Enhanced Nonlinear Optical Absorption Properties and Carrier Dynamics of Violet Phosphorene by Oxidation for Ultrafast Photonic Applications

Abstract

Violet phosphorene, an emerging two-dimensional semiconductor material, demonstrates unique potential for optoelectronics. Here, the effect of oxidation treatment on the nonlinear optical absorption and carrier dynamics properties of two-dimensional violet phosphorene nanosheets was investigated. The results reveal that partially oxidized violet phosphorene exhibits enhanced saturable absorption properties and significantly shortened carrier relaxation lifetimes. X-ray photoelectron spectroscopy and first-principles calculations indicate that the introduction of oxygen atoms forms P=O and P–O–P bonds, leading to a p-orbital hybridization and a restructuring of the electronic structure. This shifts the valence band maximum upward and lowers the conduction band minimum due to oxygen defect states, resulting in a reduced bandgap and optimized carrier dynamics. For further verification, passively Q-switched and mode-locked lasers operating at 1 μm were demonstrated, utilizing two-dimensional violet phosphorene and oxidized violet phosphorene nanosheets as saturable absorbers, respectively. Compared with violet phosphorene-based lasers, oxidized violet phosphorene-based pulsed lasers achieve better pulse-width compression in both passively Q-switched and mode-locking operations (passively Q-switched: 343.52 ns vs 412.81 ns; mode-locking: 290 fs vs 404 fs). These results confirm that oxidation engineering effectively enhances the ultrafast nonlinear optical responses of two-dimensional violet phosphorene, laying a foundation for optimizing its optoelectronic properties and ultrafast photonics applications.

Keywords

mode-locked fiber laser / nonlinear optical absorption / oxidation engineering / ultrafast carrier dynamics / violet phosphorene

References

[1] T. Okuchi, H. Ohfuji, S. Odake, H. Kagi, S. Nagatomo, M. Sugata, H. Sumiya, Appl. Phys. A Mater. Sci. Process. 2009, 96, 833.

[2] L. Pan, S. Sun, L. Zhang, K. Jiang, H. Lin, Nanoscale 2016, 8, 17350.

[3] S. J. Mihailov, C. Hnatovsky, N. Abdukerim, R. B. Walker, P. Lu, Y. Xu, X. Bao, H. Ding, M. De Silva, D. Coulas, D. Grobnic, Sensors 2021, 21, 1447.

[4] Z. Y. Zhang, A. E. H. Oehler, B. Resan, S. Kurmulis, K. J. Zhou, Q. Wang, M. Mangold, T. Süedmeyer, U. Keller, K. J. Weingarten, R. A. Hogg, Sci. Rep. 2012, 2, 477.

[5] T. P. Rasmussen, A. Rodríguez Echarri, F. J. García De Abajo, J. D. Cox, Nanoscale 2023, 15, 3150.

[6] Y. W. Wang, S. Liu, B. W. Zeng, H. Huang, J. Xiao, J. B. Li, M. Q. Long, S. Xiao, X. F. Yu, Y. L. Gao, J. He, Nanoscale 2017, 9, 4683.

[7] X. Zhang, C. Deng, T. Yu, X. Yan, W. Luo, B. Lv, J. Liu, J. Cai, H. Wei, J. Li, G. Peng, Y. Yang, S. Qin, Appl. Surf. Sci. 2024, 651, 159232.

[8] A. G. Ricciardulli, Y. Wang, S. Yang, P. Samorì, J. Am. Chem. Soc. 2022, 144, 3660.

[9] W. Chen, A. Chen, R. Zhang, J. Zeng, L. Zhang, M. Gu, C. Wang, M. Huang, Y. Guo, H. Duan, C. Hu, W. Shen, B. Niu, K. Watanabe, T. Taniguchi, J. Zhang, J. Li, X. Cai, G. Liu, Nano Lett. 2023, 23, 10821.

[10] H. Guo, C. Jia, Y. Yao, M. Bai, T. Ma, J. Zhang, J. Xia, H. Nie, B. Yao, J. He, B. Zhang, Materials 2024, 17, 2585.

[11] S. Yu, X. Wu, Y. Wang, X. Guo, L. Tong, Adv. Mater. 2017, 29, 1606128.

[12] K. Akamatsu, T. Tsuruoka, H. Nawafune, J. Am. Chem. Soc. 2005, 127, 1634.

[13] G. Nabi, B. Atiq, H. I. Elsaeedy, M. Tanveer, W. Ali, A. Riaz, Inorg. Chem. Commun. 2023, 157, 111448.

[14] F. Chu, Y. Bi, Y. Huang, G. Dai, X. Ren, L. Zhang, M. Li, B. An, Mater. Today Commun. 2024, 40, 109503.

[15] J. Lu, J. Wu, A. Carvalho, A. Ziletti, H. Liu, J. Tan, Y. Chen, A. H. Castro Neto, B. Özyilmaz, C. H. Sow, ACS Nano 2015, 9, 10411.

[16] E. Padoan, F. Contillo, M. Marafante, E. Montoneri, M. Francavilla, S. Berto, A. Baglieri, Polymers 2024, 16, 1479.

[17] Q. Zhou, Q. Chen, Y. Tong, J. Wang, Angew. Chem. Int. Ed. 2016, 55, 11437.

[18] Q. Zhong, X. Pang, J. Mater. Sci. 2023, 58, 2068.

[19] Y. Hu, X. Chang, J. Zhang, X. Liu, Appl. Phys. Lett. 2023, 123, 121902.

[20] Y. Li, K. Gao, Y. Zhang, J. Jiao, L. Zhang, G. Xie, Nano Lett. 2023, 23, 6292.

[21] A. Fali, M. Snure, Y. Abate, Appl. Phys. Lett. 2021, 118, 163105.

[22] B. Li, H. Pan, Z. Pan, H. Chu, Y. Li, S. Zhao, D. Li, Opt. Express 2025, 33, 21328.

[23] H. Pan, X. Ma, H. Chu, Y. Li, Z. Pan, S. Zhao, J. Zhang, D. Li, ACS Appl. Nano Mater. 2023, 6, 4726.

[24] Y. Gao, Y. Hu, C. Ling, G. Rui, J. He, B. Gu, Nanoscale 2023, 15, 6225.

[25] C. Hong, S. Oh, V. K. Dat, S. Pak, S. N. Cha, K.-H. Ko, G.-M. Choi, T. Low, S.-H. Oh, J.-H. Kim, Light Sci. Appl. 2023, 12, 280.

[26] L. Kong, H. Chu, Z. Pan, H. Pan, S. Zhao, D. Li, J. Mater. Chem. C 2025, 13, 4499.

[27] J. Liu, F. Yang, J. Lu, S. Ye, H. Guo, H. Nie, J. Zhang, J. He, B. Zhang, Z. Ni, Nat. Commun. 2022, 13, 3855.

[28] Y. Liang, X. Cui, F. Li, C. Stampfl, S. P. Ringer, X. Yang, J. Huang, R. Zheng, J. Phys. Chem. Lett. 2023, 14, 2950.

[29] K.-P. Wang, Z.-W. Wu, K.-F. Wang, H.-T. Xu, J. He, B. Wen, C.-J. Tong, L.-M. Liu, O. V. Prezhdo, ACS Energy Lett. 2024, 9, 5888.

[30] Q. Yao, H. Li, J. Xue, S. Jiang, Q. Zhang, J. Bao, Angew. Chem. Int. Ed. 2023, 62, e202308140.

[31] R. H. Jeong, D. I. Kim, J. W. Lee, J.-H. Yu, B. G. Jeong, H. M. Oh, M. S. Jeong, J.-H. Boo, 2D Mater. 2019, 6, 045039.

[32] X. Yu, H. J. Kim, J.-Y. Hong, Y. M. Jung, K. D. Kwon, J. Kong, H. S. Park, Nano Energy 2015, 15, 576.

[33] L. Zhang, H. Huang, B. Zhang, M. Gu, D. Zhao, X. Zhao, L. Li, J. Zhou, K. Wu, Y. Cheng, J. Zhang, Angew. Chem. 2020, 132, 1090.

[34] H. Ma, J. Yin, M. Zahid Hasan, J. Liu, Chin. Phys. Lett. 2024, 41, 047103.

[35] Y. Fu, K. Lu, A. Hu, J. Huang, L. Guo, J. Zhou, J. Zhao, O. V. Prezhdo, M. Liu, J. Am. Chem. Soc. 2023, 145, 28166.

[36] Y. Yan, J. Lin, K. Huang, X. Zheng, L. Qiao, S. Liu, J. Cao, S. C. Jun, Y. Yamauchi, J. Qi, J. Am. Chem. Soc. 2023, 145, 24218.

[37] Z. Zhuo, C. D. Pemmaraju, J. Vinson, C. Jia, B. Moritz, I. Lee, S. Sallies, Q. Li, J. Wu, K. Dai, Y.-d. Chuang, Z. Hussain, F. Pan, T. P. Devereaux, W. Yang, J. Phys. Chem. Lett. 2018, 9, 6378.

[38] S. Shen, M. Wang, Y. Zhang, Y. Lyu, D. Tian, C. Gao, Y. Long, J. Zhao, P. Yu, Adv. Mater. 2023, 35, 2301453.

[39] D. Y. Tang, L. M. Zhao, B. Zhao, Opt. Express 2005, 13, 2289.

[40] Z. Wang, H. Pan, H. Chu, Z. Pan, Y. Li, S. Zhao, D. Li, Opt. Express 2024, 32, 15472.

[41] X. Ma, H. Pan, T. Yang, Q. Liao, J. Zhang, D. Li, Adv. Opt. Mater. 2023, 11, 2202770.

Rights & permissions

2026 The Author(s). Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.