Luminescence Deactivation
Fluorescence or phosphorescence intensity decreases when the excited molecule interacts with a quencher molecule in the solution. This decrease in light emission is described by stern-volmer quenching, which mathematically relates the concentration of the quencher to the reduction in luminescent intensity or lifetime. The relation applies specifically to collision-based quenching processes in homogenous mixtures.
Linear Relationship
Luminescence modeling relates the ratio of unquenched luminescence to quenched luminescence as a linear function of the concentration of the quencher. This relationship is defined by the Stern-Volmer constant, which combines the diffusion coefficient and the lifetime of the excited state. The resulting line allows the concentration of the quencher, such as dissolved oxygen, to be calculated from the measured luminescence.
This linear relationship forms the basis for many optical sensor calibrations.
Diffusion Limit
High temperatures or low viscosities increase the rate of collision between molecules, which accelerates the quenching process. Under these conditions, the Stern-Volmer constant changes, which can distort the concentration calculations if temperature correction is not applied. This thermal dependency must be managed to maintain accuracy.
Metrological Accuracy
Quality control labs verify this relationship by measuring the sensor response in solutions of known gas concentrations. The measured data is used to calculate the Stern-Volmer constant, which must fall within the specified limits of the sensor. If the constant is outside the tolerance, the luminescent material must be replaced or the sensor recalibrated.
This testing ensures that the sensor maintains its accuracy over its operating lifetime.