# Laser-matter interactions and modern nanotechnology

Tatiana Itina

► To cite this version:

Tatiana Itina. Laser-matter interactions and modern nanotechnology: IAAM invited fellow lecture. Baltic Conference Series, IAAM (International Association of Advanced Materials), IAAM, Aug 2023, Stockholm, Sweden, Sweden. ujm-04217378

HAL Id: ujm-04217378

https://ujm.hal.science/ujm-04217378

Submitted on 25 Sep 2023

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# Laser-Matter Interactions and Modern Nanotechnology

## Tatiana E. ITINA

Laboratoire Hubert Curien, UMR CNRS 5516, Saint-Etienne, France
tatiana.itina@univ-st-etienne.fr

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From experiments to simulations,
from fundamental research to applications
# Nanoparticles and Nanocomposites

<figure><img src="image_7.png" /><figcaption>## Car industry</figcaption></figure>

<figure><img src="image_8.png" /><figcaption>## Aerospace and Defense</figcaption></figure>

<figure><img src="image_9.png" /><figcaption>## Optics and security</figcaption></figure>

<figure><img src="image_10.png" /><figcaption>## Sensors and Catalysis</figcaption></figure>

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# Laser Interactions

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In gas or in vacuum with different geometry

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In liquids or in the presence of colloids

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## Laser interaction commonly involve:

* Energy propagation, electronic excitation, light scattering, reflection and absorption

* Electron-phonon relaxation, heat diffusion, pressure wave propagation, rarefaction and tensile stress, phase transitions, mechanical fragmentation

* Material removal (ablation), plasma plume expansion, reactions, clustering, etc...

* Often multi-pulse irradiation is used with various scanning and focusing conditions

## Laser-induced nanoparticle formation

* Green synthesis methods, bio-compatibility

* Control over NP properties

* Scaling-up possibilities

* Possibility to create stable ultra-structures, nanoalloys, hybrids, etc.

* Additional laser-particle interactions involve many physical and chemical processes
Ultra-short Laser Interactions with NPs

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Propagation, absorption, local field enhancement

Local ionization and heating of the matter/liquid near
**plasma-mediated nanobubbles**

NP heating, heat transfer to the ambient medium
**thermo-mediated nanobubbles**

NP heating, melting, reshaping, sintering, evaporation

Electron ejection, injection in the ambient

NP fragmentation

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Hashimoto et al. J. PhotChem&PhotBiology (2012)

Thermo-mediated nanobubbles

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Plasma-mediated nanobubbles

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Lachaine et al. Photonics (2013)

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Strasser et al, J. Phys.Chem. C 118, 25748 (2014)
# Laser Fragmentation of NPs: MD simulations

<figure><img src="image_21.png" /><figcaption>R=50 Å, absorbed energy e=0.6 eV/mol.</figcaption></figure>

Smaller NPs

**Evaporation**

(can be also due to
Coulomb Explosion for
small clusters and fs
laser)

<figure><img src="image_22.png" /><figcaption>R=150 Å, absorbed energy e=0.6 eV/mol.</figcaption></figure>

Larger NPs

**Fragmentation due to**
**thermo-mechanical**
**effects**
# NP's Heating and Melting : Size Effects

## Melting and structural transformations: role of NP's sizes

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K. Zarschler et al. Nanomed-Nanotechnol 12, 1663-1701 (2016).

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E. Goudeli et al., AIChE 2015
Laser Energy Absorption vs NP's size

Absorption coefficient / efficiency
(beyond SPR for gold)

<figure><img src="image_26.png" /><figcaption>(a)</figcaption></figure>

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Generalized Mie theory=>

Red – Gold NPs in water

Black – Gold NPs in vacuum

peak in absorption at

R=R*~ 30 nm for Au NP in
water

<figure><img src="image_28.png" /><figcaption>(b)</figcaption></figure>

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Gold NPs in water for different
wavelength @300-800nm

peak position is shifted to
larger R=R* if wavelength rises
Experiments

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$$d_{P1} = (60 \pm 8)\text{nm}$$

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$$d_{P1} = (52 \pm 8)\text{nm}$$

$$d_{P2} = (3.5 \pm 1.4)\text{nm}$$

Werner et al. J. Phys. Chem. C, 2011, 115, 8503

Modeling

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Good correlation with
Experimental results
FeNP R=10 uc AuNP R = 20 uc

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Different sizes and species,
but the same temperatures

FeNP 1700+AuNP 1700

time

Time-evolution of energy

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* Simulation starts from a Janus configuration

* Then both particles are heated to the same temperature

* Then, the system is cooled down back to room temperature

Core-shells can be formed when one particle is much larger and is composed of a material with different cohesive energy

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E. Goudeli et al.,
AIChemE 2015
# Fragmentation vs Sintering, Additional Fragmentation

## Simulations starts from a larger janus AuCo NP, heating to 1700 K

AuCo, Au NP R = 40 un, rapidly heated up to 1700 K

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## Simulations starts from Alloy AuCo NP, R=40 uc rapid heating above Tc

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## Simulations starts from the fragmentation results, additional fragmentation takes place

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# Ion-impregnated Porous Thin Films Treated by Laser

- sol-gel mesoporous films are prepared and impregnated by saults

- these samples are then irradiated by laser

## Porous films:

SiO₂, TiO₂

Sol-gel synthesized
Porosity ~ 10%
Porous size 5-7 nm

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## Metallic NPs:

Ag, Au

Produced by soaking in metallic
salts solutions with consequent
reduction

Initial size < 3-5 nm

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## Laser irradiation:

CW
Nanosecond
Picosecond
Femtosecond

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Ion-impregnated porous glasses and semiconductors
can be used as samples for following laser-induced nano-structuring
# Au NPs in TiO₂ under Ultra-Short Laser Irradiation

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At the beginning, the matrix is solid

Y Andreeva et al.
The Journal of Physical Chemistry C
124 (18), 10209-10219, 2020

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fs laser
λ =515 nm

(a) Size distribution of gold NPs in before and after laser treatment.

(b) Calculated absorption efficiency of the nanocomposite based on TiO2 as a function of the diameter of gold NPs

(c) Calculated field distribution of gold nanoparticles in TiO2 (n=1.6) for spheres with the diameters of 50 and 90 nm.

(d) SEM images of the NPs produced in LS mode (F = 57 mJ/cm2, Vsc = 0:16 mm/s)ₜ₂
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Summary and Conclusions

* Laser is a very powerful and versatile tool suitable not only for laser ablation but also for nanoparticle synthesis.

* Particle size, composition, geometry, atomic masses, binding energies, excess energy, environment, heating/cooling protocol affect the results of laser interactions.

-NPs of smaller sizes easily melt and evaporate, while larger NPs behave more like bulk material, so that thermo-mechanical fragmentation of over-heated material plays a role in their fragmentation. Phase diagrams of NPs smaller than ~30-100 nm should account for NP's size.

-Fragmentation threshold of alloy nanoparticle strongly depends on their composition (excess energy).

-When different nanoparticles interact they may either sinter, mix or even be fragmented depending on their sizes and heating/cooling rate. To reach alloying without fragmentation NP should not be over-heated.

* Optical properties are strongly related to size and distribution of NPs after laser treatment, are controlled by laser processing parameters.