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Light emitting nanoparticles and

Plasmon enhanced fluorescence

Santa Chawla (Acharya)

Luminescent Materials Group


National Physical Laboratory, Dr. K. S. Krishnan Road
New Delhi 110012, India
Outline

 Light emitting nanoparticles (nanophosphor)

 Metal Nanoparticles - Light matter interaction

 How MNP confine EM field in nanoscale

 Plasmon enhanced fluorescence

 Recent results of plasmon enhanced fluorescence from light emitting


nanoparticles

 Plasmonic near field as sole source of excitation of nanophosphor

 Conclusions

Santa Chawla, NPL, India


Light emitting particles (Phosphors)

Excitation>Emission Excitation<Emission

Industrial
phosphors are
usually micron
size particles.

Semiconductor Exciton DA pair RE doped


Insulator
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Some Phosphors developed in our laboratory

PL Phosphor (down conversion) Up conversion Phosphor

UV IR
Excitation Excitation

Application: Lighting, Display, Solar Spectrum conversion for better


energy harvesting by Solar cell
Dual (UV & IR) excitation

IR
UV

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Luminescent nanoparticles (nanophosphor)
Nanophosphors - Phosphor particles of nanometer
dimensions

Quantum dots (size~exciton Bohr diameter,1-10 nm)

- Quantum confinement effect


- Tunable emission with size

Size Small to Large

Colour Blue to Red

Doped Nanophosphor (size ≤ 100 nm)


- Tunable emission with dopant (rare earth, transition metal)
- Tailoring electronic properties with dopant (n-/p-type semiconductor)
- Tailoring magnetic properties with dopant (transition metal …)

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Metal Nanoparticles – Light matter interaction
When optical radiation (electromagnetic field) falls on a metal
nanoparticle
 Surface electron cloud oscillates
coherently relative to a lattice of d << 
positive ions, due to the
alternating 
field of the incident radiation. Nanoparticle
d
 The coherent collective oscillation

leads to displacement of the


electron cloud from the nuclei,
thus giving rise to a surface
charge
distribution & characteristic
oscillation of the electron cloud
with respect to the positive
background.

 Each such collective oscillation


associated to different surface
charge distributionSanta
is Chawla,
known as
NPL, India
Requirements - Material with free electrons
Metals SPR
UV
Pb, In, Hg, Sn, Cd, Al
VIS
Cu, Ag, Au

Nanoparticles Flat surfaces


Au 50 nm

Localized Surface Plasmon (LSP) are Surface Plasmon Polariton (SPP) are
stationary oscillations of the conduction propagating, dispersive EM waves
electrons at optical frequencies along the coupled to the electron plasma of a
boundaries of a metal nanoparticle conductor at metal dielectric interface.
coupled to the EM field.
Plasmons – the quantized form of collective ‘Polariton’ a joint state of light and matter with
matter oscillations, are Bosons with both the quanta as Bosons.
wave-like and particle-like behaviour.
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Optical properties of metal nanoparticles
Two main effects are observed when LSPs are excited in metal nanoparticles
 Absorption (non-radiative, dissipation as heat within NP)
 Scattering (a near field component that evolves into radiative far field scattering)
The relative contribution of these components is determined by particle geometry and dielectric
medium. The total energy removed from incoming light is the sum of absorption and scattering
contributions and given by ‘Extinction’ cross section. Due to the high efficiency of interaction of
MNP with light, absorption or scattering cross sections can exceed the geometric cross sections of a
particle, such that the particle captures more light than its physical size would permit.
Gold nanorods with diff. aspect
This enables us to visualize metal nanoparticles ratio
as ‘Optical antenna’
Measurement of Absorption, Scattering
and Extinction spectrum gives the SPR
frequency.

This resonance for gold and silver nanoparticles


occurs in the visible region of the electromagnetic
spectrum. As a consequence, we are able to see the
bright colors exhibited by particles, both in
transmitted and reflected light, due to resonantly
enhanced absorption and scattering

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Nanotechnology in Roman Times: The Lycurgus Cup
Plasmons of gold nanoparticles in glass reflect green, transmit
red.
Metal nanoparticles - how they confine EM field in nanoscale
Metal nanoparticles can confine and enhance the incident
electromagnetic field around them due to:

 SPR of metal NPs (depends upon shape, size and dielectric


environment)
 Lightening rod effect (crowding of field lines and strictly depends on
the
shape of metal NP)

Enhanced EM field confined in sub wavelength region around metal NPs can
govern, control and improve physical processes such as Fluorescence,
Vibrational spectroscopy, Photovoltaics, Photoemission, Nanoscale microscopy
etc.
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Plasmon – Fluorophor interaction
 Weak coupling regime
Enhancement of spontaneous emission when an
emitter is placed close to a metallic surface of
nanostructure, where the emitter couples to
confined plasmonic modes. The fluorescence
enhancement may be tempered due to non
radiative losses on metal surface leading to
fluorescence quenching which occurs close to the
surface. Hence an optimal distance has to be
maintained between the emitter and the plasmonic
structure.

 Strong coupling regime

Confined plasmonic modes couple very strongly to


matter. Characterized by the reversible exchange
of energy between the light field and the emitter –
the Rabi oscillations which manifest as energy
splitting of the light – matter energy levels.
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Plasmonic enhancement of Fluorescence

Fluorescence Plasmon enhanced Fluorescence

UV -Visible Light UV -Visible Light

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Enhancement of Fluorescence in Nanophosphors by Metal
Nanoparticles
There is enhancement of incident electromagnetic field in MNP due to

 SPR of metal NPs (depends upon shape, size and dielectric environment)

 Lightening rod effect (strictly depends on the shape of metal NP)

When a luminescent nanoparticle is placed in proximity of metal NPs, it


experiences the enhanced EM field.

Fluorescence enhancement depends mainly on two factors

 Excitation enhancement

 Emission enhancement
For which spectral overlap of plasmon absorption band of metal NP with
either absorption band or the emission band of nanophosphor is required.
To observe enhancement of fluorescence, often a nanometer-thin dielectric
spacer layer is required to prohibit non-radiative excitation transfer from
light emitting nanoparticle to metals.

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We have chosen Silver (Ag) Nanoparticles,
Why ?

 Maximum Light Matter Interaction

 Tunability of SPR in the desired range of wavelengths

 Simplicity of methods of synthesis

 Strong localization of EM fields possible in different shapes

Santa Chawla, NPL, India


Our recent results on Plasmonic enhancement of fluorescence by Ag
NPs

Material system

 Ag NPs of different shape & size to tune SPR

 Light emitting nanoparticles

- Semiconductor
- Rare earth doped insulator

Techniques used

 Confocal Fluorescence Mapping and Spectroscopy

 Finite Difference Time Domain (FDTD) simulation for generating


near
field of Ag NPs of different shape & size

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Synthesis of Ag NP

Synthesized Ag NP colloidal solutions of different colours

Absorption spectra of Ag NPs

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Fluorescence enhancement in ZnO nanoparticles by Ag
nanospeheroid
ZnO – Ag NP Confocal Fluorescence Optical absorption
integrated system image
ZnO
0.4

Absorption
0.2

0.0

300 400 500 600 700

Wavelength (nm)
ZnO:AgY Fluorescence emission
TEM Simulated near field
spectra
600
ZnO:AgY
ZnO

550

Intensity(a.u)
500
50nm

450
400 450 500 550 600 650 700
Santa Chawla, NPL, India Wavelength(nm)
Fluorescence enhancement in ZnO nanoparticles by Ag
nanohexagons
TEM Simulated near field

2.0

1.5

Absorption
100nm
1.0

0.5

ZnO 0.0
300 400 500 600 700 800 900 1000
Wavelength (nm)
900 ZnO:AgB
ZnO:AgY
850 ZnO
800
Intensity(a.u)
750

700

650

ZnO:AgB 600

550

500

450
400 450 500 550 600 650 700
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Santa Chawla, NPL, India
Silver nanoprism enhanced Fluorescence in rare earth doped
insulator NP
YVO4:Eu3+ (YVO4:Eu3+) Ag NP
TEM Colloidal Solution TEM Colloidal Solution

PL Excitation Spectra Simulated Extinction spectra UV-Visible absorption


of single particle spectra of colloid
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Confocal Fluorescence Spectroscopy FDTD Simulation of near field of Ag
NP & Dimers

Sample E-Field Enhancement |E|2 (Z- direction)

LSPR 615nm 532nm

Single Single Single Dimer

Ag NP 22nm 260 12 23 100

Ag NP 45nm 648 39 65 2074

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Plasmonic near field as sole source of excitation of
nanophosphor

 Incident Optical frequency cannot excite nanophosphor

 Near field generated around Ag NPs in proximity excites


fluorescence IR Light

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Field enhancement of Ag
nanoprisms at different
excitation frequencies

Ag NP E-Field Enhancement |E|2 (Z-


direction)

Edge SPR 980nm


length 615nm

Single Single Single


NP NP NP Dimer
22nm 260 12 10 30

45 nm 648 39 50 152

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New J. Chemistry 37, 3991-3997 (2013)
Santa Chawla, NPL, India
Conclusions
 Ag NPs of different shape and size synthesized by colloid chemistry

 Luminescent nanoparticles of semiconductor and RE doped insulators

synthesized

 Ag NP – LNP hybrid nanostructure made with optimal separation

 Fluorescence enhancement to various degrees observed by Ag NPs of


different shape and size

 Plasmonic near field (under IR excitation) as sole source of excitation


of
nanophosphor demonstrated

 Simulation of near field by FDTD for Ag NPs of various geometry

 Importance of such metal-LNP hybrid thin film as it can be better


light
harvester for solar photovoltaic devices as a thinner layer would
reduce
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Acknowledgements
Students

Zubair Buch (M.Tech)


Vineet Duhan (Project Fellow)
Rupali Das (Research Intern)
Parikshit Phadke (M.Tech)
M.Parvaz (M.Tech)

CSIR Solar Mission TAPSUN Programme

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Thank you

Santa Chawla, NPL, India