Hybrid organic–inorganic semiconductors feature complex lattice dynamics due to the ionic character of the crystal and the softness arising from non-covalent bonds between molecular moieties and the inorganic network. Here we establish that such dynamic structural complexity in a prototypical two-dimensional lead iodide perovskite gives rise to the coexistence of diverse excitonic resonances, each with a distinct degree of polaronic character. By means of high-resolution resonant impulsive stimulated Raman spectroscopy, we identify vibrational wavepacket dynamics that evolve along different configurational coordinates for distinct excitons and photocarriers. Employing density functional theory calculations, we assign the observed coherent vibrational modes to various low-frequency (≲50 cm−1) optical phonons involving motion in the lead iodide layers. We thus conclude that different excitons induce specific lattice reorganizations, which are signatures of polaronic binding. This insight into the energetic/configurational landscape involving globally neutral primary photoexcitations may be relevant to a broader class of emerging hybrid semiconductor materials.
This is a preview of subscription content, access via your institution
Open Access articles citing this article.
Coupling to octahedral tilts in halide perovskite nanocrystals induces phonon-mediated attractive interactions between excitons
Nature Physics Open Access 09 November 2023
Nature Communications Open Access 11 July 2023
Nature Communications Open Access 21 June 2023
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Rent or buy this article
Prices vary by article type
Prices may be subject to local taxes which are calculated during checkout
The experimental data and analysis material that support the findings of this study are available in the Scholarly Materials And Research @ Georgia Tech repository (SMARTech), https://smartech.gatech.edu.
Ishihara, T., Takahashi, J. & Goto, T. Exciton state in two-dimensional perovskite semiconductor (C10H21NH3)2PbI4. Solid State Commun. 69, 933–936 (1989).
Even, J., Pedesseau, L. & Katan, C. Understanding quantum confinement of charge carriers in layered 2D hybrid perovskites. ChemPhysChem 15, 3733–3741 (2014).
Even, J. et al. Solid-state physics perspective on hybrid perovskite semiconductors. J. Phys. Chem. C 119, 10161–10177 (2015).
Saparov, B. & Mitzi, D. B. Organic–inorganic perovskites: structural versatility for functional materials design. Chem. Rev. 116, 4558–4596 (2016).
Blancon, J.-C. et al. Scaling law for excitons in 2d perovskite quantum wells. Nat. Commun. 9, 2254 (2018).
Neutzner, S. et al. Exciton-polaron spectral structures in two-dimensional hybrid lead-halide perovskites. Phys. Rev. Mater. 2, 064605 (2018).
Yaffe, O. et al. Excitons in ultrathin organic–inorganic perovskite crystals. Phys. Rev. B 92, 045414 (2015).
Srimath Kandada, A. R. & Petrozza, A. Photophysics of hybrid lead halide perovskites: The role of microstructure. Acc. Chem. Res. 49, 536–544 (2016).
Miyata, K. et al. Large polarons in lead halide perovskites. Sci. Adv. 3, e1701217 (2017).
Straus, D. B. & Kagan, C. R. Electrons, excitons, and phonons in two-dimensional hybrid perovskites: Connecting structural, optical, and electronic properties. J. Phys. Chem. Lett. 9, 1434–1447 (2018).
Thouin, F. et al. Stable biexcitons in two-dimensional metal-halide perovskites with strong dynamic lattice disorder. Phys. Rev. Mater. 2, 034001 (2018).
Kondo, T., Azuma, T., Yuasa, T. & Ito, R. Biexciton lasing in the layered perovskite-type material (C6H13NH3)2PbI4. Solid State Commun. 105, 253–255 (1998).
Quan, L. N. et al. Tailoring the energy landscape in quasi-2d halide perovskites enables efficient green-light emission. Nano Lett. 17, 3701–3709 (2017).
Su, R. et al. Room-temperature polariton lasing in all-inorganic perovskite nanoplatelets. Nano Lett. 17, 3982–3988 (2017).
Booker, E. P. et al. Vertical cavity biexciton lasing in 2D dodecylammonium lead iodide perovskites. Adv. Opt. Mater. 6, 1800616 (2018).
Senger, R. T. & Bajaj, K. K. Binding energies of excitons in polar quantum well heterostructures. Phys. Rev. B 68, 205314 (2003).
Dvorak, M., Wei, S.-H. & Wu, Z. Origin of the variation of exciton binding energy in semiconductors. Phys. Rev. Lett. 110, 016402 (2013).
Ishihara, T., Takahashi, J. & Goto, T. Optical properties due to electronic transitions in two-dimensional semiconductors (CnH2n+1NH3)2PbI4. Phys. Rev. B 42, 11099–11107 (1990).
Kataoka, T. et al. Magneto-optical study on excitonic spectra in (C6H13NH3)2PbI4. Phys. Rev. B 47, 2010–2018 (1993).
Tanaka, K. et al. Electronic and excitonic structures of inorganic–organic perovskite-type quantum-well crystal (C4H9NH3)2PbBr4. Jpn J. Appl. Phys. 44, 5923–5932 (2005).
Shimizu, M., Fujisawa, J. I. & Ishi-Hayase, J. Influence of dielectric confinement on excitonic nonlinearity in inorganic–organic layered semiconductors. Phys. Rev. B 71, 205306 (2005).
Ema, K. et al. Huge exchange energy and fine structure of excitons in an organic–inorganic quantum well material. Phys. Rev. B 73, 241310(R) (2006).
Goto, T. et al. Localization of triplet excitons and biexcitons in the two-dimensional semiconductor (CH3C6H4CH2NH3)2PbBr4. Phys. Rev. B 73, 115206 (2006).
Kitazawa, N. & Watanabe, Y. Optical properties of natural quantum-well compounds (C6H5-CnH2n-NH3)2PbBr4 (n = 1–4). J. Phys. Chem. Solids 71, 797–802 (2010).
Gauthron, K. et al. Optical spectroscopy of two-dimensional layered (C6H5C2H4-NH3)2-PbI4 perovskite. Opt. Express 18, 5912–5919 (2010).
Straus, D. B. et al. Direct observation of electron–phonon coupling and slow vibrational relaxation in organic–inorganic hybrid perovskites. J. Am. Chem. Soc. 138, 13798–13801 (2016).
Quarti, C., Marchal, N. & Beljonne, D. Tuning the optoelectronic properties of 2d hybrid perovskite semiconductors with alkyl chain spacers. J. Phys. Chem. Lett. 9, 3416–3424 (2018).
Sood, A., Menendez, J., Cardona, M. & Ploog, K. Resonance Raman scattering by confined LO and TO phonons in GaAs-AlAs superlattices. Phys. Rev. Lett. 54, 2111–2114 (1985).
Dhar, L., Rogers, J. A. & Nelson, K. A. Time-resolved vibrational spectroscopy in the impulsive limit. Chem. Rev. 94, 157–193 (1994).
Merlin, R. Generating coherent THz phonons with light pulses. Solid State Commun. 102, 207–220 (1997).
Cortecchia, D. et al. Broadband emission in two-dimensional hybrid perovskites: the role of structural deformation. J. Am. Chem. Soc. 139, 39–42 (2017).
Guo, Z., Wu, X., Zhu, T., Zhu, X. & Huang, L. Electron–phonon scattering in atomically thin 2D perovskites. ACS Nano 10, 9992–9998 (2016).
Grancini, G. et al. Role of microstructure in the electron–hole interaction of hybrid lead halide perovskites. Nat. Photon. 9, 695–701 (2015).
Haug, H. & Koch, S. W. Quantum Theory of the Optical and Electronic Properties of Semiconductors (World Scientific, London, 2008).
Ivanovska, T. et al. Vibrational response of methylammonium lead iodide: from cation dynamics to phonon–phonon interactions. ChemSusChem 9, 2994–3004 (2016).
Corno, M., Busco, C., Civalleri, B. & Ugliengo, P. Periodic ab initio study of structural and vibrational features of hexagonal hydroxyapatite Ca10(PO4)6(OH)2. Phys. Chem. Chem. Phys. 8, 2464–2472 (2006).
Brivio, F. et al. Lattice dynamics and vibrational spectra of the orthorhombic, tetragonal, and cubic phases of methylammonium lead iodide. Phys. Rev. B 92, 144308 (2015).
Quarti, C. et al. The Raman spectrum of the CH3NH3PbI3 hybrid perovskite: interplay of theory and experiment. J. Phys. Chem. Lett. 5, 279–284 (2013).
Grisanti, L. et al. Roles of local and nonlocal electron–phonon couplings in triplet exciton diffusion in the anthracene crystal. Phys. Rev. B 88, 035450 (2013).
Coropceanu, V. et al. Charge transport in organic semiconductors. Chem. Rev. 107, 926–952 (2007).
Yaffe, O. et al. Local polar fluctuations in lead halide perovskite crystals. Phys. Rev. Lett. 118, 136001 (2017).
Leguy, A. M. A. et al. Dynamic disorder, phonon lifetimes, and the assignment of modes to the vibrational spectra of methylammonium lead halide perovskites. Phys. Chem. Chem. Phys. 18, 27051–27066 (2016).
La-O-Vorakiat, C. et al. Phonon mode transformation across the orthohombic–tetragonal phase transition in a lead iodide perovskite CH3NH3PbI3: a terahertz time-domain spectroscopy approach. J. Phys. Chem. Lett. 7, 1–6 (2015).
De Silvestri, S., Cerullo, G. & Lanzani, G. Coherent Vibrational Dynamics (CRC, Boca Raton, 2008).
Lüer, L. et al. Coherent phonon dynamics in semiconducting carbon nanotubes: A quantitative study of electron–phonon coupling. Phys. Rev. Lett. 102, 127401 (2009).
Kumar, A. T., Rosca, F., Widom, A. & Champion, P. M. Investigations of amplitude and phase excitation profiles in femtosecond coherence spectroscopy. J. Chem. Phys. 114, 701–724 (2001).
Batignani, G. et al. Probing femtosecond lattice displacement upon photo-carrier generation in lead halide perovskite. Nat. Commun. 9, 1971 (2018).
Park, M. et al. Excited-state vibrational dynamics toward the polaron in methylammonium lead iodide perovskite. Nat. Commun. 9, 2525 (2018).
Emin, D. Polarons (Cambridge Univ. Press, Cambridge, 2013).
Gong, X. et al. Electron–phonon interaction in efficient perovskite blue emitters. Nat. Mater. 17, 550–556 (2018).
Neukirch, A. J. et al. Polaron stabilization by cooperative lattice distortion and cation rotations in hybrid perovskite materials. Nano Lett. 16, 3809–3816 (2016).
Zhai, Y. et al. Giant Rashba splitting in 2D organic–inorganic halide perovskites measured by transient spectroscopies. Sci. Adv. 3, e1700704 (2017).
Takagi, H., Kunugita, H. & Ema, K. Influence of the image charge effect on excitonic energy structure in organic–inorganic multiple quantum well crystals. Phys. Rev. B 87, 125421 (2013).
Zheng, R. & Matsuura, M. Polaronic effects on excitons in quantum wells. Phys. Rev. B 57, 1749–1761 (1998).
Zhu, H. et al. Screening in crystalline liquids protects energetic carriers in hybrid perovskites. Science 353, 1409–1413 (2016).
Calabrese, J. et al. Preparation and characterization of layered lead halide compounds. J. Am. Chem. Soc. 113, 2328–2330 (1991).
Dovesi, R. et al. Quantum-mechanical condensed matter simulations with crystal. Wiley Interdiscip. Rev. Comput. Mol. Sci. 8, e1360 (2018).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).
A.R.S.K. acknowledges funding from EU Horizon 2020 via a Marie Sklodowska Curie Fellowship (Global) (project no. 705874). F.T. acknowledges support from a doctoral postgraduate scholarship from the Natural Sciences and Engineering Research Council of Canada and Fond Québécois pour la Recherche: Nature et Technologies. This work is partially supported by the National Science Foundation (award 1838276). C.S. acknowledges support from the School of Chemistry and Biochemistry and the College of Science of Georgia Institute of Technology. The work at Mons was supported by the Interuniversity Attraction Pole programme of the Belgian Federal Science Policy Office (PAI 6/27) and FNRS-F.R.S. Computational resources have been provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS) under grant no. 2.5020.11. D.B. is an FNRS Research Director.
The authors declare no competing interests.
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Sections 1–5, Supplementary Figures 1–17, Supplementary Tables 1–2, Supplementary References 1–3
Video of normal mode N1 for (NBT)2PbI4 reported in Table I
Video of normal mode N2 for (NBT)2PbI4 reported in Table I
Video of normal mode N3 for (NBT)2PbI4 reported in Table I
Video of normal mode N4 for (NBT)2PbI4 reported in Table I
Video of normal mode N5 for (NBT)2PbI4 reported in Table I
Video of normal mode M1 for (PEA)2PbI4 reported in Table I
Video of normal mode M2 for (PEA)2PbI4 reported in Table I
Video of normal mode M3 for (PEA)2PbI4 reported in Table I
Video of normal mode M4 for (PEA)2PbI4 reported in Table I
Video of normal mode M5 for (PEA)2PbI4 reported in Table I
Video of normal mode M6 for (PEA)2PbI4 reported in Table I
About this article
Cite this article
Thouin, F., Valverde-Chávez, D.A., Quarti, C. et al. Phonon coherences reveal the polaronic character of excitons in two-dimensional lead halide perovskites. Nat. Mater. 18, 349–356 (2019). https://doi.org/10.1038/s41563-018-0262-7
This article is cited by
Nature Physics (2023)
Nature Communications (2023)
Nature Communications (2023)
Nature Communications (2023)
Nature Communications (2023)