Ceramics International 49 (2023) 16080–16088

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Preparation and photoluminescence properties of novel orange-red

La3Ga5SiO14:Sm3+ phosphors
Na-Na Zhang a, Yu-Guo Yang b, *, Xue-Yuan Yan a, Meng-Qi Wang a, Yuan-Yuan Zhang b,
Hua-Di Zhang b, Rui Zhang b, Cheng-Cheng Qiu b, Fu-Di Chen c, Ji-Yang Wang b
a
College of Chemistry & Chemical and Environmental Engineering, Weifang University, Weifang, 261061, PR China
b
Advanced Materials Institute, Qilu University of Technology (Shandong Academy of Sciences), Jinan, 250014, PR China
c
Shandong Shanke Zhijing Optoelectronic Technology Co. LTD, Jinan, 250109, PR China

A R T I C L E I N F O A B S T R A C T

Handling Editor: Dr P. Vincenzini In the present work, orange-red Sm3+ doped La3Ga5SiO14 phosphors were successfully formed through high
temperature solid state method at 1350 ◦ C. The phase purity, size distribution, vibrations, absorption and series
Keywords: of luminescence characteristics were studied, respectively. The X-ray diffraction and Rietveld refinements results
La3Ga5SiO14 show the single phase and crystal lattice information. The results of scanning electron microscope and energy-
Sm3+ doping
dispersive spectroscopy demonstrate the basic particle shape and verify the constituent elements for the pre­
Luminescent properties
pared samples. The infrared spectra clarify the phonon vibration properties of the La3Ga5SiO14:Sm3+ phosphors.
Thermal stability
LED The UV–visible absorption spectra indicate that the absorption properties and the corresponding band gaps. The
luminescence results show that the La3Ga5SiO14:Sm3+ phosphors emit intense orange-red emission peaking at
600 nm as excited at 401 nm. The optimum doping concentration of Sm3+ ion is x = 0.05 and the mechanism of
concentration quenching is from dipole-quadrupole interaction. In addition, the prepared phosphors have good
thermostability, and its thermal activation energy is 0.2161 ev. Finally, red and white light emitting diodes were
successfully manufactured with 395 nm chip. All experimental results show that the La3Ga5SiO14:Sm3+ phos­
phors have good application prospect in light emitting diodes.

1. Introduction deriving from the 4G5/2 → 6H5/2, 7/2, 9/2 or 11/2 transitions [7,8], and
Sm3+-doped phosphors carry intense absorption in the wavelength
Nowadays, people have paid more attention to white light emitting scope of 380–420 nm [9,10]. Besides, some phosphors doped with Sm3+
diodes (WLEDs) as a result of their high efficiency, no toxic mercury, ions can also be used for temperature sensors, submarine communica­
low-power consumption, long life, and fast response etc [1]. Phosphors tions, color displays, high-density optical storage, visible light
with rare earth (RE) doping play major roles in the preparation of solid-state lasers, etc [11].
WLEDs because of their unique optical characteristics deriving from the Phosphors generally consist of a matrix and at least one activator.
4f shell of RE ions [2–4]. The most common technique for preparing Different substrates have diverse crystal field environments, and thus
WLEDs is to combine Y3Al5O12:Ce3+ yellow phosphor with blue LED the same doping ion may emit different colors depending on substrates.
chip. However, this method lacks red emission, so it has high correlation Therefore, selection of appropriate substrate materials is conductive to
color temperature (CCT >5500 K) and low color rendering index (Ra improve the luminous properties of phosphors. Due to the random dis­
<80). To solve this problem, researchers began to look for red light tribution of Ga3+ and Si4+ ions at the 2 d Wyckoff position in the crystal
emitting materials. In general, nitrides are the essential compose in the structure, partially disordered langasite (La3Ga5SiO14) has aroused our
synthesis of red phosphors. However, higher temperature and pressure great attention. This property leads to slight changes in the crystal field
conditions of synthetic process limit its use [5,6], hence exploration for of doped RE ions, resulting in wide absorption and different luminous
materials with appropriate red or orange emission is urgent. Sm3+ ions properties [12]. Up to now, the research on La3Ga5SiO14 based phosphor
are important activators of orange-red emission in lanthanide ions is relatively few. The red light emitting characteristics of La3Ga5SiO14:
because it can produce sharp orange-red light (597 nm ~ 622 nm) Eu3+ phosphors were firstly reported on in 2008 [13], and influence of

* Corresponding author.
E-mail address: [email protected] (Y.-G. Yang).

https://doi.org/10.1016/j.ceramint.2023.01.206
Received 25 November 2022; Received in revised form 9 January 2023; Accepted 28 January 2023
Available online 31 January 2023
0272-8842/© 2023 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
 N.-N. Zhang et al. Ceramics International 49 (2023) 16080–16088

Tb3+/Eu3+ ions ratio on tunable luminescence in La3Ga5SiO14 matrix 3. Results and discussion
was studied in 2021 [14]. All those results demonstrate that La3Ga5
SiO14 matrix is very suitable for RE doping. 3.1. XRD characterization
In recent years, there have been some investigations on Sm3+ doped
phosphors based on different matrix, such as Gd2InSbO7:Sm3+ [15], Crystal structure diagram of La3Ga5SiO14, [GaO4], [GaO6] and
Ba3Lu(PO4)3:Sm3+ [16], KLaSr3(PO4)3F:Sm3+ [17], La6Ba4Si6O24F2: [SiO4] polyhedra on ab and bc planes are described in Fig. 1(a),
Sm3+ [18], YVO4:Sm3+ [19], Mg3Y2Ge3O12:Sm3+ [20], Ca9La(PO4)7: respectively. The La3Ga5SiO14 comprises of four different cation sites,
Sm3+ [21], etc. Those materials display characteristic spectra of Sm3+ where La atoms situate in dodecahedron sites, Ga1 atoms locate at oc­
ions but slightly lower thermal properties. La3Ga5SiO14 materials with tahedron sites, Ga3 atoms locate at trigonal-pyramid sites, Ga2 and Si
disordered structure have low thermal expansion coefficient, and their atoms locate at tetrahedron sites. Due to the random distribution of Si
thermal conductivity increases with temperature. In addition, La3+ ion and Ga2 atoms, La3Ga5SiO14 crystal structure is intrinsically disordered.
in La3Ga5SiO14 has similar ionic radius with Sm3+ ion, which is partic­ The partly disordered langasite La3Ga5SiO14 crystal exhibits trigonal
ularly suitable for homologation substitution. Therefore, La3Ga5SiO14 system lattice symmetry and its space group is P321 (D23), with unit-cell
matrix is a very potential phosphor matrix for Sm3+ and the properties of parameter of a (or b) = 8.168 Å, c = 5.095 Å, V = 294.38 Å3, Z = 1 (one
La3Ga5SiO14:Sm3+ phosphors are expected. In this work, series of molecular per unit) [22].
La3-xGa5SiO14:xSm3+ (x = 0.025, 0.05, 0.75, 0.1, 0.2 and 0.3) phosphors The XRD results of the La3Ga5SiO14:xSm3+ (x = 0, 0.025, 0.05,
were successfully synthesized. The crystal structure, morphology, 0.075, 0.1, 0.2 and 0.3) phosphors and the JCPD card (no. 72–2249) are
infrared and UV–vis absorption properties, luminous performance, shown in Fig. 1(b), where the observed diffraction positions of the
decay time, quantum efficient characteristics and performances of LEDs phosphors match well with the standard data and no impurity peaks
are studied. appear. These verify that they possess the same trigonal phase with P321
space group, and the doped Sm3+ ion exhibit no obvious influence on the
2. Experimental crystal structure of La3Ga5SiO14 matrix. For solid compounds containing
activated RE ions, the difference between the radius of activated and
2.1. Sample preparation substituted ions should be less than 30% [23]. For Sm3+ ions doped
La3Ga5SiO14 phosphors, the radii of activated Sm3+ and substituted La3+
La3-xGa5SiO14:Sm3+ phosphors were formed through a high tem­ ions are 1.08 and 1.16 Å. The calculated radius difference ratio is 7.5%,
perature solid state method, and the chemical materials were Sm2O3 which is much lower than 30%. Regarding the similar ionic radii of
(99.99%, Aladdin), La2O3 (99.99%, Aladdin), Ga2O3 (99.99%, Aladdin) Sm3+/La3+ ions and their same valence state, Sm3+ ions prefer to
and SiO2 (99.99%, Aladdin), respectively. Based on the chemical replace La3+ sites in La3Ga5SiO14 matrix.
composition of La3-xGa5SiO14:xSm3+ (x = 0.025, 0.05, 0.075, 0.1, 0.2 For further determining the crystallographic information of the
and 0.3), these raw materials were weighed stoichiometrically accord­ doping Sm3+ ions, the Rietveld refinements of the representative
ing to formula (1) and ground in a mortar for about 30 min. Next, put La3Ga5SiO14:0.05Sm3+phosphor were performed and the results are
them into a ball mill and then mixed for 8 h. The mixtures were then plotted in Fig. 2. All the fitting consequences are listed in Table S1 and
calcined in a muffle furnace at 1350 ◦ C for 3.5 h. Finally, the composi­ the fitting factors are acknowledged to be Rwp = 10.55%, Rp = 7.51%,
tion was taken out, and ground into fine powders for characterizations. and χ 2 = 1.032; the space group of La3Ga5SiO14:0.05Sm3+ is P321 and
its unit cell parameters are refined to be a = b = 8.147 Å, c = 5.117 Å,
(1)
and V = 294.06 Å3. These data and the detected atoms Wyckoff, site
2SiO2 + (3-x) La2O3 + 5Ga2O3 + xSm2O3 = 2La3-xSmxGa5SiO14
symmetry, coordinates and occupancy information are all provided in
Table S1.
2.2. Characterization By means of the above analysis, we obtained the unit cell parameters
of all of other samples, as listed in Table S2. We can see that on the whole
The structure of the prepared samples was performed by X-ray the incorporation of Sm3+ ions reduce the values of unit cell parameters.
powder diffraction (XRD) using a Bruker Smart PPEX II diffractometer With the increase of the Sm3+ ion doping concentration, the cell pa­
with Cu Kα radiation (λ = 1.5406 Å) and the structure refinements were rameters gradually decrease, demonstrating that the smaller Sm3+ ions
performed through Rietveld analysis by the General structure Analysis are really doped into the crystal matrix and substitute for the larger La3+
System (GSAS) program. The morphology, energy spectrum and ions. As a result, the lattice contraction and interplanar distance (d)
elemental mapping of the samples were investigated on an EM-30 PLUS decrease, and the diffraction angles (θ) increase. As shown in Fig. 1(b),
Scanning Electron Microscope (SEM) and an Energy Dispersive Spec­ the diffraction peaks shift slightly to the larger angle side, which is ac­
trometer (EDS, Oxford), respectively. Fourier transform infrared (FTIR) cording with the calculated results.
spectra were recorded in the wavenumber scope of 600–4000 cm-1 on a
Bruker ESNSOR 27 spectrophotometer. UV–Vis absorption measure­ 3.2. SEM and EDS measurements
ments in the range of 200–600 nm were obtained on a UV–Vis–NIR Cary
5000 Agilent spectrophotometer. Photoluminescence (PL) and photo­ In order to study the composition characteristics of the synthesized
luminescence excitation (PLE) measurements at room temperature were phosphors, the SEM, EDS and element mapping results of the
recorded on an FLS-980 spectrophotometer. Varying temperature-PL La3Ga5SiO14:0.3Sm3+ phosphor are listed in Fig. 3. Fig. 3(a) lists the
spectra were carried out on an F-4600 FL Spectrophotometer. The overall morphology of the La3Ga5SiO14:0.3Sm3+ phosphor at 50 μm
decay curves were determined through a Hitachi F-4500 fluorescence amplification. Since the sample is synthesized by high temperature solid
spectrophotometer. The internal absolute quantum efficiency was car­ state reactions, we can observe that the grain size is in the order of
ried on a C9920-02G system. The electroluminescence (EL) spectra of micrometers and the shape is irregular. Fig. 3(b) gives a SEM image of
red LED and WLED were performed on an OHSP-350 M LED Fast-Scan La3Ga5SiO14:0.3Sm3+ phosphor at 5 μm magnification. Fig. 3(c) makes a
Spectrophotometer. list of the corresponding EDS distribution diagram along the straight line
in Fig. 3(b). We can distinctly verify that its constituent elements are Sm,
Ga, La, O and Si. This also illustrates that Sm elements have successfully
incorporated into the La3Ga5SiO14 matrix. Fig. 3(d)–(i) draw the ele­
ments mapping of representative sample at 5 μm magnification, showing
that the La, Ga, Si, O and Sm elements distribute in the

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Fig. 1. (a) Unit cell projection of La3Ga5SiO14 and (b) XRD patterns of La3Ga5SiO14:xSm3+ (abbreviated as LGS:xSm3+, x = 0, 0.025, 0.05, 0.075, 0.1, 0.2 and
0.3) phosphors.

stretching vibrations of La–O in La3Ga5SiO14 matrix. The weak bands

those locating in the range of 1800–2500 cm-1 (the inset part of Fig. 4A)
probably results from the C–O vibration of CO2 during the synthesis
process in the air [24]. Other weak absorption bands locating at around
3500 cm-1 are possibly associated to the stretching vibrations of O–H
band. It corresponds to the absorbed water on the prepared powder
surface as the samples are in contact with environment during the
preparation and measurement processes [25]. Fig. 4(b) plots the FTIR
spectra of series of La3Ga5SiO14:Sm3+ phosphors. We can get that the
vibration spectrum does not change obviously with the Sm3+ doping
varying. It proves that the doping has not led to the changing of lattice
structure. A slightly widened infrared absorption bands are mainly from
the minor changes in cell parameters caused by substitutions of Sm3+
ions to La3+ ions [26].

3.4. UV–Vis absorption spectra

UV–Vis absorption patterns of the prepared La3Ga5SiO14:xSm3+ (x =

0.025, 0.05, 0.075, 0.1, 0.2 and 0.3) phosphors in the scope of 200–600
nm are plotted in Fig. 5. The strongest host absorption band locates at
about 220 nm is observed, which is primarily provoked from La3+ 5d
Fig. 2. Rietveld refinement of the XRD profile of orbital in the conduction band and O 2p orbital in the valence band of
La3Ga5SiO14:0.05Sm3+ phosphors. La3Ga5SiO14 [27]. The stronger absorption band locates around 260 nm,
which is majorly produced from the 4f-5d transition of Sm3+ ions [28].
La3Ga5SiO14:0.3Sm3+ phosphor homogeneously. The absorption bands locating in the scope of 300–500 nm are chiefly
triggered from f-f transition of Sm3+ ions, which correspond to the 6H5/2
→ 4D3/2, 6P7/2, 4F7/2 and 4I11/2 transitions, respectively. The UV–vis
3.3. IR spectroscopy results indicate that the formed La3Ga5SiO14:Sm3+ phosphor can be
effectively activated by UV light.
As an object illuminated by infrared light, the particles in its struc­ Fig. 6 depicts the band gaps using Tauc plot for the La3Ga5SiO14:
ture can absorb part of the energy and generate vibration energy tran­ xSm3+ (x = 0.025, 0.05, 0.075, 0.1, 0.2 and 0.3) phosphors. The band
sition. Therefore, the FTIR spectrum can reflect the crystal lattice gaps can be expressed in the following equation (2) [29]:
structure properties. According to the group theory, 23 atoms of
[αhν]2 = A(hν-Eg) (2)
La3Ga5SiO14 host can produce 66 optical vibrational modes. It can be
expressed as Γopt = 10A1 + 12A2 + 22E, where A is single mode and E is where hν represents the phonon energy, α stands for the proportional
double mode, both A2 and E modes are of infrared active. Thus the constant, Eg donates the band gap defined thorough extrapolating the
infrared vibration modes of La3Ga5SiO14 can be represented as Γ IR = curvature or the tail linear part [30]. The band gap of La3Ga5SiO14
12A2 + 22E, where 34 FTIR theoretical modes are expected in theory. matrix is estimated as 5.28 ev [14], indicating that the band gap of
FTIR spectra of series of La3Ga5SiO14:Sm3+ phosphors ranging from 600 La3Ga5SiO14 is wide enough to provide a stable environment for RE ions.
to 4000 cm-1 are plotted in Fig. 4. Fig. 4A gives the whole FTIR spectrum The band gaps of series of La3Ga5SiO14:xSm3+ phosphors are calculated
of the La3Ga5SiO14:0.025Sm3+ phosphor. A strong absorption band and the results are 4.535 ev for x = 0.025, 4.523 ev for x = 0.05, 4.521
locating at 880 cm-1 is observed, which probably corresponds to the ev for x = 0.075, 4.517 ev for x = 0.1, 4.505 ev for x = 0.2 and 4.516 ev

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Fig. 3. (a), (b) and (d) SEM images, (c) EDS patterns, and (e)–(i) elemental mapping of the representative block of La3Ga5SiO14:0.3Sm3+ phosphor.

Fig. 4. FTIR spectra of (a) La3Ga5SiO14:0.025Sm3+ and (b) La3Ga5SiO14:xSm3+ (x = 0.025, 0.05, 0.075, 0.1, 0.2 and 0.3) phosphors.

for x = 0.3, respectively. These results show that the band gap energy of 3.5. PLE and PL spectra
La3Ga5SiO14 entirely becomes narrower after doping Sm3+ ion. The
band gap decreases from x = 0.025 to 0.2 due to the band narrowing For investigation the luminescent properties of La3Ga5SiO14:Sm3+
effect, which is induced by the development of sub-levels between the phosphors, the spectra of PLE monitored at 600 nm and PL excited at
conduction band and valence band [31,32]. The band gap increases 401 nm for La3Ga5SiO14:0.025Sm3+ phosphor are drawn in Fig. 7. The
slightly for x = 0.3. This phenomenon may be attributed to the effect of PLE spectrum determined from 200 nm to 500 nm are shown in Fig. 7(a),
defect energy level in the band gap when the concentration of Sm3+ is where some characteristic peaks detected at 316, 343, 359, 373, 401,
high. In addition, the transformations of these values likely result from 413, 422 and 475 nm are ascribed to the transitions of 6H5/2 to 4L9/2,
the variation of crystallite sizes for different Sm3+ doping concentrations 6
K17/2, 4D3/2, 6P1/2, 4F7/2, 4M19/2, 4P5/2 and 4I11/2, respectively [15–21,
that affect the internal scattering process of the sample [33]. The above 37]. And the 6H5/2 → 4F7/2 transition locating at 401 nm is dominant.
phenomenon appears other Sm3+ doped articles as well [34–36]. The band locating in 200–300 nm is mainly owing to the O2− → Sm3+
charge transfer [16]. Fig. 7(b) depicts the PL spectrum of the

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dipole nature (abbreviated as MD) and electric dipole nature (abbrevi­

ated as ED), respectively, while the peak locating at 600 nm exhibits
both MD and ED natures. According to the Judd-Ofelt theory, the value
of ED/MD ratio (abbreviated as R) can be used to evaluate the crystal
field environment of Sm3+ ions. The higher value of R means the greater
asymmetry property of the crystal field. For the La3Ga5SiO14:0.025Sm3+
phosphor, the calculated R value equals to 2.05, indicating that Sm3+
ions possess high asymmetry in the lattice occupation in La3Ga5SiO14. It
is consistent with the substitution of Sm3+ to La3+ ion eight-coordinated
with C2 symmetry in La3Ga5SiO14:Sm3+ phosphors by being concluded
from the previous XRD results and the earlier report [15].
The PLE spectra of the La3Ga5SiO14:xSm3+ (x = 0.025, 0.05, 0.075,
0.1, 0.2 and 0.3) phosphors measured at room temperature (λem = 600
nm) are provided in Fig. 8(a). It is apparently found that the shape and
position of the PLE spectra show similar characteristics as the Sm3+
doping concentration changes. While the intensity shows different
trends, which increases firstly along with the growth of Sm3+ concen­
tration from x = 0.025 to x = 0.05, and then decreases from x = 0.05 to
Fig. 5. UV–Vis absorbance spectra of the La3Ga5SiO14:xSm3+ (x = 0, 0.025, x = 0.3. The determined absolute internal quantum efficiency of the
0.05, 0.075, 0.1, 0.2 and 0.3) phosphors. La3Ga5SiO14:0.05Sm3+ phosphor is 62.5%, which is greater than some
other Sm3+ ions doping materials, such as CaGdSbWO8:Sm3+ (38.4%)
[38], Sr19Mg2(PO4)14:Sm3+ (53.1%) [39], Na13Sr1⋅82Ta2(PO4)9:Sm3+
La3Ga5SiO14:0.025Sm3+ phosphor determined in the range of 500–750
(31.29%) [40] and Sr3LaNb3O12:Sm3+ (21.6%) [41], etc. In future
nm. There are four significant emission areas peaking at around 563,
works, we will continue to optimize the preparation methods and pro­
600, 645 and 710 nm, which originate from the 4G5/2 → 6H5/2 (550–570
cesses to promote the better quantum efficiency.
nm), 4G5/2 → 6H7/2 (570–630 nm), 4G5/2 → 6H9/2 (630–680 nm) and
4 When the doped Sm3+ concentration is under 0.05, the interaction
G5/2 → 6H11/2 (690–750 nm) transitions of Sm3+ ion, respectively
between Sm3+ ions is weak. As the increment of Sm3+ doping concen­
[16–21].
tration, the number of the absorbed photons increases, which conse­
As mentioned previous, the crystal field environment is important for
quentially enlarge the emission intensity. When the doped Sm3+
the luminous center. In these emission peaks of La3Ga5SiO14:Sm3+
concentration is more than 0.05, the emission intensity gradually
phosphors, the peaks locating at 563 and 645 nm exhibit magnetic

Fig. 6. Determination of the optical band gap using Tauc plot for La3Ga5SiO14: xSm3+ (x = 0.025, 0.05, 0.075, 0.1, 0.2 and 0.3) phosphors.

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Fig. 7. (a) PLE (λem = 600 nm) and (b) PL (λex = 401 nm) spectra of the La3Ga5SiO14:0.025Sm3+ phosphor.

Fig. 8. (a) PLE and (b) PL spectra of the La3Ga5SiO14:xSm3+ (x = 0.025, 0.05,
0.075, 0.1, 0.2 and 0.3) phosphors.

decreases on account of the concentration quenching. Fig. 9(a) lists the

specific relationships between the intensities of relatively strong emis­
sions at 563, 600 and 645 nm and the doped Sm3+ concentration. It is
apparently known that the optimum doping concentration of Sm3+ ions
is 0.05. Fig. 9. (a) Intensity changing versus component (x) and (b) linearity matching
Theoretically, the critical distance (Rc) may be determined from of Log (I/x) and Log(x) in La3Ga5SiO14: xSm3+ (x = 0.05, 0.075, 0.1, 0.2 and
Blasse’s equation (3) [42]: 0.3) phosphors.
[ ]13 /

Rc ≈ 2
3V
(3) radiation reabsorption, exchange interaction and electric multipole
4πZxc interaction. Mechanism of radiation reabsorption is easily excluded due
Here, V refers to the cell volume, xc means the optimal concentration to the no overlapping between the PL and PLE spectra, as depicted in
of doped Sm3+ ions, and Z is the initial cell number. For Fig. 7(a) and (b). In pace with the growing of Sm3+ concentration, the
La3Ga5SiO14:0.05Sm3+ phosphor, V = 294.06 Å3, xc = 0.05, and Z = 1, distance between two neighboring Sm3+ progressively decreases.
and thus the theoretical value of Rc can be calculated to be 22.40 Å. The Consequently, the energy transfer between Sm3+-Sm3+ may occur
nonradiative energy transfer mechanism can be divided into three types: through exchange interaction or electrical multipole interaction. Due to
the much greater Rc value (22.40 Å) than 5 Å, we can get a conclusion

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that the exchange interaction is impossible and thus the electric multi­ be owing to energy transfer, which originates from cross relaxation
pole interaction is the main cause of concentration quenching. between Sm3+ ions [16,47–49]. Based on these parameters, the mean
Electric multipole interaction can be divided into dipole-dipole lifetime constant (τ) can be determined from equation (7) [45]:
(short for d-d), dipole-quadrupole (short for d-q) and quadrupole-
A1 τ 1 2 + A2 τ 2 2
quadrupole (short for q-q) interactions. In the light of Dexter theory, τ= (7)
A1 τ 1 + A2 τ 2
formula (4) represents the relevance between the PL intensity (I) and the
doping concentration (x) [43,44]: The calculated Sm3+ lifetimes in La3Ga5SiO14:xSm3+ with x = 0.025,
0.05, 0.075, 0.1, 0.2 and 0.3 are 1.49, 1.26, 1.07, 0.88, 0.49 and 0.29 ms,
I k
= (4) respectively. The lifetime of Sm3+ ion decreases monotonically with the
x 1 + β(x)θ/3
adding of Sm3+ ions because of the non-radiative transition effect, which
can also be analyzed from formula (8) [50]:
where K and β are constants for multistage interaction, θ is the multipole
correlation constant (6 represents d-d interaction, 8 represents d-q 1
τ= (8)
interaction and 10 represents q-q interaction). formula (4) can be further Kr + Ki
reduced to formula (5).
Here, Kr and Ki represent for the radioactive and nonradioactive decay
I θ from the same state, τ is the experimental lifetime. Thanks to the energy
log = β − logx (5)
x 3 transfer between doped Sm3+ ions, the increase of Sm3+ concentration
As shown in Fig. 9(b), 1og (I/x) (I refers to the PL intensity corre­ leads to the increases of Kr and Ki, and thus the decrease of τ value.
sponding to the strongest 3G5/2 → 3H7/2 transition) and log(x) are lin­
early fitted with a slope of − 2.698. Thus θ value is approach to 8, 3.7. Thermal stability
indicating that the mechanism of concentration quenching of Sm3+ ions
in La3Ga5SiO14 matrix is d-q interaction. Thermal stability of phosphors is considered as an important factor
in evaluating its suitability of LEDs. The variable temperature-
dependent (298–500 K) PL spectra of the La3Ga5SiO14:0.05Sm3+ phos­
3.6. Decay time
phor are plotted in Fig. 11(a). We can observe that the PL declines
slightly with the improving temperature and the PL intensity at 500 K is
For luminescent materials, fluorescence lifetime measurement is
85% of that at 298 K. It demonstrates that the La3Ga5SiO14:0.05Sm3+
another important parameter. In general, the luminous attenuation
phosphor possesses excellent thermal stability. For further investigation
curves of a single and two emission centers are estimated to be single
the thermal influence on PL intensity, the thermal activation energy (Ea)
and double indexes, respectively [45]. While, the double index equation
is predicted from the following Arrhenius equation (9) [51,52]:
can also be applied to the electron relaxation in the luminescence pro­
( )
cess of agglomerated materials although there is only one emission I0 Ea
center [46]. Fig. 10 depicts the room temperature fluorescence attenu­ Ln − 1 = LnA − (9)
I KT
ation curves of series of La3Ga5SiO14:Sm3+ phosphors (λex = 401 nm and
λem = 600 nm). Where, every attenuated curve is adapted by the Here I0 and I stand for the PL intensities at starting and distinct tem­
second-order exponential attenuation formula as expressed in the peratures, A denotes constant, K means the Boltzmann constant and T is
following equation (6) [45]: temperature. The specific relevance between Ln(I0/I-1) and 1/KT is
depicted in Fig. 11(b). On the basis of the fitting line slope, the deter­
I = I0 + A1exp (-t/τ1) + A2exp (-t/τ2) (6)
mined Ea value of the La3Ga5SiO14:0.05Sm3+ is 0.2161 ev, which is
Here I0, A1 and A2 are constants, I stands for emission intensity at higher than the activation energy value of other Sm3+ doped phosphors
time of t, τ1 and τ2 are two components of fluorescence lifetime (τ1 is the as listed in Table S3. This indicates that the La3Ga5SiO14:Sm3+ phos­
fast life of the exponential component, and τ2 refers to the slow life of the phors prepared in our work possess excellent thermal stability.
exponential component). The second-order exponential behavior may
3.8. Performance of LEDs

The red LED device was assembled using La3Ga5SiO14:0.05Sm3+

phosphors and NUV 395 nm chip, and its electroluminescence (EL)
properties were measured under different currents. As shown in Fig. 12
(a), the recorded EL spectra exhibit four characteristic areas corre­
sponding to the 4G5/2 → 6H5/2, 6H7/2, 6H9/2 and 6H11/2 transitions of
Sm3+ ion, respectively, which are consistent with previous PL spectra.
The blue light at around 422 nm in the EL spectra is the unabsorbed part
of the light emitted from the chip. Other than the intensity increasing, all
the shape and position of the emission light almost remain unchanged
with the current varying from 20 to 320 mA. All the calculated Com­
mission International de I’Eclairage (CIE) coordinates are shown in
Fig. 12(b) and we can obviously get that the emitting area is slightly
affected by the currents. The WLED device was manufactured success­
fully by mixing the La3Ga5SiO14:0.05Sm3+ phosphor with commercial
(Ba, Sr)2SiO4:Eu2+ (green phosphors) and BaMgAl10O17:Eu2+ (blue
phosphors) at a mass ratio of about 4 : 2: 1. Fig. 12 (c) plots the EL results
of the manufactured WLED driven at 100 mA. The values of CCT, CIE
coordinates and Ra are 4797 K, (0.3489, 0.3392) and 91, respectively.
Other corresponding data of the red LED and WLED devices are provided
Fig. 10. Decay curves of La3Ga5SiO14: Sm3+ samples (λex = 401 nm and λem = in detail in Table S4. The comparisons of CCT and Ra for WLED devices
600 nm). containing Sm3+ doped phosphors of this work and some other works

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Fig. 11. (a) Temperature-dependent PL spectra excited at 401 nm ranging of 298–500 K (The inset is the relevance of PL intensity and temperature) and (b)
relevance of Ln(I0/I-1) and 1/KT for the La3Ga5SiO14:0.05Sm3+ phosphor.

Fig. 12. (a) EL spectra (inset: the actual photos of power off/on) and (b) CIE diagram of red LED driven at different currents, and (c) EL spectrum of WLED driven at
100 mA (inset: the actual photos of power off/on). (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of
this article.)

are listed in Table S5. The results indicate that the La3Ga5SiO14: Sm3+ Declaration of competing interest
phosphors show excellent performance in the field of WLEDs.
The authors declare that they have no known competing financial
4. Conclusion interests or personal relationships that could have appeared to influence
the work reported in this paper.
In summary, single-phased La3Ga5SiO14:Sm3+ phosphors were suc­
cessfully prepared by the high-temperature solid state reactions in air. Acknowledgements
The prepared phosphors were confirmed from XRD, SEM and EDS
measurements. UV–visible absorption results indicate that the absorp­ This work was supported by Natural Science Foundation of Shan­
tion bands are mainly resulted from the host absorption and 4f-5d or f-f dong Province, China (ZR2021ME084, ZR2020QE041, ZR2021QE199,
transitions of Sm3+ ions. Detailed vibrational properties were analyzed ZR2020LLZ009 and ZR2021QB214); the Undergraduate Teaching Re­
by FTIR spectra and Sm3+ ions have no obvious effect on the lattice form Project for Shandong Provincial Department of Education, China
vibration structure of La3Ga5SiO14 matrix. The PLE spectra of La3Ga5 (M2021363); Studio for the Leader of Scientific Research in Jinan, China
SiO14:Sm3+ phosphors detected at 600 nm exhibit some diverse excita­ (2021GXRC089); the Project for Introduced Innovation Team in Jinan,
tion bands at around 316, 343, 359, 373, 401, 413, 422 and 475 nm. The China (2020GXRC037); and Science-Education-Industry Integration
PL spectra excited at 401 nm exhibit four strong emission bands at 563, Project for Oilu University of Technology, China (2022JBZ01-07).
600, 645 and 710 nm, respectively. The strongest orange-red emission
locating at 600 nm is ascribed to 4G5/2 → 6H7/2 transitions of Sm3+ ions. Appendix A. Supplementary data
The optimum doping concentration is 0.05, and the reason to concen­
tration quenching is the dipole-quadrupole interaction. The La3Ga5 Supplementary data to this article can be found online at https://doi.
SiO14:Sm3+ phosphors exhibit a good thermal stability (Ea = 0.2161 ev). org/10.1016/j.ceramint.2023.01.206.
Both manufactured red-LED and w-LED using the
La3Ga5SiO14:0.05Sm3+ phosphor emit brilliant light. The Ra (91), CCT
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