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Nonlinear Raman Shift Induced by Exciton-to-Trion Transformation in Suspended Trilayer MoS2

Layered two-dimensional (2D) semiconductors such as molybdenum disulfide (MoS2) have recently attracted remarkable attention because of their unique physical properties. Here, we use photoluminescence (PL) and Raman spectroscopy to study the formation of the so- called trions in a synthesized freestanding trilayer MoS2. A trion is a charged quasi-particle formed by adding one electron or hole to a neutral exciton (a bound electron-hole pair). We demonstrate accurate control over the transformation of excitons to trions by tuning the power of the optical pump (laser). Increasing the power of the excitation laser beyond a certain threshold (~ 4 mW) allows modulation of trion-to-exciton PL intensity ratio as well as the spectral linewidth of both trions and excitons. Via a systematic and complementary Raman analysis we disclose a strong coupling between laser induced exciton-to-trion transformation and the characteristic phononic vibrations of MoS2. The onset of such an optical transformation corresponds to the onset of a previously unknown nonlinear Raman shift of the in-plane (E12g) and out-of-plane (A1g) vibrational modes. This coupling directly affects the well-known linear red-shift of the A1g and E12g vibrations due to heating at low laser powers, and changes it to a nonlinear and non-monotonic dependence with a blue-shift in the high laser power regime. Local reduction of the electron density upon exciton-to-trion transformation is found to be the underlying mechanism for the blue-shift at high laser powers. Our findings enrich our knowledge about the strong coupling of photonic and phononic properties in 2D semiconductors, and enable reliable interpretation of PL and Raman spectra in the high laser power regimes.