Electrodeposition of Cu Nanocubes in the Presence of Cl- and Br-

Abstract

Electrodeposition is one of the simple methods for fabricating metal and alloy thin films. Electrodeposition is performed by applying external electrical energy to conductive substrates immersing in electrolytes containing metal precursors. Metal ions or complexes are reduced on a substrate surface and form metal films. The properties of metal thin films and surface morphology of the electrodeposit can be modulated by the parameters of electrodeposition, the composition of electrolytes, i.e., the concentrations of metal precursors and additives. Furthermore, the atomic composition of alloy films can also be easily controlled by electrochemical parameters in the electrodeposition process.1 As explained, the electrodeposition process has various advantages in producing metal thin films with desired properties. However, creating nanostructures with precisely controlling their shapes in the nm scale is relatively difficult. In colloidal syntheses, various nanocrystals, including nanowires, nanospheres, octahedrons, nanocubes, and nanoplates, can be obtained by introducing shape-directing agents.2-4 In the case of electrodeposition, the template-assisted electrodeposition method is the most common to form nanostructures,5,6 and relatively few examples of shape controlling by additives have been reported. Although the formation of metal nanowires in the presence of 3,5-diamino-1,2,4-triazole (DAT) has been recently reported,7 shape control of metal deposits by additives during the electrodeposition process is still limited to few nanostructures. Electrodeposition induces metal growth relatively faster than colloidal synthesis, and a precise nucleation step is not involved in the electrodeposition, which is critical in colloidal syntheses. In this study, we have adopted pulse-reverse electrodeposition to modulate metal nucleation at the initial stage of electrodeposition and also maximize the effects of additives. Pulse-reverse electrodeposition has been researched for controlling the properties of metal thin films and changing the adsorption of additives.8,9 Therefore, pulse-reverse electrodeposition can catch up with the shape control in colloidal syntheses. This presentation will introduce how the parameters in pulse-reverse electrodeposition and additives (halide ions) affect the shape of Cu nanocrystals. References 1) T. P. Moffat, J. J. Mallett, and S. M. Hwang, “Oxygen Reduction Kinetics on Electrodeposited Pt, Pt100− x Nix , and Pt100−xCox” J. Electrochem. Soc. 156, B238 (2009)2) Y. Xia, Y. Xiong, B. Lim, and S. E. Skrabalak, “Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?” Angew. Chem. Int. Ed. 48, 60 (2009)3) K. A. Fichthorn, Z. Chen, Z. Chen, R. M. Rioux, M. J. Kim, and B. J. Wiley, “Understanding the Solution-Phase Growth of Cu and Ag Nanowires and Nanocubes from First Principles” Langmuir 37, 4419 (2021)4) D. Huo, M. J. Kim, Z. Lyu, Y. Shi, B. J. Wiley, and Y. Xia, “One-Dimensional Metal Nanostructures: From Colloidal Syntheses to Applications” Chem. Rev. 119, 8972 (2019)5) K. R. Yeo, J. Y. Eo, M. J. Kim and S.-K. Kim, “Shape Control of Metal Nanostructures by Electrodeposition and their Applications in Electrocatalysis” J. Electrochem. Soc. 169, 112502 (2022)6) C. Liu, Z. Li, P. Yu, H. W. Wong, and Z. Gu, “Vertically Aligned and Surface Roughed Pt Nanostructured Wire Array as High Performance Electrocatalysts for Methanol Oxidation” ACS Appl. Energy Mater. 1, 3973 (2018)7) T. T. H. Hoang, S. Ma, J. I. Gold, P. J. A. Kenis, and A. A. Gewirth “Nanoporous Copper Films by Additive-Controlled Electrodeposition: CO2 Reduction Catalysis” ACS Catal. 7, 3313 (2017)8) M. J. Kim, T. Lim, K. J. Park, S. K. Cho, S.-K. Kim, and J. J. Kim “Characteristics of Pulse-Reverse Electrodeposited Cu Thin Films: I. Effects of the Anodic Step in the Absence of an Organic Additive” J. Electrochem. Soc. 159, D538 (2012)9) M. J. Kim, T. Lim, K. J. Park, O. J. Kwon, S.-K. Kim, and J. J. Kim “Characteristics of Pulse-Reverse Electrodeposited Cu Thin Film: II. Effects of Organic Additives” J. Electrochem. Soc. 159, D544 (2012) Figure 1