PhD Thesis proposal form
Discipline : Physics
Doctoral School : Waves and Matter (Ondes et Matière, EDOM, ED n°288)
Thesis subject title: Electron dynamics in hybrid layers of molecules interacting with nanoparticles
studied with ultrafast laser spectroscopy
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Laboratory name and web site: ISMO http://www.ismo.u-psud.fr/spip.php?rubrique64
 PhD supervisor (contact person):
 Name: Dr Bernard Bourguignon
 Position: Director of Research at CNRS
 email: bernard.bourguignon@u-psud.fr
 Phone number: +33 1 69 15 73 87
 Thesis proposal (max 1500 words):
Electronic coupling and electron transfer between molecules and nanoparticles, and
phenomena induced by them, are key processes in hot research areas such as molecular electronics
and heterogeneous catalysis. We use IR and visible femtosecond lasers to probe molecules adsorbed
on nanoparticles through sum frequency generation (SFG) vibrational spectroscopy. From
spectroscopy we get information on particle shape and site occupancy, and from pump probe
experiments we learn about electron flow between the substrate, the nanoparticles and the molecules,
and molecular processes like photodesorption [5]. These processes are studied as a function of
nanoparticle size and insulating layer thickness between the hybrid layer and the substrate. Recent
results [1] show that chemisorption varies with size, and reveal the effects of electron confinement
inside the nanoparticles. The next developments of our research will be to study molecules adsorbed
on ordered arrays of plasmonic nanoparticles : this opens new possibilities to build more complex
hybrid layers, and investigate a larger variety of coupling types.
 Publications of the laboratory in the field (max 5):
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1. Adsorption and femtosecond dynamics of CO molecules adsorbed on nanoparticles : Ahmed
Ghalgaoui, PhD thesis, University of Paris-Sud at Orsay (2012).
2. Non invasive vibrational SFG spectroscopy reveals that bacterial adhesion can alter the
conformation of graft chains on “brush” functionalized SAM surfaces. Emilie Bulard, Ziang Guo,
Wanquan Zheng, Henri Dubost, Marie-Pierre Fontaine-Aupart, Marie-Noëlle Bellon-Fontaine, JeanMarie Herry, Romain Briandet, Bernard Bourguignon, Langmuir 27 (2011) 4928.
3. Characterization of Thin MgO Films on Ag(001) by Low-Energy Electron Diffraction and Scanning
Tunneling Microscopy. A. Ouvrard, N. Niebauer, A. Ghalgaoui, C. Barth, C. R. Henry and B.
Bourguignon, J. Phys. Chem. C. 115 (2011) 8034.
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4. Deriving the complete molecular conformation of self assembled alkanethiol molecules from Sum
Frequency Generation vibrational spectra. B. Bourguignon, W. Zheng, S. Carrez, A. Ouvrard, F.
Fournier, H. Dubost, Phys. Rev. B 79 (2009) 125433 (DOI : 1103/PhysRevB.79.125433).
5. Vibrational dynamics of adsorbed molecules in the conditions of photodesorption : pump-probe
SFG spectra of CO / Pt(111). F. Fournier, W. Zheng, S. Carrez, H. Dubost, B. Bourguignon, J. Chem.
Phys. 121, 4839 (2004).
 Specific requirements to apply, if any : a degree in Physics or Chemistry or Material Science, and
interest in either the elaboration and understanding of hybrid layers of molecules and metallic
nanoparticles, or on ultrashort laser pulses and their applications.