Sreedhara M B, Miroshnikov Yana, Zheng Kai, Houben Lothar, Hettler Simon, Arenal Raul, Pinkas Iddo, Sinha Sudarson S, Castelli Ivano E, Tenne Reshef
Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovot 7610001, Israel.
Department of Energy Conversion and Storage, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark.
J Am Chem Soc. 2022 Jun 15;144(23):10530-10542. doi: 10.1021/jacs.2c03187. Epub 2022 Jun 3.
Nanotubes of transition metal dichalcogenides such as WS and MoS offer unique quasi-1D properties and numerous potential applications. Replacing sulfur by selenium would yield ternary WSSe (0 ≤ ≤ 1; WSSe) nanotubes, which are expected to reveal strong modulation in their absorption edge as a function of selenium content, . Solid WO oxide nanowhiskers were employed as a sacrificial template to gain a high yield of the nanotubes with a rather uniform size distribution. Though sulfur and selenium belong to the same period, their chemical reactivity with oxide nanowhiskers differed appreciably. Here, the closed ampoule technique was utilized to achieve the completion of the solid-vapor reaction in short time scales instead of the conventional flow reactor method. The structure and chemical composition of the nanotubes were analyzed in detail. X-ray and electron diffractions indicated a systematic modulation of the WSSe lattice upon increasing the selenium content. Detailed chemical mapping showed that the sulfur and selenium atoms are distributed in random positions on the anion lattice site of the nanotubes. The optical excitonic features and absorption edges of the WSSe nanotubes do not vary linearly with the composition , which was further confirmed by density functional theory calculations. The WSSe nanotubes were shown to exhibit strong light-matter interactions forming exciton-polariton quasiparticles, which was corroborated by finite-difference time-domain simulations. Transient absorption analysis permitted following the excited state dynamics and elucidating the mechanism of the strong coupling. Thus, nanotubes of the ternary WSSe alloys offer strong band gap tunability, which would be useful for multispectral vision devices and other optoelectronic applications.
诸如WS和MoS等过渡金属二硫属化物纳米管具有独特的准一维特性和众多潜在应用。用硒取代硫会生成三元WSSe(0≤≤1;WSSe)纳米管,预计其吸收边会随着硒含量的变化而呈现出强烈的调制。固态WO氧化物纳米晶须被用作牺牲模板,以高产率获得尺寸分布相当均匀的纳米管。尽管硫和硒属于同一周期,但它们与氧化物纳米晶须的化学反应性有明显差异。在此,采用封闭安瓿技术在短时间内完成固-气反应,而不是传统的流动反应器方法。对纳米管的结构和化学成分进行了详细分析。X射线和电子衍射表明,随着硒含量的增加,WSSe晶格有系统的调制。详细的化学映射显示,硫和硒原子随机分布在纳米管阴离子晶格位点上。WSSe纳米管的光学激子特性和吸收边并不随成分线性变化,密度泛函理论计算进一步证实了这一点。WSSe纳米管表现出强烈的光-物质相互作用,形成激子-极化激元准粒子,时域有限差分模拟证实了这一点。瞬态吸收分析允许跟踪激发态动力学并阐明强耦合机制。因此,三元WSSe合金纳米管具有很强的带隙可调性,这对多光谱视觉器件和其他光电子应用很有用。