無電鍍製程具有可產生複合鍍層、可用於導體與非導體基材、無須繁複的設備及
操作簡單等特性，廣泛運用於產業界中，進行無電鍍製程前需先以化學藥劑粗化基材
的方式，活化表面使後續銅晶種得以沉積於基材表面，其腐蝕液將造成環境汙染且對
產線人員造成健康的威脅，故本研究將以常壓電漿微球接枝法改質聚甲基丙烯酸甲酯
(以下簡稱為 PMMA)，製程中將不會產生具有毒性之廢液，對環境及工作人員都更
加友善，希望能達到取代傳統化學藥劑法的目的。
本實驗的第一部分為將基材以不同激發功率(75W/100W/125W/150W)和不同比例
的氬氣氧氣混合氣體作為工作氣體之常壓電漿噴射束(APPJ)對 PMMA 進行表面改質，
透過 OES 分析各電漿中的激發物種，以水接觸角量測其親疏水性及其表面能變化，其
結果顯示氧氣含量為 1%的氬氧混合氣中的 O 物種及 OH 物種比例較高，水接觸角度
最低，對基材的改質效果最佳。第二部分是以不同配比的高分子薄膜原液塗佈於經電
漿改質過之基材，透過電漿改質所產生的親水性官能基團及活化點，與薄膜原液產生
接枝聚合反應，接著以水接觸角量測其親疏水性及其表面能變化、場發式電子顯微鏡
觀察其表面形貌、原子力顯微鏡測量粗糙度，傅立葉紅外線光譜分析儀鑑定薄膜中官
能基與化學鍵結之組成，最後再將經高分子薄膜接枝後基材進行無電鍍銅處理，結果
顯示僅經電漿改質但無接枝薄膜之基材表面無銅晶種沉積，經高分子薄膜(H7MPC)接
枝後基材表面產生一層均勻的銅鍍層，接著用 X-射線繞射分析進行鍍層元素分析，
確認表面無氧化物生成。使用四點探針對表面進行電阻數值測量。以百格測試鍍層的
附著程度，約達到 3B~4B，附著性優良，達到工業應用的水準。由以上之實驗結果可
證實常壓電漿微球接枝改質法可有效提高基材的親水性及粗化表面，使無電鍍的銅晶
種順利沉積於基材表面，並產生品質優良之鍍層。其後續實驗使用 LCP 作為基材，
經微球接枝後進行無電鍍銅，在 LCP 表面沉積一層緻密的銅鍍層，此技術不僅能用
於改良傳統的無電鍍前製程，也在 5G 通訊技術中有了應用的可能性。

The electroless plating process is widely used in the industry because of its notable characteristics, for example, it can produce composite coatings, can be used for conductors and non-conductor substrates without complicated equipment, and it is easy to operate. However, before the electroless plating, it’s necessary to use chromate chemicals to roughen substrate, so that the subsequent copper seed can be deposited on the surface of the substrate, and the corrosive liquid will cause environmental pollution and pose a health threat to the operating staff. In this study we will use the atmospheric pressure plasma jet (APPJ) to modify the surface of the substrate (PMMA) with grafting-polymerization technology, so there will be no toxic waste liquid produced in the process, and it is more friendly to environment and operating staff. We hope this technology can replace the traditional chromate treatment.
In the first part of the experiment, the PMMA sample were treated at different plasma power (100W/150W/200W) with various Ar /O2 mixtures, O2 contribution in Ar/ O2 mixture is varied from 0.5 to 1%. We used the OES to analysis the species of the plasma, and used water contact angle method to calculate the surface energy and the wettability of the plasma-treated sample. From the results, the plasma which uses 1% O2 /Ar as working gas has the largest quantity of the O species and the OH species, and the sample modified by 1% O2/Ar plasma shows the Best hydrophilicity.
In the second part, we used spin-coating method to coat the plasma-modified sample with HEMA-Zein solution, and the hydrophilic functional groups and activation points generated by the plasma were grafted with the polymer solution, a thin film was formed on the surface. Then, the hydrophilicity and surface energy of the film were measured by water contact angle, the surface morphology was observed by field electron microscopy (SEM), and the roughness was measured by atomic force microscopy (AFM), the functional groups and chemical bonds in the film were identified by FTIR.
In the final part, the substrate grafted with the polymer film is subjected to electroless copper plating, The result shows that the surface of the substrate modified by the plasma but without the graft film is deposited without copper, and a uniform copper plating layer is formed on the surface of the substrate after grafting with the polymer film, we use XRD to confirm that no copper oxide or cuprous oxide was formed on the surface, and the resistance value is measured by four-point probe. Then, the adhesion level of the cupper layer is measured by a Cross-cut test, which is about 3B~4B, reaching the level of industrial application.
From the above experimental results, it can be proved that the HEMA-Zein grafting method can effectively improve the hydrophilicity and roughening surface of the substrate, the electroless copper seed can be smoothly deposited on the surface of the substrate, and the plating layer with nice quality can be produced. In the subsequent experiments, LCP was used as the substrate. After HEMA-Zein grafting, electroless plating was performed. A dense copper plating layer was successfully deposited on the surface of the LCP. It means Polymer film grafting modification can be used not only to improve the traditional electroless plating process, but also possible to apply in 5G communication technology.

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