Ultra-large Macroscopic Plastic Deformation and Metalworking in Inorganic Semiconductors

doi:10.15541/jim20250437

Abstract

Abstract:

Brittleness is a major bottleneck that limits the efficient processing and manufacturing of inorganic semiconductor materials and their application in complex structural scenarios. Overcoming the intrinsic brittleness of inorganic semiconductors and achieving metal-like processing and manufacturing have long been a significant challenge in the field of materials science. In recent years, Chinese researchers have pioneered the discovery of room-temperature macroscopic ultra-large plastic strain in inorganic semiconductors, reshaping the traditional understanding of the mechanical properties of these materials. The exceptional plasticity of these materials enables various metal-like processing and manufacturing methods, resulting in diverse material forms such as sheets, foils, wires, and rods, which greatly expands the application scenarios. After years of development, ductile inorganic semiconductors have gradually emerged as an important and emerging research focus in the field of inorganic non-metallic materials. This perspective briefly reviews the research progress and development trajectory of this new direction, with a focus on representative work in materials discovery, deformation mechanisms, cold and warm processing, and exemplary applications. Finally, we tentatively outline the challenges and potential future research directions in this field.

Key words: inorganic semiconductor, ultra-large plastic deformation, metalworking, deformation mechanism, perspective

CLC Number:

TB34

FENG Hengyang, WEI Tianran, QIU Pengfei, SHI Xun. Ultra-large Macroscopic Plastic Deformation and Metalworking in Inorganic Semiconductors[J]. Journal of Inorganic Materials, 2026, 41(6): 681-688.

Figures/Tables 3

Table 1 Room-temperature elongation versus band gap of ductile inorganic semiconductors in the macroscopic bulk form[6,8,12 -13,15 -18,28,30 -38]

Material		Elongation/%
Ag₂S	1.0^[6]	4.2^[6]/14.1^[31]
Ag₂S_0.3Te_0.7	~0.11^[31]	107^[28]
Ag₂S_0.4Te_0.6	~0.11^[31]	75^[28]/15^[8]
Ag₂S_0.5Te_0.5	~0.12^[22]	52^[8]
Ag₂S_0.5Se_0.5	0.28^[32]	25^[33]
Ag₂S_1/3Se_1/3Te_1/3	~0.30^[12]	97^[12]
InSe	1.2^[13]	12^[13]/17^[34]
GaSe	2.1^[35]	11^[15]
MoS₂	1.3^[35]	9^[15]
SnSe₂	0.90^[35]	6^[15]
Defective Bi₂Te₃	0.15^[36]	8^[16]
CrSiTe₃	0.4^[37]	12^[30]
Mg₃Sb₂	0.41^[38]	7.4^[18]
Mg₃Bi₂	0^[38]	100^[17]/12.7^[18]
AgCl	3.2^[35]	34^[31]
AgBr	2.7^[35]	52^[31]

Fig. 1 Metal-like plastic processing of inorganic semiconductors[10,42,52,59] (a) Schematic diagram of processing, including rolling, extrusion and flatbed press[52]; (b, c) Iterative rolling and drawing of Ag2Te0.6S0.4[42]; (d) Room temperature twisted deformation of Ag2S0.7Te0.3[10]; (e) Warm rolling of Ag2Se film[52]; (f, g) Warm extrusion and flatbed processing of Cu2Se[52]; (h) Warm stamping of Bi0.85Sb0.15[59]

Fig. 2 Multiple functional applications of multiform ductile inorganic semiconductors[10,24,30,54 -56,58,62 -63]

References 64

[1]	谢建新. 材料加工新技术与新工艺. 北京: 冶金工业出版社, 2004: 1-13.
[2]	GREEN D J. An introduction to the mechanical properties of ceramics. Cambridge: Cambridge University Press, 1998: 210-217.
[3]	DONG S M, WANG J Y, NI D W. Structural ceramics—the cornerstone of human civilization. Journal of Inorganic Materials, 2024, 39(6): 569.
[4]	JOSHUA P. Mechanical properties of semiconductors. Cham: Springer Nature Switzerland AG, 2024: 271-272.
[5]	吴汉明. 集成电路制造大生产工艺技术. 杭州: 浙江大学出版社, 2023: 63-198.
[6]	SHI X, CHEN H Y, HAO F, et al. Room-temperature ductile inorganic semiconductor. Nature Materials, 2018, 17(5): 421.
[7]	LIANG J S, WANG T, QIU P F, et al. Flexible thermoelectrics: from silver chalcogenides to full-inorganic devices. Energy & Environmental Science, 2019, 12(10): 2983.
[8]	HE S Y, LI Y B, LIU L, et al. Semiconductor glass with superior flexibility and high room temperature thermoelectric performance. Science Advances, 2020, 6(15): eaaz8423.
[9]	GAO Z Q, YANG Q Y, QIU P F, et al. p-Type plastic inorganic thermoelectric materials. Advanced Energy Materials, 2021, 11(23): 2100883.
[10]	YANG S Q, GAO Z Q, QIU P F, et al. Ductile Ag₂₀S₇Te₃ with excellent shape-conformability and high thermoelectric performance. Advanced Materials, 2021, 33(10): 2007681.
[11]	WEI T R, QIU P F, ZHAO K P, et al. Ag₂Q-based (Q=S, Se, Te) silver chalcogenide thermoelectric materials. Advanced Materials, 2023, 35(1): 2110236.
[12]	CHEN H Y, SHAO C L, HUANG S J, et al. High-entropy cubic pseudo-ternary Ag₂(S, Se, Te) materials with excellent ductility and thermoelectric performance. Advanced Energy Materials, 2024, 14(10): 2303473.
[13]	WEI T R, JIN M, WANG Y C, et al. Exceptional plasticity in the bulk single-crystalline van der Waals semiconductor InSe. Science, 2020, 369(6503): 542.
[14]	HAN X D. Ductile van der Waals materials. Science, 2020, 369(6503): 509.
[15]	GAO Z Q, WEI T R, DENG T T, et al. High-throughput screening of 2D van der Waals crystals with plastic deformability. Nature Communications, 2022, 13: 7491.
[16]	DENG T T, GAO Z Q, LI Z, et al. Room-temperature exceptional plasticity in defective Bi₂Te₃-based bulk thermoelectric crystals. Science, 2024, 386(6726): 1112.
[17]	ZHAO P, XUE W H, ZHANG Y, et al. Plasticity in single- crystalline Mg₃Bi₂ thermoelectric material. Nature, 2024, 631(8022): 777.
[18]	LI A R, WANG Y C, LI Y Z, et al. High performance magnesium-based plastic semiconductors for flexible thermoelectrics. Nature Communications, 2024, 15: 5108.
[19]	“中国学科及前沿领域发展战略研究(2021--2035)”项目组. 中国材料科学2035发展战略. 北京: 科学出版社, 2023: 494-495.
[20]	OSHIMA Y, NAKAMURA A, MATSUNAGA K. Extraordinary plasticity of an inorganic semiconductor in darkness. Science, 2018, 360(6390): 772.
[21]	LIANG J S, QIU P F, ZHU Y, et al. Crystalline structure-dependent mechanical and thermoelectric performance in Ag₂Se_1-_xS_x system. Research, 2020, 2020: 6591981.
[22]	LIANG X, CHEN C. Ductile inorganic amorphous/crystalline composite Ag₄TeS with phonon-glass electron-crystal transport behavior and excellent stability of high thermoelectric performance on plastic deformation. Acta Materialia, 2021, 218: 117231.
[23]	PENG L M, YANG S Q, WEI T R, et al. Phase-modulated mechanical and thermoelectric properties of Ag₂S_1-_xTe_x ductile semiconductors. Journal of Materiomics, 2022, 8(3): 656.
[24]	YANG Q Y, YANG S Q, QIU P F, et al. Flexible thermoelectrics based on ductile semiconductors. Science, 2022, 377(6608): 854.
[25]	LIANG J S, LIU J, QIU P F, et al. Modulation of the morphotropic phase boundary for high-performance ductile thermoelectric materials. Nature Communications, 2023, 14: 8442.
[26]	WU H, SHI X L, MAO Y Q, et al. Optimized thermoelectric performance and plasticity of ductile semiconductor Ag₂S_0.5Se_0.5 via dual-phase engineering. Advanced Energy Materials, 2023, 13(43): 2302551.
[27]	LI N H, SHI X L, LIU S Q, et al. Strategic vacancy engineering advances record-high ductile AgCu(Te, Se, S) thermoelectrics. Nature Communications, 2025, 16: 2812.
[28]	HU H P, WANG Y C, FU C G, et al. Achieving metal-like malleability and ductility in Ag₂Te_1-_xS_x inorganic thermoelectric semiconductors with high mobility. The Innovation, 2022, 3(6): 100341.
[29]	DENG T T, GAO Z Q, QIU P F, et al. Plastic/ductile bulk 2D van der Waals single-crystalline SnSe₂ for flexible thermoelectrics. Advanced Science, 2022, 9(29): 2203436.
[30]	LUO J, CHEN J, GAO Z Q, et al. Ductile inorganic ferromagnetic semiconductor. Advanced Materials, 2026, 38(4): e14083.
[31]	HUANG H R, CHEN H Y, GAO Z Q, et al. Room-temperature wide-gap inorganic materials with excellent plasticity. Advanced Functional Materials, 2023, 33(43): 2306042.
[32]	ALEKPEROVA S M, AKHMEDOV I A, GADZHIEVA G S, et al. Giant magnetoresistance and kinetic phenomena in n-Ag₄SSe in the vicinity of a phase transition. Physics of the Solid State, 2007, 49(3): 512.
[33]	REN S H, CHEN H Y, FU H L, et al. The structural origin of extraordinary plasticity in polycrystalline semiconductors with low symmetry. Science Advances, 2025, 11(27): eadu9205.
[34]	MA Y P, HUANG H R, LIU Y F, et al. Remarkable plasticity and softness of polymorphic InSe van der Waals crystals. Journal of Materiomics, 2023, 9(4): 709.
[35]	Springer materials. (update 2025)[2025-10-30]. https://materials.springer.com/periodictable#.
[36]	陈立东, 刘睿恒, 史迅. 热电材料与器件. 北京: 科学出版社, 2018: 66-70.
[37]	CASTO L D, CLUNE A J, YOKOSUK M O, et al. Strong spin- lattice coupling in CrSiTe₃. APL Materials, 2015, 3(4): 041515.
[38]	IMAI Y, WATANABE A. Electronic structures of Mg₃Pn₂ (Pn=N, P, As, Sb and Bi) and Ca₃N₂ calculated by a first-principle pseudopotential method. Journal of Materials Science, 2006, 41(8): 2435.
[39]	MEYERS M, CHAWLA K. Mechanical behavior of materials. Cambridge: Cambridge University Press, 2008: 404-420.
[40]	MA H Q, HUANG H G, LU Z T, et al. Origin of shear induced ‘catching bonds’ on half Heusler thermoelectric compounds XFeSb (X = Nb, Ta) and SnNiY (Y = Ti, Zr, Hf). npj Computational Materials, 2024, 10: 61.
[41]	ZHANG J, LIU G H, CUI W, et al. Plastic deformation in silicon nitride ceramics via bond switching at coherent interfaces. Science, 2022, 378(6618): 371.
[42]	WANG Y C, LI A R, HONG Y R, et al. Iterative sublattice amorphization facilitates exceptional processability in inorganic semiconductors. Nature Materials, 2025, 24: 1545.
[43]	HU M Y, YANG J M, WANG Y, et al. Helical dislocation-driven plasticity and flexible high-performance thermoelectric generator in α-Mg₃Bi₂ single crystals. Nature Communications, 2025, 16: 128.
[44]	SUN Y D, MA Y P, ZHANG J Y, et al. Van der Waals semiconductor InSe plastifies by martensitic transformation. Science Advances, 2024, 10(42): eado9593.
[45]	WONG L W, YANG K, HAN W, et al. Deciphering the ultra-high plasticity in metal monochalcogenides. Nature Materials, 2024, 23(2): 196.
[46]	GE B Z, LI C, LU W Q, et al. Dynamic phase transition leading to extraordinary plastic deformability of thermoelectric SnSe₂ single crystal. Advanced Energy Materials, 2023, 13(27): 2300965.
[47]	RICE J R, THOMSON R. Ductile versus brittle behavior of crystals. Philosophical Magazine, 1974, 29(1): 73.
[48]	WU Y J, ZHANG Y, WANG X Y, et al. Twisted-layer boron nitride ceramic with high deformability and strength. Nature, 2024, 626(8000): 779.
[49]	CANTOS-PRIETO F, FALIN A, ALLIATI M, et al. Layer-dependent mechanical properties and enhanced plasticity in the van der Waals chromium trihalide magnets. Nano Letters, 2021, 21(8): 3379.
[50]	REN Q, LUN Y Z, LI Y H, et al. High-throughput screening of deformable inorganic layered semiconductors. The Journal of Physical Chemistry C, 2023, 127(16): 7870.
[51]	TAN J L, ZHANG H Y, WANG X Z, et al. Deformable monoclinic gallium telluride with high in-plane structural anisotropy. Materials Today, 2024, 80: 250.
[52]	GAO Z Q, YANG S Q, MA Y P, et al. Warm metalworking for plastic manufacturing in brittle semiconductors. Nature Materials, 2025, 24: 1538.
[53]	NAKAMURA A, LI Y. Plastic processing of bulk semiconductors. Nature Materials, 2025, 24(10): 1505.
[54]	LIANG J, ZHANG X F, WAN C L. From brittle to ductile: a scalable and tailorable all-inorganic semiconductor foil through a rolling process toward flexible thermoelectric modules. ACS Applied Materials & Interfaces, 2022, 14(46): 52017.
[55]	ZHU Y, LIANG J S, MATHAYAN V, et al. High performance full-inorganic flexible memristor with combined resistance- switching. ACS Applied Materials & Interfaces, 2022, 14(18): 21173.
[56]	ZHAO X F, YANG S Q, WEN X H, et al. A fully flexible intelligent thermal touch panel based on intrinsically plastic Ag₂S semiconductor. Advanced Materials, 2022, 34(13): 2107479.
[57]	WANG X D, TAN J L, OUYANG J, et al. Designing inorganic semiconductors with cold-rolling processability. Advanced Science, 2022, 9(30): 2203776.
[58]	WANG Q, WAN C L, WU Y, et al. Plastic inorganic van der Waals semiconductors for flexible X-ray detectors. ACS Applied Electronic Materials, 2025, 7(5): 1764.
[59]	FU L, MA Y P, PAN Z Y, et al. Warm metalworking for brittle liquid-nitrogen-temperature thermoelectric materials. Advanced Energy Materials, 2025, 15(42): e03241.
[60]	DING W J, SHEN X Y, JIN M, et al. Robust bendable thermoelectric generators enabled by elasticity strengthening. Nature Communications, 2024, 15: 9767.
[61]	FU Y Q, KANG S L, GU H, et al. Superflexible inorganic Ag₂Te_0.6S_0.4 fiber with high thermoelectric performance. Advanced Science, 2023, 10(13): 2207642.
[62]	XIN L T, HE H Y, WANG X H, et al. Single-crystalline indium selenide fibers by laser-induced recrystallization and their tunable whispering-gallery-mode lasing by pressure-modulating. Journal of the American Ceramic Society, 2024, 107(9): 5801.
[63]	LI X C, MENG Y, LI W P, et al. Multislip-enabled morphing of all-inorganic perovskites. Nature Materials, 2023, 22(10): 1175.
[64]	DONG L R, ZHANG J, LI Y Z, et al. Borrowed dislocations for ductility in ceramics. Science, 2024, 385(6707): 422.