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Intense UV upconversion through highly sensitized

NaRF4:Tm (R:Y,Yb) crystals
Cite this: RSC Adv., 2015, 5, 35858
Vishal Kale,*a Mika Lastusaari,bc Jorma Holsabcd and Tero Soukkaa

Photon upconverting luminescent hexagonal NaRF4:Tm (0.5 mol%) (R:Y3+,Yb3+) crystals with Yb3+
concentrations between 20 and 99.5 mol% were synthesized by a modied thermal coprecipitation
method. The eects of the Yb3+ sensitizer concentration on the shape, size, structure, upconversion
luminescence intensities and dynamic luminescence lifetimes were studied in detail. The intensity of
ultraviolet upconversion luminescence at 340365 nm upon 980 nm excitation increased up to
20 times with increasing Yb3+ concentration. The mechanisms for the changes in morphology, size and
UV upconversion emission are discussed. In addition, the eect of the Tm3+ concentration on the UV
Received 27th January 2015
Accepted 13th April 2015
emission of NaYbF4 crystals was investigated. The results demonstrate that the NaYbF4 with Tm3+
concentration between 0.4 to 0.8 mol% produce the most intense UV upconversion luminescence.
DOI: 10.1039/c5ra01613d
These crystals may nd applications in e.g. UV-visible solid state lasers or as an internal UV radiation
www.rsc.org/advances source for many photochemical reactions.

general, the nanocrystal structure and size highly depend on the

Introduction
Lanthanides and rare earths have gained wide research interest
during the last decades due to their unique electronic,
magnetic, optical and chemical characteristics arising from the
4f electrons.13 Lanthanide-based photon upconversion (UC)
has been known since the 1960's and photon upconverting
nanoparticles (UCNPs) are already widely applied in many
applications ranging from medical diagnostics to solar energy
harvesting.411 Photon upconversion is a nonlinear optical
process that converts the energy of two or more NIR photons
into a single emitted photon at shorter wavelength (higher
energy). Among the photon upconverting nanomaterials,
hexagonal NaYF4 (b-NaYF4) nanocrystals have been intensively
investigated as the most ecient upconversion host material
available to date, because of their low phonon energy and the
high quantum eciencies obtained.12,13 It is known that also
the nanocrystal size, structure, morphology and dopant ion
concentration play crucial roles in the UC process.1416 In
a
Department of Biotechnology, University of Turku, Tykistokatu 6 A, FI-20520 Turku,
Finland. E-mail: visoka@utu.
b
Department of Chemistry, University of Turku, FI-20014 Turku, Finland
c
Turku Centre for Materials and Surfaces (MatSurf), Turku, Finland
d
Instituto de Qumica, Universidade de Sao Paulo, Sao Paulo-SP, Brazil
Electronic supplementary information (ESI) available: Non-normalized intensity
spectra and lifetime decay of the NaY1
xYbxF4:Tm (0.5%) and NaYbF4:Tm (x%)
nanocrystal dispersion in oleic acid pumped by 980 nm laser. Table with the
summary of decay times of 3H4, 1G4 and 1D2 level of NaY1
xYbxF4:Tm (0.5%)
and NaYbF4:Tm (x%) samples with respective amplitude. Low resolution TEM
images of the bigger UCNPs. SEM-EDX analysis results of NaYbF4:Tm (0.8%)
nanocrystals. See DOI: 10.1039/c5ra01613d
synthesis temperature, while commonly used organic additives
act as shape modiers to control the morphology of UCNPs.
Currently, the research challenges comprise e.g. the optimal
dopant ion combinations and understanding the behaviour of
the relative intensities of dierent radiative transitions in
luminescence spectrum of UC materials.
In recent years, ultraviolet (UV) UC photoluminescence has
become one hot topic of optical functional materials. High
energy UV emission is extremely important in many photo-
chemical reactions in the eld of chemical biology and
advanced imaging.1719 Intense UV emitting UCNPs are of
special signicance with potential technological applications in
microelectronic devices and solid-state lasers.20 In our previous
report, it was successfully demonstrated that UV emitting
UCNPs can be used as an internal light source to form a shell
with dierent functional groups around the particles to further
facilitate their use in applications like bioassays, biosensing
and theranostics.21 The main limitation for practical applica-
tions of upconversion materials is the insucient upconversion
eciency; especially 980 nm excited UV UC photoluminescence
remains challenging because it requires at least four NIR
photons to populate the UV emitting excited states of Tm3+.
Although NIR-excited UC to visible/NIR from NaYF4 with
Er3+/Tm3+ and Yb3+ has been extensively studied, NIR-excited
UC to UV is still less understood.22,23
UV UC properties in b-NaYF4 nanocrystals containing
sensitizer Yb3+ and activator Tm3+ ions have been reported
earlier.24 The doping concentration of lanthanide ions however
seems to be very important in getting ecient UV UC emis-
sion.25 Recently, some researchers have focused their

35858 | RSC Adv., 2015, 5, 3585835865 This journal is The Royal Society of Chemistry 2015

Paper
investigations on UV UC emission enhancement by doping with
dierent ions or by a coreshell approach: e.g. Shen et al. have
demonstrated the enhanced UV emission in CaF2 coated cubic
NaYF4 (a-NaYF4) nanocrystals.26 Zeng et al. obtained higher UV
emission from NaYbF4 microtubes compared to cubic NaYF4
nanocrystals27 and Zang et al. reported the deep-ultraviolet UC
emissions from Gd3+ doped NaYF4:Yb,Tm nanorods.28 It should
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be noted that although there are a few strategies to enhance the
UV emission from UCNPs, systematic studies of sensitizer
concentration dependency of UV emission are scarce in
literature.
In this work, a simple method is presented to increase the
NIR to UV UC photoluminescence by replacing Y3+ from
NaYF4:Yb,Tm crystals with Yb3+. The eect is investigated by
stepwise increasing the sensitizer (Yb3+) concentration and
optimizing the activator (Tm3+) concentration range for the
NaYbF4 (xYb 100%) host. In addition, the inuence of
dierent Yb3+ and Tm3+ concentrations on crystal size, shape,
structure and optical properties such as UC luminescence
intensity and decay lifetime were also investigated.
Experimental section
Reagents
All of the chemicals were of analytical grade and used as
received without further purication. Yttrium, ytterbium and
thulium chloride hexahydrate (RCl3$6H2O, 99.99%), ammo-
nium uoride (NH4F, $99.99%) and sodium hydroxide (NaOH,
$98%), 1-octadecene (ODE, 90%) and oleic acid (OA, 90%) were
purchased from Sigma-Aldrich. The purities of the rare earth
chlorides are with respect to other rare earths. Absolute ethanol
and methanol were used as received.
Material synthesis
Synthesis of NaY1
xYbxF4:Tm (0.5%). The synthesis protocol
for the UCNPs was adopted from our previously published
procedure.29 Briey, the syntheses of 0.5% Tm doped
NaY1
xYbxF4 UCNPs were done by stepwise substitution of Y3+
by 20, 40, 60, 80 and 100% of the sensitizer ion Yb3+ (the
percentage of Yb3+ is with respect to the total rare earth contents
excluding the activator). In a typical experiment, 0.2 mol dm
3
RCl3$6H2O (R:Y and/or Yb, Tm) in methanol were added to a
250 cm3 two neck round-bottom ask containing 9 cm3 oleic
acid (OA) and 21 cm3 1-octadecene (ODE). The solution was
magnetically stirred and heated to 160  C under owing argon
for 40 min to form the rare earth oleate complex and then
cooled down to room temperature. Thereaer, 15 cm3 of the
methanol solutions of both NH4F (4.8 mmol) and NaOH
(3 mmol) were added and the solution was stirred for 30 min
without a protective gas sphere to evaporate methanol and to
ensure that all the uorides were consumed completely. The
temperature was then increased to 310  C and maintained there
under argon for 90 min. Aer the solution was slowly cooled
down to room temperature, absolute ethanol was added to the
reaction solution to precipitate the nanocrystals. The solution
was then transferred to the centrifuge tube and centrifuged at
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3766 g for 8 min, so that the nanoparticles separated out
completely. This washing procedure was repeated 6 times to
ensure washing away any NaF impurity that may have formed.
Finally, the nanoparticles were re-dispersed in toluene for
further experiments.
Synthesis of NaYbF4:Tm (x%). Hexagonal NaYbF4:Tm (x%)
were synthesized by replacing all Y3+ ions with the sensitizer
Yb3+ ions and varying the activator ion (Tm3+) concentration
(xTm 0.05, 0.2, 0.4, 0.6, 0.8, 1 and 5%: the percentage of Tm3+
is with respect to the total rare earth contents). The synthesis
and washing procedure is the same as that described for the
NaY1
xYbxF4:Tm (0.5%) crystals. Finally, the nanoparticles were
re-dispersed in toluene for further experiments.
Characterization
The size and morphology of the nanocrystals was characterized
by transmission electron microscopy (Tecnai12 BioTwin TEM)
with an acceleration voltage of 120 kV. The TEM specimens were
prepared by directly drying a drop of a diluted toluene disper-
sion solution of the as prepared product on the surface of a
carbon coated copper grid. The structural phase identication
of the synthesized samples was carried out with X-ray powder
diraction (XPD) using a Huber G670 image plate Guinier
camera (2q range: 4100 ) with copper Ka1 radiation (l: 1.5406
A). Data collection time was 30 min with 10 scans of the image
plate.
The crystallite size, shape and aspect ratio was calculated
from the XPD data by using the Scherrer equation30 with
instrumental correction from the full width at half maximum
(FWHM) determined for a Si reference material (NIST standard
640b):
0:9l
d with b2 bs 2
br 2
b cos q
where d (m) is the mean crystallite size, l (m) the X-ray wave-
length, b (rad) the FWHM of the chosen reection and q ( ) half
of the Bragg's angle (2q). br, bs and b are the reference, sample
and corrected FWHM respectively. The (002) and (200) reec-
tions were used for calculating the length of the hexagonal
plates and the width of the hexagonal faces, respectively, thus
giving the size and morphology of the crystallites.
The UC luminescence spectra were recorded on Varian Cary
Eclipse uorescence spectrophotometer (Varian Scientic
Instruments, Mulgrave, Australia) equipped with a 980 nm laser
diode module C2021-F1 (Roithner Lasertechnik, Vienna,
Austria). The excitation power used in the experiment was
200 mW with a focusing area of approximately 2.4 mm2. The
elemental composition was analysed by LEO 1530 Gemini
scanning electron microscope with a Thermo Scientic UltraDry
SDD X-ray detector (SEM-EDX).
Results and discussion
Phase identication and morphology
All synthesized materials showed well-dened strong and
sharp reections in their XPD patterns (Fig. 1), conrming the
RSC Adv., 2015, 5, 3585835865 | 35859

RSC Advances
good crystallinity and purity of the products. For the phos-
phors, high crystallinity is important as it means less energy
traps and strong luminescence. It has been reported that the
hexagonal NaRF4 is a by far better host lattice for high UC
emission than the cubic phase.31 All XPD patterns agreed well
with the hexagonal NaYF4 reference pattern indicating that
increased Yb3+ and Tm3+ concentrations did not induce phase
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transitions in the NaY1
xYbxF4:Tm (0.5%), and NaYbF4:Tm
(x%) crystals.32
The shape and size of the synthesized crystals were further
characterized with transmission electron microscopy (TEM).
Fig. 2 shows the typical TEM images of as prepared
NaY1
xYbxF4:Tm (0.5%) with dierent concentrations of Yb3+:
(a) 20, (b) 40, (c) 60, (d) 80, (e) 100% and NaYbF4:Tm (x%)
crystals with dierent concentrations of Tm3+: (f) 0.05, (g) 0.2,
(h) 0.4, (i) 0.6, (j) 0.8, (k) 1 and (l) 5%. The increase or decrease in
rare earth ion concentrations with respect to each other does
not aect the crystal structure, while in case of crystal size and
shape the Yb3+ and Y3+ concentrations play a vital role. UCNPs
with Yb3+ concentration up to 40% have small spherical shape
which changes to hexagonal plate when Yb3+ concentration is
Fig. 1 XPD patterns of hexagonal NaY1
xYbxF4:Tm (0.5%) with
dierent concentrations of Yb3+ (top) and NaYbF4:Tm (x%) crystals
with dierent concentrations of Tm3+ (bottom), along with a reference
pattern calculated with PowderCell33 based on structural data repor-
ted.32 The additional reections are the traces of * sodium chloride
(NaCl) and cubic NaRF4 impurities.
35860 | RSC Adv., 2015, 5, 3585835865
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increased further. On the other hand increase or decrease in the
Tm3+ ion concentration up to 0.6% keeps the particle size
unaected but further increase in the activator concentration
gives also small UCNPs as a byproduct.
As one can see from the TEM images, at low sensitizer ion
concentration, b-NaYF4: 20% Yb, 0.5% Tm nanoparticles appear
nearly spherical in shape and monodisperse. The average
diameter of the 20% Yb3+ doped nanoparticles is around 25 nm
(Fig. 2a). When the Yb3+ concentration increased further to
40%, the particles grew up to 90 nm in all directions, keeping
the spherical shape unchanged (Fig. 2b). At medium Yb3+ ion
concentration, hexagonal plates with sharp edges can be
prepared, which is shown in Fig. 2c and the average diameter
calculated is about 150 nm. When the experiment is performed
at 80% Yb3+ concentration, most of the Y3+ ions are already
replaced by Yb3+ resulting in bigger hexagonal plates with a
diameter of about 900950 nm, which are basically poly-
crystalline plates made up from many small plates (Fig. 2d) as
indicated by the Scherrer calculations. In the case of the
NaYbF4:Tm (0.5%) crystals, where all Y3+ was replaced by Yb3+,
the biggest polycrystalline hexagonal plates of about 1000 nm
are formed (Fig. 2e). According to the Scherrer calculations,
these are also polycrystalline. The low resolution TEM images
showing homogeneity and size distributions of the particles are
presented in the ESI, Fig. S6.
Fig. 2 TEM images of hexagonal NaY1
xYbxF4:Tm (0.5%) with dierent
concentrations of Yb3+: (a) 20, (b) 40, (c) 60, (d) 80, (e) 100% and
NaYbF4:Tm (x%) crystals with dierent concentrations of Tm3+: (f)
0.05, (g) 0.2, (h) 0.4, (i) 0.6, (j) 0.8, (k) 1 and (l) 5%.
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Table 1 Summary of the morphologies, structure and dimensions Regarding the growth mechanism, it is important to
obtained with TEM for the NaY1
xYbxF4:Tm (0.5%) crystals consider also the relation between the reaction temperature,
initially formed crystals and the role of the chelating agent. It is
Yb3+ Y3+
(mol%)a (mol%)a Structure Morphology Size known that the reaction temperature plays a crucial role in the
a / b phase transition of NaYF4 and also the concentration of
20 80 Hexagonal Nanosphere 25 Yb3+ embedded in NaYF4 matrix aects the temperature of the
40 60 Hexagonal Nanosphere z90 phase transition in such a way that the temperature decreases
z150
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60 40 Hexagonal Hexagonal plates

80 20 Hexagonal Hexagonal plates
100 0 Hexagonal Hexagonal plates
a mechanism for the b-NaRF4:Tm crystals with dierent Y/Yb
The percentages are with respect to the added quantity in the
synthesis.
For the NaYbF4 crystals with dierent Tm3+ ion concentra-
tions, the shape and size of the particles remains the same until
the 0.6% Tm3+ doping level, the average diameters of all
hexagonal plates being between 1000 and 1200 nm (Fig. 2fi).
The Tm3+ ion concentration of 0.8% induces the formation of
small spherical particles along with the bigger hexagonal plates.
The diameter of the large plates is about 750800 nm and that of
the small particles is up to 10 nm (Fig. 2j). The SEM-EDX anal-
ysis of both small and large particles shows that the elemental
composition is the same in both size fractions (results of 0.8%
Tm3+ sample are presented in the ESI, Fig. S5). For small
particles, the Tm3+ is not detectable by the instrument as the
concentration of Tm3+ is very small in the sample. A further
increase in the Tm3+ concentration results in an increase in the
population of small particles with about 25 nm in diameter
along with few large hexagonal plates of about 900 nm (Fig. 2k
and l). The eect of the Yb3+ and Tm3+ concentrations on the
crystal size, shape and structure are listed in Tables 1 and 2.
Crystal growth mechanisms
The experimental results show that the substitution of Y3+ in the
host lattice by Yb3+ has a clear eect on the particle morphology
and size. To investigate the formation process the sensitizer
concentrations of NaY1
xYbxF4:Tm (0.5%) were increased
stepwise by keeping all other synthesis parameters constant.
900950
with increasing the Yb3+ content.34 In the present work, 310  C
9501000 used is quite high for NaRF4 with high Yb3+ content and this
and z20 results in large particles. Fig. 3 shows the possible formation
concentrations.
In the actual process, aer dissolution and renucleation the
unstable a-NaRF4 phase is transformed to the stable b-NaRF4.
As the Yb3+ concentration in the reaction mixture increases the
formation of the initial b-NaRF4 crystals will be faster and there
is more time for crystal growth. This is because the increased
Yb3+ concentration lowers the phase transition temperature.35
The nanocrystal formation mechanism for the UCNPs with
20 and 40% Yb3+ is a one step process and the phase transition
from a / b was completed somewhat below 310  C, which
nally gives uniform 25 and 90 nm nanocrystals respectively
(Fig. 3a and b). At these lower Yb3+ concentrations the growth
rates in all directions are comparable which results in the
spherical shape.
For the 60, 80 and 100% Yb3+ samples, the a / b phase
transformation is completed well below 310  C. As the initially
formed b-NaRF4 has the hexagonal shape with an anisotropic
structure, the crystal growth is anisotropic, as well. The hexag-
onal structure has four axes; three assistant axes intersecting
each other at 60 degrees and one principle axis perpendicular to
the hexagonal (001) crystal surface (Fig. 3, inset).36,37 The growth
mechanism of the crystal depends on the growth rates along the
dierent crystal axes which results into the dierent shapes of
the nal crystals. Once the hexagonal b-NaRF4 is formed, the
oleic acid (OA) starts to show its inuence as shape modier. OA
strongly reacts with the top/bottom (001) surfaces of the
growing crystallites and lowers their surface energy, which
results into the fast growth along the assistant axes rather than
the principle axis. For the 60% Yb3+ sample, this anisotropic

Table 2 Summary of the morphologies, structure and dimensions

obtained with TEM for the NaYbF4:Tm (x%) crystals

Tm3+ (mol%)a Structure Morphology Size

0.05 Hexagonal Hexagonal plates z950

0.2 Hexagonal Hexagonal plates z10001200
0.4 Hexagonal Hexagonal plates 900950
0.6 Hexagonal Hexagonal plates 900950
0.8 Hexagonal Hexagonal plates 800 and #10
1 Hexagonal Hexagonal plates 900 and z25
5 Hexagonal Hexagonal plates 900 and z25
a
The percentages are with respect to the added quantity in the Fig. 3 Schematic representation of formation procedure of
synthesis. b-NaRF4,Tm (0.5%) with dierent Yb3+ concentrations. Inset is the
schematic diagram showing the anisotropy of the b-NaRF4 crystals.

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growth results into 130150 nm hexagonal nanoplates (Fig. 3c).
For the 80 and 100% Yb3+ samples, the temperature during the
second heating may assist the formed hexagonal plates to self-
assemble and anneal into the larger hexagonal polycrystalline
structures with about 1000 nm size (Fig. 3d and e). This
hypothesis of self-assembly of the nanoplates into larger poly-
crystals was supported by the calculations of diracting domain
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radiative relaxation are responsible for the emissions at 475,
650, 690 and 800 nm. In the samples with lower Tm3+ content
(0.05%) the simple piling of NIR photons (black thick arrows
shown in the Fig. 5) is the only way to populate the 1D2 level. It is
however not a very ecient process, because of the large energy
mismatch between the energy dierence of the 1D2 and 1G4
levels and the NIR photon energy. In the samples with Tm3+

sizes from the XPD patterns (Table 3). The data shows that, for
the 80 and 100% Yb3+ samples, the hexagonal particles formed
at the end of reaction are polycrystalline made up by aggrega-
tion of 130150 nm nanoplates.
Upconversion luminescence properties
To investigate the optical properties, the UC photo-
luminescence of colloidal NaY1
xYbxF4:Tm (0.5%) and
NaYbF4:Tm (x%) crystals (0.1 mg ml
1 suspension in oleic acid)
was measured under 980 nm diode laser excitation. As shown in
the Fig. 4a and b, six UC photoluminescence lines were clearly
resolved, centered at 346, 365, 450, 475, 649 and 800 nm, which
correspond to the 1I6 / 3F4, 1D2 / 3H6, 1D2 / 3F4, 1G4 / 3H6,
1
G4 / 3F4, and 3H4 / 3H6 transitions of Tm3+, respectively
(non-normalized intensity spectra are in the ESI, Fig. S1 and
S4). The weak emission at 511 nm arises from the transition of
1
D2 / 3H5 and the lines at 690 and 720 nm correspond to the
second order of 345 and 365 nm.38
The energy levels of Yb3+ and Tm3+ ions as well as the
proposed UC pathways under excitation at 980 nm are shown in
Fig. 5. Aer 980 nm excitation, the sensitizer ion Yb3+ transfers
energy to the neighbouring Tm3+ ions. Three successive energy
transfers from Yb3+ to Tm3+ populate the 3H5, 3F2 and 1G4 levels
of Tm3+. These energy transfer processes along with some non-
content up to 0.8%, the cross relaxation 3F2 + 3H4 / 3H6 + 1D2
between the two Tm3+ ions plays an important role in popu-
lating the 1D2 level. The radiative relaxation from the 1D2 level
gives the 365 and 450 nm emissions. Further increase in Tm3+
concentration, however, results in the depopulation of the
higher emitting levels due to self-quenching. The Tm3+ ions in
the 1D2 level can be excited to the 3P2 level by the fourth energy
transfer mechanism from Yb3+ ions which relax rapidly to the
1
I6 level giving another UV band centered at 346 nm.
To increase the eciency of the UV UC photoluminescence,
we gradually increased the amount of the sensitizer ions (Yb3+),
replacing Y3+ in the host material. As seen from the Fig. 4a, in
hexagonal NaY1
xYbxF4 crystals with xed Tm3+ concentration
at 0.5%, all the emission intensities were increased stepwise
along with the increase of the concentration of Yb3+ from 20%
to 100%. The maximum UV emission was observed with 100%
Yb3+ and the UC intensities at 346 and 365 nm emissions were
measured to be about 20 and 18 times higher than that of the
20% Yb3+ sample, respectively. Along with the increase in the
UV emission, the visible emission centered at 450 nm was also
increased 30 times. The enhancement in the UV and visible
emissions partially come from the fact that, with higher Yb3+
concentration the particle size increases, which decreases the
surface to volume ratio. This decreases the amount of surface
quenching centers and thus facilitates the high UC emission.

Table 3 Summary of decay times from the emitting 3H4, 1G4 and 1D2 level of NaY1
xYbxF4:Tm (0.5%) and NaYbF4:Tm (x%) with width to length
(W/L) ratio and morphology calculated with the Scherrer methoda

Decay times (ms)

NaY1
xYbxF4:Tm
(0.5%) x mol%# W (nm) L (nm) W/L Morphology 3
H4 / 3H6 1
G4 / 3 H 6 1
D2 / 3H6

20 27 24 1.12 Spherical 630 8 576  2 168  0.3

40 30 28 1.04 Spherical 422 5 547  2 142  0.3
60 53 34 1.55 Hexagonal plate 378 7 224  2 138  0.3
80 56 35 1.59 Hexagonal plate 440 5 362  2 157  0.4
100 149 79 1.89 Hexagonal plate 375 1 293  4 137  0.3

Decay times (ms)

NaYbF4:Tm (x%)
x mol%# W (nm) L (nm) W/L Morphology 3
H4 / 3H6 1
G4 / 3H6 1
D2 / 3H6

0.05 212* 104 2.04 Hexagonal plate 481 4 510  5 272  1

0.2 117 68 1.72 Hexagonal plate 470 5 427  0.5 235  2
0.4 92 70 1.31 Hexagonal plate 430 7 358  1 169  0.5
0.6 125 89 1.40 Hexagonal plate 321 5 256  3 125  76
0.8 146 115 1.27 Hexagonal plate 337 2 169  2 98  0.2
1 1011* 95 Hexagonal plate 275 2 148  0.5 82  0.3
5 325* 162 Hexagonal plate 70  0.5 82  3 80  10
a
Note: * the crystals are too large for Scherrer method, which commonly can treat sizes up to 150 nm, the decay time with the highest amplitude in
case of multiexponential decay, # the percentages are with respect to the added quantity in the synthesis.

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Fig. 5 Energy level diagrams of the Yb3+ and Tm3+ ions as well as the
proposed UC mechanism for UV and visible emissions along with
quenching mechanism by cross relaxation.

using the UC emission spectra of NaYbF4:Tm (xTm 0.05, 0.2,

0.4, 0.6, 0.8, 1 and 5%) crystals (Fig. 4b). The UV emission
intensity increases as the Tm3+ concentration increases from
0.05 to 0.4%; it remains steady in the range of 0.4 to 0.8% and
decreases with further increase in Tm3+ concentration. From
Fig. 4 Upconversion luminescence spectra of colloidal (a) the inset in Fig. 4b it is clear that the optimal range of the Tm3+
NaY1
xYbxF4:Tm (0.5%) (xYb 20, 40, 60, 80 and 100%) and (b) concentration for highest UV and visible emission is between
NaYbF4:Tm (x%) (xTm 0.05, 0.2, 0.4, 0.6, 0.8, 1 and 5%) crystals under 0.4 and 0.8%. The reason for such a dramatic decrease in the UV
980 nm excitation in oleic acid suspension, normalized at the emission and visible emission intensities with higher Tm3+ concentration
peak of 800 nm. The inset shows the intensity variation of all major
can be the self-quenching of the Tm3+ 1D2 and 1G4 levels.40
emissions as a function of (a) Yb3+ and (b) Tm3+ concentrations.
There are at least three dierent cross relaxation processes i.e.
1
D2 + 3H6 / 3F3 + 3H4, 1D2 + 3F3 / 1G4 + 1G4 and 1D2 + 3H6 /
3
H4 + 3F2 which are responsible for depopulating the UV emit-
The increased particle size, however, does not explain the whole
ting 1D2 energy level in samples with higher Tm3+ content (thick
enhancement mechanism as the decrease in surface to volume
black doted arrows shown in Fig. 5). Two out of these three cross
ratio aer z150 nm particle size has no such strong inuence
relaxation processes feed the 3H4 energy level which may
on the UC spectra as reported before.39 Along with particle size
explain the enhancement in the 800 nm emission with increase
there are thus other important factors which contribute to the
in the Tm concentrations up to 0.8%.
intense UV and visible emissions. The increased Yb3+ concen-
In Fig. 6, the ratio of the 365/800 nm emission intensities
tration (keeping Tm3+ concentration xed at 0.5%) increases the
were plotted at dierent (a) Yb3+ and (b) Tm3+ concentrations.
sensitization by absorbing more NIR photons and enhances the
The 365/800 nm intensity ratio from the NaY1
xYbxF4:Tm
Yb-to-Yb energy migration as well as the Yb-to-Tm energy
(0.5%) samples increases with Yb3+ concentration (Fig. 6a) and
transfer probabilities, which leads to the increase of the pop-
the highest ratio is obtained with 100% Yb3+ (the most excessive
ulation at 1I6 and 1D2 levels of the Tm3+ ions. The inset of Fig. 4a
shows the variation of the dierent emission intensities as a
function of Yb3+ concentration. Increasing the Yb3+ concentra-
tion beyond 60%, resulted in only small enhancement of the
475 and 800 nm emissions (4.5 and 2.7 times compared to 80%
and 20% Yb samples) is observed. The increased sensitization
by Yb3+ and the higher probability of energy migration due to
shorter Yb-to-Yb distances can increase the probability of UV
emission from Tm3+ which can ultimately result in the satura-
tion of the emission from the lower emitting levels.26
Fig. 6 Dependence of the upconversion luminescence intensity ratio
The eect of the Tm3+ concentration on UV photo-
of 365/800 nm emissions on the (a) Yb3+ and (b) Tm3+ doping
luminescence for the NaYbF4 crystals was also investigated concentrations.

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Fig. 7 Upconversion luminescence rise and decay proles for (ac) NaY1
xYbxF4:Tm (0.5%) and (d and e) NaYbF4:Tm (x%) UCNPs at (a/d) 800,
(b/e) 475 and (c/f) 365 nm emissions upon 980 nm excitation for 03000 ms.
sensitization). From the NaYbF4:Tm (x%) samples the highest
ratio is obtained with 0.6% Tm3+ concentration (Fig. 6b).
The emission decays of the 1D2 / 3H6 (365 nm), 1G4 / 3H6
(475 nm) and 3H4 / 3H6 (800 nm) transitions aer wide-pulse
excitation at 980 nm for the NaY1
xYbxF4:Tm (0.5%) materials
with 20100% Yb and NaYbF4 with 0.055% Tm are shown in the
Fig. 7 (non-normalized intensity decay proles are shown in the
ESI Fig. S2 and S3). The decay data were tted with single,
second or third order exponential decay functions. All the life-
times for the dierent Yb3+ and Tm3+ concentrations are listed in
Tables 3 and S1 in the ESI. Usually the bi-exponential decays
result from dierent pathways used to obtain the same emission.
When the Tm3+ concentration was xed at 0.5%, both the rise and
decay time for all the emissions were found to decrease with
increasing Yb3+ concentration (Fig. 7ac). The same trend was
observed in case of the NaYbF4 samples with dierent Tm3+
concentrations (Fig. 7df). This indicates that high sensitization
is responsible for the ecient energy transfer from Yb to Tm,
which shortens the energy transfer time and decreases both rise
and decay times. In addition to this, one possible reason for the
short decay time in case of higher dopant concentration is the
decrease in the distance between the luminescence centers and
the surface related high frequency vibrational modes which cau-
ses the non-radiative vibrational processes to be more ecient.
The noticeable decrease in the lifetime of the emitting 3H4
level with increase in Yb3+ and Tm3+ concentration can be
partially explained by the Tm / Yb energy back transfer and
self-quenching occurring among the Tm3+ ions.41
Previously, Shan et al. and Lim et al. have demonstrated the
role of particle shape on the uorescence decay times of
UCNPs.4244 As per that discussion, crystals with dierent width
to length (W/L) aspect ratios should have dierent phonon
relaxation processes which strongly aect on the uorescence
35864 | RSC Adv., 2015, 5, 3585835865
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Paper
decay. From our experiments it is observed that, in case of
samples with higher Yb content where hexagonal plates have
higher W/L ratios, the observed decays are lower, i.e. the W/L
ratio and decay time are inversely proportional to each other. It
is also interesting to notice that the NaYbF4:Tm (5%) sample
shows persistent upconversion luminescence for the 800 nm
emission (Fig. 7d), i.e. a prolonged emission, similar to what
has been reported for ZrO2:Yb3+, Er3+ earlier.45 Moreover, the
same sample shows the sharp peak in the rise curves of the
365 and 475 nm emissions indicating optically stimulated
luminescence. The explanation for these two phenomena is out
of the scope of the present report, however, and thus they will be
discussed in another report.
Conclusions
Improved NIR to UV upconversion is reported with high sensi-
tizer concentration in NaYbF4:Tm (0.5%). It was found that the
increase in the Yb3+ concentration, with corresponding
decrease in Y3+ concentration resulted in the enhanced UV
emission and improved UV (340365 nm) vs. NIR (800 nm)
emission intensity ratio. The enhancement arises from the
increased absorption by the Yb3+ ions and the increased e-
ciency of the Yb-to-Yb energy migration and the YbTm energy
transfers. The NaYbF4 host with 0.4 to 0.8% Tm3+ is the optimal
composition for UV UC photoluminescence. The eect of
dierent Yb3+ concentrations on the particle growth mecha-
nism was also studied and it was observed that higher Yb3+
content will result in self-aggregation and sintering of the
hexagonal plates into larger polycrystalline plate at the end of
the reaction. Upconversion emission decay time analyses of
UCNPs with dierent Yb3+ and Tm3+ concentrations at all major
emissions was also included. The decrease in the decay time of
This journal is The Royal Society of Chemistry 2015

Paper
the highly sensitized UCNPs with high W/L ratio indicates an
ecient energy transfer between Yb3+ and Tm3+. In prospect,
this work provided deeper understanding of the eect of the
activator and sensitizer concentrations on photon upconversion
resulting in a simple way to obtain high intensity NIR to UV
upconversion for use in optical, chemical and biological
applications.
Published on 13 April 2015. Downloaded by Indian Institute of Technology Kanpur on 06/08/2017 22:22:54.
Acknowledgements
The authors gratefully acknowledge the nancial support from
the Research Executive Agency (REA) of the European Union
under Grant Agreement number PITN-GA-2010-264772 (ITN
CHEBANA).
Notes and references
1 S. Ghosh, T. F. Rosenbaum, G. Aeppli and S. N. Coppersmith,
Nature, 2003, 425, 48.
2 G. Yi, H. Lu, S. Zhao, Y. Ge, W. Yang, D. Chen and L.-H. Guo,
Nano Lett., 2004, 4, 2191.
3 H. Schafer, P. Ptacek, K. Kompe and M. Haase, Chem. Mater.,
2007, 19, 1396.
4 S. F. Felix, E. A. Gouveia, M. T. de Araujo, A. S. B. Sombra and
A. S. Gouveia-Neto, J. Lumin., 2000, 87 and 89, 1020.
5 F. van de Rijke, H. Zijlmans, S. Li, T. Vail, A. K. Raap,
R. S. Niedbala and H. J. Tanke, Nat. Biotechnol., 2001, 19, 273.
6 J. Ryu, H.-Y. Park, K. Kim, H. Kim, J. H. Yoo, M. Kang, K. Im,
R. Grailhe and R. Song, J. Phys. Chem. C, 2010, 114, 21077.
7 J. de Wild, A. Meijerink, J. K. Rath, W. G. J. H. M. van Sark
and R. E. I. Schropp, Sol. Energy Mater. Sol. Cells, 2010, 94,
1919.
8 J. de Wild, J. K. Rath, A. Meijerink, W. G. J. H. M. van Sark
and R. E. I. Schropp, Sol. Energy Mater. Sol. Cells, 2010, 94,
2395.
9 M. Liu, Y. Lu, Z. B. Xie and G. M. Chow, Sol. Energy Mater. Sol.
Cells, 2011, 95, 800.
10 D. Chen, Y. Wang and M. Hong, Nano Energy, 2012, 1, 73.
11 S. A. Hilderbrand, F. Shao, C. Salthouse, U. Mahmood and
R. Weissleder, Chem. Commun., 2009, 4188.
12 Q. Liu, Y. Sun, T. Yang, W. Feng, C. Li and F. Li, J. Am. Chem.
Soc., 2011, 133, 17122.
13 A. D. Ostrowski, E. M. Chan, D. J. Gargas, E. M. Katz, G. Han,
P. J. Schuck, D. J. Milliron and B. E. Cohen, ACS Nano, 2012,
6, 2686.
14 F. Wang, Y. Han, C. S. Lim, Y. Lu, J. Wang, J. Xu, H. Chen,
C. Zhang, M. Hong and X. Liu, Nature, 2010, 463, 1061.
15 C. Liu, H. Wang, X. Zhang and D. Chen, J. Mater. Chem.,
2009, 19, 489.
16 J. Choi, T.-K. Tseng, M. Davidson and P. H. Holloway, J.
Mater. Chem., 2011, 21, 3113.
17 G. Han, T. Mokari, C. Ajo-Franklin and B. E. Cohen, J. Am.
Chem. Soc., 2008, 130, 15811.
18 H.-M. Lee, D. R. Larson and D. S. Lawrence, ACS Chem. Biol.,
2009, 4, 409.
19 K. Szaciowski, W. Macyk, A. Drzewiecka-Matuszek,
M. Brindell and G. Stochel, Chem. Rev., 2005, 105, 2647.
This journal is The Royal Society of Chemistry 2015
View Article Online
RSC Advances
20 X. Chen and Z. Song, J. Opt. Soc. Am. B, 2007, 24, 965.
21 S. Beyazit, S. Ambrosini, N. Marchyk, E. Palo, V. Kale,
T. Soukka, B. Tse Sum Bui and K. Haupt, Angew. Chem.,
Int. Ed., 2014, 53, 8919.
22 D. Chen, Y. Wang, Y. Yu and P. Huang, Appl. Phys. Lett., 2007,
91, 051920.
23 V. Mahalingam, F. Vetrone, R. Naccache, A. Speghini and
J. A. Capobianco, Adv. Mater., 2009, 21, 4025.
24 F. Shi, J. Wang, D. Zhang, G. Qin and W. Qin, J. Mater. Chem.,
2011, 21, 13413.
25 G. Wang, W. Qin, L. Wang, G. Wei, P. Zhu and R. Kim, Opt.
Express, 2008, 16, 11907.
26 J. Shen, G. Chen, T. Y. Ohulchanskyy, S. J. Kesseli,
S. Buchholz, Z. Li, P. N. Prasad and G. Han, Small, 2013,
19, 3213.
27 S. Zeng, G. Ren, W. Li, C. Xu and Q. Yang, J. Phys. Chem. C,
2010, 114, 10750.
28 Y. Y. Zhang, L. W. Yang, C. F. Xu, J. X. Zhong and C. Q. Sun,
Appl. Phys. B: Lasers Opt., 2010, 98, 243.
29 V. Kale, T. Soukka, J. Holsa and M. Lastusaari, J. Nanopart.
Res., 2013, 15, 1.
30 H. P. Klug and L. E. Alexander, X-ray Powder Diraction
Procedures, Wiley, New York, NY, USA, 1959.
31 K. W. Kramer, D. Biner, G. Frei, H. U. Gudel, M. P. Hehlen
and S. R. Luthi, Chem. Mater., 2004, 16, 1244.
32 E. Harju, I. Hyppanen, J. Holsa, J. Kankare, M. Lahtinen,
M. Lastusaari, L. Pihlgren and T. Soukka, Zeitschri fur
Kristallographie Proceedings, 2011, 381.
33 W. Kraus and G. Nolze, PowderCell for Windows v. 2.4,
Federal Institute for Materials Research and Testing,
Berlin, Germany, 2000.
34 T. Laihinen, M. Lastusaari, L. Pihlgren, L. V. Rodrigues and
J. Holsa, J. Therm. Anal. Calorim., 2015, DOI: 10.1007/s10973-
015-4609-x.
35 N. C. Dyck, F. C. J. M. van Veggel and G. P. Demopoulos, ACS
Appl. Mater. Interfaces, 2013, 5, 11661.
36 W. Qingqing, X. Gang and H. Gaorong, Cryst. Growth Des.,
2006, 6, 1776.
37 X. Liang, X. Wang, J. Zhuang, Q. Peng and Y. Li, Adv. Funct.
Mater., 2007, 17, 2757.
38 H. Qiu, C. Yang, W. Shao, J. Damasco, X. Wang, H. Agren,
P. Prasad and G. Chen, Nanomaterials, 2014, 4, 55.
39 A. Yin, Y. Zhang, L. Sun and C. Yan, Nanoscale, 2010, 2, 953.
40 F. W. Ostermayer, J. P. van der Ziel, H. M. Marcos, L. G. Van
Uitert and J. E. Geusic, Phys. Rev. B: Solid State, 1971, 3, 2698.
41 A. Braud, S. Girard, J. L. Doualan, M. Thuau, R. Moncorge
and A. M. Tkachuk, Phys. Rev. B: Condens. Matter Mater.
Phys., 2000, 61, 5280.
42 S. F. Lim, W. S. Ryu and R. H. Austin, Opt. Express, 2010, 18,
2309.
43 J. Shan, M. Uddi, N. Yao and Y. Ju, Adv. Funct. Mater., 2010,
20, 3530.
44 J. Shan, M. Uddi, R. Wei, N. Yao and Y. Ju, J. Phys. Chem. C,
2010, 114, 2452.
45 L. Pihlgren, T. Laihinen, L. C. V. Rodrigues, S. Carlson,
K. O. Eskola, A. Kotlov, M. Lastusaari, T. Soukka,
H. F. Brito and J. Holsa, Opt. Mater., 2014, 36, 1698.
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