目的 在聚醚醚酮（PEEK）为代表的低密度热塑性聚合物蒙皮材料表面集成功能性金属图案,可有效提升基于该材料构建的智能蒙皮天线的集成与感知能力。然而,现有制造技术无法同时兼顾图案化、强结合和高精度。本研究旨在探索一种兼具高精度和强结合能力的聚合物表面金属化方法。方法 提出绿光飞秒激光表面改性结合化学镀铜的工艺路线,在商用PEEK表面制造金属铜图案,系统研究了单脉冲能量密度对PEEK表面粗糙度和镀铜层导电性的影响规律,并对飞秒激光改性促进化学镀的机理进行了探讨。结果 随着单脉冲能量密度的增加,PEEK表面形貌由多孔结构转变为熔融凝固后的片状、絮状结构,改变了PEEK表面的粗糙度。通过优化飞秒激光加工参数,增加了PEEK表面活性官能团占比、提升了PEEK表面浸润性,最终实现飞秒激光改性区域均匀稳定化学镀铜层,铜层的方阻低至39.1 mΩ/sq,结合性能达到5B（ASTM D3359）等级。结论 飞秒激光改性辅助-化学镀技术实现了在PEEK表面局部区域制造高导电、强结合的金属铜图案。本研究为航空航天用聚合物表面功能化金属图案制造提供了新思路。

This study presents a novel and highly effective method for fabricating localized, strongly adherent, and highly conductive copper patterns on commercial polyether ether ketone (PEEK) surfaces by integrating green femtosecond laser surface modification with electroless copper plating. The core innovation lies in the precise and controllable surface activation achieved via a 515 nm femtosecond laser, which simultaneously introduces beneficial micro-/nanoscale topography and enhances surface chemistry without causing significant thermal damage to the unprocessed substrate.
The experimental methodology involved systematically modifying PEEK surfaces by a femtosecond laser (515 nm wavelength, 800 fs pulse width, 30 kHz repetition rate) with varying single-pulse energy densities (ranging from 0.38 to 2.17 J/cm²) in a cross-hatch scanning pattern (10 μm hatch spacing). This was followed by a two-step metallization process: activation in a 0.1 mol/L silver nitrate solution at 25 ℃ for 30 min, and subsequent electroless copper plating in a bath containing copper sulfate, potassium sodium tartrate, sodium hydroxide, and formaldehyde at 40 ℃ for 15 min.
A key finding was the evolution of surface morphology with the increasing energy density: from a porous, ablated structure at 0.38 J/cm² to flaky and, ultimately, flocculent microstructures dominated by melt-resolidification at 2.17 J/cm². Correspondingly, the modification depth increased from 7.2 to 41.6 μm. Crucially, the surface chemistry was profoundly altered. X-ray photoelectron spectroscopy (XPS) analysis revealed a significant increase in the proportion of highly active oxygen-containing functional groups (C==O, O—C==O) at the expense of inert C—C/C—H bonds, with this effect being more pronounced at higher energy densities. This chemical activation was accompanied by a tunable wettability transition. While low energy densities (≤0.52 J/cm²) initially increased hydrophobicity (contact angle up to ~100°) due to dominant microstructural effects (Wenzel to Cassie-Baxter transition), higher energies (0.52-1.75 J/cm²) induced a switch to stable hydrophilicity, with a minimum contact angle of 46.2°. This shift was attributed to the combined effect of disrupted air-trapping microstructures and the increased surface concentration of polar oxygen-containing groups.
These laser-induced modifications-morphology, chemistry, wettability-synergistically governed the subsequent metallization quality. At the optimal single-pulse energy density of 1.09 J/cm², the electrolessly plated copper layer exhibited exceptional performance: an extremely low sheet resistance of 39.1 mΩ/sq and superior adhesion classified as 5B according to the ASTM D3359 standard tape test. The underlying mechanism was elucidated through detailed analysis. The hydrophilic surface and abundant active sites at optimal parameters facilitated effective adsorption and anchoring of silver catalyst nanoparticles (both crystalline flakes and nanospheres) within the micro-roughness during activation. This stable catalyst layer ensured uniform and continuous copper deposition, resulting in a dense, conformal copper layer that replicated the laser-generated microstructures. The cross-sectional analysis revealed an interlocking, jagged interface between the copper and PEEK, significantly increasing the contact area and providing robust mechanical anchorage alongside enhanced chemical bonding.
In conclusion, this work demonstrates that green femtosecond laser modification is a powerful tool for the localized, precision engineering of PEEK surfaces, enabling the subsequent fabrication of integrated metal patterns with outstanding electrical conductivity and interfacial adhesion. The process avoids the drawbacks of deep etching or excessive thermal damage associated with other laser types. The detailed investigation of the energy-density-dependent interplay between surface morphology, chemistry, wettability, and final metallization performance provides new fundamental insights and a viable technical pathway for high-value applications such as functionalized polymer skins in aerospace electronics.