See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/268209537

Super hydrophobic/Super hydrophilic Transparent Nanostructured Glass

Fabricated by Wet Etching

Conference Paper · April 2014

DOI: 10.13140/2.1.3374.3043

CITATIONS READS
2 3,685

5 authors, including:

Amarendra Kumar Kunal Kashyap

Epistar Corp. National Tsing Hua University
15 PUBLICATIONS   30 CITATIONS    11 PUBLICATIONS   33 CITATIONS   

SEE PROFILE SEE PROFILE

Max Hou Jun- Jun Yeh

Pegatron Ditmanson Medical Foundation Chia-Yi Christian Hospital, Chiayi, Taiwan
26 PUBLICATIONS   199 CITATIONS    435 PUBLICATIONS   11,030 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Strength improvement by surface nanostructuring View project

asthma with gene View project

All content following this page was uploaded by Amarendra Kumar on 13 November 2014.

The user has requested enhancement of the downloaded file.

 Proceedings of the 9th IEEE International
Conference on Nano/Micro Engineered and Molecular Systems
April 13-16, 2014, Hawaii, USA

Super hydrophobic/Super hydrophilic Transparent

Nanostructured Glass Fabricated by Wet Etching
Amarendra Kumar1*, Kunal Kashyap1, Kai Wei Liao 1, Max T. Hou2ġand J. Andrew Yeh1, 3
1
Institute of Nanoengineering and Microsystems, National Tsing Hua University, Hsinchu, Taiwan
2
Department of Mechanical Engineering, National United University, Miaoli, Taiwan
3
Instrument Technology Research Center, National Applied Research Laboratories, Hsinchu, Taiwan
*Contacting Author: Amarendra Kumar, s9935584@m99.nthu.edu.tw

Abstract- Glass nanostructures were fabricated by wet chemical
etching instead of using the complicated nanolithography and
expensive dry etching process. Super hydrophilic glass with contact
angle of 1° was created using this nanostructure with 92%
transparency .Self-assembled monolayer of Perfluorodecyl-
trichlorosilane (FDTS) was used to further make the glass super
hydrophobic with contact angle of 151° without affecting its
transparency. Polysilicon layer of 300 nm was deposited on glass
substrate first and nanostructures were fabricated in this layer by
metal assisted wet chemical etching. Thermal oxidation converted
the silicon nanostructure to silicon dioxide nanostructure. This
technology is producible on mass scale and useful in preparation of
anti-fogging and self-cleaning glass.
Keywords- Glass Nanostructure; Mask less lithography; Super
hydrophilicity; Super hydrophobicity; Wet chemical etching
Introduction
dry etching technique[4]. Nanostructure formation by
lithography needs a complicated masking process for
achievement of nano scale resolution .This essentially includes
coating of antireflection layer. Normal lithography using UV
light is not suitable for nanostructure fabrication. Interference
lithography is one of the common lithography process used but
this process is complicated and not easily reproducible. Deep
reactive etching is required for etching and structure height more
than 1 um is difficult to achieve by this fabrication because of
mask limitation. For mask less lithography also etching is
required. Mask can be formed by different methods like
annealing of thin metal films [4]. For this thin metal film of few
nanometer is deposited and annealed .Annealing will turn metal
film into nano island. This nano island pattern will act as
lithography mask but non uniformity is a major issue in this case.

The hydrophilic surface which has some effects such as anti-fog,

self-cleaning, quick dry and elimination of light scattering
caused by water droplets is useful in various fields of optical
mirrors and lenses, biometric applications, building windows,
and optoelectronic devices [1-3]. Super hydrophilic surface can
be achieved by nanostructure [4], self-assembled coating of
nanoparticle [5] or coating of thin film [6]. Self-cleaning is
property of glass to clean itself without any sensing or actuation
mechanism. This can be easily achieved by super
hydrophobicity or super hydrophilicity property. In case of super
hydrophilic glass wettability of surface increases which in turn
helps the water droplet to spread over the dust and clean the
surface by taking dust with it (Fig 1). For super hydrophobic
glass water droplet will roll over the surface and carries the dust Fig. 1. Explanation of self-cleaning property by using hydrophilic and
particle away with it. It is very clear that for super hydrophobic hydrophobic property of glass
surface the cleaning process is very fast and it will be
comparatively slower for super hydrophilic surface but the All the process explained above is wafer level process. Every
overall effect will be same for both the process. Same property wafer need to process separately so it is very time consuming for
is responsible for anti-fogging also. In case of foggy industry use. This work opens the possibility of wet chemical
environment droplets can restrict the vision but if the surface is etching for glass nanostructure fabrication. In current work
super hydrophilic the contact angle is close to 1° which will not masking is not required. All the process used in current work is
allow to form any curved water surface. Similarly in the case of batch process. A complete batch of wafers can be processed
super hydrophobic surface water droplet of fog will roll quickly together for all the steps involved. Super hydrophilic glass of
off the surface which will increase visibility. Coating affects contact angle 1° and 92% transparency is fabricated by current
transparency and life time of coating is short in some wet chemical etching process. All the process involved can be
environment. Nanostructure techniques either involve easily applicable on all size wafers. Time required for all the
complicated nanolithography process [7] or highly expensive steps is also reduced by current process. Metal assisted wet

978-1-4799-4726-3/14/$31.00 © 2014 IEEE 113

chemical etching is used which is matured process for silicon nanoparticles started sinking in polysilicon layer. Height of
nanostructure fabrication. The unique advantage of this process nanostructure formed depends on etching time of the reaction.
is that it can be used for both surfaces at the same time. This will
reduce the cost to half if we need to process the wafer on both
sides. In normal case only one side is processed but for panels
and windows it is better if we process the glass on both side so
that transparency and self-cleaning property can be enhanced for
both side surface. The other unique property of glass
nanostructure is that it can be used for both super hydrophobicity
and super hydrophilicity. For normal glass contact angle is
found to be 25° but for nanostructure glass the water droplet is
almost flat and it is close to 1°. After depositing Perfluorodecyl-
trichlorosilane (FDTS) for normal glass the contact angle is 113°
but depositing FDTS on nanostructure glass the contact angle
increased to 151° which make is superhydrophobic .This study
explains that same nanostructure can be used for both super
hydrophobicity and super hydrophilicity.

Experiment
Polysilicon of 300 nm thickness was deposited on glass samples
using LPCVD at 620 °C. Thickness of polysilicon layer
deposited on quartz sample depends on the height of
nanostructure required. Polysilicon nanostructures were
fabricated by immersing silicon samples into 0.1 M AgNO3
solution for 5 minutes. This deposited a thin layer of silver
nanoparticles on polysilicon layer. After that samples were

Fig. 2. (a) Schematic illustration of process steps for fabrication of glass nano
structure using wet chemical etching (b) SEM image for glass nanostructure
formed after wet chemical etching and thermal oxidation Fig. 3. (a) Water droplet for normal glass used in the experiment (b) Image for
water droplet after dropping on super hydrophilic glass. To show the super
hydrophilicity red dye is mixed in water which can be seen as thin film (c) Image
etched in the solution of HF (49%wt) and H2O2 (30%wt) in 3:1 for super hydrophobic glass formed by depositing FDTS self-assembled
ratio [8].Silver nanoparticle present in the solution acted as monolayer on glass nanostructure
catalyst for this reaction. Silicon under the silver nanoparticle
Once we remove the sample from etching solution extra silver
got oxidized and silicon dioxide generated was etched away by
particle will be left in between the nanostructures. Extra silver
HF present in the solution. By this process the silver

114
was removed in mixture of DI water and HNO3 in 5:1 ratio. After
metal assisted etching, polysilicon nanostructures were
completely oxidized using thermal oxidation to change silicon
nanostructure into silicon dioxide nanostructure (Fig 2(a)).This
removed the unnecessary step of mask removal.
Fig. 4. (a) FDTD simulation for transparency of cone shaped nanostructure at
different heights in the visible light wavelength (b) FDTD simulation for
transparency of pillar shaped nanostructure at different heights in the visible
light wavelength
Results and Discussion
SiO2 nanostructures are the key component of super hydrophilic
surface (Fig 3(b)) .With nanostructures, the surface became
rough which increases hydrophilicity. Simulation is done using
the finite-difference time-domain (FDTD) method which
implemented in the FDTD solutions software [9]. Simulation is
performed for optimizing the polysilicon layer thickness. In
FDTD simulation, different height of nanostructure were
simulated and it was observed that 300 nm height nanostructure
115
has flatter response and better transmittance keeping all other
parameter same including pitch and density of nanostructure
(Fig 4(a))
Simulation is done for pillar shaped structure first with width of
100nm and different height structure. (Fig 3(b)) .Width is fixed
since the pitch for metal assisted wet chemical is same for all
etching time. To reproduce the experimental situation with
simulation we have created the nanostructure in unorganized
manner. For future possibilities, cone shaped structures were
also simulated. In simulation, cone shaped structure are better
Fig. 5. Transparency comparison of normal glass and nanostructures at different
wavelength in visible region
than pillar shaped structures. The transmittance response is also
flatter in case of cone shaped structure (Fig 4(b)). Normal glass
have contact angle of 25° which will cause scattering of light
due to curved surface in fogging environment. With
nanostructure, glass contact angle will be close to 1° which
minimizes the white light scattering by creating water film
instead of water droplet on glass surface. Formation of thin layer
on superhydrophobic surface is shown in Fig. 3(b). By mixing
red dye in water, the spreading of water on nanostructured glass
surface was observed. The result shows that a thin layer of liquid
was formed. With the same fabrication technique,
superhydrophobic surface was also fabricated. Self-assembled
monolayer of FDTS can increase the contact angle of normal
glass surface from 25° (Fig 3(a)) to 113° but coating of FDTS
on nanostructure glass can increase the contact angle to 151°
(Fig 3(c)).By the current wet etching process, pillar structure
was successfully fabricated and the same transparency was
received as normal glass (Fig 5). If cone shaped structures can
be fabricated by present wet chemical etching, it can be used for
creating glass with better transparency and super
hydrophilic/super hydrophobic property.
Conclusion
Present work completely removes the process of nanloscale
masking and dry etching technique for glass nanostructure
fabrication. Nanostructure surface formed is super hydrophilic
and can be easily transferred to super hydrophobic. Metal
 assisted wet chemical etching and thermal oxidation techniques
are matured, comparatively simple and inexpensive processes. .
All the processes involved are batch process and can be accepted
by industry easily.
Acknowledgements

The authors are grateful for the research support from the Sino
American Silicon Products Incorporation and Instrument
Technology Research Center (ITRC). This work was partly
supported by the National Science Council in Taiwan through
Project No NSC 100-2628-E-007-013-MY3 which is gratefully
acknowledged.

REFERENCES

[1] Y. F. Li, J. H. Zhang, S. J. Zhu, H. P. Dong, F. Jia, Z. H. Wang, et

al., "Biomimetic Surfaces for High-Performance Optics," Advanced
Materials, vol. 21, pp. 4731-+, Dec 11 2009.
[2] G. C. Park, Y. M. Song, J. H. Ha, and Y. T. Lee, "Broadband
Antireflective Glasses with Subwavelength Structures Using
Randomly Distributed Ag Nanoparticles," Journal of Nanoscience
and Nanotechnology, vol. 11, pp. 6152-6156, Jul 2011.
[3] L. K. Verma, M. Sakhuja, J. Son, A. J. Danner, H. Yang, H. C.
Zeng, et al., "Self-cleaning and antireflective packaging glass for
solar modules," Renewable Energy, vol. 36, pp. 2489-2493, Sep
2011.
[4] J. W. Leem, Y. Yeh, and J. S. Yu, "Enhanced transmittance and
hydrophilicity of nanostructured glass substrates with antireflective
properties using disordered gold nanopatterns," Optics Express, vol.
20, pp. 4056-4066, Feb 13 2012.
[5] X. M. Liu and J. H. He, "Hierarchically structured superhydrophilic
coatings fabricated by self-assembling raspberry-like silica
nanospheres," Journal of Colloid and Interface Science, vol. 314,
pp. 341-345, Oct 1 2007.
[6] J. G. Yu, X. J. Zhao, Q. N. Zhao, and G. Wang, "Preparation and
characterization of super-hydrophilic porous TiO2 coating films,"
Materials Chemistry and Physics, vol. 68, pp. 253-259, Feb 15
2001.
[7] K. C. Park, H. J. Choi, C. H. Chang, R. E. Cohen, G. H. McKinley,
and G. Barbastathis, "Nanotextured Silica Surfaces with Robust
Superhydrophobicity and Omnidirectional Broadband
Supertransmissivity," Acs Nano, vol. 6, pp. 3789-3799, May 2012.
[8] C. M. Hsieh, J. Y. Chyan, W. C. Hsu, and J. A. Yeh, "Fabrication
of wafer-level antireflective structures in optoelectronic
applications," 2007 Ieee/Leos International Conference on Optical
Mems and Nanophotonics, pp. 185-186, 2007.
[9] Lumerical Solutions (2009) FDTD Solutions version 6.5. Lumer-
ical Solutions, Vancouve

116

View publication stats