study and development of localised surface plasmon ... · study and development of localised...

Study and development of localised surface plasmon resonance based sensors using anisotropic spectroscopy

Presented by Mr. William L. Watkins

Supervised by Dr. Yves Borensztein

October the 8th, 2018

Jury members

PR. CHRISTOPHE PETIT Professeur Président

DR. HYND REMITA Directrice de recherche Rapporteur

DR. LIONEL SIMONOT Maître de conferences Rapporteur

DR. RAMDANE BENFERHAT Directeur de stratégie Examinateur

PR. DIDIER GOURIER Professeur Examinateur

DR. VIRGINIE PONSINET Chargée de recherche Examinateur

Ecole doctorale : Physique et chimie des matériaux – ED397Laboratoire : Institut des nanosciences de ParisEquipe : Physico-chimie et dynamique des surfaces

ConclusionIntroduction LSPR fundamentals Anisotropic samples H2 with Au Sensing of H2 Perspectives

2

2019 à Pau

� “Hydrogen economy”, energy of the future?


Embedded system

Electrical risks

3

� Need for H2 sensors

Explosive range

4% 70%

Pure H2Pure air

� Highly explosive in air

Hübert, T., et al. (2011). Sensors and Actuators B: Chemical, 157(2), 329–352.

Solution

Development of opticalsensing

�� 2 → 2�

Formation of Palladium hydride

Best optical sensitivity

0.1% in N20.5% in air


4

Use anisotropic plasmon as an optical method for high sensitivity sensing

� Objectives and motivations

H2 sensing with PdSurface interaction of

H2 with Au NP


5

3. Fundamental study : surface interaction of H2 with Au

o Experimental insight into the mechanismo Determination of the charge transferred

2. Fabrication of anisotropic samples

o Fabrication of Au sampleso Model the spectrao Optimising the anisotropy

4. Application study : sensing of H2 with LSPR

o Need for better optical sensing o Use of Au and Pd sensorso Use of pure Pdo Increase in sensitivity

1. LSPR fundamentals

o LSPR for sensingo Anisotropy in LSPRo Anisotropy spectroscopy


6

� Properties of metals at the nanoscale

Localised surface plasmon resonance (LSPR)

Definition: collective oscillation of conduction electron excited by an oscillating electric field

525 nm

Absorption in the case of Au in the Visible

Nanogold suspension

� �� ∝ ��

Abs cross-section Polarisability

�� 3��

� � 2��


7

� LSPR shift : Change in the medium

Increase in εm leads to red shift

�� 3��

� � 2�

∆"

LSPR used as sensors

o

NP

Adsorbed entities

Medium εm


8

� LSPR shift : Charge transfers

�� 3��

� � 2��

∆"

o

NP

Adsorbed entities

Material ε

e-

��#� � 1 �%&2

#�# � '(�1�� ') �#�

Drude model

N : conduction electron density

Decreases in N leads to red shift

LSPR used surface reactivity study

1

2

∆*

*+ �

∆",��

",��


∆"

abs

9

Spectral measurement

Curve fitting(ex: Gaussian fit)

Technique : UV-Vis spectroscopy

Easy for large shifts Hard for small shifts

∆"

� Measuring the shift : conventional technique

Issues

Absolute

• Sensitive to fluctuations : light, pollution, vibration

• Needs reference

Spectral

• Requires monochromator• Needs fitting of the curve

Monochromator

• Compromise : resolution & bulkiness

Use of anisotropy to solvethese issues

abs


B

A

10

Ellipsoid

MICROscopy anisotropy

Two maxima for the two orthogonal polarisations

A

B

� Anisotropy in LSPR

�� 3��

� � 2��

��,,-�. � ��

�� /��

Depolarisation Factor

MACROscopy anisotropy

Needs to be globallyanisotropic

A

B

Does not have to be perfect


B

A

11

� Use of Transmittance anisotropy spectroscopy

MACROscopy anisotropy

Needs to be globallyanisotropic

A

B

Does not have to be perfect

Solution : Anisotropic spectroscopy

� RAS (Aspnes)ReflectanceAnisotropySpectroscopy

� TASTransmittanceAnisotropySpectroscopy

Technique known and used

at INSPFor anisotropic metal

surface studies

Δ1

1

Absolute

DifferentialAspnes, D. E., et al (1988). Applied Physics Letters, 52(12), 957–959. Palummo, M., et al (2009). Phys. Rev. B, 79(3), 1–8. Vidal, F., et al (2006). Phys. Rev. B, 74(11), 1–7. Mazine, V., & Borensztein, Y. (2002). Phys. Rev. Let., 88(14), 147403. Borensztein, Y., et al (1993). Phys. Rev. Let., 71(14), 2334–2337.

23

345

26

6�67 869

6


12


∆"

∆"

Δ1

1

Shift influences both peaks TAS shifts as well

Absolute

Differential


13


∆"

Δ1

1 ∆"

∆:

Shift influences both peaks TAS shifts as wellCan now work at

single wavelength

Absolute

Differential

∆"

The steeper the better


14


Δ1

1

• Better reproducibility

• Signal more stable

• Better sensitivity

• No need for

monochromator nor fitting

Relative & differential

Single wavelength

Issues

Absolute

• Sensitive to fluctuations : light, pollution, vibration

• Needs reference

Spectral

• Requires monochromator• Needs fitting of the curve

Monochromator

• Compromise : resolution & bulkiness

∆"

∆:

The steeper the better


15










16

• Simple to synthesise

• Use non-expensive materials

• Large surface area samples (mm2)

• Small metallic nanoparticles (∅≃10nm)

• Global anisotropy of the sample

• Exposed nanoparticles

� Our requirements : scalability in mind


Nanoparticles

17

20 nm

17

� Known methods

Lithography

× Simple× Non-expensive× Large area× Small NPs� Anisotropic� Exposed

Zoric´, I., et al (2010). Advanced Materials, 22(41), 4628–4633.

Chemical synthesis

Li, J. et al. (2010). App. Phys. Let., 96(26), 263103.

� Simple � Non-expensive� Large area� Small NPs× Anisotropic× Exposed


18

× Simple× Non-expensive� Large area� Small NPs� Anisotropic� Exposed

R. Verre et al, (2016), Nanoscale, 8, 10576

L. Anghinolfi, et al, (2011), J. Phys. Chem., C115,14036

Sapphire monocrystal

LiF crystal

Oblique Angle Deposition on stepped surfaces

Method that inspired the thesis

Apply this method to simpler substrates

� Known methods


19

� Known methods: choice of OAD

=

Evaporation at grazing angle

Glass

Au

� Simple� Non-expensive� Large area� Small NPs� Anisotropic� Exposed


EXP

T

Dichroism

Anisotropic spectrum20

� Known methods: choice of OAD

A

B

Weak structural anisotropy

=

Evaporation at grazing angle

UV-Vis TASEvap. direction

SEM

Glass

Au

∅≃10nm

� Simple� Non-expensive� Large area� Small NPs� Anisotropic� Exposed

FFT


a2 a1

a3

Cal. Exp.

21

� Calculated with supported ellispoids

� Model the spectra

��,,-�. � ��

�� >��

Side view

?@ � 3.6nm

?� � 4.7nm

?F � 1.2nmG � 16H�

A

B para

Evap. direction

Top view

To scale

G

A perp

B

Model reproduces experiments

G

Barrera et al, (1991), Phys. Rev. B43, 13819


22

The angle controls the resonance wavelength

Working wavelength from 600nm to 800nm

The thickness controls the anisotropy (slope)

� Optimising the anisotropy

Evaporation parameters controls the shapeof the anisotropy


23










24

Knowns

H2 molecules adsorb and dissociate on the edges on the Au NPs

Charge transfer from bulk to bond

N decreases then red shift

Illas. F, et al. (2007). Chem. Com. (32), 3371–3373.

Hu, M., et al. (2013). J. Phys. Chem. C, 117, 15050–15060.

� What is and isn’t known in the lit. ?

1

2

∆*

*+ �

∆",��",��

What is the becoming of the H after adsorption ?

Unknowns

DFT

DFT

What is the charge transfer ?


25

∆I


H2 / Ar cycles on Au NP

Δ1

1

∆"

∆:

Reminder

Red shift

Watkins, W. L., & Borensztein, Y. (2017). PCCP., 19, 27397.

time


26

∆I

∆I

∆I


H2 / Ar cycles on Au NP different size

JKL MNMO

Hypothesis : PQ ∝ JKL MNMO

Δ1

1

∆"

∆:

Red shift


Reminder

�SS � 10H�

�SS � 14H�

�SS � 12H� �SS � 14H�

�SS � 16H� �SS � 11H�


27

Edges Facets


Hypothesis : Δ* ∝ '?�UVU5

PQ ∝ WXOYLZMLOML

The surfaces play a role in the reaction

mechanism


(100)

28

H – Au (100) � �[. [\ ] [. [^M_ H – Au (111) � �[. \[ ] [. [^M_

`a8a�b� � [M_

cd � 0.03U�@d � 298G

� Adsorption on the (100) or (111) ?

DFT calculations

P. Ferrin, et al, (2012) Surf. Sci.,606, 7-8, 679– 689,

Most stable surface

(111)


29

Adsorption on the edges Dissociation & desorption on the edges

Diffusion on the (100) facets

Desorption from the facets

1 2

3 4

Proposed mechanism

� New mechanism acknowledging the surface

(100)

H – Au (100) � �[. [\ ] [. [^M_

Most stable surface



30




1 2

3 4

Proposed mechanism

� New mechanism acknowledging the surface

(100)

H – Au (100) � �[. [\ ] [. [^M_

Most stable surface

Determining the charge transfer ?



31




1 2

3 4

Proposed mechanism � Adsorption on the edges 5 =�h�� c �d��1 � =�h��i

� Desorption from the edges 5′h =�h�� c′h�d�=�h��

� Migration from the edges ⟶facets 5�-� =�h�� , =�@mm�

� Migration from the facets ⟶edges 5′�-� =�@mm�, =�h��

� Desorption from the facets 5h =�@mm� � ch�d�=�@mm��

=�h��V

� 5h =�@mm� � 5nh =�h�� 5�-� =�h��, = @mm � 5n�-� = @mm , =�h�� 0

=�@mm�V

� 5�-� =�h��, = @mm � 5n�-� = @mm , =�h�� 5h =�@mm� � 0

oMJbM : edge coverage o�\[[�: surface coverage

� Kinetic analysis : determination of the coverage in H

Measure the coverage = in H

Parameter to fitF: flowofH��w�x ∝ y�z^�Watkins, W. L., & Borensztein, Y. (2017). PCCP., 19, 27397.


32

F: flowofH��w�x ∝ y�z^�

Parameter to fit

� Kinetic study : measure the coverage in H

Ar H 2

Determination of the H coverage o�\[[�



33

� Estimation of the charge transfer

We need to know the number of adsorbed H atoms

Charge transfer per H atoms



34

� Estimation of the charge transfer

12 nm

4.5 nm

Equilibrium shape

T. Kizuka and N. Tanaka, (1997) Phys. Rev. B,. 56, 16, 10079–10088

Truncated octahedron

How many Au atoms?

Surface area (100)50H��⟺ 600}~?V4��

Volume400H�F⟺ 24000}~?V4��

∆*

*� �1.5 ∙ 108F

�35U8/*

1

2

∆*

*+ �

∆",��",��

= � 16%

96�4H}~�@mm�

Charge transferred per H-Au bond

�8 + �0.2U&U5)4H



35

� What did others find ?

Charge transferred per H-Au bond

�8 + �0.2U&U5)4H

Values from the literature : DFT

Ref. System Charge transfer

X.-J. Kuang, et al, (2013) J. of Chem. Sci., 125, 2,. 401–411. }~@F �0.1U

A. Lyalin et al, (2011)Faraday Discussions,152, 0, 26 }~�m No CT

S. Zhao, et al, (2010) J. Phys. Chem. A,114, 14, 4917–4923 }~� �0.3U

F. Libisch et al, (2013) Zeitschriftfür Physikalische Chemie, 227. }~@� �0.8U

Hu, M., et al. (2013). J. Phys. Chem. C, 117, 15050–15060. }~�� Depletion bulk N

Confirmed by DFT calculationNegative charge transfer from the NP to the H-Au bond



36

� Conclusion

�8 + �0.2U&U5)4H

What is the becoming of the H after adsorption ?Q

Insight into the mechanism of H2adsorption on Au

Surfaces play a role

What is the charge transfer ?QFirst quantitative experimental

results



37










38

� Reactivity of Pd with hydrogen

Formation of Palladium hydride

� & �� ≫ 1%⟹ �� & �� + 1%⟹ � � �� a^ ≪ \% ⟹ �

H/Pd

Need to detection the� phase i.e. � a^ ≪ \%

�� 2 → 2�

Griessen, R., et al (2016). Nature Materials, 15(3), 311–317.


39

� Can Pd be used alone ?

Pd LSPR

LSPR in the near IRI. Zoric et al. , (2010), Adv. Mat., 22, 41, 4628–4633

AuPd

Qualitatif comparison with Au

Very large

Ext

inct

ion

[a.u

.] Abs [a.u.]


Wavelength(nm)

abso

rban

ce

40

� Can Pd be used alone ?

Pd LSPR

LSPR in the near IRI. Zoric et al. , (2010), Adv. Mat., 22, 41, 4628–4633

Tiny effect in the α - phase

Increase in p(H2)

Not ideal for high sensitivity sensing


41

� How are LSPR sensors made for H2 detection ?

Substrate

PdAu

Use Pd to absorb H2 and shift the LSPR of Au NPs

Evaporation of (0.2nm) Pd on Au


∆I

∆I

42



63% 16% 4% 1%

0.004%0.015%0.06%0.25%

Error gas p(H2) ≈10%

More sensitive with Pd on AuAtmospheric Pressure

(1 atm)

Room temperature (20°C)


43



∆I

0.004%0.015%0.06%0.25%


∆IBetter with more Pd

1 nm Pd on Au

More sensitive with Pd on Au

0.001% 0.0002%

Atmospheric Pressure(1 atm)

Room temperature (20°C)


44



∆I

0.004%0.015%0.06%0.25%


∆IBetter with more Pd

1 nm Pd on Au

More sensitive with Pd on Au

With our sensitivityis Au indispensable?

0.001% 0.0002%


45

� Anisotropic Pd samples : OAD

Anisotropy in the TASspectrum

Dichroism

B para

A perp

Evap. direction

Watkins, W. L., & Borensztein, Y. (2018). Sensors and Actuators B: Chemical, 273, 527–535


� � 0.95

46

� Model the anisotropy of Pd

B para

A perp

Evap. direction

� Calculated with effective medium theory

Reproduces the positionbut not the width

D. Aspnes, (1982) Thin Solid Films, 89, 249


� � 0.95

47

� Model the anisotropy of Pd

B para

A perp

Evap. direction

� Calculated with effective medium theory

Enables calculation of the hydrogenation

Distribution in f

D. Aspnes, (1982) Thin Solid Films, 89, 249


48

� Effect of hydrogenation on Pd

Exposure to H2 : spectrum

Strong damping of the anisotropy due to hydrogenation of Pd

Calculation of the hydrogenation

�

2�� → ��

� � � �h⁄ : Degree of hydrogenation

Silkin, V. M., et al(2012). Journal of Physics: Condensed Matter, 24(10), 104021


49

� H2 & Ar cycles with Pd sensor

∆I



50


∆I

Strong ∆: change& �� ≫ 1%

�&�?�U � UH�U

� & �� ≫ 1%⟹ �� & �� + 1%⟹ � � �� & �� ≪ 1% ⟹ �



51


∆I


�&�?�U � UH�U

� & �� ≫ 1%⟹ �� & �� + 1%⟹ � � �� & �� ≪ 1% ⟹ �

Weak ∆: change& �� ≪ 1%

�&�?�U � '�~VU



52


∆I


Weak ∆: change& �� ≪ 1%

Slow ∆: change& �� + 1%

�&�?�U � '�~VU�&�?�U � UH�U � � �&�?�U

� & �� ≫ 1%⟹ �� & �� + 1%⟹ � � �� & �� ≪ 1% ⟹ �



53

Origin of the drop in ∆I

� � ��

Drop in ∆Iphase diagram

� Thermodynamic: phase diagram (isotherm)

Can we get a quantitative measurement?

Quantitativemeasurement !

∆I

∆I

Silkin, V. M., et al(2012). J. of Phys., 24(10), 104021�∙ 108��

�∙ 108��


54

Quantitativemeasurement !

Most sensitive LSPR measurements of H2

Ref. Detectionlimit

Carrier gas

Response time [s]

S. Syrenova, et al., (2014) Nano Letters, 14, 5, 2655–2663 15% }5 100

’’ 4% }5 50

A. Yang, et al, (2013), ACS Nano, 8, 8, 7639–7647 2% *� 180

R. Jiang, et al, (2014), Adv. Funct. Mat., 24, 46, 7328–7337 0.2% *� �

M. Matuschek, et al, (2018)Small,14, 7, 1702990, 2018. 0.1% *� �

H. K. Yip, et al, (2017),Adv. Opt. Mat., 5, 24, 1700740 0.10% *� �

Values from the literature : LSPR with Au & Pd

� Thermodynamic: Comparison to Lit.


�∙ 108��


55

Second import specification

Quantitativemeasurement ! Ref. Detection

limitCarrier

gasResponse

time [s]


’’ 4% }5 50


R. Jiang, et al, (2014), Adv. Funct. Mat., 24, 46, 7328–7337 0.2% *� �

M. Matuschek, et al, (2018)Small,14, 7, 1702990, 2018. 0.1% *� �

H. K. Yip, et al, (2017),Adv. Opt. Mat., 5, 24, 1700740 0.10% *� �

Values from the literature : LSPR with Au & Pd

� Thermodynamic: Comparison to Lit.

Most sensitive LSPR measurements of H2


�∙ 108��


56

� Kinetic : 2 time responses

N�[Reach 90% of

signal

NJMNMZNReach readable of

signalWatkins, W. L., & Borensztein, Y. (2018). Sensors and Actuators B: Chemical, 273, 527–535


57

� Kinetic : In the β - phase

N�[Reach 90% of

signal

p(H2) N�[ NJMNMZN

4% β - phase 32� � 0.6�

0.25% α − phase



signal


58

N�[Reach 90% of

signal

p(H2) N�[ NJMNMZN

4% β - phase 32� � 0.6�

0.25% α - phase 40� � 1�

� Kinetic : In the α - phase


signalWatkins, W. L., & Borensztein, Y. (2018). Sensors and Actuators B: Chemical, 273, 527–535


59

� Kinetic : In the α - phase

The faster the better !

Could we make it faster ?

Ref. Detectionlimit

Carrier gas

Response time N�[[s]


’’ 4% }5 50


R. Jiang, et al, (2014), Adv. Funct. Mat., 24, 46, 7328–7337 0.2% *� −

M. Matuschek, et al, (2018)Small,14, 7, 1702990, 2018. 0.1% *� −

H. K. Yip, et al, (2017),Adv. Opt. Mat., 5, 24, 1700740 0.10% *� −

p(H2) N�[ NJMNMZN

4% β - phase 32� ≤ 0.6�

0.25% α - phase 40� ≤ 1�


60

� Kinetic study : Setup

∆I

Desorption kinetic independent of initial p(H2)Absorption kinetic dependent of initial p(H2)

Absorption Desorption

[. ^�%

[.[�%

[.[\�%

[.[[\%

[.[[�%

Only consider0.25 %

H/P

dH

/Pd


[. ^�%

[.[�%

[.[\�%

[.[[\%

[.[[�%

61

� Kinetics : How does it behave ?

Absorption Desorption

Kinetic expressed in terms of H/Pd

H/P

d

H/P

d


62

Reaction mechanism

� Kinetics : mechanism at play

5 h�

5 ��5��

5h��

S : surface Pd V : volume Pd

� Adsorption on the surface 5 h� � c h� &�1 � =��

� Desorption from the surface 5h�� ch��=�

� Absorption in volume 5 �� c �� =�1 � ��

� Emptying from the volume 5�� c �� 1 � =��

o : surface coverage � : volume H/Pd

=

V� 5 h� � 5h�� 5 �� 5��

�

V� 5 �� 5��

Equations to solve to find ��V�


63

� Kinetics : fitting the data

• 5 h� � c h� ��1 � =��

• 5h�� ch�� =�

• 5 �� c �� =�1 � ��• 5�� c �� 1 � =��

=

V� 5 h� � 5h�� 5 �� 5��

�

V� 5 �� 5��

Equation set

Model fits all kineticssimultaneously

Fitted values :o c h� � 1.11 ∙ 108��)?58@

o ch�� 0.235�8@

o c �� 0.214�8@

o c�� 0.111�8@

[. ^�%

[. [�%

[. [\�%

[. [[\%

[. [[�%

H/P

dH

/Pd



64


• 5 h� � c h� ��1 � =��

• OJMW � �JMW o^

• 5 �� c �� =�1 � ��• 5�� c �� 1 � =��

Equation set

[. ^�%

[. [�%

[. [\�%

[. [[\%

[. [[�%

H/P

dH

/Pd

1/(H

/Pd)


Desorption limited by surface

@��V�

2nd order


@��V�

2nd order

1/(H

/Pd)

Ln (

1-H

/Pd)

65


• 5 h� � c h� ��1 � =��

• 5h�� ch�� =�

• OL�W � �L�W o�\ � ��• 5�� c �� 1 � =��

Equation set

[. ^�%

[. [�%

[. [\�%

[. [[\%

[. [[�%

H/P

dH

/Pd

Desorption limitedby surface

Absorption limited by volume

ln�1 � ��h⁄ ��V�

1st order



66

Absorption limited by volume

Desorption limited by surface � Self regenerates

× Improvement N�[ difficultLimited by chemistry of Pd

� Kinetics : What do we learn ?


∆I

∆I

67

� Use in real world conditions

Strong effect of O2 on dielectricfunction of Pd

Effect of air & H2O (4% H2 in air | 50% humidity)

∆I

Unreactive when left in air

20% O2

Effect of O2 on Pd

Still reactive in dry & humid air (4%)

Dry air 4% Humid air 4%


Could we make it faster ?

68

� Conclusion

With our sensitivityis Au indispensable?Q

High sensitivity reached in the α phaseeven with only Pd

QKinetics limited by Pd / H2 chemistry

� High sensitivity� Auto regenerates� Wide range of p(H2)� Rapid response time� Works in air

� Quantitative reading in the α phase � Limited by the phase diagram of Pd� Kinetics limited by the Pd chemistry

Practical achievements Fundamental achievements



69

PERSPECTIVES


70

� Use of Metal Organic Frameworks as filters

� Choice : ZIF-8

� Expectations :

Permeable to H2 and not O2 nor H2O

Zn(NO2)2 +

Nano porous protective layer

Koo, W.-T., et al (2017). ACS Nano, 11(9), 9276–9285.

imidazoleZinc nitrate


71

� Use of Metal Organic Frameworks as filters

Pd 1st coat 2nd coat

Nano porous protective layer

Collaboration ENS - ESPCI : - Pr Christian Serre- Dr Antoine Tissot- Shan Dai

Koo, W.-T., et al (2017). ACS Nano, 11(9), 9276–9285.


72

� MOF in air cycles

Cycles in dry air

Does not prevent oxidation of sample, but still sensitive

Cycles after multiple days

…but still reactive

Different mechanism in air…


73

� Application in liquid medium

May be used for other type of sensing ex: protein , heavy metals, etc…

Fabrication of liquid cell

Direct industrial application


74

CONCLUSION


75

5 h�

5 ��5��

5h��

� Summary and conclusion

Techniques

Capabilities

Fundamental

Patent : FR1859255

Δ1

1

Differential

More sensitive LSPR measurements

OAD allowsSimple & effective

anisotropic samplesSingle wavelength

monitoring

TAS allows

Application

� Enables fundamental investigation of surface reactivity ideal for catalysis

� Direct application : H2 sensing � But also : biochemistry,

green chemistry


76

INSP

� Yves Borensztein� Emmanuelle Lacaze� Geoffroy Prévot� Sébastien Royer� Bernard Croset

� Dominique Demaille� Loïc Becerra� Erwan Dandeu

� Acknowledgments

Collaborations

� Fabienne Testard

� Christian Serre� Antoine Tissot� Shan Dai

PhD Co-workers

� Alberto Curcella� Léo Bossard-Giannesini� Emmanuel Puig

Physico-chimie et dynamique des surfaces (PHYSUF)

study and development of localised surface plasmon ... · study and development of localised...

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