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), 11, 10409-10419.

5. D. Avram, A. A. Patrascu, M. C. Istrate, C. Tiseanu "Toward efficient high photon order upconversion in Tm-doped LiYbF4 nanoparticles: optimization of excitation wavelength and use of pulsed excitation" submitted for publication

6. D. Avram and C. Tiseanu "Time-resolved photon order of lanthanide upconversion emission" submitted for publication

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 superioara (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 pamanturi rare, in care Mo joaca rol de dopant dar si de cation (I), si fluoruri de pamanturi rare cu structura hexagonala/cubica (II) si tetragonals (III) in care Mn este utilizat ca dopant. Intrebarile pe care ni le adresam in cadrul acestui proiect sunt urmatoarele: Cum influenteaza solubilitatea scazuta si heterovalenta TM structura locala, si prin urmare, tranzitiile de absorbtie/emisie d-d (Mn) si f-f ale Ln? Cum influenteaza excitarea selectiva, rezolvata temporal rolurile (sensibilizator, activator, mediator) jucate de TM/Ln in procesele de UPC si impactul asupra culorii emisiei, intensitatii si dinamicii? In ce masura imaginea complexa a proceselor UPC include mecanismul tip dimer Yb - Mo/Mn? Cautam raspunsuri la toate aceste intrebari utilizand o gama larga de metodici pentru rezolvarea spectrala si temporala a luminescentei: investigarea si analiza spectrelor de emisie si excitatie rezolvate temporal cu excitare selectiva monitorizand nivelele cheie de absorbtie/emisie implicate in UPC, cinetica emisiei si dependenta emisiei UPC de densitatea de energie, folosind o configuratie unica bazata 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 superioara (UPC) a emisiei lantanidelor (Ln: Yb/Er, Yb/Tm, Gd) asistate de metale tranzitionale (TM: Mo (anion), Mn divalent), in domeniul spectral si temporal. Am selectat trei clase semnificative de materiale: oxizi de pamanturi rare, in care Mo joaca rol de dopant dar si de cation (I), si fluoruri de pamanturi rare cu structura hexagonala/cubica (II) și tetragonala (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), 11, 10409-10419.

5. D. Avram, A. A. Patrascu, M. C. Istrate, C. Tiseanu "Toward efficient high photon order upconversion in Tm-doped LiYbF4 nanoparticles: optimization of excitation wavelength and use of pulsed excitation" submitted for publication

6. D. Avram and C. Tiseanu "Time-resolved photon order of lanthanide upconversion emission" submitted for publication



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

Rezultate:

Rezultatele din cadrul proiectului deschid noi orizonturi in ințelegerea si utilizarea nanoparticulelor. Am analizat modul in care proprietatile specifice ale metalelor tranziționale influenteaza comportamentul nanoparticulelor. Acest lucru ne-a permis sa schimbam modul in care sunt dezvoltate aceste particule minuscule pentru a le face mai eficiente in diferite aplicații. Pe scurt, am descoperit cum solubilitatea scazută si caracteristicile unice ale metalelor tranziționale pot modifica structura nanoparticulelor. Aceasta ne permite sa imbunatatim metodele de sinteza a nanoparticulelor, care sunt utile in imagistica de precizie, senzori luminescenti si chiar in cernelurile de securitate folosite pe bancnote. De asemenea, am descoperit noi informatii despre rolul metalului de mangan in ajustarea culorii emise de nanoparticule dopate cu ioni luminescenți de Ln. Astfel am aratat potentialul acestor nanoparticule in domeniul securitatii bancnotelor si bioimagistica, oferind noi metode ajustare a emisiei in conversie superioara din culoare verde in portocaliu. In ultima etapa a proiectului nostru, am dezvoltat nanoparticule care pot fi activate cu pulsuri laser extrem de scurte, creand densitati de putere foarte mari (> 107 W/cm2). Aceasta abordare noua in nanoscopie de conversie superioara permite obtinerea de rezolutii spațiale de sub 200 nanometri, sub limita microscoapelor confocale.

Prin aceste rezultate, ne-am propus sa aducem o contribuție semnificativa la tehnologiile viitorului, deschizand noi strategii de dezvoltare a nanoparticulelor dopate cu ioni de lantanide pentru diverse aplicații centrate pe emisia acestor metale luminescente.



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