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Strong structural phase sensitive rare-earth

Cite this: Dalton Trans., 2020, 49,
photoluminescence color flips in KLaF4:RE3+
10058 (RE3+ = Eu3+, Er3+/Yb3+) nanocrystals†
Rajat Bajaj,a Mohini Gupta, *b,c R. Nagarajan, c
A. S. Raoa and
G. Vijaya Prakash b

Received 29th March 2020,
Accepted 25th June 2020
DOI: 10.1039/d0dt01179g
rsc.li/dalton
Systematic and strong rare-earth photoluminescence (PL) color flips that are highly sensitive to structural
phase transformation in KLaF4:RE3+ (RE3+ = Eu3+, Er3+/Yb3+) nanocrystals are demonstrated. Room-temp-
erature wet chemical synthesis at various reaction times involves a systematic conversion from cubic (α,
space group Fm3̄m) to hexagonal (β, space group P6̄2m) polymorph nanocrystals of 4 to 8 nm sizes. The
unusual down-conversion photoluminescence (DC-PL) asymmetric ratio of the hypersensitive transition
(5D0 → 7F2, Red) to that of nearly invariant transition (5D0 → 7F1, Orange) (R/O from 1.2 to 3.0) of KLaF4:
Eu3+ is substantially affected by the site-selective occupancy and local symmetry around the Eu3+ ions,
according to crystal packing transformation. The NIR excited up-conversion photoluminescence (UC-PL)
of Er3+ ions produces a strong color flip from green (2H11/2 and 4S3/2) to red (4F9/2) dominated emissions
based on their cubic or hexagonal crystal packing. The site occupancy and phonon energies strongly
influence various nonlinear energy transfer mechanisms within RE3+ ion energies and the results are
explained accordingly. The present study substantially reveals the local host effects and these two distinct
polymorph nanoparticles can be potentially utilized for color-specific studies related to applications such
as color-specific biological in vitro and in vivo imaging and other optoelectronic device applications.

Introduction sibility in solvents, low phonon energy, high optical transpar-

The excellent luminescence properties of rare-earth (RE3+) ion
doped fluoride ALnF4:RE3+ nanoparticles are widely exploited
in optical devices such as solar cells, flat-panel 3D displays,
and solid-state lasers and in biomedical applications e.g.
in vitro and in vivo bioimaging and drug delivery systems.1–4
Some unique and attractive features of RE3+ ion doped fluoride
nanocrystals include the conversion ability of NIR excitation
into visible emission (up-conversion), high photochemical
stability with low hygroscopic properties and excellent disper-
a
MASR Lab, Department of Applied Physics, Delhi Technological University,
Bawana Road, New Delhi-110 042, India. E-mail: rajatbajaj@dtu.ac.in,
drsrallam@gmail.com
b
Nanophotonics Lab, Department of Physics, Indian Institute of Technology Delhi,
New Delhi-110016, India. E-mail: mohinigupta2001@gmail.com,
prakash@physics.iitd.ac.in
c
Materials Chemistry Group, Department of Chemistry, University of Delhi,
Delhi-110007, India. E-mail: rnagarajan@chemistry.du.ac.in
† Electronic supplementary information (ESI) available: Results contains the
Rietveld refinement data, laser excitation power dependence PL spectra for a
longer exposure time of KLaF4:Eu3+, powder X-ray diffraction, DRS, schematic
diagram of energy levels of KLaF4:Er3+/Yb3+ and respective studies. See DOI:
10.1039/D0DT01179G
ency in the visible-NIR region, low background and low
toxicity.5,6 Due to their significant optical transparency and
rare-earth doping capabilities, they are well-established as rare-
earth doped nanophosphors and widely used in color conver-
sion coating, in vitro and in vivo bioimaging and spectroscopic
applications.7,8 While rare-earth optical properties are almost
invariant with the host matrix, ALnF4:RE3+ nanocrystals
showed a wide range of emission properties based on the rare-
earth site occupancy and crystal packing of the host.
A broad variety of fluoride nanocrystalline materials, such
as LaF3, MF2, ALnF4, M2LnF7 and MLnF5; M = Mg, Ca, Sr, Ba,
Cd, and Pb; A = Na, K; Ln = rare-earth metals, show a wide
range of crystal phases.9–12 Phase transformation can be
achieved by changing synthesis parameters such as F : Ln3+
ratio, temperature, reaction time, high and low induced
pressure and doping of transition metals and rare-earth
ions.13–15 Different types of crystal structures such as cubic,
monoclinic, orthorhombic, and hexagonal of NaYF4 fluoride
systems have been reported.16–18 The fluoride system of KLaF4
nanocrystals is realized in two prominent polymorphs: the
cubic phase [Fm3 ˉm, (no. 255), α-KLaF4] and the hexagonal
ˉ
phase [P62m, Z = 1, (no. 189), β-KLaF4] fabricated at different
temperatures.19–21 Similarly, NaYF4 also exists in two poly-

10058 | Dalton Trans., 2020, 49, 10058–10068 This journal is © The Royal Society of Chemistry 2020
Dalton Transactions
morphs, one in a thermodynamically unstable fluoride struc-
ture (cubic, Fm3 ˉm, no. 225, Z = 4) in which the occupation of
+ 3+
Na and Y is random in the cationic site. The other poly-
morph which is hexagonal, can be derived from three struc-
tural models from P6 ˉ, Z = 1, (no. 174), P6
ˉ2m, Z = 1, (no. 189)
and P63m, Z = 1, (no. 176) space groups.16,17 In the lattice of
space group P6 ˉ2m, Z = 1, formula Na1.5Y1.5F6, there are three
cationic sites: the 1a site is occupied by Y3+, the 2d site is
shared by Na+ and Y3+ in a 3 : 1 ratio, and F− ions are popu-
lated in two different crystallographic sites-3f and 3g.22
It is essential to explore how the morphological and optical
properties change with a change in the crystal phase and local
structure of the host lattice. The emission efficiency and color
tunability are two critical factors for the application of up-con-
version materials in biomedical and industrial processes. Er3+
(activator) doping in the ALnF4 host converts efficiently near-
infrared excitation light into green and red emission bands
due to its rich energy level structure with an equal spacing and
long-lived population efficiency of transition levels. Yb3+ acts
as a sensitizer in up-conversion materials and transfers energy
to the activators because it absorbs excitation energy due to its
strong absorption properties. Eu3+ is a very well-known spec-
troscopic agent due to its site occupancy and symmetry break-
down features. Liu et al. reported that the annealing of
β-NaLuF4:Gd, Yb, and Er submicron particles at high tempera-
tures introduces structural changes and emission colors.23
Several synthesis strategies have been reported to achieve
single red emission using Mn2+ or Ce3+ doping into NaLnF4:
RE3+ by assisted energy transfer from RE3+ to Mn2+ or Ce3+.24,25
The structural sensitivity to emission intensities from the
experiments based on the heat treatment, reaction time,
chemical stoichiometry, presence of salts etc. has also been
reported.26–28
However, to date, several crystal phase polymorphs have
been reported in ALnF4 type systems, exclusively to point out
the structural features. RE3+ ions are known to be sensitive to
the site selective occupancy and crystal field effects. For
example, Eu3+ is known to be a structural probe and shows
either red (5D0 → 7F2) or orange (5D0 → 7F1) dominance,
depending on its site selectivity.29,30 Similarly, Er3+ ions show
potential upconversion emission upon NIR excitation, either
in red or green color due to various host lattice influenced
energy transfer pathways.31–33 Thus, the study of RE3+ ion
emission characteristics substantially reveals the local host
effects and a distinctly different energy transfer mechanism
and the effect of crystal polymorphs can be potentially utilized
for color-specific studies related to applications such as color-
specific biological in vitro and in vivo imaging and other opto-
electronic device applications. As such, until now, there were
no such reports on the systematic understanding of phase flip
induced optical features within a single lattice. Here, we report
the systematic synthesis and reaction time-dependent struc-
tural phase flips from the cubic (Fm3m, no. 225, Z = 4,
α-KLaF4) to hexagonal phase (P6 ˉ2m, (no. 189) Z = 1, β-KLaF4)
of KLaF4 nanocrystals doped with RE3+ (Eu3+ and Er3+/Yb3+)
and their unusual photoluminescence characteristics.
This journal is © The Royal Society of Chemistry 2020
Paper
Experimental section
KLaF4 nanoparticles were synthesized by a one-step wet chemi-
cal route. In a typical reaction, 20 ml of a methanolic solution
of 0.4362 g, (1 mmol) of La(acac)3·xH2O (Sigma Aldrich 99.0%)
was added drop-wise to the KF (0.2324 g, 4 mmol) solution
under continuous stirring at room temperature. Then, the
reaction temperature was maintained at 65 °C for various reac-
tion times (2, 4, 8, 10, 12 and 14 h). Finally, the solution was
allowed to cool to room temperature. The resultant precipitate
was isolated by centrifugation at 8000 rpm after washing
several times with methanol and dried overnight in a vacuum
oven. For the doping of rare-earth ions, 5 mol% of Eu(acac)3,
0.5 mol% of Er(acac)3 and 20 mol% of Yb(acac)3 were prepared
from EuCl3·6H2O (Sigma Aldrich 99.0%), ErCl3·6H2O (Sigma
Aldrich 99.0%), and YbCl3·6H2O (Sigma Aldrich 99.0%),
respectively, and were added dropwise to the La(acac)3·xH2O
and KF solutions.34 All chemicals were used without any
further purification.
Characterization
The powder X-ray diffraction (XRD) pattern was recorded by
using a Philips X’Pert Pro diffractometer with a point detector
in the Bragg–Brentano geometry employing Cu Kα radiation (α
= 1.54060 Å) and a power of 45 kV–40 mA. Data points were
collected from 10 to 80° after calibrating the instrument using
the Si standard externally. The Rietveld refinement of the
powder XRD data was carried out using the GSAS® software
based on the available structural data. HRTEM images were
obtained using a FEI Tecnai TF20 microscope equipped with a
field emission gun source, operating at an accelerating voltage
of 200 kV. The sample for TEM was prepared by dropping 1 μL
of a diluted nanoparticle suspension prepared in ethanol on a
carbon-coated grid and allowed to dry in a vacuum. The UV-
visible diffuse reflectance spectra (DRS) of the synthesized
samples were collected using a PerkinElmer Lambda-35 UV-
visible spectrophotometer with an integrating sphere attached,
using BaSO4 as the reference. The up-conversion and down-
conversion emissions were recorded using a custom-built
setup that consists of a 980 nm, 1 W diode laser, 405 nm,
155 mW diode laser, and monochromator-Acton SP 2300
coupled to a photomultiplier tube (calibrated with mercury
emission).
Results and discussion
Systematic evolution of the structural and photoluminescence
properties in the Eu3+ doped KLaF4 nanocrystals
(a) Structural and morphological characterization. The
crystallinity and phase identification of KLaF4:5%Eu3+ nano-
particles prepared at various reaction times were examined by
powder X-ray diffraction (Fig. 1). From the PXRD patterns, it is
clear that two prominent peaks at angles 26.04° and 43.08°
gradually emerged from 2 to 8 h of reaction time. At 2 h of
reaction time, the two peaks became broad and from a reac-
Dalton Trans., 2020, 49, 10058–10068 | 10059
Paper
Fig. 1 Powder XRD pattern of KLaF4:5% Eu3+ samples prepared at a
temperature of 65 °C at different reaction times.
tion time of 4 h onwards the peaks became very prominent
along with other peaks at angles 30.10, 50.94, 53.34, 62.7,
68.84 and 70.96°. However, at a 10 h reaction time, new
intense peaks at angles 27.42°, 28.34° and 48.90° started
appearing along with previous peaks. From 12 h of reaction
time onwards, the samples showed prominent peaks at 27.42°
and 28.34° along with other peaks at 15.62, 36.20, 39.40,
47.60, 48.24, 48.90, 55.74, 56.30, 64.26, 70.04 and 76.96°
angles. We observed that all the peaks are relatively broader,
indicating the nano-crystallinity. Furthermore, with an
increase in the reaction time, the KLaF4 sample gradually
transformed from one crystal packing to another, which was
also experimented and discussed in the following sections.
Fig. 2 (a–c) Rietveld refinement of the cubic, intermediate and hexagonal phases of 5%Eu3+ doped KLaF4 samples [the observed, calculated
( profile matching), and difference profiles are indicated respectively by blue, red, and olive-green lines and the Bragg positions by black or purple
vertical lines], and (d and e) cubic and hexagonal phase KLaF4 structural representation.
10060 | Dalton Trans., 2020, 49, 10058–10068
Dalton Transactions
The powder XRD patterns of the KLaF4:5%Eu3+ samples at
various reaction times are investigated to study the lattice para-
meters, crystal packing, phase purity and site symmetry in
detail. Fig. 2 shows the powder XRD patterns of the KLaF4
samples (of Fig. 1) along with the Rietveld refinement fits
based on the available structural data for three specific reac-
tion times.35,36 As evident from Fig. 2(a), KLaF4 at 4 h of reac-
tion time confirms the cubic phase of space group Fm3 ˉm
(JCPDS No. 75-2020; #225), whereas the 14 h reaction time
sample shows pure phase hexagonal crystal packing with space
group P6 ˉ2m (JCPDS No. 75-1927; #189) as shown in Fig. 2(c).
However, the 10 h reaction time yielded KLaF4 sample shows
mixed/intermediate phases of both cubic and hexagonal ones
(Fig. 2(b)). Therefore, the PXRD pattern categorically suggests
that there is a systematic phase transformation from the cubic
to hexagonal crystal phases with an increase of the reaction
time. Both cubic and hexagonal KLaF4 crystal packing and
phase purity are invariant even up to 21% of rare-earth ion
doping, but the spectra features show marked changes.19,20
KLaF4:5%Eu3+ (up to 8 h of reaction time) is isomorphic to
a cubic CaF2 fluorite structure and refined with one type of
high symmetry cation site with respect to the internal stan-
dards of CaF2 (Fm3 ˉm). Here Ca2+ (4a) site is randomly occu-
pied by half of K and half of La3+ ions along with F− ions at
1+
site 8c (Fig. 2(a)). The refined unit cell parameter a (Å) and
GOF values are 5.9562(50) and 1.50 S, respectively. The crystal-
lographic refinement data and reliability factors after the final
cycle of refinement are listed in the ESI, Tables S1 and S2.†
The hexagonal phase of KLaF4 (>12 h reaction time) is iso-
morphic to the β1-K2UF6 structure, with the formula of
This journal is © The Royal Society of Chemistry 2020
Dalton Transactions
(KLaF4)1.5.37 In the Rietveld refinement of β-KLaF4 of space
group P6 ˉ2m, site 1a is exclusively filled with La3+ ions while
3 1
site 2d is shared by Kþ and La3þ ions. Sites 3f and 3g are
2 2
equally occupied by six F− ions. The lattice constants a (Å), c
(Å) and GOF are calculated to be 6.529(32), 3.825(35) and 1.70
S, respectively, after the final cycle of refinement. All crystallo-
graphic structure refinement parameters are displayed in the
ESI, Tables S3 and S4.† The mixed/intermediate KLaF4 sample
at a reaction time of 10 h (Fig. 1 and 2) is slightly tricky and
composed of both cubic and hexagonal phase powder XRD
reflections. The powder XRD pattern of this sample is refined
using both cubic and hexagonal JCPDS files, and the calcu-
lated refinement parameters are cubic a (Å) = 5.938 and hexag-
onal a (Å) = 6.527 and c (Å) = 3.147 (Fig. 2(b)). In the intermedi-
ate/mixed phase, the monophase cubic nanoparticles initially
persist with cubic symmetry, but due to thermodynamic
control (reaction time), the resultant crystallite deform into a
hexagonal phase. Due to the deformation of crystal packing,
the diffraction planes have different distances and cause
different Bragg angles, as can be confirmed by a slight shift in
the angle with increasing reaction time, (with transformation
α → β). Due to a change in the distance of diffraction planes,
the lattice constants differ from the individual lattice con-
stants of pure cubic or hexagonal phases.
The crystal structure and average particle size of the as-syn-
thesized KLaF4 nanoparticles at different times of reaction
were analysed by HRTEM. The diameter of the spherical geo-
metry nanoparticles ranges from 4 to 8 nm (Fig. 3(a)), which is
close to the powder XRD Debye–Scherrer formula estimate of
Fig. 3 (a) TEM image (inset: particle size distribution) of the cubic phase of KLaF4:5%Eu3+ prepared with 4 h of reaction. (b) HRTEM image with an
inset SAED pattern. The lattice plane of (111) is indicated by white lines. Red color circles indicate the crystalline nanoparticles of the size from 4 to
8 nm. (c) and (d) TEM images for the intermediate and hexagonal phases prepared at 10 and 14 h of reaction time.
This journal is © The Royal Society of Chemistry 2020
Paper
∼6 nm, using the prominent diffraction plane of (111). In the
HRTEM image (Fig. 3(b)), the lattice fringes of the individual
nanoparticles indicate good crystallinity with the adjacent dis-
tance between two lattice fringes being calculated to be
0.33 nm corresponding to the lattice plane (1 1 1) of the cubic
KLaF4 lattice. The TEM images of the intermediate phase (10 h
reaction) and hexagonally ordered fluoride nanoparticles are
also shown in Fig. 3(c) and (d).
Now it is interesting to observe the site selectivity and
crystal packing around the RE3+ ion occupation. While the
rare-earth f–f transition energies are invariant with the host
matrix, the site occupation of RE3+ and its surrounded crystal
field strongly influences the radiative and nonradiative tran-
sitions.38 The electron cloud distortion of the cations in the
hexagonal ALnF4 arrangement is significantly different from
that of its high-symmetry cationic sites in cubic polymorphs. It
is evident from previous sections that in ALaF4 the structural
flip from the cubic to hexagonal phase is the transformation
from the more disordered to order re-arrangement of atoms in
its cationic sites.39–43 In the cubic phase of KLaF4, the La3+
ions are distributed on the site 4a which has Oh crystallo-
graphic symmetry. During the RE3+ doping, the La3+ ions are
replaced by RE3+ ions in the lattice. In the present case, the
ionic radius of RE3+ is lower than that of the La3+ ions, there-
fore, the bond length of RE-F is supposed to be smaller than
that of La-F. As a result, the co-ordination shell around the 4a
site filled with La3+ and K+ ions could be slightly distorted.
According to the microscopic model of the disorder, the local
site symmetry Oh in the cubic phase of each subset of Eu3+
Dalton Trans., 2020, 49, 10058–10068 | 10061
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ions will be eventually reduced to lower site symmetries, Cs, C2
or C1.
Similarly in the hexagonal phase, the local site symmetry
D3h (site 2d ) of each subset of RE3+ ions will be reduced to
their lower site symmetries, such as D3.44,45 Thus, the struc-
tural flip from cubic to hexagonal is expected to show signifi-
cant changes in the spectral features of the structural probe,
Eu3+ and technologically important Er3+/Yb3+ ions. Such
studies are systematically presented in the following sections.
(b) Red-to-orange (R/O) PL emission ratio sensitivity to down-
conversion photoluminescence (DC-PL) in the Eu3+doped
KLaF4 nanocrystals. The photoluminescence excitation (PLE)
and down-conversion photoluminescence (PL) spectra of
KLaF4:5%Eu3+ at different reaction times are shown in Fig. 4.
Four PL peaks (excited at λex = 395 nm) were observed at 595,
614, 650, and 700 nm corresponding to transitions 5D0 → 7FJ,
( J = 1, 2, 3, 4) respectively. The PLE spectra, monitored at λem =
614 nm of 5D0 → 7F2, show typical signature excitation peaks
of Eu3+ spanning within the 350–550 nm spectral range, orig-
inating from 7F0 and 7F1 to various excitation levels.44,45 It is
also seen that the prominence of the phonon energies in
terms of phonon-assisted side bands (PSB’s, at 22371.3 cm−1
and 22 831.0 cm−1) is associated with the electronic transition
7
F0 → 5D2 suggesting the strong microscopic environment
around the Eu3+ ions in the KLaF4 host. The schematic
diagram of all possible PLE and PL transitions of Eu3+ ions is
shown in Fig. 4(b).
To explore more about the symmetry and site occupation
local environment of Eu3+ ions in the KLaF4 host lattice pre-
pared at different reaction times, the laser-excited PL spectra
were recorded under 405 nm diode laser excitation. For all the
Fig. 4 (a) Photoluminescence excitation (PLE) spectra monitored at λem = 614 nm (5D0 → 7F2) and Down-conversion photoluminescence (DC-PL)
spectra excited at λex = 395 nm (7F0 → 5L6) for KLaF4:5%Eu3+ at various reaction times. (b) Schematic energy level diagram of Eu3+ ions in the host
lattice.
10062 | Dalton Trans., 2020, 49, 10058–10068
Dalton Transactions
reaction times, the PL spectra were dominated by lower-order
transitions 5D0 → 7FJ ( J = 0, 1, 2, 3, and 4). The weak higher-
order transitions (5D1 → 7FJ; J = 0, 1, 2) are possible when the
host possesses low phonon energies, which eventually help in
the enhancement of radiative probabilities.
Typical ALaF4 (A = Na+, K+) hosts contain relatively low
phonon energies (for cubic 316 cm−1 and hexagonal 262 cm−1)
and hence the Eu3+ ions in the as-prepared phosphors excited
to upper-level 5D2 deactivate progressively to the lowest energy
5
D1/5D0 levels by fast non-radiative multi-phonon relaxation.20,21
The study of the laser excitation power dependence spectra and
their corresponding peak intensity variation shows that the exci-
tation process is one-photon absorption (Fig. S1†). Porcher et al.
reported in low phonon KY3F10:Eu3+ that the de-excitation of
5
D2 to 5D1 is possible by achieving the energy separation of
∼2500 cm−1 utilizing seven phonon (360 cm−1) energies.46
Rabouw et al47 reported a very weak emission in NaYF4:Eu3+
from the 5D2 level and demonstrated relatively fast lifetimes for
5
D1 with respect to 5D0. In our present system, the very weak
higher-order emission from 5D1 is observed only in cubic KLaF4
but could not be detected in the hexagonal system (Fig. 5).
The laser excited PL spectra show two prominent peaks
corresponding to transitions 5D0 → 7F1 (orange) and 5D0 → 7F2
(red) at wavelengths of 595 and 614 nm respectively. The mag-
netic dipole (MD) transition 5D0 → 7F1 is not influenced by
metal–ligand bonding and insensitive to the crystal environ-
ment, while the electric dipole (ED) transition 5D0 → 7F2 is
hypersensitive and can be strongly influenced by local factors
such as the local symmetry of Eu3+ ions.44
Thus, the ratio (R/O) of the hypersensitive transition (5D0 →
7
F2, red) to that of the invariant transition (5D0 → 7F1, orange)
This journal is © The Royal Society of Chemistry 2020
Dalton Transactions
Fig. 5 (a–c) Laser excited PL spectra of Eu3+ doped KLaF4 nanoparticles excited at λex = 405 nm with a CW laser. The grey color plots in (a–c) are
with 10× magnification to visualize 5D1 transitions. (d) Asymmetric PL intensity ratios of the 5D0 → 7F2 to 5D0 → 7F1(R/O) transitions for the samples at
various reaction times.
is widely accepted to represent the degree of distortion from
the inversion symmetry and the local environment of the Eu3+
ion in the host lattice. Therefore, the asymmetric (R/O) ratio is
widely considered to be a structural probe, because the Eu
emission/excitation spectral details give insight into the rela-
tive strength of covalent and ionic bonding between the Eu3+
ions and the surrounding ligands.48,49
Longer exposure time scans are also performed to avoid any
laser-based stability issues, and the results are shown in
Fig. 5(d) and Fig. S2.† For comparison, the PL spectra related
to pure cubic phase (4 h), mixed/intermediate phase (10 h)
and pure hexagonal phase (14 h) are highlighted in Fig. 5(a)–
(c). The asymmetric ratios R/O (i.e., 5D0 → 7F2 vs. 5D0 → 7F1)
for all samples are shown in Fig. 5(d). As seen, the asymmetric
ratio R/O is invariant with the prolonged exposure of an exci-
tation laser. What is more interesting is, the R/O ratio in the
pure cubic phase is between 1.2 and 1.8, whereas in the pure
hexagonal phase, it is markedly very high and ranges between
2.6 and 3.1. The asymmetric ratio R/O = 1.2–1.8 for the cubic
phase KLaF4 nanocrystals indicates that the Eu3+ ions are
located in the centrosymmetric site. In the hexagonal phase,
these R/O values are dominated by the highly influenced
hypersensitive transition (5D0 → 7F2) and are highly perturbed
and also strongly influenced by the Eu–F covalency and local
symmetry. Thus, these studies broadly confirm that the crystal
phase flips show enormous changes in the emission spectral
features due to the different site selectivity and covalent/ionic
bonding surrounded by the RE3+ ions.
This journal is © The Royal Society of Chemistry 2020
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(c) Up-conversion photoluminescence (UP-PL) color flips
in the Er3+/Yb3+ doped KLaF4 nanocrystals. Low-phonon energy
fluoride nanocrystals with Er3+ doping along with Yb3+ as a sen-
sitizer are one of the most efficient up-conversion nanoparticles
(UCNPs) for bio-imaging in vitro and in vivo, biological lumines-
cent labels, MRI contrast agents, color displays, and super-
resolution nanoscopy.50–52 These NIR excited UCNPs have
potential to show either green (2H11/2 and 4S3/2) dominated or
red (4F9/2) dominated emissions based on their cubic or hexag-
onal crystal packing.52 The up-conversion emission spectra of
Er3+/Yb3+ are dominated by a series of energy-transfer processes
such as multi-phonon relaxation, phonon-assisted energy
migration and cross-relaxation under NIR laser excitation. The
different non-harmonic phonon coupling phenomena in the
cubic and hexagonal phases of NaYF4 were reported by the
group of L. Wang.53 They observed that the non-harmonic
phonon coupling is stronger in the disordered form of α-NaYF4
than in ordered β-NaYF4. However, to the best of our knowledge,
a comprehensive study of the green and red variation in Er3+/
Yb3+ UCNPs to crystal packing has not been reported.
The reconfirmation of the crystal packing and phase identi-
fication, similar to those of KLaF4:Eu3+ nanoparticles, by
powder XRD, has also been performed in the KLaF4:Er3+/Yb3+
nanocrystals synthesized at various reaction times and indexed
accordingly (Fig. S3†). According to the diffuse reflectance
spectra (Fig. S4†), several absorption transitions were observed
for the Er3+ (4I15/2 → 4F7/2, 2H11/2, 4I11/2,4S3/2, 4F9/2) and sensi-
tizer Yb3+ ions at 976 nm (2F7/2 → 2F5/2). A strong band edge at
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Fig. 6 (a) Up-conversion photoluminescence (UP-PL) of 0.5% Er3+/20% Yb3+ doped KLaF4 excited with a 980 nm CW laser. Inset: color camera
images are visible to the naked eye. (b) The integrated intensity ratio of the green and red emission of UCNPs prepared at different reaction times.
The transition from cubic to hexagonal polymorphs is indicated by color shaded area.
297 nm (∼3.85 eV) was observed, and it is probably masked by
strong ligand to metal (LMCT) and metal to ligand (MLCT)
type charge transfer peaks, the absorption of Yb3+ and Yb2+
valence forms etc.54–56
The multi-colour up-conversion emission spectra measured
upon 980 nm laser excitation are shown in Fig. 6(a). The three
emission peaks at 522, 544 (green) and 657 nm (red) were
attributed to the 2H11/2 → 4I15/2, 4S3/2 → 4I15/2 and 4F9/2 → 4I15/2
transitions, respectively.
The phase conversion from the cubic to hexagonal crystal
packing with the reaction time is also clearly reflected in the
up-conversion emission studies. The camera pictures of the
980 nm excited up-conversion PL from the nanoparticles, as
seen by the naked eye, are also shown in Fig. 6(a). The cubic
phase nanoparticles demonstrate intense green color, as a
result of dominant UC emissions from the 2H11/2 and 4S3/2
transitions, whereas, the hexagonal crystal packing results in
dominant red color due to the strong red-end emission from
the 4F9/2 transition. The red to green color ratio, R/G1 (2H11/2
→ 4I15/2 and 4F9/2 → 4I15/2) marked variation from 0.6 to 2.7,
confirms the same (Fig. 6(b)).
The relationship between the UC emission intensity (I) and
laser power (P) is defined by the expression I ∝ Pn, where n is
the number of pump photons absorbed per emitted up-con-
verted photon.57 The UC emissions at different powers and the
log–log plots of the UC emission intensity (I) as a function of
excitation power (P) are presented in Fig. 7. The nonlinear exci-
tation power slopes for all the prominent transitions shown in
Fig. 7(d–f ) suggest that the UC emission is promoted via a two-
photon nonlinear excitation process. In typical Er3+ systems,
the two-photon induced upconversion process via Yb3+ sensi-
tizer, follows typically I ∝ Pn, where n is in the range from 1.4
to 1.8 for various emission energies. Such values of n (<2) are
due to many factors involving phonon energies, stark splitted
energies, cross-relaxations etc.58 To ascertain the nonlinear up-
10064 | Dalton Trans., 2020, 49, 10058–10068
Dalton Transactions
conversion energy transfer processes, the laser excitation
power dependence is also examined for the nanocrystals of the
cubic (4 h reaction), mixed/intermediate (10 h) and hexagonal
(14 h) phases (Fig. 7).
The possible energy transfer UC mechanism in the Er3+/
3+
Yb doped fluoride nanoparticles is presented in Fig. S5.†
Several concurrent electron transports, non-radiative tran-
sitions and relaxation mechanisms are responsible for the pro-
duction of green/red emissions. As discussed in the previous
sections, in the cubic phase of KLaF4, doped RE3+ will be ran-
domly distributed in the lattice, at low symmetry sites. Here, in
Er3+/Yb3+ doped nanoparticles, the UC emission is from the
GSA/ESA processes [4I15/2 + pumped photon → 4I11/2 → 4F7/2]
and the energy transfer (ET) from the Yb3+ sensitizer to Er3+
activator ions. Since the absorption cross-sections of the Yb3+
ions at pump energy are higher than those of the Er3+ ions, the
energy absorbed by the sensitizer is transferred to the adjacent
energy levels of the Er3+ ions via different ET assisted UC
(ETAU) processes (Fig. S5†). In short, the Er3+ ions are excited
from the ground state to the excited state via energy transfers
ET1 and ET2 from neighbouring Yb3+ ions (4I15/2 + 2F5/2 →
4
I11/2 + 2F7/2) and (4I11/2 + 2F5/2 → 4F7/2 + 2F7/2) and then the
green-emitting levels 2H11/2, and 4S3/2 are populated by non-
radiative transitions of 4F7/2 (Fig. 7d–f ). Despite ET1 and ET2,
ET4 (4I11/2 + 4I11/2 → 4F7/2 + 4I15/2) also contributes a part to the
increment of the population of the 2H11/2, 4S3/2 states. This
process is possibly due to the long-lived 4I11/2 energy level.
Sequentially, the non-radiative relaxations from 4I11/2 populate
the 4I13/2 level. Similarly, the red-emitting level 4F9/2 of the Er3+
ions is populated through ETAU processes: (i) ET3 (4I13/2 +
2
F5/2 → 4F9/2 + 2F7/2), (ii) CR process (4F7/2 + 4I11/2 → 4F9/2 +
4
F9/2) between two adjacent Er3+ ions and (iii) energy back
transfer EBT (a) 2F7/2 (Yb3+) + 4S3/2 (Er3+) → 4I13/2 (Er3+) + 2F5/2
(Yb3+) and (b) 2F7/2 (Yb3+) + 4F7/2 (Er3+) → 4I11/2 (Er3+) + 2F5/2
(Yb3+) processes. Besides these ET and EBT processes, back
This journal is © The Royal Society of Chemistry 2020
Dalton Transactions
Fig. 7 Up-conversion PL spectra of 0.5%Er3+/20%Yb3+doped KLaF4 samples excited with a 980 nm CW diode laser at various powers from 100 mW
to 275 mW prepared at (a) 4 h (cubic), (b) 10 h (intermediate/mixed) and (c) 14 h (hexagonal) reaction times. (d–f ) log–log plot of integrated intensity
versus power calculated from the UC PL spectra shown in (a–c).
energy transfer from 4F9/2 to 4S3/2 is also possible and it
depends on the crystal packing and site occupation.58 The
green emission may be dominated by the red emission due to
the back energy transfer (BET) process of the 4F9/2 energy
level.59 During the cross-relaxation within the Er3+ ions, two
neighboring ions at energy level 4F9/2, share their energy in
such a way that one electron goes to the 4S3/2 level and another
deactivates to the lower level 4I9/2. The 4S3/2 level is also popu-
lated by the back transfer, a part of energy from the 4F9/2 level.
Finally, radiative transitions 2H11/2 → 4I15/2 (521 nm), 4S3/2 →
4
I15/2 (541 nm), and 4F9/2 → 4I15/2 (651 nm) occur in the green
and red regions. The red emission at 657 nm corresponding to
the transition 4F9/2 → 4I15/2 of hexagonal β-KLaF4:Er3+/Yb3+
(14 h of reaction time) is higher by a factor of ∼11 than that of
cubic phase α-KLaF4:Er3+/Yb3+ (4 h of reaction time). This con-
firms that the back-energy transfer (BET) due to the well-
ordered site symmetry of the Yb3+/Er3+ ions in the host lattice
occurred with the UC mechanism by two-step energy transfer
(ET) from the excited state of Yb3+ (2F5/2) to the energy level
4
I11/2 of the Er3+ ions. The BET process (a) defines the depopu-
lation in the excited levels 2H11/2/4S3/2 (Er3+) which causes
the quenching of green light (522 and 544 nm) emission.
Simultaneously, a saturation occurs in the excited level
4
I13/2 (Er3+) and an energy transformation process 2F5/2 (Yb3+) +
4
I13/2 (Er3+) → 4F9/2 (Er3+) + 2F7/2 (Yb3+) takes place and directly
This journal is © The Royal Society of Chemistry 2020
Paper
increases the population of photons in the 4F9/2 red emission
level. The CIE 1931 XY diagram of the KLaF4:Er3+/Yb3+ nano-
crystals is presented in Fig. S6.† The calculated CIE color coor-
dinates shifted from green to red with increasing reaction time.
Conclusions
In summary, we have demonstrated strong upconverted photo-
luminescence color flips from low phonon energy in biocom-
patible fluoride nanocrystals KLaF4:Er3+/Yb3+via a systematic
phase transition from the cubic (space group Fm3 ˉm) to hexag-
ˉ
onal phase (space group P62m). The systematic phase trans-
formation has been achieved by simple, one-pot room-temp-
erature wet chemistry at different reaction times, from 2 h to
14 h. The X-ray diffraction patterns were refined with cubic,
cubic/hexagonal and hexagonal phases. The obtained lattice
constants were as follows: cubic a (Å) = 5.9562(50), interme-
diated/mixed cubic a (Å) = 5.938 (14), hexagonal a (Å) = 6.5271
(18) and c (Å) = 3.147(06) and hexagonal a (Å) = 6.529(32) and c
(Å) = 3.825 (35), respectively. The nanoparticle size, size distri-
bution and crystal phase were further supported by TEM ana-
lysis. With the doping of the Eu3+ structural probe, the photo-
luminescence of the KLaF4:Eu3+ nanocrystals reveals the
specific site selectivity that is clearly distinguishable in both
Dalton Trans., 2020, 49, 10058–10068 | 10065
Paper
cubic and hexagonal polymorphs. The significant enhance-
ment in the asymmetric ratio of the red to orange (R/O) down-
conversion PL peaks, i.e., the ratio of the hypersensitive tran-
sition (5D0 → 7F2, red) to that of the invariant transition (5D0
→ 7F1, orange) supports the distortion of the local site sym-
metry, sensitive to phase transformation. These results favour-
ably suggest the deformation of site occupation from high site
symmetry (Oh) to lower site symmetries (Cs, C2 or C1) in the
cubic phase, whereas in the hexagonal crystal packing the
transformation is from D3h site symmetry to D3 lower site sym-
metry. Thus, the strong color flip, if the asymmetric ratio (R/O)
varies from 1.2 to 3.0 in the Eu3+ emission during the progress-
ive phase transformation, inadvertently confirms that Eu3+ acts
as an active spectroscopic probe for the local structure around
the rare-earth ion occupation. The phase evaluation of the
strong upconversion emitting KLaF4:0.5Er3+/20%Yb3+ nano-
crystals was performed and it was found, for the first time,
that the strong color tunability from green to red is possible by
the rearrangement of crystal packing and site symmetry. The
red to green color ratio R/G1 (2H11/2 → 4I15/2 and 4F9/2 → 4I15/2)
variation from 0.6 to 2.7 is observed during the crystal struc-
tural change from cubic to hexagonal. Such a phase-related
color change was successfully explained by the site occupancy,
the phonon energies and the strong influence of various non-
linear energy transfer mechanisms. Furthermore, the great
enhancement in the red emission (by a factor of ∼11), wit-
nessed in the hexagonal phase, is possibly due to the back-
energy transfer (BET) process between the Yb3+ and Er3+ ions.
These studies can also be further extended to other rare-earth
color markers (such as Er3+–Tm3+–Yb3+, Ho3+–Yb3+ etc.) for a
wide range of color selectivities from these biocompatible low-
cost nanocrystals. Finally, the results are of broad interest in
the sense that various polymorphs can be easily harvested and
utilized for various multi-color applications such as biological
imaging, 3D displays, LEDs, and solar cells.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The work reported in this paper is partly supported by a
DST-SERB research project (EMR/2016/007766). MG thanks
UGC-Dr D. S. Kothari for a postdoctoral fellowship (F.4-2/2006
(BSR)/PH/18-19/0040) and DST Women Scientist A (SR/WOS-A/
PM-1016/2015) for research funds. The authors thank the
DST-FIST funding for establishing the Ultrafast-Optics (UFO)
facility. The authors also thank the department and Institute
facilities of IIT Delhi.
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