Chap 7.

Optical properties of Nanomaterials

- Photo-Luminescence (PL)
- Surface Plasmon Effect

Photo-Luminescence (PL)
Conduction Band

absorption
emission

- A metastable state is necessary.

- hh
- It should have direct band gap.

Valence Band

GaAs, CdS, CdSe

CdTe

Si, TiO2, Fe2O3

 Measurement of PL: by spectrophotometer

Emission & excitation spectra

Sample

Excitation
light

Monochromator
& Slit
Light source

1. Emission mode
- Excitation wavelength is fixed.
- Obtain emission spectra as a function of wavelength.
2. Excitation mode
- Emission wavelength is fixed. (The wavelength of emission maxima).
- Obtain emission spectra as a function of the excitation wavelength.

 How to obtain emission and excitation spectra

<Experimental procedure>
1. Obtain UV-Vis. absorption spectrum to find out the absorption maxima of the sample.
This absorption maxima will be chosen as the excitation wavelength
for the PL measurement.
2. Monitor the emission spectrum by spectrophotometer. (1st measurement)
We can determine emission maxima.
3. Change the measurement mode of spectrophotometer to emission mode.
Monitor the emission intensity at this emission maxima by varying the
excitation wavelength. excitation spectrum
4. From the obtained excitation spectra, determine the optimal excitation wavelength
inducing the emission maxima.
5. Monitor emission spectrum again at this excitation wavelength. (2nd measurement)
PL from spectrophotometer

UV-Vis. absorption spectrum

Excitation
spectrum

1.0

Emission
spectrum

0.8

2nd
measurement

0.6

Absorption maxima

0.4

1st
measurement

0.2

0.0
300

350

400

450

500

550

600

300

Wavelength (nm)

400

500

Wavelength (nm)

600

700

Quantum efficiency in solar cells

External Quantum Efficiency (EQE)
The ratio of the number of charge carriers collected by the solar cell to the
number of photons irradiated to the solar cell.
Internal Quantum Efficiency (IQE)
The ratio of the number of charge carriers collected by the solar cell to
the number of photons that are absorbed by the solar cell.
EQE

number of generated electrons

number of irradiated photons

IQE

number of generated electrons

number of absorbed photons

IPCE (Incident photon to current efficiency)

EQE of the generated electrons as a function of the incident light
wavelength
APCE (Absorbed photon to current efficiency)
IQE of the generated electrons as a function of the incident light
wavelength

APCE

IPCE
LHE

LHE: light harvesting efficiency

LHE = 1 10 - absorbance

IPCE spectra

solar simulator

IPCE

Quantum Efficiancy(%)

70

COO-TBA+

60

HOOC

50

N
NCS

N
Ru

40

N
HOOC

30

NCS

COO-TBA+

20

N719

10
0
400

500

600

700

800

900

Wavelength (nm)

Quantum efficiency of photoluminescence (PL)

External Quantum Efficiency (EQE)
The ratio of number of generated photons to number of irradiated photons
Internal Quantum Efficiency (IQE)
The ratio of number of generated photons to number of absorbed photons

Quantum Efficiency (IQE

number of emitted photons
number of absorbed photons

Aquinine
sample quinine Isample
Iquinine Asample
I: emission intensity
A: absorbance
Quinine: a standard fluorescent dye
quinine = 57.7%

Quinine

- UV absorption spectra and emission spectra for the sample and quinine
are necessary.
UV-Vis. absorption spectrum

Emission spectrum by spectrophotometer

1.0

0.8

Emission
spectrum

Absorption peak
375 nm

0.6

0.4

0.2

0.0
300

350

400

450

500

Wavelength (nm)

550

600

300

400

500

Wavelength (nm)

600

700

Photoluminescence (PL) of quantum-sized nanoparticles (NP)

LUMO

HOMO
molecule

Size dependence of band gap; effective mass approximation

- R: radius of nanoparticle
- m*e and m*h : effective mass of the
electron and hole
- : bulk optical dielectric coefficient

Absorption spectra of CdSe NP

as a function of size

Band gaps of CdSe NP

as a function of size

Dots: experimentally observed band gaps

Solid line: theoretically calculated band gaps
with the effective mass approximation

Electronic spectra of samples consisting of CdS NPs with

different mean diameters (): (a) 6.4, (b) 7.2, (c) 8.0, (d) 9.3, (e)
11.6, (f) 19.4, (g) 28, and (h) 48. The excitonic transition shifts to
higher energy values along with an increase in the molar
absorption coefficient, as the particle size decrease.

 PL of binary NP

Comparison of the emission spectra among CdSe,

CdTe, and CdSe0.34Te0.66 quantum dots.

UV-Vis absorption and PL spectra of

CdSe0.34Te0.66 quantum dots in the size range
of 2.7-8.6 nm

- Binary NP emits longer wavelength, compared with CdSe or CdTe NP.

All dots were synthesized to have a mean

diameter of 5.9 nm (core plus shell) and an
overall composition of CdSe0.6Te0.4

- High Eg core / low Eg surface binary NP

does not emit PL.
- Low Eg core / high Eg surface binary NP
emits shorter wavelength PL, compared with
homogeneous binary NP.
- Gradient binary NP emits relatively shorter
wavelength PL than the homogeneous one.

 Monitoring of the delivered nanoparticles in the organ

- Attach fluorecent functional group on the surface of nanoparticles
1. -OH terminated nanoparticles
ex) SiO2, zeolite, TiO2, Si, Fe3O4, most of metal oxides
N H

Toluene
110oC, 1hr

-OH

O H

S i

O H

-O-Si

O H

NH2

(3-amino propyl)-triethoxysilane)
AP-TES
Stirring 2 hr
at 25oC

1-pyrenebutric acid

O
-O-Si

NH

Formation of amide between COOH and -NH2

2. Metal nanoparticles
ex) Au, Ag, Pt, Pd, etc.
Fluorescein isothiocyanate (FITC)

+
S
H

Surface Plasmon Effect

Plasmon: a quantum of plasma oscillation
a quasiparticle resulting from the quantization of plasma oscillations
(just as photons are quantizations of light and phonons are those of
lattice vibrations.)
Surface plasmon (SP)
Surface plasmons (SPs) are coherent oscillations of conduction electrons on
a metal surface excited by electromagnetic radiation at a metal-dielectric interface.
Surface plasmon resonance (SPR)
- Resonant, collective oscillation of valence electrons in a metal stimulated by
incident light.
- The resonance condition is established when the frequency of light photons
matches the natural frequency of surface electrons oscillating against the
restoring force of positive nuclei.

 LSPR effect
LSPR is observed in the noble-metal NPs when the incident photon
frequency is resonant with the collective oscillation of the conduction
electrons confined in the volume of the NPs.

<Schematic diagram for a localized surface plasmon of a metal sphere showing the
displacement of the electron charge cloud relative to the nuclei>

As a result, following phenomena can take place.

1) Absorption of visible-light (Surface plasmon absorption)
2) Strong light scattering
3) Enhancement of the near-field in the vicinity of particle surface

1) Surface plasmon absorption

- The spectral position and magnitude of the LSPR absorption band depends on the
size, shape, composition, and local dielectric environment.

Spherical metallic NP: Single LSPR absorption band is monitored.

Mie theory
: extinction cross section
V: NP volume
: wavelength of light
m: dielectric constant of medium
1 + i2: dielectric constant of NP

- Resonance condition is dependent on NP size

For 20 nm-sized Au NP, LSPR: 520 nm, for 100 nm-sized Au, LSPR: 600 nm

Non-spherical metallic NP
The surface plasmons are unevenly distributed around NP
shape dependence of the LSPR absorption spectra
eg.) nanorod: red-shift of LSPR absorption spectra by long axis of NR
blue-shift by short axis of NR

 Size-dependent absorption peak shift for spherical Au NP

a: 13 nm
b: 27 nm
c: 36 nm
d: 40 nm

Size increase of Au NP
red-shift of absorption peak

Au nano-rod

[Chem. Rev., 108, 494 (2008)]

2) Strong light scattering phenomena

By the particle dipole plasmon frequency, a resonantly enhanced electric field

build up inside the NP.
Induces strong light scattering
Light scattering depending on shape

Au nanocrystals in different shapes

[Chem. Rev., 108, 494 (2008)]

3) Enhancement of the near-field in the vicinity of particle surface

- Increase of electric field near the metal NP
e.g.) Enhancement of PL in Si nanocrystal by embedding Ag NP
[Solar Energy Materials & Solar Cells, 94, 1481 (2010)]

e.g.) Photocatalytic activity enhancement by embedding Ag NP

(a) Bare TiO2

(b) TiO2 with Ag/SiO2 (SiO2 shell thickness: 20 nm)
(c) TiO2 with Ag/SiO2 (SiO2 shell thickness: 5 nm)

Absorbance of TiO2 was increased by presence of Ag/SiO2.

[JACS, 130, 157 (2008)]

e.g.) Enhancement of fluorescence from organic dyes

- Fluorescence intensity of dye molecules is critically depending on the distance
between dye and Au NPs.
[Langmuir, 2013, 29, 1584-1591.]

Au NP

SiO2

Dye

Fluorescence enhancement

- If the distance between Au NP and fluorescent dye

is too short, fluorescence of dye is quenched by
FRET (fluorescence resonance energy transfer).
Fluorescence resonance
energy transfer

fluorescence
Au NP

h
Dye

Dye excitation is stimulated by LSPR