NEW SYNTHESES OF LUMINESCENT MATERIALS FROM IONIC LIQUIDS

Tessitore, Gabriella (2017). NEW SYNTHESES OF LUMINESCENT MATERIALS FROM IONIC LIQUIDS. (Dissertation, Departement für Chemie und Biochemie (DCB), Philosophisch-naturwissenschaftlichen Fakultät)

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The scope of my work was to improve the luminescence from rare earth doped compounds by
optimization of synthesis routes for the known materials or investigation of new efficient
luminescent materials. As an early stage researcher (ESR5) in the LUMINET project (Marie
Curie Fellowship Program) in “Luminescent Nanopowders”, I devoted most of my work to the
syntheses of nanoparticles doped with lanthanides. Their unique properties as emitting
materials were deeply investigated and new syntheses were proposed for β-NaGdF4: Ln3+ and
TiO2: Ln3+, see Chapter 3 and 4, respectively. The lanthanides used in this work are Eu3+, Er3+,
Yb3+, and Sm3+.
The syntheses of luminescent nanoparticles were accomplished by room temperature synthesis
in ethylene glycol for β-NaGdF4: Eu3+, Er3+ in Section 3.2, and microwave-assisted heating from
ionic liquids for β-NaGdF4: 18% Yb3+, 2% Er3+ and TiO2: Eu3+, Sm3+ in Sections 3.3 and 4.2,
respectively. The latter method allows for the synthesis of efficient luminescent nanoparticles
in anhydrous conditions due to the low vapour pressure of the ionic liquids. It corresponds to a
distinct advantage over the common synthesis methods due to the luminescence quenching
from the water molecules. Diallyldimethylammonium-based ionic liquids were used in this
work, which bear a polymerizable cation. This allows to yield luminescent nanocomposites in
an one-pot synthesis, see Section 4.2. The synthesis in ionic liquids leads to sub-10 nm
luminescence nanoparticles, whose luminescence is more efficient with respect to those
synthesized in other solvents. It is particularly of advantage for β-NaGdF4: 18% Yb3+, 2% Er3
+ upconversion luminescence nanoparticles, whose efficiency is already orders of magnitude
lower than the bulk material. The synthesis was accomplished at low temperatures with
respect to protocols in the literature and within 5 minutes, which further constitutes an
improvement. Core-shell nanoparticles were also achieved in one-pot synthesis, which reduces
the number of impurities and yield higher efficient luminescence from β-NaGdF4: 18% Yb3+, 2%
Er3+ nanoparticles.
Functionalization of upconversion nanoparticles surface was achieved with watersoluble
compounds, see Section 3.3. This step is required for application of the
upconversion nanoparticles in biological imaging. Folate-capped nanoparticles were also
synthesized for applications in targeting and imaging of cancer cells. Finally, new
titanium-based hybrid materials were produced from a sol-gel route, see Section 4.3. The
luminescence of Eu3+-doped materials was investigated and the influence of ionic liquids on the
syntheses was reported.
The luminescent materials were characterized with respect to their phase purity,
luminescence, and size by powder X-ray diffraction, luminescence spectroscopy, and
electron microscopy, respectively. Nuclear magnetic resonance, Fourier transform infrared,
and thermal analyses were further used for the characterization of the organic ligands. The
valuable results achieved benefit from user-friendly and scalable synthesis routes, which can
be easily extended to the whole lanthanide series.

Item Type:

Thesis (Dissertation)

Division/Institute:

08 Faculty of Science > Departement of Chemistry and Biochemistry

UniBE Contributor:

Tessitore, Gabriella and Krämer, Karl

Subjects:

500 Science > 540 Chemistry

Funders:

[103] European Commission FP7

Language:

English

Submitter:

Karl Krämer

Date Deposited:

24 Nov 2017 17:33

Last Modified:

05 Dec 2019 01:43

BORIS DOI:

10.7892/boris.107321

URI:

https://boris.unibe.ch/id/eprint/107321

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