Laboratory for Oxide Research and Education (LORE)
Wetting Behavior of Cerium Oxide Films
Grown by Pulsed Laser Deposition
Daniel Li, UIUC
Advisor Dr. Jeremiah Abiade
NSF-REU Symposium
University of Illinois at Chicago
Chicago, IL
8/1/2013
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
Purpose and Motivation
Build upon research that investigate the intrinsic hydrophobic
properties of REOs
Robust, hydrophobic coating compatible with existing
facilities
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
15
Azimi, Gisele, Rajeev Dhiman, Kwon Hyuk-Min, Adam T. Paxton, and Kripa K. Varanasi. "Hydrophobicity of Rare-earth
Oxide Ceramics." Nature Materials 12.4 (2013): 315-20. Nature Publishing Group, 20 Jan. 2013.
Laboratory for Oxide Research and Education (LORE)
Wetting Behavior
• Water Contact Angle
• Surface energy
• Hydrophobicity and hydrophilicity
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
9 Quéré,
David. "Wetting and Roughness." Annual Review of Materials Research 38.1 (2008): 71-99. Review in Advance. Annual
Review of Materials Research, 7 Apr. 2007.
Laboratory for Oxide Research and Education (LORE)
Applications of Hydrophobic Materials
• Waterproofing and
Lubrication
• Corrosion Prevention
• Condensation
• Self Cleaning Materials
• Heat Transfer/Cooling
Systems
[1] http://geography.swansea.ac.uk/hydrophobicity/soil_hydrophobicity.htm
[2] http://meanderinglanes.blogspot.com/2010/09/rain-on-windshield.html
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
[3] http://www.aeconline.ae/qatar-s-deputy-prime-minister-to-inaugurate-world-2s-largest-district-cooling-24893/news-files/dc2_main.jpg
[4] http://www.criticalend.com/wp-content/uploads/2009/03/balepsycho.jpg
Laboratory for Oxide Research and Education (LORE)
Cerium Oxide
Polymer Additives
•
Chemically Stable
•
High Adhesiveness
•
Thermal Transfer
•
Durability/Wear Resistance
•
Relatively Low Cost
Hydrophobic Properties diminish
substantially from thermal,
mechanical, and chemical attack
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
[1,2] http://www.rustoleum.com/product-catalog/consumer-brands/neverwet/neverwet-kit/
[3]http://www.netl.doe.gov/newsroom/features/12-2010.html
Laboratory for Oxide Research and Education (LORE)
Thin Films
Thin = less than one micron
(1000 nm)
Film = layer of material on a
substrate
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Pulsed Laser Deposition (PLD)
Process
1. Laser is focused onto a target in high vacuum or ambient gas
2. Target material is vaporized and a plasma plume is created
3. Gaseous target deposits onto substrate, thin film develops
Department of Materials Science & Engineering
Department of Mechanical Engineering
[1,2] http://tfy.tkk.fi/aes/AES/projects/prlaser/pld.htm
Laboratory for Oxide Research and Education (LORE)
PLD Factors
• KrF Excimer Laser Fluence
• Target-substrate
distance
• Number of pulses and frequency
• Deposition temperature
• Basal and gas pressure
Advantages:
- stoichiometry is preserved
- multiple targets allowable
- easily controlled growth rate
Disadvantages:
- limited uniformity, requires
small substrate
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
[1] https://rt.grc.nasa.gov/main/rlc/pulsed-laser-deposition-laboratory/
Laboratory for Oxide Research and Education (LORE)
Experimentation
I.
Pulsed laser deposition of thin film cerium oxide
(ceria) on Si at varying oxygen partial pressures and
deposition temperature
II.
WCA measurements over time with and without UV
irradiation (4 microliters, DI water)
III. X-ray photoelectron spectroscopy (XPS)
characterization
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
PLD Thin Films
Controls
Independent Variables
• Cerium Oxides onto Silicon wafer
• Target-Substrate Distance: 6.2 cm
• Oxygen Partial Pressure
KrF Excimer Laser:
2 main Cerium oxidation
states: +3, +4
• Wavelength: 248 nm (UV)
• Laser Fluence 4.5 J/cm2, 22 kV, 500 mJ
• Temperature (RT, 300, 700
degrees Celsius)
• 5000 Pulses at 5 Hz
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
[1] http://www.kruss.de/en/products/contact-angle/drop-shape-analysis-system
Laboratory for Oxide Research and Education (LORE)
PLD Depositions
Room
Temperature
300 Degrees
Celsius
700 Degrees
Celsius
2.5 E-2 Torr (T) No Oxygen
2.2 E-2 T
7.5 E-2 T
2.1 E-1 T
7.4 E-2 T
2.5 E-3 T
6.2 E-2 T
2.1 E-2 T
7.5 E-3 T
4.7 E-3 T
7.5 E-3 T
8.1 E-4 T
7.2 E-4 T
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
WCA as a function of Time Elapsed (300 degrees)
100
90
80
Oxygen
Pressure
(Torr)
Water Contact Angle
70
60
No Oxygen
2.00E-01
50
6.00E-02
40
4.70E-03
8.00E-04
30
20
10
0
0
50
100
150
200
250
300
350
400
Time Elapsed (hrs)
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
WCA as a function of Time Elapsed (Post 30 minutes UV
irradiation, 300 degrees)
100
90
80
Oxygen
Pressure
(Torr)
Water Contact Angle
70
60
No oxygen
2.00E-01
50
6.00E-02
40
4.70E-03
8.00E-04
30
20
10
0
-50
0
50
100
150
200
250
300
350
400
Time Elapsed (hours)
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
WCA as a function of Deposition Temperature
Oxygen
Pressure
(Torr)
3.0 E-2
5.0 E-2
No Oxygen
Photo provided courtesy of Sin Pui Fu, UIC
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
WCA as a function of Time Elapsed (700 degrees Celsius)
100
90
Oxygen
Pressure
(Torr)
80
Water Contact Angle
70
60
2.20E-02
7.40E-02
50
2.10E-03
40
7.50E-03
7.20E-04
30
20
10
0
0
50
100
150
200
250
300
350
400
Time Elapsed (hours)
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
WCA as a function of Time Elapsed (Post 30 minutes UV
irradiation), 700 degrees)
90
80
Oxygen
Pressure
(Torr)
Water Contact Angle
70
60
2.20E-02
50
7.20E-02
40
2.10E-03
7.50E-03
30
7.20E-04
20
10
0
0
20
40
60
80
100
120
140
Time Elapsed (hours)
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
Water Conctact Angle (WCA)
300 Degrees
Retreatment of
Previous
Samples with
UV over time
Oxygen
Pressure
(Torr)
100
90
80
70
60
50
40
30
20
10
0
No oxygen
8.00E-04
4.70E-03
0
30
60
90
120
Duration under UV (minutes)
Water Conctact Angle (WCA)
Resistance to UV:
smaller drop in WCA
700 Degrees
Oxygen
Pressure
(Torr)
90
80
70
60
50
40
30
20
10
0
2.20E-02 88
2.10E-03 90
7.50E-03 89
7.50E-04 90
30
60
90
120
Duration under UV (minutes)
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
30 minutes UV Irradiation (300 degrees Celsius)
30 minutes UV Irradiation (700 Degrees Celsius)
100
90
90
80
80
70
70
60
60
50
50
40
40
30
30
20
20
10
10
0
0
No oxygen
2.00E-01
6.00E-02
4.70E-03
2.20E-02
8.00E-04
Second Round of UV (300 Degree Celsius)
100
90
80
70
60
50
40
30
20
10
0
7.20E-02
2.10E-03
7.50E-03
7.20E-04
Second Round of UV (700 Degree Celsius)
100
90
80
70
60
50
40
30
20
10
0
No oxygen
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
8.00E-04
4.70E-03
2.20E-02
2.10E-03
7.50E-03
7.50E-04
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
WCA as a function of Time Elapsed (RT)
100
90
80
Water Conctact Angle
70
60
2.50E-02
50
7.50E-02
2.50E-03
40
7.50E-03
30
20
10
0
0
20
40
60
80
100
120
140
160
Time Elapsed (hours)
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
UV Treatment of Room Temperature
Samples over Time
Room Temperature
100
Water Conctact Angle (WCA)
90
80
Oxygen
Pressure
(Torr)
70
60
2.50E-02
50
7.50E-02
40
2.50E-03
30
7.50E-03
20
10
0
0
30
60
90
120
Duration under UV (minutes)
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
WCA over Time (after 120 minutes of
UV Irradiation)
Samples were kept in the dark
Variation in recovery to pre- UV
levels
Water Contact Angle
300 Degrees
90
80
70
60
50
40
30
20
10
0
Oxygen
Pressure
(Torr)
No oxygen
8.00E-04
4.70E-03
0
6
12
24
48
72
96
Time Elapsed After UV Irradiation (hours)
Room Temperature
700 Degrees
Oxygen
Pressure
(Torr)
Water Contact Angle
70
60
50
2.50E-02
40
7.50E-02
30
2.50E-03
20
7.50E-03
10
0
0
6
12
24
48
72
96
Time Elapsed After UV Irradiation (hours)
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Water Contact Angle
80
100
90
80
70
60
50
40
30
20
10
0
Oxygen
Pressure
(Torr)
2.20E-02
2.10E-03
7.50E-03
7.50E-04
0
6
12
24
48
72
96
Time Elapsed After UV Irradiation (hours)
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
X-Ray Photoelectron Spectroscopy (XPS)
Sample is irradiated by X-rays
- emitted electrons are measured
Useful for determining
stoichiometry
- oxidation states
- empirical formula
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
XPS Data
2.1 E-3 T, 700 C
7.5 E-3 T, 700 C
• XPS analyzed valency of Ce ions at the surface
• Ce(III)Oxide is present in higher amounts in higher oxygen pressures than Ce (IV)
Oxide
• Stoichiometry: cerium and oxygen is independent of temperature
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
Conclusions and Discussion
• Water contact angles vary initially but eventually increase and
plateau to ~ 90 degrees over a week
• UV treatment causes a significant drop in WCA but most samples
recover to pre-UV levels
• Samples that have been treated previously with UV have a greater
resistance (smaller WCA drop) than those treated for the first time;
likewise for recovering to pre-UV treatment levels
• More observed uniformity in samples created at 700 degrees, though
XPS indicates temperature has little effect on oxidation states
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
Further Work
• Run standard scan on pure cerium to determine remaining peak
features; XPS of additional samples
• Additional characterization of surface morphology with AFM and TEM
•Ultra clean storage inbetween measurements to account for
hydrocarbon contamination
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
Acknowledgements
• EEC-NSF Grant # 1062943
• Advisor Jeremiah Abiade
• Riad Alzeghier
• Jelani Hannah
• Dr. Takoudis and Dr. Jursich
• REU Staff
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
References
Deval et al “Reconfigurable hydrophobic/hydrophilic surfaces in microelectromechanical systems (MEMS)” 2004 J. Micromech. Microeng. 14 91
Sushant, Adam Paxon, and Kripa K. Varanasi. "Enhanced Condensation on Lubricant-Impregnated Nanotextured Surfaces." American Chemical Society 6.11
(2012): 10122-0129. ACS Nano. Apr.-May 2012.
3 Cao, Liangliang, Andrew K. Jones, and Vinod K. Sikka. "Anti-Icing Superhydrophobic Coatings." Langmuir Letter (2009): n. pag. American Chemical Society, Sept.
2009.
4 Nakajima, Akira. "Design of Hydrophobic Surfaces for Liquid Droplet Control." Asia Materials 3.55 (2011): 49-56. Nature. NPG, 19 May 2011.
5 Liu, Kesong, and Lei Jiang. "Metallic Surfaces with Special Wettability." Nanoscale 3.3 (2011): 825-38. RSC Publishing, 11 Jan. 2011.
6 Crick, Colin R., and Ivan P. Parkin. "A Single Step Route to Superhydrophobic Surfaces through Aerosol Assisted Deposition of Rough Polymer Surfaces: Duplicating
the Lotus Effect." Journal of Materials Chemistry 19.8 (2009): 1074-079
7 Cao, Feng, Zisheng Guan, and Dongxu Li. "Preparation of Material Surface Structure Similar to Hydrophobic Structure of Lotus Leaf." Journal of Wuhan University of
Technology-Mater. Sci. Ed. 23.4 (2008): 513-17. Aug. 2008
8 Wong, Tak-Sing, Sung Hoon Kang, and Sindy K.Y. Tang. "Bioinspired Self-repairing Slippery Surfaces with Pressure-stable Omniphobicity." Nature.com. Nature
Publishing Group, 21 Sept. 2011. Web. 08 July 2013.
9 Quéré, David. "Wetting and Roughness." Annual Review of Materials Research 38.1 (2008): 71-99. Review in Advance. Annual Review of Materials Research, 7 Apr.
2007.
10 Fowkes, F. Contact Angle, Wettability and Adhesion, American Chemical Society, 1964
11 McCarthy, T. A Perfectly Hydrophobic Surface, J. Am. Chem.Soc., 2006, 128, 9052.
12 Tanford, C. “The Hydrophobic Effect, Wiley. 1973
13 Young, Thomas. "An Essay on the Cohesion of Fluids." Philosophical Transactions of the Royal Society of London (1776-1886) 95.1 (1805): 65-87. Royal Society
Publishing.
14 Giovambattista, N., Debenedetti, P. G. & Rossky, “Enhanced surface hydrophobicity by coupling of surface polarity and topography. Proceedings of the National
Acaddemy of Sciences. USA 2009, 106 no.36,
15 Azimi, Gisele, Rajeev Dhiman, Kwon Hyuk-Min, Adam T. Paxton, and Kripa K. Varanasi. "Hydrophobicity of Rare-earth Oxide Ceramics." Nature Materials 12.4
(2013): 315-20. Nature Publishing Group, 20 Jan. 2013.
16 Adachi, G., Imanaka, N. & Kang, Z. C. Binary Rare Earth OxidesCh. 2 (KluwerAcademic, 2004).
17 K.Tsukuma, M. Shimada, “Strength, Fracture Toughness and Vickers Hardness of CeO2 Stabilized Tetragonal ZrO2 Polycrystals,” Journal of Materials Science, 20
(1985), 1178-1184.
18 Beie, H.-J., and A. Gnörich. "Oxygen Gas Sensors Based on CeO2 Thick and Thin Films." Sensors and Actuators B: Chemical 4.3-4 (1991): 393-99.
1 Joanne
2 Anand,
F. Stroosnijder, V. Guttmann, T. Fransen, J. H. W. de Wit, “Corrosion of Alloy 800H and the Effect of Surface Applied CeO2 in a Sulfidizing Oxidizing Carburizing
Environment at 700 degree-C”, Oxidation of Metals, Vol. 33, Nos. 5/6, 1990
20 Patsalas, P., S. Logothetidis, and C. Metaxa. "Optical Performance of Nanocrystalline Transparent Ceria Films." Applied Physics Letters 81.3 (2002): 466.
21 A.E. Hughes, J.D. Gorman, P.J.K. Patterson, R. Carter, Surface Interfacial Analysis 1996, 24, 634-640
22 Mohandas, E., G. Balakrishnan, and S. Tripura Sundari. "A Study of Microstructural and Optical Properties of Nanocrystalline Ceria Thin films Prepared by Pulsed
Laser Deposition." Elsevier(2010): 2520-526. Science Direct. Thin Solid Films, 10 Dec. 2010.
23 Jiang, Keren. "Fabrication and Catalytic Property of Cerium Oxide Nanomaterials."Chemistry Thesis (2011): 1-73. University of Nebraska- Lincoln, Jan. 2011.
19 M.
25 Martínez, L.,
E. Román, J.l. De Segovia, S. Poupard, J. Creus, and F. Pedraza. "Surface Study of Cerium Oxide Based Coatings Obtained by Cathodic Electrodeposition on Zinc." Applied Surface Science 257 (2011): 6202-207.
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
Atomic Force Microscopy: Cerium (IV) oxide on Si
No oxygen, 200 degrees C
Roughness: 4.61 nm
WCA: 95 degrees
5 E-2, 200 degrees C
Roughness: 4.91 nm
WCA: 44 degrees
• PLD process doesn’t seems to yield different surface morphologies
• Very different water contact angles
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Images provided by Sin-Pui Fu, UIC
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
XPS Data
Cerium
Intensity
A.u.
Stoichiometry:
7.5 E-3, 700 C
2.5 E-3, RT
2.1 E-3, 700 C
7.5 E-3 torr at 700 C Ce:O 15:1
2.1 E-3 torr at 700 C Ce:O 32:1
Binding Energy eV
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering
Laboratory for Oxide Research and Education (LORE)
Jeremiah T. Abiade
Daniel Li
jabiade@vt.edu
dli22@illinois.edu
Department of Materials Science & Engineering
Department of Mechanical Engineering