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NanoLight – Benasque 2016
CCD
Holographic superlocalization of individual metal nanoparticles:
Electrochemical impacts tracking and near-field mapping
Vitor Brasiliense, Pascal Berto, Ariadna Martinez-Marrades, Catherine Combellas, Frederic Kanoufi, Gilles Tessier
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Small objects, moving in 3 dimensional way
Dark field imaging , holography
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dissolution
2. Imaging Optical Field Distribution
3. Tracking Electrochemical Impacts
Laser
BS
BS
EM-CCD
1. Holographic Superlocalization of NP
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Laser
BS
BS
EM-CCD
Holographic Superlocalization of NP
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Hologram
Laser @532 nm
BS
BS
EM-CCD FCCD
sample
Digital Holography
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M. Gross et M.Atlan, Opt. Lett. 32, 909 (2007)
Holographie
Digital Holography
x (µm) y (µm)
z (µm)
C.Batchelor-McAuley et al., Chem. Phys. Lett. , CP Letters 31938 (2014)
Laser @532 nm
BS
BS
EM-CCD FCCD
sample
1. FT 2. SF 4. (FT)-1
∙ 𝑒𝑖 𝑘𝑧𝑧
3. Z Propagation
Particle Detection
5. Thresholding
GPU
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Localization Precision
Localisation position histograms for still particles (Au, 50 nm)
TRANSVERSE AXIAL
Nb o
f o
ccu
rre
nces
Nb o
f o
ccu
rre
nces
For SNR ≈ 70 Lateral localization precision : 3 nm Vertical localization precision : 10 nm Large investigated volume : 100x100x30 mm
(adapted from Moerner et al.)
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Imaging Optical Field Distribution
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Near-field mapping from Gold Nanoparticles
A. Martinez-Marrades, J. Rupprecht , M. Gross , G.Tessier, Optics Express 22 29191 (2014)
36000 particle detections Large Volume reconstruction
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Near-field mapping from Gold Nanoparticles
A. Martinez-Marrades, J. Rupprecht , M. Gross , G.Tessier, Optics Express 22 29191 (2014)
For more details: See P. Berto in Poster Section
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Tracking Electrochemical Impacts
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Ag
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‘
- Partial oxidation? - Single Particle? - Agglomerate Single response?
Seeing with electrochemical eyes
But...
Electrode Surface
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Ultra Micro
Electrode
Spacer solution
inlet
outlet
prism >CE/Ref UME
Cover slip
10 mm
Designing a transparent electrode
A.Patel, A.Martinez-Marrades, V.Brasiliense, et al Nanoletters 22 29191 (2014)
V.Brasiliense, et al JACS (2016 accepted) DOI: 10.1021/jacs.5b13217
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Electrode
Ag
Ag+
Ag+
Ag+
Ag+
Direct particle Oxidation: Synchronized Charge Injection/Dissolution
In presence of NO3- :
Δ𝑡
A.Patel, A.Martinez-Marrades, V.Brasiliense, et al Nanoletters 22 29191 (2014)
op
tica
l
V.Brasiliense, et al JACS (2016 accepted) DOI: 10.1021/jacs.5b13217
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A.Patel, A.Martinez-Marrades, V.Brasiliense, et al Nanoletters 22 29191 (2014)
Direct particle Oxidation: Synchronized Charge Injection/Dissolution
-e- Ag+ Ag+
Ag+
Ag
V.Brasiliense, et al JACS (2016 accepted) DOI: 10.1021/jacs.5b13217
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Oxidation in a precipitating medium (KSCN): Uncoupled Charge Injection/Dissolution
No
rmal
ize
d O
pti
cal
Inte
nsi
ty
A.Patel, A.Martinez-Marrades, V.Brasiliense, et al Nanoletters 22 29191 (2014)
V.Brasiliense, et al JACS (2016 accepted) DOI: 10.1021/jacs.5b13217
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Oxidation in a precipitating medium (KSCN): Uncoupled Charge Injection/Dissolution
Electrode
e-
e- e- e-
Ag
Ag+
Ag+
Ag+
Ag+
In presence of SCN- :
AgSCN
-e-
Ag+ Ag+
Ag+
Ag
AgSCN
A.Patel, A.Martinez-Marrades, V.Brasiliense, et al Nanoletters 22 29191 (2014)
V.Brasiliense, et al JACS (2016 accepted) DOI: 10.1021/jacs.5b13217
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Laser
BS
BS
EM-CCD
-e-
Ag+ Ag+
Ag+
Ag
AgSCN
-e- Ag+ Ag+
Ag+
Ag
Conclusions
Lateral precision : 3 nm Vertical precision : 10 nm Investigated volume : 100x100x30 mm
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P. Berto R. Kuszelewicz A.Martinez
G. Tessier F. Kanoufi
Thank you!
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Interference pattern modulated at 4Hz
Heterodyne Hologram
Laser @785 nm
BS
BS
AOM1
80 MHz
+ DF
AOM2
80MHz
Δf=¼ fCCD
EM-CCD FCCD
sample
M. Gross et al., Opt. Lett. 32, 909 (2007)
Digital Heterodyne Holography
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Demodulated Hologram
d
Laser @785 nm
BS
BS
AOM1
80 MHz
+ DF
AOM2
80MHz
Δf=¼ fCCD
EM-CCD FCCD
sample
M. Gross et al., Opt. Lett. 32, 909 (2007)
Digital Heterodyne Holography
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1. FT 2. SF
(x,y,z, Intensity) for different particles at different times, Several hundred times faster than CPU calculations
From a single hologram:
4. (FT)-1
∙ 𝑒𝑖 𝑘𝑧𝑧
3. Z Propagation
x Nb of Z plans
Particle Detection
5. Thresholding
x Nb of Holograms (for different times t)
1) Particle localization in z 2) Precise relocalization in (x,y) plan
x Nb of Nanoparticles
6. Localization
GPU
Reconstruction and Superlocalization