Self-Trapped, Thermally Equilibrated Delayed Fluorescence Enables Low-Reabsorption Luminescent Solar Concentrators Based on Gold-Doped Silver Nanoclusters.

Reabsorption-free luminescent solar concentrators (LSCs) are crucial ingredients for photovoltaic windows. Atomically precise metal nanoclusters (NCs) with large Stokes-shifted photoluminescence (PL) hold great promise for applications in LSCs. However, a fundamental understanding of the PL mechanism, particularly on the excited-state interaction and exciton kinetics, is still lacking. Herein, we studied the exciton-phonon coupling and singlet/triplet exciton dynamics for gold-doped silver NCs in a solid matrix. Following photoexcitation, the excitons can be self-trapped via strong exciton-phonon coupling. Subsequently, rapid thermal equilibration between the singlet and triplet states occurs due to the coexistence of small energy splitting and spin-orbit coupling. Finally, broadband delayed fluorescence with a large Stokes shift can be generated, namely, self-trapped, thermally equilibrated delayed fluorescence (ST-TEDF). Benefiting from superior ST-TEDF, we demonstrated efficient LSCs with minimized reabsorption.

Utilizing host-guest interaction enables the simultaneous enhancement of the quantum yield and Stokes shift in organosilane-functionalized, nitrogen-containing carbon dots for laminated luminescent solar concentrators.

Solar energy can be harvested using luminescent solar concentrators (LSCs) incorporated with edge-mounted solar cells without sacrificing their see-through visibility, thus facilitating the development of solar windows. Eco-friendly carbon dots (CDs) are promising alternatives to heavy-metal-containing quantum dots in LSC applications. Unfortunately, their solid-state quantum yield (QY) at high optical density (required by laminated LSCs) is still low (<30%) and the Stokes shift is only moderate (<100 nm). Here, we studied the host-guest interaction between aminosilane-functionalized, nitrogen-containing CDs (Si-NCDs) and a silica matrix for preparing efficient laminated LSCs. We found that a sol-gel-derived silica matrix with vacuum treatment can efficiently suppress the direct nonradiative transition of the absorbing states and selectively enhance the long-wavelength-emitting surface states. Therefore, the formed Si-NCDs@silica composites simultaneously exhibited high QYs (>60%) and large Stokes shifts (>200 nm) even at a high loading content (∼10 wt%), while still exhibiting high optical transparency. Moreover, unlike conventional QY reduction upon increasing the excitation wavelengths, such high QY values can be maintained over all excitation wavelengths in the absorption region. Benefiting from these photophysical properties, efficient laminated LSCs were simply prepared, yielding a high optical efficiency of ∼4.4%.

Electronically Coupled Gold Nanoclusters Render Deep-Red Emission with High Quantum Yields.

Electronic coupling can be used to tailor electronic states and optical properties of the luminophores. Therefore, electronically coupled systems would provide unique properties, which cannot be achieved by individual constituents. Here, electronically coupled gold nanoclusters (AuNCs) were prepared on the basis of organosilane grafting and a sol-gel-derived porous silica template. After prolonged drying, the formed AuNCs@silica composites exhibited red-shifted, line-width-narrowed, deep-red emission with high quantum yields (QYs) of ∼66% due to electronic-coupling-enhanced radiative rates and covalent-bonding-suppressed nonradiative relaxation. Meanwhile, the absorption maximum was slightly blue-shifted, leading to a large Stokes shift. All experimental findings revealed the formation of electronically coupled AuNC aggregates confined inside the nanopores and bonded to silica matrix. The mechanism is distinctly different from conventional aggregation-enhanced emission. Our work would provide great potential to engineer photophysical properties by controlling the packing modes.