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. D. Avram, A. A. Patrascu, I. Porosnicu, C. 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. D. Avram, C. Colbea, A. A. Patrascu, M. C. Istrate, V. Teodorescu, C. Tiseanu "Up-conversion emission in transition metal and lanthanide co-doped systems: dimer sensitization revisited" Scientific Reports, (2023), 13(1), 2165

3. D. Avram, C. Colbea, C. Tiseanu "Heterogeneity effects of Tm upconversion emission in Mo, Tm codoped rare-earth garnets" Journal of Alloys and Compounds, (2023), 944, 169226.

4. D. Avram, A. A. Patrascu, M. C. Istrate, C. Tiseanu "Gd-Er interaction promotes NaGdF4: Yb, Er as a new candidate for high-power density applications" Journal of Materials Chemistry C (2023), Advance Article.

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. D. Avram, A. A. Patrascu, I. Porosnicu, C. 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. D. Avram, C. Colbea, A. A. Patrascu, M. C. Istrate, V. Teodorescu, C. Tiseanu "Up-conversion emission in transition metal and lanthanide co-doped systems: dimer sensitization revisited" Scientific Reports, (2023), 13(1), 2165

3. D. Avram, C. Colbea, C. Tiseanu "Heterogeneity effects of Tm upconversion emission in Mo, Tm codoped rare-earth garnets" Journal of Alloys and Compounds, (2023), 944, 169226.

4. D. Avram, A. A. Patrascu, M. C. Istrate, C. Tiseanu "Gd-Er interaction promotes NaGdF4: Yb, Er as a new candidate for high-power density applications" Journal of Materials Chemistry C (2023), Advance Article.



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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