Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Direct ink writing of three-dimensional thermoelectric microarchitectures

Abstract

Microthermoelectric modules can be used as energy harvesters, active coolers and thermal sensors in integrated systems. However, manufacturing such modules with traditional microfabrication processes is costly and produces only two-dimensional thermoelectric films, which limit the formation of high-temperature gradients and thus the amount of power generated. Here we show that microscale three-dimensional thermoelectric architectures can be fabricated through the direct writing of particle-based thermoelectric inks. Using size control and surface oxidation, the characteristics of (Bi,Sb)2(Te,Se)3-based particle inks are engineered to create colloidal inks with high viscoelasticity and without organic binders, and the inks are directly written into complex architectures using a 3D printing process. The resulting structures exhibit high thermoelectric figures of merit of 1.0 (p type) and 0.5 (n type), which are comparable to those of bulk ingots. Microthermoelectric generators made from three-dimensionally written vertical filaments exhibit large temperature gradients and a power density of 479.0 μW cm–2.

This is a preview of subscription content, access via your institution

Access options

Buy this article

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Direct 3D writing of TE inks.
Fig. 2: Rheological properties of super-viscoelastic TE ink.
Fig. 3: TE properties of the 3D-printed samples.
Fig. 4: Fabrication and power performance of the μTEG.

Similar content being viewed by others

Data availability

The data that support the findings of this study are available from the corresponding authors upon reasonable request.

References

  1. Haras, M. & Skotnicki, T. Thermoelectricity for IoT—A review. Nano Energy 54, 461–476 (2018).

    Article  Google Scholar 

  2. Ando, J. et al. A review of the development and applications of thermoelectric microgenerators for energy harvesting. Renew. Sustain. Energy Rev. 91, 376–393 (2018).

    Article  Google Scholar 

  3. Pletcher, N. M. et al. A 52 μW wake-up receiver with –72 dBm sensitivity using an uncertain-IF architecture. IEEE J. Solid-State Circuits 44, 269–280 (2009).

    Article  Google Scholar 

  4. Gilbert, J. M. & Balouchi, F. Comparison of energy harvesting systems for wireless sensor networks. Inter. J. Autom. Comput. 5, 334–347 (2008).

    Article  Google Scholar 

  5. Zhang, Y. et al. A batteryless 19 μW MICS/ISM-band energy harvesting body sensor node SoC for ExG applications. IEEE J. Solid-State Circuits 48, 199–213 (2013).

    Article  Google Scholar 

  6. Yan, J. et al. Review of micro thermoelectric generator. J. Microelectromech. Syst. 27, 1–18 (2018).

    Article  Google Scholar 

  7. Rabaey, J. M. et al. PicoRadios for wireless sensor networks: the next challenge in ultra-low power design. In 2002 IEEE ISSCC Digest of Technical Papers, 200–201 (2002).

  8. Park, S. C. et al. A micro-thermoelectric gas sensor for detection of hydrogen and atomic oxygen. Analyst 134, 236–242 (2009).

    Article  Google Scholar 

  9. Blachowicz, T. & Ehrmann, A. 3D printed MEMS technology—recent developments and applications. Micromachines 11, 434 (2020).

    Article  Google Scholar 

  10. Dhawan, R. et al. Si0.97Ge0.03 microelectronic thermoelectric generators with high power and voltage densities. Nat. Commun. 11, 4362 (2020).

    Article  Google Scholar 

  11. Li, G. et al. Integrated microthermoelectric coolers with rapid response time and high device reliability. Nat. Electron. 1, 555–561 (2018).

    Article  Google Scholar 

  12. Hong, C. T. et al. Spray-printed CNT/P3HT organic thermoelectric films and power generators. J. Mater. Chem. A 3, 21428–21433 (2015).

    Article  Google Scholar 

  13. Wang, Y. et al. Flexible thermoelectric materials and generators: challenges and innovations. Adv. Mater. 31, 29 (2019).

    Google Scholar 

  14. Mehran, M. & Zorman, C. A. SiC MEMS: opportunities and challenges for applications in harsh environments. Thin Solid Films 355–356, 518–524 (1999).

    Google Scholar 

  15. Davidson, E. C. et al. 3D printable and reconfigurable liquid crystal elastomers with light-induced shape memory via dynamic bond exchange. Adv. Mater. 32, 1 (2020).

    Article  Google Scholar 

  16. Hensleigh, R. et al. Charge-programmed three-dimensional printing for multi-material electronic devices. Nat. Electron. 3, 216–224 (2020).

    Article  Google Scholar 

  17. Vyatskikh, A. et al. Additive manufacturing of 3D nano-architected metals. Nat. Commun. 9, 593 (2018).

    Article  Google Scholar 

  18. Lewis, J. A. & Ahn, B. Y. Device fabrication: three-dimensional printed electronics. Nature 518, 42–43 (2015).

    Article  Google Scholar 

  19. Sun, K. et al. 3D printing of interdigitated Li-ion microbattery architectures. Adv. Mater. 25, 4539–4543 (2013).

    Article  Google Scholar 

  20. Lewis, J. A. Direct ink writing of 3D functional materials. Adv. Funct. Mater. 16, 2193–2204 (2006).

    Article  Google Scholar 

  21. Jo, S. et al. Ink processing for thermoelectric materials and power-generating devices. Adv. Mater. 31, 1804930 (2019).

    Article  Google Scholar 

  22. Zhang, B. et al. Promising thermoelectric properties of commercial PEDOT:PSS materials and their Bi2Te3 powder composites. ACS Appl. Mater. Interfaces 2, 3170–3178 (2010).

    Article  Google Scholar 

  23. Kato, K. et al. Fabrication of bismuth telluride thermoelectric films containing conductive polymers using a printing method. J. Electron. Mater. 42, 1313–1318 (2013).

    Article  Google Scholar 

  24. Ou, C. et al. Fully printed organic–inorganic nanocomposites for flexible thermoelectric applications. ACS Appl. Mater. Interfaces 10, 19580–19587 (2018).

    Article  Google Scholar 

  25. He, M. et al. Thermopower enhancement in conducting polymer nanocomposites via carrier energy scattering at the organic–inorganic semiconductor interface. Energy Environ. Sci. 5, 8351–8358 (2012).

    Article  Google Scholar 

  26. Burton, M. R. et al. 3D printed SnSe thermoelectric generators with high figure of merit. Adv. Energy Mater. 9, 1900201 (2019).

    Article  Google Scholar 

  27. Su, N. et al. 3D-printing of shape-controllable thermoelectric devices with enhanced output performance. Energy 195, 116892 (2020).

    Article  Google Scholar 

  28. Kim, F. et al. 3D printing of shape-conformable thermoelectric materials using all-inorganic Bi2Te3-based inks. Nat. Energy 3, 301–309 (2018).

    Article  Google Scholar 

  29. Yang, S. E. et al. Composition-segmented BiSbTe thermoelectric generator fabricated by multimaterial 3D printing. Nano Energy 81, 105638 (2021).

    Article  Google Scholar 

  30. Kim, S. I. et al. Dense dislocation arrays embedded in grain boundaries for high-performance bulk thermoelectrics. Science 348, 109–114 (2015).

    Article  Google Scholar 

  31. Li, J.-F. et al. High-performance nanostructured thermoelectric materials. NPG Asia Mater. 2, 152–158 (2010).

    Article  Google Scholar 

  32. Saeidi-Javash, M. et al. 3D conformal printing and photonic sintering of high-performance flexible thermoelectric films using 2D nanoplates. Adv. Funct. Mater. 29, (2019).

  33. Snyder, G. J. & Toberer, E. S. Complex thermoelectric materials. Nat. Mater. 7, 105–114 (2008).

    Article  Google Scholar 

  34. Bark, H. et al. Effect of multiwalled carbon nanotubes on the thermoelectric properties of a bismuth telluride matrix. Curr. Appl. Phys. 13, S111–S114 (2013).

    Article  Google Scholar 

  35. Willenbacher, N. & Georgieva, K. in Product Design and Engineering: Formulation of Gels and Pastes (eds Bröckel, U et al.) Ch. 1, 7–49 (Wiley, 2013).

  36. Barthelmes, G. et al. Particle size distributions and viscosity of suspensions undergoing shear-induced coagulation and fragmentation. Chem. Eng. Sci. 58, 2893–2902 (2003).

    Article  Google Scholar 

  37. Luckham, P. F. & Ukeje, M. A. Effect of particle size distribution on the rheology of dispersed systems. J. Colloid Interface Sci. 220, 347–356 (1999).

    Article  Google Scholar 

  38. Chen, Z. et al. Preparation of high solid loading and low viscosity ceramic slurries for photopolymerization-based 3D printing. Ceram. Int. 45, 11549–11557 (2019).

    Article  Google Scholar 

  39. Maranzano, B. J. & Wagner, N. J. The effects of interparticle interactions and particle size on reversible shear thickening: hard-sphere colloidal dispersions. J. Rheol. 45, 1205–1222 (2001).

    Article  Google Scholar 

  40. Eom, Y. et al. Rheological design of 3D printable all-inorganic inks using BiSbTe-based thermoelectric materials. J. Rheol. 63, 291–304 (2019).

    Article  Google Scholar 

  41. Hong, B. J. et al. Successful stabilization of graphene oxide in electrolyte solutions: enhancement of biofunctionalization and cellular uptake. ACS Nano 6, 63–73 (2012).

    Article  Google Scholar 

  42. Zheng, G. et al. High thermoelectric performance of p-BiSbTe compounds prepared by ultra-fast thermally induced reaction. Energy Environ. Sci. 10, 2638–2652 (2017).

    Article  Google Scholar 

  43. Lidorenko, N. S. et al. Influence of porosity and intergrain-boundary quality on the electrical and thermal conductivities of semiconductive thermoelectric materials. Inorg. Mater. 6, 1853 (1970).

    Google Scholar 

  44. Wu, C.-A. et al. Low thermal conductivity and enhanced zT values of porous and nanostructured Cu1–xNix alloys. Chem. Eng. J. 368, 409–416 (2019).

    Article  Google Scholar 

  45. Khan, A. U. et al. Nano-micro-porous skutterudites with 100% enhancement in ZT for high performance thermoelectricity. Nano Energy 31, 152–159 (2017).

    Article  Google Scholar 

  46. Chang, P. H. et al. Giant thermoelectric effect in graphene-based topological insulators with heavy adatoms and nanopores. Nano Lett. 14, 3779–3784 (2014).

    Article  Google Scholar 

  47. Ning, H. et al. Enhanced thermoelectric performance of porous magnesium tin silicide prepared using pressure-less spark plasma sintering. J. Mater. Chem. A 3, 17426–17432 (2015).

    Article  Google Scholar 

  48. Yan, X. et al. Experimental studies on anisotropic thermoelectric properties and structures of n-type Bi2Te2.7Se0.3. Nano Lett. 10, 3373–3378 (2010).

    Article  Google Scholar 

  49. Rojas, J. P. et al. Review—Micro and nano-engineering enabled new generation of thermoelectric generator devices and applications. ECS J. Solid State Sci. Technol. 6, N3036–N3044 (2017).

    Article  Google Scholar 

  50. Francioso, L. et al. Flexible thermoelectric generator for ambient assisted living wearable biometric sensors. J. Power Sources 196, 3239–3243 (2011).

    Article  Google Scholar 

  51. Paradiso, J. A. & Starner, T. Energy scavenging for mobile and wireless electronics. IEEE Pervasive Comput. 4, 18–27 (2005).

    Article  Google Scholar 

  52. Pashinkin, A. S. et al. The heat capacity of solid antimony telluride Sb2Te3. Russ. J. Phys. Chem. 82, 878–879 (2008).

    Article  Google Scholar 

  53. Liu, W. et al. Studies on the Bi2Te3–Bi2Se3–Bi2S3 system for mid-temperature thermoelectric energy conversion. Energy Environ. Sci. 6, 552–560 (2013).

    Article  Google Scholar 

  54. Kim, M. & Cha, C. Modulation of functional pendant chains within poly(ethylene glycol) hydrogels for refined control of protein release. Sci. Rep. 8, 4315 (2018).

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the Samsung Research Funding Center of Samsung Electronics under project no. SRFC-MA1801–05. J.S.S. acknowledges the Nano-Material Technology Development Program (NRF-2018M3A7B8060697) and the Creative Materials Discovery Program (NRF-2020M3D1A1110502) through the National Research Foundation (NRF) funded by the Ministry of Science and ICT, Republic of Korea.

Author information

Authors and Affiliations

Authors

Contributions

F.K., S.E.Y., H.J., H.G.C. and J.S.S. designed the experiments, analysed the data and wrote the paper. F.K., S.E.Y., S.C., J.L., J.S.S. and K.T.K. carried out the synthesis and basic characterization of the materials. S.E.Y., H.J. and H.G.C. performed the characterization of rheological properties. F.K., S.E.Y., G.K. and S.A. performed the characterization of thermoelectric properties. F.K. and S.E.Y. carried out the fabrication and measurement of TEGs. S.K. and C.C. performed the synthesis of hydrogels. All the authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Han Gi Chae or Jae Sung Son.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature Electronics thanks Yanzhong Pei, Kyu Huong Lee and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–21, Tables 1 and 2, discussion and references.

Supplementary Video 1

Printing of a TE filament.

Supplementary Video 2

Printing of a 3D lattice.

Supplementary Video 3

Printing of p- and n-type TE filaments on a Si/SiO2 substrate.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kim, F., Yang, S.E., Ju, H. et al. Direct ink writing of three-dimensional thermoelectric microarchitectures. Nat Electron 4, 579–587 (2021). https://doi.org/10.1038/s41928-021-00622-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41928-021-00622-9

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing