# Development of optical microsensors based on Surface Plasmon Resonance for gas measurement in atmosphere

Jerome Brunet

► To cite this version:

Jerome Brunet. Development of optical microsensors based on Surface Plasmon Resonance for gas measurement in atmosphere. SENSORS2023, SETCOR, Oct 2023, ALBUFEIRA, Portugal. hal-04262389

HAL Id: hal-04262389

https://hal.science/hal-04262389v1

Submitted on 27 Oct 2023

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Distributed under a Creative Commons CC BY 4.0 - Attribution - International License
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INSTITUT
PASCAL
sciences de l'ingénierie et des systèmes

UCA
UNIVERSITÉ
Clermont
Auvergne

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cnrs
dépasser les frontières

# Development of optical microsensors based on Surface Plasmon Resonance for gas measurement in atmosphere

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## Dr Jérôme BRUNET

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jerome.brunet@uca.fr

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+33 - 4 73 40 72 47

4 Avenue Blaise Pascal UMR 6602 UCA / CNRS / SIGMA 63178 AUBIERE Cedex FRANCE

http://www.institutpascal.uca.fr

anr

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agence nationale
de la recherche

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LABORATOIRE
HUBERT CURIEN

UMR CNRS 5516 - SAINT-ÉTIENNE

UNIVERSITÉ
DE LYON

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UNIVERSITÉ
JEAN MONNET
SAINT-ÉTIENNE

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silsef

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UNIVERSITÉ
Clermont Auvergne
# Air quality monitoring : a still relevant requirement

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Air pollution : 1st environnemental cause of morbidity

99% of worldwide people live in extra-polluted countries

6,7M of premature death /year link to indoor/outdoor polluted atmospheres

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World Health
Organization

International Agency
for Research on Cancer

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World Health
Organization

outdoor air pollution classified as carcinogenic to humans

Heavy metals
Pb, As, Ni, Cd...

Carbon
monoxyde
CO

Particle Matters
PM₁₀, PM₂.₅

Nitrogen
dioxyde
NO₂

Polycyclic Aromatic
hydrocarbons
PAHs

Hydrogène
sulphide
H₂S

Nitrogen
monoxyde
NO

Sulphur
dioxyde
SO₂

Ozone
O₃

Ammonia
NH₃

Volatils organic
Compounds
VOCs

European
Environment
Agency

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Special focus on
ammonia emissions
for the period 2020-2029

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UNIVERSITÉ
Clermont Auvergne
# Sensing strategies and metrological objectives

## Materials

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Organic

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Mineral

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Nanocarbons

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Hybrid

## Transducers

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Acoustic

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Conductimetric

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Electrochemical

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Plasmonic

## Sensor-systems

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Sensors

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Filters

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Methodologies

Phase Humidity
Pressure Temperature
Incidence Flow Wavelength
Polarization

Working conditions

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# Plasmonic transducer : working principle

## Surface Plasmon Resonance

Electron density wave at metal/dielectric interfaces induced by incidence light radiation in TM mode that leads to collective electron resonance

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## SPR conditions

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M. Couture et al., Physical Chemistry Chemical Physics, 2013

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(a) Otto configuration, (b) Kretschmann configuration,

(c) a diffraction grating, (d) evanescent field at the interface

D. Zhang et al., Sensors Vol.11. (2011)
# Plasmonic transducer : optical energy transfer mode

## Simulation vs measurement

<figure><img src="image_49.png" /><figcaption>d = grating depth
λ = incident wavelength</figcaption></figure>

<figure><img src="image_50.png" /><figcaption>Λ = period
θᵢ = incidence angle</figcaption></figure>

## Modulation of energy transfer by gas adsorption

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# Suitability of phthalocyanines for SPR sensors

## Low optical absorption @ λ>800nm

<figure><img src="image_52.png" /><figcaption>Optical properties of CuPc</figcaption></figure>

## Optical properties modulated by gas adsorption

<figure><img src="image_53.png" /><figcaption>Fig. 2. Schematic diagram of the SPR measurement system.</figcaption></figure>

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<figure><img src="image_55.png" /><figcaption>Fig. 8. Time response of reflectivity for exposure to 180 vol.ppm NO<sub>2</sub>.</figcaption></figure>

## Low intrinsic conductivity

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Thin dielectric behavior

## Easy thin film processing

<figure><img src="image_57.png" /><figcaption>Drop-casting</figcaption></figure>

<figure><img src="image_58.png" /><figcaption>Langmuir-Blodgett</figcaption></figure>

Good thickness control

<figure><img src="image_59.png" /><figcaption>Thermal evaporation</figcaption></figure>
# Plasmonic sensor : elaboration and replication

<figure><img src="image_60.png" /><figcaption>## Grating elaboration by interference lithography</figcaption></figure>

<figure><img src="image_61.png" /><figcaption>## Replication by embossing process</figcaption></figure>

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# Structural and morphological characteristics of SPR sensors

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<figure><img src="image_68.png" /><figcaption>Frequency [µm⁻¹]</figcaption></figure>

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## Optical properties of CuPc

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Experimental setup for pollutant exposure

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Atmospheric air

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Typical response of SPR sensor to gas

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Cr₃nm/Au₁₄₀nm/CuPc₃₅nm

Pollutant exposure

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**Mechanism interpretation**

Gas adsorption

→ Modulation of n

→ modulation of energy transfer
Metrological performances of SPR sensors to NO₂

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$$ \text{Sensitivity S} = 0,6 \text{ mV.ppm}^{-1} $$

$$ \text{Noise } \sigma \approx 1 \text{ mV} $$

$$ \Rightarrow \text{LOD} = 3\sigma/S \approx 5\text{ppm} $$
Sensing performances of SPR sensors to NO

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NO generation

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NO₂ production

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Sensing behavior of SPR sensors vs NH₃

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Cr₃nm/Au₁₄₀nm/CuPc₅₀nm

Differential signal (mV)

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Concentration (ppm)

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Sensitivity S = 2 mV.ppm⁻¹

Noise σ ≈ 1 mV

⇒ LOD ≈ 2ppm

LOD < exposure limits (PEL, TRL, REL...)
## Sensing performances to NH₃

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Systematic recalibration before new exposure

Correction of baseline drifts

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## Repeatability @ room temperature

⇒ resolution ≈ 20ppm
# Conclusions and outlooks

* Potentialities of SPR microsensors for air pollutants monitoring established

<table><thead><tr><th>Pollutant</th><th>Δsignal @ 30 ppm</th><th>LOD (ppm)</th></tr></thead><tbody><tr><td></td><td>18mV</td><td>5</td></tr><tr><td></td><td>160mV</td><td>Few ppm</td></tr><tr><td></td><td>68mV</td><td>2</td></tr><tr><td></td><td>80mV</td><td>&lt; 20ppm</td></tr><tr><td></td><td colspan="2">Too noisy to be determined</td></tr></tbody></table>

Nature of the functional layer

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Target gas

Ongoing project

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* Key role of transducer for the discrimination of air pollutants in atmosphere

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Detector 0

Detector 1

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Reducing pollutants

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Oxidizing pollutants

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BTEX

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UNIVERSITÉ
Clermont Auvergne
Acknowledgements

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silsef

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Environnement S.A

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And now...

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