Showing papers by "Zewen Xiao published in 2017"

Searching for promising new perovskite-based photovoltaic absorbers: the importance of electronic dimensionality

Abstract: Searching for promising nontoxic and air-stable perovskite absorbers for solar cell applications has drawn extensive attention. Here, we show that a promising perovskite absorber should exhibit a high electronic dimensionality. Semiconductors that exhibit a high structural dimensionality, but a low electronic dimensionality have less promise as an absorber, because of barriers to isotropic current flow, enhanced electron/hole effective masses and fundamentally deeper defect states (more effective at causing recombination). Our concept accounts for the device performance of the perovskite-based solar cells reported in literature so far.

Parity-Forbidden Transitions and Their Impact on the Optical Absorption Properties of Lead-Free Metal Halide Perovskites and Double Perovskites.

Abstract: Using density functional theory calculations, we analyze the optical absorption properties of lead (Pb)-free metal halide perovskites (AB2+X3) and double perovskites (A2B+B3+X6) (A = Cs or monovalent organic ion, B2+ = non-Pb divalent metal, B+ = monovalent metal, B3+ = trivalent metal, X = halogen). We show that if B2+ is not Sn or Ge, Pb-free metal halide perovskites exhibit poor optical absorptions because of their indirect band gap nature. Among the nine possible types of Pb-free metal halide double perovskites, six have direct band gaps. Of these six types, four show inversion symmetry-induced parity-forbidden or weak transitions between band edges, making them not ideal for thin-film solar cell applications. Only one type of Pb-free double perovskite shows optical absorption and electronic properties suitable for solar cell applications, namely, those with B+ = In, Tl and B3+ = Sb, Bi. Our results provide important insights for designing new metal halide perovskites and double perovskites for optoel...

Progress in Theoretical Study of Metal Halide Perovskite Solar Cell Materials

Abstract: Lead halide perovskites have recently emerged as promising absorbers for fabricating low-cost and high-efficiency thin-film solar cells. The record power conversion efficiency of lead halide perovskite-based solar cells has rapidly increased from 3.8% in 2009 to 22.1% in early 2016. Such rapid improvement is attributed to the superior and unique photovoltaic properties of lead halide perovskites, such as the extremely high optical absorption coefficients and super-long photogenerated carrier lifetimes and diffusion lengths that are not seen in any other polycrystalline thin-film solar cell materials. In the past a few years, theoretical approaches have been extensively applied to understand the fundamental mechanisms responsible for the superior photovoltaic properties of lead halide perovskites and have gained significant insights. This review article highlights the important theoretical results reported in literature for the understanding of the unique structural, electronic, optical, and defect properties of lead halide perovskite materials. For comparison, we also review the theoretical results reported in literature for some lead-free perovskites, double perovskites, and nonperovskites.

Intrinsic Instability of Cs2In(I)M(III)X6 (M = Bi, Sb; X = Halogen) Double Perovskites: A Combined Density Functional Theory and Experimental Study.

Abstract: Recently, there has been substantial interest in developing double-B-cation halide perovskites, which hold the potential to overcome the toxicity and instability issues inherent within emerging lead halide-based solar absorber materials. Among all double perovskites investigated, In(I)-based Cs2InBiCl6 and Cs2InSbCl6 have been proposed as promising thin-film photovoltaic absorber candidates, with computational examination predicting suitable materials properties, including direct bandgap and small effective masses for both electrons and holes. In this study, we report the intrinsic instability of Cs2In(I)M(III)X6 (M = Bi, Sb; X = halogen) double perovskites by a combination of density functional theory and experimental study. Our results suggest that the In(I)-based double perovskites are unstable against oxidation into In(III)-based compounds. Further, the results show the need to consider reduction–oxidation (redox) chemistry when predicting stability of new prospective electronic materials, especially ...

Chemical Origin of the Stability Difference between Copper(I)- and Silver(I)-Based Halide Double Perovskites

Abstract: Recently, CuI - and AgI -based halide double perovskites have been proposed as promising candidates for overcoming the toxicity and instability issues inherent within the emerging Pb-based halide perovskite absorbers. However, up to date, only AgI -based halide double perovskites have been experimentally synthesized; there are no reports on successful synthesis of CuI -based analogues. Here we show that, owing to the much higher energy level for the Cu 3d10 orbitals than for the Ag 4d10 orbitals, CuI atoms energetically favor 4-fold coordination, forming [CuX4 ] tetrahedra (X=halogen), but not 6-fold coordination as required for [CuX6 ] octahedra. In contrast, AgI atoms can have both 6- and 4-fold coordinations. Our density functional theory calculations reveal that the synthesis of CuI halide double perovskites may instead lead to non-perovskites containing [CuX4 ] tetrahedra, as confirmed by our material synthesis efforts.

Distant-Atom Mutation for Better Earth-Abundant Light Absorbers: A Case Study of Cu2BaSnSe4

Abstract: Thin-film Cu(In,Ga)Se2 and CdTe solar cells have demonstrated high power conversion efficiencies, but they cannot provide a sustainable clean energy pathway because of the scarcity of Te and In. Here, we propose a distant-atom concept to mutate In by a group II element (Ba) and a group IV element (Sn) that are at rather different locations on the periodic table. Because of the very different electronic properties between the cations, the resultant earth-abundant orthorhombic Cu2BaSnSe4 absorber does not have the detrimental cation–cation disorder issue seen in the earth-abundant kesterite Cu2ZnSnSe4 absorber. We anticipate that Cu2BaSnSe4 solar cells should not have large open-circuit voltage deficits as seen in CuZnSnSe4 solar cells. Density functional theory calculation of the electronic and defect properties of Cu2BaSnSe4 confirms these expectations.

Electride and superconductivity behaviors in Mn 5 Si 3 -type intermetallics

Abstract: Electrides are unique in the sense that they contain localized anionic electrons in the interstitial regions. Yet they exist with a diversity of chemical compositions, especially under extreme conditions, implying generalized underlying principles for their existence. What is rarely observed is the combination of electride state and superconductivity within the same material, but such behavior would open up a new category of superconductors. Here, we report a hexagonal Nb5Ir3 phase of Mn5Si3-type structure that falls into this category and extends the electride concept into intermetallics. The confined electrons in the one-dimensional cavities are reflected by the characteristic channel bands in the electronic structure. Filling these free spaces with foreign oxygen atoms serves to engineer the band topology and increase the superconducting transition temperature to 10.5 K in Nb5Ir3O. Specific heat analysis indicates the appearance of low-lying phonons and two-gap s-wave superconductivity. Strong electron–phonon coupling is revealed to be the pairing glue with an anomalously large ratio between the superconducting gap Δ 0 and T c, 2Δ 0/k B T c = 6.12. The general rule governing the formation of electrides concerns the structural stability against the cation filling/extraction in the channel site. Coexistence of electride behavior and superconductivity is observed in a hexagonal phase of a Nb5Ir3 intermetallic with tunable electronic properties by introducing foreign atoms. A team led by Yaoqing Zhang and Hideo Hosono from Japan Science and Technology Agency and Tokyo Institute of Technology report a new hexagonal phase in the phase diagram of Nb–Ir binary intermetallics with interesting interplay of superconductivity and electride state. The electride state is formed by electrons detaching from the atoms but localizing in a one-dimensional channel space. This electride becomes a superconductor below a transition temperature of about 9.4 K, which could be enhanced to 10.5 K upon filling interstitial cavities with foreign oxygens. The results suggest a general rule governing the formation of electrides and form the basis for novel stable functional electrides.

First-Principles Understanding of the Electronic Band Structure of Copper-Antimony Halide Perovskite: The Effect of Magnetic Ordering

Abstract: We report the understanding of the electronic band structure of $Cs_4CuSb_2Cl_{12}$ perovskite through first-principles density-functional theory calculations. We find that the most stable state has the antiferromagnetic configuration where each $[CuCl_6]$ octahedral chain along the [010] direction is antiferromagnetic. The reasonable band structure of the compound can be obtained only if both the correct magnetic order and the improved exchange interaction of the Cu $\it{d}$ electrons are taken into account.