Stable alkali halide vapor assisted chemical vapor deposition of 2D HfSe₂ templates and controllable oxidation of its heterostructures

Abstract

Two-dimensional hafnium-based semiconductors and their heterostructures with native oxides have been shown unique physical properties and potential electronic and optoelectronic applications. However, the scalable synthesis methods for ultrathin layered hafnium-based semiconductor laterally epitaxy growth and its heterostructure are still restricted, also for the understanding of its formation mechanism. Herein, we report the stable sublimation of alkali halide vapor assisted synthesis strategy for high-quality 2D HfSe₂ nanosheets via chemical vapor deposition. Single-crystalline ultrathin 2D HfSe₂ nanosheets were systematically grown by tuning the growth parameters, reaching the lateral size of 6‒40 μm and the thickness down to 4.5 nm. The scalable amorphous HfO₂ and HfSe₂ heterostructures were achieved by the controllable oxidation, which benefited from the approximate zero Gibbs free energy of unstable 2D HfSe₂ templates. The crystal structure, elemental, and time dependent Raman characterization were carried out to understand surface precipitated Se atoms and the formation of amorphous Hf−O bonds, confirming the slow surface oxidation and lattice incorporation of oxygen atoms. The relatively smooth surface roughness and electrical potential change of HfO₂−HfSe₂ heterostructures indicate the excellent interface quality, which helps obtain the high performance memristor with high on/off ratio of 10⁵ and long retention period over 9000 s. Our work introduces a new vapor catalysts strategy for the synthesis of lateral 2D HfSe₂ nanosheets, also providing the scalable oxidation of the Hf-based heterostructures for 2D electronic devices.

Graphical abstract

Keywords

chemical vapor deposition / HfSe₂−HfO₂ / nanoelectronics

References

[1] T.LiT.Tu Y.SunH. FuJ.YuL.XingZ.Wang H.WangR. JiaJ.WuC.TanY.Liang Y.ZhangC. ZhangY.DaiC.QiuM.Li R.HuangL. JiaoK.LaiB.YanP.Gao H.Peng, A native oxide high-κ gate dielectric for two-dimensional electronics, Nat. Electron. 3(8), 473 (2020)

[2] Y. Zhou, D. Wu, Y. Zhu, Y. Cho, Q. He, X. Yang, K. Herrera, Z. Chu, Y. Han, M. C. Downer, H. Peng, K. Lai. Out-of-plane piezoelectricity and ferroelectricity in layered α-In₂Se₃ nanoflakes. Nano Lett., 2017, 17(9): 5508

[3] C. Chen, X. Chen, C. Wu, X. Wang, Y. Ping, X. Wei, X. Zhou, J. Lu, L. Zhu, J. Zhou, T. Zhai, J. Han, H. Xu. Air-stable 2D Cr₅Te₈ nanosheets with thickness-tunable ferromagnetism. Adv. Mater., 2022, 34(2): 2107512

[4] B. Li, Z. Wan, C. Wang, P. Chen, B. Huang, X. Cheng, Q. Qian, J. Li, Z. Zhang, G. Sun, B. Zhao, H. Ma, R. Wu, Z. Wei, Y. Liu, L. Liao, Y. Ye, Y. Huang, X. Xu, X. Duan, W. Ji, X. Duan. Van der Waals epitaxial growth of air-stable CrSe₂ nanosheets with thickness-tunable magnetic order. Nat. Mater., 2021, 20(6): 818

[5] X. Fan, R. Xin, L. Li, B. Zhang, C. Li, X. Zhou, H. Chen, H. Zhang, F. OuYang, Y. Zhou. Progress in the preparation and physical properties of two-dimensional Cr-based chalcogenide materials and heterojunctions. Front. Phys. 19, 2023, (2): 23401

[6] B. Lei, A. Li, W. Zhou, Y. Wang, W. Xiong, Y. Chen, F. Ouyang. Room-temperature ferromagnetism and half-metallicity in monolayer orthorhombic CrS₂. Front. Phys. 19, 2024, (4): 43200

[7] X. Zhu, H. Liu, L. Liu, L. Ren, W. Li, L. Fang, X. Chen, L. Xie, Y. Jing, J. Chen, S. Liu, F. Ouyang, Y. Zhou, X. Xiong. Spin glass state in chemical vapor-deposited crystalline Cr₂Se₃ nanosheets. Chem. Mater., 2021, 33(10): 3851

[8] Y. Zhou, C. Li, Y. Zhang, L. Wang, X. Fan, L. Zou, Z. Cai, J. Jiang, S. Zhou, B. Zhang, H. Zhang, W. Li, Z. Chen. Controllable thermochemical generation of active defects in the horizontal/vertical MoS₂ for enhanced hydrogen evolution. Adv. Funct. Mater., 2023, 33(46): 2304302

[9] R. Xie, W. Luo, L. Zou, X. Fan, C. Li, T. Lv, J. Jiang, Z. Chen, Y. Zhou. Low-temperature synthesis of colloidal few-layer WTe₂ nanostructures for electrochemical hydrogen evolution. Discover Nano, 2023, 18(1): 44

[10] Y. Zhou, J. L. Silva, J. M. Woods, J. V. Pondick, Q. Feng, Z. Liang, W. Liu, L. Lin, B. Deng, B. Brena, F. Xia, H. Peng, Z. Liu, H. Wang, C. M. Araujo, J. J. Cha. Revealing the contribution of individual factors to hydrogen evolution reaction catalytic activity. Adv. Mater., 2018, 30(18): 1706076

[11] Y. Zhou, H. Jang, J. M. Woods, Y. Xie, P. Kumaravadivel, G. A. Pan, J. Liu, Y. Liu, D. G. Cahill, J. J. Cha. Direct synthesis of large-scale WTe₂ thin films with low thermal conductivity. Adv. Funct. Mater., 2017, 27(8): 1605928

[12] Y. Wen, Q. Wang, L. Yin, Q. Liu, F. Wang, F. Wang, Z. Wang, K. Liu, K. Xu, Y. Huang, T. A. Shifa, C. Jiang, J. Xiong, J. He. Epitaxial 2D PbS nanoplates arrays with highly efficient infrared response. Adv. Mater., 2016, 28(36): 8051

[13] G. Wu, L. Xiang, W. Wang, C. Yao, Z. Yan, C. Zhang, J. Wu, Y. Liu, B. Zheng, H. Liu, C. Hu, X. Sun, C. Zhu, Y. Wang, X. Xiong, Y. Wu, L. Gao, D. Li, A. Pan, S. Li. Hierarchical processing enabled by 2D ferroelectric semiconductor transistor for low-power and high-efficiency AI vision system. Sci. Bull. (Beijing), 2024, 69(4): 473

[14] H. Liu, C. Zhu, Y. Chen, X. Yi, X. Sun, Y. Liu, H. Wang, G. Wu, J. Wu, Y. Li, X. Zhu, D. Li, A. Pan. Polarization-sensitive photodetectors based on highly in-plane anisotropic violet phosphorus with large dichroic ratio. Adv. Funct. Mater., 2023, 34(17): 2314838

[15] X. Sun, C. Zhu, J. Yi, L. Xiang, C. Ma, H. Liu, B. Zheng, Y. Liu, W. You, W. Zhang, D. Liang, Q. Shuai, X. Zhu, H. Duan, L. Liao, Y. Liu, D. Li, A. Pan. Reconfigurable logic-in-memory architectures based on a two-dimensional van der Waals heterostructure device. Nat. Electron., 2022, 5(11): 752

[16] J. Zhu, L. Wang, J. Wu, Y. Liang, F. Xiao, B. Xu, Z. Zhang, X. Fan, Y. Zhou, J. Xia, Z. Wang. Achieving 1.2 fm/Hz^1/2 displacement sensitivity with laser interferometry in two-dimensional nanomechanical resonators: Pathways towards quantum-noise-limited measurement at room temperature. Chin. Phys. Lett., 2023, 40(3): 038102

[17] B. Liu, W. Chu, S. Liu, Y. Zhou, L. Zou, J. Fu, M. Liu, X. Fu, F. Ouyang, Y. Zhou. Engineering the nanostructures of solution proceed In₂Se_xS_3−x films with enhanced near-infrared absorption for photoelectrochemical water splitting. J. Phys. D Appl. Phys., 2022, 55(43): 434004

[18] M. Li, H. Sun, J. Zhou, Y. Zhao. Engineering phonon thermal transport in few-layer PdSe₂. Front. Phys. 19, 2023, (3): 33203

[19] T. Zhu, Y. Zhang, X. Wei, M. Jiang, H. Xu. The rise of two-dimensional tellurium for next-generation electronics and optoelectronics. Front. Phys., 2023, 18(3): 33601

[20] Y. Wang, X. Guo, S. You, J. Jiang, Z. Wang, F. Ouyang, H. Huang. Giant quartic-phonon decay in PVD-grown α-MoO₃ flakes. Nano Res., 2023, 16(1): 1115

[21] S. H. Chae, Y. Jin, T. S. Kim, D. S. Chung, H. Na, H. Nam, H. Kim, D. J. Perello, H. Y. Jeong, T. H. Ly, Y. H. Lee. Oxidation effect in octahedral hafnium disulfide thin film. ACS Nano, 2016, 10(1): 1309

[22] M. J. Mleczko, C. Zhang, H. R. Lee, H. H. Kuo, B. Magyari-Köpe, R. G. Moore, Z. X. Shen, I. R. Fisher, Y. Nishi, E. Pop. HfSe₂ and ZrSe₂: Two-dimensional semiconductors with native high-κ oxides. Sci. Adv., 2017, 3(8): e1700481

[23] W. Zhang, Z. Huang, W. Zhang, Y. Li. Two-dimensional semiconductors with possible high room temperature mobility. Nano Res., 2014, 7(12): 1731

[24] G. Fiori, F. Bonaccorso, G. Iannaccone, T. Palacios, D. Neumaier, A. Seabaugh, S. K. Banerjee, L. Colombo. Electronics based on two-dimensional materials. Nat. Nanotechnol., 2014, 9(10): 768

[25] N. Peimyoo, M. D. Barnes, J. D. Mehew, A. De Sanctis, I. Amit, J. Escolar, K. Anastasiou, A. P. Rooney, S. J. Haigh, S. Russo, M. F. Craciun, F. Withers. Laser-writable high-κ dielectric for van der Waals nanoelectronics. Sci. Adv., 2019, 5(1): eaau0906

[26] L. Yin, K. Xu, Y. Wen, Z. Wang, Y. Huang, F. Wang, T. A. Shifa, R. Cheng, H. Ma, J. He. Ultrafast and ultrasensitive phototransistors based on few-layered HfSe₂. Appl. Phys. Lett., 2016, 109(21): 213105

[27] M. Kang, S. Rathi, I. Lee, D. Lim, J. Wang, L. Li, M. A. Khan, G. H. Kim. Electrical characterization of multilayer HfSe₂ field-effect transistors on SiO₂ substrate. Appl. Phys. Lett., 2015, 106(14): 143108

[28] M. Kang, S. Rathi, I. Lee, L. Li, M. A. Khan, D. Lim, Y. Lee, J. Park, S. J. Yun, D. H. Youn, C. Jun, G. H. Kim. Tunable electrical properties of multilayer HfSe₂ field effect transistors by oxygen plasma treatment. Nanoscale, 2017, 9(4): 1645

[29] T.KangJ. ParkH.JungH.ChoiS.M. Lee N.LeeR. G. LeeG.KimS.H. KimH.Kim C.W. YangJ. JeonY.H. KimS.Lee, High-κ dielectric (HfO₂)/2D semiconductor (HfSe₂) gate stack for low-power steep-switching computing devices, Adv. Mater. 2312747, doi: 10.1002/adma.202312747 (2024)

[30] A. L. Hector, W. Levason, G. Reid, S. D. Reid, M. Webster. Evaluation of group 4 metal bis-cyclopentadienyl complexes with selenolate and tellurolate ligands for CVD of ME₂ films (E = Se or Te). Chem. Mater., 2008, 20(15): 5100

[31] R. Yue, A. T. Barton, H. Zhu, A. Azcatl, L. F. Pena, J. Wang, X. Peng, N. Lu, L. Cheng, R. Addou, S. McDonnell, L. Colombo, J. W. P. Hsu, J. Kim, M. J. Kim, R. M. Wallace, C. L. Hinkle. HfSe₂ thin films: 2D transition metal dichalcogenides grown by molecular beam epitaxy. ACS Nano, 2015, 9(1): 474

[32] K. E. Aretouli, P. Tsipas, D. Tsoutsou, J. Marquez-Velasco, E. Xenogiannopoulou, S. A. Giamini, E. Vassalou, N. Kelaidis, A. Dimoulas. Two-dimensional semiconductor HfSe₂ and MoSe₂/HfSe₂ van der Waals heterostructures by molecular beam epitaxy. Appl. Phys. Lett., 2015, 106(14): 143105

[33] S. Li, M. E. Pam, Y. Li, L. Chen, Y. C. Chien, X. Fong, D. Chi, K. W. Ang. Wafer-scale 2D hafnium diselenide based memristor crossbar array for energy-efficient neural network hardware. Adv. Mater., 2022, 34(25): 2103376

[34] B. Zheng, Y. Chen, Z. Wang, F. Qi, Z. Huang, X. Hao, P. Li, W. Zhang, Y. Li. Vertically oriented few-layered HfS₂ nanosheets: Growth mechanism and optical properties. 2D Mater., 2016, 3(3): 035024

[35] D. Wang, X. Zhang, H. Liu, J. Meng, J. Xia, Z. Yin, Y. Wang, J. You, X. M. Meng. Epitaxial growth of HfS₂ on sapphire by chemical vapor deposition and application for photodetectors. 2D Mater., 2017, 4(3): 031012

[36] L. Fu, F. Wang, B. Wu, N. Wu, W. Huang, H. Wang, C. Jin, L. Zhuang, J. He, L. Fu, Y. Liu. Van der Waals epitaxial growth of atomic layered HfS₂ crystals for ultrasensitive near-infrared phototransistors. Adv. Mater., 2017, 29(32): 1700439

[37] W. Li, J. Zhou, S. Cai, Z. Yu, J. Zhang, N. Fang, T. Li, Y. Wu, T. Chen, X. Xie, H. Ma, K. Yan, N. Dai, X. Wu, H. Zhao, Z. Wang, D. He, L. Pan, Y. Shi, P. Wang, W. Chen, K. Nagashio, X. Duan, X. Wang. Uniform and ultrathin high-κ gate dielectrics for two-dimensional electronic devices. Nat. Electron., 2019, 2(12): 563

[38] C. Li, R. Xin, C. Y. Jiao, Z. Zhang, J. Qin, W. Chu, X. Zhou, Z. Li, Z. Wang, J. Xia, Y. Zhou. Synthesis of hetero-site nucleation twisted bilayer MoS₂ by local airflow perturbations and interlayer angle characterization. J. Cent. South Univ., 2023, 30(10): 3187

[39] X. Zhu, L. Wong, X. Fan, J. Zhao, Y. Zhou, F. Ouyang. Role of the spatial distribution of gas flow for tuning the vertical/planar growth of nonlayered two-dimensional nanoplates. Cryst. Growth Des., 2022, 22(1): 763

[40] W. Chu, R. Xin, L. Zou, X. Fan, X. Zhou, C. Li, Y. Zhou. Synthesis of nonlayered 2D α-Fe₂O₃ nanosheets by ultralow concentration precursor with Se catalysts design. Phys. Status Solidi R., 2023, 2023: 2300102

[41] D. Wang, X. Zhang, G. Guo, S. Gao, X. Li, J. Meng, Z. Yin, H. Liu, M. Gao, L. Cheng, J. You, R. Wang. Large-area synthesis of layered HfS_2(1−x)Se_2x alloys with fully tunable chemical compositions and bandgaps. Adv. Mater., 2018, 30(44): 1803285

[42] Q. Yao, L. Zhang, P. Bampoulis, H. J. W. Zandvliet. Nanoscale investigation of defects and oxidation of HfSe₂. J. Phys. Chem. C, 2018, 122(44): 25498

[43] F. Cui, X. Zhao, B. Tang, L. Zhu, Y. Huan, Q. Chen, Z. Liu, Y. Zhang. Epitaxial growth of step-like Cr₂S₃ lateral homojunctions towards versatile conduction polarities and enhanced transistor performances. Small, 2022, 18(4): 2105744

[44] F. Zhang, Z. Mo, B. Cui, S. Liu, Q. Xia, B. Li, L. Li, Z. Zhang, J. He, M. Zhong. Bandgap engineering of BiIns nanowire for wide-spectrum, high-responsivity, and polarimetric-sensitive detection. Adv. Funct. Mater., 2023, 33(49): 2306077

[45] Z. Mo, F. Zhang, D. Wang, B. Cui, Q. Xia, B. Li, J. He, M. Zhong. Ultrafast-response and broad-spectrum polarization sensitive photodetector based on Bi_1.85In_0.15S₃ nanowire. Appl. Phys. Lett., 2022, 120(20): 201105

[46] H. Chen, X. Zhou, L. Tang, Y. Chen, H. Luo, X. Yuan, C. R. Bowen, D. Zhang. HfO₂-based ferroelectrics: From enhancing performance, material design, to applications. Appl. Phys. Rev., 2022, 9(1): 011307

[47] H. Chen, L. Tang, H. Luo, X. Yuan, D. Zhang. Modulation of ferroelectricity in atomic layer deposited HfO₂/ZrO₂ multilayer films. Mater. Lett., 2022, 313: 131732

[48] S. Lai, S. Byeon, S. K. Jang, J. Lee, B. H. Lee, J. H. Park, Y. H. Kim, S. Lee. HfO₂/HfS₂ hybrid heterostructure fabricated via controllable chemical conversion of two-dimensional HfS₂. Nanoscale, 2018, 10(39): 18758

[49] X. Fan, L. Zou, W. Chu, L. Wang, Y. Zhou. Synthesis of high resistive two-dimensional nonlayered Cr₂S₃ nanoflakes with stable phosphorus dopants by chemical vapor deposition. Appl. Phys. Lett., 2023, 122(22): 222101

Declarations

The authors declare that they have no competing interests and there are no conflicts.

Electronic supplementary materials

The online version contains supplementary material available at https://doi.org/10.1007/s11467-024-1414-7 and https://journal.hep.com.cn/fop/EN/10.1007/s11467-024-1414-7.

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Grant Nos. U23A20570 and 51902346), the Science and Technology Innovation Program of Hunan Province (“HuXiang Young Talents”, Grant No. 2021RC3021), the Key Project of the Natural Science Program of Xinjiang Uygur Autonomous Region (Grant No. 2023D01D03), and the Natural Science Foundation of Hunan Province (Grant No. 2021JJ40780). This work was supported by Double Cs-corrected TEM Laboratory of the State Key Laboratory of Powder Metallurgy.

RIGHTS & PERMISSIONS

2024 Higher Education Press