Enhancing Entangled Two-Photon Absorption for Picosecond Quantum Spectroscopy

Entangled two-photon absorption (ETPA) is known to create photoinduced transitions with extremely low light intensity, reducing the risk of phototoxicity compared to classical two-photon absorption. Previous works have predicted the ETPA cross-section, σ_e, to vary inversely with the product of entanglement time (T_e) and entanglement area (A_e), i.e., σ_e ∼ 1/A_eT_e. The decreasing σ_e with increasing T_e has limited ETPA to fs-scale T_e, while ETPA applications for ps-scale spectroscopy have been unexplored. However, we show that spectral-spatial coupling, which reduces A_e as the SPDC bandwidth (σ_f) decreases, plays a significant role in determining σ_e when T_e > ∼100 fs. We experimentally measured σ_e for zinc tetraphenylporphyrin at several σ_f values. For type-I ETPA, σ_e increases as σ_f decreases down to 0.1 ps^-1. For type-II SPDC, σ_e is constant for a wide range of σ_f. With a theoretical analysis of the data, the maximum type-I σ_e would occur at σ_f = 0.1 ps^-1 (T_e = 10 ps). At this maximum, σ_e is 1 order of magnitude larger than fs-scale σ_e and 3 orders of magnitude larger than previous predictions of ps-scale σ_e. By utilizing this spectral-spatial coupling, narrowband type-I ETPA provides a new opportunity to increase the efficiency of measuring nonlinear optical signals and to control photochemical reactions requiring ps temporal precision.