Thermoelectric material including conformal oxide layers and method of making the same using atomic layer deposition

1. A method for making a thermoelectric material, the method comprising:

selecting a substrate particle from the group consisting of skutterudite-based materials, Bi 2 Te 3 -based materials half-Heusler materials, Mg 2 Si, and MnSi;

selecting an oxide precursor whose byproduct during atomic layer deposition will not degrade the substrate particle;

depositing the oxide precursor on the substrate particle via the atomic layer deposition, thereby forming a conformal oxide layer on the substrate particle without forming any oxide nanoparticles and forming the thermoelectric material; and

controlling a number of atomic layer deposition cycles to obtain a plurality of conformal oxide layers having a total oxide layer thickness ranging from about 2 nm to about 20 nm, thereby reducing thermal conductivity of the thermoelectric material without deteriorating electric transport properties of the thermoelectric material.

2. The method as defined in claim 1 wherein the half-Heusler materials are selected from the group consisting of ZrNi 1+x Sn (x=0 to 0.5), HfNi 1+x Sn (x=0 to 0.5), TiNi 1+x Sn (x=0 to 0.5), ZrCo 1+x Sb (x=0 to 0.5), HfCo 1+x Sb (x=0 to 0.5), TiCo 1+x Sb (x=0 to 0.5), a solid solution of any of these materials, and combinations thereof.

3. The method as defined in claim 1 wherein the oxide precursor is selected from the group consisting of tetrakis(dimethylamino) titanium (TDMAT), tetrakis (diethylamino) titanium (TDEAT), tetrakis(ethylmethylamino) titanium (TEMAT), methylcyclopentienyl, tris(dimethylamido) titanium, bis(diethylamino)bis(diisopropylamino)titanium (IV), tetrakis(diethylamido) titanium (IV), tetrakis(dimethylamido) titanium (IV), titanium iospropoxide, tetrakis(ethylmethylamido) titanium, and combinations thereof.

4. The method as defined in claim 1 wherein the number of the atomic layer deposition cycles ranges from 25 to 100.

5. The method as defined in claim 1 , further comprising exposing the thermoelectric material to a consolidation process to form a solid specimen of the thermoelectric material.

6. The method as defined in claim 5 wherein the consolidation process includes spark plasma sintering under vacuum.

7. The method as defined in claim 1 wherein each atomic layer deposition cycle includes:

introducing the oxide precursor and water vapor into an atomic layer deposition (ALD) chamber;

allowing a predetermined time period to pass, whereby hydrolysis of the oxide precursor and the water occur within the ALD chamber to form the conformal oxide layer and a byproduct; and

evacuating the ALD chamber to remove the byproduct using a vacuum pump.

8. A method for controlling thermal conductivity of a thermoelectric material, the method comprising:

depositing an oxide precursor on a substrate particle via an atomic layer deposition cycle, thereby forming a conformal oxide coating on the substrate particle without forming any oxide nanoparticles, wherein the substrate particle is selected from the group consisting of skutterudite-based materials, Bi 2 Te 3 -based materials, half-Heusler materials, Mg 2 Si, and MnSi; and

repeating the atomic layer deposition cycle a predetermined number of times to obtain a plurality of conformal oxide layers having a total oxide layer thickness ranging from about 2 nm to about 20 nm, whereby increasing the predetermined number of times the atomic layer deposition cycle is performed decreases the thermal conductivity.

9. The method as defined in claim 8 wherein

the oxide precursor is selected from the group consisting of tetrakis(dimethylamino) titanium (TDMAT), tetrakis (diethylamino) titanium (TDEAT), tetrakis(ethylmethylamino) titanium (TEMAT), methylcyclopentienyl, tris(dimethylamido) titanium, bis(diethylamino)bis(diisopropylamino)titanium (IV), tetrakis(diethylamido) titanium (IV), tetrakis(dimethylamido) titanium (IV), titanium iospropoxide, tetrakis(ethylmethylamido) titanium, and combinations thereof.

10. The method as defined in claim 8 wherein the predetermined number of times ranges from 25 to 100.

11. The method as defined in claim 8 , further comprising exposing the thermoelectric material to spark plasma sintering to form a solid specimen.