Assessment of polyanion (BF4− and PF6−) substitutions in hybrid halide perovskites

Hendon, Christopher H.; Yang, Ruo Xi; Burton, Lee A.; Walsh, Aron

doi:10.1039/c4ta05284f

Cited by 111 publications

(91 citation statements)

References 30 publications

(31 reference statements)

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“…FNH 3 PbI 3 shown in Figure possesses perovskite structure. One of the minimum requirements to verify this lies in the fulfillment of the “charge neutrality” condition . Per se, FNH 3 PbI 3 is the consequence of an electrical marriage between two inorganic moieties, the fluoroammonium cation (FNH

_{3}^{+}

) and the lead triiodide anion (PbI

_{3}^{-}

), showing the oxidation state of the B‐ and M‐site cations balances those of the three metal coordinated halide anions Y.…”

Section: Computational Details Results and Discussionmentioning

confidence: 99%

“…A critical aspect of some of these perovskites lies in the “direct‐to‐indirect/indirect‐to‐direct” nature of their bandgap . The view is not very surprising since this kind of bandgap transition has shown to have a significant impact on fast/slow recombination, as well as that on the extent of power conversion efficiency . This attribute has explained the extremely long charge‐carrier lifetimes and high open‐circuit voltages observed for the thin films of CH 3 NH 3 PbI 3 .…”

Section: Introductionmentioning

confidence: 99%

“…In addition, the electronic density of states (DOS) spectra are examined to provide insight into the nature of various orbital characters that have participated to build the valence and conduction bands of FNH 3 PbI 3 . An important property called carrier mass is also examined to show whether the effective mass of the electrons is competitive with that of the holes for the material, an attribute that might be useful to infer the ambipolar nature of the charge transport . The standard relationship,

m^{*} = ℏ^{2} {[\frac{\partial^{2} ɛ (k)}{\partial^{2} k}]}^{- 1}

, often invoked in solid state semiconductor physics was used to evaluate the effective masses of the charge carriers, where m* is the effective mass of the charge carrier (hole/electron), k is the wavenumber, and

ɛ (k)

is the valence/conduction band energy in k ‐space given by:

ɛ (k) = ɛ_{0} \pm \frac{ℏ^{2} k^{2}}{2 m *}

.…”

Section: Introductionmentioning

confidence: 99%

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Halogen in materials design: Fluoroammonium lead triiodide (FNH₃PbI₃) perovskite as a newly discovered dynamical bandgap semiconductor in 3D

Varadwaj

Yamashita

2018

Int J of Quantum Chemistry

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Methylammonium lead triiodide (CH3NH3PbI3) has been recognized as one of the record‐breaking materials for photovoltaics since it can potentially convert light energy into electricity @ 23%. However, it has been suffering from serious stability and environmental issues for which it is not yet put on market. To this end, experimental and theoretical studies are underway to discover versatile halide‐based perovskite compounds. In this article, we report the polymorphic geometries, stabilities, band structures, density of states spectra, and carrier effective asses of a newly identified perovskite semiconductor called fluoroammonium lead triiodide (FNH3PbI3), obtained using compositional engineering combined with periodic density functional theory electronic structure calculations. We show that this compound is stable both in the orthorhombic and pseudocubic phases. We also show that the bandgap for this material oscillates between 1.62 eV (direct) and 1.79 (indirect) for the two polymorphs examined in the pseudocubic phase, with the former and latter values corresponding to the [111] and [110] orientations of the inorganic cation FNH3+ inside the perovskite cage, respectively. Contrariwise, it is direct at Γ‐point for the polymorph examined in the orthorhombic phase. The spin orbit coupling is displayed to have profound effect on the nature and magnitude of the bandgap for this material. This, together with the very small effective masses calculated for the charge carriers comparable with those of CH3NH3PbI3, allows us to propose that FNH3PbI3 could be a possible candidate for photovoltaics, as well as for other optoelectronic applications.

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_{3}^{+}

) and the lead triiodide anion (PbI

_{3}^{-}

), showing the oxidation state of the B‐ and M‐site cations balances those of the three metal coordinated halide anions Y.…”

Section: Computational Details Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

m^{*} = ℏ^{2} {[\frac{\partial^{2} ɛ (k)}{\partial^{2} k}]}^{- 1}

ɛ (k)

is the valence/conduction band energy in k ‐space given by:

ɛ (k) = ɛ_{0} \pm \frac{ℏ^{2} k^{2}}{2 m *}

.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Halogen in materials design: Fluoroammonium lead triiodide (FNH₃PbI₃) perovskite as a newly discovered dynamical bandgap semiconductor in 3D

Varadwaj

Yamashita

2018

Int J of Quantum Chemistry

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“…[186] The employment of hexafluorophosphate and tetrafluoroborate generated mixed anion PVSK. Results indicated that BF 4 − has a more profound influence on the electronic structure compared to PF 6 − .…”

Section: F − or Pseudohalide/i Mixed Pvskmentioning

confidence: 99%

The Emergence of the Mixed Perovskites and Their Applications as Solar Cells

Xiao

Liü

Zhang

et al. 2017

Advanced Energy Materials

126

105

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The halide perovskite (PVSK) materials (with ABX3 formulation) have emerged as “dream materials” for photovoltaic (PV) applications due to their remarkable physical properties such as high optical absorption coefficient, carrier mobility, long carrier diffusion lengths, etc. These properties have enabled the PV devices to reach higher than 20% power conversion efficiencies (PCE) in record time. The further pursuit of higher PCE and improved stability brings forth increasing interests in so‐called “mixed composition” PVSK materials, consisting of partial substitution of the A, B, and/or X‐sites with alternative elements/molecules of similar size. Herein, we highlight the recent advances in developing mixed PVSK for PVs and their relevant optoelectronic properties. We mainly focus on mixed PVSK materials in the form of polycrystalline thin films, but also discuss nanostructured and two‐dimensional (2D) PVSK materials due to the increasing interest of broad readership. Efforts are exerted to elucidate the design principles of mixed PVSK and fabrication techniques for high performance optoelectronic devices, which help deepen our fundamental understanding of mixed PVSK systems. We hope this review will shed light onto the design and synthesis of mixed PVSK materials to further the progress of PVSK photovoltaics towards higher efficiencies and longer lifetimes.

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“…69,70 Also, another theoretical analysis by Hendon et al 71 proposed that the substitution of polyanions BF − 4 and PF − 6 in CsPbCl 3 instead of Cl increases the lattice parameter with more localized density of the states leading to potential interesting applications with the extension of this approach. However, further experimental support is needed to confirm these findings in cesium halide perovskites.…”

Section: Structural Optical and Morphological Properties Of Cs-lhqdsmentioning

confidence: 99%

Cesium lead halide ( CsPbX ₃, X = Cl , Br, I) perovskite quantum dots-synthesis, properties, and applications: a review of their present status

2016

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, "Cesium lead halide (CsPbX 3 , X ¼ Cl, Br, I) perovskite quantum dots-synthesis, properties, and applications: a review of their present status," J. Photon. Energy 6(4), 042001 (2016), doi: 10.1117/1.JPE.6.042001. Abstract. Metal halide-based perovskite quantum dots (QDs) have emerged as promising materials for optoelectronics and future energy applications. Among them, cesium lead halide-based perovskite quantum dots (Cs-LHQDs) have been found to be potential luminescent candidates and alternatives for the II-VI and I − III − VI 2 groups semiconductor nanoparticles. These perovskites provide an excellent quantum yield (90%) larger than any other semiconductor QDs. At present, synthesis of Cs-LHQDs has been successfully achieved through a traditional colloidal-based hot-injection method and a room temperature precipitation method. Some of the interesting results in their structural, optical, and morphological properties are being analyzed to understand their energy-transfer mechanism in the colloidal state. Morphology of nanoplates, nanowires, nanocube, and nanosheets in these materials confirms their physical parametersdependent self-assembly nature in a colloidal medium. Their potential use for light emitting diodes, photodetectors, and lasers is also highly motivated. This review provides a collective view of recent developments made in the synthesis of Cs-LHQDs and their properties. © The Authors. Published by SPIE under a Creative Commons Attribution 3.0 Unported License. Distribution or reproduction of this work in whole or in part requires full attribution of the original publication, including its DOI.

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Assessment of polyanion (BF₄⁻ and PF₆⁻) substitutions in hybrid halide perovskites

Cited by 111 publications

References 30 publications

Halogen in materials design: Fluoroammonium lead triiodide (FNH₃PbI₃) perovskite as a newly discovered dynamical bandgap semiconductor in 3D

Halogen in materials design: Fluoroammonium lead triiodide (FNH₃PbI₃) perovskite as a newly discovered dynamical bandgap semiconductor in 3D

The Emergence of the Mixed Perovskites and Their Applications as Solar Cells

Cesium lead halide ( CsPbX ₃, X = Cl , Br, I) perovskite quantum dots-synthesis, properties, and applications: a review of their present status

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Assessment of polyanion (BF4− and PF6−) substitutions in hybrid halide perovskites

Cited by 111 publications

References 30 publications

Halogen in materials design: Fluoroammonium lead triiodide (FNH3PbI3) perovskite as a newly discovered dynamical bandgap semiconductor in 3D

Halogen in materials design: Fluoroammonium lead triiodide (FNH3PbI3) perovskite as a newly discovered dynamical bandgap semiconductor in 3D

The Emergence of the Mixed Perovskites and Their Applications as Solar Cells

Cesium lead halide ( CsPbX 3, X = Cl , Br, I) perovskite quantum dots-synthesis, properties, and applications: a review of their present status

Contact Info

Product

Resources

About

Assessment of polyanion (BF₄⁻ and PF₆⁻) substitutions in hybrid halide perovskites

Halogen in materials design: Fluoroammonium lead triiodide (FNH₃PbI₃) perovskite as a newly discovered dynamical bandgap semiconductor in 3D

Halogen in materials design: Fluoroammonium lead triiodide (FNH₃PbI₃) perovskite as a newly discovered dynamical bandgap semiconductor in 3D

Cesium lead halide ( CsPbX ₃, X = Cl , Br, I) perovskite quantum dots-synthesis, properties, and applications: a review of their present status