Rheological Modulation via Rigid–Flexible Polymer Network Engineering for High‐Precision Photovoltaic Electrode Printing

Screen printing remains vital for printed electronics due to its precision and substrate adaptability. In applications such as high‐speed precision printing for silicon solar cell, the rheological properties of silver pastes are increasingly demanding. Conventional silver paste formulations suffer from insufficient shear stability and sluggish dynamic bond reorganization kinetics in polymer networks, resulting in severely degraded electrode printability. To overcome this limitation, we propose a rigid‐flexible polymer synergy strategy designed to simultaneously enhance structural stability and dynamic self‐healing capacity within the polymer network. Specifically, we employ a styrene‐maleic anhydride (SMA) copolymer as a rheology modifier. We leverage the synergistic effects of reversible hydrogen bonds in flexible chains and steric hindrance by rigid segments. This synergy enhances high‐speed printing precision. Furthermore, electrodes fabricated using this approach demonstrate a markedly improved aspect ratio while reducing silver consumption. The resulting sintered grid lines exhibit a densified cross‐section morphology with lower porosity, leading to a reduced series resistance and enhanced power conversion efficiency. Collectively, these improvements enable photovoltaic performance on par with that of state‐of‐the‐art commercial cells. This work offers a strategy for printable electrode optimization and reveals principles for designing polymer networks with tunable‐rheology, paving the way for next‐generation photovoltaic and electronic materials.