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Page 1: Plasmonic thermometry and plasmonic probes of ultrafast ...users.mrl.illinois.edu/cahill/santorini_sep16.pdfPlasmonic thermometry and plasmonic probes of ultrafast evaporation and

Plasmonic thermometry and plasmonic probes of ultrafast evaporation and condensation

David G. Cahill, Jonglo Park, and Xu XieDepartment of Materials Science and Engineering

University of Illinois at Urbana-Champaign

supported by ONR

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Motivation (big picture): Improve experimental methods for probing heat transfer, thermometry, and phase transformations at solid/iquid/vapor interfaces

• Prior study of thermal conductance of hydrophobic and hydrophilic interfaces with water

Ge et al., Phys. Rev. Lett. (2006)

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Motivation (big picture): Improve experimental methods for probing heat transfer, thermometry, and phase transformations at solid/iquid/vapor interfaces

• Prior study of fast water desorption from a hydrophilic surfaces by time-resolved ellipsometry

Min et al., J. Phys. Chem. C (2012)

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Outline

• Nanodisk sensors (prepared for us on silica by Insplorionand fabricated by us on quartz crystals) and characterization of their sensitivity and depth resolution.

• Application to interface thermal conductance and thermal diffusivity of fluids.

• Application to fast condensation and evaporation of a refrigerant (R124) from interfaces with controlled chemistry.

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Nanodisk plasmonic sensors

• Fabricated by “hole-mask colloidal lithography”

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Nanodisk plasmonic sensors

• SEM gives the most accurate measurement of diameter

• AFM gives the most accurate measurement of height

Au disk diameter 120 ± 10 nm, height 20 ± 2 nm

SEM AFM

Park and Cahill, J. Phys. Chem. C (2016)

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Sensitivity d(Tr)/dn (change in transmission coefficient with respect to optical index) approaches unity

• Coat with PMMA and take difference spectra of the absorption.

• Noise floor of pump-probe measurements is

1/2

1/2

13 1/2

0.3 ppm Hz3 mK Hz

10 m Hzliquid

liquid

nT

h −

∆ ≈

∆ ≈

∆ ≈

Tr=transmission

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Sensitivity to dn is localized to within 13 nm of the Au surface

• Atomic-layer deposition of alumina

• Alumina thickness on planar Au surface measured by ellipsometry.

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Transient absorption

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Signal is a combination of the temperature change of the Au and the temperature change of the surroundings

• Isolate the two terms using a linear combination of the response at two wavelengths.

∆ = ∆ + ∆( ) ( )

Au fluidAu fluid

d Tr d TrTr T TdT dT

0 1000 2000 3000 4000100

101

102

103

780 nm 790 nm 800 nm 810 nm 820 nm

V in (µ

V)

time (ps)

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Signal from the lateral “breathing mode” acoustic oscillation is minimized at the same wavelength that minimizes the sensitivity to fluid temperature

0 100 200 300 400 500-120

-80

-40

0

40

80

V in(d

ata)

-Vin(th

erm

al)

time (ps)

780 nm 790 nm 800 nm 810 nm 820 nm

Data after subtracting thermal response

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Numerical modeling of the temperature field

• dn/dT of the fluid dominates over dn/dT of the glass substrate so model the signal as a weighted average of the temperature of the fluid within (13 nm)*(nAl2O3/nliquid) of the Au nanodisk

• Au/silica interface conductance from an independent measurement.

Park and Cahill, J. Phys. Chem. C (2016)

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Control the surface chemistry using self-assembled monolayers (thiol bond to Au surface)

• Plasmon resonance is a built-in diagnostic for what is happening near the interface.

1.32 1.34 1.36790

800

810

820

Peak

wav

elen

gth

(nm

)

Refractive index (n)

hydrophilic

bare

hydrophobic

Water Ethanol1.0 1.2 1.4 1.6

720740760780800820840

Peak

wav

elen

gth

(nm

)

Refractive index (n)

hydrophilic

bare

hydrophobic

Hydrophilic HS(CH2)3SO3 and hydrophobic HS(CH2)9CH3

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Data acquisition and analysis for interfaces with fluid mixtures

• Shift wavelength to optimize sensitivity to fluid temperature near the interface.

• Subtract breathing mode acoustic signal by fitting to a damped oscillator

• Compare to thermal model with interface conductance as a free parameter

100 101 102 103101

102

data (810 nm) data (810 nm) 80 MW m-2 K-1 (A = 0.65, B = 0.063) 120 MW m-2 K-1 (A = 0.65, B = 0.063) 180 MW m-2 K-1 (A = 0.65, B = 0.063) 240 MW m-2 K-1 (A = 0.65, B = 0.063)

V in (µ

V)

time(ps)100 101 102 103101

102

data (810 nm) data (810 nm) 40 MW m-2 K-1 (A = 2, B = 0.25) 80 MW m-2 K-1 (A = 2, B = 0.25) 160 MW m-2 K-1 (A = 2, B = 0.25)

V in (µ

V)

time(ps)

100 % Ethanol

0% Ethanol (Water)

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Vary liquid composition between pure water and pure ethanol for hydrophobic SAM, hydrophilic SAM, and “bare” Au

• Data for pure water and pure ethanol are in agreement with prior work for planar interfaces and supported nanoparticles.

• Data for pure ethanol are relatively insensitive to the interface chemistry.

0.0 0.2 0.4 0.6 0.8 1.00

50

100

150

200

G (M

W m

-2 K

-1)

Ethanol / Water

hydrophilic

Bare

Hydrophobic

Kapitza lengthLK = Λ/G ≈ 3 nm

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Convert the dependent variable from liquid composition to a thermodynamic parameter

• Prior theory, computation, and experiment has shown a linear relationship between G and work-of-adhesion W.

(1 cos( ))W γ θ= +surface tension contact angle

Harikrishna et al. (2013)

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G∝W does not describe the interface thermal conductance of hydrophilic SAM for water/ethanol

• Water/ethanol mixture and water/surfactant,• Work-of-adhesion to hydrophobic surfaces is essentially

constant.

glucoside (C12H24O6)

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Replace bulk liquid with an adsorbed refrigerant layer as a function of pressure

plasmonic substrate

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R124 gas chromatograph analysis1-chloro-1,2,2,2-tetrafluoroethane (99.79%)1,1,1,2,2 – pentafluoropropane (0.21 %)

• Vapor pressure is ≈40 psi at lab temperature

200 300 400 500

10-1

100

101

102

Pres

sure

(psi

)

Teperature (K)

Data from NIST webbook (http://webbook.nist.gov/chemistry/)

wikipedia.org

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Same approach: measure response at peak absorption (Au temperature) and red-shifted (changes in thickness of adsorbed layer)

• Instead of measuring ∆n(15 nm); measure (n-1)∆h

P=0 P=20 psi

10-4T

λ=800 nm

λ=780 nm

770 760

790

780

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Isolate contribution from ∆h and compare to model

• Model assuming linear response

• In the frequency domain, thickness response is simply a low-pass filter applied to the temperature response

( )* ( )

( ) exp

h g t T tA tg tτ τ

∆ =

= −

P=2 psi

5

1020evaporation

condensation

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Relate the interface velocity v(t) to kinetic and thermodynamic factors

equilibrium vaporpressure at T0

volume per molecule

effective evaporation coefficient

vapor pressure at T(t)

• Isosteric heat of adsorption qiso relates changes in P to changes in T at constant coverage

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Consider a linear model where changes in P,T of the vapor are small compared to changes in vapor pressure of the adsorbed layer

pressure of the vapor

effective evaporation coefficient

isosteric heat of adsorption

• Essentially hiding all the complicated (and interesting) kinetics in the “effective evaporation coefficient”

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Relate the amplitude of the response to parameters that describe thickness h versus T at constant P

• Combine with previous definitions to yield an expression for time-scale on which thickness relaxes to a new equilibrium

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Look at response amplitude A and relaxation time τindependently and then as the ratio A/τ

– AT should be on the order of 10 times thickness h– τ is a more robust measurement and should scale with h/P– open circles for hydrophilic SAM, solid circles for

hydrophobic SAM

AT

10hSAW

calculated from hSAW

experiment

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…then the ratio A/τ

• For bulk liquid R124 at saturation pressure and room temperature

8iso

B

qk T

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Summary • Plasmonic nanodisks are powerful platform for probing

small changes in index of refraction due to temperature excursions in liquids or evaporation/condensation of thin adsorbed layers.

• Conductance and work-of-adhesion at hydrophobic interfaces are insensitive to the liquid composition.

• At hydrophilic interfaces, conductance is not a linear function of work-of-adhesion.

• Noise floor of 10-13 m Hz-1/2 for measurements of phase change from liquid to vapor.

• Adsorbed layers of R124 on the order 1 nm thickness have a time-constant on the order of 1 ns.

• Potential for studies of accommodation coefficients and vapor velocity distribution near an interface during evaporation/condensation.


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