通过表面受限氧化还原置换单电池中不足位沉积的H来沉积Pd超薄膜的电化学原子层沉积,The Journal of Physical Chemistry C

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通过表面受限氧化还原置换单电池中不足位沉积的H来沉积Pd超薄膜的电化学原子层沉积
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2017-02-16 00:00:00 , DOI: 10.1021/acs.jpcc.6b12794
Innocent Achari ₁ , Stephen Ambrozik ₁ , Nikolay Dimitrov ₁

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这项工作说明了表面限制氧化还原置换（SLRR）协议在单电池中使用欠电位沉积的H（H _UPD）作为牺牲介体的Pd超薄膜在Au上的电化学原子层沉积（E-ALD）的应用。本文介绍的简便沉积方法既不需要使用复杂的仪器，也不需要除Pd（II）氯化物络合物以外的金属离子的存在。这提供了最大的生长效率，并消除了沉积物的潜在污染，从而使Pd沉积成为“更绿色”的过程。通过开路计时电位法监测生长进度，同时通过H _UPD和Cu的循环伏安法（CV）评估相应沉积的Pd膜的粗糙度演变_UPD。CV结果表明，在长达30个SLRR循环（20个当量单层）的情况下，会沉积出光滑的Pd膜，然后迅速过渡到更高厚度的枝晶生长。通过原位扫描隧道显微镜，还证实了准2D的生长，可导致平滑且均匀的Pd膜形态。对Pd膜剥离实验结果的分析证实了这些发现。通过使用通用生长模型对不同厚度的Pd膜进行剥离所获得的电荷的比较表明，不仅吸附的而且吸收的H _UPD参与了与[PdCl ₄ ] ^2–的氧化还原交换。配比为2：1的化学计量比。提出的用于无污染Pd沉积的简便SLRR方法提供了无与伦比的简便性，并且还可以扩展到具有强H亲和力的其他导电衬底。

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Electrochemical Atomic Layer Deposition of Pd Ultrathin Films by Surface Limited Redox Replacement of Underpotentially Deposited H in a Single Cell

This work illustrates the application of a surface limited redox replacement (SLRR) protocol for the electrochemical atomic layer deposition (E-ALD) of Pd ultrathin films on Au in a single cell using underpotentially deposited H (H_UPD) as the sacrificial mediator. The facile deposition approach presented herein requires neither the use of sophisticated instrumentation nor the presence of metal ions other than the Pd(II) chloride complex. This provides for maximum growth efficiency and eliminates potential contamination of the deposit thereby rendering the Pd deposition a “greener” process. The growth progress is monitored by open circuit chronopotentiometry while the roughness evolution of accordingly deposited Pd films is assessed by cyclic voltammetry (CV) of H_UPD and Cu_UPD. The CV results indicate the deposition of smooth Pd films occurring for up to 30 SLRR cycles (20 equiv monolayers) followed by a rapid transition to dendritic growth at higher thickness. The quasi-2D growth, resulting in smooth and uniform Pd-film morphology has also been confirmed up to 20 SLRR cycles by in situ scanning tunneling microscopy. Analysis of results from Pd-film stripping experiments corroborate these findings. The comparison of charges obtained by the stripping of Pd films of different thickness with generic growth models suggests that not only adsorbed but also absorbed H_UPD participates in redox exchange with [PdCl₄]^2– complex in 2:1 stoichiometric ratio. The presented facile SLRR approach for contamination-free Pd deposition offers unsurpassed simplicity and can also be extended to other conductive substrates featuring strong H affinity.

更新日期：2017-02-16

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