Identification of large polarons and exciton polarons in rutile and anatase polymorphs of titanium dioxide

• 成果类型: Article
• 署名作者: Dai, Zhenbang; Giustino, Feliciano
• 署名单位: University of Texas System; University of Texas Austin; University of Texas System; University of Texas Austin
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-10408
• DOI: 10.1073/pnas.2414203121
• 发表日期: 2024-11-26
• 关键词: reduced states; tio2; electrons; light; band; uv

摘要

Titanium dioxide (TiO2) is a wide-gap semiconductor with numerous applications in photocatalysis, photovoltaics, and neuromorphic computing. The unique functional properties of this material critically depend on its ability to transport charge in the form of polarons, namely narrow electron wavepackets accompanied by local distortions of the crystal lattice. It is currently well established that the most important polymorphs of TiO2, the rutile and anatase phases, harbor small electron polarons and small hole polarons, respectively. However, whether additional polaronic species exist in TiO2, and under which conditions, remain open questions. Here, we provide definitive answers to these questions by exploring the rich landscape of polaron quasiparticles in TiO2 via recently developed ab initio techniques. In addition to the already known small polarons, we identify three species, namely a large hole polaron in rutile, a large quasi-two-dimensional electron polaron in anatase, and a large exciton polaron in anatase. These findings complete the puzzle on the polaron physics of TiO2 and pave the way for systematically probing and manipulating polarons in a broad class of complex oxides and quantum materials.