Zinc ions doped cesium lead bromide perovskite nanocrystals with enhanced efficiency and stability for white light-emitting diodes

Article abstract of DOI:10.1016/j.jallcom.2021.158969

All-inorganic cesium lead halide perovskite nanocrystals (NCs) are considered as an excellent candidate material for light-emitting devices (LED) displays because of their great photo-physical properties. However, the efficiency and stability of these materials are still unsatisfactory, which is the main disadvantage hindering the commercialization of the perovskite NCs based LED displays. On the other hand, the poisonous element lead (Pb) restricted the large-scale application of the perovskite NCs. Here we reported a hot-injection method by doping zinc ions into the CsPbBr3 NCs with enhanced photoluminescence (PL) properties and stability in ambient air. The doped NCs exhibit the highest photoluminescence quantum yield (PLQY) of 91.3% and a narrow full width at half-maximum (FWHM) of 15.5 nm. The improved the optical properties and stability of the doped NCs may result from the enhanced formation energies of perovskite lattices and the surface passivation. Finally, a white light-emitting diode (WLED) was fabricated by combining the green-emitting CsPbBr₃:Zn²⁺ doped NCs and red-emitting K₂SiF₆:Mn⁶⁺ phosphors along with a blue LED chip, which exhibits a luminous efficiency of 36 lm/W, a chromaticity coordinate of (0.327, 0.336), a color temperature (CCT) of 5760 K and a wide color gamut (137% of the National Television System Committee).

Full text of DOI:10.1016/j.jallcom.2021.158969

Journal of Alloys and Compounds 866 (2021) 158969
Contents lists available at ScienceDirect
Journal of Alloys and Compounds
journal homepage: www.elsevier.com/locate/jalcom
Zinc ions doped cesium lead bromide perovskite nanocrystals with
enhanced efficiency and stability for white light-emitting diodes
⁎
Renjie Chena, Yan Xua, Song Wanga, Chao Xiaa, Yunpeng Liua, Bingjie Yua, Tongtong Xuanb,c,
,
Huili Lia,⁎⁎
a Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, School of Physics and Electronic Science, East China Normal
University, Shanghai 200062, China
b College of Materials, Xiamen University, Xiamen 361005, China
c Shenzhen Research Institute of Xiamen University, Shenzhen 518000, China
a r t i c l e i n f o
a b s t r a c t
Article history:
All-inorganic cesium lead halide perovskite nanocrystals (NCs) are considered as an excellent candidate
material for light-emitting devices (LED) displays because of their great photo-physical properties. However,
the efficiency and stability of these materials are still unsatisfactory, which is the main disadvantage
hindering the commercialization of the perovskite NCs based LED displays. On the other hand, the poisonous
Received 6 November 2020
Received in revised form 9 January 2021
Accepted 26 January 2021
Available online 30 January 2021
element lead (Pb) restricted the large-scale application of the perovskite NCs. Here we reported
a
hot-injection method by doping zinc ions into the CsPbBr3 NCs with enhanced photoluminescence (PL)
properties and stability in ambient air. The doped NCs exhibit the highest photoluminescence quantum yield
(PLQY) of 91.3% and a narrow full width at half-maximum (FWHM) of 15.5 nm. The improved the optical
properties and stability of the doped NCs may result from the enhanced formation energies of perovskite
lattices and the surface passivation. Finally, a white light-emitting diode (WLED) was fabricated by combining
the green-emitting CsPbBr3:Zn2+ doped NCs and red-emitting K2SiF6:Mn6+ phosphors along with a blue LED
chip, which exhibits a luminous efficiency of 36 lm/W, a chromaticity coordinate of (0.327, 0.336), a color
temperature (CCT) of 5760 K and a wide color gamut (137% of the National Television System Committee).
© 2021 Elsevier B.V. All rights reserved.
Keywords:
Cesium lead halide perovskite
Nanocrystals
PLQY
WLED
1. Introduction
organic ligands, polymers, and silica [12,15–18]. For example,
Li et al. and Konidakis et al. encapsulated the perovskite NCs in silica
Inorganic lead halide perovskite nanocrystals (NCs) have attracted
many researchers’ attention due to their outstanding physicochemical
properties，such as high photoluminescence quantum yield (PLQY),
wide tunable emission wavelength, high defect tolerance, etc. Thus,
the perovskite NCs have great potential applications in solar cells,
Light Emitting Diodes (LEDs), and photo-electric detector [1–8].
However, the perovskite NCs suffer from poor stability because of
moisture, oxygen and heat, and toxicity of lead ions, which limits their
practical applications [6,7,9,10].
Many efforts have been made to improve the stability and reduce
the toxicity of the lead halide perovskite NCs, which can be divided
into two strategies [6,11–14]. On the one hand, to improve water
stability of the NCs through coating or encapsulation of waterproof
and AgPO3 with improved hydrolytic resistance [19,44]. Zhong et al.
reported that the encapsulation of the NCs in polymers with bright
emission and enhanced water stability [20,21]. In our previous work,
the perovskite NCs were coated with alkyl phosphate, which not
only retain excellent optical properties but also exhibit high stability
against water [22]. However, the thermodynamic stability of the
perovskite NCs is still poor, which hinders their practical applica-
tions. On the other hand, improving the stability of the perovskite
NCs by doping metal ions into perovskite structure due to the
enhancing the formation energy. For instance, Mn2+ ions were doped
into the CsPbX3 (X = Cl, Br, I) NCs with improved thermal stability
and excellent optical properties [23–26]. Moreover, the addition of
K+, Ni2+ Ce3+ can improve PLQY by modifying the lattice quality and
reducing the trap defects [24,26–28]. Therefore, doping metal ions
into the perovskite structure is an effective strategy to enhance the
comprehensive stability (water, heat, oxygen, and light) and optical
properties of the perovskite NCs.
⁎
Corresponding author at: College of Materials, Xiamen University, Xiamen
361005, China.
⁎⁎
Corresponding author.
E-mail addresses: ttxuan@xmu.edu.cn (T. Xuan), hlli@phy.ecnu.edu.cn (H. Li).
https://doi.org/10.1016/j.jallcom.2021.158969
0925-8388/© 2021 Elsevier B.V. All rights reserved.

R. Chen, Y. Xu, S. Wang et al.
Journal of Alloys and Compounds 866 (2021) 158969
Fig. 1. XRD patterns. (a) X-ray diffraction spectra patterns of perovskite NCS with a series concentration addition of Zn2+ ion, (b) zoomed picture of the (200) peak.
Zinc ions show low toxicity and smaller ionic radius (74 pm) than
that of Pb2+(119 pm) [29,30]. Simultaneously, previous reports
proved that the introduction of Zn-I could effectively passivate the
surface and inside defects of organic-inorganic hybrid perovskite
films and CsPbBr3, CsPbI3 NCs [29,30]. During the experiment and
preparing of this work, we also notice the paper in JACS [38]. In the
paper, the author produced the zinc addition perovskite NCs by post
treatment method that adding zinc bromide salt into the synthe-
sized original CsPbBr3 perovskite NCs toluene solution and there is
no obvious change in the size of NCs. Thus, the blue shift can be
attributed to the doping of Zn2+ ions. However, in our work, we
prepared the perovskite NCs by hot injection method (Supporting
Information), substituting different concentration of PbBr2 by adding
ZnBr2 salt in the precursor solution, which can influence the
crystallization process and size of the NCs. The bigger perovskite NCs
size have gotten, therefore the red shift of PL emission peak has been
observed in our work. Furthermore, we proposed to enhance
the efficiency and stability of CsPbBr3 NCs through doping Zn2+ ions
into the perovskite NCs. The doped NCs exhibit excellent optical
properties and enhanced thermal and ambient stability with the
highest PLQY of 91.3% and a narrow full width at half maximum
(FWHM) of 15.5 nm. Therefore, a white light-emitting diode (WLED)
was fabricated by combining the green-emitting CsPbBr3:Zn2+ NCs
and red-emitting K2SiF6:Mn4+ (KSF) phosphors with a blue LED chip.
The WLED shows high luminous efficiency and wide color gamut.
These indicate that the doped NCs have potential application for
liquid crystal display (LCD) backlight devices.
into the system. The enlarged diffraction peaks of (200) lattice
planes are exhibited in the Fig. 2b, it is obvious that the diffraction
peaks gradually shift to higher degree as the increasing of Zn2+
doping concentration, which indicates the shrinkage of the per-
ovskite lattices. It can be explained that the radius of Zn2+ (74 pm) is
smaller than that of the Pb2+ (119 pm) [29]. According to this result
and the previous works [29,31,32], it is convinced that zinc ion has
been doped into perovskite lattice. At same time, the FWHM of the
corresponding (200) peaks gradually becomes narrower along with
the increasing of Zn2+ concentration (Table S1, S2), the shift trend of
(100) peaks is matched with the (200) peak. According to the
Scherrer equation, it is found that the calculated grain size of these
series NCs gradually increases from 8.04 nm to 8.33 nm [33].
To further investigate the influence of Zn2+ ions doping on the
micro-morphology of the perovskite NCs, the transmission electron
microscopy (TEM) and high-resolution TEM (HR-TEM) of the NCs
were carried out，as shown in Fig. 2. All the perovskite NCs show
uniform cubic crystals. Meanwhile, with the increasing of the Zn2+
doping concentration, the average size of the NCs was increased
from 9.6 2.1 nm to 10.1 1.9 nm, 11.3 2.3 nm, 12.6 1.7 nm and
12.8 1.5 nm, which are shown in the Fig. 2(f) and S2. From the
HR-TEM images at the right upper of each figure, the lattice
space d of (100) decreases from 0.60 nm to 0.59 nm. These results
agree well with the analysis of XRD patterns data (Fig. 1), which
further proves that zinc ions were doped into the perovskite lattices.
The effect that zinc ion doping on the morphology of the perovskite
NCs is mainly focus on the adjustment of grain size. It may result
from that zinc ions have a higher charge attraction than that of Pb2+
ions, and it is easier to attract and be attracted by surrounding
bromine ions during the formation of perovskite NCs [34,35].
Furthermore, from the EDS mapping patterns in Fig. S1, zinc ions are
evenly distributed in the perovskite NCs. Combining the results of
XRD patterns and TEM images, it is safely determined that Zn ions
have been successfully doped into CsPbBr3 perovskite lattices. The
mechanism that zinc ion effect on the morphology could be sum-
marized as in Fig. 3c.
2. Results and discussion
For further exploring the effect of the introduction of Zn2+ ions on
the chemical structure, morphology, luminescence properties and
stability of doped CsPbBr3 NCs, a series of NCs were prepared by a
traditional hot injection method [31,32], which added different ratio
concentration molar of ZnBr2 compare to PbBr2(from 0%, 10%, 20%,
30%, 40%) into the original precursor [32]. The actual content of zinc
ion in these series NCs crystal have been detected by XPS and EDX
system, which are 0%, 4.5% 7.6%, 11.3%, 13.6% respectively to each
addition concentration. The X-ray diffraction (XRD) patterns of the
NCs with different Zn2+ doping concentration are shown in Fig. 1a. It
can be clearly noticed that the introduction of Zn2+ ions does not
significantly change the chemical structure or produce Impurities
To evaluate the Zn2+ ions concentration in the NCs, we further
employed the X-ray photoelectron spectroscopy (XPS) to detect the
NCs ions interaction before and after the addition of Zn ions. In
Fig. 4a and b, it shows obvious XPS signal peak of C 2s, N 2p, Pb 4f,
Br 2p, Cs 3d. The binding energy of Zn 2p1/2 and Zn 2p3/2 for
CsPbBr3:Zn2+ doped NCs is located at 1045.6 eV and 1022.3 eV,
2

R. Chen, Y. Xu, S. Wang et al.
Journal of Alloys and Compounds 866 (2021) 158969
Fig. 2. (a–e) TEM images of CsPbBr3 PNCs with different ration of ZnBr2.(a) 0%,(b) 4.5%, (c) 7.6%, (d) 11.3%, (e) 11.6%; upper right are the HRTEM patterns. (f) the average grain size
Histogram of the series NCs.
respectively, which matches well with the 2p singles of Zn2+ in
perovskite NCs [29,36,37]. The signal of Pb 4f7/2 moves from 138.6 eV
in the original NCs to the lower binding energy axis of 138.5 eV in the
doped NCs [10,30]. Meanwhile, the Br 3d orbit of different samples
exhibit similar binding energy (68.3 eV). After the split and fit of the
Br XPS peak (Fig. S5). The peak location of Br 3d3/2 and 3d5/2 are
located at the 68.3 eV, 69.4 eV, which indicates the existence of Br
element in perovskite NCs [26,45], and the other Br 3d5/2 at the peak
of 66.4 eV is attribute the existence of Br-Br bond on the NCs surface
[46,47]. There are have no obvious peak location change of Br ele-
ment in the original and doped NCs sample. This result indicates the
binding energy between Pb with Br is weakened after the in-
troduction of Zn2+ ions. By deeply considering, in the doped NCs, the
higher chemical activity element Zn2+ ions are partly substituting
the location of Pb2+ ions and interacting with Br ions, which
weakens the binding energy between Pb and Br due to the higher
chemical attraction [29,37,47]. Table S3 shows the molar ratio of Zn2+
to Pb2+ by using XPS and EDX systems, which illustrates that the
actual Zn2+ concentrations of the 0%, 10%, 20%, 30%, 40% doping
perovskite NCs samples are about 0%, 4.5%, 7.6%, 11.3%, 13.6%,
respectively.
phenomenon to the increased size and quantum size effect of the
NCs (Fig. 3) [29,36,38]. The PLQY of the perovskite NCs (Table 1) does
not continuously enhances with increase of Zn2+ doping con-
centration but presents an optimal passivation value at 11.3%, which
exhibits the highest PLQY of 91.3%, and the narrowest FWHM of
15.5 nm. The PLQY data of the original and 11.3% zinc doped sample
has been shown in the Fig. S6. As the Zn2+ doping concentration
rising to 13.6%, the excess introduction of Zinc structure perovskite
substitute the intrinsic luminescent center of CsPbBr3 perovskite
crystal, therefore the over-doped NCs owns more recombination
center and shows the low PLQY value of 76.5% [29]. As we know, the
narrower PL emission peak means higher color purity, which has
great advantage in the field of high-quality lighting and displays. It
can be attributed to the surface defect passivation and increased
formation energy [39,40]. For the further study the PL mechanism of
the perovskites NCs, we employed the transient PL spectroscopy to
detect the recombination process in the perovskite NCs (Fig. 3b).
The time-resolved PL decay curves fitted by the bi-exponential
equation [29,41].
t
t
2
)
)
I (t) = A1e(
1
+ A2e(
Furthermore, the PL properties of the perovskite NCs has been
investigated in detail. The steady-state PL spectra of pristine and
doped NCs with different Zn2+ doping concentration were shown in
Fig. 4a. As the increasing of the Zn2+ ions doping concentration from
0% to 13.6%, the PL peaks were shifted from 509.1 nm to 515.5 nm.
The absorbance edge show the uniform red shift trend after the
addition of zinc ion, which is matched with the PL emission peaks
(Fig. S3) According to previous paper, the zinc salts usually have a
large band gap, zinc ions contribute negligible effect to the in-gap
trap energy alignment of perovskite structure, so we summarize the
where A1 and A2 are the relative amplitudes, τ1 and τ2 represent the
lifetimes of the two recombination ways (fast and slow). The fast
decay process is attributed to the exciton recombination from the
conductive band to valence band, and the slow decay represents
trap-assisted recombination in its bulk or surface [8,14,42]. The NCs
with the addition of Zn2+ ion exhibits fast and slow lifetimes of
1.92 ns (A1 = 0.15) and τ2 = 71.6 ns (A2 = 0.85) and the average photo-
carrier life time of 46,8 ns, respectively. In contrast, the pristine NCs
show τ1 = 2.15 ns (A1 = 0.24) and τ2 = 57.6 ns (A2 = 0.76) and average
3

R. Chen, Y. Xu, S. Wang et al.
Journal of Alloys and Compounds 866 (2021) 158969
Fig. 3. (a) The steady-state PL spectra, (b) the Time resolved PL decay curves, (c) the mechanism that Zn ion act on perovskite NCs.
time of 43.1 ns. The longer τ2 means lower recombination rate of
photo-carrier from conductive band to defects in doped NCs, which
means there has lesser trap defects in the doped perovskite QDs.
Therefore, this result reveals that the enhanced efficiency of doped
NCs is relate to the reduced defects correspond well with the ana-
lysis of the PLQY [29].
due to enhanced formation energy, which was proved by DFT cal-
culation in their paper [23,25,43]. Meanwhile, the better crystal
quality is also benefit to the NCs stability [28]. The stability is ver-
ified by the UV–vis absorbance test (Fig. S4), the optimal doped
sample shows the lesser absorbance drop after aged for 168 h in
ambient condition. Therefore, we attribute the increased thermal
stability and ambient stability to the increase of formation energy
and better crystal quality after the doping of zinc ions.
Finally, a white light-emitting diode (WLED) was fabricated by
combining the green-emitting Zn doped CsPbBr3 perovskite NCs and
red-emitting K2SiF6:Mn6+ (KSF) phosphors with a blue-emitting LED
chip. The device shows bright white emission (Fig. 6) with a color
coordinates of (0.327, 0.336) and a correlated color temperature
(CCT) of 5760 K. Furthermore, the WLED exhibits a luminous effi-
ciency of 36 lm/W and wide color gamut (137% of National Television
System Committee, NTSC). Thus, the zinc doped NCs have great
potential in high quality displays.
Furthermore, we evaluated the thermal and air ambient stability
of pristine and 11.3% Zn2+ doped CsPbBr3 perovskite NCs by heating
them from 300 K to 420 K and then cooling down to room tem-
perature. As shown in Fig. 5a, the relative PL intensity of the doped
NCs maintained 40% of initial value at 350 K, which is higher than
the pristine CsPbBr3 NCs (26.8%). After the heating-cooling circula-
tion process, the doped NCs maintained 41.1% of the original PL in-
tensity, while the pristine NCs reversed only 26.1%. These results
indicate that the Zn2+ ions doped CsPbBr3 NCs exhibit enhanced
thermal stability. The ambient stability (Fig. 5b) of pristine and
doped NCs were studied by keeping the NCs for 168 h under ambient
conditions (at the temperature of 295 K and 30–40% RH). It is ob-
vious that after aging 168 h, the doped NCs maintained 92.1% of
original value, which is higher than the pristine NCs (76.3%). Ac-
cording to previous works, the doping of metal ions like Mn, Zn, Cd
into perovskite NCs can improve its thermal and ambient stability
3. Conclusion
In summary, we presented Zn2+ ions doped CsPbBr3 NCs with en-
hanced optical properties. The optimized doped NCs exhibit the highest
4

R. Chen, Y. Xu, S. Wang et al.
Journal of Alloys and Compounds 866 (2021) 158969
Fig. 4. XPS core spectra. (a) Full spectra of these samples (b) Pb 4f, (c) Br 3d, (d) Zn 2p.
Table 1
PLQY of 91.3% and a FWHM of 15.5 nm. Furthermore, the CsPbBr3:Zn2+
NCs show enhanced thermal and air ambient stability. Finally, a
WLED was fabricated based on green-emitting CsPbBr3:Zn2+ NCs,
red-emitting KSF phosphors, and a blue LED chip. The device shows a
wide color gamut (137% of NTSC) and a luminous efficiency of 36 lm/W.
We believe that the employment of doping Zn2+ ions into perovskites
to improve the stability and optical properties will energetically
facilitate their application in LED displays.
PL properties of the undoped and doped perovskite NCs.
Sample
Peak location (nm)
FWHM (nm)
PLQY (%)
0%
509.1
511.2
512.9
514.4
514.6
19.0
17.9
15.5
15.5
15.6
78.4 3.14
81.3 3.24
85.1 3.56
91.3 3.82
76.5 3.07
4.5%
7.6%
11.3%
13.6%
Fig. 5. Stability properties. (a) thermal stability, (b) air ambient stability.
5

R. Chen, Y. Xu, S. Wang et al.
Journal of Alloys and Compounds 866 (2021) 158969
Fig. 6. (a) The EL spectrum of based on Zn doped CsPbBr3 NCs, KSF phosphors and a blue LED chip. The inset photograph shows the WLED under working condition. (b) The color
coordinate and the color gamut of as-fabricated WLED.
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The authors declare that they have no known competing fi-
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Acknowledgements
This work is supported by Shanghai Municipal Natural Science
Foundation (No. 19ZR1415400), East China Normal University-
University of Alberta Joint Institute of Advanced Science and
Technology (JIAST) (No. 40500-20105-222053), the National Natural
Science Foundation of China (No. 51702373, No. 51472087), the
Natural Science Foundation of Fujian Province (No. 2020J01035), the
“Double-First Class” Foundation of Materials and Intelligent
Manufacturing Discipline of Xiamen University and the Fundamental
Research Funds for the Central Universities (No. 2072020078).
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ACS Appl. Mater. Interfaces 10 (2018) 39222–39227, https://doi.org/10.1021/
acsami.8b14480
Supplementary data associated with this article can be found in
the online version at doi:10.1016/j.jallcom.2021.158969.
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