Waterproof, self-adhesive and large-area patterned luminescent perovskite-polymer fiber films

doi:10.21203/rs.3.rs-2482387/v1

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Waterproof, self-adhesive and large-area patterned luminescent perovskite-polymer fiber films

https://doi.org/10.21203/rs.3.rs-2482387/v1

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The stable underwater lighting and luminescent displays of metal halide perovskite are being achieved by the perovskite-polymer strategy through the shielding effects of hydrophobic polymer microstructures. However, the investigations of the large-area patterned displays with strong self-adhesions are still restricted. Here, we electrospinning large-area and homogeneous perovskite-polymer fiber films (PPFFs) as the raw plates for pattern processing. Under the microscopic cladding of the hydrophobic polymer fibers, the perovskite nanocrystals embedded in the as-fabricated PPFFs show ultra-stable underwater luminescence for more than 90 days. The fabric strategy also brings PPFFs excellent flexibilities and electrostatic self-adhesions, greatly broadening their stereo-dimensional application scenarios. Importantly, the designed large-area PPFF blocks are fabricated by in situ laser lithography technics instead of mechanical treatments, due to the heat ablation effects of lasers, the electrostatic adhesive layered fibers on the pattern edges are stitched into a whole with higher mechanical stability and better assembling applications. This work provides a facile, low-cost, and effective strategy for stable perovskite luminescent displays, and may promote the light-emitting applications of perovskite materials in the real harsh world.

perovskite-polymer

waterproof

self-adhesive

laser ablation

luminescent display

Metal halide perovskite is becoming a kind of highly efficient material in extensive luminescent applications [1–3], such as narrow emissions [4–5], tunable wavelengths [6–8] and lifetimes [9], as well as lasers [10–14]. Moreover, benefiting from the economical precursors and low-temperature process, perovskite shows great potentiality in commercialized devices of light-emitting diodes (LEDs) and displays. Such as the Lee group reports uniform large-area colloidal perovskite nanocrystal LEDs [15], the Fan group reports large-scale spherical LEDs based on flexible perovskite quantum wire arrays [16], and the Kim group achieves large-area fluorescent arrays by using in situ crystallized perovskite nanocrystals[17].

However, their real applications, especially in large-area devices, are heavily impeded by the quick deterioration in performances over time as a result of their fragile resistance to moisture or water [18–20]. Up to now, much efforts, such as protective coating, single-crystalline phase [21–23], cross-linking of ligand [24–25], and hydrophobic organic chain intercalated layered phase [26–28], have been devoted to the stability issue. Based on these strategies, the moisture resistances in the perovskite community are indeed improved to some extent, but they are all invalid when the devices need working in the aqueous scenario, explained by the fact that perovskite materials and water molecules are not mutually isolated fundamentally, so the consequent quick hydration reaction cannot be stemmed.

Very recently, perovskite-polymer composites are attracting extensive attention on account of their integrated properties from perovskite and polymers. In this strategy, perovskite nanocrystals are designed to grow inside the polymer microstructures to achieve ultra-strong underwater stability, due to the complete micro-space isolation away from the external aqueous scenarios [29–35]. Diverse polymers also render perovskite materials many other improved performances, such as large-area preparation, non-toxic skin-touching, mechanical stretching, and so on. Such as the Lee group reports stretchable and breathable perovskite-polymer composite by using vinylidene fluoride-co-hexafluoropropylene and styrene-ethylene-butylene-styrene [36], the Wang group reports tough, stable, and self-healing luminescent perovskite-polymer matrix by using a copolymer of 2,2,2-trifluoroethyl methacrylate and 2,2,3,4,4,4-hexafluorobutyl acrylate [37], and the Su group demonstrates the water-resistant and stretchable LED based on poly(styrene-butadiene-styrene) fiber membranes [38].

Variable chemical halogens render perovskite efficient multicolor luminescence [6–8, 39–41], and colorful patterned perovskite-polymer strategies also have been proposed very recently, such as inkjet printing [17, 32, 42], swab painting [34], and three-dimensional laser lithography [43, 44]. Although they exhibit well stability and processing procedures in the lab, they are seriously dependent on the substrates and cannot be used as stand-free displays. For example, the painting approaches need subsequent solidifications and may damage the perovskite crystals. Moreover, these strategies are also inferior in massive productions, as well as the self-adhesive applications, especially on curved surfaces. While it is satisfactory to know that the recently proposed perovskite-polymer electrostatic spinning strategies [36–40] may overcome these drawbacks.

In this work, using CH₃NH₃PbX₃ (MAPbX₃) as the illuminants and hydrophobic polymethyl methacrylate (PMMA) as the protective polymer, we fabricate large-area perovskite-polymer fiber films (PPFFs) by industrial electrospinning technics on dissociating substrates. Perovskite nanocrystals are preferentially crystallized inside the polymer fibers, while in the case of superfluous precursors, the redundant crystals will start to overflow and attach to the surface of the fibers. The PPFFs of nanocrystals fully embedded in the polymer fibers show ultra-stable underwater luminescence for more than 90 days. Interestingly, due to the thermal deformation effects of polymer fibers, their temperature-related luminescence exhibits much higher recovery when PPFFs are released from 140 ^oC to room temperature, compared with bared perovskite crystals. Importantly, the designed single-color PPFF blocks can be modularized and mass-produced by laser lithographing the PPFFs through programmed graphics. The outlines of the fabricated patterns are fastened and seamed to a whole due to the laser ablation effects and low melting points of PMMA, which is very positive for mechanical stability and better assembling applications. Moreover, benefiting from the excellent flexibilities and electrostatic self-adhesions, the PPFF patterns do well in stereo-dimensional application scenarios.

2.1 The fabrications of PPFFs.

All chemical reagents are of analytical grade. N, N-dimethylformamide (DMF, 99.9%), lead halide (PbX₂, 99.999%), methylammonium halide (MAX, 99.999%) and polymethyl methacrylate (PMMA, average Mw ~ 15,000 by GPC, powder) are purchased from Sigma-Aldrich. All raw materials are used as received without further purification. The PPFFs are fabricated by electrospinning the composite perovskite-polymer precursor solutions under a high-strength electric field. For the preparation of perovskite-polymer precursor solutions, PbX₂ and MAX of desired concentrations are dissolved in DMF, then, the PMMA is dissolved in the MAPbX₃ solution with vigorously stirring for 5 h at room temperature. Importantly, the as-prepared mixed solutions need to be heated and maintained at 40 ^o C, and then the solutions are loaded into a plastic syringe equipped with a 22-gauge stainless steel needle before the electrospinning procedure. The metal needle is connected to a high-voltage source (16 kV) and maintains a constant 15 cm separated distance away from the collector connected to the ground. Under the driving of the enhancing electric field, the solution is ejected and forms the Taylor cones wherein the PMMA is electrospun to fabric fibers and the precursors crystallized to perovskite nanocrystals. When the collector rotates at 70 rpm throughout the electrospinning process, homogeneous PPFFs can be obtained.

2.2 Basic characterization of PPFFs.

Dark-field optical photographs are captured by using an optical microscope (Nikon ECLIPSE LV100ND). The transmission spectra are tested by a UV-visible spectrophotometer (UV-3600Plus, SHIMADZU). The PL spectra examinations are performed by a microscopic fluorescence spectrometer (Renishaw inVia). The microstructures of the PPFFs are characterized by scanning electron microscopy (SEM, FEI Scios02) and transmission electron microscopy (TEM, FEI Titan Cubed Themis G201). The hydrophobic angle is measured by using an optical contact angle measuring device. The chemical bond characterization is performed by Raman Spectroscopy (HORIBA LabRAM HR Evolution).

2.3 Water-proof and temperature-involved experiments.

For preparations for the long-term water-proof test, PPFFs are tailored into 2×2 cm² hand samples and then fixed to glass substrates. They are soaked in water at room temperature for different durations (day as a unit) without any other operations. We capture their luminescent images and record the PL intensities after these samples are taken out of the water and naturally dried (~ 30 min), at designed underwater timeslots. After characterizations, these samples are soaked in water again for the next underwater timeslots. For temperature-involved PL measurements, the samples are placed in the Linkam THMS600 test stage fully filled with nitrogen. The samples are heated up from room temperature (20°C) to 80°C and then cool down to 20°C for several cycles at a rate of 60°C/min. When the system reaches the designed temperature, it is held for 20 s to ensure stability. When the PL signal acquisitions are complete, the system is modulated to the following temperature state immediately.

2.4 Patterned luminescent PPFFs by laser lithography.

The Spectra-physics laser of 355 nm with ~ 15 um light spot is applied to laser lithography. The working positions and speeds of the focused lasers are designed by the CAD procedures and manipulated by a Galvano-mirror (F511) system. The edges of the patterned luminescent PPFFs can be heat-melted and dissociated from the overall films due to the ablation effects of lasers.

3.1 Fabrications and characterizations of PPFFs.

Figure 1a schematically illustrates the fabrication process of waterproof electrospinning PPFFs and their laser lithographic technic-processed patterned display with good self-adhesions. Details are described in the Experimental Sections. MAPbBr₃ is the main illuminant. PMMA is chosen as the polymer matrix in light of its nontoxic biocompatibility, good flexibility, great hydrophobicity, high transparency, well inter-solubility with perovskite precursor solvent N,-N dimethylformamide (DMF), as well as the low-cost for commercialization. Under the driving of a high-strength electrical field, Taylor cone forms and the crystallized perovskite nanocrystals are preferentially embedded into PMMA micro-fibers. Due to the strong electrostatic adhesion (EA) within these fabric fibers, the PPFFs can be easily mechanically and integrally peeled from the dissociating substrates, forming stand-free composite films. Then the large-area modularized patterns of designed color and outlines can be massively produced by the industrial laser lithographic technic and subsequently used as blocks for assembling multicolor luminescent displays.

As illustrated in Fig. 1b (i), a PPFF easily shows a large area (~ 600 cm²) with homogenous perovskite distribution (the observed colors), as well as the ultra-stable luminescence under a drop of water (inset). As a composite fabric, a piece of PPFF can float on water because of the low density and hydrophobicity of fibers (Fig. 1b (ii)). The electrospun fabric fibers render the patterned PPFFs strong EA with different smooth and roughened materials, such as glass (Fig. 1c (i)), brick wall (Fig. 1c (ii)), and stainless steel (Fig. 1c (iii)), demonstrating wide applied scenarios. As observed in Supplementary Fig. 1, a square-tailored PPFF stands up within a static aqueous scenario, showing strong and homogeneous luminescence. Its dynamic luminescent images captured in a turbulent aqueous scenario (Supplementary Video 1) in Fig. 1d show the robustness of underwater luminescence. The fluorescence microscopy image of a PPFF in Fig. 1e indicates the high-quality cubic perovskite nanocrystal inside the polymer fibers with bright green emission.

All the special performances of PPFFs apart from luminescence originate from the polymer fibers, which exhibit homogenous Fabry-Perot resonances (Fig. 1f (i)) and smooth surfaces (Fig. 1f (ii)). Thus the suitable fiber diameter, represented by the PMMA concentration in DMF (PMMA: XX mg/ml), needs to be confirmed first. As characterized by SEM in Supplementary Fig. 2, the excessively gracile polymer fibers are re-dissolved while the unduly thick fibers are cross-linked as a rigid plate. The gradient results show the flexible and stable fiber microstructures can only be fabricated when the PMMA concentration in DMF is set as 50—100 mg/ml.

3.2 Ultra-stable underwater luminescence and mechanism analysis.

Given diameter-fixed composite fibers, their performances including but not limited to luminescence are modulated by the embedded perovskite nanocrystals. The intuitive observations on the PPFFs (PMMA: 100 mg/ml) in Supplementary Fig. 3 show that along with the increasing precursor concentrations (MAPbBr₃: 2, 10, 20, 50, 100, and 200 mg/ml), besides the clearly redshifted optical color which stemmed from the crystal size-involved bandgap modulation, the PPFF surfaces are also gradually wrinkled due to the weakened EA (Supplementary Video 2). To investigate their underwater luminescence performances, two sets of PPFFs (PMMA: 100 mg/ml and 50 mg/ml) tailored as ~ 2×2 cm² pieces are prepared, shown as Supplementary Fig. 4a and 4b. The normalized Raman spectra in Supplementary Fig. 4c and 4d indicate the perovskite precursors are fully crystallized without residual precursors.

Figure 2a and 2b record two sets of luminescence images of PPFF pieces over the underwater durations, their pristine states exposed to air are displayed as the first column, and the instantaneous water-soaked states (a few seconds) are defined as the 0 day. The redshifted luminescent colors from blue to green in pristine states are explained by the crystal size-involved band-gap modulations (Fig. 2c and Fig. 2f), and corresponding photoluminescence (PL) spectra are recorded in Fig. 2d and Fig. 2g. The PL peaks of the pristine sample in Fig. 2d redshift from 500 to 555 nm (PMMA: 100 mg/ml) and those in Fig. 2g redshift from 500 to 545 nm (PMMA: 50 mg/ml). The shifting differences originate from the varied diameter of the composite fibers (Supplementary Fig. 2), and the thicker ones show broadening luminescence modulations due to the larger crystal sizes in case of broadened volume spaces and surfaces.

Figure 2e and 2h show the normalized PL spectra of 90-day water-soaked PPFFs and their PL ranges are both contracted to 500—535 nm. Figure 2i and Fig. 2j trace the ratios of real-time PL intensities to that of pristine states, their time-resolved PL spectra are recorded in Supplementary Fig. 5 and Fig. 6. Intuitively, the luminescent intensities of PPFFs fabricated from lower-concentrated precursors (MAPbBr₃: 2, 10 and 20 mg/ml) is not influenced by water at all, both in wavelengths and intensities. While the PPFFs processed in higher-concentrated precursors (MAPbBr₃: 50, 100 and 200 mg/ml) show blue-shifted luminescence with narrower PL spectra, as well as the evident intensity enhancements.

Such changed underwater luminescence performances in PPFFs of varied precursor parameters should be explained by the different distributions of perovskite nanocrystals over the polymer fibers. As illustrated in Fig. 1a, perovskite nanocrystals are preferentially crystallized inside the polymer fibers during the electrospinning process. While in the case of the superfluous precursors, the polymer fibers are gradually fulfilled, thus the overflowed crystals can only attach to the surface of polymer fibers, meanwhile, their sizes can reach microscales without nanoscale space limitations. As we all know, the perovskite PL intensity is negatively related to the crystal size, but the transition band-edge is positively related to it. Thus the brighter luminescence emitted from the internal nanocrystals is almost re-absorbed as the excitation sources by the microcrystals on the surface of composite fibers (MAPbBr₃: 50, 100 and 200 mg/ml), also causing the decrease of the total luminescence intensity (the pristine states in Fig. 2a and 2b). Thus the significant underwater luminescence enhancement is due to the surface perovskite microcrystals being hydrated and washed off by water, and then the internal brighter luminescence can emit into the free space. The PPFFs (PMMA: 100 mg/ml) show higher enhancement ratios due to the clear away of the larger-sized microcrystals from the surfaces. Such enhancement effect is almost instantaneous and irreversible, as Supplementary Video 3 recorded (MAPbBr₃: 200 mg/ml). The surface microcrystal hydration reactions also account for the narrower PL spectra due to the more homogenous size distributions of the internal perovskite nanocrystals.

More direct characterizations and analysis are discussed in Fig. 3. Here the case of nanocrystals fully embedded inside the polymer fibers is represented by the PPFFs (MAPbBr₃: 20 mg/ml), and the case of overflowed microcrystals attached to the fiber surface is illustrated by the PPFFs (MAPbBr₃: 200 mg/ml). Figure 3a display two sets of contrastive scanning electron microscope (SEM) images between pristine PPFFs ((i) MAPbBr₃: 20 mg/ml; (ii) MAPbBr₃: 200 mg/ml) and water-soaked ones ((iii) MAPbBr₃: 20 mg/ml; (iv) MAPbBr₃: 200 mg/ml). The PMMA concentration is 100 mg/ml in Fig. 3a and the analogous characterizations of PPFFs (PMMA: 50 mg/ml) are presented in Fig. 3b. The comprehensive SEM characterizations of total pristine PPFFs (MAPbBr₃: 2, 10, 20, 50, 100 and 200 mg/ml) are displayed in Supplementary Fig. 7 (PMMA: 100 mg/ml) and Fig. 8 (PMMA: 50 mg/ml), and they show that the crystals start to overflow when the MAPbBr₃ concentration reaches 50 mg/ml. That of water-soaked PPFFs are displayed in Supplementary Fig. 9 (PMMA: 100 mg/ml) and Fig. 10 (PMMA: 50 mg/ml). The unchanged water-soaked states (iii) compared with the pristine ones (i) indicate the perovskite nanocrystals embedded inside the polymer fibers are perfectly protected, while the stick-shaped PbBr₂ crystals along the fibers (iv) indicate the surface square perovskite crystals (ii) can be easily hydrated in the aqueous scenario. By the way, the composite fibers with superfluous perovskite crystals may be fractured due to the thinner fiber diameter, proven by Fig. 2b (ii).

The perovskite crystal characterizations and distributions can be much more clearly seen by the transmission electron microscope (TEM). Figure 3c (i) and 3d (i) display the longitudinal sectional TEM views of a single composite fiber from Fig. 3a (i) and 3a (ii), respectively. The high-resolved TEM (HRTEM) characterizations in a tiny area of the composite fiber are displayed in the right panel. The bright sections indicate the distributions of perovskite lattices as the strong electron scattering of heavy metal lead, and the dark ones indicate the polymer matrix. In Fig. 3c, the protective polymer layer (indicated by the solid blue square) at the edge of the composite fiber can be clearly seen, while such a polymer layer is covered by the overflowed surface microcrystals in Fig. 3d. Different from the polycrystalline nanocrystals inside the fibers, the surface crystals reach microscale at ~ 1 µm. The lattices can be clearly characterized by the HRTEM with d(110) at 2.95Å.

Due to the hydrophobicity of the esters, the micro-structured fabric PPFFs show considerably large water contact angles at 120^o—130^o. Figure 3e and Fig. 3f respectively capture the instantaneous examined results for PPFFs of pristine and water-soaked dry states (i, MAPbBr₃: 20 mg/ml; ii, MAPbBr₃: 200 mg/ml). The comprehensive instantaneous hydrophobic characterizations of total pristine and water-soaked dry PPFFs (MAPbBr₃: 2—200 mg/ml) are displayed in Supplementary Fig. 11 (PMMA: 100 mg/ml). The unchanged water contact angles after water-soaking are explained by their fabric microstructures are not affected even though the surface-contacted crystals are all hydrated in the aqueous scenario. Moreover, the instantaneous constant water contact angle independent of the crystal distribution (Supplementary Fig. 11a) indicates that the instantaneous hydration reaction is relieved by the hydrophobic polymer fibers when crystals encounter a trace amount of water. Supplementary Fig. 12 shows the real-time hydrophobic examinations of PPFFs (MAPbBr₃: 50, 100 and 200 mg/ml). Their time-resolved water contact angles drawn in Fig. 3g show that the PPFFs of thicker fibers (PMMA: 100 mg/ml) exhibit prolonged hydrophobic durations mainly due to the less-amount surface overflowed crystals (Supplementary Fig. 7 and Fig. 8).

3.3 Temperature-related luminescence.

The polymer fibers in PPFFs provide strong protection for the embedded perovskite nanocrystals against the hydration reaction in the aqueous scenario. However, whether they can maintain stable performance under temperature-varied conditions stills need to be investigated. Given that they are applied in an aqueous medium, thus the temperature range sets as 20—80 ^oC, and the PL intensities at 20 ^oC are normalized to 1 for intuitive comparison. The luminescence examinations versus varied temperatures are carried out in Fig. 4 and details are described in the Experimental Section. The bare perovskite nanocrystal sampled in Fig. 4a shows the negative temperature-related PL intensities which are mainly caused by the suppressed carriers trapping by defect states under lower temperatures. The 100% luminescence recovery at 20 ^oC after twice heating-cooling cycles indicates the perovskite crystals are not damaged. Although the polymer fibers are introduced as the protective cover in PPFFs, the heat conductions cannot be impeded due to the polymer cladding layers being non-vacuum. Thus all the PPFFs in Fig. 4b (PMMA: 100 mg/ml) and Fig. 4c (PMMA: 50 mg/ml) show almost unchanged luminescence performances, disregarding the varied perovskite distributions. The raw PL spectra of Fig. 4a are recorded in Supplementary Fig. 13, and that of PPFFs are traced in Supplementary Fig. 14 (PMMA: 100 mg/ml) and Fig. 15 (PMMA: 50 mg/ml).

Although the PMMA polymer fibers cannot stop heat conduction, they render perovskite crystals away from the pyrogenic decompositions under a higher temperature. Figure 4d displays the contrastive PL intensities recovery at 20 ^oC of bared perovskite nanocrystals and PPFFs of nanocrystals totally embedded in fibers (PMMA: 50 mg/ml, MAPbBr₃: 20 mg/ml) after going through a heating process from 20 to 140 ^oC. As recorded by black circles, the faint ~ 10% luminescence recovery at 20 ^oC indicates the pyrogenic decompositions of bare perovskite nanocrystals under higher temperatures (80—140 ^oC). While the embedded perovskite nanocrystals inside the composite fibers show ~ 80% recovery due to the environmental heat being mainly absorbed by the polymer thermal deformations. Thus the real temperatures of the perovskite nanocrystals are much lower than the around environments. The raw temperature-related PL spectra are traced in Supplementary Fig. 16.

3.4 Colorful and large-area PPFF patterns.

The tunable halogen in perovskite materials renders PPFFs a high possibility for colorful displays. Figure 5a shows the transmitted spectra from PPFFs of six different haloid constituents, their normalized PL spectra in Fig. 5b can easily cover the visible range from cyan to green and then red. The corresponding luminescent images of ~ 600 cm² PPFFs with excellent brightness and uniformity are photographed in Fig. 5c. Under the requirements of water-proof and great self-adhesion, the perovskite precursor concertation is fixed at 20 mg/ml and PMMA is set as 100 mg/ml.

For the preparations of the large-area PPFF patterns, mechanical processing may be preferred. While according to the SEM images in Fig. 1 and Fig. 3, PPFF is formed of multiple fibers arranged in layers, and despite the strong EA within these layered fibers, PPFF can be dissociated by external mechanical forces. As the side views of Fig. 5d (i) show, layer separation can be clearly seen on the edge of a pattern and it is negative for real applications. So we need to turn to another strategy, recently, the laser lithography technic is being proven as an effective method for modularization-producing [43, 44]. The nature of such a processing strategy is in situ material heat ablation under hot lasers, becomingly, the polymer fiber shows a considerable advantage for its lower melting point (~ 150 ^oC). Figure 5d (ii) displays a side view of the same pattern processed by the laser lithography. To be satisfactory, the EA-bonded fibers on the edges are re-solidified into a whole after going through a heat-melted process, namely, the edges are stitched with higher mechanical stability, which is very positive for real applications. Although the edges are physically modified, the PPFF patterns still show well EA performances, as shown in Supplementary Fig. 17 and Fig. 1c. It should be noted here that we exploit the thermal effect of the laser ablations to solve the problem of edge separations of the patterns rather its high-resolution feature in the large-area pattern processing.

Figure 5e shows the processed luminescent images of the green word logo CHINA and cyan Roman numerals with distinct outlines. Larger-size complex patterns, such as the red Chinese knot, and multi-color assembling flower can also be easily fabricated, as the luminescent images displayed in Fig. 5f. Due to the edges of the blocks being stitched into a whole, thus the mutual electrostatic adhesion can be avoided within the blocks. Despite these two-dimensional pattered luminescent displays, the laser lithography-processed patterned PPFF can also be used for stereo-dimensional luminescence displays due to its excellent electrostatic self-adhesive performances. The successful adhesion to a celluloid ball with a diameter of ~ 3 cm has been achieved in Fig. 5g, exhibiting bright and stereo luminescence displays. The arbitrary color-variation and diversiform laser-processed pattern blocks, as well as the perfect water-proof and good self-adhesion, both render the PPFFs extensive and stable luminescent displays in the real stereo world.

In summary, this work demonstrates the large-area two/three-dimensional waterproof single/multi-color luminescent patterns of perovskite-polymer materials, along with excellent flexibility and good electrostatic self-adhesion. Due to the waterproof fabric microstructures, the PPFFs of perovskite nanocrystals totally embedded show ultra-stable underwater luminescence for more than 90 days. In addition to the perfect water resistance, such polymer microstructures also protect the perovskite nanocrystals away from thermal decomposition at high temperatures (80—140 ^oC), explained by the thermal deformations of the polymer. Importantly, we proposed laser lithography as the processing strategy for the PPFF patterns to solve the problem of edge separations of the patterns, enhancing the mechanical stability and assembling applications. In a word, we are exploring the commercialization of waterproof and self-adhesive color-patterned perovskite luminescence based on industrial electrospinning and laser lithography technics, and we anticipate that our strategy will have a favorable effect on the practical application of perovskite displays.

Author contribution Zhen Yu Zhang, Yan Ming Sun, and Guo Ping Wang conceived the idea and designed the research. Ying Chen and Zhen Yu Zhang prepared the materials, fabricated the PPFF samples, and performed the experiments and optical analysis. Yan Ming Sun and Zhen Yu Zhang performed the structural characterizations and analysis. All the authors contributed to the writing of the paper.

Acknowledgements The authors wish to acknowledge the assistance on HRTEM observation received from the Electron Microscope Center of Shenzhen University.

Funding This study is supported by the National Key Research and Development Program (NKRD) (Grant Nos. 2022YFA1404500), National Natural Science Foundation of China (NSFC) (Grant Nos. 62005183, 12074267), Science and Technology Planning Project of Guangdong Province (2020B010190001), and Guangdong Natural Science Funds Grant (2021A1515012069).

Conflict of Interest The authors declare no competing interests.

Supporting Information The online version contains supplementary material available at

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No competing interests reported.

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Waterproof, self-adhesive and large-area patterned luminescent perovskite-polymer fiber films

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Abstract

Figures

1. Introduction

2. Experimental Section

2.1 The fabrications of PPFFs.

2.2 Basic characterization of PPFFs.

2.3 Water-proof and temperature-involved experiments.

2.4 Patterned luminescent PPFFs by laser lithography.

3. Results And Discussion

3.1 Fabrications and characterizations of PPFFs.

3.2 Ultra-stable underwater luminescence and mechanism analysis.

3.3 Temperature-related luminescence.

3.4 Colorful and large-area PPFF patterns.

4 Conclusion

Declarations

References

Additional Declarations

Supplementary Files

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