Professional Documents
Culture Documents
Moldovan 2013
Moldovan 2013
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.
31302-p1
The European Physical Journal Applied Physics
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
31302-p2
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.
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.
31302-p3
The European Physical Journal Applied Physics
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)
31302-p4
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
0.35
(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)
31302-p5
The European Physical Journal Applied Physics
31302-p6
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.
δ = 316 nm for glycerol on aluminum and δ = 10 nm for 62, 1286 (1989)
H2 SO4 on HOPG. We calculated the dependence of sur- 4. J.P. Cleveland, T.E. Schaffer, P.K. Hansma, Phys. Rev.
face potential energy P (e) between the interfaces (liquid- B 52, R8692 (1995)
substrate) and determined the spreading coefficient (S < 5. A. Checco, P. Guenoun, Phys. Rev. Lett. 91, 186101
0) and the disjoining pressure Π for these liquid/substrate (2003)
combinations. The calculated values for potential energies 6. Y.C. Jung, B. Bhushan, J. Vac. Sci. Technol. A 26, 777
give negative disjoining pressures Π of ∼0.4 atm at e close (2008)
to zero for glycerol on HOPG, 0.47 atm for glycerol on alu- 7. J. Yu, H. Wang, X. Liu, Int. J. Heat Mass Transfer 57,
299 (2013)
minum and ∼13 atm for H2 SO4 on HOPG. In the case of
8. J. Hu, X.D. Xiao, D.F. Ogletree, M. Salmeron, Science
H2 SO4 on HOPG the strength of the force appears to be
268, 267 (1995)
thirty times bigger than that for glycerol on HOPG and 9. A. Moldovan, M. Bota, I. Boerasu, D. Dorobantu, D.
on aluminum covered mica. Bojin, D. Buzatu, M. Enachescu, J. Optoelectron. Adv.
Mater. 15, 1101 (2013)
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)
14. P.G. de Gennes, Rev. Mod. Phys. 57, 827 (1985)
15. B.V. Derjaguin, N.V. Churaev, V.M. Muller, J.A.
Kitchener, Surface Forces (Consultants Bureau,
References New York, 1987)
16. M. Salmeron, NATO Science Series 10, 651 (2001)
1. J.N. Israelachvili, G.E. Adams, Nature 262, 774 (1976) 17. L. Xu, M. Salmeron, J. Phys. Chem. B 102, 7210
2. J.N. Israelachvili, R.K. Tandon, L.R. White, Nature 277, (1998)
120 (1979)
31302-p7