A surface science view onto cuprous oxide: Growth, termination, electronic structure and optical response

IF 8.2 1区 化学 Q1 CHEMISTRY, PHYSICAL
Niklas Nilius , Jacek Goniakowski , Claudine Noguera
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引用次数: 0

Abstract

The oxides of copper have attracted the attention of scientists already for more than hundred years. This fascination is fueled by many outstanding properties of the material, for example, a semiconducting behavior that led to the first diode fabricated in electronics, a pronounced excitonic response that stimulated an intense search for Bose-Einstein condensation, and a pivotal role in unconventional superconductivity. Despite this central position in past and present research activities, many aspects of copper oxides are not sufficiently understood to date. This applies in particular to their surface characteristics, where even fundamental questions, such as the energetically favored termination of low-index Cu2O and CuO planes, are still subject of debates. This review aims at addressing these deficiencies by compiling state-of-the-art knowledge of the surface science of copper oxides, and especially of cuprous oxide.

A first focus of the article lies in the oxidation characteristic of copper as a means to prepare well-defined oxide surfaces. It demonstrates that low-pressure oxidation only results in the formation of ultrathin precursor oxides, with properties deviating substantially from those of the bulk material. Consequently, reliable pathways to produce high-quality and bulk-compatible surfaces, either of Cu2O thin films or bulk crystals, are presented. The following chapter provides a comprehensive introduction into the atomic structure of the most relevant Cu2O surfaces, i.e., the (111), (100) and (110) planes. It gives an overview of important diffraction and microscopy experiments on the most accessible Cu2O terminations, and complements this with state-of-the-art theoretical studies to develop corresponding atomistic models. The chapter closes by presenting the atomic configurations of the most relevant Cu2O surfaces at given thermodynamic conditions.

Chapter four develops a surface-science view onto the unique optical response of cuprous oxide. After introducing the well-known bulk behavior, it highlights how optical properties can be probed on surfaces with high spectral and spatial resolution. The chapter discusses how optical near-field techniques are employed to analyze oxide excitons and their trapping at lattice defects in real-space experiments. The last chapter summarizes efforts to alter intrinsic Cu2O properties, e.g., the p-type conductivity, the width of the band gap and the exciton trapping and recombination behavior, via doping. It illuminates this topic from an experimental and theoretical viewpoint and highlights several unsolved questions related to the topic.

Despite considerable efforts, this review can only present the current state of knowledge on Cu2O surfaces, a subject that continuously advances due to new scientific findings and innovations. We nonetheless hope that it provides a comprehensive and topical overview of the unusual properties of this fascinating oxide system.

从表面科学角度看氧化亚铜:生长、终止、电子结构和光学响应
一百多年来,铜氧化物一直吸引着科学家们的目光。铜氧化物的许多杰出特性激发了科学家对它的兴趣,例如,它的半导体特性造就了电子学中的第一个二极管,它的明显激子响应激发了科学家对玻色-爱因斯坦凝聚的深入研究,以及它在非常规超导中的关键作用。尽管铜氧化物在过去和现在的研究活动中占据核心地位,但迄今为止,人们对其许多方面的了解还不够充分。这尤其体现在它们的表面特性上,即使是一些基本问题,例如低指数 Cu2O 和 CuO 平面在能量上的倾向性终止,也仍然是争论的主题。这篇综述旨在通过汇编铜氧化物,尤其是氧化亚铜表面科学的最新知识来弥补这些不足。文章首先关注铜的氧化特性,并以此为手段制备定义明确的氧化物表面。文章表明,低压氧化只能形成超薄的前驱氧化物,其特性与块状材料的特性有很大差异。因此,本文介绍了生产高质量且与块体兼容的 Cu2O 薄膜或块体晶体表面的可靠途径。下一章将全面介绍最相关的 Cu2O 表面(即 (111)、(100) 和 (110) 面)的原子结构。本章概述了对最易获得的 Cu2O 端面进行的重要衍射和显微实验,并辅以最先进的理论研究来建立相应的原子模型。本章最后介绍了在给定热力学条件下最相关的氧化亚铜表面的原子构型。第四章从表面科学的角度阐述了氧化亚铜独特的光学响应。在介绍了众所周知的块体行为之后,本章重点介绍了如何以高光谱和高空间分辨率探测表面的光学特性。该章讨论了如何在真实空间实验中利用光学近场技术分析氧化物激子及其在晶格缺陷处的捕获。最后一章总结了通过掺杂改变 Cu2O 固有特性(如 p 型电导率、带隙宽度以及激子捕获和重组行为)的工作。尽管做了大量的工作,但这篇综述只能介绍目前有关氧化铜表面的知识状况,而这一主题会随着新的科学发现和创新而不断进步。尽管如此,我们还是希望这篇综述能为我们提供一个关于这一迷人的氧化物体系的不寻常特性的全面而专题性的概述。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Surface Science Reports
Surface Science Reports 化学-物理:凝聚态物理
CiteScore
15.90
自引率
2.00%
发文量
9
审稿时长
178 days
期刊介绍: Surface Science Reports is a journal that specializes in invited review papers on experimental and theoretical studies in the physics, chemistry, and pioneering applications of surfaces, interfaces, and nanostructures. The topics covered in the journal aim to contribute to a better understanding of the fundamental phenomena that occur on surfaces and interfaces, as well as the application of this knowledge to the development of materials, processes, and devices. In this journal, the term "surfaces" encompasses all interfaces between solids, liquids, polymers, biomaterials, nanostructures, soft matter, gases, and vacuum. Additionally, the journal includes reviews of experimental techniques and methods used to characterize surfaces and surface processes, such as those based on the interactions of photons, electrons, and ions with surfaces.
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