Functionalization of Cuprous Oxide: From Doped Binary to Cu-based Ternary Oxide Films

氧化亚铜的功能化：从掺杂二元到铜基三元氧化物薄膜

• 批准号: 385079232
• 负责人: Professor Dr. Niklas Nilius
• 金额: --
• 依托单位: Institut für Physik (IFP)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/385079232?language=en
• 关键词: Functionalization; Cuprous; Oxide; Doped; Binary

The present proposal is a follow-up to previous DFG project that aimed at the preparation and characterization of cuprous oxide films with surface science methods. The expired project successfully clarified a number of fundamental questions in connection with Cu2O, a material of enormous scientific and technological relevance. The main advances concern: (i) the kinetics and thermodynamics of Cu-oxidation as probed at defined reaction conditions. For this purpose, a new optical technique was developed for the in-situ monitoring of oxidation fronts and used to establish a Cu-O phase diagram as a function of pressure and temperature(ii) the nature of Cu-O monolayer films grown on Au(111), Pt(111) and Mo(001). The experiments revealed the impossibility to grow thick Cu-oxide films in a vacuum environment(iii) a recipe to grow bulk-type Cu2O films via a high-pressure oxidation scheme(iv) the structural elucidation of the Cu2O(111) surface that always reconstructs and comprises neither low-coordinated Cu ions nor O vacancies, in contrast to all existing literature models.The availability of a new preparation scheme for bulk-type Cu2O(111) represents a firm basis to address other properties of this fascinating material during a follow-up project with these key aspects: (i) Characterization of lattice defects that dominate the electronic (p-type conductance) and chemical properties of the material(ii) Spatially resolved detection of excitons, as the fundamental optical mode of Cu2O, and their interplay with lattice imperfections(iii) Release of the dipole-forbidden nature of band gap recombination in Cu2O via doping and subsequent insertion of defect states at the band edges with favorable parity for optical transitions (iv) Extending the doping scheme towards ternary Cu-based oxides with novel optical and chemical properties, e.g. CuAlO2 and Cu2V2O7 for the photo-catalytic splitting of water.All experiments are performed with state-of-the art surface-science techniques in an UHV environment, in particular with scanning tunneling and optical nearfield microscopy at the atomic level, and will be accompanied by high-level DFT calculations.

本提案是先前DFG项目的后续项目，该项目旨在用表面科学方法制备和表征氧化亚铜薄膜。期满的项目成功地澄清了与Cu2O有关的一些基本问题，Cu2O是一种具有巨大科学和技术意义的材料。主要研究内容包括：(1)确定反应条件下铜氧化反应的动力学和热力学。为此，发展了一种新的在线监测氧化前沿的光学技术，并用它建立了随压力和温度变化的铜-氧相图(II)在Au(111)，Pt(111)和Mo(001)上生长的铜-氧单分子膜的性质。实验揭示了在真空环境中生长厚氧化铜薄膜的可能性(III)通过高压氧化机制生长体型Cu2O薄膜的配方(IV)Cu2O(111)表面总是重构且既不包含低配位的铜离子也不包含O空位的结构。与所有现有文献模型形成对比的是，块状Cu2O(111)的新制备方案的可用性代表了在后续项目期间利用这些关键方面来解决这种吸引人的材料的其他性质的坚实基础：(I)主宰材料的电子(p型电导)和化学性质的晶格缺陷的表征(Ii)作为Cu2O的基本光学模式的激子的空间分辨检测，以及它们与晶格缺陷的相互作用(Iii)通过掺杂和随后在具有有利光学跃迁奇偶性的带边插入缺陷态来释放Cu2O中禁带的偶极性质(Iv)将掺杂方案扩展到具有新的光学和化学性质的三元铜基氧化物，例如用于光催化裂解水的CuAlO2和Cu2V2O7。所有实验都是在超高真空环境下使用最先进的表面科学技术进行的，特别是在原子水平上的扫描隧道和光学近场显微镜，并将伴随着高水平的密度泛函计算。