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Multiphoton absorption of entangled photons offers ways for obtaining unique information about chemical and biological processes. Measurements with entangled photons may enable sensing biological signatures with high selectivity and at very low light levels to protect against photodamage. In this paper, we present a theoretical and experimental study of the excitation wavelength dependence of the entangled two-photon absorption (ETPA) process in a molecular system, which provides insights into how entanglement affects molecular spectra. We demonstrate that the ETPA excitation spectrum can be different from that of classical TPA as well as that for one-photon resonant absorption (OPA) with photons of doubled frequency. These results are modeled by assuming the ETPA cross-section is governed by a two-photon excited state radiative linewidth rather than by electron-phonon interactions, and this leads to excitation spectra that match the observed results. Further, we find that the two-photon-allowed states with highest TPA and ETPA intensities have high electronic entanglements, with ETPA especially favoring states with the longest radiative lifetimes. These results provide concepts for the development of quantum light–based spectroscopy and microscopy that will lead to much higher efficiency of ETPA sensors and low-intensity detection schemes. 

The design of organic light emitting diode (OLED) materials with the potential for exhibiting thermally-activated delayed fluorescence (TADF) is reported. Using computational methods (DFT/TD-DFT) as a guiding tool, six materials with a benzobisoxazole (BBO) core and donor–acceptor–donor architectures were designed by changing the conjugation position of carbazole-substituted phenyl substituents and the type of BBO isomer ( cis - vs. trans -). Experimental steady-state and transient absorption spectroscopic techniques were utilized to probe the TADF activity of these molecules. Each material was then used in host–guest OLED devices as either near-UV dopants or host with low singlet-triplet energy differences. The electroluminescent properties show that when used as dopants these materials provide near-UV emission (CIE y < 0.06 and CIE x = 0.16), whereas when used as hosts, these materials show reduced operating voltages and increased performance efficiencies when compared to commercial materials. 

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, σe, to vary inversely with the product of entanglement time (Te) and entanglement area (Ae), i.e., σe ∼ 1/AeTe. The decreasing σe with increasing Te has limited ETPA to fs-scale Te, while ETPA applications for ps-scale spectroscopy have been unexplored. However, we show that spectral−spatial coupling, which reduces Ae as the SPDC bandwidth (σf ) decreases, plays a significant role in determining σe when Te > ∼100 fs. We experimentally measured σe for zinc tetraphenylporphyrin at several σf values. For type-I ETPA, σe increases as σf decreases down to 0.1 ps−1 . For type-II SPDC, σe is constant for a wide range of σf . With a theoretical analysis of the data, the maximum type-I σe would occur at σf = 0.1 ps−1 (Te = 10 ps). At this maximum, σe is 1 order of magnitude larger than fs-scale σe and 3 orders of magnitude larger than previous predictions of ps-scale σe. 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. 

Multiple ultrafast spectroscopic techniques and quantum chemical simulations (QCS) were used to investigate the excited state dynamics of BCC-TPTA. This organic chromophore is believed to possess excited state dynamics governed by a thermally activated delayed fluorescence (TADF) mechanism with a reported internal quantum efficiency ( η IQE ) of 84%. In addition, a significant enhancement in its quantum yield ( Φ ) in solution after purging oxygen has been reported. This Φ enhancement has been widely accepted as due to a delayed fluorescence process occurring on the μs time-scale. The spectroscopic measurements were carried out both in solution and blended films, and from fs to μs time-scales. The excited state dynamics of Rhodamine B and Ir(BT) 2 (acac) were also probed for comparison. Investigations in the absence of oxygen were also carried out. Our time-correlated single photon counting (TCSPC) measurements revealed a lack of a long-lived emissive lifetime for BCC-TPTA in any of the media tested. Our ns transient absorption spectroscopy (ns TAS) experiments revealed that BCC-TPTA does not possess triplet transient states that could be linked to a delayed fluorescence process. Instead, the evidence obtained from our spectroscopic tools suggests that BCC-TPTA has the excited state dynamics of a typical fluorescence chromophore and that just comparing the Φ difference before and after purging oxygen from the solution is not an accurate method to claim excited state dynamics governed by a delayed fluorescence mechanism. Consequently, we believe that previous studies, in which the photo-physics of organic chromophores with TADF characteristics are reported, may have overlooked the influence of the host materials on the obtained optical properties in blended films.