Wavelength-tunable deep blue emission from pure bromide-based colloidal perovskite nanocrystals

Abstract

Metal halide perovskites are promising light emitters due to their tunable and highly pure emission color in visible light. However, achieving deep blue emission remains a major challenge due to low stability and intrinsic defects. Traditional methods for synthesizing blue-emitting colloidal perovskite nanocrystals (PNCs) involve organic ammonium engineering and halide engineering, which often suffer from problems such as ion migration and color instability. In this study, we demonstrate a novel central metal engineering approach that achieves deep blue emission with a wavelength of 435.8 nm from pure bromide-based PNCs at room temperature. To synthesize deep blue-emitting pure-bromide-based PNCs, we incorporate manganese bromide (MnBr₂) to the formamidinium-guanidinium lead bromide (FA_0.9GA_0.1PbBr₃) PNCs. Mn²⁺ suppresses the growth of FA_0.9GA_0.1PbBr₃ crystals during the synthesis, resulting in decreases in both particle size and dimensionality and deep blue emission by the quantum confinement effect. The emission wavelength of pure-bromide-based PNCs is controlled by varying the amount of MnBr₂. This study provides an effective and simple method for achieving deep blue emission from pure bromide-based PNCs, offering significant advantages for display technologies such as light-emitting diodes.

Keywords

Deep blue emission / perovskite nanocrystal / central metal engineering / quantum confinement effect / ligand-assisted reprecipitation

References

[1] Schmidt LC,González-Carrero S.Nontemplate synthesis of CH₃NH₃PbBr₃ perovskite nanoparticles.J Am Chem Soc2014;136:850-3

[2] Kim YH,Lee TW.Metal halide perovskite light emitters.Proc Natl Acad Sci U S A2016;113:11694-702 PMCID:PMC5081613

[3] Kim YH,Lee TW.Strategies to improve luminescence efficiency of metal-halide perovskites and light-emitting diodes.Adv Mater2019;31:1804595

[4] Koscher BA,Bronstein ND.Essentially trap-free CsPbBr₃ colloidal nanocrystals by postsynthetic thiocyanate surface treatment.J Am Chem Soc2017;139:6566-9

[5] De Roo J,Geiregat P.Highly dynamic ligand binding and light absorption coefficient of cesium lead bromide perovskite nanocrystals.ACS Nano2016;10:2071-81

[6] Wang H,Tang A.High-performance CsPb_1-xSn_xBr₃ perovskite quantum dots for light-emitting diodes.Angew Chem Int Ed2017;129:13838-42

[7] Chiba T,Ebe H.Anion-exchange red perovskite quantum dots with ammonium iodine salts for highly efficient light-emitting devices.Nature Photon2018;12:681-7

[8] Song J,Li J.Organic-inorganic hybrid passivation enables perovskite QLEDs with an EQE of 16.48%.Adv Mater2018;30:e1805409

[9] Kim YH,Kim S.Exploiting the full advantages of colloidal perovskite nanocrystals for large-area efficient light-emitting diodes.Nat Nanotechnol2022;17:590-7

[10] Kim Y,Kakekhani A.Comprehensive defect suppression in perovskite nanocrystals for high-efficiency light-emitting diodes.Nat Photonics2021;15:148-55

[11] Kong L,Zhao B.Fabrication of red-emitting perovskite LEDs by stabilizing their octahedral structure.Nature2024;631:73-9

[12] Li G,Zhu H,Tang J.Surface ligand engineering for near-unity quantum yield inorganic halide perovskite QDs and high-performance QLEDs.Chem Mater2018;30:6099-107

[13] Dong Y,Yuan F.Bipolar-shell resurfacing for blue LEDs based on strongly confined perovskite quantum dots.Nat Nanotechnol2020;15:668-74

[14] Chen C,Bai W.Highly stable CsPbI₃:Sr²⁺ nanocrystals with near-unity quantum yield enabling perovskite light-emitting diodes with an external quantum efficiency of 17.1%.Nano Energy2021;85:106033

[15] Ren Z,Sun XW.Strategies toward efficient blue perovskite light‐emitting diodes.Adv Funct Mater2021;31:2100516

[16] Bi C,Li Q,Tian J.Thermally stable copper(II)-doped cesium lead halide perovskite quantum dots with strong blue emission.J Phys Chem Lett2019;10:943-52

[17] Liu R.Blue perovskite light-emitting diodes (LEDs): a minireview.Instrum Sci Technol2020;48:616-36

[18] Shao H,Wu X.High brightness blue light-emitting diodes based on CsPb(Cl/Br)₃ perovskite QDs with phenethylammonium chloride passivation.Nanoscale2020;12:11728-34.

[19] Protesescu L,Bodnarchuk MI.Nanocrystals of cesium lead halide perovskites (CsPbX₃, X = Cl, Br, and I): novel optoelectronic materials showing bright emission with wide color gamut.Nano Lett2015;15:3692-6

[20] He X,Yang S.Fully-inorganic trihalide perovskite nanocrystals: a new research frontier of optoelectronic materials.Adv Mater2017;29

[21] Yang X,Yu M.Focus on perovskite emitters in blue light-emitting diodes.Light Sci Appl2023;12:177 PMCID:PMC10363551

[22] Polavarapu L,Feldmann J.Advances in quantum-confined perovskite nanocrystals for optoelectronics.Adv Energy Mater2017;7:1700267

[23] Sichert JA,Mutz N.Quantum size effect in organometal halide perovskite nanoplatelets.Nano Lett2015;15:6521-7

[24] Weidman MC,Stranks SD.Highly tunable colloidal perovskite nanoplatelets through variable cation, metal, and halide composition.ACS Nano2016;10:7830-9

[25] Kumar S,Yakunin S.Efficient blue electroluminescence using quantum-confined two-dimensional perovskites.ACS Nano2016;10:9720-9

[26] Kumar S,Kallikounis N.Ultrapure green light-emitting diodes using two-dimensional formamidinium perovskites: achieving recommendation 2020 Color coordinates.Nano Lett2017;17:5277-84

[27] Wang Y,Li R.Quantum-confined perovskite nanocrystals enabled by negative catalyst strategy for efficient light-emitting diodes.Small2024;20:e2402825

[28] Chu Z,Ma F.Large cation ethylammonium incorporated perovskite for efficient and spectra stable blue light-emitting diodes.Nat Commun2020;11:4165 PMCID:PMC7441179

[29] Yuan F,Zhang L.A Cocktail of multiple cations in inorganic halide perovskite toward efficient and highly stable blue light-emitting diodes.ACS Energy Lett2020;5:1062-9

[30] Jiang Y,Cui M.Spectra stable blue perovskite light-emitting diodes.Nat Commun2019;10:1868 PMCID:PMC6478869

[31] Liu Y,Du K.Efficient blue light-emitting diodes based on quantum-confined bromide perovskite nanostructures.Nat Photonics2019;13:760-4

[32] Zhang M,Zhao G.Efficient blue CsPbBr₃ perovskite nanocrystals synthesis with the assistance of zwitterionic straight chain amino acids.Colloids Surf A Physicochem Eng Asp2023;673:131793

[33] Grandhi GK,Ong SP.Jahn-Teller distortion-driven robust blue-light-emitting perovskite nanoplatelets.Appl Mater Today2020;20:100668

[34] Li X,Chen X.Deep-blue narrow-band emissive cesium europium bromide perovskite nanocrystals with record high emission efficiency for wide-color-gamut backlight displays.Mater Horiz2024;11:1294-304

[35] Xie Y,Bravić I.Highly Efficient blue-emitting CsPbBr₃ perovskite nanocrystals through neodymium doping.Adv Sci2020;7:2001698

[36] Guria AK,Adhikari SD.Doping Mn²⁺ in lead halide perovskite nanocrystals: successes and challenges.ACS Energy Lett2017;2:1014-21

[37] Feldmann S,Bravić I.Charge carrier localization in doped perovskite nanocrystals enhances radiative recombination.J Am Chem Soc2021;143:8647-53 PMCID:PMC8297723

[38] Liu W,Li H.Mn²⁺-doped lead halide perovskite nanocrystals with dual-color emission controlled by halide content.J Am Chem Soc2016;138:14954-61

[39] Liu Y,Zhu Y,Matras-postolek K.Ion exchange derived CsPbBr₃: Mn nanocrystals with stable and bright luminescence towards white light-emitting diodes.Mater Res Bull2022;153:111915

[40] Hou S,Quan Q.Efficient blue and white perovskite light-emitting diodes via manganese doping.Joule2018;2:2421-33

[41] Proppe AH,Teale S.Multication perovskite 2D/3D interfaces form via progressive dimensional reduction.Nat Commun2021;12:3472 PMCID:PMC8190276

[42] Kim YH,Kim YT.Highly efficient light-emitting diodes of colloidal metal-halide perovskite nanocrystals beyond quantum size.ACS Nano2017;11:6586-93

[43] Slimi B,Ben Assaker I,Chtourou R.Synthesis and characterization of perovskite FAPbBr_3-xI_x thin films for solar cells.Monatsh Chem2017;148:835-44

[44] Yu D,Cao F.Cation exchange-induced dimensionality construction: from monolayered to multilayered 2D single crystal halide perovskites.Adv Mater Interfaces2017;4:1700441

[45] Takeoka Y,Rikukawa M.Systematic studies on chain lengths, halide species, and well thicknesses for lead halide layered perovskite thin films.Bull Chem Soc Jpn2006;79:1607-13

[46] Zhang D,Yu Y,Yang P.Solution-phase synthesis of cesium lead halide perovskite nanowires.J Am Chem Soc2015;137:9230-3

[47] Pan A,Fan X.Insight into the ligand-mediated synthesis of colloidal CsPbBr₃ perovskite nanocrystals: the role of organic acid, base, and cesium precursors.ACS Nano2016;10:7943-54

[48] Sun S,Xu Y,Deng Z.Ligand-mediated synthesis of shape-controlled cesium lead halide perovskite nanocrystals via reprecipitation process at room temperature.ACS Nano2016;10:3648-57