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Preparation and Application of Lead Halide Perovskite-Polymer Composites

Jingjing Xiao , Mu Wang , Weijie Zhang , Xiuying Zhao , Anchao Feng , Liqun Zhang

Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (10) : 1731 -1740.

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Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (10) : 1731-1740 DOI: 10.7536/PC200904
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Preparation and Application of Lead Halide Perovskite-Polymer Composites
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Abstract

With excellent photoelectric properties, lead halide perovskite nanocrystals(NCs) show great potential in solar cells, photoelectric detection, biological imaging and other fields. However, the poor stability of lead halide perovskite NCs restricts practical applications. Within a few years, many strategies have been developed to solve the problems of poor stability of perovskite NCs, such as ion doping, surface passivation and surface cladding. Noteworthily, it is an effective strategy developed recently that enhance the stability of perovskite by embedding perovskite NCs into polymer and preparing perovskite-polymer composites. Specially, the dense polymer matrix endows the lead halide perovskite NCs with excellent water stability. This review summarizes the preparation of perovskite-polymer composites and their applications in the fields of light-emitting devices and biomedicine. At the same time, the preparation methods of perovskite-polymer composites are discussed in details, which can be classified into three types: blending, in-situ polymerization and in-situ perovskite growth/precipitation method. These methods will be a guide to overcome the limitation of perovskite NCs and impel the development of their practical application. In addition, the existing problems for encapsulating perovskite NCs into polymer matrix are highlighted, while some suggestions for further improving the performance of perovskite-polymer composites are discussed. Finally, the future development of perovskite-polymer composites is prospected.

Contents

1 Introduction

2 Preparation of lead halide perovskite-polymer composites

2.1 Blending method

2.2 In situ polymerization method

2.3 In situ perovskite growth/precipitation method

3 Application of lead halide perovskite-polymer composites

4 Conclusion and outlooks

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Keywords

lead halide perovskite / nanocrystals(NCs) / polymer / composites / light-emitting devices / biomedical

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Jingjing Xiao, Mu Wang, Weijie Zhang, Xiuying Zhao, Anchao Feng, Liqun Zhang. Preparation and Application of Lead Halide Perovskite-Polymer Composites. Progress in Chemistry, 2021, 33(10): 1731-1740 DOI:10.7536/PC200904

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1 Introduction

perovskite originally refers to perovskite oxide, the chemical formula of which was first discovered by Russian scientist Gustav Rose in the Ural Mountains CaTiO3,1839. Later, a class of substances with similar crystal structure to CaTiO3 were collectively called perovskite. Since Kojima et al applied organic-inorganic hybrid lead halide perovskite (CH3NH3PbI3) as a dye sensitizer in solar cells in 2009, a large number of studies began to focus on lead halide perovskite[1][2,3]. The molecular formula of the lead halide perovskite can be expressed as APbX3, and the crystal structure is shown in Figure 1, wherein cation A,Uch as Cs+, CH3 NH 3 + (MA+),The CH(NH2 ) 2 + (FA+) is located at the vertex of the face-centered cubic lattice,The Pb2+ is located at the core of the octahedron, and the X is located at the vertex of the octahedron, and represents a halogen Br-, a U Cl- and a U I- which can coordinate with A.
Lead halide perovskites, as a new class of optoelectronic materials, have attracted much attention due to their high luminous efficiency, high absorption coefficient and high exciton binding energy, and have been widely used in solar cells, light-emitting diodes (LEDs), lasers and photodetectors[4][5][6][2,7,8][4,9][10,11][12,13]. However, perovskites exhibit excellent photoelectric properties, while their inherent ionic properties and low formation energy make them unstable in the environment, which to some extent hinders their development[14⇓⇓~17]. The results are as follows: 1) NCs of perovskite perhalides are highly sensitive to polar solvents; 2) The properties of lead halide perovskite are easily affected by light, oxygen and heat in the environment; 3) When two lead halide perovskites with different compositions are mixed, anion exchange will occur, resulting in the shift of photoluminescence (PL)[18,19].
In recent years, various strategies have been proposed to improve the stability of perovskite NCs, such as ion doping, surface passivation and surface coating, which are briefly introduced as follows[20⇓~22]. 1) ion dope. Proper ion doping can change the crystal structure and electronic structure of lead halide perovskite, which can effectively improve its stability. In 2017, Zou et al. Found that doping with Mn2+, Cd2+ and Zn2+ can effectively improve the formation energy of lead halide perovskite, and the stability of lead halide perovskite has also been improved[23]. In 2019, Mondal et al. Doped Cd2+ into CsPbCl3NCs, which can greatly increase the photoluminescence quantum yield (PLQY) of CsPbCl3NCs from 3% to 98%[24]. 2) Surface passivation. Perovskite is an ionic crystal, and the ligand is easy to fall off from the surface. Surface passivation can be used to reduce surface defects and enhance the stability of perovskite. In 2017, Liu et al. Prepared trioctylphosphine (TOP) passivated CsPbI3 quantum dots, which can achieve nearly 100% PLQY and have high stability, and will not agglomerate in an open environment for a month[25]. In 2018, Li et al introduced silver-based passivator silver trioctylphosphine (Ag-TOP) to form an AgBr passivation layer on the surface of CsPbBr3, which improved the photothermal stability of CsPbBr3NCs[26]. 3) surface coating. Surface coating is an effective method to improve the stability of perovskite, which can isolate the lead halide perovskite NCs from the external environment.Currently, the coating materials are mainly inorganic salts, inorganic oxides, perovskite materials, macromolecules or polymers[27,28][29⇓⇓~32][33,34][35,36]. In 2018, Wei Yi and others used CaF2 microspheres to coat the CsPbX3NCs to isolate it from the external environment, thereby improving its stability[37]. In the same year, Zhong et al. Prepared nanoparticles with core-shell structure, and the shell of CsPbBr3@SiO2,SiO2 can effectively protect the CsPbBr3NCs[38].
Among the strategies described above, the method of coating perovskite NCs with polymers, i.e., the method of preparing perovskite-polymer composites, has become one of the effective ways to improve the stability of perovskite NCs. Lead halide perovskite-polymer composites have attracted much attention because they have the properties of both lead halide perovskites and polymers: on the one hand, perovskites endow polymers with excellent optical properties[39,40]; On the other hand, the polymer matrix improves the environmental stability and processability of the lead halide perovskite NCs. At present, a variety of polymers, including polystyrene (PS), polymethylmethacrylate (PMMA) and polycarbonate (PC), have been used to improve the stability of perovskite, and the perovskite-polymer composites prepared have shown broad prospects in optoelectronic devices, biomedicine and other fields[41,42][43,44][45].

2 Preparation of lead halide perovskite-polymer composites

At present, the preparation methods of perovskite-polymer composites mainly focus on blending, in-situ polymerization and in-situ perovskite growth/precipitation. Wherein, the blending method refers to preparing the perovskite NCs and the polymer separately, and then mixing the perovskite NCs and the polymer so that the perovskites NCs are embedded in the polymer; in-situ polymerization (in situ polymerization) refers to the method of synthesizing perovskite NCs and dispersing them in monomer solution, and then encapsulating perovskite NCs in polymer with the polymerization of monomer. in situ perovskite growth/precipitation (in situ perovskite growth/precipitation) generally means that the polymer is prepared first, and the perovskite NCs are synthesized in the process of compounding with the polymer. In short, the main difference between these three methods lies in the sequence of perovskite NCs and polymer synthesis.

2.1 Blending method

Blending is the first method to prepare perovskite-polymer composites. In this method, the preparation of perovskite NCs alone can ensure that the morphology and size of NCs can be well controlled, but the structure and properties of perovskite NCs are easily affected by the external environment, so it may be necessary to protect them before mixing with polymers.

2.1.1 Preparing composite film material by blending method

In general, a perovskite-polymer composite thin film can be directly obtained by dropping and coating a solution containing perovskite NCs and a polymer on a substrate. In 2015, Pathak et al. mixed pre-prepared MAPbX3 quantum dots (QDs, semiconductor nanocrystals) with PS and PMMA, and spin-coated the mixed solution on a glass substrate to form a dry film[44]. They observed that embedding NCs into the polymer matrix could prevent anion exchange, resulting in relatively stable perovskite-polymer composites and maintaining specific emission spectra. In 2016, Raja et al. Mixed CsPbBr3QDs with different nanostructures (zero-dimensional cubes, one-dimensional nanowires and two-dimensional nanoplates) into large-size hydrophobic PS, poly (styrene-ethylene-butylene-styrene) (SEBS) and poly lauryl methacrylate (PLMA).Then the mixed solution is cast on a glass slide and dried, and the prepared perovskite-polymer nano composite film has excellent water stability and light stability[46]. In the same year, Song et al. Prepared a composite film of ethyl cellulose (EC)[47]. In 2016, Wei et al encapsulated the CsPbX3QDs with flexible epoxy resin (EP), and the resulting composite showed good stability in air and water environments. PLQY could maintain more than 30 days in air and more than 85% of PL strength in water for 10 days[48].

2.1.2 Preparing composite fiber material by blending method

In addition to the typical thin film preparation technology, electrospinning technology has received extensive attention in recent years, and is considered to be a powerful tool for the preparation of nanofibers. Electrospun nanofibers can be used as an effective matrix for functional materials, such as metal nanoparticles and QDs, to prepare composite fibers for various device applications[49,50]. In 2016, Wang et al. Prepared PS fiber membranes encapsulating CsPbBr3QDs by electrospinning, and proved their stability in water and ethanol media[51]. In 2018, Satoh et al. Added CsPbX3NCs to poly (styrene-butadiene-styrene) (SBS) to prepare a mixed solution, and then embedded the CsPbX3NCs into SBS fibers by electrostatic spinning to prepare fiber films with various luminescent colors, as shown in Figure 2[52].

2.1.3 Preparation of Monodisperse Micron/Nano Composites by Blending

The perovskite NCs are embedded in macroscopically sized polymers to prepare luminescent thin films or bulk materials with good stability. Researchers have also explored some effective methods to protect the monodisperse nano/micro perovskite NCs to obtain stable monodisperse perovskite nanocomposites. In 2017, Cheng et al. Prepared high luminescent CsPbBr3-PS and CH3NH3PbBr3-PS composite microspheres with uniform morphology by swelling-shrinking strategy[41]. The process is carried out only in nonpolar toluene and hexane without the addition of any polar reagents. The prepared composite microspheres not only have high luminescent performance, but also have excellent water resistance. The composite still glows strongly after being immersed in water for nine months. In addition, even in harsh environments such as acid-base aqueous solution, phosphate buffer solution and the like, the luminescent material can still maintain high luminescent intensity. In 2018, Yang et al. Successfully prepared CsPbBr3@PS microspheres with uniform morphology from CsPbBr3-PS mixed solution by electrospray process (Figure 3), which not only retained the excellent luminescent properties of CsPbBr3QDs, but also had good anti-anion exchange and water stability[42]. After being immersed in water for 30 days, the CsPbBr3@PS microspheres still had strong luminescent properties. When they were in contact with KI solution, the PL intensity changed little, and the PL wavelength did not change after 9 H. In 2012, Liu et al. Chemically modified the surface of colloidal CsPbBr3 nanowires with an amphiphilic block copolymer, polystyrene-poly (4-vinylpyridine) (PS-b-P4VP)[53]. The obtained nanowire presents a core-shell shape, has enhanced luminescence intensity, and has water resistance and stability against anion exchange. Taking advantage of the enhanced stability, they further applied the improved Langmuir-Blodgett technique to assemble monolayers of highly oriented nanowires and studied the anisotropic optical properties.

2.2 In-situ polymerization

In general, there are few studies on the preparation of lead halide perovskite-polymer composites by in-situ polymerization. In 2017, Sun et al. Introduced 4-vinylbenzyl-dimethyl octadecyl ammonium chloride ligand (V18) on the surface of perovskite NCs, and the surface ligand V18 containing styryl provided opportunities for crosslinking and polymerization on the surface of perovskite NCs[54]. Then NCs-V18 was copolymerized with styrene and methyl methacrylate to obtain a composite with good transparency, which indicated that NCs-V18 had good compatibility with the polymer matrix. At the same time, the composites showed good processability and excellent water resistance, and could be molded into cylinder, cube, triangular prism and other shapes.After being immersed in water for 90 d, the PL strength almost did not change. In 2018, Xin et al. First dropped the perovskite precursor solution into the monomer solution to generate a CsPbBr3NCs (or a CH3NH3PbBr3NCs) which was uniformly distributed in the monomer solution, and then successfully prepared the perovskite-polymer composite by photo-initiated or thermo-initiated polymerization, as shown in Figure 4[43]. The resulting composite maintained PLQY (> 70%) in air for more than 1 month. This technology combines the formation of perovskite NCs with the polymer matrix in a one-pot reaction, avoiding the tedious separation and preparation of perovskite. PMMA, PS and poly (butyl methacrylate) (PMBA) were also used in the experiment, which showed that the method was applicable to most of the commercially available monomers and polymers. The absence of organic solvents in the preparation process (only a small amount of dimethylformamide (DMF) is needed to dissolve the perovskite precursor) is a highlight of this experiment, which indicates that the preparation of the composite is a green technology.
In some studies, perovskites have also been used as photocatalysts or photoinitiators in the synthesis of polymers. For example, CsPbI3QDs acts as a catalyst to promote the polymerization of 2,2 ', 5', 2 -trimethyl-3,4-ethylenedioxythiophene under visible light, while the resulting conductive poly (3,4-ethylenedioxythiophene) (PEDOT) encapsulates the CsPbI3QDs in the polymer network and stabilizes the morphology of the CsPbI3QDs[55]. In 2018, Tan et al. Used CsPbBr3NCs as a photoinitiator for the polymerization of vinyl monomers (such as PS and PMMA) to initiate the growth and polymerization of free radical chains on the surface of perovskite NCs under white light (Fig. 5), resulting in a high molecular weight polymer of about 200 kDa[56]. By in-situ growth of polymer chains on the surface of perovskite NCs, the CsPbBr3 can be encapsulated in the polymer matrix to form monodisperse nanoparticles, and the PLQY can be significantly improved.

2.3 In-situ perovskite growth/precipitation method

Currently, the most widely used method for the preparation of perovskite-polymer composites is in-situ perovskite growth/precipitation. This method not only avoids the need of pre-synthesis and post-treatment of perovskite NCs, but also avoids the damage to perovskite NCs caused by the polymerization process of monomers, thus protecting the stability of perovskite-NCs to the greatest extent.

2.3.1 Preparation of composite thin films and bulk materials by in-situ perovskite growth/precipitation method

Perovskite-polymer composite thin film materials and bulk materials have been prepared by embedding in-situ generated perovskite NCs into macroscopic, pre-synthesized polymers, which is inexpensive and easy to implement. In 2017, Kim et al. Used the porous template formed by gold nanoparticles (AuNPs) in polydimethylsiloxane (PDMS) to grow MAPbX3 in situ and prepare MAPbX3-PDMS composite films[57]. Firstly, a thin film composed of AuNPs and PDMS is prepared, then the AuNPs in the composite film are selectively etched by aqua regia (a mixture of nitric acid and hydrochloric acid with a molar ratio of 1:3, < 42%) to obtain a PDMS template for MAPbX3 growth, and then the PDMS template is immersed in a perovskite precursor solution, so that the MAPbX3NCs can grow in the pores previously occupied by the AuNPs, and the size of the perovskite NCs is controlled by the size of the Au NPs. This polymer template method can effectively prevent the aggregation and degradation of perovskite NCs, and the stability of perovskite NCs is also improved because PDMS prevents direct contact with the surrounding environment. The perovskite precursor can be introduced into the polymer matrix as a solute through a solvent-induced polymer swelling process, and when the solvent is volatilized from the polymer, the perovskite precursor will remain in the polymer matrix to react to form high-quality, well-dispersed perovskite nanoparticles. In 2016, Wang et al. Used this process to prepare six kinds of composite films, including MAPbBr3-PS, MAPbBr3-PC and MAPbBr3- acrylonitrile-butadiene-styrene (ABS) (Figure 6a)[45]. The composite films, except for the MAPbBr3-PMMA, had excellent water stability, with more than 93% of the original PLQY remaining after 2 months of immersion (fig. 6B). In terms of thermal stability, the PL intensities of the MAPbBr3-PS and the MAPbBr3-PC were fully restored after heating to 100 and 110.d egree. C., respectively (fig. 6C). For the MAPbBr3-ABS film, the brightness of perovskite decreases after cooling from 100 ℃, which may be caused by the degradation of the substrate. In the same year, Zhou et al. Prepared MAPbBr3/PVDF composite membranes in situ by controlling the evaporation of DMF to separate polyvinylidene fluoride (PVDF) and the crystallization of MAPbX3[58]. The strong interaction between the — NH 3 + groups in the MAPbBr3 and the —CF2— groups in the PVDF results in good compatibility between the PVDF matrix and the MAPbX3NCs prepared in situ. The resulting composite film showed enhanced PL properties with PLQY increased to (94.6 ± 1)% and improved stability against water and UV radiation. In 2016, Li et al. First dissolved EVA in toluene, then quickly added the perovskite precursor solution composed of PbBr2, CsBr, ligand and solvent to the EVA-toluene system, and prepared CsPbBr3QDs/EVA composite films after natural drying[59]. The key point of the preparation is that both the supersaturation recrystallization of the CsPbBr3QDs and the dissolution of EVA can be realized in toluene, that is, toluene can be used not only as a solvent for EVA, but also as a precipitant for CsPbBr3 in the process of supersaturation recrystallization. Benefiting from the effective protection of the EVA matrix to the CsPbBr3QDs, the prepared CsPbBr3QDs/EVA film has long-term stable luminescent characteristics in air and water. In addition, the film is flexible enough to be bent repeatedly for 1000 cycles while maintaining the same luminous intensity. In some studies, perovskite-polymer composite films with water and oxygen stability were prepared by solution spin coating with polymer added to the perovskite precursor solution[60⇓⇓~63]. In 2018, Tan Zhanao et al prepared a mixed solution containing perovskite precursor and polyethylene oxide (PEO), and then spin-coated the mixed solution on a ITO/NiOx substrate at a speed of 4000 R/min for 35 s in a nitrogen-filled glove box, and annealed at 80 ℃ for 10 min to prepare perovskite-polymer composite films[60,61]. Inspired by the room temperature perovskite reprecipitation technique, taking advantage of the porous structure of the gel, Zhang et al. Prepared CH3NH3PbBr3 quantum dots in situ and embedded them into the hydrophobic polyacrylate matrix to prepare bulk luminescent organogels[39]. The perovskite-type organic gel shows high stability at different pH values and temperatures, and can still maintain high PLQY after being soaked in water for more than 110 days. Perovskite-type organogels with different mechanical properties (from 950% gel with high elongation to 110 MPa gel with high stiffness) were obtained by changing the polymer matrix.

2.3.2 Preparation of composite fiber materials by in-situ perovskite growth/precipitation method

Some studies have focused on embedding in-situ grown/precipitated perovskite NCs into polymer fibers to improve the stability of the perovskite. In 2017, Ma et al. Established a microreactor for continuous production of perovskite NCs/PMMA nanocomposites by microfluidic spinning technology, synthesized CsPbX3NCs in situ and embedded them into PMMA[65]. No toxic solvent waste containing heavy metal ions is produced in the production process. The prepared CsPbX3NCs/PMMA fiber has good optical performance, tunable emission in the range of 450-625 nm, narrow FWHM of 18-42 nm, high color purity, high PL stability and good processability. In 2018, Chen et al. used perovskite precursor solution as the core, polymer solution as the shell, and coaxial electrospinning technology to wrap the in-situ formed MAPbX3 in polyacrylonitrile (PAN), and the MAPbX3/PAN composite nanofibers formed had a high PLQY of 30.9%[65]. In addition, due to the hydrophobic properties of the shell polymer, the nanofibers have high water resistance, and their PL strength remains unchanged after being stored in an environment with a relative humidity of 85% for one month, and their PL strength still remains more than 50% of the initial strength after being immersed in water for 48 H.

2.3.3 Preparation of monodisperse nanocomposites by in-situ perovskite growth/precipitation method

Surface ligands affect the fluorescence properties and stability of QDs[66]. Polymers are also widely used as ligands to stabilize perovskite NCs, and block copolymers can self-assemble to prepare monodisperse nanocomposites with different morphologies (such as vesicles, nanorods, etc.). In 2016, Meyns et al. Added polymaleic anhydride-1-octadecene (PMA) to the synthesis of CsPbX3NCs[40]. PMA has been shown to be an ideal ligand for encapsulating CsPbX3NCs coated with oleic acid or oleylamine, limiting the interaction between the surface of perovskite NCs and the surrounding medium, and thus improving the stability of the CsPbX3NCs. Graphene oxide grafted polyacrylic acid (GO-g-PAA) can also be used as a surface ligand to mediate the synthesis of perovskite NCs. In 2017, Pan et al. Grown CsPbBr3NCs on the surface of GO-g-PAA, and then obtained ternary CsPbBr3NC-GO-g-PAA hybrids[67]. Subsequently, the CsPbBr3NC-GO-g-PAA were self-assembled into nanorods by solvent induction (fig. 7), and the nanorod structure provided a good encapsulation for perovskite NCs, giving perovskite NCs superior environmental stability and anti-anion exchange ability. In the same year, Hou et al. Prepared perovskite-polymer nanomicelles with core-shell structure[68]. Polystyrene-b-poly (2-vinylpyridine) (PS-b-P2VP) acts as a confined nanoreactor during the crystallization of CsPbBr3, which significantly improves the photostability of CsPbBr3 in polar solvents through the combination of multi-dentate pyridine groups with perovskite NCs. Zhang et al. Selected polyvinylpyrrolidone (PVP) as a capping ligand to form a protective layer on the surface of in-situ perovskite NCs, which stabilized the particle size of perovskite NCs at about 30 nm[69]. The perovskite NCs were then embedded into polystyrene microspheres (MHSs) by assembling PS chains on them. The obtained luminescent CsPbX3NCs@MHSs has no toxicity and high water stability, and can be used as a probe for biological imaging. In 2018, Yang et al. Dropped a perovskite precursor solution composed of PbBr2 and MABr into a toluene solution of polystyrene-polyoxyethylene block copolymer (PS-b-PEO), and immediately observed a green colloidal solution.PS-b-PEO grafted MAPbBr3QDs were successfully prepared, and then self-assembled into well-defined vesicular nanostructures with PLQY of 43%, high color purity and average PL lifetime of 164 ns by precipitation in n-hexane and hydration in water, respectively[70]. The obtained perovskite nanostructure also shows excellent thermal stability and photostability in water, has low cytotoxicity, and shows a bright prospect in cell imaging.

3 Application of Perovskite-Polymer Composites

The dense polymer matrix plays a good role in protecting the perovskite NCs, improves the instability problem of the perovskite NCs in application, and prolongs the service life of the luminophor. The prepared perovskite-polymer composite materials have great potential in the fields of solar cells, light-emitting device preparation, biomedicine and the like.
The application of perovskite-polymer composites in the field of solar cells has attracted much attention. In 2015, Su et al. First incorporated a polymer additive into the perovskite precursor solution to adjust the morphology of the perovskite layer during film formation[71]. The experiments show that polyethylene glycol (PEG) additive can delay the growth and aggregation of perovskite NCs, so that the perovskite-polymer composite film with few voids and high coverage can be prepared.When it is used in perovskite solar cells with planar heterostructure, the functional conversion efficiency (PCE) is improved from 10. 58% to 13. 20%. In 2016, Zhao et al. Prepared perovskite solar thin films with the same PEG additive, with a PCE of 16%, which showed strong self-healing or waterproof effect under steam spray[63]. The perovskite film and the corresponding device can be rapidly restored to their original state and performance after being subjected to vapor spraying and drying in air.
LEDs can efficiently convert electrical energy into light energy, and have a wide range of uses in modern society, such as lighting and displays. Perovskite-polymer composite thin films have been widely used in the fabrication of light-emitting diodes (LEDs) due to their low cost, good uniformity and excellent luminescent properties. A white light emitting diode device can be prepared by integrating a green light emitting MAPbBr3/PVDF composite film and a red light emitting K2SiF6:Mn4+(KSF) phosphor with a blue InGaN chip, as shown in fig. 8 (a), and the corresponding electroluminescence (EL) spectrum is shown in fig. 8 (B)[58]. The device produces white light emission at a current of 20 mA and has a wide color gamut with luminous efficiency up to the 109 lm·W-1,121%NTSCstandard (100% match ratio). The color coordinates of the obtained white LEDs were (0.272, 0.278), as shown in the CIE diagram of fig. 8 (d). In 2018, Xin et al. fabricated white LEDs by stacking pre-prepared CsPbBr3-PMMA films and KSF composites on commercial blue LEDs (454 nm)[43]. The color coordinates of the obtained white LEDs are (0.324, 0.321), which are closer to the standard coordinates of white light.
Lead halide perovskite NCs with bright luminescence properties are also attractive for fluorescent biological applications, but their lead toxicity and instability in water hinder their development in this field. Hydrophobic polymer encapsulation can not only improve the water stability of perovskite NCs, prevent anion exchange, but also prevent lead leakage, which opens up a way for the development of perovskite NCs in the biomedical field. In 2017, Zhang et al. Cultured macrophages with 1 mL of fresh medium and 10 μL of phosphate-buffered saline (PBS) containing CsPbX3NCs@MHSs for 24 H[69]. Confocal fluorescence images showed that NCs @ MHSs entered living cells. Intense intracellular emission was observed under radiation excitation at 325-375 nm (Fig. 9a-2, b-2, c-2). The PL spectra of NCs @ MHSs in living cells (dashed lines in Fig. 9 d ~ f) are identical to those of the corresponding CsPbX3NCs colloidal solution (solid lines), and the PL intensity change is negligible after several hours of excitation. This experiment proves that the CsPbX3NCs@MHSs is an ideal probe for biological imaging. In 2018, Yang et al. Prepared water-stable MAPbBr3QD@PS-b-PEO vesicles, and cytotoxicity experiments showed that more than 90% of human cervical epithelial cancer (HeLa) cells survived when the concentration was lower than 30μg·mL-1, indicating low cytotoxicity and suitable for cell imaging[70].

4 Conclusion and prospect

In this paper, starting from the preparation of lead halide perovskite-polymer composites, three common preparation methods are summarized. The characteristic of the blending method is that the perovskite NCs and the polymer need to be prepared in advance, and the morphology and size of the perovskite NCs can be well controlled, but because of its poor stability, it needs to be protected before being mixed with the polymer; In-situ polymerization refers to the process of preparing perovskite first and then polymerizing monomers. Perovskite NCs can play a photoactive role in the polymerization of monomers, but at the same time, polymerization conditions (including thermal polymerization and long-term UV polymerization) can lead to the aggregation and decomposition of perovskite NCs, and significantly reduce PLQY. At present, it is a relatively perfect strategy to introduce polymerizable ligands on the surface of perovskite NCs first, and then make polymer chains grow in situ on the surface of perovskite NCs through further reaction between ligands and monomers. The advantages of the in-situ perovskite growth/precipitation method for preparing the perovskite-polymer composite material are obvious: compared with the blending method, the method avoids the need of pre-synthesis and post-treatment of perovskite NCs; compared with the in-situ polymerization method, the method avoids the influence of the polymerization process on perovskite NCs and protects the stability of perovskite-NCs to the greatest extent. At present, the perovskite-polymer composite materials obtained by three different preparation methods have shown excellent performance in the photoelectric field, such as LED devices, solar cells, biological imaging, fluorescent labeling and other applications.At the same time, the application of this kind of composite materials in other photoelectric converters, lighting and flexible displays also shows great potential for development.
Overall, the polymer matrix brings significant advantages to perovskite NCs. 1) Polymer encapsulation is a reliable solution to improve the stability of perovskites. Perovskite-polymer composites have high environmental stability, especially the formation of a dense protective layer on perovskite NCs gives them excellent water resistance. 2) Different monomer choices give the perovskite-polymer composites controllable mechanical properties, such as stiffness and flexibility, and the preparation process is relatively simple. And 3) the polymer reduces the overflow of toxic lead in the perovskite to a certain extent, and is beneficial to environmental protection and biological application.
However, there are still many problems in polymer-coated perovskite NCs: the thermal stability of perovskite-polymer composites is limited; The coating of the insulating polymer matrix not only isolates the contact between the perovskite and the environment, but also sacrifices the conductivity of the perovskite NCs, which affects the application of its photoelectric properties. In addition, most perovskite-polymer composite preparation processes use large amounts of anhydrous organic solvents, which are not environmentally friendly. In a word, the research on improving the stability of perovskite NCs by polymer coating needs further exploration and development.

References

Publishing order | Descend order by publishing year | Descend order by cited within
[1]

Kojima A, Teshima K, Shirai Y, Miyasaka T. J. Am. Chem. Soc., 2009, 131(17): 6050.
[2]

Liu M Z, Johnston M B, Snaith H J. Nature, 2013, 501(7467): 395.
[3]

Lee M M, Teuscher J, Miyasaka T, Murakami T N, Snaith H J. Science, 2012, 338(6107): 643.
[4]

Yantara N, Bhaumik S, Yan F, Sabba D, Dewi H A, Mathews N, Boix P P, Demir H V, Mhaisalkar S. J. Phys. Chem. Lett., 2015, 6(21): 4360.
[5]

Stoumpos C C, Malliakas C D, Kanatzidis M G. Inorg. Chem., 2013, 52(15): 9019.
[6]

Li X M, Wu Y, Zhang S L, Cai B, Gu Y, Song J Z, Zeng H B. Adv. Funct. Mater., 2016, 26(15): 2584.
[7]

Jeon N J, Noh J H, Yang W S, Kim Y C, Ryu S, Seo J, Seok S I. Nature, 2015, 517(7535): 476.
[8]

Zhao D W, Wang C L, Song Z N, Yu Y, Chen C, Zhao X Z, Zhu K, Yan Y F. ACS Energy Lett., 2018, 3(2): 305.
[9]

Sun C, Zhang Y, Ruan C, Yin C Y, Wang X Y, Wang Y D, Yu W W. Adv. Mater., 2016, 28(45): 10088.
[10]

Xing G C, Mathews N, Lim S S, Yantara N, Liu X F, Sabba D, Grätzel M, Mhaisalkar S, Sum T C. Nat. Mater., 2014, 13(5): 476.
[11]

Chen S T, Roh K, Lee J, Chong W K, Lu Y, Mathews N, Sum T C, Nurmikko A. ACS Nano, 2016, 10(4): 3959.
[12]

Zhou L, Yu K, Yang F, Zheng J, Zuo Y H, Li C B, Cheng B W, Wang Q M. Dalton Trans., 2017, 46(6): 1766.
[13]

Dou L T, Yang Y, You J B, Hong Z R, Chang W H, Li G, Yang Y. Nat. Commun., 2014, 5(1): 1.
[14]

Roesch R, Faber T, von Hauff E, Brown T M, Lira-Cantu M, Hoppe H. Adv. Energy Mater., 2015, 5(20): 1501407.
[15]

Leijtens T, Eperon G E, Noel N K, Habisreutinger S N, Petrozza A, Snaith H J. Adv. Energy Mater., 2015, 5(20): 1500963.
[16]

Xu Y, Cao M M, Xiao C, Li H L. Journal of Liaocheng University(Nat.Sci.), 2019, 32(1): 69.
[17]

( 徐妍, 曹蒙蒙, 夏超, 李会利. 聊城大学学报(自然科学版), 2019, 32(1): 69.)
[18]

Xie Q F, Wang X Z, Li Y, Ma Y H. Journal of Shenzhen Institute of Information Technology, 2018, 16(2):56.
[19]

( 谢启飞, 王新中, 李玥, 马艳红. 深圳信息职业技术学院学报, 2018, 16(2):56.)
[20]

Nedelcu G, Protesescu L, Yakunin S, Bodnarchuk M I, Grotevent M J, Kovalenko M V. Nano Lett., 2015, 15(8): 5635.
[21]

Akkerman Q A, D'Innocenzo V, Accornero S, Scarpellini A, Petrozza A, Prato M, Manna L. J. Am. Chem. Soc., 2015, 137(32): 10276.
[22]

Wei Y, Cheng Z Y, Lin J. Chem. Soc. Rev., 2019, 48(1): 310.
[23]

Fan Q H, Zu Y Q, Li L, Dai J F, Wu Z X. Acta Phys. Sin., 2020, 69(11): 118501.
[24]

( 樊钦华, 祖延清, 李璐, 代锦飞, 吴朝新. 物理学报, 2020, 69(11): 118501.)
[25]

Lou S Q, Xuan T T, Wang J. Opt. Mater.: X, 2019, 1: 100023.
[26]

Zou S H, Liu Y S, Li J H, Liu C P, Feng R, Jiang F L, Li Y X, Song J Z, Zeng H B, Hong M C, Chen X Y. J. Am. Chem. Soc., 2017, 139(33): 11443.
[27]

Mondal N, De A, Samanta A. ACS Energy Lett., 2019, 4(1): 32.
[28]

Liu F, Zhang Y H, Ding C, Kobayashi S, Izuishi T, Nakazawa N, Toyoda T, Ohta T, Hayase S, Minemoto T, Yoshino K, Dai S Y, Shen Q. ACS Nano, 2017, 11(10): 10373.
[29]

Li H B, Qian Y, Xing X, Zhu J F, Huang X Y, Jing Q, Zhang W H, Zhang C F, Lu Z D. J. Phys. Chem. C, 2018, 122(24): 12994.
[30]

Dirin D N, Benin B M, Yakunin S, Krumeich F, Raino G, Frison R, Kovalenko M V. ACS Nano, 2019, 13(10): 11642.
[31]

Liu K K, Liu Q, Yang D W, Liang Y C, Sui L Z, Wei J Y, Xue G W, Zhao W B, Wu X Y, Dong L, Shan C X. Light.: Sci. Appl., 2020, 9(1): 1.
[32]

Leng M Y, Yang Y, Zeng K, Chen Z W, Tan Z F, Li S R, Li J H, Xu B, Li D B, Hautzinger M P, Fu Y P, Zhai T Y, Xu L, Niu G D, Jin S, Tang J. Adv. Funct. Mater., 2018, 28(1): 1704446.
[33]

Liu H Y, Tan Y S, Cao M H, Hu H C, Wu L Z, Yu X Y, Wang L, Sun B Q, Zhang Q. ACS Nano, 2019, 13(5): 5366.
[34]

Zhou W L, Zhao Y L, Wang E S, Li Q N, Lou S Q, Wang J, Li X M, Lian Q, Xie Q J, Zhang R Q, Zeng H B. J. Phys. Chem. Lett., 2020, 11(8): 3159.
[35]

Zhang Q G, Wang B, Zheng W L, Kong L, Wan Q, Zhang C Y, Li Z C, Cao X Y, Liu M M, Li L. Nat. Commun., 2020, 11(1): 1.
[36]

Lou S Q, Zhou Z, Xuan T T, Li H L, Jiao J, Zhang H W, Gautier R, Wang J. ACS Appl. Mater. Interfaces, 2019, 11(27): 24241.
[37]

Wang S X, Bi C H, Yuan J F, Zhang L X, Tian J J. ACS Energy Lett., 2018, 3(1): 245.
[38]

Zhang J B, Jiang P F, Wang Y, Liu X F, Ma J M, Tu G L. ACS Appl. Mater. Interfaces, 2020, 12(2): 3080.
[39]

Wu H, Wang S, Cao F, Zhou J P, Wu Q Q, Wang H R, Li X M, Yin L Q, Yang X Y. Chem. Mater., 2019, 31(6): 1936.
[40]

Wei Y, Xiao H, Xie Z X, Liang S, Liang S S, Cai X C, Huang S S, Al Kheraif A A, Jang H S, Cheng Z Y, Lin J. Adv. Opt. Mater., 2018, 6(11): 1701343.
[41]

Zhong Q X, Cao M H, Hu H C, Yang D, Chen M, Li P L, Wu L Z, Zhang Q. ACS Nano, 2018, 12(8): 8579.
[42]

Zhang Y C, Zhao Y S, Wu D, Xue J J, Qiu Y, Liao M, Pei Q B, Goorsky M S, He X M. Adv. Mater., 2019, 31(37): 1902928.
[43]

Meyns M, Perálvarez M, Heuer-Jungemann A, Hertog W, Ibáñez M, Nafria R, Genç A, Arbiol J, Kovalenko M V, Carreras J, Cabot A, Kanaras A G. ACS Appl. Mater. Interfaces, 2016, 8(30): 19579.
[44]

Wei Y, Deng X R, Xie Z X, Cai X C, Liang S S, Ma P A, Hou Z Y, Cheng Z Y, Lin J. Adv. Funct. Mater., 2017, 27(39): 1703535.
[45]

Yang X L, Xu T J, Zhu Y H, Cai J, Gu K L, Zhu J R, Wang Y W, Shen J H, Li C Z. J. Mater. Chem. C, 2018, 6(30): 7971.
[46]

Xin Y M, Zhao H J, Zhang J Y. ACS Appl. Mater. Interfaces, 2018, 10(5): 4971.
[47]

Pathak S, Sakai N, Wisnivesky Rocca Rivarola F, Stranks S D, Liu J W, Eperon G E, Ducati C, Wojciechowski K, Griffiths J T, Haghighirad A A, Pellaroque A, Friend R H, Snaith H J. Chem. Mater., 2015, 27(23): 8066.
[48]

Wang Y N, He J, Chen H, Chen J S, Zhu R D, Ma P, Towers A, Lin Y, Gesquiere A J, Wu S T, Dong Y J. Adv. Mater., 2016, 28(48): 10710.
[49]

Raja S N, Bekenstein Y, Koc M A, Fischer S, Zhang D D, Lin L W, Ritchie R O, Yang P D, Alivisatos A P. ACS Appl. Mater. Interfaces, 2016, 8(51): 35523.
[50]

Song Y H, Yoo J S, Kang B K, Choi S H, Ji E K, Jung H S, Yoon D H. Nanoscale, 2016, 8(47): 19523.
[51]

Wei S S, Zhu H C, Zhang J, Wang L, An M Q, Wang Y L, Zhang X T, Liu Y C. J. Alloys Compd., 2019, 789: 209.
[52]

Kuo C C, Wang C T, Chen W C. Macromol. Mater. Eng., 2008, 293(12): 999.
[53]

Chen J Y, Chiu Y C, Shih C C, Wu W C, Chen W C. J. Mater. Chem. A, 2015, 3(29): 15039.
[54]

Wang Y W, Zhu Y H, Huang J F, Cai J, Zhu J R, Yang X L, Shen J H, Jiang H, Li C Z. J. Phys. Chem. Lett., 2016, 7(21): 4253.
[55]

Lin C C, Jiang D H, Kuo C C, Cho C J, Tsai Y H, Satoh T, Su C. ACS Appl. Mater. Interfaces, 2018, 10(3): 2210.
[56]

Liu H, Siron M, Gao M Y, Lu D, Bekenstein Y, Zhang D D, Dou L T, Alivisatos A P, Yang P D. Nano Res., 2020, 13(5): 1453.
[57]

Sun H Z, Yang Z Y, Wei M Y, Sun W, Li X Y, Ye S Y, Zhao Y B, Tan H R, Kynaston E L, Schon T B, Yan H, Lu Z H, Ozin G A, Sargent E H, Seferos D S. Adv. Mater., 2017, 29(34): 1701153.
[58]

Chen K, Deng X H, Dodekatos G, Tüysüz H. J. Am. Chem. Soc., 2017, 139(35): 12267.
[59]

Wong Y C, de Andrew Ng J, Tan Z K. Adv. Mater., 2018, 30(21): 1800774.
[60]

Cha W, Kim H J, Lee S, Kim J. J. Mater. Chem. C, 2017, 5(27): 6667.
[61]

Zhou Q C, Bai Z L, Lu W G, Wang Y T, Zou B S, Zhong H Z. Adv. Mater., 2016, 28(41): 9163.
[62]

Li Y, Lv Y, Guo Z Q, Dong L B, Zheng J H, Chai C F, Chen N, Lu Y J, Chen C. ACS Appl. Mater. Interfaces, 2018, 10(18): 15888.
[63]

Wang Z B, Wang F Z, Sun W D, Ni R H, Hu S Q, Liu J Y, Zhang B, Alsaed A, Hayat T, Tan Z A. Adv. Funct. Mater., 2018, 28(47): 1804187.
[64]

Wang Z B, Luo Z, Zhao C Y, Guo Q, Wang Y P, Wang F Z, Bian X M, Alsaedi A, Hayat T, Tan Z A. J. Phys. Chem. C, 2017, 121(50): 28132.
[65]

Masi S, Rizzo A, Aiello F, Balzano F, Uccello-Barretta G, Listorti A, Gigli G, Colella S. Nanoscale, 2015, 7(45): 18956.
[66]

Zhao Y C, Wei J, Li H, Yan Y, Zhou W K, Yu D P, Zhao Q. Nat. Commun., 2016, 7(1): 1.
[67]

Ma K Z, Du X Y, Zhang Y W, Chen S. J. Mater. Chem. C, 2017, 5(36): 9398.
[68]

Tsai P C, Chen J Y, Ercan E, Chueh C C, Tung S H, Chen W C. Small, 2018, 14(22): 1704379.
[69]

Wen D, Yu Y H, Fu C, Zhang W Y, Zhang Z T. J. Jianghan Univ. Nat. Sci. Ed., 2015, 43(1): 12.
[70]

( 文丹, 喻艳华, 付成, 张玮莹, 张正涛. 江汉大学学报(自然科学版), 2015, 43(1): 12.)
[71]

Pan A Z, Jurow M J, Qiu F, Yang J, Ren B Y, Urban J J, He L, Liu Y. Nano Lett., 2017, 17(11): 6759.
[72]

Hou S C, Guo Y Z, Tang Y G, Quan Q M. ACS Appl. Mater. Interfaces, 2017, 9(22): 18417.
[73]

Zhang H H, Wang X, Liao Q, Xu Z Z, Li H Y, Zheng L M, Fu H B. Adv. Funct. Mater., 2017, 27(7): 1604382.
[74]

Yang S, Zhang F, Tai J, Li Y, Yang Y, Wang H, Zhang J X, Xie Z G, Xu B, Zhong H Z, Liu K, Yang B. Nanoscale, 2018, 10(13): 5820.
[75]

Chang C Y, Chu C Y, Huang Y C, Huang C W, Chang S Y, Chen C A, Chao C Y, Su W F. ACS Appl. Mater. Interfaces, 2015, 7(8): 4955.
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