Dynamically Disordered Lattice in a Layered Pb-I-SCN Perovskite Thin Film Probed by Two-Dimensional Infrared Spectroscopy

Nishida, Jun; Breen, John P.; Lindquist, Kurt P.; Umeyama, Daiki; Karunadasa, Hemamala I.; Fayer, Michael D.

doi:10.1021/jacs.8b03787

Title: Dynamically Disordered Lattice in a Layered Pb-I-SCN Perovskite Thin Film Probed by Two-Dimensional Infrared Spectroscopy

Journal Article · Thu Jul 19 00:00:00 EDT 2018 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.8b03787· OSTI ID:1788259

^[1]; Breen, John P. ^[2]; Lindquist, Kurt P. ^[2];

^[3];

^[2];

^[2]

Stanford Univ., CA (United States); Univ. of Colorado, Boulder, CO (United States)
Stanford Univ., CA (United States)
Stanford Univ., CA (United States); National Institute for Materials Science (NIMS), Tsukuba (Japan)

The dynamically flexible lattices in lead-halide perovskites may play important roles in extending carrier recombination lifetime in 3D perovskite solar-cell absorbers and in exciton self-trapping in 2D perovskite white-light phosphors. Here, two-dimensional infrared (2D IR) spectroscopy was applied to study a recently reported Pb-I-SCN layered perovskite. The Pb-ISCN perovskite was spin-coated on a SiO₂ surface as a thin film, with a thickness of ~100 nm, where the S¹²CN^– anions were isotopically diluted with the ratio of S¹²CN:S¹³CN=5:95 or 1:99 to avoid vibrational coupling and excitation transfer between adjacent SCN^– anions. The minor S¹²CN^– component was the principal vibrational probe that reported on the structural evolution through 2D IR spectroscopy. Spectral diffusion was observed with a time constant of 4.1 ± 0.3 ps. Spectral diffusion arises from small structural changes that result in sampling of frequencies within the distribution of frequencies that comprise the inhomogeneously broadened absorption spectrum of the in the Pb-I-SCN layered perovskite. These transitions among discrete local structures are distinct from oscillatory phonon motions of the lattice. To accurately evaluate the structural dynamics through measurement of spectral diffusion, the vibrational coupling between adjacent SCN^– anions had to be carefully treated. Although the inorganic layers of typical 2D perovskites are structurally isolated from each other, the 2D IR data demonstrated that the layers of the Pb-I-SCN perovskite are vibrationally coupled. When both S¹²CN^– and S¹³CN^– were pumped simultaneously, cross-peaks between S¹²CN and S¹³CN vibrations and an oscillating 2D band shape of the S¹²CN^– vibration were observed. Both observables demonstrate vibrational coupling between the closest SCN^– anions, which reside in different inorganic layers. The thin films and the isotopic dilution produced exceedingly small vibrational echo signal fields; measurements were made possible using the near-Brewster’s angle reflection pump-probe geometry.

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Research Organization:: Stanford Univ., CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); US Air Force Office of Scientific Research (AFOSR)

Grant/Contract Number:: FG02-84ER13251; FG03-84ER13251; FA9550-16-1-0104

OSTI ID:: 1788259

Journal Information:: Journal of the American Chemical Society, Vol. 140, Issue 31; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 46 works

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References (59)

Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells Kojima, Akihiro; Teshima, Kenjiro; Shirai, Yasuo Journal of the American Chemical Society, Vol. 131, Issue 17, p. 6050-6051 https://doi.org/10.1021/ja809598r	journal	May 2009
Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites Lee, M. M.; Teuscher, J.; Miyasaka, T. Science, Vol. 338, Issue 6107, p. 643-647 https://doi.org/10.1126/science.1228604	journal	October 2012
Light and oxygen induced degradation limits the operational stability of methylammonium lead triiodide perovskite solar cells Bryant, Daniel; Aristidou, Nicholas; Pont, Sebastian Energy & Environmental Science, Vol. 9, Issue 5 https://doi.org/10.1039/C6EE00409A	journal	January 2016
In situ investigation of degradation at organometal halide perovskite surfaces by X-ray photoelectron spectroscopy at realistic water vapour pressure Chun-Ren Ke, Jack; Walton, Alex S.; Lewis, David J. Chemical Communications, Vol. 53, Issue 37 https://doi.org/10.1039/C7CC01538K	journal	January 2017
Iodide management in formamidinium-lead-halide–based perovskite layers for efficient solar cells Yang, Woon Seok; Park, Byung-Wook; Jung, Eui Hyuk Science, Vol. 356, Issue 6345 https://doi.org/10.1126/science.aan2301	journal	June 2017
Perovskite solar cells with CuSCN hole extraction layers yield stabilized efficiencies greater than 20% Arora, Neha; Dar, M. Ibrahim; Hinderhofer, Alexander Science, Vol. 358, Issue 6364 https://doi.org/10.1126/science.aam5655	journal	September 2017
Excitons in two-dimensional layered perovskite compounds: (C6H5C2H4NH3)2Pb(Br,I)4 and (C6H5C2H4NH3)2Pb(Cl,Br)4 Kitazawa, Nobuaki Materials Science and Engineering: B, Vol. 49, Issue 3 https://doi.org/10.1016/S0921-5107(97)00132-3	journal	October 1997
Intrinsic White-Light Emission from Layered Hybrid Perovskites Dohner, Emma R.; Jaffe, Adam; Bradshaw, Liam R. Journal of the American Chemical Society, Vol. 136, Issue 38 https://doi.org/10.1021/ja507086b	journal	September 2014
Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by millimeter‐wave spectroscopy Poglitsch, A.; Weber, D. The Journal of Chemical Physics, Vol. 87, Issue 11, p. 6373-6378 https://doi.org/10.1063/1.453467	journal	December 1987
Local Polar Fluctuations in Lead Halide Perovskite Crystals Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z. Physical Review Letters, Vol. 118, Issue 13 https://doi.org/10.1103/PhysRevLett.118.136001	journal	March 2017
Real-Time Observation of Organic Cation Reorientation in Methylammonium Lead Iodide Perovskites Bakulin, Artem A.; Selig, Oleg; Bakker, Huib J. The Journal of Physical Chemistry Letters, Vol. 6, Issue 18 https://doi.org/10.1021/acs.jpclett.5b01555	journal	August 2015
Light-induced picosecond rotational disordering of the inorganic sublattice in hybrid perovskites Wu, Xiaoxi; Tan, Liang Z.; Shen, Xiaozhe Science Advances, Vol. 3, Issue 7 https://doi.org/10.1126/sciadv.1602388	journal	July 2017
Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber Stranks, S. D.; Eperon, G. E.; Grancini, G. Science, Vol. 342, Issue 6156, p. 341-344 https://doi.org/10.1126/science.1243982	journal	October 2013
Excitons versus free charges in organo-lead tri-halide perovskites D’Innocenzo, Valerio; Grancini, Giulia; Alcocer, Marcelo J. P. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4586	journal	April 2014
Understanding the Outstanding Power Conversion Efficiency of Perovskite-Based Solar Cells Collavini, Silvia; Völker, Sebastian F.; Delgado, Juan Luis Angewandte Chemie International Edition, Vol. 54, Issue 34 https://doi.org/10.1002/anie.201505321	journal	July 2015
Direct Observation of Ultrafast Exciton Dissociation in Lead Iodide Perovskite by 2D Electronic Spectroscopy Jha, Ajay; Duan, Hong-Guang; Tiwari, Vandana ACS Photonics, Vol. 5, Issue 3 https://doi.org/10.1021/acsphotonics.7b01025	journal	December 2017
Electroabsorption Spectroscopy Measurements of the Exciton Binding Energy, Electron–Hole Reduced Effective Mass, and Band Gap in the Perovskite CH ₃ NH ₃ PbI ₃ Ziffer, Mark E.; Mohammed, Joseph C.; Ginger, David S. ACS Photonics, Vol. 3, Issue 6 https://doi.org/10.1021/acsphotonics.6b00139	journal	April 2016
Screening in crystalline liquids protects energetic carriers in hybrid perovskites Zhu, H.; Miyata, K.; Fu, Y. Science, Vol. 353, Issue 6306 https://doi.org/10.1126/science.aaf9570	journal	September 2016
Rashba Spin–Orbit Coupling Enhanced Carrier Lifetime in CH ₃ NH ₃ PbI ₃ Zheng, Fan; Tan, Liang Z.; Liu, Shi Nano Letters, Vol. 15, Issue 12 https://doi.org/10.1021/acs.nanolett.5b01854	journal	November 2015
Excitons in self-organized semiconductor/insulator superlattices: PbI-based perovskite compounds Muljarov, E. A.; Tikhodeev, S. G.; Gippius, N. A. Physical Review B, Vol. 51, Issue 20 https://doi.org/10.1103/PhysRevB.51.14370	journal	May 1995
White-Light Emission from Layered Halide Perovskites Smith, Matthew D.; Karunadasa, Hemamala I. Accounts of Chemical Research, Vol. 51, Issue 3 https://doi.org/10.1021/acs.accounts.7b00433	journal	February 2018
Large polarons in lead halide perovskites Miyata, Kiyoshi; Meggiolaro, Daniele; Trinh, M. Tuan Science Advances, Vol. 3, Issue 8 https://doi.org/10.1126/sciadv.1701217	journal	August 2017
Concepts and Methods of 2D Infrared Spectroscopy Hamm, Peter; Zanni, Martin Cambridge University Press https://doi.org/10.1017/CBO9780511675935	book	January 2011
Subpicosecond conformational dynamics of small peptides probed by two-dimensional vibrational spectroscopy Woutersen, S.; Mu, Y.; Stock, G. Proceedings of the National Academy of Sciences, Vol. 98, Issue 20 https://doi.org/10.1073/pnas.201169498	journal	September 2001
Picosecond dynamics of a membrane protein revealed by 2D IR Mukherjee, P.; Kass, I.; Arkin, I. T. Proceedings of the National Academy of Sciences, Vol. 103, Issue 10 https://doi.org/10.1073/pnas.0508833103	journal	February 2006
Ultrafast Hydrogen-Bond Dynamics in the Infrared Spectroscopy of Water Fecko, C. J. Science, Vol. 301, Issue 5640 https://doi.org/10.1126/science.1087251	journal	September 2003
Chemical exchange 2D IR of hydrogen-bond making and breaking Kim, Y. S.; Hochstrasser, R. M. Proceedings of the National Academy of Sciences, Vol. 102, Issue 32 https://doi.org/10.1073/pnas.0504865102	journal	July 2005
Ultrafast Dynamics of Solute-Solvent Complexation Observed at Thermal Equilibrium in Real Time Zheng, J. Science, Vol. 309, Issue 5739 https://doi.org/10.1126/science.1116213	journal	August 2005
Site-Specific Coupling of Hydration Water and Protein Flexibility Studied in Solution with Ultrafast 2D-IR Spectroscopy King, John T.; Kubarych, Kevin J. Journal of the American Chemical Society, Vol. 134, Issue 45 https://doi.org/10.1021/ja307401r	journal	November 2012
Water Dynamics: Vibrational Echo Correlation Spectroscopy and Comparison to Molecular Dynamics Simulations Asbury, John B.; Steinel, Tobias; Stromberg, C. The Journal of Physical Chemistry A, Vol. 108, Issue 7 https://doi.org/10.1021/jp036266k	journal	February 2004
Ultrafast 2D-IR vibrational echo spectroscopy: a probe of molecular dynamics Park, S.; Kwak, K.; Fayer, M. D. Laser Physics Letters, Vol. 4, Issue 10 https://doi.org/10.1002/lapl.200710046	journal	October 2007
Frequency-frequency correlation functions and apodization in two-dimensional infrared vibrational echo spectroscopy: A new approach Kwak, Kyungwon; Park, Sungnam; Finkelstein, Ilya J. The Journal of Chemical Physics, Vol. 127, Issue 12 https://doi.org/10.1063/1.2772269	journal	September 2007
Synthesis, Single-Crystal Structure and Characterization of (CH ₃ NH ₃ ) ₂ Pb(SCN) ₂ I ₂ Daub, Michael; Hillebrecht, Harald Angewandte Chemie International Edition, Vol. 54, Issue 38 https://doi.org/10.1002/anie.201506449	journal	September 2015
Red-to-Black Piezochromism in a Compressible Pb–I–SCN Layered Perovskite Umeyama, Daiki; Lin, Yu; Karunadasa, Hemamala I. Chemistry of Materials, Vol. 28, Issue 10 https://doi.org/10.1021/acs.chemmater.6b01147	journal	May 2016
Photovoltaic Properties of Two-Dimensional (CH ₃ NH ₃ ) ₂ Pb(SCN) ₂ I ₂ Perovskite: A Combined Experimental and Density Functional Theory Study Xiao, Zewen; Meng, Weiwei; Saparov, Bayrammurad The Journal of Physical Chemistry Letters, Vol. 7, Issue 7 https://doi.org/10.1021/acs.jpclett.6b00248	journal	March 2016
Halide Perovskites under Pressure: Accessing New Properties through Lattice Compression Jaffe, Adam; Lin, Yu; Karunadasa, Hemamala I. ACS Energy Letters, Vol. 2, Issue 7 https://doi.org/10.1021/acsenergylett.7b00284	journal	June 2017
Growth of CH3NH3PbI3 cuboids with controlled size for high-efficiency perovskite solar cells Im, Jeong-Hyeok; Jang, In-Hyuk; Pellet, Norman Nature Nanotechnology, Vol. 9, Issue 11 https://doi.org/10.1038/nnano.2014.181	journal	August 2014
Enhanced nonlinear spectroscopy for monolayers and thin films in near-Brewster’s angle reflection pump-probe geometry Nishida, Jun; Yan, Chang; Fayer, Michael D. The Journal of Chemical Physics, Vol. 146, Issue 9 https://doi.org/10.1063/1.4977508	journal	March 2017
How to turn your pump–probe instrument into a multidimensional spectrometer: 2D IR and Vis spectroscopiesvia pulse shaping Shim, Sang-Hee; Zanni, Martin T. Phys. Chem. Chem. Phys., Vol. 11, Issue 5 https://doi.org/10.1039/B813817F	journal	January 2009
Comparisons of 2D IR measured spectral diffusion in rotating frames using pulse shaping and in the stationary frame using the standard method Karthick Kumar, S. K.; Tamimi, A.; Fayer, M. D. The Journal of Chemical Physics, Vol. 137, Issue 18 https://doi.org/10.1063/1.4764470	journal	November 2012
Ultrafast to Ultraslow Dynamics of a Langmuir Monolayer at the Air/Water Interface Observed with Reflection Enhanced 2D IR Spectroscopy Yan, Chang; Thomaz, Joseph E.; Wang, Yong-Lei Journal of the American Chemical Society, Vol. 139, Issue 46 https://doi.org/10.1021/jacs.7b06602	journal	November 2017
Thiocyanate as a Local Probe of Ultrafast Structure and Dynamics in Imidazolium-Based Ionic Liquids: Water-Induced Heterogeneity and Cation-Induced Ion Pairing Ren, Zhe; Brinzer, Thomas; Dutta, Samrat The Journal of Physical Chemistry B, Vol. 119, Issue 13 https://doi.org/10.1021/jp512851v	journal	March 2015
Dynamics in the Isotropic Phase of Nematogens Using 2D IR Vibrational Echo Measurements on Natural-Abundance ¹³ CN and Extended Lifetime Probes Sokolowsky, Kathleen P.; Fayer, Michael D. The Journal of Physical Chemistry B, Vol. 117, Issue 48 https://doi.org/10.1021/jp4071955	journal	November 2013
Structural dynamics inside a functionalized metal–organic framework probed by ultrafast 2D IR spectroscopy Nishida, Jun; Tamimi, Amr; Fei, Honghan Proceedings of the National Academy of Sciences, Vol. 111, Issue 52 https://doi.org/10.1073/pnas.1422194112	journal	December 2014
Structural Dynamics of a Catalytic Monolayer Probed by Ultrafast 2D IR Vibrational Echoes Rosenfeld, D. E.; Gengeliczki, Z.; Smith, B. J. Science, Vol. 334, Issue 6056 https://doi.org/10.1126/science.1211350	journal	October 2011
Coupling of Carbon Dioxide Stretch and Bend Vibrations Reveals Thermal Population Dynamics in an Ionic Liquid Giammanco, Chiara H.; Kramer, Patrick L.; Yamada, Steven A. The Journal of Physical Chemistry B, Vol. 120, Issue 3 https://doi.org/10.1021/acs.jpcb.5b11454	journal	January 2016
Distinguishing Population and Coherence Transfer Pathways in a Metal Dicarbonyl Complex Using Pulse-Shaped Two-Dimensional Infrared Spectroscopy Marroux, Hugo J. B.; Orr-Ewing, Andrew J. The Journal of Physical Chemistry B, Vol. 120, Issue 17 https://doi.org/10.1021/acs.jpcb.6b02979	journal	April 2016
Perturbed free induction decay in ultrafast mid-IR pump–probe spectroscopy Yan, Suxia; Seidel, Marco Thomas; Tan, Howe-Siang Chemical Physics Letters, Vol. 517, Issue 1-3 https://doi.org/10.1016/j.cplett.2011.10.013	journal	November 2011
Dynamics of Isolated Water Molecules in a Sea of Ions in a Room Temperature Ionic Liquid Wong, Daryl B.; Giammanco, Chiara H.; Fenn, Emily E. The Journal of Physical Chemistry B, Vol. 117, Issue 2 https://doi.org/10.1021/jp310086s	journal	January 2013
Vibrational Anharmonicities Revealed by Coherent Two-Dimensional Infrared Spectroscopy Golonzka, O.; Khalil, M.; Demirdöven, N. Physical Review Letters, Vol. 86, Issue 10 https://doi.org/10.1103/PhysRevLett.86.2154	journal	March 2001
Mode-specific intermolecular vibrational energy transfer. II. Deuterated water and potassium selenocyanate mixture Bian, Hongtao; Wen, Xiewen; Li, Jiebo The Journal of Chemical Physics, Vol. 133, Issue 3 https://doi.org/10.1063/1.3458825	journal	July 2010
Infrared Spectroscopic Signatures of Phase Segregation in P3HT−Porphyrin Blends Eigner, Audrey A.; Konold, Patrick E.; Massari, Aaron M. The Journal of Physical Chemistry B, Vol. 113, Issue 44 https://doi.org/10.1021/jp9052242	journal	November 2009
Orientational correlation functions and polarization selectivity for nonlinear spectroscopy of isotropic media. I. Third order Tokmakoff, A. The Journal of Chemical Physics, Vol. 105, Issue 1 https://doi.org/10.1063/1.471856	journal	July 1996
Taking apart the two-dimensional infrared vibrational echo spectra: More information and elimination of distortions Kwak, Kyungwon; Rosenfeld, Daniel E.; Fayer, M. D. The Journal of Chemical Physics, Vol. 128, Issue 20 https://doi.org/10.1063/1.2927906	journal	May 2008
Organic Cation Rotation and Immobilization in Pure and Mixed Methylammonium Lead-Halide Perovskites Selig, Oleg; Sadhanala, Aditya; Müller, Christian Journal of the American Chemical Society, Vol. 139, Issue 11 https://doi.org/10.1021/jacs.6b12239	journal	March 2017
Investigating the Role of the Organic Cation in Formamidinium Lead Iodide Perovskite Using Ultrafast Spectroscopy Taylor, Victoria C. A.; Tiwari, Devendra; Duchi, Marta The Journal of Physical Chemistry Letters, Vol. 9, Issue 4 https://doi.org/10.1021/acs.jpclett.7b03296	journal	February 2018
Efficient and stable perovskite solar cells prepared in ambient air irrespective of the humidity Tai, Qidong; You, Peng; Sang, Hongqian Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11105	journal	April 2016
Pseudohalide (SCN ^– )-Doped MAPbI ₃ Perovskites: A Few Surprises Halder, Ansuman; Chulliyil, Ramya; Subbiah, Anand S. The Journal of Physical Chemistry Letters, Vol. 6, Issue 17 https://doi.org/10.1021/acs.jpclett.5b01327	journal	August 2015
Efficient and reproducible CH ₃ NH ₃ PbI _3−x (SCN) _x perovskite based planar solar cells Chen, Yani; Li, Bobo; Huang, Wei Chemical Communications, Vol. 51, Issue 60 https://doi.org/10.1039/C5CC03615A	journal	January 2015

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Title: Dynamically Disordered Lattice in a Layered Pb-I-SCN Perovskite Thin Film Probed by Two-Dimensional Infrared Spectroscopy

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