Post on 28-Dec-2015
Electrical transport in ZnO and TiO2 nanowires (for solar cell
application)
Chun-Chung Su and Chao-Cheng Kaun
Advanced Computation & Modeling Group
Introduction (I)
Titanium dioxide and zinc oxide are cheap, nontoxic and photostable semiconductor : widely used in the photovoltaic devices and photo catalysis.
The electron-donating molecules such as catechol and ascorbic acid absorbed on the surface could affect the solid surface state and lower the optical absorption threshold to visible sunlight.
The dye-sensitized solar cell (DSSC), often called the “Gratzel cell” is a promising route toward harvesting solar energy.
Introduction (II)
1D nanowires provide benefits in two respects: 1.) due to high length-to-diameter ratio and a total
length reaching hundreds of micrometers, visible light scattering and absorption are much enhanced
2.) the 1D geometry facilitate rapid, diffusion-free electron transport to the electrodes
Despite intensive studies on surface-based and nanoparticle-based DSSCs, the mechanism and electronic coupling between a nanowire and a dye molecule has hardly been addressed.
Example (I)Nanowire dye-sensitized solar cells
Traditional nanoparticle film are replaced by the crystalline ZnO nanowires (NWs).The direct electrical pathways provided by the NWs ensure the rapid collection of carriers generated throughout the device.
Nature Material, 4, p455 (2005)
Example (II)[Fe(CN)6]4- sensitization of TiO2
nanoparticles
Charge injection from the dye molecule to the conduction band of the nanoparticle.
JACS, 126, p15024 (2004)
The structure of ZnO
The primitive unit cell of ZnO is the wurtzite phase :the space group is P63mc , hexagonal. ZnO nanowires can grow along the [0001] direction, having hexagonal or triangular cross section.Choose (n=26, triangular) as our system.Wire diameter is about 6 angstrom.
Side view Top view
Band structure and Transmission of ZnO NW
Our resultCalculated from VASP
Ref.: APL 91,031914 (2007)
Structure of Au-ZnO-Au systems
Length of ZnO unit : 1cell : L=0.591nm 2cell : L=1.135nm 3cell : L=1.668nm 4cell : L=2.205nm 5cell : L=2.783nm 6cell : L=3.281nm
Two optimized structures: 1.optimized ZnO NW + Au lead 2.optimized ZnO NW include 1 layer Au +Au lead
L Scattering region
Transmission of Au-ZnO-Au system
An obvious transmission peak appear in Au-ZnO-Au system,
ex: 3cell and 4cell systems.
Tunneling behavior of ZnO NW
G~G0exp(-βn) , n is number of ZnO cell
β=1.583 (relax only ZnO NW) =1.262 (relax include 1 layer Au)
The structure of TiO2
TiO2 nano-crystalline: mostly anatase (70%), then rutile (30%) ,when size 15~30 nm.
The primitive unit cell of TiO2 in the anatase structure : the space group is I41/amd, tetragonal.
Anatase
Structure of TiO2 [010] nanowire
After optimization
]100[
]010[
]100[
]101[
Three simple Dye Molecules
catechol Cyanidin Fe(CN)64-
Red: Fe
Yellow: C
Grey: N
Band and orbital of dye-TiO2 NW
Band and orbital of dye-ZnO NW
Future Work
Construct TiO2 NW and ZnO NW sensitized by different dye molecules.
Construct NW-dye/NW junction system and NW-dye/metal junction system.
Investigate the transport properties and electronic coupling between the nanowire and molecules.