Confining Mn2+-Doped Lead Halide Perovskite in Zeolite-Y as

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Functional Inorganic Materials and Devices

Confining Mn2+-Doped Lead Halide Perovskite in Zeolite-Y as Ultrastable orange-red Phosphor Composites for White Light-Emitting-Diodes Shi Ye, Jiayi Sun, Yuhong Han, Yayun Zhou, and Qinyuan Zhang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b08342 • Publication Date (Web): 06 Jul 2018 Downloaded from http://pubs.acs.org on July 7, 2018

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ACS Applied Materials & Interfaces

Confining Mn2+-doped Lead Halide Perovskite in Zeolite-Y as Ultra-stable Orange-red Phosphor Composites for White Light-Emitting-Diodes Shi Ye*, Jia-Yi Sun, Yu-Hong Han, Ya-Yun Zhou, and Qin-Yuan Zhang* State Key Laboratory of Luminescent Materials and Devices, and Guangdong Provincial Key Laboratory of Fiber Laser Materials and Applied Techniques, South China University of Technology, Guangzhou 510641, China. E-mail: [email protected], [email protected]

Abstract CsPbX3 (X = Cl, Br, I) perovskite quantum dots (QDs) have arisen to be competitive candidate luminescent materials in the photoelectric fields due to their superior luminescent properties. However, the major drawback of poor resistance to temperature, moisture and irradiation of light, especially for the red QDs with I-, hinders their practical applications. Herein, we synthesized Mn2+-doped-CsPbCl3 embedded in the cage of zeolite-Y as a new orange-red phosphor for white Light-emitting diode (WLED). The composites have significant improved resistance to both elevated temperature and water over the bare Mn2+-doped QDs. And the former exhibits little degradation while the latter shows apparent decline upon the irradiation of lights in the orange LED devices, which are fabricated by employing each material as color conversion phosphor coated on a 365 nm UV chip. A WLED is also achieved with a 365 nm UV chip coated by a CsPb(Cl0.5,Br0.5)3–Y blue phosphor and a CsPb0.75Mn0.25Cl3–Y orange phosphor. The device possesses a CIE coordinate of (0.34, 0.36), correlated color temperature (CCT) of 5336 K and color rendering index (CRI) of 81.

Keywords: perovskite quantum dots, Mn2+ doped, zeolites, stability, white LED

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Introduction Recently, all inorganic perovskite (CsPbX3, X = Cl, Br, I) QDs have aroused much attention and the field is advancing rapidly1-6. Their outstanding optical properties including high photoluminescence quantum yields (PLQYs), tunable and narrow emissions over the entire visible spectral range, as well as less sensitive to oxygen and moisture than their hybrid counterparts7-8, make them particularly promising candidate materials for many applications such as phosphor-converted WLEDs, lasing and so on9-23. Though various studies on CsPbX3 QDs as color-conversion phosphors have made great progress to date, poor stability is still a main drawback severely restricting their practical applications24, especially for the red QDs with I-. In addition to the poor resistance to elevated temperature and moisture25-35, the anion-mixed red QDs with I- suffer strong spinodal decomposition thermodynamically upon irradiation of light

36-37

. Therefore, great efforts have been

devoted to prepare more stable perovskite QDs through various approaches such as embedding QDs in polymeric matrix like PMMA or polystyrene as well as in inorganic matrix like mesoporous silica or zeolites1-2, 30, 38-39, coating with polymer or silica24, 27-28, high chloride doping in surface25, and X-ray lithography on QDs films29. As a matter of course, doping other cations is supposed to be an alternative way and Mn2+ is experimentally and theoretically proved to be an effective option40. There is some other report showing that Mn2+ has good compatibility of cations in CsPbCl3 and it provide a new exciton transition pathway to alter the emission41-43. The resulted orange-red emission of Mn2+ in perovskite QDs makes it as a promising substituent red phosphor for WLEDs. Additionally, there is another merit to use Mn2+ as dopant in perovskite QDs, that is, it reduces the usage of toxic component Pb2+. Actually, the research on complete or partial substitution of Pb by other less toxic elements besides Mn has been done44-48. Various methods were reported to prepare Mn2+ doped CsPbX3 40-41, 49-55

. It is also reported that further improvement on stability can be achieved for

Mn2+ doped CsPbX3 nanostructure constructed through a core-isocrystalline shell structure or silica-coating56-57. Our previous research evidently demonstrates the 2


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improvement on irradiation of light or duration in the air by encapsulating the CsPbX3 in porous zeolite 39. Accordingly, confining the Mn2+-doped CsPbCl3 in porous zeolite as orange-red phosphor would accomplish further improvement on the resistance to elevated temperature, water and irradiation. In this research, we successfully synthesized Mn2+ doped CsPbX3 perovskite embedded in zeolite-Y (Cs(Pb,Mn)Cl3–Y) by a facile two-step synthesis method. The zeolites were first exchanged with Cs+ ions by an ion-exchange reaction from aqueous solution. Afterwards Cs+-exchanged zeolites reacted with PbX2 and MnX2 (with X = Cl, Br, or the mixture of two) ions to form perovskite QDs. The emission of the composites can be adjusted by controlling Mn2+ contents or varying halide ions. Besides the benefit of reduced toxic lead content, the composites show better resistance to elevated temperature and water than the bare perovskite QDs. Furthermore, a LED with CsPb0.75Mn0.25Cl3–Y (short for CsPb0.75Mn0.25Cl3–zeolite-Y) as the color-converted material is assembled and exhibits a superior working stability. A WLED is also fabricated by coating a 365 nm ultraviolet (UV) chip with CsPb(Cl0.5,Br0.5)3–Y and CsPb0.75Mn0.25Cl3–Y as phosphors. The device produces white light with a CIE coordinate of (0.34, 0.36), correlated color temperature (CCT) of 5336 K and color rendering index (CRI) of 81.

Experimental Section Materials and chemicals. M+-zeolite-Y (M+ = NH4+, Na+, SiO2/ Al2O3 = 5.2 in molar ratio, Alfa Aesar), cesium bromide (CsBr, Alfa Aesar, 99.9%), oleic acid (OA, Aladdin, analytical reagent(AR)), 1-octadecene (ODE, Sigma-Aldrich, 90%), oleylamine (OAm, Aladdin, 8090%), lead chloride (PbCl2, Alfa Aesar, 99.999%), lead bromide (PbBr2, Alfa Aesar, 99.999%), manganese chloride (MnCl2, Alfa Aesar, ultra-dry, 99.99%), manganese bromide (MnBr2, Alfa Aesar, anhydrous, 99%), n-trioctylphosphine (TOP, Strem, 97%), n-hexane (Aladdin, 97%), isopropanol (AR, Fuyu Chemicals), silicone resin A and silicone resin B (Dow Corning, OE 6550), 365 nm UV LED chip (Sanan optoelectronics). All the chemicals were used without 3



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further purification. Preparation of Cs+-Y. 1.0 g of zeolite-Y was dispersed in 10.0 mL aqueous solution of 1.0 mol/ L CsBr. Then the mixture was stirred in a water bath at 70 ºC for 24 h. The products were centrifuged and washed with deionized water for twice, and then dried in air at 80 ºC for 12 h. Preparation of PbX2 and MnX2 solution. A specific molar ratio of PbX2 and MnX2 were mixed with ODE (5.0 mL) in a 50 mL three-neck flask and dried under vacuum for 30 min at 120 °C. OA (2.0 mL) and OAm (2.0 mL) were injected under N2 atmosphere. After complete dissolution of the PbX2 and MnX2 salt, the solution was naturally cooled down to room temperature under N2 atmosphere. A higher temperature of 150 ºC and the addition of TOP (1.0 mL) were necessary to dissolve PbCl2. Synthesis of Cs(Pb,Mn)X3–Y. Firstly, ODE (5.0 mL) and Cs+-Y (0.5 g) were mixed in a 50 mL three-neck flask, and dried under vacuum for 30 min at 120 ºC. Then the temperature was raised to 130~170 ºC under N2 atmosphere followed by the injection of PbX2 and MnX2 solution. The mixture was stirred for approximately 15 min and then cooled down with an ice-water bath. Finally, the product was washed with n-hexane and isopropanol twice and centrifuged. The composites were dried at 60 ºC under vacuum for 10 h. Synthesis of Cs(Pb,Mn)Cl3 perovskite QDs. The Cs-precursor was prepared following a procedure -f the Reference 2. A specific molar ratio of PbCl2 and MnCl2 were mixed with ODE (5.0 mL) in a 50 mL three-neck flask and dried under vacuum for 30 min at 120 °C. OA (2.0 mL) and OAm (2.0 mL) were injected under N2 atmosphere. After complete dissolution of the PbCl2 and MnCl2 salt, the temperature was raised to 150 ºC and 0.5 mL Cs-precursor was swiftly injected into the mixture. After reaction for approximately 5s the system was cooled down with an ice-water bath. After centrifugation, products were dispersed in n-hexane. The droplets of Cs(Pb, Mn)Cl3 QDs were deposited on a glass slide to prepare a film for measurement. Synthesis of CsPb(Cl0.5,Br0.5)3–Y. The composite was prepared following the 4


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same procedure as in Reference 39. Fabrication of LED Devices. (1) For the LED device in Figure 6, 0.02 g of silicone resin A and 0.02 g of silicone resin B were mixed with 0.02 g CsPb0.75Mn0.25Cl3–Y composite (2.0 mg of bare QDs is used for a comparison device) and the mixture was stirred thoroughly and dried at 60 ºC. Afterwards the phosphor mixture was deposited on a 365 nm UV LED chip and cured at 150 ºC. (2) For the WLED device in Figure 7, 0.02 g of silicone resin A and 0.02 g of silicone resin B were

mixed

with

0.01

g

CsPb0.75Mn0.25Cl3–Y

composite,

then

0.01

g

CsPb(Cl0.5,Br0.5)3–Y was added. The mixture was stirred thoroughly and dried at 60 ºC. Afterwards the phosphor mixture was deposited on a 365 nm UV LED chip and cured at 150 ºC. Measurement and Characterization. XRD patterns of the as-synthesized samples were measured on a Rigaku D/ max-IIIA X-ray diffractometer using Cu-Kα radiation (λ = 1.5418 Å). SEM images were obtained using a FEI Nova Nano SEM 430 field-emission scanning electron microscopy (FESEM). The TEM images were recorded on a JEOL JEM-2100F transmission electron microscope. The HRTEM images and elemental mapping of resin-embedded sections of CsPb0.62Mn0.38(Cl,Br)3– Y were taken on a FEI Tecnai G2 F30. The Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES) measurements of metal elements were carried out on Variance 2000e, while the content of N element was given by Thermo Fisher Scientific Flash2000. Photoluminescence spectra were recorded on an Edinburgh Instruments FLS 920 spectrometer with a red-sensitive photomultiplier tube (PMT, R928), and the temperature-dependent photoluminescence spectra were measured with a temperature controller system on the basis. Fluorescence lifetimes were measured on a Hamamatsu Photonics C11367-11. The optical properties of LEDs and WLEDs were obtained using an HAAS2000 integrated sphere with an analyzer system of EVERFINE. The water resistance measurement was done on the same integrated sphere for those samples deposited on a glass slide, which are immersed in water contained with a glass bottle. 5



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Results and Discussion 1. Synthesis of Cs(Pb,Mn)X3–Y composites Cs(Pb,Mn)X3–Y composites are synthesized by a facile two-step in-situ synthesis. Firstly, Cs+-exchanged zeolite-Y (Cs+-Y) is prepared with purchased M+-Y immerged in an aqueous CsBr solution at 60 ºC under vigorous stirring. Secondly, the dried Cs+-Y crystals are dispersed in 1-octadecene (ODE) and react with an organic solution (OA, oleic acid; OAm, oleylamine) of PbX2 and MnX2 (X = Cl, Br, or a mixture of two) at 130~170 ºC for 15 min under N2 atmosphere (Figure 1). This method can achieve in-situ synthesis of Cs(Pb,Mn)X3 inside the cages of zeolite-Y (Equation 1):

Cs+-Y + Pb2+ + Mn2+ + 3X- → Cs(Pb,Mn)X3–Y

(1)

Figure 1. Schematic illustration of the two-step synthesis of Cs(Pb,Mn)X3–Y composites, involving Cs+ ion exchange followed by reaction with PbX2 and MnX2.

2. Composition, Structure and Morphology Elemental analysis techniques were used to determine the contents of balanced cation M+ in zeolites before and after ion exchange reaction, and the ratio of Pb2+ to 6


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Mn2+ in different composites. It can be found in Table 1 that about 60% of balanced cation M+ (M+= NH4+, Na+) inside the cages of the zeolite is exchanged by the Cs+. Table 2 shows that the deduced Mn2+ content increases as its feed ratio increasing. Also, it can be found that for the similar Pb /Mn feed ratio, Mn2+ are more likely to be incorporated into the composites containing both Cl- and Br- ions, rather than those with a single halogen. The contents of the perovskite halides are evaluated by the contents of Pb2+ since there is still some Cs+ unreacted with lead halides according to the previous work 39. Table 1. The contents of the balanced cation M+ in zeolites before and after ion exchange reaction. Samples Element Contents Contents + zeolite–Y Na(Na ) 15.32 g/kg 0.6664 mol/Kg + N(NH4 ) 34.20 g/kg 2.4411 mol/Kg Cs–Y Na(Na+) 11.46 g/kg 0.4985 mol/Kg + N(NH4 ) 6.80 g/kg 0.4854 mol/Kg + Cs(Cs ) 235.67 g/kg 1.7732 mol/Kg

Table 2. Compositions of different Cs(Pb,Mn)X3–Y composites. Chemicals PbCl2/ MnCl2 PbBr2/ MnCl2

Feed ratio 1:1 1:3 1:5 1:1 1:3 1:5

Deduced formula CsPb0.91Mn0.09Cl3–Y CsPb0.81Mn0.19Cl3–Y CsPb0.75Mn0.25Cl3–Y CsPb0.82Mn0.18(Cl,Br)3–Y CsPb0.64Mn0.36(Cl,Br)3–Y CsPb0.62Mn0.38(Cl,Br)3–Y

Deduced contents of perovskites 0.4697 mol/kg 0.3086 mol/kg 0.1946 mol/kg 0.2093 mol/kg 0.1249 mol/kg 0.0974 mol/kg

Figure 2a shows X-ray diffraction (XRD) patterns of the CsPbxMn1-x(Cl,Br)3–Y composites with different Pb /Mn molar ratios. The diffraction angles of all samples match well with reference pattern #00-043-0168, suggesting that the composite crystals remain the framework structure of zeolite-Y. And it’s obvious that the relative intensities of several diffraction peaks change significantly (those at around 10.2 º, 15.6 º, 18.7 º, 20.4 º), which is likely caused by the CsPbxMn1-x(Cl,Br) 3 embedded in 7



the

zeolites39.

There

is

no

apparent XRD

peaks

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originating

from

the

CsPbxMn1-x(Cl,Br)3 perovskite, probably owing to that most CsPbxMn1-x(Cl,Br)3 are located inside pores of the zeolite. Also, the diffraction peaks of perovskite crystals with sub-nano size dispersed in zeolite pores should be much weaker than that of the micron-sized zeolite-Y host. Figure 2b, c gives the scanning electron microscopy (SEM) images of the original zeolite-Y and CsPb0.62Mn0.38(Cl,Br)3–Y composite. The morphology of two samples is similar, with 0.5~1.0 µm length of sides and smooth surfaces.

Figure 2. (a) X-ray diffraction patterns of the CsPbxMn1-x(Cl,Br)3–Y composites with Pb-to-Mn molar feed ratios of 1:1 (blue), 1:3 (purple), 1:5 (orange) and the JCPDS reference pattern #00-043-0168 (black bars). SEM images of (b) the original zeolite-Y, and (c) the CsPb0.62Mn0.38(Cl,Br)3–Y composite.

The embedding of perovskite halides can be directly observed using transmission electron microscopy (TEM). Figure 3a, b shows a TEM image of a CsPb0.62Mn0.38(Cl,Br)3–Y composite grain (was cut into pieces) and its corresponding 8


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elemental mapping by means of energy-dispersive X-ray (EDX) spectroscopy. Separate elemental maps were exhibited in Figure S1a~i. Figure 3c is a high-resolution TEM (HRTEM) image of one piece of the grain in Figure 3a. In order to minimize the collapse of the framework structure of the zeolites caused by the electron beam, the image was recorded within 10 s at a low operating voltage of 120 KV. The lattice fringes are clearly shown in the image spaced by 14.2 Å, corresponding to the spacing of the (111) lattice planes of the FAU zeolites (JCPDF #00-043-0168). Owing to the instability nature of the zeolite and perovskite halides upon electron beam bombardment, it is quite tough to capture the fingerprints of both at the same time. However, all the chemical elements of CsPb0.62Mn0.38(Cl,Br)3 can be found throughout the cross-section of the zeolite fragment pieces in Figure 3b and Figure S1. More analogous evidences of the perovskites embedded in the zeolites can be referred to our previous report on the undoped perovskite halides in the zeolites 39. It is also proved by the difference of luminescence behaviour between the composites and bare perovksite QDs, which will be discussed in the photoluminescence section.

Figure 3. (a) High-angle annular dark-field scanning TEM image, and b) elemental mapping by energy-dispersive X-ray (EDX) spectroscopy of a CsPb0.62Mn0.38(Cl,Br)3–Y composite particle (resin-embedded sections). (c) A high-resolution (HRTEM) zoom-in of a part of the crystal.

3. Photoluminescence Properties

9



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Figure 4. (a) Emission spectra of the CsPbxMn1-xCl3–Y composites and b) CsPbxMn1-x(Cl,Br)3–Y composites. (c) Photoluminescence decay curve of the CsPb0.75Mn0.25Cl3–Y composite monitored at 408 nm with excitation of 365 nm. (d) Photoluminescence decay curve of the CsPb0.75Mn0.25Cl3–Y composite monitored at 600 nm with excitation of 365 nm.

Figure 4a shows the emission spectra of CsPbxMn1-xCl3–Y composites, which are similar to those previously reported for freely dispersed CsPbxMn1-xCl3 perovskite QDs41, 49, 56, 58-59. When Mn2+ doping concentration is low, there is only one narrow emission peak at 408 nm with the full width at half-maximum (FWHM) of 10 nm, which is assigned to the exciton emission of perovskite in the composites. With the increase of Mn2+ content, a broad emission with the FWHM of about 80 nm appears at ~600 nm, which is derived from the 4T1-6A1 transition of Mn2+ in CsPbCl3 crystal41. The intensity of Mn2+-emission enhances with increased Mn2+ content, and the emission position exhibits some red-shift. As for CsPbxMn1-x(Cl,Br)3–Y composite, 10


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the emission spectra are similar. Elevating the MnCl2 contents, the emission from CsPb(Cl,Br)3 crystal shows gradual blueshift and the Mn2+-emission appears. However, the band gap between the conduction band and the valence band of CsPb(Cl,Br)3 gradually narrows as the Br- concentration increases in CsPbCl3, which is not conducive to the energy transfer from exciton to Mn2+49, 58. Therefore, it can be seen that CsPbxMn1-xCl3–Y is more likely to achieve energy transfer from excitons to Mn2+, resulting in stronger red emission. When the halogen element in the composites is changed from chlorine to bromine completely, the band gap of perovskite crystal is too narrow to observe the energy transfer from excitons to Mn2+ for the CsPbxMn1-xBr3–Y composite49. The photoluminescence decay curves of the CsPb0.75Mn0.25Cl3–Y samples in Figure. 4c, d also confirmed their origin. The 408 nm emission exhibits a multi-exponential decay, which is consistent with the previous report of the pure perovskite QDs embedded in zeolite-Y39. The 1/e lifetime is about 0.68 ns ascribing to the CsPbCl3–Y host radiative lifetime, and the longer lifetime of 9.53 ns is due to temporary

charge-carrier

trapping60-61.

The

600

nm

emission

shows a

mono-exponential decay with a lifetime of 0.98 ms, which is assigned to the Mn2+ emission with energy transferred from excitons of perovskite QDs41, 58, 62.

11



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Figure 5. (a) Temperature-dependent emission spectra of the CsPb0.75Mn0.25Cl3–Y composite. (b) The tendency of purple and red emission intensity of CsPb0.75Mn0.25Cl3–Y as a function of temperature. (c) The tendency of purple and red emission intensity of QDs film as a function of temperature. (d) The tendency of emission intensity of QDs film and the composite as a function of time immersed in water.(The time was counted when the samples were immerged in water, not including the time we took the measurement of photoluminescence spectra. Since it is not an in-situ characterization method, the actual time of duration in water would be much longer than the recorded one.)

According to our previous research, the zeolite encapsulation can effectively improve the performance of CsPbX3–Y composites over bare QDs at elevated temperature39. Figure 5a, b shows the temperature-dependent emission of the CsPb0.75Mn0.25Cl3–Y composite. With the increase of temperature, the intensities of the two emission peaks exhibit distinct tendencies. The CsPbCl3-related emission becomes weaker because of the temperature quenching and the peak position is 12


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almost fixed at around 410 nm. While the Mn2+-related emission gradually enhances resulting from the intensified exciton-to-Mn2+ energy transfer. It shows a blueshift due to the changes of ligand field strength on Mn2+ caused by thermal expansion of the perovskite lattice at elevated temperature41, 50. Then the temperature quenching effect dominates, causing gradual decline of both emission intensities. Compared with bare perovskite QDs in Figure 5c, we can see that zeolite matrix can slow down the temperature quenching significantly (specially for the purple emission of perovskite host), proving that encapsulation effect of the zeolites are indeed beneficial to the thermal quenching resistance of Cs(Pb,Mn)Cl3 luminescence. Temperature-dependent emission of CsPbxMn1-x(Cl,Br)3 with similar properties is also shown in Figure S2b, c. The porous nature of the zeolite structure results in a lower thermal conductivity of the composites, which may lower the temperature of the embedded perovskites and apparently improve the temperature-dependent performance. Also, we investigated the water-resistance of the composites. The CsPb0.75Mn0.25Cl3–Y composite and QDs film on glass slide were both immersed in water and the spectra were measured immediately after varied duration time in water (Figure 5d). Obviously, the degradation rate of CsPb0.75Mn0.25Cl3 in zeolites is much slower than that of bare perovskite QDs film. After immersing for 3 min, bare perovskite QDs film shows almost no emission while CsPb0.75Mn0.25Cl3–Y retains about 60% of the initial intensity. Therefore, it can be concluded that the Cs(Pb,Mn)X3 is embedded inside the zeolites and the composites can achieve a much better resistance to moisture. There may be two causes for this phenomenon. On one hand, the porous nature of the zeolite creates a barrier for the water molecular to attack the embedded perovskites. On the other hand, it may be more difficult for the perovskites in the zeolite to decompose to some extent due to the confining effect of the porous structure. As we know, the perovskite lead halides containing iodide ions tend to decompose, even though the zeolites have been reported to slightly improve their stability over bare CsPb(Br,I)3 QDs39. As seen above, the CsPb0.75Mn0.25Cl3–Y composite exhibits a much better performance in resistance to moisture and elevated temperature in 13



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orange-red region. Thus, it becomes a promising candidate phosphor in color-converted LED applications.

4. Performance of phosphor-converted LED and WLED To test the stability of the composites upon irradiation of light, LED was fabricated with UV chip and CsPb0.75Mn0.25Cl3–Y as color-converted materials. Figure 6a shows the spectra of the LED device operating at a current of 50~300 mA. CsPb0.75Mn0.25Cl3–Y composite exhibits a gradually-enhancing emission as the current increases, indicating that the composite shows no decomposition toward the 365 nm UV light irradiation. The inset demonstrates the photograph of the LED device working at 300 mA with the color coordinate of (0.48, 0.48) (shown in Figure S3a). Another LED consisting of bare QDs with analogous composition as color-converted material was also fabricated for comparison. Current-dependent spectra are also presented in Figure S3b. Within a duration time of 10 h at 300 mA driving current, the LED with composites shows an increasing luminous efficiency at the beginning of operation time. This may be resulted from the enhancing Mn2+-related emission under elevating temperature produced by the LED chip. Also, there is little loss of luminous efficiency after the device working for 10 h. While LED with bare QDs exhibit an apparent continuous decline of up to 40%. The significantly-improved performance makes the CsPbxMn1-xCl3–Y composites a promising candidate as orange-red phosphors.

14


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Figure 6. (a) Output spectra of the LED, composed of a 365 nm UV chip and a CsPb0.75Mn0.25Cl3–Y orange phosphor as a function of driving current. Inset is the corresponding LED device photograph operated at 300 mA. (b) The tendency of luminous efficiency of LED as a function of operation time.

Figure 7. (a) Output spectrum of a WLED consisting of a 365 nm UV chip, a CsPb(Cl0.5,Br0.5)3–Y blue phosphor and a CsPb0.75Mn0.25Cl3–Y orange phosphor (driven current of 200 mA). Inset is the photograph of the WLEDs device. (b) The corresponding CIE coordinates of the WLED. (c) Output spectra of WLED as a function of driving current.

Finally, we assembled a WLED by coating the silicone resin mixture of CsPb(Cl0.5,Br0.5)3–Y (blue) and CsPb0.75Mn0.25Cl3–Y (orange) composites on a commercially available 365 nm LED chip. Figure 7a is the spectrum of above WLED device operating at 200 mA. Under the excitation of UV chip, CsPb (Cl0.5, Br0.5)3–Y produces a narrow blue emission and CsPb0.75Mn0.25Cl3–Y gives an orange broad emission, resulting in a white light with CIE coordinates of (0.34, 0.36) shown in Figure 7b. The CCT and CRI of the WLED are 5336 K and 81, respectively. The driving-current-dependent spectra (Figure 7c) show that both blue and orange emissions of composites are gradually enhanced as the current increases, and the CIE coordinates of device exhibit little variation (Figure S4), indicating that the CsPb0.75Mn0.25Cl3–Y composite is a potential orange-red component for WLED. 15



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Conclusions In summary, the composite of Mn2+-doped CsPbCl3 perovskite embedded in zeolite-Y was successfully prepared through a facile two-step synthesis method. The as-synthesized composites have been proved to have much better resistance to elevated temperature and moisture compared to the bare perovskite QDs. They can be used as orange-red color-converted materials in LEDs with superior stability against irradiation of UV LED chip, which also behave much better than the bare orange-red QDs with iodine ions and make the composites potentially intriguing for WLED application.

Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI:

•

Additional figures and images, EDX images, PL spectra and CIE coordinate diagrams.

Acknowledgements The authors would like to thank Dr. Xianfeng Yang for the TEM measurements, Miss Tingting Deng and Miss Ting Wang for the SEM measurements. This work is jointly supported by the NSFC (Grant Nos. 51772104), National Key R&D program (2016YFB0401702), the Tip-top Scientific and Technical Innovative Youth Talents of Guangdong Special Support Program (2016TQ03C100), and the Guangdong Natural Science Funds for Distinguished Young Scholars (2014A030306009).

References (1) Li, X.; Wu, Y.; Zhang, S.; Cai, B.; Gu, Y.; Song, J.; Zeng, H., CsPbX3 Quantum Dots for Lighting and Displays: Room-Temperature Synthesis, Photoluminescence Superiorities, Underlying Origins and White Light-Emitting Diodes. Adv. Funct. Mater. 2016, 26, 2435-2445. 16


Page 17 of 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(2) Protesescu, L.; Yakunin, S.; Bodnarchuk, M. I.; Krieg, F.; Caputo, R.; Hendon, C. H.; Yang, R. X.; Walsh, A.; Kovalenko, M. V., Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut. Nano Lett. 2015, 15, 3692-3696. (3) Nedelcu, G.; Protesescu, L.; Yakunin, S.; Bodnarchuk, M. I.; Grotevent, M. J.; Kovalenko, M. V., Fast Anion-Exchange in Highly Luminescent Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, I). Nano Lett. 2015, 15, 5635-5640. (4) Akkerman, Q. A.; D'Innocenzo, V.; Accornero, S.; Scarpellini, A.; Petrozza, A.; Prato, M.; Manna, L., Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions. J. Am. Chem. Soc. 2015, 137, 10276-10281. (5) Guhrenz, C.; Benad, A.; Ziegler, C.; Haubold, D.; Gaponik, N.; Eychmüller, A., Solid-State Anion Exchange Reactions for Color Tuning of CsPbX3 Perovskite Nanocrystals. Chem. Mater. 2016, 28, 9033-9040. (6) Tong, Y.; Bladt, E.; Ayguler, M. F.; Manzi, A.; Milowska, K. Z.; Hintermayr, V. A.; Docampo, P.; Bals, S.; Urban, A. S.; Polavarapu, L.; Feldmann, J., Highly Luminescent Cesium Lead Halide Perovskite Nanocrystals with Tunable Composition and Thickness by Ultrasonication. Angew. Chem. Int. Ed. 2016, 55, 13887-13892. (7) Swarnkar, A.; Chulliyil, R.; Ravi, V. K.; Irfanullah, M.; Chowdhury, A.; Nag, A., Colloidal CsPbBr3 Perovskite Nanocrystals: Luminescence beyond Traditional Quantum Dots. Angew. Chem. Int. Ed. 2015, 54, 15424-15428. (8) Kulbak, M.; Cahen, D.; Hodes, G., How Important Is the Organic Part of Lead Halide Perovskite Photovoltaic Cells? Efficient CsPbBr3 Cells. J. Phys. Chem. Lett. 2015, 6, 2452-2456. (9) Yantara, N.; Bhaumik, S.; Yan, F.; Sabba, D.; Dewi, H. A.; Mathews, N.; Boix, P. P.; Demir, H. V.; Mhaisalkar, S., Inorganic Halide Perovskites for Efficient Light-Emitting Diodes. J. Phys. Chem. Lett. 2015, 6, 4360-4364. (10) Song, J.; Li, J.; Li, X.; Xu, L.; Dong, Y.; Zeng, H., Quantum Dot Light-Emitting Diodes Based on Inorganic Perovskite Cesium Lead Halides (CsPbX3 ). Adv. Mater. 2015, 27, 7162-7167. (11) Zhang, X.; Xu, B.; Zhang, J.; Gao, Y.; Zheng, Y.; Wang, K.; Sun, X. W., All-Inorganic Perovskite Nanocrystals for High-Efficiency Light Emitting Diodes: Dual-Phase CsPbBr3-CsPb2Br5 Composites. Adv. Funct. Mater. 2016, 26, 4595-4600. (12) Li, G.; Rivarola, F. W.; Davis, N. J.; Bai, S.; Jellicoe, T. C.; de la Pena, F.; Hou, S.; Ducati, C.; Gao, F.; Friend, R. H.; Greenham, N. C.; Tan, Z. K., Highly Efficient Perovskite Nanocrystal Light-Emitting Diodes Enabled by a Universal Crosslinking Method. Adv. Mater. 2016, 28, 3528-3534. (13) Yu, J. C.; Kim, D. W.; Kim da, B.; Jung, E. D.; Park, J. H.; Lee, A. Y.; Lee, B. R.; Di Nuzzo, D.; Friend, R. H.; Song, M. H., Improving the Stability and Performance of Perovskite Light-Emitting Diodes by Thermal Annealing Treatment. Adv. Mater. 2016, 28, 6906-6913. (14) Swarnkar, A.; Marshall, A. R.; Sanehira, E. M.; Chernomordik, B. D.; Moore, D. T.; Christians, J. A.; Chakrabarti, T.; Luther, J. M., Quantum dot–induced phase stabilization of a-CsPbI3 perovskite for high-efficiency photovoltaics. Science 2016, 354, 92-95. (15) Sidhik, S.; Esparza, D.; Martínez-Benítez, A.; Lopez-Luke, T.; Carriles, R.; Mora-Sero, I.; de la Rosa, E., Enhanced Photovoltaic Performance of Mesoscopic Perovskite Solar Cells by Controlling the Interaction between CH3NH3PbI3 Films and CsPbX3 Perovskite Nanoparticles. J. Phys. Chem. C 2017, 121, 4239-4245. (16) Lv, L.; Xu, Y.; Fang, H.; Luo, W.; Xu, F.; Liu, L.; Wang, B.; Zhang, X.; Yang, D.; Hu, W.; Dong, 17



Page 18 of 21

A., Generalized colloidal synthesis of high-quality, two-dimensional cesium lead halide perovskite nanosheets and their applications in photodetectors. Nanoscale 2016, 8, 13589-13596. (17) Ramasamy, P.; Lim, D. H.; Kim, B.; Lee, S. H.; Lee, M. S.; Lee, J. S., All-inorganic cesium lead halide perovskite nanocrystals for photodetector applications. Chem. Commun. 2016, 52, 2067-2070. (18) Eaton, S. W.; Lai, M.; Gibson, N. A.; Wong, A. B.; Dou, L.; Ma, J.; Wang, L. W.; Leone, S. R.; Yang, P., Lasing in robust cesium lead halide perovskite nanowires. Proc. Natl. Acad. Sci. U. S. A. 2016, 113, 1993-1998. (19) Yakunin, S.; Protesescu, L.; Krieg, F.; Bodnarchuk, M. I.; Nedelcu, G.; Humer, M.; De Luca, G.; Fiebig, M.; Heiss, W.; Kovalenko, M. V., Low-threshold amplified spontaneous emission and lasing from colloidal nanocrystals of caesium lead halide perovskites. Nat. Commun. 2015, 6, 8056. (20) Xu, Y.; Chen, Q.; Zhang, C.; Wang, R.; Wu, H.; Zhang, X.; Xing, G.; Yu, W. W.; Wang, X.; Zhang, Y.; Xiao, M., Two-Photon-Pumped Perovskite Semiconductor Nanocrystal Lasers. J. Am. Chem. Soc. 2016, 138, 3761-3768. (21) Fu, Y.; Zhu, H.; Stoumpos, C. C.; Ding, Q.; Wang, J.; Kanatzidis, M. G.; Zhu, X.; Jin, S., Broad Wavelength Tunable Robust Lasing from Single-Crystal Nanowires of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, I). ACS Nano 2016, 10, 7963-7972. (22) Park, K.; Lee, J. W.; Kim, J. D.; Han, N. S.; Jang, D. M.; Jeong, S.; Park, J.; Song, J. K., Light-Matter Interactions in Cesium Lead Halide Perovskite Nanowire Lasers. J. Phys. Chem. Lett. 2016, 7, 3703-3710. (23) Lin, C. C.; Meijerink, A.; Liu, R. S., Critical Red Components for Next-Generation White LEDs. J. Phys. Chem. Lett. 2016, 7, 495-503. (24) Meyns, M.; Peralvarez, M.; Heuer-Jungemann, A.; Hertog, W.; Ibanez, M.; Nafria, R.; Genc, A.; Arbiol, J.; Kovalenko, M. V.; Carreras, J.; Cabot, A.; Kanaras, A. G., Polymer-Enhanced Stability of Inorganic Perovskite Nanocrystals and Their Application in Color Conversion LEDs. ACS Appl. Mater. Interfaces 2016, 8, 19579-19586. (25) Dastidar, S.; Egger, D. A.; Tan, L. Z.; Cromer, S. B.; Dillon, A. D.; Liu, S.; Kronik, L.; Rappe, A. M.; Fafarman, A. T., High Chloride Doping Levels Stabilize the Perovskite Phase of Cesium Lead Iodide. Nano Lett. 2016, 16, 3563-3570. (26) Zhou, J.; Huang, F.; Lin, H.; Lin, Z.; Xu, J.; Wang, Y., Inorganic halide perovskite quantum dot modified YAG-based white LEDs with superior performance. J. Mater. Chem. C 2016, 4, 7601-7606. (27) Sun, C.; Zhang, Y.; Ruan, C.; Yin, C.; Wang, X.; Wang, Y.; Yu, W. W., Efficient and Stable White LEDs with Silica-Coated Inorganic Perovskite Quantum Dots. Adv. Mater. 2016, 28, 10088-10094. (28) Huang, H.; Chen, B.; Wang, Z.; Hung, T. F.; Susha, A. S.; Zhong, H.; Rogach, A. L., Water resistant CsPbX3 nanocrystals coated with polyhedral oligomeric silsesquioxane and their use as solid state luminophores in all-perovskite white light-emitting devices. Chem. Sci. 2016, 7, 5699-5703. (29) Palazon, F.; Akkerman, Q. A.; Prato, M.; Manna, L., X-ray Lithography on Perovskite Nanocrystals Films: From Patterning with Anion-Exchange Reactions to Enhanced Stability in Air and Water. ACS Nano 2016, 10, 1224-1230. (30) Wang, H. C.; Lin, S. Y.; Tang, A. C.; Singh, B. P.; Tong, H. C.; Chen, C. Y.; Lee, Y. C.; Tsai, T. L.; Liu, R. S., Mesoporous Silica Particles Integrated with All-Inorganic CsPbBr3 Perovskite Quantum-Dot Nanocomposites (MP-PQDs) with High Stability and Wide Color Gamut Used for Backlight Display. Angew. Chem. Int. Ed. 2016, 55, 7924-7929. (31) Dirin, D. N.; Protesescu, L.; Trummer, D.; Kochetygov, I. V.; Yakunin, S.; Krumeich, F.; Stadie, N. P.; Kovalenko, M. V., Harnessing Defect-Tolerance at the Nanoscale: Highly Luminescent Lead Halide 18


Page 19 of 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Perovskite Nanocrystals in Mesoporous Silica Matrixes. Nano Lett. 2016, 16, 5866-5874. (32) Huang, S.; Li, Z.; Kong, L.; Zhu, N.; Shan, A.; Li, L., Enhancing the Stability of CH3NH3PbBr3 Quantum Dots by Embedding in Silica Spheres Derived from Tetramethyl Orthosilicate in "Waterless" Toluene. J. Am. Chem. Soc. 2016, 138, 5749-5752. (33) Chen, Z.; Gu, Z. G.; Fu, W. Q.; Wang, F.; Zhang, J., A Confined Fabrication of Perovskite Quantum Dots in Oriented MOF Thin Film. ACS Appl. Mater. Interfaces 2016, 8, 28737-28742. (34) Song, Y. H.; Yoo, J. S.; Kang, B. K.; Choi, S. H.; Ji, E. K.; Jung, H. S.; Yoon, D. H., Long-term stable stacked CsPbBr3 quantum dot films for highly efficient white light generation in LEDs. Nanoscale 2016, 8, 19523-19526. (35) Song, Y. H.; Choi, S. H.; Yoo, J. S.; Kang, B. K.; Ji, E. K.; Jung, H. S.; Yoon, D. H., Design of long-term stable red-emitting CsPb(Br0.4,I0.6 )3 perovskite quantum dot film for generation of warm white light. Chem. Eng. J. 2017, 313, 461-465. (36) Wang, Y.; Sun, X.; Shivanna, R.; Yang, Y.; Chen, Z.; Guo, Y.; Wang, G. C.; Wertz, E.; Deschler, F.; Cai, Z.; Zhou, H.; Lu, T. M.; Shi, J., Photon Transport in One-Dimensional Incommensurately Epitaxial CsPbX3 Arrays. Nano Lett. 2016, 16, 7974-7981. (37) Wang, Y.; Chen, Z.; Deschler, F.; Sun, X.; Lu, T. M.; Wertz, E. A.; Hu, J. M.; Shi, J., Epitaxial Halide Perovskite Lateral Double Heterostructure. ACS Nano 2017, 11, 3355-3364. (38) Pathak, S.; Sakai, N.; Wisnivesky Rocca Rivarola, F.; Stranks, S. D.; Liu, J.; Eperon, G. E.; Ducati, C.; Wojciechowski, K.; Griffiths, J. T.; Haghighirad, A. A.; Pellaroque, A.; Friend, R. H.; Snaith, H. J., Perovskite Crystals for Tunable White Light Emission. Chem. Mater. 2015, 27, 8066-8075. (39) Sun, J.-Y.; Rabouw, F. T.; Yang, X.-F.; Huang, X.-Y.; Jing, X.-P.; Ye, S.; Zhang, Q.-Y., Facile Two-Step Synthesis of All-Inorganic Perovskite CsPbX3 (X = Cl, Br, and I) Zeolite-Y Composite Phosphors for Potential Backlight Display Application. Adv. Funct. Mater. 2017, 27, 1704371. (40) Zou, S.; Liu, Y.; Li, J.; Liu, C.; Feng, R.; Jiang, F.; Li, Y.; Song, J.; Zeng, H.; Hong, M.; Chen, X., Stabilizing Cesium Lead Halide Perovskite Lattice through Mn(II) Substitution for Air-Stable Light-Emitting Diodes. J. Am. Chem. Soc. 2017, 139, 11443-11450. (41) Liu, H.; Wu, Z.; Shao, J.; Yao, D.; Gao, H.; Liu, Y.; Yu, W.; Zhang, H.; Yang, B., CsPbxMn1-xCl3 Perovskite Quantum Dots with High Mn Substitution Ratio. ACS Nano 2017, 11, 2239-2247. (42) Li, F.; Xia, Z.; Gong, Y.; Gu, L.; Liu, Q., Optical properties of Mn2+ doped cesium lead halide perovskite nanocrystals via a cation–anion co-substitution exchange reaction. J. Mater. Chem. C 2017, 5, 9281-9287. (43) Li, F.; Xia, Z.; Pan, C.; Gong, Y.; Gu, L.; Liu, Q.; Zhang, J. Z., High Br(-) Content CsPb(Cl yBr1y)3 Perovskite Nanocrystals with Strong Mn(2+) Emission through Diverse Cation/Anion Exchange Engineering. ACS Appl. Mater. Interfaces 2018, 10, 11739-11746. (44) Jellicoe, T. C.; Richter, J. M.; Glass, H. F.; Tabachnyk, M.; Brady, R.; Dutton, S. E.; Rao, A.; Friend, R. H.; Credgington, D.; Greenham, N. C.; Bohm, M. L., Synthesis and Optical Properties of Lead-Free Cesium Tin Halide Perovskite Nanocrystals. J. Am. Chem. Soc. 2016, 138, 2941-2944. (45) Leng, M.; Chen, Z.; Yang, Y.; Li, Z.; Zeng, K.; Li, K.; Niu, G.; He, Y.; Zhou, Q.; Tang, J., Lead-Free, Blue Emitting Bismuth Halide Perovskite Quantum Dots. Angew. Chem. Int. Ed. 2016, 55, 15012-15016. (46) Chen, Q.; Chen, L.; Ye, F.; Zhao, T.; Tang, F.; Rajagopal, A.; Jiang, Z.; Jiang, S.; Jen, A. K.; Xie, Y.; Cai, J.; Chen, L., Ag-Incorporated Organic-Inorganic Perovskite Films and Planar Heterojunction Solar Cells. Nano Lett. 2017, 17, 3231-3237. (47) van der Stam, W.; Geuchies, J. J.; Altantzis, T.; van den Bos, K. H.; Meeldijk, J. D.; Van Aert, S.; 19



Page 20 of 21

Bals, S.; Vanmaekelbergh, D.; de Mello Donega, C., Highly Emissive Divalent-Ion-Doped Colloidal CsPb1-xMxBr3 Perovskite Nanocrystals through Cation Exchange. J. Am. Chem. Soc. 2017, 139, 4087-4097. (48) Shao, H.; Bai, X.; Cui, H.; Pan, G.; Jing, P.; Qu, S.; Zhu, J.; Zhai, Y.; Dong, B.; Song, H., White light emission in Bi3+/Mn2+ ion co-doped CsPbCl3 perovskite nanocrystals. Nanoscale 2018, 10, 1023-1029. (49) Liu, W.; Lin, Q.; Li, H.; Wu, K.; Robel, I.; Pietryga, J. M.; Klimov, V. I., Mn2+-Doped Lead Halide Perovskite Nanocrystals with Dual-Color Emission Controlled by Halide Content. J. Am. Chem. Soc. 2016, 138, 14954-14961. (50) Huang, G.; Wang, C.; Xu, S.; Zong, S.; Lu, J.; Wang, Z.; Lu, C.; Cui, Y., Postsynthetic Doping of MnCl2 Molecules into Preformed CsPbBr3 Perovskite Nanocrystals via a Halide Exchange-Driven Cation Exchange. Adv. Mater. 2017, 29, 1700095. (51) Xu, W.; Li, F.; Lin, F.; Chen, Y.; Cai, Z.; Wang, Y.; Chen, X., Synthesis of CsPbCl3-Mn Nanocrystals via Cation Exchange. Adv. Optical Mater. 2017, 5, 1700520. (52) Zhu, J.; Yang, X.; Zhu, Y.; Wang, Y.; Cai, J.; Shen, J.; Sun, L.; Li, C., Room-Temperature Synthesis of Mn-Doped Cesium Lead Halide Quantum Dots with High Mn Substitution Ratio. J. Phys. Chem. Lett. 2017, 8, 4167-4171. (53) Parobek, D.; Dong, Y.; Qiao, T.; Son, D. H., Direct Hot-Injection Synthesis of Mn-Doped CsPbBr3 Nanocrystals. Chem. Mater. 2018, 30, 2939-2944. (54) Mir, W. J.; Jagadeeswararao, M.; Das, S.; Nag, A., Colloidal Mn-Doped Cesium Lead Halide Perovskite Nanoplatelets. ACS Energy Lett. 2017, 2, 537-543. (55) Wang, Q.; Zhang, X.; Jin, Z.; Zhang, J.; Gao, Z.; Li, Y.; Liu, S. F., Energy-Down-Shift CsPbCl3:Mn Quantum Dots for Boosting the Efficiency and Stability of Perovskite Solar Cells. ACS Energy Lett. 2017, 2, 1479-1486. (56) Xu, K.; Lin, C. C.; Xie, X.; Meijerink, A., Efficient and Stable Luminescence from Mn2+ in Core and Core-Isocrystalline Shell CsPbCl3 Perovskite Nanocrystals. Chem. Mater. 2017, 29, 4265-4272. (57) Chen, D.; Fang, G.; Chen, X., Silica-Coated Mn-Doped CsPb(Cl/Br)3 Inorganic Perovskite Quantum Dots: Exciton-to-Mn Energy Transfer and Blue-Excitable Solid-State Lighting. ACS Appl. Mater. Interfaces 2017, 9, 40477-40487. (58) Parobek, D.; Roman, B. J.; Dong, Y.; Jin, H.; Lee, E.; Sheldon, M.; Son, D. H., Exciton-to-Dopant Energy Transfer in Mn-Doped Cesium Lead Halide Perovskite Nanocrystals. Nano Lett. 2016, 16, 7376-7380. (59) Lin, C. C.; Xu, K. Y.; Wang, D.; Meijerink, A., Luminescent manganese-doped CsPbCl3 perovskite quantum dots. Sci. Rep. 2017, 7, 45906. (60) Rabouw, F. T.; Kamp, M.; van Dijk-Moes, R. J.; Gamelin, D. R.; Koenderink, A. F.; Meijerink, A.; Vanmaekelbergh, D., Delayed Exciton Emission and Its Relation to Blinking in CdSe Quantum Dots. Nano Lett. 2015, 15, 7718-7725. (61) Gao, Y.; Peng, X., Photogenerated excitons in plain core CdSe nanocrystals with unity radiative decay in single channel: the effects of surface and ligands. J. Am. Chem. Soc. 2015, 137, 4230-4235. (62) Rossi, D.; Parobek, D.; Dong, Y.; Son, D. H., Dynamics of Exciton–Mn Energy Transfer in Mn-Doped CsPbCl3 Perovskite Nanocrystals. J. Phys. Chem. C 2017, 121, 17143-17149.

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TOC The composite of Mn2+-doped CsPbCl3 perovskite embedded in zeolite-Y was successfully prepared, which has much better resistance to elevated temperature and moisture compared to the bare perovskite QDs.

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Confining Mn2+-Doped Lead Halide Perovskite in Zeolite-Y as

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