Project Title:             Transition Metal Assisted UP Conversion in Lanthanide doped (nano)particles: Resolving the                                              mechanisms in spectral and temporal domains

Project Code:            PN-III-P4-ID-PCE-2020-1553

Contract Nr. :            62/2021

Project Funded by:  UEFISCDI, Ministry of Education, Research, Youth and Sport, Romania 

Period:                       2021 - 2023

Project Leader:        Carmen TISEANU

Contract Value:        1 198 032 RON


Project Summary  

       Our primary goal is to develop a unitary description of transition metal (TM: Mo anion, bivalent Mn) assisted lanthanide (Ln: Yb/Er, Yb/Tm, Gd) upconversion (UPC) emission in both spectral and temporal domains. Three relevant classes of materials are selected: rare-earth based oxides, where Mo is employed as both dopant and host cation (I), and Rare-Earth fluorides with hexagonal/cubic (II) and tetragonal (III) lattice structures, where Mn is employed as dopant. The questions we address in this proposal are: How the low solubility and heterovalency of transition metals impact on the local structure, and hence d-d (Mn) and f-f absorption/emission transitions of Ln? How does spectral selective and time-resolved/gated excitation influences the different roles (sensitizer, activator, mediator) played by TM/Ln in UPC processes with impact on the emission colour, intensity and dynamics? To what extent the complex picture of UPC processes includes (if at all) the Yb - Mo/Mn dimer mechanism? We seek answers to all these questions using a battery of spectral and temporal resolved luminescence approaches: investigation and analysis of site selective, time-resolved emission and excitation spectra monitoring all key absorption/emission levels involved in UPC, emission decays and energy density dependencies by using unique configuration based on tunable pulsed excitation laser with controlled beam profile.


Project Objectives:

    Our primary goal is to develop a unitary description of transition metal (TM: Mo anion, bivalent Mn) assisted lanthanide (Ln: Yb/Er, Yb/Tm, Gd) upconversion (UPC) emission in both spectral and temporal domains. Three relevant classes of materials are selected: rare-earth based oxides, where Mo is employed as both dopant and host cation (I), and Rare-Earth fluorides with hexagonal/cubic (II) and tetragonal (III) lattice structures, where Mn is employed as dopant.


Project Team:



Papers Published in ISI Journals

1. Daniel Avram, Andrei A. Patrascu , Ioana Porosnicu and Carmen Tiseanu, "Emission colour tuning of Mn, Yb, Er-NaGdF4 upconverting nanoparticles by energy density variation and pulse modulation", Optical Materials Express, 2022, 12(5), 1894-1906

2. Daniel Avram, Claudiu Colbea, Andrei A. Patrascu, Marian Cosmin Istrate, Valentin Teodorescu and Carmen Tiseanu, "Up-conversion emission in transition metal and lanthanide co-doped systems: dimer sensitization revisited", under review

3. Daniel Avram, Claudiu Colbea, Carmen Tiseanu "Heterogeneity effects of Tm upconversion emission in Mo, Tm codoped rare-earth garnets" under review.

4. Daniel Avram, Andrei A. Patrascu, Carmen Tiseanu "Shifting the energy density saturation level of Yb-Er upconversion: NaGdF4 versus NaYF4 nanoparticles" under review




International Conferences

 1. D. Avram, C. Colbea, C. Tiseanu "Local symmetry effects on the upconversion emission intensity, shape and mechanisms under pulsed excitation" UPCONline 2021, 06 - 09 april 2021, Online Conference. (Oral presentation)

2. Daniel Avram, Claudiu Colbea, Andrei A. Patrascu și Carmen Tiseanu "Upconversion emission properties in transition metal, lanthanide co-doped systems: a spectral selective, time-resolved investigation", Spectral sHapIng For biomedical and energy applicaTions International Conference (SHIFT 2022) 10-14.10.2022, La Laguna, Spania (Oral presentation)



Project Acquisitions

Tunable OPO laser (410 - 2500 nm) - Opotek RADIANT QX4130


Detaliile proiectului in limba romana (RO)

Titlul Proiectului:             Conversia superioara a emisiei lantanidelor asistata de metale tranziționale: Elucidarea                                                      mecanismelor in domeniul spectral si temporal (TUPLAN)

Codul Proiectului:            PN-III-P4-ID-PCE-2020-1553

Nr. Contractului:             62/2021

Agentia Finantatoare:   UEFISCDI, Ministry of Education, Research, Youth and Sport, Romania 

Durata:                              2021 - 2023

Director de Proiect:        Carmen TISEANU

Valoarea totala:              1 198 032 RON


Abstract

       Scopul principal al proiectului este de a descrie, in mod unitar, mecanismele de conversie superioară (UPC) a emisiei lantanidelor (Ln: Yb/Er, Yb/Tm, Gd) asistate de metale tranziționale (TM: Mo (anion), Mn divalent), in domeniul spectral si temporal. Am selectat trei clase semnificative de materiale: oxizi de pămānturi rare, in care Mo joaca rol de dopant dar si de cation (I), si fluoruri de pămānturi rare cu structura hexagonală/cubică (II) și tetragonală (III) in care Mn este utilizat ca dopant. Īntrebările pe care ni le adresăm īn cadrul acestui proiect sunt următoarele: Cum influențează solubilitatea scăzută și heterovalența TM structura locală, și prin urmare, tranzițiile de absorbție/emisie d-d (Mn) și f-f ale Ln? Cum influențează excitarea selectivă, rezolvată temporal rolurile (sensibilizator, activator, mediator) jucate de TM/Ln īn procesele de UPC si impactul asupra culorii emisiei, intensității și dinamicii? Īn ce măsură imaginea complexă a proceselor UPC include mecanismul tip dimer Yb - Mo/Mn? Căutăm răspunsuri la toate aceste īntrebări utilizānd o gamă largă de metodici pentru rezolvarea spectrala si temporala a luminescentei: investigarea și analiza spectrelor de emisie și excitație rezolvate temporal cu excitare selectiva monitorizānd nivelele cheie de absorbție/emisie implicate īn UPC, cinetica emisiei și dependența emisiei UPC de densitatea de energie, folosind o configurație unică bazată pe un laser pulsat tunabil cu profil bine definit.


Obiectivele Proiectului:

    Scopul principal al proiectului este de a descrie, in mod unitar, mecanismele de conversie superioară (UPC) a emisiei lantanidelor (Ln: Yb/Er, Yb/Tm, Gd) asistate de metale tranziționale (TM: Mo (anion), Mn divalent), in domeniul spectral si temporal. Am selectat trei clase semnificative de materiale: oxizi de pămānturi rare, in care Mo joaca rol de dopant dar si de cation (I), si fluoruri de pămānturi rare cu structura hexagonală/cubică (II) și tetragonală (III) in care Mn este utilizat ca dopant.


Echipa Proiectlui:



Articole publicate in reviste cotate ISI

1. Daniel Avram, Andrei A. Patrascu , Ioana Porosnicu and Carmen Tiseanu, "Emission colour tuning of Mn, Yb, Er-NaGdF4 upconverting nanoparticles by energy density variation and pulse modulation", Optical Materials Express, 2022, 12(5), 1894-1906

2. Daniel Avram, Claudiu Colbea, Andrei A. Patrascu, Marian Cosmin Istrate, Valentin Teodorescu and Carmen Tiseanu, "Up-conversion emission in transition metal and lanthanide co-doped systems: dimer sensitization revisited", trimis spre publicare.

3. Daniel Avram, Claudiu Colbea, Carmen Tiseanu "Heterogeneity effects of Tm upconversion emission in Mo, Tm codoped rare-earth garnets"
trimis spre publicare.

4. Daniel Avram, Andrei A. Patrascu, Carmen Tiseanu "Shifting the energy density saturation level of Yb-Er upconversion: NaGdF4 versus NaYF4 nanoparticles"
trimis spre publicare.




Conferinte Internationale

 1. D. Avram, C. Colbea, C. Tiseanu "Local symmetry effects on the upconversion emission intensity, shape and mechanisms under pulsed excitation" UPCONline 2021, 06 - 09 april 2021, Online Conference. (prezentare orala)

2. Daniel Avram, Claudiu Colbea, Andrei A. Patrascu și Carmen Tiseanu "Upconversion emission properties in transition metal, lanthanide co-doped systems: a spectral selective, time-resolved investigation", Spectral sHapIng For biomedical and energy applicaTions International Conference (SHIFT 2022) 10-14.10.2022, La Laguna, Spania (prezentare orala)



Achizitii in cadrul Proiectului

Laser tunabil OPO (410 - 2500 nm) - Opotek RADIANT QX4130

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