1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
Theoretical calculations
The electronic structures of CuS were computed using the extended
Hückel theory41 with the parameters provided in YAeHMOP42. The
Brillouin zone was sampled with 405 k-points selected based on the
method of Ramirez and Böhm43. The extended Hückel theory was
employed instead of the density functional theory (DFT). This is
because the DFT calculations of CuS resulted in a zero-energy gap near
the Fermi level44, although the 400-nm light is known to induce the
bandgap excitation experimentally. The DFT + U calculations
also yielded a significantly small energy gap (~0.2 eV) in comparison
with the 400-nm light44. These indicate that DFT cannot reproduce
the experimental observation. Moreover, the extended Hückel
theory describes the band structure well, consistent with the
experiments.
Nature Communications | (2023)14:4471
15.
16.
17.
18.
19.
Faraday, M. X. The Bakerian lecture: experimental relations of gold
(and other metals) to light. Philos. Trans. R. Soc. Lond. 147,
145–181 (1857).
Fusella, M. A. et al. Plasmonic enhancement of stability and
brightness in organic light-emitting devices. Nature 585,
379–382 (2020).
Brongersma, M. L., Halas, N. J. & Nordlander, P. Plasmon-induced
hot carrier science and technology. Nat. Nanotechnol. 10,
25–34 (2015).
Sytwu, K. et al. Driving energetically unfavourable dehydrogenation
dynamics with plasmonics. Science 371, 280–283 (2021).
Naldoni, A., Shalaev, V. M. & Brongersma, M. L. Applying plasmonics to a sustainable future. Science 356, 908–909 (2017).
Mueller, N. S. et al. Deep strong light–matter coupling in plasmonic
nanoparticle crystals. Nature 583, 780–784 (2020).
Bloch, J., Cavalleri, A., Galitski, V., Hafezi, M. & Rubio, A. Strongly
correlated electron–photon systems. Nature 606, 41–48 (2022).
Basov, D. N., Averitt, R. D. & Hsieh, D. Towards properties on
demand in quantum materials. Nat. Mater. 16, 1077–1088 (2017).
Lei, D. Y. et al. Optically-triggered nanoscale memory effect in a
hybrid plasmonic-phase changing nanostructure. ACS Photonics 2,
1306–1313 (2015).
Schumacher, L. et al. Precision plasmonics with monomers and
dimers of spherical gold nanoparticles: nonequilibrium dynamics at
the time and space limits. J. Phys. Chem. C. 123, 13181–13191 (2019).
Wang, Y. et al. In situ investigation of ultrafast dynamics of hot
electron-driven photocatalysis in plasmon-resonant grating structures. J. Am. Chem. Soc. 144, 3517–3526 (2022).
Ligges, M. et al. Observation of ultrafast lattice heating using time
resolved electron diffraction. Appl. Phys. Lett. 94, 101910 (2009).
Devkota, T., Brown, B. S., Beane, G., Yu, K. & Hartland, G. V. Making
waves: radiation damping in metallic nanostructures. J. Chem. Phys.
151, 080901 (2019).
Hu, M. et al. Vibrational response of nanorods to ultrafast laser
induced heating: theoretical and experimental analysis. J. Am.
Chem. Soc. 125, 14925–14933 (2003).
Sakamoto, M. et al. Clear and transparent nanocrystals for infraredresponsive carrier transfer. Nat. Commun. 10, 406 (2019).
Luther, J. M., Jain, P. K., Ewers, T. & Alivisatos, A. P. Localized surface
plasmon resonances arising from free carriers in doped quantum
dots. Nat. Mater. 10, 361–366 (2011).
Lian, Z. et al. Near infrared light induced plasmonic hot hole transfer
at a nano-heterointerface. Nat. Commun. 9, 2314 (2018).
Goel, S., Chen, F. & Cai, W. Synthesis and biomedical applications
of copper sulfide nanoparticles: from sensors to theranostics. Small
10, 631–645 (2014).
Xie, Y. et al. Metallic-like stoichiometric copper sulfide nanocrystals: phase- and shape-selective synthesis, near-infrared surface
Article
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
plasmon resonance properties, and their modeling. ACS Nano 7,
7352–7369 (2013).
Ma, G. et al. Self-assembly of copper sulfide nanoparticles into
nanoribbons with continuous crystallinity. ACS Nano 7,
9010–9018 (2013).
Ludwig, J. et al. Ultrafast hole trapping and relaxation dynamics in
p-Type CuS nanodisks. J. Phys. Chem. Lett. 6, 2671–2675 (2015).
Gehring, G. A. & Gehring, K. A. Co-operative Jahn-Teller effects.
Rep. Prog. Phys. 38, 1–89 (1975).
Bersuker, I. B. & Polinger, V. Z. Vibronic Interactions in Molecules
and Crystals (Springer-Verlag, 1989).
Hada, M., Nishina, Y. & Kato, T. Exploring structures and dynamics of
molecular assemblies: ultrafast time-resolved electron diffraction
measurements. Acc. Chem. Res. 54, 731–743 (2021).
Rini, M. et al. Control of the electronic phase of a manganite
by mode-selective vibrational excitation. Nature 449, 72–74
(2007).
Eichberger, M. et al. Snapshots of cooperative atomic motions in
the optical suppression of charge density waves. Nature 468,
799–802 (2010).
Fiebig, M., Miyano, K., Tomioka, Y. & Tokura, Y. Visualization of the
local insulator-metal transition in Pr0.7Ca0. 3MnO3. Science 280,
1925–1928 (1998).
Ohmasa, M., Suzuki, M. & Takéuchi, Y. A refinement of the crystal
structure of covellite, CuS. Mineral. J. 8, 311–319 (1977).
Ishikawa, T. et al. Direct observation of collective modes coupled to
molecular orbital–driven charge transfer. Science 350,
1501–1505 (2015).
Hada, M. et al. Bandgap modulation in photoexcited topological
insulator Bi2Te3 via atomic displacements. J. Chem. Phys. 145,
024504 (2016).
Park, D.-W. et al. Fabrication and utility of a transparent graphene
neural electrode array for electrophysiology, in vivo imaging, and
optogenetics. Nat. Protoc. 11, 2201–2222 (2016).
Ceulemans, A. & Vanquickenborne, L. G. The epikernel principle.
Struct. Bond 71, 125–159 (1989).
Li, Q., van de Groep, J., Wang, Y., Kik, P. G. & Brongersma, M. L.
Transparent multispectral photodetectors mimicking the human
visual system. Nat. Commun. 10, 4982 (2019).
Hartland, G. V., Besteiro, L. V., Johns, P. & Govorov, A. O. What’s so
hot about electrons in metal nanoparticles. ACS Energy Lett. 2,
1641–1653 (2017).
Guzelturk, B. et al. Dynamic lattice distortions driven by surface
trapping in semiconductor nanocrystals. Nat. Commun. 12,
1860 (2021).
Krawcyzk, K. M. et al. Anisotropic, nonthermal lattice disordering
observed in photoexcited PbS quantum dots. J. Phys. Chem. C. 125,
22120–22132 (2021).
Kato, T., Haruta, N. & Sato, T. Vibronic Coupling Density. (Springer
Nature, 2021).
Guzmán-Verri, G. G., Brierley, R. T. & Littlewood, P. B. Cooperative
elastic fluctuations provide tuning of the metal-insulator transition.
Nature 576, 429–432 (2019).
Fausti, D. et al. Light-Induced superconductivity in a stripe-ordered
cuprate. Science 331, 189–191 (2011).
Momma, K. & Izumi, F. VESTA 3 for three-dimensional visualization
of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44,
1272–1276 (2011).
Hoffmann, R. An extended Hückel theory. I. hydrocarbons. J. Chem.
Phys. 39, 1397–1412 (1963).
Landrum, G. & Glassey W. Yet Another Extended Hückel Molecular
Orbital Package (YAeHMOP) http://yaehmop.sourceforge.net.
Nature Communications | (2023)14:4471
https://doi.org/10.1038/s41467-023-40153-9
43. Ramirez, R. & Böhm, M. C. Asymmetric units and weighting factors
for numerical integration procedures in any crystal symmetry. Int. J.
Quantum Chem. 34, 571–594 (1988).
44. Morales-García, A., Soares, A. L., Dos Santos, E. C., de Abreu, H. A. &
Duarte, H. A. First-principles calculations and electron density
topological analysis of covellite (CuS). J. Phys. Chem. A 118,
5823–5831 (2014).
45. Link, S. & El-Sayed, M. A. Optical properties and ultrafast dynamics
of metallic nanocrystals. Annu. Rev. Phys. Chem. 54,
331–366 (2003).
46. Hartland, G. V. Coherent excitation of vibrational modes in metallic
nanoparticles. Annu. Rev. Phys. Chem. 57, 403–430 (2006).
Acknowledgements
The temperature-dependent XRD experiments were conducted at the
BL5S2 of Aichi Synchrotron Radiation Center, Aichi Science & Technology Foundation, Aichi, Japan (Proposal No. 202206170). M.S. is
grateful to Tetsuri Nishikawa, Hiroki Morishita, and Norikazu Mizuochi
for Hall measurements, Keito Sano for XRD measurement, Hsu Shihchen for sample preparation and M.H. is grateful to Yuri Saida, Yui
Iwasaki, Shin Ueno, and Wataru Yajima for experimental assistance.
M.S. and M.H. are grateful to Satoshi Ohmura for fruitful discussions.
F.U. is grateful to Dr. Ayako Hashimoto at NIMS for supporting the lightirradiation TEM experiment. This work was supported by the ‘Joint
Usage/Research Program on Zero-Emission Energy Research’ of the
Institute of Advanced Energy, Kyoto University (ZE2020C-8), NIMS
Electron Microscopy Analysis Station, Nanostructural Characterisation
Group, and JSPS KAKENHI Grant Numbers: JP22K05253 in Scientific
Research (C) (T.S.), JP21H04638 in Scientific Research (A) (M.S.),
JP20H01832 in Scientific Research (B) (M.H.), and JP20H04657 in
Scientific Research on Innovative Areas (M.H.). This work was also
supported by the JST FOREST Program (Grant Number JPMJFR201M,
JPMJFR211V) (M.S., M.H.), the Adaptable and Seamless Technology
transfer Program through Target-driven R&D (A-STEP): JST Grant
Number JPMJTR20T1 (M.S.), and the Ministry of Education, Culture,
Sports, Science and Technology (MEXT) Program for Development of
Environmental Technology using Nanotechnology (Global Research
Center for Environment and Energy Based on Nanomaterials Science)
(F.U.). A part of this work was supported by NIMS microstructural
characterization platform as a program of ‘Nanotechnology Platform’
of MEXT Grant Number: JPMXP09A21NM0083 (F.U.). Numerical calculations were carried out using the Supercomputer System of the
Institute for Chemical Research, Kyoto University, Academic Center for
Computing and Media Studies (ACCMS), Kyoto University, and the
Research Centre for Computational Science, Okazaki (Project: 22IMS-C065).
Author contributions
M.S. conceived the concept of this work and designed the all experiments and carried out material fabrication and device application. M.H.
carried out the time-resolved electron diffraction measurement, and
shadow imaging experiments. F.U. carried out the electron diffraction
measurement in TEM with and without light irradiation and simulation of
atomic displacement. T.S. and W.O. carried out the theoretical calculations. M.S. wrote the manuscript. All authors participated in the discussion of the research.
Competing interests
The authors declare no competing interests.
Article
Additional information
Supplementary information The online version contains
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Correspondence and requests for materials should be addressed to
Masanori Sakamoto or Masaki Hada.
Peer review information Nature Communications thanks R. J. Dwayne
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