journal article·2015-08

Photooxidation and quantum confinement effects in exfoliated black phosphorus

Alexandre Favron, Etienne Gaufrès, Frédéric Fossard, Anne-Laurence Phaneuf-L’Heureux, Nathalie Y-W. Tang, Pierre L. Lévesque, Annick Loiseau, Richard Leonelli, Sébastien Francoeur, Richard Martel

Nature Materials· Volume 14· Issue 8
Publisher page

Abstract

Thin layers of black phosphorus have recently raised interest owing to their two-dimensional (2D) semiconducting properties, such as tunable direct bandgap and high carrier mobilities. This lamellar crystal of phosphorus atoms can be exfoliated down to monolayer 2D-phosphane (also called phosphorene) using procedures similar to those used for graphene. Probing the properties has, however, been challenged by a fast degradation of the thinnest layers on exposure to ambient conditions. Herein, we investigate this chemistry using in situ Raman and transmission electron spectroscopies. The results highlight a thickness-dependent photoassisted oxidation reaction with oxygen dissolved in adsorbed water. The oxidation kinetics is consistent with a phenomenological model involving electron transfer and quantum confinement as key parameters. A procedure carried out in a glove box is used to prepare mono-, bi- and multilayer 2D-phosphane in their pristine states for further studies on the effect of layer thickness on the Raman modes. Controlled experiments in ambient conditions are shown to lower the A(g)(1)/A(g)(2) intensity ratio for ultrathin layers, a signature of oxidation.
Source: europepmc · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: 2D Materials and Applications · MXene and MAX Phase Materials · Graphene research and applications

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (41)

Show source-provided references
1. Bridgeman, P. W. Two new modifications of phosphorus. J. Am. Chem. Soc. 36, 1344–1363 (1914).10.1021/ja02184a002 ↗
2. Hultgren, R., Gingrich, N. S. & Warren, B. E. The atomic distribution in red and black phosphorus and the crystal structure of black phosphorus. J. Chem. Phys. 3, 351–355 (1935).10.1063/1.1749671 ↗
3. Keyes, R. The electrical properties of black phosphorus. Phys. Rev. 92, 580–584 (1953).10.1103/PhysRev.92.580 ↗
4. Warschauer, D. Electrical and optical properties of crystalline black phosphorus. J. Appl. Phys. 34, 1853–1860 (1963).10.1063/1.1729699 ↗
5. Appalakondaiah, S., Vaitheeswaran, G., Lèbegue, S., Christensen, N. E. & Svane, A. Effect of van der Waals interactions on the structural and elastic properties of black phosphorus. Phys. Rev. B 86, 035105 (2012).10.1103/PhysRevB.86.035105 ↗
6. Li, L. et al. Black phosphorus field-effect transistors. Nature Nanotech. 9, 372–377 (2014).10.1038/nnano.2014.35 ↗
7. Liu, H. et al. Phosphorene: An unexplored 2D semiconductor with a high hole mobility. ACS Nano 8, 4033–4041 (2014).10.1021/nn501226z ↗
8. Zhang, S. et al. Extraordinary photoluminescence and strong temperature/angle-dependent Raman responses in few-layer phosphorene. ACS Nano 8, 9590–9596 (2014).10.1021/nn503893j ↗
9. Liu, H., Du, Y., Deng, Y. & Ye, P. D. Semiconducting black phosphorus: Synthesis, transport properties and electronic applications. Chem. Soc. Rev. 44, 2732–2743 (2015).10.1039/C4CS00257A ↗
10. Reich, E. S. Phosphorene excites materials scientists. Nature 506, 19 (2014).10.1038/506019a ↗
11. Park, C-M. & Sohn, H-J. Black phosphorus and its composite for lithium rechargeable batteries. Adv. Mater. 19, 2465–2468 (2007).10.1002/adma.200602592 ↗
12. Asahina, H. & Morita, A. Band structure and optical properties of black phosphorus. J. Phys. C 17, 1839–1852 (1984).10.1088/0022-3719/17/11/006 ↗
13. Yau, S-L., Moffat, T. P., Bard, A. J., Zhang, Z. & Lerner, M. M. STM of the (010) surface of orthorhombic phosphorus. Chem. Phys. Lett. 198, 383–388 (1992).10.1016/0009-2614(92)85069-M ↗
14. Yoshihara, A., Fujimura, T., Oka, Y., Fujisaki, H. & Shirotani, I. Surface Brillouin scattering in black phosphorus. Phys. Rev. B 34, 7467–7470 (1986).10.1103/PhysRevB.34.7467 ↗
15. Zhang, C. D. et al. Surface structures of black phosphorus investigated with scanning tunneling microscopy. J. Phys. Chem. C 113, 18823–18826 (2009).10.1021/jp907062n ↗
16. Koenig, S. P., Doganov, R. A., Schmidt, H., Castro Neto, A. H. & Özyilmaz, B. Electric field effect in ultrathin black phosphorus. Appl. Phys. Lett. 104, 103106 (2014).10.1063/1.4868132 ↗
17. Castellanos-Gomez, A. et al. Isolation and characterization of few-layer black phosphorus. 2D Mater. 1, 025001 (2014).10.1088/2053-1583/1/2/025001 ↗
18. Wood, J. D. et al. Effective passivation of exfoliated black phosphorus transistors against ambient degradation. Nano Lett. 14, 6964–6970 (2014).10.1021/nl5032293 ↗
19. Du, Y., Ouyang, C., Shi, S. & Lei, M. Ab initio studies on atomic and electronic structures of black phosphorus. J. Appl. Phys. 107, 093718 (2010).10.1063/1.3386509 ↗
20. International Union of Pure and Applied Chemistry (IUPAC) Compendium of Chemical Terminology, 2nd edn (eds McNaught, A. D. & Wilkinson, A.) (Blackwell Scientific Publications, 1997)
21. Holleman, A. F. & Wiberg, N. Inorganic Chemistry (Academic Press, 2001).
22. Meitl, M. A. et al. Transfer printing by kinetic control of adhesion to an elastomeric stamp. Nature Mater. 5, 33–38 (2006).10.1038/nmat1532 ↗
23. Sugai, S. & Shirotani, I. Raman and infrared reflection spectroscopy in black phosphorus. Solid State Commun. 53, 753–755 (1985).10.1016/0038-1098(85)90213-3 ↗
24. Vanderborgh, C. A. & Schiferl, D. Raman studies of black phosphorus from 0.25 to 7.7 GPa at 15 K. Phys. Rev. B 40, 9595–9599 (1989).10.1103/PhysRevB.40.9595 ↗
25. Akahama, Y., Kobayashi, M. & Kawamura, H. Raman study of black phosphorus up to 13 GPa. Solid State Commun. 104, 311–315 (1997).10.1016/S0038-1098(97)00325-6 ↗
26. Sari, S. S. et al. Graphene field-effect transistors with parylene gate dielectric. Appl. Phys. Lett. 95, 242104 (2009).10.1063/1.3273396 ↗
27. Aguirre, C. M. et al. The role of the oxygen/water redox couple in suppressing electron conduction in field-effect transistors. Adv. Mater. 21, 3087–3091 (2009).10.1002/adma.200900550 ↗
28. Levesque, P. L. et al. Probing charge transfer at surface using graphene transistors. Nano Lett. 11, 132–137 (2011).10.1021/nl103015w ↗
29. Brunel, D. et al. Control over the interface properties of carbon nanotube-based optoelectronic memory devices. Appl. Phys. Lett. 102, 013103 (2013).10.1063/1.4773486 ↗
30. Memming, R. Semiconductor Electrochemistry (Wiley-VCH, 2001).
31. Ryu, S. et al. Reversible basal plane hydrogenation of graphene. Nano Lett. 8, 4597–4602 (2008).10.1021/nl802940s ↗
32. Lu, W. et al. Plasma-assisted fabrication of monolayer phosphorene and its Raman characterization. Nano Res. 7, 853–859 (2014).10.1007/s12274-014-0446-7 ↗
33. Tonndorf, P. et al. Photoluminescence emission and Raman response of monolayer MoS2, MoSe2, and WSe2 . Opt. Express 21, 4908–4916 (2013).10.1364/OE.21.004908 ↗
34. Terrones, H. et al. New first order Raman-active modes in few layered transition metal dichalcogenides. Sci. Rep. 4, 4215 (2014).10.1038/srep04215 ↗
35. Lee, C. et al. Anomalous lattice vibrations of single- and few-layer MoS2 . ACS Nano 4, 2695–2700 (2010).10.1021/nn1003937 ↗
36. Shahil, K. M. F. et al. Micro-Raman spectroscopy of mechanically exfoliated few-quintuple layers of Bi2Te3, Bi2Se3, and Sb2Te3 materials. J. Appl. Phys. 111, 054305 (2012).10.1063/1.3690913 ↗
37. Luo, X. et al. Effects of lower symmetry and dimensionality on Raman spectra in two-dimensional WSe2 . Phys. Rev. B 88, –195313 (2013).10.1103/PhysRevB.88.195313 ↗
38. Yamamoto, M. et al. Strong enhancement of Raman scattering from a bulk-inactive vibrational mode in few-layer MoTe2 . ACS Nano 8, 3895–3903 (2014).10.1021/nn5007607 ↗
39. Xia, F., Wang, H. & Jia, Y. Rediscovering black phosphorus as an anisotropic layered material for optoelectronics and electronics. Nature Commun. 5, 4458 (2014).10.1038/ncomms5458 ↗
40. Moulder, J. F., Stickle, W. F., Sobol, P. E. & Bomben, K. D. Handbook of X-ray Photoelectron Spectroscopy (Perkin-Elmer, 1992).
41. Wang, Y. & Sherwood, P. M. A. Phosphorus pentoxide (P2O5) by XPS. Surf. Sci. Spectra 9, 159–165 (2002).10.1116/11.20030115 ↗