Exploring the oxidation mechanisms of black phosphorus: a review
Source abstract
Abstract
Black phosphorus (BP) has unmatched application advantages as a two-dimensional semiconductor in electronic and optoelectronic devices owing to its tunable direct bandgap, high carrier mobility, and significant in-plane anisotropy. However, the commercial use of BP is limited owing to its instability. BP oxidizes easily under ambient conditions, leading to device performance degradation. The oxidation behavior and mechanisms of BP are understood to a certain extent, with a few reviews outlining the reported results. Nevertheless, no review has attempted to discuss the inconsistencies that have emerged from studies of BP oxidation. The roles of light, oxygen, and water in the process of BP oxidation are reviewed herein, accompanied by a critical discussion of important and inconsistent results. Because defects and edges inevitably exist in BP, the formation and chemical activity of defects and edge configurations of BP are comprehensively examined for the first time. The final part of this paper provides insights toward a deeper understanding of BP oxidation and possible passivation strategies.
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Research context
OpenAlex topics: 2D Materials and Applications · Perovskite Materials and Applications · MXene and MAX Phase Materials
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (100+)
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1. Novoselov KS, Geim AK, Morozov SV et al (2004) Electric field effect in atomically thin carbon films. Science 306:666–669. https://doi.org/10.1126/science.110289610.1126/science.1102896 ↗
2. Karakachian H, Nguyen TTN, Aprojanz J et al (2020) One-dimensional confinement and width-dependent bandgap formation in epitaxial graphene nanoribbons. Nat Commun 11:6380. https://doi.org/10.1038/s41467-020-19051-x10.1038/s41467-020-19051-x ↗
3. Yang H, Valenzuela SO, Chshiev M et al (2022) Two-dimensional materials prospects for non-volatile spintronic memories. Nature 606:663–673. https://doi.org/10.1038/s41586-022-04768-010.1038/s41586-022-04768-0 ↗
4. Gaufres E, Fossard F, Gosselin V et al (2019) Momentum-resolved dielectric response of free-standing mono-, bi-, and trilayer black phosphorus. Nano Lett 19:8303–8310. https://doi.org/10.1021/acs.nanolett.9b0392810.1021/acs.nanolett.9b03928 ↗
5. Li L, Kim J, Jin C et al (2017) Direct observation of the layer-dependent electronic structure in phosphorene. Nat Nanotechnol 12:21–25. https://doi.org/10.1038/nnano.2016.17110.1038/nnano.2016.171 ↗
6. Liu J, Zhou Y, Zhu W (2020) Determining bandgap of black phosphorus using capacitance. Appl Phys Lett 116:183103. https://doi.org/10.1063/5.001016510.1063/5.0010165 ↗
7. Li L, Yu Y, Ye GJ et al (2014) Black phosphorus field-effect transistors. Nat Nanotechnol 9:372–377. https://doi.org/10.1038/nnano.2014.3510.1038/nnano.2014.35 ↗
8. Radisavljevic B, Radenovic A, Brivio J et al (2011) Single-layer MoS2 transistors. Nat Nanotechnol 6:147–150. https://doi.org/10.1038/nnano.2010.27910.1038/nnano.2010.279 ↗
9. Mak KF, Lee C, Hone J et al (2010) Atomically thin MoS2: a new direct-gap semiconductor. Phys Rev Lett 105:136805. https://doi.org/10.1103/PhysRevLett.105.13680510.1103/PhysRevLett.105.136805 ↗
10. Xia F, Wang H, Jia Y (2014) Rediscovering black phosphorus as an anisotropic layered material for optoelectronics and electronics. Nat Commun 5:4458. https://doi.org/10.1038/ncomms545810.1038/ncomms5458 ↗
11. Mao N, Wang X, Lin Y et al (2019) Direct observation of symmetry-dependent electron-phonon coupling in black phosphorus. J Am Chem Soc 141:18994–19001. https://doi.org/10.1021/jacs.9b0797410.1021/jacs.9b07974 ↗
12. Zhang G, Huang S, Wang F et al (2020) The optical conductivity of few-layer black phosphorus by infrared spectroscopy. Nat Commun 11:1847. https://doi.org/10.1038/s41467-020-15699-710.1038/s41467-020-15699-7 ↗
13. Lee SY, Yee KJ (2022) Black phosphorus phase retarder based on anisotropic refractive index dispersion. 2D Mater 9:015020. https://doi.org/10.1088/2053-1583/ac3a9910.1088/2053-1583/ac3a99 ↗
14. Zhong Q (2022) Intrinsic and engineered properties of black phosphorus. Mater Today Phys 28:100895. https://doi.org/10.1016/j.mtphys.2022.10089510.1016/j.mtphys.2022.100895 ↗
15. Li Q, Wu J, Liu Y et al (2021) Recent advances in black phosphorus-based electrochemical sensors: a review. Anal Chim Acta 1170:338480. https://doi.org/10.1016/j.aca.2021.33848010.1016/j.aca.2021.338480 ↗
16. Biswas S, Grajower MY, Watanabe K et al (2021) Broadband electro-optic polarization conversion with atomically thin black phosphorus. Science 374:448–453. https://doi.org/10.1126/science.abj705310.1126/science.abj7053 ↗
17. Kim H, Uddin SZ, Lien DH et al (2021) Actively variable-spectrum optoelectronics with black phosphorus. Nature 596:232–237. https://doi.org/10.1038/s41586-021-03701-110.1038/s41586-021-03701-1 ↗
18. Grillo A, Pelella A, Faella E et al (2022) Memory effects in black phosphorus field effect transistors. 2D Mater 9:015028. https://doi.org/10.1088/2053-1583/ac3f4510.1088/2053-1583/ac3f45 ↗
19. Li G, Qi X, Wu J et al (2022) Ultrasensitive, label-free voltammetric determination of norfloxacin based on molecularly imprinted polymers and Au nanoparticle-functionalized black phosphorus nanosheet nanocomposite. J Hazard Mater 436:129107. https://doi.org/10.1016/j.jhazmat.2022.12910710.1016/j.jhazmat.2022.129107 ↗
20. Li G, Wu J, Qi X et al (2022) Molecularly imprinted polypyrrole film-coated poly(3,4-ethylenedioxythiophene):polystyrene sulfonate-functionalized black phosphorene for the selective and robust detection of norfloxacin. Mater Today Chem 26:101043. https://doi.org/10.1016/j.mtchem.2022.10104310.1016/j.mtchem.2022.101043 ↗
21. Kim M, Kim HG, Park S et al (2019) Intrinsic correlation between electronic structure and degradation: from few-layer to bulk black phosphorus. Angew Chem Int Ed 58:3754–3758. https://doi.org/10.1002/anie.20181174310.1002/anie.201811743 ↗
22. Wood JD, Wells SA, Jariwala D et al (2014) Effective passivation of exfoliated black phosphorus transistors against ambient degradation. Nano Lett 14:6964–6970. https://doi.org/10.1021/nl503229310.1021/nl5032293 ↗
23. Island JO, Steele GA, van der Zant HS et al (2015) Environmental instability of few-layer black phosphorus. 2D Mater 2:011002. https://doi.org/10.1088/2053-1583/2/1/01100210.1088/2053-1583/2/1/011002 ↗
24. Abellan G, Wild S, Lloret V et al (2017) Fundamental insights into the degradation and stabilization of thin layer black phosphorus. J Am Chem Soc 139:10432–10440. https://doi.org/10.1021/jacs.7b0497110.1021/jacs.7b04971 ↗
25. Li M, Mao C, Ling L (2022) In situ visualization on surface oxidative corrosion with free radicals: black phosphorus nanoflake as an example. Environ Sci Technol 56:361–367. https://doi.org/10.1021/acs.est.1c0656710.1021/acs.est.1c06567 ↗
26. Hu Z, Li Q, Lei B et al (2017) Water-catalyzed oxidation of few-layer black phosphorous in a dark environment. Angew Chem Int Ed 56:9131–9135. https://doi.org/10.1002/anie.20170501210.1002/anie.201705012 ↗
27. Yi Z, Ma Y, Zheng Y et al (2019) Fundamental insights into the performance deterioration of phosphorene due to oxidation: a GW method investigation. Adv Mater Interfaces 6:1801175. https://doi.org/10.1002/admi.20180117510.1002/admi.201801175 ↗
28. Shen W, Sun Z, Huo S et al (2022) Directly evaluating the optical anisotropy of few-layered black phosphorus during ambient oxidization. Adv Opt Mater 10:2102018. https://doi.org/10.1002/adom.20210201810.1002/adom.202102018 ↗
29. Moreno-Moreno M, Lopez-Polin G, Castellanos-Gomez A et al (2016) Environmental effects in mechanical properties of few-layer black phosphorus. 2D Mater 3:031007. https://doi.org/10.1088/2053-1583/3/3/03100710.1088/2053-1583/3/3/031007 ↗
30. Favron A, Gaufres E, Fossard F et al (2015) Photooxidation and quantum confinement effects in exfoliated black phosphorus. Nat Mater 14:826–832. https://doi.org/10.1038/nmat429910.1038/nmat4299 ↗
31. Zhou Q, Chen Q, Tong Y et al (2016) Light-induced ambient degradation of few-layer black phosphorus: mechanism and protection. Angew Chem Int Ed 55:11437–11441. https://doi.org/10.1002/anie.20160516810.1002/anie.201605168 ↗
32. Ziletti A, Carvalho A, Campbell DK et al (2015) Oxygen defects in phosphorene. Phys Rev Lett 114:046801. https://doi.org/10.1103/PhysRevLett.114.04680110.1103/PhysRevLett.114.046801 ↗
33. Wang Y, Yang B, Wan B et al (2016) Degradation of black phosphorus: a real-time 31P NMR study. 2D Mater 3:035025. https://doi.org/10.1088/2053-1583/3/3/03502510.1088/2053-1583/3/3/035025 ↗
34. Laurent BS, Dey D, Yu L et al (2021) Atomic-scale investigation of oxidation at the black phosphorus surface. ACS Appl Electron Mater 3:4066–4072. https://doi.org/10.1021/acsaelm.1c0055810.1021/acsaelm.1c00558 ↗
35. Zhang S, Zhang X, Lei L et al (2019) pH-dependent degradation of layered black phosphorus: essential role of hydroxide ions. Angew Chem Int Ed 58:467–471. https://doi.org/10.1002/anie.20180998910.1002/anie.201809989 ↗
36. Zhang D, Liu HM, Shu X et al (2020) Nanocopper-loaded black phosphorus nanocomposites for efficient synergistic antibacterial application. J Hazard Mater 393:122317. https://doi.org/10.1016/j.jhazmat.2020.12231710.1016/j.jhazmat.2020.122317 ↗
37. Chen W, Du W, Zhang H et al (2022) Hemin-loaded black phosphorus-based nanosystem for enhanced photodynamic therapy and a synergistic photothermally/photodynamically activated inflammatory immune response. Biomater Adv 140:213091. https://doi.org/10.1016/j.bioadv.2022.21309110.1016/j.bioadv.2022.213091 ↗
38. Shaw ZL, Kuriakose S, Cheeseman S et al (2021) Broad-spectrum solvent-free layered black phosphorus as a rapid action antimicrobial. ACS Appl Mater Interfaces 13:17340–17352. https://doi.org/10.1021/acsami.1c0173910.1021/acsami.1c01739 ↗
39. Liu Y, Li Z, Fan F et al (2021) Boosting antitumor sonodynamic therapy efficacy of black phosphorus via covalent functionalization. Adv Sci 8:e2102422. https://doi.org/10.1002/advs.20210242210.1002/advs.202102422 ↗
40. Kuntz KL, Wells RA, Hu J et al (2017) Control of surface and edge oxidation on phosphorene. ACS Appl Mater Interfaces 9:9126–9135. https://doi.org/10.1021/acsami.6b1611110.1021/acsami.6b16111 ↗
41. Guan J, Zhu Z, Tomanek D (2014) Phase coexistence and metal-insulator transition in few-layer phosphorene: a computational study. Phys Rev Lett 113:046804. https://doi.org/10.1103/PhysRevLett.113.04680410.1103/PhysRevLett.113.046804 ↗
42. Zhu Z, Tomanek D (2014) Semiconducting layered blue phosphorus: a computational study. Phys Rev Lett 112:176802. https://doi.org/10.1103/PhysRevLett.112.17680210.1103/PhysRevLett.112.176802 ↗
43. Wu M, Fu H, Zhou L et al (2015) Nine new phosphorene polymorphs with non-honeycomb structures: a much extended family. Nano Lett 15:3557–3562. https://doi.org/10.1021/acs.nanolett.5b0104110.1021/acs.nanolett.5b01041 ↗
44. Zhang L, Huang H, Zhang B et al (2020) Structure and properties of violet phosphorus and its phosphorene exfoliation. Angew Chem Int Ed 59:1074–1080. https://doi.org/10.1002/anie.20191276110.1002/anie.201912761 ↗
45. Zhang C, Lian J, Yi W et al (2009) Surface structures of black phosphorus investigated with scanning tunneling microscopy. J Phys Chem C 113:18823–18826. https://doi.org/10.1021/jp907062n10.1021/jp907062n ↗
46. Mao N, Lin Y, Bie YQ et al (2021) Resonance-enhanced excitation of interlayer vibrations in atomically thin black phosphorus. Nano Lett 21:4809–4815. https://doi.org/10.1021/acs.nanolett.1c0091710.1021/acs.nanolett.1c00917 ↗
47. Morita A (1986) Semiconducting black phosphorus. Appl Phys A 39:227–242. https://doi.org/10.1007/BF0061726710.1007/BF00617267 ↗
48. Castellanos-Gomez A, Vicarelli L, Prada E et al (2014) Isolation and characterization of few-layer black phosphorus. 2D Mater 1:025001. https://doi.org/10.1088/2053-1583/1/2/02500110.1088/2053-1583/1/2/025001 ↗
49. Zhang T, Wan Y, Xie H et al (2018) Degradation chemistry and stabilization of exfoliated few-layer black phosphorus in water. J Am Chem Soc 140:7561–7567. https://doi.org/10.1021/jacs.8b0215610.1021/jacs.8b02156 ↗
50. Kwon H, Seo SW, Kim TG et al (2016) Ultrathin and flat layer black phosphorus fabricated by reactive oxygen and water rinse. ACS Nano 10:8723–8731. https://doi.org/10.1021/acsnano.6b0419410.1021/acsnano.6b04194 ↗
51. Ahmed T, Balendhran S, Karim MN et al (2017) Degradation of black phosphorus is contingent on UV–blue light exposure. npj 2D Mater Appl 1:18. https://doi.org/10.1038/s41699-017-0023-510.1038/s41699-017-0023-5 ↗
52. Walia S, Sabri Y, Ahmed T et al (2016) Defining the role of humidity in the ambient degradation of few-layer black phosphorus. 2D Mater 4:015025. https://doi.org/10.1088/2053-1583/4/1/01502510.1088/2053-1583/4/1/015025 ↗
53. Wang H, Yang X, Shao W et al (2015) Ultrathin black phosphorus nanosheets for efficient singlet oxygen generation. J Am Chem Soc 137:11376–11382. https://doi.org/10.1021/jacs.5b0602510.1021/jacs.5b06025 ↗
54. Kim S, Jung Y, Lee JY et al (2016) In situ thickness control of black phosphorus field-effect transistors via ozone treatment. Nano Res 9:3056–3065. https://doi.org/10.1007/s12274-016-1188-510.1007/s12274-016-1188-5 ↗
55. He D, Zhang Z, Xing Y et al (2020) Black phosphorus/graphitic carbon nitride: a metal-free photocatalyst for “green” photocatalytic bacterial inactivation under visible light. Chem Eng J 384:123258. https://doi.org/10.1016/j.cej.2019.12325810.1016/j.cej.2019.123258 ↗
56. He D, Jin D, Cheng F et al (2022) Development of a metal-free black phosphorus/graphitic carbon nitride heterostructure for visible-light-driven degradation of indomethacin. Sci Total Environ 804:150062. https://doi.org/10.1016/j.scitotenv.2021.15006210.1016/j.scitotenv.2021.150062 ↗
57. Jana D, Jia S, Bindra AK et al (2020) Clearable black phosphorus nanoconjugate for targeted cancer phototheranostics. ACS Appl Mater Interfaces 12:18342–18351. https://doi.org/10.1021/acsami.0c0271810.1021/acsami.0c02718 ↗
58. Ding Q, Sun T, Su W et al (2022) Bioinspired multifunctional black phosphorus hydrogel with antibacterial and antioxidant properties: a stepwise countermeasure for diabetic skin wound healing. Adv Healthc Mater 11:e2102791. https://doi.org/10.1002/adhm.20210279110.1002/adhm.202102791 ↗
59. Huang J, He B, Zhang Z et al (2020) Aggregation-induced emission luminogens married to 2D black phosphorus nanosheets for highly efficient multimodal theranostics. Adv Mater 32:e2003382. https://doi.org/10.1002/adma.20200338210.1002/adma.202003382 ↗
60. Liang M, Zhang M, Yu S et al (2020) Silver-laden black phosphorus nanosheets for an efficient in vivo antimicrobial application. Small 16:e1905938. https://doi.org/10.1002/smll.20190593810.1002/smll.201905938 ↗
61. Li Z, Zhao C, Fu Q et al (2022) Neodymium (3+)-coordinated black phosphorus quantum dots with retrievable NIR/X-ray optoelectronic switching effect for anti-glioblastoma. Small 18:e2105160. https://doi.org/10.1002/smll.20210516010.1002/smll.202105160 ↗
62. Qi F, Ji P, Chen Z et al (2021) Photosynthetic cyanobacteria-hybridized black phosphorus nanosheets for enhanced tumor photodynamic therapy. Small 17:e2102113. https://doi.org/10.1002/smll.20210211310.1002/smll.202102113 ↗
63. Edmonds MT, Tadich A, Carvalho A et al (2015) Creating a stable oxide at the surface of black phosphorus. ACS Appl Mater Interfaces 7:14557–14562. https://doi.org/10.1021/acsami.5b0129710.1021/acsami.5b01297 ↗
64. Wang G, Pandey R, Karna SP (2015) Phosphorene oxide: stability and electronic properties of a novel two-dimensional material. Nanoscale 7:524–531. https://doi.org/10.1039/c4nr05384b10.1039/c4nr05384b ↗
65. Luo W, Zemlyanov DY, Milligan CA et al (2016) Surface chemistry of black phosphorus under a controlled oxidative environment. Nanotechnology 27:434002. https://doi.org/10.1088/0957-4484/27/43/43400210.1088/0957-4484/27/43/434002 ↗
66. Grasseschi D, Bahamon D, Maia F et al (2017) Oxygen impact on the electronic and vibrational properties of black phosphorus probed by synchrotron infrared nanospectroscopy. 2D Mater 4:035028. https://doi.org/10.1088/2053-1583/aa821010.1088/2053-1583/aa8210 ↗
67. Plutnar J, Sofer Z, Pumera M (2018) Products of degradation of black phosphorus in protic solvents. ACS Nano 12:8390–8396. https://doi.org/10.1021/acsnano.8b0374010.1021/acsnano.8b03740 ↗
68. Kim DK, Chae J, Hong SB et al (2018) Interface engineering for a stable chemical structure of oxidized-black phosphorus via self-reduction in AlOx atomic layer deposition. Nanoscale 10:22896–22907. https://doi.org/10.1039/c8nr06652c10.1039/c8nr06652c ↗
69. Niu X, Li Y, Zhang Y et al (2018) Photo-oxidative degradation and protection mechanism of black phosphorus: insights from ultrafast dynamics. J Phys Chem Lett 9:5034–5039. https://doi.org/10.1021/acs.jpclett.8b0206010.1021/acs.jpclett.8b02060 ↗
70. Huang Y, Qiao J, He K et al (2016) Interaction of black phosphorus with oxygen and water. Chem Mater 28:8330–8339. https://doi.org/10.1021/acs.chemmater.6b0359210.1021/acs.chemmater.6b03592 ↗
71. Kistanov AA, Cai Y, Zhou K et al (2016) The role of H2O and O2 molecules and phosphorus vacancies in the structure instability of phosphorene. 2D Mater 4:015010. https://doi.org/10.1088/2053-1583/4/1/01501010.1088/2053-1583/4/1/015010 ↗
72. Naclerio AE, Zakharov DN, Kumar J et al (2020) Visualizing oxidation mechanisms in few-layered black phosphorus via in situ transmission electron microscopy. ACS Appl Mater Interfaces 12:15844–15854. https://doi.org/10.1021/acsami.9b2111610.1021/acsami.9b21116 ↗
73. Elbadawi C, Queralt RT, Xu ZQ et al (2018) Encapsulation-free stabilization of few-layer black phosphorus. ACS Appl Mater Interfaces 10:24327–24331. https://doi.org/10.1021/acsami.8b0418010.1021/acsami.8b04180 ↗
74. Wang G, Slough WJ, Pandey R et al (2016) Degradation of phosphorene in air: understanding at atomic level. 2D Mater 3:025011. https://doi.org/10.1088/2053-1583/3/2/02501110.1088/2053-1583/3/2/025011 ↗
75. Kumar J, Shrivastava M (2022) First-principles molecular dynamics insight into the atomic level degradation pathway of phosphorene. ACS Omega 7:696–704. https://doi.org/10.1021/acsomega.1c0535310.1021/acsomega.1c05353 ↗
76. Oh KH, Jung SW, Kim KS (2020) Tracing the initial state of surface oxidation in black phosphorus. Appl Surf Sci 504:144341. https://doi.org/10.1016/j.apsusc.2019.14434110.1016/j.apsusc.2019.144341 ↗
77. Wang S, Li J, Zhao Y et al (2020) Effective passivation of black phosphorus against atmosphere by quasi-monolayer of F4TCNQ molecules. Appl Phys Lett 117:061602. https://doi.org/10.1063/5.001511910.1063/5.0015119 ↗
78. Wang C, Niu D, Wang S et al (2018) Energy level evolution and oxygen exposure of fullerene/black phosphorus interface. J Phys Chem Lett 9:5254–5261. https://doi.org/10.1021/acs.jpclett.8b0229310.1021/acs.jpclett.8b02293 ↗
79. Li W, Wang Z, Zhao F et al (2020) Phosphorene degradation: visualization and quantification of nanoscale phase evolution by scanning transmission X-ray microscopy. Chem Mater 32:1272–1280. https://doi.org/10.1021/acs.chemmater.9b0481110.1021/acs.chemmater.9b04811 ↗
80. Yang T, Dong B, Wang J et al (2015) Interpreting core-level spectra of oxidizing phosphorene: theory and experiment. Phys Rev B 92:125412. https://doi.org/10.1103/PhysRevB.92.12541210.1103/PhysRevB.92.125412 ↗
81. Gómez-Pérez JF, Correa JD, Pravda CB et al (2020) Dangling-to-interstitial oxygen transition and its modifications of the electronic structure in few-layer phosphorene. J Phys Chem C 124:24066–24072. https://doi.org/10.1021/acs.jpcc.0c0654210.1021/acs.jpcc.0c06542 ↗
82. Zhang L, Vasenko AS, Zhao J et al (2019) Mono-elemental properties of 2D black phosphorus ensure extended charge carrier lifetimes under oxidation: time-domain ab initio analysis. J Phys Chem Lett 10:1083–1091. https://doi.org/10.1021/acs.jpclett.9b0004210.1021/acs.jpclett.9b00042 ↗
83. Zhang Z, Li S, Qiao D et al (2021) Black phosphorus nanosheet encapsulated by zeolitic imidazole framework-8 for tumor multimodal treatments. ACS Appl Mater Interfaces 13:43855–43867. https://doi.org/10.1021/acsami.1c0400110.1021/acsami.1c04001 ↗
84. Yan S, Song H, Wan LF et al (2020) Hydroxyl-assisted phosphorene stabilization with robust device performances. Nano Lett 20:81–87. https://doi.org/10.1021/acs.nanolett.9b0311510.1021/acs.nanolett.9b03115 ↗
85. Zhao Y, Sun Z, Zhang B et al (2022) Unveiling the degradation chemistry of fibrous red phosphorus under ambient conditions. ACS Appl Mater Interfaces 14:9925–9932. https://doi.org/10.1021/acsami.1c2488310.1021/acsami.1c24883 ↗
86. Hu W, Yang J (2015) Defects in Phosphorene. J Phys Chem C 119:20474–20480. https://doi.org/10.1021/acs.jpcc.5b0607710.1021/acs.jpcc.5b06077 ↗
87. Zhang R, Wu X, Yang J (2016) Blockage of ultrafast and directional diffusion of Li atoms on phosphorene with intrinsic defects. Nanoscale 8:4001–4006. https://doi.org/10.1039/c5nr06856h10.1039/c5nr06856h ↗
88. Gaberle J, Shluger AL (2018) Structure and properties of intrinsic and extrinsic defects in black phosphorus. Nanoscale 10:19536–19546. https://doi.org/10.1039/c8nr06640j10.1039/c8nr06640j ↗
89. Pei W, Zhou S, Zhao J et al (2020) Optimization of photocarrier dynamics and activity in phosphorene with intrinsic defects for nitrogen fixation. J Mater Chem A 8:20570–20580. https://doi.org/10.1039/D0TA08553G10.1039/D0TA08553G ↗
90. Kripalani DR, Cai Y, Xue M et al (2019) Metastable interlayer Frenkel pair defects in black phosphorus. Phys Rev B 100:224107. https://doi.org/10.1103/PhysRevB.100.22410710.1103/PhysRevB.100.224107 ↗
91. Kundu S, Naik MH, Jain M (2020) Native point defects in mono and bilayer phosphorene. Phys Rev Mater 4:054004. https://doi.org/10.1103/PhysRevMaterials.4.05400410.1103/PhysRevMaterials.4.054004 ↗
92. Rijal B, Tan AMZ, Freysoldt C et al (2021) Charged vacancy defects in monolayer phosphorene. Phys Rev Mater 5:124004. https://doi.org/10.1103/PhysRevMaterials.5.12400410.1103/PhysRevMaterials.5.124004 ↗
93. Podlivaev AI, Openov LA (2015) Out-of-plane path of the Stone-Wales transformation in graphene. Phys Lett A 379:1757–1761. https://doi.org/10.1016/j.physleta.2015.04.01010.1016/j.physleta.2015.04.010 ↗
94. Banhart F, Kotakoski J, Krasheninnikov AV (2011) Structural defects in graphene. ACS Nano 5:26–41. https://doi.org/10.1021/nn102598m10.1021/nn102598m ↗
95. Kiraly B, Hauptmann N, Rudenko AN et al (2017) Probing single vacancies in black phosphorus at the atomic level. Nano Lett 17:3607–3612. https://doi.org/10.1021/acs.nanolett.7b0076610.1021/acs.nanolett.7b00766 ↗
96. Li X, Ma L, Wang D et al (2016) Point defects in lines in single crystalline phosphorene: directional migration and tunable band gaps. Nanoscale 8:17801–17808. https://doi.org/10.1039/c6nr05414e10.1039/c6nr05414e ↗
97. Yao F, Cai Y, Xiao Z et al (2020) In situ transmission electron microscopy study of the formation and migration of vacancy defects in atomically thin black phosphorus. 2D Mater 8:025004. https://doi.org/10.1088/2053-1583/abce0910.1088/2053-1583/abce09 ↗
98. Babar R, Kabir M (2019) Mechanistic insights in phosphorene degradation. Phys Rev Mater 3:074008. https://doi.org/10.1103/PhysRevMaterials.3.07400810.1103/PhysRevMaterials.3.074008 ↗
99. Huang J, Tao B, Zhang Q et al (2022) Defect-induced different band alignment and transport of all-phosphorene devices from first principles. ACS Appl Electron Mater 4:2070–2076. https://doi.org/10.1021/acsaelm.2c0021210.1021/acsaelm.2c00212 ↗
100. Sha ZD, Pei QX, Wan Q et al (2017) Failure mechanism of phosphorene by nanoindentation. J Phys Chem C 121:4708–4713. https://doi.org/10.1021/acs.jpcc.6b1307110.1021/acs.jpcc.6b13071 ↗