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Micro- and nanoscale characterization of hydrophobic and hydrophilic leaf surfaces

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2006 Nanotechnology 17 2758

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INSTITUTE OF PHYSICS PUBLISHING NANOTECHNOLOGY
Nanotechnology 17 (2006) 2758–2772 doi:10.1088/0957-4484/17/11/008

Micro- and nanoscale characterization of

hydrophobic and hydrophilic leaf surfaces
Bharat Bhushan1 and Yong Chae Jung
Nanotribology Laboratory for Information Storage and MEMS/NEMS (NLIM), The Ohio
State University, 650 Ackerman Road, Suite 255, Columbus, OH 43202-1107, USA

E-mail: [email protected]

Received 13 February 2006, in final form 29 March 2006

Published 16 May 2006
Online at stacks.iop.org/Nano/17/2758
Abstract
Superhydrophobic surfaces as well as low adhesion and friction are desirable
for various industrial applications. Certain plant leaves are known to be
hydrophobic in nature due to their roughness and the presence of a thin wax
film on the surface of the leaf. The purpose of this study is to fully
characterize the leaf surfaces on the micro- and nanoscale while separating
out the effects of the micro- and the nanobumps of hydrophobic leaves on the
hydrophobicity. Hydrophilic leaves were also studied to better understand the
role of wax and roughness. Furthermore, the adhesion and friction properties
of hydrophobic and hydrophilic leaves were studied. Using an optical profiler
and an atomic/friction force microscope (AFM/FFM), measurements were
made to fully characterize the leaf surfaces. It is shown that the nanobumps
play a more important role than the microbumps in the hydrophobic nature as
well as friction of the leaf. This study will be useful in developing
superhydrophobic surfaces.
(Some figures in this article are in colour only in the electronic version)

1. Introduction surface, and occurs when the surfaces have a contact angle
of less than 90◦ , whereas if the surface is hydrophobic, the
Superhydrophobic surfaces are of considerable interest for value of the contact angle is greater than 90◦ . Surfaces
various technological applications due to their extreme water with a contact angle between 150◦ and 180◦ are called
repellent properties. Advances in nanotechnology, including superhydrophobic. The contact angle depends on several
micro/nanoelectromechanical systems (MEMS/NEMS), have factors, such as surface energy, roughness, the manner of
stimulated development of new materials and design of surface preparation, and surface cleanliness (Adamson 1990,
surfaces which should require hydrophobic surfaces and Israelachvili 1992, Bhushan 1999, 2002, 2005).
interfaces with low adhesion and friction. Hydrophobic (water- Superhydrophobic surfaces also have very low water
repellent) surfaces can be constructed either by using low contact angle hysteresis. The contact angle hysteresis is the
surface energy materials or by chemically treating surfaces difference between the advancing and receding contact angles.
with materials such as polytretafluoroethylene, silicon, or If additional liquid is added to a sessile drop, the contact
wax. Another technique that can be used to increase the line advances and an advancing contact angle is measured.
hydrophobicity of a hydrophobic surface is to increase the Alternatively, if liquid is removed from the drop, the contact
surface area by increasing surface roughness. If a surface angle decreases to a receding value before the contact retreats.
is initially hydrophilic, then introducing roughness to that For a droplet moving along the solid surface, the contact angle
surface will make it even more hydrophilic (Wenzel 1936, at the front of the droplet (advancing contact angle) is greater
Nosonovsky and Bhushan 2005). Wetting (hydrophilic than that at the back of the droplet (receding contact angle), due
property) is characterized by the static contact angle, or to roughness and surface heterogeneity, resulting in the contact
simply contact angle, made between a water droplet and a angle hysteresis. In addition to high contact angle, another
wetting property of interest for liquid flow applications is a
1 Author to whom any correspondence should be addressed.
very low water roll-off angle, which denotes the angle to which

0957-4484/06/112758+15$30.00 © 2006 IOP Publishing Ltd Printed in the UK 2758

 Micro- and nanoscale characterization of hydrophobic and hydrophilic leaf surfaces

a surface may be tilted for roll-off of water drops (i.e., very low and presented optimal designs for superhydrophobic surfaces.
water contact angle hysteresis) (Extrand 2002, Kijlstra et al For a rough surface, a composite solid–liquid–air interface may
2002). form with air pockets trapped in the valleys between asperities,
Analytical models have been presented in the past to as opposed to the homogeneous solid–liquid interface. The
determine how roughness affects hydrophobicity. Wenzel transition to the composite solid–liquid–air interface results in
(1936) developed the first model, which is based on the a decrease in the solid–liquid contact area, so that the liquid
consideration of net energy decrease during the spreading of contacts the solid at the peaks of the asperities. Transition
a droplet on a rough surface. A rough surface has a larger to the composite interface can decrease the contact angle
solid–liquid interface area, leading to a larger net energy. hysteresis, so that a drop would move more easily, and can
It is responsible for the increase in the contact angle for a increase the contact angle. Highly hydrophobic surfaces
hydrophobic surface and the decrease in contact angle for a have been fabricated directly by incorporating high roughness
hydrophilic surface. Wenzel developed an equation that relates to the surface, and high contact angles have been reported
the contact angles of rough and smooth surfaces, θ and θ0 for surfaces with micrometre- and nanometre-scale roughness
respectively, using the roughness factor Rf , (Hozumi and Takai 1998, Coulson et al 2000, Miwa et al
2000, Oner and McCarthy 2000, Lau et al 2003). Recent
cos θ = Rf cos θ0 . (1) studies have been carried out on nanopatterned polymers
that show that introducing roughness will either increase the
The roughness factor is defined as the ratio of the total hydrophobicity or hydrophilicity, depending on whether the
surface area of the rough surface and the projected area of initial flat surface is hydrophobic or hydrophilic, respectively
the rough surface or the footprint of the total surface area. (Burton and Bhushan 2005).
The model predicts that roughness enhances hydrophobicity if Tribological properties play an important role in many
θ0 > 90◦ . If θ0 is less than 90◦ , then the contact angle for applications requiring hydrophobic surfaces. Therefore, it
the rough surface will decrease with increasing Rf . Shibuichi is important to study the adhesion and friction properties of
et al (1996) measured the contact angle for various liquids on hydrophobic surfaces. Wetting results in the formation of
a rough surface and found that for wetting liquids the contact menisci at the interface between solid bodies during sliding
angle decreases with increasing roughness, whereas for non- contact, which increases adhesion and friction (Bhushan
wetting liquids it increases. 1999, 2002). Understanding the combination of surface
It is noted that equation (1) is only valid for moderate characterization along with the adhesion and friction properties
values of Rf , when −1
Rf cos θ0
1. For high can allow improved hydrophobic surfaces to be created.
roughness, a wetting liquid will be completely absorbed by Many researchers have paid attention to the study of
the rough surface cavities while a non-wetting liquid cannot hydrophobic materials that can be found in nature. The leaf
penetrate into surface cavities, resulting in the formation of surfaces of hundreds of different plant species have been
air pockets, leading to a composite solid–liquid–air interface. studied to see the effect of roughness on hydrophobicity
Cassie and Baxter (1944) extended Wenzel’s equation, which (Neinhuis and Barthlott 1997, Wagner et al 2003). In
was originally developed for the homogeneous solid–liquid comparison with other plant species, lotus leaves have a very
interface, for the composite interface. For this case, there are high contact angle with water and show strong self-cleaning
two sets of interfaces: a liquid–air interface with the ambient properties known as the ‘lotus effect’ (Barthlott and Neinhuis
environment surrounding the droplet, and a flat composite 1997).
interface under the droplet involving solid–liquid, liquid–air, Burton and Bhushan (2006) studied the effects of the
and solid–air interfaces. In order to calculate the contact angle microbumps and the wax (crystals that are a mixture of large
for the composite interface, the equation is given by: hydrocarbon molecules, measuring about 1 nm in diameter) of
hydrophobic leaves on the hydrophobicity. They used contact
cos θ = Rf f SL cos θ0 − f LA (2) mode AFM to make measurements, which had the potential
to damage the soft leaves. It is expected that tapping mode
where fSL and f LA are fractional flat geometrical areas of would be more desirable to make roughness measurements of
the solid–liquid and liquid–air interfaces under the droplet, biological leaves. Therefore tapping mode AFM is used in this
respectively. This model shows that when roughness increases paper for surface characterization. While the study by Burton
the contact angle approaches 180◦ , however, it does not provide and Bhushan (2006) focused on microbumps, it is expected that
any particular form of dependence of the areas of the solid– nanobumps on the top of a microbump may play an important
liquid and liquid–air interfaces, and does not explain under role in surface wettability, and their morphology and their
which conditions the composite interface forms. Johnson and effects have not been studied to date. In this study, the role of
Dettre (1964) showed that the homogeneous and composite microbumps and nanobumps is examined by analysing surface
interfaces correspond to the two metastable states of a droplet. characterization on the micro- and nanoscale of hydrophobic
Even though it may be geometrically possible for the system leaves. As a comparison, hydrophilic leaves were also studied
to become composite, it may be energetically profitable for the to better understand the role of wax and roughness. As well as
liquid to penetrate into valleys between bumps and to form the measuring and characterizing surface roughness using various
homogeneous interface. methods of measurement, the contact angle and adhesion and
Based on an understanding of the effect of roughness friction properties of these leaves were also measured. An
on the contact angle and the roughness distribution found in examination of these properties and a quantitative analysis of
leaves, Nosonovsky and Bhushan (2005, 2006) proposed a the surface structure and their interpretations are the subject of
stochastic model for roughness-induced hydrophobic surfaces this paper.

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B Bhushan and Y C Jung

effect’ (Barthlott and Neinhuis 1997). Then a 20 × 20 mm

square was cut from the leaf between the veins, and was placed
on the measuring platform and attached using double sided
tape. For optical profiler measurements, the fresh leaves were
scanned as soon as possible after being cut to reduce the effect
of the dynamic shrinking that occurs after being cut. The height
variation in lotus leaves is too large to be measured using an
AFM, therefore they were measured in the dry state. They were
dried for 24 h before being measured, because after this time
period the leaves had shrunk their maximum amount down to
about 4 µm, and the leaf surface was stable with time (Burton
and Bhushan 2006). To determine the presence of wax crystals
on hydrophobic and hydrophilic leaves, acetone was used to
remove the surface layer, but the original structures of the
leaves with the wax present and the wax removed were similar
(Burton and Bhushan 2006). The contact angle for various
leaves was measured before and after removing the surface
layer.

2.2. Instrumentation
To examine the surface of the leaves, SEM micrographs were
taken using a JEOL JSM-820 scanning electron microscope.
Fresh leaf samples were affixed to aluminium stubs using
double-sided conductive tape and air dried. All specimens
Figure 1. Scanning electron micrographs of the relatively rough, were sputter-coated with a less than 10 nm thick Au/Pd coating.
water-repellent leaf surface, such as Nelumbo nucifera (lotus) and
Colocasia esculenta and the relatively smooth, wettable leaf The contact angle, a measure of surface hydrophobicity,
surfaces, such as Fagus sylvatica and Magnolia grandiflora. was measured using a Rame-Hart model 100 contact angle
goniometer and water droplets of deionized water. All
measurements were made at 22 ± 1 ◦ C and 50 ± 5% RH. The
2. Experimental details measurements were reproducible to within ±2◦ .
As mentioned earlier, the tall bumps on freshly cut lotus
2.1. Samples and colocasia leaves cannot be measured using an AFM.
In order to obtain the surface dimensions that represent the
For this study, two hydrophobic leaves—lotus and colocasia— surface structure found on the leaves found in nature, an optical
and two hydrophilic leaves—fagus and magnolia—were profiler (NT-3300, Wyko Corp., Tuscon, AZ) was used for all
selected. Lotus and colocasia are characterized by papillose of the leaves. The tall bumps on the leaves are well within
epidermal cells responsible for the creation of papillae or the Z -range limitation of the optical profiler of 2 mm, and
bumps on the surfaces, and an additional layer of epicuticular therefore the entire vertical range of the leaf can be measured.
waxes which are a mixture of large hydrocarbon molecules A greater Z -range is a distinct advantage over other types of
measuring about 1 nm in diameter. Fagus and magnolia are surface roughness measurements, but it has a maximum lateral
characterized by sunken and raised nervature, respectively resolution of approximately 0.6 µm (Bhushan 1999, 2002). A
(Barthlott and Neinhuis 1997). The four leaves were obtained scan size of 60 µm × 50 µm, which is the highest magnification
from two different sources. Lotus (Nelumbo nucifera) and for the optical profiler, was used to scan the leaves.
fagus (Fagus sylvatica) leaves only grow during warmer For additional surface roughness, adhesion and friction
periods of the year. They need, at least, a constant temperature measurements, microscale and nanoscale measurements were
of 18 ◦ C to grow, and typically grow from the end of May carried out using a commercial AFM (D3100, Nanoscope IIIa
to the beginning of October. Therefore, research on these controller, Digital Instruments, Santa Barbara, CA). This AFM
leaves needs to be carried out during this period. On the has a Z -range of about 7 µm, and cannot be used to make
other hand, colocasia (Colocasia esculenta) and magnolia measurements of fresh lotus and colocasia because the P –V
(Magnolia grandiflora) grow throughout the year and are distance of fresh lotus and colocasia is greater than 15 µm.
readily available. Lotus was obtained from Aquarius Water Therefore, dried lotus and colocasia, which have a lower
Gardens in Ramsey, Indiana and colocasia, fagus, and P –V distance, were measured. The scan size used in these
magnolia were obtained from the Franklin Park Conservatory measurements was 50 µm. However, as the P –V distance
in Columbus, Ohio. Figure 1 shows the micrographs of each of roughness for both lotus and colocasia is low enough to
leaf measured using scanning electron microscopy (SEM). make measurements on top of the microbumps in a 2 µm scan,
Due to their biological nature, plants get contaminated nanoscale measurements were carried out on both the fresh and
with various particles. Each leaf was cleaned by placing it dried states. The P –V distance of fresh fagus and magnolia is
under running water, which will remove any contaminants due low enough that fresh leaves can be measured with an AFM at
to the self-cleaning ability of the leaves, known as the ‘lotus both 50 and 2 µm. A 2 µm scan was selected on the top of a

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 Micro- and nanoscale characterization of hydrophobic and hydrophilic leaf surfaces

microbump obtained in the 50 µm surface height map. From

the 2 µm surface height map, nanoscale roughness, namely
nanobumps, can be observed. For a 2 µm scan size image, it
is difficult to locate the top region of microbumps since the
AFM system does not have a closed loop feedback system.
Therefore, 2 µm measurements were carried out using the
following multiple-stage zoom technique. First, an image was
taken with a 50 µm scan size. It was then reduced to 10 µm
and finally to 2 µm in order to measure nanobumps on top of
the microbumps.
Two different AFM techniques—contact mode and
tapping mode for comparison—and three different AFM tips
were used in this study. In contact mode, a triangular Si3 N4
cantilever with a nominal tip radius of 30 nm and a nominal
spring constant of 0.06 N m−1 with normal loads (50 nN
in microscale and 2 nN in nanoscale) was used to measure
surface roughness. In tapping mode, a square pyramidal
Si(100) tip with a native oxide layer which had a nominal
radius of 20 nm on a rectangular Si(100) cantilever with a
spring constant of 3 N m−1 and at a natural frequency of
82 kHz was used to measure surface roughness more precisely.
Adhesion and friction measurements were made using a 15 µm
radius borosilicate ball that was mounted on a triangular Si3 N4 Figure 2. Schematic diagram describing the method used to
cantilever with a nominal spring constant of 0.58 N m−1 calculate the true surface area of the leaf surface from an AFM scan.
obtained from Bioforce Nanosciences, Ames, Iowa. A large
tip radius was used to measure contributions from several
microbumps and a large number of nanobumps. Friction force a surface is limited to a square scan size and is only used with
was measured under a constant load using a 90◦ scan angle at AFM scans. Using this approximation for Rf , calculations can
a velocity of 10 µm s−1 for both 50 and 2 µm scans (Bhushan be made on contact angles of the flat surface if the contact angle
1999, 2002, 2005). All of the surface height maps and friction of the rough surface is measured based on the assumption that
measurements were measured in both a 50 µm × 50 µm scan the surface is homogeneous. For a solid–liquid interface, the
and a 2 µm × 2 µm scan size to show different microbumps and Wenzel equation is used, and for a composite solid–liquid–air
nanobumps on the leaf surface. Adhesive force was measured interface, the Cassie–Baxter equation is used.
using the single point measurement of a force calibration plot
(Bhushan 1999, 2002, 2003, 2005). All measurements were 2.4. Probability density function
made at 22 ± 1 ◦ C and 50 ± 5% RH.
A statistical program was developed to calculate the
probability density functions (PDF) in order to study roughness
2.3. Roughness factor distribution on micro- and nanoscales. The shape of the PDF
The roughness factor, Rf , needs to be calculated to incorporate offers useful information on the behaviour of the roughness
the effect of roughness on the contact angle. If a surface is a distribution (Bhushan 1999, 2002). The function p(z) provides
flat plane then Rf would be equal to one, whereas if roughness the probability of locating a point z at a specific height. From
the definition, it is known that
is added to the surface then Rf will increase. To obtain an
approximation of the Rf for the two different leaves, a model d
p(z) = P(z) = P  (z), (3)
was developed to calculate the true surface area and the area dz
footprint and produce their ratio. This model uses the AFM where P(z) is the probability distribution function. Equa-
scans of the leaves and uses the height of each data point, along tion (3) can be rewritten in discrete form as,
with its location in the matrix of data points to determine the
Pr{z j < Z
z j + z} P(z j + z) − P(z j )
total surface area. Figure 2 is a schematic diagram showing p(z j ) = =
how the true area is calculated for each scan area. For an
z z
d P(z j )
n × n matrix of data points, there are (n − 1) × (n − 1) = , (4)
patches of area that are created. For each patch, a hypotenuse z
is made to form two right triangles. Using the Z -height for which suggests that the PDF can be constructed by plotting
each data point along with its position in the matrix, the area of the proportion of surface heights lying between two specific
the two triangles created can be calculated and added together heights, z j and z j + z , as a function of height z j .
to get the entire area of the patch. Using this technique for Given N points with surface height z i , for i =
each patch and adding all the patches together will give an 1, 2, . . . , N , and the sampling number of equal intervals M ,
each interval z is given as
approximation for the true surface area for the scan, and we
can divide that by the total scan area or footprint to get the max(z i ) − min(z i )
ratio, Rf . This method of calculating the roughness factor for
z = . (5)
M

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B Bhushan and Y C Jung

For each interval, the proportion is given by

N
1(z j )
Pr{z j < Z
z j + z} = i=1
, (6)
N
where,

1 if z j < z i
z j + z
1(z i ) =
0 else.
Now Pr{z j < Z
z j + z} from equation (6) is used in
equation (4) to obtain p(z j ).
A statistical program to calculate the PDF using this
algorithm was written in Fortran 95, and the graphic software
Origin is used to plot the standardized PDFs. The procedure for
generating the PDF is as follows: (1) calculate the maximum
value and the minimum value of surface heights from the
measured surfaces; (2) determine the interval z given the
sampling number of equal intervals M using equation (5); (3)
calculate the proportion for each interval using equation (6),
and compute the PDF using equation (4). Sixty sampling
points for a rough surface are used to generate the PDF.

3. Results and discussion

3.1. Contact angle measurements

Figure 3(a) shows the contact angles for the hydrophobic
and hydrophilic leaves before and after using acetone. After
using acetone, for the hydrophobic leaves the contact angle
dramatically reduced, but on the contrary, for the hydrophilic Figure 3. Contact angle measurements and calculations for the leaf
leaves the contact angle was almost unchanged. This suggests surfaces, (a) both before and after removing the surface layer and
that wax does not exist on the hydrophilic leaves. In contrast, (b) both fresh and dried leaves. The contact angle on a smooth
surface for the four leaves was obtained using the roughness factor
hydrophobic leaves have a thin wax film on the surface of the calculated.
leaf and consequently, the combination of this wax and the
roughness of the leaf creates a superhydrophobic surface.
The contact angles for leaves with smooth surfaces were
measured using an AFM. It is found that the dried leaf ( P –V
calculated using equation (1) and the calculated Rf (to be height = 7 µm, mid-width = 15 µm, and peak radius =
presented later) and the contact angle of the four leaves. These 18 µm) has taller bumps than a fresh leaf ( P –V height =
are also presented in figure 3(a). The approximate values of 3 µm, mid-width = 12 µm, and peak radius = 15 µm),
Rf for lotus and colocasia are 5.6 and 8.4 and for fagus and which increases the roughness, and the contact angle decreases,
magnolia are 3.4 and 3.8, respectively. The contact angles on leading to a more hydrophilic surface.
smooth surfaces for the four leaves, therefore, can be calculated
using these values. Based on the calculations, the contact
3.2. Surface characterization using an optical profiler
angles on smooth surface were approximately 99◦ for lotus and
96◦ for colocasia. For both fagus and magnolia, the contact As stated previously, the use of an optical profiler allowed
angles for the smooth surfaces were approximately 86◦ and measurements to be made on fresh leaves, which have a large
88◦ . A further discussion on the effect of Rf on the contact P –V distance. Three different surface height maps can be seen
angle will be presented later. for hydrophobic and hydrophilic leaves in figure 4(a). In each
Figure 3(b) shows the contact angles for both fresh and figure, a 3D map and a flat map along with a 2D profile in a
dried states for the four leaves. There is a decrease in the given location of the flat 3D map are shown. A scan size of
contact angle for all four leaves when they are dried. For 60 µm × 50 µm was used to obtain a sufficient amount of
lotus and colocasia, this decrease is present because it is found bumps to characterize the surface but also to maintain enough
that a fresh leaf has taller bumps than a dried leaf (data to resolution to get an accurate measurement.
be presented later), which will give a larger contact angle, The structures found with the optical profiler correlate
according to equation (1). When the surface area is at a well with the SEM images shown in figure 1. The bumps on the
maximum compared with the footprint area, as with a fresh lotus leaf are distributed on the entire surface, but the colocasia
leaf, the roughness factor will be at a maximum and will leaf shows a very different structure to that of the lotus. The
only reduce when shrinking has occurred after drying. To surface structure for colocasia not only has bumps similar to
understand the reason for the decrease in the contact angle after lotus but surrounding each bump, a ridge is present that keeps
drying of hydrophilic leaves, dried magnolia leaves were also the bumps separated. With these ridges, the bumps have a

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 Micro- and nanoscale characterization of hydrophobic and hydrophilic leaf surfaces

(a)

Figure 4. (a) Surface height maps and 2D profile of hydrophobic and hydrophilic leaves using an optical profiler. For lotus, fagus and
magnolia leaves, a microbump is defined as a single, independent microstructure protruding from the surface. For colocasia, a microbump is
defined as a single, independent protrusion from the leaf surface, whereas a ridge is defined as a structure that surrounds each bump and is
completely interconnected on the leaf. (b) Curve fit for a bump on hydrophobic and hydrophilic leaves using an optical profiler. The radius of
curvature is calculated from the parabolic curve fit of the bump.

hexagonal packing geometry which allows for the maximum has been given to the profiles to show how closely the profile
number of bumps in a given area. The bumps of lotus and both is followed. The radius of curvature for any function is known
bumps and ridges of colocasia contribute to the hydrophobic to be:
nature since they both increase the Rf factor and result in air (1 + y  (x)2 )3/2
R(x) = (7)
pockets between the droplet of water and the surface. In fagus y  (x)
and magnolia height maps, short bumps on the surface can where R(x) = radius of curvature, y  (x) = first derivative of
be seen. This means that with decreased bump height, the the function, and y  (x) = second derivative of the function.
probability of air pocket formation decreases, and the bumps By using the second-order curve fit of the profiles, the radius
have a less beneficial effect on the contact angle. of curvature can be found.
Figure 4(b) shows the 2D profiles for all of the leaves. A Using these optical surface height maps, different
curve has been fitted to each profile to show exactly how the statistical parameters of bumps and ridges can be found to
bump shape behaves. For each leaf a second-order curve fit characterize the surface: peak to valley ( P –V ) height, mid-

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B Bhushan and Y C Jung

(b)

Figure 4. (Continued.)

width, and peak radius (Bhushan 1999, 2002). Here, mid- even at loads as low as 2 nN. This could be due to the
width is defined as the width of the bump at a height equal substantial frictional force generated as the probe scanned over
to half of peak to mean value. Table 1 shows these quantities the sample. The frictional force can damage the sample. The
found in the optical height maps for four leaves. Comparing tapping mode technique allows high resolution topographic
the hydrophobic and hydrophilic leaves, it can be seen that the imaging of sample surfaces that are easily damaged, loosely
P –V height for bumps of lotus and colocasia is much taller held to their substrate, or difficult to image by other AFM
than that for bumps of fagus and magnolia. The peak radius techniques (Bhushan 1999, 2002). As shown in figure 5, with
for bumps of lotus and colocasia is also smaller than that for the tapping mode technique, the soft and fragile leaves can be
bumps of fagus and magnolia. However, the values of mid- imaged successfully. Therefore the tapping mode technique
width for bumps of the four leaves are similar. was used to examine the surface roughness of the hydrophobic
and hydrophilic leaves using an AFM in this study.
3.3. Leaf characterization using an AFM
3.3.1. Comparison of two techniques. To measure 3.3.2. Surface characterization. It was stated earlier that
topographic imaging of the leaf surfaces, both contact and because of the large P –V distance of the lotus leaf, AFM
tapping modes were used to characterize the lotus leaf. cannot be used in the conventional way. A new method was
Figure 5 shows surface height maps of dried lotus obtained developed to fully determine the bump profiles. In order
using the two techniques. In contact mode, the local height to compensate for the large P –V distance, two scans were
variation for a lotus leaf was observed in a 50 µm scan size. made for each height: one measurement that scans the tops
However, little height variation was obtained in a 2 µm scan, of the bumps and another measurement that scans the bottom

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 Micro- and nanoscale characterization of hydrophobic and hydrophilic leaf surfaces

Table 1. Microbump and nanobump map statistics for hydrophobic

and hydrophilic leaves, measured in both fresh and dried leaves using
an optical profiler and AFM.
Microbump (µm) Nanobump (µm)
Scan size (50 µm × 50 µm) Scan size (2 µm × 2 µm)
P –V Mid- Peak P –V Mid- Peak
Leaf height width radius height width radius
Lotus
Fresh 13a 10a 3a 0.78b 0.40b 0.15b
Dried 9b 10b 4b 0.67b 0.25b 0.10b
Colocasia
Bump 9a
15a
5a 0.53b 0.25b 0.07b
Fresh
Ridge 8a 7a 4a 0.68b 0.30b 0.12b
Bump 5b 15b 7b 0.48b 0.20b 0.06b
Dried
Ridge 4b 8b 4b 0.57b 0.25b 0.11b
Fagus
a a a
5 10 15
Fresh 0.18b 0.04b 0.01b
4b 5b 10b
Magnolia
a a a
4 13 17
Fresh 0.07b 0.05b 0.04b
3b 12b 15b
a
Data measured using optical profiler.
b
Data measured using AFM.

or valleys of the bumps. The total height of the bumps is

embedded within the two scans. Figure 6(a) shows the 50 µm
surface height maps obtained using this method. The 2D
profiles in the right column take the profiles from the top
scan and the bottom scan for each scan size and splice them
together to get the total profile of the leaf. The 2 µm surface
height maps for both fresh and dried lotus can also be seen
in figure 6(a). This scan area was selected on the top of a
microbump obtained in the 50 µm surface height map. It can
be seen that nanobumps are randomly and densely distributed Figure 5. Surface height maps showing the top scan and bottom scan
on the entire surface of lotus. in a 50 µm scan size, and the bump peak scan selected in a 2 µm
scan size for a lotus leaf in contact mode and tapping mode. Two
Figure 6(b) shows the 50 and 2 µm surface height maps methods were used to obtain high resolution of nanotopography for a
for colocasia. When colocasia is dried there is sufficient piezo lotus leaf.
travel to scan the P –V distance for the 50 µm scan size.
Therefore, the entire surface profile can be measured in a single
scan. Also, both bump and ridge height maps in 2 µm were is the most important section of the bump, as it is the location
selected on the top of a microscale bump and ridge obtained in where the water droplets first come into contact with the
the 50 µm surface height map. These AFM images for micro- surface. Therefore, looking at the peak of the bump and curve
and nanoscale bumps and ridges show similar morphology to fitting that profile will give a good approximation of the surface
that in the SEM images in figure 1 and the optical profiler radius of curvature. All four profiles have been analysed using
images in figure 4. a second-order curve fit to show how these bumps behave. The
The surface height maps for the hydrophilic leaves in radius of curvature was found using equation (7).
figure 6(c) were measured in both 50 and 2 µm scan sizes. For
Using the AFM surface height maps, different statistical
fagus and magnolia, microbumps were found on the surface
parameters of bumps and ridges can be obtained: P –V height,
and the P –V distance of these leaves is lower than that of lotus
mid-width, and peak radius. These quantities for four leaves
and colocasia. It can be seen in the 2 µm surface height maps
are listed in table 1. It can be seen that the values correlate well
that nanobumps selected on the peak of the microbump have
with the values obtained from optical profiler scans except for
an extremely low P –V distance.
the bump heights, which decrease by more than half because
Figures 7(a)–(c) show the curve fit of bumps from the top
of leaf shrinkage.
scan from the lotus leaf, and the bumps and ridges profile from
the colocasia leaf, and bumps from the fagus and magnolia
leaves. Due to the piezo travelling problem mentioned earlier, 3.3.3. Adhesive force and friction. Adhesive force and the
only the top of the bump for lotus is used for curve fitting. This coefficient of friction of hydrophobic and hydrophilic leaves

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B Bhushan and Y C Jung

(a)

Figure 6. (a) Surface height maps and 2D profile showing the top scan and bottom scan of a dried lotus leaf in a 50 µm scan because the P –V
distance of a dried lotus leaf is greater than the Z -range of an AFM, and both fresh and dried lotus in a 2 µm scan. (b) Surface height maps
and 2D profile of colocasia using an AFM in both 50 and 2 µm scans. (c) Surface height maps and 2D profile of fagus and magnolia using an
AFM in both 50 and 2 µm scans.

using AFM are presented in figure 8. Reproducibility for sample will occur and the adhesive force will increase. After
both adhesive force and coefficient of friction is ±5% for the leaf has dried, the moisture that was in the plant material
all measurements. For each type of leaf, adhesive force is gone, and there is not as much deformation of the leaf when
measurements were made for both fresh and dried leaves using the tip comes into contact with the leaf sample. Hence, the
a 15 µm radius tip. It is found that the dried leaves had a lower adhesive force is decreased because the real area of contact has
adhesive force than the fresh leaves. Adhesive force arises decreased.
from several sources in changing the presence of a thin liquid The adhesive force of fagus and magnolia is higher than
film, such as an adsorbed water layer, that causes meniscus that of lotus and colocasia. The reason is that the real area
bridges to build up around the contacting and near contacting of contact between the tip and leaf sample is expected to be
bumps as a result of surface energy effects (Bhushan 1999, higher in hydrophilic leaves than that in hydrophobic leaves
2002). When the leaves are fresh there is moisture within the because of their high affinity to water and consequently higher
plant material that causes the leaf to be soft, and when the meniscus forces (Bhushan 1999, 2002).
tip comes into contact with the leaf sample, the sample will The coefficient of friction was only measured on a dried
deform and a larger real area of contact between the tip and plant surface with the same sliding velocity (10 µm s−1 ) in

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 Micro- and nanoscale characterization of hydrophobic and hydrophilic leaf surfaces

(b)

Figure 6. (Continued.)

different scan sizes, rather than including the fresh surface the coefficient of friction also decreases in each leaf. The
because the P –V was too large to scan back and forth with reason for such dependence is the scale dependent nature of the
the AFM to obtain friction force. As expected, the coefficient roughness of the leaf surface. Figure 6 shows AFM topography
of friction for hydrophobic leaves is lower than that for images and 2D profiles of the surfaces for different scan sizes.
hydrophilic leaves due to the real area of contact between The scan size dependence of the coefficient of friction has
the tip and leaf sample, similar to the adhesive force results. been reported previously (Poon and Bhushan 1995, Koinkar
When the scan size from microscale to nanoscale decreases, and Bhushan 1997, Tambe and Bhushan 2004).

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B Bhushan and Y C Jung

(c)

Figure 6. (Continued.)

3.3.4. PDFs and roughness parameters. The probability 50 µm scan. It can be seen that the heights of the nanobumps
density functions (PDFs) of the AFM data of leaf surfaces on the surface of hydrophilic leaves are small compared with
were constructed for hydrophobic and hydrophilic leaves using those on the surface of hydrophobic leaves. Generally, a
the previously mentioned PDF statistical program, as shown in correlation length, β ∗ represents the wavelength structure of
figure 9. PDFs in the 2 µm scan are closer to the Gaussian a random surface. It is found that the correlation lengths of
rough surface than those in the 50 µm scan. lotus and colocasia are less than those of fagus and magnolia
For comparison of surface characterization between in both 50 and 2 µm scans. A surface with a high negative
microbumps and nanobumps, statistical software was used to skewness has a larger number of local maxima above the mean,
calculate roughness distribution parameters σ, β ∗ , Sk and K mostly located near the summit, as compared to a Gaussian
which correspond to standard deviation, correlation length, distribution; for a positive skewness, the converse is true.
skewness, and kurtosis, respectively (Bhushan 1999, 2002). A surface with a low kurtosis has a larger number of local
Data for all leaves at both 50 and 2 µm scans are presented in maxima above the mean randomly distributed as compared
table 2. Values of σ for lotus and colocasia are approximately to that of a Gaussian distribution; again, for a high kurtosis
ten times larger than those for fagus and magnolia in the 2 µm the converse is true (Bhushan 1999, 2002). Sk and K for
scan, but on the other hand, they are almost the same in the hydrophobic and hydrophilic leaves in both 50 and 2 µm scans

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 Micro- and nanoscale characterization of hydrophobic and hydrophilic leaf surfaces

(a)

Figure 7. (a) Curve fit for a bump on a lotus leaf using an AFM. The
radius of curvature is calculated from the parabolic curve fit of the
bump. (b) Curve fit for bump and ridge on a colocasia leaf using an
AFM. The radius of curvature is also calculated from the parabolic
curve fit. (c) Curve fit for bumps on fagus and magnolia leaves using
an AFM. The radius of curvature is also calculated from the
parabolic curve fit of the bump.

Table 2. Roughness parameters of both microbumps and nanobumps

for hydrophobic and hydrophilic leaves obtained using AFM.
Leaf Scan size State σ (µm) β ∗ (µm) Sk K
50 µm Dried 1.1 4.8 2.0 6.7
Lotus Fresh 0.10 0.44 −0.36 3.3
2 µm
Dried 0.11 1.1 −0.41 3.4
50 µm Dried 1.3 6.7 0.01 1.9
2 µm Fresh 0.09 0.24 0.11 2.5
Colocasia bump Dried 0.09 0.25 −0.11 2.6
2 µm Fresh 0.10 0.48 −0.19 2.7
ridge Dried 0.08 0.31 −0.49 4.1 (b)
50 µm Fresh 0.90 20 −0.17 2.4
Fagus Figure 7. (Continued.)
2 µm Fresh 0.03 1.3 −0.38 2.7
50 µm Fresh 0.63 13 0.21 2.3
Magnolia
2 µm Fresh 0.01 0.64 0.45 3.6
Roughness factors for various leaves are presented in table 3.
As mentioned earlier, the open space between asperities on
are compared in table 3. PDF and roughness parameters of a surface has the potential to collect air, and its probability
the surface can help to characterize the surface structure of the appears to be higher in nanobumps as the distance between
hydrophobic and hydrophilic leaves. bumps in the nanoscale is smaller than those in microscale.
Using roughness factor values, along with the contact angles
3.3.5. Role of microbumps versus nanobumps. The (θ ) from both hydrophobic and hydrophilic surfaces; 153◦
approximation of the roughness factor for the leaves on and 152◦ in lotus and colocasia, and 76◦ and 84◦ in fagus
the micro- and nanoscale was made using AFM scan data. and magnolia, respectively, the contact angles (θ0 ) for the

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B Bhushan and Y C Jung

Figure 8. Adhesive force for both fresh and dried leaves, and the
coefficient of friction for dried leaves for both 50 and 2 µm scan size
for hydrophobic and hydrophilic leaves. All measurements were
made using a 15 µm radius borosilicate tip. Reproducibility for both
adhesive force and coefficient of friction is ±5% for all
measurements.

Table 3. Roughness factor and contact angle (θ = θ − θ0 )

calculated using Rf on the smooth surface for hydrophobic and
hydrophilic leaves measured using an AFM, both microscale and
nanoscale.
Leaf
(c) (contact angle) Scan size State Rf θ

Figure 7. (Continued.) 50 µm Dried 5.6 54a

Lotus (153◦ ) Fresh 20 61b
2 µm
Dried 16 60b
50 µm Dried 8.4 56a
smooth surfaces can be calculated using the Wenzel equation 2 µm Fresh 18 60b
(equation (1)) for microbumps and the Cassie–Baxter equation Colocasia (152◦ ) Bump Dried 14 59b
(equation (2)) for nanobumps. Contact angles (θ ) calculated 2 µm Fresh 18 60b
using Rf on the smooth surface can be found in table 3. It Ridge Dried 15 59b
can be seen that the roughness factors and the differences (θ ) Fagus (76◦ ) 50 µm Fresh 3.4 −10a
2 µm Fresh 5.3 2b
between θ and θ0 on the nanoscale are higher than those in Magnolia (84◦ ) 50 µm Fresh 3.8 −4a
the microscale. This means that nanobumps on the top of a 2 µm Fresh 3.6 14b
microbump increase the contact angle more effectively than
a
microbumps. In the case of hydrophilic leaves, the values of Calculations made using Wenzel equation.
b
Rf and θ change very little on both scales. Calculations made using Cassie–Baxter equation. We
assume that the contact area between the droplet and air
Based on the data in figure 8, the coefficient of friction is the half of the whole area of the rough surface.
values in the nanoscale are much lower than those in the
microscale. It is clearly observed that friction values are scale
dependent. The height of a bump and the distance between earlier that contact angle hysteresis decreases and contact angle
bumps in microscale is much larger than those in nanoscale, increases due to the decreased contact with the solid surface
which may be responsible for larger values of friction force on caused by the air pockets beneath the droplet. The surface with
the microscale. nanobumps has a high roughness factor compared with that
A difference between microbumps and nanobumps for of microbumps. With large distances between microbumps,
surface enhancement of water repellency is the effect on the probability of air pocket formation decreases, and is
contact angle hysteresis, in other words, the ease with which responsible for high contact angle hysteresis. Therefore, on the
a droplet of water can roll on the surface. It has been stated surface with nanobumps the contact angle is high and contact

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 Micro- and nanoscale characterization of hydrophobic and hydrophilic leaf surfaces

Figure 9. Probability density function of hydrophobic and hydrophilic leaves obtained using AFM in 50 and 2 µm scans. PDFs were
calculated using a statistical program.

angle hysteresis is low, and drops rebound easily and can set a superhydrophobic surface. Roughness factors of nanobumps
into a rolling motion with a small tilt angle. are much larger than those of microbumps and are responsible
for the increase in contact angle for hydrophobic surfaces. For
4. Conclusions the water droplets sitting on the nanobumps, with decreased
spacing between bumps, the probability of air pocket formation
In this paper, we have investigated what makes surfaces
hydrophobic by analysing surface roughness, adhesion and increases, and the contact angle increases and contact angle
friction data for hydrophobic and hydrophilic leaves on the hysteresis decreases (Cassie–Baxter equation). In the case of
microscale and nanoscale. Attempting to remove the surface the hydrophilic leaves, while the height of the microbumps can
layer, it was found that no wax exists on the hydrophilic leaves be comparable to that of the hydrophobic leaves, the height of
but a thin wax film exists on the hydrophobic leaves. The the nanobumps is small. From the analysis of roughness on
combination of wax and roughness of the leaf is what creates the micro- and nanoscale, it is found that the nanobumps on

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Kijlstra J, Reihs K and Klamt A 2002 Roughness and topology of
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