Electron–phonon interaction in efficient perovskite blue emitters

ABSTRACT Low-dimensional perovskites have—in view of their high radiative recombination rates—shown great promise in achieving high luminescence brightness and colour saturation. Here we

investigate the effect of electron–phonon interactions on the luminescence of single crystals of two-dimensional perovskites, showing that reducing these interactions can lead to bright blue

emission in two-dimensional perovskites. Resonance Raman spectra and deformation potential analysis show that strong electron–phonon interactions result in fast non-radiative decay, and

that this lowers the photoluminescence quantum yield (PLQY). Neutron scattering, solid-state NMR measurements of spin–lattice relaxation, density functional theory simulations and

experimental atomic displacement measurements reveal that molecular motion is slowest, and rigidity greatest, in the brightest emitter. By varying the molecular configuration of the ligands,

we show that a PLQY up to 79% and linewidth of 20 nm can be reached by controlling crystal rigidity and electron–phonon interactions. Designing crystal structures with electron–phonon

interactions in mind offers a previously underexplored avenue to improve optoelectronic materials' performance. Access through your institution Buy or subscribe This is a preview of

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RIGID DION–JACOBSON-TYPE TWO-DIMENSIONAL PEROVSKITES Article 16 May 2024 SUPPRESSING PHASE DISPROPORTIONATION IN QUASI-2D PEROVSKITE LIGHT-EMITTING DIODES Article Open access 25 January 2023

LIGAND SIZE EFFECTS IN TWO-DIMENSIONAL HYBRID COPPER HALIDE PEROVSKITES CRYSTALS Article Open access 01 July 2021 REFERENCES * Forrest, S. R. et al. Highly efficient phosphorescent emission

from organic electroluminescent devices. _Nature_ 395, 151–154 (1998). Article  Google Scholar  * Yang, X., Xu, X. & Zhou, G. Recent advances of the emitters for high performance

deep-blue organic light-emitting diodes. _J. Mater. Chem. C. Mater. Opt. Electron. Devices_ 3, 913–944 (2015). Article  Google Scholar  * Ponce, F. A. & Bour, D. P. Nitride-based

semiconductors for blue and green light-emitting devices. _Nature_ 386, 351–359 (1997). Article  Google Scholar  * Nakamura, S., Pearton, S. & Fasol, G. _The Blue Laser Diode_ 1–5

(Springer, Berlin, 2000). * Nanishi, Y. Nobel Prize in Physics: the birth of the blue LED. _Nat. Photon._ 8, 884–886 (2014). Article  Google Scholar  * Shirasaki, Y., Supran, G. J., Bawendi,

M. G. & Bulović, V. Emergence of colloidal quantum-dot light-emitting technologies. _Nat. Photon._ 7, 933–933 (2013). Article  Google Scholar  * Gong, X. et al. Highly efficient quantum

dot near-infrared light-emitting diodes. _Nat. Photon._ 10, 253–257 (2016). Article  Google Scholar  * Reshchikov, M. A. & Korotkov, R. Y. Analysis of the temperature and excitation

intensity dependencies of photoluminescence in undoped GaN films. _Phys. Rev. B_ 64, 115205 (2001). Article  Google Scholar  * Viswanath, A. K., Lee, J. I., Kim, D., Lee, C. R. & Leem,

J. Y. Exciton–phonon interactions, exciton binding energy, and their importance in the realization of room-temperature semiconductor lasers based on GaN. _Phys. Rev. B_ 58, 16333–16339

(1998). Article  Google Scholar  * ReshchikovM. A. & KorotkovR. Y. Analysis of the temperature and excitation intensity dependencies of photoluminescence in undoped GaN films. _Phys.

Rev. B_ 64, 115205 (2001). Article  Google Scholar  * Hauswald, C. et al. Origin of the nonradiative decay of bound excitons in GaN nanowires. _Phys. Rev. B_ 90, 1–9 (2014). Article  Google

Scholar  * Shan, W. et al. Binding energy for the intrinsic excitons in wurtzite GaN. _Phys. Rev. B_ 54, 16369–16372 (1996). Article  Google Scholar  * Chen, J. et al. Crystal structure and

temperature-dependent luminescence characteristics of KMg4(PO4)3:Eu2+ phosphor for white light-emitting diodes. _Sci. Rep._ 5, 9673 (2015). Article  Google Scholar  * Janulevicius, M. et al.

Luminescence and luminescence quenching of highly efficient Y2Mo4O15:Eu3+ phosphors and ceramics. _Sci. Rep._ 6, 26098 (2016). Article  Google Scholar  * George, N. C., Denault, K. A. &

Seshadri, R. Phosphors for solid-state white lighting. _Annu. Rev. Mater. Res._ 43, 481–501 (2013). Article  Google Scholar  * Lee, J. et al. Deep blue phosphorescent organic light-emitting

diodes with very high brightness and efficiency. _Nat. Mater._ 15, 1–8 (2015). Google Scholar  * Knupfer, M. Exciton binding energies in organic semiconductors. _Appl. Phys. A_ 77, 623–626

(2003). Article  Google Scholar  * Christensen, R. L., Drake, R. C. & Phillips, D. Time-resolved fluorescence anisotropy of perylene. _J. Phys. Chem._ 90, 5960–5967 (1986). Article 

Google Scholar  * Stranks, S. D. & Snaith, H. J. Metal-halide perovskites for photovoltaic and light-emitting devices. _Nat. Nanotech._ 10, 391–402 (2015). Article  Google Scholar  *

Sargent, E. H. et al. Structural, optical, and electronic studies of wide-bandgap lead halide perovskites. _J. Mater. Chem. C._ 3, 8839–8843 (2015). Article  Google Scholar  * Maculan, G. et

al. CH3NH3PbCl3 single crystals: inverse temperature crystallization and visible-blind UV-photodetector. _J. Phys. Chem. Lett._ 6, 3781–3786 (2015). Article  Google Scholar  * Li, J., Gan,

L., Fang, Z., He, H. & Ye, Z. Bright tail states in blue-emitting ultrasmall perovskite quantum dots. _J. Phys. Chem. Lett._ 8, 6002–6008 (2017). Article  Google Scholar  * Wang, S., Bi,

C., Yuan, J., Zhang, L. & Tian, J. Original core–shell structure of cubic CsPbBr3@amorphous CsPbBr _x_ perovskite quantum dots with a high blue photoluminescence quantum yield of over

80%. _ACS Energy Lett._ 3, 245–251 (2018). Article  Google Scholar  * Zhitomirsky, D., Voznyy, O., Hoogland, S. & Sargent, E. H. Measuring charge carrier diffusion in coupled colloidal

quantum dot solids. _ACS Nano_ 7, 5282–5290 (2013). Article  Google Scholar  * Kondo, T. et al. Resonant third-order optical nonlinearity in the layered perovskite-type material

(C6H13NH3)2PbI4. _Solid State Commun._ 105, 503–506 (1998). Article  Google Scholar  * Saparov, B. & Mitzi, D. B. Organic–inorganic perovskites: structural versatility for functional

materials design. _Chem. Rev._ 116, 4558–4596 (2016). Article  Google Scholar  * Smith, M. D., Jaffe, A., Dohner, E. R., Lindenberg, A. M. & Karunadasa, H. I. Structural origins of

broadband emission from layered Pb–Br hybrid perovskites. _Chem. Sci._ 8, 4497–4504 (2017). Article  Google Scholar  * Solis-Ibarra, D., Smith, I. C. & Karunadasa, H. I. Post-synthetic

halide conversion and selective halogen capture in hybrid perovskites. _Chem. Sci._ 6, 4054–4059 (2015). Article  Google Scholar  * Zhou, C. et al. Highly efficient broadband yellow phosphor

based on zero-dimensional tin mixed-halide perovskite. _ACS Appl. Mater. Interfaces_ 9, 44579–44583 (2017). Article  Google Scholar  * Zhou, C. et al. Luminescent zero-dimensional organic

metal halide hybrids with near-unity quantum efficiency. _Z. Chem. Sci._ 9, 586–593 (2018). Article  Google Scholar  * Liang, D. et al. Color-pure violet-light-emitting diodes based on

layered lead halide perovskite nanoplates. _ACS Nano_ 10, 6897–6904 (2016). Article  Google Scholar  * Kawano, N. et al. Effects of organic moieties on luminescence properties of

organic−inorganic layered perovskite-type compounds. _J. Phys. Chem. C_ 118, 9101–9106 (2014). Article  Google Scholar  * Dou, L. et al. Atomically thin two-dimensional organic–inorganic

hybrid perovskites. _Science_ 349, 1518–1521 (2015). Article  Google Scholar  * Yuan, Z., Shu, Y., Tian, Y., Xin, Y. & Ma, B. A facile one-pot synthesis of deep blue luminescent lead

bromide perovskite microdisks. _Chem. Commun._ 51, 16385–16388 (2015). Article  Google Scholar  * Saidaminov, M. I. et al. Planar-integrated single-crystalline perovskite photodetectors.

_Nat. Commun._ 6, 8724 (2015). Article  Google Scholar  * Müller, P. Practical suggestions for better crystal structures. _Crystallogr. Rev._ 15, 57–83 (2009). Article  Google Scholar  *

Jeon, N. J. et al. Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells. _Nat. Mater._ 13, 897–903 (2014). Article  Google Scholar  * Shi, D. et al. Low

trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals. _Science_ 347, 519–522 (2015). Article  Google Scholar  * Kitazawa, N. Excitons in

two-dimensional layered perovskite compounds: (C6H5C2H4NH3)2Pb(Br,I)4 and (C6H5C2H4NH3)2Pb(Cl,Br)4. _Mater. Sci. Eng. B_ 49, 233–238 (1997). Article  Google Scholar  * Franceschetti, A.,

Wei, S.-H. & Zunger, A. Absolute deformation potentials of Al, Si, and NaCl. _Phys. Rev. B_ 50, 17797–17801 (1994). Article  Google Scholar  * Guo, Z., Wu, X., Zhu, T., Zhu, X. &

Huang, L. Electron–phonon scattering in atomically thin 2D perovskites. _ACS Nano_ 10, 9992–9998 (2016). Article  Google Scholar  * Zaccai, G. How soft is a protein? A protein dynamics force

constant measured by neutron scattering. _Science_ 288, 1604–7 (2000). Article  Google Scholar  * de Mello, J. C., Wittmannn, H. F. & Friend, R. H. An improved experimental

determination of external photoluminescence quantum efficiency. _Adv. Mater._ 9, 230 (1997). Article  Google Scholar  * Spectral Database of Organic Compounds (SDBS). National Institute of

Advanced Industrial Science and Technology. _National Institute of Advanced Industrial Science and Technology_ http://www.aist.go.jp/aist_e/latest_research/2004/20041118/20041118.html

(2004). * Zheng, K. et al. High excitation intensity opens a new trapping channel in organic–inorganic hybrid perovskite nanoparticles. _ACS Energy Lett._ 1, 1154–1161 (2016). Article 

Google Scholar  * Kawano, N. et al. Effects of organic moieties on luminescence properties of organic–inorganic layered perovskite-type compounds. _J. Phys. Chem. C_ 118, 9101–9106 (2014).

Article  Google Scholar  Download references ACKNOWLEDGEMENTS This publication is based in part on work supported by the Ontario Research Fund Research Excellence Program and by the Natural

Sciences and Engineering Research Council (NSERC) of Canada. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the

Oak Ridge National Laboratory. The authors thank Dr J. Britten for SCXRD measurements, M. Crawford and L. Quan for discussions and E. Palmiano, R. Wolowiec and D. Kopilovic for their help

during the course of this study. AUTHOR INFORMATION AUTHORS AND AFFILIATIONS * Department of Electrical and Computer Engineering, University of Toronto, Toronto, ON, Canada Xiwen Gong, 

Oleksandr Voznyy, Ankit Jain, Wenjia Liu, Randy Sabatini, Grant Walters, Golam Bappi, Mingjian Yuan, Riccardo Comin & Edward H. Sargent * Department of Chemistry, University of

Rochester, Rochester, NY, USA Zachary Piontkowski & David McCamant * Department of Chemistry, University of Toronto, Toronto, ON, Canada Sergiy Nokhrin, Oleksandr Bushuyev & Shana O.

Kelley * Department of Pharmaceutical Sciences, Leslie Dan Faculty of Pharmacy, University of Toronto, Toronto, ON, Canada Shana O. Kelley Authors * Xiwen Gong View author publications You

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CONTRIBUTIONS X.G. and E.H.S. designed and directed this study. X.G. led the experimental work. A.J. and O.V. contributed to DFT simulations. X.G. and W.L. carried out the PLQY measurements

and analysis. Z.P., R.S. and D.M. carried out RR spectroscopy and analysis. R.S. carried out TA measurements. S.N. and O.B. carried out NMR measurement. G.W. carried out the neutron

scattering experiments and analysis. M.Y. prepared perovskite precursors. All authors contributed to writing the manuscript. CORRESPONDING AUTHOR Correspondence to Edward H. Sargent. ETHICS

DECLARATIONS COMPETING INTERESTS The authors declare no competing interests. ADDITIONAL INFORMATION PUBLISHER’S NOTE: Springer Nature remains neutral with regard to jurisdictional claims in

published maps and institutional affiliations. SUPPLEMENTARY INFORMATION SUPPLEMENTARY INFORMATION 13 Figures, 5 Tables, 3 references CIF FILES 4 CIF files = 1. C4 cif room temperature, 2.

C4 cif low temperature, 3. PhC2 room temperature, 4. PhC2 low temperature RIGHTS AND PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE Gong, X., Voznyy, O., Jain, A.

_et al._ Electron–phonon interaction in efficient perovskite blue emitters. _Nature Mater_ 17, 550–556 (2018). https://doi.org/10.1038/s41563-018-0081-x Download citation * Received: 01

November 2017 * Accepted: 12 April 2018 * Published: 14 May 2018 * Issue Date: June 2018 * DOI: https://doi.org/10.1038/s41563-018-0081-x SHARE THIS ARTICLE Anyone you share the following

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