The band alignment and the interfacial electronic coupling of van der Waals heterojunctions formed by the Poly[3-hexylthiophene-2,5-diyl] (P3HT) semiconductor polymer and the mechanically exfoliated black phosphorous (BP) multilayers were investigated using different spectroscopies techniques. The energy band alignment was assessed using Ultraviolet (UPS) and X-ray (XPS) photoelectron spectroscopies. The result of this analysis shows that the P3HT-BP interface presents a type I band alignment with conduction band minimum and the valence band maximum located in the BP layer. A valence band offset of 0.45 eV and a conduction band offset of 1.25 eV parameters were found. Near-Edge X-ray Absorption Fine Structure (NEXAFS) and resonant Auger (RAS) synchrotron-based spectroscopies were used to investigate the interfacial electronic coupling between BP and P3HT. Interfacial charge transfer times obtained from core hole clock approach and using the S1s core-hole lifetime as a reference time were used as quantitative parameters to measure the degree of electronic coupling. We found that the π*(S=C) electronic state is the faster electron delocalization pathway from the P3HT to the BP conduction band and therefore there is a strong electronic coupling between these states. This result was supported from density functional theoretical calculations.

使用不同的光谱学技术研究了由聚[3-己基噻吩-2,5-二基]（P3HT）半导体聚合物和机械剥离的黑色磷（BP）多层形成的范德华异质结的能带排列和界面电子耦合。使用紫外线（UPS）和X射线（XPS）光电子能谱仪评估能带对准。分析的结果表明，P3HT-BP界面呈现出一种I型能带排列，导带最小值和价带最大值位于BP层中。发现价带偏移为0.45 eV，导带偏移为1.25 eV。基于近边缘X射线吸收精细结构（NEXAFS）和基于共振俄歇（RAS）同步加速器的光谱学被用于研究BP和P3HT之间的界面电子耦合。从芯孔时钟方法获得的界面电荷转移时间，以S1s的芯孔寿命为参考时间，被用作定量参数，以测量电子耦合程度。我们发现π*（S = C）电子态是从P3HT到BP导带的更快的电子离域路径，因此这些状态之间存在强电子耦合。密度泛函理论计算支持了该结果。从芯孔时钟方法获得的界面电荷转移时间，以S1s的芯孔寿命为参考时间，被用作定量参数来测量电子耦合程度。我们发现π*（S = C）电子态是从P3HT到BP导带的更快的电子离域路径，因此这些状态之间存在强电子耦合。密度泛函理论计算支持了该结果。从芯孔时钟方法获得的界面电荷转移时间，以S1s的芯孔寿命为参考时间，被用作定量参数，以测量电子耦合程度。我们发现π*（S = C）电子态是从P3HT到BP导带的更快的电子离域路径，因此在这些态之间存在强电子耦合。密度泛函理论计算支持了该结果。