Recent progress in thermoelectric layered cobalt oxide thin films
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Abstract
Abstract Oxide-based thermoelectric materials that show a high figure of merit are promising because of their good chemical and thermal stabilities and their relative harmlessness compared with chalcogenide-based state-of-the-art thermoelectric materials. Although several high-ZT thermoelectric oxides (ZT > 1) have been reported thus far, their reliability levels are low due to the lack of careful observations of their stabilities at elevated temperatures. Herein, we review the epitaxial film growth and thermoelectric properties of representative p-type layered cobalt oxides: Na3/4CoO2, Ca1/3CoO2, Sr1/3CoO2, Ba1/3CoO2, and Ca3Co4O9. Among these specimens, Ba1/3CoO2 and Ca3Co4O9 are stable in air at elevated temperatures (~600 °C). The ZT of Ba1/3CoO2 reaches ~ 0.55 at 600 °C in air, which is reliable and the highest among thermoelectric oxides. Moreover, this value is comparable to those of p-type PbTe and p-type SiGe.
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OpenAlex topics: Advanced Thermoelectric Materials and Devices · Thermal Expansion and Ionic Conductivity · Perfectionism, Procrastination, Anxiety Studies
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References (83)
Show source-provided references
1. Rowe, D. M. CRC Handbook of TheThe authors declare no competing interestsrmoelectrics. (CRC Press, 1995).
2. Goldsmid, H. J. Introduction to Thermoelectricity. (Springer, 2010).10.1007/978-3-642-00716-3 ↗
3. Seebeck, T. J. Abh. K. Akad. Wiss. 265 (1823).
4. Tritt, T. M. & Subramanian, M. A. Thermoelectric materials, phenomena, and applications: A bird’s eye view. MRS Bull. 31, 188–194 (2006).10.1557/mrs2006.44 ↗
5. Snyder, G. J. & Toberer, E. S. Complex thermoelectric materials. Nat. Mater. 7, 105–114 (2008).10.1038/nmat2090 ↗
6. Venkatasubramanian, R., Siivola, E., Colpitts, T. & O’Quinn, B. Thin-film thermoelectric devices with high room-temperature figures of merit. Nature 413, 597–602 (2001).10.1038/35098012 ↗
7. Zhao, L. D. et al. Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals. Nature 508, 373 (2014).10.1038/nature13184 ↗
8. Rhyee, J. S. et al. Peierls distortion as a route to high thermoelectric performance in In4Se3–δ crystals. Nature 459, 965–968 (2009).10.1038/nature08088 ↗
9. Snyder, G. J., Christensen, M., Nishibori, E., Caillat, T. & Iversen, B. B. Disordered zinc in Zn4Sb3 with phonon-glass and electron-crystal thermoelectric properties. Nat. Mater. 3, 458–463 (2004).10.1038/nmat1154 ↗
10. Zhao, L. D. et al. Ultrahigh power factor and thermoelectric performance in hole-doped single-crystal SnSe. Science 351, 141–144 (2016).10.1126/science.aad3749 ↗
11. Hsu, K. F. et al. Cubic AgPbmSbTe2+m: Bulk thermoelectric materials with high figure of merit. Science 303, 818–821 (2004).10.1126/science.1092963 ↗
12. Chung, D. Y. et al. CsBi4Te6: A high-performance thermoelectric material for low-temperature applications. Science 287, 1024–1027 (2000).10.1126/science.287.5455.1024 ↗
13. Kim, S. I. et al. Dense dislocation arrays embedded in grain boundaries for high-performance bulk thermoelectrics. Science 348, 109–114 (2015).10.1126/science.aaa4166 ↗
14. Jiang, B. et al. High-entropy-stabilized chalcogenides with high thermoelectric performance. Science 371, 830–834 (2021).10.1126/science.abe1292 ↗
15. Jiang, B. et al. High figure-of-merit and power generation in high-entropy GeTe-based thermoelectrics. Science 377, 208–213 (2022).10.1126/science.abq5815 ↗
16. Zhao, L.-D. et al. BiCuSeO oxyselenides: new promising thermoelectric materials. Energy Environ. Sci. 7, 2900–2924 (2014).10.1039/C4EE00997E ↗
17. Liu, Y. et al. Remarkable Enhancement in Thermoelectric Performance of BiCuSeO by Cu Deficiencies. J. Am. Chem. Soc. 133, 20112–20115 (2011).10.1021/ja2091195 ↗
18. Yang, J. H. & Stabler, F. R. Automotive Applications of Thermoelectric Materials. J. Electron. Mater. 38, 1245–1251 (2009).10.1007/s11664-009-0680-z ↗
19. Korzhuev, M. A. & Katin, I. V. On the Placement of Thermoelectric Generators in Automobiles. J. Electron. Mater. 39, 1390–1394 (2010).10.1007/s11664-010-1332-z ↗
20. Kim, S. K. et al. Thermoelectric Power Generation System for Future Hybrid Vehicles Using Hot Exhaust Gas. J. Electron. Mater. 40, 778–783 (2011).10.1007/s11664-011-1569-1 ↗
21. Vining, C. B. An inconvenient truth about thermoelectrics. Nat. Mater. 8, 83–85 (2009).10.1038/nmat2361 ↗
22. Koumoto, K. et al. Thermoelectric Ceramics for Energy Harvesting. J. Am. Ceram. Soc. 96, 1–23 (2013).10.1111/jace.12076 ↗
23. Koumoto, K., Terasaki, I. & Funahashi, R. Complex oxide materials for potential thermoelectric applications. MRS Bull. 31, 206–210 (2006).10.1557/mrs2006.46 ↗
24. Koumoto, K., Wang, Y. F., Zhang, R. Z., Kosuga, A. & Funahashi, R. Oxide ‘Thermoelectric Materials: A Nanostructuring Approach. Annu. Rev. Mater. Res. 40, 363–394 (2010).10.1146/annurev-matsci-070909-104521 ↗
25. Hogarth, C. A. & Andrews, J. P. Variation with Oxygen Pressure of the Thermoelectric Power of Cadmium Oxide. Philos. Mag. 40, 273–282 (1949).10.1080/14786444908561249 ↗
26. Parravano, G. Thermoelectric Behavior of Nickel Oxide. J. Chem. Phys. 23, 5–10 (1955).10.1063/1.1740562 ↗
27. Hutson, A. R. Electronic Properties of ZnO. J. Phys. Chem. Solids 8, 467–472 (1959).10.1016/0022-3697(59)90392-0 ↗
28. Arvin, M. J. Electrical Conductivity and Thermoelectric Power of Indium Oxide. J. Phys. Chem. Solids 23, 1681 (1962).10.1016/0022-3697(62)90252-4 ↗
29. Frederikse, H. P. R., Thurber, W. R. & Hosler, W. R. Electronic transport in strontium titanate. Phys. Rev. 134, A442 (1964).10.1103/PhysRev.134.A442 ↗
30. Thurber, W. R. & Mante, A. J. H. Thermal Conductivity and Thermoelectric Power of Rutile (TiO2). Phys. Rev. 139, 1655 (1965).10.1103/PhysRev.139.A1655 ↗
31. Marley, J. A. & Dockerty, R. C. Electrical Properties of Stannic Oxide Single Crystals. Phys. Rev. 140, A304 (1965).10.1103/PhysRev.140.A304 ↗
32. Young, A. P. & Schwartz, C. M. Electrical Conductivity and Thermoelectric Power of Cu2O. J. Phys. Chem. Solids 30, 249-& (1969).10.1016/0022-3697(69)90306-0 ↗
33. Griffiths, B. A., Elwell, D. & Parker, R. Thermoelectric Power of System NiFe2O4–Fe3O4. Philos. Mag. 22, 163 (1970).10.1080/14786437008228161 ↗
34. Bednorz, J. G. & Muller, K. A. Possible High-Tc Superconductivity in the Ba–La–Cu–O System. Z. Phys. B Con. Mat. 64, 189–193 (1986).10.1007/BF01303701 ↗
35. Cooper, J. R., Alavi, B., Zhou, L. W., Beyermann, W. P. & Gruner, G. Thermoelectric-Power of Some High-Tc Oxides. Phys. Rev. B 35, 8794–8796 (1987).10.1103/PhysRevB.35.8794 ↗
36. Chen, J. T., Mcewan, C. J., Wenger, L. E. & Logothetis, E. M. Determination of Charge-Carriers in Superconducting La-Ba-Cu-O by Thermoelectric Measurements. Phys. Rev. B 35, 7124–7125 (1987).10.1103/PhysRevB.35.7124 ↗
37. Lee, S. C. et al. Thermoelectric-Power and Superconducting Properties of YBa2Cu3O7-δ and RBa2Cu3O7-δ. Phys. Rev. B 37, 2285–2288 (1988).10.1103/PhysRevB.37.2285 ↗
38. Mitra, N. et al. Thermoelectric-Power of the Tl-Ca-Ba-Cu-O Superconductor. Phys. Rev. B 38, 7064–7066 (1988).10.1103/PhysRevB.38.7064 ↗
39. Ohtaki, M., Koga, H., Tokunaga, T., Eguchi, K. & Arai, H. Electrical-Transport Properties and High-Temperature Thermoelectric Performance of (Ca0.9M0.1)MnO3 (M = Y, La, Ce, Sm, In, Sn, Sb, Pb, Bi). J. Solid State Chem. 120, 105–111 (1995).10.1006/jssc.1995.1384 ↗
40. Ohtaki, M., Tsubota, T., Eguchi, K. & Arai, H. High-temperature thermoelectric properties of (Zn1–xAlx)O. J. Appl. Phys 79, 1816–1818 (1996).10.1063/1.360976 ↗
41. Terasaki, I., Sasago, Y. & Uchinokura, K. Large thermoelectric power in NaCo2O4 single crystals. Phys. Rev. B 56, 12685–12687 (1997).10.1103/PhysRevB.56.R12685 ↗
42. Masset, A. C. et al. Misfit-layered cobaltite with an anisotropic giant magnetoresistance: Ca3Co4O9. Phys. Rev. B 62, 166–175 (2000).10.1103/PhysRevB.62.166 ↗
43. Funahashi, R. et al. An oxide single crystal with high thermoelectric performance in air. Jpn. J. Appl. Phys. 39, L1127–L1129 (2000).10.1143/JJAP.39.L1127 ↗
44. Okuda, T., Nakanishi, K., Miyasaka, S. & Tokura, Y. Large thermoelectric response of metallic perovskites: Sr1–xLaxTiO3 (0 ≤ x ≤ 0.1). Phys. Rev. B 63, 113104 (2001).10.1103/PhysRevB.63.113104 ↗
45. Ohta, S., Nomura, T., Ohta, H. & Koumoto, K. High-temperature carrier transport and thermoelectric properties of heavily La- or Nb-doped SrTiO3 single crystals. J. Appl. Phys. 97, 034106 (2005).10.1063/1.1847723 ↗
46. Ohta, S. et al. Large thermoelectric performance of heavily Nb-doped SrTiO3 epitaxial film at high temperature. Appl. Phys. Lett. 87, 092108 (2005).10.1063/1.2035889 ↗
47. Fergus, J. W. Oxide materials for high temperature thermoelectric energy conversion. J. Eur. Ceram. Soc. 32, 525–540 (2012).10.1016/j.jeurceramsoc.2011.10.007 ↗
48. Acharya, M., Jana, S. S., Ranjan, M. & Maiti, T. High performance (ZT > 1) n-type oxide thermoelectric composites from earth abundant materials. Nano Energy 84, 105905 (2021).10.1016/j.nanoen.2021.105905 ↗
49. Biswas, S. et al. Selective Enhancement in Phonon Scattering Leads to a High Thermoelectric Figure-of-Merit in Graphene Oxide-Encapsulated ZnO Nanocomposites. ACS Appl. Mater. Interfaces 13, 23771–23786 (2021).10.1021/acsami.1c04125 ↗
50. Ohta, H. et al. Reactive solid-phase epitaxial growth of NaxCoO2 (x ~0.83) via lateral diffusion of Na into a cobalt oxide epitaxial layer. Cryst. Growth Des. 5, 25–28 (2005).10.1021/cg049818c ↗
51. Ohta, H. et al. Surface modification of glass substrates for oxide heteroepitaxy: Pasteable three-dimensionally oriented layered oxide thin films. Adv. Mater. 18, 1649 (2006).10.1002/adma.200502606 ↗
52. Sugiura, K. et al. Fabrication and thermoelectric properties of layered cobaltite, γ-Sr0.32Na0.21CoO2 epitaxial films. Appl. Phys. Lett. 88, 082109 (2006).10.1063/1.2178768 ↗
53. Sugiura, K. et al. Thermoelectric properties of the layered cobaltite Ca3Co4O9 epitaxial films fabricated by topotactic ion-exchange method. Mater. Trans. 48, 2104–2107 (2007).10.2320/matertrans.E-MRA2007864 ↗
54. Zhang, X. et al. Ba1/3CoO2: A Thermoelectric Oxide Showing a Reliable ZT of ~0.55 at 600 °C in Air. ACS Appl. Mater. Interfaces 14, 33355–33360 (2022).10.1021/acsami.2c08555 ↗
55. Sugiura, K. et al. High electrical conductivity of layered cobalt oxide Ca3Co4O9 epitaxial films grown by topotactic ion-exchange method. Appl. Phys. Lett. 89, 032111 (2006).10.1063/1.2234277 ↗
56. Kurita, D., Ohta, S., Sugiura, K., Ohta, H. & Koumoto, K. Carrier generation and transport properties of heavily Nb-doped anatase TiO2 epitaxial films at high temperatures. J. Appl. Phys. 100, 096105 (2006).10.1063/1.2362990 ↗
57. Lee, K. H., Ishizaki, A., Kim, S. W., Ohta, H. & Koumoto, K. Preparation andthermoelectric properties of heavily Nb-doped SrO(SrTiO3)1 epitaxial films. J. Appl. Phys. 102, 033702 (2007).10.1063/1.2764221 ↗
58. Singh, D. J. Electronic structure of NaCo2O4. Phys. Rev. B 61, 13397–13402 (2000).10.1103/PhysRevB.61.13397 ↗
59. Koshibae, W. & Maekawa, S. Electronic state of a CoO layer with hexagonal structure: A Kagome lattice structure in a triangular lattice. Phys. Rev. Lett. 91, 257003 (2003).10.1103/PhysRevLett.91.257003 ↗
60. Koshibae, W. & Maekawa, S. Effects of spin and orbital degeneracy on the thermopower of strongly correlated systems. Phys. Rev. Lett. 87, 236603 (2001).10.1103/PhysRevLett.87.236603 ↗
61. Wang, Y. Y., Rogado, N. S., Cava, R. J. & Ong, N. P. Spin entropy as the likely source of enhanced thermopower in NaxCo2O4. Nature 423, 425–428 (2003).10.1038/nature01639 ↗
62. Lee, M. et al. Large enhancement of the thermopower in NaxCoO2 at high Na doping. Nat. Mater. 5, 537–540 (2006).10.1038/nmat1669 ↗
63. Fujita, K., Mochida, T. & Nakamura, K. High-temperature thermoelectric properties of NaxCoO2–δ single crystals. Jpn. J. Appl. Phys. 40, 4644–4647 (2001).10.1143/JJAP.40.4644 ↗
64. Takada, K. et al. Superconductivity in two-dimensional CoO2 layers. Nature 422, 53–55 (2003).10.1038/nature01450 ↗
65. Venimadhav, A. et al. Structural and transport properties of epitaxial NaxCoO2 thin films. Appl. Phys. Lett. 87, 172104 (2005).10.1063/1.2117619 ↗
66. Chang, W. J. et al. Fabrication and low temperature thermoelectric properties of NaxCoO2 (x = 0.68 and 0.75) epitaxial films by the reactive solid-phase epitaxy. Appl. Phys. Lett. 90, 061917 (2007).10.1063/1.2437131 ↗
67. Sugiura, K. et al. Anisotropic carrier transport properties in layered cobaltate epitaxial films grown by reactive solid-phase epitaxy. Appl. Phys. Lett. 94, 152105 (2009).10.1063/1.3119631 ↗
68. Krockenberger, Y. et al. Epitaxial growth of NaxCoO2 thin films by pulsed-laser deposition. Appl. Phys. Lett. 86, 191913 (2005).10.1063/1.1927272 ↗
69. Brinks, P. et al. Enhanced Thermoelectric Power Factor of NaxCoO2 Thin Films by Structural Engineering. Adv. Energy Mater. 4, 201301927 (2014).10.1002/aenm.201301927 ↗
70. Lee, M. et al. Enhancement of the thermopower in NaxCoO2 in the large-x regime (x ≥ 0.75). Phys. B 403, 1564–1568 (2008).10.1016/j.physb.2007.10.320 ↗
71. Mizutani, A., Sugiura, K., Ohta, H. & Koumoto, K. Epitaxial film growth of LixCoO2 (0.6 ≤ x ≤ 0.9) via topotactic ion exchange of Na0.8CoO2. Cryst. Growth Des. 8, 755 (2008).10.1021/cg060637f ↗
72. Sugiura, K. et al. Structural Transformation of Ca-Arrangements and Carrier Transport Properties in Ca0.33CoO2 Epitaxial Films. Appl. Phys. Express 2, 035503 (2009).10.1143/APEX.2.035503 ↗
73. Sugiura, K. et al. Epitaxial film growth and superconducting behavior of sodium-cobalt oxyhydrate, NaxCoO2-yH2O (x ~0.3, y ~1.3). Inorg. Chem. 45, 1894–1896 (2006).10.1021/ic051865m ↗
74. Cushing, B. L., Falster, A. U., Simmons, W. B. & Wiley, J. B. A multivalent ion exchange route to lamellar calcium cobalt oxides, CaxCoO2 (x ≤ 0.5). Chem Commun 23, 2635–2636 (1996).10.1039/cc9960002635 ↗
75. Cushing, B. L. & Wiley, J. B. Topotactic routes to layered calcium cobalt oxides. J. Solid State Chem. 141, 385–391 (1998).10.1006/jssc.1998.7957 ↗
76. Yang, H. X. et al. Structural properties and cation ordering in layered hexagonal CaxCoO2. Phys. Rev. B 73 (2006).10.1103/PhysRevB.73.014109 ↗
77. Huang, R. et al. Direct observations of Ca ordering in Ca0.33CoO2 thin films with different superstructures. Appl. Phys. Lett. 93, 014109 (2008).
78. Huang, R. et al. Microstructure evolution of Ca0.33CoO2 thin films investigated by high-angle annular dark-field scanning transmission electron microscopy. J. Mater. Res. 24, 279–287 (2009).10.1557/JMR.2009.0020 ↗
79. Liu, J., Huang, X., Yang, D., Xu, G. & Chen, L. Synthesis and physical properties of layered BaxCoO2. Dalton Trans. 43, 15414 (2014).10.1039/C4DT01674B ↗
80. Liu, J., Huang, X., Yang, D., Wan, S. & Xu, G. High-temperature thermoelectric properties of layered BaxCoO2. Scr. Mater. 100, 63–65 (2015).10.1016/j.scriptamat.2014.12.014 ↗
81. Cho, H. J., Takashima, Y., Nezu, Y., Onozato, T. & Ohta, H. Anisotropic Heat Conduction in Ion-Substituted Layered Cobalt Oxides. Adv. Mater. Interfaces 7, 1901816 (2020).10.1002/admi.201901816 ↗
82. Takashima, Y. et al. Layered Cobalt Oxide Epitaxial Films Exhibiting Thermoelectric ZT = 0.11 at Room Temperature. J. Mater. Chem. A 9, 274–280 (2021).10.1039/D0TA07565E ↗
83. Kang, K. et al. Fabrication and Thermoelectric Properties of Freestanding Ba1/3CoO2 Single-Crystalline Films. ACS Appl. Electron. Mater. 5, 5749–5754 (2023).10.1021/acsaelm.3c01129 ↗