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 semi-conductors
 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 electrochemical
etching of titanium foil. The side view (B), top view(C), and magnified
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 (HOOC-CH2-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 films (A)
OTE/TiO2(NP)/CdSe (solid lines) and (B) (Ti/TiO2(NT)/CdSe (dashed lines).
 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 mW/cm2;
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 nanostructure-based
 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 ( Tio2-CdSe)
 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%).