Abstract
Pyroelectricity describes the generation of electricity by temporal temperature change in polar materials1,2,3. When free-standing pyroelectric materials approach the 2D crystalline limit, how pyroelectricity behaves remained largely unknown. Here, using three model pyroelectric materials whose bonding characters along the out-of-plane direction vary from van der Waals (In2Se3), quasi-van der Waals (CsBiNb2O7) to ionic/covalent (ZnO), we experimentally show the dimensionality effect on pyroelectricity and the relation between lattice dynamics and pyroelectricity. We find that, for all three materials, when the thickness of free-standing sheets becomes small, their pyroelectric coefficients increase rapidly. We show that the material with chemical bonds along the out-of-plane direction exhibits the greatest dimensionality effect. Experimental observations evidence the possible influence of changed phonon dynamics in crystals with reduced thickness on their pyroelectricity. Our findings should stimulate fundamental study on pyroelectricity in ultra-thin materials and inspire technological development for potential pyroelectric applications in thermal imaging and energy harvesting.
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Acknowledgements
This work is supported by the Air Force Office of Scientific Research under award number FA9550-18-1-0116, the US National Science Foundation under award numbers 1916652, 2031692 and 2024972, and the NYSTAR Focus Center at Rensselaer Polytechnic Institute under award number C180117. This paper is also supported by the U.S. National Science Foundation (Platform for the Accelerated Realization, Analysis, and Discovery of Interface Materials (PARADIM)) under Cooperative Agreement No. DMR-1539918 and made use of the Cornell Center for Materials Research (CCMR) Shared Facilities, which are supported through the NSF MRSEC Program (no. DMR-1719875). We thank J. Liu for the discussion on the mechanism of pyroelectricity. This research used resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under contract DE-AC02-06CH11357.
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J.S., J.J. and L.Z. conceived and developed the idea and planned the experiments. J.J. and L.Z. prepared the samples and devices and performed optical, scanning electron microscopy and AFM measurements. L.Z., J.J. and Y.H. performed the pyroelectric measurements. H.Z. performed synchrotron XRD measurements. P.B. and Y.S. performed MD simulations. Y.H. performed SHG measurements. J.J. performed Raman measurements. Y.G. and J.J. performed TEM and STEM measurements. B.W. and R.J. performed XRD measurements. Z.C., S.P. and X.W. contributed to the experimental set-ups and crystal growth. Y.X. performed AFM and RHEED measurements. Z.L. performed EBSD measurements. J.J. and L.Z. processed the data and J.J., L.Z. and J.S. interpreted the results. J.J. and L.Z. wrote the initial draft. J.S. revised the manuscript. C.M., Y.C., C.S., G.-C.W., T.-M.L., D.G., Y.-Y.S., N.K., E.F. and all the other authors were involved in the discussion for data analysis. J.S. supervised the project.
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Extended data figures and tables
Extended Data Fig. 1 MD simulations in model HCP sheets.
a, Mean square displacement \(\left\langle {{u}_{l}}^{2}\right\rangle \) along in-plane directions as a function of time step in model sheets with out-of-plane bonding strengths of εe and εe/2 and thicknesses of 32 layers (left), 16 layers (middle) and ten layers (right). Insets are the corresponding model sheets. εe, σ0 and t0 are the energy, length and time units, respectively (see Methods). b, Average \(\left\langle {{u}_{l}}^{2}\right\rangle \) as a function of out-of-plane bonding strength and thickness. c, Percentage change of average \(\left\langle {{u}_{l}}^{2}\right\rangle \) as a function of thickness. The sheet with stronger out-of-plane bonding strength has more pronounced dimensionality effect on \(\left\langle {{u}_{l}}^{2}\right\rangle \). Grey arrows are guides for the eyes.
Extended Data Fig. 2 Crystal lattice dynamics in In2Se3 and CBNO.
a, Temperature-dependent (from 293 to 423 K) Raman spectra at around 109 cm−1 (\({{\rm{A}}}_{{\rm{g}}}^{2}\) mode) in a thick In2Se3 sheet (280 nm, left panel) and a thin In2Se3 sheet (29 nm, right panel). b, Temperature-dependent (from 293 to 673 K) Raman spectra at around 587 cm−1 (in-plane mode) in a thick CBNO sheet (730 nm, left panel) and a thin CBNO sheet (35 nm, right panel). Dashed lines are guides for the eyes. c–e, Peak position (c), FWHM (d) and mean square amplitude \(\left\langle {Q}_{j}^{2}\right\rangle \) (e) of the \({{\rm{A}}}_{{\rm{g}}}^{2}\) phonon of In2Se3 as a function of temperature in the thick sheet (half-filled squares in cyan) and thin sheet (half-filled circles in orange). f–h, Peak position (f), FWHM (g) and mean square amplitude \(\left\langle {Q}_{j}^{2}\right\rangle \) (h) of the in-plane phonon of CBNO as a function of temperature in the thick sheet (half-filled squares in cyan) and thin sheet (half-filled circles in orange). The inset of f is a schematic of the in-plane mode of CBNO. Cyan and orange lines are linear fittings.
Supplementary information
Supplementary Information
This file contains Supplementary Discussions 1–7, Supplementary Figs 1–48 and Supplementary Tables 1 and 2.
Video 1
Molecular dynamics simulation of ten layers with strong interlayer bond strength.
Video 2
Molecular dynamics simulation of ten layers with weak interlayer bond strength.
Video 3
Molecular dynamics simulation of 16 layers with strong interlayer bond strength.
Video 4
Molecular dynamics simulation of 16 layers with weak interlayer bond strength.
Video 5
Molecular dynamics simulation of 32 layers with strong interlayer bond strength.
Video 6
Molecular dynamics simulation of 32 layers with weak interlayer bond strength.
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Jiang, J., Zhang, L., Ming, C. et al. Giant pyroelectricity in nanomembranes. Nature 607, 480–485 (2022). https://doi.org/10.1038/s41586-022-04850-7
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DOI: https://doi.org/10.1038/s41586-022-04850-7
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