Homomeric chains of intermolecular bonds scaffold octahedral germanium perovskites

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Perovskites with low ionic radii metal centres (for example, Ge perovskites) experience both geometrical constraints and a gain in electronic energy through distortion; for these reasons, synthetic attempts do not lead to octahedral [GeI6] perovskites, but rather, these crystallize into polar non-perovskite structures1,2,3,4,5,6. Here, inspired by the principles of supramolecular synthons7,8, we report the assembly of an organic scaffold within perovskite structures with the goal of influencing the geometric arrangement and electronic configuration of the crystal, resulting in the suppression of the lone pair expression of Ge and templating the symmetric octahedra. We find that, to produce extended homomeric non-covalent bonding, the organic motif needs to possess self-complementary properties implemented using distinct donor and acceptor sites. Compared with the non-perovskite structure, the resulting [GeI6]4− octahedra exhibit a direct bandgap with significant redshift (more than 0.5 eV, measured experimentally), 10 times lower octahedral distortion (inferred from measured single-crystal X-ray diffraction data) and 10 times higher electron and hole mobility (estimated by density functional theory). We show that the principle of this design is not limited to two-dimensional Ge perovskites; we implement it in the case of copper perovskite (also a low-radius metal centre), and we extend it to quasi-two-dimensional systems. We report photodiodes with Ge perovskites that outperform their non-octahedral and lead analogues. The construction of secondary sublattices that interlock with an inorganic framework within a crystal offers a new synthetic tool for templating hybrid lattices with controlled distortion and orbital arrangement, overcoming limitations in conventional perovskites.

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Crystallographic data for the structures reported in this article have also been deposited at the Cambridge Crystallographic Data Centre, with deposition numbers indicated in the Supplementary Information. Data are also available on request.

Chiara, R., Morana, M. & Malavasi, L. Germanium-based halide perovskites: materials, properties, and applications. Chempluschem 86, 879–888 (2021).

Article CAS PubMed Google Scholar

Stoumpos, C. C. et al. Hybrid germanium iodide perovskite semiconductors: active lone pairs, structural distortions, direct and indirect energy gaps, and strong nonlinear optical properties. J. Am. Chem. Soc. 137, 6804–6819 (2015).

Article CAS PubMed Google Scholar

Ke, W. & Kanatzidis, M. G. Prospects for low-toxicity lead-free perovskite solar cells. Nat. Commun. 10, 965 (2019).

Article ADS PubMed PubMed Central Google Scholar

Chen, M. et al. Highly stable and efficient all-inorganic lead-free perovskite solar cells with native-oxide passivation. Nat. Commun. 10, 16 (2019).

Article ADS CAS PubMed PubMed Central Google Scholar

Glück, N. & Bein, T. Prospects of lead-free perovskite-inspired materials for photovoltaic applications. Energy Environ. Sci. 13, 4691–4716 (2020).

Article Google Scholar

Xiao, Z., Song, Z. & Yan, Y. From lead halide perovskites to lead-free metal halide perovskites and perovskite derivatives. Adv. Mater. 31, 1803792 (2019).

Article CAS Google Scholar

Desiraju, G. R. Crystal engineering: from molecule to crystal. J. Am. Chem. Soc. 135, 9952–9967 (2013).

Article CAS PubMed Google Scholar

Mukherjee, A. Building upon supramolecular synthons: some aspects of crystal engineering. Cryst. Growth Des. 15, 3076–3085 (2015).

Article CAS Google Scholar

Fu, Y. et al. Metal halide perovskite nanostructures for optoelectronic applications and the study of physical properties. Nat Rev Mater 4, 169–188 (2019).

Article ADS CAS Google Scholar

Nayak, P. K., Mahesh, S., Snaith, H. J. & Cahen, D. Photovoltaic solar cell technologies: analysing the state of the art. Nat Rev Mater 4, 269–285 (2019).

Article ADS CAS Google Scholar

Kim, J. Y., Lee, J. W., Jung, H. S., Shin, H. & Park, N. G. High-efficiency perovskite solar cells. Chem. Rev. 120, 7867–7918 (2020).

Article CAS PubMed Google Scholar

Kojima, A., Teshima, K., Shirai, Y. & Miyasaka, T. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J. Am. Chem. Soc. 131, 6050–6051 (2009).

Article CAS PubMed Google Scholar

Hailegnaw, B., Kirmayer, S., Edri, E., Hodes, G. & Cahen, D. Rain on methylammonium lead iodide based perovskites: possible environmental effects of perovskite solar cells. J. Phys. Chem. Lett. 6, 1543–1547 (2015).

Article CAS PubMed Google Scholar

Babayigit, A., Ethirajan, A., Muller, M. & Conings, B. Toxicity of organometal halide perovskite solar cells. Nat. Mater. 15, 247–251 (2016).

Article ADS CAS PubMed Google Scholar

Siebentritt, S. et al. Heavy alkali treatment of Cu(In,Ga)Se2 solar cells: surface versus bulk effects. Adv. Energy Mater. 10, 1903752 (2020).

Article CAS Google Scholar

Hoye, R. L. Z. et al. Fundamental carrier lifetime exceeding 1 µs in Cs2AgBiBr6 double perovskite. Adv. Mater. Interfaces 5, 1800464 (2018).

Article Google Scholar

Seo, D. K., Gupta, N., Whangbo, M. H., Hillebrecht, H. & Thiele, G. Pressure-induced changes in the structure and band gap of CsGeX3 (X = Cl, Br) studied by electronic band structure calculations. Inorg. Chem. 37, 407–410 (1998).

Article CAS PubMed Google Scholar

Filip, M. R. & Giustino, F. The geometric blueprint of perovskites. Proc. Natl Acad. Sci. USA 115, 5397–5402 (2018).

Article ADS CAS PubMed PubMed Central Google Scholar

Li, X. et al. Tolerance factor for stabilizing 3D hybrid halide perovskitoids using linear diammonium cations. J. Am. Chem. Soc. 144, 3902–3912 (2022).

Article CAS PubMed Google Scholar

Fedorovskiy, A. E., Drigo, N. A. & Nazeeruddin, M. K. The role of Goldschmidt’s tolerance factor in the formation of A2BX6 double halide perovskites and its optimal range. Small Methods 4, 1900426 (2020).

Article CAS Google Scholar

Yamada, K., Mikawa, K., Okuda, T. & Knight, K. S. Static and dynamic structures of CD3ND3GeCl3 studied by TOF high resolution neutron powder diffraction and solid state NMR. J. Chem. Soc. Dalton Trans. 10, 2112–2118 (2002).

Article Google Scholar

Yamada, K. et al. Structural phase transitions of the polymorphs of CsSnI3 by means of Rietveld analysis of the X-ray diffraction. Chem. Lett. 20, 801–804 (1991).

Article Google Scholar

Varignon, J., Bibes, M. & Zunger, A. Origins versus fingerprints of the Jahn–Teller effect in d-electron ABX3 perovskites. Phys Rev Res 1, 033131 (2019).

Article CAS Google Scholar

Albright, T. A., Burdett, J. K. & Whangbo, M. H. Orbital Interactions in Chemistry. 2nd edn (Wiley, 2013).

Schwarz, U., Wagner, F., Syassen, K. & Hillebrecht, H. Effect of pressure on the optical-absorption edges of CsGeBr3 and CsGeCl3. Phys. Rev. B Condens. Matter Mater. Phys. 53, 12545–12548 (1996).

Article ADS CAS Google Scholar

Thiele, G., Rotter, H. W. & Schmidt, K. D. Kristallstrukturen und Phasentransformationen von Caesiumtrihalogenogermanaten(II) CsGeX3 (X = Cl, Br, I). ZAAC J. Inorg. Gen. Chem. 545, 148–156 (1987).

CAS Google Scholar

Christensen, A. N. et al. A ferroelectric chloride of perowskite type crystal structure of CsGeCl3. Acta Chem. Scand. 19, 421–428 (1965).

Article CAS Google Scholar

Saparov, B. & Mitzi, D. B. Organic-inorganic perovskites: structural versatility for functional materials design. Chem. Rev. 116, 4558–4596 (2016).

Article CAS PubMed Google Scholar

Jana, M. K. et al. Structural descriptor for enhanced spin-splitting in 2D hybrid perovskites. Nat. Commun. 12, 4982 (2021).

Article ADS CAS PubMed PubMed Central Google Scholar

Cavallo, G. et al. The halogen bond. Chem. Rev. 116, 2478–2601 (2016).

Article CAS PubMed PubMed Central Google Scholar

Varadwaj, P. R., Varadwaj, A. & Marques, H. M. Halogen bonding: a halogen-centered noncovalent interaction yet to be understood. Inorganics (Basel) 7, 40 (2019).

Article CAS Google Scholar

Metrangolo, P., Canil, L., Abate, A., Terraneo, G. & Cavallo, G. Halogen bonding in perovskite solar cells: a new tool for improving solar energy conversion. Angew. Chem. Int. Ed. Engl. 61, e202114793 (2022).

Article CAS PubMed PubMed Central Google Scholar

Ball, M. L., Milic, J. V. & Loo, Y. L. The emerging role of halogen bonding in hybrid perovskite photovoltaics. Chem. Mater. 23, 8 (2021).

Google Scholar

Fu, X. et al. Halogen-halogen bonds enable improved long-term operational stability of mixed-halide perovskite photovoltaics. Chem 7, 3131–3143 (2021).

Article CAS Google Scholar

Baur, W. H. The geometry of polyhedral distortions. Predictive relationships for the phosphate group. Acta Crystallogr. B 30, 1195–1215 (1974).

Article CAS Google Scholar

Baldrighi, M. et al. Polymorphs and co-crystals of haloprogin: an antifungal agent. CrystEngComm 16, 5897–5904 (2014).

Article CAS Google Scholar

Wang, P. X. et al. Structural distortion and bandgap increase of two-dimensional perovskites induced by trifluoromethyl substitution on spacer cations. J. Phys. Chem. Lett. 11, 10144–10149 (2020).

Article CAS PubMed Google Scholar

Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

Article CAS Google Scholar

Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).

Article ADS CAS Google Scholar

Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

Article ADS CAS PubMed Google Scholar

Payne, M. C., Teter, M. P., Allan, D. C., Arias, T. A. & Joannopoulos, J. D. Iterative minimization techniques for ab initio total-energy calculations: molecular dynamics and conjugate gradients. Rev. Mod. Phys. 64, 1045–1097 (1992).

Article ADS CAS Google Scholar

Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).

Article ADS MathSciNet Google Scholar

Krukau, A. V., Vydrov, O. A., Izmaylov, A. F. & Scuseria, G. E. Influence of the exchange screening parameter on the performance of screened hybrid functionals. J. Chem. Phys. 125, 5029 (2006).

Article Google Scholar

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We acknowledge the crystallographic services provided by J. Ovens from the X-Ray Core Facility at the University of Ottawa. This work was financially supported by Huawei Technologies Canada Co., Ltd and the Natural Sciences and Engineering Research Council of Canada.

The Edward S. Rogers Department of Electrical and Computer Engineering, University of Toronto, Toronto, Ontario, Canada

Amin Morteza Najarian, Hao Chen, Randy Sabatini, Chao Zheng, Sjoerd Hoogland & Edward H. Sargent

Department of Physical and Environmental Sciences, University of Toronto Scarborough, Toronto, Ontario, Canada

Filip Dinic & Oleksandr Voznyy

Department of Chemistry, University of Toronto, Toronto, Ontario, Canada

Filip Dinic, Alan Lough & Oleksandr Voznyy

Département de Chimie, Université de Montréal, Montréal, Québec, Canada

Thierry Maris

Department of Chemistry, University of Victoria, Victoria, British Columbia, Canada

Makhsud I. Saidaminov

Institut de Ciències Fotòniques, The Barcelona Institute of Science and Technology, Barcelona, Spain

F. Pelayo García de Arquer

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A.M.N., S.H. and E.H.S. conceived the idea. A.M.N. designed the experiments. A.M.N. synthesized and characterized the crystals. A.L. and T.M. resolved the crystal structures. A.M.N. and H.C. fabricated the devices. F.D., C.Z. and O.V. did the theoretical calculations and simulations. M.I.S., F.P.G.d.A., S.H. and E.H.S. provided advice. A.M.N., R.S. and E.H.S. composed the manuscript. All authors discussed the results, edited and commented on the manuscript.

Correspondence to Edward H. Sargent.

The authors declare no competing interests.

Nature thanks the anonymous reviewers for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

A plot of Baur distortion index vs a, Bond angle variance b, Quadratic elongation c, Effective coordination number d, Bond distortion $(\triangle d)$ e, Polyhedral volume f, Average bong length. Octahedral perovskites are identified by the yellow circles in each graph. See Supplementary note 4 for the definition of each metric.

(PMA)2GeI4; b, (4F-PMA)2GeI4; c, (4Cl-PMA)2GeI4 with indicated view axis.

(4Br-PMA)2GeI4; b, (4I-PMA)2GeI4; c, (3F-PMA)2GeI4 with indicated view axis.

a, view at the a-c crystal axis of the crystal. b, Titled view to show donor and acceptor sites of the XB bonding.

a, View at the a-b crystal axis. b, titled view to show donor and acceptor sites of the HB bonding.

using: a, F-PMA; b, Cl-PMA; c, I-PMA as cations.

using: a, F-PMA; b, Cl-PMA; c, I-PMA as cations. Note that for both cases, the contribution of the density of state on the organic parts is negligible, and thus organic molecules are not shown in the figure. Dark grey and red sphere represent the Ge and I atoms, respectively. Green and yellow colours are used for representation of positive and negative isosurfaces.

Each example includes the possible route for the propagation of intermolecular bonding.

Supplementary Information file containing Supplementary Notes 1–4, Supplementary Table 1 and Supplementary Figs. 1–18. The crystallographic data of the structures presented in this article have been archived at the Cambridge Crystallographic Data Centre, and the deposition numbers are specified. Additionally, we have made available the CIF files for these structures as Supplementary Data.

CIF files for the structures presented in this article are named according to the crystal composition, and the structure andmolecular entity abbreviations can be found in Fig. 2a.

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Morteza Najarian, A., Dinic, F., Chen, H. et al. Homomeric chains of intermolecular bonds scaffold octahedral germanium perovskites. Nature (2023). https://doi.org/10.1038/s41586-023-06209-y

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Received: 24 May 2022

Accepted: 12 May 2023

Published: 12 July 2023

DOI: https://doi.org/10.1038/s41586-023-06209-y

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