The mechanisms behind extreme susceptibility of photon avalanche emission to quenching

TL;DR

This paper investigates the mechanisms behind the extreme susceptibility of photon avalanche emission to quenching, revealing how energy transfer processes disrupt PA and suggesting its potential as an ultra-sensitive detection method.

Contribution

It provides a detailed analysis of how resonant energy transfer affects photon avalanche emission, introducing new insights into controlling and utilizing PA in sensing applications.

Findings

Energy transfer increases PA threshold and decreases nonlinearity.

Quenching sensitivity is highly dependent on acceptor ion concentration.

PA can serve as an ultra-sensitive fluorescence-based sensor.

Abstract

The photon avalanche (PA) process that emerges in lanthanide-doped crystals yields a threshold and highly nonlinear (of the power law order > 5) optical response to photoexcitation. PA emission is the outcome of excited-state absorption combined with a cross-relaxation process, which creates positive and efficient energy looping. In consequence, this combination of processes should be highly susceptible to small perturbations in energy distribution and thus can be hindered by other competitive 'parasite' processes such as energy transfer (ET) to quenching sites. Although luminescence quenching is a well-known phenomenon, the exact mechanisms of susceptibility of PA to resonant energy transfer (RET) remain poorly understood limiting practical applications. A deeper understanding of these mechanisms may pave the way to new areas of PA exploitation. This study focuses on the investigation of the LiYF$_{4}$:3%Tm$^{3+}$ PA system co-doped with $Nd^{3+}$ acceptor ions, which was found to impact both the looping and emitting levels and thus to effectively disrupt PA emission, causing an increase in the PA threshold ($I_{th}$) and a decrease in PA nonlinearity ($S_{max}$). Our complementary modelling results revealed that the ET from the looping level increased $I_{th}$ and $S_{max}$, whereas the ET from the emitting level diminished $S_{max}$ and the final emission intensity. Ultimately, significant PA emission quenching demonstrates a high relative sensitivity ($S_{R}$) to infinitesimal amounts of $Nd^{3+}$ acceptors, highlighting the potential for PA to be utilized as an ultra-sensitive, fluorescence-based reporting mechanism that is suitable for the detection and quantification of physical and biological phenomena or reactions.