2D perovskites; excitonic materials; fluorinated organic spacer; phase transition; temperature dependence; Chemistry (all); General Chemistry
Abstract :
[en] Low-dimensional hybrid perovskites have triggered significant research interest due to their intrinsically tunable optoelectronic properties and technologically relevant material stability. In particular, the role of the organic spacer on the inherent structural and optical features in two-dimensional (2D) perovskites is paramount for material optimization. To obtain a deeper understanding of the relationship between spacers and the corresponding 2D perovskite film properties, we explore the influence of the partial substitution of hydrogen atoms by fluorine in an alkylammonium organic cation, resulting in (Lc)2PbI4 and (Lf)2PbI4 2D perovskites, respectively. Consequently, optical analysis reveals a clear 0.2 eV blue-shift in the excitonic position at room temperature. This result can be mainly attributed to a band gap opening, with negligible effects on the exciton binding energy. According to Density Functional Theory (DFT) calculations, the band gap increases due to a larger distortion of the structure that decreases the atomic overlap of the wavefunctions and correspondingly bandwidth of the valence and conduction bands. In addition, fluorination impacts the structural rigidity of the 2D perovskite, resulting in a stable structure at room temperature and the absence of phase transitions at a low temperature, in contrast to the widely reported polymorphism in some non-fluorinated materials that exhibit such a phase transition. This indicates that a small perturbation in the material structure can strongly influence the overall structural stability and related phase transition of 2D perovskites, making them more robust to any phase change. This work provides key information on how the fluorine content in organic spacer influence the structural distortion of 2D perovskites and their optical properties which possess remarkable importance for future optoelectronic applications, for instance in the field of light-emitting devices or sensors.
Disciplines :
Chemistry
Author, co-author :
García-Benito, Inés; Group for Molecular Engineering of Functional Materials, Institute of Chemical Sciences and Engineering, EPFL Valais Wallis, Sion, Switzerland
Quarti, Claudio ; Université de Mons - UMONS ; Univ Rennes, ENSCR, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) - UMR 6226, Rennes, France
Queloz, Valentin I E; Group for Molecular Engineering of Functional Materials, Institute of Chemical Sciences and Engineering, EPFL Valais Wallis, Sion, Switzerland
Hofstetter, Yvonne J; Integrated Centre for Applied Physics and Photonic Materials and Centre for Advancing Electronics Dresden (CFAED), Technical University of Dresden, Dresden, Germany
Becker-Koch, David; Integrated Centre for Applied Physics and Photonic Materials and Centre for Advancing Electronics Dresden (CFAED), Technical University of Dresden, Dresden, Germany
Caprioglio, Pietro; Institute of Physics and Astronomy, University of Potsdam, Potsdam, Germany ; Young Investigator Group Perovskite Tandem Solar Cells, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Berlin, Germany
Neher, Dieter; Institute of Physics and Astronomy, University of Potsdam, Potsdam, Germany
Orlandi, Simonetta; CNR - Istituto di Scienze e Tecnologie Chimiche "G. Natta" (CNR-SCITEC), Milan, Italy
Cavazzini, Marco; CNR - Istituto di Scienze e Tecnologie Chimiche "G. Natta" (CNR-SCITEC), Milan, Italy
Pozzi, Gianluca; CNR - Istituto di Scienze e Tecnologie Chimiche "G. Natta" (CNR-SCITEC), Milan, Italy
Even, Jacky; Univ Rennes, INSA Rennes, CNRS, Institut FOTON - UMR 6082, Rennes, France
Nazeeruddin, Mohammad Khaja; Group for Molecular Engineering of Functional Materials, Institute of Chemical Sciences and Engineering, EPFL Valais Wallis, Sion, Switzerland
Vaynzof, Yana; Integrated Centre for Applied Physics and Photonic Materials and Centre for Advancing Electronics Dresden (CFAED), Technical University of Dresden, Dresden, Germany
Grancini, Giulia; Group for Molecular Engineering of Functional Materials, Institute of Chemical Sciences and Engineering, EPFL Valais Wallis, Sion, Switzerland ; Dipartimento di Chimica Fisica, University of Pavia, Pavia, Italy
Research Institute for Materials Science and Engineering Research Institute for Complex Systems
Funding text :
We acknowledge Prof. Raffaella Buonsanti for the use of the Fluorolog system for the data reported in Figure 2. CQ was greatly indebted to Dr. Boubacar Traore of FOTON institut, INSA RENNES, for the explanation of the calculation the dielectric profile response. CQ and JE acknowledge support from Agence Nationale pour la Recherche (MORELESS project).This work was supported by the Swiss National Science Foundation (SNSF) funding through the Ambizione Energy project HYPER (Grant Number PZENP2¯173641) and the Toyota Technical Center through the project PeLED. 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. GG acknowledges the HY-NANO project that has received funding from the European Research Council (ERC) Starting Grant 2018 under the European Union’s Horizon 2020 research and innovation programme (Grant agreement No. 802862). This work was supported by the DFG (SFB 1249, Project C04 and VA 991/2-1).We acknowledge Prof. Raffaella Buonsanti for the use of the Fluorolog system for the data reported in Figure 2. CQ was greatly indebted to Dr. Boubacar Traore of FOTON institut, INSA RENNES, for the explanation of the calculation the dielectric profile response. CQ and JE acknowledge support from Agence Nationale pour la Recherche (MORELESS project). Funding. This work was supported by the Swiss National Science Foundation (SNSF) funding through the Ambizione Energy project HYPER (Grant Number PZENP21 73641) and the Toyota Technical Center through the project PeLED. 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. GG acknowledges the HY-NANO project that has received funding from the European Research Council (ERC) Starting Grant 2018 under the European Union's Horizon 2020 research and innovation programme (Grant agreement No. 802862). This work was supported by the DFG (SFB 1249, Project C04 and VA 991/2-1).
Barman S., Venkataraman N. V., Vasudevan S., Seshadri R., (2003). Phase transitions in the anchored organic bilayers of long-chain alkylammonium lead iodides (CnH2n+1NH3)2PbI4; n = 12, 16, 18. J. Phys. Chem. B 107, 1875–1883. 10.1021/jp026879h
Billing D., Lemmerer A., (2008). Synthesis, characterization and phase transitions of the inorganic–organic layered perovskite-type hybrids [(CnH2n+1NH3)2PbI4] (n = 12, 14, 16, and 18). New J. Chem. 32, 1736–1746. 10.1039/b805417g
Billing D. G., Lemmerer A., (2007). Synthesis, characterization and phase transitions in the inorganic-organic layered perovskite-type hybrids [(CnH2n+1NH3)2PbI4], n = 4, 5, and 6. Acta Crystallogr. Sect. B 63, 735–747. 10.1107/S010876810703175817873443
Blancon J.-C., Stier A. V., Tsai H., Nie W., Stoumpos C. C., Traoré B., et al. (2018). Scaling law for excitons in 2D perovskite quantum wells. Nat. Commun. 9:2254. 10.1038/s41467-018-04659-x29884900
Cahen D., Kahn A., (2003). Electron energetics at surfaces and interfaces: concepts and experiments. Adv. Mater. 15, 271–277. 10.1002/adma.200390065
Cao H. D., Stoumpos C. C., Farha K. O., Hupp J. T., Kanatzidis M. G., (2015). 2D Homologous perovskites as light-absorbing materials for solar cell applications. J. Am. Chem. Soc. 137, 7843–7850. 10.1021/jacs.5b0379626020457
Chen Y., Sun Y., Peng J., Tang J., Zheng K., Liang Z., (2018). 2D ruddlesden–popper perovskites for optoelectronics. Adv. Mater. 30:1703487. 10.1002/adma.20170348729028138
Correa-Baena J.-P., Abate A., Saliba M., Tress W., Jacobsson T. J., Grätzel M., et al. (2017). The rapid evolution of highly efficient perovskite solar cells. Energy Environ. Sci. 10, 710–727. 10.1039/C6EE03397K
Cortecchia D., Neutzer S., Kandada A. R. S., Mosconi E., Meggiolaro D., De Angelis F., et al. (2017). Broadband emission in two-dimensional hybrid perovskites: the role of structural deformation. J. Am. Chem. Soc. 139, 39–42. 10.1021/jacs.6b1039028024394
Dolzhenko Y. I., Inabe T., Maruyama Y., (1986). In situ x-ray observation on the intercalation of weak interaction molecules into perovskite-type layered crystals (C9H19NH3)2PbI4 and (C10H21NH3)2CdCl4. Bull. Chem. Soc. Jpn. 59, 563–567. 10.1246/bcsj.59.563
Du K., Tu Q., Zhang X., Han Q., Liu J., Zauscher S., et al. (2017). Two-dimensional lead(II) halide-based hybrid perovskites templated by acene alkylamines: crystal structures, optical properties, and piezoelectricity. Inorg. Chem. 56, 9291–9302. 10.1021/acs.inorgchem.7b0109428749133
Even J., Pedesseau L., Dupertuis M.-A., Jancu J.-M., Katan C., (2012). Electronic model for self-assembled hybrid organic/perovskite semiconductors: reverse band edge electronic states ordering and spin-orbit coupling. Phys. Rev. B 86:205301. 10.1103/PhysRevB.86.205301
Even J., Pedesseau L., Jancu J.-M., Katan C., (2013). Importance of spin–orbit coupling in hybrid organic/inorganic perovskites for photovoltaic applications. J. Phys. Chem. Lett. 4, 2999–3005. 10.1021/jz401532q
Even J., Pedesseau L., Katan C., Kepenekian M., Lauret J.-S., Sapori D., et al. (2015). Solid-state physics perspective on hybrid perovskite semiconductors. J. Phys. Chem. C 119, 10161–10177. 10.1021/acs.jpcc.5b00695
Even J., Pedesseau L., Kepenekian M., (2014). Electronic surface states and dielectric self-energy profiles in colloidal nanoscale platelets of CdSe. Phys. Chem. Chem. Phys. 16, 25182–25190. 10.1039/C4CP03267E25331688
Fassl P., Lami V., Bausch A., Wang Z., Klug M. T., Snaith H. J., et al. (2018). Fractional deviations in precursor stoichiometry dictate the properties, performance, and stability of perovskite photovoltaic devices. Energy Environ. Sci. 11, 3380–3391. 10.1039/C8EE01136B30713584
Frisch J. M., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., et al. (2016). Gaussian 16, Revision C.01. Wallingford CT: Gaussian Inc.
Gan L., Li J., Fang Z., He H., Ye Z., (2017). Effects of organic cation length on exciton recombination in two-dimensional layered lead iodide hybrid perovskite crystals. J. Phys. Chem. Lett. 8, 5177–5183. 10.1021/acs.jpclett.7b0208328959879
Gao Y., (2010). Surface analytical studies of interfaces in organic semiconductor devices. Mater. Sci. Eng. R Rep. 68, 39–87. 10.1016/j.mser.2010.01.001
García-Benito I., Quarti C., Queloz V. I. E., Orlandi S., Zimmermann I., Cavazzini M., et al. (2018). Fashioning fluorous organic spacers for tunable and stable layered hybrid perovskites. Chem. Mater. 30, 8211–8220. 10.1021/acs.chemmater.8b03377
Giannozzi P., Andreussib O., Brumme T., Bunau O., Buongiorno Nardelli M., Calandra M., et al. (2017). Advanced capabilities for materials modelling with quantum ESPRESSO. J Phys. 29:46. 10.1088/1361-648X/aa8f7929064822
Giorgi G., Yamashita K., Palummo M., (2018). Nature of the electronic and optical excitations of ruddlesden–popper hybrid organic–inorganic perovskites: the role of the many-body interactions. J. Phys. Chem. Lett. 9, 5891–5896. 10.1021/acs.jpclett.8b0265330244580
Haruyama J., Sodeyama K., Han L., Tateyama Y., (2014). Termination dependence of tetragonal CH3NH3PbI3 surfaces for perovskite solar cells. J. Phys. Chem. Lett. 5, 2903–2909. 10.1021/jz501510v26278097
Hong X., Ishihara T., Nurmikko A., (1992). V. Dielectric confinement effect on excitons in PbI4-based layered semiconductors. Phys. Rev. B 45, 6961–6964. 10.1103/PhysRevB.45.6961
Irfan Ding H., Gao Y., Small C., Kim D. Y., Subbiah J., et al. (2010). Energy level evolution of air and oxygen exposed molybdenum trioxide films. Appl. Phys. Lett. 96:243307. 10.1063/1.3454779
Ishihara T., Hong X., Ding J., Nurmikko A., (1992). V. Dielectric confinement effect for exciton and biexciton states in PbI4-based two-dimensional semiconductor structures. Surf. Sci. 267, 323–326. 10.1016/0039-6028(92)91147-4
Ishihara T., Takahashi J., Goto T., (1990). Optical properties due to electronic transitions in two-dimensional semiconductors (CnH2n+1NH3)2PbI4. Phys. Rev. B 42, 11099–11107. 10.1103/PhysRevB.42.110999995391
Kamminga M. E., Fang H.-H., Filip M. R., Giustino F., Baas J., Blake G. R., et al. (2016). Confinement effects in low-dimensional lead iodide perovskite hybrids. Chem. Mater. 28, 4554–4562. 10.1021/acs.chemmater.6b00809
Katan C., Mercier N., Even J., (2019). Quantum and dielectric confinement effects in lower-dimensional hybrid perovskite semiconductors. Chem. Rev. 119, 3140–3192. 10.1021/acs.chemrev.8b0041730638375
Keldysh L. V., (1979). Coulomb interaction in thin semiconductor and semimetal films. JETP Lett. 29, 658–661.
Kitazawa N., Aono M., Watanabe Y., (2011). Synthesis and luminescence properties of lead-halide based organic–inorganic layered perovskite compounds (CnH2n+1NH3)2PbI4 (n=4, 5, 7, 8, and 9). J. Phys. Chem. Solids 72, 1467–1471. 10.1016/j.jpcs.2011.08.029
Knutson J. L., Martin J. D., Mitzi D. B., (2005). Tuning the band gap in hybrid tin iodide perovskite semiconductors using structural templating. Inorg. Chem. 44, 4699–4705. 10.1021/ic050244q15962978
Kumagai M., Takagahara T., (1989). Excitonic and nonlinear-optical properties of dielectric quantum-well structures. Phys. Rev. B 40, 12359–12381. 10.1103/PhysRevB.40.123599991869
Lee K., Murray É. D., Kong L., Lundqvist B. I., Langreth D. C., (2010). Higher-accuracy van der Waals density functional. Phys. Rev. B 82:81101. 10.1103/PhysRevB.82.081101
Lemmerer A., Billing D. G., (2012). Synthesis, characterization and phase transitions of the inorganic–organic layered perovskite-type hybrids [(CnH2n+1NH3)2PbI4], n = 7, 8, 9, and 10. Dalt. Trans. 41, 1146–1157. 10.1039/C0DT01805H
Lermer C., Birkhold S. T., Moudrakovski I. L., Mayer P., Schoop L. M., Schmidt-Mende L., et al. (2016). Toward fluorinated spacers for MAPI-derived hybrid perovskites: synthesis, characterization, and phase transitions of (FC2H4NH3)2PbCl4. Chem. Mater. 28, 6560–6566. 10.1021/acs.chemmater.6b02151
Mao L., Tsai H., Nie W., Ma L., Im J., Stoumpos C. C., et al. (2016). Role of organic counterion in lead- and tin-based two-dimensional semiconducting iodide perovskites and application in planar solar cells. Chem. Mater. 28, 7781–7792. 10.1021/acs.chemmater.6b03054
Mao L., Wu Y., Stoumpos C. C., Traore B., Katan C., Even J., et al. (2017). Tunable white-light emission in single-cation-templated three-layered 2D perovskites (CH3CH2NH3)4Pb3Br10–xClx. J. Am. Chem. Soc. 139, 11956–11963. 10.1021/jacs.7b0614328745881
Marongiu D., Saba M., Quochi F., Mura A., Bongiovanni G., (2019). The role of excitons in 3D and 2D lead halide perovskites. J. Mater. Chem. C 7, 12006–12018. 10.1039/C9TC04292J
Misra R. K., Cohen B.-E., Iagher L., Etgar L., (2017). Low-dimensional organic–inorganic halide perovskite: structure, properties, and applications. ChemSusChem 10, 3712–3721. 10.1002/cssc.20170102628703944
Mitzi B. D., Medeiros R. D., Malenfant R. L. P., (2002). Intercalated organic–inorganic perovskites stabilized by fluoroaryl–aryl interactions. Inorg. Chem. 41, 2134–2145. 10.1021/ic011190x11952366
Mitzi D. B., (2001). Templating and structural engineering in organic–inorganic perovskites. J. Chem. Soc. Dalt. Trans. 1–12. 10.1039/b007070j
Miyata A., Mitioglu A., Plochocka P., Portugall O., Wang J. T.-W., Stranks S. D., et al. (2015). Direct measurement of the exciton binding energy and effective masses for charge carriers in organic–inorganic tri-halide perovskites. Nat. Phys. 11, 582–587. 10.1038/nphys3357
Naik V. V., Vasudevan S., (2010). Melting of an anchored bilayer: molecular dynamics simulations of the structural transition in (CnH2n+1NH3)2PbI4 (n = 12, 14, 16, 18). J. Phys. Chem. C 114, 4536–4543. 10.1021/jp910300v
NREL solar cell efficiency chart. (2019). Available online at: https://www.nrel.gov/pv/assets/pdfs/pv-efficiency-chart.20190103.pdf (accessed 26 July, 2019).
Olthof S., Meerholz K., (2017). Substrate-dependent electronic structure and film formation of MAPbI3 perovskites. Sci. Rep. 7:40267. 10.1038/srep4026728084313
Pedesseau L., Sapori D., Traoré B., Robles R., Fang H.-H., Loi M. A., et al. (2016). Advances and promises of layered halide hybrid perovskite semiconductors. ACS Nano 10, 9776–9786. 10.1021/acsnano.6b0594427775343
Quarti C., De Angelis F., Beljonne D., (2017). Influence of surface termination on the energy level alignment at the CH3NH3PbI3 perovskite/C60 interface. Chem. Mater. 29, 958–968. 10.1021/acs.chemmater.6b03259
Quarti C., Marchal N., Beljonne D., (2018). Tuning the optoelectronic properties of two-dimensional hybrid perovskite semiconductors with alkyl chain spacers. J. Phys. Chem. Lett. 9, 3416–3424. 10.1021/acs.jpclett.8b0130929870266
Sapori D., Kepenekian M., Pedesseau L., Katan C., Even J., (2016). Quantum confinement and dielectric profiles of colloidal nanoplatelets of halide inorganic and hybrid organic–inorganic perovskites. Nanoscale 8, 6369–6378. 10.1039/C5NR07175E26705549
Schnier T., Emara J., Olthof S., Meerholz K., (2017). Influence of hybrid perovskite fabrication methods on film formation, electronic structure, and solar cell performance. JoVE e55084. 10.3791/5508428287555
Schulz P., Edri E., Kirmayer S., Hodes G., Cahen D., Kahn A., (2014). Interface energetics in organo-metal halide perovskite-based photovoltaic cells. Energy Environ. Sci. 7, 1377–1381. 10.1039/c4ee00168k
Senanayak S. P., Yang B., Thomas T. H., Giesbrecht N., Huang W., Gann E., et al. (2017). Understanding charge transport in lead iodide perovskite thin-film field-effect transistors. Sci. Adv. 3:e1601935. 10.1126/sciadv.160193528138550
Shi E., Gao Y., Finkernauer B. P., Akriti Coffey A. H., Dou L., (2018). Two-dimensional halide perovskite nanomaterials and heterostructures. Chem. Soc. Rev. 47, 6046–6072. 10.1039/C7CS00886D29564440
Smith M. D., Pedesseau L., Kepenekian M., Smith I. C., Katan C., Even J., et al. (2017). Decreasing the electronic confinement in layered perovskites through intercalation. Chem. Sci. 8, 1960–1968. 10.1039/C6SC02848A28451311
Soler J. M., Artacho E. D., Gale J., García A., Junquera J., Ordejón P., et al. (2001). The SIESTA method for ab initio order-N materials simulation. J Phys. 14:11. 10.1088/0953-8984/14/11/302
Stoumpos C. C., Cao D. H., Clark D. J., Young J., Rondinelli J., Joon I. J., et al. (2016). Ruddlesden–popper hybrid lead iodide perovskite 2D homologous semiconductors. Chem. Mater. 28, 2852–2867. 10.1021/acs.chemmater.6b00847
Straus D. B., Kagan R. C., (2018). Electrons, excitons, and phonons in two-dimensional hybrid perovskites: connecting structural, optical, and electronic properties. J. Phys. Chem. Lett. 9, 1434–1447. 10.1021/acs.jpclett.8b0020129481089
Tanaka K., Kondo T., (2003). Bandgap and exciton binding energies in lead-iodide-based natural quantum-well crystals. Sci. Technol. Adv. Mater. 4, 599–604. 10.1016/j.stam.2003.09.019
Traore B., Pedesseau L., Assam L., Che X., Blancon J.-C., Tsai H., et al. (2018). Composite nature of layered hybrid perovskites: assessment on quantum and dielectric confinements and band alignment. ACS Nano. 12, 3321–3332. 10.1021/acsnano.7b0820229481060
Umebayashi T., Asai K., Kondo T., Nakao A., (2003). Electronic structures of lead iodide based low-dimensional crystals. Phys. Rev. B 67:155405. 10.1103/PhysRevB.67.155405
Van Gompel W. T. M., Herckens R., Van Hecke K., Ruttens B., D'Haen J., Lutsen L., et al. (2019). Towards 2D layered hybrid perovskites with enhanced functionality: introducing charge-transfer complexes via self-assembly. Chem. Commun. 55, 2481–2484. 10.1039/C8CC09955C30734783
Wang R., Mujahid R., Duan Y., Wand Z.-K., Yang Y., (2019). A review of perovskites solar cell stability. Adv. Funct. Mater. 29:1808843. 10.1002/adfm.201808843
Wei Y., Audebert P., Galmiche L., Lauret J. S., Deleporte E., (2013). Synthesis, optical properties and photostability of novel fluorinated organic-inorganic hybrid (R-NH3)2PbX4 semiconductors. J. Phys. D. Appl. Phys. 46:13. 10.1088/0022-3727/46/13/135105
Wei Y., Lauret J. S., Galmiche L., Audebert P., Deleporte E., (2012). Strong exciton-photon coupling in microcavities containing new fluorophenethylamine based perovskite compounds. Opt. Express 20:10399. 10.1364/OE.20.01039922535130
Yaffe O., Chernikov A., Norman Z. M., Zhong Y., Velauthapillai A., van der Zande A., et al. (2015). Excitons in ultrathin organic-inorganic perovskite crystals. Phys. Rev. B 92:45414. 10.1103/PhysRevB.92.045414
Yang Y., Ostrowski D. P., France R. M., Zhu k., van de Lagemaat J., Luther J. M., et al. (2016). Observation of a hot-phonon bottleneck in lead-iodide perovskites. Nat. Photonics 10, 53–59. 10.1038/nphoton.2015.213
Yu F., Yao K., Shi L. Y., Wang H. Z., Fu Y., You X. Q., et al. (2007). Novel two-dimensional molecular space material with regular double bonds. Chem. Mater. 19, 335–337. 10.1021/cm0620842
Zhang F., Zhang H., Zhu L., Qin L., Wang Y., Hu Y., (2019). Two-dimensional organic–inorganic hybrid perovskite field-effect transistors with polymers as bottom-gate dielectrics. J. Mater. Chem. C 7, 4004–4012. 10.1039/C8TC06249H
Zheng K., Chen Y., Sun Y., Chen J., Chábera P., Schaller R., et al. (2018). Inter-phase charge and energy transfer in Ruddlesden–Popper 2D perovskites: critical role of the spacing cations. J. Mater. Chem. A 6, 6244–6250. 10.1039/C8TA01518J
