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Vapour–liquid–solid–solid growth of two-dimensional non-layered β-Bi2O3 crystals with high hole mobility

Abstract

Currently, p-type two-dimensional (2D) materials lag behind n-type ones in both quantity and performance, hindering their use in advanced p-channel transistors and complementary logic circuits. Non-layered materials, which make up 95% of crystal structures, hold the potential for superior p-type 2D materials but remain challenging to synthesize. Here we show a vapour–liquid–solid–solid growth of atomically thin (<1 nm), high-quality, non-layered 2D β-Bi2O3 crystals on a SiO2/Si substrate. These crystals form via a transformation from layered BiOCl intermediates. We further realize 2D β-Bi2O3 transistors with room-temperature hole mobility and an on/off current ratio of 136.6 cm2 V−1 s−1 and 1.2 × 108, respectively. The p-type nature is due to the strong suborbital hybridization of Bi 6s26p3 with O 2p4 at the crystal’s M-point valence band maximum. Our work can be used as a reference that adds more 2D non-layered materials to the 2D toolkit and shows 2D β-Bi2O3 to be promising candidate for future electronics.

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Fig. 1: Theoretical and experimental atomic structures of 2D non-layered β-Bi2O3.

Fig. 2: VLSS growth mechanism of 2D non-layered β-Bi2O3.

Fig. 3: Band structure evolution and p-type conduction mechanism of 2D non-layered β-Bi2O3.

Fig. 4: FET performance of p-type 2D non-layered β-Bi2O3.

Data availability

All relevant data supporting the findings of this study are available within the Article and its Supplementary Information file and from the corresponding authors upon reasonable request. Source data are provided with this paper.

References

Wu, F. et al. Vertical MoS2 transistors with sub-1-nm gate lengths. Nature 603, 259–264 (2022).

CASPubMedGoogle Scholar

Chhowalla, M., Jena, D. & Zhang, H. Two-dimensional semiconductors for transistors. Nat. Rev. Mater. 1, 16052 (2016).

CASGoogle Scholar

Jiang, J., Xu, L., Qiu, C. & Peng, L. Ballistic two-dimensional InSe transistors. Nature 616, 470–475 (2023).

CASPubMedGoogle Scholar

Liu, Y. et al. Promises and prospects of two-dimensional transistors. Nature 591, 43–53 (2021).

CASPubMedGoogle Scholar

Liu, Y., Duan, X., Huang, Y. & Duan, X. Two-dimensional transistors beyond graphene and TMDCs. Chem. Soc. Rev. 47, 6388–6409 (2018).

CASPubMedGoogle Scholar

Rhodes, D., Chae, S. H., Ribeiro-Palau, R. & Hone, J. Disorder in van der Waals heterostructures of 2D materials. Nat. Mater. 18, 541–549 (2019).

CASPubMedGoogle Scholar

Hu, W. et al. Ambipolar 2D semiconductors and emerging device applications. Small Methods 5, 2000837 (2020).

Google Scholar

Yu, X., Marks, T. J. & Facchetti, A. Metal oxides for optoelectronic applications. Nat. Mater. 15, 383–396 (2016).

CASPubMedGoogle Scholar

Favron, A. et al. Photooxidation and quantum confinement effects in exfoliated black phosphorus. Nat. Mater. 14, 826–832 (2015).

CASPubMedGoogle Scholar

Pei, J. et al. Producing air-stable monolayers of phosphorene and their defect engineering. Nat. Commun. 7, 10450 (2016).

CASPubMedPubMed CentralGoogle Scholar

Kong, L., Chen, Y. & Liu, Y. Recent progresses of NMOS and CMOS logic functions based on two-dimensional semiconductors. Nano Res. 14, 1768–1783 (2021).

CASGoogle Scholar

Xiong, Y. et al. P-type 2D semiconductors for future electronics. Adv. Mater. 35, 2206939 (2023).

CASGoogle Scholar

Mounet, N. et al. Two-dimensional materials from high-throughput computational exfoliation of experimentally known compounds. Nat. Nanotechnol. 13, 246–252 (2018).

CASPubMedGoogle Scholar

Zhao, Z. et al. A general thermodynamics-triggered competitive growth model to guide the synthesis of two-dimensional nonlayered materials. Nat. Commun. 14, 958 (2023).

CASPubMedPubMed CentralGoogle Scholar

Balan, A. et al. Non-van der Waals quasi-2D materials; recent advances in synthesis, emergent properties and applications. Mater. Today 58, 164–200 (2022).

CASGoogle Scholar

Li, N. et al. Synthesis and optoelectronic applications of a stable p-type 2D material: α-MnS. ACS Nano 13, 12662–12670 (2019).

CASPubMedGoogle Scholar

Kaur, H. & Coleman, J. N. Liquid-phase exfoliation of nonlayered non-van-der-Waals crystals into nanoplatelets. Adv. Mater. 34, 2202164 (2022).

CASGoogle Scholar

Liu, K. et al. Puffing ultrathin oxides with nonlayered structures. Sci. Adv. 8, eabn2030 (2022).

CASPubMedPubMed CentralGoogle Scholar

Xiao, X. et al. Facile large-scale synthesis of β-Bi2O3 nanosphere as a highly efficient photocatalyst for the degradation of acetaminophen under visible light irradiation. Appl. Catal. B Environ. 140–141, 433–443 (2013).

Google Scholar

Gong, Q. et al. Structural defects on converted bismuth oxide nanotubes enable highly active electrocatalysis of carbon dioxide reduction. Nat. Commun. 10, 2807 (2019).

PubMedPubMed CentralGoogle Scholar

Qiu, Y. et al. Controlled synthesis of bismuth oxide nanowires by an oxidative metal vapor transport deposition technique. Adv. Mater. 18, 2604–2608 (2006).

CASGoogle Scholar

Pérez-Mezcua, D. et al. Photochemical solution processing of films of metastable phases for flexible devices: the β-Bi2O3 polymorph. Sci. Rep. 6, 39561 (2016).

PubMedPubMed CentralGoogle Scholar

Schulman, D. S., Arnold, A. J. & Das, S. Contact engineering for 2D materials and devices. Chem. Soc. Rev. 47, 3037–3058 (2018).

CASPubMedGoogle Scholar

Zhou, J. et al. A library of atomically thin metal chalcogenides. Nature 556, 355–359 (2018).

CASPubMedGoogle Scholar

Zhang, B. Y. et al. Hexagonal metal oxide monolayers derived from the metal–gas interface. Nat. Mater. 20, 1073–1078 (2021).

CASPubMedGoogle Scholar

Zavabeti, A. et al. High-mobility p-type semiconducting two-dimensional β-TeO2. Nat. Mater. 4, 277–283 (2021).

CASGoogle Scholar

Wang, Y. et al. P-type electrical contacts for 2D transition-metal dichalcogenides. Nature 610, 61–66 (2022).

PubMedGoogle Scholar

Salazar-Pérez, A. J. et al. Structural evolution of Bi2O3 prepared by thermal oxidation of bismuth nano-particles. Superf. Vacío 18, 4–8 (2005).

Google Scholar

Pereira, A. L. J. et al. Isostructural second-order phase transition of β-Bi2O3 at high pressures: an experimental and theoretical study. J. Phys. Chem. C 118, 23189–23201 (2014).

CASGoogle Scholar

Tran‐Phu, T. et al. Nanostructured β‐Bi2O3 fractals on carbon fibers for highly selective CO2 electroreduction to formate. Adv. Funct. Mater. 30, 1906478 (2019).

Google Scholar

Wu, J. et al. Epitaxial growth of 2D ultrathin metastable γ-Bi2O3 flakes for high performance ultraviolet photodetection. Small 18, 2104244 (2021).

Google Scholar

Yang, J. et al. Formation of two-dimensional transition metal oxide nanosheets with nanoparticles as intermediates. Nat. Mater. 18, 970–976 (2019).

CASPubMedGoogle Scholar

Weng, S. et al. Facile in situ synthesis of a Bi/BiOCl nanocomposite with high photocatalytic activity. J. Mater. Chem. A 1, 3068–3075 (2013).

CASGoogle Scholar

Li, S. et al. Vapour–liquid–solid growth of monolayer MoS2 nanoribbons. Nat. Mater. 17, 535–542 (2018).

CASPubMedGoogle Scholar

Bellet-Amalric, E. et al. Regulated dynamics with two monolayer steps in vapor–solid–solid growth of nanowires. ACS Nano 16, 4397–4407 (2022).

CASPubMedGoogle Scholar

Greyson, E. C., Babayan, Y. & Odom, T. W. Directed growth of ordered arrays of small-diameter ZnO nanowires. Adv. Mater. 16, 1348–1352 (2004).

CASGoogle Scholar

Yang, P. et al. Thickness tunable wedding-cake-like MoS2 flakes for high-performance optoelectronics. ACS Nano 13, 3649–3658 (2019).

CASPubMedGoogle Scholar

Li, S. et al. Halide-assisted atmospheric pressure growth of large WSe2 and WS2 monolayer crystals. Appl. Mater. Today 1, 60–66 (2015).

Google Scholar

Wu, J., Mao, N., Xie, L., Xu, H. & Zhang, J. Identifying the crystalline orientation of black phosphorus using angle-resolved polarized Raman spectroscopy. Angew. Chem. Int. Ed. 54, 2366–2369 (2015).

CASGoogle Scholar

Wu, J. et al. High electron mobility and quantum oscillations in non-encapsulated ultrathin semiconducting Bi2O2Se. Nat. Nanotechnol. 12, 530–534 (2017).

CASPubMedGoogle Scholar

Mark, K. F. et al. Atomically thin MoS2: a new direct-gap semiconductor. Phys. Rev. Lett. 105, 136805 (2010).

Google Scholar

Shi, J. et al. Wide bandgap oxide semiconductors: from materials physics to optoelectronic devices. Adv. Mater. 33, 2006230 (2021).

CASGoogle Scholar

Heinemann, M., Eifert, B. & Heiliger, C. Band structure and phase stability of the copper oxides Cu2O, CuO, and Cu4O3. Phys. Rev. B 87, 115111 (2013).

Google Scholar

Quackenbush, N. F. et al. Origin of the bipolar doping behavior of SnO from X-ray spectroscopy and density functional theory. Chem. Mater. 25, 3114–3123 (2013).

CASGoogle Scholar

Li, L. et al. Black phosphorus field-effect transistors. Nat. Nanotechnol. 9, 372–377 (2014).

CASPubMedGoogle Scholar

Zhao, T. et al. Substrate engineering for wafer-scale two-dimensional material growth: strategies, mechanisms, and perspectives. Chem. Soc. Rev. 52, 1650–1671 (2023).

CASPubMedGoogle Scholar

Cui, X. et al. Multi-terminal transport measurements of MoS2 using a van der Waals heterostructure device platform. Nat. Nanotechnol. 10, 534–540 (2015).

CASPubMedGoogle Scholar

Zhang, X. et al. Molecule-upgraded van der Waals contacts for Schottky-barrier-free electronics. Adv. Mater. 33, 2104935 (2021).

CASGoogle Scholar

Kong, L. et al. Doping-free complementary WSe2 circuit via van der Waals metal integration. Nat. Commun. 11, 1866 (2020).

CASPubMedPubMed CentralGoogle Scholar

Liu, Y. et al. Approaching the Schottky–Mott limit in van der Waals metal–semiconductor junctions. Nature 557, 696–700 (2018).

CASPubMedGoogle Scholar

Zhou, H. et al. Large area growth and electrical properties of p-type WSe2 atomic layers. Nano Lett. 15, 709–713 (2015).

CASPubMedGoogle Scholar

Radisavljevic, B. et al. Single-layer MoS2 transistors. Nat. Nanotechnol. 6, 147–150 (2011).

CASPubMedGoogle Scholar

Li, T. et al. Epitaxial growth of wafer-scale molybdenum disulfide semiconductor single crystals on sapphire. Nat. Nanotechnol. 16, 1201–1207 (2021).

CASPubMedGoogle Scholar

Download references

Acknowledgements

This work was supported by the National Key R&D Program of China (no. 2024YFB3612400, H.Z.), the National Natural Science Foundation of China (nos 52372152, X.C.; 92064007, X.C.; 62274089, X.S.; U24A20286, H.Z.; 52131304, H.Z.; and 62261160392, H.Z.) and the Natural Science Foundation of Jiangsu Province (nos BZ2024038, X.C. and BK20190476, X.C.).

Author information

Author notes

These authors contributed equally: Yunhai Xiong, Duo Xu, Yousheng Zou.

Authors and Affiliations

MIIT Key Laboratory of Advanced Display Materials and Devices, Jiangsu Engineering Research Center for Quantum Dot Display, Institute of Optoelectronics & Nanomaterials, School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing, China

Yunhai Xiong, Duo Xu, Yousheng Zou, Lili Xu, Xiufeng Song, Kairui Qu, Tong Zhao, Jie Gao, Jialin Yang, Shengli Zhang, Xiang Chen & Haibo Zeng

National Laboratory of Solid State Microstructures, Jiangsu Key Laboratory of Artificial Functional Materials, College of Engineering and Applied Sciences and Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, China

Yujie Yan, Jianghua Wu & Peng Wang

Department of Chemistry, University of Warwick, Coventry, UK

Chen Qian

CAS Key Laboratory of Nano-Bio Interface & Key Laboratory of Nanodevices and Applications, i-Lab, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, China

Kai Zhang

Department of Physics, University of Warwick, Coventry, UK

Peng Wang

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Yunhai Xiong

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