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Electrically driven long-range solid-state amorphization in ferroic In2Se3

Nature volume 635, pages 847–853 (2024)Cite this article

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Abstract

Electrically induced amorphization is uncommon and has so far been realized by pulsed electrical current in only a few material systems, which are mostly based on the melt–quench process1. However, if the melting step can be avoided and solid-state amorphization can be realized electrically, it opens up the possibility for low-power device applications2,3,4,5. Here we report an energy-efficient, unconventional long-range solid-state amorphization in a new ferroic β″-phase of indium selenide nanowires through the application of a direct-current bias rather than a pulsed electrical stimulus. The complex interplay of the applied electric field perpendicular to the polarization, current flow parallel to the van der Waals layer and piezoelectric stress results in the formation of interlayer sliding defects and coupled disorder induced by in-plane polarization rotation in this layered material. On reaching a critical limit of the electrically induced disorder, the structure becomes frustrated and locally collapses into an amorphous phase6, and this phenomenon is replicated over a much larger microscopic-length scale through acoustic jerks7,8. Our work uncovers previously unknown multimodal coupling mechanisms of the ferroic order in materials to the externally applied electric field, current and internally generated stress, and can be useful to design new materials and devices for low-power electronic and photonic applications.

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Fig. 1: TEM characterization of as-synthesized β″-In2Se3 nanowires.
Fig. 2: Amorphization induced by a d.c. voltage in a β″-In2Se3 nanowire device.
Fig. 3: STEM analysis of a β″-In2Se3 nanowire device exhibiting sliding faults after applying a series of d.c. I–V sweeps before amorphization.
Fig. 4: In situ biasing DFTEM imaging of β″-In2Se3 nanowire device and observation of amorphization.

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The datasets generated and analysed during the current study are included with the Article or available from the corresponding authors upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This work was supported by the ONR-MURI (grant no. N00014-17-1-2661) and partially supported by the US NSF (FuSe; no. 2328743), US Air Force Office of Scientific Research (award no. FA9550-23-1-0189) and ANRF-SERB:CRG/2022/003506, Government of India. Support from NSF-MRSEC/DMR-2309043 seed grant is also acknowledged. P.N. acknowledges Indian Institute of Science (IISc) start-up seed grant and Infosys young researcher award. Electron microscopy and PFM measurements were carried out at the Advanced Facility for Microscopy and Microanalysis and the Micro Nano Characterization Facility in IISc. Device fabrication work and electron microscopy was conducted at the Singh Center for Nanotechnology, which is supported by the NSF National Nanotechnology Coordinated Infrastructure Program under grant no. NNCI-2025608 and through the University of Pennsylvania Materials Research Science and Engineering Center (MRSEC) (grant no. DMR-1720530). P.N. and S.K.P. are grateful for the support received from V. Dey in setting up a robust biasing system for the in situ TEM experiments.

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Author notes

  1. These authors contributed equally: Gaurav Modi, Shubham K. Parate

Authors and Affiliations

  1. Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, PA, USA

    Gaurav Modi, Andrew C. Meng, Utkarsh Khandelwal, James Horwath, Peter K. Davies, Eric A. Stach & Ritesh Agarwal

  2. Centre for Nanoscience and Engineering, Indian Institute of Science, Bengaluru, India

    Shubham K. Parate, Anudeep Tullibilli & Pavan Nukala

  3. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

    Choah Kwon & Ju Li

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Contributions

G.M. and R.A. conceptualized the project, and along with P.N. and S.K.P., designed the experiments and analysed the data. G.M. performed the nanowire synthesis, device fabrication, electrical characterization, in situ and ex situ TEM experiments, device modelling and finite element analysis. S.K.P. and P.N. performed the ex situ HAADF-STEM imaging, and in situ DFTEM biasing experiments. C.K. and J.L. carried out the DFT calculations. A.C.M. helped with the four-dimensional STEM polarization mapping. U.K. helped with the nanowire synthesis. A.T. and P.N. performed the PFM measurements and analysis. J.H. assisted with the in situ TEM heating setup. E.A.S. provided suggestions for the TEM characterization. P.K.D. helped with the structure interpretation and data analysis. G.M. and R.A. wrote the manuscript with inputs from S.K.P. and P.N. All authors discussed the results and commented on the final manuscript.

Corresponding authors

Correspondence to Pavan Nukala or Ritesh Agarwal.

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E.A.S. is an equity holder in Hummingbird Scientific. The other authors declare no competing interests.

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Nature thanks Junwei Zhang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Peer reviewer reports are available.

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Extended data figures and tables

Extended Data Fig. 1 TEM characterization of amorphized β″-In2Se3 nanowire device upon application of d.c. voltage.

(a) Evolution of current in the nanowire device with time when the device is held at different fixed d.c. voltages. Amorphization occurs at 20 V and is preceded by a rapid decrease in current with time. (b) Low magnification TEM image of the nanowire device after amorphization. (c) EDX elemental mapping of indium and selenium in the amorphized region of the nanowire. (d) DF-TEM image of the nanowire after amorphization. The contrast from the crystal-amorphous interface can be seen at the left side of the nanowire, where a part of the interface is shown in the HR-TEM image in (e). Electron diffraction and HR-TEM image from the (f) paraelectric crystalline phase and (g) amorphous regions of the nanowire device. The dashed white lines in (d) indicate the regions where the images were combined. Scale bars: (b) 1 µm, (d) 200 nm, (e) 5 nm, (f) and (g) 2 nm.

Supplementary information

Supplementary Information (download PDF )

Supplementary Notes 1–10, Figs. 1–30 and references.

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Supplementary Video 1 (download MP4 )

DFTEM in situ biasing video of a β″-In2Se3 nanowire device showing the subtle evolution of structure at low d.c. biasing voltages (≤5 V). The inset shows the magnification of the region indicated by the yellow circle.

Supplementary Video 2 (download MP4 )

DFTEM in situ biasing video of a β″-In2Se3 nanowire device showing the structure evolution at intermediate d.c. biasing voltages (15–25 V). The DFTEM imaging contrast, which originates due to strain fields from interacting domains, fluctuates concomitantly with the current (or local field) fluctuations. The inset shows the corresponding current–voltage–time (I–V–t) plot.

Supplementary Video 3 (download MP4 )

DFTEM in situ biasing video of a β″-In2Se3 nanowire device showing d.c.-biasing-induced amorphization immediately following the current fluctuations observed in Supplementary Video 2. The inset shows the corresponding I–V–t plot.

Supplementary Video 4 (download MP4 )

Evolution of the SAED data of a β″-In2Se3 nanowire with temperature during the in situ TEM heating experiment (Supplementary Fig. 23). The temperature profile over time is shown in Supplementary Fig. 23b. The superlattice reflections disappear at 250 °C (T > TCurie) due to the β″–β phase transition but reappear on cooling due to the β–β″ transition.

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Modi, G., Parate, S.K., Kwon, C. et al. Electrically driven long-range solid-state amorphization in ferroic In2Se3. Nature 635, 847–853 (2024). https://doi.org/10.1038/s41586-024-08156-8

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