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NMR spectroscopy probes microstructure, dynamics and doping of metal halide perovskites

Nature Reviews Chemistry volume 5, pages 624–645 (2021)Cite this article

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Abstract

Solid-state magic-angle spinning NMR spectroscopy is a powerful technique to probe atomic-level microstructure and structural dynamics in metal halide perovskites. It can be used to measure dopant incorporation, phase segregation, halide mixing, decomposition pathways, passivation mechanisms, short-range and long-range dynamics, and other local properties. This Review describes practical aspects of recording solid-state NMR data on halide perovskites and how these afford unique insights into new compositions, dopants and passivation agents. We discuss the applicability, feasibility and limitations of 1H, 13C, 15N, 14N, 133Cs, 87Rb, 39K, 207Pb, 119Sn, 113Cd, 209Bi, 115In, 19F and 2H NMR in typical experimental scenarios. We highlight the pivotal complementary role of solid-state mechanosynthesis, which enables highly sensitive NMR studies by providing large quantities of high-purity materials of arbitrary complexity and of chemical shifts calculated using density functional theory. We examine the broader impact of solid-state NMR on materials research and how its evolution over seven decades has benefitted structural studies of contemporary materials such as halide perovskites. Finally, we summarize some of the open questions in perovskite optoelectronics that could be addressed using solid-state NMR. We, thereby, hope to stimulate wider use of this technique in materials and optoelectronics research.

Key points

  • Solid-state NMR is an excellent method to study the local structure of metal halide perovskite components and their dopants.

  • NMR does not require long-range order and, therefore, can identify and quantify amorphous components.

  • NMR can be used to study dynamics occurring on the picosecond to second timescale.

  • Most nuclei in the periodic table can be studied using solid-state NMR.

  • Typical NMR sample size is between 1 and 100 mg.

  • Interactions between perovskites and passivation agents can be readily studied.

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Fig. 1: Challenges related to studying the structure and dynamics of metal halide perovskites.
Fig. 2: Typical longitudinal relaxation times T1 for nuclei in metal halide perovskites.
Fig. 3: Identification, quantification and proximity of organic cations in solid metal halide perovskites.
Fig. 4: 13C and 15N cryo-NMR tell us phase compositions of hybrid metal halide perovskites.
Fig. 5: 13C and 15N cryo-NMR reveal the phase composition of layered haloplumbate materials.
Fig. 6: Speciation of diamagnetic metal ion dopants in metal halide perovskites.
Fig. 7: Speciation of paramagnetic metal ion dopants in metal halide perovskites.
Fig. 8: 207Pb NMR of solid Pb halide perovskites reveals halide coordination and mixing.
Fig. 9: Solid-state NMR of B-site cations in metal halide perovskites.
Fig. 10: Incorporation of dopants and motional degrees of freedom as probed by nuclei sensitive to dynamics.

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Acknowledgements

This work has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement no. 841136. This work was supported by Swiss National Science Foundation grant no. 200020_178860. S.D.S. acknowledges the Royal Society and Tata Group (UF150033). C.P.G. acknowledges the Royal Society.

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Authors and Affiliations

  1. Cavendish Laboratory, Department of Physics, University of Cambridge, Cambridge, UK

    Dominik J. Kubicki & Samuel D. Stranks

  2. Department of Chemistry, University of Cambridge, Cambridge, UK

    Dominik J. Kubicki & Clare P. Grey

  3. Department of Chemical Engineering and Biotechnology, University of Cambridge, Cambridge, UK

    Samuel D. Stranks

  4. Laboratory of Magnetic Resonance, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland

    Lyndon Emsley

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  1. Dominik J. Kubicki
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  2. Samuel D. Stranks
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D.J.K. wrote the article, with contributions from S.D.S., C.P.G. and L.E.

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Glossary

Magic-angle spinning

(MAS). An experimental protocol in which the solid sample is spun at high rates (typically 10–100 kHz) around an angle of 54.7356° relative to the external magnetic field, leading to substantially improved spectral resolution.

Cross-polarization

(CP). An experimental protocol allowing the detection of various nuclei with substantially improved sensitivity by transferring to them the intrinsically higher polarization of nearby 1H.

Dynamic nuclear polarization

(DNP). A sensitivity-enhancement NMR protocol that allows signal enhancements of up to ~660×, particularly from surfaces, which translate to up to 440,000× faster signal acquisition.

Spin diffusion

(SD). The process of continuous energy exchange between abundant spins of the same isotope (for example, 1H, 19F) driven by dipolar couplings and, therefore, makes it possible to detect spatial proximities between different species in the NMR spectrum.

Quadrupolar effects

The asymmetrical distribution of negative charge around quadrupolar nuclei (I > 1/2) leads to complex lineshapes that depend on the extent of asymmetry. These effects are a powerful tool to study local electronic environments.

Transverse relaxation

Also referred to as T2 relaxation, this is the process after pulse excitation by which the initially coherent system of nuclear spins loses its phase coherence, leading to finite linewidths in the NMR spectrum. Large values of relaxation time T2 indicate slower transverse relaxation and result in narrower linewidths. Structural dynamics and paramagnetic dopant concentrations are important contributors to the value of T2.

Longitudinal relaxation

This T1 relaxation process sees a nucleus return to thermal equilibrium after being perturbed. The value of the relaxation time T1 limits how frequently an NMR pulse sequence can be repeated to improve the overall signal-to-noise ratio. Structural dynamics and paramagnetic dopant concentrations are important contributors to the value of T1.

Nuclear quadrupole resonance

(NQR). A spectroscopic technique in which the magnetic resonance signal from quadrupolar nuclei is detected in the absence of an external magnetic field. It yields information complementary to NMR and, in the case of halogens, is often more practical.

Paramagnetic relaxation enhancement

(PRE). The unpaired electron(s) of a paramagnetic species, such as a transition metal ion, can couple strongly to NMR-active nuclei and cause rapid T1 and T2 relaxation. This effect is distance dependent and provides a means of studying paramagnetic dopant incorporation into materials.

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Kubicki, D.J., Stranks, S.D., Grey, C.P. et al. NMR spectroscopy probes microstructure, dynamics and doping of metal halide perovskites. Nat Rev Chem 5, 624–645 (2021). https://doi.org/10.1038/s41570-021-00309-x

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