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Cite This: ACS Omega 2019, 4, 2577−2583 http://pubs.acs.org/journal/acsodf

Silica-Based Organic−Inorganic Hybrid Fluorescent Ink for Security

Applications
Kanakangi S. Nair,†,‡ Pullanchiyodan Abhilash,† and Kuzhichalil P. Surendran*,†,‡
†
Materials Science and Technology Division, National Institute for Interdisciplinary Science and Technology (NIIST-CSIR),
Thiruvananthapuram 695019, India
‡
Academy of Scientific and Innovative Research (AcSIR), CSIR-HRDC, Ghaziabad, Uttar Pradesh 201002, India

ABSTRACT: A facile formulation of fast-drying fluorescent

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ink made from nanostructured fluorescent silica nanocrystals

is presented. The rheostable viscous ink suitable for screen
printing was developed by careful selection of organic vehicle
components, which was later printed onto various rigid and
Downloaded via 171.247.77.90 on September 12, 2021 at 10:11:07 (UTC).

flexible substrates. Photoluminescence studies of the printed

film confirmed that the formulated ink composition did not
show noticeable influence on the excitation property of the fluorescent silica. The developed cost-effective and fast-curing
fluorescent silica ink with desirable luminescent property makes it a suitable candidate for information encryption, optical
devices, and energy conversion applications.

■ INTRODUCTION
In recent years, fluorescent nanoparticles have attracted much
attention in emergent fields such as nanobiotechnology,
photonics, and optoelectronics.1,2 Commonly used fluorescent
materials are organically modified silica, hydrophobic and
hydrophilic organic polymers, semiconducting organic poly-
mers, quantum dots, carbonaceous nanomaterials such as
carbon dots, carbon nanoclusters, and nanotubes, metal
particles, and metal oxides.3,4 However, when considering
limitations such as low detection efficiency, complicated
processing, and toxicity, hybrid structures formed of an organic
dye molecule-incorporated inorganic matrix are highly
recommended.5 This core−shell architecture has an added
benefit of designing new geometries by incorporating multiple
functionalities into a single nanoparticle.6,7 Of various
inorganic matrixes, the silica matrix has been widely studied
because of its biocompatibility nature. Moreover, silica can act
as a mechanically and chemically stable vehicle, thereby
protecting the encapsulated dye from external perturbations.8,9
Fluorescent silica nanoparticles have pertinent applications in
the field of information technology, biotechnology, and
medicine owing to their tunable size, optical transparency,
high hydrophilicity, biocompatibility, and low cytotoxicity.10
Recently, fluorescent inks have also been used as security
markers with the objective of preventing theft and forgery.11,12
Recent advances have been focussed on organic fluorophore-
encapsulated hybrid structures because of their increased
brightness and photostable matrix compared to the single
organic dye. Incorporation of dyes into the silica matrix can be
easily achieved with either covalent bonding13 or noncovalent
bonding14 of the dye with the silica matrix. Considering several
advantages, the noncovalent approach is the most preferable
way to encapsulate the fluorophores inside the sol−gel-derived
colloidal silica matrix.15 The well-known Stöber method was
traditionally chosen for sol−gel synthesis of monodisperse
nanomicrometer-sized silica particles. In such a typical process,
the molecular precursor of silica is initially reacted with water
in an alcoholic solution and then the resultant molecules are
assembled together to build larger complex structures.16
Several modifications were carried out to achieve size-
controlled synthesis of silica nanoparticles.17,18 In 2005, Ow et
al. successfully synthesized nanometer-sized fluorescent silica
nanoparticles through a modified Stöber route, in which a
core−shell architecture consisting of a fluorophore-rich center
was capped within a siliceous shell.19 With the aid of a similar
core−shell architecture, silica nanoparticles incorporated with
fluorescent dyes were also developed subsequently by Burns et
al. for chemical sensor applications.20 In an interesting work
published in 2013, Yoo and Pak synthesized size-controlled
fluorescent silica nanoparticles through a reverse (water in oil)
microemulsion method.21 Because the dye-doped silica
nanoparticles are susceptible to leakage and irreversible
photodestruction when dispersed in organic solvents, control-
ling their dye leakage is highly crucial in security applications.
In the present study, a double-layer approach was developed to
reduce the dye leakage, wherein the fluorophore molecules are
encapsulated in the silica matrix. Here, the second outermost
silica layer, created by the condensation of alkoxy silane, will
successfully incorporate the organic fluorophores into the silica
double layer through electrostatic attraction.
For practical printed tag applications, screen printing is a
widely adopted strategy. Development of a colloidal
fluorescent ink is a challenge because the ink’s vehicle contains
dispersants, solvents, and binders, whose presence can
Received: November 28, 2018
Accepted: January 21, 2019
Published: February 4, 2019

© 2019 American Chemical Society 2577 DOI: 10.1021/acsomega.8b03313

ACS Omega 2019, 4, 2577−2583
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eventually lead to photodegradation. In general, fluorescent
inks provide a platform for a wide range of applications in
domains such as information storage, bioimaging, smart
packaging, and nanoelectronics.22 For the past few years,
carbon dots and functionalized carbon dots, and coumarin
derivative fluorescent ink were extensively studied.23 In 2012,
low toxic and biocompatible carbon dot-based fluorescent ink
was formulated and its distinct fluorescent properties were
studied.24 Gao et al. reported green route synthesis of
nitrogen-doped carbon dots, and their performance as
fluorescent ink and electrocatalysts were demonstrated.25
Metal-free water-soluble graphitic carbon nitride quantum
dots as invisible security ink was developed by Song et al. for
data security applications.24 Recently, nitrogen-doped gra-
phene dots and magnesium−nitrogen-embedded carbon dots
were reported for anticounterfeiting and copper metal sensing
applications, respectively.26,27 For anticounterfeiting applica-
tions, inkjet printing of colloidal photonic crystals was
extensively studied.28−30
So far, no serious attempts were made toward formulating
leak-free core−shell based fluorescent silica - ink having stable
luminescence and low toxicity. Herein, we report the
formulation of a stable screen-printable fluorescent ink by
choosing fluorescent double-layered silica nanoparticles as the
filler, Butvar as the binder, and sodium dodecyl sulfate (SDS)
as the dispersant. The presently adopted core−shell
architecture-based ink is advantageous because it prevents
cluster formation. Owing to its stable fluorescence and good
solubility in ethanol medium, our quick-dry fluorescent ink can
find applications in the field of printable fluorescent tags.
■ MATERIALS AND METHODS
Tetraethyl orthosilicate (TEOS, 99%), 3-(aminopropyl)-
triethoxysilane (APTS, 98%), fluorescein (free acid,
C12H20O5), ammonium hydroxide (NH4OH, 28−30 wt %
ammonia), cyclohexane (C6H12, 99%), 1-hexanol (C6H5OH,
98%), poly vinyl butyral (PVB) (registered trademark of
Solutia, Inc. as Butvar), and SDS were purchased from Aldrich
Chemicals Co. Brij35 [a polymer of ethylene glycol and
dodecyl ether ((C2H4O)23C12H25OH)] was received from
Merck Chemicals. All the raw materials and solvents were used
as received without any further purification.
Synthesis of Fluorescent Double-Layered Silica
Nanoparticles. Fluorescent double-layered silica nanopar-
ticles were synthesized in a reverse microemulsion method.21 A
reverse microemulsion (water in oil, W/O) is an isotropic and
thermodynamically stable single-phase system that consists of
water, oil, and surfactant, which is highly stable than normal
emulsion method. The water droplets were first stabilized by
surfactant molecules and then get dispersed in the bulk oil
phase, which serves as reactors for the synthesis of nano-
particles. In brief, Brij35 (5.4 g, 1.6 mmol) was added with
38.5 mL of cyclohexane and 8 mL of 1-hexanol, and the
solution was kept under sonication until a transparent clear
solution was obtained. Deionized water (1.7 mL) was added
and sonicated further for 15 min. To the clear solution, 0.5
mmol of TEOS was added and stirred for 30 min. Prior to
hydrolysis and condensation of TEOS, aqueous fluorescein
(0.4 mL of 1 × 10−2 M, 1.6 μmol) was mixed to the reverse
microemulsion. In the microemulsion, TEOS was initially
hydrolyzed by adding ammonia and later condensed in the
presence of fluorescein to generate fluorescein-doped silica
nanoparticles. Without breaking the microemulsion system,
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APTS (0.5 mmol) was then added into the above reaction
mixture before removing excess fluorescein, where APTS has
been hydrolyzed and condensed on the surface of the
fluorescein-doped silica nanoparticles. This sequential process
helped the formation of the second layer of silica and finally
yielded the core−shell structured double-layered silica nano-
particles. The synthesized double-layered silica nanoparticles
have good solubility in aqueous medium and were separated
from ethanol by centrifugation. The microemulsion was then
destabilized by adding acetone, centrifuged, and washed with
ethanol four to five times to obtain fluorescent double-layered
silica nanoparticles.
Formulation and Screen Printing of Fluorescent
Silica Ink. A stable dispersed fluorescent ink can be developed
by judiciously blending the double-layered silica nanoparticles
with a suitable surfactant, binder, and carrier solvent.31 In the
present work, 60 wt % fluorescent silica, PVB (Butvar), and
SDS and ethanol were chosen as the filler, binder, and
surfactant, respectively. Here, the ink formulation was begun
with mixing of 2 wt % dispersant (w.r.t filler) with ethanol in
order to enhance the dispersion process. The process was
carried out for 10 min on a magnetic stirrer. Later on,
fluorescent silica nanoparticles were added and stirred
continuously for another 6 h, followed by the addition of the
binder. The whole solution was stirred again for 24 h to derive
a homogeneous viscous ink. The ink was screen-printed with
the desired pattern with the aid of a screen mesh having 350
counts. The customized screen mesh in the present study was
created by coating the screen in photoemulsion and curing the
areas which are required, and the surplus emulsion was washed
off to obtain the desired pattern.32
Characterization. The nanoparticles and the core−shell
structure were analyzed by high-resolution transmission
electron microscopy (HRTEM) (FEI Tecnai G2 30S-TWIN,
FEI Company, Hillsboro, OR). The rheological characteristics
of the ink were measured using a Rheo plus32 rheometer
(Anton Paar, Ashland, VA, USA) operating in both rotational
and oscillation modes. Screen printing was done through
semiautomatic screen printer (EKRA, Germany) which
operated at a printing speed of ∼30 cm/s. The ink was
screen-printed on various substrates, and the surface
morphology was analyzed by using a scanning electron
microscope (Zeiss EVO 18 Cryo SEM, Jena, Germany). The
surface roughness of the printed film was analyzed by atomic
force microscopy (AFM) (MultiMode, Bruker, Germany).
UV−vis spectra of the solution state were recorded with a UV
spectrophotometer (UV-1800 Shimadzu) in the range of 200−
900 nm. The absorption properties of the printed pattern were
characterized using a UV−vis near-infrared source (Ocean
Optics). Excitation and emission spectra of the solution and
film states were recorded with a Spex-Fluorolog FL22
spectrofluorimeter equipped with a double grating 0.22 m
Spex 1680 monochromator and a 450 W Xe lamp as the
excitation source.
■
RESULTS AND DISCUSSION
Microstructural Analysis of Fluorescent Double-
Layered Silica Nanoparticles. As described earlier, the
fluorescent double-layered silica nanoparticles were developed
by the coupling of fluorescein species as a core in core−shell
architecture. One of the principal merits of this procedure is
that the size of the silica nanoparticles can be effectively
tailored by changing the water-to-surfactant ratio. These cores
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can act as nuclei for the growth of the silica shell, thereby
protecting the encapsulated dyes.19 For a screen-printable
stable dispersed ink, uniform particle size distribution is more
preferred because of microstructural homogeneity consider-
ations. Prior to the ink formulation, particle size and
morphology analyses were carried out by TEM. Sample
preparation was done by suspending double-layered silica
nanoparticles in ethanol medium, and the particle size and
morphology were studied. TEM analysis of the above-
mentioned monodispersed solution was carried out by drop-
casting it onto a copper grid, and the microscopic images are
depicted in Figure 1. TEM images clearly show the spherical
Figure 1. (a−c) TEM micrographs of fluorescent silica nanoparticles
in ethanol medium, under different magnifications.
morphology of the fluorescent nanoparticles, and the average
particle size of double-layered silica nanoparticles comes
around 70−80 nm, which is in the desirable range to maintain
the colloidal stability of the ink suspension. 33 Thin
mesoporous shells are uniformly coated over the silica core
surface at a thickness of ∼15 nm. The peculiar architecture
effectively protects the fluorescein dye molecules within the
matrix and was developed in a uniform and orderly fashion.
The security features inscribed using invisible fluorescent
inks have widespread applications in passports, bank notes, and
credit cards. Maintaining the fluorescence intensity in the
printed ink is a challenge because the ink contains other
organic components such as solvents, dispersants, binders, and
homogenizers. The formation of double-layered silica nano-
particles with encapsulated dye molecules and their journey
into a flatbed printed structure are schematically shown in
Figure 2.
Figure 2. Schematic description of the synthesis of screen-printable
fluorescent double-layered silica ink.
Ink printability is a function of both physical and chemical
properties of the filler, additives, and solvents employed in the
ink formulation. In the typical formulation of ink, the role of
SDS is to effectively disperse the filler nanoparticles in the
solvent and thereby improve the colloidal stability of the ink. It
will also help to decrease the coagulation of the ink. Ethanol
acts as a vehicle for the uniform distribution of the filler and
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also controls the drying rate of the formulated ink. Because of
the high volatile nature of ethanol, it facilitates the drying rate
compared to aqueous-based screen-printable inks.34,35 As is
obvious, the purpose of the binder is to uniformly distribute
the filler nanoparticles in the polymer matrix and to increase
the adhesion of the fluorescent ink onto the substrate to which
it is printed. Ideal proportional mixing of the filler, binder, and
dispersants enables uniform printing and better adhesion of the
printed pattern. In a stable ink suspension, the particle size and
hence the mass of the dispersed filler phase should be as low as
possible so that its kinetic energy is too small to overcome the
electrostatic repulsion between charged layers of the dispersing
vehicle phase. Hence, along with particle size, viscosity is a
critical property of any ink for high-precision smooth printing.
The rheological analysis of the formulated ink is given in
Figure 3. For effective screen printing, the viscosity should be
in the range of 1−10 Pa s.36,37 From viscosity and shear stress
plots, shown in Figure 3a, it is clear that with increased shear
rate, the viscosity of the ink gets decreased. With the addition
of SDS, colloidal stability of the formulated ink was maintained
and the formulated ink showed a viscosity of 12 Pa s at a lower
shear rate of 10 s−1 which further got decreased to about 9 Pa s
at a higher shear rate. By increasing the shear rate, viscosity
becomes substantially thinner and hence causes the ink to flow
readily because of its pseudo-plastic behavior, which is clearly
visible in the depicted plot. Another dynamic property of the
ink is its viscoelastic nature, defined by the elastic/solid-like
(storage modulus, G′) and viscous/liquid-like (loss modulus,
G″) (see Figure 3b) behaviors. From the figure, it is clear that
the value of G″ is higher than G′ in the given range of strain.
This further confirmed the liquid-like behavior of the
formulated ink, which is necessary to perform high aspect
ratio screen printing.38,39 Hence, the viscosity and dynamic
viscoelastic properties of the ink are proved to be feasible for
screen printing.
The photographic image of the viscous ink and printed
patterns is shown in Figure 4. Fine screen printing can be
achieved through a leveling process, and it depends upon
certain factors such as rheology, surface tension, and flow time
characteristics of the ink and also the mesh size and quality of
both squeegee and screen.40 During the screen printing
process, the ink was forced to flow through the screen mesh
openings, thereby producing high shear rates. As it passes
through, the ink obtained its lowest viscosity, and once the
screen is removed, the mechanical shear forces cease, and at
the same moment, the ink is deposited onto the substrate.
Thus, several patterns corresponding to the screen mesh could
be printed on various flexible and rigid substrates. Figure 4a
shows the NIIST-CSIR emblem screen-printed on a flexible
Mylar film under visible light. It is worth noting that the
printed pattern shows stable green emission under UV light
(365 nm), as seen in Figure 4b. Figure 4c shows the bright
fluorescence of the formulated ink under handheld UV light.
Quality of printed films was examined through scanning
electron micrographs, as depicted in Figure 5. The current ink
formulation facilitates fast and natural drying of printed
patterns typically less than 20 s because of the high volatile
nature of the solvent chosen, ethanol, compared to aqueous-
based screen-printable inks. The printed ink was found to be
cured within seconds soon after the screen printing process,
and this helps to produce a homogenized film without much
porosity. This is clearly visible from scanning microscopy
images. Figure 5a shows the low-resolution scanning electron
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Figure 3. (a) Variation of viscosity with the shear rate. The inset given is the photographic image of the developed highly viscous ink and (b)
dynamic viscoelastic properties of the developed double-layered fluorescent silica ink.
Figure 4. Photographs of (a) fluorescent ink printed on a flexible
Mylar substrate, (b) under a handheld UV lamp, showing bright green
emission, and (c) fluorescent ink under UV light.
Figure 5. (a) High-resolution surface image of the printed layer, (b,c)
low-magnification surface images, and (d) cross-sectional image of the
printed film showing thickness of the printed layer.
Figure 6. (a) 2D and (b) 3D AFM images of the screen-printed film in the tapping mode.
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microscopy (SEM) image of printed film, where the
agglomerates of modified nanoparticles formed micron-sized
spherical particles. From the high-magnification images of
Figure 5b,c, it is evident that the filler particles were uniformly
distributed, thus making the printing more or less uniform.
However, along with uniform distribution, a fractional amount
of porosity could be found in the microstructure, which might
be as a result of high evaporation of organic solvents used in
the ink preparation. Figure 5d shows the cross-sectional
microstructure of the fluorescent ink printed on the Mylar film.
The cross-sectional image clearly presents a clear morpho-
logical distinction between the printed film and the substrate,
with a thickness of the printed layer around 15 μm. The
thickness was found to be uniform throughout the layer, which
further implies the homogeneity of the printed pattern.
Figure 6 illustrates the surface topographies of the screen-
printed film. A clear microstructure of the printed fluorescent
silica layer is clearly visible from the 3D AFM images. A typical
3D image of the printed film shows minor bumps and valleys,
which can be minimized by using a hard flood, while holding
the screen off the platen and also using a soft stroke during
printing.34,36 The unevenness of the printed film was measured
from kurtosis topography, and a value of around 2.30 was
obtained. If the surface has relatively high mountains and low
valleys, the kurtosis value is less than 3, which is typically
referred as platykurtoic.41 A kurtosis value greater than 3
signifies the surface contains high peaks and low valleys, and
the distribution curve is called as leptokurtoic. As seen, the
present screen-printed fluorescent silica layer surface is
platykurtoic. From AFM images, the average surface roughness
(Ra) and the root-mean-square roughness (Rq) of the film were
estimated and were found to be 87.3 and 107 nm, respectively.
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Figure 7. (a) Absorption spectra of synthesized fluorescent silica nanoparticles and developed film and (b) emission spectra of the film. Inset:
Photostability of the printed film under continuous irradiation.
These values were in good agreement with the earlier reports
on screen-printable inks.34,36 Profile symmetry information was
obtained from the skewness value of the film. Because bumps
and valleys are predominant in the developed film, the
expected skewness moment is negative. The present film
gained a skewness of around −0.237, confirming the bumps
and valleys nature of the film.34 The obtained surface
roughness and skewness are good enough for screen-printing
applications.
Fluorescent studies of the as-synthesized double-layered
silica nanoparticles and the printed surface with a suitable
excitation wavelength spectrum were carried out. Both
nanoparticles and the printed surface emit bright fluorescence
with discrete peak emission. Absorption and emission
properties of the synthesized fluorescent silica nanoparticles
and the developed film are presented in Figure 7a,b,
respectively. The absorption spectra of double-layered nano-
particles show bright and strong emission, confirming the
successful doping of the dye within the silica matrix. The
maximum emission wavelength of double-layered silica nano-
particles obtained is at 519 nm, which is more or less in
concordance with earlier reports.21 However, the emission
intensity of the fluorescent printed pattern obtained was lower
compared to that of the corresponding fluorescent silica
nanoparticles. A similar trend was observed for excitation
spectra of the printed film and fluorescent silica nanoparticles.
Emission spectra of both powder and film were obtained upon
excitation at a wavelength of 470 nm. As shown, the strongest
fluorescence emission is observed for fluorescent double-
layered nanoparticles at a wavelength of 530 nm upon
excitation. The same excitation wavelength was used to excite
the fluorescent silica-printed film on the Mylar substrate, where
the emission was obtained at a wavelength of 525 nm. The
emission wavelength and corresponding intensity of the
printed film were slightly altered. The intensity discrepancy
in both absorption and excitation spectra is mainly due to the
additional components such as the binder and dispersant
added for the formulation of rheostable ink. These additives
are indispensable but may reduce the intensity counts of the
film, showing less absorption and emission intensity compared
to core−shell-structured fluorescent silica nanoparticles.42
However, it is clear that the intensity of emission spectra of
the printed film was not significantly affected by the ink
components, which further confirms the fluorescence stability
of the developed film to be similar to core−shell architecture.
For practical applications, photostability of the printed film
should be investigated through continuous irradiation. The
normalized fluorescence data plotted against irradiation
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duration carried on for 180 min are shown in the inset of
Figure 7b. Emission intensity was found to be decreased by
26% of its initial value at 60 min. After 180 min of continuous
irradiation, the apparent drop was only 28%, as shown in the
figure. These studies unveil the excellent photostability of the
printed film over time, which is ideally suited for practical
applications.
■ CONCLUSIONS
UV-readable fluorescent inks have potential applications in
optical reading systems, intelligence information, and auto-
matic identification systems. However, sustaining the fluo-
rescence at the printed level requires a lot of optimization in
synthetic chemistry and ink formulation. With the aim of
developing a fast-curing fluorescent ink, we synthesized
fluorescent silica nanoparticles through a modified Stöber
method. Morphology and particle size of synthesized particles
were analyzed through TEM micrographs. The rheostable
viscous ink of fluorescent silica was formulated by choosing
ethanol as the solvent system, whereas SDS and Butvar were
used as the dispersant and the binder, respectively. The
microstructure, surface roughness, and emission properties of
the developed ink were measured. Even though the printed
film got less intensity than corresponding fluorescent nano-
particles, the peak position of the film was not much affected.
Hence, the developed ink provides promising applications in
the fields of automatic identification, optical devices, and
information encryption.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: kpsurendran@niist.res.in. Phone: +91 471 2515258.
Fax: +91 471 2491712.
ORCID
Kuzhichalil P. Surendran: 0000-0001-5269-1489
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors acknowledge the Department of Science and
Technology (DST-SERB) SR/S2/CP-114/2012, New Delhi,
for research fellowship. We would like to express our
indebtedness to Dr. Subrata Das for extending the fluorescence
facility and fruitful discussion. The authors are also thankful to
Dr. P. Prabhakar Rao and Kiran for extending the use of SEM
and HRTEM facilities, respectively. The authors would like to
acknowledge A. Peer Mohammed for recording rheology
studies.
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■
REFERENCES
(1) Bridot, J.-L.; Faure, A.-C.; Laurent, S.; Rivière, C.; Billotey, C.;
Hiba, B.; Janier, M.; Josserand, V.; Coll, J.-L.; Vander Elst, L.; Muller,
R.; Roux, S.; Perriat, P.; Tillement, O. Hybrid Gadolinium Oxide
Nanoparticles: Multimodal Contrast Agents for in Vivo Imaging. J.
Am. Chem. Soc. 2007, 129, 5076−5084.
(2) Burns, A. A.; Vider, J.; Ow, H.; Herz, E.; Penate-Medina, O.;
Baumgart, M.; Larson, S. M.; Wiesner, U.; Bradbury, M. Fluorescent
Silica Nanoparticles with Efficient Urinary Excretion for Nano-
medicine. Nano Lett. 2009, 9, 442−448.
(3) Wolfbeis, O. S. An overview of nanoparticles commonly used in
fluorescent bioimaging. Chem. Soc. Rev. 2015, 44, 4743−4768.
(4) Sarma, D.; Prabu, M.; Biju, S.; Reddy, M. L. P.; Natarajan, S.
Synthesis, Structure and Optical Studies of a Family of Three-
Dimensional Rare-Earth Aminoisophthalates [M(μ2-OH)-
(C8H5NO4)] (M = Y3+, La3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+,
Dy3+, and Er3+). Eur. J. Inorg. Chem. 2010, 3813−3822.
(5) Ha, S.-W.; Camalier, C. E.; Beck, G. R., Jr.; Lee, J.-K. New
method to prepare very stable and biocompatible fluorescent silica
nanoparticles. Chem. Commun. 2009, 2881−2883.
(6) Jackson, J. B.; Halas, N. J. Silver Nanoshells: Variations in
Morphologies and Optical Properties. J. Phys. Chem. B 2001, 105,
2743−2746.
(7) Lal, S.; Westcott, S. L.; Taylor, R. N.; Jackson, J. B.; Nordlander,
P.; Halas, N. J. Light Interaction between Gold Nanoshells Plasmon
Resonance and Planar Optical Waveguides. J. Phys. Chem. B 2002,
106, 5609−5612.
(8) Kim, Y.-J.; Ha, S.-W.; Jeon, S.-M.; Yoo, D. W.; Chun, S.-H.;
Sohn, B.-H.; Lee, J.-K. Fabrication of Triacetylcellulose−
SiO2Nanocomposites by Surface Modification of Silica Nanoparticles.
Langmuir 2010, 26, 7555−7560.
(9) Jung, H.-S.; Moon, D.-S.; Lee, J.-K. Quantitative Analysis and
Efficient Surface Modification of Silica Nanoparticles. J. Nanomater.
2012, 2012, 1−8.
(10) Burns, A.; Ow, H.; Wiesner, U. Fluorescent core-shell silica
nanoparticles: towards ″Lab on a Particle″ architectures for
nanobiotechnology. Chem. Soc. Rev. 2006, 35, 1028−1042.
(11) Chen, C.; Yu, Y.; Li, C.; Liu, D.; Huang, H.; Liang, C.; Lou, Y.;
Han, Y.; Shi, Z.; Feng, S. Facile Synthesis of Highly Water-Soluble
Lanthanide-Doped t-LaVO4 NPs for Antifake Ink and Latent
Fingermark Detection. Small 2017, 13, 1702305.
(12) Li, M.; Yao, W.; Liu, J.; Tian, Q.; Liu, L.; Ding, J.; Xue, Q.; Lu,
Q.; Wu, W. Facile synthesis and screen printing of dual-mode
luminescent NaYF4:Er,Yb (Tm)/carbon dots for anti-counterfeiting
applications. J. Mater. Chem. C 2017, 5, 6512−6520.
(13) Van Blaaderen, A.; Vrij, A. Synthesis and characterization of
colloidal dispersions of fluorescent, monodisperse silica spheres.
Langmuir 1992, 8, 2921−2931.
(14) Yamauchi, H.; Ishikawa, T.; Kondo, S. Surface characterization
of ultramicro spherical particles of silica prepared by w/o micro-
emulsion method. Colloids Surf. 1989, 37, 71−80.
(15) Auger, A.; Samuel, J.; Poncelet, O.; Raccurt, O. A comparative
study of non-covalent encapsulation methods for organic dyes into
silica nanoparticles. Nanoscale Res. Lett. 2011, 6, 328.
(16) Stö ber, W.; Fink, A.; Bohn, E. Controlled growth of
monodisperse silica spheres in the micron size range. J. Colloid
Interface Sci. 1968, 26, 62−69.
(17) Rossi, L. M.; Shi, L.; Quina, F. H.; Rosenzweig, Z. Stöber
Synthesis of Monodispersed Luminescent Silica Nanoparticles for
Bioanalytical Assays. Langmuir 2005, 21, 4277−4280.
(18) Hartlen, K. D.; Athanasopoulos, A. P. T.; Kitaev, V. Facile
Preparation of Highly Monodisperse Small Silica Spheres (15 to >200
nm) Suitable for Colloidal Templating and Formation of Ordered
Arrays. Langmuir 2008, 24, 1714−1720.
(19) Ow, H.; Larson, D. R.; Srivastava, M.; Baird, B. A.; Webb, W.
W.; Wiesner, U. Bright and Stable Core−Shell Fluorescent Silica
Nanoparticles. Nano Lett. 2005, 5, 113−117.
2582
Article
(20) Burns, A.; Sengupta, P.; Zedayko, T.; Baird, B.; Wiesner, U.
Core/Shell Fluorescent Silica Nanoparticles for Chemical Sensing:
Towards Single-Particle Laboratories. Small 2006, 2, 723−726.
(21) Yoo, H.; Pak, J. Synthesis of highly fluorescent silica
nanoparticles in a reverse microemulsion through double-layered
doping of organic fluorophores. J. Nanopart. Res. 2013, 15, 1609.
(22) Hrytsenko, O.; Hrytsenko, D.; Shvalagin, V.; Grodziuk, G.;
Andriushyna, N. The Influence of Parameters of Ink-Jet Printing on
Photoluminescence Properties of Nanophotonic Labels Based on Ag
Nanoparticles for Smart Packaging. J. Nanomater. 2017, 2017, 1−9.
(23) Ataeefard, M.; Nourmohammadian, F. Producing fluorescent
digital printing ink: Investigating the effect of type and amount of
coumarin derivative dyes on the quality of ink. J. Lumin. 2015, 167,
254−260.
(24) Song, Z.; Lin, T.; Lin, L.; Lin, S.; Fu, F.; Wang, X.; Guo, L.
Invisible Security Ink Based on Water-Soluble Graphitic Carbon
Nitride Quantum Dots. Angew. Chem., Int. Ed. 2016, 55, 2773−2777.
(25) Gao, S.; Chen, Y.; Fan, H.; Wei, X.; Hu, C.; Wang, L.; Qu, L. A
green one-arrow-two-hawks strategy for nitrogen-doped carbon dots
as fluorescent ink and oxygen reduction electrocatalysts. J. Mater.
Chem. A 2014, 2, 6320−6325.
(26) Pang, Y.; Zhao, R.; Lu, Y.; Liu, J.; Dong, X.; Xi, F. Facile
preparation of N-doped graphene quantum dots as quick-dry
fluorescent ink for anti-counterfeiting. New J. Chem. 2018, 42,
17091−17095.
(27) Bhati, A.; Anand, S. R.; Saini, D.; Khare, P.; Dubey, P.; Sonkar,
S. K. Self-Doped Nontoxic Red-Emitting Mg-N-embedded Carbon
Dots for Imaging, Cu (II) Sensing and Fluorescent Ink. New J. Chem.
2018, 42, 19548−19556.
(28) Cui, L.; Li, Y.; Wang, J.; Tian, E.; Zhang, X.; Zhang, Y.; Song,
Y.; Jiang, L. Fabrication of large-area patterned photonic crystals by
ink-jet printing. J. Mater. Chem. 2009, 19, 5499−5502.
(29) Hou, J.; Zhang, H.; Su, B.; Li, M.; Yang, Q.; Jiang, L.; Song, Y.
Four-Dimensional Screening Anti-Counterfeiting Pattern by Inkjet
Printed Photonic Crystals. Chem.Asian J. 2016, 11, 2680−2685.
(30) Hou, J.; Li, M.; Song, Y. Patterned Colloidal Photonic Crystals.
Angew. Chem., Int. Ed. 2017, 57, 2544−2553.
(31) Yin, Y.; Huang, R.; Bu, G.; Wang, C. Investigation of disperse
fluorescent ink formulation via thermal transfer printing for polyester
substrate. Text. Res. J. 2016, 87, 2146−2153.
(32) Leach, R.; Pierce, R. The Printing Ink Manual, 5th ed.; Springer
Netherlands, 1999.
(33) Zeng, Y.; Grandner, S.; Oliveira, C. L. P.; Thünemann, A. F.;
Paris, O.; Pedersen, J. S.; Klapp, S. H. L.; von Klitzing, R. Effect of
particle size and Debye length on order parameters of colloidal silica
suspensions under confinement. Soft Matter 2011, 7, 10899−10909.
(34) Varghese, J.; Surendran, K. P.; Sebastian, M. T. Room
temperature curable silica ink. RSC Adv. 2014, 4, 47701−47707.
(35) Remadevi, A.; Kesavapillai Sreedeviamma, D.; Surendran, K. P.
Printable Hierarchical Nickel Nanowires for Soft Magnetic
Applications. ACS Omega 2018, 3, 14245−14257.
(36) Pullanchiyodan, A.; Surendran, K. P. Formulation of Sol-Gel
Derived Bismuth Silicate Dielectric Ink for Flexible Electronics
Applications. Ind. Eng. Chem. Res. 2016, 55, 7108−7115.
(37) Joseph, A. M.; Nagendra, B.; Bhoje Gowd, E.; Surendran, K. P.
Screen-Printable Electronic Ink of Ultrathin Boron Nitride Nano-
sheets. ACS Omega 2016, 1, 1220−1228.
(38) Somalu, M. R.; Muchtar, A.; Baboli, M. G.; Yufit, V.; Shapiro, I.
P.; Xiao, P.; Brandon, N. P. Understanding the Relationship between
Ink Rheology and Film Properties for Screen-Printed Nickel/Scandia-
Stabilized-Zirconia Anodes. ECS Trans. 2013, 57, 1321−1330.
(39) Alias, R.; Shapee, S. M. Rheological behaviors and their
correlation with printing performance of silver paste for LTCC tape.
Rheology; InTech, 2012.
(40) Kapur, N.; Abbott, S. J.; Dolden, E. D.; Gaskell, P. H.
Predicting the Behavior of Screen Printing. IEEE Trans. Compon.,
Packag., Manuf. Technol. 2013, 3, 508−515.
DOI: 10.1021/acsomega.8b03313
ACS Omega 2019, 4, 2577−2583
ACS Omega Article

(41) Gadelmawla, E. S.; Koura, M. M.; Maksoud, T. M. A.; Elewa, I.

M.; Soliman, H. H. Roughness parameters. J. Mater. Process. Technol.
2002, 123, 133−145.
(42) Barbera-Guillem, E. Fluorescent ink compositions comprising
functionalized fluorescent nanocrystals. U.S. Patent 6,576,155 B1,
2003.

2583 DOI: 10.1021/acsomega.8b03313

ACS Omega 2019, 4, 2577−2583