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Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 perovskites for solar cell applications.

ABSTRACT: Hybrid AMX3 perovskites (A = Cs, CH3NH3; M = Sn, Pb; X = halide) have revolutionized the scenario of emerging photovoltaic technologies, with very recent results demonstrating 15% efficient solar cells. The CH3NH3PbI3/MAPb(I(1-x)Cl(x))3 perovskites have dominated the field, while the similar CH3NH3SnI3 has not been exploited for photovoltaic applications. Replacement of Pb by Sn would facilitate the large uptake of perovskite-based photovoltaics. Despite the extremely fast progress, the materials electronic properties which are key to the photovoltaic performance are relatively little understood. Density Functional Theory electronic structure methods have so far delivered an unbalanced description of Pb- and Sn-based perovskites. Here we develop an effective GW method incorporating spin-orbit coupling which allows us to accurately model the electronic, optical and transport properties of CH3NH3SnI3 and CH3NH3PbI3, opening the way to new materials design. The different CH3NH3SnI3 and CH3NH3PbI3 electronic properties are discussed in light of their exploitation for solar cells, and found to be dominantly due to relativistic effects. These effects stabilize the CH3NH3PbI3 material towards oxidation, by inducing a deeper valence band edge. Relativistic effects, however, also increase the material band-gap compared to CH3NH3SnI3, due to the valence band energy downshift (~0.7?eV) being only partly compensated by the conduction band downshift (~0.2?eV).

SUBMITTER: Umari P

PROVIDER: S-EPMC5394751 | biostudies-literature | 2014 Mar

REPOSITORIES: biostudies-literature

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Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 perovskites for solar cell applications.

Umari Paolo P Mosconi Edoardo E De Angelis Filippo F

Scientific reports 20140326

Hybrid AMX3 perovskites (A = Cs, CH3NH3; M = Sn, Pb; X = halide) have revolutionized the scenario of emerging photovoltaic technologies, with very recent results demonstrating 15% efficient solar cells. The CH3NH3PbI3/MAPb(I(1-x)Cl(x))3 perovskites have dominated the field, while the similar CH3NH3SnI3 has not been exploited for photovoltaic applications. Replacement of Pb by Sn would facilitate the large uptake of perovskite-based photovoltaics. Despite the extremely fast progress, the material ...[more]

PMID: 24667758

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Project description:We report an all-electron, atomic orbital (AO)-based, two-component (2C) implementation of the GW approximation (GWA) for closed-shell molecules. Our algorithm is based on the space-time formulation of the GWA and uses analytical continuation (AC) of the self-energy, and pair-atomic density fitting (PADF) to switch between AO and auxiliary basis. By calculating the dynamical contribution to the GW self-energy at a quasi-one-component level, our 2C-GW algorithm is only about a factor of 2-3 slower than in the scalar relativistic case. Additionally, we present a 2C implementation of the simplest vertex correction to the self-energy, the statically screened G3W2 correction. Comparison of first ionization potentials (IPs) of a set of 67 molecules with heavy elements (a subset of the SOC81 set) calculated with our implementation against results from the WEST code reveals mean absolute deviations (MAD) of around 70 meV for G0W0@PBE and G0W0@PBE0. We check the accuracy of our AC treatment by comparison to full-frequency GW calculations, which shows that in the absence of multisolution cases, the errors due to AC are only minor. This implies that the main sources of the observed deviations between both implementations are the different single-particle bases and the pseudopotential approximation in the WEST code. Finally, we assess the performance of some (partially self-consistent) variants of the GWA for the calculation of first IPs by comparison to vertical experimental reference values. G0W0@PBE0 (25% exact exchange) and G0W0@BHLYP (50% exact exchange) perform best with mean absolute deviations (MAD) of about 200 meV. Explicit treatment of spin-orbit effects at the 2C level is crucial for systematic agreement with experiment. On the other hand, eigenvalue-only self-consistent GW (evGW) and quasi-particle self-consistent GW (qsGW) significantly overestimate the IPs. Perturbative G3W2 corrections increase the IPs and therefore improve the agreement with experiment in cases where G0W0 alone underestimates the IPs. With a MAD of only 140 meV, 2C-G0W0@PBE0 + G3W2 is in best agreement with the experimental reference values.

Dataset Information

Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 perovskites for solar cell applications.

Publications

Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 perovskites for solar cell applications.

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