{"title":"正交(100)NaTaO3 薄膜的尺寸和应变特性:DFT 综合研究","authors":"","doi":"10.1016/j.commatsci.2024.113335","DOIUrl":null,"url":null,"abstract":"<div><p>The modulation of perovskite oxide thin films’ properties, through both intrinsic and extrinsic methods, has been extensively studied to enhance their photocatalytic performance. We employed <em>ab initio</em> density functional theory calculations to investigate the layer-dependent structural and electronic properties of orthorhombic NaTaO<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span> thin films. Our findings reveal that slabs comprising five, four, and three layers retain the non-magnetic and semiconducting characteristics of the bulk material, with their properties progressively converging towards those of an infinite-surface slab as the number of layers increases. Biaxial in-plane strain induces a linear change in the structure of surface TaO<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> tetrahedra, thereby altering the film’s band gap. Notably, the two-layer slab exhibits a transitional behavior between the bulk-like nature of thicker films and the unique features of a NaTaO<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span> monolayer, showing heightened sensitivity to strain. Under compression, this bilayered system acquires bulk-like properties, whereas its strain-free state is magnetic and metallic akin to the monolayer. Similar transitions are observed in the latter, though under higher compression values. We provide an in-depth discussion of the structural and electronic mechanisms underlying these transitions. Additionally, the relative band-edge alignment with water-splitting photocatalytic potentials underscores the complex interplay between strain and dimensionality. This work offers valuable insights towards the design of more efficient photocatalysts, highlighting the potential of engineered NaTaO<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span> thin-film structures for advancing photocatalytic applications.</p></div>","PeriodicalId":10650,"journal":{"name":"Computational Materials Science","volume":null,"pages":null},"PeriodicalIF":3.1000,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Dimensionality and strain-dependent properties of Orthorhombic (100) NaTaO3 thin films: A comprehensive DFT investigation\",\"authors\":\"\",\"doi\":\"10.1016/j.commatsci.2024.113335\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The modulation of perovskite oxide thin films’ properties, through both intrinsic and extrinsic methods, has been extensively studied to enhance their photocatalytic performance. We employed <em>ab initio</em> density functional theory calculations to investigate the layer-dependent structural and electronic properties of orthorhombic NaTaO<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span> thin films. Our findings reveal that slabs comprising five, four, and three layers retain the non-magnetic and semiconducting characteristics of the bulk material, with their properties progressively converging towards those of an infinite-surface slab as the number of layers increases. Biaxial in-plane strain induces a linear change in the structure of surface TaO<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> tetrahedra, thereby altering the film’s band gap. Notably, the two-layer slab exhibits a transitional behavior between the bulk-like nature of thicker films and the unique features of a NaTaO<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span> monolayer, showing heightened sensitivity to strain. Under compression, this bilayered system acquires bulk-like properties, whereas its strain-free state is magnetic and metallic akin to the monolayer. Similar transitions are observed in the latter, though under higher compression values. We provide an in-depth discussion of the structural and electronic mechanisms underlying these transitions. Additionally, the relative band-edge alignment with water-splitting photocatalytic potentials underscores the complex interplay between strain and dimensionality. This work offers valuable insights towards the design of more efficient photocatalysts, highlighting the potential of engineered NaTaO<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span> thin-film structures for advancing photocatalytic applications.</p></div>\",\"PeriodicalId\":10650,\"journal\":{\"name\":\"Computational Materials Science\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.1000,\"publicationDate\":\"2024-09-03\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Computational Materials Science\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0927025624005561\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Computational Materials Science","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0927025624005561","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
为了提高包晶氧化物薄膜的光催化性能,人们通过内在和外在方法对其特性进行了广泛的研究。我们采用 ab initio 密度泛函理论计算来研究正交态 NaTaO3 薄膜随层变化的结构和电子特性。我们的研究结果表明,由五层、四层和三层组成的板坯保留了块体材料的非磁性和半导体特性,随着层数的增加,其特性逐渐向无限面板坯的特性靠拢。双轴面内应变会引起表面 TaO4 四面体结构的线性变化,从而改变薄膜的带隙。值得注意的是,双层板坯表现出一种介于较厚薄膜的块状性质和单层 NaTaO3 的独特特征之间的过渡行为,显示出对应变的高度敏感性。在压缩条件下,这种双层体系具有类似于块状的特性,而其无应变状态则具有类似于单层的磁性和金属性。在后者中也观察到了类似的转变,不过压缩值更高。我们深入讨论了这些转变背后的结构和电子机制。此外,相对带边排列与水分裂光催化电位的关系突出了应变与尺寸之间复杂的相互作用。这项工作为设计更高效的光催化剂提供了宝贵的见解,凸显了工程化 NaTaO3 薄膜结构在推进光催化应用方面的潜力。
Dimensionality and strain-dependent properties of Orthorhombic (100) NaTaO3 thin films: A comprehensive DFT investigation
The modulation of perovskite oxide thin films’ properties, through both intrinsic and extrinsic methods, has been extensively studied to enhance their photocatalytic performance. We employed ab initio density functional theory calculations to investigate the layer-dependent structural and electronic properties of orthorhombic NaTaO thin films. Our findings reveal that slabs comprising five, four, and three layers retain the non-magnetic and semiconducting characteristics of the bulk material, with their properties progressively converging towards those of an infinite-surface slab as the number of layers increases. Biaxial in-plane strain induces a linear change in the structure of surface TaO tetrahedra, thereby altering the film’s band gap. Notably, the two-layer slab exhibits a transitional behavior between the bulk-like nature of thicker films and the unique features of a NaTaO monolayer, showing heightened sensitivity to strain. Under compression, this bilayered system acquires bulk-like properties, whereas its strain-free state is magnetic and metallic akin to the monolayer. Similar transitions are observed in the latter, though under higher compression values. We provide an in-depth discussion of the structural and electronic mechanisms underlying these transitions. Additionally, the relative band-edge alignment with water-splitting photocatalytic potentials underscores the complex interplay between strain and dimensionality. This work offers valuable insights towards the design of more efficient photocatalysts, highlighting the potential of engineered NaTaO thin-film structures for advancing photocatalytic applications.
期刊介绍:
The goal of Computational Materials Science is to report on results that provide new or unique insights into, or significantly expand our understanding of, the properties of materials or phenomena associated with their design, synthesis, processing, characterization, and utilization. To be relevant to the journal, the results should be applied or applicable to specific material systems that are discussed within the submission.