Quantum Dot Solar

Cells.
Tuning Photoresponse
through
Size and Shape Control
of CdSe-TiO2
Architecture
Kiarash Kiantaj
EEC235/Spring 2008

Introduction

Sensitization of mesoscopic Tio2

with dyes (11% efficiency)
Short band gap semi-conductors to
transfer electrons to large band gap
semi-conductors
Sensitizers: CdS, PbS, Bi2S3 CdSe,
InP (short gap)
TiO2 , SnO2 ( large gap)

Short band gap semiconductors

Harvesting visible light energy.

Electron injection under visible light
Fast charge recombination low
efficiency

Semiconductor Quantum
dots

Visible light harvesting assemblies

Size quantization
Tune visible response
Vary band energies

Open up ways utilize hot electrons

and multiple carriers with single
photon.

Quantized CdSe Particles and

Their Deposition on TiO2
Particulate Films and Nanotubes

Random versus Directed Electron Transport through

Support Architectures, (a) TiO2 Particle and (b) TiO2 Nanotube
Films Modified with CdSe Quantum Dots

- Absorption spectra of 3.7, 3.0, 2.6, and 2.3 nm diameter CdSe

quantum dots in toluene.
- Shift due to quantization

Deposition of QD on Tio2 films

Scanning electron micrographs of (A) TiO2 particulate film cast

on OTE and (B, C, and D) TiO2 nanotubes prepared by electrochem
etching of titanium foil. The side view (B), top view(C), and magnifie
view (D) illustrate the tubular morphology of the film

Photograph of 2.3, 2.6,

3.0, and 3.7 nm
diameter CdSe
quantum dots
(A)in toluene,
(B)anchored on TiO2
particulate films
(OTE/TiO2(P)/CdSe,
(C) attached to TiO2
nanotube array
(Ti/TiO2(NT)/CdSe).

40-50 nm particles ( diameter)

Electro chemical etching of Ti in fluoride Tio2 nanotubes
80-90 nm ( diameter) , 8 um long

Growth details

Constant absorption monolayer

CdSe
Linear increase in absorption with
TiO2 thickness
CdSe quantum dots and TiO2 binding
: bifunctional linker molecules (HOOCCH2-CH2-SH)

carboxylate and thiol functional

groups

Absorption spectra

Peaks due to the 1S exciton transitions

Binding of CdSe to TiO2

Absorption spectra of (a) 3.7, (b) 3.0, (c) 2.6, and (d) 2.3 nm
diameter CdSe quantum dots anchored on nanostructured TiO2 fi
OTE/TiO2(NP)/CdSe (solid lines) and (B) (Ti/TiO2(NT)/CdSe (dash

Selectively harvest light

CdSe maintains quantization
properties after binding
Absorbance = 0.7 more than 80%
absorption of light below the onset.
Uniform coverage of CdSe is similar
to modified mesoscopic TiO2 with
sensitizing dyes.

Photoelectrochemistry of
TiO2 Films Modified with
CdSe
Quantum Dots

Open circuit voltage

Short current circuit
Open circuit voltage is
same for all. (650+-20 mV)
Injected electrons relax to
lowest conduction band
conduction band
level of TiO2+ redox = 600 mV

Photocurrent response depends on

particle size

Photocurrent response of (A) OTE/TiO2(NP)/CdSe and (B)

(Ti/TiO2(NT)/CdSe electrodes. Individual traces correspond to
(a) 3.7, (b) 3.0, (c) 2.6,
and (d) 2.3 nm diameter CdSe quantum dots anchored on
nanostructured TiO2 films (excitation >420 nm, 100 mW/cm2;
electrolyte, 0.1 M Na2S solution).

Maximum photocurrent 3.0 nm CdSe

Two opposing effects:
1- decreasing size shift of the
conduction bad to more negative
potential driving force for charge
injection
2- decreasing size smaller response in
visible region less photocurrent

I-V characteristics of (A) OTE/TiO2(NP)/CdSe and (B) (Ti/

TiO2(NT)/CdSe electrodes (excitation >420 nm; intensity 100 m
electrolyte, 0.1 M Na2S solution.)
Under the applied potential charge recombination is minimized.

Tuning the Photoelectrochemical

Response through Size
Quantization.
- incident photon to charge carrier efficiency
(IPCE)

Photocurrent action spectra

A) OTE/TiO2(NP)/CdSe and
(B) (Ti/TiO2(NT)/CdSe electrodes

nanotube TiO2 films

generally absorb more light than nanoparticle TiO2
films, this
difference accounts for a no more than a 5% increase
in overall
photons absorbed. Comparing this with a 10%
improvement
in IPCE of the nanotube film over the nanoparticle film
demonstrates the measurable advantage of a nanotube
architecture
for facilitating electron transport in nanostructurebased
semiconductor films.

Design of Rainbow Solar

Cells

Artistic Impression of a Rainbow Solar Cell

Assembled with Different-Sized CdSe Quantum Dots on a TiO2
Nanotube Array

Conclusion

Size dependent charge injection ( Tio2CdSe)

Morphology dependence
Overall power efficiency of about 1%
with 3nm
CdSe QD
Maximum IPCE value (45%) obtained
with CdSe/TiO2(NT) is greater than that
of CdSe/TiO2(NP) (35%).