Project Title:                  Temporally and spectrally resolved luminescence of lanthanide's doped tetravalent                                        nano-oxides: A unitary approach 

Project Code:                  PN-II-ID-PCE-2011-3-0534

Contract Nr. :                  309/2011

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

Period:                             2011 - 2016

Project Leader:               Carmen TISEANU

Contract Value:               1.500.000 RON


Project Summary  

        Our proposal is focused on a particular class of luminescent nano-oxides, namely lanthanide (Ln3+) doped CeO2, (I) ZrO2 (II) and CexZr1-xO2 (III) which attract tremendous attention as advanced ceramics, catalysts, sensors and luminescent materials. These applications rely on their unique, but still not well understood, structures and physical properties. The broad aim of the project is to identify, describe and provide novel insights on the structure - luminescence relationships occurring in the lanthanide doped I - III. Our original approach is based on the unitary investigation of their luminescence and structural properties. The lanthanide dopants will exhibit VIS to NIR emission via down- and up- conversion excitation. At the heart of our studies are the temporally and spectrally resolved luminescence investigations. We believe that our proposal will deepen the fundamental knowledge on the Ln3+- I - III host interactions at the nanoscale with strong impact on luminescence and structure-derived applications.


Project Objectives:

I. In-depth description of the nanoscale environments at the lanthanides sites in CeO2 (I), ZrO2 (II) and CexZr1-xO2 (III)
II. Luminescence of redox active lanthanides doped I and III

III. Novel insights into the Ln3+ - Ln3+ and Ln3+ I - III interactions

IV. Assessment of the potential of I - III hosts as emission up- converters



Project Team:


Project Annual Reports (Romanian):

Stage 2011:
Contract Value: 33.000,00 RON

Raport stiintific privind implementarea proiectului in perioada octombrie 2011 - decembrie 2011

Stage 2012:
Contract Value: 705.000,00 RON

Raport stiintific privind implementarea proiectului in perioada ianuarie - decembrie 2012

Stage 2013:
Contract Value: 251.028,91 RON

Raport stiintific privind implementarea proiectului in perioada octombrie 2011 - decembrie 2013

Stage 2014:
Contract Value: 102.997,00 RON

Raport stiintific privind implementarea proiectului in perioada ianuarie 2014 - decembrie 2014

Stage 2015:
Contract Value: 131.632,00 RON

Raport stiintific privind implementarea proiectului in perioada ianuarie 2015 - decembrie 2015

Stage 2016:

Contract Value:  276.337,09 RON
Raport stiintific privind implementarea proiectului in perioada 2011 - 2016

Interim project evaluation (2011 - 2013) The project has been top rated as A+.

Project Synthetic Report (English)


Project Publications and Papers Published in ISI Journals

 1. C. Tiseanu, V. I. Parvulescu, M. Boutonnet, B. Cojocaru, P. Primus, C. Teodorescu, C. Solans,  M. Sanchez - Dominquez, "Surface versus volume effects in luminescent ceria nanocrystals synthesized by oil in-water microemulsion method" Phys. Chem. Chem. Phys. (2011), 13, 17135-17145

2. C. Tiseanu, B. Cojocaru, V. Parvulescu, M. Sanchez Dominiguez, P. A. Primus, M. Boutonnet, "Order and disorder effects in nano-ZrO2 investigated by micro-Raman and spectrally and temporarily resolved photoluminescence" Phys. Chem. Chem. Phys. 14(37), 12970-12981(2012) (IF = 3.829)

3. C. Tiseanu, V. Parvulescu, B. Cojocaru, Kelly Pemartin, M. Sanchez Dominguez, M. Boutonnet, "In situ Raman and Time-Resolved Luminescence Investigation of Local Structure of ZrO2 in the Amorphous to Crystalline Phase Transition " J. Phys. Chem. C. 116(31), 16776-16783(2012) (IF= 4.805)

4. C. Tiseanu, V. Parvulescu, M. Sanchez Dominguez, M. Boutonnet, "Temperature induced conversion from surface to bulk sites in Eu3+- impregnated CeO2" J. Appl. Phys. 112(1), 013521 (2012) (IF = 2.168)

5. C. Tiseanu, B. Cojocaru, D. Avram, V. Parvulescu, M. Sanchez Dominguez "Isolated versus Sm3+-defect associations in CeO2: a spectroscopy investigation" J. Phys. D: Appl. Phys. 46, 275302 (2013) (IF = 2.521)

6. G. Seisenbaeva, J.-M. Nedelec, G. Daniel, C. Tiseanu, V. Parvulescu, V. Pol, L. Abrego, V. Kessler "Mesoporousanatase TiO2  nanorods as robust anodes for Li-ion batteries - a detailed insight into formation mechanism", Chem. Eur. J. 19(51), 17439-17444 (2013) (IF = 5.696)

7. D. Avram, C. Rotaru, B. Cojocaru, M. Sanchez-Dominguez, M. Florea, C. Tiseanu "Heavily impregnated ceria nanoparticles with europium oxide: spectroscopic evidences for homogenous solid solutions and intrinsic structure of Eu3+ - oxygen environments", J. Mater. Sci., 49(5), 2117-2126 (2014) (IF = 2.371)

8. C. Tiseanu, V. Parvulescu, D. Avram, B. Cojocaru, M. Boutonnet, M. Sanchez-Dominguez "Local structure and nanoscale homogeneity of CeO2-ZrO2: Differences and similarities to parent oxides revealed by luminescence with temporal and spectral resolution", Phys. Chem. Chem. Phys. 16, 703-710 (2014) (IF = 4.493)

9. C. Tiseanu, V. Parvulescu, D. Avram, B. Cojocaru, N. Apostol, A. V. Vela-Gonzalez, M. Sanchez-Dominguez "Structural down- and phase selective up- conversion emission properties of mixed valent Pr doped into oxides with tetravalent cations", Phys. Chem. Chem. Phys. 16, 5793-5802 (2014) (IF = 4.493)

10. C. Tiseanu, V. Parvulescu, D. Avram, B. Cojocaru, M. Sanchez-Dominguez "Exceptional capability of CeO2- ZrO2 to "dissolve" europium oxide established by X-ray Diffraction, Raman and time-resolved luminescence spectroscopy", Dalton Trans. 43(20), 7622-7630 (2014) (IF = 4.197)

11. D. Avram, C. Gheorghe, C. Rotaru, B. Cojocaru, M. Florea, V. Parvulescu, C. Tiseanu "Lanthanide - lanthanide and lanthanide - defect interactions in co - doped ceria revealed by luminescence spectroscopy", J. Alloys Compd. 616, 535-541 (2014) ( IF = 2.999)

12. V. I. Parvulescu, C. Tiseanu "Local structure in CeO2 and CeO2 - ZrO2 nanoparticles probed by Eu luminescence", Catal. Today, 253, 33-39 (2015) (2014 IF = 3.893)

13. D. Avram, M. Sanchez-Dominguez, B. Cojocaru, M. Florea, V. Parvulescu, C. Tiseanu "Toward a Unified Description of Luminescence – Local Structure Correlation in Ln Doped CeO2 Nanoparticles: Roles of Ln Ionic Radius, Ln Concentration and Oxygen Vacancies", J. Phys. Chem. C 119(28), 16303-16313 (2015) (2014 IF = 4.772)

14. D. Avram, A. Urda, B. Cojocaru, I. Tiseanu, M. Florea, C. Tiseanu "Pure and almost pure NIR emission of Tm and Tm, Yb - CeO2 under UV, X - ray and NIR up - conversion excitation: Key roles of level selective antenna sensitization and charge - compensation", Phys. Chem. Chem. Phys. 17(46), 30988-30992 (2015) (2014 IF = 4.493)

15. D. Avram, B. Cojocaru, M. Florea, C. Tiseanu "Advances in luminescence of lanthanide doped Y2O3: case of S6 sites", Opt. Mater. Express 6(5), 1635-1643 (2016) (2014 IF = 2.844)

16. M. Florea, D. Avram, B. Cojocaru, I. Tiseanu, V. Parvulescu, C. Tiseanu "Defects induced tunable near infrared emission of Er - CeO2 by heterovalent co - dopants" Phys. Chem. Chem. Phys. 18 , 18268-18277 (2016) (2014 IF= 4.493)

17. D. Avram, I. Porosnicu, B. Cojocaru, M. Florea, C. Tiseanu "Time-gated down-/up-conversion emission of Ho-CeO2 and Ho, Yb-CeO2 nanoparticles" J. Lumin. (2016) 179, 256-271


Project Conferences and Summer Schools

 1. C. Tiseanu, V. Parvulescu, Magali Boutonnet, B. Cojocaru, M. Sanchez Dominguez "Local structure of Ln3+-doped tetravalent nano-oxides" 4th International Symposium on Structure-Property Relantionships in Solid State Materials, Bordeaux, France, 24-29.06.2012

 2. C. Tiseanu, V. Parvulescu, Magali Boutonnet, B. Cojocaru, M. Sanchez Dominguez "Local structure of Ln3+-doped tetravalent nano-oxides" XI International  Conference on Nanostructured Materials, Palace Convention Center, Rhodes, Greece, 26-31.08.2012 

3. D. Avram, B. Cojocaru, N. Gheorghe, C. Tiseanu "Cubic and low symmetry centers in Eu3+ and Sm3+ doped CeO2 nanoparticles. Effects of dopant concentration and thermal treatment" XI International Krutyn Summer School 2012, Krutyn, Poland, 23-29.09.2012 

4. D. Avram, 10th European short course on "Principles and Applications of Time-Resolved Fluoroscence Spectroscopy" Berlin, Germany, 29.10-01.11.2012

5. D. Avram, B. Cojocaru, M. Florea, C. Tiseanu "Cubic and low symmetry of Eu3+ doped CeO2 nanoparticles: micro-Raman and luminescence spectroscopic study" 12th National Seminar of nanoscience and nanotechnology , The Romanian Academy Library, Bucharest, 16.05.2013

6. D. Avram, C. Tiseanu "Cubic and low symmetry centres in Eu3+/Sm3+ doped CeO2 nanoparticles: a micro-Raman and luminescence spectroscopic study" Bucharest University Faculty of Physics 2013 Meeting, Bucharest,  21.06.2013

7. C. Tiseanu, D. Avram, B. Cojocaru, V. Parvulescu "Nanoscale homogeneity in luminescent lanthanide-doped nano - oxides", European Congress and Exhibition on Advanced Materials and Processes 2013, Sevilla, Spain, 08.09-13.09.2013

8. C. Tiseanu "Interactions between ceria host and lanthanide dopants probed by luminescence spectroscopy" FUNDAMENTALS AND APPLICATIONS OF CERIUM DIOXIDE IN CATALYSIS, Udine, Italy, 11-14.07.2014

9. D. Avram, C. Tiseanu "IR, NIR and Vis to NIR and Vis up - Conversion Emission in Er doped BiOCl" JUNIOR EUROMAT 2014, Lausanne, Switzerland, 21-25.07.2014

10. D. Avram, C. Tiseanu "Infrared and Near-Infrared to Visible and Near-Infrared up-conversion emission of Yb - Ln (Ln= Er, Tm) co-doped CeO2 nanoparticles for biological applications" The 4th International Colloquium 'Physics of Materials' - PM-4, Bucharest, Romania, 13-14.11.2014

11. D. Avram, B. Cojocaru, M. Florea, V. Parvulescu, C. Tiseanu "Luminescence properties of CeO2 doped with Ln ions under optical and X-ray excitation modes," The 4th International Conference on the Physics of Optical Materials and Devices, ICOM 2015, 31 August - 04 September 2015, Budva, Montenegro; Book of Abstracts, ISBN: 978-86-7306-134-4, p. 53, presentation S9-O30-165 

12. D. Avram, B. Cojocaru, M. Florea, I. Porosnicu, V. Parvulescu, and C. Tiseanu, “Role of defects in shaping the emission of Ln doped CeO2,” 2016 International Conference on Defects in Insulating Materials (ICDIM 2016)", 10-15 July 2016, Lyon, France; presentation Th-P-16 (poster presentation). 

13. I. Porosnicu, D. Avram, B. Cojocaru, M. Florea and C. Tiseanu, " Down and up-conversion processes in Ho3+ and Ho3+, Yb3+ co-doped CeO2 nanoparticles", 2016, 16th International Balkan Workshop on Applied Physics and Materials Science (IBWAP 2016), 7-8 July, Constanta, Romania, (poster presentation)

14.  D. Avram, B. Cojocaru, M. Florea and C. Tiseanu, “Magnetic dipole emission of lanthanide doped Y2O3 and CeO2”, 2016, The 5th International Conference from Nanoparticles and Nanomaterials to Nanodevices and Nanosystems (IC4N), June 26-30, Porto Heli, Argolid-Peloponnese, Greece;  poster no. 2-15 (poster presentation). 


Master Theses 

1. Radu Daniel Avram - " Spectrally and temporally resolved luminescence of lanthanide doped nano-oxides", Faculty of Physics, University of Bucharest (June 2013), Advisor: Dr. Carmen Tiseanu
2. Ioana Porosnicu - "Down and Up-conversion processes in Ho and Ho,Yb doped
CeO2  nanoparticles", Faculty of Physics, University of Bucharest (June 2016), Advisor: Dr. Carmen Tiseanu


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