A Zero-Dimensional Mixed-Anion Hybrid Halogenobismuthate(III) Semiconductor: Structural, Optical, and Photovoltaic Properties

Hoefler, Sebastian F.; Rath, Thomas; Fischer, Roland; Latal, Christine; Hippler, Dorothee; Κολιογιώργος, Αθανάσιος; Galanakis, I.; Bruno, Annalisa; Fian, Alexander; Dimopoulos, Théodoros; Trimmel, Gregor

doi:10.1021/acs.inorgchem.8b01161

Cited by 26 publications

(19 citation statements)

References 71 publications

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“…XPS Bi 4f7/2 core-level shows that metallic bismuth (peaks at 157.0 eV) is present (Figure 3d). The reduction of metallic bismuth has been reported to be a consequence of X-ray irradiation [29,30]. The most likely mechanism for this is analogous to reported Pb 0 evolution from MAPbI3 under the XPS environment, that is X-ray induced photolysis of any metal halide salts present in the film (PbI2 in the reported case, or BiI3 in our case).…”

Section: Resultssupporting

confidence: 77%

Two-Step Synthesis of Bismuth-Based Hybrid Halide Perovskite Thin-Films

et al. 2021

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Lead halide perovskites have been revolutionary in the last decade in many optoelectronic sectors. Their bismuth-based counterparts have been considered a good alternative thanks to their composition of earth-abundant elements, good chemical stability, and low toxicity. Moreover, their electronic structure is in a quasi-zero-dimensional (0D) configuration, and they have recently been explored for use beyond optoelectronics. A significant limitation in applying thin-film technology is represented by the difficulty of synthesizing compact layers with easily scalable methods. Here, the engineering of a two-step synthesis in an air of methylammonium bismuth iodide compact thin films is reported. The critical steps of the process have been highlighted so that the procedure can be adapted to different substrates and application areas.

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Section: Resultssupporting

confidence: 77%

Two-Step Synthesis of Bismuth-Based Hybrid Halide Perovskite Thin-Films

et al. 2021

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“…The stronger the non-covalent (hydrogen) bond is, the higher the mobility should be. In (HpipeH 2 ) 2 Bi 2 I 10 ·2H 2 O, very strong hydrogen bonds provoke reduction of the band gap from 2.0–2.2 eV, typical for compounds built of 0D Bi/I anions [ 53 , 54 ], to as low as 1.8 eV. The latter ensures efficient absorption of the solar light, which is favorable for the creation of light-harvesting materials for new solar cells.…”

Section: Resultsmentioning

confidence: 99%

Assembling Polyiodides and Iodobismuthates Using a Template Effect of a Cyclic Diammonium Cation and Formation of a Low-Gap Hybrid Iodobismuthate with High Thermal Stability

et al. 2020

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Exploiting a template effect of 1,4-diazacycloheptane (also known as homopiperazine, Hpipe), four new hybrid iodides, (HpipeH2)2Bi2I10·2H2O, (HpipeH2)I(I3), (HpipeH2)3I6·H2O, and (HpipeH2)3(H3O)I7, were prepared and their crystal structures were solved using single crystal X-ray diffraction data. All four solid-state crystal structures feature the HpipeH22+ cation alternating with Bi2I104–, I3–, or I– anions and solvent water or H3O+ cation. HpipeH22+ assembles anionic and neutral building blocks into polymer structures by forming four strong (N)H···I and (N)H···O hydrogen bonds per cation, with the H···I distances ranging from 2.44 to 2.93 Å and H···O distances of 1.88–1.89 Å. These hydrogen bonds strongly affect the properties of compounds; in particular, in the case of (HpipeH2)2Bi2I10·2H2O, they ensure narrowing of the band gap down to 1.8 eV and provide high thermal stability up to 240 °C, remarkable for a hydrated molecular solid.

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“…2b,d). The presence of a non-uniform, inhomogeneous surface coverage would lead to the presence of pinholes, which are the cause of short-circuits and defect sites limiting the photovoltaic performance 34 . Therefore, the presence of a complete coverage would reduce the probability of shunting by an improved separation between the electron and the hole transport layer 35 .…”

Section: Resultsmentioning

confidence: 99%

Co-evaporation as an optimal technique towards compact methylammonium bismuth iodide layers

Momblona

Kanda

Mensi

et al. 2020

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the most studied perovskite-based solar cells reported up to date contain the toxic lead in its composition. photovoltaic research and development towards non-toxic, lead-free perovskite solar cells are critical to finding alternatives to reduce human health concerns associated with them. Bismuth-based perovskite variants, especially in the form of methylammonium bismuth iodide (MBi), is a good candidate for the non-toxic light absorber. However, the reported perovskite variant MBI thin films prepared by the solution process so far suffers from poor morphology and surface coverage. In this work, we investigate for the first time the optoelectronic, crystallographic and morphological properties of MBI thin films prepared via thermal co-evaporation of MAI and BiI 3. We find by modifying the precursor ratio that the layer with pure MBI composition lead to uniform, compact and homogeneous layers, broadening the options of deposition techniques for lead-free based perovskite solar cells. Organic-inorganic metal halide perovskites have emerged as promising candidates for the next generation of photovoltaics (PV) given their unprecedented rise in power conversion efficiency (PCE) achieving 25.2% 1 Beyond their superior optoelectronic properties, low cost and high versatility 2-5 , their instability and lead toxicity are at present major concerns, which greatly limit their incorporation into marketable products. Significant efforts are therefore oriented into the search of stable and non-toxic perovskite materials, yet real alternatives based on lead-free components are still missing. Among the various lead-free perovskites variants proposed in the literature, Sn-based materials have demonstrated promising efficiencies leading to a PCE value of 9.6% 6. However, Sn-based perovskites suffer from inevitable oxidation of Sn 2+ to Sn 4+ , providing a source of inhomogeneity and pinholes that are further enhanced by their fast crystallization 7. As a result, the most straightforward candidates possessing similar electronic properties to Pb 2+ , which are suitable for light-harvesting, are Ge 2+ , Sb 3+ or Bi 3+ cations. While Ge-based perovskites suffer from material instability due to hydrolytic decomposition in humid environment 8-10 , Sb-based perovskites show limited photovoltaic performances in spite of their good chemical stability 8. Bismuth is a heavy metal with a stable oxidation state, little toxicity, and a similar polarizable electron density than Pb 11. Thanks to the formation of BiX 6 3− octahedron, it can also form perovskites with diverse dimensionalities and phases, from which methylammonium bismuth iodide ((CH 3 NH 3) 3 Bi 2 I 9 , MBI) is at the forefront 9. MBI is a wide-bandgap semiconductor with a zero-dimensional structure having reduced toxicity, high stability and promising photovoltaic efficiency 12. Despite such remarkable potential, its use is limited by the low quality of the films resulted from conventional spin-coating deposition, which produces non-compact MBI layers with poor coverage and crysta...

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A Zero-Dimensional Mixed-Anion Hybrid Halogenobismuthate(III) Semiconductor: Structural, Optical, and Photovoltaic Properties

Cited by 26 publications

References 71 publications

Two-Step Synthesis of Bismuth-Based Hybrid Halide Perovskite Thin-Films

Two-Step Synthesis of Bismuth-Based Hybrid Halide Perovskite Thin-Films

Assembling Polyiodides and Iodobismuthates Using a Template Effect of a Cyclic Diammonium Cation and Formation of a Low-Gap Hybrid Iodobismuthate with High Thermal Stability

Co-evaporation as an optimal technique towards compact methylammonium bismuth iodide layers

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