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Abstract
One-step precipitation of CsPbBr3 QDs in silicate glass was successfully achieved by picosecond laser pulses. Enabled by spatially selective modification, luminescent QDs are well protected by the inorganic glass matrix. The combination of high-power and high-speed scanning system provides a convenient and flexible route for large-scale in situ fabrication of CsPbBr3 QDs. The dependence of photoluminescence (PL) intensity and absorption band was systematically investigated, and the formation mechanism was briefly discussed. Notable stabilities of CsPbBr3 QDs against moisture, high temperature as well as ultraviolet (UV) radiation were verified by water-proof and thermal/UV-dependent PL tests. Prospective use for light-emitting device and anti-counterfeiting were also demonstrated.
© 2022 Optica Publishing Group under the terms of the Optica Open Access Publishing Agreement
1. Introduction
Metal halide perovskite quantum dots (CsPbX3 QDs, X = Cl, Br, I) have appeared as a brand new series of materials for the manufacture of high-performing optoelectronic devices such as photodetectors [1,2], optical information storage [3–7] and high definition displays [8–12].They have become as the amazing rookie in the domain of science and industry due to their extraordinary photoelectronic properties such as high quantum yields, narrow full width at half maximum (FWHM) in emission spectra and tunable wavelengths covering in visible full-spectral range [11,13,14]. Presently, most CsPbX3 QDs exist in the form of colloids, which are normally prepared by hot-injection and room-temperature synthesis [15–17]. However, the stabilities of CsPbX3 QDs are susceptible to external environment such as humidity and temperature, which severely restrict their industrialization [18]. Hence, it is necessary to use inorganic envelopes to encapsulate CsPbX3 QDs or allow them to be generated directly in solid matrixes such as glass to improve their stabilities [19,20].
Glass formed by high temperature melting has developed into a forceful host due to its excellent chemical inertness and mechanical properties, which can provide a robust and stable environment for QDs [21,22]. CsPbX3 QDs can be precipitated in glass by heat-treatment [23,24], self-crystallization [25], or ultrafast laser-irradiation combined with subsequent heat-treatment [26–28]. In 2016, Ai et al. firstly synthesized CsPbBr3 QDs in phosphate glass by heat-treatment [29]. Thereafter, multi-color tunable emission covering the entire visible spectra by heat-treatment were achieved by varying the molar ratio of the halide source [30]. Traditionally, heat-treatment is a favorable way to realize controllable nucleation and crystal growth, and the optical properties of QDs can be guaranteed for a long-term period [31,32].
In comparison with glass self-crystallization or heat-treatment crystallization, femtosecond laser, due to its short pulse width and high peak power, can induce high transient temperature field, which was sufficient for the nuclei formation of QDs [26,27]. In 2020, highly luminescent CsPbBr3 QDs were reversibly fabricated in situ, which decomposed and reproduced through femtosecond laser-irradiation and heat-treatment [28]. In that study, a two-step fabrication method was advocated with femtosecond laser for nucleation while thermal annealing for further growth of CsPbBr3 QDs. However, intended for industrialized application, a rapid, economic and eco-friendly route for mass production of stable CsPbBr3 QDs was in urgent need. Compared to 1 kHz low repetition frequency femtosecond lasers, high repetition rate picosecond lasers not only possess the superiority of high peak power for nonlinear optical absorption, but also generate enough thermal accumulation for nuclei growth. Therefore, high repetition rate picosecond lasers are expected to achieve one-step precipitation of CsPbBr3 QDs, and at the same time, maintain a higher-efficiency and a lower cost. Recently, three-dimensional (3D) direct lithography of perovskite nanocrystals with tunable composition and bandgap in glasses was successfully achieved, which was a pioneering work and a milestone in history of fabricating perovskite nanocrystals [33].
In this work, one-step precipitation of CsPbBr3 QDs in silicate glass was specially focused on picosecond laser pulses. The dependence of PL and absorption properties on pulse energy and number was systematically investigated. Intended for industrialized application, water-proof and thermal/UV-dependent PL tests were carried out to verify the thermal, humidity and UV light stabilities of CsPbBr3 QDs. Finally, two demonstrations of light-emitting device and fluorescent labels for anti-counterfeiting were proposed.
2. Experimental procedures
2.1 Sample preparation
The precursor glass (PG) with a stoichiometric composition (in mol%) of 41SiO2−34B2O3−11ZnO-6Cs2CO3-2PbO-6NaBr was fabricated via a melt-quenching route. Reagent grade powders were mixed thoroughly in corundum crucible and melted at 1350 °C for 30 min in ambient atmosphere. The glass melts were then removed from the furnace, cast on a preheated graphite plate and splash-cooled by pressing with a stainless-steel plate. The solidified glass samples were subsequently heated at 350 °C in a muffle furnace and kept for 4 h to release the strain, thereby yielding colorless and transparent glasses. For the application demonstration of light-emitting device, glass samples were cut and polished into a given size of 6 mm × 6 mm× 2 mm. If not specifically addressed, all the other glass samples were carefully polished to regular size of 10 mm × 10 mm × 2 mm for experiments and tests.
2.2 Laser treatment and characterization
A picosecond (ps) laser (Atlantic 355, Ekspla) with a wavelength of 1064 nm, pulse width of 10 ps, and a repetition frequency range of 100-400 kHz was used for the precipitation of CsPbBr3 QDs. Laser pulse energy was varied from 15.4 to 28.4 µJ. The precursor glass samples were placed on a three-dimensional translational stage (Prior Stage II), and linearly polarized laser beam was guided into a microscope and focused into the sample at a depth of 150 µm beneath the sample surface by a 5× objective lens (NA = 0.3). By implementing a parallel line raster pattern process, CsPbBr3 QDs were precipitated in the region with a dimension of 8.4× 8.4 mm2. The line spacing and scanning speed was set as 30 µm and 300 µm/s, respectively.
The fluorescence spectra and lifetime of the precipitated CsPbBr3 QDs were measured with instrument FLS1000 (Edinburgh instruments Ltd., UK). The corresponding spectral and time resolution were 1 nm and 0.039 ns, respectively. An UV-VIS-NIR spectrophotometer (Lambda 750, Perkin Elmer, USA) with a resolution of 0.5 nm was used to record the absorbance of the irradiated glass samples in the wavelength range of 300–1200 nm. Differential scanning calorimetry (DSC) was performed with STA 409PC (Netzsch, Germany) in ambient atmosphere with a heating rate of 10 K/min in the temperature range of 100–750 °C. X-ray diffraction (XRD) patterns of the CsPbBr3 QDs in glass matrix were recorded with an X-ray diffractometer (D8 Discover, Bruker, Germany) with a resolution of 0.02° in the range from 10° to 70°, and the crystal morphology and size distribution were analyzed using a field emission transmission electron microscope (TEM) (Tecnai G2 F20, FEI, USA). In addition, the demonstration of light emitting diode (LED) was tested by using HP9000 LED photochromic and electrical integrated test system.
3. Results and discussion
3.1 One-step precipitation of CsPbBr3 QDs by picosecond laser pulses
The intense green luminescence under the excitation of 365 nm UV light in Fig. 1(a) clearly demonstrated that in situ formation of CsPbBr3 QDs was achieved in the glass matrix during the one-step processing of picosecond laser pulses. It was confirmed that heat accumulation provided by the repetition rates ranging from 100 kHz to 350 kHz not only forms the seeds of crystal nuclei, but also produces a subsequent hardening process in the glass, allowing the seeds to grow further into QDs [33,34]. The DSC analysis (Fig. 1(b)) indicated that the glass transition temperature (Tg) was around 470 °C. It indicated that the glass matrix was high-temperature resistant and may not induce structural or functional damage when the operating temperature was below Tg, thus effectively defending QDs from ion migration caused by external thermal shock. From the following XRD measurements (Fig. 1(c)), only typical amorphous structure was found from PG, indicating that no detectable nanocrystalline phases were present in the as-prepared glass specimen. However, distinct diffraction peaks emerged in the glass matrix irradiated by picosecond laser pulses. These diffraction peaks were in perfect accordance with the crystalline phase of CsPbBr3 (JCPDS No. 54-0752). Transmission electron microscopy (TEM) images in Fig. 1(d) also confirmed the homogeneous precipitation of CsPbBr3 QDs with radii around 4-6 nm among the glass matrix. The lattice fringes could be observed in a higher resolution image (Fig. 1(e)), and the distance between neighboring crystal lattice fringes was ∼ 0.26 nm, and it corresponded to the (210) crystal facet of CsPbBr3. Selected area electron diffraction (SEAD) showed that the QDs in the glass matrix with multilayer concentric diffraction rings correspond to the (211), (300) and (420) facets of CsPbBr3 (Fig. 1(f)).
Fig. 1. (a) Optical images of PG and CsPbBr3 QDs in glass matrix under natural light and 365 nm UV light; (b) DSC curve of PG; (c) XRD patterns of PG and CsPbBr3 QDs-embedded glass matrix; (d) TEM and (e) HRTEM images and (f) the SAED pattern of the CsPbBr3 QDs in glass matrix. (Samples for both XRD and TEM measurements were fabricated by picosecond laser at pulse energy of 20.4 µJ and repetition rate of 250 kHz)
The dependence of photoluminescence (PL) spectra on pulse energy and repetition rate was systematically investigated, and the corresponding trend graphs of center wavelength, PL intensity as well as FWHM were also plotted (Fig. 2). As clearly be seen, with 365 nm UV light excitation, no obvious PL could be detected from the PG, whereas CsPbBr3 QDs-embedded glasses featured characteristic green emission. With pulse energy increasing from 15.4 µJ to 28.4 µJ (repetition rate fixed at 250 kHz), the PL intensity increased accordingly, and there also existed a slight redshift of center wavelength from 504 nm to 508 nm (Fig. 2(a)). Moreover, the FWHM of the emission bands got progressively narrower from approximate 30 nm to 24 nm (Fig. 2(b)). All the information derived from the emission bands demonstrated that the average size of CsPbBr3 QDs became larger with the rise of single pulse energy. And due to the quantum confinement effect, the band gap energy of CsPbBr3 QDs exhibited a corresponding decrease [26,35]. Similar spectra analysis was also conducted with laser repetition rate adjusted from 100 kHz to 400 kHz (single pulse energy fixed at 18.6 µJ) (Fig. 3(c)–3(d)). The redshift of the center wavelength and the narrowing trend of FWHM were also appeared. However, the PL intensity of CsPbBr3 QDs enhanced firstly and then weakened. This phenomenon indicated that proper heat accumulation was favorable for the growth of CsPbBr3 QDs, while too much heat will cause irreversible destruction to glass matrix, which was detrimental for CsPbBr3 QDs.
Fig. 2. PL spectra of CsPbBr3 QDs in glass matrix induced by picosecond laser with (a) laser pulse energy ranging from 0 to 28.4 µJ at a fixed repetition rate of 250 kHz and (c) repetition rates ranging from 0 to 400 kHz at single pulse energy of 18.6 µJ; The dependence of FWHM and PL intensity on (b) laser pulse energy and (d) repetition rate.
Fig. 3. Absorption spectra of CsPbBr3 QDs in glass matrix induced by picosecond laser with (a) laser pulse energy ranging from 0 to 28.4 µJ at repetition rate of 250 kHz and (b) repetition rate ranging from 0 to 400 kHz at single pulse energy of 18.6 µJ; (c) Optical images of glass matrix before and after laser irradiation; (d) Lifetime of CsPbBr3 QDs.
From Fig. 3(a)–3(c), it was found that PG was highly transparent in visible and near-infrared regions. This indicated that the formation of CsPbBr3 QDs inside transparent glass relies on nonlinear multiphoton absorption through interaction with a short-pulse laser. With the increasing of the pulse energy and repetition rate, the baselines of the absorption band were elevated to higher level. And at the same time, the absorption edges exhibited a redshift, also due to the larger size of CsPbBr3 QDs [13,31]. From Fig. 1(a) and Fig. 3(c), both can see that the color of glass matrix was changed from transparent to pale yellow, and eventually deep yellow in daylight with increasing pulse energy and repetition rate. Color change was an important feature signifying the formation of CsPbBr3 QDs. That is to say, in addition to the nonlinear multiphoton absorption, heat accumulation enabled by high repetition rate was also an important factor for the generation of CsPbBr3 QDs. By regulating laser pulse energy and repetition rate, high level transparency of glass matrix can still be maintained while with considerable PL intensity achieved. This ensures the application for anti-counterfeiting, which will be especially discussed in section 3.3. The PL decay curve of CsPbBr3 QDs followed well a double exponential function τ=A1exp(-t/τ1) + A2exp(-t/τ2). PL lifetime was defined as the time when PL intensity decreased to e−1 fold of the initial intensity. By fitting the curve in Fig. 3(d), the lifetime of CsPbBr3 QDs precipitated at pulse energy of 28.4 µJ and repetition rate of 250 kHz was calculated to be 1.82 ns. And following the same way, the lifetime of all the other samples was fitted to be in the range of 1.4–2.28 ns.
3.2 Stabilization tests of CsPbBr3 QDs glass
Despite the excellent luminescent performance, the thermal and moisture stabilities of CsPbBr3 QDs are the main factors restricting their applications in LEDs, solar cells, AR/VR and so on [36,37]. In this experiment, CsPbBr3 QDs embedded-glass matrix was subjected to a cyclic heating-cooling procedure from 25 °C to 150 °C (Fig. 4(a)). With temperature increasing, PL intensity decreased. Meanwhile, a slight blueshift of center wavelength appeared, which means that bandgap energy of the CsPbBr3 QDs is temperature-dependent. In the cooling procedure, PL intensity increased, and the center wavelength returned to the original spectral positions. As depicted in Fig. 4(b), the integrated PL intensity almost completely recovered after the heating-cooling cycle. This temperature-dependent spectral shift of PL was mainly induced by thermal expansion and electron-phonon interaction, which was illustrated in Fig. 4(c) [38,39]. These reversible spectra and intensity of PL observed during the heating-cooling in the range from room temperature to 150 °C showed that these CsPbBr3 QDs in glass were also very stable, without observable degradation and change in size.
Fig. 4. (a) Temperature-dependent PL spectra and (b) integral PL intensity of CsPbBr3 QDs-embedded glass (fabricated at repetition rate of 250 kHz and pulse energy of 25.1 µJ) recorded in heating-cooling cycling experiment from 25 °C to 150 °C; (c) Schematic illustrations of one-step precipitation of CsPbBr3 QDs and lattices thermal expansion in heating-cooling cycle.
Moisture-proof test of CsPbBr3 QDs-embedded glass matrix was also conducted. When kept in water at room temperature, spectra shape of the PL band did not show any obvious change, and the integral PL intensity decreased less than 5% during the 8-week test (Fig. 5(a)). Accordingly, from the optical photographs, no discernible decrease of PL intensity could be observed (Fig. 5(b)). Hence, one can conclude that the CsPbBr3 QDs encapsulated in the glass matrix exhibit excellent resistance against both moisture and heat invasion, which is in favor for long-term device operation.
Fig. 5. Moisture-proof test of CsPbBr3 QDs-embedded glass matrix immersed in water. (a) The PL intensity and (b) optical luminescent photographs with extended storage time.
3.3 Applications: light-emitting device and anti-counterfeiting
Due to the good chemical, mechanical and optical properties of silicate glass, along with the excellent luminescent performance of CsPbBr3 QDs, hence the CsPbBr3 QDs-embedded glass matrix warrant the great potential for various light-emitting applications. One demonstration of light-emitting device constructed by coupling a thin sheet of green-emitting CsPbBr3 QDs-embedded glass (fabricated at repetition rate of 100 kHz and pulse energy of 16.8 µJ) with a 365 nm UV chip was illustrated in Fig. 6(a)–6(b). Compared with traditional powder photo-conversion materials, glass slice can be directly encapsulated on 365 nm UV chip for photoluminescence. In addition, because of its better transparency and low UV light scattering, glass can improve the light-conversion efficiency and has become the preferred material for various optical devices [31]. The dependence of emission intensity and the CIE chromaticity coordinates on forward bias current were illustrated in Fig. 6(c)–6(d). With the current increasing from 20 mA to 500 mA, the intensity of green luminescence firstly enhanced, and then tended to be relatively stable. The coordinates in corresponding CIE chromaticity diagram were relatively concentrated with the current ranging from 20 mA to 200 mA, indicating that the UV-stability of CsPbBr3 QDs-embedded glass slice could be realized in a proper current range [40].
Fig. 6. (a) Panoramic view and (b) close-up of light-emitting device made with CsPbBr3 QDs-embedded glass slice (fabricated at repetition rate of 100 kHz and pulse energy of 16.8 µJ) and 365 nm UV chip. The dependence of (c) emission spectra and (d) CIE chromaticity coordinates on forward bias current.
In section 3.1, we have discussed that color change of CsPbBr3 QDs-embedded glass can be regulated by pulse energy and repetition rate. When laser pulse energy and repetition rate were both comparatively low, CsPbBr3 QDs precipitated zone appeared still relatively transparent, and the written pattern was almost invisible by naked eye under sunlight. With laser pulse energy and repetition rate increased, discernable color of yellow can be observed, which featured the effect of interior coloring. The two conditions can both ensure the possibility of anti-counterfeiting. Two carton pictures of rabbit and butterfly were fabricated at laser pulse energy of 27.8 µJ and repetition rate of 200 kHz (Fig. 7(a)). With excitation of 365 nm UV light, vivid green images clearly appeared (Fig. 7(b)). Apart from carton pictures, any other anti-counterfeiting patterns can also be written in the glass matrix, including characters, two-dimension code, barcode, geometric design, etc.
Fig. 7. CsPbBr3 QDs-embedded glasses with a rabbit and a butterfly fabricated in them (a) under sunlight and (b) UV-365 nm exposure.
This technology has advantages over the traditional anti-counterfeiting methods. Firstly, typical green luminescence related to CsPbBr3 QDs is stable in four seasons and highly tolerant to external temperature variations. So it is effective against unauthorized production. Besides, by using a computer-controlled 3D XYZ stage, laser spatially selective machining with two or three-dimensional copyright patterns can be achieved. In addition, the focusing lens was used to precisely control where QDs formation occurred, and the line width could be reduced down to micron dimension, leading to miniaturization of anti-counterfeiting pattern, hence it is difficult to duplicate. Finally, the combination of high-repetition rate picosecond laser pulses and high-speed scanning systems can realize highly efficient and stable one-step deposition of anti-counterfeiting patterns, providing a rapid, economic and eco-friendly route for mass production of QDs-embedded fluorescent labels for anti-counterfeiting.
4. Conclusion
In conclusion, the one-step precipitation of CsPbBr3 QDs in silicate glass was successfully achieved by picosecond laser direct writing technique. The results showed that high-repetition rate picosecond laser not only provided transient high-temperature field for nucleation, but also generated sufficient heat accumulation to promote the seeds to grow up into CsPbBr3 QDs. By adjusting laser pulse energy and repetition rate, PL intensity, absorption band as well as color appearance could be regulated. Besides, CsPbBr3 QDs encapsulated in glass matrix exhibited excellent resistance against moisture, heat and UV invasion, which was in favor for long-term device operation. On the basis of the great luminescent performance and the notable stability of CsPbBr3 QDs-embedded glass, two demonstrations of light-emitting device and fluorescent labels used for anti-counterfeiting were illustrated, and their advantages were discussed. High-repetition rate picosecond laser, featuring a rapid, economic and eco-friendly route for mass production of stable CsPbBr3 QDs, will advocate more applications in photovoltaic fields such as information storage, three-dimensional display and anti-counterfeit label.
Funding
Shanghai Sailing Program (20YF1455200); National Natural Science Foundation of China (12104470).
Disclosures
The authors declare no conflicts of interest.
Data availability
Data underlying the results presented in this paper are not publicly available at this time but may be obtained from the authors upon reasonable request.
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