Article

pubs.acs.org/Langmuir

Generation of Aspherical Optical Lenses via Arrested Spreading and

Pinching of a Cross-Linkable Liquid
Abhijit Chandra Roy,†,‡ Mridul Yadav,† Edward Peter Arul,†,⊥ Anubhav Khanna,¶
and Animangsu Ghatak*,†,‡,§
†
Department of Chemical Engineering, and ‡Center for Environmental Science and Engineering, Indian Institute of Technology,
Kanpur,208016, India
§
INM-Leibniz Institute for New Materials and Saarland University, Campus D 2 2, 66123 Saarbrucken, Germany
⊥
Central Electrochemical Research Institute, CECRI (CSIR), Karaikudi, Sivaganga-630006, Tamil Nadu India
¶
Department of Chemical Engineering, Manipal Institute of Technology, Manipal, 576104, Karnataka India
*
S Supporting Information

ABSTRACT: Aspherical optical lenses with spatially varying curvature are

desired for capturing high quality, aberration free images in numerous optical
applications. Conventionally such lenses are prepared by multistep top-down
processes which are expensive, time-consuming, and prone to high failure rate.
In this context, an alternate method is presented here based on arrested
spreading of a sessile drop of a transparent, cross-linkable polymeric liquid on a
solid substrate heated to an elevated temperature. Whereas surface tension
driven flow tends to render it spherical, rapid cross-linking arrests such flow so
that nonequilibrium aspherical shapes are attained. It is possible to tune also the initial state of the drop via delayed pinching of a
liquid cylinder which precedes its release on the substrate. This method has led to the generation of a wide variety of optical
lenses, ranging from spherical plano convex to superspherical solid immersion to exotic lenses not achieved via conventional
methods.

■ INTRODUCTION
In general, for spherical optical lenses, parallel rays of light
which are closer to the optical axis converge at a point further
away from where the rays occur at the periphery of the lens,
that is, marginal rays converge. This phenomenon which causes
the image to be blurred is known as spherical aberration.
Conventionally, such aberration is eliminated by simultaneously
using several lenses and optical components, thereby rendering
an optical instrument complex, bulky, and difficult to handle. In
contrast, optical lenses with spatially varying curvature,
commonly known as aspherical lenses, can significantly reduce
such optical defects. In fact, a single aspherical lens can replace
a large system of several optical components yet maintain large
numerical aperture, thus facilitating compact design and ease of
operation. Naturally, there exists a huge demand for such lenses
in a large variety of applications such as optical metrology,1
beam shaping,2 spectroscopy,3 acousto-optics,4 optical micros-
copy,5 laser physics6 and so on. Conventionally, fabrication of
aspherical lenses with complex surface profiles involve multi-
step top-down processes such as molding, grinding, and
polishing of hard materials. These processes require use of
high precision machines, sophisticated control algorithms,
precise control of temperature, humidity, and importantly
highly skilled workmanship.7 All these factors render these
processes time-consuming, complex, prone to high rate of
rejection, and expensive. Hence there is a need for novel yet
simple fabrication methods for making aspherical lenses and
compact optical systems.
Several attempts have been made for preparing lenses via
bottom-up approaches driven by one or more surfaces or body
forces. For example, a UV curable polymeric liquid drop has
been subjected to a large electrostatic field which distorts it to
one with parabolic to even conic shape,8 resulting in lenses with
very high curvature, that is, high magnification but small
aberration. This method has been adapted also for preparing an
array of microlenses (MLA) by combining the idea of
microchannel-assisted generation of droplets of UV curable
material9 and distortion of these droplets under electric field.10
However, these lenses are not suitable for applications requiring
very high numerical aperture. MLA has been generated also by
spatially varying electric field-induced dewetting of a UV
curable thin polymeric film deposited on a substrate;11 a
structured electrode works as a template here for generating
lenses of different size, but the lenses nevertheless remain
spherical. Recently cylindrical microfluidic channels were
subjected to elastocapillary forces for designing optofluidic
lenses with adjustable focus.12 These lenses were aspherical, but
their cylindrical geometry limited their use in many microscopy
applications. Lenses were prepared also by cross-linking a
Received: December 18, 2015
Revised: May 7, 2016
Published: May 20, 2016

© 2016 American Chemical Society 5356 DOI: 10.1021/acs.langmuir.5b04631

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Figure 1. (a) Schematic of experiment in which small quantity of the cross-linkable oligomer is released on a substrate maintained at an elevated
temperature. (b) Top view of a lens captured using 3D optical profiler. (c−f) Side views of lenses of mass 5.3 mg fabricated at 80−200 °C on OTS-
coated silicon wafer. The curvature of these lenses is 0.19, 0.42, 0.74, and 0.76 mm−1, respectively. (g,h) Lenses of mass 5.3 mg fabricated on FC-
coated silicon wafer. (i) Convex−concave lens prepared using convex surface of another lens as substrate. (j) Biconvex lens prepared using convex
surface of another lens as substrate. (k) Lens-filter prepared by mixing oil soluble dye Sudan 2 with the cross-linkable liquid. Scale bar for figures a−k
represents 1 mm. (l−o) Typical images of variety of microscopic objects captured using above lenses as in experiment of Figure S5. Micrograph (l)
represents red blood cells (RBCs) from a healthy person which was magnified using a lens as in Figure 1e. Micrograph (m) represents RBCs affected
by malaria pathogen Plasmodium falciparum; this image was captured using a lens fabricated by dispensing ml = 3.3 mg of liquid on an OTS-coated
substrate maintained at 150 °C. Micrograph (n) represents neuron cell, captured by a lens (ml = 2.9 mg; substrate, OTS-coated plate at 200 °C).
Micrograph (o) representing E. coli bacteria was captured with lens (ml = 0.6 mg; substrate, OTS coated silicon wafer at 150 °C). The conic constant
for lenses used in images 1(l−o) are k = 0.25, 0.19, 0.12, and −0.2, respectively. The scale bar in each of (l−o) represents 10 μm.

hanging polymeric drop, for which the combined effect of

gravity and surface tension resulted in an aspherical profile.13
For these forces to be comparable, the bond number defined as
Bo = ρgL2/γ is required to be of the order of 1. Here ρ and γ
represent respectively the density and surface tension of the
liquid, whereas, l represents a characteristic length scale, for
example, diameter of the liquid drop. Bo ≪ 1 would result in a
spherical lens, whereas, Bo ≫ 1 would drive it to flow forming a
falling cylinder of liquid, both of which are unsuitable for
making aspherical lenses. Importantly in none of these
methods, has substrate condition, for example, its wettability,
been examined for understanding its influence on the final
shape and optical performance of the lens. Nevertheless, these
methods demonstrate the possibility of shaping the surface of a
cross-linkable liquid via manipulation of surface forces, although
the scope of it is limited to attaining essentially equilibrium
profiles. It is however possible to generate a large variety of
nonequilibrium shapes by tuning the dynamic balance of
surface tension-driven hydrodynamic flow and the kinetics of
the cross-linking reaction. To this end, we have made use of
arrested spreading of a sessile drop of a thermally cross-linkable
liquid on a chemically modified substrate maintained at an
elevated temperature to generate lenses which assume
aspherical profile. Furthermore, we have combined this effect
with delayed pinching of a liquid cylindrical bridge to tune the
initial state of the drop which has resulted in oblate to prolate
spheroids, to “solid immersion lenses”14−16 in a single-step
process. We have tuned our method further to generate plano-
convex to biconvex lenses, combined lens-filter system to lenses
having variety of exotic profiles not attainable in conventional
processes. We have demonstrated also the application of these
lenses by capturing magnified images of several microscopic
objects.
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■ RESULTS AND DISCUSSION
Generation and Characterization of Lenses. In essence,
our method involves dispensing a small volume of an optically
transparent prepolymer liquid, for example, Sylgard 184
elastomer (mixed with the cross-linking agent in 10:1 w/w)
on a preheated substrate, for example, silicon wafer coated with
self-assembled monolayer (SAM) of octadecyltrichlorosilane
(OTS) or 1H1H2H2H-perfluorooctyltrichlorosilane (FC) and
heated uniformly to a desired temperature. The liquid was
released using a digitally controlled motorized dispenser placed
at an optimized vertical height from the substrate. For height
>7 mm, air bubbles appeared within the lens, because of
entrapment of air film sandwiched between the liquid puddle
and the substrate (Supporting Information, Figure S1); for very
small height <3 mm, the temperature of the syringe outlet
increased so that the liquid inside the needle began to cross-link
before it could be released. Therefore, the height of the
dispenser was maintained at 5−7 mm. The substrate temper-
ature was varied from 80 to 200 °C. At lower temperature
range, the liquid spreads forming a spherical cap with
equilibrium contact angle: < 20° and ∼60° on OTS and FC
coated plates, respectively.17 However, for substrates main-
tained at elevated temperature, the liquid cross-links in the
vicinity of the substrate soon after it is released, which pins the
contact line and arrests its spreading. Eventually, the drop gets
completely cross-linked to a solid lens which was optically
smooth at its surface with root-mean-square roughness <0.2 nm
(Figure S2) and was symmetric in the azimuthal plane (Figure
1b and Figure S3). The refractive index (r.i.) of the lens
material is ηS = 1.435 for the wavelength of light λ = 532 nm.18
Optical micrographs in Figure 1c−f show that on an HC coated
substrate, for liquid of mass ml = 5.3 mg, the contact angle θ
varies from 10 to 160° for TS increased from 80 to 200 °C.
Optical micrographs in Figure 1g show that larger contact
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Figure 2. (a−c) Sequence of optical micrographs depicts spreading of a drop of PDMS of ml = 3.5 mg on HC-coated substrates maintained at
different temperatures, TS = 80, 150, and 200 °C, respectively. (d) The spreading radius of the lenses is plotted against time for the oligomer liquid
mixed with (solid line) and without (dashed line) the curing agent. (e) The contact angle θ of cross-linked lenses is scaled with substrate
temperature TS as ζ = (1 − cos θ)/TS3 and is plotted against mass of liquid ml used for forming the lenses. At the inset we present the raw data of θ
with respect to TS and ml used for making the plot. The symbols □, ○, ◊, and △ represent TS = 80, 120, 150, and 200 °C, respectively.

angles are achieved on a FC-coated substrate because of their
oleophobocity.19 Here, contact angle θ ≥ 90° represents a solid
immersion lens (solid counterpart of liquid/oil immersion lens)
consisting of a truncated sphere, sliced at a distance exceeding
its radius of curvature.15,16 Beside solid immersion lenses
(SILs) and similar other plano-convex lenses, our method
allows also the fabrication of convex−concave lenses (Figure
1i) via use of the convex surface of another lens as the substrate
and biconvex lenses (Figure 1j) via the use of concave
substrates (detail presented in Supporting Material Figure S4).
We fabricated also an SIL-filter (Figure 1k) by mixing an oil
soluble dye, for example, Sudan 2 with the precross-linked
liquid. Thus, a large variety of lenses could be fabricated via
manipulation of TS, ml, substrate wettability, and even its
specific topography. In Figure 1l−o, we present magnified
images of a variety of microscopic objects that were captured
using these lenses fixed to a homemade microscope fitted with
a CCD camera (Figure S5). Image 1(l), represents the red
blood cells (average size 5−8 μm) in a healthy adult captured
with a lens of magnification (Figure S6), M = 1900×, prepared
by dispensing a liquid drop of mass, ml = 2.6 mg on OTS
coated silicon wafer at TS = 150 °C. A similar lens with M =
550× was used to capture the magnified view of the blood cells
of a malaria (pathogen Plasmodium falciparum) affected patient
(Figure 1m); image 1n captures a star-shaped neuron cell.
Image 1o, represent E. coli bacteria captured using a lens of
(mass 0.6 mg, conic constant κ = −0.2). We estimated the
numerical aperture (NA) of lenses, which for hemispherical
SILS is defined as20 NA = ηs sin θM; but for superspherical
Weierstrass SIL, for which the plane surface of the lens exists at
a distance R/ηS from the half plane,15,16 NA increases to20 NA
= η2s sin θM. In both cases θM is the incidence angle of the
marginal focused ray at the interface of the flat interface of lens
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and air as shown in Figure 1h. It is worth noting that the lenses
in our method Figure 1c−h are not exactly spherical caps but
are truncated ellipsoids which when placed on a smooth PDMS
layer of identical r.i. and desired thickness, form a Weierstrass
supersphere system of which the optical path length equates to
R(1 + 1/ηS). Thus, when the PDMS lens as in Figure 1h is
bonded to a layer of thickness 400 μm, the marginal rays
directly converge without any refraction at the PDMS−air
interface with θM = 45.82°, resulting in effective numerical
aperture as high as NA = 1.477. We examine below how the
dispensed drop of given mass of a cross-linkable liquid evolves
on a substrate maintained at an elevated temperature leading to
the formation of lenses of desired curvature and conic constant
and the competing effects involved.
Dynamics of Wetting, Cross-Linking, and Resultant
Geometric Features of Lenses. Figure 2a−c depicts the
evolution of a sessile drop (∼3.5 mg) on OTS-coated silicon
wafer heated to TS = 80−200 °C. At TS = 80 °C, the drop was
found to spread for longer period, ∼10 s, thereby acquiring the
spherical profile. However, at an elevated temperature of the
substrate, that is, TS = 150 °C and 200 °C, spreading continued
only for a fraction of a second: ∼0.1 s, within which the drop
pinned following cross-linking in the vicinity of the substrate.
Figure 2d shows the evolution of the spreading radius r(t) for
different TS using two different types of liquid: oligomers mixed
with/without the cross-linking agent. Thus, both liquids have
similar viscosity (3500 cP) and surface tension (22 mN/m) and
they in fact spread similarly initially: the spreading radius for all
cases increases with time via a power law type relation: r(t) ≈
t0.45±0.04. However, at later time they behave differently as the
substrate temperature is increased. For lower temperature of
the substrate, for example, TS = 80 °C, both the cross-linkable
liquid and the one without cross-linker continue to spread with
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Figure 3. (a) Phase diagram of conic constant k as a function of TS and ml. (b) Conic constant data from several experiments scale linearly with k ≈
ml/TS5. Symbols □, ○, △, and ◊ represent substrate temperature, TS = 80, 90, 120, and 150 °C, respectively. (c) The maximum curvature κ of lenses
in the vicinity of vertex is scaled as κ−2 and is plotted against ml/TS5. All data fall on a single master line.
r(t) ≈ t0.14±0.014, similar to the well-known Tanner’s law for the
spreading of viscous liquid on a solid substrate.21,22 In fact the
exponent 0.14 matches also with that obtained for Monte Carlo
simulation of droplet spreading.23 However, as the substrate
temperature is increased, for example, TS > 150 °C, the kinetics
of the cross-linking reaction overcomes the rate of spreading of
the liquid and the drop stops spreading because of pinning in
the vicinity of the substrate. The two different spreading
regimes that we observe here are common in the spreading of
many viscous liquids on a substrate, and are known to be
dictated by two different singularities: one, soon after the liquid
drop makes contact with the substrate, very similar to
coalescence of pendant drops of liquid; and the other, which
occurs at a later time at the vicinity of the contact line of the
spreading front.24,25 In fact, initial rapid spreading of the drop
follows the same dynamics as that of drop coalescence, r(t) ≈
t1/2 remaining independent of the substrate; it is only at a later
time that the contact line singularity takes over and because of
viscous dissipation, the spreading dynamics slows down. In the
inset of Figure 2(e), we plot the contact angle θ of lenses as a
function of substrate temperature TS and mass of liquid ml used
for making the lenses. In general, surface tension of a liquid is
known to decrease with increase in temperature, leading to
enhanced spreading and diminished contact angle. In contrast,
here, because of cross-linking at elevated temperature, the
viscosity of the liquid increases, so that it exhibits little or no
ability to flow. The equilibrium contact angle θ is found to
increase with TS and depend rather strongly on it. However,
similar to a viscous liquid,26 θ varies weakly with ml, θ ≈ m0.1 l .
Analysis of several sets of data suggests that θ, written as (1 −
cos θ), varies with TS as (1 − cos θ) ≈ TS3, as shown in Figure
2e. It is to be noted that ϕ(θ) = (1 − cos θ) is a measure of
extent of spreading or wetting of the liquid on the substrate,
ϕ(θ) = 0 representing complete wetting to ϕ(θ) = 2 denoting a
perfectly nonwetting state. In our experiments, ϕ(θ) as high as
1.94, that is, contact angle θ = 160° is attained for TS = 200 °C.
Elevated temperature of the substrate affects also the
sphericity of the lens which is examined by obtaining the 2D
profile of the lenses and then fitting the data to the following
aspheric equation27
κr 2
z= + A1r 4 + A 2 r 6 + ...
1+ 1 − (1 + k)κ 2r 2
(1)
where z is the height from the vertex of the curved surface, r is
the radial coordinate, κ defines the curvature in the vicinity of
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Article
the vertex of the surface, and k is the conic constant. The nature
of the surface profile is determined by k:28 k < −1, k = −1, −1 <
k < 0, k = 0, and k > 0 represent respectively a hyperboloid,
paraboloid, prolate spheroid, spheroid, and oblate spheroid
surface (details presented in Figure S7). Nonlinear regression
with Levenberg−Marquardt algorithm29 was used to obtain κ
and k. Since inclusion of higher order terms, r4, r6, ..., increased
the fit accuracy insignificantly, these terms were not used for
fitting the data. Figure 3a and Supporting Figure S8 show the
phase diagram of conic constant k and curvature κ of lenses as a
function of lens mass ml and substrate temperature TS. For
constant TS, k decreases with decrease in ml, but κ increases.
Similarly, for constant ml, the same effect on κ and k was
observed when TS was increased. Beyond TS = 150 °C, no
further alteration in κ and k were observed because limitation in
heat transfer no longer allows the effect of TS to be felt away
from the substrate. An estimate of curvature of a spherical cap
can be made for a given mass of liquid ml and contact angle θ, κ
= (πρ/3ml)1/3((1 − cos θ)(2 + cos θ))2/3, in which ρ is the
density of the liquid. Noting that in most of our experiments θ
remains somewhat larger than π/2 so that cos θ ≪ 2, and as
obtained earlier, (1 − cos θ) ≈ TS3 (TS in °C), the curvature
can be expected to scale as κ ∼ TS2/ml1/3. Thus, this relation
captures the experimental observation that lens geometry
depends strongly on TS and ml, both. In Figure 3b,c we show
the exact dependence of curvature κ and conic constant k on
these parameters as deduced from the analysis of several sets of
experimental data. The conic constant k from different
experiments scales as k ≈ ml/TS5, whereas curvature κ is
found to scale as κ ≈ TS5/2(°C)/ml1/2 (or κ−2 ≈ ml/TS5),
somewhat different from that predicted above, because the
lenses in our experiments do not remain exactly spherical, so
here κ represents curvature in the vicinity of their vertex.
Second, for a larger mass of liquid, the flattening effect of
gravity too influences κ and k which is not incorporated into
the analysis.
In fact, the relative effect of surface tension and gravity on a
liquid drop can be understood in terms of capillary length
defined as, lC = γ /ρg , where γ is the surface tension of the
liquid, ρ is its density, and g is acceleration due to gravity. For
PDMS, γ = 21.5 mN/m and ρ = 1026.9 kg/m3, the capillary
length is estimated as lC = 1.46 mm, implying that, liquid drops
with diameter larger than this value are expected to be affected
by gravity. In other words, when the mass of liquid used for
making the lenses exceeds mC = ρ × VC = ρ × lC3 ≈ 3.2 mg,
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Figure 4. (a−e) Sequence of images depicts the process of forming lenses via a combined effect of arrested spreading and liquid cylinder pinching. A
needle (diameter D = 1.6−2.5 mm) with a hanging blob of liquid was brought within a vertical height of l = 0.4−0.8 mm from the substrate so that
the liquid blob comes in contact with it; the syringe needle was then retracted vertically up at different speeds, vw = 0.2−1.5 mm/sec. (f−h) High
frame rate camera was used to capture the evolution of the liquid cylinder leading to pinching and thereafter attainment of the equilibrium shape.
The series of plots 1−6 in each case represent the corresponding profiles of the liquid cylinder captured at different time τ. The set of plots f−h
represent the needle retraction speed vw = 0.2, 0.312, and 1.5 μm/sec, respectively.

effect of gravity becomes dominant in shaping the droplet
profile: the drop turns oblate with conic constant k estimated to
be positive.
The data presented in Supporting Information, Figure S8 and
those in Figure 3 show that curvature as high as 2 mm−1 and
conic constant as low as 0.1 are attained. While, with increase in
κ, the ability of the lenses to magnify an object increases, with a
decrease in k the spherical aberration of the lenses diminishes
and both the conditions are simultaneously satisfied. Never-
theless, k continues to remain ≥0, even for the combined effect
of very small ml and large TS, although, prolate spheroids with
negative k are preferred for many applications. To understand
the range of parameters which can lead to negative k, the
competing effect, importantly the characteristic time scales of
transient transfer of heat through a progressively cross-linking
liquid and concomitant surface tension induced flow in the
vicinity of the vertex of the lens is considered. Since the cross-
linking reaction occurs almost instantaneously in the vicinity of
the substrate, particularly for those at elevated temperature, the
reaction time scale is expected to be small. In contrast, transfer
of heat and material through the drop are expected to occur at
comparatively slower rate. Within the liquid drop, the heat
flows from the substrate−liquid interface toward its vertex via
conduction (remaining symmetric in the meridian plane), along
with it the cross-linking front also propagates upward.
Conduction remains the primary mode of heat transfer, as at
elevated temperature cross-linking leads to increase in viscosity
which minimizes the effect of convection. The time scale for
heat transfer τQ can be shown (Supporting Information, Figure
S9) to scale with density ρ, specific heat Cp, and thermal
conductivity K of the liquid as τQ ≈ ρCpd2/K; here height d of
the drop is the characteristic distance through which the heat
conduction occurs. In the absence of gravity (drop diameter <
capillary length26), surface tension driven flow allows the drop
to attain the stable spherical shape in the vicinity of the vertex,
the characteristic time for which can be shown to depend on
viscosity μ and surface tension γ of liquid: τS ≈ μd/γ. The
relative magnitude of these two time scales determines the
specific shape of the final lens: for τQ < τS, the lens is expected
to turn aspheroid, whereas for the reverse case, it is expected to
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become a sphere. The ratio of these two time scales leads to a
dimensionless number NK = τS/τQ = μK/γρCpd which suggests
that an aspheroid is expected for larger values of NK, that is, for
a liquid with large viscosity and thermal conductivity but
smaller surface tension and specific heat. However, for these
material properties remaining unaltered, NK can be increased by
decreasing d, that is, by using diminishing quantity of liquid for
forming the lens and by delaying the effect of surface tension
driven flow.
Delayed Pinching of a Liquid Cylinder. The above
possibility was explored by modifying the one-step process
described in Figure 1a. Here, the needle was first brought
within 0.4−0.8 mm vertical height of the preheated substrate
with a blob of desired size of the cross-linkable liquid hanging at
its tip (Figure 4a). The liquid contacted the substrate, but was
not allowed to detach from the needle tip; instead, soon after
the liquid began to spread on the substrate, it was retracted by
moving the syringe up (Figure 4b−d) at a desired speed, vw =
0.2−4.0 mm/sec. A liquid bridge was formed which first got
stretched, eventually pinching off at a critical pull-off distance
(Figure 4e). Followed by pinching, the liquid cylinder tended
to assume the spherical shape before it got cross-linked.
However, for a small quantity of dispensed liquid, the lens
assumed aspherical profiles with negative k. The dynamic
evolution of the dispensed liquid leading to pinching of the
liquid cylinder and then attainment of the final shape of the lens
is captured in sequence of optical micrographs in Figure 4f−h.
Here a needle of diameter D = 1.6 mm was first brought within
0.8 mm of a substrate maintained at TS = 150 °C and was then
withdrawn at vw = 0.2, 0.312, and 1.5 mm/sec, respectively. The
series of plots in Figure 4f−h shows that, after pinching of the
cylinder, the shape of the liquid drop does not change
everywhere, but only beyond certain height hcross from the
substrate, as depicted by the dashed lines. The cross-linking
front propagates from the substrate to this height before
pinching occurs. For needle retraction velocity, vw = 0.2, 0.312,
and 1.5 mm/sec, this height was found to be 0.63, 0.4, 0.2 mm
which were attained within time, τ < 5, 3, and 1 s, respectively.
With the representative numbers of thermal conductivity K =
0.15 W/mK, specific heat Cp = 1.46 kJ/kgK, and density ρ =
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Figure 5. Lenses prepared as in Figure 4 were used for capturing magnified images of microscopic objects, for example, a TEM copper grid. (a−h)
Optical micrographs correspond to two sets of lenses prepared at two different retraction speeds of the syringe needle: vw = 0.312 (a−d) and 0.5 (e−
h) mm/sec. Insets show lenses prepared with liquid blobs of different sizes hanging from the needle. Magnified image of a TEM copper grid of size
21 μm × 21 μm was captured using the above lenses in combination with a 10× microscope objective as in Figure S11. The magnification M and
conic constant k of lens system for micrographs (a−d) were calculated to be (M, k) (a) 600×, 0.28; (b) 800×, 0.15; (c) 1660×, − 0.2; and (d)
1970×, − 0.63. Those for micrographs (e−h) were calculated to be (M, k) (e) 700×, 0.006; (f) 900×, − 0.11; (g)1250×, − 0.3; and (h) 1800×, −
0.86. The scale bar, in all images, represents 1 mm. (i, j) Profiles depict trace of lenses corresponding to Figure 3a−d (vw = 0.312 mm/sec) and
Figure 3e−h (vw = 0.5 mm/sec). The solid and dashed lines represent actual and scaled profiles, respectively. The scaled profiles are obtained such
that the base radius of scaled traces 2′−4′ match with that of lens 1. For both sets of plots, traces 1−4 correspond to lenses in Figure 3a−d and
Figure 3e−h, respectively. (k) A typical profile of normalized intensity, I/I0 as obtained along the dashed line on image (a) is plotted with respect to
distance n. The slope of this plot at the locations of sharp change in intensity are obtained as a measure of the optical resolution of the lenses. (l) The
bar chart shows the resolution for lenses as in images a−h. The error bars represent the standard deviation of data from several measurements.

965 kg/m3 of PDMS, the characteristic time for heat transfer to
a height d = 0.63 mm is estimated as τQ ≈ 3.7 s which matches
rather closely with ∼5 s as observed in experiments. Two
different limits of the needle retraction velocity can be
considered: for a very small value of vw < 0.2 mm/sec, the
cross-linking front reaches almost the tip of the needle resulting
in a defective lens (Figure S10). For a large value of vw > 0.5
mm/sec, the cross-linking front remains far away from the lens
vertex, so flow driven by surface tension gets sufficient time
leading to an equilibrium spherical profile of the lens.
Therefore, an intermediate speed of retraction, for example,
vw = 0.312 mm/sec was found to be optimum for generating
the prolate spheroids. In fact a wide range of lenses from SILs
to prolate spheroids could be generated as shown in insets of
images in Figure 5a−d which were prepared on OTS-coated
silicon wafer at TS = 150 °C using a needle of diameter D = 1.6
mm and retraction velocity vw = 0.312 mm/sec. In the vicinity
of the lens vertex, the lens profile was found to vary from oblate
(positive k) to prolate (negative k) spheroid as the quantity of
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dispensed liquid was diminished: for the lens in Figure 5a, k =
0.28, but with a decrease in ml, it decreased to −0.63 (lens in
Figure 5d). To have a measure of magnification of these lenses,
magnified images of a TEM grid (Figure 5a−h) were captured
by the experiment described in Figure S11, which shows that
magnification as high as ∼2000 times could be achieved. A
similar set of lenses (insets of images in Figure 5e−h) with
somewhat larger k resulted when vw was increased to 0.5 mm/
sec. Faster pinching allows the pinched cylinder to equilibrate
over longer time, before getting cross-linked, thereby resulting
in nearly self-similar spherical caps. Self-similarity of shapes is
examined in Figure 5i,j where solid lines represent the traces of
lenses in images 5a−d and images 5e−h, respectively. The
abscissa and ordinate of these traces were multiplied with a
scaling factor defined as the ratio of base radius of lens 1 to that
of that particular lens and plotted as the dashed lines. For
example, for traces 2 and 3 in Figure 5j (vw = 0.5 mm/sec) the
scaling factors were calculated as 1.29 and 1.78, respectively.
The resultant scaled profiles represented by dashed lines 2′ and
DOI: 10.1021/acs.langmuir.5b04631
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Langmuir Article

Figure 6. Lenses were prepared as in Figure 4 but by retracting the needle vertically up in multiple steps. In all cases an OTS-coated silicon wafer was
used as the substrate. (a) The lens at the inset was fabricated using a needle of diameter D = 1.6 mm and retracted vertically up continuously at vw =
1.5 mm/sec. A TEM grid of size 21 μm × 21 μm was magnified using this lens in combination with a 10× microscope objective as in Figure S11. The
magnification and conic constant of this lens were found to be M = 420× and k = 0.53. (b) The lens was prepared by retracting a needle of diameter
D = 2.5 mm at vw = 1.25 mm/sec in two different steps with an intermediate resting step for 4 s at a vertical height of l = 2.0 mm from the substrate.
The magnification and conic constant of this lens were M = 680× and k = −0.03. (c, d) Wing of a mosquito was captured at two different
magnifications by using two different lenses. The lens for capturing image c was prepared by simultaneously retracting the needle and withdrawing
the dispensed liquid from the substrate maintained at TS = 110 °C. (e, f) The lenses were fabricated on substrates maintained at TS = 200 °C using a
needle of D = 1.6 mm, which was retracted at 1.25 mm/sec in two different steps with an intermediate resting step for 1 s at vertical height 1 mm and
1.5 mm, respectively. (g) The lens was fabricated by retracting the needle in equal steps of 0.5 mm but at different speed vw = 0.312, 1.5, 2.1, and 3.75
mm/sec. (h) The needle was retracted in multiple steps of different retraction speed and step sizes: (1.5 mm/sec, 0.4 mm), (0.625 mm/sec, 0.3
mm), (0.312 mm/sec, 0.2 mm), (0.156 mm/sec, 0.1 mm), and (312 μm/sec, until pinching off the cylinder). The scale bar, wherever not mentioned,
represents 1 mm.

3′ superimpose on solid line 1, signifying that lenses in images
5e−g were nearly self-similar. However, self-similarity broke
down for trace 4 where rapid cross-linking of a small quantity of
liquid did not allow surface tension driven equilibrium to be
attained. In contrast, the traces in Figure 5i, (corresponding to
vw = 0.312 mm/sec) were neither self-similar nor spherical
signifying a diminished effect of surface tension at smaller vw. In
Figure 5 we present also a measure of optical resolution of
lenses which was obtained from the intensity profile of images
captured by them. For example, in Figure 5k we show a typical
intensity profile measured along the dashed line n on Figure 5a.
The slope of such a profile at the locations of rapid change in
intensity was obtained as such locations represent transition
from masked, that is, dark to unmasked, that is, bright portion
of the image. A large value of the slope signifies high resolution.
The bar chart in Figure 5l represents the resolution of lenses as
in Figure 5a−h.
Needle Retracted in Steps at Variable Speed. While in
a previous experiment the needle was retracted vertically up
from the substrate at uniform speed, we will now show that
several exotic lens shapes result when the needle retraction
speed is suitably programmed. In Figure 6 we present these
results in which the needle was retracted in multiple equal or
different steps of identical or different retraction velocity.
Similarly lenses were prepared also via simultaneous retraction
of the needle following dispensing the liquid on the substrate
and then withdrawal of the same. These sequence of multiple
steps result in large variety of lenses, for example, ones with a
large negative conic constant, lenses having side steps, and the
ones the curvature of which vary drastically in the meridian
5362
plane, albeit remaining symmetric in the azimuthal plane. The
usefulness of these lenses was demonstrated by capturing the
magnified image of a TEM copper grid as in Figure S12 and
also microscopic objects such as scales on the wings of a
mosquito. Figure S12 show that an object can be focused at
multiple locations along the optical axis because of their specific
shape. Thus, these experiments open up the possibility of
tuning the optical characteristics of the lens via several
parameters which are to be dynamically controlled and
optimized for attaining specific optical performance.
Reproducibility of Lenses. To examine the reproducibility
of lenses prepared via methods presented in Figure 1 and
Figure 4, a large number of lenses, fabricated at identical
conditions, were analyzed. For example, a needle of diameter
1.6 mm was used to dispense a liquid drop of @7.8 mg on an
OTS-coated silicon wafer maintained at TS = 110 °C as in
Figure 1a. The side view of 45 such lenses was analyzed for
obtaining the distribution p(κ) of maximum curvature κ in the
vicinity of their vertex. Since 45 is a statistically significant
number, it accurately captures the lens variability. In Figure 7a
we plot p(κ) as a function of κ for substrate temperature
varying from TS = 110−180 °C. p(κ) was calculated by
obtaining the number fraction of lenses that had curvature
within a given range. The distribution gets somewhat narrower
for higher temperature (TS ≈ 180 °C) of the substrate,
implying that rapid cross-linking, or rapid increase in viscosity
has a dampening effect on perturbations as expected. For each
case, the distribution results in an average value and a standard
deviation, which are plotted in Figure 7b. Here we have
presented also the data for similar lenses prepared on FC-
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Langmuir
Figure 7. Figure depicts the reproducibility of lenses presented as in
Figure 1a. (a) The bar chart depicts the probability distribution p(κ) of
maximum curvature of lenses (in the vicinity of the vertex) prepared
under a set of identical conditions, for example quantity of cross-
linkable liquid ml = 7.6 ± 0.2 mg dispensed using a needle of diameter
D = 1.6 mm on a substrate which is an OTS-coated silicon wafer
maintained at specific TS. (b) The bar chart represents the average
curvature κ̅ extracted from the above data and plotted against TS for
both OTS- and FC-coated substrates. (c) Average conic constant k̅ of
the lenses corresponding to plot a are plotted against TS for both OTS-
and FC-coated substrates. The right most bar in panels b and c
correspond to lenses prepared by the method presented in Figure 4:
an OTS-coated silicon wafer heated to 150 °C temperature was used
as the substrate and the needle (diameter 1.6 mm) retraction speed
was maintained at 0.321 mm/sec. The error bars in all cases represent
the standard deviation of the data.
coated substrate at identical conditions. In all cases the standard
deviation is found to be within 5% of the average value, and the
reproducibility of lenses are similar for these two different
surfaces. In Figure 7c, we plot the average conic constant k̅ of
these lenses as a function of TS. Here too, the standard
deviation diminishes with increase in TS, that is, for lenses with
decreasing conic constant. To test the reproducibility of lenses
prepared by the method presented in Figure 4, a large set of
lenses were prepared by maintaining identical conditions. The
right most bar in the bar charts in Figure 7b,c and the data
presented in Figure S13 show that for these lenses too the error
remains with 5% of the average value.
■
SUMMARY
We have presented a novel route for producing high quality
aspherical optical lenses by using the coupled effect of arrested
spreading and pinching of a dispensed liquid drop along with
rapid crosslinking to produce wide ranging lenses: solid
immersion lenses with large numerical aperture to prolate
spheroids with negative conic constant to compact optical
devices such as lens-filters. In particular we make use of
competing dynamics of spreading of a drop of cross-linkable
liquid on a substrate and the unidirectionally progressing cross-
5363
Article
linking reaction of the liquid to achieve different aspherical
shapes. This particular feature of our method contrasts to
others including those in which spherical lenses are generated
by simply dispensing a cross-linkable liquid onto a substrate.30
Importantly, large curvature, that is, high magnification of
lenses, and negative conic constant, that is, minimal aberration,
are simultaneously attained in a single-step process which
makes it amenable to easy scaleup. We have introduced also a
dimensionless quantity to account for the competing effect of
the cross-linking reaction and surface tension driven flow which
finally determine the optical characteristics of the lens. The
generality of the fabrication method is demonstrated by
preparing lenses of various sizes and shapes including exotic
shapes not achieved by any conventional methods. We have
demonstrated also the use of these lenses by capturing
magnified images of several microscopic objects. Importantly
we have shown that images captured using these lenses
compare well with those captured by conventional microscope
objectives (Figure S14).
■ EXPERIMENTAL SECTION
Polydimethylsiloxane (PDMS) (Sylgard 184, procured from Dow
Corning, USA) was used for preparing the lenses. Silicon wafers
procured from Nanoshel (USA) were used as substrates. Silane
molecules, octadecyltrichlorosilane (OTS), 1H1H2H2H-perfluorooc-
tyltrichlorosilane (FC) molecules purchased from Sigma-Aldrich
(USA) were used for surface chemical modification of the substrate
by forming self-assembled monolayers (SAM). A digitally controlled
motorized dispenser procured from Holmarc, India, was used to
release droplets of PDMS from the syringe needles. A digitally
controlled hot plate procured from CAT, Germany, was used to
uniformly heat the substrate.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.lang-
muir.5b04631.
Optimal height for releasing liquid drop for making
lenses; AFM imaging of the surface of the lenses;
characterization of azimuthal symmetry; fabrication of
convex-concave and biconvex lens; Figures and other
experimental details as described in the text (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: aghatak@iitk.ac.in.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
A.G. acknowledges financial assistance from Department of
Science and Technology, Government of India, through Grant
DST/TM/SERI/2k11/80(G).
■
REFERENCES
(1) Born, M.; Wolf, E. Principles of Optics, 7th ed.; Cambridge Univ.
Press: 1999, Vol. 211.
(2) Hoffnagle, J. A.; Jefferson, C. M. Beam shaping with a plano-
aspheric lens pair. Opt. Eng. 2003, 42, 3090.
(3) Shalyapin, V. N.; Goicoechea, L. J. Deep optical imaging and
spectroscopy of the lens system SDSS J1339 + 1310. Astron. Astrophys.
2014, 568, 1−11.
DOI: 10.1021/acs.langmuir.5b04631
Langmuir 2016, 32, 5356−5364
Langmuir Article

(4) Kaplan, A.; Friedman, N.; Davidson, N. Acousto-optic lens with (30) Sokuler, M.; Gheber, A. L. Nano fountain pen manufacture of
very fast focus scanning. Opt. Lett. 2001, 26, 1078. polymer lenses for nano-biochip applications. Nano Lett. 2006, 6 (4),
(5) Gambin, Y.; Legrand, O.; Quake, S. R. Microfabricated rubber 848−853.
microscope using soft solid immersion lenses. Appl. Phys. Lett. 2006,
88, 174102.
(6) Cao, Z.; Wang, K.; Wu, Q. Aspherical anamorphic lens for
shaping laser diode beam. Opt. Commun. 2013, 305, 53.
(7) Kim, H. S.; Kim, E. J.; Song, B. S. Diamond turning of large off-
axis aspheric mirrors using a fast tool servo with on-machine
measurement. J. Mater. Process. Technol. 2004, 146, 349.
(8) Zhan, Z.; Wang, K.; Yao, H.; Cao, Z. Fabrication and
characterization of aspherical lens manipulated by electrostatic field.
Appl. Opt. 2009, 48 (22), 4375.
(9) Zhu, X.; Zhu, L.; Chen, H.; Yang, M.; Zhang, W. Fabrication of
multi-scale micro-lens arrays on hydrophobic surfaces using a drop-on-
demand droplet generator. Opt. Laser Technol. 2015, 66, 156.
(10) O’Neill, F. T.; Owen, G.; Sheridan, J. T. Alteration of the profile
of ink-jet-deposited UV-cured lenses using applied electric fields. Optik
2005, 116, 158.
(11) Li, X.; Tian, H.; Ding, Y.; Shao, J.; Wei, Y. Electrically templated
dewetting of a UV-curable prepolymer film for the fabrication of a
concave microlens array with well-defined curvature. ACS Appl. Mater.
Interfaces 2013, 5, 9975−9982.
(12) Roy, A. C.; Ghatak, A. Design of an adaptable optofluidic
aspherical lens by using the elastocapillary effect. Adv. Opt. Mater.
2014, 2, 874.
(13) Lee, W. M.; Upadhya, A.; Reece, P. J.; Phan, T. G. Fabricating
low cost and high performance elastomer lenses using hanging
droplets. Biomed. Opt. Express 2014, 5, 1626.
(14) McCloskey, D.; Donegan, J. F. Planar elliptical solid immersion
lens based on a cartesian oval. Appl. Phys. Lett. 2013, 103, 091101.
(15) Mansfield, S. M.; Kino, G. S. Spectrometric determination of the
refractive index of optical wave guiding materials used in Lab-On-a-
Chip applications. Appl. Phys. Lett. 1990, 57 (24), 2615.
(16) Mansfield, S. M.; Studenmund, W. R.; Kino, G. S.; Osato, K.
High-numerical-aperture lens system for optical storage. Opt. Lett.
1993, 18 (4), 305.
(17) Chaudhury, M. K.; Whitesides, G. M. Direct Measurement of
interfacial interactions between semispherical lenses and flat sheets of
poly(dimethylsiloxane) and their chemical derivatives. Langmuir 1991,
7, 1013.
(18) Cardenas-Valencia, A. M.; Dlutowski, J.; Fries, D.; Langebrake,
L. Spectrometric determination of the refractive index of optical wave
guiding materials used in Lab-On-a-chip applications. Appl. Spectrosc.
2006, 60, 322.
(19) Chaudhury, M. K.; Whitesides, G. M. Direct measurement of
interfacial interactions between semispherical lenses and flat sheets of
poly(dimethylsiloxane) and their chemical derivatives. Langmuir 1991,
7, 1013−1025.
(20) Terris, B. D.; Mamin, H. J.; Rugar, D. Near-field optical data
storage. Appl. Phys. Lett. 1996, 68 (2), 141.
(21) Gennes, P. G. De. Wetting: statics and dynamics. Rev. Mod.
Phys. 1985, 57 (3), 827.
(22) Marmur, A. Adv. Colloid Interface Sci. 1983, 19, 75.
(23) Milchev, A.; Binder, K. Droplet spreading: A Monte Carlo test
of Tanner’s law. J. Chem. Phys. 2002, 116, 7691−7694.
(24) Biance, A.-L.; Clanet, C.; Quéré, D. First Steps in the spreading
of a liquid droplet. Phys. Rev. E 2004, 69, 016301.
(25) Eddi, A.; Winkels, K. G.; Snoeijer, J. H. Short time dynamics of a
viscous drop spreading. Phys. Fluids 2013, 25, 013102.
(26) Blokhuis, E.; Shilkrot, M.; Widom, B. Young‘s Law with Gravity.
Mol. Phys. 1995, 86 (4), 891.
(27) Kweon, G.; Kim, C. H. Aspherical Lens Design by Using a
Numerical Analysis. J. Korean Phys. Soc. 2007, 51, 93.
(28) Hecht, E. Optics, 4th ed.; Addison-Wesley: 2002.
(29) Levenberg, K. A method for the solution of certain non-linear
problems in least squares. Quart. Appl. Math. 1944, 2, 164.

5364 DOI: 10.1021/acs.langmuir.5b04631

Langmuir 2016, 32, 5356−5364