Second Harmonic Generation by Multilayer Graphenes and its Dependence on Stacking Order and Encapsulation Environment

In this work, we analyze the effects of external influences on the second harmonic generation (SHG) signal produced by multilayer graphenes. Specifically, we vary the encapsulation conditions and doping of graphenes, seeking to identify SHG "fingerprints" that are unsensitive to external perturbations. We identify characteristic features in the infrared regime that may be used as a stacking-order fingerprint for the mixed stacking tetralayer and the trilayer polytypes caused by a strong double resonance effect. Further to this, we find that the tetralayers systematically produce an SHG response that is significantly larger as compared to the trilayers. We then studied the SHG signal by the tetralayer polytypes in the terahertz regime and demonstrated the signal is highly sensitive the environmental conditions. Furthermore, we also find that accidental doping of graphene will strongly suppress the SHG signal in this regime. The above findings emphasize the need for a spectral approach to the identification of stacking order by SHG. Thus, measurements at one frequency are insufficient to confidently identify the stacking order due to the environmental sensitivities, since SHG can be readily induced with a comparable magnitude in the centrosymmetric polytypes through external symmetry-breaking.