From Zero- to One-Dimensional, Opportunities and Caveats of Hybrid Iodobismuthates for Optoelectronic Applications

Abstract

The association of the electron acceptor 4,4'-amino-bipyridinium (AmV 2+ ) dication and BiI3 in an acidic solution affords three organic−inorganic hybrid materials, (AmV)3(BiI6)2 ( 1), (AmV)2(Bi4I16) (2), and (AmV)BiI5 (3), whose structures are based on isolated BiI6 3− and Bi4I16 4− anion clusters in 1 and 2, respectively, and on a one-dimensional (1D) chain of trans-connected corner-sharing octahedra in 3. In contrast with known methylviologen-based hybrids, these compounds are more soluble in polar solvents, allowing thin film formation by spin-coating. (AmV)BiI5 exhibits a broad absorption band in the visible region leading to an optical bandgap of 1.54 eV and shows a PV effect as demonstrated by a significant open-circuit voltage close to 500 mV. The electronic structure of the three compounds has been investigated using first-principles calculations based on density functional theory (DFT). Unexpectedly, despite the trans-connected cornershared octahedra, for (AmV)BiI5, the valence state shows no coupling along the wire direction, leading to a high effective mass for holes, while in contrast, the strong coupling between Bi 6px orbitals in the same direction at the conduction band minimum suggests excellent electron transport properties. This contributes to the low current output leading to the low efficiency of perovskite solar cells based on (AmV)BiI5. Further insight is provided for trans-and cis-MI5 1D model structures (M = Bi or Pb) based on DFT investigations.

A semiconductive copper iodobismuthate hybrid: structure, optical properties and photocurrent response

“…Representative examples include [La(DMSO) 8 ]Bi 2 I 9 (2.21 eV), [Bi(DMSO) 8 ]Bi 2 I 9 (2.17 eV), [AmV]BiI 5 (1.54 eV), [PiC 2 ] 2 Bi 2 I 10 (2.08 eV), PiC 5 BiI 5 (1.73 eV), [PiC 5 ] 2 Bi 4 I 16 (2.10 eV), [HpipeH 2 ] 2 Bi 2 I 10 ·2H 2 O (1.80 eV), LiBiI 4 ·5H 2 O (1.70 eV), KBiI 4 ·H 2 O (1.76 eV), [CH 3 NH 3 ] 3 Bi 2 Br 9 (2.50 eV), [H 2 MPP] 2 AgBiI 8 (2.26 eV), [APP] 4 AgBiI 8 ·H 2 O (2.12 eV), [AMP] 4 AgBiI 8 ·H 2 O (2.07 eV), [Ni(bipy) 3 ]AgBiBr 6 (2.06 eV), [NH 4 ] 3 Bi 2 I 9 (2.04 eV), [C 8 H 20 N] 2 Ag 2 Bi 4 I 16 (1.93 eV) and [Et 4 N] 2 Cu 2 Bi 2 I 10 (1.89 eV). 16,20,23–25,30,39,46–50…”

“…The documented [Bi x I y ] ( y −3 x )− anionic moieties ranged from some zero-dimensional (0D) clusters, one-dimensional (1D) chains and few two-dimensional (2D) layers, as exemplified by 0D-[Bi 2 I 8 ] 2− , 0D-[Bi 2 I 10 ] 4− , 0D-[Bi 3 I 12 ] 3− , 0D-[Bi 4 I 16 ] 4− , 0D-[Bi 5 I 18 ] 3− , 0D-[Bi 8 I 30 ] 6− , 1D-[BiI 4 ] − , 1D-[BiI 5 ] 2− , 1D-[Bi 4 I 14 ] 2− , 1D-[Bi 6 I 22 ] 4− , 2D-[Bi 2/3 I 4 ] 2− and 2D-[Bi 2 I 7 ] − . 8–17 In order to further acquire more complicated motifs, an effective strategy is to design and fabricate heterometal iodobismuthates by embedding the second types of metal ions, typically monovalent Cu + and Ag + . This huge progress had been demonstrated by [C 12 H 18 N 2 S 2 ] 2 AgBiI 8 , [C 3 H 9 NI] 4 AgBiI 8 , [APP] 4 AgBiI 8 ·H 2 O, [AMP] 4 Ag 2 Bi 2 I 16 ·H 2 O, [C 6 H 16 N 2 ] 2 CuBiI 8 ·0.5H 2 O, [C 6 H 16 N 2 ] 2 AgBiI 8 ·H 2 O, [C 8 H 18 N] 4 CuBiI 8 , [C 6 H 16 N 2 ] 2 CuBiI 8 , [C 7 H 16 N] 4 CuBiI 8 , [C 6 H 16 N 2 ] 2 CuBiI 8 ·H 2 O, [C 6 H 14 N] 4 CuBiI 8 ·H 2 O, [C 5 H 13 N 2 ] 4 AgBiI 8 ·H 2 O and [H 2 MPP] 2 AgBiI 8 .…”

Water‐Resistant Lead‐Free Perovskitoid Single Crystal for Efficient X‐Ray Detection

“…Bi 3+ can be linked to halides, forming various connective modes, such as [BiI ] n . [12][13][14][15][16][17] 1D bismuth-based perovskitoid materials have shown great potential for X-ray detectors. (H 2 MDAP)BiI 5 (H 2 MDAP = N-methyl-1,3-diaminopropanium) exhibited a sensitivity of 1 µC Gy air −1 cm −2 , as reported in 2019.…”

A 3D Lead Iodide Hybrid Based on a 2D Perovskite Subnetwork

“…Even though not quantitative, it is worth noticing that the here-computed bandgap (1.60 eV) is greater than the ones computed at the same level of theory not only for 3D halide perovskites, but also for typical 2D ones (1.1-1.3 eV). Still, it remains smaller than bandgaps of related 1D-like compounds (2.0 eV) [33]. This is indicative that the electronic dimensionality of the 3D (HPA)6(MA)Pb5I17 structure is intermediate between 1D and 2D.…”