Solid State Communications 305 (2020) 113765

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Solid State Communications

journal homepage: http://www.elsevier.com/locate/ssc

Communication

Efficient and stable solid state luminophores with colloidal quantum

dots-based silica monolith
Hao Chang a, b, Hongxing Dong a, *, Jingtai Zhao c, Long Zhang a, d, **
a
Key Laboratory of Materials for High Power Laser, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800, China
b
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China
c
School of Material Science and Engineering, Shanghai University, Shanghai, 200444, China
d
IFSA Collaborative Innovation Center, Shanghai Jiao Tong University, Shanghai, 200240, China

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

Communicated by P. Hawrylak The inherent unsatisfactory configurational and poor chemical stability of colloidal quantum dots (CQDs) are the
main impediments hindering their broad device operation. In this work, we synthesized colloidal quantum dots-
Keywords: silica monolith (CQDs-SM) solid-state luminophores with different emission colors through a simple sol-gel
A. Colloidal quantum dots method. The synthetic method, the morphologies of the composites and optical properties measurement in
B. Sol-gel methods
our work is in a new regime not studied before. Thermostability test indicated that the encapsulated CQDs-SM
C. Photoluminescence
composites samples had excellent stability against elevated temperature compared with that of fresh CQDs.
D. Optical properties enhancement
Furthermore, the as-prepared CQDs-SM displays excellent photoluminescence stability in the air atmosphere for
several months. The light emission also efficiently sustained stable with no measurable decrease for over 100 h
under continuous UV laser illumination, which can be attributed to the SiO2 capping layer protecting the CQDs
from degradation and agglomeration. It is quite obvious that the remarkable optical performances and novel
synthesis method used here will offer CQDs-SM composites a new platform for applications in light sources and
displays.

1. Introduction or matrices, which can effectively suppress the photo-degradation and

Colloidal quantum dots (CQDs) was recognized as an ideal material
for applications in optoelectronic fields because of their good color
purity, broad absorption, narrow emission and high photoluminescence
quantum efficiency. Their emission colors can be adjusted to the whole
visible region via changing the size or composition, having great
development potentials of spectrum-tunable light emitting devices and
displays [1–3]. However, the widely recognized instability issue of CQDs
is the main hinder for their practical applications [4–6]. Especially, fast
material degeneration will occur when CQDs are exposed to oxygen,
high temperature, or harsh operate conditions because of the larger
surface areas and higher activities. Therefore, it is highly desirable to
develop a fabricating process that is facile, mass-productive and
repeatable to improve the chemical stability and photostability of the
nanocrystals. The main approach is incorporate CQDs into a composite
agglomeration of CQDs.
Very recently, great efforts have been made in this field. Several
surface passivation methods, such as encapsulation using polymers,
reverse microemulsion methods or silica coating, have been reported for
nanoparticles. Embedding CQDs in polymers can prevent agglomeration
and achieve uniform dispersion [7,8]. However, the performance is
usually limited under operating conditions because the polymers suffer
from a confined thermal range and low damage threshold. The high
oxygen diffusion coefficient of polymers also exhibited limited protec­
tion of CQDs from photo-oxidation. A reverse microemulsion method
[9–11], which the silica shell layer grown right above the surface of
isolated CQDs. The thick silica layer limits the concentration of CQDs in
the composite and CQDs suffered from severely reduced photo­
luminescence in this process. CQDs also have been encapsulated in the
silica monolith by the sol-gel reaction [12–15]. Most inorganic optical

* Corresponding author. Key Laboratory of Materials for High Power Laser, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences,
Shanghai 201800, China.
** Corresponding author. Key Laboratory of Materials for High Power Laser, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences,
Shanghai 201800, China.
E-mail addresses: hongxingd@siom.ac.cn (H. Dong), lzhang@siom.ac.cn (L. Zhang).

https://doi.org/10.1016/j.ssc.2019.113765
Received 8 April 2019; Received in revised form 29 May 2019; Accepted 15 October 2019
Available online 17 October 2019
0038-1098/© 2019 Elsevier Ltd. All rights reserved.
H. Chang et al.
quality matrices materials are rigid and airtight. Among them, silica is a
good option for protect the core materials against damage due to its
excellent optical properties and chemical stability. However, the cova­
lent silica network has inherent incompatibilities with the surface
chemistry of CQDs. It will cause the nanoparticles more easily to coag­
ulate and the aggregated CQDs would increase reabsorption and light
scattering, reducing the quantum efficiency. Furthermore, the ligands
on the CQDs surface suffered detachment in the severe acid-stage hy­
drolysis conditions, leading to substantial surface defects, which could
quench the luminescence of CQDs. Thus, it is urgent to develop a new
strategy to achieve highly luminescent and effectively suppress the
degradation of CQDs to realize their practical applications.
In our work, we report a modified sol-gel method for preparing
CQDs-silica monolith while maintaining excellent optical properties.
The 3D solid-state luminophores we synthesized are rigid and airtight
with machinability. The microstructures and morphologies are different
with other sol-gel composites. We systematically studied the photo­
luminescence behavior of the CQDs-SM, in the temperature range of
80–475 K. Comparing with the results of fresh CQDs, the CQDs-SM ex­
hibits an enhanced stability against the heat. Thermostability and
quenching mechanism analyses of CQDs give a comprehensive and clear
physical image of the protection for the optical properties of CQDs.
Furthermore, the obtained CQDs-SM samples were used as solid state
luminescent materials with remarkable stable optical properties under
atmospheric conditions over months. Even when operated under high-
power UV radiation, the light emission maintained its initial lumines­
cence for 100 h without any decay. And the wavelength can be
completing tunable across the whole visible spectral, by modifying size
or composition of the doping CQDs. The results obtained prove that our
strategy is a practical method for enhancing the material stability for
CQDs, representing a significant step towards the applications of full-
color displays and other novel photoelectronic devices.
2. Material and methods
The novel and facile route sol-gel methods were applied to embed­
ding CQDs in stiff, transparent solid matrices in the cause of synthesizing
highly efficient and stable monolithic CQDs nanocomposites (Fig. 1).
Tetramethoxysilane (TMOS) was chosen as silica precursors for the
higher hydrolysis rate than frequently used tetraethylorthosilicate
(TEOS). First, TMOS (1.2 mmol) and ethanol (0.6 mmol) were mixed
under magnetic stirring in an atmospheric environment for 3 min. Then,
the mixture was added to another beaker in which contained CQDs
(0.3 mmol) and 3-mercaptopropyltrimethoxysilane (3-MPS) (0.3 mmol),
keeping the mixture on stirring for about 5 min. The CdSe/ZnS CQDs
was chosen as the gain medium as their excellent optical performances.
MPA was employed as the covering ligand of the CQDs, which can
protect the nanoparticles to remain stable in a wide range of pH values
[16]. Propylamine acts as a basic catalyst, which can rapidly reduce the
solidification time from few days to several minutes and neutralize the
mixture to alkalescency to protect the CQDs [6,17]. Furthermore, the
long organic chains of 3-MPS tends to combine with the sulphion (S2 )
on the CQDs surface shell, which protects the stability of the CQDs, as
well as cross-link the CQDs with the covalent silica network to eliminate
Fig. 1. Schematic diagram of the sol-gel process for synthesizes the CQDs-SM nanocomposites.
2
Solid State Communications 305 (2020) 113765
interface incompatibilities. After which, the resultant solution was
divided into several molds, and solidification took place in a few minutes
until a dense structure was obtained.
3. Results and discussion
Fig. 2a shows as-prepared samples with different emission colors
under room light. The microstructures of CQDs and silica-coated CQDs
are tested by transmission electron microscopy (TEM). Fig. 2b shows the
TEM images of the fresh CQDs solution, which are monodisperse parti­
cles with a fine crystalline structure, with a tendency to agglomeration.
After the sol-gel coating process, the shape of CQDs remains preserved
and the dispersion is more uniformly (Fig. 2c). The grey shadow areas in
Fig. 2c demonstrate the presence of amorphous silica surrounding the
CQDs nanoparticles instead of growing on the surface of CQDs, forming
mechanically robust and airtight silica monolith. Scanning electron
microscopy (SEM) together with energy-dispersive X-ray spectroscopy
(EDS) was used to investigate the surface morphology and elemental
composition of these composites. Fig. 2d is the typical SEM image of
synthesized composites. The top-right inset of Fig. 2d clearly shows the
smooth surface of the samples. Also, the elementary composition of
CQDs-SM composites is analyzed through EDS measurements. In
Fig. 2e–j, the well-known compositions of Si, O, Cd, Se, Zn, S are also
examined, confirming the formation of CQDs-SM composites. It is
obvious that the six object elements are uniformly distributed
throughout the selected square area marked in Fig. 2d, thus demon­
strating that CQDs are successfully and uniformly embedded in the silica
monolith. Furthermore, the remarkable stability of the CQDs-SM sam­
ples against environmental oxygen, light and heat as analyzed further
below demonstrates that this method provides successful surface pro­
tection for CQDs.
As is well known, the optical properties usually decrease after the
CQDs experience a high-temperature heating [18,19]. To find out
whether our samples have heatendurance, the research of PL behavior
for the CQDs and CQDs-SM at various temperatures is an inevitable and
significant work. As presented in Fig. 3, the PL emission spectrums of the
CQDs solution and CQDs in silica monolith were recorded at different
temperatures. Consist of the results obtained from other reports for
nanoparticles at elevated temperatures [20], as the thermal treatment
temperature increased, the photoluminescence intensity reduced
significantly with the emission peak clearly red-shifted. When the tem­
perature increases from 80 to 475 K, the CQDs solution photo­
luminescence intensity drop significantly (decrease of about 97%), and
the emission peak shifted about 33 nm. Compared with that, the emis­
sion of CQDs in silica monolith shows a lesser decrease of about 66%,
and the emission peak has a red-shift of ~14 nm. It is found that the
optical emission properties of the CQDs in silica monolith composites
maintained stably at the high temperature. As we all know, the ther­
mally induced interfacial tension and atomic dislocation is the most
likely origin of nonradiative trapping centers and surface defects of
CQDs [6]. And, more intense molecular thermal motion at high tem­
perature will lead the capping ligands of the CQDs detached, which can
be explained for the binding energy shift. When capped CQDs in the
silica-based network, the inactivation ligands cannot detach and leave
H. Chang et al. Solid State Communications 305 (2020) 113765

Fig. 2. (a) Optical images of the different composites with different emission wavelengths. (b) TEM images of fresh CQDs solution. Inset: high-resolution TEM image
of individual CQDs. (c) TEM images of CQDs-SM composites. (d) SEM images for the surface morphology of CQDs-SM composites. (e–j) Elemental mapping shows the
uniform allocation of silicon, oxygen, cadmium, selenium, zinc and sulfur. (For interpretation of the references to color in this figure legend, the reader is referred to
the Web version of this article.)

Fig. 3. (Color online) PL spectra of CQDs solution (a) and CQDs in silica monolith (b) at different working temperatures for the same excitation conditions. (For
interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)

the surface, thus forestalling the degradation of CQDs. The inorganic
shell also eliminates the surface defect states and improved temperature
tolerance of the CQDs for excellent optical performance at elevated
temperatures. That may explain for the enhanced thermostability of
CQDs in silica monolith than those monodisperse CQDs in solution.
It is well known that most CQDs nanoparticles subjected to atmo­
sphere instability because of the self-aggregation and sensitive to oxy­
gen, light under atmospherically environment, which pares their
practical light emission application [21,22]. The long-term stability of
the synthetic CQDs-SM composites was thus monitored after being
stored over the course of months under ambient atmosphere. As the
results are shown in Fig. 4a, only a slight different could be detected in
the PL spectra, which suggests that the optical properties of CQDs-SM
showed no change over the course of months under ambient atmo­
sphere. The above results suggest that the air stability was remarkably
enhanced after silica coating. This may due to the covalent silica
network that served as a maskant prevent CQDs from oxidation.
Furthermore, the stability of emission intensity for the CQDs-silica
monolith composites was investigated as a function of pumping time.
As can be seen from Fig. 4b, the almost constant integrated emission
intensity was recorded by continuously UV laser pumping in the air for
over 100 h, while the samples were still strongly fluorescent just like the

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H. Chang et al. Solid State Communications 305 (2020) 113765

Fig. 4. (Color online) (a) Emission spectra of the CQDs-SM stored for one day to six months under atmospheric conditions. (b) The plot of the integrated emission
intensity of a CQDs-SM sample under continuous pulsed UV laser radiation for 100 h. The inset displays the emission spectrum before and after 100 h irradiation. (c)
PLQY of the CQDs solution and CQDs-SM composites as a function of time in air. (For interpretation of the references to color in this figure legend, the reader is
referred to the Web version of this article.)

beginning, indicating a remarkable operate lifetime tolerant to ambient

condition. According to previous reports about semiconductor CQDs
[4–6], the significantly enhanced environment and continuous opera­
tion stability under atmospheric conditions observed here could be due
to the form of a coating layer that prevents unexpected photo-oxidation
under UV light conditions. To apply CQDs in practical optoelectronic
applications in the future, such as light emission devices, it is necessary
to form the silica shell to effectively protect the CQDs for reliable and
environmentally friendly lighting applications. To evaluate the protec­
tion of the optical properties for CQDs, photoluminescence quantum
yield (PLQY) test was measured using an absolute PLQY spectrometer
under an excitation wavelength of 325 nm. Fig. 4c shows the PLQY of
CQDs solution and CQDs-SM composites stored in air for a different
time. The PLQY of the fresh CQDs solution was high up to about 70%.
Very interestingly, the PLQY of the CQDs-SM composites was main­
tained at 95% (PLQY�66.5%) of the initial fresh CQDs solution, which
strongly suggests that our modified sol-gel method is highly efficient and
retaining the original PLQY of CQDs. As shown in Fig. 4c, the PLQY of
pure CQDs solution was decreased to nearly zero after being stored in air
for about 3 days and the CQDs-SM composites maintained initial PLQY
for 7 days. Moreover, the PLQY of the CQDs-SM composites was still Fig. 5. (Color online) (a) Real-color image of the different CQDs doped silica
retained about 65%, which we made 6 months ago. These results indi­ monolith composites excited by ultraviolet light. (b) Emission spectra of the six
CQDs-SM composites covering the entire visible spectrum. (For interpretation
cate that our prepared CQDs-SM composites exhibit great protection of
of the references to color in this figure legend, the reader is referred to the Web
the photoluminescence properties for the CQDs.
version of this article.)
This is a common phenomenon for light emitting devices that the
chromaticity coordinates shifts with the temperature increasing
[23–25]. The CQDs-SM composites samples with tolerance to thermal
fluorescence quenching provide promising applications in light emitting 4. Conclusions
to overcome the chromaticity coordinates shifts. As we mentioned
before, our sol-gel method is not only a facile route to prepare the In conclusion, we have developed facile and effective sol-gel
monolithic composites but also a universal process for solidifyingother methods for the synthesis of high luminescent and photostable CQDs-
nanoparticles, especially environmentally sensitive functional mole­ silica monolith composites. The embedded CQDs maintained the
cules. Fig. 5a shows the optical images of the different CQDs doped silica initial optical properties and dispersed homogeneously in the final
monolith under the excitation of an ultraviolet lamp at room tempera­ products. We systematically studied the thermal PL behavior of the
ture. Through compositional modulations or change size of the nano­ resultant composites, which exhibit substantially improved photo­
particles, the band gap energies and emission colors displayed excellent stability against heat compared with the pure CQDs. Furthermore,
tunability. Fig. 5b shows the normalized emission spectra of the six encapsulating CQDs into silica monolith allows for strong photostability
CQDs-SM composites samples under excitation by 325 nm UV laser under the environmental condition for several months, as well as the
source and the emission spectral covers the entire visible region from remarkable operation stability under high-power UV radiation for more
violet to red. Furthermore, the optical properties of as-prepared six than 100 h with no emission decay. This facile route can be applied to
composites are investigated as bright light emitting from the whole CQDs and other nanoparticles, particularly environmentally sensitive
sample, which indicates the uniform distribution of the doped CQDs nanomaterials. Our results provide a new platform for the design and
nanoparticles. The obtained high-efficient CQDs-SM composites suggest utilization of CQDs as solid state luminophores for further applications
that it is important to protect the CQDs from thermal quenching and in light-emitting devices and displays.
prevent the aggregation of nanoparticles. The excellent device perfor­
mances demonstrate the as-prepared composites as a reliable lumines­
cent material for light display applications.

4
H. Chang et al.
Acknowledgment
This work was financially supported by the National Nature Science
Foundation of China (NSFC) (61875256, 61675219).
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