Int J of Appl Glass Sci - 2021 - Vel Zquez - Structural and Optical Properties in Tm3 Tm3 Yb3 Doped NaLuF4

Received: 20 February 2021
| Revised: 24 May 2021

| Accepted: 9 June 2021
DOI: 10.1111/ijag.16322
SPECIAL ISSUE ARTICLE
Structural and optical properties in Tm3+/Tm3+–Yb3+ doped

NaLuF4 glass-ceramics
Jose J. Velázquez1 |Rolindes Balda2,3 | Joaquin Fernández4 | Giulio Gorni5,6 |

Mercedes Sedano5 | Alicia Durán5 | Dušan Galusek1,7 | Maria J. Pascual5
1
FunGlass, Alexander Dubček
University of Trenčín, Trenčín, Slovakia Abstract
2
Applied Physic Department I, Superior Transparent NaLuF4 glass-ceramics (GCs) doped with Tm3+ and Tm3+/Yb3+ have
School of Engineering, Basque Country been prepared by melting-quenching followed by thermal treatment at tempera-
University, Bilbao, Spain
3
tures near the glass transition temperature. The crystallization process has been
Materials Physics Center, CSIC-UPV/
EHU, San Sebastian, Spain studied using X-ray diffraction (XRD) and high-resolution transmission electron
4
Donostia International Physics Center, microscopy (HRTEM). NaLuF4 nanocrystals (NCs) ranging 9–30 nm in size are
San Sebastian, Spain the only crystalline phase, the crystal size increasing with the dopant concentra-
5
Ceramic and Glass Institute (ICV- tion. Energy dispersive X-ray (EDX) measurements confirm the Tm3+ and Yb3+
CSIC), Madrid, Spain
6
incorporation in the NCs. Optical characterization included the analysis of up-
Cells, ALBA Synchrotron, Cerdanyola
del Vallès, Spain conversion (UC) as well as the Near-infrared (NIR) luminescence. NIR emission
7
Joint Glass Centre of the IIC SAS, spectra of Tm3+ and Yb3+ in co-doped samples confirmed an efficient energy
TnUAD, and FChPT STU, Trenčín, transfer between both ions. No UC emissions are observed in Tm3+ single-doped
Slovakia
glass and GCs. Yb3+ incorporation favors the Tm3+-Tm3+ UC processes resulting
Correspondence in Tm3+ blue, yellowish-red and NIR UC emissions after excitation at 975 nm.
Jose J. Velázquez, FunGlass, Alexander Blue UC emission is also observed in the codoped samples after Tm3+ excitation
Dubček University of Trenčín,
Študentská 2, 911 50 Trenčín, Slovakia.
at 791 nm. These effects were more evident for the GCs compared to the base
Email: jose.velazquez@tnuni.sk glasses, confirming the RE ions incorporation in the NCs. As a result, these GCs
can be used to tune the UC emission from NIR to blue by selective excitation.
Funding information
Euskal Herriko Unibertsitatea,
KEYWORDS
Grant/Award Number: GIU17/014;
European Regional Development Fund, crystallization, glass ceramics, glass manufacturing, optical properties, photo luminescence,
Grant/Award Number: 313011R453 processing, secondary
and 313011W442; Ministerio de
Economía y Competitividad, Grant/
Award Number: MAT2017-87035-
C2-1-P/-2-P; the European Union´s
Horizon 2020 research and innovation
programme, Grant/Award Number:
739566; Gobierno del Pais Vasco, Eusko
Jaurlaritza, Grant/Award Number:
PIBA2018-24
This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any
medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.
© 2021 The Authors. International Journal of Applied Glass Science published by American Ceramics Society and Wiley Periodicals LLC
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2
486 2 LIŠKA
VELÁZQUEZ
VELÁZQUEZ et al..AL.
et ET
al
| I N T RO
1 niobyl(3+) DU
cation CT
(NbO3+
ION
), which enters deformed polyhe- 2.3 | previous
In our Multivariate
works,curve
28–30 resolution
sodium lutetium fluo-
dra (octahedra, tetragonal pyramids) with a coordination- ride glass-ceramics doped with ErF3 and codoped with
16,17
Thecovalent
search bond for newto oxygen.
and more developed luminescent ErFThe multivariate curve resolution (MCR) method19,26-28 de-
3-YbF3 were studied in detail from a structural and
systems is still a challenge due to the wide range of composes
optical the set ofand
perspective experimental
for their Raman spectra
suitable use inin the spec-
optical
optical applications that requires higher efficiencies, tra of Transparent
fibers. pseudo pure components
GCs based(called
on a loadings) and relative
cubic solid solu-
such2 as| plasma
METHOD display panels; white light-emitting di- abundances
tion NaxLu2x−1 ofFthese components (called scores). It is essen-
7x−3 were successfully synthesized and
odes; fluorescent lamps, optical biosensors or biological tial to emphasize
the incorporation of RE that MCR3+ does not use any data of the sys-
ions was confirmed by XRD
2.1 |andThermodynamic
markers, laser cooling of solids. model 1–6of
Between these and energy dispersive X-ray result
tem composition. The MCR must be compared
spectroscopy (EDX).28 with
In
Shakhmatkin
systems, rare-earthand (RE)-Vedishcheva
doped nanostructured oxy- thethepresent
result ofwork,
Malfaitthe
's spectra decomposition
crystallization based on the
mechanism, TD
and
fluoride glass-ceramics (OxGCs) are very interesting model.
structural and optical properties of Tm -doped and 3+
Especially
materials dueintothethe field of oxide glasses,
combination of thethelow thermodynamic
phonon- Tm3+–Yb3+ co-doped GCs are reported from the same
model of Shakhmatkin
energy (300-400cm ) fluoride −1 and Vedishcheva
nanocrystals has been successfully
(NCs), with base glass composition, 70SiO2–5Al2O3–2AlF3–2Na2O–
applied in previous years. 1-9
the mechanical, thermal, and chemical properties The SVTDM model considers
of 3 | 3Lu
18NaF– E XP E RIM E NTAL PA RT
2O3 (mol%). Particular attention is paid to
glasses and melts
7,8 to be an ideal solution
oxide glasses. Moreover, the controlled crystallization formed by salt prod- the effect of co-doping and RE3+-ion concentration on
ucts of equilibrium
mechanism chemicalNCs
allows obtaining reactions
withof simple
sizes up starting
to 50 nm sub- theRaman spectra were
crystallization measured
kinetics and UC at room
and NIRtemperature
emissions. using
stances, e.g. oxides, halides, etc. These salt-like products have a confocal microscope (LabRam HR, Horiba Jobin–Yvon)
in which the RE ions are incorporated, dismissing the
the identical stoichiometry as the crystalline compounds that with backscattering geometry and 532 nm excitation line of
Rayleigh scattering and maintaining the transparency.9
exist in the phase diagram of the system under consideration.
Glass-ceramics based on LaF3, YF3, and RLnF4
The model does not use any adjustable parameters. Only the
| EXlaser.
2 Nd:YAG For correction of the temperature dependent
PERIMENTAL PROCED U RE
population of phonon levels, the intensities of Raman spectra
(R = K, Na)10–13 phases have been described as efficient
molar Gibbs energies of pure crystalline phases and the ana- were reduced using the Gammon–Shuker relation 29:
luminescent materials. In particular, sodium lanthanide Glasses with the composition 70SiO 2– 5Al 2O 3– 2AlF 3–
lytical composition of the considered system are used as input
tetrafluorides, with the general formula NaLnF4, (with 2Na 2O–red 18NaF– 3Lu 2O 3 −(mol%) doped with xTmF ,
parameters. The minimization of the system's Gibbs energy I ( 𝜈𝜈 ) = ( 𝜈𝜈 0 − 𝜈𝜈 ) 4 𝜈𝜈 [ 1 − exp. ( − h𝜈𝜈∕kT) ] I( 𝜈𝜈 ) 3(1)
Ln = Gd, Y, La, or Lu) have been reported to be ideal x = 0.1, 0.5 and codoped with yYbF 3, y = 0, 1, and 2
has to be performed with respect to the molar amount of each
hosts for RE3+ ions that can act as emitting centers and (mol%) have been prepared by the melting- quenching
system species constrained by the overall system composition where 𝜈𝜈 and 𝜈𝜈 are the frequency of excitation light and the
have been widely studied.14–17 method. 0This composition was based on a previous
to reach the equilibrium system composition.18,19 The present- Raman shift respectively. T is the thermodynamic temperature,
NaLuF4 exhibits two possible crystalline phases, study of the research group. 30 The raw materials on
day databases of thermodynamic properties comprising the k is the Boltzmann constant, and I(ω) is the measured Raman
cubic (α) and hexagonal (β), and it is an exceptional reagent grade were SiO 2 sand (Saint- Gobain, 99.6%),
molar Gibbs energies of various species (e.g. the FACT data- intensity. More details can be found in.16,17 Raman spectra were
converter host for RE3+ ions.18,19 Nevertheless, the num- Al 2O 3 (Panreac), Na 2CO 3 (Panreac, 99.5%), NaF
base20,21) enable the routine construction of the Shakhmatkin multiplied by a constant, thus the maximum value of spectral
ber and
of publications
Vedishcheva model regardingfor many NaLuF 4 GCs multicomponent
significant obtained by (Panreac, 99.95%),
intensity equals to one. Lu 2O 3 (Alfa Aesar, 99.9%), AlF 3
melting- quenching is relatively scarce
glass systems. However, in many cases, mainly of mainly due tosilicate
non- the (Alfa Aesar, 99.9%), TmF 3 (Aldrich, 99.99%), and YbF 3
difficulty to obtain the
multicomponent glassdesired
systems, crystalline
the needed phase with the
thermodynamic (Alfa Aesar, 99.999%). The raw materials were mixed
20,21
proper degree of crystallization.
data are not found in any contemporary thermodynamic GCs from the baseda-
| REmixer
in 4a Turbula SU LT for
S 3ANDh. TheD batches of 100 g. were
ISC USSION
composition 70SiO
tabase. In our previous 2 – 8.5B
work,O
2 3 – 9.5Na
6,22 CO
we proposed
2 3 – 6NaF- 6LuF
a method 3for calcined at 1250°C for 0.5 h and melted at 1650°C for
(mol%) wereestimates
obtaining developed by Chen
of missing et al.22 In this
thermodynamic work, by
parameters 1 hOninthe a Pt
basiscrucible cm 3 in volume
with 125structural
of experimental data16,17 ten covered
system
visible UC luminescence
reproducing the structuralwas obtained after excitation
information. with a Pt capwere
components andconsidered
then quenched on Nb
in the ZnO- a brass mold.
2 5 2 5 ther-
O - P O
at 980 nm of Yb3+ ions and subsequent energy transfer The melting process was repeated
modynamic model of Shakhmatkin and Vedishcheva twice to improve– ZnO
to Er3+ or Tm3+. The UC luminescence intensity of the the(Z),
glass homogeneity. The glasses were
Nb2O5 (Nb), P2O5 (P), ZnP4O11 (ZP2), Zn(PO3)2 (ZP), annealed at
GCs2.2 | Decomposition
increase around 10000 and of2000
Raman times,spectra
respectively,
based 580°C for 30 min to remove residual
Zn2P2O7 (Z2P), Zn3(PO4)2 (Z3P), NbO(PO3)3 (1/2NbP3), stresses. From
compared
on glass to composition
the corresponding fromglass. Kück et al.23 de-
TD model now(NbO)on,4(Pthe obtained glass samples will be labelled
2O7)3 (Nb2P3), and NbOPO4 (1/2NbP). The equi-
scribed the optical properties of the Pr3+-doped pure as librium
G0.1Tm, molar G0.5Tm,
amountsG0.5Tm-of SVTDM 1Yb,system
and G0.5Tm-
components 2Yb,re-
3+ 3+
Na7The
Lu13F 46 crystalline
method of numerical phaseanalysis
and concluded
of Raman that thatwas
spectra forcalculated
0.1, 0.5 for TmxNb and 1, and 2 Yb concentrations
2O5·50ZnO·(50-x)P2O5, (x = 0, 1, 3, 5, 7,
system is suitable for use in cascade-
suggested by Malfait and his collaborators. emitting23-25phosphors
The basic as- (in10mol%), respectively;
, 12) glasses from thecorresponding
results of structuralglass- ceramics
analysis pub-
for Xe discharge
sumption lamps.
of this method is that the Raman spectra are the will be denoted
lished in 16,17
are as GC. Glassin specimens
summarized Table 1 togetherwerewith heat-the
From
sum of thethe different
partial RE Raman Tm3+ ions
ions,spectra exhibitby
(generated interest-
the indi- treated at 600°C
structural groupingsfor 20 h, usingby
represented a heating rate(i.e.
the Qn units of 10°C/
tetrahe-
ing vidual
characteristics
structuralthat in conjunction
elements) multipliedwith by the Yb3+ ions of
theabundance mindron toPO get the ncorresponding
4 with bridging oxygen GCs. atoms)To of perform
consideredthe sys-
make them
these suitable
structural candidates
elements. The for laser
series of operation
Raman spectra at 0.8ob- optical characterization,
tem components. polished glass sheets (1cm
24–26 3+
andtained
1.5 μm. TheofTm
for a series glassesionswithhave three compositions
different metastable ex- span x 1cmThe and thickness
molar amountsofreported2 mm)inheat- Tabletreated at 600°C
1 correspond to lit-
1
cited
a linear D2, 1space
levels,vector G4, and with3
Ha4 dimension
that allows the by
given emission
a numberin of during
tle bit20 h wereglass
changed selected. One polished
composition sheet ofwith
when compared basethe
the independent
blue, red, and infraredelements
structural regions after pumping.elements
(i.e. structural Anotherthat glass of each
prescribed one,composition and with-x)P2O5
i.e. xNb2O5·50ZnO·(50 the same, (x =shape
0, 1, 3,
independently
characteristic change
is that their relative
the emission the 3H4 level
fromabundance) with
to differ-
the was5, also
7, 10,used
12). This actual glass composition
for comparison is given in Table
with the corresponding
ground state coincides with the window of the silica fibers is
ent partial Raman spectra (PRS). Each measured spectrum 2 together
glass- ceramics. with the glass transition temperature.
nearrecorded
0.8 μm. with any scale,many
Moreover, i.e. it isdifferent
known exceptenergy fortransfer
the size of The The molar Gibbs
thermal energies
properties ofoftheZ, Nb, P, and glasses
obtained Z3P were taken
(glass
20,21
a multiplication
channels are possible between Yb3+ – Tm3+ due to the ex-
factor. from the temperature
transition FACT database. The unknown
(Tg), softening point molar
(Td), Gibbs
and
istence of significant resonance energy levels.27 thermal expansion coefficient (α)) were determined by
| |4873
VELÁZQUEZ
VELÁZQUEZet
etal.
al. 2
dilatometry. The dilatometric analysis was carried out microscope operating at niobyl(3+)
200 kV cation (NbO3+), which
and providing a pointenters deform
using a Netzsch Gerätebau dilatometer, model 402 PC/1 resolution of 0.19 nm. The TEM was equipped with an with a co
dra (octahedra, tetragonal pyramids)
16,17
with a heating rate of 5°C /min in the air; the estimated EDXS energy dispersivecovalent bond to oxygen.
X-ray spectrometer (INCA x-sight,
error of Tg is ±2°C. The thermal expansion coefficient was Oxford Instruments). EDX analysis was performed in
determined in the range 100°C–450°C. STEM mode, with a probe size of ca. 1 nm. Samples were
The chemical composition of the glass samples, fo- prepared by dispersing the 2 fine | M E T HOD
powder in ethanol with ul-
cussing on the Fluorine content, was analyzed by X-ray trasonic agitation; a droplet of the suspension was put on a
fluorescence spectroscopy (XRF) using a PANalytical copper holey carbon grid. 2.1 | Thermodynamic model of
spectrometer. All oxides were determined employing the Shakhmatkin
Conventional transmission spectra and wereVedishcheva
performed
melting method with Li2B4O7, whereas elemental fluorine with a Cary 5 spectrophotometer. The steady-state emis-
analysis was performed on pressed pellets of powdered sion measurements were Especially
made within theafield of oxide ring
Ti-sapphire glasses, the ther
glass (63 μm, 0.3 g) in order to avoid fluorine volatilization. −1 model of Shakhmatkin
laser (0.4 cm linewidth) as exciting light. The and Vedishcheva
fluores- has been s
1-9
Sieved glass-ceramic powders with the particle size applied in previous
cence was analyzed with a 0.25 monochromator, years. Theand SVTDM mode
<63 μm were used for both XRD and TEM analysis. XRD the signal was detectedglasses by anand melts to IR
extended be an ideal solution formed b
Hamamatsu
measurements have been performed with an X-ray dif- ucts of equilibrium
H10330A-75 photomultiplier and finally amplified chemical reactionsby of simple s
stances, e.g. oxides, halides, etc. These salt-like pr
fractometer D8 ADVANCE (Bruker) equipped with a Lynx a standard lock-in technique. Visible emission was
the identical stoichiometry as the crystalline com
Eye detector. The patterns were collected with monochro- detected by a Hamamatsu R636 photomultiplier. All
exist in the phase diagram of the system under co
matic CuKα1 radiation (λ = 1.54056 Å). Diffractograms measurements were performed at room temperature.
The model does not use any adjustable paramete
were collected in the range in the 10 ≤ 2θ ≤ 70° using a Accuracy of emission measurements is between 3% and
molar Gibbs energies of pure crystalline phases a
step size of 0.02 ° and 1 s. the acquisition time for each 5% depending on the experimental conditions.
lytical composition of the considered system are u
step. This technique was used to achieve two objectives;
parameters. The minimization of the system's G
determination of the crystalline phase and estimation of
has to be performed with respect to the molar amo
the crystal size. For crystalline phases determination, the 3 | RESULTS AND DISCUSSIO N
system species constrained by the overall system c
EVADiffractPLUS software was used meanwhile mean
to reach the equilibrium system composition.18,19 T
crystal sizes were resolved from the Scherrer equation 3.1 | Thermal, XRD, and HRTEM
day databases of thermodynamic properties com
with the corresponding errors.31 analysis molar Gibbs energies of various species (e.g. the
base20,21) enable the routine construction of the S
0.94 ⋅ 𝜆 Transparent glasses were and obtained
Vedishcheva after melting
model for manyfor the
significant mult
∅= ,
√ (1) different dopant concentrations. As expected, the corre-
2
cos𝜃 𝛽 − 𝛽 i 2 glass systems. However, in many cases, mainly of
sponding XRD patternsmulticomponent
(not shown) did glassnot reveal the
systems, theneeded ther
presence of any crystalline phase. Thermal properties
data are not found in any contemporary thermod
where θ is the angle of the diffraction maximum, β its were characterized by tabase.
dilatometric analysis work,
In our previous and results
6,22
we proposed a
full width at half maximum (FWHM), βi the instrumen- are shown in Table 1. Tobtaining
g does not show any constant
estimates of missing thermodynamicin- pa
tal broadening and λ is the wavelength. The θ and β pa- creasing tendency withreproducing
the dopant the content, but information.
structural the doped
rameters were obtained by fitting the most intense peaks and codoped samples present Tg values ranging from
to pseudo-Voigt functions. 566°C to 589°C.
High-resolution transmission electron microscopy At the same time, the | Decomposition
2.2 thermal expansion coefficient of Raman spect
−1
(HR-TEM), including scanning transmission microscopy- (α) has the same valueon as glass
in the composition
undoped glass,from 7.9°CTD , model
−1
high angle annular dark field (STEM-HAADF) and X-ray decreasing for the codoped glasses down to 7.3°C with
3+
energy dispersive spectroscopy (EDXS), were recorded the increasing amountThe of Yb method ions. Similar behaviour
of numerical analysis of Raman s
on a JEOL 2100 field emission gun transmission electron was found by the authors for the same
suggested by Malfait composition but
and his collaborators. 23-25
T
sumption of this method is that the Raman spe
sum of the partial Raman spectra (generated b
T A B L E 1 Fluorine loss (%), Glass transition temperature (Tg), softening point temperature (Td) and thermal expansion coefficient (α) of
vidual structural elements) multiplied by the ab
undoped and doped glasses. Mean NCs size and thermal expansion coefficient (α) of corresponding GCs
these structural elements. The series of Raman
F loss α 10−6 (°C−1) tained NCs
for asize
series of αglasses
10−6 (°Cwith−1
) different compo
Glass (%) ±0.5 Tg (°C) ±2 Td (°C) ±5 GCs a linear(nm)vector
±1 space±0.5 with a dimension given by a
Undoped 48 7.9 579 663 Undoped independent9 structural8.6elements (i.e. structural el
G0.1Tm 42 7.9 583 664 GC0.1Tm
independently
12
change 8.2
their relative abundance)
ent partial Raman spectra (PRS). Each measured
G0.5Tm 45 7.9 566 648 GC0.5Tm 15 8.6
recorded with any scale, i.e. it is known except fo
G0.5Tm−1Yb 42 7.6 589 685 GC0.5Tm−1Yb 27 7.9
a multiplication factor.
G0.5Tm−2Yb 52 7.3 572 673 GC0.5Tm−2Yb 30 9.0
| |
4
488 2 LIŠKA
VELÁZQUEZ
et ET
al
niobyl(3+) cation (NbO3+), which enters deformed polyhe- 2.3 | Multivariate curve resolution
dra (octahedra, tetragonal pyramids) with a coordination-
covalent bond to oxygen.16,17 The multivariate curve resolution (MCR) method19,26-28 de-
composes the set of experimental Raman spectra in the spec-
tra of pseudo pure components (called loadings) and relative
2 | METHOD abundances of these components (called scores). It is essen-
tial to emphasize that MCR does not use any data of the sys-
2.1 | Thermodynamic model of tem composition. The MCR result must be compared with
Shakhmatkin and Vedishcheva the result of Malfait's spectra decomposition based on the TD
model.
Especially in the field of oxide glasses, the thermodynamic
model of Shakhmatkin and Vedishcheva has been successfully
applied in previous years.1-9 The SVTDM model considers 3 | E XP E RIM E NTAL PA RT
glasses and melts to be an ideal solution formed by salt prod-
ucts of equilibrium chemical reactions of simple starting sub- Raman spectra were measured at room temperature using
the identical stoichiometry as the crystalline3+compounds that with backscattering 3+
geometry
3+
and 532 nm excitation line of
F I Gexist
U R Ein1the(A) XRDdiagram
phase patternsof forthe
undoped,
systemxTm under-doped (x = 0.1, 0.5 mol%)
consideration. Nd:YAGand 0.5Tm –yYbcorrection
laser. For -codoped of (y =the1, temperature
2 mol%) GCs.dependent
(B) Magnified regions of (111) peak of the corresponding GCs
The model does not use any adjustable parameters. Only the population of phonon levels, the intensities of Raman spectra
doped and codoped with Er3+ and Yb3+ ions.28 Moreover, magnified region correspondings to the (111) crystallo-
parameters. The minimization of the system's Gibbs energy Ired ( 𝜈𝜈 ) = ( 𝜈𝜈 0 − 𝜈𝜈 ) − 4 𝜈𝜈 [ 1 − exp. ( − h𝜈𝜈∕kT) ] I( 𝜈𝜈 ) (1)
Sroda, Gorni and de Pablos-Martin et al. also observed a graphic plane, Figure 1B, shows a constant shift towards
similar effect in different oxyfluoride glasses.16,32,33 The lower angles with the increasing content of RE3+ dopant
system species constrained by the overall system composition where 𝜈𝜈 0 and 𝜈𝜈 are the frequency of excitation light and the
thermal expansion coefficient of GCs samples 18,19 was also ions, mainly due to incorporation of the larger Tm3+ (ionic
to reach the equilibrium system composition. The present- Raman shift respectively. T is the thermodynamic temperature,
measured and the values are shown in Table 1. In general, radius, rion = 0.88 Å) and Yb3+ ions (rion = 0.87 Å) that
all GCs show higher values than the glass samples but in substitute the Lu3+ (rion = 0.85 Å) increasing the unit cell
the range 20,21of error. This behavior is opposite to that ob- volume associated to the cubic phase.
base ) enable the routine construction of the Shakhmatkin multiplied by a constant, thus the maximum value of spectral
served
and by Reben and
Vedishcheva Środa
model forinmany
PbF2significant
NCs glass, where the
multicomponent Table 1 equals
intensity also showsto one.the mean size of NCs calculated by
addition of fluorine decreased the thermal
glass systems. However, in many cases, mainly of 34 expansion co-
non-silicate using the Scherrer equation. The increasing dopant con-
efficient and weakened
multicomponent glassthe structure
systems, the ofneeded
the glass. In our
thermodynamic tent results in increasing size, varying from 9 to 30 nm. In
case,data are not found in any contemporary thermodynamic da- this
it seems that the amount of fluorine incorporation
| the
4 case, REdopant
SU LTcontent S AND plays D aISCnotable
USSION
36,37
role in crys-
in the structure due to
tabase. In our previous work,the addition6,22 of dopant is not suffi-
we proposed a method for tal growth as observed for other GCs. The increasing
cient to affect the structure of the glassy phase
obtaining estimates of missing thermodynamic parameters by in the GCs. NCs size is also related to the
On the basis of experimental structural data close relationship
16,17 between
ten system
Table 1 also the
reproducing presents the information.
structural estimated F loss of each glass thecomponents
crystallization activation in
were considered energy
the ZnO- andNbdoping level.
2 5 P2O5 ther-
O -
obtained from the chemical analysis of the corresponding Crystallization activation energy
modynamic model of Shakhmatkin and Vedishcheva – ZnOdecreases with the in-
38
glasses. From these results, the fluorine loss varies be- creasing doping level. Thus, samples
(Z), Nb2O5 (Nb), P2O5 (P), ZnP4O11 (ZP2), Zn(PO3)2 (ZP), with higher dopant
tween2.242 |andDecomposition
52 wt%. The chemical of Raman analysis of the other
spectra based concentration
Zn2P2O7 (Z2P), are more
Zn3(PO susceptible to crystallize.
4)2 (Z3P), NbO(PO3)3 (1/2NbP3),
components
on glass(not shown) displays
composition fromvalues TD modelroughly in agree- HRTEM
(NbO) together with EDX techniques were used to
4(P2O7)3 (Nb2P3), and NbOPO4 (1/2NbP). The equi-
ment with the nominal ones. These values indicate that look deeply
librium molarintoamounts
the nanostructure
of SVTDM system and dopants
components distri- re-
a high fluorine loss occurs during the
The method of numerical analysis of Raman spectra was melting process bution, see Figures 2 and 3. HRTEM micrographs
calculated for xNb2O5·50ZnO·(50-x)P2O5, (x = 0, 1, 3, 5, 7, of the
duesuggested
to the high by melting
Malfait andtemperatures
his collaborators.involved,
23-25 at around
The basic as- glasses, 10, 12)Figure
glasses2A,B,from the show the oftypical
results structuralwell- dispersed
analysis pub-
1650°C,
sumptionas is of
expected in these
this method compositions.
is that the Raman spectra are the phase- separated
lished in 16,17
are amorphous
summarized in droplets. These phase-
Table 1 together with the
Taking
sum of into accountRaman
the partial the effectspectraof the dopantby
(generated addition
the indi- separated
structuraldroplets
groupings arerepresented
the precursors by theofQthen NaLuF
units NCs
(i.e. 4tetrahe-
28–30,35 28
on the
vidualglass Tg andelements)
structural our previous results,
multiplied the heat of that
by the abundance will
dron POform
4 with after
n adequate
bridging oxygen heat treatment
atoms) of observed
considered sys-
treatment temperature and time were selected
these structural elements. The series of Raman spectra ob- as 600°C in Figure
tem components. 2C,D. Moreover, HRTEM micrographs of
during
tained20 for
h. Figure
a series1A shows the
of glasses withXRD patterns
different of the cor-
compositions span GC0.5Tm– The molar2Yb showamounts a broad
reported crystal distribution
in Table 1 correspond thattofits lit-
responding GCs samples.
a linear vector space with The results for given
a dimension the different
by a numberdop- of well tlewith a pseudo-
bit changed Voight
glass function centered
composition at 13 nmwith
when compared (inset the
ant independent
concentrations are almost
structural elementsidentical with the diffraction
(i.e. structural elements that Figure 2C), confirming
prescribed one, i.e. xNbthe results obtained
2O5·50ZnO·(50 -x)P2O5 by, (XRD
x = 0,dif- 1, 3,
independently
maxima that are change
assigned theirtorelative
sodiumabundance)
lutetium with differ- fraction.
fluoride 5, 7, 10It, 12 ). Thisbeactual
should notedglassthat composition is given inLaF
unlike the hexagonal Table3
33,39
cubicentsolid
partial Raman with
solution spectra (PRS). Each
a general measured
formula NaxLuspectrum
2x-1F7x-3 is oxyfluoride
2 together NCs, with the glass
cubic transition
NaLuF4temperature.
NCs form from each
recorded with
as previously reported in.28,30
any scale, i.e.The
it is peaks
knownbecomeexcept for the size of phase-The
narrower molar Gibbs
separated energies
droplet, this of is Z, Nb, P,behavior
typical and Z3P were taken
of alkali
20,21
andamore
multiplication
intense whenfactor. increasing dopant content indi- from the tetrafluoride
lanthanide FACT database. NCs.13,40,41 TheThe unknown
size of molar
the NCs Gibbsis
cating that the NCs growth is favoured. Moreover, the thus similar to the size of the precursor phase-separated
| |4895
VELÁZQUEZ
VELÁZQUEZet
etal.
al. 2
F I G U R E 2 (A) and (C) HRTEM

(A) (B) niobyl(3+) cation (NbO3+), which enters deform
micrograph of 0.5Tm3+ doped glass and
dra (octahedra, tetragonal pyramids) with a co
GC treated at 600°C-20 h; size distribution
covalent bond to oxygen.16,17
of the NCs is shown as insets in (C). (B)
Magnified image of phase separation
droplets. (D) HRTEM micrograph of
0.5Tm3+-doped GCs with corresponding 2 | M E T HOD
SAED image shown as an inset
2.1 | Thermodynamic model of
Shakhmatkin and Vedishcheva
Especially in the field of oxide glasses, the ther

model of Shakhmatkin and Vedishcheva has been s
applied in previous years.1-9 The SVTDM mode
(C) (D)
glasses and melts to be an ideal solution formed b
ucts of equilibrium chemical reactions of simple s
has to be performed with respect to the molar amo
molar Gibbs energies of various species (e.g. the
base20,21) enable the routine construction of the S
regions, and then they grow more with the adequate heat the spectra as a functionandofVedishcheva
wavelengthmodel for theforglass
manyand significant mult
treatment in temperature and time.28 Moreover, the Fast GC samples codoped glass withsystems.
0.5TmFHowever,
3- 1YbF (in
3 in many mol%).
cases, mainly of
Fourier Transformation (FFT) from HRTEM micrographs The spectra show the bands corresponding
multicomponent glass to the transi-
systems, the needed ther
3
revealed crystalline structures with interplanar distances tions starting from thedata H6 are
ground
not stateintoany
found thecontemporary
different thermod
of 0.31 nm, attributed to (111) planes of the sodium lute- higher levels 1D2, 1G4, 3tabase.
F2, 3F3In, 3H 3
4, previous
our H5, and work,3
F4 of6,22Tmwe3+
proposed a
tium fluoride cubic phase. together with the 2F7/2 → 2
F5/2 absorption
obtaining Yb3+. As
estimates ofofmissing can
thermodynamic pa
To further study, the elemental composition and the be seen, the samples arereproducing
transparent thewith a transmittance
structural information.
incorporation of the RE3+ ions in the NCs, EDX analy- as high as 91% and 89% for the glass and glass-ceramic,
sis in STEM mode was performed for the Tm3+-doped respectively. After the heat treatment, the absorption edge
and Tm3+-Yb3+ codoped GCs (Figure 3). This indicates 2.2 | Decomposition
is shifted to longer wavelengths in the GC sample. of This
Raman spect
the nanocrystals are Na- and Lu-rich, with the Tm3+ and red-shift has been attributed
on glass to composition
the scattering from of short-TD model
Yb3+ ions concentrated in the nanocrystals, similarly to wavelength light by the NCs present in the GC sample.43,44
previously observed for different fluoride NCs and RE3+ The spectra obtained for Thethemethod
glass and of glass- ceramic
numerical sam- of Raman s
analysis
dopants.14,16,42 The presence of the Tm3+ and Yb3+ ions in ples doped with 2 mol% YbF
suggested are similar, except for
3 by Malfait and his collaborators. the 23-25
T
3+
the NCs supports the results obtained by XRD patterns in double Yb band intensity.sumption of this method is that the Raman spe
which the diffraction maxima are shifted to lower angles, sum of the partial Raman spectra (generated b
suggesting the incorporation of the RE3+ ions in the crys- vidual structural elements) multiplied by the ab
tal structure of the NCs. 3.2.2 | NIR luminescence
tained for a series of glasses with different compo
The near-infrared emission
a linearin vector
the 900– space2200withnm spectral given by a
a dimension
3.2 | Optical properties range was obtained for independent
the single doped samples
structural elementsat room
(i.e. structural el
temperature by excitingindependently
at 791 nm inchange their with
resonance relative
theabundance)
3.2.1 | Transmission spectra 3 3+
H4 (Tm ) level. The codoped samples were also excited measured
ent partial Raman
2
spectra
2
(PRS). Each
at 975 nm in resonancerecorded
with thewith F7/2any→scale,F5/2i.e. it is known except fo
absorption
3+ a multiplication factor.
The transmission spectra were obtained for all samples in of Yb . This wavelength corresponds to the maximum ab-
the 300–2000 nm range. As an example, Figure 4 shows sorption of Yb3+ ions in these matrices. The fluorescence
| |
6
490 2 LIŠKA
VELÁZQUEZ
et ET
al
niobyl(3+)
(A) cation (NbO3+), which enters deformed polyhe-
(B) 2.3 | Multivariate curve resolution
model.
the identical stoichiometry as the crystalline compounds that with backscattering geometry and 532 nm excitation line of
exist in the phase diagram of the system under consideration. Nd:YAG laser. For correction of the temperature dependent
(C)molar Gibbs energies of pure crystalline phases and the ana- (D) were reduced using the Gammon–Shuker relation 29:
to reach the equilibrium system composition.18,19 The present- Raman shift respectively. T is the thermodynamic temperature,
base20,21) enable the routine construction of the Shakhmatkin multiplied by a constant, thus the maximum value of spectral
and Vedishcheva model for many significant multicomponent intensity equals to one.
glass systems. However, in many cases, mainly of non-silicate
multicomponent glass systems, the needed thermodynamic
data are not found in any contemporary thermodynamic da- 4 | RE SU LT S AND D ISC USSION
tabase. In our previous work,6,22 we proposed a method for
obtaining estimates of missing thermodynamic parameters by On the basis of experimental structural data16,17 ten system
reproducing the structural information. components were considered in the ZnO-Nb2O5-P2O5 ther-
modynamic model of Shakhmatkin and Vedishcheva – ZnO
(Z), Nb2O5 (Nb), P2O5 (P), ZnP4O11 (ZP2), Zn(PO3)2 (ZP),
2.2 | Decomposition of Raman spectra based Zn2P2O7 (Z2P), Zn3(PO4)2 (Z3P), NbO(PO3)3 (1/2NbP3),
on glass composition from TD model (NbO)4(P2O7)3 (Nb2P3), and NbOPO4 (1/2NbP). The equi-
librium molar amounts of SVTDM system components re-
F I G U R E 3 (A) and (C) STEM image of NaLuF4 NCs in GC0.5Tm3+ and GC0.5Tm3+–2Yb3+. (B) and (D) EDX of a line scan crossing
sameTheaLuFmethod of numerical
4 NCs in GC0.5Tm
3+
andanalysis
GC0.5Tm of3+–Raman
2Yb3+ spectra was calculated for xNb2O5·50ZnO·(50-x)P2O5, (x = 0, 1, 3, 5, 7,
suggested by Malfait and his collaborators.23-25 The basic as- 10, 12) glasses from the results of structural analysis pub-
sumption of this method is that the Raman spectra are the lished in16,17 are summarized in Table 1 together with the
spectra
sum corresponding to the single
of the partial Raman spectradoped samples
(generated by doped
the indi- with increasing
structural Tm3+ represented
groupings concentration as is
by the Qnshown in Figure
units (i.e. tetrahe-
3+
withvidual
0.1 and 0.5Tmelements)
structural (in mol%) are shown
multiplied by theinabundance
Figure 5. of 5. This
dron reduction
PO4 with ninbridging
the intensity
oxygenofatoms)
the 1450 nm emission
of considered sys-
Thethese
spectra show a strong emission band centered
structural elements. The series of Raman spectra ob- around with concentration
tem components. has been attributed to cross- relaxation
3
1650tained
nm which corresponds
for a series of glassestowith F4 → 3Hcompositions
the different 6 transition to-span between The3molar
H4 → 3amounts
F4 and 3F 3
4 → H6in
reported transitions that enhance
Table 1 correspond to lit-
45,46
gether withvector
a linear a less space
intensewithemission
a dimension bandgivencentered
by a around
number of thetlelatter.
bit changed glass composition when compared with the
3 3
1450independent
nm and corresponding
structural elements to the (i.e. Hstructural
4 → F4 transition.
elements that The emission
prescribed one, spectra
i.e. xNb2ofO5the codoped-x)P2O5
·50ZnO·(50 samples , (xobtained
= 0, 1, 3,
3 3
Theindependently
long-wavelength changetailtheir
of therelative
F4 →abundance)
H6 emission with
is differ-
not 5, 7, the
under 10, 12 ). This
same actual glass composition
experimental conditions is bygiven in Table
exciting at
3+
ent partial Raman spectra (PRS). Each
completely observed due to the upper limit of the detec- measured spectrum is 2 together with the glass transition temperature.
791 nm show, in addition to the Tm emissions around
tor. recorded
Similar with anyare
spectra scale, i.e. it is known
obtained for theexcept for the
glass and size of 1450 The
glass- andmolar
1650Gibbs the Yb3+
nm, energies (2FNb,
of Z, 5/2 P,
→and 2
Z3P
F7/2 were taken
) emission
20,21 3+
a multiplication
ceramic samples, but factor.
the ratio of the emission intensity of from 1000
around the FACT
nm. Thedatabase.
presence of The
theunknown
Yb emission molar after
Gibbs
the transition 3H4 → 3F4 to that of the 3F4 → 3H6 decreases excitation of Tm3+ ions confirms the energy transfer from
| |4917
VELÁZQUEZ
VELÁZQUEZet
etal.
al. 2
niobyl(3+)
Moreover, the presence of energycation (NbO3+from
transfer ), whichYb3+enters deform
to Tm3+ is demonstrateddra by(octahedra, the 3F4 with a co
tetragonalofpyramids)
the observation
3 3+ 16,17
covalent bond to oxygen.
→ H6 Tm emission after excitation at 975 nm in res-
onance with the Yb3+ absorption at 975 nm, as shown
in Figure 7. This figure shows the spectra of the glass
2 | codoped
and glass-ceramic samples M E T with
HOD 1 and 2 mol%
3+
of Yb . As can be seen, the emission intensity for the
co-doped samples with2.1 2 mol% | Thermodynamic
of Yb3+ is around twice model of
Shakhmatkin
those of the samples with 1 mol%. Moreover, and Vedishcheva
compared
3+
to the emission obtained under Tm excitation at
Especially
791 nm, the intensity of the 3F4 → in 3the
H6 field of oxide
increases glasses, the ther
around
model 3+of Shakhmatkin and
four times when exciting Yb ions. This is in agreement Vedishcheva has been s
1-9
applied in previous years.
with the high absorption cross-section of Yb at 975 nm3+ The SVTDM mode
glasses
if compared with the one of Tmand3+melts
at 791to benm.
an ideal
The solution
2
F5/2 formed b
F I G U R E 4 Transmission spectra for glass and glass-ceramic (Yb )→ H5(Tm ) energy transfer followed by nonradi- of simple s
3+ 3 3+ ucts of equilibrium chemical reactions
(GC) samples codoped with 0.5 mol% Tm3+and 1 mol% Yb3+ stances,3 e.g. oxides, halides, etc. These salt-like pr
ative processes populate the F4 emitting level.
Tm3+ to Yb3+ ions. As an example, Figure 6 displays the 3.2.3 | NIR to visible up-conversion (UC)
emission spectra for the codoped samples with 0.5Tm-
1Yb. After excitation of level 3H4, the energy transfer to Up-conversion (UC) emission from Tm3+ ions in the co-
the 2F5/2 state of Yb3+ ions occurs. Although the 3H4 and doped samples has been observed at room temperature
3 has to be performed with respect to the molar amo
H5 levels of Tm3+ are located at higher and lower ener- after 975 nm excitation. The UC emission spectra show
gies respectively, a non-resonant phonon-assisted energy bands at 478, 651, 700, and 800 nm corresponding to the
transfer (PAET) between both ions takes place.47,48 1
G4 → 3H6, 1G4 → 3F4, 3F2,3 → 3H6, and 3H4 → 3H6 transi-
The NIR luminescence intensities of the Tm3+ emis- tions of Tm3+ ions respectively.
sions measured under 791 nm (Tm3+) excitation, in the Figure 8 shows that the20,21
increase in the UC intensity
base ) enable the routine construction of the S
single and codoped samples with 1 mol% of Yb3+ (Figures in the GCs with respect to those obtained
and Vedishcheva modelin forthe
many glass.
significant mult
5B and 6) are quite similar for the 3F4→3H6 transition and However, this increment is not as big as expected. Thus,
glass systems. However, in many cases, mainly of
nearly independent of the presence of Yb3+. However, the the small increase in the UC emission
multicomponent intensity
glass systems, in the
theneeded ther
intensity of the 3H4→3F4 transition slightly decreases with GCs, if compared with data
the untreated glass deserves a par-
are not found in any contemporary thermod
the addition of Yb3+ ions probably due to the Tm3+→Yb3+ ticular comment. It looks like that
tabase. after
In our the heat
previous treatment
work, 6,22
we proposed a
energy transfer. Once the 3H4 level is populated by the ab- the fraction of RE3+ ions in the amorphous and crystal-
obtaining estimates of missing thermodynamic pa
sorption of 791 nm photons, energy is transferred to the line phases could change if compare
reproducing with those
the structural of the
information.
2
F5 state of Yb3+. precursor glass. In particular, the presence of Yb3+ ions
2.2 | Decomposition of Raman spect

on glass composition from TD model
The method of numerical analysis of Raman s

suggested by Malfait and his collaborators.23-25 T
sumption of this method is that the Raman spe
sum of the partial Raman spectra (generated b
vidual structural elements) multiplied by the ab
a linear vector space with a dimension given by a
independent structural elements (i.e. structural el
independently change their relative abundance)
ent partial Raman spectra (PRS). Each measured
recorded with any scale, i.e. it is known except fo
a multiplication
F I G U R E 5 Room temperature emission spectra of Tm3+ ions in the single doped glass and GC samples doped withfactor.
(A) 0.1 and (B)
0.5 mol% Tm3+
| |
8
492 2 LIŠKA
VELÁZQUEZ
et ET
al
niobyl(3+) cation (NbO3+), which enters deformed polyhe- competing 2.3 | with Multivariate
Tm3+ ions curve resolution
in a finite crystalline volume
dra (octahedra, tetragonal pyramids) with a coordination- would reduce the density of the UC centers and, therefore,
covalent bond to oxygen.16,17 theThe
UCmultivariate
efficiency. curve resolution (MCR) method
19,26-28
de-
composes
Moreover, theincreasing
set of experimental
the Yb Raman3+
contentspectra
up toin2the spec-
mol%
tra not
does of pseudo
lead to pure
an components
increase in (calledthe totalloadings)
Tm3+ UC and relative
lumi-
2 | METHOD abundances
nescence. of these the
Moreover, components (called scores).
overall intensity It is This
is lower. essen-
tial to emphasize that MCR does
effect could be attributed to energy migration among not use any data of the sys-
2.1 | Thermodynamic model of tem
3+ composition. The MCR result must be compared with
Yb ions due to the higher concentration, to energy
Shakhmatkin and Vedishcheva the transfer
back result of Malfait
from Tm 's spectra
3+
to Yb decomposition
3+
and/or to based
energy ontrans-
the TD
model.
fer to quencher centers. 49
Especially in the field of oxide glasses, the thermodynamic The UC processes involved in the population of the rel-
model of Shakhmatkin and Vedishcheva has been successfully evant emitting states of Tm3+ ion are depicted in Figure
applied in previous years.1-9 The SVTDM model considers 9. 3 | EtheXP
Firstly, YbE 3+RIM E NTAL PA RT
ion at the ground state was excited to
glasses and melts to be an ideal solution formed by salt prod- the 2F state by absorbing one 975 nm photon and then
5/2
F I Gucts
U R of
E equilibrium chemical emission
6 Room temperature reactionsspectra
of simple
of Tm starting
3+
and sub- transferred
Raman spectra were measured
the energy to Tm3+ ions at room temperature
in the ground state using
3+stances, e.g. oxides, halides, etc. These salt-like products have a confocal microscope (LabRam HR, Horiba Jobin– Yvon)
Yb ions in the codoped glass and GC samples codoped with following the mechanism F5/2 → F7/2 (Yb ): H6 → 3H5
2 2 3+ 3
the
3+identical
3+ stoichiometry as the crystalline
0.5Tm -1Yb obtained under excitation at 791 nm compounds that with backscattering geometry and 532 nm excitation line of
(Tm3+) (ET1). The 3H5 level decays mainly non-radiatively
exist in the phase diagram of the system under consideration. Nd:YAG laser. For correction of the temperature dependent
populating the 3F4 (Tm3+) state. Then, a second energy
18,19
to reach the equilibrium system composition. The present- Raman shift respectively. T is the thermodynamic temperature,
20,21
base ) enable the routine construction of the Shakhmatkin multiplied by a constant, thus the maximum value of spectral
multicomponent glass systems, the needed thermodynamic
data are not found in any contemporary thermodynamic da- 4 | RE SU LT S AND D ISC USSION
tabase. In our previous work,6,22 we proposed a method for
obtaining estimates of missing thermodynamic parameters by On the basis of experimental structural data16,17 ten system
F I Greproducing
U R E 7 Room the structural information.
temperature components
emission spectra of Tm3+ ions in the glass and GC samples werecodoped
considered
with (A)in the ZnO-
0.5Tm 3+ Nb3+
-1Yb 2Oand
5-P2(B)
O5 ther-
3+ 3+
0.5Tm -2Yb obtained under excitation at 975 nm modynamic model of Shakhmatkin and Vedishcheva – ZnO
(Z), Nb2O5 (Nb), P2O5 (P), ZnP4O11 (ZP2), Zn(PO3)2 (ZP),
2.2 | Decomposition of Raman spectra based Zn2P2O7 (Z2P), Zn3(PO4)2 (Z3P), NbO(PO3)3 (1/2NbP3),
on glass composition from TD model (NbO)4(P2O7)3 (Nb2P3), and NbOPO4 (1/2NbP). The equi-
librium molar amounts of SVTDM system components re-
The method of numerical analysis of Raman spectra was calculated for xNb2O5·50ZnO·(50-x)P2O5, (x = 0, 1, 3, 5, 7,
suggested by Malfait and his collaborators.23-25 The basic as- 10, 12) glasses from the results of structural analysis pub-
sumption of this method is that the Raman spectra are the lished in16,17 are summarized in Table 1 together with the
sum of the partial Raman spectra (generated by the indi- structural groupings represented by the Qn units (i.e. tetrahe-
vidual structural elements) multiplied by the abundance of dron PO4 with n bridging oxygen atoms) of considered sys-
these structural elements. The series of Raman spectra ob- tem components.
tained for a series of glasses with different compositions span The molar amounts reported in Table 1 correspond to lit-
a linear vector space with a dimension given by a number of tle bit changed glass composition when compared with the
independent structural elements (i.e. structural elements that prescribed one, i.e. xNb2O5·50ZnO·(50-x)P2O5, (x = 0, 1, 3,
independently change their relative abundance) with differ- 5, 7, 10, 12). This actual glass composition is given in Table
ent partial Raman spectra (PRS). Each measured spectrum is 2 together with the glass transition temperature.
recorded with any scale, i.e. it is known except for the size of The molar Gibbs energies of Z, Nb, P, and Z3P were taken
20,21
F I GaUmultiplication
R E 8 Room factor.
temperature UC emission spectra obtained under 975from the FACT
nm excitation database.
for glass (blue line) andTheGC unknown
(red line)molar
samplesGibbs
codoped with 1 (A) and 2 (B) Yb3+
| |4939
VELÁZQUEZ
VELÁZQUEZet
etal.
al. 2
niobyl(3+)
To obtain information about thecation (NbO3+
processes ), whichinenters deform
involved
dra (octahedra, tetragonal pyramids) with a co
the UC emission after 975 nm excitation, the UC emission
16,17
covalent bond to oxygen.
spectra have been obtained at different pump power den-
sities. The dependence of the UC emission on the pump
power density is related to the number of photons (n) in-
volved in the process and | M
2 gives E T HODabout the UC
information
mechanisms according to the relation
2.1 | Thermodynamic model of
IemShakhmatkin
∝ Ppump . and Vedishcheva
)n
(2)
(
Especially in the field of oxide glasses, the ther

Figure 10 shows themodel of Shakhmatkin
logarithmic plot ofand the1-Vedishcheva
UC
9
blue has been s
3 3 applied in previous
and NIR ( H4→ H6) emission intensities of the co-doped years. The SVTDM mode
GC sample with 0.5TmF glasses and melts to be an ideal solution formed b
3−1YbF3 (in mol%) as a func-
tion of the pump power laser density. chemical
ucts of equilibrium As can be reactions
seen of simple s
for the blue emission, the slope is 2.08 which indicates
that two photons are required to excite the electrons
to the 1G4 state. The slope in the case of the 3H4 → 3H6
transition is 1.58. However, it is clear from the energy
level diagram of Tm3+ ions (Figure 9) that two photons
are needed to populate this level and three photons are
needed to populate the 1G4 level. UC to the 3H4 level
F I G U R E 9 Energy level diagram of Yb3+ and Tm3+ ions has to be performed with respect to the molar amo
occurs via two successive energy transfers from Yb3+
together with the different energy transfer processes (ET) system species constrained by the overall system c
ions in the 2F5/2 excited state. An excited Yb3+ ion in the
responsible for the upconverted emissions after excitation at 2 to reach the equilibrium system composition.18,19 T
F5/2 state transfers its energy nonresonantly to a Tm3+
975 nm (Yb3+) day databases of thermodynamic properties com
ion in the ground state 3H6, exciting it to the 3H5 state
from where the 3F4 level 20,21 is populated (ET1 in Figure
base ) enable the routine construction of the S
10 9). A second Yb3+ ionand transfers
Vedishcheva its energy
model to
for the
many
3+
Tmsignificant mult
Integrated Intensity (arb. units)
3 3
ion promoting it fromglass the systems.
F4 to the F excited state
However, in many cases, mainly of
2,3
(ET2 in Figure 9) and then decays glass
multicomponent nonradiatively
systems, thetoneeded ther
the3H4 level. A third energy
data are transfer
not found in1 any an
step from excited
contemporary thermod
1 Slope: 1.58 Yb3+ ion can excite thetabase.
Tm3+In ionsour previous 4work,6,22(ET3
to the G level we proposed a
in Figure 9). The observedobtainingslopes in Figure
estimates 10 indicate
of missing thermodynamic pa
the presence of a saturation
reproducing effectthe which
structural reduces the
information.
0 experimental power dependence. The obtained power
Slope: 2.08 dependences represent the lower limit of the number of
| Decomposition of Raman spect
50,51
photons involved in the 2.2UC mechanisms.
This behavior, previously
on glass observed
composition in other from systems, TD model
0 has been attributed to the competition between the decay
100.0 1,000.0 rate of the intermediateThestates and the
method of UC rates. When
numerical analysis UC of Raman s
Power Density (W/cm2) dominates over linear decay for the depletion of the inter-
suggested by Malfait and his collaborators.23-25 T
mediate excited states, the slope of
sumption of the
thisluminescence
method is thatfrom the Raman spe
FIGURE 10 Logarithmic plot of the pump power dependence 52
the upper state n is almost
sumlinear.
of the partial Raman spectra (generated b
of the blue ( G4 → 3H6) and NIR (3H4 → 3H6) integrated emission
1
No UC emissions were vidual observed
structuralinelements)
the singlemultiplied
doped by the ab
intensities for the GC sample codoped with 0.5Tm3+-1Yb3+ samples excited at 791 and 975 nm. However,
these structural elements. The series UC of Raman
3+
emission of Tm ionstained is also forobserved
a series of in the codoped
glasses with different compo
glass and glass- ceramics samples
a linear vector withspace 1with anda dimension
2 mol% given by a
transfer process involving Yb3+ and Tm3+ ions can occur Yb3+ under 791 nm excitation
independent (see Figureelements
structural 11). This is structural el
(i.e.
through the mechanism 2F5/2 → 2F7/2 (Yb3+):3F4 → 3F2,3 independently
probably due to the reduction of change their relative
the interionic dis-abundance)
(Tm3+) (ET2). Subsequent multiphonon relaxation from tances between the Tm ent3+partial
ions Raman
in the spectra (PRS). Each
NCs favored by measured
level 3F2,3 populates the 3H4 state and a third energy trans- 3+
the presence of Yb recorded with any scale,
ions, increasing i.e. it is known except fo
the probability
fer upconversion process, 2F5/2 → 2F7/2 (Yb3+):3H4 → 1G4 of the Tm3+-Tm3+ energy a multiplication
transfer. The factor.
UC mechanism
(Tm3+) (ET3) populates the 1G4 state.46 of Tm3+-Yb3+ codoped samples is as follows. After
| |
10 2
494 LIŠKA
VELÁZQUEZ
et ET
al
model.
F I Gstances,
U R E 1e.g. oxides,
1 Room halides, etc.
temperature These salt-emission
upconversion like products have
spectra a under
obtained confocal microscope
791 nm excitation (LabRam
for the glassHR,
(blueHoriba
line) andJobin–
GC (redYvon)
3+
line)the identical
samples codopedstoichiometry as theYbcrystalline
with (A) 1 mol% mol% Yb3+. that
and (B) 2compounds The insetwith backscattering
in Figure 11B shows the geometry
pump powerand 532 nm excitation
dependence line of
of the blue
exist in the phase diagram of the system under consideration.
UC emission Nd:YAG laser. For correction of the temperature dependent
excitation of the ground state absorption at 791 nm, as confirmed by XRD and HRTEM. Shift to lower angles
a photon with this energy populates the 3H4 level and of XRD red maxima with respect to the undoped-based GCs
parameters. The minimization of the system 3+ 's Gibbs 3+ energy I ( 𝜈𝜈 ) = ( 𝜈𝜈 0 − 𝜈𝜈 ) − 4 𝜈𝜈 [ 1 − exp. 3+( − h𝜈𝜈∕kT) ] I( 𝜈𝜈 ) (1)
then the energy is transferred from Tm to Yb ions. indicate the incorporation of the Tm and Yb3+ ions in
This transfer is non-resonant with an energy mis- the NCs, also confirmed by STEM-EDX analysis. This is
match of about 1800 cm−1. The Yb3+ ions excited 18,19 to the also demonstrated by the luminescence results. Energy
2 to reach the equilibrium system composition. The present- Raman shift respectively. T is the thermodynamic temperature,
F5/2 state transfer the energy to Tm3+ ions previously transfer between Yb3+ and Tm3+ ions is confirmed by the
day databases of thermodynamic properties comprising the k is the Boltzmann constant, and I(ω) is the 3+ measured Raman
excited in the 3H4 level which results in blue and red NIR and UC conversion emissions after 16,17Yb excitation at
molar Gibbs energies 1of various3species 53 (e.g. the FACT data- intensity. More details can be found in. Raman spectra were
emissions 20,21from levels G 4 and F 2,3. In order to ana- 975. NIR Yb3+ (2F5/2 → 2F7/2) emission around 1000 nm
base ) enable the routine construction of the Shakhmatkin multiplied by a constant, 3+ thus the maximum value of spectral
lyzeandtheVedishcheva
upconversion modelmechanism which populates
for many significant the
multicomponent is also observed
intensity equals after Tm excitation at 791 nm due to a
to one.
1
G4 glass
level,systems.
the dependence of the blue integrated
However, in many cases, mainly of non-silicate emis- non- resonant phonon- assisted energy transfer (PAET) be-
sionmulticomponent
intensity on the pump
glass power
systems, thedensity
neededhas been an-
thermodynamic tween both ions. Visible UC emissions are only observed
3+ 3+ 3+
alyzed for the GC sample codoped with
data are not found in any contemporary thermodynamic da- 2 mol% Yb . in 4Tm | -Yb RE SU codoped
LT Ssamples,
AND D thus
ISC
3+
confirming
USSION
3+
the ef-
Thetabase.
inset In inour Figure 11B
previous shows
work, 6,22 the logarithmic plot
we proposed a method for fective energy transfer between Yb and Tm ions. The
1 3 3+ 3+
of the blue ( G
obtaining estimates 4 → H ) emission as a function
of6missing thermodynamic parameters by of the addition of Yb also favours the
On the basis of experimental structural data UC emission
16,17 of Tm
ten system
pump power density
reproducing for 791
the structural nm excitation. The depen-
information. after excitationwere
components in codoped
considered samples
in the compared
ZnO-Nb2Oto the sin-
5-P2O5 ther-
dence is nearly quadratic with a slope of 1.64 which Tm3+ doped
glemodynamic ones, where no UC emission
model of Shakhmatkin and Vedishcheva – ZnO is observed.
indicates a two-photon UC process in contrast with the These
(Z), Nbeffects are more pronounced in the GCs samples
2O5 (Nb), P2O5 (P), ZnP4O11 (ZP2), Zn(PO3)2 (ZP),
2.2 | Decomposition of Raman spectra based
result under 975 nm excitation in which the blue emis- dueZn2P2O7 (Z2P), Zn3of
to the reduction (POthe interionic distances after the
4)2 (Z3P), NbO(PO3)3 (1/2NbP3),
sionon is glass
the result of a threefrom
composition photon TDUC process. Since
model incorporation
(NbO)4(P2O7of )3 the RE ionand
(Nb2P3), in NbOPO
the NCs. Codoped samples
4 (1/2NbP). The equi-
the probability of a two-photon mechanism is higher canlibrium
be thus usedamounts
molar to tuneofthe UC emission
SVTDM from NIR to
system components re-
thanThe that of a three- photon mechanism,
method of numerical analysis of Raman spectra was the UC blue blue by the selectivity of the excitation.
calculated for xNb2O5·50ZnO·(50-x)P2O5, (x = 0, 1, 3, 5, 7,
emission
suggested intensity
by Malfait observed for the codoped
and his collaborators. 23-25 samples
The basic as- 10, 12) glasses from the results of structural analysis pub-
under 791 nm
sumption of excitation
this methodisishigherthat thethan Ramanunder 975 are
spectra nmthe ACKNOWLEDGEMENTS
lished in16,17 are summarized in Table 1 together with the
excitation.
sum of the partial Raman spectra (generated by the indi- This work groupings
structural was supported by MINECO
represented under(i.e.
by the Qn units Projects
tetrahe-
vidual structural elements) multiplied by the abundance of MAT2017- dron PO487035-with nC2- 1-P/-2-oxygen
bridging P (AEI/FEDER, UE), Basque
atoms) of considered sys-
these structural elements. The series of Raman spectra ob- Country Government
tem components. PIBA2018- 24 and Basque Country
|
4 tainedCO forN C LUSION
a series S different compositions span University
of glasses with GIU17/014.
The molar amountsThis article
reported inisTable
part of the dissemina-
1 correspond to lit-
a linear vector space with a dimension given by a number of tion tleactivities
bit changed of project FunGlass. This
glass composition whenproject has received
compared with the
Oxyfluoride
independent GCs with elements
structural a cubic (i.e. solution
structuralof elements
the typethat fundingprescribedfromone, thei.e.European Union´s -x)P2O5
xNb2O5·50ZnO·(50 Horizon , (x2020
= 0, 1re-, 3,
Naxindependently
Lu2x-1F7x-3 NCs change
havetheirbeenrelative abundance)
successfully with differ-
obtained by 5, 7, and
search 10, 12 ). This actual
innovation glass composition
programme under grant is given in Table
agreement
the ent partialquenching
melting Raman spectra (PRS).and
method Each measured spectrum
subsequent crystal- is No2739566.
togetherThiswitharticle
the glass
wastransition temperature.
also created in the frame of the
recorded
lization with any
process scale,
using ani.e. it is known
optimized except
heat for the size
treatment at of project The molarfor
Centre Gibbs energies of
Functional andZ, Surface
Nb, P, and Z3P were taken
Functionalized
20,21
600°Ca multiplication
during 20h. factor. The treatment allows precipitation of from(CEGLASS),
Glass the FACT database. ITMS codeThe unknown molaropera-
is 313011R453, Gibbs
NaLuF4 NCs with a mean size in the range of 9–30 nm, tional program Research and innovation, co-funded from
| | 495
VELÁZQUEZ
VELÁZQUEZet
etal.
al. 2 11
on the photoluminescence of Nd3+ doped transparent oxyfluo-

European Regional Development Fund. This research niobyl(3+) cation (NbO3+), which enters deform
ride glass-ceramics. CrystEngComm. 2018;20(38):5760–71.
work has been supported by the Research Agency of the 14.
dra (octahedra, tetragonal pyramids)
Velázquez JJ, Balda R, Fernández J, Gorni G, Pascual L, Chen
with a co
16,17
Ministry of Education, Science, Research and Sport of the covalent bond to oxygen.
G, et al. Transparent oxyfluoride glass-ceramics with NaGdF4
Slovak Republic, by the project: Advancement and sup- nanocrystals doped with Pr3+ and Pr3+–Yb3+. J Lumin.
port of R&D for "Centre for diagnostics and quality testing 2018;193:61–9.
of materials" in the domains of the RIS3 SK specialization, 15. 2
de Pablos-Martín A, Mather | ME
GC, T HOD
Muñoz F, Bhattacharyya S,
Acronym: CEDITEK II., ITMS2014+ code 313011W442. Höche TH, Jinschek JR, et al. Design of oxy-fluoride glass-
2.1 4 nano-
ceramics containing NaLaF |Thermodynamic model of
crystals. J Non Cryst Solids.
2010;356(52–54):3071–Shakhmatkin
9. and Vedishcheva
ORCID 16. de Pablos-Martín A, Méndez-Ramos J, del-Castillo J, Durán A,
Jose J. Velázquez https://orcid. Rodríguez VD, Pascual MJ. Crystallization and up-conversion
org/0000-0001-7672-0539 Especially in the field of oxide glasses, the ther
luminescence properties of Er3+/Yb3+-doped NaYF4-based
Rolindes Balda https://orcid.org/0000-0001-6882-3167 nano-glass-ceramics. Jmodel
Eur Ceramof Shakhmatkin and Vedishcheva
Soc. 2015;35(6):1831– 40. has been s
1-9
Giulio Gorni https://orcid.org/0000-0001-8227-9022 17. applied in previous years.
Liu Q, Sun Y, Yang T, Feng W, Li C, Li F. Sub-10 nm hexagonal The SVTDM mode
Alicia Durán https://orcid.org/0000-0002-0067-1934 lanthanide-doped NaLuF glasses and melts to be an ideal solution formed b
4 upconversion nanocrystals for sensi-
tive bioimaging in vivo.ucts
J Am ofChem
equilibrium chemical reactions
Soc. 2011;133(43):17122– 5. of simple s
Dušan Galusek https://orcid.org/0000-0001-5995-8780
18. Wei Y, Liu X, Chi X, Weistances, e.g.H.
R, Guo oxides,
Intense halides, etc. These
upconversion in salt-like pr
Maria J. Pascual https://orcid.
novel transparent NaLuF :Tb3+, Yb3+
the4identical glass–ceramics.
stoichiometry as Jthe
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org/0000-0002-6833-9663 Compd. 2013;578:385–exist8. in the phase diagram of the system under co
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the structural information. components were considered in the ZnO-Nb2O5-P2O5 ther-
2020;10(7):1425. modynamic model of Shakhmatkin and Vedishcheva – ZnO
41. Liu F, Ma E, Chen D, Yu Y, Wang Y. Tunable red-green up- How
(Z), Nbto cite this article: Velázquez JJ, Balda
2O5 (Nb), P2O5 (P), ZnP4O11 (ZP2), Zn(PO3)2 (ZP),
2.2 | Decomposition of Raman spectra based
conversion luminescence in novel transparent glass ce-
Zn2P2O7 (Z2P),J, Gorni
R, Fernández Zn3(POG,4)2Sedano (Z3P),M, Durán A,
NbO(PO
3+ 3 33+
) et al.
(1/2NbP3),
ramics containing Er: NaYF4 nanocrystals. J Phys Chem B. Structural and optical properties in Tm /Tm –
2006;110(42):20843–6.
(NbO) 4(P2O7)3 (Nb2P3), and NbOPO4 (1/2NbP). The equi-
Yb3+ doped
librium molar NaLuF
amounts 4 glass- ceramics.system
of SVTDM Int J Appl Glass re-
components
42. Balda R, Gorni G, Velázquez JJ, Pascual MJ, Durán A,
The methodJ. Chapter
Fernández of numerical analysis of
16 performance of Raman
Nd as spectra
3+
structural was Sci. 2021;12:485–496. https://doi.org/10.1111/ijag.16322
calculated for xNb2O5·50ZnO·(50-x)P2O5, (x = 0, 1, 3, 5, 7,
23-25
suggested
probe of rare-by earth
Malfait and his collaborators.
distribution The basic as-
in transparent nanostructured 10, 12) glasses from the results of structural analysis pub-
sumption of this
glass-ceramics. In: method
Di Bartolo is D,
that the Raman
Silvestri L, Cesaria spectra are the
M, Collins lished in16,17 are summarized in Table 1 together with the
J, editors.
sum of the Quantum
partial Nano-
Raman Photonics.
spectra NATO Scienceby
(generated forthe
Peaceindi- structural groupings represented by the Qn units (i.e. tetrahe-
vidual structural elements) multiplied by the abundance of dron PO4 with n bridging oxygen atoms) of considered sys-
these structural elements. The series of Raman spectra ob- tem components.
tained for a series of glasses with different compositions span The molar amounts reported in Table 1 correspond to lit-
a linear vector space with a dimension given by a number of tle bit changed glass composition when compared with the
independent structural elements (i.e. structural elements that prescribed one, i.e. xNb2O5·50ZnO·(50-x)P2O5, (x = 0, 1, 3,
independently change their relative abundance) with differ- 5, 7, 10, 12). This actual glass composition is given in Table
ent partial Raman spectra (PRS). Each measured spectrum is 2 together with the glass transition temperature.
recorded with any scale, i.e. it is known except for the size of The molar Gibbs energies of Z, Nb, P, and Z3P were taken
a multiplication factor. from the FACT database.20,21 The unknown molar Gibbs

Int J of Appl Glass Sci - 2021 - Vel Zquez - Structural and Optical Properties in Tm3 Tm3 Yb3 Doped NaLuF4

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Received: 20 February 2021

| Revised: 24 May 2021

SPECIAL ISSUE ARTICLE

Structural and optical properties in Tm3+/Tm3+–Yb3+ doped

Jose J. Velázquez1 |Rolindes Balda2,3 | Joaquin Fernández4 | Giulio Gorni5,6 |

F I G U R E 2 (A) and (C) HRTEM

Especially in the field of oxide glasses, the ther

2.2 | Decomposition of Raman spect

The method of numerical analysis of Raman s

Especially in the field of oxide glasses, the ther

on the photoluminescence of Nd3+ doped transparent oxyfluo-

ples and applications. Phys Today. 1995;48(2):56–8.

–glass-ceramic fibers doped with Er3+ and Yb3+. RSC Adv.

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