Eur. Phys. J. Appl. Phys.

(2013) 64: 31302

DOI: 10.1051/epjap/2013130235
THE EUROPEAN
PHYSICAL JOURNAL
APPLIED PHYSICS
Regular Article

Scanning polarization force microscopy investigation of contact

angle and disjoining pressure of glycerol and sulfuric acid on
highly oriented pyrolytic graphite and aluminum
Antoniu Moldovan1 , Petru-Marian Bota1 , Teodor Dan Poteca2 , Iulian Boerasu1 , Dionezie Bojin1 , Daniela Buzatu1 ,
and Marius Enachescu1,3,a
1
Center for Surface Science and NanoTechnology, University “Politehnica” of Bucharest, 313 Splaiul Independentei,
Bucharest 060042, Romania
2
Medical and Pharmacy University “Carol Davila”, 37 Dionisie Lupu, Bucharest 020022, Romania
3
Academy of Romanian Scientists, 54 Splaiul Independentei, Bucharest 050094, Romania

Received: 13 May 2013 / Received in final form: 11 September 2013 / Accepted: 6 September 2013
Published online: 9 December 2013 – c EDP Sciences 2013

Abstract. For liquid droplets of sub-micrometer dimensions, the study of wetting properties (quantified by
contact angle, disjoining pressure, spreading coefficient, etc.) is possible using the relatively new technique
known as scanning polarization force microscopy (SPFM). This non-contact scanning probe microscopy
technique was successfully implemented in our laboratory in order to study the wetting properties of
glycerol and sulfuric acid on the surface of highly oriented pyrolytic graphite (HOPG) and glycerol on
aluminum film deposited on mica. An AC polarization bias of 3 V at 3 kHz frequency was applied be-
tween a conductive atomic force microscope tip and the substrate. The resulting polarization force was
measured with high accuracy, allowing non-contact topography profile measurements of liquid micro- and
nanodroplets. The dependence of the contact angle on droplet height was determined in order to calculate
the values of the spreading coefficient and the disjoining pressure between the liquid and substrates. The
calculated potential energies give disjoining pressure values of ∼0.4 atm for glycerol on HOPG, ∼0.47 atm
for glycerol on aluminum and ∼13 atm for H2 SO4 on HOPG. In the case of H2 SO4 on HOPG the strength
of the force appears to be thirty times bigger than that for glycerol on HOPG and aluminum.

1 Introduction we report about the study of wetting properties

(quantified by contact angle, disjoining pressure, spread-
Wetting phenomena, related to the contact between liq- ing coefficient, etc.) using a relatively new technique
uids and solids, are extremely common in nature and have known as scanning polarization force microscopy (SPFM),
been studied for many years. The energy needed to initially implemented at Lawrence Berkeley National
create a unit area of surface or interface is the surface Laboratory [8]. SPFM represents an extension of the
energy or surface tension and influences the wetting phe- atomic force microscopy technique and offers a new way
nomena. Many experimental methods have been devel- to investigate surface properties of very soft/liquid sur-
oped to study these phenomena [1–4]. Optical methods faces – such as topography, microscopic contact angle,
for example are suitable for studying the shape of droplets dielectric constant, etc. – which are not always accessi-
larger than a few micrometers, in order to derive the con- ble to other surface characterization techniques. SPFM
tact angle values. With the rapid development of micro- has demonstrated its usefulness in studies of these prop-
and nano-electromechanical systems (MEMS/NEMS) in erties, by directly measuring the shape of nanometer size
the last decades, the interest for the study of wetting liquid droplets [9], of lyposomes and other various bio-
properties at the respective scale is continuously grow- membranes [10] on surfaces.
ing. Advances in understanding wetting properties at the The SPFM technique offers the possibility to measure
micro- and nanoscale would help address numerous is- directly the values of contact angle (is a direct measure-
sues related to adhesion, friction, wear, etc. of components ment), without additional intermediary steps and without
in MEMS/NEMS. Techniques of the scanning probe mi- any contact between the probing tip and the liquid, by
croscopy (SPM) family have been employed for the deter- comparison with the work described by Jung and
mination of wetting properties for sub-micrometer [5,6] Bhushan [6] where a multiple step approach is proposed
to millimeter size liquid droplets [7]. In the present work for the determination of contact angle values of micro-
a and nanodroplets. Moreover, SPFM is suitable for any
e-mail: [email protected]
liquid surface geometry (such as droplets formed on

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heterogeneous surfaces, double merging droplets, pancake- The above relation shows that the electrostatic force has
like liquid crystal droplets [11], liquid films, etc.). Studies three terms with different time-dependencies: F0ω , the
of wetting properties by direct measurement of the topog- first term which is constant; Fω , the second term with
raphy in non-contact AFM have been reported [5,7], even ωt time dependence; F2ω , the third term with 2ωt time de-
though the stable operation of AFM in true non-contact pendence. Moreover, the amplitude of the Fω term
on liquid surfaces can be extremely challenging. In con- depends on the vertical gradient of the tip-sample ca-
ventional AFM imaging (contact, non-contact, intermit- pacitance and on the local surface potential Vsurf . The
tent contact), avoiding tip contamination in the case of amplitude of the F2ω term depends only on the verti-
biological/soft samples is very difficult. Being a truly non- cal gradient of the capacitance, which depends on the
contact scanning probe technique, SPFM is highly suitable tip-sample separation and the dielectric properties of the
for a large number of applications: from the study of liq- sample/material.
uid micro- and nanodroplets or films to the study of liv- The polarization force acting on the tip will cause a
ing viable biological materials (cells, tissues) or any kind proportional bending of the cantilever. The bending can
of soft materials which might become damaged/altered be measured by the laser lever detection technique em-
by even the slightest contact of a scanning tip. Moreover, ployed in usual AFM experiments (Fig. 1): a laser light
SPFM can provide qualitative and quantitative informa- is reflected off the back of the cantilever and falls on a
tion about the local dielectric properties of samples in position sensitive detector (PSD). The output signal of
various fields: nanoelectronics, MEMS/NEMS, micro- and the detector is proportional to the bending of the can-
nanobiology etc. [12,13]. tilever and, consequently, to the polarization force.
The SPFM technique is based on the measurement and Thus, the PSD signal will have the same time depen-
control of the electrostatic polarization force between a dence as the polarization force. The three components of
conductive sharp tip and the investigated surface. A polar- the signal (0ω, 1ω and 2ω) are separated by a lock-in tech-
ization bias is applied on a conductive AFM tip held a few nique. As the amplitude of the 2ω component depends
tens of nanometers (10–20 nm) above the surface of the on the vertical gradient of the tip-surface capacitance, it
sample. The intense electric field surrounding the tip apex, can be used to trace the topography of the surface. It
generated by the tip charge and the image charge, creates is fed to the input of the feedback loop which controls
a long range attractive electrostatic force for conductive the tip-sample separation. The topography of the surface
materials or an attractive electric polarization force for is reconstructed from the signal which drives the vertical
dielectric materials. elongation of the scanner in order to maintain constant
If the polarization bias has a DC component (VDC ) amplitude of the 2ω signal during scanning.
and an AC component of the form Vtip sin(ωt), and the The wetting properties of liquids are related to the po-
local surface potential is Vsurf , the net bias between tip tential energy between the liquid-gas and liquid-substrate
and sample will be V (t) = VDC − Vsurf + Vtip sin(ωt). By interfaces by the following relation [14] for the microscopic
the coarse approximation of the tip-surface system with a contact angle θ, θ2 = θ02 + γ2 [P (e) + eΠ(e)], where e is
parallel plate capacitor, the electrostatic force will be: the height of the droplet; P (e) is the potential energy
  between the interfaces; θ02 = − γ2 P (0) is the macroscopic
c 2 1 2
F (t) = (VDC − Vsurf ) + Vtip contact angle squared; P (0) is the spreading coefficient
d 2 S = γsv − γsl − γ, which characterizes the wetting proper-
c 1c 2 ties of a surface by a given liquid at short ranges. If S > 0,
+ 2 (VDC − Vsurf ) Vtip sin(ωt) − V cos(2ωt).
d 2 d tip the liquid will completely wet the surface and if S < 0
(1) a finite contact angle will exist, determined by Young’s

Fig. 1. Detection and feedback mechanism in SPFM mode.

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 A. Moldovan et al.: Contact angle and disjoining pressure by SPFM

equation γ cos θ = γsv − γsl ; γsv is the solid-vapor sur- of a more extensive study involving corrosion experiments
face energy; γsl is the solid-liquid surface energy; γ is the at the microscopic scale. Pure glycerol has a boiling point

liquid-vapor surface energy; Π(e) = − dP de = −P (e) is the of 290 ◦ C at normal atmospheric pressure and a density
disjoining pressure [15] which characterizes the wetting of 1.26 g/cm3 at room temperature. Concentrated (98%)
properties at short ranges and is related to the spreading sulfuric acid has a boiling point of 337 ◦ C at normal at-
∞
coefficient by the relation S = 0 Π(x)dx = P (e)e→0 . mospheric pressure and a density of 1.84 g/cm3 at room
The contact angle θ depends on the interfacial ener- temperature. In our calculations we have used the values
gies and is influenced by the disjoining pressure. Hence, of 73 mJ/m2 and 64 mJ/m2 for the surface tensions of
the height dependence of the potential energy between the H2 SO4 solution and glycerol, respectively.
interfaces P (e) can be determined from the height depen- The HOPG substrates were freshly cleaved prior to the
dence of the microscopic contact angle θ(e). We investi- experiments. The aluminum film was deposited on freshly
gated the contact angle and disjoining pressure of glycerol cleaved mica by thermal evaporation in vacuum. The sub-
and sulfuric acid on highly oriented pyrolytic graphite and strates were verified by AFM and optical microscopy prior
glycerol on aluminum covered mica. We chose scanning to the deposition of liquid droplets.
polarization force microscopy technique, implemented re- Glycerol droplets were created on the substrates by
cently in our lab, as it is the only technique that combines condensation: the substrates were held upside down inside
the advantages of providing relatively easy, direct topo- a Berzelius glass containing heated glycerol, at a height of
graphical measurements in true non-contact, on virtually ∼5 mm from the liquid surface. After a few seconds the
any shape of liquid or soft surfaces, at the nanometer scale, surface of the substrates achieved a “foggy” appearance,
including the possibility to measure simultaneously local which proved the presence of microscopic droplets. This
dielectric properties. was confirmed by further optical microscopy inspection
(Figs. 3a–3c).
Sulfuric acid droplets (50% vol.) were created on the
2 Experimental studies of wetting phenomena substrates by casting a macroscopic drop (∼50 μL) and
then absorbing the liquid at one corner of the substrate
2.1 Apparatus description with the aid of a lens cleaning tissue, avoiding contact be-
tween the tissue and the substrate surface. The substrates
The topography measurements were carried out in our appeared dry at a first inspection with the naked eye.
laboratory using scanning polarization force microscopy, However, optical microscopy images revealed the presence
a powerful technique for nondestructive imaging of liq- of liquid droplets of various sizes and shapes (Fig. 3b).
uids and/or soft materials. The SPFM measurements were The droplets deposition took place at room temperature
conducted in ambient air (room temperature, RH = 50%) and ∼50% relative humidity.
using a modified home-built AFM system controlled by
commercial electronics (RHK SPM100 and PLLPro2).
The samples were placed on steel carriers which were elec- 3 Results and discussions
trically connected to the ground of the system. SPFM
measurements were carried out in AC mode, with a bias of
3.1 Optical microscopy
3 V amplitude and 3 kHz frequency applied between the
conductive tip and ground. Commercial conductive coated
(Pt and Cr/Au), contact mode silicon tips were used for Optical images of the freshly cleaved substrates revealed
the measurements (Mikromasch, Nanosensors, AppNano). smooth surfaces, almost free of defects over relatively large
The nominal spring constant of the cantilevers was less areas (several square millimeters). The images shown in
than 1 N/m. Figure 2, having a field of view of ∼70 μm × 55 μm, are
Optical microscopy images were also recorded, using typical for the distribution of glycerol and H2 SO4 droplets
an Olympus upright optical microscope, with its ×50 and on the substrates. These macroscopic types of measure-
×100 objectives. ments assured us our droplets deposition techniques were
well working.

2.2 Preparation of substrates and deposition of micro-

and nanodroplets 3.2 SPFM analysis

Glycerol and sulfuric acid were chosen for the formation Figure 3 shows typical SPFM-AC topography images of
of liquid droplets on highly oriented pyrolytic graphite the samples after the deposition of the droplets on HOPG
(HOPG). On aluminum covered mica, the droplets were and aluminum. The images show that the dispersion of
formed by glycerol. Both liquids were chosen primarily the droplets depends on liquid type and substrate. The de-
because of their low vapor pressure at room tempera- posited droplets have shapes close to spherical caps, which
ture, which ensures a very low evaporation rate during allows us to use the theoretical model of de Gennes [14] in
the experiments. Additionally, glycerol suited the tech- order to determine the surface potential energy P (e) be-
nique developed for the creation of nanodroplets – de- tween glycerol/H2 SO4 and HOPG and between glycerol
scribed in detail below. Sulfuric acid was chosen as part and aluminum.

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Fig. 2. Optical microscopy images of the samples after the deposition of the droplets: (a) glycerol on HOPG; (b) sulfuric acid
on HOPG; (c) glycerol on aluminum covered mica.

(a) (b)

(c)
Fig. 3. Typical SPFM-AC images of the samples after the deposition of the droplets: (a) glycerol on HOPG, 5 µm × 5 µm;
(b) sulfuric acid on HOPG, 3 µm × 3 µm; (c) glycerol on aluminum covered mica, 5 µm × 5 µm.

Droplet profiles were extracted from the SPFM meniscus meets the surface of the substrate, measured
topography images taken on the samples, by plotting the through the liquid – as shown in Figure 5a.
height versus lateral displacement along horizontal seg- For micro- and nano-droplets, as shown in Figures 4
ments taken across the point of maximum height for each and 5b, the liquid meniscus does not meet the solid surface
chosen droplet. All the analyzed profiles belong to droplets at a precise angle and the graph of the line-cut profile has
that were chosen to have circularly symmetric shape and two inflection points (one on each side of the section). In
to cover the entire range of dimensions in the available this case the contact angle is calculated by measuring the
SPFM topographical images. Some of the profiles are plot- slope (first derivative) of the line-cut profile at these in-
ted in Figure 4 for both glycerol and sulfuric acid on flection points [16]. Contact angle values corresponding to
HOPG and for glycerol on aluminum. the analyzed droplets were plotted as a function of droplet
height.
3.3 Contact angle measurements Figures 6 and 7 show the results for glycerol and H2 SO4
respectively, on HOPG and aluminum covered mica. A de-
For a macroscopic liquid droplet the contact angle is de- crease of contact angle with droplet height is observed for
fined as the angle at which the surface of the liquid all cases, which indicates that the surface potential P (e)

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 A. Moldovan et al.: Contact angle and disjoining pressure by SPFM

(a) (b)

(c)
Fig. 4. Line-cut profiles of droplets of: (a) glycerol on HOPG, (b) sulfuric acid on HOPG, (c) glycerol on aluminum.

0.45

0.40 θo= 0.462 rad

H2SO4/HOPG
Contact angle (rad)

0.35
(a) (b)
Fig. 5. Schematic drawing of the contact angle for the case of: 0.30
(a) macroscopic droplet, (b) microscopic droplet.
0.25

0.45 0.20

0.40
0.15
0.35 6 8 10 12 14 16 18
Contact angle (rad)

Droplet height (nm)

0.30
Fig. 7. Dependence of contact angle on droplet height for
0.25 H2 SO4 deposited on HOPG.
Glycerol/HOPG
0.20 θo= 0.4 rad
Glycerol/Al is negative, i.e., the interaction forces between surfaces are
0.15 θo= 0.66 rad
hydrophobic or attractive.
0.10

0.05 3.4 Potential energy measurements

0 50 100 150 200 250 300
Droplet height (nm) Using relation θ2 = θ02 + γ2 [P (e) + eΠ(e)] and the depen-
dence of contact angle on droplet height (Figs. 6 and 7),
Fig. 6. Dependence of contact angle on droplet height for we calculated the dependence of surface potential energy
glycerol deposited on HOPG and on aluminum covered mica.
P (e) between the surfaces for glycerol/H2 SO4 on HOPG

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Droplet height (nm) Droplet height (nm)


Fig. 8. Semilog plot of P (e) – eP (e) vs. e, the droplet height, Fig. 9. Semilog plot of P (e) – eP  (e) vs. e, the droplet height,
for glycerol deposited on HOPG and on aluminum covered for H2 SO4 on HOPG.
mica.

In the case of glycerol on HOPG and on aluminum, the

and glycerol on aluminum covered mica. The results are values for spreading coefficient indicate a very weak hy-
shown in Figures 8 and 9. The macroscopic contact an- drophobic interaction by comparison with surface tension
gle θ0 was determined as an exponential fitting parameter of glycerol; the value for spreading coefficient indicates a
for the microscopic contact angle dependencies. In a re- value ten times (on HOPG) respectively four times (on
lated experiment [9], dealing with the wetting of mica by Al) smaller by comparison with surface tension of glyc-
glycerol, we measured the macroscopic contact angle by erol, and in the case of H2 SO4 on HOPG the value for
optical methods and the results are in good agreement spreading coefficient indicates a five times smaller value
with the value found in literature [7]. by comparison with surface tension of H2 SO4 .
On HOPG and aluminum, glycerol and H2 SO4 form These potential energies give negative disjoining pres-
droplets whose shapes are close to spherical caps. The con- sures Π of ∼0.4 atm at e close to zero for glycerol on
tact angle varies with height as shown in Figures 6 and 7. HOPG, 0.47 atm for glycerol on aluminum and ∼13 atm
The decrease of the contact angle with decreasing droplet for H2 SO4 on HOPG. In the case of H2 SO4 on HOPG
height indicates that the surface potential P (e) is negative the strength of the force appears to be thirty times bigger
and an exponential dependence P (e) = P0 exp (−e/δ) [17] than that for glycerol on HOPG/Al.
with distance gives a good fit (Figs. 8 and 9). From the fit-
ting parameters, P0 and δ, we determine the dependence
of the potential energy on droplet height:
4 Conclusions
−3 2
P (e) = −6 × 10 exp(−e/150 nm)J/m
We have shown that SPFM, this extension of the atomic
for glycerol on HOPG, force microscopy technique, is useful for imaging the deli-
P (e) = −15 × 10−3 exp(−e/316 nm)J/m
2
cate surfaces of liquid films and nanodroplets. SPFM can
for glycerol on Al, be used also to study the effect of long range surface forces
on the shape of nanodroplets and on contact
P (e) = −13 × 10−3 exp(−e/10 nm)J/m
2
angle values. The interaction potential and disjoining pres-
for H2 SO4 on HOPG. sure can be obtained from measurements of contact an-
gle versus nanodroplet size. We successfully implemented
The exponential dependence of surface potential energy SPFM technique for the study of the wetting properties of
P (e) in all cases indicates attractive interaction between glycerol on HOPG and aluminum, and H2 SO4 on HOPG.
the liquid–substrate interfaces, having a decay length δ = We obtained nanometer resolution topographical images
150 nm for glycerol on HOPG, δ = 316 nm for glycerol of the surfaces after the deposition of the micro- and nan-
on aluminum and δ = 10 nm for H2 SO4 on HOPG, which odroplets, which confirm the conclusions from the coarse
dominates over the characteristic length of the van der optical microscopy analysis: the dispersion of the droplets
Waals interactions. varies with liquid type and substrate. The dependence of
The strength of the potential at e = 0 nm gives the the contact angle on droplet height was verified for both
spreading coefficient S for each liquid on HOPG: liquids by analyzing the micro- and nanodroplet profiles
and a decrease of contact angle with droplet height was
S = P (0) = −6 × 10−3 J/m2 for glycerol on HOPG,
observed. This indicates that the surface potential P (e) is
S = P (0) = −15 × 10−3 J/m2 for glycerol on Al, negative in all cases and also has an exponential depen-
S = P (0) = −13 × 10−3 J/m2 for H2 SO4 on HOPG. dence with droplet height, P (e) = P0 exp(−e/δ) having

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 A. Moldovan et al.: Contact angle and disjoining pressure by SPFM

a force decay length δ = 150 nm for glycerol on HOPG, 3. F. Heslot, A.M. Cazabat, P. Levinson, Phys. Rev. Lett.
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give negative disjoining pressures Π of ∼0.4 atm at e close (2008)
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This work was supported by the Romanian Ministry of 10. K. Reder-Christ, P. Schmitz, M. Bota, U. Gerber, H.
National Education and by the European Union through the Falkenstein-Paul, C. Fuß, M. Enachescu, G. Bendas,
European Regional Development Fund under project Sensors 13, 12392 (2013)
POSCCE-O212-2009-2/12689/717 and by the Romanian Min- 11. L. Xu, M. Salmeron, S. Bardon, Phys. Rev. Lett. 84, 1519
istry of National Education under projects ERA-NET 4-001/ (2000)
07.04.2011 and IFA-CEA C2-08/01.03.2012. 12. L. Fumagalli, G. Ferrari, M. Sampietro, G. Gomila, Appl.
The authors also acknowledge the financial support of the Phys. Lett. 91, 243110 (2007)
European Union and the Romanian Government, received 13. L. Fumagalli, G. Ferrari, M. Sampietro, G. Gomila, Nano
through grant POSDRU/107/1.5/S/76813. Lett. 9, 1604 (2009)
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