Oxygen quantification in trace amounts is essential in many fields of science and technology. Optical oxygen sensors proved invaluable tools for oxygen measurements in a broad concentration range but until now neither optical nor electrochemical oxygen sensors were able to quantify oxygen in the sub-nanomolar concentration range. Herein we present new optical oxygen sensing materials with unmatched sensitivity. They rely on the combination of ultra-long decaying (several hundred milliseconds lifetime) phosphorescent boron- and aluminium-chelates and highly oxygen-permeable and chemically stable perfluorinated polymers. The sensitivity of the new sensors is improved up to 20-fold compared to state-of-the-art analogues. The limits of detection are as low as 5 parts per billion, volume in gas phase under atmospheric pressure or 7 picomolar in solution. The sensors enable completely new applications for monitoring of oxygen in previously inaccessible concentration ranges.
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