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<p>The metallization of through-holes (THs) in high-density interconnect (HDI) printed circuit boards (PCBs) demanded precise control over copper electrodeposition uniformity to ensure device reliability. This work systematically evaluated a series of n-alkyl pyridinium quaternary ammonium salts—namely lauryl pyridinium chloride (LPC, C12), tetradecyl pyridinium chloride (TPC, C14), and tetradecyl pyridinium chloride (CPC, C16)—as novel levelers for enhancing TH copper filling performance. Electrochemical analyses revealed a distinct chain-length-dependent behavior: LPC (C12) exhibited exceptional convection-dependent adsorption, accelerating copper deposition at TH centers (low convection) while suppressing it at openings (high convection), and achieved a remarkable throwing power (TP) of 122.0%, indicating super-filling capability. In contrast, TPC and CPC (C14/C16) induced stronger overall inhibition but yield lower TPs (94.7% and 88.4%, respectively). Quantum chemical calculations correlated the increasing alkyl chain length with reduced frontier orbital energy gaps, thereby enhancing adsorption strength. Morphological and crystallographic analyses confirmed that LPC promoted uniform, refined grains via optimal competitive adsorption with polyethylene glycol (PEG) and bis(3-sulfopropyl) disulfide (SPS). The C12 alkyl chain struck an ideal balance between adsorption and desorption kinetics, enabling superior bottom-up filling. This work established a molecular design principle for levelers tailored to HDI applications and offered practical strategies for optimizing PCB plating processes.</p> Graphical Abstract <p></p>

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Optimizing through-hole copper filling in PCBs: n-Alkyl Pyridinium quaternary ammonium salts as chain-length-dependent levelers

  • 期刊论文

  • 发表日期：

    2026年7月30日

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  • Zhikuan Wang,
  • Mengxin Ren,
  • Wangwang Cheng,
  • Wei Huang,
  • Qunjie Xu,
  • Chuanyun Wan

摘要

The metallization of through-holes (THs) in high-density interconnect (HDI) printed circuit boards (PCBs) demanded precise control over copper electrodeposition uniformity to ensure device reliability. This work systematically evaluated a series of n-alkyl pyridinium quaternary ammonium salts—namely lauryl pyridinium chloride (LPC, C12), tetradecyl pyridinium chloride (TPC, C14), and tetradecyl pyridinium chloride (CPC, C16)—as novel levelers for enhancing TH copper filling performance. Electrochemical analyses revealed a distinct chain-length-dependent behavior: LPC (C12) exhibited exceptional convection-dependent adsorption, accelerating copper deposition at TH centers (low convection) while suppressing it at openings (high convection), and achieved a remarkable throwing power (TP) of 122.0%, indicating super-filling capability. In contrast, TPC and CPC (C14/C16) induced stronger overall inhibition but yield lower TPs (94.7% and 88.4%, respectively). Quantum chemical calculations correlated the increasing alkyl chain length with reduced frontier orbital energy gaps, thereby enhancing adsorption strength. Morphological and crystallographic analyses confirmed that LPC promoted uniform, refined grains via optimal competitive adsorption with polyethylene glycol (PEG) and bis(3-sulfopropyl) disulfide (SPS). The C12 alkyl chain struck an ideal balance between adsorption and desorption kinetics, enabling superior bottom-up filling. This work established a molecular design principle for levelers tailored to HDI applications and offered practical strategies for optimizing PCB plating processes.

Graphical Abstract