Preparation of selective conductive copper patterns by pen-on-paper writing combined with electroless plating

Abstract

Conductive Cu patterns were constructed on flexible paper via selectively electroless plating method, which including multistep procedures, namely, 3-aminopropyltrimethoxysilane (APTMS)-modification, selective Cu0-seeding and Cu-lines deposition. Herein, the Cu0 activation process could be divided into two stages: the Cu2+-absorption in cupric citrate solution and subsequently the Cu2+-reduction using a roller pen filled with sodium borohydride ink. The interaction of APTMS onto paper was confirmed by FT-IR measurement and the results indicated that the –NH2 groups originating from APTMS were grafted on the paper. The elemental analysis of the samples in each step was conducted using XPS measurement. Paper-based conductive patterns were investigated by SEM, XRD and Scotch®-tape test. SEM images illustrated that the Cu lines on the APTMS modified paper substrate was compact and composed of ball-shaped copper nuclei. Moreover, the Cu lines could be selectively plated on the required area of the paper substrate. XRD analysis showed that the obtained Cu patterns had a structure with Cu (1 1 1) preferred orientation, revealing an excellent electromigration resistivity. The resultant Cu patterns exhibited an admired adhesion to modified paper, while the Cu patterns obtained in absence of APTMS modification suffered a failure in the adhesive Scotch®-tape test. The resistivity of copper patterns characterized by the digital four-point probe was 10.3 µΩ cm, which was 6.3 times of the bulk Cu. Meanwhile, paper-based Cu pattern remained excellent conductivity after multifolding. Those results indicated that the method proposed in the present work offered a robust and efficient alternative to manufacture flexible electronics.