Molecular Engineering of Pure 2D Lead‐Iodide Perovskite Solar Absorbers Displaying Reduced Band Gaps and Dielectric Confinement

Febriansyah, Benny; Lekina, Yulia; Ghosh, Biplab; Harikesh, Padinhare Cholakkal; Koh, Teck Ming; Li, Yongxin; Shen, Zexiang; Mathews, Nripan; England, Jason

doi:10.1002/cssc.202000028

Cited by 16 publications

(29 citation statements)

References 60 publications

(85 reference statements)

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“…Structural Properties: First, we have optimized the geometries by taking the experimentally reported crystal structures as the initial guess. [31][32][33]16 Optimized structures are shown in Figure 2 and Figure S1. So, the noncovalent interaction can be due to the H-bond formation.…”

Section: Resultsmentioning

confidence: 99%

“…England and co-workers have illustrated in their recent work that the intercalation of di-cations between inorganic layers can be beneficial as it requires single organic layer stacking compared to double organic layer stacking in mono-cation based systems. 16 Motivated from their work, we have included pyridinium based di-cation, pyridinium ethyl amine and its positional isomers (Figure 1) in our study. The presence of dipositive charge develops more rigid geometry of the cations.…”

Section: Introductionmentioning

confidence: 99%

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Understanding the role of spacer cation in 2D layered halide perovskites to achieve stable perovskite solar cells

2022

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Understanding the role of spacer cation in 2D layered halide perovskites to achieve stable perovskite solar cells

2022

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“…In particular, short perpendicular contacts favour superior charge transport. 34,48 As a 49 the band centred at 580 nm can be attributed to excitonic absorptions of the tin iodide lattice. As observed for 2D iodoplumbates, the excitonic transition of ImEA[SnI4] is blue-shifted relative to those of (100)-oriented 2D tin iodide perovskites, which range from 600 nm to 700 nm.…”

Section: Resultsmentioning

confidence: 99%

Formation of Corrugated n = 1 2D Tin Iodide Perovskites and Their Use as Lead-Free Solar Absorbers

et al. 2021

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Major strides have been made in the development of materials and devices based around low-dimensional hybrid group 14 metal halide perovskites. Thus far, this work has mostly focused upon compounds containing highly toxic Pb, with the analogous less toxic Sn materials being comparatively poorly evolved. In response, the study herein aims to (i) provide insight into the impact of templating cation upon the structure of 2D tin iodide perovskites, and (ii) examine their potential as light absorbers for photovoltaic (PV) cells. It was discovered through systematic tuning of organic dications, that imidazolium rings are able to induce formation of (110)-oriented materials, including the first examples of "3 × 3" corrugated Sn-I perovskites. This structural outcome is a consequence of a combination of supramolecular interactions of the two endocyclic N-atoms in the imidazolium functionalities with the Sn-I framework and the higher tendency of Sn 2+ ions to stereochemically express their 5s 2 lone pairs relative to the 6s 2 electrons of Pb 2+ . More importantly, the resulting materials feature very short separations between their 2D inorganic layers with iodide-iodide (I•••I) contacts as small as 4.174 Å, which is amongst the shortest ever recorded for 2D tin iodide perovskites. The proximate inorganic distances, combined with the polarizable nature of the imidazolium moiety, eases the separation of photogenerated charge within the materials. This is evident from the excitonic activation energies as low as 83(10) meV, measured for ImEA[SnI4]. When combined with superior light absorption capabilities relative to their lead congeners, this allowed fabrication of lead-free solar cells with incident photon-to-current and power conversion efficiencies of up to 70 % and 2.26 %, respectively, which are amongst the highest values reported for pure 2D group 14 metal halide perovskites. In fact, these values are superior to the corresponding lead iodide material, which demonstrates that 2D Sn-based materials have significant potential as less toxic alternatives to their Pb counterparts. Supporting InformationCrystal structures of hybrid lead iodide perovskites (cif files).Experimental procedures, materials synthesis, additional spectra and crystallographic data (pdf).The Supporting Information is available free of charge on the ACS Publications website.

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“…Due to the large variability of substitution and type of these, only examples based on or closely related to the (2-aminoethyl)pyridine structure will be discussed here (see the supporting information for amine comparison). Recent work by Febriansyah, Lekina et al (2020) compared the structural effect of positional isomers of the (2-aminoethyl) substituent to the pyridine ring. In their work they reported an increase in the interlayer I-I separations consistent with the movement of the (2-aminoethyl) substituent away from the N of the pyridine ring.…”

Section: More Complex Derivativesmentioning

confidence: 99%

Structural chemistry of layered lead halide perovskites containing single octahedral layers

McNulty

Lightfoot

2021

IUCrJ

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We present a comprehensive review of the structural chemistry of hybrid lead halides of stoichiometry APbX 4, A 2PbX4 or A A′PbX 4, where A and A′ are organic ammonium cations and X = Cl, Br or I. These compounds may be considered as layered perovskites, containing isolated, infinite layers of corner-sharing PbX 4 octahedra separated by the organic species. First, over 250 crystal structures were extracted from the CCDC and classified in terms of unit-cell metrics and crystal symmetry. Symmetry mode analysis was then used to identify the nature of key structural distortions of the [PbX 4]∞ layers. Two generic types of distortion are prevalent in this family: tilting of the octahedral units and shifts of the inorganic layers relative to each other. Although the octahedral tilting modes are well known in the crystallography of purely inorganic perovskites, the additional layer-shift modes are shown to enormously enrich the structural options available in layered hybrid perovskites. Some examples and trends are discussed in more detail in order to show how the nature of the interlayer organic species can influence the overall structural architecture; although the main aim of the paper is to encourage workers in the field to make use of the systematic crystallographic methods used here to further understand and rationalize their own compounds, and perhaps to be able to design-in particular structural features in future work.

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Molecular Engineering of Pure 2D Lead‐Iodide Perovskite Solar Absorbers Displaying Reduced Band Gaps and Dielectric Confinement

Abstract: Supporting Information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Cited by 16 publications

References 60 publications

Understanding the role of spacer cation in 2D layered halide perovskites to achieve stable perovskite solar cells

Understanding the role of spacer cation in 2D layered halide perovskites to achieve stable perovskite solar cells

Formation of Corrugated n = 1 2D Tin Iodide Perovskites and Their Use as Lead-Free Solar Absorbers

Structural chemistry of layered lead halide perovskites containing single octahedral layers

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