a specific pH range in the presence of a ligand coordinated to the metal ion, the fine crystallization of the precipitate is strong. Inspired, it has been found that the crystallinity of the metal hydroxide, which is a precursor of the metal fine particles, is precipitated in the state of an amorphous compound in which the crystallinity is significantly lower than that of the metal fine particles, and that the amorphous compound can be recovered alone. In addition, a semiconductor composed of an oxide crystal, a conductor composed of a metal crystal, etc. can be obtained by subjecting the amorphous compound gel composed of the amorphous compound and the organic solvent to heating, light irradiation, etc. under specific conditions. As a result, the present invention has been completed. That is, the gist of the present invention is the invention described in the following (1) to (33).

(1) It is composed of an amorphous compound having a crystallinity of 5% or less formed by bonding one or more hydroxyl groups to a metal element, and an organic solvent (S) that is liquid at room temperature. Amorphous compound gel (hereinafter sometimes referred to as the first embodiment).
(2) The amorphous compound gel according to (1), wherein the metal element is one or more selected from copper, zinc, tin, and nickel.
(3) The amorphous compound gel according to (1) or (2) above, wherein the boiling point of the organic solvent (S) at normal pressure is 60 ° C. or higher.
(4) The amorphous compound gel according to any one of (1) to (3), wherein a boiling point of the organic solvent (S) at normal pressure is 350 ° C. or less.
(5) An organic compound (S1) in which the organic solvent (S) has at least one hydroxyl group, and one or two hydrogen atoms are bonded to the carbon atom to which the hydroxyl group is bonded. The amorphous compound gel according to any one of (1) to (4), wherein the amorphous compound gel is included.

(6) The organic compound (S1) is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2,2- Dimethyl-1-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 2,2 dimethyl-1-propanol, 3-methyl- 2-butanol, 2-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-2-hexanol, 2-methyl-3-hexanol, 1-heptanol, 2-heptanol, 4- Heptanol, 2-ethyl-1-hexanol, 1-octanol, 2-octanol, ethylene glyco Diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-butene-1,4-diol, 2 , 3-butanediol, pentanediol, hexanediol, octanediol, glycerol, 1,1,1-trishydroxymethylethane, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 1,2,6- (1) to (5) above, characterized by being one or more selected from hexanetriol, 1,2,3-hexanetriol, and 1,2,4-butanetriol The amorphous compound gel according to any one of the above.
(7) The amorphous compound gel according to any one of (1) to (6), wherein a lactam compound (L) is mixed in the amorphous compound gel.
(8) The amorphous compound gel according to any one of (1) to (7), wherein the molecular structure of the amorphous compound is a hydrate.
(9) The amorphous compound gel according to any one of (1) to (8), wherein the molecular structure of the amorphous compound includes a carboxyl group.
(10) The amorphous compound gel according to any one of (1) to (9), wherein the amorphous compound does not have a long-period structure of 100 nm or more.

(11) In a reaction solution having a pH of 4.0 to 11.0 containing a metal ion and a ligand that forms a coordination bond to the metal ion, it is derived from the metal ion by an electrolytic reaction in which a current is passed between the anode and the cathode. A method for producing an amorphous compound gel, which comprises precipitating an amorphous compound to be precipitated and mixing the amorphous compound with an organic solvent (S) (hereinafter sometimes referred to as a second embodiment).
(12) The method for producing an amorphous compound gel according to (11), wherein the metal ion is one or more selected from copper, zinc, tin, and nickel.
(13) The amorphous as described in (11) or (12) above, wherein the metal ion forms a complex with the ligand, and the total formation constant of the complex is 1 to 10. Method for producing compound gel.
(14) The ligand is one or more selected from acetate ion, oxalate ion, propionate ion, malonate ion, tartrate ion, and pyrophosphate ion, The method for producing an amorphous compound gel according to any one of 11) to (13).

(15) Any one of (11) to (14) above, wherein one or two selected from alkali metal ions and alkaline earth metal ions are dissolved in the reaction solution A method for producing an amorphous compound gel according to claim 1.
(16) The method for producing an amorphous compound gel according to (15), wherein the alkali metal ion is one or more selected from lithium ion, sodium ion, and potassium ion.
(17) The method for producing an amorphous compound gel according to (15), wherein the alkaline earth metal ion is a calcium ion.
(18) The method for producing an amorphous compound gel according to any one of (11) to (17), wherein the lactam compound (L) is dissolved in the reaction solution.
(19) One or two selected from 2-pyrrolidone, alkyl-2-pyrrolidone, and hydroxyalkyl-2-pyrrolidone, wherein the lactam compound (L) has a 5-membered ring structure having 4 to 12 carbon atoms It is a seed | species or more, The manufacturing method of the amorphous compound gel as described in said (18) characterized by the above-mentioned.

(20) The alkyl-2-pyrrolidone is N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, Nn-propyl-2-pyrrolidone, Nn-butyl- 2-pyrrolidone, N-iso-butyl-2-pyrrolidone, Nn-octyl-2-pyrrolidone, 3-methyl-2-pyrrolidone, 4-methyl-2-pyrrolidone, N-methyl-3-methyl-2- The method for producing an amorphous compound gel according to (19), wherein the method is one or more selected from pyrrolidone and N-methyl-4-methyl-2-pyrrolidone.
(21) The hydroxyalkyl-2-pyrrolidone is selected from N- (hydroxymethyl) -2-pyrrolidone, N- (2-hydroxyethyl) -2-pyrrolidone, and N- (3-hydroxypropyl) -2-pyrrolidone The method for producing an amorphous compound gel according to (19), wherein the method is one or more kinds.

(22) The amorphous compound gel according to any one of (1) to (10) is applied to a base material, and preliminarily prepared at a temperature not higher than the boiling point of the organic solvent (S) in an air atmosphere or an inert gas atmosphere. A method for producing an oxide crystal (hereinafter, sometimes referred to as a third embodiment), characterized in that after drying, heating, light irradiation, or light irradiation under heating is performed.
(23) The light source of the light irradiation is a xenon lamp, the discharge light emission voltage is in the range of 1000 to 3000 V, and the oxide crystal is one or more selected from copper, zinc, tin, and nickel The method for producing an oxide crystal according to (22) above, wherein the oxide crystal is a semiconductor or a conductor of the oxide.
(24) The amorphous compound gel according to any one of (1) to (10) is applied to a base material, and preliminarily prepared at a temperature not higher than the boiling point of the organic solvent (S) in an air atmosphere or an inert gas atmosphere. A metal crystal manufacturing method (hereinafter, also referred to as a fourth embodiment), characterized in that after drying, heating, light irradiation, or light irradiation under heating is performed.
(25) The metal crystal according to (24), wherein the light source of the light irradiation is a xenon lamp, a discharge light emission voltage is in a range of 500 to 5000 V, and the metal crystal is a copper conductor. Body manufacturing method.
(26) Two or more of the amorphous compound gels according to any one of (1) to (10) above are mixed and applied to a substrate, and the organic solvent (S) is applied in an air atmosphere or an inert gas atmosphere. ), After preliminary drying at a temperature lower than the boiling point, heating, light irradiation, or light irradiation under heating is performed, which is hereinafter referred to as a fifth embodiment. There).
(27) The amorphous compound gel according to any one of (1) to (10) above and a compound salt of a metal element or a metalloid element are mixed and applied to a substrate, and the atmosphere or an inert gas atmosphere Among them, after preliminary drying at a temperature lower than the boiling point of the organic solvent (S), heating, light irradiation, or light irradiation under heating is performed, a method for producing a transparent conductor (hereinafter, It may be called the sixth embodiment).

(28) The amorphous compound gel according to any one of (1) to (10) is applied to a base material, and preliminarily prepared at a temperature lower than the boiling point of the organic solvent (S) in an air atmosphere or an inert gas atmosphere. After drying, the oxide crystal formed by heating, light irradiation, or light irradiation under heating is the main peak of the maximum intensity in X-ray diffraction using CuKα as the X-ray source. An oxide crystal having a half-value width at 2θ in a range of 0.2 ° or less (hereinafter sometimes referred to as a seventh embodiment).
(29) The oxide crystal according to (28), wherein the oxide crystal has an open cell type three-dimensional network structure, and an average diameter of the network is 20 to 500 nm. body.
(30) The oxide crystal as described in (28) or (29) above, wherein the ten-point average roughness (JISB-0601) of the surface of the oxide crystal is 20 to 200 nm.
(31) The amorphous compound gel according to any one of (1) to (10) is applied to a base material, and preliminarily prepared at a temperature lower than the boiling point of the organic solvent (S) in an air atmosphere or an inert gas atmosphere. After drying, the metal crystal formed by heating, light irradiation, or light irradiation under heating is the main peak 2θ which is the maximum intensity in X-ray diffraction using CuKα as the X-ray source. A metal crystal body having a half-value width in the range of 0.2 ° or less (hereinafter sometimes referred to as an eighth embodiment).
(32) The metal crystal according to (31), wherein the metal crystal has an open cell type three-dimensional network structure, and an average diameter of the network is 20 to 500 nm.
(33) The metal crystal as described in (31) or (32) above, wherein the surface of the metal crystal has a ten-point average roughness (JISB-0601) of 20 to 200 nm.

Since the production method of the amorphous compound by the electrolysis method of the present invention can easily increase the amount of production by controlling the electrolysis conditions, the amorphous metal compound can be easily used compared with the production methods by the conventional chemical treatment. And a production method that can be produced in large quantities. Furthermore, since it is an electrode reaction, a desired element can be easily introduced into the product as in the case of electroplating, so that the semiconductor characteristics (p-type and n-type) by the dopant can also be controlled.
Such an amorphous compound gel can easily form a metal crystal or an oxide crystal by heating with low energy or light irradiation, and can be made into a conductor and a semiconductor depending on the formation conditions. Furthermore, the metal crystal and oxide crystal formed from the amorphous compound gel of the present invention can control nano-order smoothness and structure, and can also form an open-cell three-dimensional network nanoporous film. It is. By controlling the structure of the metal crystal or oxide crystal, it can be a new material that realizes new characteristics such as transmittance, thermal conductivity, and catalytic activity.

2 is an electron microscope (SEM) photograph of the amorphous compound gel produced in Example 1. FIG. It is an electron microscope (SEM) photograph of the metal crystal produced in Example 13-1. It is an electron microscope (SEM) photograph of the metal crystal produced in Comparative Example 8-2. 2 is a result of X-ray diffraction (XRD) of an amorphous compound gel produced in Example 1. FIG. It is a result of the X-ray diffraction (XRD) of the metal crystal produced in Example 13-1.

[1] Amorphous compound gel (first embodiment), [2] A method for producing an amorphous compound gel (second embodiment), [3] A method for producing an oxide crystal (third) Embodiment), [4] Method for producing metal crystal (fourth embodiment), [5] Method for producing transparent conductor (fifth embodiment), [6] Method for producing transparent conductor (sixth embodiment) Embodiment), [7] Oxide crystal (Seventh Embodiment), and [8] Metal crystal (Eighth Embodiment) will be described.
The “amorphous” in the present invention means a crystal having a crystallinity of 5% or less as described above, and does not necessarily need to be completely amorphous.

[1] Amorphous compound gel (first embodiment)
The “amorphous compound gel” according to the first embodiment of the present invention is a liquid at room temperature with an amorphous compound having a crystallinity of 5% or less, in which one or more hydroxyl groups are bonded to a metal element. It is characterized by comprising an organic solvent (S).
The amorphous compound gel of the present invention has high selectivity when forming a metal crystal as a conductor or an oxide crystal as a semiconductor from an amorphous compound having a hydroxyl group by heating, light irradiation or the like. Furthermore, the amorphous compound in the amorphous compound gel is complexed with a ligand such as a hydrate or a carboxyl group as shown in the chemical formula described later, so that the amount of active radical species generated and the crystallinity after the structural change can be improved. Control, that is, control of steric structure (oration) by multimolecular bond between the molecule in the ligand that has formed a complex with a broken hydroxyl group and the metal element or metalloid element. It becomes possible.

  The bond between the hydroxyl group and the like in the amorphous compound and the metal element is easily cut by heating or light irradiation. At this time, atomic diffusion occurs more easily in the amorphous gel having a two-dimensional structure than in the metal crystal. Therefore, the structural change is more likely to occur than when the crystal structure is taken. When the diffusing atom is a metal element, the conductor can be formed with lower energy than the sintering reaction of the metal fine particles. In addition, by adjusting the energy conditions of heating and light irradiation, a three-dimensional structure is formed by polymolecular bonds between the cleaved hydroxyl group and the molecule in the ligand that formed the complex and the metal element ( By generating (oration), it becomes possible to form a metal crystal or oxide crystal having a specific structure.

It has been reported that hydroxide is produced as a precursor of copper fine particles in the conventional process for producing electrolytic copper fine particles (Mikiko Saito, Tomoaki Ishii, Hidemichi Fujiwara, Takayuki Honma; 2012 Electrochemical Society of Japan The 79th Annual Meeting, 1G31.), This hydroxide was usually converted into fine metal particles by an electrolytic reaction, and its physical properties were not clear. Therefore, the nature of the complex formed by the metal ions and ligands in the reaction solution, pH, organic additives, electrolysis conditions, etc. were examined. It was possible to find conditions for selective generation rather than fine particles.
In addition, it was confirmed that this precursor gel can be separated from the metal fine particles and recovered alone by a filter treatment or the like. When this precursor gel was analyzed, the crystallinity was remarkably low and it was found to be in an amorphous state. The mechanism by which the precursor gel is formed on the electrode in an amorphous state without being converted into metal fine particles is not clear, but in an alkaline reaction field with a large overvoltage formed in the vicinity of the electrode, the crystallization of the electrolytic reaction product is fine. Is strongly promoted, and the crystallinity of the precursor is significantly lower than that of the metal fine particles, the presence of a specific complex, and the electrolysis conditions in a specific pH range, more preferably electrolysis with an organic additive or the like interposed It is presumed that under the conditions, the precursor is stabilized as a gel and can be recovered from the electrode.

(1) Metal element It is preferable that the said metal element is 1 type, or 2 or more types selected from copper, zinc, tin, and nickel. These metals are metal elements that can be applied to a method of manufacturing a semiconductor made of an oxide crystal or a conductor made of a metal crystal, which will be described later. Copper, zinc, tin, and nickel are elements to which the electrolytic method can be applied. It can be said that the metal element that can be handled has a high formability of the amorphous compound in the present application.

(2) Amorphous compound (a) Functional group and crystallinity of amorphous compound The amorphous compound constituting the amorphous compound gel of the present invention is an amorphous compound having a crystallinity of 5% or less formed by bonding hydroxyl groups. . The amorphous compound gel can be formed into a structure suitable for a conductor pattern, a catalyst, or the like by light irradiation or heating.
In the present invention, the amorphous compound does not necessarily need to be completely amorphous, but if the crystallization of the gel is excessive, it becomes difficult to change to a desired crystal structure with low energy, so the upper limit of the crystallinity is 5%.
(B) Molecular structure of amorphous compound The molecular structure of the amorphous compound is preferably a hydrate. Because the molecular structure of the amorphous compound is a hydrate, the amount of active radicals generated and the structure change by improving the stability of the gel and complexing with ligands such as hydrates and carboxyl groups described later Later crystallinity can be controlled.

The molecular structure of the amorphous compound preferably contains a carboxyl group in addition to the hydroxyl group. As the molecular structure of the amorphous compound contains a carboxyl group, it becomes easier to improve the stability of the gel and to form a complex with a ligand such as a hydrate or a carboxyl group. The improvement of the control of the crystallinity can be expected later.
As a compound having such a hydrate and a carboxyl group, Cu ₂ (OH) ₂ (CH ₃ COO) _X (H ₂ O) _Y , Zn ₂ (OH) ₂ (CH ₃ COO) _X (H ₂ O) _{Y, Sn 2 (OH) 2} (CH 3 COO) X (H 2 O) Y, Ni 2 (OH) 2 (CH 3 COO) X (H 2 O) Y ( wherein, X is a 1 to 2 It is an integer, and Y is an integer of 1 or more and 6 or less.
(C) Long-period structure of amorphous compound The amorphous compound constituting the amorphous compound gel does not have a long-period structure of 100 nm or more. Thus, if the amorphous compound does not have a long-period structure of 100 nm or more, the crystallinity is lowered, and the long-period regular structure is reduced unlike the crystalline metal. This can be confirmed from observation of an image obtained from an electron microscope (SEM, TEM).

(3) Organic solvent (S)
The amorphous compound gel of the present invention exists in a state where the amorphous compound is mixed with an organic solvent (S) that is liquid at room temperature. The organic solvent (S) is applied to a substrate, and then the amorphous compound gel is heated or irradiated with light in an air atmosphere or an inert gas atmosphere to conduct a semiconductor or the like made of an oxide crystal, or a conductive material made of a metal crystal. In order to form a body, the boiling point of the organic solvent (S) at normal pressure is desirably 60 ° C. or higher, and desirably 350 ° C. or lower.
From the viewpoint of volatility of the organic solvent for the amorphous compound gel to be in a stable state at room temperature, the boiling point of the organic solvent (S) at normal pressure is desirably 60 ° C. or higher. If the boiling point is less than 60 ° C., the organic solvent (S) may evaporate, resulting in instability of the gel. On the other hand, in order to prevent the organic solvent from remaining as an impurity in the oxide crystal or metal crystal when light irradiation or heating from the amorphous compound gel, the boiling point of the organic solvent (S) at normal pressure is low. It is desirable that it is 350 degrees C or less.

  The organic solvent (S) contains an organic compound (S1) having at least one hydroxyl group and having one or two hydrogen atoms bonded to the carbon atom to which the hydroxyl group is bonded. Preferably it is. Among organic solvents, it is expected that the stability of the amorphous compound gel is enhanced by the organic compound having at least one hydroxyl group. In addition, the organic compound (S1) in which one or two hydrogen atoms are bonded to the carbon atom to which the hydroxyl group is bonded further improves the stability of the amorphous compound gel and removes hydrogen during light irradiation or heating. It is possible to increase the reducing power by making it easy to separate.

(A) Organic compound (S1)
From the above, as the organic compound (S1), alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2,2-dimethyl-1-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 2,2 dimethyl-1-propanol, 3-methyl-2-butanol, 2-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-2-hexanol, 2-methyl-3-hexanol, 1-heptanol, 2- Heptanol, 4-heptanol, 2-ethyl-1-hexanol, 1-octanol, and 2- Octanol; diols such as ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-butene- 1,4-diol, 2,3-butanediol, pentanediol, hexanediol, and octanediol; which are triols, glycerol, 1,1,1-trishydroxymethylethane, 2-ethyl-2-hydroxymethyl-1 , 3-propanediol, 1,2,6-hexanetriol, 1,2,3-hexanetriol, and 1,2,4-butanetriol; preferable.
(B) Other organic solvent (S)
As an organic solvent (S) that can be used for forming an amorphous compound gel by mixing with an amorphous compound, in addition to the organic compound (S1), lactone compounds that are cyclic esters include γ-butyllactone, δ- Examples include valerolactone and the like, and n-hexadecane and n-heptadecane, which are aliphatic hydrocarbons having 12 to 17 carbon atoms.

(4) Lactam compound (L)
It is preferable to mix the lactam compound (L) with the amorphous compound.
When the lactam compound (L) is mixed with the amorphous compound of the present invention, the crystal structure is improved when the stability of the gel is improved and the metal crystal or oxide crystal is formed by light irradiation or heating. It is expected to promote the reaction to
The preferable chemical structure and the like of the lactam compound (L) will be described in the section “Second embodiment”.

[2] Method for producing amorphous compound gel (second embodiment)
The “method for producing an amorphous compound gel” according to the second embodiment of the present invention includes a reaction solution having a pH of 4.0 to 11.0, which includes a metal ion and a ligand that forms a coordinate bond to the metal ion. In the method, an amorphous compound derived from a metal ion is precipitated by an electrolytic reaction between the anode and the cathode, and the amorphous compound is mixed with an organic solvent (S).
In the above electrolytic reaction, in order to promote fine crystallization of the precipitate, the precipitation reaction mediated by the organic compound proceeds in an alkaline reaction field with a large overvoltage formed in the vicinity of the electrode. The crystallinity of the metal hydroxide is significantly lower than that of the nanoparticles and becomes amorphous.
In the method for producing an amorphous compound gel by the electrode reaction according to the present invention, it is easy to increase the production amount by employing an electrolysis method. Therefore, the production amount is simpler than the production methods using chemical treatment so far. It becomes possible to increase more. Furthermore, since it is an electrode reaction, a desired element can be easily introduced into the product as in the case of electroplating, so that the semiconductor characteristics (p-type and n-type) can be controlled by the dopant.

(1) Metal ions The metal ions are preferably one or more selected from copper, zinc, tin, and nickel. Copper, zinc, tin, and nickel are elements that can be formed by an electrolytic method, and are excellent in the formation of an amorphous compound in the present invention. Examples of other metal ions include palladium, cobalt, chromium, cadmium, indium and the like, although the formation of the amorphous compound is somewhat inferior.
(2) Ligand that forms a coordinate bond to a metal ion Preferred ligands to be added to the electrolytic reaction solution during the electrolytic reaction include acetate ion, oxalate ion, propionate ion, malonate ion, and tartaric acid. 1 type or 2 types or more selected from ion and pyrophosphate ion are mentioned. These ligands coordinate with the metal ions generated by the electrolytic reaction and contribute to the formation and stabilization of the amorphous compound.
(3) In the production of an electrolytic reaction amorphous compound gel, an amorphous compound gel derived from metal ions is deposited by an electrolytic reaction in which a current is passed between the anode and the cathode in the following reaction solution containing metal ions.
(A) Reaction solution Since an electrolysis reaction between the anode and the cathode is performed, the reaction solution is preferably a conductive hydrophilic solution, a mixed solution obtained by adding a hydrophilic compound such as methanol or ethanol to an aqueous solution, and A hydrophilic solution can be used, but an aqueous solution is preferred.

(B) pH and the total formation constant of the complex formed by the metal ion and the ligand The pH of the reaction solution is in the range of 4.0 to 11.0, and further formed by the metal ion and the ligand. The overall formation constant of the complex is preferably 1-10.
In order to form an amorphous compound by the electrolytic method, an overvoltage is large and an appropriate alkaline reaction field accompanying a pH increase in the vicinity of the electrode is required. If the pH is less than the lower limit of the pH range, not only the pH increase is insufficient and the gel formation efficiency is lowered, but also the gel detached from the electrode may be dissolved in the acidic bulk solution. On the other hand, if the upper limit of the above pH range is exceeded, it is necessary to form a strong complex for stabilizing the metal salt as an electrolytic bath, but it is difficult to dissociate the ligand in the electrode reaction field, so it is a precursor. The formation of gel is hindered and the production efficiency is remarkably lowered, and in some cases, a plating film may be formed.
Moreover, it is preferable that the total formation constant of the complex formed with a metal ion and a ligand is 1-10 from the dissociation point of the ligand which does not inhibit gel formation. When there are a plurality of ligands, the strongest ligand is selected from the ligands having a concentration sufficient to coordinate with the total amount of metal ions present in the reaction solution.
The total formation constant of the complex is as follows: (i) Chemistry Handbook 4th Edition, Foundation II, (ii) J. Mass Spectrom. Soc. Jpn. Vol. 60, No. 2, P25, 2012, (iii) Basic It is shown in Education, Analytical Chemistry (published by Tokyo Bunkasha).
Examples of metal ions forming such a ligand include one or more selected from acetate ion, oxalate ion, propionate ion, malonate ion, tartrate ion, and pyrophosphate ion. it can. Such metal ions are ligands that do not inhibit gel formation and contribute to improved stability when incorporated into the molecular structure of the gel.

(C) Additive Electrolytic reduction reaction solution desirably contains, as additives, alkali metal ions or alkaline earth metal ions described below and lactam compound (L).
(C-1) It is preferable that one or two kinds selected from alkali metal ions and alkaline earth metal ions are dissolved in the alkali metal ion and alkaline earth metal ion reaction solution. When alkali metal ions and / or alkaline earth metal ions are dissolved in the reaction solution, the effect of stabilizing the alkaline reaction field and suppressing the electrolytic formation of metal ions from becoming dendritic can be expected. From the viewpoints of economy, availability, etc., the alkali metal ions can include lithium ions, sodium ions, and potassium ions, and the alkaline earth metal ions can include calcium ions.

(C-2) Lactam compound (L)
The presence of the lactam compound (L) in the reaction solution can be expected to promote the decrease in crystallinity of the precipitate through an alkaline reaction field. A lactam compound is a general term for a compound in which a carboxyl group and an amino group are generally condensed by dehydration, and has a —CO—NR— (R may be hydrogen) bond in a part of the ring. The lactam compound (L) used in the present invention is selected from 2-pyrrolidone, alkyl-2-pyrrolidone, and hydroxyalkyl-2-pyrrolidone having a 5-membered ring structure having 4 to 12 carbon atoms. It is preferable that it is 1 type, or 2 or more types.

The alkyl-2-pyrrolidone includes N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, Nn-propyl-2-pyrrolidone, Nn-butyl-2- Pyrrolidone, N-iso-butyl-2-pyrrolidone, Nn-octyl-2-pyrrolidone, 3-methyl-2-pyrrolidone, 4-methyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, And one or more selected from N-methyl-4-methyl-2-pyrrolidone.
The hydroxyalkyl-2-pyrrolidone is selected from N- (hydroxymethyl) -2-pyrrolidone, N- (2-hydroxyethyl) -2-pyrrolidone, and N- (3-hydroxypropyl) -2-pyrrolidone. It is preferable that it is 1 type, or 2 or more types.

(D) Electrolytic reaction A method for producing an amorphous compound gel by the above electrolytic method is illustrated below. In addition, this invention is not limited to the following illustration. Examples of the cathode (cathode) material in the reaction solution include a rod-like electrode such as platinum, carbon, copper, and stainless steel, a plate-like electrode, and a nanostructure electrode such as a dot electrode. As an anode (anode) material, , Copper, carbon, platinum, titanium, stainless steel, zinc, tin, nickel, iridium and other rod-shaped, plate-shaped, and net-shaped electrodes.
An amorphous compound gel derived from metal ions is deposited on the cathode surface by an electrolytic reaction in which a reaction solution containing metal ions is supplied into the electrolytic cell and a voltage is applied between the working electrode cathode and the auxiliary electrode anode. can do. Moreover, it becomes possible to deposit an amorphous compound gel also from the vicinity of an anode by making the material of an anode into the target metal seed | species. The pH in the reaction solution needs to be in the range of 4.0 to 11.0. It is also possible to introduce the dopant element into the amorphous compound gel by adding a water-soluble salt containing a dopant element for controlling semiconductor characteristics to the reaction solution.

As electrolysis conditions, the current density is preferably 0.01 to 200 A / dm ² , more preferably about 3 to 100 A / dm ² , and can be a pulse current in addition to direct current. The temperature of the reaction solution is preferably 0 to 50 ° C, more preferably 5 to 25 ° C. As the temperature rises, the production reaction rate becomes faster, and as the temperature becomes lower, the crystallinity of the produced amorphous compound gel tends to decrease and the stability over time tends to improve. The electrolysis time is preferably 1 to 60 minutes, more preferably 3 to 40 minutes. After the completion of the electrolytic reaction, the gel-like amorphous compound can be separated from the reaction solution by an operation such as filter treatment, and can be recovered by washing with water.
The amorphous compound gel of the present invention can be obtained by mixing the amorphous compound obtained by the above method with an organic solvent (S) that is liquid at room temperature, such as alcohol, and then stirring.

[3] Method for producing oxide crystal (third embodiment)
The “method for producing an oxide crystal” according to the third embodiment of the present invention is a method in which the amorphous compound gel described in the first embodiment is applied to a substrate, and the reaction is performed in an air atmosphere or an inert gas atmosphere. In addition, after preliminary drying at a temperature below the boiling point of the organic solvent (S), heating, light irradiation, or light irradiation under heating is performed.

(1) Application of amorphous compound gel to substrate The method of applying an amorphous compound gel on a substrate is not particularly limited, and gravure printing, screen printing, spray coating, spin coating, dip coating, bar coating, knife coating. , Offset printing, flexographic printing, inkjet printing, dispenser printing, and the like can be used. Of these, screen printing and spin coating are preferred from the viewpoint that a thick and uniform coating film can be efficiently formed.
The substrate for applying the amorphous compound gel of the present invention to form a crystal structure is not particularly limited as long as the shape can be maintained in the temperature range in each step where energy is applied by heating or light irradiation. There is no. For example, inorganic materials such as ceramics such as alumina (Al ₂ O ₃ ), aluminum nitride (AlN), silicon carbide (SiC) and various glasses, thermoplastic resins and thermosetting resins (for example, epoxy resins, polymethyl methacrylate, A plate-like material, a sheet-like material, a film-like material, or the like formed of a polymer material such as a plastic such as polycarbonate, polystyrene, or polyimide) can be used.

(2) The amorphous compound gel on the pre-dried substrate can be dried in an air atmosphere or an inert gas atmosphere after coating. For example, using a normal method such as a heat treatment furnace or a hot plate, it is heated for 0.5 to 10 minutes and dried from about 10% by mass to about 40 to 80% by mass. At this time, if the drying is performed at a temperature equal to or higher than the boiling point of the organic solvent (S), the volume rapidly decreases and the gel structure may be destabilized and the formation of a uniform film may be hindered. Need to dry. The drying temperature is preferably 30 ° C. below the boiling point of the organic solvent (S). As for the concentration of the amorphous compound in the amorphous compound gel at the time of drying, if the concentration is too low, decomposition products of the organic solvent may remain after heating or light irradiation, while if the concentration is too high, the next heating or There is a possibility that the gel deteriorates during the light irradiation. Further, it is desirable that drying is performed in an air atmosphere or an inert gas atmosphere such as nitrogen or argon, and after drying, the sample is immediately removed and cooled to room temperature.

(3) Heating, light irradiation, and light irradiation under heating In the present invention, after drying the amorphous compound gel coated on the substrate, heating, light irradiation, in an air atmosphere or an inert gas atmosphere, Alternatively, an oxide crystal is formed by light irradiation under heating.
There is no restriction | limiting in particular about the method of heating, For example, a heat treatment furnace, a hotplate, etc. can be used. In order to control the atmosphere and heating rate during heating, it is desirable to use an atmosphere substitution type heat treatment furnace.
The light irradiation method is not particularly limited to means for generating light (electromagnetic waves), and for example, a light source such as a xenon lamp, a mercury lamp, a continuous laser oscillator, or a pulsed laser oscillator can be used. Among these, from the viewpoint of controlling the characteristics of the formed oxide crystal according to the light irradiation conditions, it has a wide spectral distribution continuous from ultraviolet to infrared, and the spectral distribution is also constant with respect to the change of the discharge light emission voltage. It is preferable to use a xenon lamp having good reactivity of the amorphous compound gel of the present invention.
In addition, it is also possible to adopt a method of irradiating light under heating, and it can be expected that the controllability of the characteristics of the oxide crystal formed in this case will be increased.

Since the specific conditions for forming an oxide crystal by heating, light irradiation, or light irradiation under heating vary depending on the type of metal element and organic solvent (S) of the amorphous compound gel to be used, generally Although it cannot be said, an oxide crystal formed by heating, light irradiation, or light irradiation under heating is referred to with reference to the conditions described in (a) to (c) in the following item (4). Preferred conditions can be easily found by analysis and analysis with a microscopic Raman spectroscopic apparatus. In the case of heating, generally when the heating temperature is lowered, and when the heating time is shortened, the crystal structuring from the amorphous compound to the oxide crystal tends to be slow or insufficient, while when the heating temperature is increased, Further, when the heating time is lengthened, the crystal structure tends to progress from the amorphous compound to the metal crystal.
In addition, when irradiating light using a xenon lamp as a light source, generally, the lower the discharge light emission voltage, the shorter the irradiation time, the slower or insufficient the crystal structuring from the amorphous compound to the oxide crystal. On the other hand, as the discharge light emission voltage becomes higher and the irradiation time becomes longer, the crystal structure tends to progress from the amorphous compound to the metal crystal. In some cases, the amorphous compound remains after heating or light irradiation.

(4) Example of production method of oxide crystal The production method of the oxide crystal using the amorphous compound gel is exemplified below. In addition, this invention is not limited to the following illustration.
First, after adjusting the density | concentration of the amorphous compound in an amorphous compound gel to about 10 mass%, it stirs well using an ultrasonic homogenizer. Next, after the amorphous compound gel is applied on the substrate with a spin coater or the like, the concentration of the amorphous compound in the amorphous compound gel is increased from about 10% by mass to about 40 to 80% by mass using an organic solvent (such as a hot plate). Dry at a temperature below the boiling point of S). Then, light irradiation is performed under heating, light irradiation, or heating in an air atmosphere or an inert gas atmosphere.
(A) About the temperature at the time of heat-heating processing, the boiling point vicinity of the organic solvent (S), specifically within about 10 degreeC or less of boiling point is preferable. If the heating temperature is too low, the reaction rate of crystal structuring is reduced, while if the heating temperature is too high, a non-uniform crystal structure may be formed. Moreover, it is preferable to make the temperature increase rate into the range of 5-50 degrees C / min. After reaching the heating temperature, the crystal structuring proceeds by holding for 5 to 60 minutes, and the target oxide crystal can be obtained.

(B) It is preferable to use a wavelength of 100 to 4000 nm, particularly a wavelength from the ultraviolet region to the near infrared region, as the wavelength of the irradiated light when irradiating light. By adjusting the light irradiation conditions using a xenon lamp (wavelength range: 300 to 1300 nm) among the light sources, an oxide crystal specific to the irradiation conditions can be obtained. Irradiation conditions using a xenon lamp are preferably within a range of discharge light emission voltage of 1000 to 3000 V and a pulse width of 500 to 5000 μsec. The light irradiation time is generally preferably about 100 μsec to 3 msec per irradiation, and particularly preferably in the range of 150 μsec to 700 μsec.
The distance between the light source of the xenon lamp and the substrate is preferably about 5 to 100 mm.
(C) Light irradiation under heating Even in the method of light irradiation under heating, the amorphous oxide gel is crystallized within the range of the above heating conditions and light irradiation conditions to obtain the target oxide crystal. Can do.

(5) Manufacturing Method of Oxide Semiconductor or Conductor “Oxide Semiconductor or Conductor Manufacturing Method”, which is one of the third embodiments of the present invention, is such that the light source of the light irradiation is a xenon lamp. Discharge emission voltage is in the range of 1000 to 3000 V, and the oxide crystal is a semiconductor or conductor of one or more oxides selected from copper, zinc, tin, and nickel And

(A) An oxide semiconductor or conductor selected from copper, zinc, tin, and nickel In the method for producing an oxide semiconductor or conductor using the amorphous compound gel, copper, zinc, tin, and An oxide semiconductor of cuprous oxide, zinc oxide, nickel oxide, and tin oxide can be manufactured from an amorphous nickel compound at low cost and with low energy, and an oxide semiconductor or conductor film can be formed with high efficiency. Note that the oxide semiconductor or conductor in the third embodiment is not limited to an oxide semiconductor selected from copper, zinc, tin, and nickel.

(B) Oxide Semiconductor and Conductor Manufacturing Method Light irradiation using a xenon lamp as a light source in order to form an oxide semiconductor or conductor of cuprous oxide, zinc oxide, nickel oxide, and tin oxide described above. It is particularly preferable to use it.
First, after adjusting the concentration of amorphous compound such as copper, zinc, tin, and nickel in the amorphous compound gel to about 10% by mass, the mixture is thoroughly stirred using an ultrasonic homogenizer. Next, after applying an amorphous compound gel on the substrate with a spin coater or the like, it is dried from about 10 mass% to about 40 to 80 mass% using a hot plate or the like. Thereafter, as described below, light irradiation is performed under light irradiation or heating in an air atmosphere or an inert gas atmosphere.

(i) In the range of discharge light emission voltage of 1000 to 3000 V of the light irradiation xenon lamp, the pulse width is 500 to 5000 μsec, and the light irradiation time is generally preferably about 100 μsec to 3 msec per irradiation, and particularly preferably in the range of 150 μsec to 700 μsec. . If the discharge light emission voltage is less than 1000 V, the energy required for forming the oxide semiconductor film is insufficient, and if it exceeds 3000 V, the crystallization reaction of the gel may become unstable and a uniform structure may not be obtained. Further, the distance between the light source of the xenon lamp and the substrate is preferably 5 to 100 mm. By adjusting the light irradiation conditions of the xenon lamp, an oxide semiconductor or conductor specific to the irradiation conditions can be obtained.
(ii) Light irradiation under heating Also in the method of light irradiation under heating, the above-mentioned light irradiation conditions can be adopted, and the heating conditions are temperatures that are about 40-50 ° C. lower than the boiling point of the organic solvent (S). It is preferable to heat at a temperature range of 50 ° C. or higher.

[4] Method for producing metal crystal (fourth embodiment)
According to a fourth embodiment of the present invention, “a method for producing a metal crystal” is obtained by applying the amorphous compound gel described in the first embodiment to a base material in an air atmosphere or an inert gas atmosphere. After preliminary drying at a temperature not higher than the boiling point of the organic solvent (S), heating, light irradiation, or light irradiation under heating is performed.
(1) Application of Amorphous Compound Gel to Base Material As the metal element in the amorphous compound gel, copper, zinc, tin, nickel and the like described in the first embodiment can be used, but are limited to these metal elements. It is not something.
The means for “applying the amorphous compound gel to the substrate” is the same as that described in the item (1) of the third embodiment.
(2) Pre-drying The same as described in item (2) in the third embodiment.

(3) Heating, light irradiation, and light irradiation under heating In the present invention, the amorphous compound gel provided on the substrate is heated, irradiated with light, or under heating in an air atmosphere or an inert gas atmosphere. Light irradiation is performed to form a metal crystal. The heat treatment method and the light irradiation method are the same as those described in the item (3) in the third embodiment. In addition, when the method of irradiating light under heating is adopted, it can be expected that the controllability of the characteristics of the formed metal crystal is also increased.
The specific conditions for forming the metal crystal by the above-mentioned heating, light irradiation, or light irradiation under heating vary depending on the type of the metal element and the organic solvent (S) of the amorphous compound gel to be used. Although there is no, X-ray analysis of the metal crystal formed by heating, light irradiation, or light irradiation under heating with reference to the conditions described in (a) to (c) in the following item (4), Preferred conditions can be easily found by analysis with a microscopic Raman spectroscopic apparatus. When heating, generally, the lower the heating temperature and the shorter the heating time, the slower or insufficient the crystal structuring from the amorphous compound to the metal crystal. On the other hand, the higher the heating temperature and the longer the heating time, the more the crystal structure tends to progress to the metal crystal. Further, when light is irradiated using a xenon lamp as a light source, generally, the lower the discharge light emission voltage and the shorter the irradiation time, the slower or insufficient the crystal structuring of the metal crystal. On the other hand, as the discharge light emission voltage increases, the crystal structure tends to progress to the metal crystal body as the irradiation time decreases. In some cases, the amorphous compound remains after heating or light irradiation.

(4) Example of production method of metal crystal An example of a production method of a metal crystal using the amorphous compound gel is illustrated below. In addition, this invention is not limited to the following illustration.
First, after adjusting the density | concentration of the amorphous compound in an amorphous compound gel to about 10 mass%, it stirs well using an ultrasonic homogenizer. Next, after applying an amorphous compound gel on a substrate with a spin coater or the like, it is dried to about 40 to 80% by mass using a hot plate or the like. Thereafter, light irradiation is performed under heat treatment, light irradiation, or heating in an air atmosphere or an inert gas atmosphere.
(A) Heat treatment The same as described in the item (4) of the third embodiment.

(B) It is preferable to use a wavelength of 100 to 4000 nm, particularly a wavelength from the ultraviolet region to the near infrared region, as the wavelength of the irradiated light when irradiating light. In the present invention, it is particularly preferable to use a xenon lamp (wavelength range: 300 to 1300 nm), and by adjusting the light irradiation conditions, a metal crystal unique to the irradiation conditions can be obtained. In the range of the discharge light emission voltage of 500 to 5000 V of the xenon lamp, the pulse width is 500 to 5000 μsec, and the light irradiation time is generally preferably about 800 μsec to 10 msec per irradiation, and particularly preferably in the range of 1 msec to 5 msec. Further, the distance between the light source of the xenon lamp and the substrate is preferably 5 to 100 mm.
(C) Light irradiation under heating Also in the method of light irradiation under heating, the range of the above heating conditions and light irradiation conditions can be adopted.

(5) Conductor Manufacturing Method A “conductor manufacturing method” which is an example of the fourth embodiment of the present invention is that the light source of the light irradiation is a xenon lamp and the discharge light emission voltage is in the range of 500 to 5000V. And the metal crystal is a copper conductor.
(A) Conductor whose metal crystal is copper In the method for producing a metal crystal using the amorphous compound gel, when an amorphous compound of copper is used, a conductor film is produced with high efficiency, low cost and low energy. can do.
(B) Method for producing copper conductor After adjusting the concentration of the amorphous compound in the copper amorphous compound gel to about 10% by mass, the mixture is thoroughly stirred using an ultrasonic homogenizer. Next, after applying an amorphous compound gel on a base material with a spin coater or the like, it is dried from about 10 mass% to about 40 to 80 mass% using a hot plate or the like. Thereafter, light irradiation is performed under light irradiation or heating in an air atmosphere or an inert gas atmosphere.

(i) Light irradiation In the production of the conductor, a conductor specific to the irradiation condition can be obtained by adjusting the light irradiation condition of the xenon lamp. In the range of the discharge light emission voltage of 500 to 5000 V of the xenon lamp, the pulse width is 500 to 5000 μsec, and the light irradiation time is generally preferably about 800 μsec to 10 msec per irradiation, and particularly preferably in the range of 1 msec to 5 msec. It is preferable that If the discharge light emission voltage is less than 500 V, the energy required for forming the conductor film is insufficient, and if it exceeds 5000 V, the crystallization reaction of the gel may become unstable and a uniform structure may not be obtained. Further, the distance between the light source of the xenon lamp and the substrate is preferably 5 to 100 mm.
(ii) Light irradiation under heating In the case of light irradiation under heating, it is possible within the range of the above light irradiation conditions. And it is preferable to heat in a temperature range of 50 ° C. or higher.

[5] Manufacturing method of transparent conductor (fifth embodiment)
The “transparent conductor manufacturing method” according to the fifth embodiment of the present invention is a mixture of two or more of the amorphous compound gels described in the first embodiment, applied to a substrate, and then in an air atmosphere. Alternatively, preliminary drying is performed at a temperature lower than the boiling point of the organic solvent (S) in an inert gas atmosphere, and then heating, light irradiation, or light irradiation under heating is performed.
(1) Mixing two or more types of amorphous compound gels By mixing two or more types of amorphous compound gels of the present invention, a transparent conductor film can be produced with high efficiency, low cost, and low energy. For example, copper-aluminum-oxygen (CuAlO ₂ ), zinc-tin-oxygen (ZnSnO ₃ , Zn ₂ SnO ₄ ), zinc-aluminum—from two or more of amorphous compound gels such as copper, zinc, tin, and nickel A transparent conductor derived from oxygen (ZnO—Al) or the like is formed. In addition, the kind of amorphous compound gel which forms a transparent conductor is not limited to the said illustration, The combination of the metal element which can form a transparent conductor can be selected with reference to a well-known transparent conductor. Is possible.

(2) Application to the substrate, preliminary drying, subsequent heating, light irradiation, or application of the light-irradiated amorphous compound gel to the substrate under heating is described in the item (1) in the third embodiment. The preliminary drying is the same as described in the item (2) in the third embodiment.
In addition, as a transparent base material for forming the transparent conductive film on which the mixture of the amorphous compound gel of the present invention is applied, the shape can be maintained in the temperature range in each step where energy is added by heating or light irradiation. If so, there is no particular limitation. For example, plates made of inorganic materials such as various types of glass, polymer materials such as thermoplastic resins and thermosetting resins (for example, plastics such as epoxy resin, polymethyl methacrylate, polycarbonate, polystyrene, and polyimide) A sheet-like material, a film-like material, or the like can be used. The visible light transmittance of the transparent substrate is usually 90% or more, preferably 95% or more. In the production of the transparent conductor of the present invention, it is particularly preferable to use light irradiation using a xenon lamp as a light source, and the discharge light emission voltage of the xenon lamp is in a range of 1000 to 3000 V as light irradiation conditions for forming the transparent conductor. It is preferable that

(3) Illustration of production method of transparent conductor A production method of a transparent conductor using the mixture of the amorphous compound gels is exemplified below. In addition, this invention is not limited to the following illustration.
First, the concentration of a mixture of amorphous compound gels in which the metal element is copper, zinc, tin, nickel, or the like is adjusted to about 30% by mass, and then stirred well. A method for mixing and dispersing the amorphous compound gel or the like in an organic solvent is not particularly limited, and a conventionally known dispersion method may be appropriately employed. For example, it may be dispersed in an organic solvent while performing mechanical pulverization or pulverization using ultrasonic waves. In this case, if necessary, an operation of adjusting the metal concentration ratio or dissolving a dopant element for increasing the electrical conductivity in an organic solvent may be performed.
Next, a mixture of amorphous compound gels is applied onto a substrate with a spin coater or the like, and then dried from about 30% by mass to about 40 to 80% by mass using a hot plate or the like. Thereafter, heating, light irradiation, light irradiation under heating, or the like described below is performed in an air atmosphere or an inert gas atmosphere.

(A) About the temperature at the time of heat-heating processing, the boiling point vicinity of the organic solvent (S), specifically within about 10 degreeC or less of boiling point is preferable. If the heating temperature is too low, the efficiency of crystal structuring is reduced, while if the heating temperature is too high, a non-uniform crystal structure may be formed. Moreover, it is preferable to make the temperature increase rate into the range of 5-50 degrees C / min. After reaching the heating temperature, by holding for 2 to 60 minutes, crystal structuring progresses, and the intended transparent conductor can be obtained.
(B) Light irradiation In the present invention, a transparent conductor peculiar to the irradiation condition can be obtained by adjusting the light irradiation condition of the xenon lamp. The discharge light emission voltage of the xenon lamp is in the range of 1000 to 3000 V, the pulse width is 500 to 5000 μsec, generally about 500 μsec to 5 msec per irradiation, and particularly preferably in the range of 1 msec to 3 msec. If the discharge light emission voltage is less than 1000V, the energy required for film formation of the transparent conductor is insufficient, and if it exceeds 3000V, the crystallization reaction of the gel may become unstable and a uniform structure may not be obtained. Further, the distance between the light source of the xenon lamp and the substrate is preferably 5 to 100 mm.

(C) Light irradiation under heating In the case of performing light irradiation under heating, it is possible to adopt the range of the above light irradiation conditions. A temperature range of about 50 ° C. or lower and 50 ° C. or higher is preferable.
By the method as described above, a transparent conductive film made of a metal-metal oxide or the like is formed on a transparent substrate. This transparent conductive film is a thin film made of two or more metals, and has transparency and at the same time exhibits conductivity. In addition, these transmittance | permeability and resistivity can be measured by the method mentioned later in an Example, for example.
The transparent conductor obtained by the above production method is, for example, a touch panel, a liquid crystal display, an LED (light emitting element), an organic EL display, a flexible display, a display electrode such as a plasma display, a solar cell electrode, a heat ray reflective film of a window It is suitably used for applications such as antistatic films.
In the above production method, the mixture of amorphous compound gels is directly applied on a transparent substrate. However, in transparent electrode applications such as devices such as liquid crystal displays, a colored film (color An intermediate film such as a filter may be interposed, and a mixture of amorphous compound gels may be applied directly on them.

[6] Manufacturing method of transparent conductor (sixth embodiment)
A “transparent conductor manufacturing method” according to a seventh embodiment of the present invention includes mixing the amorphous compound gel described in the first embodiment and a compound salt of a metal element or a metalloid element to form a substrate. It is applied to the substrate, preliminarily dried at a temperature lower than the boiling point of the organic solvent (S) in an air atmosphere or an inert gas atmosphere, and then heated, irradiated with light, or irradiated with light under heating. And
(1) Mixed amorphous compound gel and compound salt of metal element or metalloid element and mixed amorphous compound gel and compound salt of metal element or metalloid element to use the transparent conductor film with high efficiency Thus, it can be manufactured at low cost and low energy. For example, copper-aluminum-oxygen (CuAlO ₂ ), zinc-tin-oxygen (ZnSnO ₃ ) from one or more of amorphous compound gels such as copper, zinc, tin, and nickel and metal salts such as aluminum and germanium. , Zn ₂ SnO ₄ ), zinc-aluminum-oxygen (ZnO—Al), etc., a transparent conductor is formed. The combination of the amorphous compound gel and the compound salt of the metal element or metalloid element is not limited to the above examples, and the combination of metal elements capable of forming a transparent conductor is referred to a known transparent conductor. Can be selected.

(2) Application to the substrate, preliminary drying, subsequent heating, light irradiation, or application of the light-irradiated amorphous compound gel to the substrate under heating is described in the item (1) in the third embodiment. The preliminary drying is the same as that described in the item (2) in the third embodiment.
In addition, about the transparent base material for apply | coating the mixture of the amorphous compound gel of this invention and forming a transparent conductive film, it is the same as that of the description content of (2) term in 5th Embodiment.
In the production of the transparent conductor of the present invention, it is particularly preferable to use light irradiation using a xenon lamp as a light source. As light irradiation conditions for forming the transparent conductor, the discharge light emission voltage of the xenon lamp is 1000 to 3000 V, generally 1 About 500 μsec to 5 msec per irradiation is preferable, and a range of 1 msec to 3 msec is particularly preferable.

(3) Illustrative method for producing transparent conductor A method for producing a transparent conductor using a mixture of the amorphous compound gel and a compound salt of a metal element or a metalloid element will be exemplified below. In addition, this invention is not limited to the following illustration.
Add to the amorphous compound gel such as copper, zinc, tin, nickel, etc., until the compound salt of metal element or semi-metal element such as aluminum and germanium is uniformly mixed until it becomes about twice the concentration of the amorphous compound gel, Stir well.
A method for mixing and dispersing the amorphous compound gel or the like in an organic solvent is not particularly limited, and a conventionally known dispersion method can be employed. For example, it can be dispersed in an organic solvent while performing mechanical pulverization or pulverization using ultrasonic waves. In this case, if necessary, the metal concentration ratio can be adjusted, or an operation of dissolving a dopant element for increasing the conductivity in an organic solvent can be performed.
Next, after applying a mixture such as an amorphous compound gel on the substrate with a spin coater or the like, it is dried from about 30 mass% to about 40 to 80 mass% using a hot plate or the like. Thereafter, heating, light irradiation, or light irradiation under heating is performed in an air atmosphere or an inert gas atmosphere.

(A) About the temperature at the time of heat-heating processing, the boiling point vicinity of the organic solvent (S), specifically within about 10 degreeC or less of boiling point is preferable. If the heating temperature is too low, the efficiency of crystal structuring is reduced, while if the heating temperature is too high, a non-uniform crystal structure may be formed. Moreover, it is preferable to make the temperature increase rate into the range of 5-50 degrees C / min. After reaching the heating temperature, by holding for 2 to 60 minutes, crystal structuring progresses, and the intended transparent conductor can be obtained.
(B) Light irradiation In the present invention, a transparent conductor peculiar to the irradiation condition can be obtained by adjusting the light irradiation condition of the xenon lamp. The discharge light emission voltage of the xenon lamp is in the range of 1000 to 3000 V, the pulse width is 500 to 5000 μsec, generally about 500 μsec to 5 msec per irradiation, and the range of 1 msec to 3 msec is particularly preferable. If the discharge light emission voltage is less than 1000V, the energy required for film formation of the transparent conductor is insufficient, and if it exceeds 3000V, the crystallization reaction of the gel may become unstable and a uniform structure may not be obtained. Further, the distance between the light source of the xenon lamp and the substrate is preferably 5 to 100 mm.

(C) Light irradiation under heating Also in the method of light irradiation under heating, crystallization is possible within the range of the above light irradiation conditions, and the heating conditions are about 40 to 50 ° C. lower than the boiling point of the organic solvent (S). It is preferable to heat at a temperature range of 50 ° C. or higher at a temperature below.
By the method as described above, a transparent conductive film made of a metal-metal oxide or the like is formed on a transparent substrate. This transparent conductive film is a thin film made of a polycrystal containing two or more kinds of metals or metalloids, and exhibits transparency as well as conductivity. In addition, these transmittance | permeability and resistivity can be measured by the method mentioned later in an Example, for example.
The transparent conductor obtained by the manufacturing method of the sixth embodiment is, for example, a display electrode such as a touch panel, a liquid crystal display, an LED (light emitting element), an organic EL display, a flexible display, a plasma display, a solar cell electrode, and a window. It is suitably used for applications such as glass heat ray reflective films and antistatic films. In the manufacturing method of the sixth embodiment described above, the mixture of the amorphous compound gels is directly applied on the transparent substrate. However, in the transparent electrode application such as a device such as a liquid crystal display, the transparent substrate is used. An intermediate film such as a colored film (color filter) may be interposed on the surface, and the mixture of the amorphous compound gel may be directly applied on them.

[7] Oxide crystal (seventh embodiment)
The “oxide crystal” according to the seventh embodiment of the present invention is obtained by applying the amorphous compound gel described in the first embodiment to a base material, and in an air atmosphere or an inert gas atmosphere. After preliminary drying at a temperature lower than the boiling point of (S), an oxide crystal formed by heating, light irradiation, or light irradiation under heating is an X-ray using CuKα as an X-ray source. In diffraction, the half width at 2θ of the main peak, which is the maximum intensity, is in the range of 0.2 ° or less.
(1) Application of Amorphous Compound Gel to Substrate, Pre-drying, Subsequent Heating, Light Irradiation, etc., “Application of Amorphous Compound Gel to Substrate, Pre-Drying, Subsequent Heating , “Light irradiation, or light irradiation under heating” is the same as described in the items (1) to (3) in the third embodiment.
(2) Oxide Crystal In the seventh embodiment, the characteristics of the “oxide crystal” are described in the following item (a), and preferable characteristics are described in the following items (b) to (c).

(B) Half width at main peak 2θ which is the maximum intensity in X-ray diffraction The “oxide crystal” of the seventh embodiment of the present invention is the maximum in X-ray diffraction using CuKα as an X-ray source. The half width at 2θ of the main peak as the intensity is in the range of 0.2 ° or less.
Generally, as crystallization progresses and the crystallite size increases, the peak half-value width in X-ray diffraction decreases. In the oxide crystal formed from the amorphous compound gel according to the first embodiment of the present invention, particularly in the X-ray diffraction using CuKα as the X-ray source, the half-width at 2θ of the main peak which is the maximum intensity is By crystallizing to about 0.2 ° or less, properties unique to the oxide crystal structure such as crystallite size distribution, surface roughness, porosity, catalytic activity, thermal conductivity, resistivity, reflectance, etc. Can be controlled stably. In terms of electrical characteristics, the larger the grain boundary density, the worse the characteristics, so a larger crystallite size is better. Therefore, the oxide crystal of the seventh embodiment was processed by heating, light irradiation, or the like until the half-width at 2θ of the main peak, which is the maximum intensity, was 0.2 ° or less in X-ray diffraction. Those are particularly preferred.

(B) Open cell type three-dimensional network structure The “oxide crystal” of the seventh embodiment of the present invention is an open cell type three-dimensional network structure, and the average diameter of the network structure is 20 to 500 nm. It is preferable that
In the seventh embodiment, the open cell type three-dimensional network structure is a mesh-like structure having a space in which solids composed of dense solid columns or flat plates constituting a cell are connected in a three-dimensional manner. It is a porous structure. As the cell structure, in addition to the open cell type, a closed cell type and an intermediate cell structure in which both an open cell type and a closed cell type coexist are known. Includes not only the open cell type but also the intermediate cell structure. In the seventh embodiment of the present invention, the average diameter of the network of oxide crystals having an open cell type three-dimensional network structure is not particularly limited, but is preferably 20 to 500 nm. The presence of such fine holes allows removal of the solvent remaining during the sintering, thereby enabling the formation of a structure that does not impair the adhesion. Since the network-like porous structure can be controlled by the “method for producing an oxide crystal” according to the third embodiment of the present invention, the crystallite size distribution, the surface roughness, the pores There is a feature that the controllability of the characteristics such as the rate, the catalytic activity, the thermal conductivity, the resistivity and the reflectance is large.
(C) Ten-point average roughness of oxide crystal surface The ten-point average roughness (JISB-0601) of the surface of the “oxide crystal” of the seventh embodiment of the present invention is 20 to 200 nm. Is preferred. Since the “oxide crystal” of the seventh embodiment formed from the “amorphous compound gel” of the first embodiment of the present invention can control the smoothness of the film surface in nano order, Fine adjustment of characteristics such as catalyst activity, thermal conductivity, resistivity, and reflectance can be performed according to the surface roughness and other purposes of use.

[8] Metal crystal (eighth embodiment)
The “metal crystal” according to the eighth embodiment of the present invention is obtained by applying the amorphous compound gel described in the first embodiment to a base material, and in an air atmosphere or an inert gas atmosphere, an organic solvent ( In the X-ray diffraction using CuKα as the X-ray source, the metal crystal formed by performing preliminary drying at a temperature lower than the boiling point of S) and then performing heating, light irradiation, or light irradiation under heating is used. The half width at 2θ of the main peak which is the maximum intensity is in the range of 0.2 ° or less.
(1) Application of Amorphous Compound Gel to Substrate, Preliminary Drying, Subsequent Heating, Light Irradiation, etc. in the Eighth Embodiment of the Present Invention, “Application of Amorphous Compound Gel to Substrate, Preliminary Drying, Subsequent Heating , “Light irradiation, or light irradiation under heating” is the same as described in the items (1) to (4) in the fourth embodiment.
(2) Metal Crystal In the eighth embodiment, the characteristics of the “metal crystal” are described in the following item (A), and preferable characteristics are described in the following items (B) to (C).

(A) Half width at main peak 2θ which is the maximum intensity in X-ray diffraction The “metal crystal body” according to the eighth embodiment of the present invention is the maximum in X-ray diffraction using CuKα as an X-ray source. The half width at 2θ of the main peak as the intensity is in the range of 0.2 ° or less.
Generally, as crystallization progresses and the crystallite size increases, the peak half-value width in X-ray diffraction decreases. In the metal crystal formed from the amorphous compound gel of the eighth embodiment, in particular, in the X-ray diffraction using CuKα as the X-ray source, the half width at 2θ of the main peak which is the maximum intensity is 0.2 °. By crystallizing to the following extent, properties unique to the metal crystal structure such as crystallite size distribution, surface roughness, porosity, catalytic activity, thermal conductivity, resistivity, and reflectivity are stably controlled. become able to. In terms of electrical characteristics, the larger the grain boundary density, the worse the characteristics, so a larger crystallite size is better. Accordingly, the metal crystal body of the ninth embodiment is particularly preferably one that is heated or irradiated with light until the half-value width at 2θ of the main peak, which is the maximum intensity, becomes 0.2 ° or less in X-ray diffraction. .

(B) Open cell type three-dimensional network structure The “metal crystal” according to the eighth embodiment of the present invention is an open cell type three-dimensional network structure, and the average diameter of the network structure is 20 to 500 nm. It is preferable that
The open cell type three-dimensional network structure is the same as that of the seventh embodiment (2). In the metal crystal body having an open cell type three-dimensional network structure according to the eighth embodiment, the average diameter of the network is not particularly limited, but is preferably 20 to 500 nm. The presence of such fine holes allows removal of the solvent remaining during the sintering, thereby enabling the formation of a structure that does not impair the adhesion. Since the network-like porous structure can be controlled by the method for producing a metal crystal of the present invention, crystallite size distribution, surface roughness, porosity, catalytic activity, thermal conductivity, resistivity There is a feature that controllability of characteristics such as reflectance is large.
(C) Ten-point average roughness of metal crystal surface The ten-point average roughness (JISB-0601) of the “metal crystal” according to the eighth embodiment of the present invention is preferably 20 to 200 nm.
Since the “metal crystal body” of the eighth embodiment formed from the “amorphous compound gel” of the first embodiment of the present invention can control the smoothness of the film surface in nano order, the above-mentioned Fine adjustment of characteristics such as catalyst activity, thermal conductivity, resistivity, and reflectance can be performed according to the surface roughness and other purposes of use.

EXAMPLES The present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
The evaluation method in a present Example and a comparative example is described below. These evaluation results are shown in Tables 1-7.
(1) Observation method of product Structural change of the amorphous compound gel produced by observation using a scanning electron microscope (SEM) and the amorphous compound gel obtained by heating, irradiating the produced amorphous compound, etc. It was confirmed.
(2) Presence or absence of acicular aggregates When observed at a magnification of 1000 using a scanning electron microscope (SEM), 1% or less of micron-sized acicular precipitates in the observed image (the percentage is In the case of “[area occupied by needle-like condensed structure / area of all structure] × 100 (%)”), acicular aggregation is regarded as “none” and 1% When it exceeded, the acicular aggregation was set as “present”.

(3) Crystal structure analysis of product The crystallinity of the product was analyzed using an X-ray diffractometer (manufactured by Rigaku Corporation, model: Geigerflex RAD-A) and the X-ray source was CuKα. A compound having a crystallinity of 5% or less represented by the following calculation formula (1) was regarded as a substantially amorphous compound.
Crystallinity (%) = [Ic / (Ic + Ia)] × 100 (1)
(Ic represents the crystalline scattering integral intensity, and Ia represents the amorphous scattering integral intensity.)
(4) Identification method of molecular structure of product Microscopic Raman spectrometer (manufactured by Tokyo Instruments, model: Nanofinder @ 30) and Fourier transform infrared spectrophotometer (manufactured by JASCO Corporation, model: FT / IR) -4100) to identify the compound species of the metal or metalloid elements in the product. In the microscopic Raman spectroscope, a sample was applied to the nano-sized uneven structure (Ag or Cu) capable of increasing the Raman scattering intensity by localized surface plasmon resonance and analyzed as necessary.
(5) Measuring method of volume resistivity, carrier concentration, carrier moving speed Low resistance measurement by direct current four-terminal method for each metal crystal and oxide crystal volume resistivity, carrier concentration, carrier mobility, Van der It calculated | required by using the Hall effect measurement by Paw method together.

[Example 1]
(1) Preparation of copper-based amorphous compound gel by electrolytic method Copper acetate (II) monohydrate ((CH ₃ COO) ₂ Cu · 1H ₂ O) 200 g as a copper ion, N-vinyl-2 as an organic additive 10 L (liter) of an aqueous reaction solution was prepared using 600 g of pyrrolidone (carbon atoms: 6) and 27.5 g of sodium acetate trihydrate (CH ₃ COONa · 3H ₂ O) as an alkali metal ion. The pH of the reaction aqueous solution was about 5.8.
Next, in this aqueous solution, an electric current was passed between a rod cathode made of SUS304 (cathode electrode) and a platinum plate anode (anode electrode) at a bath temperature of 15 ° C. and a current density of 30 A / dm ² for 30 minutes, near the cathode outer surface. A copper-based compound containing a gel substance was deposited.
The aqueous solution after completion of the electrolytic reaction was passed through a stainless steel mesh filter (mesh: 10 to 100 μm) to separate the copper fine particle slurry and the gel substance. Thereafter, the gel material was washed with water to recover the gel material. 15 g of the gel product obtained by the above method was mixed with 15 g of ethylene glycol as a solvent and stirred for 1 hour or longer to obtain a copper-based amorphous compound gel.

(2) Evaluation of the product (a) Structure observation of the product After the above-prepared copper-based amorphous compound gel was passed through a filter (manufactured by Whatman, trade name: Anodisc) and washed with water to remove the solvent by drying. Observation with a scanning electron microscope (SEM) was performed. As a result, it was confirmed that an amorphous structure having a range of 0.05 to 500 μm was formed. Moreover, acicular aggregates were not observed.
(B) Crystal structure analysis of the product After the obtained copper-based amorphous compound gel was coated on a glass substrate and vacuum-dried and analyzed by X-ray diffraction, a crystalline diffraction peak was not clearly seen. Since the crystallinity was 0%, it was judged to be in an amorphous state.

(C) Identification of the molecular structure of the product The obtained copper-based amorphous compound gel was applied onto a nanostructured electrode and analyzed with a microscopic Raman spectroscopic device. As a main component, copper hydroxide (Cu (OH) ₂ ) was used. Since the attributed peak was detected, it was determined that the product of this example was a copper-based amorphous compound gel mainly composed of copper hydroxide. In addition, it belongs to copper hydrate (Cu- (OH)-(H ₂ O)) adsorbed with hydroxide ions and pyrrolidone group (C ₄ H ₆ NO) derived from N-vinyl-2-pyrrolidone. Peak was also detected as a minor component. Furthermore, when the analysis by a Fourier transform infrared spectrophotometer was also performed, the attribution peak of the carboxyl group derived from an acetic acid was observed.
From these analysis results, a hydrate having a molecular structure close to Cu ₂ (OH) ₂ (CH ₃ COO) _X (H ₂ O) _Y (where X and Y are integers) is also formed as a by-product. N-vinyl-2-pyrrolidone was present in a dispersed form in the gel (denoted as a mixture in the table, hereinafter the same). ICP emission spectroscopic analysis also confirmed that the gel contained a trace amount of sodium.

[Example 2]
(1) Preparation of copper-based amorphous compound gel by electrolytic method A copper-based amorphous compound gel was obtained in the same manner as in Example 1 except that glycerol was used as the solvent mixed with the gel product.
(2) Evaluation of the product (a) Structure observation of the product After the above-prepared copper-based amorphous compound gel was passed through a filter (manufactured by Whatman, trade name: Anodisc) and washed with water to remove the solvent by drying. Observation with a scanning electron microscope (SEM) was performed. As a result, it was confirmed that an amorphous structure having a range of 0.05 to 500 μm was formed. Moreover, acicular aggregates were not observed.
(B) Crystal structure analysis of the product After the obtained copper-based amorphous compound gel was coated on a glass substrate and vacuum-dried and analyzed by X-ray diffraction, a crystalline diffraction peak was not clearly seen. Since the crystallinity was 0%, it was judged to be in an amorphous state.

(C) Identification of the molecular structure of the product The obtained copper-based amorphous compound gel was applied onto a nanostructured electrode and analyzed with a microscopic Raman spectroscopic device. As a main component, copper hydroxide (Cu (OH) ₂ ) was used. Since the attributed peak was detected, it was determined that the product of this example was a copper-based amorphous compound gel mainly composed of copper hydroxide. In addition, it belongs to copper hydrate (Cu- (OH)-(H ₂ O)) adsorbed with hydroxide ions and pyrrolidone group (C ₄ H ₆ NO) derived from N-vinyl-2-pyrrolidone. Peak was also detected as a minor component. Furthermore, when the analysis by a Fourier transform infrared spectrophotometer was also performed, the attribution peak of the carboxyl group derived from an acetic acid was observed.
From these analysis results, a hydrate having a molecular structure close to Cu ₂ (OH) ₂ (CH ₃ COO) _X (H ₂ O) _Y (where X and Y are integers) is also formed as a by-product. N-vinyl-2-pyrrolidone was determined to exist in a dispersed form in the gel. ICP emission spectroscopic analysis also confirmed that the gel contained a trace amount of sodium.

[Example 3]
(1) Preparation of copper-based amorphous compound gel by electrolytic method A copper-based amorphous compound gel was obtained in the same manner as in Example 1 except that ethanol was used as the solvent to be mixed with the gel product.
(2) Evaluation of the product (a) Structure observation of the product After the above-prepared copper-based amorphous compound gel was passed through a filter (manufactured by Whatman, trade name: Anodisc) and washed with water to remove the solvent by drying. Observation with a scanning electron microscope (SEM) was performed. As a result, it was confirmed that an amorphous structure having a range of 0.05 to 500 μm was formed. Moreover, acicular aggregates were not observed.
(B) Crystal structure analysis of the product After the obtained copper-based amorphous compound gel was coated on a glass substrate and vacuum-dried and analyzed by X-ray diffraction, a crystalline diffraction peak was not clearly seen. Since the crystallinity was 2%, it was judged to be in an amorphous state.

(C) Identification of the molecular structure of the product The obtained copper-based amorphous compound gel was applied onto a nanostructured electrode and analyzed with a microscopic Raman spectroscopic device. As a main component, copper hydroxide (Cu (OH) ₂ ) was used. Since the attributed peak was detected, it was determined that the product of this example was a copper-based amorphous compound gel mainly composed of copper hydroxide. In addition, it belongs to copper hydrate (Cu- (OH)-(H ₂ O)) adsorbed with hydroxide ions and pyrrolidone group (C ₄ H ₆ NO) derived from N-vinyl-2-pyrrolidone. Peak was also detected as a minor component. Furthermore, when the analysis by a Fourier transform infrared spectrophotometer was also performed, the attribution peak of the carboxyl group derived from an acetic acid was observed.
From these analysis results, a hydrate having a molecular structure close to Cu ₂ (OH) ₂ (CH ₃ COO) _X (H ₂ O) _Y (where X and Y are integers) is also formed as a by-product. N-vinyl-2-pyrrolidone was judged to be present in a dispersed form in the gel. ICP emission spectroscopic analysis also confirmed that the gel contained a trace amount of sodium.

[Example 4]
(1) Preparation of copper-based amorphous compound gel by electrolytic method Copper acetate (II) monohydrate ((CH ₃ COO) ₂ Cu · 1H ₂ O) 200 g as a copper ion, 1-n-octyl as an organic additive Using 20 g of 2-pyrrolidone (carbon atoms: 12) and 90 g of calcium acetate monohydrate ((CH ₃ COO) ₂ Ca · H ₂ O) as an alkaline earth metal ion, Liter) was prepared. The pH of the reaction aqueous solution was about 5.7.
Next, 15 g of the obtained gel-like product is mixed with 15 g of γ-butyrolactone as a solvent in the reaction aqueous solution in the same manner as described in Example 1, and stirred for 1 hour or longer to obtain a copper-based product. An amorphous compound gel was obtained.
(2) Evaluation of the product (a) Structure observation of the product After the above-prepared copper-based amorphous compound gel was passed through a filter (manufactured by Whatman, trade name: Anodisc) and washed with water to remove the solvent by drying. Observation with a scanning electron microscope (SEM) was performed. As a result, it was confirmed that an amorphous structure having a range of 0.05 to 500 μm was formed. Moreover, acicular aggregates were not observed.

(B) Crystal structure analysis of the product After the obtained copper-based amorphous compound gel was coated on a glass substrate and vacuum-dried and analyzed by X-ray diffraction, a crystalline diffraction peak was not clearly seen. Since the crystallinity was 0%, it was judged to be in an amorphous state.
(C) Identification of the molecular structure of the product The obtained copper-based amorphous compound gel was applied onto a nanostructured electrode and analyzed with a microscopic Raman spectroscopic device. As a main component, copper hydroxide (Cu (OH) ₂ ) was used. Since the attributed peak was detected, it was determined that the product of this example was a copper-based amorphous compound gel mainly composed of copper hydroxide. Further, copper hydrate (Cu- (OH)-(H ₂ O)) adsorbed with hydroxide ions and pyrrolidone group derived from 1-n-octyl-2-pyrrolidone (C ₄ H ₆ NO) The peak attributed to was also detected as a minor component. Furthermore, when the analysis by a Fourier transform infrared spectrophotometer was also performed, the attribution peak of the carboxyl group derived from an acetic acid was observed. From these analysis results, a hydrate having a molecular structure close to Cu ₂ (OH) ₂ (CH ₃ COO) _X (H ₂ O) _Y (where X and Y are integers) is also formed as a by-product. It was determined that 1-n-octyl-2-pyrrolidone was present in a dispersed form in the gel. It was also confirmed from ICP emission spectroscopic analysis that a trace amount of calcium was contained in the gel.

[Example 5]
(1) Preparation of copper-based amorphous compound gel by electrolytic method Copper acetate (II) monohydrate ((CH ₃ COO) ₂ Cu · 1H ₂ O) 200 g as copper ions, N- (2- hydroxyethyl) -2-pyrrolidone (number of carbon atoms: 6) 50 g, and monohydrate _((CH 3 COO of calcium acetate as an alkaline earth metal ion) using _{2 Ca · H 2 O) 90g} , reaction A 10 L (liter) aqueous solution was prepared. The pH of the reaction aqueous solution was about 5.7.
Next, 15 g of the obtained gel-like product is mixed with 15 g of n-hexadecane as a solvent by the same method as described in Example 1 in the aqueous reaction solution, and stirred for 1 hour or more to obtain a copper-based product. An amorphous compound gel was obtained.
(2) Evaluation of the product (a) Structure observation of the product After the above-prepared copper-based amorphous compound gel was passed through a filter (manufactured by Whatman, trade name: Anodisc) and washed with water to remove the solvent by drying. Observation with a scanning electron microscope (SEM) was performed. As a result, it was confirmed that an amorphous structure having a range of 0.05 to 500 μm was formed. Moreover, acicular aggregates were not observed.

(B) Crystal structure analysis of the product After the obtained copper-based amorphous compound gel was coated on a glass substrate and vacuum-dried and analyzed by X-ray diffraction, a crystalline diffraction peak was not clearly seen. Since the crystallinity was 0%, it was judged to be in an amorphous state.
(C) Identification of the molecular structure of the product The obtained copper-based amorphous compound gel was applied onto a nanostructured electrode and analyzed with a microscopic Raman spectroscopic device. As a main component, copper hydroxide (Cu (OH) ₂ ) was used. Since the attributed peak was detected, it was determined that the product of this example was a copper-based amorphous compound gel mainly composed of copper hydroxide. Further, copper hydrate adsorbed with hydroxide ions (Cu- (OH)-(H ₂ O)) and a pyrrolidone group derived from N- (2-hydroxyethyl) -2-pyrrolidone (C ₄ H ₆ NO) was also detected as a secondary component. Furthermore, when the analysis by a Fourier transform infrared spectrophotometer was also performed, the attribution peak of the carboxyl group derived from an acetic acid was observed.
From these analysis results, a hydrate having a molecular structure close to Cu ₂ (OH) ₂ (CH ₃ COO) _X (H ₂ O) _Y (where X and Y are integers) is also formed as a by-product. It was determined that N- (2-hydroxyethyl) -2-pyrrolidone was present in a dispersed form in the gel. It was also confirmed from ICP emission spectroscopic analysis that a trace amount of calcium was contained in the gel.

[Example 6]
(1) Preparation of copper-based amorphous compound gel by electrolytic method Copper acetate (II) monohydrate ((CH ₃ COO) ₂ Cu · 1H ₂ O) 200 g as a copper ion, N-vinyl-2 as an organic additive -800 g of pyrrolidone (carbon atoms: 6), 137 g of sodium acetate trihydrate (CH ₃ COONa · 3H ₂ O) as alkali metal ions, and monohydrate of calcium acetate as alkaline earth metal ions ((CH ₃ COO) ₂ Ca · H ₂ O) (90 g) was used to prepare 10 L (liter) of an aqueous reaction solution. The pH of the aqueous reaction solution was about 6.4.
Next, in this aqueous solution, an electric current was passed between the rod cathode made of SUS304 (cathode electrode) and the platinum plate anode (anode electrode) at a bath temperature of 5 ° C. at a current density of 30 A / dm ² for 30 minutes, near the outer surface of the cathode. A copper-based compound containing a gel substance was deposited.
The reaction aqueous solution after completion of the electrolytic reaction was passed through a mesh filter (mesh: 10 to 100 μm) to separate the copper fine particle slurry and the gel substance. Thereafter, the gel material was washed with water to remove the aqueous reaction solution.
15 g of the gel product obtained by the above method was mixed with 15 g of ethylene glycol as a solvent and stirred for 1 hour or longer to obtain a copper-based amorphous compound gel.

(2) Evaluation of the product (a) Structure observation of the product After the above-prepared copper-based amorphous compound gel was passed through a filter (manufactured by Whatman, trade name: Anodisc) and washed with water to remove the solvent by drying. Observation with a scanning electron microscope (SEM) was performed. As a result, it was confirmed that an amorphous structure having a range of 0.05 to 500 μm was formed. Moreover, acicular aggregates were not observed.
(B) Crystal structure analysis of the product After the obtained copper-based amorphous compound gel was coated on a glass substrate and vacuum-dried and analyzed by X-ray diffraction, a crystalline diffraction peak was not clearly seen. Since the crystallinity was 0%, it was judged to be in an amorphous state.

(C) Identification of the molecular structure of the product The obtained copper-based amorphous compound gel was applied onto a nanostructured electrode and analyzed with a microscopic Raman spectrometer. A peak attributed to the product (Cu- (OH)-(H ₂ O)) was detected. In addition, peaks attributable to copper hydroxide (Cu (OH) ₂ ) and a pyrrolidone group (C ₄ H ₆ NO) derived from N-vinyl-2-pyrrolidone were also detected as subcomponents. Furthermore, when the analysis by a Fourier transform infrared spectrophotometer was also performed, the attribution peak of the carboxyl group derived from an acetic acid was observed.
From these analysis results, the product of this example is a hydrate having a molecular structure close to Cu ₂ (OH) ₂ (CH ₃ COO) _X (H ₂ O) _Y (where X and Y are integers). It was judged that it was a copper-type amorphous compound gel which has as a main component. Copper hydroxide (Cu (OH) ₂ ) was formed as a by-product, and N-vinyl-2-pyrrolidone was judged to be present in a dispersed form in the gel. ICP emission spectroscopic analysis also confirmed that the gel contained sodium and calcium.
The results of Examples 1 to 6 are summarized in Table 1.

[Example 7]
(1) Preparation of copper-based amorphous compound gel by electrolytic method 200 g of N-methyl-2-pyrrolidone (carbon atoms: 5) as organic additives, 100 g of 2-pyrrolidone (carbon atoms: 5), acetic acid as alkali metal ions trihydrate _{(CH 3 COONa · 3H 2 O} ) 70g of sodium, using decahydrate _{(Na 4 P 2 O 7 ·} 10H 2 O) 56g of sodium pyrophosphate, the reaction solution 10L (the liter) Prepared. The pH of the aqueous reaction solution was about 8.5.
Next, in this aqueous solution, a copper cathode (cathode electrode) and a copper anode (anode electrode) are energized for 15 minutes at a bath temperature of 10 ° C. and an electrolytic voltage of 20 V to supply copper ions from the anode to the reaction aqueous solution. Thus, a copper-based compound containing a gel substance was deposited in the vicinity of the anode outer surface and the cathode outer surface.
The reaction aqueous solution after completion of the electrolytic reaction was passed through a stainless steel mesh filter (mesh: 10 to 100 μm) to separate the copper fine particle slurry and the gel substance. Thereafter, the gel material was washed with water to remove the aqueous reaction solution.
10 g of the gel product obtained by the above method was mixed with 10 g of glycerol as a solvent and stirred for 1 hour or longer to obtain a copper-based amorphous compound gel.

(2) Evaluation of the product (a) Structure observation of the product After the above-prepared copper-based amorphous compound gel was passed through a filter (manufactured by Whatman, trade name: Anodisc) and washed with water to remove the solvent by drying. Observation with a scanning electron microscope (SEM) was performed. As a result, it was confirmed that an amorphous structure having a range of 0.05 to 500 μm was formed. Moreover, acicular aggregates were not observed.
(B) Crystal structure analysis of the product After the obtained copper-based amorphous compound gel was coated on a glass substrate and vacuum-dried and analyzed by X-ray diffraction, a crystalline diffraction peak was not clearly seen. Since the crystallinity was 0%, it was judged to be in an amorphous state.

(C) Identification of the molecular structure of the product The obtained copper-based amorphous compound gel was applied onto a nanostructured electrode and analyzed with a microscopic Raman spectroscopic device. As a main component, copper hydroxide (Cu (OH) ₂ ) was used. Since the attributed peak was detected, it was determined that the product of this example was a copper-based amorphous compound gel mainly composed of copper hydroxide. In addition, copper hydrate adsorbed with hydroxide ions (Cu- (OH)-(H ₂ O)) and pyrrolidone group derived from N-methyl-2-pyrrolidone and 2-pyrrolidone (C ₄ H ₆ A peak attributed to NO) was also detected as a secondary component. Furthermore, when the analysis by a Fourier transform infrared spectrophotometer was also performed, the attribution peak of the carboxyl group derived from acetic acid and the attribution peak of the POP bond derived from pyrophosphoric acid were observed.
From these analysis results, Cu ₂ (OH) ₂ (CH ₃ COO) _X (H ₂ O) _Y and Cu ₂ (OH) ₂ (P ₂ O ₇ ) _X (H ₂ O) _Y (X, Y are Hydrates with molecular structures close to each other are also formed as by-products, and N-methyl-2-pyrrolidone and 2-pyrrolidone are present in a dispersed form in the gel. It was judged. ICP emission spectroscopic analysis also confirmed that the gel contained sodium.

[Example 8]
(1) Preparation of copper-based amorphous compound gel by electrolytic method Copper acetate (II) monohydrate ((CH ₃ COO) ₂ Cu · 1H ₂ O) 200 g as copper ions, polyvinyl pyrrolidone (molecular weight: molecular weight: 3500) 500 g and 90 g of calcium acetate monohydrate ((CH ₃ COO) ₂ Ca · H ₂ O) as alkaline earth metal ions were used to prepare 10 L (liter) of an aqueous reaction solution. The pH of the reaction aqueous solution was about 5.7.
Next, by the same method as described in Example 1 in the aqueous reaction solution, 5 g of the obtained gel-like product is mixed with 5 g of ethylene glycol as a solvent and stirred for 1 hour or longer to obtain a copper-based amorphous. A compound gel was obtained.

(2) Evaluation of the product (a) Structure observation of the product After the above-prepared copper-based amorphous compound gel was passed through a filter (manufactured by Whatman, trade name: Anodisc) and washed with water to remove the solvent by drying. Observation with a scanning electron microscope (SEM) was performed. As a result, it was confirmed that an amorphous structure having a range of 0.05 to 500 μm was formed. Moreover, acicular aggregates were not observed.
(B) Crystal structure analysis of the product After the obtained copper-based amorphous compound gel was applied on a glass substrate and vacuum-dried and analyzed by X-ray diffraction, a crystalline diffraction peak was not clearly seen. Since the crystallinity was 3%, it was judged to be in an amorphous state.

(C) Identification of the molecular structure of the product The obtained copper-based amorphous compound gel was applied onto a nanostructured electrode and analyzed with a microscopic Raman spectroscopic device. As a main component, copper hydroxide (Cu (OH) ₂ ) was used. Since the attributed peak was detected, it was determined that the product of this example was a copper-based amorphous compound gel mainly composed of copper hydroxide. Moreover, the peak attributed to the hydrate of copper (Cu- (OH)-(H ₂ O)) adsorbed with hydroxide ions and the pyrrolidone group (C ₄ H ₆ NO) derived from polyvinylpyrrolidone is also a minor component. As detected. Furthermore, when the analysis by a Fourier transform infrared spectrophotometer was also performed, the attribution peak of the carboxyl group derived from an acetic acid was observed.
From these analysis results, a hydrate having a molecular structure close to Cu ₂ (OH) ₂ (CH ₃ COO) _X (H ₂ O) _Y (where X and Y are integers) is also formed as a by-product. The polyvinylpyrrolidone was judged to be present in a dispersed form in the gel. It was also confirmed from ICP emission spectroscopic analysis that a trace amount of calcium was contained in the gel.

[Example 9]
(1) Preparation of copper-based amorphous compound gel by electrolytic method 196 g of copper (II) pyrophosphate trihydrate (Cu ₂ P ₂ O ₇ · 1H ₂ O) as copper ion, 10 of sodium pyrophosphate as alkali metal ion hydrate _{(Na 4 P 2 O 7 ·} 10H 2 O) 1130g, and using the monohydrate _{((CH 3 COO) 2 Ca} · H 2 O) 90g of calcium acetate as an alkaline earth metal ion, 10 L (liter) of an aqueous reaction solution was prepared. The pH of the aqueous reaction solution was about 10.
Next, in this aqueous solution, a current was passed between a rod cathode made of SUS304 (cathode electrode) and a platinum plate anode (anode electrode) at a bath temperature of 5 ° C. and a current density of 20 A / dm ² for 30 minutes, and was brought near the cathode outer surface. A copper-based compound containing a gel substance was deposited.
The reaction aqueous solution after completion of the electrolytic reaction was passed through a stainless steel mesh filter (mesh: 10 to 100 μm) to separate the copper fine particle slurry and the gel substance. Thereafter, the gel material was washed with water to remove the aqueous reaction solution.
15 g of the gel product obtained by the above method was mixed with 15 g of ethylene glycol as a solvent and stirred for 1 hour or longer to obtain a copper-based amorphous compound gel.

(2) Evaluation of the product (a) Structure observation of the product After the above-prepared copper-based amorphous compound gel was passed through a filter (manufactured by Whatman, trade name: Anodisc) and washed with water to remove the solvent by drying. Observation with a scanning electron microscope (SEM) was performed. As a result, it was confirmed that in addition to the formation of amorphous structures in the range of 0.05 to 500 μm, acicular aggregates were mixed.

(B) Crystal structure analysis of the product After the obtained copper-based amorphous compound gel was coated on a glass substrate and vacuum-dried and analyzed by X-ray diffraction, a crystalline diffraction peak was not clearly seen. Since the crystallinity was 4%, it was judged to be in an amorphous state.
(C) Identification of the molecular structure of the product The obtained copper-based amorphous compound gel was applied onto a nanostructured electrode and analyzed with a microscopic Raman spectroscopic device. As a main component, copper hydroxide (Cu (OH) ₂ ) was used. Since the attributed peak was detected, it was determined that the product of this example was a copper-based amorphous compound gel mainly composed of copper hydroxide. In addition, a peak attributed to a copper hydrate (Cu- (OH)-(H ₂ O)) adsorbed with hydroxide ions was also detected as a secondary component. Furthermore, when the analysis by a Fourier transform infrared spectrophotometer was also performed, the attribution peak of the carboxyl group derived from acetic acid and the attribution peak of the POP bond derived from pyrophosphoric acid were observed.
From these analysis results, Cu ₂ (OH) ₂ (CH ₃ COO) _X (H ₂ O) _Y and Cu ₂ (OH) ₂ (P ₂ O ₇ ) X (H ₂ O) _Y (X, Y are It was judged that hydrates having molecular structures close to each other were also formed as by-products. ICP emission spectroscopic analysis also confirmed that the gel contained sodium and calcium.

[Example 10]
(1) Preparation of zinc-based amorphous compound gel by electrolytic method Zinc acetate dihydrate ((CH ₃ COO) ₂ Zn · 2H ₂ O) 220 g as zinc ions, N-vinyl-2-pyrrolidone (as organic additive) The reaction aqueous solution 10L (liter) was prepared using 600 g of carbon atoms: 6) and 68.7 g of sodium acetate trihydrate (CH ₃ COONa · 3H ₂ O) as an alkali metal ion. The pH of the reaction aqueous solution was about 5.8.
Next, in this aqueous solution, an electric current was passed between a rod cathode made of SUS304 (cathode electrode) and a platinum plate anode (anode electrode) at a bath temperature of 15 ° C. and a current density of 30 A / dm ² for 30 minutes, near the cathode outer surface. A zinc-based compound containing a gel substance was deposited.
The reaction aqueous solution after completion of the electrolytic reaction was passed through a stainless steel mesh filter (mesh: 10 to 100 μm) to separate the zinc fine particle slurry and the gel substance. Thereafter, the gel material was washed with water to remove the aqueous reaction solution. 15 g of the gel product obtained by the above method was mixed with 15 g of ethylene glycol as a solvent and stirred for 1 hour or longer to obtain a zinc-based amorphous compound gel.

(2) Evaluation of the product (a) Observation of the structure of the product After the zinc-based amorphous compound gel prepared above was washed with water while passing through a filter (manufactured by Whatman, trade name: Anodisc), and the solvent was removed by drying. Observation with a scanning electron microscope (SEM) was performed. As a result, it was confirmed that an amorphous structure in the range of 0.1 to 500 μm was formed. Moreover, acicular aggregates were not observed.
(B) Crystal structure analysis of the product After applying the obtained zinc-based amorphous compound gel on a glass substrate, vacuum drying and analyzing by X-ray diffraction, no crystalline diffraction peak is clearly seen. Since the crystallinity was 0%, it was judged to be in an amorphous state.

(C) Identification of the molecular structure of the product The obtained zinc-based amorphous compound gel was applied onto a nanostructured electrode and analyzed with a microscopic Raman spectroscopic device. As a main component, zinc hydroxide (Zn (OH) ₂ ) Since an attributed peak was detected, it was determined that the product of this example was a zinc-based amorphous compound gel containing zinc hydroxide as a main component. Moreover, it belongs to the hydrate of zinc (Zn- (OH)-(H ₂ O)) adsorbed with hydroxide ions and the pyrrolidone group (C ₄ H ₆ NO) derived from N-vinyl-2-pyrrolidone. Peak was also detected as a minor component. Furthermore, when the analysis by a Fourier transform infrared spectrophotometer was also performed, the attribution peak of the carboxyl group derived from an acetic acid was observed.
From these analysis results, a hydrate having a molecular structure close to Zn ₂ (OH) ₂ (CH ₃ COO) _X (H ₂ O) _Y (where X and Y are integers) is also formed as a by-product. N-vinyl-2-pyrrolidone was determined to exist in a dispersed form in the gel. ICP emission spectroscopic analysis also confirmed that the gel contained a trace amount of sodium.

[Example 11]
(1) Preparation of tin-based amorphous compound gel by electrolysis method 250 g of tin acetate ((CH ₃ COO) ₂ Sn) as tin ions, 800 g of N-methyl-2-pyrrolidone (carbon atoms: 5) as an organic additive, and alkali Using 68.7 g of sodium acetate trihydrate (CH ₃ COONa · 3H ₂ O) as a metal ion, 10 L (liter) of an aqueous reaction solution was prepared. The pH of the reaction aqueous solution was about 5.8.
Next, in this aqueous solution, an electric current was passed between a rod cathode made of SUS304 (cathode electrode) and a platinum plate anode (anode electrode) at a bath temperature of 15 ° C. and a current density of 30 A / dm ² for 30 minutes, near the cathode outer surface. A tin-based compound containing a gel substance was deposited.
The aqueous reaction solution after completion of the electrolytic reaction was passed through a stainless steel mesh filter (mesh: 10 to 100 μm) to separate the tin fine particle slurry and the gel substance. Thereafter, the gel material was washed with water to remove the aqueous reaction solution.
15 g of the gel-like product obtained by the above method was mixed with 15 g of ethylene glycol as a solvent and stirred for 1 hour or longer to obtain a tin-based amorphous compound gel.

(2) Evaluation of product (a) Structure observation of product After the above-prepared tin-based amorphous compound gel was passed through a filter (manufactured by Whatman, product system: Anodisco) and washed with water to remove the solvent by drying. Observation with a scanning electron microscope (SEM) was performed. As a result, it was confirmed that an amorphous structure in the range of 0.2 to 500 μm was formed. Moreover, acicular aggregates were not observed.
(B) Crystal structure analysis of the product After the obtained tin-based amorphous compound gel was applied on a glass substrate and vacuum-dried and analyzed by X-ray diffraction, a crystalline diffraction peak was not clearly seen. Since the crystallinity was 0%, it was judged to be in an amorphous state.

(C) Identification of the molecular structure of the product The obtained tin-based amorphous compound gel was applied onto a nanostructured electrode and analyzed with a microscopic Raman spectroscopic device. As a result, tin hydroxide (Sn (OH) ₂ ) was used as the main component. Since an attributed peak was detected, it was determined that the product of this example was a tin-based amorphous compound gel containing tin hydroxide as a main component. Moreover, hydrates of tin hydroxide ions adsorbed - and _{(Sn- (OH) (H 2} O)), assigned to a pyrrolidone group _{(C 4} H 6 NO) derived from N- vinyl-2-pyrrolidone Peak was also detected as a minor component. Furthermore, when the analysis by a Fourier transform infrared spectrophotometer was also performed, the attribution peak of the carboxyl group derived from an acetic acid was observed.
From these analysis results, a hydrate having a molecular structure close to Sn ₂ (OH) ₂ (CH ₃ COO) _X (H ₂ O) _Y (where X and Y are integers) is also formed as a by-product. N-methyl-2-pyrrolidone was determined to exist in a dispersed form in the gel. ICP emission spectroscopic analysis also confirmed that the gel contained a trace amount of sodium.

[Example 12]
(1) Preparation of nickel-based amorphous compound gel by electrolytic method Nickel acetate tetrahydrate ((CH ₃ COO) ₂ Ni · 4H ₂ O) 260 g as nickel ions, N-methyl-2-pyrrolidone (organic additive) 10 L (liter) of an aqueous reaction solution was prepared using 800 g of carbon atoms: 5) and 27.5 g of sodium acetate trihydrate (CH ₃ COONa · 3H ₂ O) as an alkali metal ion. The pH of the reaction aqueous solution was about 5.0.
Next, in this aqueous solution, an electric current was passed between a rod cathode made of SUS304 (cathode electrode) and a platinum plate anode (anode electrode) at a bath temperature of 15 ° C. and a current density of 30 A / dm ² for 30 minutes, near the cathode outer surface. A nickel-based compound containing a gel substance was deposited.
The reaction aqueous solution after completion of the electrolytic reaction was passed through a stainless steel mesh filter (mesh: 10 to 100 μm) to separate the nickel fine particle slurry and the gel substance. Thereafter, the gel material was washed with water to remove the aqueous reaction solution.
15 g of the gel product obtained by the above method was mixed with 15 g of ethylene glycol as a solvent and stirred for 1 hour or longer to obtain a nickel-based amorphous compound gel.

(2) Evaluation of product (a) Structure observation of product After the nickel-based amorphous compound gel prepared above was washed with water while passing through a filter (manufactured by Whatman, trade name: Anodisc), the solvent was removed by drying. Observation with a scanning electron microscope (SEM) was performed. As a result, it was confirmed that an amorphous structure in the range of 0.2 to 500 μm was formed. Moreover, acicular aggregates were not observed.
(B) Crystal structure analysis of the product After applying the obtained nickel-based amorphous compound gel on a glass substrate, vacuum drying and analysis by X-ray diffraction, no crystalline diffraction peak is clearly seen. Since the crystallinity was 0%, it was judged to be in an amorphous state.
(C) Identification of the molecular structure of the product The obtained nickel-based amorphous compound gel was applied onto a nanostructured electrode and analyzed with a microscopic Raman spectroscopic device. As a result, nickel hydroxide (Ni (OH) ₂ ) was used as the main component. Since an attributed peak was detected, it was determined that the product of this example was a nickel-based amorphous compound gel containing nickel hydroxide as a main component. Moreover, it belongs to nickel hydrate (Ni- (OH)-(H ₂ O)) adsorbed with hydroxide ions and pyrrolidone group (C ₄ H ₆ NO) derived from N-methyl-2-pyrrolidone. Peak was also detected as a minor component. Furthermore, when the analysis by a Fourier transform infrared spectrophotometer was also performed, the attribution peak of the carboxyl group derived from an acetic acid was observed.
From these analysis results, a hydrate having a molecular structure close to Ni ₂ (OH) ₂ (CH ₃ COO) _X (H ₂ O) _Y (where X and Y are integers) is also formed as a by-product. N-methyl-2-pyrrolidone was determined to exist in a dispersed form in the gel. ICP emission spectroscopic analysis also confirmed that the gel contained a trace amount of sodium.
The results of Examples 7 to 12 are summarized in Table 2.

[Comparative Example 1]
(1) Preparation of copper-based compound gel by electrolytic method A copper-based compound gel was obtained in the same manner as in Example 1 except that water was used as the solvent to be mixed with the gel product.
(2) Evaluation of product (a) Structure observation of product After the copper-based compound gel prepared above was passed through a filter (manufactured by Whatman, trade name: Anodisco) and washed with water to remove the solvent by drying, Observation with a scanning electron microscope (SEM) was performed. As a result, it was confirmed that an amorphous structure having a range of 0.05 to 500 μm was formed. Moreover, acicular aggregates were not observed.
(B) Crystal structure analysis of the product The obtained copper-based compound gel was applied on a glass substrate, vacuum-dried and analyzed by X-ray diffraction. As a result, a crystalline diffraction peak was detected and the degree of crystallinity was detected. Of 6%, it was judged that crystallization was in progress.

(C) Identification of the molecular structure of the product When the obtained copper-based compound gel was applied onto a nanostructured electrode and analyzed with a microscopic Raman spectrometer, it was attributed to copper hydroxide (Cu (OH) ₂ ) as the main component. Since the peak which detects was detected, it was judged that it was a copper-type compound gel which has copper hydroxide as a main component. Further, copper oxide (CuO), copper hydrate adsorbed with hydroxide ions (Cu— (OH) — (H ₂ O)), and pyrrolidone group derived from N-vinyl-2-pyrrolidone (C A peak attributed to ₄ H ₆ NO) was also detected as a minor component. Furthermore, when the analysis by a Fourier transform infrared spectrophotometer was also performed, the attribution peak of the carboxyl group derived from an acetic acid was observed.
From these analysis results, a hydrate having a molecular structure close to copper oxide (CuO), Cu ₂ (OH) ₂ (CH ₃ COO) _X (H ₂ O) _Y (where X and Y are integers) is also obtained. It was formed as a by-product and N-vinyl-2-pyrrolidone was judged to be present in a dispersed form in the gel. ICP emission spectroscopic analysis also confirmed that the gel contained a trace amount of sodium.

[Comparative Example 2]
(1) Preparation of copper compound by electrolytic method A copper compound was obtained in the same manner as in Example 1 except that 1000 g of 2-aminoethanol was used as the organic additive.
(2) Evaluation of the product (a) Structure observation of the product The above-prepared copper compound was washed with water while passing through a filter (manufactured by Whatman, trade name: Anodisco), and the solvent was dried and removed, followed by scanning. Observation with a scanning electron microscope (SEM) was performed. As a result, it was confirmed that a particulate structure having a primary particle diameter of 100 to 800 nm and a secondary particle diameter of 1 to 100 μm was formed. In addition, needle-shaped aggregates of 1 to 50 μm in which the crystal shape was aggregated in a dendrite shape were observed.
(B) Crystal structure analysis of the product After the obtained copper compound was applied on a glass substrate, it was vacuum dried and analyzed by X-ray diffraction. As a result, a crystalline diffraction peak attributed to copper was clearly detected. Since the crystallinity was 60%, it was judged to be crystalline copper particles.

(C) Identification of the molecular structure of the product The obtained copper-based compound was applied onto the nanostructure electrode and analyzed with a microscopic Raman spectroscopic device. Peaks attributed to cuprous oxide (Cu ₂ O) and copper hydroxide (Cu (OH) ₂ ) were also detected. Furthermore, when the analysis by a Fourier-transform infrared spectrophotometer was also performed, the attribution peak of the amino group derived from 2-aminoethanol was obtained.
From these analysis results, cuprous oxide (Cu ₂ O) and copper hydroxide (Cu (OH) ₂ ) are formed as by-products, and 2-aminoethanol is attached to the particle surface. It was judged. ICP emission spectroscopic analysis also confirmed that a trace amount of sodium was contained.

[Comparative Example 3]
(1) Preparation of copper compound by electrolytic method A copper compound was obtained in the same manner as in Example 1 except that 1000 g of N, N-dimethylformamide was used as the organic additive.
(2) Evaluation of the product (a) Structure observation of the product The above-prepared copper compound was washed with water while passing through a filter (manufactured by Whatman, trade name: Anodisco), and the solvent was dried and removed, followed by scanning. Observation with a scanning electron microscope (SEM) was performed. As a result, it was confirmed that a particulate structure having a primary particle diameter of 100 to 600 nm and a secondary particle diameter of 1 to 100 μm was formed. In addition, needle-shaped aggregates of 1 to 50 μm in which the crystal shape was aggregated in a dendrite shape were observed.
(B) Crystal structure analysis of the product After the obtained copper compound was applied on a glass substrate, it was vacuum dried and analyzed by X-ray diffraction. As a result, a crystalline diffraction peak attributed to copper was clearly detected. Since the crystallinity was 65%, it was judged to be crystalline copper particles.

(C) Identification of the molecular structure of the product The obtained copper-based compound was applied onto the nanostructure electrode and analyzed with a microscopic Raman spectroscopic device. Peaks attributed to cuprous oxide (Cu ₂ O) and copper hydroxide (Cu (OH) ₂ ) were also detected. Furthermore, when analysis was performed using a Fourier transform infrared spectrophotometer, an assigned peak of an amide group derived from N, N-dimethylformamide was observed.
From these analysis results, cuprous oxide (Cu ₂ O) and copper hydroxide (Cu (OH) ₂ ) are formed as by-products, and N, N-dimethylformamide is attached to the particle surface. It was judged. ICP emission spectroscopic analysis also confirmed that a trace amount of sodium was contained.

[Comparative Example 4]
(1) Preparation of copper compound by electrolytic method A copper compound was obtained in the same manner as in Example 1 except that 500 g of polyvinyl alcohol (molecular weight: 500) was used as the organic additive.
(2) Evaluation of the product (a) Structure observation of the product The above-prepared copper compound was washed with water while passing through a filter (manufactured by Whatman, trade name: Anodisco), and the solvent was dried and removed, followed by scanning. Observation with a scanning electron microscope (SEM) was performed. As a result, it was confirmed that a particulate structure having a primary particle diameter of 200 to 900 nm and a secondary particle diameter of 1 to 100 μm was formed. In addition, needle-shaped aggregates of 1 to 50 μm in which the crystal shape was aggregated in a dendrite shape were observed.
(B) Crystal structure analysis of the product After the obtained copper compound was applied on a glass substrate, it was vacuum dried and analyzed by X-ray diffraction. As a result, a crystalline diffraction peak attributed to copper was clearly detected. Since the crystallinity was 65%, it was judged to be crystalline copper particles.

(C) Identification of the molecular structure of the product When the obtained copper-based compound was applied onto the nanostructure electrode and analyzed with a microscopic Raman spectroscopic device, the peak attributed to copper (Cu) as the main component and the subcomponent peak attributable to cuprous oxide (Cu 2 _O) was also detected. Furthermore, when the analysis by a Fourier-transform infrared spectrophotometer was also performed, the attribution peak of polyvinyl alcohol was obtained.
From these analysis results, cuprous oxide (Cu ₂ O) was also formed as a by-product, and it was determined that polyvinyl alcohol was adhered to the particle surface. It was also confirmed from ICP emission spectroscopic analysis that a trace amount of sodium was contained.

[Comparative Example 5]
(1) Preparation of copper-based compound by electrolytic method 134 g of copper (II) chloride (CuCl ₂ ) as copper ions, 100 g of 2-pyrrolidone (carbon atoms: 4) as an organic additive, and sodium chloride (NaCl as an alkali metal ion) ) 11.7 g was used to prepare 10 L (liter) of aqueous reaction solution. The pH of the reaction aqueous solution was about 3.8.
Next, when an electrolytic reaction was performed in the reaction aqueous solution in the same manner as described in Example 1, a plating film was mainly formed on the electrode surface.
(2) Crystal structure analysis of product When the obtained plated film was analyzed by X-ray diffraction, a crystalline diffraction peak attributed to copper was clearly detected and the crystallinity was 75%. It was judged to be a crystalline copper film.

[Comparative Example 6]
(1) Preparation of copper-based compound by electrolytic method Tetraammine copper (II) sulfate salt ([Cu (NH ₃ ) ₄ ] SO ₄ , copper sulfate (II) pentahydrate (CuSO ₄ .5H ₂ O) as copper ions ) Use 250 g and 3500 g of aqueous ammonia (NH ₃ , 30% aqueous solution), 100 g of 2-pyrrolidone (carbon atoms: 4) as an organic additive, and 14.4 g of sodium sulfate (NaSO ₄ ) as an alkali metal ion Thus, 10 L (liter) of an aqueous reaction solution was prepared. The pH of the aqueous reaction solution was about 11.5.
Next, when an electrolytic reaction was performed in the reaction aqueous solution in the same manner as described in Example 1, a plating film was mainly formed on the electrode surface.
(2) Crystal structure analysis of product When the obtained plated film was analyzed by X-ray diffraction, a crystalline diffraction peak attributed to copper was clearly detected and the crystallinity was 80%. It was judged to be a crystalline copper film.
The results of Comparative Examples 1-6 are summarized in Table 3.

[Example 13]
(1) Preparation of sample for evaluation After putting the amorphous compound gel obtained in Examples 1 to 3 and 9 to 12 into a test tube and adjusting the concentration to 10% by mass with each dispersion solvent, an ultrasonic homogenizer was used. After stirring well, an amorphous compound gel was obtained.
(2) Light irradiation The amorphous compound gel obtained was applied to a glass substrate (size: 2 cm × 2 cm) with a spin coater, and 1 to 5 in a temperature range of 50 to 180 ° C. using a hot plate in a nitrogen gas atmosphere. After heating for 30 minutes to dry the coating film to 70% by mass, the sample was immediately removed and cooled to room temperature. Thereafter, the xenon lamp light (wavelength range: 300 to 1300 nm) from a distance of 25 mm to a discharge light emission voltage of 300 to 5000 V, a pulse width of 500 to 5000 μsec and a range of 1 to 3 times (irradiation time per 2 msec) Irradiated with.
(3) The amorphous compound gel obtained by heating was applied to a glass substrate (size: 2 cm × 2 cm) with a spin coater, and each was for 1 to 5 minutes in a nitrogen gas atmosphere at a temperature range of 50 to 180 ° C. using a hot plate. After heating to dry the coating film to 40% by mass, the sample was immediately removed and cooled to room temperature. Thereafter, the sample was placed in an atmosphere-controlled heat treatment furnace and heated in a nitrogen gas atmosphere at a temperature increase rate of 30 ° C./min. After reaching 200 ° C., it was kept for 30 minutes and then slowly cooled to room temperature in a heat treatment furnace.

(4) Light irradiation under heating The obtained amorphous compound gel was applied to a glass substrate (size: 2 cm × 2 cm) with a spin coater, and a temperature range of 80 to 150 ° C. using a hot plate in a nitrogen gas atmosphere. Then, the coating film was dried for 1 to 5 minutes to 50% by mass, and then the sample was immediately removed and cooled to room temperature. Thereafter, the xenon lamp light (wavelength range: 300 to 1300 nm) is heated at a temperature range of 100 to 200 ° C. from a distance of 25 mm to a discharge light emission voltage of 500 to 3000 V and a pulse width of 500 to 5000 μsec. Irradiation was performed within a range of irradiation (irradiation time per irradiation: 2 msec). The evaluation results are summarized in Tables 4 and 5.

[Comparative Example 8]
A sample for evaluation was prepared in the same manner as in Example 13 except that the amorphous compound gel of Example 13 was the product obtained in Comparative Examples 2 to 5, and then formed by light irradiation and heating. The obtained crystallized film was evaluated. These evaluation results are summarized in Table 6.

[Consideration of formed crystallized film]
For the metal crystallized, the resistivity of the crystallized film prepared from the samples obtained in Comparative Examples 2 to 5 was 4.5 × 10 ^{−4 to} 9.0 × 10 ⁻³ μΩcm, The resistivity of the crystallized film prepared from the samples obtained in Examples 1 to 3 and 9 to 12 showed a small resistivity of 10 ⁻⁵ μΩcm or less. When the sintered structure was observed with a scanning electron microscope, the sample formed from the amorphous compound gel (FIG. 1 (Example 1)) was a dense and continuous nanoporous structure (FIG. 2 (Example 13-1)). However, in the comparative example outside the scope of the present invention, the structure was sparse and discontinuous (FIG. 3 (Comparative Example 8-2)). Furthermore, the X-ray diffraction of the amorphous compound gel in FIG. 1 (FIG. 4) did not clearly show a crystalline diffraction peak, but the X-ray diffraction of the continuous nanoporous film after crystallization in FIG. In FIG. 5), a crystalline diffraction peak was clearly seen. From this, it was found that the amorphous compound gel of the present invention can be easily crystallized and the structure can be controlled. Moreover, in the form of the present invention, by adjusting the light irradiation condition and the heating condition, a structure showing semiconductor carrier concentration and carrier mobility characteristics was obtained, but the comparison is outside the scope of the present invention. It was not obtained in the example.
Further, under the conditions of heating and light irradiation in Example 13, the nanoporous structure of the obtained oxide crystal and metal crystal mainly forms an open cell type three-dimensional network structure, and It was also found that the average diameter of the network having a network structure of 20 to 500 nm and the ten-point average roughness (JISB-0601) of the surface can be adjusted in the range of 20 to 200 nm.
Thus, it was confirmed that the amorphous compound gel of the present invention can make a conductor and a semiconductor by light irradiation or heat treatment.

[Example 14]
The amorphous compound gel obtained in Examples 10 and 11 above is put into a test tube so that the weight ratio is 2: 1, and the concentration is adjusted to 30% by mass with an ethylene glycol solvent, and then an ultrasonic homogenizer may be used. Stir. The adjusted amorphous compound gel was applied to a transparent substrate (non-alkali glass (Corning, product name :) 1737) with a spin coater so as to have a dry film thickness of 100 nm, and a hot plate was used in a nitrogen gas atmosphere. After heating at 120 ° C. for 3 minutes to dry the coating film, the sample was immediately removed and cooled to room temperature. Thereafter, light from a xenon lamp (wavelength range: 300 to 1300 nm) was irradiated from a distance of 25 mm three times with a discharge light emission voltage of 1500 V and a pulse width of 2000 μsec (an irradiation time of 1 msec per time) to obtain a transparent conductive substrate. . The obtained transparent conductive substrate had a resistivity of 1.5 × 10 ⁻¹ Ω · cm, and a transmittance of about 80% in the visible region and about 85% in the infrared region. When the crystalline phase of the conductive film in this transparent conductive substrate was analyzed by X-ray diffraction and a transmission electron microscope (TEM-EDX), it was a Zn ₂ SnO ₄ type polycrystalline body.

[Example 15]
The amorphous compound gel obtained in Example 1 above and aluminum lactate ([CH ₃ CH (OH) COO] ₃ Al) as a compound salt are placed in a test tube at a weight ratio of 6: 4, and ethylene glycol is added. After adjusting the concentration to 30% by mass with a solvent, the mixture was thoroughly stirred using an ultrasonic homogenizer. The adjusted amorphous compound gel was applied to a transparent substrate (non-alkali glass (Corning, product name :) 1737) with a spin coater so as to have a dry film thickness of 100 nm, and a hot plate was used in a nitrogen gas atmosphere. After heating at 120 ° C. for 3 minutes to dry the coating film, the sample was immediately removed and cooled to room temperature. Thereafter, light from a xenon lamp (wavelength range: 300 to 1300 nm) was irradiated from a distance of 25 mm three times with a discharge light emission voltage of 1500 V and a pulse width of 2000 μsec (an irradiation time of 1 msec per time) to obtain a transparent conductive substrate. . The obtained transparent conductive substrate had a resistivity of 5.5 × 10 ² Ω · cm and a transmittance of about 60% in the visible region and about 70% in the infrared region. When the crystal phase of the conductive film in this transparent conductive substrate was analyzed by X-ray diffraction and a transmission electron microscope (TEM-EDX), it was a CuAlO ₂ type polycrystal.

Claims (25)

  It is composed of an amorphous compound having a crystallinity of 5% or less formed by bonding one or two or more hydroxyl groups to a metal element, and an organic solvent (S) that is liquid at room temperature, and a lactam compound (L) An amorphous compound gel characterized by being mixed.   The amorphous compound gel according to claim 1, wherein the metal element is one or more selected from copper, zinc, tin, and nickel.   The amorphous compound gel according to claim 1 or 2, wherein a boiling point of the organic solvent (S) at normal pressure is 60 ° C or higher.   The amorphous compound gel according to any one of claims 1 to 3, wherein the boiling point of the organic solvent (S) at normal pressure is 350 ° C or lower.   The organic solvent (S) includes an organic compound (S1) having at least one hydroxyl group and having one or two hydrogen atoms bonded to the carbon atom to which the hydroxyl group is bonded. The amorphous compound gel according to any one of claims 1 to 4, wherein the gel is characterized.   The organic compound (S1) is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2,2-dimethyl-1 -Propanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 2,2 dimethyl-1-propanol, 3-methyl-2-butanol 2-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-2-hexanol, 2-methyl-3-hexanol, 1-heptanol, 2-heptanol, 4-heptanol, 2 -Ethyl-1-hexanol, 1-octanol, 2-octanol, ethylene glycol, Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-butene-1,4-diol, 2, 3-butanediol, pentanediol, hexanediol, octanediol, glycerol, 1,1,1-trishydroxymethylethane, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 1,2,6-hexane The amorphous compound gel according to claim 5, wherein the gel is one or more selected from triol, 1,2,3-hexanetriol, and 1,2,4-butanetriol.   The amorphous compound gel according to claim 1, wherein a molecular structure of the amorphous compound is a hydrate.   The amorphous compound gel according to claim 1, wherein the molecular structure of the amorphous compound includes a carboxyl group.   The amorphous compound gel according to any one of claims 1 to 8, wherein the amorphous compound does not have a long-period structure of 100 nm or more.   In a reaction solution having a pH of 4.0 to 11.0 containing a metal ion, a ligand that forms a coordination bond to the metal ion, and a lactam compound (L), an electrolytic reaction is performed by passing an electric current between the anode and the cathode. A method for producing an amorphous compound gel, comprising depositing an amorphous compound derived from metal ions and mixing the amorphous compound with an organic solvent (S).   The method for producing an amorphous compound gel according to claim 10, wherein the metal ion is one or more selected from copper, zinc, tin, and nickel.   The method for producing an amorphous compound gel according to claim 10 or 11, wherein the metal ion forms a complex with the ligand, and the total formation constant of the complex is 1 to 10.   The ligand is one or more selected from acetate ion, oxalate ion, propionate ion, malonate ion, tartrate ion, and pyrophosphate ion. The manufacturing method of the amorphous compound gel in any one of.   The amorphous compound according to any one of claims 10 to 13, wherein one or two selected from alkali metal ions and alkaline earth metal ions are dissolved in the reaction solution. A method for producing a gel.   The method for producing an amorphous compound gel according to claim 14, wherein the alkali metal ion is one or more selected from lithium ion, sodium ion, and potassium ion.   The method for producing an amorphous compound gel according to claim 14, wherein the alkaline earth metal ions are calcium ions.   The lactam compound (L) has one or more selected from 2-pyrrolidone, alkyl-2-pyrrolidone, and hydroxyalkyl-2-pyrrolidone having a 5-membered ring structure having 4 to 12 carbon atoms The method for producing an amorphous compound gel according to any one of claims 10 to 16, wherein the method is provided.   The alkyl-2-pyrrolidone is N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, Nn-propyl-2-pyrrolidone, Nn-butyl-2-pyrrolidone. N-iso-butyl-2-pyrrolidone, Nn-octyl-2-pyrrolidone, 3-methyl-2-pyrrolidone, 4-methyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, and The method for producing an amorphous compound gel according to claim 17, wherein the method is one or more selected from N-methyl-4-methyl-2-pyrrolidone.   1 wherein the hydroxyalkyl-2-pyrrolidone is selected from N- (hydroxymethyl) -2-pyrrolidone, N- (2-hydroxyethyl) -2-pyrrolidone, and N- (3-hydroxypropyl) -2-pyrrolidone. The method for producing an amorphous compound gel according to claim 17, wherein the method is a seed or two or more kinds. Applying the amorphous compound gel according to any one of claims 1 to 9 to a substrate,
After performing preliminary drying at a temperature below the boiling point of the organic solvent (S) in an air atmosphere or an inert gas atmosphere,
A method for producing an oxide crystal, characterized by performing heating, light irradiation, or light irradiation under heating. The light source of the light irradiation is a xenon lamp, the discharge light emission voltage is in the range of 1000 to 3000V,
21. The oxide crystal according to claim 20, wherein the oxide crystal is a semiconductor or a conductor of one or more oxides selected from copper, zinc, tin, and nickel. Body manufacturing method. Applying the amorphous compound gel according to any one of claims 1 to 9 to a substrate,
After performing preliminary drying at a temperature below the boiling point of the organic solvent (S) in an air atmosphere or an inert gas atmosphere,
It is characterized by performing heating, light irradiation, or light irradiation under heating.
A method for producing a metal crystal. The light source of the light irradiation is a xenon lamp, the discharge light emission voltage is in the range of 500 to 5000V,
The method for producing a metal crystal according to claim 22, wherein the metal crystal is a copper conductor. Mixing two or more of the amorphous compound gels according to any one of claims 1 to 9, and applying to a substrate,
In air atmosphere or inert gas atmosphere, after preliminary drying at a temperature lower than the boiling point of the organic solvent (S), heating, light irradiation, or light irradiation under heating is performed,
A method for producing a transparent conductor. Mixing the amorphous compound gel according to any one of claims 1 to 9 with a compound salt of a metal element or a metalloid element, and applying the mixture to a substrate,
In air atmosphere or inert gas atmosphere, after preliminary drying at a temperature lower than the boiling point of the organic solvent (S), heating, light irradiation, or light irradiation under heating is performed,
A method for producing a transparent conductor.

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