nanomaterials

Article
Cs(Pb,Mn)Br3 Quantum Dots Glasses with Superior Thermal
Stability for Contactless Electroluminescence
Green−Emitting LEDs
Aochen Du 1,2 , Wenxiao Zhao 1,2 , Yu Peng 1,2 , Xinzhi Qin 1,2 , Zexi Lin 1,2 , Yun Ye 1,2, *, Enguo Chen 1,2, *,
Sheng Xu 1,2 and Tailiang Guo 1,2

1 College of Physics and Information Engineering, Fuzhou University, Fuzhou 350100, China
2 Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China,
Fuzhou 350100, China
* Correspondence: [email protected] (Y.Y.); [email protected] (E.C.)

Abstract: CsPbX3 (X = Cl, Br or I) perovskite quantum dots (PQDs) have gained increasing interest
due to their superior performance in photoelectric applications. In our work, a series of Mn2+ doped
CsPbBr3 PQDs were successfully prepared in glasses by melt quenching and in situ crystallization
technique. Due to the 4 T1 (4 G)→6 A1 (6 S) transition of Mn2+ , a slight red shift from 510 nm to 516 nm
was found, with the FWHM expansion from 18 nm to 26 nm. The PQDs@glasses showed excellent
thermal stability, and the exciton binding energy reached a high level of 412 meV. The changes of
the electronic structure after Mn doping CsPbBr3 can be demonstrated by first principles. Finally, a
contactless electroluminescence device with the PQDs@glasses was designed based on the principle
of electromagnetic induction, which is a potential application for detecting distance in sterile and
dust−free environments.

Keywords: perovskite quantum dots glass; first principle; superior thermal stability; contactless
electroluminescent devices; exciton binding energy
Citation: Du, A.; Zhao, W.; Peng, Y.;
Qin, X.; Lin, Z.; Ye, Y.; Chen, E.; Xu, S.;
Guo, T. Cs(Pb,Mn)Br3 Quantum Dots
Glasses with Superior Thermal
1. Introduction
Stability for Contactless
Electroluminescence Green−Emitting
Light emitting diodes (LEDs) are gradually replacing traditional light sources and
LEDs. Nanomaterials 2023, 13, 17. becoming the first choice of ideal light sources due to their advantages of high luminous
https://doi.org/10.3390/ efficiency, friendly environment, and considerable economic benefits [1–3]. In recent years,
nano13010017 phosphor conversion materials have become a research hotspot of mainstream international
scientific research institutions. Cesium lead halide perovskite quantum dots (PQDs) have
Academic Editors: Xiao-Ke Liu and
attracted extensive attention in many optoelectronic devices, such as solar cells, LEDs,
Jean-Pierre Bucher
photodetectors, and excitation devices, because of the adjustable emission wavelength,
Received: 24 October 2022 narrow−band emission, large absorption, and high photoluminescence quantum yield
Revised: 6 December 2022 (PLQY) [4–7]. However, PQDs still have the problem of poor stability, especially in terms
Accepted: 15 December 2022 of moisture and heat. A general solution is to embed the PQDs into matrix materials,
Published: 20 December 2022 which helps to expand perovskite to a wider range of applications. In 2017, the stability of
PQDs was improved by coating silicon and aluminum [8]. Moreover, it was dispersed in
a polymethylmethacrylate (PMMA) matrix and then this film was prepared for LEDs [9].
Unfortunately, the stability problem has not been completely solved. Finding more stable
Copyright: © 2022 by the authors.
coating materials is a fundamental step to make PQDs more widely used in the field of
Licensee MDPI, Basel, Switzerland.
This article is an open access article
lighting and displays. Lead toxicity is another key drawback of the lead−based perovskite
distributed under the terms and
materials. The strategy of glass−coated PQDs not only plays an important role in improv-
conditions of the Creative Commons ing stability, but also inhibits lead pollution to a certain extent. The Cs4 PbBr6 PQDs@glasses
Attribution (CC BY) license (https:// prepared by Li displayed strong exciton recombination and green luminescence, combined
creativecommons.org/licenses/by/ with narrow full width at half maximum (FWHM), high PLQY, and long−term stabil-
4.0/). ity [10]. Liu prepared blue LEDs with CsPb0.64 Sn0.36 Br3 PQDs@glasses and commercial red

Nanomaterials 2023, 13, 17. https://doi.org/10.3390/nano13010017 https://www.mdpi.com/journal/nanomaterials

Nanomaterials 2023, 13, 17 2 of 11

phosphors [11]. Therefore, a new strategy of doping ions was studied to reduce the lead
pollution. Some researches replaced Pb2+ with other metal cations (such as Sn2+ , Bi3+ , and
Eu2+ ) to obtain lead−free perovskite [4,11]. Due to the spectral characteristics of Mn2+ ions,
Mn2+ ions can not only reduce the toxicity of perovskite glasses, but also be a promising
candidate to regulate the photoluminescence of perovskite glasses. The d−d transition
of Mn2+ doped materials can provide narrow FWHM (18–45nm), which enables many
researches on narrow−band green light materials doped with Mn2+ . For example, the
Mn2+ doped oxynitride, a green−emitting phosphor, γ−AlON:Mn,Mg, exhibits a FWHM
of 44 nm [12], whereas the FWHM values are 42 nm and 42 nm for Zn2 SiO4 :Mn2+ [13]
and Cs3 MnBr5 :Mn2+ [14], respectively. Therefore, the strategy of replacing Pb2+ with Mn2+
not only reduces the toxicity of the PQDs@glasses, but also regulates the luminescent
properties of the PQDs@glasses. However, to date, there are few researches on Mn2+ doped
PQDs@glasses for LEDs, especially in contactless electroluminescence devices.
Herein, we have successfully prepared Mn2+ doped CsPbBr3 PQDs@glasses. The
optical properties, micromorphology, and thermal stability of the PQDs@glasses were
systematically studied. The changes of electronic structure after Mn2+ doping CsPbBr3
were studied by first principles. The PQDs@glasses and a blue InGaN chip were directly
fabricated together into LEDs. The PQDs@glasses can not only effectively improve the
stability of PQDs, enhance the water oxygen resistance of the composite, but also effectively
avoid the leakage of toxic heavy metal lead, greatly reducing its impact on the environment
and human health. Moreover, the preparation is cost−effective, and the cost is appropriate,
which has great application prospects in the future LED field. A contactless electrolumi-
nescence device is designed based on the principle of electromagnetic induction. These
PQDs@glasses show potential for future lighting and display applications, which also
provides a new idea for the application of contactless distance measurement.

2. Experiment
2.1. Synthesis
Cs(Pb,Mn)Br3 PQDs@glasses were prepared by traditional melt quenching and heat
treatment. Firstly, the glass components of the 40SiO2− 36B2 O3− 11ZnO raw materials
were weighed and ground in an agate thoroughly. Secondly, the perovskite components,
2CsCO3− (2 − x)Pb3 O4−x MnCO3− 9NaBr, were added into the agate and mixed with the
glass matrix thoroughly. The weight ratio between glass components and perovskite
components is 4.6. After grinding and mixing evenly, it was transferred to a clean alumina
crucible. Thirdly, the mixture was then melted under the ambient atmosphere at 1200 ◦ C
for 10 min, and the melt portion was poured into a preheated graphite mold at 400 ◦ C and
was quickly pressed with a preheated copper plate at 400 ◦ C. Then it was annealed in a
muffle furnace at 400 ◦ C for 3 h and cooled naturally to room temperature. This process
can effectively eliminate the stress. When the muffle furnace temperature dropped to the
room temperature, the precursor glasses could be obtained. Finally, after the precursor
glasses were placed in a muffle furnace at 480 ◦ C for 10 h for heat treatment, the samples
could be obtained when the muffle furnace temperature dropped to room temperature.
The sample size was Φ10 mm × 1 mm. The samples were grounded with sandpaper
until the surface was flat and smooth without a trace, which could be used for the further
test characterization.

2.2. Characterization
The structural analysis of the Cs(Pb,Mn)Br3 PQDs@glasses was carried out by using
X-ray diffraction (XRD, PANalytical, X’pert Highscore Plus, Almelo, The Kingdom of the
Netherlands) measurements with a Cu Kα radiation source (λ = 1.54 Å generated at 40 kV
and 40 mA). The microstructure of the sample was observed by a transmission electron
microscope (TEM, FEI, Tecnai G2 F20, OR, USA). Optical properties were studied by using a
UV−Vis spectrometer (UV−Vis, Hitachi U−4100, Tokyo, Japan) and a photoluminescence
spectroscopy (PL, Hitachi F−4600, Tokyo, Japan). The photochromic properties under
Nanomaterials 2023, 13, 17 3 of 11

different blue−LED powers were detected using a high accuracy array spectroradiometer
(HASS−2000, Hangzhou, China). Tesla coils used in the contactless electroluminescence
devices were produced by Wuhan Stark Technology Co., Ltd. (Wuhan, China)

2.3. Calculation Details

The band structure and density of states of Cs(Pb,Mn)Br3 were investigated via the
CASTEP code on the basis of DFT within the plane wave pseudopotential approach.
Geometry optimization was first performed by using the Broyden–Fletcher–Goldfarb–
Shannon (BFGS) method. The convergence tolerance was selected with the differences
in total energy, the maximal ionic Hellmann–Feynman force, the stress tensor, and the
maximal displacement being within 1.0 × 10−5 eV per atom, 0.03 eV Å−1 , 0.05 Gpa,
and 1.0 × 10−3 Å, respectively. A plane wave basis set with a kinetic energy cutoff of
430 eV was used. A K−point sampling scheme of a 3 × 3 × 3 Monkhorst–Pack grid was
utilized to present Brillouin−zone integration. The calculations were conducted within the
generalized gradient approximations, using the exchange and correlation function. The
convergence criterion for the self−consistent field (SCF) was set to 1.0 × 10−6 eV per atom
in the whole process.

2.4. Design of Contactless Electroluminescent Devices

Tesla coil is actually a high−voltage double coil resonant transformer, whose principle
is to use the transformer to boost the ordinary voltage, and then charge the resonant
capacitor of the primary LC circuit. When a certain voltage value is reached, resonance
occurs and the secondary coil resonates. The energy of the primary coil is transferred to the
secondary coil. When the voltage of the secondary coil is high enough, the arc can be seen
to break through the air. The schematic diagram of a contactless electroluminescent device
is shown in Figure 1. The device includes an external AC current, an electronic oscillator,
and a transmission coil. These coils are tightly wound copper wires. When the AC current
passes, the magnetic flux is generated, and in the receiver device, the same type of coil is
embedded in the output circuit. The receiving coil picks up these AC magnetic fields and
Nanomaterials 2023, 13, x FOR PEERcauses
REVIEWcurrent, which is then converted into DC current through the power rectifier4 and of 11
voltage regulator, thus giving LED current to emit light.

Figure 1. 2D and 3D schematic diagram of a contactless electroluminescent device. The lower right
Figure 1. 2D and 3D schematic diagram of a contactless electroluminescent device. The lower right
corner is the 3D schematic diagram.
corner is the 3D schematic diagram.
3. Results and Discussion
3.1. Crystal Structure and Microstructure
The XRD patterns of the Cs(Pb0.9Mn0.1)Br3 PQDS@glasses were investigated, as shown
in Figure 2a. The crystal structure of Cs(Pb,Mn)Br3 satisfies the general formula ABX3, in
which the A sites are occupied by Cs+ ions, the B sites are occupied by metal cations (Pb2+
or Mn2+), Pb2+ are partly replaced by Mn2+, and the X sites are occupied by Br−. The sche-
matic is shown in the interior of Figure 2a. These peaks are consistent with the cubic phase
 3. Results and Discussion
3.1. Crystal Structure and Microstructure
The XRD patterns of the Cs(Pb0.9Mn0.1)Br3 PQDS@glasses were investigated
Nanomaterials 2023, 13, 17 in Figure 2a. The crystal structure of Cs(Pb,Mn)Br3 satisfies the general 4 of 11formul
which the A sites are occupied by Cs+ ions, the B sites are occupied by metal ca
or Mn2+), Pb2+ are partly replaced by Mn2+, and the X sites are occupied by Br−.
3.matic
Resultsis and
shownDiscussion
in the interior of Figure 2a. These peaks are consistent with the c
3.1. Crystal Structure
(PDF#54−0752) of and CsPbBr
Microstructure
3. On this basis, the characteristic diffraction pea
The XRD patterns of
Cs(Pb0.9Mn0.1)Br3 PQDS@glassesthe Cs(Pb 0.9 Mn0.1 )Br3 PQDS@glasses
have were investigated,
2θ values centered as shown
at approximately 21
in Figure 2a. The crystal structure of Cs(Pb,Mn)Br3 satisfies the general formula ABX3 ,
37.73,
in whichand the A43.88, which
sites are correspond
occupied by Cs+ ions, to the
theB(1 0 0),
sites are (2 0 0), (2by1metal
occupied 1), and (2 2 0) pla
cations
cubic
(Pb 2+ or phase
2+
Mn ), Pbof CsPbBr
2+ are partly3, replaced
respectively.
by Mn The
2+ , andXRD results
the X sites indicatebythe
are occupied Br formation
− . The o
PQDs inisthe
schematic shownglass matrix.
in the interior of Figure 2a. These peaks are consistent with the cubic
phase (PDF#54−0752) of CsPbBr3 . On this basis, the characteristic diffraction peaks of the
Figure 2b shows the TEM image of this sample, which helps to further u
Cs(Pb0.9 Mn0.1 )Br3 PQDS@glasses have 2θ values centered at approximately 21.47, 30.66,
the morphology
37.73, and 43.88, which and distribution
correspond of0 the
to the (1 0), (2Cs(Pb,Mn)Br PQDs
0 0), (2 1 1), and3 (2 in the
2 0) planes glass ma
of the
ously,
cubic theofPQDs
phase CsPbBrare well coated
3 , respectively. Thewith
XRD the glasses,
results indicateand the lattice
the formation of spacing
CsPbBr3 of 0.24
PQDs in the glass matrix.
responds to the (2 0 0) crystal plane.

Figure
Figure 2. (a)
2. (a) XRDXRD patterns
patterns of0.9Cs(Pb
of Cs(Pb 0.9Mn
Mn0.1 )Br 0.1)Br3 PQDS@glasses,
3 PQDS@glasses, and also
and also the standard thecrystal
cubic standard cub
structure of CsPbBr
structure of CsPbBr 3 (JCPDS#54 − 0752). The internal picture shows the
3 (JCPDS#54−0752). The internal picture shows the Cs(Pb,Mn)Br nanocrystals
3 Cs(Pb,Mn)Br3 nan
precipitated
precipitated fromfrom
glasses. (b) HRTEM
glasses. images of images
(b) HRTEM Cs(Pb0.7 Mn
of0.3 )Br3 PQDS@glasses.
Cs(Pb 0.7Mn0.3)Br3 PQDS@glasses.

Figure 2b shows the TEM image of this sample, which helps to further understand the
3.2. Opticaland
morphology Properties and
distribution Thermal
of the Stability
Cs(Pb,Mn)Br 3 PQDs in the glass matrix. Obviously, the
PQDs are well coated with the glasses, and the lattice spacing of 0.241 nm corresponds to
As shown in Figure 3a, with the increase in Mn2+ doping, the luminescenc
the (2 0 0) crystal plane.
trend of first increasing and then decreasing. This may be attributed to the enh
3.2. Optical
of the Properties of
transition andMn
Thermal Stability
2+ corresponding to the typical 4T1 (4G)→6A1 (6S). It can be
As shown in Figure 3a, with the increase in Mn2+ doping, the luminescence shows a
trend of first increasing and then decreasing. This may be attributed to the enhancement
of the transition of Mn2+ corresponding to the typical 4 T1 (4 G)→6 A1 (6 S). It can be seen
from the luminous details in Figure 3b that after doping Mn2+ , the luminous intensity first
increases and then decreases, and is the strongest at x = 0.02, accompanied by a slight
red shift (510–516 nm), and the FWHM of the emission band gradually increases from
18 to 26 nm. Figure 3c depicts the UV−Vis absorbance spectra of the Cs(Pb1−x Mnx )Br3
PQDS@glasses (x = 0, 0.1) in the wavelength range from 400 to 600 nm. Band gap is one
of the important characteristics of the host of luminescent materials. To determine the
absorption edge from the obtained absorption spectra of the host, the Kubelka–Munk
absorption coefficient (K/S) relationship is often used and is presented below [15,16]:

(αhν)2 = ED hν − Eopt


(1)
 is a tightly bound Frenkel exciton, rather than the Wannier–Mott exciton coupled to
lattice vibration [23]. The exciton binding energy of the Cs(Pb,Mn)Br3 PQDS@glasses
much higher than that of the CsPbBr3 bulk perovskite previously reported [24,25]. The
fore, the high exciton binding energy may be attributed to the minute nanoscale dim
Nanomaterials 2023, 13, 17 5 of 11
sions of Cs(Pb,Mn)Br3 PQDs and its coating with glasses. The high exciton binding ener
proves that perovskite glass has excellent thermal stability.

Figure 3. (a)3.PL
Figure spectra.
(a) PL spectra.(d)
(d)Temperature−dependent
Temperature−dependent PL spectraPL spectra of0.9Cs(Pb
of Cs(Pb 0.9Mn
Mn0.1 )Br 0.1)Br3 PQDS@glas
3 PQDS@glasses.
The detailed
The detailed FWHM, emission intensities, and peak positions of (b) PL and (e) temperature−(e)
FWHM, emission intensities, and peak positions of (b) PL and temperature−
dependent
pendent PL spectra
PL spectra of the PQDS@glasses.
of the PQDS@glasses. (c) Absorption(c) Absorption
spectra spectra(xof= 0,
of PQDS@glasses. PQDS@glasses.
0.1) (f) Integrated (x
PL = 0, 0.1)
Integrated PL emission intensity as a function of 1/T.
emission intensity as a function of 1/T.

According to Lambert–Beer law, the absorbance is proportional to the absorption

3.3. Electronic
coefficient, Structure
that is Equation (2):
Figure 4a,e shows the electron density A = Kα for CsPbBr3 and Cs(Pb0.875Mn0.125)Br (2)3. The el
tron where
density A isdifference
the absorbance,is the charge
K can density
be regarded as adifference between of
constant independent thethesuperposition
absorption of
coefficient, which
self−consistent can be obtained
pseudo−charge from Equations
density and the atomic(1) and (2):
charge density. The negative cha
density means the loss of electrons, and the positive charge density means the(3)acquisit
(Ahν)2 = K2 ED (hν − Eopt )
of electrons. Generally speaking, Br acquires electrons while Pb and Mn lose electrons
is obviousLetthat
C = MnK2 EDis, then
more Equation
likely (4)to can
losebeelectrons
rewritten as follows:
than Pb. The electron localization fu
tion (ELF) provides a new description of the chemical bond for almost all kinds
(Ahν)2 = C(hν − Eopt ) (4)
of co
pounds. ELF is a 3D real space function with the values ranging from 0 to 1. In the reg
around theIf the value of (Ahν)2 is
high−equivalent, taken as the
extremely lowvertical coordinate
frequency, and the value
the electrons haveofstrong
hν is locali
taken as the horizontal coordinate, then Equation (4) can be
tion and are not easy to be exhausted. In the region surrounded by the low equival regarded as a linear equation
y = C( x −Eopt ). In a geometric sense, Eopt represents the intercept of the line on the X−axis,
ELF, that
theis,electron localization
a linear equation is weak,
is obtained and the
by a linear fittingelectron
of part ofistheeasy
line to be delocalized
so that it intersects to oth
regions.
the XThe
−axis. value
The xof ELFof=the
value 0.5intersection
corresponds is thetowidth
the electron−gas−like
of the band gap. The pair valueprobability.
of C in F
ure 4b,f shows
Equation (4) the electron
represents the density
slope of thedifference for CsPbBr
line. In Figure 3 and
1, the slopes of Cs(Pb,Mn)Br
these two lines 3are. Pb and M
50.4 (x = 0) and 103.9 (x = 0.1), respectively.
are located in the region surrounded by the equivalents of low value of ELF, thus form
Preferably, in crystalline materials, the main optical transitions should be direct transi-
an ionic bond between Pb/Mn and Br.
tions, because their translational symmetry is a result of defining the wave vector [17]. As
The calculated
given in the inset ofand predicted
Figure 3c, the band directional
−gap energy band
of thegap (Eg3) PQDS@glasses
CsPbBr is 1.792 eV (Figurehost is 5a), a
the minimum
calculated to conduction
be approximatelyband2.35 (CBM)
eV byand the maximum
extrapolation, which isvalence
consistentband
with(VBM)
previousare loca
results [18]. When Mn 2+ replaces Pb2+ more, the band gap becomes larger. When x = 0.1,
at k−point of G. When Mn doping concentration is 12.5%, the band gap decreases to 1.1
the band gap has changed from 2.36 eV to 2.35 eV. This is consistent with the trend of the
eV (Figure 5c). Figure 5b shows the calculation results of the total and partial DOSs
calculation results.
CsPbBr3,The indicating that the
thermal stability top
of the PQDof glass
the hasvalence band influence
an important is dominated by the orbitals of
on the photochromic
whileperformance
the CBM is mainly constituted
parameters. Therefore, the bytemperature
the orbitals of Pb. After
dependence curveMn wasis
2+ doped, the loc
measured
ized to
energy levels
determine thefrom Mn2+ofappear
feasibility the PQD above
glassthe valence
in the phosphor band and justmaterials.
conversion at the CBM As as sho
shown in Figure 3d, with the increase in temperature, the emission peak appears as a blue
Nanomaterials 2023, 13, 17 6 of 11

shift (from 514 nm to 510 nm), while the FWHM was increased from 19 nm to 36 nm, and
the luminous intensity decreases gradually. The small blue shift of the Mn2+ emission is
ascribed to the lattice expansion. This phenomenon has been reported before [19]. The
decrease in luminescence intensity with the increase in temperature is caused by the
non−radiative transition of the luminescence center and lattice relaxation [20]. In order
to further clarify the photoluminescence mechanism of the PQDs in glasses, the exciton
binding energy was deeply studied by fitting the relationship between the integrated
intensity and the inverse temperature (1/T) from 293.15 K to 473.15 K. Therefore, the
Arrhenius formula can be used to fit the temperature−dependent curve [21]:

I0
IT = (5)
1 + Ae−Eb /Kb T
where IT and I0 are the integrated PL emission intensities at the temperatures T and 0 K,
respectively. Eb is the exciton binding energy, and Kb is the Boltzmann constant 0.025852 eV
(T = 300 K). According to the formula fitting, the value of A is 1.09 × 109 . As shown in
Figure 3f, the exciton binding energy at high temperature is 412 meV. When the exciton
binding energy exceeds 100 meV, the electron hole pairs are closely bound together, and it
is almost impossible to diffuse with the phonons [22]. Here, it is assumed that the exciton is
a tightly bound Frenkel exciton, rather than the Wannier–Mott exciton coupled to the lattice
vibration [23]. The exciton binding energy of the Cs(Pb,Mn)Br3 PQDS@glasses is much
higher than that of the CsPbBr3 bulk perovskite previously reported [24,25]. Therefore,
the high exciton binding energy may be attributed to the minute nanoscale dimensions of
Cs(Pb,Mn)Br3 PQDs and its coating with glasses. The high exciton binding energy proves
that perovskite glass has excellent thermal stability.

3.3. Electronic Structure

Figure 4a,e shows the electron density for CsPbBr3 and Cs(Pb0.875 Mn0.125 )Br3 . The
electron density difference is the charge density difference between the superposition of the
self−consistent pseudo−charge density and the atomic charge density. The negative charge
density means the loss of electrons, and the positive charge density means the acquisition
of electrons. Generally speaking, Br acquires electrons while Pb and Mn lose electrons. It is
obvious that Mn is more likely to lose electrons than Pb. The electron localization function
(ELF) provides a new description of the chemical bond for almost all kinds of compounds.
ELF is a 3D real space function with the values ranging from 0 to 1. In the region around
the high−equivalent, extremely low frequency, the electrons have strong localization and
are not easy to be exhausted. In the region surrounded by the low equivalent ELF, the
electron localization is weak, and the electron is easy to be delocalized to other regions. The
value of ELF = 0.5 corresponds to the electron−gas−like pair probability. Figure 4b,f shows
the electron density difference for CsPbBr3 and Cs(Pb,Mn)Br3 . Pb and Mn are located in
the region surrounded by the equivalents of low value of ELF, thus forming an ionic bond
between Pb/Mn and Br.
The calculated and predicted directional band gap (Eg ) is 1.792 eV (Figure 5a), and the
minimum conduction band (CBM) and the maximum valence band (VBM) are located at
k−point of G. When Mn doping concentration is 12.5%, the band gap decreases to 1.161 eV
(Figure 5c). Figure 5b shows the calculation results of the total and partial DOSs of CsPbBr3 ,
indicating that the top of the valence band is dominated by the orbitals of Br while the CBM
is mainly constituted by the orbitals of Pb. After Mn2+ is doped, the localized energy levels
from Mn2+ appear above the valence band and just at the CBM as shown in Figure 5d,
which leads to the possible additional transition. Since the energy level of Mn is located at
CBM, the photogenerated electrons in the semiconductors can easily jump from CBM to
Mn. This process, together with the above energy transfer, leads to efficient luminescence
of Mn2+ . The detailed partial density of the states of CsPbBr3 and Cs(Pb0.875 Mn0.125 )Br3 is
shown in Figure 6.
 in Figure 5d, which leads to the possible additional transition. Since the energy level
MninisFigure
located5d,atwhich
CBM, leads to the possible electrons
the photogenerated additionalintransition. Since the energy
the semiconductors leveljum
can easily o
Mn is located at CBM, the photogenerated electrons in the semiconductors can easily
from CBM to Mn. This process, together with the above energy transfer, leads to efficie jump
from CBM to Mn. This process, together with the above energy transfer, leads to efficien
Nanomaterials 2023, 13, 17 luminescence of Mn2+2+. The detailed partial density of the states of 7CsPbBr of 11 3 an
luminescence of Mn . The detailed partial density of the states of CsPbBr 3 and
Cs(Pb0.875Mn0.125)Br3 is shown in Figure 6.
Cs(Pb0.875Mn0.125)Br3 is shown in Figure 6.

Figure
Figure 4. 4.
Figure (a,e)
(a,e) Electron
Electron
4. (a,e) density,
density,
Electron (b,f)electron
density,(b,f)
(b,f) electron
electron density
density
density difference,
difference,
difference, (c,g) (c,g)
(c,g)electron
electron
electron localization
function function
localization
localization functio
and (d,h)
and (d,h) crystal
crystal
and (d,h) structure
structure
crystal structure of CsPbBr
ofofCsPbBr 3
CsPbBr33 andand Cs(Pb
andCs(Pb
Cs(Pb 0.875
Mn
0.875 Mn
Mn 0.125
)Br
0.125 )Br
)Br. 3
3 ..
0.875 0.125 3

Figure 5. (a,c) Band structure, (b,d) partial density of states of CsPbBr3 and Cs(Pb0.875Mn0.125)Br3,
suggesting
Figure 5. (a,c)that
Bandthestructure,
perovskite(b,d)
CsPbBr 3 belongs to a direct band−gap semiconductor.
partial density of states of CsPbBr3 and Cs(Pb0.875Mn0.125)Br3,
Figure 5. (a,c) Band structure, (b,d) partial density of states of CsPbBr3 and Cs(Pb0.875 Mn0.125 )Br3 ,
suggesting that that
suggesting the the
perovskite
perovskiteCsPbBr belongs
CsPbBr33 belongs to to a direct
a direct bandband−gap semiconductor.
−gap semiconductor.
Nanomaterials 2023, 13, 17 8 of 11
Nanomaterials 2023, 13, x FOR PEER REVIEW 8 of 11

Nanomaterials 2023, 13, x FOR PEER REVIEW 8 of

Figure 6. Detailed partial density of states of CsPbBr3 and Cs(Pb0.875Mn0.125)Br3. (a,b,c,e,f) Partial
Figure 6. Detailed partial density of states of CsPbBr3 and Cs(Pb0.875 Mn0.125 )Br3 . (a,b,c,e,f) Partial
Figure
density of states of 6.0.875
Cs(Pb Detailed
Mn0.125partial densityPartial
)Br3. (d,g,h,i) of states of CsPbBr
density 3 and of
of states Cs(Pb 0.875Mn
CsPbBr 3. 0.125)Br3. (a,b,c,e,f) Partial
density of states of Cs(Pbof0.875
density Mnof
states )Br3 0.875
Cs(Pb
0.125 . (d,g,h,i) Partial
Mn0.125)Br density of states of CsPbBr .
3. (d,g,h,i) Partial density of states3 of CsPbBr3.

3.4.
3.4. Performance
Performance of of LED
LED Devices
Devices
3.4. Performance of LED Devices
Figure 7a–e depict the photochromic
Figure 7a–e depict the photochromic characteristics
characteristics of the 3 PQDs@glasses
of the Cs(Pb,Mn)Br Cs(Pb,Mn)Br3
PQDs@glasses under Figure 7a–e depict
blue−emitting the photochromic characteristics of the Cs(Pb,Mn)B
under blue−emitting excitation in an LED lighting system. With the increaseWith
excitation in an LED lighting system.
PQDs@glasses under blue−emitting excitation in an LED lighting system. With the i
the
in the in-
input
crease
power in of the
the input
blue power
LED, of thewave
blue band
LED, gradually
the blue wave band gradually increases, the
crease inthe
theblue
input power of the blue LED, increases,
the bluethe green
wave wave
band band first
gradually increases, t
green wave
increases band
and then first increasesThe
decreases. andluminescence
then decreases. The luminescence
reaches the maximum reaches
when the
the maxi-
input
green wave band first increases and then decreases. The luminescence reaches the max
mum
powerwhen the input
is loaded power
at 4when
W. This isphenomenon
loaded at 4 W. This phenomenon is called luminescence
mum the input power is is called
loaded atluminescence saturation,
4 W. This phenomenon is which is
called luminescen
saturation, which
usually related to is
theusually
thermal related
quenchingto the thermal
property. quenching
With the property.
increase in x, With
the the increase
emission peak
saturation, which is usually related to the thermal quenching property. With the increa
in
of x,
thethe emission
green light peak
in x, the of
gradually theincreases.
emissiongreen
peaklight gradually
of The
the greenlight
green increases.
light reaches
gradually The green
the light
highest
increases. reaches
when
The =the
greenx light
0.1.reaches t
highest
Figure 7f when
showsx highest
=the
0.1.light
Figure 7f shows
distribution the light
curves distribution
of the LEDs, curves
and it of
can the
be LEDs,
seen that and
the
when x = 0.1. Figure 7f shows the light distribution curves of the LEDs, and it c it can
light
be
of seen that the
the LEDs light
is evenly
be of
seen the the
LEDs
distributed
that is evenly
inof
light space. distributed
the LEDs is evenly indistributed
space. in space.

Figure 7. (a–e) ELFigure

spectra7. of
(a–e) EL spectra
Cs(Pb,Mn)Br of Cs(Pb,Mn)Brwith
3 PQDs@glasses
3 PQDs@glasses
different Mnwith different
2+ doping Mn2+ doping concent
concentrations.
Figure 7. (a–e) EL spectra
tions. (f) of Cs(Pb,Mn)Br
Light distribution 3 PQDs@glasses with different Mn2+ doping concentra-
curves of the blue LEDs encapsulated with Cs(Pb,Mn)Br 3 PQDs@glass
(f) Light
tions. distribution
(f) Light curves
distribution of theofblue
curves the LEDs encapsulated
blue LEDs with with
encapsulated Cs(Pb,Mn)Br 3 PQDs@glasses.
Cs(Pb,Mn)Br 3 PQDs@glasses.
Nanomaterials 2023, 13, 17
Nanomaterials 2023, 13, x FOR PEER REVIEW 9 of 11 9

3.5. Design and Application of Contactless

3.5. Design and ApplicationElectroluminescence Devices
of Contactless Electroluminescence Devices
The relationship between
The the distance
relationship between andthespectra
distanceofand
the spectra
LEDs and Tesla
of the coilsand
LEDs − coils i
in xTesla
and z−directions andis shown in Figure
z−directions 8a,b. The
is shown internal
in Figure curve
8a,b. The is internal
measured by anisoscilloscope
curve measured by an osc
under differentscope
voltageunderanddifferent
frequency. The and
voltage emission of theThe
frequency. LEDs is proportional
emission of the LEDstoisthe proportion
frequency. When thethe frequency
frequency. When is relatively high, is
the frequency the LEDs is high,
relatively always theon,
LEDsas seen by the
is always on, as see
naked eye. As shown in Figure 8b, the x − direction refers to the horizontal distance
the naked eye. As shown in Figure 8b, the x−direction refers to the horizontal dist between
the LEDs and the coils center,
between the LEDs andand z−direction
the the refers
coils center, andtothethez−direction
vertical distance
refers tobetween
the vertical dist
the LEDs and the coils center. It can be seen from Figure 8a that
between the LEDs and the coils center. It can be seen from Figure in x − direction, the8aphotolu-
that in x−direc
minescence intensity of the LEDs decreases
the photoluminescence sharply
intensity withLEDs
of the the increase
decreases in distance.
sharply withAs shown
the increase in
in Figure 8c, the photoluminescence
tance. As shown in Figure intensity
8c, theof
photoluminescence −direction
the LEDs in the zintensity decreases
of the LEDs in the z−d
linearly with thetion
increase in distance.
decreases linearlyFigure
with the8d increase
refers to in
thedistance.
EL spectra of the
Figure 8dCs(Pb,Mn)Br
refers to the3EL spectr
PQDs@glass−encapsulated
the Cs(Pb,Mn)Br LEDs on the contactless electroluminescence
3 PQDs@glass−encapsulated devices.
LEDs on the contactless The
electroluminesc
devices. The−Cs(Pb,Mn)Br
Cs(Pb,Mn)Br3 PQDs@glass encapsulated3 LEDs excited by contactless LEDs
PQDs@glass−encapsulated electroluminescence
excited by contactless
devices are potential candidatesdevices
troluminescence for distance sensors.candidates for distance sensors.
are potential

Figure 8. The
Figure 8. The relationship relationship
between between
the distance and the distance
spectra and
of the spectra
LEDs andof the LEDs
Tesla and
coils in (a)Tesla coils in (a) x−
x− and
(c) z−directions. (b) Schematic diagram of contactless electroluminescence devices. (d) EL spect
(c) z−directions. (b) Schematic diagram of contactless electroluminescence devices. (d) EL spectra of
the LEDs encapsulated with Cs(Pb,Mn)Br3 PQDs@glasses by contactless electroluminescence
the LEDs encapsulated with Cs(Pb,Mn)Br3 PQDs@glasses by contactless electroluminescence devices.
vices.
4. Conclusions
4. Conclusions
In summary, a series of green luminescence Mn2+ doping CsPbBr3 PQDs@glasses
In summary,
were successfully synthesized a series
by melt of green
quenching andluminescence Mn2+ doping
in situ crystallization. CsPbBr
These 3 PQDs@gla
samples
can be stable in humid air for several months. The Cs(Pb,Mn)Br3 PQDs@glasses have high These s
were successfully synthesized by melt quenching and in situ crystallization.
exciton bindingples can be
energy (412stable
meV) in humid air forexcellent
and exhibit several months. The Cs(Pb,Mn)Br
luminescent PQDs@glasses
properties. 3 Pb 2+ is h
high exciton 2+binding energy (412 meV) and exhibit excellent
6 luminescent
partially substituted by Mn to reduce the toxicity. Moreover, due to the A1 ( S) transition 6 properties.
is2+
partially substituted by Mn2+ to reduce the toxicity. Moreover, due to the 6A1 (6S) tra
of 4 T1 (4 G)→Mn , there is a slight red shift (510–516 nm), and the FWHM ranges from
18 nm to 26 nm.tion
Theof
4T1 (4G)→Mn2+, there is a slight red shift (510–516 nm), and the FWHM ranges f
electronic structure, total density of states, and partial density of states
of Cs, Pb, Mn, and Br are studied by first principles, and the charge transfer between atoms
Nanomaterials 2023, 13, 17 10 of 11

were also studied. A contactless electroluminescence device was designed based on the
principle of electromagnetic induction, and the LEDs encapsulated with the Cs(Pb,Mn)Br3
PQDs@glasses were successfully illuminated. The contactless electroluminescence LEDs
encapsulated with the Cs(Pb,Mn)Br3 PQDs@glasses have potential application prospects in
detecting distance in sterile and dust−free environment.

Author Contributions: Conceptualization, A.D., Y.Y., E.C. and S.X.; methodology, A.D., W.Z., Y.P.,
X.Q. and Z.L.; software, A.D.; validation, Y.Y. and E.C.; formal analysis, A.D.; investigation, A.D.;
resources, Y.Y.; data curation, X.Q.; writing—original draft preparation, A.D.; writing—review and
editing, W.Z.; visualization, A.D.; supervision, E.C. and Y.Y.; project administration, E.C. and Y.Y.;
funding acquisition, T.G. All authors have read and agreed to the published version of the manuscript.
Funding: This work was financially supported by the National Key Research and Development
Program of China (Grant No. 2021YFB3600404), the Major Special Projects of Department of Science
and Technology of Fujian Province (Grant No. 2021HZ021001); the Natural Science Foundation of
Fujian Province (Grant No. 2022J01130129); and the Science & Technology Innovation Laboratory for
Optoelectronic Information of Fujian, China (Grant No. 2020ZZ112).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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