JP5256560B2 - n-type zinc antimony compound thermoelectric semiconductor - Google Patents

Description

The present invention relates to a thermoelectric semiconductor material that directly converts heat into electric power, and more particularly to an n-type zinc antimony compound thermoelectric semiconductor.

  Thermoelectric semiconductors that convert thermal energy into electrical energy are attracting attention as energy conversion materials.

  FIG. 5 is an explanatory diagram schematically illustrating the configuration and operating principle of a thermo-electric conversion device (thermoelectric power generation module) using a conventional thermoelectric semiconductor.

  This thermoelectric conversion device (thermoelectric power generation module) 101 has a structure in which a p-type thermoelectric semiconductor 102 and an n-type thermoelectric semiconductor 103 are sandwiched between a high temperature side electrode 105 and a low temperature side electrode 106.

  The p-type thermoelectric semiconductor 102 and the n-type thermoelectric semiconductor 103 are bonded to the high temperature side electrode 105 through the bonding portion 107.

  Further, the p-type thermoelectric semiconductor 102 and the n-type thermoelectric chip 103 are joined to the low temperature side electrode 106 through the joint portion 108.

  In the thermo-electric direct conversion device (thermoelectric power generation module) 101, when heat H 1 is supplied to the high temperature side electrode 105, the heat H 1 is transmitted to the p-type thermoelectric semiconductor 102 and the n-type thermoelectric semiconductor 103 via the joint 107. Then, along the heat flow H 2 passing through the p-type thermoelectric semiconductor 102 and the n-type thermoelectric semiconductor 103, holes 110 that are semiconductor carriers are formed inside the p-type thermoelectric semiconductor 102, and semiconductors are formed inside the n-type thermoelectric semiconductor 103. The electrons 111 serving as carriers move toward the low-temperature side electrode 106 bonded to the p-type thermoelectric semiconductor 102 or the n-type thermoelectric semiconductor 103 via the bonding portion 108.

  On the other hand, the heat flow Hf that passes through the semiconductor chips 102 and 103 becomes heat H3 that passes through the low temperature side electrode 106 and is released from the low temperature side electrode.

  When an appropriate electrical load 113 is connected to the outside of the thermo-electric direct conversion device (thermoelectric power generation module) 101 via the current extraction means 115, the movement of the semiconductor carrier As the flow I, it can be taken out of the thermo-electric direct conversion device (thermoelectric power generation module) 101 and used.

  That is, the thermoelectric generation of the thermo-electric conversion device (thermoelectric generation module) 101 supplies heat to one side (high temperature side electrode 105) of the thermo-electric conversion device (thermoelectric generation module) 101, and from the other low temperature end. This is a power generation system that generates power by releasing heat and extracting a part of the heat returned to the thermoelectric semiconductor as electricity.

  That is, power generation is performed by generating an electromotive force by diffusing carriers generated in the high temperature part (holes in the p-type and electrons in the n-type) to the low temperature side. Thermoelectric power generation modules use p-type materials and n-type materials with different carriers. The power generation conversion efficiency (energy conversion efficiency) η is determined by the following equation indicating the performance of each material.

Here, α _p , ρ _p , and κ _p represent the Seebeck coefficient (V / k), the specific resistance (Ωm), and the thermal conductivity (W / mK) indicating the electromotive force per 1 K temperature difference of the p-type thermoelectric semiconductor. α _n , ρ _n , and κ _n represent a Seebeck coefficient (V / K), a specific resistance (Ωm), and a thermal conductivity (W / mk) indicating an electromotive force per 1 K temperature difference of the n-type thermoelectric semiconductor. Each _{T h, T c, R L} , R e is hot end temperature (K), the cold end temperature (K), indicating the external load resistor (Omega), the internal resistance (Omega).

Z is a material figure of merit (K ⁻¹ ). The higher the value of Z, the higher the energy conversion efficiency η of thermoelectric power generation. Therefore, if the high temperature end temperature and the low temperature end temperature are determined, the energy conversion efficiency η of the thermoelectric power generation is determined by the figure of merit Z of this material.
Here, zinc antimony compounds (Zn—Sb, more specifically, ZnSb, β-Zn ₄ Sb ₃ ) are known as one of thermoelectric conversion semiconductor materials.

  FIG. 6 is a correlation diagram showing the relationship between thermoelectric figure of merit and temperature of various materials of p-type thermoelectric semiconductors.

  The zinc antimony compound (Zn—Sb) shows a high figure of merit Z in comparison with other materials between 500K and 700K, indicating that it has a high potential as a power generation material.

  By the way, it is known that an impurity element is added to the p-type control of the zinc antimony compound (Zn—Sb).

Specifically, it is known to add an impurity element such as Pb, Ga, Sn, Au, In, Te, Ag, and Al for the production of the p-type zinc antimony compound (Zn—Sb). (See Non-Patent Document 1, Patent Documents 1 and 2.)
By the way, it has been reported that the n-type control of the zinc antimony compound (Zn—Sb) can be obtained by adding Te.

M. Telks, “Thermoelectric couple”, US Patent 2229482, Jan. 21, 1941 M. Telks, “Thermoelectric alloys”, US Patent 2366881, Jan. 9, 1945 JP-A-2005-277120

N. L. Kostur and V. I. Psarev, “Electrical properties of doped single crystals of ZnSb”, Soviet Physics Journal, Izvestiya VUZ. Fizika, vol.10, No.2, pp.39-43, 1967 A. Abou-Zeid and G. Scheider, “Te-Doped n-Type ZnSb”, phys. Stat. Sol. (A) 6, K101 (1971)

  However, since Te is also used as an impurity in the production of the p-type zinc antimony compound (Zn—Sb), it is said that it is obtained by adding Te, an n-type zinc antimony compound ( Zn—Sb) has poor reproducibility and has not been put into practical use (see Non-Patent Document 2).

  Therefore, using a p-type zinc antimony compound (Zn-Sb) having high performance as a p-type thermoelectric semiconductor and a p-type zinc antimony compound (Zn-Sb), a pn type as shown in FIG. It is difficult to put the thermo-electric conversion device (thermoelectric power generation module) 101 having a pair into a practical use as a thermoelectric power generation system.

  The present invention has been made to solve the above problems, and provides an n-type zinc antimony compound to which an n-type impurity of a zinc antimony compound (Zn-Sb) replacing Te is added. It is aimed.

As a result of diligent efforts in researching n-type impurities of zinc antimony compounds (Zn-Sb) replacing Te for many years, the present inventors have melted zinc antimony compounds as impurities in zinc antimony compounds (Zn-Sb). Nitrides such as Zn ₃ N ₂ , GaN and InN can be added at 0.05 at. % To 10.00 at. It has been found that an n-type semiconductor is obtained by adding in the range of%.

That is, the n-type zinc antimony compound thermoelectric semiconductor according to claim 1, zinc antimony compounds which converts heat directly into electricity and nitride were added, an n-type zinc antimony compound thermoelectric semiconductor, nitride The material is at least one selected from the group consisting of Zn ₃ N ₂ , GaN and InN.

Here, the term “zinc antimony compound” used in the present specification means, for example, ZnSb, β-Zn ₄ Sb ₃ .

N-type zinc antimony compound thermoelectric semiconductor according to claim 2, the n-type zinc antimony compound thermoelectric semiconductor according to claim 1, a nitride, 0.05 at. % Or more and 10.00 at. It added in the range below%.

Here, at least one nitride selected from the group consisting of Zn ₃ N ₂ , GaN and InN, which can be melted into the zinc antimony compound, is added to the zinc antimony compound at 0.05 at. % Or more and 10.00 at. % Or less, the addition of at least one nitride selected from the group consisting of Zn ₃ N ₂ , GaN and InN to 0.05 at. It is not preferable to add an amount of less than or equal to% because the effect of adding impurities cannot be obtained. On the other hand, at least one nitride selected from the group consisting of Zn ₃ N ₂ , GaN and InN is 10.00 at. If more than% is added, the number of carriers generated due to the added impurities increases too much, and the Seebeck coefficient is lowered and the thermoelectric performance Z is adversely affected.

The n-type zinc antimony compound thermoelectric semiconductor according to claim 3 is an n-type zinc antimony compound thermoelectric semiconductor according to claim 1 or 2, wherein the zinc antimony compound is ZnSb or β-Zn ₄ Sb _3. It is.

  According to the present invention, an n-type zinc antimony compound (Zn-Sb) can be produced by impurities other than Te. Therefore, a p-type zinc antimony compound (Zn-Sb) and a p-type zinc antimony compound ( As a result, it is possible to modularize a pn type thermoelectric power generation system using Zn—Sb). As a result, electric energy can be efficiently obtained from heat.

It is a flowchart which shows roughly the process of manufacturing an example of the n-type zinc antimony type compound thermoelectric semiconductor which concerns on this invention. It is a flowchart which shows roughly the process of manufacturing another example of the n-type zinc antimony type compound thermoelectric semiconductor which concerns on this invention. It is a flowchart which shows roughly the process of manufacturing another example of the n-type zinc antimony type compound thermoelectric semiconductor which concerns on this invention. It is a flowchart which shows roughly the process of manufacturing another example of the n-type zinc antimony type compound thermoelectric semiconductor which concerns on this invention. It is explanatory drawing which shows typically the structure and operating principle of the thermo-electric conversion apparatus (thermoelectric power generation module) using the conventional thermoelectric semiconductor. It is a correlation diagram which shows the relationship between the thermoelectric figure of merit of various materials of a p-type thermoelectric semiconductor, and temperature.

  Hereinafter, an n-type zinc antimony compound thermoelectric semiconductor and a method for producing the same according to the present invention will be exemplarily described with reference to the drawings.

  FIG. 1 is a flowchart schematically showing a process for manufacturing an example of an n-type zinc antimony-based compound thermoelectric semiconductor according to the present invention.

First, as shown in step S1 in FIG. 1, the raw material is in accordance with the stoichiometric composition of ZnSb, 50 at. % Zn-50 at. % Sb and ZnSb is further added with Zn ₃ N ₂ , GaN or InN at 0.05 at. % Or more and 10.00 at. % So as to be in the range of not more than%.

In addition, when Zn ₃ N ₂ is added, the whole is 50 at. % Zn-50 at. The addition amount (x) of N was set to Zn _1-x Sb + xZn ₃ N ₂ so that only N can be added to% Sb.

As Comparative Example 1, according to the stoichiometric composition of ZnSb without adding Zn ₃ N ₂ , GaN, or InN, 50 at. % Zn-50 at. What weighed so that it might become% Sb was prepared.

The purity of each of Zn, Sb, Zn ₃ N _2, GaN, and InN was 99.99% or higher (4N or higher).

In addition, each of Zn, Sb, Zn ₃ N ₂ , GaN, and InN used as a raw material had a particle size in the range of 32 μm to 3 m.

This is because when the particle sizes of Zn, Sb, Zn ₃ N ₂ , GaN and InN used as raw materials are less than 32 μm, the surfaces of the raw materials of Zn, Sb, Zn ₃ N ₂ , GaN and InN are oxidized. This is because it has an adverse effect. On the other hand, when the particle diameters of Zn, Sb, Zn ₃ N ₂ , GaN, and InN used as raw materials exceed 3 mm, it is difficult to put these materials in a quartz tube that dissolves them. Because.

  Next, as shown in step S2 in FIG. 1, the weighed raw materials were put in a quartz tube and vacuum-sealed.

  Next, after dissolving at 650 ° C. for 5 hours (h), heat treatment (450 ° C. for 100 hours (h)) was performed to complete the peritectic reaction.

  Next, in order to determine whether the obtained sample was p-type or n-type, the Seebeck coefficient indicating the electromotive force per 1 K of temperature difference was measured.

  Here, the case where the Seebeck coefficient is positive is p-type, and the case where it is negative is n-type.

In the measurement of the Seebeck coefficient, heaters are attached to both ends of the sample near room temperature, and the electromotive force V ₀ when the temperature difference T ₀ between both ends becomes 0K or approximately 0K is measured as the background. The electromotive force V when 3K or approximately 3K was applied as the temperature difference T was measured and calculated from the following equation.

In addition, the Seebeck coefficient of the obtained zinc antimony compound was measured using a product name / model number: “Retestest 8300” (manufactured by Toyo Technica Co., Ltd.).

  Table 1 shows the composition and Seebeck coefficient of the obtained zinc antimony compound.

As shown in Table 1, an n-type zinc antimony compound (ZnSb) having a negative Seebeck coefficient could be obtained.

In addition, as a result of experimentation with various addition amounts of at least one nitride selected from the group consisting of Zn ₃ N ₂ , GaN and InN with respect to zinc antimony compound (ZnSb), as a result of experiment, zinc antimony compound (ZnSb) with at least one nitride selected from the group consisting of Zn ₃ N ₂ , GaN, and InN at 0.05 at. % Is not preferable because the effect of adding impurities cannot be obtained. On the other hand, at least one nitride selected from the group consisting of Zn ₃ N ₂ , GaN and InN is added at 10.00 at. It has been clarified that the addition of more than% exceeds the number of carriers generated by the added impurities, the Seebeck coefficient is lowered, and the thermoelectric performance Z is adversely affected. .

  FIG. 2 is a flowchart schematically showing a process for manufacturing another example of the n-type zinc antimony compound thermoelectric semiconductor according to the present invention.

First, as shown in step S11 in FIG. 2, the raw material is 57.14 at. So as to follow the stoichiometric composition of Zn ₄ Sb ₃ . % Zn-42.86 at. % Sb, and Zn ₃ N ₂ , GaN or InN is added to Zn ₄ Sb ₃ at 0.51 at. % Or more and 10.00 at. %.

Also, when adding _Zn 3 _{N 2,} whole, 57.14At. % Zn-42.86 at. The amount of addition (x) of N was set to Zn _4-x Sb ₃ + xZn ₃ N ₂ so that only N can be added to% Sb. As Comparative Example 2, Zn ₃ N ₂ , GaN, and InN were added. No addition, according to ZnSb stoichiometric composition, 50 at. % Zn-50 at. What weighed so that it might become% Sb was prepared.

  The purity of each material was 99.99% or higher (4N or higher).

In addition, each of Zn, Sb, Zn ₃ N ₂ , GaN, and InN used as a raw material had a particle size in the range of 32 μm to 3 m.

This is because when the particle sizes of Zn, Sb, Zn ₃ N ₂ , GaN and InN used as raw materials are less than 32 μm, the surfaces of the raw materials of Zn, Sb, Zn ₃ N ₂ , GaN and InN are oxidized. This is because it has an adverse effect. On the other hand, when the particle diameters of Zn, Sb, Zn ₃ N ₂ , GaN, and InN used as raw materials exceed 3 mm, it is difficult to put these materials in a quartz tube that dissolves them. Because.

Also, when adding _Zn 3 _{N 2,} whole, 57.14At. % Zn-42.86 at. The addition amount (x) of N was set to Zn _4−x Sb + xZn ₃ N ₂ so that only N can be added to% Sb.

  Next, as shown in step S12 in FIG. 2, the weighed raw materials were put in a quartz tube and vacuum sealed.

  Next, after dissolving at 650 ° C. for 5 hours (h), heat treatment (450 ° C. for 100 hours (h) and then 400 ° C. for 100 hours (h)) is performed to complete the peritectic reaction. did.

  next. In order to determine whether the obtained sample was p-type or n-type, the Seebeck coefficient indicating the electromotive force per 1 K of temperature difference was measured.

  Here, the case where the Seebeck coefficient is positive is p-type, and the case where it is negative is n-type.

  The Seebeck coefficient of the obtained zinc antimony compound was measured in the same manner as in Example 1 using the product name / model number: “Retestest 8300” (manufactured by Toyo Technica Co., Ltd.).

  Table 2 shows the composition and Seebeck coefficient of the obtained zinc antimony compound.

As a result shown in Table 2, an n-type zinc antimony compound (β-Zn ₄ Sb ₃ ) having a negative Seebeck coefficient could be obtained.

In addition, as a result of an experiment in which the addition amount of at least one nitride selected from the group consisting of Zn ₃ N ₂ , GaN and InN was variously changed with respect to the zinc antimony compound (Zn ₄ Sb ₃ ), With respect to the antimony compound (Zn ₄ Sb ₃ ), at least one nitride selected from the group consisting of Zn ₃ N ₂ , GaN and InN is added at 0.05 at. % Is not preferable because the effect of adding impurities cannot be obtained. On the other hand, at least one nitride selected from the group consisting of Zn ₃ N ₂ , GaN and InN is added at 10.00 at. It has been clarified that the addition of more than% exceeds the number of carriers generated by the added impurities, the Seebeck coefficient is lowered, and the thermoelectric performance Z is adversely affected. .

  FIG. 3 is a flowchart schematically showing a process of manufacturing another example of the n-type zinc antimony compound thermoelectric semiconductor according to the present invention.

  First, as shown in step S21 in FIG. 3, the raw material is set to 50 at. So as to follow the stoichiometric composition of ZnSb. % Zn-50 at. Weighed to be% Sb.

Further, as Comparative Example 3, according to the stoichiometric composition of ZnSb without adding Zn ₃ N ₂ , GaN, or InN, 50 at. % Zn-50 at. What weighed so that it might become% Sb was prepared.

  The purity of each material was 99.99% or higher (4N or higher).

In addition, each of Zn, Sb, Zn ₃ N ₂ , GaN, and InN used as a raw material had a particle size in the range of 32 μm to 3 m.

This is because when the particle sizes of Zn, Sb, Zn ₃ N ₂ , GaN and InN used as raw materials are less than 32 μm, the surfaces of the raw materials of Zn, Sb, Zn ₃ N ₂ , GaN and InN are oxidized. This is because it has an adverse effect. On the other hand, when the particle diameters of Zn, Sb, Zn ₃ N ₂ , GaN, and InN used as raw materials exceed 3 mm, it is difficult to put these materials in a quartz tube that dissolves them. Because.

In addition, when Zn ₃ N ₂ is added, the whole is 50 at. % Zn-50 at. The added amount (x) of N was set to Zn _1-x Sb + xZn ₃ N ₂ so that it could be added by adding only N so as to be% Sb.

  Next, as shown in step S22 in FIG. 3, the weighed raw materials were put in a quartz tube and vacuum-sealed.

  Next, after dissolving at 650 ° C. for 5 hours (h), heat treatment (450 ° C. for 100 hours (h)) was performed to complete the peritectic reaction.

Next, as shown in step S23 in FIG. 3, Zn ₃ N ₂ , GaN, or InN is further added to 0.01 at. % To 4.00 at. %.

Next, in an argon atmosphere, ZnSb and Zn ₃ N ₂ , GaN or InN were put into a pulverization vessel, and pulverized for 30 hours (h) with a planetary ball mill, and mechanical alloying treatment was performed. Silicon nitride ceramic balls were used as the grinding balls. The weight ratio of the pulverized ball, ZnSb, and Zn ₃ N ₂ , GaN, or InN was 20: 1.

Next, in the process shown in Step S23 in FIG. 3, ZnSb and Zn ₃ N ₂ , GaN or InN are put in a pulverization container in an argon atmosphere, and pulverized for 30 hours (h) with a planetary ball mill. The product was classified with a sieve having an opening of 100 μm to obtain a powder (see step S24 in FIG. 3).

  Next, as shown in Step S25 in FIG. 3, the powder obtained by the process shown in Step S23 was hot pressed to obtain a sintered body. The sintered mold was carbon, and hot pressing was performed for 1 hour at a temperature of 400 ° C. and a pressure of 39 MPa.

  next. In order to determine whether the obtained sample was p-type or n-type, the Seebeck coefficient indicating the electromotive force per 1 K of temperature difference was measured.

  Here, the case where the Seebeck coefficient is positive is p-type, and the case where it is negative is n-type.

  The Seebeck coefficient of the obtained zinc antimony compound was measured in the same manner as in Example 1 using the product name / model number: “Retestest 8300” (manufactured by Toyo Technica Co., Ltd.).

  Table 3 shows the composition and Seebeck coefficient of the obtained zinc antimony compound.

  FIG. 4 is a flowchart schematically showing a process for manufacturing another example of the n-type zinc antimony-based compound thermoelectric semiconductor according to the present invention.

First, as shown in step S31 in FIG. 4, the raw material is 57.14 at. So as to follow the stoichiometric composition of Zn ₄ Sb ₃ . % Zn-42.86 at. Weighed to be% Sb.

Further, as Comparative Example 4, according to the Zn ₄ Sb ₃ stoichiometric composition without adding Zn ₃ N ₂ , GaN and InN, 57.14 at. % Zn-42.86 at. What weighed so that it might become% Sb was prepared.

  The purity of each material was 99.99% or higher (4N or higher).

In addition, each of Zn, Sb, Zn ₃ N ₂ , GaN, and InN used as a raw material had a particle size in the range of 32 μm to 3 m.

This is because when the particle sizes of Zn, Sb, Zn ₃ N ₂ , GaN and InN used as raw materials are less than 32 μm, the surfaces of the raw materials of Zn, Sb, Zn ₃ N ₂ , GaN and InN are oxidized. This is because it has an adverse effect. On the other hand, when the particle diameters of Zn, Sb, Zn ₃ N ₂ , GaN, and InN used as raw materials exceed 3 mm, it is difficult to put these materials in a quartz tube that dissolves them. Because.

Also, when adding _Zn 3 _{N 2,} whole, 57.14At. % Zn-42.86 at. The addition amount (x) of N was set to Zn _4−x Sb ₃ + xZn ₃ N ₂ so that only N can be added to% Sb.

  Next, as shown in step S32 in FIG. 4, it was placed in a weighed raw material quartz tube and vacuum-sealed.

Next, after dissolving at 650 ° C. for 5 hours (h), heat treatment (45
100 hours (h) at 0 ° C and then 100 hours (h) at 400 ° C.

Next, in FIG. 4, as shown in step S33, with respect to _Zn 4 Sb ₃ that has been subjected to the heat treatment, _further, the Zn ₃ N 2, GaN or InN, 0.01 at. % To 4.00 at. Weighed so as to be in the range of %%. In an argon atmosphere, Zn ₄ Sb ₃ and Zn ₃ N ₂ , GaN or InN were put into a pulverization vessel, and pulverized with a planetary ball mill for 30 hours (h) to perform mechanical alloying treatment. Silicon nitride ceramic balls were used as the grinding balls. The weight ratio of pulverized balls, Zn ₄ Sb ₃ , Zn ₃ N ₂ , GaN or InN was 20: 1.

In FIG. 4, in the step shown in Step 33, Zn ₄ Sb ₃ and Zn ₃ N ₂ , GaN or InN are put in a pulverization vessel in an argon atmosphere and pulverized for 30 hours (h) by a planetary ball mill. 4, the pulverized product was classified with a sieve having an opening of 100 μm in the step shown in Step 32 to obtain powder (in FIG. 4, refer to Step S34).

  Next, as shown in step S35 in FIG. 4, the powder obtained by the process shown in step S34 was hot pressed to obtain a sintered body. The sintered mold was carbon, and hot pressing was performed for 1 hour at a temperature of 400 ° C. and a pressure of 39 MPa.

  next. In order to determine whether the obtained sample was p-type or n-type, the Seebeck coefficient indicating the electromotive force per 1 K of temperature difference was measured.

  Here, the case where the Seebeck coefficient is positive is p-type, and the case where it is negative is n-type.

  The Seebeck coefficient of the obtained zinc antimony compound was measured in the same manner as in Example 1 using the product name / model number: “Retestest 8300” (manufactured by Toyo Technica Co., Ltd.).

  Table 3 shows the Seebeck coefficient of the obtained zinc antimony compound.

As shown in Table 3, zinc antimony compounds (ZnSb, β-Zn ₄ Sb ₃ ) having a negative Seebeck coefficient could be obtained.

In addition, with respect to the zinc antimony-based compound (ZnSb or Zn ₄ Sb ₃ ), the results of experiments with various amounts of addition of at least one nitride selected from the group consisting of Zn ₃ N ₂ , GaN and InN being varied In addition, at least one nitride selected from the group consisting of Zn ₃ N ₂ , GaN and InN is added to the zinc antimony compound (ZnSb or Zn ₄ Sb ₃ ) at 0.05 at. % Is not preferable because the effect of adding impurities cannot be obtained. On the other hand, at least one nitride selected from the group consisting of Zn ₃ N ₂ , GaN and InN is added at 10.00 at. It has been clarified that the addition of more than% exceeds the number of carriers generated by the added impurities, the Seebeck coefficient is lowered, and the thermoelectric performance Z is adversely affected. .

In addition, according to Example 3, an n-type zinc antimony compound (ZnSb, β-Zn ₄ Sb ₃ ) having a characteristic that the Seebeck coefficient is negative as in the dissolution methods of Examples 1 and 2 is obtained by a mechanical alloying method. It was revealed that

  According to the present invention, it becomes possible to modularize a p-n type thermoelectric power generation system, which can efficiently obtain electric energy from heat and contribute to the creation of a new energy recovery industry.

101 Heat-electricity direct conversion device (thermoelectric power generation module)
102 p-type thermoelectric semiconductor 103 n-type thermoelectric semiconductor 105 high-temperature side electrode 106 low-temperature side electrode 107, 108 junction 110 hole 111 electron 113 electrical load

Claims (3)

An n-type zinc antimony compound thermoelectric semiconductor in which a nitride is added to a zinc antimony compound that directly converts heat into electric power , wherein the nitride is selected from the group of Zn ₃ N ₂ , GaN, and InN An n-type zinc antimony-based compound thermoelectric semiconductor that is at least one type . The nitride is added at 0.05 at. % Or more and 10.00 at. % Were added in the following ranges, n-type zinc antimony compound thermoelectric semiconductor according to claim 1. The n-type zinc antimony compound thermoelectric semiconductor according to claim 1 or 2 , wherein the zinc antimony compound is ZnSb or β-Zn ₄ Sb ₃ .