Insights into the structural complexity and local disorder of crystalline AsTe3 from semi-automated first-principles modelling†

IF 2.9 3区 化学 Q3 CHEMISTRY, PHYSICAL
Sylvian Cadars, Olivier Masson, Jean-Paul Laval, Firas E. Shuaib, Andrea Piarristeguy, Gaëlle Delaizir and Assil Bouzid
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Abstract

A semi-automated workflow relying on atomic-scale modelling is introduced to explore and understand the yet-unsolved structure of the crystalline AsTe3 material, recently obtained from crystallization of the parent AsTe3 glass, which shows promising properties for thermoelectric applications. The seemingly complex crystal structure of AsTe3 is investigated with density functional theory, from the stand point of As/Te disorder, in a structural template derived from elemental-Te (Teel), following experimental findings from combined X-ray total scattering and diffraction. Our workflow includes a combinatorial structure generation step followed by successive structure selection and relaxation steps with progressively-increasing accuracy levels and a multi-criterion evaluation procedure. A small set of high quality models with common structural features emerge, all consisting of intergrowth domains typically below 1 nm in thickness and with the local compositions and structures of Teel and α-As2Te3, but with different thicknesses and relative arrangements, which points to the presence of such defects in crystalline AsTe3. While predictions of the electronic bandgaps are in excellent agreement with the experimental value for our best models, we find that some of these defects may be associated with the locally-increased density of states around the Fermi level, potentially contributing to the overall electronic conductivity, which, along with intrinsic structural complexity, is among the key features of the reported outstanding thermoelectric properties of this compound.

Abstract Image

半自动化第一原理模型对晶体ase3结构复杂性和局部无序性的洞察
介绍了一种依赖于原子尺度建模的半自动化工作流程,以探索和理解尚未解决的晶体AsTe3材料的结构,该材料最近从母体AsTe3玻璃的结晶中获得,显示出热电应用的良好性能。根据x射线全散射和衍射的实验结果,从As/Te无序的角度,用密度泛函理论在元素-Te (Teel)的结构模板中探讨了看似复杂的AsTe3晶体结构。我们的工作流程包括一个组合结构生成步骤,随后是连续的结构选择和放松步骤,其精度水平逐步提高,以及一个多标准评估程序。出现了一小组具有共同结构特征的高质量模型,它们都由厚度一般小于1 nm的互生长畴组成,具有Teel和α-As2Te3的局部成分和结构,但厚度和相对排列不同,这表明as2te3晶体中存在此类缺陷。虽然电子带隙的预测与我们最佳模型的实验值非常一致,但我们发现其中一些缺陷可能与费米能级附近局部增加的态密度有关,这可能有助于整体电子导电性,这与固有结构复杂性一起,是该化合物报告的杰出热电性能的关键特征之一。
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来源期刊
Physical Chemistry Chemical Physics
Physical Chemistry Chemical Physics 化学-物理:原子、分子和化学物理
CiteScore
5.50
自引率
9.10%
发文量
2675
审稿时长
2.0 months
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.
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