Quantum-mechanical effects in photoluminescence from thin crystalline gold films

Alan R. Bowman; Alvaro Rodríguez Echarri; Fatemeh Kiani; Fadil Iyikanat; Ted V. Tsoulos; Joel D. Cox; Ravishankar Sundararaman; F. Javier García de Abajo; Giulia Tagliabue

doi:10.1038/s41377-024-01408-2

Your Location：

Home >

Browse articles >

Quantum-mechanical effects in photoluminescence from thin crystalline gold films

Article

- Quantum-mechanical effects in photoluminescence from thin crystalline gold films
- Light: Science & Applications Vol. 13, Issue 4, Pages: 783-794(2024)
- Affiliations：
- Author bio：
  
  jgiulia.tagliabue@epfl.ch
- Funds：
- DOI：10.1038/s41377-024-01408-2
  CLC：
- Received：13 October 2023，
  
  Revised：01 February 2024，
  
  Accepted：2024-02-06，
  
  Published Online：19 April 2024，
  
  Published：2024-12
- Accepted：
Scan QR Code
Alan R. Bowman, Alvaro Rodríguez Echarri, Fatemeh Kiani, et al. Quantum-mechanical effects in photoluminescence from thin crystalline gold films[J]. Light: science & applications, 2024, 13(4): 783-794.
DOI：

Alan R. Bowman, Alvaro Rodríguez Echarri, Fatemeh Kiani, et al. Quantum-mechanical effects in photoluminescence from thin crystalline gold films[J]. Light: science & applications, 2024, 13(4): 783-794. DOI： 10.1038/s41377-024-01408-2.

摘要

Abstract

Luminescence constitutes a unique source of insight into hot carrier processes in metals

including those in plasmonic nanostructures used for sensing and energy applications. However

being weak in nature

metal luminescence remains poorly understood

its microscopic origin strongly debated

and its potential for unraveling nanoscale carrier dynamics largely unexploited. Here

we reveal quantum-mechanical effects in the luminescence emanating from thin monocrystalline gold flakes. Specifically

we present experimental evidence

supported by first-principles simulations

to demonstrate its photoluminescence origin (i.e.

radiative emission from electron/hole recombination) when exciting in the interband regime. Our model allows us to identify changes to the measured gold luminescence due to quantum-mechanical effects as the gold film thickness is reduced. Excitingly

such effects are observable in the luminescence signal from flakes up to 40 nm in thickness

associated with the out-of-plane discreteness of the electronic band structure near the Fermi level. We qualitatively reproduce the observations with first-principles modeling

thus establishing a unified description of luminescence in gold monocrystalline flakes and enabling its widespread application as a probe of carrier dynamics and light-matter interactions in this material. Our study paves the way for future explorations of hot carriers and charge-transfer dynamics in a multitude of material systems.

This work studies luminescence from monocrystalline gold flakes down to 13 nm thick. It reveals this signal is photoluminescence

with signals reproduced by density functional theory

resolving a decade-old puzzle.

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=70084846&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=70084846&type=small

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=70084846&type=middle

关键词

Keywords

references

Newton, E. H. A History of Luminescence: From the Earliest Times Until 1900. (Philadelphia: American Philosophical Society, 1957).

A.G. Wintle , Fifty years of luminescence dating . Archaeometry 50 , 276 - 312 ( 2008 ). http://doi.org/10.1111/j.1475-4754.2008.00392.x http://doi.org/10.1111/j.1475-4754.2008.00392.x

G.D. Gilliland , Photoluminescence spectroscopy of crystalline semiconductors . Mater. Sci. Eng.: R: Rep. 18 , 99 - 399 ( 1997 ). http://doi.org/10.1016/S0927-796X(96)00195-7 http://doi.org/10.1016/S0927-796X(96)00195-7

M. Stolterfoht et al. , Visualization and suppression of interfacial recombination for high-efficiency large-area pin perovskite solar cells . Nat. Energy 3 , 847 - 854 ( 2018 ). http://doi.org/10.1038/s41560-018-0219-8 http://doi.org/10.1038/s41560-018-0219-8

N. Heidary , K.H. Ly , N. Kornienko , Probing CO 2 conversion chemistry on nanostructured surfaces with operando vibrational spectroscopy . Nano Lett. 19 , 4817 - 4826 ( 2019 ). http://doi.org/10.1021/acs.nanolett.9b01582 http://doi.org/10.1021/acs.nanolett.9b01582

A. Mooradian , Photoluminescence of metals . Phys. Rev. Lett. 22 , 185 - 187 ( 1969 ). http://doi.org/10.1103/PhysRevLett.22.185 http://doi.org/10.1103/PhysRevLett.22.185

H. Altug et al. , Advances and applications of nanophotonic biosensors . Nat. Nanotechnol. 17 , 5 - 16 ( 2022 ). http://doi.org/10.1038/s41565-021-01045-5 http://doi.org/10.1038/s41565-021-01045-5

A.K. Sharma , C. Marques , Design and performance perspectives on fiber optic sensors with plasmonic nanostructures and gratings: a review . IEEE Sens. J. 19 , 7168 - 7178 ( 2019 ). http://doi.org/10.1109/JSEN.2019.2915274 http://doi.org/10.1109/JSEN.2019.2915274

E. Cortés et al. , Challenges in plasmonic catalysis . ACS Nano 14 , 16202 - 16219 ( 2020 ). http://doi.org/10.1021/acsnano.0c08773 http://doi.org/10.1021/acsnano.0c08773

M. Magdy , A conceptual overview of surface-enhanced Raman scattering (SERS) . Plasmonics 18 , 803 - 809 ( 2023 ). http://doi.org/10.1007/s11468-023-01807-y http://doi.org/10.1007/s11468-023-01807-y

D.J. de Aberasturi , A.B. Serrano-Montes , L.M. Liz-Marzán , Modern applications of plasmonic nanoparticles: from energy to health . Adv. Opt. Mater. 3 , 602 - 617 ( 2015 ). http://doi.org/10.1002/adom.201500053 http://doi.org/10.1002/adom.201500053

A. Rodríguez Echarri et al. , Nonlinear photoluminescence in gold thin films . ACS Photon. 10 , 2918 - 2929 ( 2023 ). http://doi.org/10.1021/acsphotonics.3c00644 http://doi.org/10.1021/acsphotonics.3c00644

S. Großmann et al. , Nonclassical optical properties of mesoscopic gold . Phys. Rev. Lett. 122 , 246802 ( 2019 ). http://doi.org/10.1103/PhysRevLett.122.246802 http://doi.org/10.1103/PhysRevLett.122.246802

A. Tcherniak et al. , One-photon plasmon luminescence and its application to correlation spectroscopy as a probe for rotational and translational dynamics of gold nanorods . J. Phys. Chem. C 115 , 15938 - 15949 ( 2011 ). http://doi.org/10.1021/jp206203s http://doi.org/10.1021/jp206203s

Y. Sivan et al. , Crossover from nonthermal to thermal photoluminescence from metals excited by ultrashort light pulses . ACS Nano 17 , 11439 - 11453 ( 2023 ). http://doi.org/10.1021/acsnano.3c01016 http://doi.org/10.1021/acsnano.3c01016

M.R. Beversluis , A. Bouhelier , L. Novotny , Continuum generation from single gold nanostructures through near-field mediated intraband transitions . Phys. Rev. B 68 , 115433 ( 2003 ). http://doi.org/10.1103/PhysRevB.68.115433 http://doi.org/10.1103/PhysRevB.68.115433

Y.Y. Cai et al. , Photoluminescence of gold nanorods: purcell effect enhanced emission from hot carriers . ACS Nano 12 , 976 - 985 ( 2018 ). http://doi.org/10.1021/acsnano.7b07402 http://doi.org/10.1021/acsnano.7b07402

Y.Y. Cai et al. , Anti-stokes emission from hot carriers in gold nanorods . Nano Lett. 19 , 1067 - 1073 ( 2019 ). http://doi.org/10.1021/acs.nanolett.8b04359 http://doi.org/10.1021/acs.nanolett.8b04359

T. Jollans et al. , Effective electron temperature measurement using time-resolved anti-stokes photoluminescence . J. Phys. Chem. A 124 , 6968 - 6976 ( 2020 ). http://doi.org/10.1021/acs.jpca.0c06671 http://doi.org/10.1021/acs.jpca.0c06671

M. Barella et al. , In situ photothermal response of single gold nanoparticles through hyperspectral imaging anti-stokes thermometry . ACS Nano 15 , 2458 - 2467 ( 2021 ). http://doi.org/10.1021/acsnano.0c06185 http://doi.org/10.1021/acsnano.0c06185

A. Carattino , M. Caldarola , M. Orrit , Gold nanoparticles as absolute nanothermometers . Nano Lett. 18 , 874 - 880 ( 2018 ). http://doi.org/10.1021/acs.nanolett.7b04145 http://doi.org/10.1021/acs.nanolett.7b04145

W. Chen et al. , Intrinsic luminescence blinking from plasmonic nanojunctions . Nat. Commun. 12 ,( 2021 ). http://doi.org/10.1038/s41467-021-22679-y http://doi.org/10.1038/s41467-021-22679-y

G.W. Lu et al. , Plasmonic sensing via photoluminescence of individual gold nanorod . J. Phys. Chem. C 116 , 25509 - 25516 ( 2012 ). http://doi.org/10.1021/jp309450b http://doi.org/10.1021/jp309450b

E. Pensa et al. , Spectral screening of the energy of hot holes over a particle plasmon resonance . Nano Letters 19 , 1867 - 1874 ( 2019 ). http://doi.org/10.1021/acs.nanolett.8b04950 http://doi.org/10.1021/acs.nanolett.8b04950

S.A. Lee et al. , Spectroscopic signatures of plasmon-induced charge transfer in gold nanorods . J. Chem. Phys. 156 , 064702 ( 2022 ). http://doi.org/10.1063/5.0078621 http://doi.org/10.1063/5.0078621

P.Y. Yu et al. , Resonance Raman scattering at the forbidden yellow exciton in Cu 2 O . Phys. Rev. Lett. 30 , 283 - 286 ( 1973 ). http://doi.org/10.1103/PhysRevLett.30.283 http://doi.org/10.1103/PhysRevLett.30.283

M.V. Klein , Equivalence of resonance Raman scattering in solids with absorption followed by luminescence . Phys. Rev. B 8 , 919 - 921 ( 1973 ). http://doi.org/10.1103/PhysRevB.8.919 http://doi.org/10.1103/PhysRevB.8.919

J.R. Solin , H. Merkelo , Resonant scattering or absorption followed by emission . Phys. Rev. B 12 , 624 - 629 ( 1975 ). http://doi.org/10.1103/PhysRevB.12.624 http://doi.org/10.1103/PhysRevB.12.624

J.T. Hugall , J.J. Baumberg , Demonstrating photoluminescence from Au is electronic inelastic light scattering of a plasmonic metal: the origin of SERS backgrounds . Nano Lett. 15 , 2600 - 2604 ( 2015 ). http://doi.org/10.1021/acs.nanolett.5b00146 http://doi.org/10.1021/acs.nanolett.5b00146

S.X. Wu et al. , The connection between plasmon decay dynamics and the surface enhanced Raman spectroscopy background: inelastic scattering from non-thermal and hot carriers . J. Appl. Phys. 129 , 173103 ( 2021 ). http://doi.org/10.1063/5.0032763 http://doi.org/10.1063/5.0032763

J. Mertens et al. , How light is emitted by plasmonic metals . Nano Letters 17 , 2568 - 2574 ( 2017 ). http://doi.org/10.1021/acs.nanolett.7b00332 http://doi.org/10.1021/acs.nanolett.7b00332

D. Huang et al. , Photoluminescence of a plasmonic molecule . ACS Nano 9 , 7072 - 7079 ( 2015 ). http://doi.org/10.1021/acsnano.5b01634 http://doi.org/10.1021/acsnano.5b01634

K.Q. Lin et al. , Intraband Hot-electron photoluminescence from single silver nanorods . ACS Photon. 3 , 1248 - 1255 ( 2016 ). http://doi.org/10.1021/acsphotonics.6b00238 http://doi.org/10.1021/acsphotonics.6b00238

Y.Y. Cai et al. , Light emission from plasmonic nanostructures . J. Chem. Phys. 155 , 060901 ( 2021 ). http://doi.org/10.1063/5.0053320 http://doi.org/10.1063/5.0053320

M. Yorulmaz et al. , Luminescence quantum yield of single gold nanorods . Nano Lett. 12 , 4385 - 4391 ( 2012 ). http://doi.org/10.1021/nl302196a http://doi.org/10.1021/nl302196a

T. Fröhlich , C. Schönenberger , M. Calame , Additional peak appearing in the one-photon luminescence of single gold nanorods . Opt. Lett. 41 , 1325 - 1328 ( 2016 ). http://doi.org/10.1364/OL.41.001325 http://doi.org/10.1364/OL.41.001325

C. Lumdee , B.F. Yun , P.G. Kik , Gap-plasmon enhanced gold nanoparticle photoluminescence . ACS Photon. 1 , 1224 - 1230 ( 2014 ). http://doi.org/10.1021/ph500304v http://doi.org/10.1021/ph500304v

L. Khriachtchev , L. Heikkilä , T. Kuusela , Red photoluminescence of gold island films . Appl. Phys. Lett. 78 , 1994 - 1996 ( 2001 ). http://doi.org/10.1063/1.1359491 http://doi.org/10.1063/1.1359491

T.V. Shahbazyan , Theory of plasmon-enhanced metal photoluminescence . Nano Lett. 13 , 194 - 198 ( 2013 ). http://doi.org/10.1021/nl303851z http://doi.org/10.1021/nl303851z

G. Baffou , Anti-stokes thermometry in nanoplasmonics . ACS Nano 15 , 5785 - 5792 ( 2021 ). http://doi.org/10.1021/acsnano.1c01112 http://doi.org/10.1021/acsnano.1c01112

F. Kiani , G. Tagliabue , High aspect ratio au microflakes via gap-assisted synthesis . Chem. Mater. 34 , 1278 - 1288 ( 2022 ). http://doi.org/10.1021/acs.chemmater.1c03908 http://doi.org/10.1021/acs.chemmater.1c03908

F.J. García de Abajo , Colloquium : light scattering by particle and hole arrays . Rev. Mod. Phys. 79 , 1267 - 1290 ( 2007 ). http://doi.org/10.1103/RevModPhys.79.1267 http://doi.org/10.1103/RevModPhys.79.1267

PHASIS. Epitaxial gold Au(111) thin film grown on mica substrate. https://www.phasis.ch/products/epitaxial-gold-au-111 https://www.phasis.ch/products/epitaxial-gold-au-111 (accessed on 22/01/2024).

F. Wackenhut , A.V. Failla , A.J. Meixner , Multicolor microscopy and spectroscopy reveals the physics of the one-photon luminescence in gold nanorods . J. Phys. Chem. C 117 , 17870 - 17877 ( 2013 ). http://doi.org/10.1021/jp407353r http://doi.org/10.1021/jp407353r

O.P. Varnavski et al. , Femtosecond excitation dynamics in gold nanospheres and nanorods . Phys. Rev. B 72 , 235405 ( 2005 ). http://doi.org/10.1103/PhysRevB.72.235405 http://doi.org/10.1103/PhysRevB.72.235405

S.A. Lee et al. , D -Band hole dynamics in gold nanoparticles measured with time-resolved emission upconversion microscopy . Nano Lett. 23 , 3501 - 3506 ( 2023 ). http://doi.org/10.1021/acs.nanolett.3c00622 http://doi.org/10.1021/acs.nanolett.3c00622

E. Dulkeith et al. , Plasmon emission in photoexcited gold nanoparticles . Phys. Rev. B 70 , 205424 ( 2004 ). http://doi.org/10.1103/PhysRevB.70.205424 http://doi.org/10.1103/PhysRevB.70.205424

A.R. Bowman et al. , Extracting decay-rate ratios from photoluminescence quantum efficiency measurements in optoelectronic semiconductors . Phys. Rev. Appl. 17 , 044026 ( 2022 ). http://doi.org/10.1103/PhysRevApplied.17.044026 http://doi.org/10.1103/PhysRevApplied.17.044026

L.A. Blanco , F.J. García de Abajo , Spontaneous light emission in complex nanostructures . Phys. Rev. B 69 , 205414 ( 2004 ). http://doi.org/10.1103/PhysRevB.69.205414 http://doi.org/10.1103/PhysRevB.69.205414

K.M. McPeak et al. , Plasmonic films can easily be better: rules and recipes . ACS Photon. 2 , 326 - 333 ( 2015 ). http://doi.org/10.1021/ph5004237 http://doi.org/10.1021/ph5004237

C. Cho et al. , Efficient vertical charge transport in polycrystalline halide perovskites revealed by four-dimensional tracking of charge carriers . Nat. Mater. 21 , 1388 - 1395 ( 2022 ). http://doi.org/10.1038/s41563-022-01395-y http://doi.org/10.1038/s41563-022-01395-y

A.M. Brown et al. , Nonradiative plasmon decay and hot carrier dynamics: effects of phonons, surfaces, and geometry . ACS Nano 10 , 957 - 966 ( 2016 ). http://doi.org/10.1021/acsnano.5b06199 http://doi.org/10.1021/acsnano.5b06199

P. Karna et al. , Direct measurement of ballistic and diffusive electron transport in gold . Nano Lett. 23 , 491 - 496 ( 2023 ). http://doi.org/10.1021/acs.nanolett.2c03781 http://doi.org/10.1021/acs.nanolett.2c03781

R. Sundararaman et al. , Theoretical predictions for hot-carrier generation from surface plasmon decay . Nat. Commun. 5 ,( 2014 ). http://doi.org/10.1038/ncomms6788 http://doi.org/10.1038/ncomms6788

A.M. Brown et al. , Ab initio phonon coupling and optical response of hot electrons in plasmonic metals . Phys. Rev. B 94 , 075120 ( 2016 ). http://doi.org/10.1103/PhysRevB.94.075120 http://doi.org/10.1103/PhysRevB.94.075120

A.M. Brown et al. , Experimental and ab initio ultrafast carrier dynamics in plasmonic nanoparticles . Phys. Rev. Lett. 118 , 087401 ( 2017 ). http://doi.org/10.1103/PhysRevLett.118.087401 http://doi.org/10.1103/PhysRevLett.118.087401

R. Sundararaman et al. , JDFTx: software for joint density-functional theory . SoftwareX 6 , 278 - 284 ( 2017 ). http://doi.org/10.1016/j.softx.2017.10.006 http://doi.org/10.1016/j.softx.2017.10.006

P. Würfel , The chemical potential of luminescent radiation . J. Phys. C: Solid State Phys. 15 , 3967 ( 1982 ). http://doi.org/10.1088/0022-3719/15/18/012 http://doi.org/10.1088/0022-3719/15/18/012

W. van Roosbroeck , W. Shockley , Photon-radiative recombination of electrons and holes in germanium . Phys. Rev. 94 , 1558 - 1560 ( 1954 ). http://doi.org/10.1103/PhysRev.94.1558 http://doi.org/10.1103/PhysRev.94.1558

A. Drezet , Description of spontaneous photon emission and local density of states in the presence of a lossy polaritonic inhomogeneous medium . Phys. Rev. A 95 , 043844 ( 2017 ). http://doi.org/10.1103/PhysRevA.95.043844 http://doi.org/10.1103/PhysRevA.95.043844

P. Apell , R. Monreal , S. Lundqvist , Photoluminescence of noble metals . Phys. Scr. 38 , 174 - 179 ( 1988 ). http://doi.org/10.1088/0031-8949/38/2/012 http://doi.org/10.1088/0031-8949/38/2/012

Y. Sivan , Y. Dubi , Theory of “hot” photoluminescence from Drude metals . ACS Nano 15 , 8724 - 8732 ( 2021 ). http://doi.org/10.1021/acsnano.1c00835 http://doi.org/10.1021/acsnano.1c00835

B. Ostovar et al. , Increased intraband transitions in smaller gold nanorods enhance light emission . ACS Nano 14 , 15757 - 15765 ( 2020 ). http://doi.org/10.1021/acsnano.0c06771 http://doi.org/10.1021/acsnano.0c06771

M. Magnozzi et al. , Plasmonics of Au nanoparticles in a hot thermodynamic bath . Nanoscale 11 , 1140 - 1146 ( 2019 ). http://doi.org/10.1039/C8NR09038F http://doi.org/10.1039/C8NR09038F

P. Giannozzi et al. , QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials . J. Phys.: Condens. Matter 21 , 395502 ( 2009 ).

A. Marini et al. , Yambo: an ab initio tool for excited state calculations . Comput. Phys. Commun. 180 , 1392 - 1403 ( 2009 ). http://doi.org/10.1016/j.cpc.2009.02.003 http://doi.org/10.1016/j.cpc.2009.02.003

J.A. Kurvits , M.M. Jiang , R. Zia , Comparative analysis of imaging configurations and objectives for Fourier microscopy . J. Opt. Soc. Am. A 32 , 2082 ( 2015 ). http://doi.org/10.1364/JOSAA.32.002082 http://doi.org/10.1364/JOSAA.32.002082

K. Frohna et al. , Nanoscale chemical heterogeneity dominates the optoelectronic response of alloyed perovskite solar cells . Nat. Nanotechnol. 17 , 190 - 196 ( 2021 ). http://doi.org/10.1038/s41565-021-01019-7 http://doi.org/10.1038/s41565-021-01019-7

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

No data

Related Author

No data

Related Institution

No data

⁰