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Warm metalworking for plastic manufacturing in brittle semiconductors

Nature Materials (2025)Cite this article

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Abstract

Semiconductors are the core of modern electronics1. Because of their brittleness, semiconductors are usually processed by the complicated techniques of sputtering or deposition2,3,4, instead of the effective and versatile metalworking methods like rolling, extrusion and pressing used with metals5. Here we show that brittle semiconductors can be plastically manufactured with an extensibility as large as ~3,000% using warm metalworking, that is, plastic manufacturing at slightly elevated temperatures (empirically below 500 K). Many bulk brittle semiconductors, such as Cu2Se, Ag2Se and Bi90Sb10, can be processed like metals below 400–500 K into free-standing, large and high-quality films with a thickness from the macro-scale to the micrometre scale. A model based on temperature-dependent collective atomic displacement and thermal vibration is proposed to explain the superior plasticity. The warm-metalworked films can retain the excellent and tunable physical properties of the bulk versions, such as a high carrier mobility up to ~5,000 cm2 V−1 s−1 and tunable electrical conductivities over six orders of magnitude by adjusting the chemical composition. A case study in film thermoelectric devices demonstrates ultra-high normalized output power densities of 43–54 μW cm−2 K−2. This work suggests that brittle semiconductors can be manufactured by warm metalworking for applications in various electronics.

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Fig. 1: Extraordinary plastic processability of inorganic semiconductors by warm-metalworking methods.
Fig. 2: Temperature-dependent mechanical properties of inorganic semiconductors.
Fig. 3: Physical model for temperature-dependent plasticity.
Fig. 4: TE materials and devices manufactured by warm-metalworking methods.

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All data are available in this article, the extended data and the Supplementary Information.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (2024YFF0505900, X.S.) and the National Natural Science Foundation of China (grants T2122013, T.-R.W.; 52232010, X.S.; and 92463310, T.-R.W.).

Author information

Author notes

  1. These authors contributed equally: Zhiqiang Gao, Shiqi Yang, Yupeng Ma.

Authors and Affiliations

  1. State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai, China

    Zhiqiang Gao, Yupeng Ma, Tian-Ran Wei, Xiaoqin Zeng & Xun Shi

  2. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, China

    Zhiqiang Gao, Shiqi Yang, Xiaohui Chen, Wenwen Zheng, Pengfei Qiu, Lidong Chen & Xun Shi

  3. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, China

    Xiaohui Chen, Wenwen Zheng, Pengfei Qiu, Lidong Chen & Xun Shi

  4. National Engineering Research Center of Light Alloy Net Forming, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai, China

    Xiaoqin Zeng

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Contributions

T.-R.W. and X.S. designed the project. Z.G., T.-R.W., X.C., W.Z. and P.Q. prepared the samples and measured the mechanical properties. Z.G. performed the calculations. S.Y. and Z.G. fabricated the device and measured the performance. Y.M. performed transmission electron microscopy tests. Z.G. and T.-R.W. collected the data, developed the model and provided explanations under the guidance of L.C., X.Z. and X.S.; Z.G., T.-R.W., L.C. and X.S. wrote and edited the paper. All authors contributed helpful discussions to this work.

Corresponding authors

Correspondence to Tian-Ran Wei, Lidong Chen or Xun Shi.

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Nature Materials thanks Qi An, Yang Lu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Warm metalworking of inorganic semiconductors.

Warm rolling of (a) Ag2Te (393 K), Cu2Se (493 K), Bi90Sb10 (493 K), and (b) Ag2Se (393 K). (c) Warm extrusion of Cu2Se at 493 K. Warm flatbed press of (d) Cu2Se (493 K) and (e) Ag2Se (393 K).

Extended Data Fig. 2 Bending stress-strain curves of various materials at different temperatures.

(a) Ag2Te, (b) Ag2S, (c) Ag2Se, (d) Cu2Se, (e) AgCuS, (f) AgCuSe, (g) PbTe, (h) Bi90Sb10, (i) Mg3Sb2, and (j) Mg3Bi2.

Extended Data Fig. 3 Brittle-to-ductile transition temperature Ttrans vs. melting point Tm for diverse inorganic materials.

Data are obtained by experimental measurement in this work or taken from literature (see Supplementary Table 1 and references therein). The range bars of experimental Ttrans denote the largest and smallest values due to the non-trivial temperature intervals in measurement.

Extended Data Fig. 4 SEM images of the fractured surfaces after warm fracturing.

(a) Ag2Te, (b) AgCuSe, (c) Ag2Se, (d) AgCuS, (e) Cu2Se, and (f) Bi90Sb10.

Extended Data Fig. 5 SEM images of slip bands after warm compression.

(a) Ag2Se, (b) Ag2S, (c) Ag2Te, (d) Cu2Se, (e) AgCuSe, (f) AgCuS, (g) Bi90Sb10, and (h) Mg3Bi2.

Extended Data Fig. 6 TEM characterization of grain size and morphology before and after warm rolling.

TEM images of Ag2Se (a1, a2), Cu2Se(b1, b2), Bi90Sb10 (c1, c2) and AgCuSe (d1, d2) before (a1-d1) and after (a2-d2) warm rolling.

Extended Data Fig. 7 TEM characterization of Cu2Se after warm rolling.

(a) The TEM image and (b) corresponding HRTEM image of Cu2Se after warm rolling, the fast Fourier transform selected area electron diffraction (FFT-SAED) images of grain (c) #1, (d) #2, (e) #3 in (b).

Extended Data Fig. 8 Effect of warm working on electrical properties.

The (a, d, g) electrical conductivity, (b, e, h) Seebeck coefficient, and (c, f, i) power factor of Ag2Se, Cu2Se, and Mg3Bi1.5Sb0.49Te0.01 materials before and after warm rolling.

Extended Data Fig. 9 Vickers hardness and bending strength before and after warm rolling.

(a) Vickers hardness of Ag2Se, Cu2Se, AgCuSe, and AgCuS before and after being rolled from 1.0 mm to 0.5 mm, (b-e) Bending stress-strain curves of of Ag2Se, Cu2Se, AgCuSe, and AgCuS before and after being rolled from the thickness of 1.0 mm to 0.5 mm.

Extended Data Fig. 10 Effect of warm working on Hall mobility.

Hall mobility of Ag2Se, Ag2Te, and AgCuSe before and after warm rolling.

Supplementary information

Supplementary Information

Supplementary Figs. 1–9, Tables 1 and 2, text and references.

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Gao, Z., Yang, S., Ma, Y. et al. Warm metalworking for plastic manufacturing in brittle semiconductors. Nat. Mater. (2025). https://doi.org/10.1038/s41563-025-02223-9

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