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Multifunctional surfaces produced by femtosecond laser pulses

A. Y. Vorobyev and Chunlei Guo


Citation: Journal of Applied Physics 117, 033103 (2015); doi: 10.1063/1.4905616
View online: http://dx.doi.org/10.1063/1.4905616
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JOURNAL OF APPLIED PHYSICS 117, 033103 (2015)

Multifunctional surfaces produced by femtosecond laser pulses


A. Y. Vorobyeva) and Chunlei Guob)
The Institute of Optics, University of Rochester, Rochester, New York 14627, USA

(Received 6 October 2014; accepted 26 December 2014; published online 20 January 2015)
In this study, we create a multifunctional metal surface by producing a hierarchical
nano/microstructure with femtosecond laser pulses. The multifunctional surface exhibits combined
effects of dramatically enhanced broadband absorption, superhydrophobicity, and self-cleaning. The
superhydrophobic effect is demonstrated by a falling water droplet repelled away from a structured
surface with 30% of the droplet kinetic energy conserved, while the self-cleaning effect is shown
by each water droplet taking away a significant amount of dust particles on the altered surface.
C 2015
The multifunctional surface is useful for light collection and water/dust repelling. V
AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4905616]

I. INTRODUCTION

Nature provides many examples of multifunctional properties on a biological surface.1,2 One of the examples is the
water-repelling lotus leaves.1,3,4 The lotus leaves have a number of functionalities, such as superhydrophobicity, selfcleaning, and defense against pathogens.1,3 Studies have
shown that the lotus leaf surface has a hierarchical structure
containing a larger micro-scale structure in the range of
1050 lm and a finer structure in the range of 200 nm2 lm.1,3
This hierarchical structure along with a hydrophobic epicuticular wax coating imparts the superhydrophobicity to lotus
leaves. Furthermore, the hierarchical surface structure significantly reduces the adhesion of contaminants to the surface.3
Both enhanced hydrophobicity and reduced contaminant adhesion produce the lotus self-cleaning effect, often referred as
the lotus effect.3 The lotus self-cleaning is achieved when
water drops roll over the leaves, pick up the dust particles, and
carry them away when rolling off the leaves. Another example
of the multifunctional biological surface is the Morpho butterfly wing. The surface structures of the wings produce a blue
color and also make the wing surface superhydrophobic and
self-cleaning.5,6
Recently, studies have shown that femtosecond laser
surface processing can produce surface structures that can
significantly modify optical712 or wetting1215 properties of
metals. However, the metal blackening711 and wetting
effect1315 were each demonstrated individually. Here, we
demonstrate a laser nano/microstructuring technique to create a combined black, superhydrophobic, and self-cleaning
effect on a metal surface. The enhanced light absorption is
useful whenever light collection is needed, for example, in
sensors and solar energy absorbers. The superhydrophobicity
and self-cleaning effects will repel water and dust, and
improve the performance and reduce the maintenance of the
devices that utilize these surfaces. Furthermore, the superhydrophobicity should also enable other highly desirable
functionalities, such as anti-corrosion,16 anti-icing,1719 antibiofouling,19,20 anti-microbial,21 low flow resistance,21,22
a)

Electronic mail: vorobyev@optics.rochester.edu


Electronic mail: guo@optics.rochester.edu

b)

0021-8979/2015/117(3)/033103/5/$30.00

and platelet anti-adhesion,23 which are intrinsically associated with the superhydrophobicity. Using anti-icing as an
example, water drops do not have enough time to freeze on a
superhydrophobic surface before they roll off the surface.24
Some potential applications for anti-icing surfaces include
protection of aerofoils, power transmission lines, pipes of air
conditioners and refrigerators, and radar or telecommunication antennas.24,25
II. EXPERIMENTAL SETUP

In this study, we use an amplified Ti:sapphire laser system that generates 65-fs pulses with a central wavelength of
800 nm and at a maximum pulse repetition rate of 1 kHZ.
The laser beam is focused onto the sample surface by a lens
onto a sample mounted on a computerized XY-translation
stage. The samples in our study are platinum, titanium, and
brass. Each sample is textured with an array of parallel
microgrooves covered by extensive nanostructures. The
platinum sample is processed at laser fluence of 9.8 J/cm2.
The titanium sample is processed at laser fluence of 7.6 J/
cm2. Brass is processed at laser fluence of 3.9 J/cm2. The
orientation of microgrooves is controlled by the scan direction. A scanning electron microscope (SEM) and a 3D laser
scanning microscope are used to examine the surface structures. Superhydrophobic properties are studied by measuring both water contact angle and the surface tilt angle for
water sliding. The self-cleaning properties are studied with
real-life dust particles collected from a vacuum cleaner. For
cleaning, we use rolling and falling water drops. The rolling
drops with nearly zero kinetic energy are produced by
pipetting water drops near the sample surface, while the
falling drops are produced by pipetting drops at a height of
38 cm above the sample surface. The diameter of the
pipetted water drops is in the range of 25 mm. The selfcleaning action is recorded with a video camera. To characterize the optical properties, we measure the total hemispherical optical reflection of the samples using a PerkinElmer Lambda 900 spectrophotometer and Bruker IFS 66/S
FTIR spectrometer, each equipped with an integrating
sphere. The two spectrometers allow us to measure the

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C 2015 AIP Publishing LLC


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A. Y. Vorobyev and C. Guo

J. Appl. Phys. 117, 033103 (2015)

FIG. 1. (a) Photograph of superhydrophobic black platinum; (b) laser microscopy image showing micro-structures on the platinum surface; (c) and (d) SEM
images showing the detailed hierarchical structures on the platinum surface; (e) and (f) laser microscopy images showing surface structures on brass and
titanium.

spectral reflectance in the wavelength range of 0.252.5 lm


and 2.516 lm, respectively.
III. RESULTS AND DISCUSSION

A laser-treated platinum surface is shown in Fig. 1(a).


The treated surface appears velvet black at all viewing angles,
indicating a significant increase of optical absorption. A hierarchical surface structure produced on platinum is shown in
Figs. 1(b)1(d). This structure is an array of parallel microgrooves covered by extensive nanostructures. The microgroove spacing is about 100 lm and the depth is about 75 lm.
Our SEM study shows that the smallest nanoscale features are
about 510 nm. Following the laser treatment, superhydrophobicity develops after the sample is exposed to air.14 To

characterize the hydrophobicity of the treated platinum surface, we measure the water contact angle on the surface to be
158 , and a water drop will slide on the treated surface at a tilt
angle of only 4 . More remarkably, when a drop of water is
released and falls towards the treated surface, the water droplet is repelled by the treated surface to such a degree that it
bounces off the surface, lands again due to gravity, and bounces again and off the treated surface area, as shown in Fig. 2.
Here, the water drop is released 19 mm above the surface,
reaches a height of 5.3 mm after the first bounce, and lands
13.75 mm away from the first bounce before bouncing off the
surface. About 30% of the water droplet kinetic energy is conserved from the first bounce. The two bouncing motions last
less than 0.5 s, and the laser-treated surface remains completely dry afterwards [Fig. 2(f)].

FIG. 2. (a)(f) Video clips showing a water droplet bouncing off a superhydrophobic black platinum surface. The surface has a tilt angle of 8 .

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A. Y. Vorobyev and C. Guo

J. Appl. Phys. 117, 033103 (2015)

FIG. 3. (a)(e) Video clips showing a superhydrophobic platinum surface self-cleaned by water droplets. The surface has a tilt angle of 8 ; (f) an untreated
platinum surface accumulates a puddle of water with floating dusts.

A decrease of surface tension on a solid surface can also


enhance the hydrophobicity.26 Therefore, another approach
to increase the hydrophobicity is to decrease the surface tension by coating a hydrophobic layer on the solid surface. The
largest water contact angle ever achieved through coating on
a smooth surface is only about 120 ,21,27 which is far less
than 150 , the minimum water contact angle required being
qualified as superhydrophobicity. However, a combination
of surface structuring and a hydrophobic chemical coating
can produce strong superhydrophobicity.26 Metals are
intrinsically hydrophilic; immediately after femtosecond
laser surface structuring, they first become more hydrophilic,
but the exposure to air turns the metals superhydrophobic.
This transition is explained by chemical interaction between
the surface and the ambient CO2, resulting in an accumulation of carbon and its compounds on the laser-treated surface.14,28 We believe that the laser-induced surface
nanostructures also play an important role in enhancing this
chemical interaction due to nanochemical effects.29
In nature, self-cleaning occurs on a superhydrophobic
surface with water from rain, dew, and fog. These water
sources supply falling, rolling, and sliding drops. The rolling
and falling drops are more efficient in removing dust particles than the sliding drops.30 Figure 3 shows self-cleaning
of dust particles on the black platinum by applying a string
of water drops. The dust particles are a collection of real-life
dusts from a vacuum cleaner; the size of the particles is in
the range of 0.12 mm. Video clips in Fig. 3 and a supplementary video in Fig. 4 (Multimedia view) show that the
dust particles are taken away by the dropping water, and
afterwards superhydrophobic surface becomes virtually
clean and remains completely dry. In contrast, we can see
that water sticks to the untreated area even upside down. We
also apply water on an untreated platinum sample covered

with dust particles. In contrast to our superhydrophobic surface, water remains on the untreated surface with all the dust
particles floating inside [Fig. 3(f)]. After water vaporizes, all
the dust particles will remain on the surface. In our study, we
repeatedly perform 20 cleanings on the superhydrophobic
surface and did not observe any degradation of the
self-cleaning effect.
Self-cleaning surfaces should have the following properties: (i) large water contact angle exceeding 150 , (ii) small
sliding angle (<10 ) to cause water drops easily roll off the
surface, and (iii) the adhesion between the surface and dust
particles on the surface should be smaller than that between
the dust particles and water.3,27,3133 The surface structures
we produced benefit self-cleaning in two ways. First, the surface structures turn a metal surface superhydrophobic; second, the surface structures also reduce the adhesion of dust
particles to the solid surface.3 We also produce

FIG. 4. Supplementary video demonstrating the self-cleaning effect of the platinum sample. (Multimedia view) [URL: http://dx.doi.org/10.1063/1.4905616.1]

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A. Y. Vorobyev and C. Guo

multifunctional black and superhydrophobic titanium and


brass surfaces, and they show similar superhydrophobic and
self-cleaning behaviors as Pt.
To characterize the optical property of the three multifunctional surfaces, we measure the wavelength dependent
reflectance of their surfaces with the spectrophotometer and
FTIR spectrometer, and results of these measurements are
shown in Fig. 5. For comparison, we also measure the reflectance of mechanically polished surfaces of the three metals
before laser treatment. We can see that the multifunctional
surfaces have a very low reflectance over a broad range of
wavelengths. The reflectance in the visible wavelengths is in
a range of 1.3%3.5%, 3.3%4.1%, and 4.2%4.5% for
brass, Pt, and Ti, respectively. For comparison, the reflectance of mechanically polished surfaces of the three samples
is much higher as shown in Fig. 5. Because of the extremely
low reflectance, all three sample surfaces appear pitch black.
Furthermore, these surfaces also have low reflectance in the
near infrared, which increases with wavelength slightly for
Pt and Ti but significantly for brass. At 16 lm, the absorption
is 9% for Pt, 18% for Ti, and 73% for brass. The measured
reflectance shows that the black Pt and Ti surfaces are excellent broadband absorbers of electromagnetic radiation from
the ultraviolet to mid-infrared.
It is known that absorptance, A, of a clean structured
metallic surface is given by Ak AINTR k ASS k,
where AINTR is the intrinsic absorptance of a flat, clean, and
ideally smooth surface and ASS is the contribution of surface
structures.34 The dramatically enhanced absorption of our
structured surface over a broad spectral range comes from
several mechanisms. The surface structures smaller than
light wavelength (nanostructures and fine microstructures)
enhance absorptance through antireflection effect of the
graded refractive index formed by subwavelength surface
textures at the air/solid interface.35 Furthermore, these subwavelength surface structures significantly enhance absorptance through plasmonic absorption.3639 On the other hand,

J. Appl. Phys. 117, 033103 (2015)

the surface structures greater than the light wavelength


enhance absorptance through light trapping in surface cavities and the Fresnel angular dependent reflection. All these
absorption mechanisms contribute to the broadband high
absorption, leading to the structural black color in the visible
spectral range. Previously, it has been shown that the absorption of semiconductors can be enhanced through laserassisted chemical reactions using SF6 and H2S that leave
sulfur in the surface layer.40 In contrast, the blackening of
metals in air is due to surface structuring and not associated
with the change in elemental composition.8,10 The enhanced
absorption can also be produced on metals with other femtosecond laser-induced surface structures.10,11 Finally, we note
that the hierarchical surface structures we produced on Pt
and Ti are more optimized for the broadband absorption in
the wavelength range of 0.2516 lm. In the past, we demonstrated that the surface structures on metals can also be
optimized for efficient absorption in the THz range,41 where
regular metals are perfect reflectors.
One application for the enhanced light absorption is building better solar absorbers for efficient conversion of solar
energy to thermal42 or electrical energy through thermoelectric
generators.43,44 Solar radiation is broadband and mainly composes of ultraviolet (k < 0.4 lm), visible (0.4 < k < 0.7 lm),
and infrared radiation (0.7 < k < 100 lm). At the sea level, the
fraction of solar energy in the ultraviolet, visible, and infrared
wavelengths are about 4%, 42%, and 54%, respectively. From
practical point of view, almost all solar energy is contained in
the wavelength range of 0.2 < k < 3 lm.43 Fig. 5 shows that
our samples have a very high absorptance in this wavelength
range, especially for Pt and Ti. An ideal solar energy absorber
should not only absorb solar energy efficiently in this wavelength range but also minimize radiative thermal loss to the
environment at longer wavelengths. Therefore, the ideal wavelength dependent reflectance should be R(k) 0 at
0.3 < k < 3 lm and R(k) 1 at 3 < k < 50 lm.43 A dashed line
in Fig. 5 shows this ideal reflectance. To provide high reflectance at k > 3 lm, the surface structures we created on brass
contain shallow microgrooves covered by nanostructures.
Figure 1 shows a comparison of the microgrooves of brass versus Ti and Pt. The microgroove depth is about 10 lm for brass,
but 50 and 75 lm for Ti and Pt. Because a shallower microgroove traps less infrared radiation at longer wavelengths,
brass sample has a significantly higher reflectance in the infrared. We believe that a closer resemblance of the ideal reflection step function can be achieved by further optimizing the
structural period and depth. In contrast to a femtosecond laser
processing technique developed for enhancing light absorption
in semiconductor photovoltaic cells,45,46 our work enables metals to absorb solar energy more efficiently for conversion to
electricity in devices such as thermoelectric generators44 or
conversion to heat in devices such as solar hot water tanks.42
IV. CONCLUSION

FIG. 5. Spectral reflectance of the black brass, black platinum, and black titanium as a function of wavelength. Spectral reflectance of three mechanically polished metals without laser treatment is also shown for a
comparison. Dashed line shows the spectral reflectance of an ideal solar
absorber.

In summary, we create a multifunctional metal surface by


producing a hieratical nano- and micro-structures with femtosecond laser pulses. The multifunctional surfaces exhibit
combined effects of dramatically enhanced broadband light

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033103-5

A. Y. Vorobyev and C. Guo

absorption, superhydrophobicity, and self-cleaning. This surface also has other highly desirable functionalities such as
anti-corrosion, anti-icing, anti-biofouling, and self-sanitation,
since these properties are directly related to
superhydrophobicity.
ACKNOWLEDGMENTS

This work was supported by Bill & Melinda Gates


Foundation and U.S. Air Force Office of Scientific Research.
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