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Complex Fluids and Multiphase Transport Lab

Photoinduced wettability conversion of ZnO nanorods
1, Mayer


2, Chhasatia


2, Shah


2 Yang

and Ying

2 Sun

of Mechanical Engineering, University of Tulsa, Tulsa, OK 2Department of Mechanical Engineering and Mechanics, Drexel University, Philadelphia, PA


The wettability of surfaces is important in many industrial processes such as cleaning, drying, painting, coatings, adhesion, and pesticide application. The most common method of evaluating wettability is by measuring the contact angle as shown below. [1] Advances in nanotechnology have stimulated the development of new materials and devices which should require both superhydrophobic surfaces θ with contact angles between 150° and 180° and superhydrophilic surfaces with contact angles approaching 0°. One such application is the use of nanostructured, stimuli-responsive surfaces for two-phase heat transfer enhancement. Zinc oxide (ZnO) has been widely studied as a potential material for these applications due to its potential to form nanostructured surfaces as well its photoactive nature. The objective of this study is to create a superhydrophobic ZnO nanorod surface that can undergo a photoinduced conversion to a hydrophilic surface.

Effect of ODP deposition
• Depositing ODP on smooth ZnO film decreased the surface energy of the solid and increased the contact angle (CA) from 34° to 124°.
CA=34° CA=124°

RESULTS (continued)
Sonication in isopropanol after the ODP deposition leads to a more complete ODP monolayer by washing away excess ODP.

500 nm

500 nm

Bare ZnO film

ZnO film w/ ODP

Uncoated nanorods

Nanorods w/ ODP monolayer



• ZnO nanorods were grown on indium tin oxide (ITO) coated glass substrates using a two step solution method adapted from the work of Vayssieres [2] and Majidi and Baxter [3].
500 nm 500 nm ZnO nanorods

Contact Angle (degrees)

• Depositing ODP onto ZnO nanorods caused the drop to change from a Wenzel state, where the drop completely penetrates into the texture of the rough surface, to a Cassie-Baxter state, where the drop sits on top of the surface with trapped air underneath.

Effect of UV illumination UV illumination dramatically increases the hydrophilicity of the nanorod surface, completely changing the wettability.
160 140 120 100 80 60 40 20 0 0 4 8 12 16 20 Length of UV Illumination (hours) 24

Bare ZnO nanorods Wenzel state

ZnO nanorods w/ ODP Cassie-Baxter state

Effect of ZnO nanorods
• When both surfaces are coated in ODP, the change in contact angle shown below from a film to a nanorod surface suggests that the increase is due to the added physical roughness of the nanorod surface, allowing air to be trapped underneath the drop.
CA=124° CA=166°

• The deposition of ODP on ZnO nanorods creates a more hydrophobic surface than on a smooth ZnO film due to the additional roughness created by the nanorods. • ODP deposited on ZnO nanorods then sonicated in isopropanol forms a self-assembled monolayer, allowing for air to be trapped underneath the drop. • UV illumination increases the hydrophilicity of the nanorod surface. • Future work will attempt to make this conversion faster, as well as reversible, allowing for easy control of wetting properties.



• ZnO films are created by spin coating a solution of zinc acetate and ethanolamine in ethanol onto an ITO coated glass substrate then annealing at high temperature. • Octadecylphosphonic acid (ODP) self-assembled monolayers were created using a chemical bath deposition (CBD) method adopted from the work of Zhang et al. [4]. The nanorod-covered subsrates were immersed in a solution of ODP dissolved in heptane and isopropanol for 48 hours then sonicated in isopropanol for one hour. • Surface wettability was quantified using the contact angle of a water drop measured by a CCD goniometer. • UV illumination was performed using a lamp with a wavelength peak at 365 nm positioned 1 inch from the substrate with an intensity of approximately 215 mW/cm2.

ZnO film w/ ODP

ZnO nanorods w/ ODP

• This additional roughness can be quantified by assuming either a Wenzel state (drop fills in the space around rods) or a Cassie-Baxter state (drop sits on top of both surface and trapped air) [5]. • Assuming a Wenzel state where R is the ratio of the actual surface area to the projected surface area: cosrough R=  1.75 cos smooth
• Assuming a Cassie-Baxter state where f is the fraction of liquid that is contacting the solid:

1. 2. 3. 4. Extrand, Langmuir 2002, 18, 7991-7999 Vayssieres, Advanced Materials 2003, 15, 464-466. Majidi, Baxter, Electrochimica Acta 2011, 56, 2703–2711. Zhang, et al., Journal of Physical Chemistry C 2007, 111, 1452114529. 5. Quéré, Reports on Progress in Physics 2005, 68, 2496-2532.

• NSF EEC-1005090 “iREU: Interdisciplinary Research Experience for Undergraduates in Medicine, Energy, and Advanced Manufacturing”

cosrough 1 f=  0.064 cos smooth 1
• This means the drop is sitting on almost 95% air.