# Patent

## Title
Thermoelectric conversion material and producing method thereof, and thermoelectric conversion element using the same

## Abstract

Thermoelectric conversion materials, expressed by the following formula: Bi1-xMxCu1-wOa-yQ1yTeb-zQ2z. Here, M is at least one element selected from the group consisting of Ba, Sr, Ca, Mg, Cs, K, Na, Cd, Hg, Sn, Pb, Mn, Ga, In, Tl, As and Sb; Q1 and Q2 are at least one element selected from the group consisting of S, Se, As and Sb; x, y, z, w, a, and b are 0≦x<1, 0<w<1, 0.2<a<4, 0≦y<4, 0.2<b<4, 0≦z<4 and x+y+z>0. These thermoelectric conversion materials may be used for thermoelectric conversion elements, where they may replace thermoelectric conversion materials in common use, or be used along with thermoelectric conversion materials in common use.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. Ser. No. 14/175,513, filed on Feb. 7, 2014, which is a divisional of U.S. Ser. No. 13/531,186, filed on Jun. 22, 2012, now issued as U.S. Pat. No. 8,715,538, which is a continuation of U.S. Ser. No. 12/906,917, filed on Oct. 18, 2010, now issued as U.S. Pat. No. 8,226,843, which is a continuation of International Application No. PCT/KR2008/007041 filed Nov. 28, 2008, which claims priorities to Korean Patent Applications Nos. 10-2008-0085240, 10-2008-0097779 and 10-2008-0111557 filed in Republic of Korea on Aug. 29, 2008, Oct. 6, 2008 and Nov. 11, 2008, respectively, the entire contents of which are incorporated herein by reference.


TECHNICAL FIELD
The present invention provides new thermoelectric conversion material, their method of preparation, and thermoelectric conversion elements by using the same.
BACKGROUND OF THE INVENTION
The thermoelectric conversion element is applied to thermoelectric conversion power generation or thermoelectric conversion cooling. For example, for the thermoelectric conversion power generation, a temperature difference is applied to the thermoelectric conversion element to generate thermoelectromotive force, and then the thermoelectromotive force is used to convert thermal energy into electric energy.
Energy conversion efficiency of the thermoelectric conversion element depends on ZT value that is a performance index of thermoelectric conversion material. ZT value is determined by Seebeck coefficient, electric conductivity and thermal conductivity. In more detail, ZT value is in proportion to electric conductivity and square of Seebeck coefficient and in reverse proportion to thermal conductivity. Thus, in order to enhance the energy conversion efficiency of a thermoelectric conversion element, it is required to develop thermoelectric conversion materials with high Seebeck coefficient, high electric conductivity or low thermal conductivity.
DISCLOSURE
Technical Problem
An object of the present invention is to provide new thermoelectric conversion material having excellent thermoelectric conversion performance.
Another object of the present invention is to provide a method for producing the above new thermoelectric conversion material.
Furthermore, another object of the present invention is to provide a thermoelectric conversion element using the new thermoelectric conversion material.
Technical Solution
As a result of the research for thermoelectric conversion material, compositions of the formula 1 are proposed in the present invention. It was found that these new compounds may be used as thermoelectric conversion materials of thermoelectric conversion elements, and so on.

Bi1-xMxCu1-wOa-yQ1yTeb-zQ2z  Formula 1

where M is at least one element selected from the group consisting of Ba, Sr, Ca, Mg, Cs, K, Na, Cd, Hg, Sn, Pb, Mn, Ga, In, Tl, As and Sb; Q1 and Q2 are at least one element selected from the group consisting of S, Se, As and Sb with 0≦x<1, 0<w<1, 0.2<a<4, 0≦y<4, 0.2<b<4, 0≦z<4 and x+y+z>0.
According to the present invention, a, y, b and z are preferably a=1, 0≦y<1, b=1 and 0≦z<1, respectively.
In other case, x, w, a, y, b and z are preferably 0≦x<0.15, 0<w≦0.2, a=1, 0≦y<0.2, b=1 and 0<z<0.5, respectively. Here, M is preferably any one selected from the group consisting of Sr, Cd, Pb and Tl, and Q1 and Q2 are preferably Se or Sb, respectively.
In another aspect of the present invention, it provides methods for producing thermoelectric conversion materials expressed by the formula 1 by heating mixtures of Bi2O3, Bi, Cu, Te, and at least one selected from the group consisting of elemental Ba, Sr, Ca, Mg, Cs, K, Na, Cd, Hg, Sn, Pb, Mn, Ga, In, Tl, As and Sb, or their oxides.
Alternatively, the present invention provides methods for producing thermoelectric conversion materials expressed by the formula 1 by heating mixtures of Bi2O3, Bi, Cu, Te, at least one selected from the group consisting of elemental S, Se, As, and Sb, or their oxides, and optionally at least one selected from the group consisting of elemental Ba, Sr, Ca, Mg, Cs, K, Na, Cd, Hg, Sn, Pb, Mn, Ga, In, Tl, As, and Sb, or their oxides.
In the method according to the present invention, the sintering process is preferably executed at temperatures of 400 to 570° C.
Advantageous Effects
The new thermoelectric conversion materials of the present invention may replace thermoelectric conversion materials in common use, or be used along with thermoelectric conversion materials in common use. In particular, the thermoelectric conversion materials may be useful for thermoelectric conversion elements due to their excellent thermoelectric conversion performance.



DESCRIPTION OF DRAWINGS
Other objects and aspects of the present invention will become apparent from the following description of embodiments with reference to the accompanying drawing in which:
FIG. 1 shows Rietveld refinement profiles for BiCuOTe, comparing X-ray diffraction pattern with a calculated pattern from a structural model;
FIG. 2 shows the crystal structure of BiCuOTe;
FIG. 3 shows X-ray diffraction pattern of BiCu0.9OTe;
FIG. 4 shows Rietveld refinement profiles for Bi0.98Pb0.02CuOTe, comparing X-ray diffraction pattern with a calculated pattern from a structural model;
FIG. 5 shows the crystal structure of Bi0.98Pb0.02CuOTe;
FIG. 6 shows X-ray diffraction pattern of Bi0.9Pb0.1CuOTe;
FIG. 7 shows X-ray diffraction pattern of Bi0.9Cd0.1CuOTe;
FIG. 8 shows X-ray diffraction pattern of Bi0.9Sr0.1CuOTe;
FIG. 9 shows Rietveld refinement profiles for BiCuOSe0.5Te0.5, comparing X-ray diffraction pattern with a calculated pattern from a structural model;
FIG. 10 shows the crystal structure of BiCuOSe0.5Te0.5;
FIG. 11 shows X-ray diffraction pattern of Bi0.9Tl0.1CuOTe;
FIG. 12 shows X-ray diffraction pattern of BiCuOTe0.9Sb0.1;
FIG. 13 shows electrical conductivities, Seebeck coefficients, thermal conductivities, and ZT values of BiCuOTe at different temperatures;
FIG. 14 shows electrical conductivities, Seebeck coefficients, thermal conductivities, and ZT values of Bi0.9Sr0.1CuOTe at different temperatures;
FIG. 15 shows electrical conductivities, Seebeck coefficients, thermal conductivities, and ZT values of Bi0.9Cd0.1CuOTe at different temperatures;
FIG. 16 shows electrical conductivities, Seebeck coefficients, thermal conductivities, and ZT values of Bi0.9Pb0.1CuOTe at different temperatures;
FIG. 17 shows electrical conductivities, Seebeck coefficients, thermal conductivities, and ZT values of Bi0.98Pb0.02CuOTe at different temperatures; and
FIG. 18 shows electrical conductivities, Seebeck coefficients, thermal conductivities, and ZT values of Bi0.9Tl0.1CuOTe at different temperatures.
FIG. 19 shows electrical conductivities, Seebeck coefficients, thermal conductivities, and ZT values of Bi0.95Pb0.05Cu0.960 Te0.95Se0.05 at different temperatures.



BEST MODE
Compositions of the thermoelectric conversion materials of the present invention are expressed by the following formula 1.

Bi1-xMxCu1-wOa-yQ1yTeb-zQ2z  Formula 1

In the formula 1, M is at least one element selected from the group consisting of Ba, Sr, Ca, Mg, Cs, K, Na, Cd, Hg, Sn, Pb, Mn, Ga, In, Tl, As and Sb, and Q1 and Q2 are at least one element selected from the group consisting of S, Se, As and Sb with 0≦x<1, 0<w<1, 0.2<a<4, 0≦y<4, 0.2<b<4, 0≦z<4 and x+y+z>0.
In the formula 1, x, y, and z are preferably 0≦x≦1⁄2, 0≦y≦a/2 and 0≦z≦b/2, respectively.
In the formula 1, a, y, b and z of the formula 1 are preferably a=1, 0≦y<1, b=1 and 0≦z<1, respectively. In other cases, x, w, a, y, b and z may be respectively 0≦x<0.15, 0<w≦0.2, a=1, 0≦y<0.2, b=1 and 0≦z<0.5. Here, M is preferably any one selected from the group consisting of Sr, Cd, Pb and Tl, and Q1 and Q2 are preferably Se or Sb, respectively.
For the thermoelectric conversion materials of the formula 1, it is more preferred that x, a, y, b and z of the formula 1 are respectively 0<x<0.15, a=1, y=0, b=1 and z=0, and M is any one selected from the group consisting of Sr, Cd, Pb and Tl. In addition, in the formula 1 where x, a, y, b and z of the formula 1 are respectively x=0, a=1, y=0, b=1 and 0<z≦0.5, and Q2 is Se or Sb.
Meanwhile, the thermoelectric conversion materials expressed by the formula 1 may be produced by mixing powders of Bi2O3, Bi, Cu and Te and then vacuum-sintering the mixture, but the present invention is not limited thereto.
Also, the thermoelectric conversion materials expressed by the formula 1 may be produced by heating mixtures of Bi2O3, Bi, Cu, Te, and at least one selected from the group consisting of Ba, Sr, Ca, Mg, Cs, K, Na, Cd, Hg, Sn, Pb, Mn, Ga, In, Tl, As and Sb, or their oxides in an evacuated silica tube, however the present invention is not limited thereto.
In addition, the thermoelectric conversion materials expressed by the formula 1 may be produced by heating mixtures of Bi2O3, Bi, Cu, Te, at least one element selected from the group consisting of S, Se, As and Sb, or their oxides, and optionally at least one selected from the group consisting of Ba, Sr, Ca, Mg, Cs, K, Na, Cd, Hg, Sn, Pb, Mn, Ga, In, Tl, As, and Sb, or their oxides in an evacuated silica tube, however the present invention is not limited thereto.
The thermoelectric conversion materials of the present invention may be produced by sintering mixtures in a flowing gas such as Ar, He or N2, which partially includes hydrogen or does not include hydrogen. The sintering process is preferably executed at a temperature of 400 to 750° C., more preferably 400 to 570° C.
MODE FOR INVENTION
Hereinafter, the preferred embodiment of the present invention will be described in detail based on examples. However, the embodiments of the present invention may be modified in various ways, and the scope of the present invention should not be interpreted as being limited to the examples. The embodiments of the present invention are provided just for explaining the present invention more perfectly to those having ordinary skill in the art.
Example 1
BiCuOTe
In order to prepare BiCuOTe, 1.1198 g of Bi2O3 (Aldrich, 99.9%, 100 mesh), 0.5022 g of Bi (Aldrich, 99.99%, <10 μm), 0.4581 g of Cu (Aldrich, 99.7%, 3 μm), and 0.9199 g of Te (Aldrich, 99.99%,  ̃100 mesh) were well mixed by using agate mortar, and then heated in an evacuated silica tube at 510° C. for 15 hours, thereby obtaining BiCuOTe powder.
The powder X-ray diffraction (XRD) data were collected at room temperature on a Bragg-Brentano diffractometer (Bruker Advance D8 XRD) with a Cu X-ray tube (λ=1.5406 Å, 50 kV, 40 mA). The step size was 0.02 degree.
TOPAS program (R. W. Cheary, A. Coelho, J. Appl. Crystallogr. 25 (1992) 109-121; Bruker AXS, TOPAS 3, Karlsruhe, Germany (2000)) was used in order to determine the crystal structure of the obtained material. The analysis results are shown in Table 1 and FIG. 2.













TABLE 1





Atom
site
x
y
z
Occup.
Beq





















Bi
2c
0.25
0.25
0.37257(5)
1
0.56(1)


Cu
2a
0.75
0.25
0
1
0.98(3)


O
2b
0.75
0.25
0.5
1
0.26(12)


Te
2c
0.25
0.25
0.81945(7)
1
0.35(1)









Crystallographic data obtained from Rietveld refinement of BiCuOTe [Space group I4/nmm (No. 129), a=4.04138(6) Å, c=9.5257(2) Å]
FIG. 1 shows a Rietveld refinement profile that compares observed X-ray diffraction pattern of BiCuOTe with a calculated X-ray diffraction pattern from a structural model. FIG. 1 shows that the measured pattern well agrees with the calculated pattern according to Table 1, which implies that the material obtained in this example is BiCuOTe.
As shown in FIG. 2, the BiCuOTe exhibits a natural super-lattice structure in which Cu2Te2 layers and Bi2O2 layers are repeated along a c-crystalline axis. Also, it can be said that BiTeCu layers and O layers are repeated along the c-crystalline axis in the natural super-lattice structure.
Example 2
BiCu0.9OTe
In order to prepare BiCu0.9OTe, 1.1371 g of Bi2O3 (Aldrich, 99.9%, 100 mesh), 0.51 g of Bi (Aldrich, 99.99%, <10 μm), 0.4187 g of Cu (Aldrich, 99.7%, 3 μm), and 0.9342 g of Te (Aldrich, 99.99%,  ̃100 mesh) were well mixed by using agate mortar, and then heated in an evacuated silica tube at 510° C. for 15 hours, thereby obtaining BiCu0.9TeO powder.
X-ray diffraction analysis was conducted for the sample in the same way as the example 1. As shown in FIG. 3, the material obtained in the example 2 was identified as BiCu0.9TeO.
Example 3
Bi0.98Pb0.02CuOTe
In order to prepare Bi0.98Pb0.02CuOTe, 2.5356 g of Bi2O3 (Aldrich, 99.9%, 100 mesh), 1.1724 g of Bi (Aldrich, 99.99%, <10 μm), 1.0695 g of Cu (Aldrich, 99.7%, 3 μm), 0.0751 g of PbO (Canto, 99.5%), and 2.1475 g of Te (Aldrich, 99.99%,  ̃100 mesh) were well mixed by using agate mortar, and then heated in an evacuated silica tube at 510° C. for 15 hours, thereby obtaining Bi0.98Pb0.02CuOTe powder.
The powder X-ray diffraction (XRD) data were collected at room temperature on a Bragg-Brentano diffractometer (Bruker D4-Endeavor XRD) with a Cu X-ray tube (λ=1.5406 Å, 50 kV, 40 mA). The step size was 0.02 degree.
TOPAS program (R. W. Cheary, A. Coelho, J. Appl. Crystallogr. 25 (1992) 109-121; Bruker AXS, TOPAS 3, Karlsruhe, Germany (2000)) was used in order to determine the crystal structure of the obtained material. The analysis results are shown in Table 2 and FIG. 5.













TABLE 2





Atom
site
x
y
z
Occup.
Beq.





















Bi
2c
0.25
0.25
0.37225(12)
0.98
0.59(4)


Pb
2c
0.25
0.25
0.37225(12)
0.02
0.59(4)


Cu
2a
0.75
0.25
0
1
1.29(10)


O
2b
0.75
0.25
0.5
1
0.9(4)


Te
2c
0.25
0.25
0.81955(17)
1
0.55(5)









Crystallographic data obtained from Rietveld refinement of Bi0.98Pb0.02CuOTe [Space group P4/nmm (No. 129), a=4.04150(4) Å, c=9.53962(13) Å]

FIG. 4 shows a Rietveld refinement profile that compares observed X-ray diffraction pattern of Bi0.98Pb0.02CuOTe with calculated pattern of a structural model. FIG. 4 shows that the measured pattern well agrees with the calculated pattern according to Table 2, which implies that the material obtained in this example is Bi0.98Pb0.02CuOTe.
As shown in FIG. 5, the Bi0.98Pb0.02CuOTe exhibits a natural super-lattice structure in which Cu2Te2 layers and (Bi,Pb)2O2 layers where Pb is partially substituted in place of Bi are repeated along a c-crystalline axis. Also, it can be said that (Bi,Pb)TeCu layers and O layers are repeated along the c-crystalline axis in the natural super-lattice structure.
Example 4
Bi0.9Pb0.1CuOTe
In order to prepare Bi0.9Pb0.1CuOTe, 1.2721 g of Bi2O3 (Aldrich, 99.9%, 100 mesh), 0.6712 g of Bi (Aldrich, 99.99%, <10 μm), 0.6133 g of Cu (Aldrich, 99.7%, 3 μm), 0.215 g of PbO (Canto, 99.5%), and 1.2294 g of Te (Aldrich, 99.99%,  ̃100 mesh) were well mixed by using agate mortar, and then heated in an evacuated silica tube at 510 r for 15 hours, thereby obtaining Bi0.9Pb0.1CuOTe powder.
X-ray diffraction analysis was conducted for the sample in the same way as the example 3. As shown in FIG. 6, the material obtained in the example 4 was identified as Bi0.9Pb0.1CuOTe.
Example 5
Bi0.9Cd0.1CuOTe
In order to prepare Bi0.9Cd0.1CuOTe, 1.3018 g of Bi2O3 (Aldrich, 99.9%, 100 mesh), 0.6869 g of Bi (Aldrich, 99.99%, <10 μm), 0.6266 g of Cu (Aldrich, 99.7%, 3 μm), 0.1266 g of CdO (Strem, 99.999%), and 1.2582 g of Te (Aldrich, 99.99%,  ̃100 mesh) were well mixed by using agate mortar, and then heated in an evacuated silica tube at 510° C. for 15 hours, thereby obtaining Bi0.9Cd0.1CuOTe powder.
X-ray diffraction analysis was conducted for the sample in the same way as the example 3. As shown in FIG. 7, the material obtained in the example 5 was identified as Bi0.9Cd0.1CuOTe.
Example 6
Bi0.9Sr0.1CuOTe
In order to prepare Bi0.9Sr0.1CuOTe, 1.0731 g of Bi2O3 (Aldrich, 99.9%, 100 mesh), 0.5662 g of Bi (Aldrich, 99.99%, <10 μm), 0.5165 g of Cu (Aldrich, 99.7%, 3 μm), 1.0372 g of Te (Aldrich, 99.99%,  ̃100 mesh), and 0.0842 g of SrO were well mixed by using agate mortar. Here, SrO was obtained by thermally treating SrCO3 (Alfa, 99.994%) at 1125° C. for 12 hours in the air. The material obtained by thermal treatment was confirmed as SrO by X-ray diffraction analysis.
The mixture was then heated in an evacuated silica tube at 510° C. for 15 hours, thereby obtaining Bi0.9Sr0.1CuOTe powder.
The powder X-ray diffraction (XRD) data were collected at room temperature on a Bragg-Brentano diffractometer (Bruker D8 Advance XRD) with a Cu X-ray tube (λ=1.5406 Å, 50 kV, 40 mA). The step size was 0.02 degree. FIG. 8 shows that the material obtained in the example 6 is Bi0.9Sr0.1CuOTe.
Example 7
BiCuOSe0.5Te0.5 
In order to prepare BiCuOSe0.5Te0.5, 1.9822 g of Bi2O3 (Aldrich, 99.9%, 100 mesh), 0.889 g of Bi (Aldrich, 99.99%, <10 μm), 0.811 g of Cu (Aldrich, 99.7%, 3 μm), 0.5036 g of Se (Aldrich, 99.99%), and 0.8142 g of Te (Aldrich, 99.99%,  ̃100 mesh) were well mixed by using agate mortar, and then heated in an evacuated silica tube at 510° C. for 15 hours, thereby obtaining BiCuOSe0.5Te0.5 powder.
The powder X-ray diffraction (XRD) data were collected at room temperature on a Bragg-Brentano diffractometer (Bruker D4-Endeavor XRD) with a Cu X-ray tube (40 kV, 40 mA). The step size was 0.02 degree. At this time, variable 6 mm slit was used as a divergence slit. The results are shown in FIG. 9. Crystal structure analysis was executed in the same way as the example 3. The analysis results are shown in Table 3 and FIG. 10.













TABLE 3





Atom
site
x
y
z
Occup.
Beq.





















Bi
2c
0.25
0.25
0.36504(9)
1
0.86(2)


Cu
2a
0.75
0.25
0
1
2.00(9)


O
2b
0.75
0.25
0.5
1
1.9(3)


Te
2c
0.25
0.25
0.82272(14)
0.5
0.61(4)


Se
2c
0.25
0.25
0.82252(14)
0.5
0.55(5)









Crystallographic data obtained from Rietveld refinement of BiCuOSe0.5Te0.5 [Space group P4/nmm (No. 129), a=3.99045(11) Å, c=9.2357(4) Å]

FIG. 9 shows that the measured pattern well agrees with the calculated pattern from the results in Table 3, and as a result the material obtained in this example is identified as BiCuOSe0.5Te0.5.
As shown in FIG. 10, the BiCuOSe0.5Te0.5 exhibits a natural super-lattice structure in which Cu2(Te,Se)2 layers and Bi2O2 layers are repeated along a c-crystalline axis. Also, it can be said that Bi(Te,Se)Cu layers and O layers are repeated along the c-crystalline axis in the natural super-lattice structure.
Example 8
Bi0.9Tl0.1CuOTe
In order to prepare Bi0.9Tl0.1CuOTe, 1.227 g of Bi2O3 (Aldrich, 99.9%, 100 mesh), 0.7114 g of Bi (Aldrich, 99.99%, <10 μm), 0.6122 g of Cu (Aldrich, 99.7%, 3 μm), 1.2293 g of Te (Aldrich, 99.99%,  ̃100 mesh), and 0.22 g of Tl2O3 (Aldrich) were well mixed by using agate mortar.
The mixture was then heated in an evacuated silica tube at 510° C. for 15 hours, thereby obtaining Bi0.9Tl0.1CuOTe powder.
X-ray diffraction analysis was conducted for the sample in the same way as the example 3. As shown in FIG. 11, the material obtained in the example 8 was identified as Bi0.9Tl0.1CuOTe.
Example 9
BiCuOTe0.9Sb0.1 
In order to prepare BiCuOTe0.9Sb0.1, 1.4951 g of Bi2O3 (Aldrich, 99.9%, 100 mesh), 0.6705 g of Bi (Aldrich, 99.99%, <10 μm), 0.6117 g of Cu (Aldrich, 99.7%, 3 μm), 1.1054 g of Te (Aldrich, 99.99%,  ̃100 mesh), and 0.1172 g of Sb (Kanto chemical, Cat. No. 01420-02) were well mixed by using agate mortar.
The mixture was then heated in an evacuated silica tube at 510° C. for 15 hours, thereby obtaining BiCuOTe0.9Sb0.1 powder.
X-ray diffraction analysis was conducted for the sample in the same way as the example 3. As shown in FIG. 12, the material obtained in the example 9 was identified as BiCuOTe0.9Sb0.1.
Example 10
Bi0.95Pb0.05Cu0.96OTe0.95Se0.05 
In order to prepare Bi0.95Pb0.05Cu0.96OTe0.95Se0.05, 3.7785 g of Bi2O3 (Aldrich, 99.9%, 100 mesh), 1.4404 g of Bi (Aldrich, 99.99%, <10 μm), 1.4840 g of Cu (Aldrich, 99.7%, 3 μm), 0.2520 g of Pb (Alfa aesar, 99.9%, 200 mesh), 2.9489 g of Te (Aldrich, 99.99%, 100 mesh), and 0.0960 g of Se (Alfa aesar, 99.999%, 200 mesh) were well mixed by using agate mortar.
The mixture was then heated in an evacuated silica tube at 500° C. for 12 hours, thereby obtaining Bi0.95Pb0.05Cu0.96OTe0.95Se0.05 powder.
X-ray diffraction analysis was conducted for the sample in the same way as the example 3, and the material obtained in the example 10 was identified as Bi0.95Pb0.05Cu0.96OTe0.95Se0.05.
Evaluation of Thermoelectric Conversion Performance
Powder samples obtained in Examples 1, 3 to 6, 8 and 10 were shaped into cylinders with a diameter of 4 mm and a length of 15 mm (for electrical conductivity and Seebeck coefficient measurements), and disks having a diameter of 10 mm and a thickness of 1 mm (for thermal conductivity measurements) by using CIP at the pressure of 200 MPa. Subsequently, the resultant disks and cylinders were heated in an evacuated silica tube at 510° C. for 10 hours (for 12 hours for Example 10).
For the sintered cylinders, electric conductivity and Seebeck coefficient were measured by using a ZEM-2 (Ulvac-Rico, Inc.) The measurement results are shown in FIGS. 13 to 19. For example, at 346 K thermal conductivities of BiCuOTe and Bi0.98Pb0.02CuOTe were measured as 0.25 W/m/K and 0.35 W/m/K, respectively, which are significantly lower than those of Bi2Te3 (1.9 W/m/K, T. M. Tritt, M. A. Subramanian, MRS Bulletin 31 (2006) 188-194) and Co4Sb12:In0.2 (2 W/m/K, T. He, J. Chen, D. Rosenfeld, M. A. Subramanian, Chem. Mater. 18 (2006) 759-762) which are representative thermoelectric conversion materials.
Meanwhile, for the sintered disks, thermal conductivity was measured by using TC-9000 (Ulvac-Rico, Inc) (using a LFA457 (Netzsch) for Example 10). The measurement results are shown in FIGS. 13 to 19.
ZT value of each sample was calculated using the measured values. The calculated results are shown in FIGS. 13 to 19.

## Claims

1. Thermoelectric conversion materials, expressed by the following formula 1:


Bi1-xMxCu1-wOa-yQ1yTeb-zQ2z  Formula 1


where M is at least one element selected from the group consisting of Ba, Sr, Ca, Mg, Cs, K, Na, Cd, Hg, Sn, Pb, Mn, Ga, In, Tl, As and Sb; Q1 and Q2 are at least one element selected from the group consisting of S, Se, As and Sb; x, y, z, w, a, and b are 0≦x<1, 0<w<1, 0.2<a<4, 0≦y<4, 0.2<b<4, 0≦z<4, b>z and x+y+z>0.

2. The thermoelectric conversion materials according to claim 1,
wherein x, y and z of the formula 1 are respectively 0≦x≦1/2, 0≦y≦a/2 and 0≦z≦b/2.

3. The thermoelectric conversion materials according to claim 1,
wherein a, y, b and z of the formula 1 are respectively a=1, 0≦y<1, b=1 and 0≦z<1.

4. The thermoelectric conversion materials according to claim 3,
wherein x, w, a, y, b and z of the formula 1 are respectively 0≦x<0.15, 0≦w<0.2, a=1, 0≦y<0.2, b=1 and 0≦z<0.5.

5. The thermoelectric conversion materials according to claim 3,
wherein M of the formula 1 is any one selected from the group consisting of Sr, Cd, Pb and Tl.

6. The thermoelectric conversion materials according to claim 3,
wherein Q1 and Q2 of the formula 1 are respectively Se or Sb.

7. The thermoelectric conversion materials according to claim 3,
wherein x, w, a, y, b and z of the formula 1 are respectively 0≦x<0.15, 0<w≦0.2, a=1, 0≦y<0.2, b=1 and 0≦z<0.5; M is any one selected from the group consisting of Sr, Cd, Pb and Tl; Q1 and Q2 are respectively Se or Sb.

8. The thermoelectric conversion materials according to claim 7,
wherein x, a, y, b and z of the formula 1 are respectively 0<x<0.15, a=1, y=0, b=1 and z=0.

9. The thermoelectric conversion materials according to claim 7,
wherein x, y and z of the formula 1 are respectively x=0, a=1, y=0, b=1 and 0<z≦0.5.

10. A method for producing thermoelectric conversion materials,
wherein Bi2O3, Bi, Cu, Te, and at least one selected from the group consisting of Ba, Sr, Ca, Mg, Cs, K, Na, Cd, Hg, Sn, Pb, Mn, Ga, In, Tl, As and Sb, or their oxides, are mixed and then sintered to produce the thermoelectric conversion materials expressed by the formula 1 in the claim 1.

11. The method for producing thermoelectric conversion materials according to claim 10,
wherein the sintering process is executed at a temperature of 400 to 570° C.

12. A method for producing thermoelectric conversion materials,
wherein Bi2O3, Bi, Cu, and Te are mixed with at least one selected from the group consisting of S, Se, As and Sb, or their oxides, and then at least one selected from the group consisting of Ba, Sr, Ca, Mg, Cs, K, Na, Cd, Hg, Sn, Pb, Mn, Ga, In, Tl, As and Sb, or their oxides, are selectively further mixed thereto and then sintered to produce the thermoelectric conversion materials expressed by the formula 1 in the claim 1.

13. The method for producing thermoelectric conversion materials according to claim 12,
wherein the sintering process is executed at a temperature of 400 to 570° C.

14. A thermoelectric conversion element, which includes the thermoelectric conversion materials defined in claim 1.