Journal of Luminescence 181 (2017) 411–420

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Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin

Full Length Article

Are rare earth phosphates suitable as hosts for upconversion

luminescence? Studies on nanocrystalline REPO4 (RE ¼ Y, La, Gd, Lu)
doped with Yb3 þ and Eu3 þ , Tb3 þ , Ho3 þ , Er3 þ or Tm3 þ ions
Artur Tymiński, Tomasz Grzyb n
Department of Rare Earths, Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznań , Poland

art ic l e i nf o a b s t r a c t

Article history: Rare earth phosphate nanomaterials doped with lanthanide ions (Yb3 þ , Ho3 þ , Er3 þ , Tm3 þ , Tb3 þ and
Received 1 August 2016 Eu3 þ ) showing upconversion (UC) luminescence may play an important role in photonics, optics, elec-
Received in revised form tronics and in biomedical diagnostics. Year by year, the significance of rare earth compounds increases.
11 September 2016
Here, we present structural, morphological and spectroscopic investigations on REPO4 nanoparticles,
Accepted 13 September 2016
Available online 17 September 2016
which were successfully synthesized by the co-precipitation method followed by annealing at 1000°C.
Obtained tetragonal (YPO4, LuPO4) and monoclinic (LaPO4, GdPO4) nanocrystals were single phase and
Keywords: homogeneous, with dimensions not exceeding 75 nm. These samples exhibited strong luminescence
Luminescence when excited in NIR range (975–978 nm) and the UC mechanisms were proposed. After initial photon
Upconversion
absorption by Yb3 þ ions, the energy transfer (ET) to emitting ions (Ho3 þ , Er3 þ , Tm3 þ , Tb3 þ , Eu3 þ )
Rare earth phosphates
occurred. Luminescence rise and decay times were short with the exception for Tb3 þ and Eu3 þ ions,
Nanomaterials
Energy transfer which showed up to 5 ms long luminescence. Dependencies of integral luminescence intensity on laser
energy indicated that, most of the transitions were two-photon what is typical value for this kind of ions.
However, some of transitions were three- and even four-photon (especially in Tm3 þ ions) and some of
slope values were lower than two, what was caused by the saturation and local thermal effects.
& 2016 Elsevier B.V. All rights reserved.

1. Introduction absorption (ESA), cooperative energy transfer upconversion (CET),

photon avalanche (PA) and energy migration upconversion (pos-
In the past few decades much attention has been paid to syn- sible in core-shell structures) [3–6]. The UC phenomenon is
thesize efficient phosphors containing rare earth ions (RE). Over observed not only in lanthanides, but also in transition metals and
the years, nanotechnology has gained a lot of significance in actinides [7].
creating new kinds of materials, which are important in science Investigated compounds are guest-host systems, in which,
and technology and may be used for various applications [1,2]. A Ln3 þ ions, are embedded in inorganic host lattice. Lanthanide ions,
very interesting feature of the lanthanide (Ln3 þ ) co-doped nano- added in low concentrations, provide luminescent centers capable
particles is ability to exhibit upconversion (UC) emission. of emitting upconversion luminescence when excited. The most
Upconversion phenomenon is defined as the anti-Stokes efficient and well known UC systems are these based on the Yb3 þ
luminescent process, in which higher-energy photons are gener- and Ho3 þ , Er3 þ and Tm3 þ ions doped in 0.5–3% (or around 20%
ated from lower radiation through sequential or simultaneous for Yb3 þ ions) [8–11]. Selection of proper host materials is also
indispensable for the ion-ion distance, coordination number and
absorption of two or more photons or energy transfers. Usually,
spatial arrangement in three-dimensional space, which deter-
the long-wavelength excitation by a NIR or IR radiation leads to
mines the emission efficiency [5,8,12].
the emission of short-wavelength radiation in UV or visible spec-
Rare earth orthophosphates can be considered as excellent hosts
trum. Starting from the first studies in the sixties of the twentieth
for Ln3 þ ions, especially for above mentioned Ho3 þ , Er3 þ and Tm3 þ ,
century to the present day, several different UC mechanisms were
but they can be also doped with Ce3 þ , Tb3 þ or Eu3 þ ions [13–15].
distinguished: energy transfer upconversion (ETU, also known as
These materials have many excellent properties, such as high che-
addition de photon par transferts d’energie, APTE), excited state mical, thermal and photostability, high quantum yields of their
emission, high refraction index and low solubility in water [6,16–18].
n
Corresponding author. The properties of nanocrystalline REPO4 can be utilized in a variety of
E-mail address: tgrzyb@amu.edu.pl (T. Grzyb). potential applications: plasma display panels, cathode ray tubes,

http://dx.doi.org/10.1016/j.jlumin.2016.09.028
0022-2313/& 2016 Elsevier B.V. All rights reserved.
412 A. Tymiński, T. Grzyb / Journal of Luminescence 181 (2017) 411–420

lasers, upconversion and quantum cutting emissions, catalyst and and then evaporated to remove an excess of acid and to obtain
sensors, nuclear waste disposal and protective coatings, proton appropriate nitrates. The concentrations of solutions were 1M.
conductivity (for instance in hydrogen fuel cells), lamp phosphors, The total amounts of reagents were calculated for 1 g of pre-
amplification in optical communications, contrast agents in fluores- cipitate. Typical synthesis was started by mixing rare earth nitrate
cence and magnetic resonance imaging, IR sensors, solar spectrum solutions, 75 mL of deionized water and 25 ml of glycerin in a 200
converters and light emitting diodes [15–17,19–23]. Moreover, mL beaker. Glycerin was used in order to stabilize the nano-
orthophosphates may be used in forming different core/shell struc- particles size and prevent aggregation of particles. The mixture
tures, bifunctional magnetic fluorescent materials being applicable in was heated and stirred magnetically until it reached 50 °C. Then,
diagnostics, rare earth phosphate ceramics, ceramic-ceramic fiber the 50 mL of aqueous ammonium phosphate solution (with 50%
composites and multifunctional down- and up-converting magnetic excess), used as a precipitating agent, was added drop wise. The
nanomaterials excitable both with UV and NIR radiation [18,24–31]. white suspension was obtained immediately and it has been stir-
Upconverting nanoparticles can be synthesized by many differ- red for 30 minutes, while maintaining the temperature in the
ent methods: sol–gel process, hydro- and solvothermal methods, range of 50–52 °C. After that, the suspension was centrifuged and
thermal decomposition, combustion method, micro-emulsion or washed with water and ethanol four times. The precipitate was
reverse micelle methods and co-precipitation method [3,12,32]. The separated from the solution and it was dried in 80°C for several
latter one was selected to synthesize Ln3 þ co-doped REPO4 nano- days. Next, the samples were annealed in air atmosphere at
materials due to its simplicity, high speed of the process not 1000 °C for 2 h in order to remove organic impurities and form
requiring specialized reaction vessels or complex procedures. In this nanocrystalline product. After that products were grounded in an
method, the reagents are mostly inorganic salts. Nanoparticles’ sizes agate mortar and the white nanopowders were obtained.
and morphology are controlled and stabilized with use of capping Rare earth phosphate matrices REPO4 were co-doped with the
ligands, i.e. organic compounds like glycerin, citric acid, ethylene- lanthanide ions: 20% Yb3 þ /1% Ho3 þ , 20% Yb3 þ /1% Er3 þ , 20% Yb3 þ /
diaminetetraacetic acid (EDTA), di-n-octadecyldithiophosphate, 0.5% Tm3 þ , 10% Yb3 þ /20% Tb3 þ and 10% Yb3 þ /20% Tb3 þ /5%Eu3 þ .
polyethylenimine (PEI) or polyvinylpyrrolidone (PVP). However, XRD patterns were measured with use of Bruker AXS D8
final nanocrystals often can be formed after additional annealing or Advance diffractometer (Cu Kα radiation at 1.5418 Å) in a 2θ range
calcination of a dry precipitate [3,12,33,34]. from 6° to 60° with a 0.05° step scan mode. The reference data was
In the present work, the studies on REPO4 (RE¼ Y3 þ , La3 þ , taken from the JCPDS database (Joint Committe on Powder Dif-
Gd 3þ
and Lu3 þ ) nanoparticles, doped with Yb3 þ /Ho3 þ , Yb3 þ / fraction Standards). Maud (version 2.55) software was used to
Er3 þ , Yb3 þ /Tm3 þ , Yb3 þ /Tb3 þ and Yb3 þ /Tb3 þ /Eu3 þ ions, showing perform Rietveld refinement of cell parameters and phase quan-
intense upconversion luminescence are reported. We show the tities. TEM images were obtained by a high resolution FEI Tecnai
G2 20X TWIN transmission electron microscope with an accel-
results of morphological and structural investigations including
erating voltage of 200 kV. Spectroscopic analyses, including mea-
transmission electron microscopy (TEM), energy-dispersive X-ray
surements the excitation and emission spectra, luminescence
spectroscopy (EDX) and powder X-ray diffraction (XRD) analyses.
decays and dependencies of the luminescence intensity on the
In our studies we mainly focused on the spectroscopic properties
laser energy were performed at room temperature with Quanta-
of the prepared samples, such as excitation and emission spectra,
Master™ 40 spectrophotometer equipped with an Opolette 355LD
luminescence decays and dependencies of the luminescence
UVDM tunable laser, which had a repetition rate of 20 Hz, as the
intensity on the laser energy in order to better understand the UC
excitation source and detector (Hamamatsu 928 photomultiplier).
process. Luminescence, observable by the naked eye, based mainly
Upconversion luminescence pictures were done with use of a solid
on the energy transfer processes (ET) and cooperative energy
state 980 nm laser (Dragon Lasers) as the excitation source, a
transfer processes between sensitizing and emitting ions.
Canon EOS 550D camera and a KG3 Colored Glass Bandpass Filter
According to our knowledge, up-converting REPO4-based
(315–710 nm).
materials are poorly investigated, especially in the case of LuPO4
host compound. Herein we report for the first time the properties
of materials based on LuPO4 host compound co-doped with Yb3 þ /
3. Results and discussion
Ho3 þ , Yb3 þ /Er3 þ , Yb3 þ /Tm3 þ , Yb3 þ /Tb3 þ and Yb3 þ /Tb3 þ /Eu3 þ
ions. Chosen concentrations of dopant ions, were optimal for the
3.1. Structure and morphology
UC intensity and based on our previous research. Moreover, in
comparison to the previous work of our team, we expanded the
Lanthanide phosphates can be obtained with several crystalline
research of phosphate nanoparticles of YPO4:Yb3 þ /Ho3 þ and
structures, such as hexagonal, tetragonal and monoclinic types.
YPO4:Yb3 þ /Tb3 þ /Eu3 þ , as well as LaPO4:Yb3 þ /Ho3 þ and GdPO4: These materials typically crystallize in polymorphic type of mon-
Yb3 þ /Tb3 þ /Eu3 þ co-doped samples, previously unknown azite (from La to Gd) or zircon-type xenotime structure (from Tb to
[9,31,35–37]. As a result, the scope of the presented research was Lu) [22,30,31,38,39]. The XRD patterns of prepared REPO4 nano-
increased with broader range of samples and comparison their particles are shown in Fig. 1. All prepared compounds were single
spectroscopic properties. phase, homogeneous and had good crystallinity. No impurities
were detected. Diffractograms show relatively wide peaks, espe-
cially in the case of YPO4 and LuPO4 samples what is caused by the
2. Experimental nanocrystallinity of the products. That is also confirmed in TEM
images (see Fig. 2). The YPO4:Yb3 þ /Ln3 þ samples (JCPDS File no.
Ln3 þ co-doped phosphate nanoparticles were synthesized by 79754) and LuPO4:Yb3 þ /Ln3 þ samples (JCPDS File no. 79761)
precipitation method. For the synthesis, following reagents were crystallized as tetragonal phases with I41/amd space group, while
used: Y2O3, La2O3, Gd2O3, Lu2O3, Yb2O3, Ho2O3, Er2O3, Tm2O3, LaPO4:Yb3 þ /Ln3 þ (JCPDS File No. 79741) and GdPO4:Yb3 þ /Ln3 þ
Tb4O7 and Eu2O3 from Stanford Materials (99.99% pure, United (JCPDS File No. 79753) samples were monoclinic with a P21/n
States), nitric acid, HNO3 from POCh. S.A. (65%, ultrapure, Poland), space group. Host lattice ions were successfully replaced by co-
ammonium phosphate monobasic, NH4H2PO4 from Sigma Aldrich doping ions because of small differences in ionic radii between
(ACS reagent 98%, Poland) and glycerin, C3H8O3 from POCh. S.A. them (coordination number ¼9): r(Y3 þ ) ¼1.075 Å, r(La3 þ ) ¼1.216
(99% pure, Poland). Rare earth oxides were dissolved in nitric acid Å, r(Gd3 þ )¼1.107 Å, r(Lu3 þ )¼1.032 Å, r(Yb3 þ ) ¼1.042 Å, r
 A. Tymiński, T. Grzyb / Journal of Luminescence 181 (2017) 411–420 413

Fig. 1. XRD patterns of synthesized materials after annealing at 1000 °C.

(Eu3 þ )¼ 1.12 Å, r(Tb3 þ )¼ 1.095 Å, r(Ho3 þ ) ¼1.072 Å, r(Er3 þ )¼ 3.2. Spectroscopic properties
1.062 Å, r(Tm3 þ ) ¼1.052 Å [40,41]. As a result of this replacement,
the cell parameters decreased in YPO4, LaPO4 and GdPO4-based Fig. 3 depicts excitation and emission spectra for the prepared
materials. Doping by Yb3 þ , Ho3 þ , Er3 þ and Tm3 þ ions were samples under NIR laser excitation. Excitation spectra are com-
neutral for the size of crystal cell of LuPO4 nanomaterials, because posed of very wide and intense bands, with spectral width close to
Lu3 þ ions have similar ionic radius to the dopant ions. However, 100 nm. Their presence is a good confirmation of absorption of NIR
replacing the Lu3 þ ions by Tb3 þ or Eu3 þ caused increase of cell photons. It also confirms the energy transfer from Yb3 þ to lumi-
volumes as the difference between these ions is high enough to nescent, Ln3 þ ions. The most effective absorption was in the range
give visible effects. Discussed changes can be seen in the Supple- of 975 to 978 nm for various samples and it is related to the
mentary material in Table S1 where cell parameters are collected. transition from the 2F7/2 ground to the 2F5/2 excited states of Yb3 þ
The co-precipitation method allowed to the synthesis of well ions. The difference in the position of the peaks maxima comes
formed, fine crystalline nanoparticles with no inclusions and with from the different lattice parameters and coordination numbers of
their average sizes less than 100 nm. Fig. 2 shows TEM images of the dopant ions in the phosphate matrices containing different
the selected Ln3 þ co-doped REPO4 materials after annealing at rare earth ions. The Yb3 þ ions can be excited differently what is
1000 °C. As can be seen, the phosphate materials are slightly dif- connected with transitions between different Stark splitting levels
ferent in their morphology. Most of them had round-shaped – four on the ground state 2F7/2 and three on the excited 2F5/2 level
nanoparticles with irregular surface and tendency to agglomera- [42,43]. This results in differences on the shape of excitation
tion. Generally, average sizes were in the range of about 22–77 nm spectra (especially visible in more sharp bands of the Tb3 þ /Eu3 þ
and LuPO4 matrices were the smallest. What is worth noting is the co-doped samples) and, as is mentioned earlier, depend on local
fact that products with tetragonal crystal structure had smaller crystal field and crystal symmetry. After absorption, the sensitizer
sizes than those with monoclinic structure. ions (Yb3 þ ) transfer the energy in several ways to the activator
EDX spectra of selected samples are presented in Supplemen- ions (Ho3 þ , Er3 þ , Tm3 þ , Tb3 þ and Eu3 þ ), which finally emit bright
tary material, Fig. S1. The analysis confirmed composition of the luminescence.
prepared materials. Peaks from the host ions (Y, Gd, La, P and O) Upconversion emission spectra were recorded in the range of
and dopant elements (Yb, Er, Tb, Tm) are strong and clearly visible. 300–850 nm for all prepared samples which covers the near
There can be also seen other peaks from C, Cu, Mg and Al, which ultraviolet, visible and near-infrared region. Intense, narrow and
have the origin in the grids used for the EDX analysis method. The sharp emission bands can be observed in the emission spectra as
dopants ions’ molar concentrations were analysed also by ICP-OES the result of the f–f transitions of lanthanide ions.
(see Supplementary material, Table S2). The results indicated that In the case of Ho3 þ co-doped samples, after initial absorption
the elemental composition of the synthesized samples was as of the NIR photons by the Yb3 þ ions, energy was transferred to
desired. Ho3 þ ions dispersed in the host lattice. As can be clearly seen in
414 A. Tymiński, T. Grzyb / Journal of Luminescence 181 (2017) 411–420

Fig. 2. TEM images of selected co-doped REPO4 nanomaterials prepared at 1000 °C.

the spectra for all Yb3 þ /Ho3 þ co-doped samples, the most intense In the case of Yb3 þ /Tm3 þ co-doped matrices, bright blue UC
and wide emission bands were in the range of the red color (with luminescence was observed, as the major emission bands were in
maximum at 640 nm for LaPO4 matrix and about 650 nm for other the blue light spectrum (471–478 nm), corresponding to the
matrices). They corresponded to the electronic transition from the 1
G4-3H6 transitions of Tm3 þ ions. There were also another bands
5
F5 excited energy state to the 5I8 ground state of Ho3 þ ions. This in the blue spectrum (at about 450 nm), overlapped with the
electronic transition determined the red color of the observed major peaks, which corresponded to the 1D2-3F4 transition.
luminescence. Less intense bands correlated with 5S2, 5F4-5I8 Intense emission bands were also observed at about 646 nm
transitions were observed in the 534–535 nm range. In the NIR (1G4-3F4 transition) and in the NIR spectrum: at 795 nm in YPO4
spectral range (around 745 nm) lay the least intense bands cor- and LuPO4 samples and 791 nm for LaPO4 and GdPO4 samples
related with 5S2, 5F4-5I7 electronic transitions. (3H4-3H6 transition). The least intense bands were recorded for
The most intense emission bands, measured for the REPO4: the each sample in the NUV region, with maximum at around 360
Yb3 þ /Er3 þ nanomaterials, centered at 536 nm and 541 nm in the nm. They were connected with the 1D2-3H6 transition of
case of LuPO4 host compound. They were correlated with the 4S3/ Tm3 þ ions.
3þ
4
2- I15/2 transition of Er ions, responsible for the green emis- Analyses of the emission spectra revealed that all of the Yb3 þ /
3þ
sion. At around 514 nm, there can be observed less intense band, Tb co-doped REPO4 nanomaterials had the most intense emis-
corresponded to 2H11/2-4I15/2 electronic transition. Another sion bands centered at 534 nm (533 nm for YPO4). They correlated
strong emission band, divided in two parts, was observed at 658 with the 5D4-7F5 transition of Tb3 þ ions. In these ions, electronic
nm (647 nm for LaPO4) and was correlated with 4F9/2-4I15/2 transitions, can occur between the 5D4 excited state and 7FJ com-
transition. Emission also occurred at 398 nm (400 nm for GdPO4) ponents of the ground state (where J¼1–6). Therefore, the mea-
what was the effect of 4H9/2-4I15/2 transition and at 461 nm (464 sured luminescence spectra, revealed also emission bands at 480
nm for LaPO4), as the result of 4F3/2-4I15/2 transition. nm (5D4-7F6), 576 nm (579 nm for YPO4 and 580 nm for LuPO4),
 A. Tymiński, T. Grzyb / Journal of Luminescence 181 (2017) 411–420 415

Fig. 3. Excitation (dashed line) and emission (solid line) spectra of REPO4: Yb3 þ /Ln3 þ matrices under NIR laser excitation.

5
D4-7F4 and at 612 nm (5D4-7F3). In the case of emission spectra the combination of the emission of these ions. Absorbed energy
of YPO4 and LuPO4 matrices, there can be hardly seen also two can be transferred from Yb3 þ via Tb3 þ to Eu3 þ ions. In YPO4 and
another peaks: 639 nm (5D4-7F2) and at 662 nm (5D4-7F1). The LuPO4 matrices the major peaks were at 609 nm and 610 nm
Yb3 þ /Tb3 þ co-doped samples exhibited bright, green UC respectively and were connected with the 5D0-7F2 transition of
luminescence. Eu3 þ . It is an electric-dipole transition, sensitive for the changes of
In the Yb3 þ /Tb3 þ /Eu3 þ co-doped phosphates there were two local symmetry of Eu3 þ ions. The magnetic-dipole transition,
emitting ions: Tb3 þ and Eu3 þ , therefore the emission spectra are 5
D0-7F1 occurred at about 585 nm. In LaPO4 and GdPO4 matrices
416 A. Tymiński, T. Grzyb / Journal of Luminescence 181 (2017) 411–420

this transition played the most important role, as the most intense doped YPO4 matrix differs the most from the other co-doped YPO4
bands were recorded at 585 nm and 586 nm respectively. Similarly matrices (it’s the biggest) and that difference is the most notice-
to the remaining materials emission bands connected with able of all samples. Also here, there are three kinds of co-doping
5
D0-7F2 hypersensitive transition of Eu3 þ ions had maxima at ions (Yb3 þ , Tb3 þ and Eu3 þ ) which replace Y3 þ crystal positions.
604 and 602 nm. However, all samples exhibited an orange UC Dopant’s ions can be located in the volume of nanoparticles or on
luminescence, so the 5D0-7F2 transition had the greatest impact their surface. These differences may have a slight impact on cell
on the emission. Emission also occurred at 640 nm (5D0-7F3) and parameters, but a big one on upconversion luminescence, causing
in the range of 688 - 691 nm (5D0-7F4, bands divided into two increase of the luminescence intensity. Furthermore, the shape of
components). Two intense emission bands visible at 481 nm and the 5D0-7F2 hypersensitive emission band of Eu3 þ ions differs in
534 nm are attributed to 5D4-7F6 and 5D4-7F5 transitions of tetragonal and monoclinic matrices, which also indicates the
Tb3 þ ions, respectively. Luminescence emission images taken for crystal lattice changes.
YPO4 are presented in Fig. 4. Differences between tetragonal and monoclinic Yb3 þ /Tm3 þ co-
Interesting is fact that luminescence intensity of Yb3 þ /Tb3 þ / doped matrices were also observed as the ratio between blue and
3þ
Eu co-doped YPO4 sample was the most intense from the other red emission peaks (1G4-3H6 and 1G4-3F4 transitions) changed
similarly doped samples and one form the best emitting in gen- with the type of host compound. For all these samples the major
eral. This may be caused by the impact of local crystal environ- band was observed in blue spectral region. Hoverer, in tetragonal
ment, as the YPO4-based materials had tetragonal crystal struc- matrices blue bands were more intense than red bands, so the blue/
ture, as well as these based on LuPO4 matrices. In these com- red ratio was higher. This observation was correlated with different
pounds the crucial point might be the difference in ionic radii symmetry of Ln3 þ ions between tetragonal (D4h) and monoclinic
between Y3 þ and Lu3 þ ions. Cell volume of Yb3 þ /Tb3 þ /Eu3 þ co- (C2h) samples. Also other factors can influence this factor, like small

Fig. 4. Color of Yb3 þ /Ln3 þ co-doped YPO4 matrices under 977 nm solid state laser irradiation. Similar color was observed for other matrices.

Table 1
Calculated luminescence lifetimes of REPO4 (RE¼ Y, La, Gd, Lu) co-doped nanoparticles (λex ¼ 978 nm).

Sample Transitions Luminescence lifetimes [ls]

YPO4:Ln3 þ LaPO4:Ln3 þ GdPO4:Ln3 þ LuPO4:Ln3 þ

20% Yb3 þ , 1% Ho3 þ 5

F3-5I8 (  475 nm) 41.4 7 0.1 78.5 70.3 63.0 7 0.1 47.6 0 70.3
5
S2,5F4-5I8 (  535 nm) 16.8 7 0.1 30.0 70.3 23.4 7 0.2 13.3 70.1
5
F5-5I8 (  639 nm) 32.4 7 0.2 56.5 70.2 39.4 7 0.1 25.4 7 0.1
5
S2,5F4-5I7 (  744 nm) 17.4 7 0.1 30.8 70.2 21.5 7 0.2 14.0 70.2
20% Yb3 þ , 1% Er3 þ 4
H9/2-4I15/2 (  400 nm) 6.9 7 0.02 12.3 7 0.1 6.6 7 0.1 6.2 7 0.1
2
H11/2-4I15/2 (  514 nm) 13.17 0.1 29.9 70.1 22.6 7 0.2 10.2 70.1
4
S3/2-4I15/2 (  538 nm) 13.2 7 0.1 28.5 70.2 18.1 7 0.2 10.40 70.04
4
F9/2-4I15/2 (  648 nm) 16.8 7 0.1 34.5 70.4 22.2 7 0.2 12.8 7 0.1
20% Yb3 þ , 0.5% Tm3 þ 1
D2-3H6 (  360 nm) 49.07 0.6 49.47 0.5 42.2 7 0.2 34.4 7 0.4
1
G4-3H6 (  472 nm) 64.47 0.2 88.9 70.2 73.5 7 0.1 48.87 0.1
1
G4-3F4 (  645 nm) 67.4 7 0.3 89.5 70.2 79.9 7 0.2 49.37 0.1
3
F3-3H6 (  721 nm) 47.6 7 0.5 46.8 70.4 44.2 7 0.3 32.7 7 0.3
3
H4-3H6 (  795 nm) 78.3 7 0.3 79.8 70.2 73.7 7 0.2 52.7 7 0.2
10% Yb3 þ , 20% Tb3 þ 5
D4-7F6 (  481 nm) 2240.071.2 103.9 7 0.8 4586.0 7 3.0 2635.07 0.7
5
D4-7F5 (  533 nm) 2288.0 7 1.5 5122.0 7 6.0 4625.0 7 3.0 2616.9 7 0.6
5
D4-7F4 (  579 nm) 2287.0 7 1.1 5158.0 7 9.3 4614.0 7 3.0 2578.0 7 0.5
10%Yb3 þ , 20%Tb3 þ , 5%Eu3 þ 5
D4-7F5 (  533 nm) 377.7 7 0.9 5.3 70.1 593.0 7 3.2 278.8 70.8
5
D0-7F1 (  586 nm) 1552.6 70.7 2164.0 72.8 2057.0 7 1.7 1506.07 1.1
5
D0-7F4 (  688 nm) 1579.0 7 1.0 2363.0 73.2 2248.0 7 1.8 1547.0 7 1.4
 A. Tymiński, T. Grzyb / Journal of Luminescence 181 (2017) 411–420 417

differences in experiment conditions (laser energy, air tempera- where I0 is the initial intensity at t¼ 0, I1 is the intensity added by
ture), phase purity or particle and cell sizes [37]. energy transfer, τr is a luminescence rise time and τd is a lumi-
Table 1 shows calculated luminescence lifetime values for the nescence decay time. Determined lifetimes vary for all samples
samples annealed at 1000 °C, excited by a NIR laser (975–978 nm). and they define the time when luminescence intensity decreases
Recorded emission decays (see Figs. S2–S5 in the Supplementary to approximately 0.01% of initial values. In the Yb3 þ and Ho3 þ /
material). Er3 þ /Tm3 þ doped matrices the lifetime values were relatively
Luminescence decays are the confirmation of the energy transfer short (even 6.2 7 0.1 ms in GdPO4:20% Yb3 þ /1%Er3 þ ) and exceed
processes between sensitizing and acceptor ions, especially in Yb3 þ / 80 ms only in the LaPO4:20% Yb3 þ /0.5%Tm3 þ sample (1G4-3H6
Ln3 þ co-doped matrices. After switching off the excitation source, and 1G4-3F4 transitions). Lifetime shortening may be caused by
the luminescence intensity rose in time for about 5 to 50 ms similarly quenching processes, including concentration quenching (rela-
in Yb3 þ /Ho3 þ , Yb3 þ /Er3 þ and Yb3 þ /Tm3 þ samples. Relatively long tively high phonon energy of REPO4 matrices, 1050 cm-1 for LaPO4)
rise times of Yb3 þ /Tb3 þ and Yb3 þ /Tb3 þ /Eu3 þ co-doped samples [3],[44]. In the Yb3 þ and Tb3 þ /Eu3 þ doped samples, determined
were in the range of about 90 to 900 ms (the longest in the case of lifetimes have much higher values and here, the luminescence
LaPO4:10% Yb3 þ /20%Tb3 þ /5%Eu3 þ ). In comparison to Ho3 þ , Er3 þ time extension as the result of CET process can be observed. The
and Tm3 þ ions, where the energy transfer occurs quickly, in Tb3 þ cooperative energy transfer from two Yb3 þ ions to one Tb3 þ ion
and Eu3 þ the rise time was longer due to cooperative energy transfer followed by further ET to Eu3 þ ion involves long energy migration
between two Yb3 þ and one Tb3 þ ions and subsequent another and requires more time. It is also correlated with the electronic
energy transfer to Eu3 þ ion [9,18]. structure of Tb3 þ which plays an important role, because there is a
Calculated luminescence lifetimes were fitted with use of the big energy gap between 5D4 and ground state levels. Another
equation: important factor may be a large distance between sensitizing and
emitting ions. There is a Yb3 þ concentration shortage (10%) in
I ¼ ½I0 þ I1ð1  exp  ðt=τ rÞÞexp  ðt=τdÞ; ð1Þ comparison to other matrices (20%), and higher concentration of

Fig. 5. The laser energy dependences of the integrated UC intensity measured in Yb3 þ /Ln3 þ co-doped REPO4 samples.
418 A. Tymiński, T. Grzyb / Journal of Luminescence 181 (2017) 411–420

emitting ions (20% in comparison to 0.5-1% of Ho3 þ , Er3 þ or Tm3 þ for 1G4-3H6 (479 nm) transition in GdPO4: Yb3 þ /Tm3 þ and 3.5 7
ions). Hence, the distances between ions are higher and it can 0.2 for 1D2-3F4 (453 nm) transition in LaPO4: Yb3 þ /Tm3 þ ).
affect the luminescence decay times. The calculated luminescence Determined slope values are in some cases, relatively low with
lifetimes ranged from about 1.5 to 5.1 ms and the value deter- the values of about one (1.1 70.1 in YPO4:Yb3 þ /Ho3 þ , 545 nm and
mined for 5D4-7F6 transition (5158.0 70.1 ms) in LaPO4:10% 1.0 7 0.1 in GdPO4:Yb3 þ /Tb3 þ /Eu3 þ , 537 nm) and even lower
Yb3 þ ;20%Tb3 þ was the highest from all samples described in this than unity, for example 0.9 70.1 and 0.1 7 0.1 in LuPO4:Yb3 þ /
article. As can be seen, the exception from this tendency was Tb3 þ /Eu3 þ , 536 nm and LaPO4:Yb3 þ /Ho3 þ , 475 nm, respectively.
5
D4-7F5 transition of Tb3 þ ions in REPO4:10% Yb3 þ /20%Tb3 þ /5% The emissions in these samples were the most probably affected
Eu3 þ sample, which lifetime did not exceeded 600 ms. The lifetime by the occurrence of quenching processes. Also, the saturation and
of this Tb3 þ transition was shortened because of the energy local thermal effects may have the impact on the luminescence
migration from Tb3 þ to Eu3 þ and Eu3 þ percentage concentration intensity. The first one is caused by competition between occur-
(5%) is smaller than Tb3 þ (20%). The conclusion is that lumines- ring upconversion processes and nonradiative processes, such as
cence decay of Tb3 þ ions and luminescence rising of Eu3 þ multiphonon or cross-relaxation and energy transfer to impurities
occurred simultaneously. which are responsible for the depletion of Ln3 þ intermediate
The dependencies of integral luminescence intensity on the states under continuous excitation. When the slope value is lower
laser energy were studied in order to fully understand the than theoretical one, corresponding to the number n of absorbed
upconversion process. Fig. 5 shows the log–log plots of UC emis- photons necessary to populate an emitting state, it indicates that
sion intensities on leaser energy of the Yb3 þ /Ln3 þ co-doped intermediate levels are depopulated by nonradiative processes.
phosphates. Linear fitting was done and calculated coefficients of Otherwise, when UC process is the most significant in inter-
determination R2 were not lower than 0.9. The observed slope mediate states depletion, the slope value is close to the number of
values allowed us to estimate the number of photons involved in photons n (theoretical value) [49–51].
The local thermal effect originates form the laser exposure and
the process. Investigated UC intensities were measured in a wide
results in the increase of temperature of the sample. If this process
range of laser energies from 22 to even 760 mJ for some samples.
is very significant, the UC luminescence may be quenched and the
Generally, linear tendency between UC intensity and laser
slope values could be much lower than unity and can become even
energy can be observed when the double logarithmic scale is used.
negative [47,52].
The relation between the UC intensity IUC and the pumping
Considering emission and excitation spectra, luminescence
intensity IP can be express by the equation:
decays and slope values, the upconversion process mechanisms
I UC ¼ αðI P Þn ; ð2Þ can be illustrated in the form of scheme presented below (Fig. 6).
In realistic systems the population mechanism is more complex
where α is a proportionality factor and the exponent n represents than the basic model we present here.
the number of photons involved in the UC process [45–47]. Most of The mechanism of UC processes observed in Yb3 þ /Ho3 þ co-
the calculated for samples slope values were in the range of one to doped phosphate matrices led to red UC luminescence. Firstly, in
two and that suggest two-photon emission, involving energy this two-photon process, the Yb3 þ ions absorb NIR photons and
transfer process between Yb3 þ and other ions. Values above two, are excited from 2F7/2 to 2F5/2 electronic state. After that, the
observed in some of the Yb3 þ /Tm3 þ and Yb3 þ /Tb3 þ co-doped energy is transferred to 5I6 excited energy state of Ho3 þ ions.
samples, for instance 2.370.1 for 5D4-7F4 (586 nm) transition in Absorption of the next photon leads to excitation to 5F4 level and
YPO4:Yb3 þ /Tb3 þ as well as 2.870.1 for 1G4-3H6 (477 nm) tran- subsequent non-radiative transitions to the 5F5 level. Finally,
sition in LaPO4:Yb3 þ /Tm3 þ , indicate that three-photon process luminescence can be observed due to 5F5-5I8 radiative transition.
occurred. In order to excite Tb3 þ ions by three photons, two-step Photon emission can also occur from other excited states, 5F4 and
mechanism must be involved: ETU preceded by CET from Yb3 þ 5
S2 (populated by absorption of a second photon) to 5I8 and 5I7
ions. After first energy transfer, Tb3 þ are in their 5D4 excited state levels (green spectral region and NIR region, respectively).
and then another photon can by transferred yielding higher excited In the Yb3 þ /Er3 þ -doped materials, previously absorbed energy
states of Tb3 þ ions [48]. Whereas Tm3 þ ions undergo three is transferred from Yb3 þ ions to Er3 þ ions, which are excited to
sequential photon transfers through ETU, in order to achieve their the 4I11/2 energy level. Here, next photon can be absorbed and then
1
G4 excited state. The two highest slope values are even higher than the 4F7/2 energy level is populated. Next, the non-radiative tran-
three and they may suggest the four-photon absorption (3.170.1 sitions to 2H11/2 and 4S3/2 electronic states give the emission at 514

Fig. 6. Scheme of energy levels and UC mechanisms in REPO4 Yb3 þ /Ln3 þ co-doped matrices under NIR excitation. ET means energy transfer process, CET means cooperative
energy transfer process. Solid arrows represent radiative transitions and dashed arrows represent non-radiative transitions.
 A. Tymiński, T. Grzyb / Journal of Luminescence 181 (2017) 411–420 419

nm (2H11/2-4I15/2) and at 536 nm (4S3/2-4I15/2). The latter tran- dopants. Luminescence decays analyses revealed short population
sition is responsible for an intense green emission of samples. The of emitting ions and relatively short UC lifetimes (not exceeding 90
4
S3/2 excited state of Er3 þ ions can be decreased to lower, 4F9/2 ms), except Yb3 þ /Tb3 þ and Yb3 þ /Tb3 þ /Eu3 þ co-doped matrices,
energy state due to other non-radiative transition and followed by which have lifetime values up to 5 ms, what is typical for this
the emission of red photon (4F9/2-4I15/2, 658 nm). The above kinds of ions. The most intense UC luminescence was observed in
mentioned transitions result from two-photon processes. How- Yb3 þ /Tb3 þ /Eu3 þ co-doped YPO4 and Yb3 þ /Tm3 þ co-doped LaPO4
ever, also three-photon processes are possible which require the and GdPO4 samples. The determined dependencies of UC emission
absorption of another photon: transition from the 4S3/2 to 4G7/2 on laser energy showed, that almost all of the investigated UC
level. Then, non-radiative transitions to lower lying 4H9/2 and 4F3/2 processes were two-photon, with some exceptions for Yb3 þ /Tm3 þ
levels are needed to obtain the emission from these levels to transitions (three- and four-photon). Also other processes, such as
ground 4I15/2 state at 398 and 461 nm, respectively. saturation and local thermal effects were observed, lowering slope
Three-photon emission was observed in the case of Yb3 þ /Tm3 þ values. Summarizing, the studied REPO4 matrices are good hosts
ions. In this system energy transfer occurs from the 2F5/2 excited for upconverting Ln3 þ ions. Nanomaterials based on them may be
state of Yb3 þ ions to the 3F2 state of Tm3 þ ions. Then, the non- further developed and applied in many areas.
radiative transition occurs to the 3H4 level, from which the next
photon absorption can be feasible and leads to population of the
1
G4 excited state. Third photon absorption from this level to the Acknowledgments
1
D2 state results in the emission of light with wavelength of 450
nm connected with the relaxation to the 3F4 state of Tm3 þ ions. Funding for this research was provided by the Polish National
From the 1D2 excited state also relaxation to the 3H6 ground state Science Center (Grant no. DEC-2011/03/D/ST5/05701).
may occur with emission of the UV light (around 360 nm). Three
photon process is also involved in 1G4-3H6 transition (471 - 478
nm). First, energy is transferred from Yb3 þ ion to the 3H2 level of
Appendix A. Supplementary material
Tm3 þ ions and is followed by deactivation to 3F4 level. Next,
another photon is absorbed to the 3F2 state, which depopulate to
3 Supplementary data associated with this article can be found in
H4 level (here, the photon emission from this level to ground
the online version at http://dx.doi.org/10.1016/j.jlumin.2016.09.028.
state occurs in NIR spectral region). Finally, absorption of the next
photon results in population of the 1G4 state, what leads to the
blue emission. From this state, there can be possible another
emission correlated with 1G4-3F4 transition (646 nm). References
In the Yb3þ /Tb3 þ -doped materials a slightly different mechanism
was observed. In these samples, after NIR excitation of Yb3 þ ions the [1] W. Di, X. Zhao, S. Lu, X. Wang, H. Zhao, Thermal and photoluminescence
properties of hydrated YPO4:Eu3 þ nanowires, J. Solid State Chem. 180 (2007)
cooperative energy transfer into excited-state energy levels of Tb3 þ 2478–2484, http://dx.doi.org/10.1016/j.jssc.2007.06.025.
ions occurs. Then, the 5D4 level of Tb3 þ ions is populated, from which [2] G. Wang, Q. Peng, Y. Li, Lanthanide-doped nanocrystals: synthesis, optical-
the emission is possible. In our materials an intense green emission magnetic properties, and applications, Acc. Chem. Res. 44 (2011) 322–332,
http://dx.doi.org/10.1021/ar100129p.
occurred at 534 nm (5D4-7F5). Also another transitions to 7FJ states [3] M.V. DaCosta, S. Doughan, Y. Han, U.J. Krull, Lanthanide upconversion nano-
were observed, where J¼ 1–6. In Yb3þ /Tb3þ /Eu3 þ co-doped matrices particles and applications in bioassays and bioimaging: a review, Anal. Chim.
the mechanism responsible for the observed emission is similar, with Acta 832 (2014) 1–33, http://dx.doi.org/10.1016/j.aca.2014.04.030.
[4] F. Auzel, Upconversion and anti-Stokes processes with f and d ions in solids,
the exception that much energy is transferred further from Tb3þ (5D4 Chem. Rev. (2004), http://dx.doi.org/10.1021/cr020357g.
level) to Eu3 þ ions (5D1 level) [53]. It can be possible due to the similar [5] G. Chen, H. Qiu, P.N. Prasad, X. Chen, Upconversion nanoparticles: design,
energies of these levels. Next, the non-radiative process occurs from nanochemistry, and applications in theranostics, Chem. Rev. (2014), http://dx.
5 doi.org/10.1021/cr400425h.
D1 to 5D0 level of Eu3þ . There are several radiative transitions pos- [6] S. Lee, K. Teshima, S. Mori, M. Endo, S. Oishi, Selective growth of upconverting
sible from this level (to FJ states, where J¼ 1–4). But the most probable, YbPO4 :Ln (Ln ¼Er or Tm) crystals in a micro reaction cell, Cryst. Growth Des.
in the case of our materials, and responsible for the intense orange 10 (2010) 1693–1698, http://dx.doi.org/10.1021/cg9012729.
[7] J. Chen, J.X. Zhao, Upconversion nanomaterials: synthesis, mechanism, and
emission, is correlated with 5D0-7F2 transition (610 nm). Emission of
applications in sensing, Sensors 12 (2012) 2414–2435, http://dx.doi.org/
Tb3þ ions also occurs in these matrices, so the emission spectra are 10.3390/s120302414.
the combination of Tb3 þ and Eu3þ ions (see Fig. 4). [8] M. Haase, H. Schäfer, Upconverting nanoparticles, Angew. Chem. – Int. Ed. 50
(2011) 5808–5829, http://dx.doi.org/10.1002/anie.201005159.
[9] T. Grzyb, Bright and tunable up-conversion luminescence through cooperative
energy transfer in Yb3 þ , Tb3 þ and Eu3 þ co-doped LaPO4 nanocrystals, RSC
4. Conclusions Adv. (2013), http://dx.doi.org/10.1039/c3ra44596h.
[10] A. Santana-Alonso, J. Méndez-Ramos, A.C. Yanes, J. del-Castillo, V.D. Rodríguez,
White light up-conversion in transparent sol–gel derived glass-ceramics con-
Up-converting rare earth phosphate nanomaterials were suc- taining Yb3 þ –Er3 þ –Tm3 þ triply-doped YF3 nanocrystals, Mater. Chem. Phys.
cessfully prepared with use of the precipitation method followed 124 (2010) 699–703, http://dx.doi.org/10.1016/j.matchemphys.2010.07.038.
by annealing in the air at 1000 °C. This method gave us homo- [11] V.D. Rodríguez, J. Méndez-Ramos, V.K. Tikhomirov, J. Del-Castillo, A.C. Yanes,
V.V. Moshchalkov, Understanding the up-conversion dynamics in high effi-
geneous, single phase and nanocrystalline products with the ciency Yb3 þ –Tm3 þ systems for solar cells, Opt. Mater. (Amst.) 34 (2011)
desired elemental composition. Obtained round and oblong- 179–182, http://dx.doi.org/10.1016/j.optmat.2011.08.006.
shaped nanoparticles had the dimensions of 22–77 nm. Spectro- [12] M. Lin, Y. Zhao, S. Wang, M. Liu, Z. Duan, Y. Chen, et al., Recent advances in
synthesis and surface modification of lanthanide-doped upconversion nano-
scopic measurements showed that the most effective photon particles for biomedical applications, Biotechnol. Adv. (2012), http://dx.doi.
absorption was in the range of 975 and 978 nm and was correlated org/10.1016/j.biotechadv.2012.04.009.
with excitation of the Yb3 þ ions in used co-doping pairs. In the [13] A.K. Singh, K. Kumar, A.C. Pandey, S.B. Rai, D. Kumar, Multi-phonon assisted
upconversion emission and power dependence studies in LaF3:Er3 þ phosphor,
next step, the energy transfer process to emitting ions occurred: in
Spectrochim. Acta A Mol. Biomol. Spectrosc. (2013), http://dx.doi.org/10.1016/
Yb3 þ /Ho3 þ , Yb3 þ /Er3 þ and Yb3 þ /Tm3 þ as well as in Yb3 þ /Tb3 þ j.saa.2013.01.018.
and Yb3 þ /Tb3 þ /Eu3 þ systems. But, in the last two, the cooperative [14] H. Guo, F. Li, J. Li, H. Zhang, Luminescent properties of Eu-doped transparent
energy transfer between Yb3 þ and Tb3 þ ions was necessary and glass-ceramics containing YPO4 nanocrystals, J. Am. Ceram. Soc. 94 (2011)
1651–1653, http://dx.doi.org/10.1111/j.1551-2916.2011.04532.x.
subsequent another energy transfer from Tb3 þ to Eu3 þ ions. All of [15] Z. Xu, Y. Cao, C. Li, P. Ma, X. Zhai, S. Huang, et al., Urchin-like GdPO4 and
that resulted in intense emission with color depended of used co- GdPO4:Eu3 þ hollow spheres – hydrothermal synthesis, luminescence and
420 A. Tymiński, T. Grzyb / Journal of Luminescence 181 (2017) 411–420

drug-delivery properties, J. Mater. Chem. 21 (2011) 3686, http://dx.doi.org/ [35] T. Grzyb, R.J. Wiglusz, A. Gruszeczka, S. Lis, Down- and up-converting dual-
10.1039/c0jm03333b. mode YPO4:Yb3 þ ,Tb3 þ nanocrystals: synthesis and spectroscopic properties,
[16] M.L. Debasu, D. Ananias, S.L.C. Pinho, C.F.G.C. Geraldes, L.D. Carlos, J. Rocha, Gd, Dalton Trans. 43 (2014) 17255–17264, http://dx.doi.org/10.1039/c4dt02234c.
Yb,Tb)PO4 up-conversion nanocrystals for bimodal luminescence–MR ima- [36] T. Grzyb, A. Gruszeczka, R.J. Wiglusz, S. Lis, The effects of down- and up-
ging, Nanoscale 4 (2012) 5154, http://dx.doi.org/10.1039/c2nr31226c. conversion on dual-mode green luminescence from Yb3 þ and Tb3 þ -doped
[17] M.L. Debasu, D. Ananias, J. Rocha, O.L. Malta, L.D. Carlos, Energy-transfer from LaPO4 nanocrystals, J. Mater. Chem. C 1 (2013) 5410, http://dx.doi.org/10.1039/
Gd(iii) to Tb(iii) in (Gd,Yb,Tb)PO4 nanocrystals, Phys. Chem. Chem. Phys. 15 c3tc31100g.
(2013) 15565, http://dx.doi.org/10.1039/c3cp52365a. [37] T. Grzyb, A. Gruszeczka, S. Lis, Up-conversion luminescence of Yb3 þ and Er3 þ
[18] T. Grzyb, A. Gruszeczka, R.J. Wiglusz, S. Lis, The effects of down- and up- doped YPO4, LaPO4 and GdPO4 nanocrystals, J. Lumin. 175 (2016) 21–27, http:
conversion on dual-mode green luminescence from Yb3 þ - and Tb3 þ -doped //dx.doi.org/10.1016/j.jlumin.2016.02.021.
LaPO4 nanocrystals, J. Mater. Chem. C 1 (2013) 5410–5418, http://dx.doi.org/ [38] N. Clavier, R. Podor, N. Dacheux, Crystal chemistry of the monazite structure, J.
10.1039/c3tc31100g. Eur. Ceram. Soc. 31 (2011) 941–976, http://dx.doi.org/10.1016/j.jeurceramsoc.
[19] D. Hou, H. Liang, M. Xie, X. Ding, J. Zhong, Q. Su, et al., Bright green-emitting, 2010.12.019.
energy transfer and Gd under VUV-UV excitation, Opt. Express 19 (2011) [39] J.C. Nipko, M. Loewenhaupt, W. Reichardt, M. Braden, L. a Boatner, Lattice
761–773. dynamics of LuPO4, J. Alloys Compd. 250 (1997) 573–576.
[20] D. Bregiroux, F. Audubert, D. Bernache-Assollant, Densification and grain [40] Y.Q. Jia, Crystal radii and effective ionic radii of the rare earth ions, J. Solid
growth during solid state sintering of LaPO4, Ceram. Int. 35 (2009) 1115–1120, State Chem. 95 (1991) 184–187, http://dx.doi.org/10.1016/0022-4596(91)
http://dx.doi.org/10.1016/j.ceramint.2008.05.005. 90388-X.
[21] F. Meiser, C. Cortez, F. Caruso, Biofunctionalization of fluorescent rare-earth- [41] R.D. Shannon, Revised Effective Ionic Radii, and Systematic Studies of Inter-
doped lanthanum phosphate colloidal nanoparticles, Angew. Chemie Int. Ed. atomie Distances in Halides and Chaleogenides bond strength-bond length
43 (2004) 5954–5957, http://dx.doi.org/10.1002/anie.200460856. relationships , and plots of (1) radii vs volume, (2) radii vs coordination partial
[22] M. Yang, H. You, G. Jia, Y. Huang, Y. Song, Y. Zheng, et al., Selective synthesis of occupancy of cation sites, coval, Acta Crystallogr. A32 (1976) 751–767, http:
hexagonal and monoclinic LaPO4:Eu3 þ nanorods by a hydrothermal method, //dx.doi.org/10.1107/S0567739476001551.
J. Cryst. Growth 311 (2009) 4753–4758, http://dx.doi.org/10.1016/j.jcrysgro. [42] L. Zhang, T. Xue, D. He, M. Guzik, G. Boulon, Influence of Stark splitting levels
2009.09.027. on the lasing performance of Yb3 þ in phosphate and fluorophosphate glasses,
[23] S. Chawla, V. Kumar, P. Rani, D. Singh, Efficient multiphoton upconversion and Opt. Express 23 (2015) 1505–1511, http://dx.doi.org/10.1364/OE.23.001505.
synthesis route dependent emission tunability in GdPO4:Ho3 þ ,Yb3 þ nano- [43] S.A. Klimin, M.N. Popova, E.P. Chukalina, B.Z. Malkin, A.R. Zakirov, E. Antic-
crystals, RSC Adv. (2014) 36101–36105, http://dx.doi.org/10.1039/C4RA04795H. Fidancev, Ph. Goldner, P. Aschehoug, G. Dhalenne, Stark structure of the Yb3 þ
[24] T. Shimizu, T. Isobe, Relation between shell thickness and near infrared pho- ion levels in (YbxY1 – x)2Ti2O7 and the crystal field in rare-earth titanates with
toluminescence of LaPO4:Yb3 þ /GdPO4 core/shell nanoparticles, Mater. Lett. a pyrochlore structure, Phys. Solid State 47 (2005) 1425, http://dx.doi.org/
110 (2013) 180–183, http://dx.doi.org/10.1016/j.matlet.2013.08.017. 10.1134/1.2014481.
[25] M. Runowski, K. Dąbrowska, T. Grzyb, P. Miernikiewicz, S. Lis, Core/shell-type [44] A. de Pablos-Martín, A. Durán, M.J. Pascual, Nanocrystallisation in oxyfluoride
nanorods of Tb3 þ -doped LaPO4, modified with amine groups, revealing systems: mechanisms of crystallisation and photonic properties, Int. Mater.
reduced cytotoxicity, J. Nanoparticle Res. 15 (2013) 2068, http://dx.doi.org/ Rev. 57 (2012) 165–186, http://dx.doi.org/10.1179/1743280411Y.0000000004.
10.1007/s11051-013-2068-5. [45] R. Scheps, Upconversion laser processes, Ptog. Quant. Electron. 20 (1996)
[26] Z. Xu, P. Ma, C. Li, Z. Hou, X. Zhai, S. Huang, et al., Monodisperse core–shell 271–358, http://dx.doi.org/10.1016/0079-6727(95)00007-0.
structured up-conversion Yb(OH)CO3@YbPO4:Er3 þ hollow spheres as drug [46] M. Pollnau, D. Gamelin, S. Lüthi, H. Güdel, M. Hehlen, Power dependence of
carriers, Biomaterials 32 (2011) 4161–4173, http://dx.doi.org/10.1016/j. upconversion luminescence in lanthanide and transition-metal-ion systems,
biomaterials.2011.02.026. Phys. Rev. B 61 (2000) 3337–3346, http://dx.doi.org/10.1103/PhysRevB.61.3337.
[27] V. Kumar, S. Singh, R.K. Kotnala, S. Chawla, GdPO4:Eu3 þ nanoparticles with [47] Y. Lei, H. Song, L. Yang, L. Yu, Z. Liu, G. Pan, et al., Upconversion luminescence,
intense orange red emission suitable for solar spectrum conversion and their intensity saturation effect, and thermal effect in Gd2O3:Er3,Yb3 þ nanowires, J.
multifunctionality, J. Lumin. 146 (2014) 486–491, http://dx.doi.org/10.1016/j. Chem. Phys. 123 (2005) 174710, http://dx.doi.org/10.1063/1.2087487.
jlumin.2013.10.040. [48] T. Grzyb, K. Kubasiewicz, A. Szczeszak, S. Lis, Energy migration in YBO3:Yb3 þ ,
[28] C. Ming, F. Song, L. An, X. Ren, Y. Yuan, Y. Cao, et al., Research on up- and down- Tb3 þ materials: down- and upconversion luminescence studies, J. Alloys
conversion emissions of Er3 þ /Yb3 þ co-doped phosphate glass ceramic, Opt. Mater. Compd. 686 (2016) 951–961, http://dx.doi.org/10.1016/j.jallcom.2016.06.230.
(Amst.) 35 (2012) 244–247, http://dx.doi.org/10.1016/j.optmat.2012.08.004. [49] J. Castañeda, Saturation effect of up-conversion luminescence from erbium-
[29] X. Yu, F. Song, C. Zou, L. Luo, C. Ming, W. Wang, et al., Temperature dependence doped, silica-titania sol-gel powders, J. Rare Earths 29 (2011) 420–425, http:
of luminescence behavior in Er3 þ /Yb3 þ co-doped transparent phosphate glass //dx.doi.org/10.1016/S1002-0721(10)60472-3.
ceramics, Opt. Mater. (Amst.) 31 (2009) 1645–1649, http://dx.doi.org/10.1016/ [50] J. Castañeda-Contreras, M.A. Meneses-Nava, O. Barbosa-García, R. Chiu-Zárate,
j.optmat.2009.03.017. M.V. Félix, R. Rodriguez, Up-conversion luminescence saturation under pulsed
[30] D. Bregiroux, S. Lucas, E. Champion, F. Audubert, D. Bernache-Assollant, Sin- excitation of erbium-doped, SiO2TiO2 solgel powders, J. Lumin. 130 (2010)
tering and microstructure of rare earth phosphate ceramics REPO4 with 2356–2361, http://dx.doi.org/10.1016/j.jlumin.2010.07.019.
RE ¼ La, Ce or Y, J. Eur. Ceram. Soc. 26 (2006) 279–287, http://dx.doi.org/ [51] L. Guo, Y.Y. Wang, J. Zhang, P. Dong, Crystal structure and up- and down-
10.1016/j.jeurceramsoc.2004.11.004. conversion properties of Yb3 þ , Ho3 þ codoped BaGdF5 solid-solution with
[31] T. Grzyb, A. Gruszeczka, R.J. Wiglusz, Z. Śniadecki, B. Idzikowski, S. Lis, Mul- different morphologies, Cryst. Eng. Comm. 14 (2012) 3131, http://dx.doi.org/
tifunctionality of GdPO4:Yb3 þ ,Tb3 þ nanocrystals – luminescence and mag- 10.1039/c2ce06616e.
netic behaviour, J. Mater. Chem. 22 (2012) 22989–22997, http://dx.doi.org/ [52] L. Tao, W. Xu, Y. Zhu, L. Xu, H. Zhu, Y. Liu, et al., Modulation of upconversion
10.1039/c2jm34863b. luminescence in Er3 þ , Yb3 þ -codoped lanthanide oxyfluoride (YOF, GdOF,
[32] H. Lai, Y. Du, M. Zhao, K. Sun, L. Yang, Effects of different organic additives on LaOF) inverse opals, J. Mater. Chem. C. 2 (2014) 4186–4195, http://dx.doi.org/
the formation of YPO4:Eu3 þ nano-/microstructures under hydrothermal 10.1039/c4tc00024b.
conditions with enhanced photoluminescence, Ceram. Int. 40 (2014) [53] T. Grzyb, Bright and tunable up-conversion luminescence through cooperative
1885–1891, http://dx.doi.org/10.1016/j.ceramint.2013.07.094. energy transfer in Yb3 þ , Tb3 þ and Eu3 þ co-doped LaPO4 nanocrystals, RSC
[33] Y. Wei, F. Lu, X. Zhang, D. Chen, Polyol-mediated synthesis of water-soluble Adv. 4 (2014) 2590–2595, http://dx.doi.org/10.1039/c3ra44596h.
LaF3:Yb,Er upconversion fluorescent nanocrystals, Mater. Lett. 61 (2007)
1337–1340, http://dx.doi.org/10.1016/j.matlet.2006.07.029.
[34] T. Grzyb, S. Lis, Photoluminescent properties of LaF3:Eu3 þ and GdF3:Eu3 þ
nanoparticles prepared by co-precipitation method, J. Rare Earths 27 (2009)
588–592, http://dx.doi.org/10.1016/S1002-0721(08)60294-X.