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Room Temperature Synthesis of Mn-Doped Cesium Lead Halide Quantum Dots with High Mn Substitution Ratio Jingrun Zhu, Xiaoling Yang, Yihua Zhu, Yuanwei Wang, Jin Cai, Jianhua Shen, Luyi Sun, and Chunzhong Li J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.7b01820 • Publication Date (Web): 18 Aug 2017 Downloaded from http://pubs.acs.org on August 18, 2017

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The Journal of Physical Chemistry Letters

Room Temperature Synthesis of Mn-Doped Cesium Lead Halide Quantum Dots with High Mn Substitution Ratio Jingrun Zhu,† Xiaoling Yang,† Yihua Zhu,*,† Yuanwei Wang,† Jin Cai,† Jianhua Shen,† Luyi Sun,‡ and Chunzhong Li*,†

†

Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science

and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China. ‡

Department of Chemical & Biomolecular Engineering and Polymer Program, Institute of

Materials Science, University of Connecticut, Storrs, Connecticut 06269, United States.

*E-mail: [email protected]. *E-mail: [email protected].

ACS Paragon Plus Environment

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ABSTRACT: Here we report the room temperature, atmospheric synthesis of Mn-doped cesium lead halide (CsPbX3) perovskite QDs. The synthesis is performed without any sort of protection and the dual-color emission mechanism is revealed by density functional theory. The Mn concentration reaches a maximum atomic percentage of 37.73 at%, which is significantly higher in comparison to those achieved in earlier reports via high temperature hot injection method. The optical properties of as-prepared nanocrystals (NCs) remain consistent even after several months. Therefore, red-orange LEDs were fabricated by coating the composite of PS and as-prepared QDs onto ultraviolet LED chips. Additionally, the present approach may open up new methods for doping other ions in CsPbX3 QDs under room temperature, the capability of which is essential for applications such as memristors and other devices.

TOC GRAPHICS


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The last eight years have witnessed the successful development of lead halide perovskite possessing unique optical and electrical properties. Lead halide perovskite QDs have proven to be an ideal material for solar cells,1-2 lasers,3 light-emitting devices,4-7 biosensors8 and memristors.9 In particular perovskite, as a promising photovoltaic material, has exhibited high efficiency in power conversion, skyrocketing from 3.8 %10 to 22.1 %11 in less than seven years. Halide lead perovskites have frequently been developed as extremely promising light-emitting materials, since many groups focus on the potential to challenge silicon solar cells. The organic-inorganic hybrid perovskite (CH3NH3)PbX3 (X = Cl, Br, I) QDs have been shown to exhibit narrow full-width at half-maximum (FWHM), as well as highly efficient photoluminescence (PL) tunable over the entire visible spectral range.12-14 Devices which emit light in the infrared to violet (ca. 400 nm) can be fabricated by regulating the nanocrystal size and by cation substitution or blending.15,16 Friend et al. reported bright light-emitting diodes with the demonstration of electroluminescence in the near-infrared to green range by tuning the halide compositions.12 However, a shortcoming of the hybrid organic-inorganic perovskite is that it is greatly sensitive to humidity and heat. Compared to the hybrid organic-inorganic perovskite QDs, the all inorganic perovskite (CsPbX3) QDs show the same optical properties17 but higher stability18 and thus are outstanding candidates for optoelectronics. Zeng et al. synthesized cesium lead perovskite nanocrystals at room temperature by supersaturated crystallization.4 Synthesis by room temperature supersaturated crystallization is economically superior to the method of high temperature hot injection due to comparatively low processing cost and simple operations. Although there are many advantages of all inorganic lead halide perovskite QDs, the high toxicity of lead is cause for serious concern due to impacts on both environmental and public


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health in commercial applications.19 Therefore, the development of lead-free all inorganic perovskite quantum dots is imperative in order to eliminate the risks and consequences associated with lead toxicity. In recent years, substantial efforts have been aimed toward decreasing the content of Pb via Mn-doped perovskite QDs because of the numerous advantages of manganese, including low toxicity and high abundance.20 Interestingly, MnII substitution perovskite quantum dots display dual-color emission. Sheldon and coworker reported on Mn-doped cesium lead halide perovskite (Mn: CsPbX3) QDs, synthesized via the high temperature hot injection method.21 In addition, Klimov and coworker studied the mechanisms of interactions occurring between the impurity and the host.22 Unfortunately, when subjected to high temperatures the doped Mn2+ ions in QDs tend to be ejected to the surface of NCs which leads to an unfavorably low Mn substitution ratio, a phenomenon known as self-annealing.23 Meanwhile, the self-annealing process suggests that an ultrahigh level of doping can be realized with a lower temperature, typically 300 K. Furthermore, the intensity of broad Mn2+ emission of CsPbxMn1-xClyBr3-y (0 < x < 1, 0 < y < 3) is much weaker because Pb2+ substitutes Mn2+ in the process of postsynthetic anion exchange.22 To the best of our knowledge, studies on high Mn substitution ratio perovskite QDs via one-pot synthesis at room-temperature under atmosphere as well as research on the mechanism of dual-color emission based on density functional theory have not yet been reported. Herein we report one-pot synthesis of Mn-doped CsPbX3 via room temperature supersaturated crystallization method under atmosphere. Following synthesis, we then fabricate red-orange LEDs by coating the composite of as-prepared QDs and PS onto the ultraviolet LED chips. Our approach is derived and modified from previous supersaturation crystallization and coprecipitation experiments. The sources of Mn2+ and Pb2+ were simultaneously transferred from


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polar solvent to nonpolar solvent. Compared to the work of Klimov22 and other works,21,24,25 we demonstrated higher level Mn doping of cesium lead halide perovskite QDs (The Mn ratio is up to 37.73 at %). As the Mn substitution ratios increase, the PL peak intensity of broad Mn2+ emission is enhanced, making possible the manifestation of orange-red perovskite QDs LEDs. Finally, calculations of partial electronic density of states (PDOS) were performed in order to reveal the dual-color emission mechanism. The one-pot room temperature synthesis of Mn-doped perovskite QDs can be briefly described as the introduction of a solution of inorganic ions to a poor solution such as toluene. In a typical synthesis of Mn-doped perovskite QDs, PbBr2 and CsBr were dissolved in a mixture of DMF, oleylamine (OAm) and oleic acid (OA) as the precursor. MnCl2 was then dissolved in DMF as the source of Mn2+ and Cl-. 1 mL precursor solution and 0.2 mL MnCl2 solution were simultaneously added into the toluene container under vigorous stirring. The bright orange emission was observed after several seconds. The emission color can be tuned by simply changing the Mn-to-Pb molar feed ratios. All above operations were completed at approximately 300 K under atmosphere and without any sort of protection. Any side-products and large particles were removed from the crude solution by centrifuging for 10 minutes at 4500 rpm. Acetonitrile was subsequently added into the supernatant followed by 10000 rpm centrifugation for 15 minutes. The precipitates were then re-dispersed in n-hexane in preparation for further characterization. Transmission electron microscopy (TEM) measurements indicate that the length of as-prepared Mn2+-doped perovskite NCs is approximately 11 nm (Figure 1). High-resolution transmission electron microscopy (HRTEM) reveals that the as-prepared Mn2+-doped perovskite QDs maintain good crystallinity with a cubic morphology. The results of HRTEM illuminate obvious crystal lattices in the as-prepared Mn2+-doped perovskite NCs with


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the interplanar distance of ~0.56 nm (Figure 1d), which is well consistent with the (100) plane of the cubic CsPbCl3. Power X-ray diffraction (XRD, Figure 2a) indicates as well that the as-prepared Mn2+-doped perovskite QDs is highly crystalline. Interestingly, in this work, we used the PbBr2 solution as the precursor while both HRTEM and XRD indicate that the crystal phase is consistent with tetragonal phase CsPbCl3 (PDF#18-0366), but not with CsPbBr3 or CsMnCl3. Furthermore, the MnCl2 content in the nanocrystals is ultrahigh, with Mn concentration up to 37.73 at% (Figure S1) as revealed by ICP-MS. All of the above demonstrates that we prepared remarkable NCs possessing ultrahigh Mn substation ratio by one-pot room temperature synthesis, with results that are in strong agreement with our previous prediction which was based on self-annealing.

Figure 1. Morphological and structural characterizations of Mn-doped perovskite NCs. TEM images of as-prepared NCs with Mn-to-Pb molar feed ratios of 0 (a), 2.0 (b), 5.0 (c) and 7.5 (d). TEM and (inset) HRTEM images of CsPbBr3 NCs.


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As previously mentioned, the host crystal is tetragonal phase CsPbCl3 but not CsPbBr3. Inspired by the work of Erwin et al.,26 which attaches great importance to strong binding of dopant ions as it relates to impurity incorporation and material overgrowth, we investigated the potential role of bond strengths by analyzing the energy of hemolytic dissociation. As shown in the Table S2, the dissociation energy of Mn-Cl and Pb-Cl is higher than that of Mn-Br and Pb-Br, which is beneficial for Mn2+, Pb2+ and Cl- ions in the reforming of host crystals. Therefore, the mix solutions prefer to form CsPbxMn1-xClyBr3-y NCs. Figure 2b compares the PL spectra of Mn-doped perovskite NCs with MnCl2-PbBr2 molar feed ratios of 2.0, 5.0 and 7.5. The PL emission spectra shows dual-color emission peaks, including a narrow band-edge emission from excitons and a broad band emission from Mn2+ (FWHM ca. 100 nm). The band-edge spectral features are consistent with previous reports, which can be attributed to the parent NCs (CsPbClyBr3-y).27,28 The broad band emission, centering at ~600 nm, can be attributed to Mn2+ d-d emission, namely, 4T1-6A1 transition.21 As shown in the Table S3, the maximum PLQY of Mn2+ is up to 40.0 % and the maximum total PLQY is 41.6 % while the Mn/Pb feed ratio is 5.0. However, when the Mn/Pb feed ratio is 7.5 both the PLQY of Mn2+ and the total PLQY dramatically decreased which can be attributed to the increase of intrinsic defects, including surface and internal defects. Interestingly, closer inspection indicates that, with the increase of MnCl2 solution, the band-edge emission peaks shift to blue while the broad band emission peaks shift to red, despite no obvious change of NC size, observations which differ from the previous work.21,22,24,25,29. More details regarding these results can be found in the Supporting Information Figure S2 and Figure S3. The blue-shift of the band-edge emission is consistent with previous reports of anion exchange and is directly related to halide content. The red-shift of broad band emission peaks of Mn-doped NCs is likely caused by enhanced Mn-Mn


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interactions.19 Moreover, as shown in the Figure 2c, the absorption spectra show a blue shift with increasing Mn substitution ratio, which also confirms the increase of Cl- in the NCs. The PL spectrum for the Mn2+ emission peak resembles the absorption spectrum, indicating that it is sensitized by the host NC (Figure 2d).

Figure 2. (a) XRD patterns of as-prepared NCs with Mn-to-Pb molar feed ratios of 1.0, 2.0, 5.0 and 7.5, respectively. (b) Normalized PL spectra of as-prepared NCs with Mn-to-Pb molar feed ratios of 2.0, 5.0 and 7.5. (c) Absorption spectra of Mn-doped perovskite NCs of varying MnCl2 content. (d) The optical properties of Mn-doped perovskite QDs with Mn-to-Pb molar feed ratios of 2.0.

Figure 3 illustrates the partial density of state (PDOS) of CsPbCl3, CsPb0.875Mn0.125Cl3 and CsPb0.75Mn0.25Cl3, respectively. The PDOS of CsPbCl3 shows that the conduction band and the upper valence band are mainly dominated by the electrons of Pb (4p) and Cl (3p) orbits, while Cs


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seem to have no apparent contribution.

This may explain the band-edge emission of CsPbCl3

QDs. However, as shown in Figure 3, besides the contribution of Pb (4p) and Cl (3p) orbits, the contribution of Mn (d) orbits is obvious to both the conduction band and the upper valence band. Additionally, the energy of d-d transition in Mn2+ ions is lower than the energy gap of CsPbCl3, causing energy transfer between excitons and Mn2+ ions. The calculation results imply that dual-color emission is most likely caused by the band-edge emission of CsPbCl3 QDs in conjunction with the d-d transition in Mn2+ ions.

Figure 3. PDOS of CsPbCl3, CsPb0.875Mn0.125Cl3 and CsPb0.75Mn0.25Cl3, respectively.

Inspired by previous work regarding perovskite LEDs, we herein investigated the stability of the as-prepared Mn-doped perovskite QDs. The PL spectra of as-prepared NCs in n-hexane exhibit no apparent change after several months, despite the metastability of the Mn-doped NCs. Thus we fabricated LEDs by casting the composites of the as-prepared QDs and PS onto


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commercial ultraviolet LED chips. As Figure 4 shows, the LEDs exhibit bright orange-red emission. The Figure S6 shows the color coordinate of QD-based LED devices from different Mn concentrations. The color coordinate is (0.5917, 0.4027) while the Mn substitution is up to ~37 %.

Figure 4. Diagram of light-emitting devices by coating the composites of Mn-doped perovskite QDs onto 390 nm LED chips.

In summary, we carried out one-pot room temperature synthesis of CsPbxMn1-xClyBr3-y perovskite QDs, demonstrating that the low temperature reaction prefers to form metastable phase. The subsequent calculations of PDOS imply that d-d transition of Mn2+ and band edge emission from excitons presumably lead to dual-color emission. It should be noted that the room temperature synthesis of as-prepared perovskite QDs provides a unique opportunity to systematically study the interactions between the semiconductor host or the impurity and the semiconductor host. These interactions are particularly relevant in that they control such properties of perovskite QDs as PL and the radiative decay rate from excitons. Furthermore, the as-prepared perovskite QDs exhibit bright orange emission owing to an ultrahigh level of Mn


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doping. This method makes lead-free perovskite QDs possible and also affirms the possibility of doping other ions (such as Li+, Zn2+, Co2+, Sn2+ and even Cu2+) in perovskite QDs at room temperature, presenting new avenues for various applications based on metal ion doping perovskite materials such as LEDs, biosensors, memristors and so forth. AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected]. *E-mail: [email protected]. Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (21322607, 21406072, 21471056, 21676093 and 91534202), the Basic Research Program of Shanghai (15JC1401300), the Key Scientific and Technological Program of Shanghai (14521100800), the International Science and Technology Cooperation Program of China (2015DFA51220), and the Fundamental Research Funds for the Central Universities (222201718002). ASSOCIATED CONTENT Supporting Information. The synthesis procedure, elemental analysis and additional absorption and PL spectra


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REFERENCES (1)

Yang, M.; Zhang, T.; Schulz, P.; Li, Z.; Li, G.; Kim, D. H.; Guo, N.; Berry, J. J.; Zhu, K.;

Zhao, Y. Facile Fabrication of Large-Grain CH3NH3PbI3-xBrx Films for High-Efficiency Solar Cells via CH3NH3Br-Selective Ostwald Ripening. Nat. Commun.. 2016, 7, 12305. (2)

Li, W.; Fan, J.; Mai, Y.; Wang, L.; Aquointermediate Assisted Highly Orientated

Perovskite Thin Films toward Thermally Stable and Efficient Solar Cells. Adv. Energy Mater. 2017, 7, 1601433. (3)

Zhu, H.; Fu, Y.; Meng, F.; Wu, X.; Gong, Z.; Ding, Q.; Gustafsson, M. V.; Trinh, M. T.;

Jin, S.; Zhu, X. Y.; Lead Halide Perovskite Nanowire Lasers with Low Lasing Thresholds and High Quality Factors. Nat. Mater. 2015, 14, 636-642. (4)

Li, X, M ; Wu, Y.; Zhang, S, L.; Cai, B.; Gu, Y.; Song, J. Z.; Zeng, H. B. 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. (5)

Li, J.; Xu, L.; Wang, T.; Song, J.; Chen, J.; Xue, J.; Dong, Y.; Cai, B.; Shan, Q.; Han, B.;

Zeng, H. 50-Fold EQE Improvement up to 6.27% of Solution-Processed All-Inorganic Perovskite CsPbBr3 QLEDs via Surface Ligand Density Control. Adv. Mater. 2017, 29, 1603885. (6)

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. (7)

Zeng, H.; Duan, G.; Li, Y.; Yang, S.; Xu, X.; Cai, W.; Blue Luminescence of ZnO


12

Page 13 of 16

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


Nanoparticles Based on Non-Equilibrium Processes: Defect Origins and Emission Controls. Adv. Funct. Mater. 2010, 20, 561-572. (8)

Wang, Y.; Zhu, Y.; Huang, J.; Cai, J.; Zhu, J.; Yang, X.; Shen, J.; Jiang, H.; Li, C. J.

Perovskite Quantum Dots-Based Monolithic Electrospun Fiber Membrane as an Ultrastable and Ultrasensitive Fluorescent Sensor in Aqueous Medium. J. Phys. Chem. Lett. 2016, 7, 4253-4258. (9)

Yan, K.; Chen, B.; Hu, H.; Chen, S.; Dong, B.; Gao, X.; Xiao, X.; Zhou, J.; Zou, D. First

Fiber-Shaped Non-Volatile Memory Device Based on Hybrid Organic-Inorganic Perovskite. Adv. Electronic Mater. 2016, 2, 1600160. (10)

Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. Organometal Halide Perovskites as

Visible-Light Sensitizers for Photovoltaic Cells. J. Am. Chem. Soc. 2009, 131, 6050-6051. (11)

Saliba, M.; Matsui, T.; Seo, J. Y.; Domanski, K.; Correa-Baena, J. P.; Nazeeruddin, M.

K.; Zakeeruddin, S. M.; Tress, W.; Abate, A.; Hagfeldt, A. et al. Cesium-Containing Triple Cation Perovskite Solar Cells: Improved Stability, Reproducibility and High Efficiency. Energy Environ. Sci. 2016, 9, 1989-1997. (12)

Tan, Z. K.; Moghaddam, R. S.; Lai, M. L.; Docampo, P.; Higler, R.; Deschler, F.; Price,

M.; Sadhanala, A.; Pazos, L. M.; Credgington, D. et al. Bright Light-Emitting Diodes Based on Organometal Halide Perovskite. Nat. Nanotechnol. 2014, 9, 687-692. (13)

Ning, Z.; Gong, X.; Comin, R.; Walters, G.; Fan, F.; Voznyy, O.; Yassitepe, E.; Buin, A.;

Hoogland, S.; Sargent, E. H. Quantum-Dot-in-Perovskite Solids. Nature 2015, 523, 324-328. (14)

Zhao, Y.; Xu, X.; You, X. Colloidal Organometal Halide Perovskite (MAPbBrxI3−x, 0 ≤ x


13


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

Page 14 of 16

≤ 3) Quantum Dots: Controllable Synthesis and Tunable Photoluminescence. Sci. Rep. 2016, 6, 35931. (15) Green, M. A.; Ho-Baillie, A.; Snaith, H. J. The Emergence of Perovskite Solar Cells. Nat. Photonics 2014, 8, 506-514. (16)

Sichert, J. A.; Tong, Y.; Mutz, N.; Vollmer, M.; Fischer, S.; Milowska, K. Z.; Garcia

Cortadella, R.; Nickel, B.; Cardenas-Daw, C.; Stolarczyk, J. K. et al. Quantum Size Effect in Organometal Halide Perovskite Nanoplatelets. Nano lett. 2015, 15, 6521-6527. (17)

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. (18)

Sutton, R. J.; Eperon, G. E.; Miranda, L.; Parrott, E. S.; Kamino, B. A.; Patel, J. B.;

Hörantner, M. T.; Johnston, M. B.; Haghighirad, A. A.; Moore, D. T. Bandgap-Tunable Cesium Lead Halide Perovskites with High Thermal Stability for Efficient Solar Cells. Adv. Energy Mater. 2016, 6, 1502458. (19) 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. (20)

Cheng, F.; Shen, J.; Peng, B.; Pan, Y.; Tao, Z.; Chen, J. Rapid Room-Temperature

Synthesis of Nanocrystalline Spinels as Oxygen Reduction and Evolution Electrocatalysts. Nat. Chem. 2011, 3, 79-84.


14

Page 15 of 16

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


(21)

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. (22)

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. (23)

Nag, A.; Chakraborty, S.; Sarma, D. D. To Dope Mn2+ in a Semiconducting Nanocrystal.

J. Am. Chem. Soc. 2008, 130, 10605-10611. (24)

van der Stam, W.; Geuchies, J. J.; Altantzis, T.; van den Bos, K. H.; Meeldijk, J. D.; Van

Aert, S.; 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. (25)

Lin, C. C.; Xu, K. Y.; Wang, D.; Meijerink, A. Luminescent Manganese-Doped CsPbCl3

Perovskite Quantum Dots. Sci. Rep. 2017, 7, 45906. (26)

Erwin, S. C.; Zu, L.; Haftel, M. I.; Efros, A. L.; Kennedy, T. A.; Norris, D. J. Doping

Semiconductor Nanocrystals. Nature 2005, 436, 91-94. (27)

Parobek, D.; Dong, Y.; Qiao, T.; Rossi, D.; Son, D. H. Photoinduced Anion Exchange in

Cesium Lead Halide Perovskite Nanocrystals. J. Am. Chem. Soc. 2017, 139, 4358-4361. (28)

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


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Page 16 of 16

Anion Exchange Reactions. J. Am. Chem. Soc. 2015, 137, 10276-10281. (29)

Mir, W. J.; Jagadeeswararao, M.; Das, S.; Nag, A. Colloidal Mn-Doped Cesium Lead

Halide Perovskite Nanoplatelets. ACS Energy Lett. 2017, 2, 537-543.


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