Abstract
Addressing the critical challenge in n-type Bi2Te3-based films where the strong coupling among the Seebeck coefficient, electrical conductivity, and thermal conductivity limits thermoelectric performance, this work fabricates Bi2Te2.7Se0.3 films with thicknesses of 500, 650, and 800 nm on flexible substrates using dual-target magnetron co-sputtering combined with high-temperature annealing (673 K, 2 h). We systematically investigate the synergistic regulation of film thickness on texture, grain boundary structure, and electro-thermal transport. XRD and EBSD analyses reveal that increasing thickness decreases the (0111) orientation factor from 0.55 to 0.40, disperses the texture, and increases the proportion of high-angle grain boundaries (HAGBs) from 84.9% to 86.9%, accompanied by grain refinement. The Hall mobility follows a T-1.5 temperature dependence, confirming that acoustic phonon scattering dominates carrier transport. Concurrently, the energy filtering effect induced by the increased HAGBs enhances the Seebeck coefficient while maintaining a stable carrier concentration (around 1019 cm-3). All three films exhibit ultra-low total thermal conductivities of only 0.89-0.91 . Consequently, the 800 nm film achieves an outstanding room-temperature zT value of 1.14. This work establishes an intrinsic “thickness-texture-grain boundary-transport” correlation, providing key insights into thickness engineering for optimizing flexible, in-plane thermoelectric films.
Keywords
Bi₂Te₃-based filmsThickness effect(0111) orientationThermoelectric performance
References
- Y. Xiong, Y. Shi, G. Dong, T. Wang, X. Chen, S. Zhou, E. Min, J. Feng, J. Li, R. Liu, R. Sun, Uniaxial orientated Bi2Te2.7Se0.3 polycrystalline films with excellent thermoelectric performance for flexible generators, J. Mater. Sci. Technol. 252 (2026) 48-56, http://doi.org/10.1016/j.jmst.2025.05.080.DOI ↗Google Scholar ↗
- H. Abe, M. Takashiri, S. Hara, T. Arai, N. Sasaki, S. Tanaka, Performance evaluation of flexible thermoelectric generator with Bi2Te3 thin-film, Appl. Therm. Eng. 248 (2024) 123258, http://doi.org/10.1016/j.applthermaleng.2024.123258.DOI ↗Google Scholar ↗
- M. Haras, T. Skotnicki, Thermoelectricity for IoT – A review, ACS Nano. 54 (2018) 461-476, http://doi.org/10.1016/j.nanoen.2018.10.013.DOI ↗Google Scholar ↗
- X. He, X.-L. Shi, X. Wu, C. Li, W.-D. Liu, H. Zhang, X. Yu, L. Wang, X. Qin, Z.-G. Chen, Three-dimensional flexible thermoelectric fabrics for smart wearables, Nat. Commun. 161 (2025) 57889, http://doi.org/10.1038/s41467-025-57889-1.DOI ↗Google Scholar ↗
- M. Du, J. Ouyang, K. Zhang, Flexible Bi2Te3/PEDOT nanowire sandwich-like films towards high-performance wearable cross-plane thermoelectric generator and temperature sensor array, Journal of Materials Chemistry A 1130 (2023) 16039-16048, http://doi.org/10.1039/d3ta02876c.DOI ↗Google Scholar ↗
- Q. Zhang, K. Deng, L. Wilkens, H. Reith, K. Nielsch, Micro-thermoelectric devices, Nat. Electron. 56 (2022) 333-347, http://doi.org/10.1038/s41928-022-00776-0.DOI ↗Google Scholar ↗
- L. Fan, J. Tang, L. Wu, S. Zhang, F. Liu, J. Yao, L. Guo, Rapid growth of high-performance Bi2Te3 thin films by laser annealing at room temperature, Appl. Surf. Sci. 639 (2023) 158164, http://doi.org/10.1016/j.apsusc.2023.158164.DOI ↗Google Scholar ↗
- N.A. Musri, Y. Putthisigamany, P. Chelvanathan, N.M. Yatim, F.L.M. Redzuan, U. Syafiq, Performance improvement of a thin film thermoelectric generator via optimisation of the deposition parameters, Mater. Adv. 622 (2025) 8529-8540, http://doi.org/10.1039/d5ma00823a.DOI ↗Google Scholar ↗
- N. Nandihalli, A short account of thermoelectric film characterization techniques, Mater. Today Phys. 36 (2023) 101173, http://doi.org/10.1016/j.mtphys.2023.101173.DOI ↗Google Scholar ↗
- G. Li, J. Garcia Fernandez, D.A. Lara Ramos, V. Barati, N. Pérez, I. Soldatov, H. Reith, G. Schierning, K. Nielsch, Integrated microthermoelectric coolers with rapid response time and high device reliability, Nat. Electron. 110 (2018) 555-561, http://doi.org/10.1038/s41928-018-0148-3.DOI ↗Google Scholar ↗
- M. Hyland, H. Hunter, J. Liu, E. Veety, D. Vashaee, Wearable thermoelectric generators for human body heat harvesting, Appl. Energy 182 (2016) 518-524, http://doi.org/10.1016/j.apenergy.2016.08.150.DOI ↗Google Scholar ↗
- Y. Song, H. Yu, Y. Ran, H. Zeng, W. Li, J. He, K. Tai, Z. Yu, High-performance flexible wavy-structure thermoelectric generator based on (Bi, Sb)2Te3 films for energy harvesting, J. Power Sources 600 (2024) 234260, http://doi.org/10.1016/j.jpowsour.2024.234260.DOI ↗Google Scholar ↗
- Q. Zou, H. Shang, D. Huang, B. Xie, L. Zhang, K. Wang, H. Dong, C. Li, H. Gu, F. Ding, Bi2Te3-based flexible thermoelectric generator for wearable electronics, Appl. Phys. Lett. 1202 (2022) 023902, http://doi.org/10.1063/5.0078389.DOI ↗Google Scholar ↗
- B. Jiang, Y. Yu, J. Cui, X. Liu, L. Xie, High-entropy-stabilized chalcogenides with high thermoelectric performance, Science 371 (2021) 830-834, http://doi.org/10.1126/science.abe1292.DOI ↗Google Scholar ↗
- J. Dong, A. Suwardi, X.Y. Tan, N. Jia, K. Saglik, R. Ji, X. Wang, Q. Zhu, J. Xu, Q. Yan, Challenges and opportunities in low-dimensional thermoelectric nanomaterials, Mater. Today. 66 (2023) 137-157, http://doi.org/10.1016/j.mattod.2023.04.021.DOI ↗Google Scholar ↗
- J. He, T.M. Tritt, Advances in thermoelectric materials research: Looking back and moving forward, Science 3576358 (2017) aak9777, http://doi.org/10.1126/science.aak9997.DOI ↗Google Scholar ↗
- G.J. Snyder., E.S. Toberer, Complex thermoelectric materials, Nat. Mater. 7 (2008) 105-114, http://doi.org/10.1038/nmat2090.DOI ↗Google Scholar ↗
- S. Kim, D.Y. Hyeon, D. Lee, J.H. Bae, K.-I. Park, Fully flexible thermoelectric and piezoelectric hybrid generator based on a self-assembled multifunctional single composite film, Mater. Today Phys. 35 (2023) 101103, http://doi.org/10.1016/j.mtphys.2023.101103.DOI ↗Google Scholar ↗
- G. Dong, J. Feng, G. Qiu, Y. Yang, Q. Chen, Y. Xiong, H. Wu, Y. Ling, L. Xi, C. Long, J. Lu, Y. Qiao, G. Li, J. Li, R. Liu, R. Sun, Oriented Bi2Te3-based films enabled high performance planar thermoelectric cooling device for hot spot elimination, Nat. Commun. 151 (2024) 54017, http://doi.org/10.1038/s41467-024-54017-3.DOI ↗Google Scholar ↗
- J. Zhou, J. Feng, H. Li, D. Liu, G. Qiu, F. Qiu, J. Li, Z.Z. Luo, Z. Zou, R. Sun, R. Liu, Modulation of Vacancy Defects and Texture for High Performance n‐Type Bi2Te3 via High Energy Refinement, Small 1924 (2023) 2300654, http://doi.org/10.1002/smll.202300654.DOI ↗Google Scholar ↗
- C. Hu, K. Xia, C. Fu, X. Zhao, T. Zhu, Carrier grain boundary scattering in thermoelectric materials, Energy & Environmental Science 154 (2022) 1406-1422, http://doi.org/10.1039/D1EE03802H.DOI ↗Google Scholar ↗
- A.K. Lucid, J.F. Troncoso, J. Kohanoff, S. Fahy, I. Savić, Structure and thermal boundary resistance of basal plane twin boundaries in Bi2Te3, Phys. Chem. Chem. Phys. 2717 (2025) 9262-9274, http://doi.org/10.1039/d4cp04211e.DOI ↗Google Scholar ↗
- D. Mao, Y. Zhou, Y. Yu, Y. Wang, M. Han, Q. Meng, Y. Lu, J. Feng, M. Kong, H. Yang, Q. Gan, X. Xu, L. Xie, G.W. Ho, J. He, Scalable and sustainable manufacturing of twin boundary-enhanced flexible Bi0.4Sb1.6Te3 films with high thermoelectric performance, Joule 812 (2024) 3313-3323, http://doi.org/10.1016/j.joule.2024.08.009.DOI ↗Google Scholar ↗
- K. Pang, L. Miao, Q. Zhang, Q. Pan, Y. Liu, H. Shi, J. Li, W. Zhou, Z. Zhang, Y. Zhang, G. Wu, X. Tan, J.G. Noudem, J. Wu, P. Sun, H. Hu, G.-Q. Liu, J. Jiang, Gradient Nanotwins and Enhanced Weighted Mobility Synergistically Upgrade Bi0.5Sb1.5Te3 Thermoelectric and Mechanical Performance, Adv. Funct. Mater. 3425 (2024) 2315591, http://doi.org/https://doi.org/10.1002/adfm.202315591.DOI ↗Google Scholar ↗
- Y. Ling, M. Han, J. Xie, G. Qiu, G. Dong, E. Min, P. Zhang, X. Zeng, R. Liu, R. Sun, Thermal conductivity measurement of thermoelectric films using transient Photo-Electro-Thermal technique, Measurement 217 (2023) 113058, http://doi.org/10.1016/j.measurement.2023.113058.DOI ↗Google Scholar ↗
- C. Chiritescu, C. Mortensen, D.G. Cahill, D. Johnson, P. Zschack, Lower limit to the lattice thermal conductivity of nanostructured Bi2Te3-based materials, J. Appl. Phys. 1067 (2009) 073503, http://doi.org/10.1063/1.3226884.DOI ↗Google Scholar ↗
- S. Baral, I. Rajput, M.K. Dasoundhi, D. Kumar, A. Lakhani, Role of defects on carrier dynamics and transport mechanism in Bi2Te3 single crystals, Materials Today Chemistry 32 (2023) 101646, http://doi.org/10.1016/j.mtchem.2023.101646.DOI ↗Google Scholar ↗
- F.K. Lotgering, Topotactical reactions with ferrimagnetic oxides having hexagonal crystal structures—I, J. Inorg. Nucl. Chem. 92 (1959) 113-123, http://doi.org/10.1016/0022-1902(59)80070-1.DOI ↗Google Scholar ↗
- S. Mahieu, P. Ghekiere, D. Depla, R. De Gryse, Biaxial alignment in sputter deposited thin films, Thin Solid Films 5154 (2006) 1229-1249, http://doi.org/https://doi.org/10.1016/j.tsf.2006.06.027.DOI ↗Google Scholar ↗
- C.V. Thompson, Structure Evolution During Processing of Polycrystalline Films, Annu. Rev. Mater. Res. 2000 (2000) 159-190, http://doi.org/https://doi.org/10.1146/annurev.matsci.30.1.159.DOI ↗Google Scholar ↗
- T. Gong, L. Gao, L. Kang, M. Shi, G. Hou, S. Zhang, D. Meng, J. Li, W. Su, Ultrahigh Power Factor of Sputtered Nanocrystalline N‐Type Bi2Te3 Thin Film via Vacancy Defect Modulation and Ti Additives, Adv. Sci. 1138 (2024) 2403854, http://doi.org/10.1002/advs.202403845.DOI ↗Google Scholar ↗
- Z. Li, T. Deng, P. Qiu, C. Ming, Z. Gao, L. Chen, X. Shi, Plasticity of Bi2Te3-family thermoelectric crystals, Nat. Commun. 161 (2025) 5190, http://doi.org/10.1038/s41467-025-60465-2.DOI ↗Google Scholar ↗
- J. Zhu, X. Zhang, M. Guo, J. Li, J. Hu, S. Cai, W. Cai, Y. Zhang, J. Sui, Restructured single parabolic band model for quick analysis in thermoelectricity, npj Computational Materials 71 (2021) 116, http://doi.org/10.1038/s41524-021-00587-5.DOI ↗Google Scholar ↗
- R. Franz, G. Wiedemann, Ueber die Wärme-Leitungsfähigkeit der Metalle, Ann. Phys. 1658 (1853) 497-531, http://doi.org/10.1002/andp.18531650802.DOI ↗Google Scholar ↗
- D.G. Cahill, S.K. Watson, R.O. Pohl, Lower limit to the thermal conductivity of disordered crystals, Physical Review B 4610 (1992) 6131-6140, http://doi.org/10.1103/PhysRevB.46.6131.DOI ↗Google Scholar ↗
- S. Dharavath, S. Singh, S. Kodali, R.K. Dash, Thickness-dependent correlated study of structural and thermophysical properties of Bi-rich Bi2Te3 thin films prepared by thermal evaporation, Ceram. Int. 5125, Part B (2025) 46049-46057, http://doi.org/https://doi.org/10.1016/j.ceramint.2025.07.317.DOI ↗Google Scholar ↗