Eur. Phys. J.

E (2023) 46:113
https://doi.org/10.1140/epje/s10189-023-00374-8
THE EUROPEAN
PHYSICAL JOURNAL E
Regular Article - Soft Matter

Drying behaviour of nanofluid sessile droplets on

self-affine vis-à-vis corrugated nanorough surfaces
Deeksha Rani and Subhendu Sarkara

Surface Modification and Applications Laboratory (SMAL), Department of Physics, Indian Institute of Technology Ropar,
Nangal Road, Rupnagar, Punjab 140001, India

Received 1 September 2023 / Accepted 24 October 2023 / Published online 24 November 2023
© The Author(s), under exclusive licence to EDP Sciences, SIF and Springer-Verlag GmbH Germany,
part of Springer Nature 2023

Abstract In recent years, evaporative self-assembly of sessile droplets has gained considerable attention
owing to its wide applicability in many areas. While the phenomenon is well studied for smooth and isotrop-
ically rough (self-affine) surfaces, investigations comparing the outcomes on self-affine vis-à-vis corrugated
surfaces remains to be done. In this experimental work, we compare the wetting and evaporation dynam-
ics of nano-colloidal microlitre droplets on self-affine and corrugated nanorough surfaces having identical
roughnesses and interface properties. The coupled influence of particle size, concentration, and surface
structuring has been explored. Differences in wettability and evaporation dynamics are observed, which
are explained via the interaction between wetting fluid and anisotropic surface roughness. Our findings
exhibit different temporal behaviour of contact radius and angle in the evaporation process of the droplets.
Further, the corrugated surface exhibits anisotropic wettability with a monotonic change in droplet shape
as evaporation proceeds, finally giving rise to irregular dried patterns. The scaled rim width and crack
spacing of the particulate deposits are examined. Our results can inspire fabrication of surfaces that can
facilitate direction-dependent droplet motion for specific applications.

1 Introduction the surface [9,10]. The dried droplet patterns can be

The phenomenon of surface wetting and evaporation-
induced particle self-assembly has been an area of active
theoretical as well as experimental research since it was
first introduced by Young [1,2]. The topic gained atten-
tion due to its wide applicability in areas like print-
ing, lubrication, coating, waterproofing, microfluidics,
forensics, biotechnology, nanochromatography, analyte
detection, etc. [3–7]. The evaporation of a sessile droplet
on a surface satisfying Laplace’s equation [8] is primar-
ily governed by the evaporation flux from the droplet
surface associated with pinning or depinning of the
droplet. This effect has led to several interesting phe-
nomena reported both by experimental and theoreti-
cal groups during the last few years. In this context,
the evaporation dynamics of microlitre-sized droplets of
colloidal suspensions exhibit spatio-temporal behaviour
at the solid–liquid interface, wherein it can get pinned,
eventually producing a ring-shaped deposition pattern,
often referred to as the “coffee ring effect” (CRE) as a
result of particle migration towards the pinned three-
phase contact line (CL) owing to non-uniform evapora-
tive fluxes [2]. The formation of deposits and flow fields
may, however, be hindered by flow convection within
the drop as a result of variations in surface tension along
a
e-mail: sarkar@iitrpr.ac.in (corresponding author)
influenced by the internal flows, solute properties, con-
tact line dynamics, atmospheric conditions, wettability
of surface, and interparticle as well as particle–substrate
interactions.
Especially for the case of droplet evaporation, sev-
eral studies to date focus on the investigation of
the evaporation patterns, the evaporation modes [11],
particle–liquid–substrate interactions [12], hydropho-
bicity (hydrophilicity) of the substrate [13], etc. An
ideal solid surface is considered to be atomically
smooth, and hence, its wetting and subsequent evap-
oration characteristics are decided by the interfacial
free energies [14]. On the contrary, a real (or fabri-
cated) surface is topographically rough at the macro- or
micro-scale or chemically heterogeneous. The presence
of such textured topography is one of the key factors
that directly affect the interaction between the liquid
and substrate [15]. In particular, when a pure liquid is
put on a self-affine surface [16,17], the droplet usually
preserves its typical hemispherical shape thereby con-
fining itself at the CL leading to enhancement in evapo-
ration rate [13,18]. This usually arises due to the liquid
interacting with the asperities of the rough surface and
driving it to expand laterally at the surface, resulting
in an increase in liquid–vapour area and a decrease in
surface tension at the contact line. Studies suggest that
surface structuring including shape, width and height

123
113 Page 2 of 11
of substrate nano-asperities can influence several pro-
cesses like droplet evaporation [19], interfacial particle–
substrate forces [20], dried droplet morphology [21], etc.
Surface roughness can, however, be classified into
isotropic (self-affine) as well as anisotropic ones. For
self-affine roughness geometries and chemical hetero-
geneities, the sessile droplets exhibit an isotropic beha
viour in terms of its shape and CL uniformity [22,23].
Experimenting with pure liquid sessile droplets, Chen
et al. demonstrated that the droplet contact angle
(CA) and the evaporation modes are influenced by
μm sized and spaced asperities [24]. Garg and co-
workers showed that superwetting behaviour can be
achieved using similar structures of ZnO micropillars
having spatial periodicities of μm order [25]. Recently,
work by Hou and co-workers suggested the role of the
topographical parameters in affecting the surface ten-
sion at the CL thereby leading to Cassie–Wenzel tran-
sitions [26]. In contrast, topographically anisotropic
surfaces in the forms of parallel lines, grooves, wrin-
kles, pillars, etc., present a non-uniform shape and
apparent contact angle at the CL thereby exhibit-
ing anisotropic wetting behaviour [27,28]. Of late,
this phenomenon has gathered considerable interest
owing to potential applications in microfluidics, direc-
tional flow control devices, air-cooling applications,
heat exchangers, drainage enhancement, MEMS, etc.
[29]. The physical origins of the anisotropic wetting
phenomenon are attributed to the liquid CL encoun-
tering a physical discontinuity [30] or chemical het-
erogeneity present on a substrate [31]. On anisotropic
surfaces, droplets prefer to spread or roll freely along
parallel orientation of grooves, while being restrained
in other orthogonal direction or vice-versa. Zhao and
co-workers had observed weak anisotropic wetting phe-
nomenon of water droplets on polymer surfaces exhibit-
ing shallow periodic grooves of 0.4 μm periodicity and
50 nm depth [32]. Studies on different hierarchical sys-
tems imprinted on polystyrene (PS) and PMMA thin
films with 2 μm height and 250 nm pitch clearly indi-
cate a comparatively good anisotropic wettability [28].
A further study showed that wavy microscopic struc-
tures fabricated on PDMS surfaces having a periodic-
ity of 41 μm with a root-mean-square (rms) roughness
variation between 20 and 140 nm exhibited wettability
changes from anisotropic to isotropic with the increase
in surface roughness [33].
Although the above studies explored the wetting
phenomenon, they lacked information on the follow-
ing aspects. Firstly, the evaporation dynamics was not
explored in any of the above studies. Secondly, they
were all done using pure water on microstructured sur-
faces. It is imminent, in this context, that a study
on nanostructured surfaces using nano-colloidal water
droplets will yield interesting results. Further, droplets
of colloidal suspensions on such surfaces could exhibit
unconventional evaporation dynamics influenced by
particle-surface interactions at scales 103 orders of mag-
nitude different from what is normally experienced on
surfaces with μm sized structures. Consequentially, this
123
Eur. Phys. J. E (2023) 46 :113
will lead to interesting anisotropic drying patterns on
the substrate surface.
In this work, we systematically investigated in detail
the wetting and evaporation characteristics of droplets
of colloidal suspensions on self-affine vis-à-vis corru-
gated nano-patterned surfaces having identical root-
mean-square (rms) roughnesses. The latter helped in
distinguishing the effect of overall roughness from that
of its intricate surface morphology. Both surfaces exhib-
ited particular sets of evaporation modes depending
on the surface morphology, with the periodic rough
surface showing a monotonically increasing anisotropic
wettability which can be explained in the light of pin-
ning in the presence of corrugation crests. In addition,
droplet deformation was also observed on the periodic
surface, which corroborated with the transitions taking
place in the different modes of evaporation for the sur-
faces. Finally, the deposition patterns formed by the
dried droplets on both surfaces were studied in the
light of the corresponding morphological characteris-
tics. Delaminated effects were examined in the dried
deposits and explained in light of stress effects.
2 Experimental methods
Samples of size 1 cm × 1 cm were cut from undoped sil-
icon wafers of orientation (100) with a diameter ∼ 2
and resistivity ∼ 100 ohm-cm. The samples were con-
secutively cleaned with acetone and isopropanol by
ultrasonication for 10 min, respectively. Rinsing with
de-ionized (DI) water (ρ ≈ 18.2MΩ@250 C, Total car-
bon content (TOC) < 5 ppb and Bacterial count <
0.1 CFU/mL) was followed thereafter using a Milli-
pore DirectQ water purification system. For wet etch-
ing, HNA solution (using HF, HNO3 , and CH3 COOH
by volume ratio of 3:3:5) was prepared [34]. A homo-
geneous solution was made using a magnetic stirrer for
10 min, and then, the sample was etched ultrasonically
for 2 min. Samples were washed with de-ionized water
and dried after etching. The etching time was optimized
to achieve a certain surface roughness. A second set
of samples was prepared by low-energy Ar+ ion beam
irradiation at 500 eV incident beam energy and 13.3
mA incident beam current using a Kaufman type 4 cm
broad beam ion source. Upon evacuation, a base pres-
sure of 4 × 10−7 mbar was achieved prior to bombard-
ment inside the vacuum chamber. The ion beam was
incident at an angle of 67◦ to the surface normal. Ion
irradiation was done for 5 mins which amounted to a
total fluence of 2.5 × 1019 ions cm−2 [35,36]. Both the
above processes render the top surface amorphous. The
resulting surfaces were investigated by field emission
scanning electron microscope (FESEM) (JEOL JSM-
7610F Plus, JEOL Ltd., Japan). The surfaces were
also investigated using atomic force microscopy (AFM)
which was operated in the tapping mode with 512 × 512
lines of image resolution and 3 and 5 μm scan sizes. All
samples were analysed utilizing AFM data to calculate
periodicity, roughness and other surface properties.
Eur. Phys. J. E (2023) 46 :113
For the sessile drop evaporation experiments, col-
loidal solutions of Ludox silica nanoparticles (Sigma-
Aldrich) with average particle sizes of 12 nm (HS-30;
30 wt% suspension in H2 O) and 22 nm (TMA; 34 wt%
suspension in H2 O) were used. The colloidal concen-
trations employed for the studies were 0.2, 0.5 and
0.7 vol%. These were achieved by diluting the above
nanoparticle solutions with appropriate amounts of DI
water in order to make the concentrations the same. To
ensure homogeneity, the colloidal suspension was son-
icated for 20 mins prior to each experiment. A 1 μL
sessile droplet was drop cast on each sample using an
inbuilt micropipette in the drop shape analyser (Kruss
DSA25E). Evaporation of sessile droplet was carried
out with measurement of base diameter, wetting con-
tact angle and volume. Advancing and receding con-
tact angles were obtained during the onset of contact
line motion while injecting or withdrawing liquid using
a Theta Flex optical tensiometer (Biolin Scientific).
This involved the insertion of a stainless steel syringe
tip with 0.5 mm outer diameter into a 5 μL droplet
and gradually changing the volume at a flow rate of
1 μL/min. All experiments were performed in a tem-
perature and humidity-controlled chamber at 25 ± 1◦ C
and 40 ± 5% relative humidity. The resulting deposition
patterns were studied using a Nikon Eclipse LV100ND
optical microscope with ∼ 5×to 50× magnification. All
experiments were repeated 4–5 times to ensure repro-
ducibility.
3 Result
3.1 Surface morphology
Figure 1 shows FESEM images of the nanostructured
surfaces. It is clear that the wet etched surface (WES)
shows an isotropic self-affine morphology where the
surface heights scale by different amounts in different
directions [16], whereas the ion irradiated surface (IIS)
shows an anisotropic morphology with nanometer-order
corrugated structures formed on its surface in a pref-
erential direction. Additionally, Fig. S1 of Supporting
Information (SI) shows 2 × 2 μm2 AFM 2D topograph-
ical images of the above surfaces. The 2D Fast Fourier
Transformation (FFT) insets corroborate the observed
periodicities since the WES morphology shows a circu-
lar FFT pattern with no characteristic spots. The FFT
for the IIS surface on the other hand shows distinct
side-lobes, thereby indicating the presence of periodic
structures with a characteristic wavelength. The sur-
face uniformity is evident from both the FESEM and
AFM images. AFM measurements reveal that the root-
mean-square (rms) roughness of the chemically etched
surface is 3.5 ± 0.2 nm while that of the irradiated sur-
face is 3.6 ± 0.3 nm (± indicates the standard devia-
tion in measurements). These values have been aver-
aged over 4–5 scans acquired at different places across
the sample. In addition, the corrugations formed on the
irradiated surface have a periodicity of 40 nm as esti-
Page 3 of 11 113
mated from the line profile measurements. Other sta-
tistical data pertaining to AFM analyses are furnished
in Table 1 of SI. The roughness evolution for the chemi-
cally etched surface is primarily governed by the chem-
ical kinetics that gains control over the etching mecha-
nism [34]. The reaction encompasses an oxidation step
followed by a dissolution of silicon oxide. For IIS on
the other hand, the evolved roughness and periodic-
ity are ascribed to the self-organization of the surface
atoms caused by an energetic ion beam as explained
in literature [35–38]. More importantly, the orienta-
tion of the nano-corrugations formed on the surface is
an outcome of irradiation-induced instabilities due to
curvature-dependent sputtering and a surface-diffusive
smoothing mechanism which reduces the surface ten-
sion of the irradiated surface.
3.2 Wettability of surface
Figure 2 shows representative optical images for ses-
sile droplets of colloidal suspensions on the isotropic
(Fig. 2a) and anisotropic surfaces (Fig. 2b, c) in direc-
tions parallel and perpendicular to the direction of cor-
rugations, respectively. The schematic (not to scale)
shows measurement geometry for parallel and perpen-
dicular directions with respect to the corrugation direc-
tion. IIS samples were marked on the back side indicat-
ing the ion beam direction prior to irradiation. This
acted as a reference for the subsequent experiments of
AFM and droplet angle to ascertain the relative ori-
entation of the corrugations with respect to the mark.
For the WES, the contact angle (CA) was found to
be the same irrespective of the direction of measure-
ment, implying that it exhibits isotropic wettability
with a slightly hydrophobic nature evidenced by a con-
tact angle of about 96◦ as displayed in Fig. 2a. This is
primarily due to strong pinning of the sessile droplet
on the isotropic nanorough surface which can be con-
firmed by a higher contact angle hysteresis caused by
the asperities on WES (Table 2 in SI). Studies suggest
that the presence of surface asperities pin the CL con-
siderably, leading to an increase in particle concentra-
tion reaching the random-packing limit at times much
earlier than what happens for a flat surface [39]. The
closely spaced height fluctuations contribute towards
this strong pinning phenomenon. The drop takes a
spherical-cap shape, and CA is found to be uniform
along the CL as noticed in a previous study [40]. The
corrugated surface, on the other hand, exhibits static
contact angles measured in orthogonal directions, i.e.
both parallel and perpendicular to the corrugations.
These angles are found to be slightly less than that
of the WES. The lowest CA and better wettability
were exhibited by IIS in the parallel orientation, while
the highest by WES. It is further observed that mea-
surements in the perpendicular direction show larger
contact angles (75◦ ) than the parallel one (69◦ ). This
clearly suggests formation of elliptical droplets as com-
pared to the spherical ones for the case of WES. The
corresponding CA measurements have been taken care
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113 Page 4 of 11
Fig. 1 Field-emission scanning electron microscopy (FESEM) images showing surface topographies of a WES and b IIS
surfaces, respectively
Fig. 2 Top panel: Schematic (not to scale) showing top
view of droplets on WES and IIS. The orthogonal view-
ing directions for IIS are shown by red arrows with respect
to the corrugation periodicities. Bottom panel: Side view of
1 μL droplets of colloidal suspensions of 0.5 vol% concen-
of by elliptical fits using the Young–Laplace method by
considering the surface curvature of the droplet result-
ing from the equilibrium between surface tension and
weight of the liquid [41]. The irradiated substrate, thus,
shows hydrophilicity with anisotropic wettability lead-
ing to a droplet deformation during evaporation. The
anisotropicity was further confirmed by advancing and
receding angle experiments, leading to the demonstra-
tion of contact angle hysteresis for the two cases (Table
2 of SI) indicating the pinning effect at CL caused by
surface asperities. It is observed that the perpendicular
123
Eur. Phys. J. E (2023) 46 :113
tration and 12 nm particle size showing apparent wetting
contact angle on a WES and IIS in b parallel and c per-
pendicular direction of corrugations. Yellow arrows indicate
the droplet contact line from where the measurements have
been made
direction exhibits larger hysteresis as well as contact
angle as compared to the parallel one. For compari-
son, experiments were also carried out for non-colloidal
water droplets to observe the pinning effect and sep-
arate out the influence of colloidal particles on the
wetting phenomenon (results given below). Anisotropic
wettability has been observed in earlier studies as well
[30,32]. Their results showed that the apparent CA
when observed in a direction parallel to the corruga-
tions/grooves was higher than that for the perpendicu-
lar direction. It is to be noted here that the corrugations
Eur. Phys. J. E (2023) 46 :113
accounted for their cases were in the μm range, while
for the present study they are in the range of nanome-
ters. Considering the shorter wavelength (40 nm) of the
corrugations for the present case in comparison with
the larger ones (∼ μm) as found in the earlier stud-
ies, the pinning of the droplet is effectively dominated
by the crests of the undulations when the droplet is
observed in the parallel direction. A deciding factor here
is the number of crests over which the droplet rests. For
the present case, the number is very high as compared
to earlier studies since the wavelength is in the range
of nanometers. A lower apparent CA (for the corru-
gated surface in the parallel direction) than the WES
can be explained by the fact that the pinning by the
well-separated corrugation crests is slightly lower than
the densely placed height fluctuations for the isotropic
rough surface. Hence, the squeezing is less for the par-
allel configuration [40]. In the perpendicular direction,
the droplet is stretched along the corrugations. How-
ever, the few defects along the corrugations act as pin-
ning centres for the droplet. The three-phase CL thus
resembles closer to a pristine surface (p-Si), except for
the presence of a few defects at certain places. This
leads to an initial CA of 75◦ which is quite close to that
of a pristine Si (73◦ ) surface. The above considerations
explain the differing behaviour observed in the present
work with respect to the earlier ones. Finally, in order to
check the surface chemical homogeneity/heterogeneity,
X-ray photoelectron spectroscopy (XPS) studies were
conducted on the surfaces. These measurements (Fig.
S2 in SI) ascertained that the surface chemistries are
almost identical for the surfaces.
Figure 3 depicts the wetting contact angles on
nanostructured p-Si surfaces for various colloidal con-
centrations of the droplet. For comparison, data for
pure water (0% conc.) have also been furnished. It is
observed that CA on the WES varies from 95◦ to 102◦ .
For the IIS, the contact angles exhibit an increasing
value for both orientations in the range of 67◦ to 77◦ .
In addition, the corrugated surface shows an anisotropic
Fig. 3 Measurement of the wetting contact angles of a
micro-liter sessile droplet on WES, IIS and pristine Si (p-Si)
surface
Page 5 of 11 113
wetting behaviour for the droplet of colloidal suspen-
sion, with a maximum contact angle difference of 6◦
between parallel and perpendicular directions. For all
the rough surfaces, it is observed that the larger parti-
cle size shows a higher CA for lower concentrations. The
contact angles increase with increasing particle con-
centration and size which indicates that the dispersed
nanoparticles alter the force balance near the CL. This
is envisaged to be an outcome of particle–surface and
particle–particle interactions via Derjaguin–Landau–
Verwey–Overbeek (DLVO) forces [20,42], as discussed
in SI. These interactions become more effective as evap-
oration proceeds since the surface-to-volume ratio of
particles increases, eventually leading to more particle-
surface interactions. However, droplets having smaller
particle sizes are also effective in raising CA for identical
droplet volumes but for higher concentrations. Radiom
et al. reported similar findings in their work for parti-
cle size 260 nm and concentrations ranging from 0.05 to
2 vol% [43]. However, in their case, the substrate was
considered to be smooth and hydrophilic.
Further, an estimation of total free energy change
(ΔG) based on a thermodynamic model [32] reveals dif-
ferent values for the orthogonal directions. This model
separates out the free energy contributions due to sur-
face roughness and the shape of the sessile drop. Thus,
it can differentiate between isotropic and anisotropic
wetting on a rough surface through CL characteris-
tics along the two orthogonal directions of a corrugated
surface. According to the model, the total free energy
change (ΔG) for a sinusoidal corrugated surface is given
by
 
x
ΔG = −L γla cosθ + L γla (H0 − z )2 + x2 − H0
cosα
(1)
Here, L is the length of the CL, γla and θ have their
usual meanings, x is the horizontal projection of the
distance that the CL has moved across, α is the angle
defined by the corrugation (ripple) amplitude (d) and
wavelength (λ) (tan α = 2d/λ), H0 is the initial length
of the liquid front and z is the height of the three-
phase contact point from z = 0. The free energy of
adhesion is found to be negative for both the surfaces,
indicating the aggregation and adhesion of particles on
them. For IIS, ΔG/L is in the range −114 μJ/m and
−81 μJ/m in the parallel and perpendicular directions,
respectively, for smaller particle and lower volume frac-
tion as shown in Fig. 4. Thus, the parallel direction
indicates the least surface energy among the two con-
figurations. While in case of WES, the value of ΔG/L
is found to be −19 μJ/m which is larger than IIS. In
contrast, Zhao et al. demonstrated that the free energy
of a water droplet on micron-sized (both in terms of
depth and wavelength) grooves was greater in the par-
allel than in the perpendicular direction [32]. In their
case, the droplet CL length was of the order of μm
while for the present case it is of the order of mm. This
resulted in the second term on the rhs of Eq. 1 to be
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113 Page 6 of 11
Fig. 4 Total free energy change (ΔG) as a function of col-
loidal concentration with different particle sizes for WES
and IIS
positive with respect to the first one in the study by
Zhao. In the present study, this turns out to be the
opposite, i.e. first term is greater than the second one.
3.3 Evaporation characteristics
The evaporation dynamics of the colloidal sessile droplet
on WES and IIS for the particle size of 12 nm with
respect to change in contact angle and normalized
droplet radius (R/R0 ) is shown in Fig. 5. For compar-
ison, data for pure water (0 vol%) are also plotted for
each case. Here, R0 is the initial radius and R is the
radius at a particular instant of time. All plots have
been made as a function of total normalized evaporation
period (T /T0 ). Here, T0 is the total time of evaporation
and T is a particular instant of time during the evap-
oration process. The evaporation of the sessile droplet
on a substrate takes place in three stages, i.e. CCR
(constant contact radius) mode, CCA (constant contact
angle) mode and MM (Mixed) mode [24,39]. On WES,
the droplet predominantly evaporates in the CCR mode
with a steady reduction in CA almost till the end where
both angle and radius decrease during the short-lived
MM mode of evaporation as shown in Fig. 5a. Isotropic
roughness at the nanoscale contributes to intense pin-
ning of droplet at CL where most of the evaporation
occurs in CCR mode thereby exhibiting a strong coffee-
ring effect. This is primarily due to the availability of
numerous isotropically distributed height fluctuations
in the form of pinning sites [39]. For IIS substrates,
droplet evaporation was studied in parallel and per-
pendicular directions of the corrugations as depicted
in Fig. 5b, c, respectively. For both orientations, the
droplet evaporates in CCR mode first, then in CCA
mode, and lastly in MM. The existence of 3 differ-
ent modes of evaporation for the case of IIS is simi-
lar to that of a pristine Si surface reported earlier [39].
However, the CCR mode observed for corrugated IIS
is a short-lived one as compared to that of WES. The
total evaporation times were observed to be different
for the surfaces. For WES and IIS, the times were 12–
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Eur. Phys. J. E (2023) 46 :113
15 and 8–10 min, respectively, for all combination sets
of nanoparticle sizes and concentrations.
During differential evaporation on IIS, the droplet
radius and angle decline with time and essentially
approach zero, indicating the switching from CCR
mode to CCA mode of evaporation. This transition is
determined by the CCR/CCA ratio which is calculated
with respect to the normalized time (T /T0 ). For all
concentrations, the CCR/CCA ratio was found to be
0.6 for parallel configuration and 0.5 for the perpen-
dicular direction of the corrugations as evaluated from
the data of Fig. 5b, c, respectively. The time span of
CCA modes is affected by the periodicity of corruga-
tions, which contributes to the receding of the droplet
CL more in a perpendicular direction. This receding is
driven by the adhesion between particle–substrate at
CL and further influenced by the surface periodicity,
roughness, and interfacial wetting states [44]. In gen-
eral, the transition between the modes of evaporation
is determined by the nature of the defects, with surfaces
having dense height fluctuations acting as hydrophobic
surfaces and surfaces with comparatively largely spaced
protrusions acting as hydrophilic ones as found in our
experiments and discussed above (Sect. 3.2).
Figure 6 depicts the variation in contact angle and
base radius (normalized) of the droplet of colloidal sus-
pension on WES and IIS in parallel and perpendicu-
lar directions for the larger particle size (22 nm). The
overall distribution of modes of evaporation on both
surfaces with orientations was reported to be similar to
the smaller particle size. For the determination of the
CCR/CCA ratio, the parallel direction shows a ratio of
0.4 and the perpendicular direction that of 0.2 as calcu-
lated from Fig. 6b, c, respectively. With an increase in
the particle size, the receding time of the CL at CCA
mode increases with a reduction in CCR mode dura-
tion, as particles are loosely deposited next to each
other at the CL during evaporation. However, smaller
size particles easily get pinned at the CL and can get
closely packed during evaporation with comparatively
larger CCR mode. Therefore, particle size decides the
adhesion forces acting between particles and substrate
as well as among particles inside the fluid during evap-
oration [42]. The particle deposition near the CL is the
result of the competition between these forces exerted
on each of the particles. During evaporation, as the
inward surface tension force overcomes all interfacial
forces, the depinning of the CL occurs faster for larger
particle sizes [45]. Thus, the coupled effect of topo-
graphical periodicity, associated pinning sites and par-
ticle size dominate the depinning of droplet boundary
in the perpendicular orientation.
The hydrophilic IIS shows a prominent signature of
anisotropic wettability for the sessile droplet which is
driven by the periodicity of the asperities and can be
experimentally observed during evaporation. In order to
visualize the droplet deformation during evaporation,
the normalized droplet radii in the parallel and per-
pendicular directions were plotted as a function of nor-
malized evaporation time as shown in Fig. 7. It is clear
that, initially, the wetting area of the drop is almost cir-
Eur. Phys. J. E (2023) 46 :113 Page 7 of 11 113

Fig. 5 Variation in contact angle and radius with normalized time during evaporation of 12 nm particle size colloidal
droplet on a WES and IIS in b parallel and c perpendicular view direction. Data for pure water droplets have been added
for reference

Fig. 6 Variation in contact angle and radius with normalized time during evaporation of 22 nm particle size colloidal
droplet on a WES and IIS in b parallel and c perpendicular view direction. Data for pure water droplets have been added
for reference

123
113 Page 8 of 11
Fig. 7 Temporal deformation profiles of droplets on IIS surface during evaporation from both directional view (i.e. parallel
and perpendicular) with corresponding concentrations and particle sizes. Color bar on the right indicates normalized time
of evaporation (T /T0 )
cular as observed, although perturbed by the presence
of corrugations. At this point, the radii for both direc-
tions remain in CCR mode. However, as observed from
Fig. 7, after a normalized time of T /T0 = 0.27 for the
12 nm particles and T /T0 = 0.15 for the 22 nm particles
the radius (R⊥ ) in the perpendicular direction changes
to CCA mode while that in the parallel direction (R )
still remains in the earlier mode, thereby resulting in a
shape change of the droplet from circular to elliptical
one. Figure S3 of SI shows a representative plot of such
a temporal radii evolution for 0.2 vol% concentration
and a particle size of 12 nm. The typical evolution of
the radii during the evaporation process shows a mono-
tonic decrease until the complete disappearance of the
droplet. However, it is evident that the residual drop
becomes more oblate as evaporation proceeds, suggest-
ing that slippage of the contact line along the grooves
takes place more readily than across the corrugation
peaks, with particle size and concentration having an
impact on the magnitude of the effect. Occurrence of
anisotropic shapes guided by underneath corrugated
or other geometrical topographies have been observed
but only for non-colloidal droplets earlier [22,46]. Such
topographies give rise to stick–slip motion, which even-
tually decides the shape of the sessile droplet during
the evaporation event. The presence of nanoparticles
and nano-roughened surfaces, as reported in our study,
exhibits a monotonic change of droplet shape till the
end of the evaporation cycle.
123
Eur. Phys. J. E (2023) 46 :113
3.4 Deposition pattern
The role of evaporation dynamics on the final distribu-
tion of silica nanoparticles was investigated using opti-
cal microscopy. The final deposition patterns left when
the solvent gets entirely evaporated are collectively
dependent on the interaction between the colloidal par-
ticles and substrate. Figure 8 shows the observed micro-
scopic images of the deposits on WES and IIS. Fig-
ure 8a–c and d–f refers to WES for different particle
sizes and concentrations, while Fig. 8g–i and j–l refers
to those for IIS. The patterns deposited on WES clearly
exhibit the widest coffee-ring due to intense pinning
along the droplet CL whereas irregular patterns are
formed on IIS. The particle concentration in the droplet
has a considerable impact on the final deposition pat-
terns. Particles travelling towards CL during evapora-
tion contribute to ring thickness as particle concentra-
tion and its size, both increases. In the deposit patterns,
two separate regions can be defined, the exterior region
referring to the area outside the deposits that resem-
ble ring-like patterns and the interior region referring
to the area inside the deposits in the annular region.
Figure 9a plots the scaled rim width (with respect
to the dried droplet radius) with the colloidal concen-
tration. As a droplet dries while shrinking in size and
the particles get deposited at the rim, the rim width
increases while the dried droplet radius decreases in
size. Hence, a higher value on the y-axis of the plot
refers to deposition as well as shrinkage of a droplet. On
Eur. Phys. J. E (2023) 46 :113
Fig. 8 Optical images of final deposition pattern of droplets of colloidal suspensions with 12 nm and 22 nm particle size
on a–f WES and g–l IIS for various particle concentrations
WES, particles are easily transported to the edge where
they remain pinned, thereby leading to a relatively large
number of particles being located at the ring after evap-
oration. With the enhancement of the coffee-ring effect
due to increasing size of the particle, the cross-sectional
area of the ring increases. Thus, the value of rim width
to the radius of deposition remains low between 0.1 to
0.2 because the radius of all deposits remains almost
same while the thickness of ring increases. For the
case of IIS, the deposits become smaller than in WES
patterns due to depinning of CL, but the rim width
rises concurrently with particle concentration, which is
also evident from Fig. 8. As a result, the scaled rim
width is significantly enhanced from 0.25 to 0.6 with
an increase in particle concentration. Simultaneously
for both cases, this ratio degraded with the increment
in particle dimension as rim width is directly propor-
tional to the size of particle [2].
The accumulation of nanoparticles occurs with evap-
oration of the droplet of colloidal suspension, resulting
in a generation of particulate film over the solid sub-
strates. During the last phases, cracks are formed owing
to development of capillary stress inside the films. For
both cases, with increasing particle size the total num-
ber of cracks decreases while the distance between adja-
cent cracks increases as evident from Fig. 9b. This is
a direct outcome of the capillary stress (σ) and par-
ticle size (Rp ) having an inverse relationship, given
by σ = 2γ/Rp , where γ is the surface tension [47].
Therefore, the stress for small particles becomes sig-
nificantly larger leading to an enhancement in crack
density. The separation between cracks was evaluated
as 34.8 ± 5.7 μm on WES for the case of 12 nm parti-
Page 9 of 11 113
cles at a concentration of 0.2 vol%, which increases to
59.4 ± 7.6 μm as the concentration of particles of the
droplet increases to 0.5 vol%. Similar trend is observed
for the higher particle size as well, which goes from
80.1 ± 5.5 to 117.6 ± 10.6 μm with all concentrations.
On the other hand, after an initial period of slippage
and repinning of CL during evaporation, it becomes evi-
dent that the patterns deposited on IIS exhibit charac-
teristics similar to those commonly associated with the
coffee ring effect. However, this substrate also exhibits
crack spacing with large fluctuations due to irregular-
ity in the shape of the deposit. The deposits obtained
by higher concentration drying droplets delaminate
from the solid substrate due to large stress generated
between the layers of deposits. The deposit patterns
for 0.7 vol% concentration small particle droplets show
delamination phenomena for both substrates, although
the effect is more pronounced for IIS. In general, delam-
ination occurs when a nanoparticle-laden particulate
layer gets detached from the substrate [48], as indi-
cated in Fig. 8a, g. Thus, it shows that there is no
dependency on periodicity in case of delamination. The
delamination behaviour of particulates on rough sub-
strates reduces, with no trace of any separation of film
composed of higher-sized nanoparticles.
4 Conclusion
To summarize, we experimentally study and compare
the evaporation characteristics of nano-colloidal ses-
sile droplets on self-affine vis-à-vis corrugated (period-
123
113 Page 10 of 11
Fig. 9 a Ratio of rim width with the radius of deposition and b Crack spacing with colloidal concentration plotted for
deposition pattern observed on the rough surfaces for different particle sizes
icity ∼ 40 nm), yet identically rough substrates hav-
ing an rms roughness of ∼ 3.5 nm. For an ideally
smooth solid surface, the isotropic wetting behaviour
is decided by the interfacial free energies [14] whereas
for a rough substrate, its interaction with the liquid
gains dominance [15]. Thus, the study of evaporation
dynamics on identical rough surfaces with large differ-
ence in (an)isotropicity becomes imperative. The sur-
faces, WES and IIS, are fabricated using chemical and
ion-beam routes, respectively. The wettability, evapo-
ration kinetics and deposition patterns were investi-
gated in conjunction with textured surfaces and par-
ticles of varying size and concentration. The study
unveils the enhancement in hydrophobicity on WES,
whereas IIS exhibits anisotropic wettability in paral-
lel and perpendicular directions to the surface period-
icities. This finding differs from previous studies con-
ducted on anisotropic micro-structured surfaces, which
primarily focused on non-colloidal droplets [28,30,32].
The present results have been explained in the light of
pinning by the corrugation crests for the anisotropic
surface.
The droplet was found to evaporate in CCR-MM
modes on WES, whereas CCR-CCA-MM modes were
seen on IIS, with CCA being the predominant dry-
ing mode. Evaporation studies carried out in orthog-
onal directions reveal that the ratio of the CCR to
CCA mode evaporation regimes was greater in parallel
directions to the corrugations in IIS. With an increase
in particle size, this ratio reduces due to depinning
which occurs more rapidly at the CL. The presence
of nanoparticles and nano-roughened periodic surfaces
exhibited a monotonic change of droplet shape till the
end of the evaporation cycle. Thus, IIS is responsible
for forming distorted ring arrangements, while WES
leads to the generation of coffee-ring patterns. The
study of dried droplet pattern shows that the rim width
and crack spacing get more pronounced with particle
concentration and size for both surfaces. The forma-
tion of cracks and their spacing were discussed as a
consequence of capillary stress during the evaporation
123
Eur. Phys. J. E (2023) 46 :113
process. Finally, delamination was found to occur for
smaller particles and larger concentrations on both sur-
faces, but was more noticeable for the periodic one. Our
findings impart insight into drying of sessile droplets
of colloidal suspensions on nanorough anisotropic sur-
faces compared to isotropic ones. The results obtained
can serve as useful guidelines for designing other func-
tional surfaces for applications in areas of condensa-
tion [49], preferential fluid mass transfer [50], forced
droplet motion [51], etc. Thus, our insights can cater to
fabrication of surfaces that manipulate droplets, par-
ticularly by utilizing micro/nano channels during the
drying process thereby advancing microfluidic areas of
application.
Supplementary information The online version con-
tains supplementary material available at https://doi.org/
10.1140/epje/s10189-023-00374-8.
Acknowledgements The authors thank DST-SERB India
(Grant No. CRG/2018/001258) for partial financial support
related to this work. We also thank the Central Research
Facility, IIT Ropar for AFM, FESEM and XPS measure-
ments. Deeksha Rani also would like to thank the Univer-
sity Grants Commission (UGC), Government of India, for
financial support through a research fellowship.
Data availability The datasets generated during and/or
analysed during the current study are available from the
corresponding author on reasonable request.
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