Photoaccelerated hot carrier transfer at <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mi>MoS</mml:mi><mml:mn>2</mml:mn></mml:msub><mml:mo>/</mml:mo><mml:msub><mml:mi>WS</mml:mi><mml:mn>2</mml:mn></mml:msub></mml:mrow></mml:math>: A first-principles study
Zhi-Guo Tao, Guojun Zhu, Weibin Chu, Xin-Gao Gong, Ji-Hui Yang
Abstract
Charge transfer in type-II heterostructures plays important roles in determining device performance for photovoltaic and photocatalytic applications. However, current theoretical studies of charge transfer process do not consider the effects of operating conditions such as illuminations and yield systemically larger interlayer transfer time of hot electrons in ${\mathrm{MoS}}_{2}/{\mathrm{WS}}_{2}$ compared to experimental results. Here in this work, we propose a general picture that illumination can induce interfacial dipoles in type-II heterostructures, which can accelerate hot carrier transfer by reducing the energy difference between the electronic states in separate materials and enhancing the nonadiabatic couplings. Using the first-principles calculations and the ab initio nonadiabatic molecular dynamics, we demonstrate this picture using ${\mathrm{MoS}}_{2}/{\mathrm{WS}}_{2}$ as a prototype. The calculated characteristic time for the interlayer transfer (60 fs) and the overall relaxation (700 fs) processes of hot electrons is in good agreement with the experiments. We further find that illumination mainly affects the ultrafast interlayer transfer process but has little effect on the relatively slow intralayer relaxation process. Therefore, the overall relaxation process of hot electrons has a saturated time with increased illumination strengths. The illumination-accelerated charge transfer is expected to universally exist in type-II heterostructures.