Disphenoidal Zero-Dimensional Lead, Tin, and Germanium Halides: Highly Emissive Singlet and Triplet Self-Trapped Excitons and X-ray Scintillation

Morad, Viktoriia; Shynkarenko, Yevhen; Yakunin, Sergii; Brumberg, Alexandra; Schaller, Richard D.; Kovalenko, Maksym V.

doi:10.1021/jacs.9b02365

Title: Disphenoidal Zero-Dimensional Lead, Tin, and Germanium Halides: Highly Emissive Singlet and Triplet Self-Trapped Excitons and X-ray Scintillation

Journal Article · 17 June 2019 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.9b02365 · OSTI ID:1571634

Morad, Viktoriia ^[1];

^[1];

^[2];

^[3];

^[1]

ETH Zürich (Switzerland); Empa—Swiss Federal Laboratories for Materials Science and Technology (Switzerland)
Northwestern Univ., Evanston, IL (United States)
Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)

Low-dimensional metal halides have been researched as optoelectronic materials for the past two decades. Zero-dimensional halides of ns² elements (Sn, Pb, Sb) have recently gained attention as highly efficient broadband light emitters. These compounds comprise discrete metal halide centers, isolated by bulky organic cations. Herein, we report isostructural halide complexes of Ge(II), Sn(II), and Pb(II) with a 1-butyl-1-methyl-piperidinium cation (Bmpip), featuring unusual disphenoidal coordination with a highly stereoactive lone pair. Spectrally broad, bright emission from highly localized excitons, with quantum efficiencies of up to 75%, is observed in blue to red spectral regions for bromides (for Pb, Sn, and Ge, respectively) and extends into the near-infrared for Bmpip₂SnI₄ (peak at 730 nm). In the case of Sn(II) and Ge(II), both singlet and triplet excitonic emission bands have been observed. Furthermore, Bmpip₂SnBr₄ and Bmpip₂PbBr₄ exhibit X-ray-excited luminescence (radioluminescence) with brightness being commensurate with that of a commercial inorganic X-ray scintillator (NaI:Tl).

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1571634

Journal Information:: Journal of the American Chemical Society, Vol. 141, Issue 25; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (39)

Metal-halide perovskites for photovoltaic and light-emitting devices Stranks, Samuel D.; Snaith, Henry J. Nature Nanotechnology, Vol. 10, Issue 5 https://doi.org/10.1038/nnano.2015.90	journal	May 2015
Efficient and stable emission of warm-white light from lead-free halide double perovskites Luo, Jiajun; Wang, Xiaoming; Li, Shunran Nature, Vol. 563, Issue 7732 https://doi.org/10.1038/s41586-018-0691-0	journal	November 2018
Coherent single-photon emission from colloidal lead halide perovskite quantum dots Utzat, Hendrik; Sun, Weiwei; Kaplan, Alexander E. K. Science, Vol. 363, Issue 6431 https://doi.org/10.1126/science.aau7392	journal	February 2019
Sequential deposition as a route to high-performance perovskite-sensitized solar cells Burschka, Julian; Pellet, Norman; Moon, Soo-Jin Nature, Vol. 499, Issue 7458, p. 316-319 https://doi.org/10.1038/nature12340	journal	July 2013
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
Detection of gamma photons using solution-grown single crystals of hybrid lead halide perovskites Yakunin, Sergii; Dirin, Dmitry N.; Shynkarenko, Yevhen Nature Photonics, Vol. 10, Issue 9 https://doi.org/10.1038/nphoton.2016.139	journal	July 2016
Crystal Growth of the Perovskite Semiconductor CsPbBr ₃ : A New Material for High-Energy Radiation Detection Stoumpos, Constantinos C.; Malliakas, Christos D.; Peters, John A. Crystal Growth & Design, Vol. 13, Issue 7 https://doi.org/10.1021/cg400645t	journal	June 2013
Solution-processed hybrid perovskite photodetectors with high detectivity Dou, Letian; Yang, Yang (Micheal); You, Jingbi Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6404	journal	November 2014
High-Performance Flexible Broadband Photodetector Based on Organolead Halide Perovskite Hu, Xin; Zhang, Xiaodong; Liang, Lin Advanced Functional Materials, Vol. 24, Issue 46 https://doi.org/10.1002/adfm.201402020	journal	September 2014
Non-dissipative internal optical filtering with solution-grown perovskite single crystals for full-colour imaging Yakunin, Sergii; Shynkarenko, Yevhen; Dirin, Dmitry N. NPG Asia Materials, Vol. 9, Issue 9 https://doi.org/10.1038/am.2017.163	journal	September 2017
Nontemplate Synthesis of CH ₃ NH ₃ PbBr ₃ Perovskite Nanoparticles Schmidt, Luciana C.; Pertegás, Antonio; González-Carrero, Soranyel Journal of the American Chemical Society, Vol. 136, Issue 3 https://doi.org/10.1021/ja4109209	journal	January 2014
Nanocrystals of Cesium Lead Halide Perovskites (CsPbX ₃ , X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut Protesescu, Loredana; Yakunin, Sergii; Bodnarchuk, Maryna I. Nano Letters, Vol. 15, Issue 6 https://doi.org/10.1021/nl5048779	journal	February 2015
Metal Halide Perovskite Nanocrystals: Synthesis, Post-Synthesis Modifications, and Their Optical Properties Shamsi, Javad; Urban, Alexander S.; Imran, Muhammad Chemical Reviews, Vol. 119, Issue 5 https://doi.org/10.1021/acs.chemrev.8b00644	journal	February 2019
Structural Diversity in White-Light-Emitting Hybrid Lead Bromide Perovskites Mao, Lingling; Guo, Peijun; Kepenekian, Mikaël Journal of the American Chemical Society, Vol. 140, Issue 40 https://doi.org/10.1021/jacs.8b08691	journal	September 2018
Low-Dimensional Organometal Halide Perovskites Lin, Haoran; Zhou, Chenkun; Tian, Yu ACS Energy Letters, Vol. 3, Issue 1 https://doi.org/10.1021/acsenergylett.7b00926	journal	November 2017
Organic−Inorganic Layered and Hollow Tin Bromide Perovskite with Tunable Broadband Emission Fu, Pengfei; Huang, Menglin; Shang, Yuequn ACS Applied Materials & Interfaces, Vol. 10, Issue 40 https://doi.org/10.1021/acsami.8b07673	journal	September 2018
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
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
Self-Assembly of Broadband White-Light Emitters Dohner, Emma R.; Hoke, Eric T.; Karunadasa, Hemamala I. Journal of the American Chemical Society, Vol. 136, Issue 5 https://doi.org/10.1021/ja411045r	journal	January 2014
Highly Emissive Self-Trapped Excitons in Fully Inorganic Zero-Dimensional Tin Halides Benin, Bogdan M.; Dirin, Dmitry N.; Morad, Viktoriia Angewandte Chemie International Edition, Vol. 57, Issue 35 https://doi.org/10.1002/anie.201806452	journal	July 2018
Luminescent zero-dimensional organic metal halide hybrids with near-unity quantum efficiency Zhou, Chenkun; Lin, Haoran; Tian, Yu Chemical Science, Vol. 9, Issue 3 https://doi.org/10.1039/C7SC04539E	journal	January 2018
Broad-Band Emission in a Zero-Dimensional Hybrid Organic [PbBr ₆ ] Trimer with Intrinsic Vacancies Zhou, Jun; Li, Mingze; Ning, Lixin The Journal of Physical Chemistry Letters, Vol. 10, Issue 6 https://doi.org/10.1021/acs.jpclett.9b00238	journal	March 2019
Near-Unity Photoluminescence Quantum Yield in Blue-Emitting Cs ₃ Cu ₂ Br _{5– x} I _x (0 ≤ x ≤ 5) Roccanova, Rachel; Yangui, Aymen; Nhalil, Hariharan ACS Applied Electronic Materials, Vol. 1, Issue 3 https://doi.org/10.1021/acsaelm.9b00015	journal	February 2019
The Structures of s ² Metal Complexes in the Ground and sp Excited States Vogler, Arnd; Nikol, Hans Comments on Inorganic Chemistry, Vol. 14, Issue 4 https://doi.org/10.1080/02603599308048663	journal	January 1993
Luminescence of lead chloride and lead bromide single crystals de Gruijter, W. C. Physics Letters A, Vol. 34, Issue 5 https://doi.org/10.1016/0375-9601(71)90855-3	journal	March 1971
Charge separation of excitons and the radiative recombination process in PbBr 2 crystals Iwanaga, Masanobu; Watanabe, Masayuki; Hayashi, Tetsusuke Physical Review B, Vol. 62, Issue 16 https://doi.org/10.1103/PhysRevB.62.10766	journal	October 2000
Self-trapped states and related luminescence in PbCl 2 crystals Iwanaga, Masanobu; Shirai, Masanobu; Tanaka, Koichiro Physical Review B, Vol. 66, Issue 6 https://doi.org/10.1103/PhysRevB.66.064304	journal	August 2002
Optical properties of SnCl ₂ phosphor Nara, Jun-ichi; Adachi, Sadao Journal of Applied Physics, Vol. 109, Issue 8 https://doi.org/10.1063/1.3576118	journal	April 2011
Photoluminescence of PbBr2, PbCl2 and β-PbF2 single crystals Eijkelenkamp, A. J. H. Journal of Luminescence, Vol. 15, Issue 2 https://doi.org/10.1016/0022-2313(77)90020-5	journal	June 1977
Low-temperature X-ray and photoluminescence of lead halide crystals Liidja, G.; Plekhanov, Vl. Journal of Luminescence, Vol. 6, Issue 2 https://doi.org/10.1016/0022-2313(73)90042-2	journal	March 1973
High Defect Tolerance in Lead Halide Perovskite CsPbBr ₃ Kang, Jun; Wang, Lin-Wang The Journal of Physical Chemistry Letters, Vol. 8, Issue 2 https://doi.org/10.1021/acs.jpclett.6b02800	journal	January 2017
Crystal structure of 1,2-vinylenbis(triphenylphosphonium) dibromide dihydrate, [Ph3P-CH=CH-PPh3][Br]2 · 2H2O Blachnik, R.; Reuter, H.; Wiest, Τ. Zeitschrift für Kristallographie - New Crystal Structures, Vol. 215, Issue 2 https://doi.org/10.1515/ncrs-2000-0229	journal	February 2000
Bromoplumbate mit kettenförmigen und isolierten Anionen: (Bzl4P)2[Pb3Br8], (Bzl4P)2[Pb3Br8(dmf)2], (Bzl4P)[PbBr3], (Bzl4P)2[PbBr4] und (Bzl4P)4[Pb2Br6][PbBr4] Gröger, Henriette; Lode, Christine; Vollmer, Heike Zeitschrift für anorganische und allgemeine Chemie, Vol. 628, Issue 1 https://doi.org/10.1002/1521-3749(200201)628:1<57::AID-ZAAC57>3.0.CO;2-P	journal	January 2002
Spin–Orbit Interactions Greatly Accelerate Nonradiative Dynamics in Lead Halide Perovskites Li, Wei; Zhou, Liujiang; Prezhdo, Oleg V. ACS Energy Letters, Vol. 3, Issue 9 https://doi.org/10.1021/acsenergylett.8b01226	journal	August 2018
Alkali halide crystals containing impurity ions with the ns2 ground-state electronic configuration† Jacobs, P. W. M. Journal of Physics and Chemistry of Solids, Vol. 52, Issue 1 https://doi.org/10.1016/0022-3697(91)90059-9	journal	January 1991
Influence of the Anion on Lone Pair Formation in Sn(II) Monochalcogenides: A DFT Study Walsh, Aron; Watson, Graeme W. The Journal of Physical Chemistry B, Vol. 109, Issue 40 https://doi.org/10.1021/jp051822r	journal	October 2005
The origin of the stereochemically active Pb(II) lone pair: DFT calculations on PbO and PbS Walsh, Aron; Watson, Graeme W. Journal of Solid State Chemistry, Vol. 178, Issue 5 https://doi.org/10.1016/j.jssc.2005.01.030	journal	May 2005
Photoluminescence of germanium(II), tin(II), and lead(II) chloride complexes in solution Nikol, Hans; Becht, Alexander; Vogler, Arnd Inorganic Chemistry, Vol. 31, Issue 15 https://doi.org/10.1021/ic00041a021	journal	July 1992
Sunlike White-Light-Emitting Diodes Based on Zero-Dimensional Organic Metal Halide Hybrids Worku, Michael; Tian, Yu; Zhou, Chenkun ACS Applied Materials & Interfaces, Vol. 10, Issue 36 https://doi.org/10.1021/acsami.8b12474	journal	August 2018

Cited By (6)

Hybrid Metal Halides with Multiple Photoluminescence Centers Li, Mingze; Zhou, Jun; Zhou, Guojun Angewandte Chemie International Edition, Vol. 58, Issue 51 https://doi.org/10.1002/anie.201911419	journal	November 2019
Crystal structure and luminescence properties of lead-free metal halides (C ₆ H ₅ CH ₂ NH ₃ ) ₃ MBr ₆ (M = Bi and Sb) Chen, Da; Dai, Fulong; Hao, Shiqiang Journal of Materials Chemistry C https://doi.org/10.1039/d0tc00562b	journal	January 2020
Hybrid Metal Halides with Multiple Photoluminescence Centers Li, Mingze; Zhou, Jun; Zhou, Guojun Angewandte Chemie, Vol. 131, Issue 51 https://doi.org/10.1002/ange.201911419	journal	November 2019
Rb ₂ CuX ₃ (X = Cl, Br): 1D All‐Inorganic Copper Halides with Ultrabright Blue Emission and Up‐Conversion Photoluminescence Creason, Tielyr D.; Yangui, Aymen; Roccanova, Rachel Advanced Optical Materials, Vol. 8, Issue 2 https://doi.org/10.1002/adom.201901338	journal	November 2019
Exploring Organic Metal Halides with Reversible Temperature‐Responsive Dual‐Emissive Photoluminescence Jiang, Xiaomei; Xia, Shengqing; Zhang, Jian ChemSusChem, Vol. 12, Issue 24 https://doi.org/10.1002/cssc.201902481	journal	October 2019
Hybrid Metal Halides with Multiple Photoluminescence Centers Li, Mingze; Zhou, Jun; Zhou, Guojun ETH Zurich https://doi.org/10.3929/ethz-b-000377326	text	January 2019

Linked Research (3)

Similar Records

Luminescent hybrid halides with various centering metal cations (Zn, Cd and Pb) and diverse structures

Journal Article · 2023 · Dalton Transactions · OSTI ID:2420375

Fan, Liubing; Hao, Shiqiang; He, Shihui; +5 more

Dynamic Lone Pairs and Fluoride-Ion Disorder in Cubic-BaSnF₄

Journal Article · 2023 · Journal of the American Chemical Society · OSTI ID:2202498

Mercadier, Briséïs; Coles, Samuel W.; Duttine, Mathieu; +7 more

Bulk Assembly of Zero-Dimensional Organic Lead Bromide Hybrid with Efficient Blue Emission

Journal Article · 2019 · ACS Materials Letters · OSTI ID:1607040

Lin, Haoran; Zhou, Chenkun; Chaaban, Maya; +11 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE

CCDC 1897911: Experimental Crystal Structure Determination Viktoriia, Morad,; Yevhen, Shynkarenko,; Sergii, Yakunin, https://doi.org/10.5517/ccdc.csd.cc21pxym The current record is supplemented by this dataset	dataset	January 2019
CCDC 1897912: Experimental Crystal Structure Determination Viktoriia, Morad,; Yevhen, Shynkarenko,; Sergii, Yakunin, https://doi.org/10.5517/ccdc.csd.cc21pxzn The current record is supplemented by this dataset	dataset	January 2019
CCDC 1897913: Experimental Crystal Structure Determination Viktoriia, Morad,; Yevhen, Shynkarenko,; Sergii, Yakunin, https://doi.org/10.5517/ccdc.csd.cc21py0q The current record is supplemented by this dataset	dataset	January 2019