Interplay between Cation "Coloring" and Stereochemically Active Lone Pairs in AgBiS2 Thin Films
Kristopher M Koskela1, Anindya Pakhira2, Marissa J Strumolo1
1Department of Chemistry, University of Southern California, Los Angeles, California 90089-3502, United States.
Inorganic Chemistry
|May 13, 2025
Summary
Solution-processed silver bismuth sulfide (AgBiS2) thin films reveal that local nanodomains influence stereochemical activity. This impacts the material's structure and optoelectronic properties, offering insights into complex material behavior.
Area of Science:
- Materials Science
- Solid State Chemistry
- Thin Film Deposition
Background:
- Stereochemical activity of lone pairs, particularly Bi3+ 6s2, significantly influences crystal structure and properties.
- Understanding local structural variations is crucial for tuning the optoelectronic performance of materials like AgBiS2.
Purpose of the Study:
- To investigate the stereochemical activity of Bi3+ 6s2 lone pairs in AgBiS2 thin films.
- To correlate local structural features with the material's average structure and optoelectronic properties.
Main Methods:
- Fabrication of AgBiS2 thin films using novel thiol-amine precursor inks.
- Dual-space analysis combining Bragg diffraction and hard X-ray photoelectron spectroscopy (HAXPES).
- Density functional theory (DFT) and crystal orbital Hamilton population (COHP) analyses.
Main Results:
- A rock salt-like average structure was observed, with local distortions attributed to cation ordering.
- Bi-rich and Ag-rich nanodomains were found to amplify stereochemical activity.
- Mixed and cation-ordered nanodomains exhibited reduced stereochemical activity, explaining the average Fm3m structure.
Conclusions:
- The nanoscopic mixing of segregated and ordered domains governs the structural complexity of AgBiS2.
- Local structural variations, driven by lone pair activity, impact the material's anharmonicity and noncentrosymmetry.
- These findings provide critical insights into the structure-property relationships for AgBiS2 thin films.
More Related Videos
16:11Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
Published on: June 8, 2022
2.2K
08:54Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid
Published on: January 25, 2020
5.6K
Related Concept Videos
02:42Valence Bond Theory
8.4K
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
8.4K
03:02Colors and Magnetism
11.4K
Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
11.4K
02:52Stereoisomerism
11.7K
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
11.7K
02:34Structural Isomerism
19.0K
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly,...
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly,...
19.0K
02:51Metal-Ligand Bonds
20.4K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
20.4K