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Most available Ln(III)\u2010based luminescent thermometers require a calibration process with a reference thermal probe (secondary thermometers) and recurrent calibrations are mandatory, particularly when the thermometers are used in different media. This is sometimes impractical and a medium\u2010independent calibration relation is postulated, which is potentially inaccurate. Thus, the determination of the temperature based on well\u2010grounded physical principles by primary thermometers is the only way to overcome these challenges. Despite being considered one of the most important developments in luminescence thermometry, primary luminescent thermometers are scarce. Primary thermometers requiring calibration are proposed, implemented, and validated at one known temperature (primary\u2010T), which are also self\u2010referencing, employing ratiometric data from the excitation spectrum of Ln(III). By combining with the emission spectrum, thermometers not requiring calibration (primary\u2010S) are devised. An Eu(III)\u2010\u03b2\u2010diketonate complex is used as a proof\u2010of\u2010concept, but the approach is universal and other Ln(III)\u2010based materials can be explored. Because many thermometric parameters are employed for temperature prediction an unprecedented very high accuracy of 0.2% in the physiological range is obtained.<\/jats:p>","DOI":"10.1002\/adom.202200770","type":"journal-article","created":{"date-parts":[[2022,7,19]],"date-time":"2022-07-19T08:02:38Z","timestamp":1658217758000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":37,"title":["Novel and High\u2010Sensitive Primary and Self\u2010Referencing Thermometers Based on the Excitation Spectra of Lanthanide Ions"],"prefix":"10.1002","volume":"10","author":[{"given":"Keyla M. 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