JP2017011218A - Composition for thermoelectric conversion thin film formation and method for producing thermoelectric conversion thin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoelectric conversion thin film forming composition capable of synthesizing a thermoelectric conversion thin film at low temperature.SOLUTION: The thermoelectric conversion thin film forming composition contains thermoelectric conversion particles and a copper formate amine complex in which a primary amine is coordinated with copper formate. The molar equivalent ratio of the thermoelectric conversion particles to the copper formate is 1:0.3 to 0.6. The thermoelectric conversion particles are made of a silicide material containing at least one of magnesium silicide, manganese silicide, and iron silicide. The thermoelectric conversion thin film forming composition can be formed on a flexible substrate which is a plastic film or paper.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a composition for forming a thermoelectric conversion thin film capable of synthesizing a thermoelectric conversion thin film at a low temperature, and a method for producing a thermoelectric conversion thin film using the composition for forming a thermoelectric conversion thin film.

  The thermoelectric conversion element has a power generation function based on the Seebeck effect. The power generation function is obtained by causing a temperature difference between both ends of the thermoelectric conversion element. The structure of the thermoelectric conversion element is such that, for example, P-type thermoelectric conversion elements and N-type thermoelectric conversion elements are alternately connected in series between two electrode plates.

  Thermoelectric conversion elements are required to have improved output density and energy conversion efficiency, and are required to improve the heat resistance of the elements because they generate electricity due to the temperature difference between the two ends of the element. Since bismuth-tellurium-based thermoelectric conversion elements are limited to a low temperature of 300 ° C. or less, a magnesium silicide-based thermoelectric conversion element that can operate at higher temperatures than bismuth-tellurium-based thermoelectric conversion elements is proposed. (Patent Documents 1 and 2).

  The magnesium silicide-based thermoelectric conversion elements disclosed in Patent Documents 1 and 2 are prepared by preparing a magnesium silicide-based powder and sintering the element. Examples of the pressure sintering method for sintering while applying pressure include a hot press sintering method in which a raw material powder is pressed with a punch, an electric current pressure sintering method, and a discharge plasma sintering method.

  The hot press sintering method is a method in which a raw material powder is mainly filled in a graphite mold and heated while being mechanically uniaxially pressed by a punch. The raw powder is heated by heating a graphitic mold with a heater or the like. This is a method of sintering while heating.

  The electrification and pressure sintering method is mainly used to energize the raw material powder between punches by filling the sintering powder made of graphite with the raw material powder and passing a current through the punch that becomes an electrode while mechanically uniaxially pressing with a punch. In the sintering method, the raw material powder is heated by Joule heating of the raw material powder.

  Spark plasma sintering (SPS) is a form of current-pressure sintering. In the spark plasma sintering method, by performing pulse energization, spark discharge occurs at the beginning of energization, resulting in the purification and activation effect of the powder particle surface, promoting the sintering of the raw material powder,・ In the second half, Joule heating and thermal diffusion by electromagnetic energy and electric field diffusion effect promote the progress of densification.

  In these hot press sintering method, electric pressure sintering method, and discharge plasma sintering method, a sintered body having a high density ratio is obtained, and a thermoelectric conversion element having a power density and energy conversion efficiency close to theoretical values is obtained.

  By the way, a thermoelectric conversion element that can directly convert waste heat from equipment or facilities or heat energy such as body temperature into electric power is a familiar energy conversion element, and is expected to spread more widely. If a thermoelectric conversion thin film with a thin thermoelectric conversion material can be formed on a flexible substrate such as a plastic film or paper, the thermoelectric conversion element can be installed without being constrained by the shape of the installation location, and mass diffusion is also possible. It becomes possible.

JP 2000-054009 A JP 2005-133202 A

  However, in the above-described technology, since thermoelectric conversion particles are produced by sintering under pressure at high temperature, it becomes difficult to form a thermoelectric conversion thin film on a flexible substrate. It becomes an obstacle.

  The present invention has been made in view of such problems, and is a composition for forming a thermoelectric conversion thin film capable of synthesizing a thermoelectric conversion thin film at a low temperature, and a thermoelectric conversion thin film using the composition for forming a thermoelectric conversion thin film. An object is to provide a manufacturing method.

  The composition for forming a thermoelectric conversion thin film according to the present invention includes thermoelectric conversion particles and a copper formate amine complex formed by coordinating a primary amine to copper formate.

  According to the present invention, since the thermoelectric conversion thin film can be synthesized at a low temperature, it is possible to form the thermoelectric conversion thin film on the flexible substrate, and mass diffusion of the thermoelectric conversion elements becomes possible.

It is a graph showing changes in the Seebeck coefficient by a molar ratio of mg 2 _Si. It is a diagram showing changes in power factor due to the molar ratio of mg 2 _Si. It is a figure which shows the change of the output factor by a temperature increase rate.

Hereinafter, embodiments of the present invention will be specifically described with reference to the accompanying drawings. However, the embodiments are for facilitating understanding of the principle of the present invention, and the scope of the present invention is as follows. The present invention is not limited to the embodiments, and other embodiments in which those skilled in the art appropriately replace the configurations of the following embodiments are also included in the scope of the present invention.
[Composition for forming a thermoelectric conversion thin film]
The composition for forming a thermoelectric conversion thin film according to the present invention includes thermoelectric conversion particles and a copper formate amine complex formed by coordination of a primary amine with copper formate. By using a copper formate complex obtained by coordinating a primary amine to copper formate, the composition for forming a conductive film of the present invention can be sintered at a relatively low temperature, and the copper formate amine during sintering. Cu produced by reduction of Cu ²⁺ , the central metal of the complex, covers the thermoelectric conversion particles and functions as a conductive path.

Thermoelectric conversion particles are particles made of a thermoelectric conversion material that is a metal-based semiconductor thermoelectric conversion material, and there are no particular limitations on the thermoelectric conversion material, but silicide-based materials, Heusler-based materials, half-Heusler-based materials, skutterudite-based materials It is preferable to use a metal-based semiconductor thermoelectric conversion material such as magnesium silicide (for example, Mg ₂ Si), manganese silicide (for example, MnSi _1.7 ), and iron silicide (for example, FeSi ₂ ). Is more preferable, and among these, magnesium silicide rich in reserves is most preferable. When the particle size of the thermoelectric conversion particle increases, the specific surface area decreases, and the area of the contact surface between the particles decreases, which may hinder the formation of the conductive path described above. Therefore, the average particle diameter of the thermoelectric conversion particles is preferably 20 μm or less. Magnesium silicide is a mixed powder in which a dopant element such as Mn, Al, Sn, Zn, or Sb that exhibits N-type semiconductor characteristics, or a dopant element powder such as Ag or Cu that exhibits P-type semiconductor characteristics is added. It is also possible to use it.

  A copper formate copper complex formed by coordinating a primary amine to copper formate can be synthesized by mixing copper formate and a primary amine.

  Copper formate and primary amine may be mixed as they are, or may be mixed as an aqueous solution, an organic solvent solution or an organic solvent suspension. The mixing of copper formate and primary amine is preferably performed using a suitable stirrer or mixer at a temperature of about 0 to 100 ° C.

  The molar equivalent ratio of primary amine to copper formate is preferably 1: 1-4. The primary amine not only coordinates to copper formate to form a copper formate amine complex, but can also be contained as a solvent for mixing the thermoelectric conversion particles and the copper formate copper complex.

In the formic acid copper amine complex, it is preferable that formate anion and primary amine each coordinate two molecules each to Cu ²⁺ which is a central metal. The two primary amines may be of the same type or different types.

In the composition for forming a thermoelectric conversion thin film, the molar equivalent ratio of the thermoelectric conversion particles to copper formate is preferably 1: 0.3 to 0.6.
When the ratio of thermoelectric conversion particles to copper formate is less than 1: 0.3, Cu may be generated excessively and Cu may be short-circuited to form a conductive path appropriately. On the other hand, when the ratio of the thermoelectric conversion particles to copper formate is larger than 1: 0.6, there may be a case where a small amount of Cu is generated and a conductive path connecting the thermoelectric conversion particles is not properly formed.

Copper formate can be a compound containing formate ions and copper ions. Examples of the copper compound having formate ion include copper formate (II), basic copper formate (II) (for example, Cu ₃ (HCOO) ₂ (OH) ₄ , Cu ₂ (HCOO) (OH) ₃ , Cu ( HCOO) (OH), etc.), copper formate bisurea dihydrate, and the like, which may be generally distributed or prepared by a known method. Among these, copper (II) formate is preferable from the viewpoint of industrial availability. Copper (II) formate is usually distributed as a hydrate or an anhydride, and any of them may be used. However, the stability of the composition for forming a thermoelectric conversion thin film is further improved, and the conductivity is further improved. From the viewpoint of improving, copper (II) formate with a low water content is preferable, and copper (II) formate anhydride is more preferable.

  The primary amine is not particularly limited, and examples thereof include a monoalkylamine in which one or more hydrogen atoms of an alkyl group may be substituted with a substituent, and one or more hydrogen atoms in an aryl group. A monoarylamine optionally substituted with a substituent, a mono (heteroaryl) amine optionally substituted with one or more hydrogen atoms of a heteroaryl group, and one or more alkylene or arylene groups And diamines in which the hydrogen atom may be substituted with a substituent.

  The alkyl group constituting the monoalkylamine may be a linear, branched, or cyclic alkyl group, a linear alkyl group having 1 to 19 carbon atoms, or a branched alkyl group having 3 to 19 carbon atoms. Or a cyclic alkyl group having 3 to 6 carbon atoms is preferred.

  Examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. Group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl Group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 1 -Ethyl-1-methylpropyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methyl Hexyl group, 5-methylhexyl group, 1,1-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 4 , 4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 4-ethylpentyl group, 2,2,3-trimethylbutyl group, 1-propylbutyl group, n-octyl Group, isooctyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 5-ethylhexyl group, 1,1-dimethylhexyl group, 2,2-dimethylhexyl group, 3,3-dimethyl group Ruhexyl, 4,4-dimethylhexyl, 5,5-dimethylhexyl, 1-propylpentyl, 2-propylpentyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl Group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and icosyl group.

  Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, an isobornyl group, a 1-adamantyl group, and a 2-adamantyl group. Group and tricyclodecyl group can be exemplified.

  Specific examples of preferable monoalkylamines include n-propylamine, 2-ethylhexylamine, tert-butylamine, n-octadecylamine (stearylamine), and cyclohexylamine.

  The aryl group constituting the monoarylamine is preferably a phenyl group, a 1-naphthyl group or a 2-naphthyl group.

  Of the primary amines mentioned above, octylamine is preferred. Octylamine is an alkylamine having 8 carbon atoms and may be linear or branched. As such octylamine, those generally distributed can be appropriately used. For example, normal octylamine; tert-octylamine; 2-, 3-, 4-octaneamine; 2-, 3-, 4 There are numerous isomers including-, 5-, 6-methylheptylamine; 2-, 3-ethylhexylamine. Among these, the octylamine according to the present invention is not particularly limited, but normal octylamine is preferable from the viewpoint of industrial availability.

  The composition for forming a thermoelectric conversion thin film of the present invention is an arbitrary composition such as an anticorrosive, a solvent, a thickener, a surfactant, an electric conduction site smoothing agent, and a surface tension adjuster as long as the effects of the present invention are not impaired. An additive may be further contained. As these additives, those generally used according to the purpose can be appropriately used, and are not particularly limited.

  The solvent is not particularly limited as long as it does not react with each component in the composition for forming a thermoelectric conversion thin film of the present invention, and examples thereof include alcohols, ethers, esters, aliphatic hydrocarbons, and aromatics. 1 type (s) or 2 or more types selected from the group which consists of group hydrocarbons are mentioned. Examples of alcohols include hexanol, heptanol, octanol, cyclohexanol, benzyl alcohol, and terpineol. Examples of ethers include diethyl ether, diisobutyl ether, dibutyl ether, methyl-tert-butyl ether, methyl cyclohexyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofuran, tetrahydropyran, 1 , 4-dioxane and the like. Examples of the esters include methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, and γ-butyrolactone. Examples of the aliphatic hydrocarbon include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, cyclohexane, decalin and the like. Examples of aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, n-propylbenzene, i-propylbenzene, n-butylbenzene, mesitylene, chlorobenzene, dichlorobenzene, and the like.

  Examples of the electrical conduction site leveling agent include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl. Ether, tetraethylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, pentaethylene glycol dimethyl ether, etc. Oxygen compounds, and the like, may be used in combination of two or more be used one of these singly.

The surface tension adjusting agent is not particularly limited as long as it does not react with each component in the composition for forming a thermoelectric conversion thin film of the present invention, and examples thereof include alcohols, glycols, ethers, esters, carbonization. Examples thereof include organic solvents such as one selected from the group consisting of hydrogens and aromatic hydrocarbons, or a mixture of two or more compatible types. Specifically, as alcohols, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, sec-butyl alcohol, pentanol, hexanol, heptanol, octanol, cyclohexanol , Benzyl alcohol, terpineol, etc., and glycols include ethylene glycol, propylene glycol, butylene glycol, pentanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, etc., and ethers include Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol Examples thereof include diethyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, and the esters include methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, propion Examples of hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, and cyclohexane. Decalin and the like, and examples of the aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, n-propylbenzene, i-propylbenzene, n-butylbenzene, mesitylene, chlorobenzene, dichlorobenzene and the like.
[Thermoelectric conversion element]
Below, the thermoelectric conversion element of this invention is demonstrated.

  The thermoelectric conversion element of this invention is a thermoelectric conversion element which has a base material, a pair of electrodes, and the thermoelectric conversion layer formed with the composition for thermoelectric conversion thin film formation of this invention mentioned above.

  A base material is not specifically limited, A well-known base material can be used suitably, for example, flexible substrates, such as a plastic film and paper, resin, glass, a silicon-type semiconductor, a compound semiconductor, a metal, a metal oxide, metal nitride Wood, and the like; and composite materials thereof. One of these may be used alone, or two or more may be used in combination.

  Specifically, low density polyethylene resin, high density polyethylene resin, ABS resin (acrylonitrile-butadiene-styrene copolymer synthetic resin), acrylic resin, styrene resin, vinyl chloride resin, polyester resin (polyethylene terephthalate), polyacetal resin, polysulfone Resin, polyetherimide resin, polyetherketone resin, cellulose derivatives and other resin base materials; uncoated printing paper, finely coated printing paper, coated printing paper (art paper, coated paper), special printing paper, copy paper (PPC paper), unbleached wrapping paper (both kraft paper for heavy bags, both kraft paper), bleached wrapping paper (bleached kraft paper, pure white roll paper), coated paper, chip ball, corrugated cardboard and other paper base materials; Glass substrates such as soda glass, borosilicate glass, silica glass, and quartz glass; Amorph Silicon-based semiconductors such as silicon and polysilicon; compound semiconductors such as CdS, CdTe, and GaAs; metal substrates such as copper plates, iron plates, and aluminum plates; alumina, sapphire, zirconia, titania, yttrium oxide, indium oxide, ITO (indium) Metals such as tin oxide), IZO (indium zinc oxide), Nesa (tin oxide), ATO (antimony-doped tin oxide), fluorine-doped tin oxide, zinc oxide, AZO (aluminum-doped zinc oxide), gallium-doped zinc oxide Other inorganic base materials such as oxide base materials, aluminum nitride, silicon carbide; paper-phenolic resin, paper-epoxy resin, paper-polyester resin paper-resin composite, glass cloth-epoxy resin, glass cloth-polyimide Examples thereof include composite base materials such as resin, glass cloth-fluorine resin and other glass-resin composites.In the present invention, since heat treatment can be performed at a low temperature, it is preferable to select a flexible substrate such as the above-described plastic film or paper as the base material, thereby making the thermoelectric conversion element into the shape of the installation location. It can be installed without restrictions, and mass dissemination is also possible. Although the thickness of a base material can be suitably selected according to the intended purpose, For example, when a plastic film is used, it is possible to set it as 5-500 micrometers.

  The electrode of the thermoelectric conversion element is not particularly limited. For example, a conductive paste in which conductive fine particles such as silver, copper, and aluminum are dispersed, a transparent electrode such as ITO and ZnO, and a metal electrode such as silver, copper, gold, and aluminum , Carbon materials such as CNT and graphene; organic materials such as PEDOT / PSS.

  The thermoelectric conversion layer of the thermoelectric conversion element is not particularly limited as long as it is formed by the composition for forming a thermoelectric conversion thin film of the present invention.

Although the formation method of a thermoelectric conversion layer is not specifically limited, The thermoelectric conversion layer can be formed by apply | coating the composition of this invention on a base material, and forming into a film. A known method can be appropriately used as the film forming method, and is not particularly limited. For example, a squeegee method, a screen printing method, a dip coating method, a spray coating method, a spin coating method, an ink jet method, a coating method using a dispenser, etc. Is mentioned. The shape of application may be planar or dot-shaped, and is not particularly limited. As a coating amount which apply | coats this composition to a base material, it can apply | coat so that the film thickness after drying may be in the range of 0.01-5000 micrometers, Preferably it is the range of 0.1-1000 micrometers.
[Method for producing thermoelectric conversion thin film]
The manufacturing method of the thermoelectric conversion thin film concerning this invention provides the composition for thermoelectric conversion thin film formation concerning this invention on a base material, and the coating-film formation process which forms a coating film, and 120 ~ A thermoelectric conversion thin film forming step of performing a low-temperature heat treatment at 200 ° C. to form a thermoelectric conversion thin film.

  The base material is not particularly limited as described above, but a flexible substrate such as a plastic film or paper can be selected. The method for forming the coating film is not particularly limited as described above, and for example, a squeegee method, a spin coating method, a blade coating method, or the like can be used.

  Next, low-temperature heat treatment at 120 to 200 ° C. is performed on the coating film. The method of the low-temperature heat treatment is not particularly limited, and for example, a hot air dryer or the like can be used. In addition, it is desirable that the boiling point of the primary amine coordinated with copper formate is 15 to 35 ° C., preferably 20 ° C. higher than the heating temperature at the time of heat treatment. The heat treatment is preferably performed in an atmosphere of an inert gas such as nitrogen or argon. Mg and Si contained in the thermoelectric conversion particles are easily oxidizable elements. When an oxidizing component is contained in the atmosphere, these elements are easily oxidized and the energy conversion efficiency is lowered. Use. The thickness of the formed thermoelectric conversion thin film is, for example, 0.1 μm to 1000 μm, and preferably 1 μm to 300 μm.

The sample was copper formate and octylamine, Mg ₂ Si having an average particle size of 5.7 μm was used as thermoelectric conversion particles, and the mixing molar ratio was 1: 3: 0.3 to 0.6. After mixing copper formate and octylamine, a composition for forming a thermoelectric conversion thin film was obtained by adding and mixing Mg ₂ Si particles. Next, a 15 × 40 mm frame (height 0.2 mm) is produced on the glass (APS coat) substrate surface using a masking tape, and the obtained conductive material precursor composition is squeegeeed in the frame. Applied. The film thickness was 200 μm. Thereafter, heat treatment was performed in nitrogen using a hot plate. The nitrogen flow rate during the heat treatment was 4 L / min, and the heat treatment was performed by raising the temperature from room temperature to 180 ° C. at 0.5 to 5 ° C./min, and then holding at that temperature for 20 minutes.

  The Seebeck coefficient of the synthesized film was measured using a Seebeck tester. The Seebeck tester uses two thermocouples, contacts the two thermocouples with a sample, and measures the temperature difference and electromotive force generated between the two terminals. The voltage when both ends were 23 ° C. and 27 ° C. was measured to determine the Seebeck coefficient α. The surface resistivity of the film was measured by the four probe method, and the electric conductivity r was obtained from the film thickness measured with an optical microscope. In the measurement of thin film electrical resistance, in the case of the two-terminal method, a voltage drop due to contact resistance occurs between the electrode and the sample surface. In the case of the four-terminal method, the current application terminal and the voltage measurement terminal must be separated. Thus, the resistance is measured by eliminating the contact resistance. The output factor P was calculated by the following formula (1).

P = α ² / r (1)

The Seebeck coefficient of the test piece produced by changing the molar ratio of Mg ₂ Si from 0.3 to 0.6 and setting the heating rate to 5 ° C./min is shown in FIG. The Seebeck coefficient increased as the molar ratio of Mg ₂ Si increased, and increased particularly from 0.3 to 0.35. From these results, we succeeded in synthesizing thermoelectric conversion thin films at low temperature.

The electrical conductivity of the test piece shown in FIG. 1 is measured, and the calculation result of the output factor is shown in FIG. The output factor was a maximum at an almost constant value when the molar ratio of Mg ₂ Si was 0.35 to 0.4. This is because there is little change in electrical conductivity where the molar ratio is low, and conversely, the Seebeck coefficient has changed greatly from 0.3 to 0.35. On the other hand, when the molar ratio is high, the electrical conductivity greatly decreases as the molar ratio increases.

Next, FIG. 3 shows an output factor of a test piece manufactured by changing the molar ratio of Mg ₂ Si to 0.4 and changing the heating rate from 0.5 to 5 ° C./min. The output factor reached its maximum at 1 ° C / min, then decreased, and decreased at 3 ° C / min, then increased. From the above results, the highest output factor was shown when the molar ratio of Mg ₂ Si was 0.4 and the heating rate was 1 ° C./min.

  It can utilize for manufacture of a thermoelectric conversion element.

Claims (9)

  A composition for forming a thermoelectric conversion thin film, comprising thermoelectric conversion particles and a copper formate copper complex formed by coordinating a primary amine to copper formate.   The composition for forming a thermoelectric conversion thin film according to claim 1, wherein the molar equivalent ratio of the thermoelectric conversion particles to copper formate is 1: 0.3 to 0.6.   The composition for forming a thermoelectric conversion thin film according to claim 1, wherein the thermoelectric conversion particles are made of a silicide material containing at least one of magnesium silicide, manganese silicide, and iron silicide.   The composition for forming a thermoelectric conversion thin film according to claim 1, wherein the molar equivalent ratio of the primary amine to the copper formate is from 1: 1 to 4.   The composition for forming a thermoelectric conversion thin film according to claim 1, wherein the primary amine is a primary amine having 1 to 19 carbon atoms. A thermoelectric conversion element having a substrate, a pair of electrodes, and a thermoelectric conversion layer,
The thermoelectric conversion element in which the said thermoelectric conversion layer was formed with the composition for thermoelectric conversion thin film formation of Claim 1. Applying the composition for forming a thermoelectric conversion thin film according to claim 1 on a substrate to form a coating film,
A method for producing a thermoelectric conversion thin film comprising: a thermoelectric conversion thin film forming step of performing a low-temperature heat treatment at 120 to 200 ° C. on the coating film to form a thermoelectric conversion thin film.   The said base material is a flexible substrate, The manufacturing method of the thermoelectric conversion thin film of Claim 7 characterized by the above-mentioned.   9. The method of manufacturing a thermoelectric conversion thin film according to claim 8, wherein the flexible substrate is a plastic film or paper.

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