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.
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The datasets generated and analysed during the study are available from the corresponding authors upon request.
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This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the US Department of Energy under award no. DE-SC0004993. A portion of the ultrafast spectroscopy work was performed at the Center for Nanoscale Materials, a US Department of Energy Office of Science User Facility, and supported by the US Department of Energy, Office of Science, under contract no. DE-AC02-06CH11357. G.T. acknowledges support from the Swiss National Science Foundation through the Early Postdoc.Mobility Fellowship, grant no. P2EZP2_159101 and the Advanced Mobility Fellowship, grant no. P300P2_171417. We also thank M. V. Pavliuk for assistance in conducting ultrafast transient absorption spectroscopy measurements from planar Au films on p-GaN substrates.
The authors declare no competing interests.
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Full infrared probe spectrum (λprobe = 1850–2250 cm−1) obtained from Au/p-GaN upon 530 nm pump pulse at an incident power of 400 μW. The plot shown in Fig. 2b shows the temporal rise and decay taken at 2060 cm−1 (λprobe = 4.85 μm).
Extended Data Fig. 2 Power-dependent transient infrared absorption spectroscopy of Au/p-GaN heterostructures.
Ultrafast transient rise and decay probed at 2060 cm−1 (λprobe = 4.85 μm) obtained from Au/p-GaN upon 530 nm pump pulse at several different incident powers.
a, Full infrared probe spectrum (λprobe = 1900–2300 cm−1) obtained from Au/ZrO2 upon 530 nm pump pulse at an incident power of 500 μW. b, Ultrafast transient rise and decay probed at 2060 cm−1 (λprobe = 4.85 μm) obtained from Au/p-GaN (black points), bare p-GaN (open circles), and Au/ZrO2 (grey points) upon 530 nm pump pulse at an incident power of 500 μW (Au/p-GaN and Au/ZrO2) and 750 μW (bare p-GaN). The red line shows a fit to the experimental Au/p-GaN data, which exhibits an instrument-limited rise time of less than 200 fs. No signal was obtained from either bare p-GaN or Au/ZrO2 heterostructures.
Extended Data Fig. 4 Power-dependent pump-probe studies of visible-light transient absorption spectroscopy from Au/p-GaN heterostructures.
a, Power-dependent dynamics of the transient bleach at 560 nm from 200 μW to 500 μW pump power. b, Power-dependent differential transient absorption spectra (λprobe = 450 – 750 nm) from Au/p-GaN heterostructures cut at 350 fs.
Extended Data Fig. 5 Power-dependent pump-probe studies of visible-light transient absorption spectroscopy from Au/Al2O3 heterostructures.
a, Power-dependent dynamics of the transient bleach at 550 nm from 100 μW to 400 μW pump power. b, Power-dependent differential transient absorption spectra (λprobe = 450 – 750 nm) from Au/p-GaN heterostructures cut at 350 fs.
Extended Data Fig. 6 Power-dependent pump-probe studies of visible-light transient absorption spectroscopy from Au/SiO2 heterostructures.
a, Power-dependent dynamics of the transient bleach at 586 nm from 100 μW to 400 μW pump power. b, Power-dependent differential transient absorption spectra (λprobe = 450 – 750 nm) from Au/SiO2 heterostructures cut at 370 fs.
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Tagliabue, G., DuChene, J.S., Abdellah, M. et al. Ultrafast hot-hole injection modifies hot-electron dynamics in Au/p-GaN heterostructures. Nat. Mater. 19, 1312–1318 (2020). https://doi.org/10.1038/s41563-020-0737-1
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