Surface chemistry mediates thermal transport in three-dimensional nanocrystal arrays

Abstract

Arrays of ligand-stabilized colloidal nanocrystals with size-tunable electronic structure are promising alternatives to single-crystal semiconductors in electronic, optoelectronic and energy-related applications1,2,3,4,5. Hard/soft interfaces in these nanocrystal arrays (NCAs) create a complex and uncharted vibrational landscape for thermal energy transport that will influence their technological feasibility. Here, we present thermal conductivity measurements of NCAs (CdSe, PbS, PbSe, PbTe, Fe3O4 and Au) and reveal that energy transport is mediated by the density and chemistry of the organic/inorganic interfaces, and the volume fractions of nanocrystal cores and surface ligands. NCA thermal conductivities are controllable within the range 0.1–0.3 W m−1 K−1, and only weakly depend on the thermal conductivity of the inorganic core material. This range is 1,000 times lower than the thermal conductivity of silicon, presenting challenges for heat dissipation in NCA-based electronics and photonics. It is, however, 10 times smaller than that of Bi2Te3, which is advantageous for NCA-based thermoelectric materials.

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Figure 1: Structure and heat capacity of NCA films.
Figure 2: vDOS of a 2.8-nm-diameter Au nanocrystal and its individual constituents (Au core and a dodecanethiol ligand) predicted from lattice dynamics calculations.
Figure 3: Effects of NCA geometry and temperature on thermal conductivity.
Figure 4: Effects of NCA chemistry on thermal conductivity.

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Acknowledgements

We thank M. V. Kovalenko, A. Ruditskiy and J. M. Kurley for the synthesis of CdSe nanocrystals, and S. Wyant and S. Majumdar for help in FDTR preparations. S.M.R. and D.V.T. acknowledge support from the II-VI Foundation and NSF CAREER Award (DMR-0847535). J.A.M. and W-L.O. acknowledge support from the AFOSR Young Investigator Program (FA95501110030) and the NSF CAREER Award (ENG-1149374). A.J.H.M. acknowledges support from the AFOSR Young Investigator Program (FA95501010098). This work used facilities supported by the NSF MRSEC Program under Award Number DMR-0213745 and the facilities at the Center for Nanoscale Materials, a US Department of Energy, Office of Science, Office of Basic Energy Sciences User Facility under Contract No. DE-AC02-06CH11357.

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W-L.O. conducted the FDTR measurements on the NCAs, molecular dynamics simulations and lattice dynamics calculations. S.M.R. synthesized NCAs, conducted TGA, DSC and absorption spectra measurements, and took SEM, TEM and AFM images. W-L.O. and S.M.R. wrote the paper. D.V.T., A.J.H.M. and J.A.M. edited the paper. All authors discussed the data and commented on the manuscript.

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Correspondence to Dmitri V. Talapin or Jonathan A. Malen.

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Ong, W., Rupich, S., Talapin, D. et al. Surface chemistry mediates thermal transport in three-dimensional nanocrystal arrays. Nature Mater 12, 410–415 (2013). https://doi.org/10.1038/nmat3596

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