STUDY OF OPTOELECTRONIC

PROPERTIES IN TIO
2

NANOSTRUCTURES USING IN-SITU
TEM
Motivation
Why TiO
2
?
TiO
2
has important applications
Photocatalysis (water splitting, decomposition of
pollutants)
Photoactive in UV
Stable against photodegradation
Solar cells (Dye sensitized solar cells)
TiO
2
is a well known material and a prototypical
one for studying fundamental optical and
electrical proceses.
Interests on TiO
2

Increase absorption in
visible light.
Increase photocatalytic
activity
Some approaches
Band engineering
Doping and codoping
Dye sensitization
Composites
Capping
Surface effects
Comparison of bandgaps for different
materials a with aqueous electrolyte PH 1
Hagfeldt, Anders, and Michael Graetzel. "Light-induced redox reactions in
nanocrystalline systems." Chemical Reviews 95.1 (1995): 49-68.

In-situ TEM experiments
Electrical and optical holder
Capability to introduce light trough an optical fiber with
concomitant electrical measurements (STM tip)
Zhu, Y., et al. "Multimodal Optical Nanoprobe for
Advanced In-Situ Electron Microscopy." Microscopy
Today 20.06 (2012): 32-37.

Example of an
elctrical/optical holder
Diagram of the experiment
Piezodriven W tip
Nanoparticle
Back contact
A
Incident
light
In-situ TEM experiments
(preliminary project)
Two phases: 1
st
electrical measurements, 2
nd
electrical
and optical experiments
Electrical measurements will be done with a small
tungsten tip (apex ratio smaller than 20nm)




Carlton, C. E., O. Lourie, and P. J. Ferreira.
"In-situ TEM nano-indentation of individual
single-crystal nanoparticles." Microsc.
Microanal 13 (2007): 576.
Example of
manipulation of a
nanoparticle with a
piezodriven
nanoindenter:
In-situ TEM experiments
1. Electrical measurements
Charge transport considerations:
Schottky barrier formation
Effect of the NP morphology
Strain effects on electronic structure
Tunneling
Other effects (imperfections, dopants,
resonant tunneling, etc.)

In-situ experiments
2. Optical and Electrical measurements
considerations
Charge carrier generation
Effects of surface (band bending, hole trapping, recombination
centers)
Optical confinement effects (Exciton Bohr radius of TiO
2
is 1 to
10 nm)
Charge separation mechanisms
Effect of morphology
Barriers and tunneling
Bias voltage (Stark effects)
Recombination processes