Issue

Vol. 18 (2026)

Violet Arsenic Phosphorus: Switching p-Type into High Performance n-Type Semiconductor by Arsenic Substitution

https://doi.org/10.1007/s40820-025-01956-1
Rui Zhai
State Key Laboratory of Electrical Insulation and Power Equipment, Center of Nanomaterials for Renewable Energy, School of Electrical Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, People’s Republic of China
Zhuorui Wen
State Key Laboratory of Electrical Insulation and Power Equipment, Center of Nanomaterials for Renewable Energy, School of Electrical Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, People’s Republic of China
Xuewen Zhao
State Grid Integrated Energy Service Group Co., Ltd., Beijing 100052, People’s Republic of China
Junyi She
State Key Laboratory of Electrical Insulation and Power Equipment, Center of Nanomaterials for Renewable Energy, School of Electrical Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, People’s Republic of China
Mengyue Gu
State Key Laboratory of Electrical Insulation and Power Equipment, Center of Nanomaterials for Renewable Energy, School of Electrical Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, People’s Republic of China
Fanqi Bu
State Key Laboratory of Electrical Insulation and Power Equipment, Center of Nanomaterials for Renewable Energy, School of Electrical Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, People’s Republic of China
Chang Huang
Instrumental Analysis Center of Xi’an Jiaotong University, Xian Jiaotong University, Xi’an 710049, People’s Republic of China
Guodong Meng
State Key Laboratory of Electrical Insulation and Power Equipment, Center of Nanomaterials for Renewable Energy, School of Electrical Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, People’s Republic of China
Yonghong Cheng
State Key Laboratory of Electrical Insulation and Power Equipment, Center of Nanomaterials for Renewable Energy, School of Electrical Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, People’s Republic of China
Jinying Zhang
State Key Laboratory of Electrical Insulation and Power Equipment, Center of Nanomaterials for Renewable Energy, School of Electrical Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, People’s Republic of China

Corresponding Author: Jinying Zhang

jinying.zhang@mail.xjtu.edu.cn

Nano-Micro Letters, Vol. 18 (2026), Article Number: 145

Abstract

Violet phosphorus, a recently explored layered elemental semiconductor, has attracted much attention due to its unique photoelectric, mechanical properties, and high hole mobility. Herein, violet arsenic phosphorus has for the first time been synthesized by a molten lead method. The crystal structure of violet arsenic phosphorus (P83.4As0.6, CSD-2408761) was determined by single crystal X-ray diffraction to have similar structure as that of violet phosphorus, where P12 is occupied by arsenic/phosphorus (As/P) atoms as mixed occupancy sites As1/P12. The arsenic substitution has been demonstrated to tune the band structure of violet phosphorus, switching p-type of violet phosphorus to high-performance n-type violet arsenic phosphorus. The effective electron mass along the < 010 > direction is significantly reduced from 1.792 to 0.515 m0 by arsenic substitution, resulting in an extremely high electron mobility of 2622.503 cm2 V⁻1 s⁻1. The field effect transistor built with P83.4As0.6 nanosheets was measured to have a high electron mobility (137.06 cm2 V⁻1 s⁻1, 61.2 nm), even under ambient conditions for 5 h, much higher than the hole mobility of violet phosphorene nanosheets (4.07 cm2 V⁻1 s⁻1, 73.3 nm). This work provides a new idea for designing phosphorus-based materials for field effect transistors, giving significant potential in complementary metal–oxide–semiconductor applications.


Highlights:
1 Violet arsenic phosphorus (VP-As) single crystals were synthesized and characterized by single crystal X-ray diffraction to be P83.4As0.6 (CSD-2408761), the P12 is occupied by arsenic/phosphorus as a mixed occupancy site.
2 The p-type VP has been switched into n-type VP-As, the effective electron mass was significantly reduced and resulted in high electron mobility of 2622.503 cm2 V−1 s−1.
3 High electron mobility of 137.06 cm2 V−1 s−1 has been achieved from field effect transistor, much higher than the hole mobility of VP.

Keywords

Violet phosphorus Arsenic substitution n-type semiconductor High mobility Field effect transistor
Zhai, Rui, Zhuorui Wen, Xuewen Zhao, Junyi She, Mengyue Gu, Fanqi Bu, Chang Huang, Guodong Meng, Yonghong Cheng, and Jinying Zhang. 2026. “Violet Arsenic Phosphorus: Switching P-Type into High Performance N-Type Semiconductor by Arsenic Substitution”. Nano-Micro Letters 18 (January):145. https://doi.org/10.1007/s40820-025-01956-1.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. H. Thurn, H. Krebs, Über Struktur und Eigenschaften der Halbmetalle. XXII. Die Kristallstruktur des Hittorfschen Phosphors. Acta Crystallogr. Sect. B Struct. Crystallogr. Cryst. Chem. 25(1), 125–135 (1969). https://doi.org/10.1107/s0567740869001853
  2. L. Zhang, X. Li, F. Yao, L. Li, H. Huang et al., Fast identification of the crystallographic orientation of violet phosphorus nanoflakes with preferred in-plane cleavage edge orientation. Adv. Funct. Mater. 32(18), 2111057 (2022). https://doi.org/10.1002/adfm.202111057
  3. B. Zhang, L. Zhang, C. Chen, M. Gu, Y. Cheng et al., Friction anisotropy of violet phosphorene and its surface structure direction identification. 2D Mater. 9(2), 025002 (2022). https://doi.org/10.1088/2053-1583/ac4813
  4. B. Zhang, L. Zhang, Z. Wang, Y. Li, Y. Cheng et al., Cross structured two-dimensional violet phosphorene with extremely high deformation resistance. J. Mater. Chem. A 9(24), 13855–13860 (2021). https://doi.org/10.1039/D1TA02595C
  5. Y. Wang, M. Jin, M. Gu, X. Zhao, J. Xie et al., Synthesis of violet phosphorus with large lateral sizes to facilitate nano-device fabrications. Nanoscale 15(29), 12406–12412 (2023). https://doi.org/10.1039/D3NR01113E
  6. H. Ma, H. Fang, X. Xie, Y. Liu, H. Tian et al., Optoelectronic synapses based on MXene/violet phosphorus van der Waals heterojunctions for visual-olfactory crossmodal perception. Nano-Micro Lett. 16(1), 104 (2024). https://doi.org/10.1007/s40820-024-01330-7
  7. H. Pan, X. Ma, H. Chu, Y. Li, Z. Pan et al., Few-layered violet phosphorene nanostructures as saturable absorbers for stable soliton mode-locking operations in an ultrafast fiber laser. ACS Appl. Nano Mater. 6(6), 4726–4733 (2023). https://doi.org/10.1021/acsanm.3c00218
  8. X. Ma, H. Pan, T. Yang, Q. Liao, J. Zhang et al., Optical absorption and second-harmonic generation in violet phosphorene: experimental and theoretical aspects. Adv. Opt. Mater. 11(9), 2202770 (2023). https://doi.org/10.1002/adom.202202770
  9. M. Gu, L. Zhang, S. Mao, Y. Zou, D. Ma et al., Violet phosphorus: an effective metal-free elemental photocatalyst for hydrogen evolution. Chem. Commun. 58(92), 12811–12814 (2022). https://doi.org/10.1039/D2CC04461G
  10. S. Wang, X. Zhao, Z. Liu, X. Yang, B. Pang et al., Violet phosphorus-Fe3O4 as a novel photocatalysis-self-Fenton system coupled with underwater bubble plasma to efficiently remove norfloxacin in water. Chem. Eng. J. 452, 139481 (2023). https://doi.org/10.1016/j.cej.2022.139481
  11. X. Wang, M. Ma, X. Zhao, P. Jiang, Y. Wang et al., Phase engineering of 2D violet/black phosphorus heterostructure for enhanced photocatalytic hydrogen evolution. Small Struct. 4(10), 2300123 (2023). https://doi.org/10.1002/sstr.202300123
  12. R. Zhai, Z. Wang, M. Gu, H. Liu, X. Zhao et al., Electron gathering at violet phosphorene-Ag interface for photoreduction of CO2 to ethylene. Appl. Catal. B Environ. Energy 361, 124603 (2025). https://doi.org/10.1016/j.apcatb.2024.124603
  13. J. Singh, Effective mass of charge carriers in amorphous semiconductors and its applications. J. Non-Crys. Solids 299–302, 444–448 (2002). https://doi.org/10.1016/s0022-3093(01)00957-7
  14. C. Goffaux, V. Lousse, J. Vigneron, Complete minigaps for effective-mass carriers in three-dimensional semiconductor superlattices. Phys. Rev. B 62, 7133–7137 (2000). https://doi.org/10.1023/A:1013366325187
  15. T. Chu, Z. Chen, Electrically tunable bandgaps in 2D layered materials. In: 2016 IEEE International Conference on Electron Devices and Solid-State Circuits (EDSSC). IEEE (2016), pp. 25–29. https://doi.org/10.1109/EDSSC.2016.7785202
  16. J. Wu, H. Yuan, M. Meng, C. Chen, Y. Sun et al., High electron mobility and quantum oscillations in non-encapsulated ultrathin semiconducting Bi2O2Se. Nat. Nanotechnol. 12(6), 530–534 (2017). https://doi.org/10.1038/nnano.2017.43
  17. Y. Hu, P. Xie, M. De Corato, A. Ruini, S. Zhao et al., Bandgap engineering of graphene nanoribbons by control over structural distortion. J. Am. Chem. Soc. 140(25), 7803–7809 (2018). https://doi.org/10.1021/jacs.8b02209
  18. S. Yang, P. Zhang, A.S. Nia, X. Feng, Exfoliation and engineering of 2D materials through electrochemistry. CCS Chem. 6(10), 2368–2391 (2024). https://doi.org/10.31635/ccschem.024.202403878
  19. M.-H. Shang, J. Zhang, S. Wei, Y. Zhu, L. Wang et al., Bi-doped Sb2S3 for low effective mass and optimized optical properties. J. Mater. Chem. C 4(22), 5081–5090 (2016). https://doi.org/10.1039/c6tc00513f
  20. G. Bhowmik, K. Gruenewald, G. Malladi, T. Mowll, C. Ventrice et al., Tunable photoluminescence of atomically thin MoS2 via Nb doping. MRS Adv. 4(10), 609–614 (2019). https://doi.org/10.1557/adv.2019.24
  21. Y. Jin, Z. Zeng, Z. Xu, Y.-C. Lin, K. Bi et al., Synthesis and transport properties of degenerate P-type Nb-doped WS2 monolayers. Chem. Mater. 31(9), 3534–3541 (2019). https://doi.org/10.1021/acs.chemmater.9b00913
  22. S.-H. Su, Y.-T. Hsu, Y.-H. Chang, M.-H. Chiu, C.-L. Hsu et al., Band gap-tunable molybdenum sulfide selenide monolayer alloy. Small 10(13), 2589–2594 (2014). https://doi.org/10.1002/smll.201302893
  23. B. Liu, M. Köpf, A.N. Abbas, X. Wang, Q. Guo et al., Black arsenic–phosphorus: layered anisotropic infrared semiconductors with highly tunable compositions and properties. Adv. Mater. 27(30), 4423–4429 (2015). https://doi.org/10.1002/adma.201501758
  24. Y. Yu, B. Xing, J. Yao, X. Niu, Y. Liu et al., N-type doping of black phosphorus single crystal by tellurium. Nanotechnology 31(31), 315605 (2020). https://doi.org/10.1088/1361-6528/ab8c08
  25. R. Enderlein, N.J. Horing, Fundamentals of Semiconductor Physics and Devices. Singapore: World Scientific, (1997). https://doi.org/10.1142/2866
  26. A. Brown, S. Rundqvist, Refinement of the crystal structure of black phosphorus. Acta Crystallogr. 19(4), 684–685 (1965). https://doi.org/10.1107/S0365110X65004140
  27. M. Liu, S. Feng, Y. Hou, S. Zhao, L. Tang et al., High yield growth and doping of black phosphorus with tunable electronic properties. Mater. Today 36, 91–101 (2020). https://doi.org/10.1016/j.mattod.2019.12.027
  28. L. Zhang, H. Huang, B. Zhang, M. Gu, D. Zhao et al., Structure and properties of violet phosphorus and its phosphorene exfoliation. Angew. Chem. Int. Ed. 59(3), 1074–1080 (2020). https://doi.org/10.1002/anie.201912761
  29. F. Baumer, Y. Ma, C. Shen, A. Zhang, L. Chen et al., Synthesis, characterization, and device application of antimony-substituted violet phosphorus: a layered material. ACS Nano 11(4), 4105–4113 (2017). https://doi.org/10.1021/acsnano.7b00798
  30. X. Zhao, M. Gu, R. Zhai, Y. Zhang, M. Jin et al., Violet antimony phosphorus with enhanced photocatalytic hydrogen evolution. Small 19(41), e2302859 (2023). https://doi.org/10.1002/smll.202302859
  31. L. Zhang, H. Huang, Z. Lv, L. Li, M. Gu et al., Phonon properties of bulk violet phosphorus single crystals: temperature and pressure evolution. ACS Appl. Electron. Mater. 3(3), 1043–1049 (2021). https://doi.org/10.1021/acsaelm.0c00731
  32. D. Vithanage, U. Abu, M.R. Khan Musa, K.J. Tasnim, H. Weerahennedige et al., High-pressure response of vibrational properties of b-AsxP1-x: in situ Raman studies. Nanotechnology 34(46), acef28 (2023). https://doi.org/10.1088/1361-6528/acef28
  33. W. Hong, M. Kitta, Q. Xu, Bimetallic MOF-derived FeCo-P/C nanocomposites as efficient catalysts for oxygen evolution reaction. Small Meth 2(12), 1800214 (2018). https://doi.org/10.1002/smtd.201800214
  34. H. Jin, Z. Kou, W. Cai, H. Zhou, P. Ji et al., P-Fe bond oxygen reduction catalysts toward high-efficiency metal–air batteries and fuel cells. J. Mater. Chem. A 8(18), 9121–9127 (2020). https://doi.org/10.1039/D0TA02334E
  35. B. Elsener, D. Atzei, A. Krolikowski, A. Rossi, Effect of phosphorus concentration on the electronic structure of nanocrystalline electrodeposited Ni–P alloys: an XPS and XAES investigation. Surf. Interface Anal. 40(5), 919–926 (2008). https://doi.org/10.1002/sia.2802
  36. S. Wu, S.S. Neo, Z. Dong, F. Boey, P. Wu, Tunable ionic and electronic conduction of lithium nitride via phosphorus and arsenic substitution: a first-principles study. J. Phys. Chem. C 114(39), 16706–16709 (2010). https://doi.org/10.1021/jp1045047
  37. J. Yamauchi, Y. Yoshimoto, Y. Suwa, Core-level shifts in X-ray photoelectron spectroscopy of arsenic defects in silicon crystal: a first-principles study. AIP Adv. 10(11), 115301 (2020). https://doi.org/10.1063/5.0025316
  38. H.A. Bullen, M.J. Dorko, J.K. Oman, S.J. Garrett, Valence and core-level binding energy shifts in realgar (As4S4) and pararealgar (As4S4) arsenic sulfides. Surf. Sci. 531(3), 319–328 (2003). https://doi.org/10.1016/S0039-6028(03)00491-6
  39. V. Kumar, S.K. Sharma, T.P. Sharma, V. Singh, Band gap determination in thick films from reflectance measurements. Opt. Mater. 12(1), 115–119 (1999). https://doi.org/10.1016/S0925-3467(98)00052-4
  40. X. Li, B. Kang, F. Dong, Z. Zhang, X. Luo et al., Enhanced photocatalytic degradation and H2/H2O2 production performance of S-pCN/WO2. Nano Energy 81, 105671 (2021). https://doi.org/10.1016/j.nanoen.2020.105671
  41. S. Zhang, S. Ma, X. Hao, Y. Wang, B. Cao et al., Controllable preparation of crystalline red phosphorus and its photocatalytic properties. Nanoscale 13(45), 18955–18960 (2021). https://doi.org/10.1039/d1nr06530k
  42. X. Ma, Y. Dai, M. Guo, B. Huang, The role of effective mass of carrier in the photocatalytic behavior of silver halide-based Ag@AgX (X=Cl, Br, I): a theoretical study. ChemPhysChem 13(9), 2304–2309 (2012). https://doi.org/10.1002/cphc.201200159
  43. J.-Y. Noh, H. Kim, H.-H. Nahm, Y.-S. Kim, D.H. Kim et al., Cation composition effects on electronic structures of In–Sn–Zn–O amorphous semiconductors. J. Appl. Phys. 113(18), 183706 (2013). https://doi.org/10.1063/1.4803706
  44. Z.M. Gibbs, F. Ricci, G. Li, H. Zhu, K. Persson et al., Effective mass and Fermi surface complexity factor from ab initio band structure calculations. NPJ Comput. Mater. 3, 8 (2017). https://doi.org/10.1038/s41524-017-0013-3
  45. W. Ahmad, A. Abbas, U. Younis, J. Zhang, S.H. Aleithan et al., Advancements in optoelectronics: harnessing the potential of 2D violet phosphorus. Adv. Funct. Mater. 34(52), 2410723 (2024). https://doi.org/10.1002/adfm.202410723
  46. C.E. Dreyer, A. Janotti, C.G. Van de Walle, Effects of strain on the electron effective mass in GaN and AlN. Appl. Phys. Lett. 102(14), 142105 (2013). https://doi.org/10.1063/1.4801520
  47. M.G. Silveirinha, N. Engheta, Transformation electronics: tailoring the effective mass of electrons. Phys. Rev. B 86(16), 161104 (2012). https://doi.org/10.1103/physrevb.86.161104
  48. W. Wunderlich, H. Ohta, K. Koumoto, Enhanced effective mass in doped SrTiO3 and related perovskites. Phys. B Condens. Matter 404(16), 2202–2212 (2009). https://doi.org/10.1016/j.physb.2009.04.012
  49. Z. Sun, B. Zhang, Y. Zhao, M. Khurram, Q. Yan, Synthesis, exfoliation, and transport properties of quasi-1D van der Waals fibrous red phosphorus. Chem. Mater. 33(15), 6240–6248 (2021). https://doi.org/10.1021/acs.chemmater.1c02136
  50. N. Wang, N. Mao, Z. Wang, X. Yang, X. Zhou et al., Electrochemical delamination of ultralarge few-layer black phosphorus with a hydrogen-free intercalation mechanism. Adv. Mater. 33(1), e2005815 (2021). https://doi.org/10.1002/adma.202005815
  51. A.G. Ricciardulli, Y. Wang, S. Yang, P. Samorì, Two-dimensional violet phosphorus: a p-type semiconductor for (opto)electronics. J. Am. Chem. Soc. 144(8), 3660–3666 (2022). https://doi.org/10.1021/jacs.1c12931
  52. S. Yuan, C. Shen, B. Deng, X. Chen, Q. Guo et al., Air-stable room-temperature mid-infrared photodetectors based on hBN/black arsenic phosphorus/hBN heterostructures. Nano Lett. 18(5), 3172–3179 (2018). https://doi.org/10.1021/acs.nanolett.8b00835
  53. Y. Wang, J.C. Kim, Y. Li, K.Y. Ma, S. Hong et al., P-type electrical contacts for 2D transition-metal dichalcogenides. Nature 610(7930), 61–66 (2022). https://doi.org/10.1038/s41586-022-05134-w
  54. X. Liu, A. Islam, N. Yang, B. Odhner, M.A. Tupta, J. Guo, P.X. Feng, Atomic layer MoTe2 field-effect transistors and monolithic logic circuits configured by scanning laser annealing. ACS Nano 15(12), 19733–19742 (2021). https://doi.org/10.1021/acsnano.1c07169
  55. Y. Wang, A. Slassi, J. Cornil, D. Beljonne, P. Samorì, Tuning the optical and electrical properties of few-layer black phosphorus via physisorption of small solvent molecules. Small 15(47), e1903432 (2019). https://doi.org/10.1002/smll.201903432
  56. H. Shi, S. Fu, Y. Liu, C. Neumann, M. Wang et al., Molecularly engineered black phosphorus heterostructures with improved ambient stability and enhanced charge carrier mobility. Adv. Mater. 33(48), 2105694 (2021). https://doi.org/10.1002/adma.202105694
  57. W. Ahmad, M.U. Rehman, L. Pan, W. Li, J. Yi et al., Ultrasensitive near-infrared polarization photodetectors with violet phosphorus/InSe van der Waals heterostructures. ACS Appl. Mater. Interfaces 16(15), 19214–19224 (2024). https://doi.org/10.1021/acsami.4c01396
  58. J. Kim, W. Park, J.-H. Lee, M.-J. Seong, Simultaneous growth of Ga2S3 and GaS thin films using physical vapor deposition with GaS powder as a single precursor. Nanotechnology 30(38), 384001 (2019). https://doi.org/10.1088/1361-6528/ab284c
  59. G.B. Blanchet, C.R. Fincher, M. Lefenfeld, J.A. Rogers, Contact resistance in organic thin film transistors. Appl. Phys. Lett. 84(2), 296–298 (2004). https://doi.org/10.1063/1.1639937
  60. D. Natali, L. Fumagalli, M. Sampietro, Modeling of organic thin film transistors: effect of contact resistances. J. Appl. Phys. 101, 014501 (2007). https://doi.org/10.1063/1.2402349
  61. Y.-T. Huang, Y.-H. Chen, Y.-J. Ho, S.-W. Huang, Y.-R. Chang et al., High-performance InSe transistors with ohmic contact enabled by nonrectifying barrier-type indium electrodes. ACS Appl. Mater. Interfaces 10(39), 33450–33456 (2018). https://doi.org/10.1021/acsami.8b10576
  62. Y. Wang, J.C. Kim, R.J. Wu, J. Martinez, X. Song et al., Van der Waals contacts between three-dimensional metals and two-dimensional semiconductors. Nature 568(7750), 70–74 (2019). https://doi.org/10.1038/s41586-019-1052-3
  63. W. Chen, R. Zhang, M. Gu, L. Zhang, B. Xie et al., An ultrahigh-contrast violet phosphorus van der Waals phototransistor. Adv. Opt. Mater. 12(2), 2301399 (2024). https://doi.org/10.1002/adom.202301399
  64. W. Zawadzki, Electron dynamics in crystalline semiconductors. Acta Phys. Pol. A. 123(1), 132 (2013). https://doi.org/10.12693/aphyspola.123.132
  65. Y. Liu, P. Sahoo, J.P.A. Makongo, X. Zhou, S.-J. Kim et al., Large enhancements of thermopower and carrier mobility in quantum dot engineered bulk semiconductors. J. Am. Chem. Soc. 135(20), 7486–7495 (2013). https://doi.org/10.1021/ja311059m
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY FILE

Most read articles by the same author(s)