Group-IV monochalcogenides belong to a family of 2D layered materials. Monolayers of group-IV monochalcogenides GeS, GeSe, SnS and SnSe have been theoretically predicted to exhibit a large shift current owing to a spontaneous electric polarization at room temperature. Using THz emission spectroscopy, we find that above band gap photoexcitation with ultrashort laser pulses results in emission of nearly single-cycle THz pulses due to a surface shift current in multi-layer, sub-μm to few- μm thick GeS and GeSe, as inversion symmetry breaking at the crystal surface enables THz emission by the shift current. Experimental demonstration of THz emission by the surface shift current puts this layered group-IV monochalcogenides forward as a candidate for next generation shift current photovoltaics, nonlinear photonic devices and THz sources.
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