Creating Optically Transparent, Durable

Superhydrophobic Thin Film Coatings

Chadwick L. Riggs, Dr. Tolga Aytug, Dr. J ohn T. Simpson
Partnerships Directorate
Oak Ridge National Laboratory
Oak Ridge, TN USA
riggscl@ornl.gov



Abstract Oak Ridge National Laboratory (ORNL) has
developed a new method for forming rugged optically
transparent superhydrophobic (SH) thin-film coatings.
This surface treatment offers high optical transparency,
mechanical durability, and other enhanced properties
using controllable processes. Attaining both high
hydrophobicity and optical transparency usually requires
complicated, specialized techniques and time-consuming
processes, with resulting films of poor SH quality or
adhesion [1]. Many competing SH surface treatments use
reagents that may pose risks to human health and the
environment [2], and are limited to laboratory research
and not suitable for commercial applications.

This new process combines the ability to reliably apply
complex coatings via industrially scalable, low-cost
processes; and an ORNL patented technology for creating
differentially etched SH disordered composite materials
(US Patent #7,258,731) with existing and novel methods to
reliably apply complex coatings via industrially scalable,
low-cost processes to produce optically transparent,
nanostructured SH surfaces (patent pending). This
combination of ORNL technologies produces stable SH
transparent thin film coatings that are strongly adhered to
glass (or other) substrates. They are virtually
indistinguishable from the underlying glass template, and
are naturally somewhat antireflective and UV blocking.
The commercial viability of this technique includes glass
related applications such as automotive windshields and
residential windows, specialty optics, electronic, solar and
military optical components.

Initial work has focused on fused silica substrates. These
concepts and methods will be extended to alternate
optically transparent materials in future phases of this
work. This technology is available for licensing and
ORNL is actively seeking commercialization partners. An
industry symposium focused on this technology is
scheduled for Wednesday, September 5, 2012 at ORNL
(http://www.ornl.gov/adm/partnerships/events/superhydro
phobic2012/index.shtml).

Keywords- Nano-textured, Optically Transparent, Durable
Superhydrophobic, Thin Film, Coating, Anti-fogging, Anti-
fouling

I. Introduction

Integrating superhydrophobicity and transparency
within the same surface presents significant challenges [3].
Hydrophobicity typically competes with transparency because
the surface features (i.e., surface roughness) associated with
hydrophobicity are typically light scattering, making surfaces
appear opaque or translucent; and additionally, surfaces with
large roughness usually exhibit weak mechanical stability.
While there have been reports of superhydrophobic
transparent coatings in the literature, these films are mostly
based on roughened polymers [4], sol-gel [5,6], spray-on
powder coatings [7], or self-assembly of nano-arrays or nano-
structures onto surfaces [2,3,8]. The polymer-based films are
typically not bounded to the substrate well enough to be
sufficiently durable for most application requirements. Harsh
chemical treatment procedures (i.e., chemical solvents) tend to
Fig. 1 SEM micrograph of glass surface after treatment to
induce thermal spinodal phase separation, followed by
preferential removal by etching.


degrade the physical properties of the underlying materials.
Powder based coatings also exhibit weak durability due to
application-specific binding agents [7]. Sol-gel based coatings
can offer better bonding; however, they generally exhibit poor
hydrophobic qualities (low water contact angle) due to the
lack of nanoscale sharpness and porosity. Coatings based on
nanoarrays or nanoparticles have similar problems to polymer
or sol-gel based films, and in addition exhibit relatively poor
homogeneity. Furthermore, fabrication of these nanostructure
assemblies involves elaborate processing schemes that render
them unsuitable for large-scale development and production.
The ORNL approach overcomes many of these common
problems. New fabrication methods achieve very high levels
of mechanical, thermal and environmental stability; using cost
effective industry standard equipment and inherently scalable
manufacturing processes. The surface nano/microstructure and
low-surface energy modification responsible for
superhydrophobicity also results in surface morphology that
can trap small air pockets, enhancing the hydrophobic
properties. Due to the feature sizes of the nanostructured
coating, the process also results in coatings that are also
intrinsically antireflective over visible wavelengths, and
inherently ultraviolet (UV) radiation blocking.

II. Economic Significance

Specific potential products include residential and
vehicle windows, optical lenses and filters (instruments,
sensors, goggles and eyeglasses, science, satellites, weapon
systems, etc.), and photovoltaic glass. The worldwide market
for this technology is significant:
Global coated float glass market >$20 billion
US coated float glass >$7 billion this year
Solar glass market >$600 million

III. Methods

This project combines two critical ORNL strengths:
our industrially scalable physical vapor deposition facilities
(that fabricate extremely uniform thin film coatings), and
novel fabrication methods that produce differentially-etched,
nanostructured superhydrophobic surface structures [9-11].

The coating by physical vapor deposition: Using
physical vapor deposition processes (magnetron sputtering),
we form uniform and strongly bonded optical thin films (100-
500 nm thick) using a specially developed sputtering target
composition. This builds on ORNLs previous extensive
expertise of sputtering oxides onto high temperature
superconducting tapes to provide buffer-layer architectures.
The particles sputter onto the surface at high impact and with
various angles of incidence to produce highly dense films with
exceptional adherence and coverage, even on irregular
surfaces. Furthermore, we have shown that other sputtering
techniques can easily be adapted for complex, continuous and
large area depositions.

The method to produce a superhydrophobic thin
film: This component enables the post-deposition
transformation of the phase-separating coating into a
completely adhered, transparent and superhydrophobic thin
glass film, with additional functionalities of visible-light anti-
reflectivity and UV opacity. This ORNL patented process [9-
11] can produce nanostructured materials/templates with the
precise control of surface features that is required to satisfy
both superhydrophobicity and transparency. The basic
approach of making such films is to begin with phase-
separating glass that is capable of spinodally (i.e., non-
nucleation, continuous phase) decomposing when properly
thermally processed. These phase separated, structurally
connected features scatter light due to the slight differences in
the phases refractive indexes. This light scattering is
wavelength dependent and is known as Raleigh scattering.
Once the coating has been applied and phase-separated
(typically by heat treating) into a spinodal pattern, a controlled
level of differential etching is required in order to completely
remove one phase and partially remove another phase of the
spinodal structure. The resulting surface structure has a very
porous, reticulated network with extremely small funnel
cake or coral appearance (see Fig. 1). The final step is to
covalently bond a chemically hydrophobic self-assembled-
monolayer (SAM) to the etched nanofeatured surface, which
transforms the nano-structured glass surface from hydrophilic
to superhydrophobic. To achieve optical transparency, the size
of the underlying structure should be substantially smaller
than the wavelength of visible light (< 100 nm). The
dimensions of the spinodal features can be controlled by
adjusting the processing parameters, and when the spinodal
structure features are small (~20 nm) the glass film surface
primarily scatters ultraviolet light and passes all other light,
thus appearing transparent while blocking UV radiation. The
coating thickness can be adjusted by sputtering time and/or
etch parameters such that it can also become antireflective to
visible light (over a broad spectrum). The final material
character of the coating and substrate are similar (virtually
identical if the substrate is amorphous silica); the resulting
entity will be essentially monolithic, providing game-changing
advances of both fundamental and practical significance.

IV. Results to Date

Some basic properties and performance levels attained on
fused silica platforms are outlined below.
Superhydrophobicity
Droplet contact angle >170
Roll off angle <10
Optical transparency (>95%) over a broad range
Anti-reflectance (<1%)
High density and uniformity
Durability (including scratch and crack resistance)
Reduces transmittance in UV-regime
Transmittance: 93% (600 nm), 94% (2000 nm)
Broadband and omnidirectional
Can be quickly adopted
Can be engineered to perform as a graded index coating

V. Summary

A new method for forming rugged optically
transparent superhydrophobic thin-film coatings has been


developed. Initial results are promising; suggesting
applications that include residential and vehicle windows,
optical lenses and filters (instruments, sensors, goggles and
eyeglasses), photovoltaic glass, and more. ORNL is actively
seeking commercialization partners. An industry symposium
focused on this technology is scheduled for September 5, 2012
(http://www.ornl.gov/adm/partnerships/events/superhydropho
bic2012/index.shtml).

VI. Inventor Bios

Dr. Tolga Aytug is a research staff
member of the Chemical Sciences
Division at the Oak Ridge National
Laboratory (ORNL) and an Adjunct
Assistant Professor in the Department of
Physics and Astronomy, at The University
of Tennessee. He received his PhD in
Physics from the University of Kansas,
Lawrence, KS. Aytug has extensive experience in the
synthesis and development of advanced thin film materials
using physical and chemical vapor deposition, and chemical
solution approaches, coupled with advanced material
properties characterization.

Dr. John Simpson received a PhD in
Optical Sciences from the University of
Arizona. A former IBM researcher, Dr.
Simpson has been with ORNL for nearly
ten years, and has been the primary
inventor of the broad and deep ORNL
superhydrophobic materials IP portfolio.
His current research is focused on nano-
fabrication over large areas with applications to metamaterials,
superhydrophobic structures, photonic crystal fibers, and
various other technology areas.

VII. References

[1] X. Zhang, F. Shi, J. Niu, Y. J iang, and Z. Wang,
Superhydrophobic surfaces: from structural control
to functional application, Journal of Materials Chemistry 18,
621 (2008)
[2] Y. Gao, Y. Huang, S. Feng, G. Gu, F-L. Qing, Novel
superhydrophobic and highly oleophobic PFPE-modified
silica nanocomposite, Journal of Materials Science 45, 460
(2010)
[3] G. Gu, H. Dang, Z. Zhang, and Z. Wu, Fabrication and
characterization of transparent superhydrophobic thin films
based on silica nanoparticles, Applied physics A 83, 131
(2006)
[4] H. Y. Erbil, A. L. Demirel, Y. Avci, and O. Mert,
Transformation of a simple plastic into a superhydrophobic
surface, Science 299, 1377 (2003)
[5] K. Tadanaga, N. Katata, and T. Minami, Super-Water-
Repellent Al2O3 Coating Films with High Transparency,
Journal of American Ceramic Society 80, 1040 (1997)
[6] H.M. Shang, Y. Wang, K. Takahashi, and G. Z. Cao,
Nanostructured superhydrophobic surfaces,
Journal of Materials Science 40, 3587 (2005)
[7]http://www1.eere.energy.gov/industry/nanomanufacturing/
pdfs/nanostructured_superhydrophobic_coatings.pdf
[8] X. Y. Ling, I. Y. Phang, G. J . Vancso, J. Huskens, and D.
N. Reinhoudt, Stable and Transparent Superhydrophobic
Nanoparticle Films, Langmuir 25, 3260 (2009)
[9] Composite, Nanostructured, Super-Hydrophobic
Material, B. R. DUrso and J .T. Simpson, US Patent No.
7258731B2, Aug. (2007)
[10] Transparent, Super-Hydrophobic, Disordered Composite
Material, B. R. DUrso and J .T. Simpson, US Patent No.
0184247A1, Aug. (2007)
[11] Superhydrophobic Transparent Glass (STG) Thin Film
Articles, US Patent pending.