Broadband Emission via a Photon Avalanche in a Lanthanide-Trimesic Acid Metal-Organic Framework

TL;DR

This paper demonstrates broadband photon avalanche emission in lanthanide-trimesic acid MOFs, revealing a cooperative process involving organic ligand states that broadens the scope of PA materials beyond traditional inorganic systems.

Contribution

It introduces a novel PA mechanism in MOFs involving ligand triplet states, expanding the range of materials capable of nonlinear broadband emission.

Findings

PA occurs via ligand triplet states, not just lanthanide ions

Crystallinity influences PA efficiency and emission characteristics

Broadband nonlinear emission comparable to inorganic nanoparticles

Abstract

Infrared-triggered photon upconversion in porous materials presents intriguing prospects for combined functionalities such as molecular sponge, energy harvesting and conversion functionalities. Metal-organic frameworks (MOFs) are one of the most versatile classes of porous crystals. So far only two-photon upconverting processes have been realized in MOFs both by ligand based triplet-triplet annihilation and directly in lanthanide ions. Here we report on Yb3+/Er3+-trimesate-based MOFs that exhibit photon avalanche (PA) characteristics. The PA process conventionally occurs through cross-relaxation within the lanthanide emitter manifold. In contrast, here PA proceeds in the organic molecule part and relies on a cooperative process, involving multiple emission centers. The IR photons are first absorbed and upconverted into high energy electronic population by the action of the lanthanide ions (Yb3+ and Er3+ are the sensitizer and the activator, respectively). Subsequently, the electrons are funneled into electronically coupled triplet states of the trimesate ligand, enabling accumulation in the organic matrix. This reservoir acts as source for a highly nonlinear spectrally broadband emission, arising mainly from ligand triplet states. The nonlinearity factor is comparable with the well-established PA inorganic nanoparticles. We prove that the PA is strongly related to the degree of crystallinity of the MOF: not well-formed frameworks support only the characteristic Er3+ emission with only linear increase as a function of the excitation power. Our work paves a path towards vastly expanding the range of materials exhibiting PA, well beyond a limited set of lanthanide ions. Moreover, it provides a path for much broader control of the PA emission characteristics.