Cross-polarized and stable second harmonic generation from monocrystalline copper

Second-harmonic generation (SHG) is a powerful surface-specific probe for centrosymmetric materials, with broad relevance to energy and biological interfaces. Plasmonic nanomaterials have been extensively utilized to amplify this nonlinear response. Yet, material instability has constrained most studies to gold, despite the significance of plasmonic metals such as copper for catalysis. Here, we demonstrate stable and anisotropic SHG from monocrystalline copper, overcoming long-standing challenges associated with surface degradation. By leveraging an on-substrate synthesis approach that yields atomically flat and oxidation-resistant Cu microflakes, we enable reliable SHG measurements and reveal a strong cross-polarized response with C 3 v surface symmetry. The SHG signal remains stable over 3 h of continuous femtosecond excitation, highlighting the remarkable optical robustness of the Cu microflakes. These results reinforce the viability of monocrystalline Cu as a robust platform for nonlinear nanophotonics and surface-sensitive spectroscopy, expanding the range of copper-based optical applications.