Critical Power Density: A Metric To Compare the Excitation Power Density Dependence of Photon Upconversion in Different Inorganic Host Materials.

In photon upconversion (UC) based on triplet-triplet annihilation, the upconversion photoluminescent quantum yield (UC-PLQY) depends on the excitation power density in a way that can be described by a single figure of merit. This figure of merit, the threshold value, allows the excitation power density required for efficient UC-PLQY to be compared between different triplet-triplet annihilation systems. Here, we investigate the excitation power density dependence of two-photon UC processes in a series of four lanthanide-doped inorganic host materials (oxides, fluorides, and chlorides) all doped with 18 mol % Yb3+ sensitizer ions and 2 mol % Er3+ activator ions. We demonstrate that an analogous figure of merit, which we call the critical power density (CPD), accurately describes the UC power dependence of these samples. Better CPD values are obtained when the lifetime of the intermediate states is long. The UC-PLQY at the CPD is linked to the saturation UC-PLQY. Thus, a measurement of the UC-PLQY at this low power density can be used to estimate the theoretical saturation UC-PLQY in the absence of deleterious effects such as laser-induced heating. This is compared to another method to estimate the saturation based on the CPD model, namely, taking half of the level's PLQY under direct excitation. Our careful analysis of the upconversion spectra as a function of excitation power density gives several insights into the differing upconversion pathways in the hosts and proves to be a useful tool for their comparison.

Excitonically Coupled States in Crystalline Coordination Networks.

When chromophores are brought into close proximity, noncovalent interactions (π-π/CH-π) can lead to the formation of excitonically coupled states, which bestow new photophysical properties upon the aggregates. Because the properties of the new states not only depend on the strength of intermolecular interactions, but also on the relative orientation, supramolecular assemblies, where these parameters can be varied in a deliberate fashion, provide novel possibilities for the control of photophysical properties. This work reports that core-substituted naphthalene diimides (cNDIs) can be incorporated into surface-mounted metal- organic structures/frameworks (SURMOFs) to yield optical properties strikingly different from conventional aggregates of such molecules, for example, formed in solution or by crystallization. Organic linkers are used, based on cNDIs, well-known organic chromophores with numerous applications in different optoelectronic devices, to fabricate MOF thin films on transparent substrates. A thorough characterization of the properties of these highly ordered chromophoric assemblies reveals the presence of non-emissive excited states in the crystalline material. Structural modulations provide further insights into the nature of the coupling that gives rise to an excited-state energy level in the periodic structure.

Guest-responsive polaritons in a porous framework: chromophoric sponges in optical QED cavities.

Introducing porous material into optical cavities is a critical step toward the utilization of quantum-electrodynamical (QED) effects for advanced technologies, e.g. in the context of sensing. We demonstrate that crystalline, porous metal-organic frameworks (MOFs) are well suited for the fabrication of optical cavities. In going beyond functionalities offered by other materials, they allow for the reversible loading and release of guest species into and out of optical resonators. For an all-metal mirror-based Fabry-Perot cavity we yield strong coupling (∼21% Rabi splitting). This value is remarkably large, considering that the high porosity of the framework reduces the density of optically active moieties relative to the corresponding bulk structure by ∼60%. Such a strong response of a porous chromophoric scaffold could only be realized by employing silicon-phthalocyanine (SiPc) dyes designed to undergo strong J-aggregation when assembled into a MOF. Integration of the SiPc MOF as active component into the optical microcavity was realized by employing a layer-by-layer method. The new functionality opens up the possibility to reversibly and continuously tune QED devices and to use them as optical sensors.

Correction: Guest-responsive polaritons in a porous framework: chromophoric sponges in optical QED cavities.

[This corrects the article DOI: 10.1039/D0SC02436H.].

Highly Efficient La2O3:Yb3+,Tm3+ Single-Band NIR-to-NIR Upconverting Microcrystals for Anti-Counterfeiting Applications.

Efficient single-band NIR-to-NIR upconversion (UC) emission is strongly desired for many applications such as fluorescent markers, plastic recycling, and biological imaging. Herein, we report highly efficient single-band NIR-to-NIR UC emission in La2O3:Yb3+,Tm3+ (LYT) microcrystals. Under 980 nm laser excitation, LYT exhibits a NIR UC emission at ∼795 nm (Tm3+: 3H4 → 3H6) and blue UC emission at ∼476 nm; the NIR UC emission is dominant, with the intensity ratio of the NIR to blue INIR/ Iblue > 100. Remarkably, a high absolute UC quantum yield (UCQY) of 3.4% is obtained for the single-band NIR UC emission of LYT at a relatively low excitation power density of 7.6 W/cm2. This value is much higher than the reported values of a single-band NIR UC for rare-earth-based UC materials in literature, such as the well-known benchmark UC materials of ß-NaYF4:Yb3+,Er3+ (∼0.9%, with a excitation power density of 9 W/cm2) and Gd2O2S:Yb3+,Er3+ (∼1.9%, with a excitation power density of 20 W/cm2). The high absolute UCQY of single-band NIR UC emission combined with their facile preparation hints at their potential application in anti-counterfeiting, verified by the proof-of-concept demonstration of fluorescent labeling of a transparent IMT pattern.