{"title":"Prediction of ternary alkaline-earth metal Sn(II) and Pb(II) chlorides with potential applications as p-type transparent conductors","authors":"Li Wang, Tingting Lin, Jia Wang, Chao Fang, Yuwei Li, Yuancun Qiao","doi":"10.1039/d4cp03090g","DOIUrl":null,"url":null,"abstract":"Non-metallic Sn(II) and Pb(II) compounds, particularly those with <em>p</em>-type properties, are essential functional materials due to their notable electronic arrangement and chemical characteristics. The presence of additional Sn(II) and Pb(II) chlorides is suggested by the existence of known Sn(II) and Pb(II) compounds. By utilizing first-principles calculations and swarm intelligence structure search techniques, we have predicted the existence of up to seven new ternary alkaline-earth metal chlorides: <em>AB</em>Cl<small><sub>4</sub></small> (where <em>A</em> = Sr and <em>B</em> = Sn or Pb) and <em>AB</em><small><sub>2</sub></small>Cl<small><sub>6</sub></small> (where <em>A</em> = Mg, Ca, or Ba and <em>B</em> = Sn, or <em>A</em> = Ca or Sr and <em>B</em> = Pb). These seven chlorides are in the divalent state. The interaction between Sn-5<em>s</em> (or Pb-6<em>s</em>) and Cl-3<em>p</em> in these compounds creates an anti-bonding effect in the upper valence bands, which enhances defect tolerance and promotes high <em>p</em>-type conductivity. These stable chlorides exhibit notable electronic properties, including wide band gaps ranging from 3.91 to 4.94 eV, broad hole effective masses ranging from 0.93 to 5.62 m<small><sub>0</sub></small>, and high valence band alignments ranging from 6.83 to 8.38 eV under vacuum. Specifically, Ca/BaSn<small><sub>2</sub></small>Cl<small><sub>6</sub></small> and CaPb<small><sub>2</sub></small>Cl<small><sub>6</sub></small> have the potential to be used as <em>p</em>-type transparent conductors due to their favorable properties, including a lower hole effective mass (0.93 m<small><sub>0</sub></small> for CaPb<small><sub>2</sub></small>Cl<small><sub>6</sub></small>) and higher ionization potentials (6.83/7.05 eV for Ba/CaSn<small><sub>2</sub></small>Cl<small><sub>6</sub></small>). Furthermore, the predicted CaPb<small><sub>2</sub></small>Cl<small><sub>6</sub></small> crystal exhibits an attenuated negative linear compressibility and negative zero-linear-compressibility of the <em>c</em>-axis in different pressure ranges due to the wine-rack structure. This report highlights potential applications for alkaline-earth metal Sn(II) and Pb(II) chlorides, including their use as transparent conductors, particularly the <em>p</em>-type.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":2.9000,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical Chemistry Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4cp03090g","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Non-metallic Sn(II) and Pb(II) compounds, particularly those with p-type properties, are essential functional materials due to their notable electronic arrangement and chemical characteristics. The presence of additional Sn(II) and Pb(II) chlorides is suggested by the existence of known Sn(II) and Pb(II) compounds. By utilizing first-principles calculations and swarm intelligence structure search techniques, we have predicted the existence of up to seven new ternary alkaline-earth metal chlorides: ABCl4 (where A = Sr and B = Sn or Pb) and AB2Cl6 (where A = Mg, Ca, or Ba and B = Sn, or A = Ca or Sr and B = Pb). These seven chlorides are in the divalent state. The interaction between Sn-5s (or Pb-6s) and Cl-3p in these compounds creates an anti-bonding effect in the upper valence bands, which enhances defect tolerance and promotes high p-type conductivity. These stable chlorides exhibit notable electronic properties, including wide band gaps ranging from 3.91 to 4.94 eV, broad hole effective masses ranging from 0.93 to 5.62 m0, and high valence band alignments ranging from 6.83 to 8.38 eV under vacuum. Specifically, Ca/BaSn2Cl6 and CaPb2Cl6 have the potential to be used as p-type transparent conductors due to their favorable properties, including a lower hole effective mass (0.93 m0 for CaPb2Cl6) and higher ionization potentials (6.83/7.05 eV for Ba/CaSn2Cl6). Furthermore, the predicted CaPb2Cl6 crystal exhibits an attenuated negative linear compressibility and negative zero-linear-compressibility of the c-axis in different pressure ranges due to the wine-rack structure. This report highlights potential applications for alkaline-earth metal Sn(II) and Pb(II) chlorides, including their use as transparent conductors, particularly the p-type.
期刊介绍:
Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions.
The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.