A fundamental understanding of hot-carrier dynamics in photo-excited metal nanostructures is needed to unlock their potential for photodetection and photocatalysis. Despite numerous studies on the ultrafast dynamics of hot electrons, so far, the temporal evolution of hot holes in metal–semiconductor heterostructures remains unknown. Here, we report ultrafast (t < 200 fs) hot-hole injection from Au nanoparticles into the valence band of p-type GaN. The removal of hot holes from below the Au Fermi level is observed to substantially alter the thermalization dynamics of hot electrons, reducing the peak electronic temperature and the electron–phonon coupling time of the Au nanoparticles. First-principles calculations reveal that hot-hole injection modifies the relaxation dynamics of hot electrons in Au nanoparticles by modulating the electronic structure of the metal on timescales commensurate with electron–electron scattering. These results advance our understanding of hot-hole dynamics in metal–semiconductor heterostructures and offer additional strategies for manipulating the dynamics of hot carriers on ultrafast timescales.

需要对光激发金属纳米结构中的热载流子动力学有基本的了解，才能释放出它们在光检测和光催化方面的潜力。尽管对热电子的超快动力学进行了大量研究，但到目前为止，金属-半导体异质结构中热空穴的时间演化仍然未知。在这里，我们报告超快（ŧ <200 fs）将Au纳米颗粒热空穴注入p型GaN的价带中。观察到从Au Fermi能级以下去除热空穴会实质上改变热电子的热化动力学，从而降低峰值电子温度和Au纳米粒子的电子-声子耦合时间。第一性原理计算表明，通过在与电子-电子散射相称的时间尺度上调节金属的电子结构，热空穴注入可以改变金纳米颗粒中热电子的弛豫动力学。这些结果提高了我们对金属-半导体异质结构中热空穴动力学的理解，并提供了在超快时间尺度上操纵热载流子动力学的其他策略。