Bismuth Iodide Hybrid Organic‐Inorganic Crystal Structures and Utilization in Formation of Textured BiI<sub>3</sub> Film

Nørby, Peter; Jørgensen, Mads Ry Vogel; Johnsen, Simon; Iversen, Bo B.

doi:10.1002/ejic.201501418

Cited by 15 publications

(25 citation statements)

References 25 publications

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“…As shown in the photograph ( Figure 5), bare BiI 3 displays a dark black color, whereas Cs 3 Bi 2 I 9 is red. This evident color change strongly supports the formation of a BiI 3 coordination complex, Cs 3 Bi 2 I 9 , when the precursors were dissolved in DMF [62,63].…”

Section: Optical Characterizationsupporting

confidence: 54%

Pb-Free Cs3Bi2I9 Perovskite as a Visible-Light-Active Photocatalyst for Organic Pollutant Degradation

et al. 2020

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In our work, we employed Cs3Bi2I9 as a visible-light-active photocatalyst, synthesized with a low-temperature solvothermal method. The morphological and structural properties of the as-prepared perovskite were investigated, and the results were compared to previous studies to confirm its nature and the quality of the synthesis procedure. Transient absorption spectroscopy was applied in order to investigate the generation and lifetime of photogenerated charge carriers, revealing their formation after visible light excitation. The potential photocatalytic activity of the as-prepared metal halide perovskite was applied for the removal of Rhodamine B in aqueous solution, demonstrating an excellent activity of 93% after 180 min under visible-light irradiation. The current research aims to provide insights into the design of a new visible-light-active photocatalyst, Cs3Bi2I9, selected for its high application value in the field of advanced materials for light harvesting.

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Section: Optical Characterizationsupporting

confidence: 54%

Pb-Free Cs3Bi2I9 Perovskite as a Visible-Light-Active Photocatalyst for Organic Pollutant Degradation

et al. 2020

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“…We explain the role of SVA temperature and water concentration by considering the BiI 3 –DMF complexation chemistry. Nørby et al 28 have determined via single-crystal X-ray diffraction (XRD) that the carbonyl oxygen in DMF complexes with the Bi 3+ center to give a solvent complex crystal with a unit cell of Bi(DMF) 8 –Bi 3 I 12 . Octahedral complexes such as BiI 3 typically undergo ligand exchange via a dissociative interchange mechanism ( I d ).…”

Section: Resultsmentioning

confidence: 99%

“…The unit cell volume of the BiI 3 –DMF solvent crystal is 6507.2 Å 3 , and it contains four Bi(DMF) 8 –Bi 3 I 12 moieties, that is, a volume of 406.7 Å 3 per BiI 3 . 28 Pure BiI 3 , in contrast, has a unit cell volume of 1016.7 Å 3 with six BiI 3 moieties per unit cell, 42 that is, a volume of 169 Å 3 per BiI 3 . This means that there is a volume increase and, concomitantly, a thickness increase of the orange phase of a factor of 2.4 compared with the BiI 3 film.…”

Section: Resultsmentioning

confidence: 99%

“…Similar texturing has been found in BiI 3 films that have formed from BiI 3 –DMSO complexes. 28 Because the 2D sheets of edge-shared BiI 6 octahedra are only weakly connected by van der Waals forces, it is expected that in-plane transport should exhibit larger mobility than perpendicular to the 2D sheets. Hence, the films that turned orange during SVA should show a better carrier transport parallel to the substrate and worse transport perpendicular to the substrate plane than the films that did not change color.…”

Section: Resultsmentioning

confidence: 99%

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Solution-Processed BiI₃ Films with 1.1 eV Quasi-Fermi Level Splitting: The Role of Water, Temperature, and Solvent during Processing

2018

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We present a mechanistic explanation of the BiI 3 film formation process and an analysis of the critical factors in preparing high-quality solution-processed BiI 3 films. We find that complexation with Lewis bases, relative humidity, and temperature are important factors during solvent vapor annealing (SVA) of films. During SVA, water vapor and higher temperatures limit the formation of the BiI 3 –dimethylformamide coordination complex. SVA with an optimized water content and temperature produces films with 300–500 nm grains. Films that formed solvent coordination compounds at lower temperatures showed preferential crystal orientation after solvent removal, and we elucidate its implications for carrier transport. Addition of dimethyl sulfoxide to highly concentrated tetrahydrofuran–BiI 3 inks prevents film cracking after spin-coating. We have measured a quasi-Fermi level splitting of 1.1 eV and a diffusion length of 70 nm from films processed with optimal temperature and humidity. The best device produced by optimized SVA has a power conversion efficiency of 0.5%, I sc of ∼4 mA/cm 2 , and V OC of ∼400 mV. The low photocurrent and voltage we attribute to the low diffusion length and the unfavorable band alignment between the absorber and the adjacent transport layers. The deep understanding of the relationship between morphology/crystal structure and optoelectronic properties gained from this work paves the way for future optimization of BiI 3 -based solar cells.

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“…Another important aspect is the chemical stability of the exfoliated surfaces or films at ambient conditions. This point has received less attention in the case of BiI 3 despite its known reactivity: As a Lewis acid, BiI 3 is prone toward adduct formation with Lewis bases, such as pyridine or even commonly used polar solvent molecules, and easily adds additional iodide ions forming iodido bismuthates like (CH 3 NH 3 ) 3 Bi 2 I 9 . BiI 3 can also be hydrolyzed to BiOI in aqueous solution, a process that is suppressed by the presence of an additional iodide ion source such as HI .…”

Section: Introductionmentioning

confidence: 99%

Chemical Surface Reactivity and Morphological Changes of Bismuth Triiodide (BiI₃) under Different Environmental Conditions

et al. 2020

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Layered metal halides like BiI 3 are of current interest in connection with both 2D materials and photovoltaics.Here, we present a facile new method for the preparation of millimeter-sized BiI 3 single crystals. We use these crystals to study the surface reactivity of their (001) cleavage planes toward various environmental conditions by measuring morphological changes using atomic force microscopy and analyzing the formed species by means of X-ray photoelectron spectroscopy and X-ray diffraction methods. We find that freshly cleaved samples show atomically flat surface regions extending over several micrometers and reveal steps corresponding to single BiI 3 layers. However, we also find that the surface deteriorates in air on a time scale of hours. By studying samples cleaved and stored under different conditions, we identify water as the agent initiating the changes in surface morphology, while under inert gas and dry oxygen, the surface stays intact. On the basis of the analysis of deteriorated long-term-stored samples we identify BiOI as the main product of hydrolysis. We also observe a second long-term decomposition route for samples stored under dynamic vacuum, where formation of BiI whiskers occurs. Overall, our findings emphasize the challenges associated with the surface reactivity of BiI 3 but also demonstrate that well-ordered BiI 3 surfaces can be obtained, which indicates that preparation of extended, atomically smooth BiI 3 monolayers by exfoliation from bulk crystals should be possible.

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Bismuth Iodide Hybrid Organic‐Inorganic Crystal Structures and Utilization in Formation of Textured BiI₃ Film

Abstract: Abstract:Two new and one redetermination of metastable bismuth iodide hybrid organic-inorganic structure incorporating the solvents 2,3,4,5-tetrahydrothiophene 1

Cited by 15 publications

References 25 publications

Pb-Free Cs3Bi2I9 Perovskite as a Visible-Light-Active Photocatalyst for Organic Pollutant Degradation

Pb-Free Cs3Bi2I9 Perovskite as a Visible-Light-Active Photocatalyst for Organic Pollutant Degradation

Solution-Processed BiI₃ Films with 1.1 eV Quasi-Fermi Level Splitting: The Role of Water, Temperature, and Solvent during Processing

Chemical Surface Reactivity and Morphological Changes of Bismuth Triiodide (BiI₃) under Different Environmental Conditions

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Bismuth Iodide Hybrid Organic‐Inorganic Crystal Structures and Utilization in Formation of Textured BiI3 Film

Abstract: Abstract:Two new and one redetermination of metastable bismuth iodide hybrid organic-inorganic structure incorporating the solvents 2,3,4,5-tetrahydrothiophene 1

Cited by 15 publications

References 25 publications

Pb-Free Cs3Bi2I9 Perovskite as a Visible-Light-Active Photocatalyst for Organic Pollutant Degradation

Pb-Free Cs3Bi2I9 Perovskite as a Visible-Light-Active Photocatalyst for Organic Pollutant Degradation

Solution-Processed BiI3 Films with 1.1 eV Quasi-Fermi Level Splitting: The Role of Water, Temperature, and Solvent during Processing

Chemical Surface Reactivity and Morphological Changes of Bismuth Triiodide (BiI3) under Different Environmental Conditions

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Product

Resources

About

Bismuth Iodide Hybrid Organic‐Inorganic Crystal Structures and Utilization in Formation of Textured BiI₃ Film

Solution-Processed BiI₃ Films with 1.1 eV Quasi-Fermi Level Splitting: The Role of Water, Temperature, and Solvent during Processing

Chemical Surface Reactivity and Morphological Changes of Bismuth Triiodide (BiI₃) under Different Environmental Conditions