Electrogenerated chemiluminescence (ECL) has been extensively used in ultrasensitive electroanalysis because it can be generated electrochemically without using expensive optics and light sources. Visible ECL emission can be obtained with a reasonable quantum yield and stability. Blue ECL is rare and often suffers from stability and poor quantum efficiency. Blue ECL emission at 473 nm from organometallic halide perovskite nanocrystals (PNCs), CH3NH3PbCl1.08Br1.92, is reported here for the first time using tripropylamine (TPrA) as co-reactant. The blue ECL emission peak resembles its photoluminescence peak position. In addition to this blue emission peak, the ECL spectra of CH3NH3PbCl1.08Br1.92 PNCs also showed a broad ECL peak at 745 nm. Generation of the second ECL peak at 745 nm from CH3NH3PbCl1.08Br1.92 PNCs was can be explained by the existence of surface trap states on as-synthesized PNC due to incomplete surface passivation. Halide anion tunability of ECL emission from CH3NH3PbX3 (X: Cl, Br, I) PNCs is also demonstrated. The fluorescence microscopy image of single PNC and stability of selected single PNCs are presented in this with simultaneous acquisition of fluorescence spectra using 405-nm laser excitation. The photoluminescence (PL) decay was described by PL lifetime (τ) of 1.2 ns. The effect of the addition of surfactants (oleic acid and n-octylamine) on the fluorescence intensity and stability of CH3NH3PbCl1.08Br1.92 PNCs is also discussed.
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Bella F, Griffini G, Correa-Baena J-P, Saracco G, Grätzel M, Hagfeldt A, et al. Improving efficiency and stability of perovskite solar cells with photocurable fluoropolymers. Science. 2016;354(6309):203–6. https://doi.org/10.1126/science.aah4046.
Tsai H, Nie W, Blancon J-C, Stoumpos CC, Asadpour R, Harutyunyan B, et al. High-efficiency two-dimensional Ruddlesden-Popper perovskite solar cells. Nature. 2016;536(7616):312.
Stranks SD, Snaith HJ. Metal-halide perovskites for photovoltaic and light-emitting devices. Nat Nanotechnol. 2015;10(5):391.
Kojima A, Teshima K, Shirai Y, Miyasaka T. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J Am Chem Soc. 2009;131(17):6050–1.
Tan Z-K, Moghaddam RS, Lai ML, Docampo P, Higler R, Deschler F, et al. Bright light-emitting diodes based on organometal halide perovskite. Nat Nanotechnol. 2014;9(9):687–92.
Kim YH, Cho H, Heo JH, Kim TS, Myoung N, Lee CL, et al. Multicolored organic/inorganic hybrid perovskite light-emitting diodes. Adv Mater. 2015;27(7):1248–54.
Zhang Q, Ha ST, Liu X, Sum TC, Xiong Q. Room-temperature near-infrared high-Q perovskite whispering-gallery planar nanolasers. Nano Lett. 2014;14(10):5995–6001.
Sutherland BR, Hoogland S, Adachi MM, Wong CT, Sargent EH. Conformal organohalide perovskites enable lasing on spherical resonators. ACS Nano. 2014;8(10):10947–52.
Huang H, Susha AS, Kershaw SV, Hung TF, Rogach AL. Control of emission color of high quantum yield CH3NH3PbBr 3 perovskite quantum dots by precipitation temperature. Adv Sci. 2015;2(9):1500194.
Xing G, Mathews N, Lim SS, Yantara N, Liu X, Sabba D, et al. Low-temperature solution-processed wavelength-tunable perovskites for lasing. Nat Mater. 2014;13(5):476.
Dohner ER, Jaffe A, Bradshaw LR, Karunadasa HI. Intrinsic white-light emission from layered hybrid perovskites. J Am Chem Soc. 2014;136(38):13154–7.
Era M, Morimoto S, Tsutsui T, Saito S. Organic-inorganic heterostructure electroluminescent device using a layered perovskite semiconductor (C6H5C2H4NH3)2PbI4. Appl Phys Lett. 1994;65(6):676–8.
Miao W. Electrogenerated chemiluminescence and its biorelated applications. Chem Rev. 2008;108(7):2506–53.
Zou G, Tan X, Long X, He Y, Miao W. Spectrum-resolved dual-colorelectrochemiluminescence immunoassay for simultaneous detection of two targets with nanocrystals as tags. Anal Chem. 2017;89(23):13024–9.
Wusimanjiang Y, Meyer A, Lu L, Miao W. Effects of multi-walled carbon nanotubes on the electrogenerated chemiluminescence and fluorescence of CdTe quantum dots. Anal Bioanal Chem. 2016;408(25):7049–57.
Ding Z, Quinn BM, Haram SK, Pell LE, Korgel BA, Bard AJ. Electrochemistry and electrogenerated chemiluminescence from silicon nanocrystal quantum dots. Science. 2002;296(5571):1293–7.
Myung N, Ding Z, Bard AJ. Electrogenerated chemiluminescence of CdSe nanocrystals. Nano Lett. 2002;2(11):1315–9.
Myung N, Bae Y, Bard AJ. Effect of surface passivation on the electrogenerated chemiluminescence of CdSe/ZnSe nanocrystals. Nano Lett. 2003;3(8):1053–5.
Zhou H, Liu J, Zhang S. Quantum dot-based photoelectric conversion for biosensing applications. Trends Anal Chem. 2015;67:56–73.
Muzyka K. Current trends in the development of the electrochemiluminescent immunosensors. Biosens Bioelectron. 2014;54:393–407.
Huang Y, Fang M, Zou G, Zhang B, Wang H. Monochromatic and electrochemically switchable electrochemiluminescence of perovskite CsPbBr 3 nanocrystals. Nanoscale. 2016;8(44):18734–9.
Tan X, Zhang B, Zou G. Electrochemistry and electrochemiluminescence of organometal halide perovskite nanocrystals in aqueous medium. J Am Chem Soc. 2017;139(25):8772–6.
Huang Y, Long X, Shen D, Zou G, Zhang B, Wang H. Hydrogen peroxide involved anodic charge transfer and electrochemiluminescence of all-inorganic halide perovskite CsPbBr 3 nanocrystals in an aqueous medium. Inorg Chem. 2017;56(17):10135–8.
Cai Z, Li F, Xu W, Xia S, Zeng J, He S, et al. Colloidal CsPbBr 3 perovskite nanocrystal films as electrochemiluminescence emitters in aqueous solutions. Nano Res. 2018;11(3):1447–55.
Wu Y, Wang P, Zhu X, Zhang Q, Wang Z, Liu Y, et al. Composite of CH3NH3PbI3 with reduced graphene oxide as a highly efficient and stable visible-light photocatalyst for hydrogen evolution in aqueous HI solution. Adv Mater. 2018;30(7):1704342.
Wang Z, Liu W, Xu C, Ji B, Zheng C, Zhang X. Excellent deep-blue emitting materials based on anthracene derivatives for non-doped organic light-emitting diodes. Opt Mater. 2016;58:260–7.
Zhu M, Yang C. Blue fluorescent emitters: design tactics and applications in organic light-emitting diodes. Chem Soc Rev. 2013;42(12):4963–76.
Yang X, Xu X, Zhou G. Recent advances of the emitters for high performance deep-blue organic light-emitting diodes. J Mater Chem C. 2015;3(5):913–44.
Zhang Z-Y, Wang H-Y, Zhang Y-X, Hao Y-W, Sun C, Zhang Y, et al. The role of trap-assisted recombination in luminescent properties of organometal halide CH3NH3PbBr 3 perovskite films and quantum dots. Sci Rep. 2016;6:27286.
Hines MA, Guyot-Sionnest P. Synthesis and characterization of strongly luminescing ZnS-capped CdSe nanocrystals. J Phys Chem. 1996;100(2):468–71.
Miao W, Choi J-P, Bard AJ. Electrogenerated chemiluminescence 69: the tris (2,2‘-bipyridine) ruthenium(II),(Ru(bpy) 2+3 )/Tri-n-propylamine (TPrA) system revisited—a new route involving TPrA•+ cation radicals. J Am Chem Soc. 2002;124(48):14478–85.
Li C, Wei J, Sato M, Koike H, Xie Z-Z, Li Y-Q, et al. Halide-substituted electronic properties of organometal halide perovskite films: direct and inverse photoemission studies. ACS Appl Mater Interfaces. 2016;8(18):11526–31.
Noh JH, Im SH, Heo JH, Mandal TN, Seok SI. Chemical management for colorful, efficient, and stable inorganic–organic hybrid nanostructured solar cells. Nano Lett. 2013;13(4):1764–9.
Zhang F, Zhong H, Chen C, Wu X-G, Hu X, Huang H, et al. Brightly luminescent and color-tunable colloidal CH3NH3PbX3 (X = Br, I, Cl) quantum dots: potential alternatives for display technology. ACS Nano. 2015;9(4):4533–42.
We would like to thank the financial support from the National Science Foundation (NSF award CHE 1508192 and OIA-1539035). We also thank Central Analytical Facility at The University of Alabama for providing TEM instrument for this study. The technical support from Mr. Johnny Goodwin during TEM analysis of PNCs is greatly appreciated.
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Wusimanjiang, Y., Yadav, J., Arau, V. et al. Blue Electrogenerated Chemiluminescence from Halide Perovskite Nanocrystals. J. Anal. Test. 3, 125–133 (2019). https://doi.org/10.1007/s41664-018-0082-4
- ECL (electrogenerated chemiluminescence)
- Photoluminescence (PL)
- Perovskite nanocrystals (PNCs)
- Blue light emission
- Photoluminescence quantum yield (PLQY)