Carrasco Ismael S S, Alves Sidiney G, Aarão Reis Fábio D A
International Center for Condensed Matter Physics and Instituto de Física, Universidade de Brasília, Brasília DF, 70919-970, Brazil.
Departamento de Estatística, Física e Matemática, Universidade Federal de São João Del-Rei, 36490-972, Ouro Branco, MG, Brazil.
Phys Chem Chem Phys. 2022 Nov 23;24(45):27856-27865. doi: 10.1039/d2cp03264c.
We study a thin-film electrodeposition model that represents the relaxation of the deposited material by adatom diffusion on quenched crystal topographies and considers simple mechanisms of cation flux in the electrolyte. The results of numerical simulations with collimated flux and a rapid cation reduction in contact with the deposit relate the surface roughness and the adatom hop numbers with two model parameters. A comparison with the results of a collective diffusion model for vapor deposition shows differences in the surface morphologies but similarities in scaling relations, which suggest thermally activated (Arrhenius) forms for the parameters of the electrodeposition model and relate one of them to the applied current. Simulations with purely diffusive cation flux and possible pore formation in simple cubic lattices show the growth of self-organized structures with leaf shapes (dendrites) above a compact layer that covers the flat electrode. The thickness of this layer and the average dendrite size also obey scaling relations in terms of the model parameters, which predict that both sizes decrease with the applied current, in agreement with recent experimental studies. Under all flux conditions, an increase in adatom diffusivity with temperature implies an increase in the average sizes of low-energy surface configurations, independently of their particular shapes. Finally, we note that a previously proposed model for electrodeposition produced similar morphologies, but the quantitative relations for the characteristic sizes differ from those of the present model, which also advances with a consistent interpretation of temperature effects.
我们研究了一种薄膜电沉积模型,该模型通过在淬火晶体形貌上的吸附原子扩散来描述沉积材料的弛豫过程,并考虑了电解质中阳离子通量的简单机制。准直通量和与沉积物接触时阳离子快速还原的数值模拟结果将表面粗糙度和吸附原子跳跃数与两个模型参数联系起来。与气相沉积集体扩散模型的结果比较表明,表面形貌存在差异,但标度关系相似,这表明电沉积模型参数具有热激活(阿仑尼乌斯)形式,并将其中一个参数与施加电流联系起来。简单立方晶格中纯扩散阳离子通量和可能的孔隙形成的模拟表明,在覆盖平面电极的致密层之上会生长出具有叶状(枝晶)的自组织结构。该层的厚度和平均枝晶尺寸也遵循模型参数的标度关系,这预测这两个尺寸都会随着施加电流的增加而减小,这与最近的实验研究一致。在所有通量条件下,吸附原子扩散率随温度的增加意味着低能表面构型的平均尺寸增加,而与它们的具体形状无关。最后,我们注意到,先前提出的电沉积模型产生了类似的形貌,但特征尺寸的定量关系与本模型不同,本模型还对温度效应进行了一致的解释。