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All-electrochemical synthesis of tunable fine-structured nanoporous copper films

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Abstract

Nanoporous copper (np-Cu) films that feature fine ligament length scales and high surface area are prepared using an all-electrochemical approach. The two-step routine involves initially the electrodeposition of CuxZn(100−x) precursor alloy films with controlled thickness and composition from a pyrophosphate bath. This is followed by a selective oxidative removal or dealloying of Zn that leads to a surface area increase (by up to 22 times per one µm thickness of the precursor alloy). In this article, we present a systematic investigation of the impact of three factors on the as-synthesized np-Cu structure: (1) dealloying bath composition, (2) atomic composition (at.%) of precursor alloy, and (3) addition of Ni. Our results show that varying the dealloying bath composition allows for tunable ligament and pore sizes that are due to the anion-induced (ClO4−, SO42−, or Cl−) modified surface diffusivity of Cu. The increase in surface area is also proportionally scalable by modifying the Cu content (12–42 at.%) in the precursor alloy. Thus, np-Cu films with porosity length scales in the range of 20–33 nm were obtained. A further np-Cu length scale refinement down to 10–12 nm was achieved after dealloying of a ternary Cu–Zn–Ni(3%) alloy. Overall, the strict parameter control yields a wide range of nano-scaled np-Cu films with specific surface characteristics, which may be suitable for various applications including microelectronic packaging, sensing, and catalysis.

Impact statement

We are presenting the first (to the best of our knowledge) comprehensive study on a proposed all-electrochemical approach for the synthesis of nanoporous (np) Cu films with controllable thickness, porosity length scale, and pore-ligament ratio (pore-volume). The novelty of this approach is the use of electrochemical means to synthesize the precursor alloy (Cu–Zn in this work, also Cu–Mn, Cu–Al, etc.) followed by its subsequent dealloying, as opposed to most other approaches that employ dealloying of commercially available bulk precursor alloys and/or thin alloy films deposited in ultrahigh vacuum. The cost-effective use of electrodeposition routines allows for strict composition, thickness, and shape control of the deposit. Also, the deposition of precursor alloys with a desired composition (in turn) enables the development of np-Cu films with controlled pore-ligament length scale as well as pore-ligament ratio. Finally, the proposed approach allows for fine-tuning of the structure, morphology, and ligament/surface elemental content of the as-synthesized np-Cu structure by introducing additional doping metals (Ni) into the precursor alloy. Overall, the systematic study of the proposed approach largely enables versatile and scalable synthetic routes for the preparation of np-Cu-based architectures for a variety of applications ranging from electrocatalysis (CO2 fixation, H2 energy, fuel cells), sensing and actuation (NO3− reduction, NO2− analysis), environmental remediation (tap water purification from toxic compounds), and 2.5/3D electronic packaging (realization of Cu-on-Cu bonding or defect-free and limited in Sn, Cu-Sn micro-bonding in miniaturized devices).

Graphical abstract

Preparation of fine-structured nanoporous copper films using an all-electrochemical method.

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Data availability

The authors declare that the data supporting the findings of this study are available within this article and its supplementary information files. Also, all raw data files are available upon request from the authors.

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Acknowledgments

This research was supported by the Semiconductor Research Corporation (SRC) and Binghamton University through the Center for Heterogeneous Integration Research on Packaging (CHIRP) Task 2878.011. The authors also acknowledge Krystal Lee for assistance with the XRD experiments and Anju Sharma for her help with XPS characterization and data analysis.

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Authors and Affiliations

  1. Department of Chemistry, Binghamton University, The State University of New York, Binghamton, USA

    Ezer Castillo, Jackson Zhang & Nikolay Dimitrov

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  1. Ezer Castillo
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  2. Jackson Zhang
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  3. Nikolay Dimitrov
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Contributions

E.C.—conceptualization, literature review, methodology, resources, data curation, validation, investigation, visualization, writing (original draft, review and editing); J.Z.—data curation, validation, writing (review and editing); N.D.—supervision, conceptualization, project administration, funding acquisition, writing (review and editing).

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Correspondence to Nikolay Dimitrov.

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The authors have no relevant financial or non-financial interest to disclose.

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Castillo, E., Zhang, J. & Dimitrov, N. All-electrochemical synthesis of tunable fine-structured nanoporous copper films. MRS Bulletin 47, 913–925 (2022). https://doi.org/10.1557/s43577-022-00323-4

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