Atomic structure and electronic properties of lead and tin based hybrid halide perovskite surface for photovoltaic applications

Khanal, Rabi; Ayers, Nicholas; Banerjee, Soumik; Choudhury, Samrat

doi:10.1063/1.5111569

Cited by 10 publications

(17 citation statements)

References 56 publications

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“…In P4/ mmm, the smaller octahedral volume prevents the free rotation of the MA + ions that can occur with larger octahedra in the I4/ mcm space group, and thus, MAPbI 3 with thelonger Pb−I bond length forms the I4/mcm tetragonal phase while MAPbCl 3 with the shorter Pb−Cl bond length forms the P4/mmm tetragonal phase. 33 When MAPbBr 3 crystals are subjected to pressure, the volume of the unit cell and the Pb− Br bond length decrease. 34 This results in the disappearance of the P4/mmm (γ) phase at pressures above 43.2 MPa.…”

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“…Khanal and co-workers attributed the formation of either the P 4/ mmm or I 4/ mcm tetragonal phase to the B–X bond. In P 4/ mmm , the smaller octahedral volume prevents the free rotation of the MA + ions that can occur with larger octahedra in the I 4/ mcm space group, and thus, MAPbI 3 with thelonger Pb–I bond length forms the I 4/ mcm tetragonal phase while MAPbCl 3 with the shorter Pb–Cl bond length forms the P 4/ mmm tetragonal phase . When MAPbBr 3 crystals are subjected to pressure, the volume of the unit cell and the Pb–Br bond length decrease .…”

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confidence: 99%

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Bismuth Doping Alters Structural Phase Transitions in Methylammonium Lead Tribromide Single Crystals

Jedlicka

Wang

Mutch

et al. 2021

J. Phys. Chem. Lett.

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We study the effects of bismuth doping on the crystal structure and phase transitions of single crystals of the perovskite semiconductor methylammonium lead tribromide, MAPbBr 3 . By measuring the temperature-dependent specific heat capacity (C p ) we find that, as the Bi doping level increases, the temperatures for the bismuth structural phase transitions shift, and the phase boundary assigned to the transition from the cubic to tetragonal phase decreases in temperature. Furthermore, after doping we only observe one phase transition between 135 and 155 K, in contrast to two transitions observed in the undoped single crystal. These results appear strikingly similar to the previously reported effects of mechanical pressure on the perovskite structure. Using X-ray diffraction, we show that, as more Bi is incorporated into the crystal, the lattice constant decreases, as predicted by density functional theory (DFT). Based on the lattice contraction and DFT, we propose that bismuth substitutional doping on the lead site is dominant, resulting in Bi Pb + centers which induce compressive chemical strain that alters the crystalline phase transitions. TOC GRAPHICSKEYWORDS Bismuth doping, MAPbBr 3 perovskite, specific heat capacity, lattice contraction, X-ray diffraction, Halide perovskites have emerged as promising semiconductor materials for applications including solar cells, light-emitting diodes, photodetectors, and lasers. [1][2][3][4] They exhibit unique and tunable optoelectronic properties via facile tailoring of the chemical composition of the structure.In the archetypal perovskite ABX3 crystal structure, A represents a monovalent cation species (A = Cs + , CH3NH3 + (MA + ), or (NH2)2CH3 + (FA + )), B represents a divalent cation (B = Pb +2 , Sn +2 ), and X represents a halide (X = Cl -, Br -, I -). Diverse electronic and structural motifs are thereby accessible by modification of the chemical composition and the dimensionality of the material. 5

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confidence: 99%

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confidence: 99%

Bismuth Doping Alters Structural Phase Transitions in Methylammonium Lead Tribromide Single Crystals

Jedlicka

Wang

Mutch

et al. 2021

J. Phys. Chem. Lett.

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“…This approach has proven to provide reliable results for structure and thermodynamic properties of perovskites. 31,34,41,47,58,59 The errors associated with GGA and resulting from not including SOC may affect the location of band edges and band gaps. 60 However, these errors should not change the specific trend in the energy and the conclusion made in this study.…”

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“…Significant effort by the perovskite community has brought critical understanding of bulk perovskite structures and their properties. − Some of the recent investigations have contributed to the basic knowledge of perovskite surfaces − and their interfaces ,,, with ETLs like graphene and TiO 2 . However, most of the theoretical studies performed at the interface have mainly addressed the relative location of the band edges.…”

Section: Introductionmentioning

confidence: 99%

“…In the perovskite/PCBM interface, the structural morphology of PCBM and its interaction with the atomic species on the perovskite surface , have been shown to be critical. On the perovskite surface, different groups of atoms, PbI 2 or CH 3 NH 3 I, are available for bonding depending on the terminating layer of the perovskite surface . PCBM has various anchoring sites, such as O, H, or C, available with a 360° rotational degree of freedom .…”

Section: Introductionmentioning

confidence: 99%

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Study of Structure and Electronic Properties of Heterointerfaces for Photovoltaic Applications

et al. 2020

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The linkage between the atomic structure and the electronic property is complex for heterointerfaces involving multicomponent organic−inorganic systems because of large configurations and chemical possibilities. Understanding the structure−property relationship at the interface becomes further complicated with an asymmetric structure of organic molecules compared to the interface between planer solids. Here, we report on ab inito molecular dynamics (AIMD) simulations of the perovskite/PCBM ([6,6]-phenyl-C 61 -butyric acid methyl ester) interface, where PCBM is an asymmetric molecule. Our AIMD calculations help us to navigate the vast number of possible atomic configurations of the interface. We have found that PCBM prefers to bind with the perovskite surface via an ester moiety over its fullerene moiety. The bonding at the interface and its stability are sensitive to the chemical composition at the perovskite surface, the PbI 2 -terminated surface making a stronger binding ≈1 eV with PCBM, compared to the MAI-terminated surface. Later, we systematically studied the role of atomic defects on the perovskite surface and interface and linked it to interface stability and electronic properties.

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Energetics of Solvent-Based Deposition of Fullerene Derivative on the Inorganic–Organic Hybrid Lead Halide Perovskite Surface

2019

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The elementary processes that govern particle deposition on substrates during solution processing of thin films are not well understood due to the complex interactions between solute−solvent, solute−substrate, and solvent−substrate. This study presents a fundamental step-by-step systematic analysis of the deposition of a rather complex molecule, the [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), with seemingly infinite orientational configurations, on the (110) surface of methylammonium lead iodide (CH 3 NH 3 PbI 3 ) perovskite in a solvated environment. We employed the adaptive biasing force (ABF) method in conjunction with classical molecular dynamics (MD) simulations to determine the potential of mean force (PMF) and corresponding configurations of deposited PCBM in the presence of chlorobenzene (CB) and vacuum. Our calculations underscore the impact of solvent on the energetics of deposition and the resulting configurations of deposited PCBM. In the presence of solvent, the most energetically favorable configuration occurs when the carbonyl oxygen (CO) of PCBM is attached with a Pb atom of perovskite surface with the fullerene (C60) pointing away from the surface. The corresponding binding energy between PCBM and perovskite is 12.9 kcal/mol at 325 K and increases with increasing temperature. In contrast, in a vacuum, the most energetically favorable configuration occurs when both C60 moiety and the CO atom of PCBM are associated with the perovskite surface resulting in a stronger binding energy of 23.6 kcal/mol due to the absence of solvent screening. We investigated the different energetic contributions that govern the overall deposition process. In solvated systems, the deposited configurations are stabilized primarily by entropic contribution due to loss of solvent structure around both perovskite surface and PCBM during deposition.

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Atomic structure and electronic properties of lead and tin based hybrid halide perovskite surface for photovoltaic applications

Cited by 10 publications

References 56 publications

Bismuth Doping Alters Structural Phase Transitions in Methylammonium Lead Tribromide Single Crystals

Bismuth Doping Alters Structural Phase Transitions in Methylammonium Lead Tribromide Single Crystals

Study of Structure and Electronic Properties of Heterointerfaces for Photovoltaic Applications

Energetics of Solvent-Based Deposition of Fullerene Derivative on the Inorganic–Organic Hybrid Lead Halide Perovskite Surface

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