Sub-2-nm-droplet-driven growth of amorphous metal chalcogenides approaching the single-layer limit
Source abstract
Abstract
Atom-thin amorphous materials (for example, amorphous monolayer carbon) offer a designable material platform for fundamental studies of the disorder system, as well as the development of various applications. However, their growth at a single layer remains challenging since their thermodynamically favourable grains are neither two dimensional nor layered. Here we demonstrate the growth of 1-nm-thick, amorphous metal chalcogenides at a wafer scale using a nanodroplet-driven nanoribbon-to-film strategy. Metal clusters are initially liquified into 1-2 nm droplets at 120 °C, and they then orchestrate the growth of amorphous single-layer nanoribbons, which eventually merge into a continuous centimetre-scale film. Phase-field simulations, combined with our characterizations, suggest a non-equilibrium kinetic growth mechanism, which can be applicable to various films, for example, PtSex, IrSex, PdSex and RhSex. The synthesized films exhibit a range of unique properties, including tunable conductivity through disorder modulation, high work functions and remarkable catalytic activity, making them promising candidates for hole-injection contacts in p-type transistors and hydrogen production applications. This work opens a pathway for the synthesis of non-layered materials approaching the single-layer limit.
Source: europepmc · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Phase-change materials and chalcogenides · Quantum Dots Synthesis And Properties · Chalcogenide Semiconductor Thin Films
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (45)
Show source-provided references
1. Liu, Y. et al. Promises and prospects of two-dimensional transistors. Nature 591, 43–53 (2021).10.1038/s41586-021-03339-z ↗
2. Meng, Z., Stolz, R. M., Mendecki, L. & Mirica, K. A. Electrically-transduced chemical sensors based on two-dimensional nanomaterials. Chem. Rev. 119, 478–598 (2019).10.1021/acs.chemrev.8b00311 ↗
3. Pomerantseva, E. & Gogotsi, Y. Two-dimensional heterostructures for energy storage. Nat. Energy 2, 17089 (2017).10.1038/nenergy.2017.89 ↗
4. Chia, X. & Pumera, M. Characteristics and performance of two-dimensional materials for electrocatalysis. Nat. Catal. 1, 909–921 (2018).10.1038/s41929-018-0181-7 ↗
5. Zhang, H. & Han, Y. Compression-induced polycrystal-glass transition in binary crystals. Phys. Rev. X 8, 041023 (2018).
6. Cocke, D. L. Heterogeneous catalysis by amorphous materials. JOM 38, 70–75 (1986).10.1007/BF03257931 ↗
7. Yang, Z., Hao, J. & Lau, S. P. Synthesis, properties, and applications of 2D amorphous inorganic materials. J. Appl. Phys. 127, 220901 (2020).10.1063/1.5144626 ↗
8. He, Y. et al. Amorphizing noble metal chalcogenide catalysts at the single-layer limit towards hydrogen production. Nat. Catal. 5, 212–221 (2022).10.1038/s41929-022-00753-y ↗
9. Toh, C. T. et al. Synthesis and properties of free-standing monolayer amorphous carbon. Nature 577, 199–203 (2020).10.1038/s41586-019-1871-2 ↗
10. Tian, H. et al. Disorder-tuned conductivity in amorphous monolayer carbon. Nature 615, 56–61 (2023).10.1038/s41586-022-05617-w ↗
11. Hong, S. et al. Ultralow-dielectric-constant amorphous boron nitride. Nature 582, 511–514 (2020).10.1038/s41586-020-2375-9 ↗
12. Zhang, T., Wang, J., Wu, P., Lu, A.-Y. & Kong, J. Vapour-phase deposition of two-dimensional layered chalcogenides. Nat. Rev. Mater. 8, 799–821 (2023).10.1038/s41578-023-00609-2 ↗
13. Sun, L. et al. Chemical vapour deposition. Nat. Rev. Methods Primers 1, 5 (2021).10.1038/s43586-020-00005-y ↗
14. Xu, M. et al. Reconfiguring nucleation for CVD growth of twisted bilayer MoS2 with a wide range of twist angles. Nat. Commun. 15, 562 (2024).10.1038/s41467-023-44598-w ↗
15. Greene, J. E. in Handbook of Deposition Technologies for Films and Coatings (Third Edition) (ed. Martin, P. M.) 554–620 (William Andrew Publishing, 2010).10.1016/B978-0-8155-2031-3.00012-0 ↗
16. Li, S. et al. Vapour–liquid–solid growth of monolayer MoS2 nanoribbons. Nat. Mater. 17, 535–542 (2018).10.1038/s41563-018-0055-z ↗
17. Suzuki, H. et al. Wafer-scale fabrication and growth dynamics of suspended graphene nanoribbon arrays. Nat. Commun. 7, 11797 (2016).10.1038/ncomms11797 ↗
18. Nanda, K. K., Sahu, S. N. & Behera, S. N. Liquid-drop model for the size-dependent melting of low-dimensional systems. Phys. Rev. A 66, 013208 (2002).10.1103/PhysRevA.66.013208 ↗
19. Li, K., Wang, T., Wang, W. & Gao, X. Lattice vibration properties of MoS2/PtSe2 heterostructures. J. Alloy. Compd. 820, 153192 (2020).10.1016/j.jallcom.2019.153192 ↗
20. Zhou, J. et al. Epitaxial synthesis of monolayer PtSe2 single crystal on MoSe2 with strong interlayer coupling. ACS Nano 13, 10929–10938 (2019).10.1021/acsnano.8b09479 ↗
21. Hu, D. et al. Unveiling the layer-dependent catalytic activity of PtSe2 atomic crystals for the hydrogen evolution reaction. Angew. Chem. Int. Ed. 58, 6977–6981 (2019).10.1002/anie.201901612 ↗
22. Huang, L. et al. Catalyzed kinetic growth in two-dimensional MoS2. J. Am. Chem. Soc. 142, 13130–13135 (2020).10.1021/jacs.0c05057 ↗
23. Jiang, Q. et al. High chemical potential driven amorphization of Pd-based nanoalloys. Small Methods 7, 2201513 (2023).10.1002/smtd.202201513 ↗
24. Yuan, Q., Xu, Z., Yakobson, B. I. & Ding, F. Efficient defect healing in catalytic carbon nanotube growth. Phys. Rev. Lett. 108, 245505 (2012).10.1103/PhysRevLett.108.245505 ↗
25. Li, X. et al. Advances in heterogeneous single-cluster catalysis. Nat. Rev. Chem. 7, 754–767 (2023).10.1038/s41570-023-00540-8 ↗
26. Wang, X. et al. Single-atom engineering to ignite 2D transition metal dichalcogenide based catalysis: fundamentals, progress, and beyond. Chem. Rev. 122, 1273–1348 (2022).10.1021/acs.chemrev.1c00505 ↗
27. Liu, D.-Q. et al. Tailoring interfacial charge transfer of epitaxially grown IR clusters for boosting hydrogen oxidation reaction. Adv. Energy Mater. 13, 2202913 (2023).10.1002/aenm.202202913 ↗
28. Shi, Y. et al. Site-specific electrodeposition enables self-terminating growth of atomically dispersed metal catalysts. Nat. Commun. 11, 4558 (2020).10.1038/s41467-020-18430-8 ↗
29. Lou, Y. et al. Pocketlike active site of Rh1/MoS2 single-atom catalyst for selective crotonaldehyde hydrogenation. J. Am. Chem. Soc. 141, 19289–19295 (2019).10.1021/jacs.9b06628 ↗
30. Luo, Z. et al. Chemically activating MoS2 via spontaneous atomic palladium interfacial doping towards efficient hydrogen evolution. Nat. Commun. 9, 2120 (2018).10.1038/s41467-018-04501-4 ↗
31. Kim, K. S. et al. Growth-based monolithic 3D integration of single-crystal 2D semiconductors. Nature 636, 615–621 (2024).10.1038/s41586-024-08236-9 ↗
32. Zhang, K. et al. Epitaxial substitution of metal iodides for low-temperature growth of two-dimensional metal chalcogenides. Nat. Nanotechnol. 18, 448–455 (2023).10.1038/s41565-023-01326-1 ↗
33. Qin, B. et al. General low-temperature growth of two-dimensional nanosheets from layered and nonlayered materials. Nat. Commun. 14, 304 (2023).10.1038/s41467-023-35983-6 ↗
34. Xia, H. et al. The practice of reaction window in an electrocatalytic on-chip microcell. Nat. Commun. 14, 6838 (2023).10.1038/s41467-023-42645-0 ↗
35. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).10.1103/PhysRevB.59.1758 ↗
36. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).10.1103/PhysRevB.54.11169 ↗
37. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).10.1103/PhysRevB.50.17953 ↗
38. Perdew, J. P. & Wang, Y. Accurate and simple analytic representation of the electron-gas correlation energy. Phys. Rev. B 45, 13244–13249 (1992).10.1103/PhysRevB.45.13244 ↗
39. Perdew, J. P. et al. Atoms, molecules, solids, and surfaces: applications of the generalized gradient approximation for exchange and correlation. Phys. Rev. B 46, 6671–6687 (1992).10.1103/PhysRevB.46.6671 ↗
40. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).10.1103/PhysRevLett.77.3865 ↗
41. Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 32, 1456–1465 (2011).10.1002/jcc.21759 ↗
42. Wang, V., Xu, N., Liu, J.-C., Tang, G. & Geng, W.-T. VASPKIT: a user-friendly interface facilitating high-throughput computing and analysis using VASP code. Comput. Phys. Commun. 267, 108033 (2021).10.1016/j.cpc.2021.108033 ↗
43. Borcia, R., Borcia, I. D. & Bestehorn, M. Static and dynamic contact angles—a phase field modelling. Eur. Phys. J. 166, 127–131 (2009).
44. He, Y. et al. Engineering grain boundaries at the 2D limit for the hydrogen evolution reaction. Nat. Commun. 11, 57 (2020).10.1038/s41467-019-13631-2 ↗
45. Karma, A. & Plapp, M. Spiral surface growth without desorption. Phys. Rev. Lett. 81, 4444–4447 (1998).10.1103/PhysRevLett.81.4444 ↗