Editor-in-Chief, Nanoscience & Nanotechnology Letter (NNL)

Principal Editor ， Journal of Materials Research (JMR)

Fellow, Institute of Materials, Minerals and Mining, UK (IOMMM)
President, Thin Films Society (TFS)

Hello from Singapore!

(currently on sabbatical
@Central Iron & Steel Research Institute, Beijing
北京钢铁研究总院 ) 65-6790 4400
fax. 65-6791 1859/6792 4062
email: msyzhang@ntu.edu.sg
http://www.ntu.edu.sg/home/msyzhang
Prof. Sam Zhang
School of Mechanical & Aerospace Engineering
Nanyang Technological University
50 Nanyang Avenue
Singapore 639798
 Anodic Titania Nanotube Arrays for Application
in Dye-Sensitized Solar Cells
Sam Zhang, Lidong Sun
School of Mechanical and Aerospace Engineering
Nangyang Technological University, Singapore
•Lidong Sun; Sam Zhang, Xiao Wei Sun, Xiaodong He, Effect of Electric Field Strength on
the Length of Anodized Titania Nanotube Arrays, Journal of Electroanalytical Chemistry :
in press (2009)
•Lidong Sun, Sam Zhang, Xiaowei Sun, Xiaodong He, Effect of TiO2 Nanotube
Geometries on the Performance of Dye-Sensitized Solar Cells, Journal of Nanoscience
and Nanotechnolog, Journal of Nanoscience and Nanotechnology, 10 : 1-10 (2009)
Outline

1. Dye-Sensitized Solar Cell (DSSC)

 typical structure and working principle
 why choose titania (TiO2) nanotube array
 current TiO2 nanotube array based DSSCs
2. Nanoparticle or Nanotube Array?
 efficiency: 11% vs. 7%
3. Nanoparticle + Nanotube Array
 composite structure
4. Anodic Titania Nanotube Array
5. Conclusions
Particle vs Nanotube array in DSSC

• drastically reduced connections

electrons scattered at connections
• vectorial
randomlytranspoprt
walk to the collecting electrode
• comparable
large surfacesurface
area area with nanoparticle
based photoanode
TiO2 Electrolyte Counter Electrode
TCO Dye Limit the
Enable thephotoanode
photoanodethickness
thicknessto approx.
larger than1010µm
µm
M. Grätzel, J. Photochem. Photobiol. A: Chem. 164 (2004): 3
Achieveoflight-harvesting
Inhibit absorption low-energy photons
 Problems in TiO2 Nanotube Array Based DSSCs

(a) (b)

• short nanotube array (less than 5 µm, • reflected by platinized counter electrode
compared to optimal 20~30 µm) • absorbed by iodine in the electrolyte
• increased resistance of FTO during • Increased barrier layer thickness by
annealing approx. 1 µm during annealing

L. Sun, S. Zhang, X. W. Sun, X. He, Chapter 2,

Anodized Titania Nanotube Array and its Application in Dye-Sensitized Solar Cells, in Vol. 3,
CRC Handbook of Nanostructured Thin Films and Coatings Edited by Sam Zhang,
Published by CRC Press Taylor & Francis Group, in press, 2009
Another Issue: Effective Surface Area

Nanoparticles (fcc packing) Nanotubes (hcp)

R 5 typical nanoparticle size

 comparable surface area
r 3 15 ~20 nm
R 5 r = 9 nm
 SNT < SNP
r 3
R = 15 nm D = 30 nm
R radius of nanotube
r radius of nanoparticle
L. Sun, S. Zhang, X. W. Sun, X. He, Chapter 2, Too small to achieve!
Anodized Titania Nanotube Array and its Application in Dye-Sensitized Solar Cells, in Vol. 3,
CRC Handbook of Nanostructured Thin Films and Coatings Edited by Sam Zhang,
Published by CRC Press Taylor & Francis Group, in press, 2009
Another Issue: Effective Surface Area

L. Sun, S. Zhang, X. W. Sun, X. He, J. Nanosci. Nanotechnol. 10 (2010): 1-10

Consequences:

Less effective area  less

efficiency!
That explains why most nanotube array DSSCs are
less efficient than nanoparticle counterpart
Nanoparticle + Nanotube Array?
 Composite Structure

TiO2 nanotube
TiO2 nanoparticle

In combination of
 nanotube array: superior electron transport and suppressed
electron recombination
 nanoparticle: high surface area
Anodic Titania Nanotube Array
Preparation & Characterization
Electrochemical Anodization: Experimental Set Up
 Electrochemical Anodization: Principle

 
Ti foil
Pt

Ethylene Glycol
+
anion
2 vol% H2O cation
+
0.3 wt% NH4F

Ti → Ti4+ + 4e 2H+  2e → H2

+
Ti4+  2H2O / 2OH → TiO2  4H+/ 2H
TiO2  6HF → [TiF6]2  2H2O  2H+
Surface morphology and
cross-sectional view of
the as-anodized titania
nanotube arrays for different
anodizing durations:

2 h  (a, d)
14 h  (b, e)
24 h  (c, f)

L. Sun, S. Zhang, X. W. Sun, X.

He,
J. Electroanal. Chem. (2009)
Variation of Length

Longer nanotube arrays are obtainable at higher potential

for longer anodizing duration.

L. Sun, S. Zhang, X. W. Sun, X. He, J. Electroanal. Chem. (2009)

Accepted.
Variation of Pore Diameter

25 V 40 V 50 V 60 V

40 mm 30 mm 20 mm 13 mm

Pore diameter of the nanotubes increases with applied potential,

whereas decreases with increased working distance.

L. Sun, S. Zhang, X. W. Sun, X. He, J. Electroanal. Chem. (2009)

Accepted.
TEM Images of As-anodized Nanotubes

The as-anodized nanotubes are

amorphous.
 XRD Patterns
a
a annealed
r a a
r a a a

as-prepared
Intensity (a. u.)

Ti substrate

20 30 40 50 60 70 80
2 (degree)
As anodized, the nanotubes are amorphous; after annealing, mainly
anatase phase (with a little rutile phase).
Conclusions

• Longer titania nanotube arrays are obtainable at higher

applied potential for prolonged durations. Length of the
nanotubes can be controlled from ~500 nm to ~120 m;
• Pore diameter of the nanotubes increases with applied
potential, whereas decreases with increased working
distance;
• The as-anodized titania nanotubes are amorphous. The
nanotubes crystallize mainly into anatase phase upon
annealing.
• The composite structure of nanoparticle-nanotube array
points to another direction for efficiency enhancement in
DSSCs;
Thanks for your attention!
M. A. Green, K. Emery, Y. Hishikawa and W. Warta, Prog. Photovolt: Res. Appl. 17 (2009): 320-326