journal article·2021-02-22Open access

In situ electron microscopy study of structural transformations in 2D CoSe2

Dnyaneshwar S. Gavhane, Heleen van Gog, Balu Thombare, Gaurav Lole, L. Christiaan Post, Mahendra A. More, Marijn A. van Huis

Abstract

Abstract Thermally induced structural transformation of 2D materials opens unique avenues for generating other 2D materials by physical methods. Imaging these transitions in real time provides insight into synthesis routes and property tuning. We have used in situ transmission electron microscopy (TEM) to follow thermally induced structural transformations in layered CoSe2. Three transformation processes are observed: orthorhombic to cubic-CoSe2, cubic-CoSe2 to hexagonal-CoSe, and hexagonal to tetragonal-CoSe. In particular, the unit-cell-thick orthorhombic structure of CoSe2 transforms into cubic-CoSe2 via rearrangement of lattice atoms. Cubic-CoSe2 transforms to hexagonal-CoSe at elevated temperatures through the removal of chalcogen atoms. All nanosheets transform to basal-plane-oriented hexagonal 2D CoSe. Finally, the hexagonal to tetragonal transformation in CoSe is a rapid process wherein the layered morphology of hexagonal-CoSe is broken and islands of tetragonal-CoSe are formed. Our results provide nanoscopic insights into the transformation processes of 2D CoSe2 which can be used to generate these intriguing 2D materials and to tune their properties by modifying their structures for electro-catalytic and electronic applications.
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Research context

OpenAlex topics: 2D Materials and Applications · Chalcogenide Semiconductor Thin Films · Advanced Thermoelectric Materials and Devices

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

References (42)

Show source-provided references
1. Cheng, L. et al. Ultrathin WS2 nanoflakes as a high‐performance electrocatalyst for the hydrogen evolution reaction. Angew. Chem. Int. Ed. 53, 7860–7863 (2014).10.1002/anie.201402315 ↗
2. Cheng, R. et al. Few-layer molybdenum disulfide transistors and circuits for high-speed flexible electronics. Nat. Commun. 5, 5143 (2014).10.1038/ncomms6143 ↗
3. Steinleitner, P. et al. Direct observation of ultrafast exciton formation in a monolayer of WSe2. Nano Lett. 17, 1455–1460 (2017).10.1021/acs.nanolett.6b04422 ↗
4. Zhou, H. et al. Large area growth and electrical properties of p-type WSe2 atomic layers. Nano Lett. 15, 709–713 (2014).10.1021/nl504256y ↗
5. Chhowalla, M. et al. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 5, 263 (2013).10.1038/nchem.1589 ↗
6. Empante, T. A. et al. Chemical vapor deposition growth of few-layer MoTe2 in the 2H, 1T′, and 1T phases: tunable properties of MoTe2 films. ACS Nano 11, 900–905 (2017).10.1021/acsnano.6b07499 ↗
7. Zhou, Y. et al. Pressure-induced Td to 1T′ structural phase transition in WTe2. AIP Adv. 6, 075008 (2016).10.1063/1.4959026 ↗
8. Lin, Y.-C., Dumcenco, D. O., Huang, Y.-S. & Suenaga, K. Atomic mechanism of the semiconducting-to-metallic phase transition in single-layered MoS2. Nat. Nanotechnol. 9, 391 (2014).10.1038/nnano.2014.64 ↗
9. Enyashin, A. N. et al. New route for stabilization of 1T-WS2 and MoS2 phases. J. Phys. Chem. C 115, 24586–24591 (2011).10.1021/jp2076325 ↗
10. Kappera, R. et al. Phase-engineered low-resistance contacts for ultrathin MoS2 transistors. Nat. Mater. 13, 1128 (2014).10.1038/nmat4080 ↗
11. Nayak, A. P. et al. Pressure-induced semiconducting to metallic transition in multilayered molybdenum disulphide. Nat. Commun. 5, 3731 (2014).10.1038/ncomms4731 ↗
12. Wang, L., Xu, Z., Wang, W. & Bai, X. Atomic mechanism of dynamic electrochemical lithiation processes of MoS2 nanosheets. J. Am. Chem. Soc. 136, 6693–6697 (2014).10.1021/ja501686w ↗
13. Basu, M. et al. Heterostructure of Si and CoSe2: a promising photocathode based on a non‐noble metal catalyst for photoelectrochemical hydrogen evolution. Angew. Chem. Int. Ed. 54, 6211–6216 (2015).10.1002/anie.201502573 ↗
14. Chen, P. et al. Phase‐transformation engineering in cobalt diselenide realizing enhanced catalytic activity for hydrogen evolution in an alkaline medium. Adv. Mater. 28, 7527–7532 (2016).10.1002/adma.201601663 ↗
15. Brostigen, G. & Kjekshus, A. Relationships between the structure types pyrite, marcasite, and arsenopyrite. Acta Chem. Scand. 24, 2983–2992 (1970).10.3891/acta.chem.scand.24-2983 ↗
16. Gao, M.-R. et al. An efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation. Nat. Commun. 6, 5982 (2015).10.1038/ncomms6982 ↗
17. Xu, Y. F., Gao, M. R., Zheng, Y. R., Jiang, J. & Yu, S. H. Nickel/nickel (II) oxide nanoparticles anchored onto cobalt (IV) diselenide nanobelts for the electrochemical production of hydrogen. Angew. Chem. Int. Ed. 52, 8546–8550 (2013).10.1002/anie.201303495 ↗
18. Zheng, Y.-R. et al. Cobalt diselenide nanobelts grafted on carbon fiber felt: an efficient and robust 3D cathode for hydrogen production. Chem. Sci. 6, 4594–4598 (2015).10.1039/C5SC01335F ↗
19. Dodony, I., Posfal, M. & Buseck, P. R. Structural relationship between pyrite and marcasite. Am. Mineral. 81, 119–125 (1996).10.2138/am-1996-1-215 ↗
20. Fleet, M. Structural aspects of the marcasite-pyrite transformation. Canad. Mineral. 10, 225–231 (1970).
21. Zhang, H. et al. Polymorphic CoSe2 with mixed orthorhombic and cubic phases for highly efficient hydrogen evolution reaction. ACS Appl. Mater. Int. 7, 1772–1779 (2015).10.1021/am507373g ↗
22. Campos, C. et al. Hexagonal CoSe formation in mechanical alloyed Co75Se25 mixture. Sol. Stat. Commun. 131, 265–270 (2004).10.1016/j.ssc.2004.03.044 ↗
23. Umeyama, N. et al. Synthesis and magnetic properties of NiSe, NiTe, CoSe, and CoTe. Jap. J. Appl. Phys. 51, 053001 (2012).10.1143/JJAP.51.053001 ↗
24. Wilfong, B. et al. Frustrated magnetism in the tetragonal CoSe analog of superconducting FeSe. Phys. Rev. B 97, 104408 (2018).10.1103/PhysRevB.97.104408 ↗
25. Zhou, X. et al. Metastable layered cobalt chalcogenides from topochemical deintercalation. J. Am. Chem. Soc. 138, 16432–16442 (2016).10.1021/jacs.6b10229 ↗
26. Nekooi, P., Akbari, M. & Amini, M. K. CoSe nanoparticles prepared by the microwave-assisted polyol method as an alcohol and formic acid tolerant oxygen reduction catalyst. Int. J. Hydrogen Energy 35, 6392–6398 (2010).10.1016/j.ijhydene.2010.03.134 ↗
27. Zhang, Y. et al. Nitrogen-doped yolk–shell-structured CoSe/C dodecahedra for high-performance sodium ion batteries. ACS Appl. Mater. Int. 9, 3624–3633 (2017).10.1021/acsami.6b13153 ↗
28. van Huis, M. A. et al. Atomic imaging of phase transitions and morphology transformations in nanocrystals. Adv. Mater. 21, 4992–4995 (2009).10.1002/adma.200902561 ↗
29. Cabán-Acevedo, M., Faber, M. S., Tan, Y., Hamers, R. J. & Jin, S. Synthesis and properties of semiconducting iron pyrite (FeS2) nanowires. Nano Lett. 12, 1977–1982 (2012).10.1021/nl2045364 ↗
30. Sun, R., Chan, M. & Ceder, G. First-principles electronic structure and relative stability of pyrite and marcasite: Implications for photovoltaic performance. Phys. Rev. B 83, 235311 (2011).10.1103/PhysRevB.83.235311 ↗
31. Kong, D., Wang, H., Lu, Z. & Cui, Y. CoSe2 nanoparticles grown on carbon fiber paper: an efficient and stable electrocatalyst for hydrogen evolution reaction. J. Am. Chem. Soc. 136, 4897–4900 (2014).10.1021/ja501497n ↗
32. Campos, C. et al. Structural studies of cobalt selenides prepared by mechanical alloying. Phys. B Condens. Matter 324, 409–418 (2002).10.1016/S0921-4526(02)01461-8 ↗
33. Sutter, E. et al. Electron-beam induced transformations of layered tin dichalcogenides. Nano Lett. 16, 4410–4416 (2016).10.1021/acs.nanolett.6b01541 ↗
34. Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).10.1016/0927-0256(96)00008-0 ↗
35. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169 (1996).10.1103/PhysRevB.54.11169 ↗
36. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953 (1994).10.1103/PhysRevB.50.17953 ↗
37. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758 (1999).10.1103/PhysRevB.59.1758 ↗
38. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865 (1996).10.1103/PhysRevLett.77.3865 ↗
39. Dion, M., Rydberg, H., Schröder, E., Langreth, D. C. & Lundqvist, B. I. Van der Waals density functional for general geometries. Phys. Rev. Lett. 92, 246401 (2004).10.1103/PhysRevLett.92.246401 ↗
40. Klimeš, J., Bowler, D. R. & Michaelides, A. Chemical accuracy for the van der Waals density functional. J. Phys. Condens. Matter 22, 022201 (2009).10.1088/0953-8984/22/2/022201 ↗
41. Garcı́a-Garcı́a, F. J., Larsson, A.-K., Norèn, L. & Withers, R. L. The crystal structures of Co3Se4 and Co7Se8. Sol. Stat. Sci. 6, 725–733 (2004).10.1016/j.solidstatesciences.2004.03.030 ↗
42. Liang, L. et al. Metallic single‐unit‐cell orthorhombic cobalt diselenide atomic layers: robust water‐electrolysis catalysts. Angew. Chem. Int. Ed. 54, 12004–12008 (2015).10.1002/anie.201505245 ↗