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 65-6790 4400 北京钢铁研究总院 )
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 o , 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

• drasticallyscattered connections electrons reduced at connections • vectorial transpoprt collecting electrode randomly walk to the • comparable surface area with nanoparticle large surface area based photoanode
TiO2 TCO Dye Electrolyte Counter Electrode

Limit the photoanode thickness larger than 10 µm Enablethe photoanode thickness to approx. 10 µm Achieve light-harvesting Inhibit absorption of low-energy photons

M. Grätzel, J. Photochem. Photobiol. A: Chem. 164 (2004): 3

Problems in TiO2 Nanotube Array Based DSSCs
(a) (b)

• short nanotube array (less than 5 µm, compared to optimal 20~30 µm) • increased resistance of FTO during annealing

• reflected by platinized counter electrode • absorbed by iodine in the electrolyte • Increased barrier layer thickness by 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 ≈ r 3 R 5 > r 3

comparable surface area SNT < SNP

typical nanoparticle size 15 ~20 nm r = 9 nm 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, 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

Too small to achieve!

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 + 2 vol% H2O + 0.3 wt% NH4F

anion cation

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 r r a a a

annealed
a a

Intensity (a. u.)

as-prepared

Ti substrate

20

30

40

2θ (degree)

50

60

70

80

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 µ 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

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