Hydroxyethyl cellulose (HEC) has been commonly used in a variety of complex formulations for acid copper plating. However, the roles of HEC acting in acid copper plating still lacks of systematic investigation. To explore the efficacy of HEC in the deposition of the ultra-thin electrodeposited copper foil (ED-Cu), we designed a simple formulation system, in which HEC was used as the single organic additive. Using electron backscatter diffraction (EBSD), microstructures of the prepared ED-Cu was comprehensively investigated. The results showed that the ED-Cu was characterized by a mixed distribution of columnar and equiaxed crystals. Grain morphology, dislocation density and crystal orientation of the ED-Cu could be regulated by HEC concentration. According to the cyclic voltammetry (CV) and chronoamperometry (CA) results, the introduction of HEC between 0–200 ppm led to a polarizing effect, which marginally increased with the HEC concentration. Meanwhile, the increase of HEC concentration enhanced the nucleation rates of copper and reduced the grain size during instantaneous nucleation. The introduction of the HEC also altered the preferred orientation of the ED-Cu foil. Mechanical results showed that the optimum concentration of HEC addition was 125 mg l−1.
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