1 s2.0 S0079678619300366 Main
1 s2.0 S0079678619300366 Main
1 s2.0 S0079678619300366 Main
A R T I C LE I N FO A B S T R A C T
Keywords: The photoluminescent phosphor materials nowadays are extremely important source of light to fulfill the
RE ion technological demand over the conventional light source for eco-friendly environment. This review brings the
Photoluminescence morphological and optical properties of the chemically engineered rare earth doped photoluminescent materials
Energy transfer at one platform. The recent developments have been incorporated and different processes involved in the
Surface modifier
morphological changes of these materials are discussed. The optical properties of different mono-, di- and tri-rare
Sensitizer
earth doped phosphors have been analyzed and evaluated using various sensitizers and surface modifiers. The
photoluminescence intensity of the materials is greatly affected by changing the morphology of the phosphors
via some sensitizers and surface modifiers. The large photoluminescence intensity thus obtained has been
summarized due to change in the morphology. The future aspects of change in the morphological properties of
the chemically engineered rare earth doped phosphors have been also proposed.
∗
Corresponding author.
∗∗
Corresponding author.
E-mail addresses: ramsagaryadav@gmail.com (R.S. Yadav), sbrai49@yahoo.co.in (S.B. Rai).
https://doi.org/10.1016/j.progsolidstchem.2019.100267
Fig. 2. Schematic diagrams of (a) downconversion (DC), (b) upconversion (UC) and (c) quantum cutting (QC) processes in the RE ion.
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for the activator ion in which the concentration of the activator, surface 2. Variation in morphological properties of the photoluminescent
modifier and sensitizer can be optimized with the photoluminescence materials
intensity. The selection of the host is generally carried out on the basis
of phonon frequency. The host matrix possesses either the higher or The RE doped phosphors are very promising photoluminescent
lower phonon frequency. If the host has higher phonon frequency the materials as they exhibit intense photoluminescence with sharp and
molecules of the host may vibrate rapidly and the activator ions present narrow band profiles. This could become possible due to the presence of
in the excited states relax non-radiatively due to multi-phonon relaxa- large number of meta-stable states present in the RE ions. These levels
tion. As a result, the photoluminescence intensity of the phosphor is are excited with a particular source of light. The activator ions are
decreased considerably. On the other hand, the host with low phonon called as luminescence centers, which are responsible for generation of
frequency strongly reduces the non-radiative relaxation of the ions. If light of the desired colors. The color emitted by the RE ions vary from
the activator ions present in the excited state may stay for longer time one RE ion to the other RE ions.
they emit relatively larger photoluminescence intensity. Thus, the host
materials should be chosen with low phonon frequency. The mor- 2.1. Singly RE doped phosphor materials
phology of the host matrices can be improved noticeably by in-
corporating some sensitizers and surface modifiers. These additives not The Eu3+ ion is a one of the RE ion responsible for producing red
only have improved the morphology of the host matrices but also en- emission in the phosphor materials and it is an essential part of the
hance the photoluminescence intensity of the activator ions to a great white light emitting materials. Generally, the efficiency of white emit-
extent [56–60]. Therefore, the host materials should be selected on the ting materials strongly buried with the low rendering capacity of red
ground of low phonon frequency. color. To our knowledge, Lavine et al. have developed the first red
The photoluminescence intensity of the RE doped phosphor mate- emitting Eu3+ doped YVO4 phosphor in 1964, which was used as a
rials have been studied by various researchers in different host mate- primary color in television [76]. In recent years, a series of different RE
rials [61–68]. They have reported that the host should contain low doped phosphors (such as Ce, Tb, Eu, Sm, Dy, Er, Tm, Ho and Yb) were
phonon frequency. The phonon frequency of the host lattice can be prepared by various researchers in different host materials [77–87].
reduced by incorporating some impurity ions, which can occupy the They have observed intense blue, green and red emissions on excitation
places at the interstitial sites. They can be accommodated in the space with proper light sources. The intense photoluminescence was achieved
present in between the atoms/ions, which can reduce the vibration of due to change in morphology of the phosphor materials.
the molecules in the host materials. Thus, by reducing the lattice vi- Lai et al. have studied the photoluminescent properties of the Tm3+
brations one can achieve larger photoluminescence intensity arising doped LiBaPO4 phosphor synthesized by microwave and conventional
from the RE ions. sintering methods and reported the enhanced blue photoluminescence
due to morphological change in the case of microwave sintering method
1.3. Morphology of the phosphor materials [85]. Zhang et al. have also synthesized the Eu3+ doped Bi4Si3O12 red
phosphor by microwave and conventional sintering methods and ob-
The morphology of the phosphor materials can be tuned depending served intense photoluminescence in the microwave method [86].
on the nature of the host matrix and the RE ions. The synthesis pro- However, He et al. have discussed the effect of local structure of Ce3+
cedure plays a vital role for determining not only the morphology of the ions on the photoluminescent properties of the Y3Al5O12:Ce nano-par-
phosphor but also the size of the particles. There are various approaches ticles [87]. They have studied the effect of calcination temperature and
to synthesize the phosphor materials, such as solid state reaction concentration of the Ce3+ ions on the photoluminescence intensity. The
method, solution combustion method, sol-gel method, co-precipitation photoluminescence intensity was found to increase on increasing cal-
method, hydrothermal method, template method, spray pyrolysis, cination temperature from 830 to 1030 °C whereas it decreases rapidly
chemical vapor deposition method, etc. In these methods, the particles on increasing concentration of the Ce3+ ions. They have recorded the
size varies from sub-micron range to a nano-meter range. In some cases, XRD patterns of the phosphor samples on increasing calcination tem-
the ultrafine particles are formed, which are known as quantum dots perature and concentration of Ce3+ ions.
(QDs). The shapes of the particles are found to vary with the synthesis It is deduced that when the temperature of the phosphor was in-
procedures [69–75]. creased the XRD peaks of the phosphor was observed intense and sharp,
It has been well established that the morphology of the phosphor which reveals crystallinity nature of these phosphors. On the other
materials can be tuned either by changing the synthesis procedures or hand, the XRD peaks of Y3Al5O12(YAG) phosphor are shifted towards
by introducing some sensitizers and surface modifiers. The solid state lower angle side on increasing concentrations of the Ce3+ ions due to
reaction method yields the particles size in sub-micron range whereas the higher ionic radii of Ce3+ than Y3+ ions. This reflects larger crys-
the phosphor synthesized by solution reaction method gives the parti- tallinity in the phosphor sample. The effects of calcinations temperature
cles size in the range of the sub-micron to nano-meter scale. However, and concentration of the Ce3+ ions are shown in Fig. 4.
the phosphor materials synthesized by the procedures, such as sol-gel They have also recorded the scanning electron micrographs of the
method, co-precipitation method, hydrothermal method, pechini phosphor samples at different temperatures and concentrations of the
method, spray pyrolysis, chemical vapor deposition method, etc. pro- Ce3+ ions and observed a significant change in the morphology of the
duce the particles in the nano-meter range. The nano-meter sized par- samples, which are shown in Fig. 5. It is clear from the figure that not
ticles are widely used in the biological studies to see the interaction of only the calcinations process but also concentration of the ions in-
the tissues with the phosphor materials. They can easily penetrate in the creases the particles size of the phosphor. This induces an increase in
biological cells and tissues. They are used for various applications, such the photoluminescence intensity of the phosphor materials.
as photo-thermal treatment, cancer therapy, photo-dynamic therapy, The emission spectra of the YAG:Ce samples with different tem-
bio-imaging, color tomography (CT) scan, magnetic resonance imaging peratures and concentrations of Ce3+ ions are shown in Fig. 6. It is clear
(MRI), etc. The size of the particles is adjusted in such a way that they from the figures that the emission intensity of the Ce3+ ions increases
should have high surface to volume ratio to meet out the specific on increasing the calcination temperature up to 1030 °C due to an
properties. The optical band gap of the nano-particles can also be tuned improvement in crystallinity while it is decreased at 1080 °C due to
to obtain the photoluminescence of the desired colors. The quantum cross relaxation in the Ce3+ ions. When the samples were prepared with
dots (QDs) are suitable materials to accomplish the purpose of photo- different concentrations (i.e. from 0.0055 to 0.0550 mol%) the emission
luminescence via tuning the optical band gap of the particles of the intensity is found to decrease regularly due to concentration quenching.
desired materials. It is concluded that the calcination temperature and concentrations of
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Fig. 4. XRD patterns of (a) YAG:Ce sample sintered at different temperatures for 3 h and (b) YAG:Ce samples sintered at 1030 °C for 3 h with different Ce3+
concentration. (Reproduced with permission from Ref. [87] copyright 2017, Nature).
the activator ions can efficiently affect the morphological properties of The size of the nano-particles is reduced remarkably (i.e. from
the photoluminescent (PL) materials. 50 nm to 15 nm) for the doping of Lu to La ions; however, the shape of
In an interesting work, Zhao et al. have prepared a series of Sr2ScF7 the nano-particles is changed to spherical with uniform diameter. When
nano-crystals by hydrothermal procedure with different RE ions, such the samples were prepared with different surfactants, such as NH4F,
as Ce, Tb, Eu, Sm, Dy, Er, Tm, Ho and Yb; and studied the upconversion NaF and NaBF4 at different pH values (pH = 2, 7 and 10) the surface
(UC)/downconversion (DC) photoluminescent properties [88]. morphology of the samples were altered significantly and they are
They have discussed the impact of pH values, F− sources and dif- shown in Fig. 8. It has been noticed that the length and width of the
ferent surfactants on the particles size of the crystals and found dif- nano-rods changed from 120 nm and 1.5 μm and from 40 nm to 80 nm
ferent morphologies for the prepared samples i.e. nanorods, quad- with the NH4F, NaF and NaBF4 surfactants, respectively.
rangular microplates, cubes and polyhedrons (see Fig. 7). The These authors have also studied the effect of different morphologies
morphology of the pure Sr2ScF7 is found to uniform with identical on the photoluminescence intensity of the nano-particles and it is
nanorods and their size is observed with a length of 120 nm and width shown in Fig. 9.
50 nm. When the 30% RE ions were introduced in the pure crystal, the Fig. 9 shows the upconversion spectra of the Sr2ScF7:10% Yb3+, 1%
shape and size of the crystal were modified considerably. Er3+ samples on excitation with 976 nm, which show the green and red
Fig. 5. SEM micrographs: (a–f) YAG:Ce sample-1 sintered at different temperatures for 3 h and (e, g–i) YAG:Ce samples with different Ce3+-doped concentrations
sintered at 1030 °C for 3 h.(Reproduced with permission from Ref. [87] copyright 2017, Nature).
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Fig. 6. (a) The PLE and (b) PL spectra of pure YAG (dash line) and YAG:Ce sample-1 sintered at different temperatures for 3 h (λem = 525 nm). The inset in Fig. 6(b)
shows variation of PL intensity (I) and emission peak position (II) with the calcination temperature. (c) The gaussian fitted (dashed) and decomposed components
(dotted) of the PL spectra of YAG:Ce sample-1 (1030 °C, 3 h). (d) The PL emission spectra of YAG:Ce samples with different Ce3+-doped concentrations (1030 °C, 3 h).
The inset of Fig. 6(d) is variation of the PL intensity (M) and emission peak position (N) with different Ce3+-doped concentrations (λex = 454 nm). (Reproduced with
permission from Ref. [87] copyright 2017, Nature).
emissions. The intensity of these emissions changes with the mor- and surface modifiers. It has been found that the efficiency of the
phology of the samples. Fig. 9 also shows the downconversion spectra phosphor materials was improved by modifying the morphology
of the Sr2ScF7:5 Eu3+ samples upon 394 nm excitation source (see through a sensitizer ion. In the singly RE doped phosphor, the Bi3+ ion
Fig. 9(b)). It is clear from the figure that the sample emits red emission is found to improve the morphology and photoluminescence intensity
at 595 nm and the photoluminescence intensity of the samples is of the phosphor. The Bi3+ ion emits a broad band in the blue-green
morphology dependent. Thus, the photoluminescence intensity greatly regions and efficiently transfers its energy to other activator ions. The
depends on pH values, F− sources and different surfactants, which af- addition of Bi3+ ion not only modifies the local structure of the phos-
fected particles size of the crystals. phor materials but also improves photoluminescence intensity to a large
Recently, Freiria et al. have studied the effect of different con- extent. Orihashi et al. have prepared the Eu3+, Bi3+ co-doped CaZrO3
centrations of the Dy3+ ions on the morphology and photo- phosphor by solid state reaction method. They have studied the effect of
luminescence intensity of the Dy3+ doped LaNbO4 phosphor [89]. The Bi3+ ion on the morphological and optical properties of the phosphor
phosphor samples were synthesized by one-step spray pyrolysis [90]. They have observed a 13 time enhancement in the emission in-
method. They have reported the spherically shaped particles in the tensity of the Eu3+ bands, which occurs due to energy transfer from
phosphor while the particles size varies with the increase in the con- Bi3+ to Eu3+ ions. It has been also observed that the crystallinity of the
centration of Dy3+ ions. The Dy3+ doped LaNbO4 phosphor emits in- phosphor materials is also improved in presence of Bi3+ ions.
tense yellow emission at 575 nm alongwith weak blue (at 477 nm) and The similar observation has been also reported by our group in the
red (at 664 nm) emissions on excitation with 254 nm. The photo- Tb3+, Bi3+ co-doped Y2O3 nano-phosphor. We have also found an en-
luminescence intensity initially increases then found to decrease due to hancement in the photoluminescence intensity due to energy transfer
concentration quenching at higher concentrations. from Bi3+ to Tb3+ ions [91]. In this work, the crystallinity and the
As has been mentioned earlier, the calcination temperature, con- particles size of the phosphor was increased remarkably in presence of
centrations, pH values, fluoride sources and surfactants play a very Bi3+ ions. In an interesting work, Huang et al. have reported host
crucial role for the morphology and photoluminescence intensity of the sensitized energy transfer in the Eu3+ doped CaW1-xMoxO4 phosphor
phosphor materials appreciably. The photoluminescence intensity of [92]. The sample gives intense red photoluminescence on excitations
the phosphor can be further enhanced by incorporating some sensitizers with 280, 393 and 467 nm wavelengths. The photoluminescence
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Fig. 7. SEM micrographs of (A) pure Sr2ScF7 nanocrystals, (B) 30% Lu3+, (C) 30% Yb3+, (D) 30% Tm3+, (E) 30% Dy3+, (F) 30% Tb3+, (G) 30% Eu3+, (H) 30%
Sm3+ and (I) 30% La3+ doped Sr2ScF7 nanocrystals, respectively. (Reproduced with permission from Ref. [88] copyright 2017, Royal Society of Chemistry).
intensity also depends on the excitation wavelength and it is optimum transfer. Recently, Lu et al. have studied the photoluminescence prop-
for 393 nm excitation. This is due to large absorption cross section of erties of the Eu3+, Bi3+ co-doped La3Ga5GeO14 phosphor and reported
the Eu3+ ion for 393 nm wavelength. The energy transfer takes place the enhanced red color in presence of Bi3+ ions [93].
from MoO4 group to Eu3+ ions. They have observed an 8.3 times im- Our group has also prepared the Bi3+/Yb3+ co-doped gadolinium
provement in the photoluminescence intensity of the phosphor in pre- tungstate phosphor synthesized through solid state reaction method
sence of MoO4 group, which is due to change in morphology and energy and studied the quantum cutting (QC) phenomenon [94]. In this case,
Fig. 8. SEM images of Sr2ScF7 crystals prepared at different pH values and using different F−sources, respectively. The pH and F− source are indicated in each
picture. (Reproduced with permission from Ref. [88] copyright 2017, Royal Society of Chemistry).
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Fig. 9. The photoluminescence emission spectra of the Sr2ScF7:10% Yb3+, 1% Er3+ (A) and Sr2ScF7:5% Eu3+ (B) samples with various morphologies. (Reproduced
with permission from Ref. [88] copyright 2017, Royal Society of Chemistry).
Fig. 10. SEM micrographs of the 1 mol% Bi3+, 5 mol% Yb3+ co-doped gadolinium tungstate phosphors in absence (a) and presence of Li+ ion (b). (Reproduced with
permission from Ref. [94] copyright 2016, American Chemical Society).
when Li+ ion is co-doped in the phosphor the crystallinity and particles note that on addition of Li+ ion, the intensity of the visible band further
size of the phosphor are improved considerably. The effect of Li+ ion on decreased continuously whereas that of the NIR region initially in-
the morphology of the phosphor is shown in Fig. 10. The particles of the creases then decreased further due to concentration quenching. The
phosphor are spherically agglomerated to each other and it is larger for concentration of Li+ ion is found to be optimum at 3 mol% in the
doping of Li+ ion. The particles size of the phosphor lies in the sub- phosphor. The quantum efficiency is thereby increased up to 43% in
micron range. presence of Li+ ion.
The Bi3+/Yb3+ co-doped phosphor gives visible and NIR emissions In addition to this, the morphology and photoluminescence in-
upon 355 nm excitation. We have tried to improve the efficiency of NIR tensity can be also influenced by doping some alkali metal ions (i.e.
emission by co-doping the Li+ ion. As the concentrations of Yb3+ions Li+, Na+ and K+). Prakashbabu et al. have prepared the Eu3+ doped
are increased the intensity of the visible band decreases regularly while ZrO2 nano-phosphor by solution combustion method and studied the
that of the NIR region initially increases then decreased due to con- effect of Li+ ion on the photoluminescence intensity of the phosphor
centration quenching. This occurs due to energy transfer from Bi3+ to sample as a charge compensator. They have found the enhanced in-
Yb3+ ions. The presence of Li+ ion in the phosphor also enhances the tensity due to larger crystallinity and charge compensation effect in
intensity of NIR emission up to 3 times (see Fig. 11). It is interesting to presence of Li+ ion [95]. J. Kim has studied the effect of alkali (i.e. Li+,
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respectively. It is clear from the figure that as the atomic number of the
alkali metal ions increases the corresponding excitation intensity de-
creases. It is also evident from the emission spectra that the trend of the
photoluminescence intensity is found to decrease as the atomic number
of the alkali metal ions increases. The alkali ion influences the struc-
tural properties of the phosphor in the present case. Park et al. have also
reported the effect of alkali ions on the photoluminescence intensity of
the Eu3+ doped Ca3Al2O6 phosphor in terms of charge compensator
[97]. It has been observed that the photoluminescence intensity of the
phosphor decreases on addition of alkali ions, which is due to non-
incorporation of the alkali ions into the host lattice.
If the sensitizer ion is also present with alkali ions in the phosphor
samples the photoluminescence intensity is found to enhance many
folds. In an interesting work, Ran et al. have studied the effect of sen-
sitizer alongwith alkali ions on the morphology and photoluminescent
intensity of the phosphors [98]. They have also synthesized the Eu3+
doped ZnMoO4 phosphor by solid state reaction method using Bi3+ and
alkali (Li+, Na+ and K+) ions. Initially, the photoluminescence in-
tensity is increased due to energy transfer from Bi3+ to Eu3+ ions. The
Fig. 11. Effect of Li+ concentration (i.e. 0, 3, 5 and 7 mol%) on the emission addition of alkali ions improves the crystallinity and modifies the local
intensity of 1 mol% Bi3+, 5 mol% Yb3+ co-doped gadolinium tungstate phos-
symmetry around the RE ions. This increases the photoluminescence
phors. (Reproduced with permission from Ref. [94] copyright 2016, American
intensity of the phosphor and the order of increment has been found as
Chemical Society).
Na+ > Li+ > K+. The morphological properties of the phosphor
strongly depend on the selection of the host and dopant ions. Thus, the
Na+ and K+) ions on the optical properties of the molybdate and photoluminescence intensity of the RE ion is significantly affected by
tungstate phosphors [96]. He has prepared the Eu3+ doped molybdate addition of sensitizers and surface modifiers.
and tungstate phosphors by sol-gel based Pechini sol-gel method co-
doping with alkali (Li+, Na+ and K+) ions. The effect of alkali ions on
the morphology of the phosphor seems minor irrespective of synthesis 2.2. Doubly RE doped phosphor materials
method. The sample prepared by solid state reaction method grows the
larger particles compared to sol-gel based Pechini method. Fig. 12 The RE co-doped phosphor materials have been widely investigated
shows the effect of alkali ions and synthesis methods on the mor- using structural and optical properties. The photoluminescence in-
phology of the phosphor. The shapes and size of the particles are dif- tensity of the RE ion can also be enhanced using some sensitizers and
ferent to each other and they are agglomerated due to calcination of the surface modifiers as discussed earlier. In this case, the RE ions absorb
phosphor at higher temperature. the proper incident photons and give the downconversion emission.
The photoluminescence intensity of the molybdate and tungstate Some of the RE ions efficiently transfer their excitation energy to the
phosphors was enhanced in the order of K+ < Na+ < Li+ and alkali other RE ions. The energy transfer generally takes place due to
metal ions co-doped molybdate phosphors show slightly higher optical matching of energy levels of both the ions. The ion, which transfers its
properties than those of tungstate phosphors (see Fig. 13). The (Li+, energy, is known as donor ion whereas the energy absorbed by the ion
Na+ and K+) and Eu3+ co-doped molybdate and tungstate phosphors is known as acceptor ion, respectively. The energy transfer can improve
are named as (LEM, NEM and KEM) and (LEW, NEW and KEW), the photoluminescence intensity of the RE ion and can also lead to
Fig. 12. Effect of alkali ions (a–c) and synthesis methods (d) on the morphology of the phosphor samples. (Reproduced with permission from Ref. [96] copyright
2017, American Chemical Society).
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Fig. 13. Excitation (a) and emission (b) spectra of different molybdate and tungstate phosphors in presence of alkali (i.e. Li+, Na+ and K+) ions. (Reproduced with
permission from Ref. [96] copyright 2017, American Chemical Society).
generate white light by tuning the concentrations of the donor and the et al. have studied the QC process in the Tm3+ doped Gd2O2S phosphor
acceptor ions. In this sequence, Cao et al. have prepared the Eu3+, for spectral conversion [103]. Yu et al. have also studied the QC in the
Sm3+, Bi3+ co-doped LiLaMo2O8 phosphor through a high temperature Ho3+, Yb3+ co-doped KLu2F7 phosphor synthesized by solid state re-
solid state reaction method and obtained intense red downconversion action method [104]. The energy transfer from Ho3+ to Yb3+ ions
photoluminescence due to energy transfer from (Sm3+ and Bi3+) ions enhances the NIR emission up to 5 times. The internal quantum yield
to Eu3+ ion [99]. has been calculated to be ~191%. The QC has also been studied in the
Similarly, Xia et al. have also prepared the single phase Eu3+, Tb3+, Pr3+, Yb3+ co-doped Ca3Ga2Ge3O12 phosphor due to energy transfer
Bi3+ co-doped LaPO4 phosphor synthesized by solid state reaction from Pr3+ to Yb3+ ions.
method. The annealed phosphor samples reveal good crystallinity in the On the other hand, the upconversion in the RE ions arises due to
case of Eu3+, Tb3+ and Bi3+ doped and co-doped LaPO4 phosphor energy transfer between them. The energy transfer occurs in the up-
samples [100]. They have observed an intense red photoluminescence conversion process due to sequential and cooperative processes. In this
due to energy transfer from (Tb3+ and Bi3+) ions to Eu3+ ion. Jeon process, the Yb3+ ion is used as sensitizer and has large absorption
et al. have synthesized the Ca2La8(GeO4)6O2:Tb3+/Sm3+ nanocrystal- cross section for near infrared (NIR) light [105]. The RE ion absorbs
line phosphor through sol gel method and observed white light emis- NIR (980 nm) light weakly and gives poor photoluminescence intensity.
sion in the phosphor due to energy transfer from Sm3+ and Tb3+ ions The energy absorbed by the Yb3+ ion is transferred to the other RE ions.
[101]. The effect of annealing and energy transfer has also been studied This induces an improvement in the photoluminescence intensity of the
by our group in the Sm3+, Tb3+, Li+ co-doped Y2O3 nano-phosphor co-doped phosphor samples. Dubey et al. have prepared the Er3+,
[102]. It was observed that the annealing induces crystallinity in the Yb3+, Li+ tri-doped NaYF4 phosphor by hydrothermal method and the
phosphor and yields larger particles size, which promotes larger ex- crystallinity and particles size of the phosphor is improved in presence
citation of the ions in the upper energy states. The energy transfer from of Li+ ion [106].
Tb3+ and Sm3+ ions and concentration variation leads to produce Fig. 14 shows the effect of Li+ ion on the morphology and particles
white light emission in the co-doped phosphor. Once the energy distribution of the phosphor. The particles size is increased from 766 to
transfer takes place the photoluminescence intensity of the Tb3+ ion is 874 nm in presence of Li+ ion. It is also clear from the figure that the
found to decrease whereas that of the Sm3+ ion is increased. This leads particles are randomly distributed and agglomerated to each other. The
to color tunability for the co-doped phosphor. The presence of Li+ ion sample emits the upconverted blue, green and red emissions. The pre-
enhances the photoluminescence intensity of the white light sig- sence of Li+ ion enhances the photoluminescence intensity of the co-
nificantly. doped phosphor samples significantly. Due to the smaller ionic radii
The energy transfer process can also lead to an interesting phe- Li+ ion (~68 p.m.), it occupies the Na+ (~97 p.m.) site and causes
nomenon known as quantum cutting (QC). The quantum cutting phe- lattice distortion around the Er3+ ion. The photoluminescence intensity
nomenon is basically used in solar spectral conversion. It can be em- of the phosphor decreases due to concentration quenching after a cer-
ployed in the energy harvesting using the RE ions. Following this, Yu tain concentration of Li+ ions (see Fig. 15). The inset figure shows a
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Fig. 14. FE-SEM image of (a) 1.0 mol% Er3+, 5.0 mol% Yb3+ co-doped and (b) 1.0 mol% Er3+, 5.0 mol% Yb3+, 30 mol% Li+ tri-doped NaYF4 phosphors. (c) Particle
size calculation from the histogram for the co-doped phosphor and (d) Particle size calculation from the histogram for tri-doped phosphor samples. (Reproduced with
permission from Ref. [106] copyright 2017, Elsevier).
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Fig. 16. TEM images and size distributions of the Er3+, Yb3+ co-doped NaScF4 nanocrystals with reaction time of 2 h (a)–(b), 3 h (c)–(d), 12 h (e)–(f) respectively; (g)
and (h) SEM image of Er3+, Yb3+ co-doped NaScF4 nanocrystals with the reaction time of 2 h and 12 h, respectively; (i) EDX image of Er3+, Yb3+ co-doped NaScF4
nanocrystals synthesized in 12 h. (Reproduced with permission from Ref. [108] copyright 2017, Elsevier).
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change in the intensity with Li+ ion concentrations for the co-doped monoclinic crystalline phases are formed as Gd2WO6 and Gd2(WO4)3.
phosphor. The addition of Li+ ion influences the phase fraction in the two cases
The concentration quenching has also been studied by Zhang et al. and enhances the UC emission intensity of the Ho3+/Yb3+ co-doped
in the Tm3+, Yb3+ co-doped Gd2(WO4)3 phosphor under 980 and phosphors [109]. The phosphor sample gives intrinsic optical bistability
808 nm excitation sources [107]. They have prepared the samples with (IOB) and the nature of hysteresis curves is found to reverse in presence
different concentrations of the Tm3+ ions (i.e. 0.1, 0.5, 1.5 and 2.5 mol of Li+ ion in the Ho3+/Yb3+ co-doped phosphors. Li et al. have studied
%) and Yb3+ ions (i.e. 1, 5, 10 and 25 mol%). The concentration the effect of alkali (i.e. Li+, Na+ and K+), alkaline (i.e. Mg2+, Ca2+,
quenching took place after 0.1 and 10 mol% concentrations of Tm3+ Sr2+ and Ba2+), Y3+, Gd3+ and Lu3+ ions on the UC and temperature
and Yb3+ ions, respectively. The morphology of the phosphor materials sensing properties in the Er3+, Yb3+co-doped ScVO4 nano/micro par-
can be also tuned with increasing reaction time of the synthesis pro- ticles [110]. When these ions are co-doped in the phosphor they can
cedure. occupy the substitutional and/or interstitial sites and modify the cor-
Zhang et al. have prepared a water soluble Er3+, Yb3+ co-doped responding crystal structure of the host. The effect of different additives
NaScF4 nano-crystals by changing the reaction time from 2 h to 12 h on the morphology of the phosphor is shown in Fig. 18, which reveals a
and found a color tunable phosphor [108]. The effect of reaction time non-uniform distribution of the nano/micro particles with different
on the morphology of the phosphor is shown in Fig. 16. It is clear from shapes and sizes.
the figure that when the sample is prepared in 2 h the particles sized is The co-doping of the ions modifies the morphology of the Er3+,
3+
~90 nm (see Fig. 16(a)). As the time is increased from 3 to 12 h the Yb co-doped ScVO4 phosphors. As a result, the photoluminescence
particles become with smooth surface and their size is reduced to 50 nm intensity of the Er3+ bands was enhanced up to 6.1, 4.1, 2.4, 2.5, 3.7,
(see Fig. 16(c and e)). Fig. 16 (g & h) show the SEM morphology of the 4.7, 2.3, 2.2, 2.6 and 3.4 times in presence of Li+, Na+, K+, Mg2+,
phosphor materials prepared for 2 h and 12 h reaction times, respec- Ca2+, Sr2+, Ba2+, Y3+, Gd3+ and Lu3+ ions, respectively. In an in-
tively. The morphology of the nano-crystals is observed with smooth teresting work, the effect of Bi3+ ion has been studied on the photon
surface for 12 h reaction time. Fig. 16(i) shows the EDX spectrum of the upconversion and intrinsic optical bistability in the Er3+/Yb3+ co-
Er3+, Yb3+ co-doped NaScF4 nano-crystal and verifies the presence of doped La2O3 phosphor by our group and found a 65 times enhancement
Na, Sc, F, Er and Yb elements in the sample. in the UC emission intensity of the phosphor. The doping of Bi3+ ion
The reaction time of the sample directly related to the UC emission improves the crystallinity and particles size of the phosphor [111].
intensity of the phosphor materials. They have observed a change in the When Bi3+ ion is co-doped in the phosphor the intensity of NIR ab-
green and red colors emitted by sample. Initially, the intensity of green sorption band is increased, which supports the large absorption for the
color is smaller than that of red color for the reaction time at 2 h as the Yb3+ ion. It also decreased the optical band gap of the phosphor. These
surface of the nano-balls is relatively less smooth and contains crystal collective properties induce large improvement in the UC emission in-
defects. This increases a non-radiative transition probability and the tensity.
lower excited (4F9/2) level is populated. When the reaction time is in-
creased the intensity of green color increases regularly while that of red 2.3. Triply RE doped phosphor materials
color, it is decreased.
This is due to the fact that as the reaction time increases the surface The triply RE doped phosphor materials are of great scientific im-
of the nano-balls becomes smoother with improved crystallinity, which portance and originate very interesting optical properties. The energy
reduces the crystal defects in the nano-crystals. The reduction in surface transfer between them yields new era of the applications in different
defects ultimately improves the radiative transitions of the green color dimensions. They emit color tunable light leading to generation of
in the samples. Thus, the intensity of the green emission is enhanced white light emission [112–114]. Some efforts have been made to im-
significantly, which is shown in Fig. 17. prove the efficiency of these emissions by incorporating some surface
Recently, our group has studied the effect of Li+ ion on frequency modifiers. The surface modifier can modify the local structure followed
upconversion and intrinsic optical bistability in the Ho3+/Yb3+ co- by enhancing the photoluminescence intensity of the phosphors. Ku-
doped gadolinium tungstate phosphor. In this phosphor, two mari et al. have studied the effect of Li+ ion on the upconverted white
light emitted from Ho3+/Tm3+/Yb3+/Li+:Gd2(MoO4)3 nanophosphors
[115]. When the Li+ ion is co-doped in the Ho3+/Tm3+/
Yb3+:Gd2(MoO4)3 nanophosphors the UC emission intensity is en-
hanced by many times due to local field modifications around the RE
ions.
The enhancement in the UC emission intensity of white light has
also been studied by our group in the Tm3+/Yb3+/Ho3+ co-doped
Na4ZnW3O12 nano-crystalline phosphor in presence of Li+ ion [116]. In
our case, the addition of Li+ ion increases the crystallinity and the
particles size of the phosphor. Li+ ion with smaller ionic size replaces
Na+ ion and a contraction in the lattice parameters has been observed
due to shifting of XRD peak position towards higher angle side. The
effect of Li+ ion on the morphology of the phosphor is shown in Fig. 19.
The SEM micrographs show an increase in the particles size of the
phosphor in presence of Li+ ion.
When the Li+ ion is doped in the phosphor materials the particles
size is found to increase. It has been also mentioned earlier that the
incorporation of additional surface modifiers improve the morphology
of the co-doped materials. As a result, the particles size of the phosphor
materials is increased. The larger particle can efficiently absorb large
number of the incident photons and can increase the UC photo-
Fig. 17. UC luminescence spectra of the Er3+, Yb3+ co-doped NaScF4 nano- luminescence intensity of the phosphor [117]. It has been reported that
crystals with synthesized reaction time 12-2 h under 980 nm excitations the presence of Li+ ion reduces the optical quenching centers present in
(Reproduced with permission from Ref. [108] copyright 2017, Elsevier). the phosphor sample. In this way, the UC photoluminescence intensity
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R.S. Yadav, et al. Progress in Solid State Chemistry 57 (2020) 100267
Fig. 18. SEM of (a) optically-inert ions free, (b) Gd3+, (c) Li+, (d) Ca2+, (e) Li+/Gd3+, (f) Ca2+/Gd3+, (g) Li+/Ca2+, (h) Li+/Ca2+/Gd3+ co-doped ScVO4:10%
Yb3+/2% Er3+ phosphors. (Reproduced with permission from Ref. [110] copyright 2017, Royal Society of Chemistry).
of the phosphor can be enhanced in presence of Li+ ion. The effect of parameters and the XRD peaks are shifted towards lower angle side. On
Li+ ion on the UC photoluminescence intensity of the phosphor is the other hand, when the Li+ ions are co-doped in the NaZnPO4
shown in Fig. 20. It is clear from the figure that the UC photo- phosphor the XRD peaks are shifted towards higher angle side due to
luminescence intensity of the phosphor is enhanced up to two times in smaller ionic radii of Li+ ion compared to that of Na+ ion. The effect of
presence of Li+ ion due to an increase in crystallinity, particles size and all the co-dopants on the XRD patterns is shown in Fig. 21(a–c). The
reduction in optical quenching centers. Mahalingam et al. have also authors have also calculated the crystallite size of the phosphor and
observed enhanced white light emission in the Tm3+/Yb3+/Ho3+ co- found a high dependency on the dopants addition.
doped GdVO4 phosphor in presence of Li+ ion [118]. The FESEM micrographs have been recorded in absence and pre-
Recently, Facanha et al. have studied the effect of Li+ ion on the sence of Li+ ions and they are shown in Fig. 21 (d–e). The addition of
structural and optical properties of the Er3+/Tm3+/Yb3+ co-doped Li+ ions reflects the visibility of distinct particles with rod-shaped
NaZnPO4 phosphors. They have found that the addition of Li+ ions structures. The particles size of the phosphor decreases on addition of
improved the local symmetry around the RE ions and affected the Li+ ions, which may affect the emission intensity of the phosphor.
emission intensity arising from the phosphor [119]. It has been also Fig. 21 (f)) shows the EDAX analysis that confirms the presence of Na,
observed that the white light emission takes place from the Er3+/ Zn, P, Er, Yb and Tm elements in the phosphor [121–123].
Tm3+/Yb3+ ions in the NaZnPO4 phosphor host. Mukhopadhyay et al. These authors have also measured the emission intensity of Er3+/
have prepared the Er3+/Tm3+/Yb3+ co-doped NaZnPO4 phosphors in Tm , Er3+/Tm3+/Yb3+ and Er3+/Tm3+/Yb3+/Li+ co-doped
3+
absence and presence of Li+ ion through high temperature solid state NaZnPO4 phosphors on excitation with 976 nm source and it is shown
reaction method [120]. They have studied the effect of Li+ ion on the in Fig. 22. The figure shows that when the Er3+/Tm3+ ions are co-
structural, morphological and optical properties of the Er3+/Tm3+/ doped in the NaZnPO4 phosphor the sample emits poor emission in-
Yb3+ co-doped NaZnPO4 phosphors. They have recorded the XRD tensity.
patterns in both the cases and found slight shifting of XRD peaks to- On the other hand, when an appropriate amount of Yb3+ ion is
wards lower angle side due to Er3+/Tm3+/Yb3+ co-doping at the Zn- added in the co-doped phosphor the emission intensity was enhanced in
sites. In this phosphor, the ionic radii of Na+, Zn2+, P5+, Er3+, Yb3+, many folds. Interestingly, on addition of Li+ ions in the Er3+/Tm3+/
Tm3+ and Li+ ions are 0.102, 0.74, 0.38, 0.89, 0.868, 0.88 and Yb3+ co-doped phosphor the emission intensity of the phosphor was
0.76 nm, respectively. When the higher ionic radii ions are doped at the further enhanced significantly. This is due to change in crystal field
substitutional sites of Zn2+ ions there is an expansion in the lattice caused by Li+ ions occupancy at Na+ substitutional sites in the
Fig. 19. SEM micrographs of the annealed (a) Tm3+/Yb3+/Ho3+ and (b) its Li+ doped Na4ZnW3O12 nano-crystalline phosphors. (Reproduced with permission from
Ref. [116] copyright 2016, Royal Society of Chemistry).
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R.S. Yadav, et al. Progress in Solid State Chemistry 57 (2020) 100267
Fig. 20. UC emission spectra of the annealed (0.7 mol%) Tm3+/(0.5 mol%) Ho3+/(3.0 mol%) Yb3+ co-doped and its (5 mol%) Li+ doped Na4ZnW3O12 nano-
crystalline phosphors on excitation with 976 nm. (Reproduced with permission from Ref. [116] copyright 2016, Royal Society of Chemistry).
NaZnPO4 phosphor. size of the phosphor. The concentrations of the donor and acceptor ions
also change the morphology of the phosphors. The reaction time also
affects the morphology of the phosphor. The sensitizer ion not only
3. Conclusions changes the morphology of the phosphor but also takes part in the
energy transfer. The surface modifier improves both the crystallinity
This review summarizes large number of phosphors synthesized and the particles size of the phosphor. All these parameters are directly
through different methods. The effect of synthesis procedure, annealing related to the optical properties of the phosphor and enhance the
process, concentrations of the donor and acceptor ions, reaction time, photoluminescence intensity of the phosphor materials significantly.
sensitizers and surface modifiers on the morphology of the phosphor
has been discussed in detail. The synthesis procedure plays a major role
in the morphology of the chemically engineered phosphors. The an-
nealing/calcination process improves the crystallinity and the particles
Fig. 21. XRD patterns and W–H plots of (a) Er3+/Tm3+, (b) Er3+/Tm3+/Yb3+ and (c) Er3+/Tm3+/Yb3+/Li+ co-doped NaZnPO4 phosphors. FESEM images of
Er3+/Tm3+/Yb3+ (d) and Er3+/Tm3+/Yb3+/Li+ co-doped NaZnPO4 phosphors (e) and (f) EDAX analysis of Er3+/Tm3+/Yb3+ co-doped NaZnPO4 phosphor.
(Reproduced with permission from Ref. [120] copyright 2017, Royal Society of Chemistry).
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R.S. Yadav, et al. Progress in Solid State Chemistry 57 (2020) 100267
Fig. 22. Emission spectra of Er3+/Tm3+, Er3+/Tm3+/Yb3+ and Er3+/Tm3+/Yb3+/Li+ co-doped NaZnPO4 phosphors on excitation with 976 nm laser. (Reproduced
with permission from Ref. [120] copyright 2017, Royal Society of Chemistry).
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