Specification
A POLYMERIC FILM EMBEDDED WITH SILVER NAN0 PARTICLES AND A METHOD FOR PREPARING THE SAME
FIELD OF THE INVENTION
The present invention relates to a polymeric film embedded with silver nano particles and a
method for preparing the same, wherein the silver nano-particles grown in situ. More
particularly, the said films are useful in applications where antibacterial find utility, such as
purification of drinking water. The said films having strong nonlinear absorption, positive
nonlinear refraction, and efficient optical limiting in the femtosecond regime.
BACKGROUND AND THE PRIOR ART OF THE TNVENTTON
.Antibacterial efficacy of silver is known for a long time. Among heavy metals which are
antibacterial, silver is the most popular one because of its activity against a wide spectrum of
prokaryotes while being relatively harmless to eukaryotes. In recent years, there has been
considerable interest in employing nanometric silver particles as antibacterial agents in several ,
applications. Silver nanoparticles have been used in the colloidal state as well as in the for111 of
embeddings in polymers, foams, fibers and textiles. The ultra small dimensio.ns lead to large
surface arealvolume ratio and hence enhanced activity; it is also likely to facilitate specific
1 binding to ceU membrane leading to the bactericidal action.
In the past yPars several methods have been developed for the bottom-up synthesis of silver
nanoparticles through soft chemical protocols. Colloidal silver was directly used in several
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j antibacterial qplications reported.
'The US Patent 6894085 discloses that the incorporation of nanosized metal particles into
cyclodextrin-containing material leads to a "relative" barrier material having excellent barrier
properties. Also, it has been found that the presence of nanosized metal or metal alloy particles in
a barrier material such as thermoplastic material, wherein said material comprises cyclodextrin
derivatives, may be advantageous in achieving excellent barrier properties. The barrier material
of the said invention may provide improved barrier resistance to a variety of permeants andlor
impurities. Tie diffusion of volatile substances through the barrier material may be prevented by
b adding compatible derivatized cyclodextrin and nanosized metal particles to thc matcrial uscd.
Nowever, US6894085 relates to barrier materials, the essential function being thc prevcntion of
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passage of permeants including odors. US6894085 uses primarily nanoparticulatc zinc
US6894085 does not mention any in situ growth of the nanomaterial inside polymcr films.
Another US patent document 7052765 relates to the preparing of master batches and fibres of!
polyesters con4aining silver nanoparticles. The said document discloses several reducing agents
added externally for forming silver nanoparticles and does not use the polymer as the reducing
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agent. Some 1:3f the steps in the preparing procedure disclosed in US7052765 involve
temperatures 250 - 3 5 0 ' ~p~re ssures up to 2.5 atm and processing times of 5 - .I2 11.
US7052765 does not mention any in situ growth of the nanomaterial inside cast polymer 61n1s1
US7052765 does not address purification of water by antibacterial action.
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The inventors nave strong believe that preparing of polymer composites of the nanoparticlcs is
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h:ghly desirable since it facilitates: (i) coating of surfaces of varying size and shape, (ii)
controlled release of the metal atoms/ions or even restriction of the bactericidal action to contact-
Itilling, (iii) rehse and perhaps regeneration, and (iv) monitoring of the bactcricidal agent through
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successive action cycles. .
Therefore, methodology has been developed for the preparing of silver nano particle e~nbedded
poly (vinyl alohol) films, is not only very simple and safe to implement, but also likely to provc
highly econoGical. The highlights of the method include the use o l aqueous medium for thc
preparing proc.essl deployment of the bio-compatible and bio-degradable polymer itself as the
reducing agenf, mild thermal annealing for generating the metal and in situ generation of the
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nanoparticles mside the polymer matrix which serves as the stabilizer as well.
Among :he several avenues, where anti-bacterial finds utility, purification of drinlcing water is
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cone of the <,,st critical and important. The antibacterial agent used should be non-toxic to
humans at the concentrations being used, effective against a wide range of pathogens and cheap
end easy to fa.3ricate. One of the efficient and convenient ways to deploy the agent in a donlestic
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setting would;%e as a coating on stirring devices. The methodology developed for the preparing
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-'v' of silver nanoparticle-embedded polymer film is unique and meets all these demands. "l'lie
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experiments discussed below establish that the bactericidal agent (Ag-PVA film) can be used
efficiently and lrepeatedly in several action cycles, allowing simultaneously, its monitoring using
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spectroscopy and microscopy.
r ...
1 ae applncants/ have developed an extremely simple and economically viable methodology for
the preparing of silver nanoparticle-embedded poly (vinyl alcohol) film. 'The highlights of
present method include the use of aqueous medium for the preparing process, deployment of the
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bio-compatibl{ and bio-degradable polymer itself as the reducing agent, mild thermal annealing
for generatingtthe metal and in situ generation of the nanoparticles inside the polyn~er matrix
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which serves a; the stabilizer for the nanoparticles as well. This protocol can be used to fabricate
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supported as dell as free-standing films. The metallpolymer ratio and the heating conditions can
br tuned to actieve control on the size and shape and therefore the activity of nanoparticles.
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The methodol!,gy applicants have developed for preparing of silver nano particle &bedded
polymer film 1s unique and meets all these demands. In addition, the applicants have found that
bactericidal a$ent can be used efficiently and repeatedly in several action cycles, allowing
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simultaneousl~i,t s monitoring using spectroscopy 'and microscopy.
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OBJECTIVES OF THE INVENTION
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r .. 1 he primary o3jective of the present invention to provide a polymeric film embedded with silver
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r-ano panticles'and a method for preparing the same.
Yet another oAjective of the present invention is to provide a polymeric film having antibacterial
capabilities.
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Yet another objective of the present invention is to provide a silver nano particles are grown in
silu inside poiy (vinyl alcohol) film supported by glass substrates.
Yet another objective of the present invention is to provide simple & econonlic viable method
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for preparing bf silver nano particle embedded PVA film.
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L- SUMMARY OF THE INVENTION
The applican!s have developed an extremely simple and economically viable methodology for
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the preparing of silver nano particle embedded poly (vinyl alcohol) film. The highlights of
present meth?d include the use of aqueous medium for the preparing process, dcploynicnt of thc
bio-compatible and bio-degradable polymer itself as the reducing agent, mild thermal annealing
for generating the metal and in situ generation of the nano particles insidc thc polymcr matrix
which serves as the stabilizer for the nano particles as well. This protocol can bc used to fabricate
supported as ! a l l as free-standing films. The metallpolymer ratio and thc hcating conditions can
be tuncd to achieve control on the size and shape and therefore the activity of nano particles.
Silver nano >articles are formed in situ inside poly (vinyl alcohol) film by a simple and
convenient photocol leading to nano particle-embedded films supported on glass substrates. A
srotocol is dtveloped for the preparing of freestanding films, PVAIAg-PVAIPVA. Nonlinear
optical studiek using femtosecond pulse laser reveal appreciable nonlinear absorption and optical
:imiting capability of these films at the. ultra fast time scales. The positive nonlinearity observed
is relatively &re andof potential utility in fabricating devices with graded nonlinear refractive
indices. The freestanding films facilitate unambiguous estimation of the nonlinear refractive
index and su&eptibility which are comparable to those reported earlier fir supported films under
femtosecond laser irradiation. The current study establishes a convenient route to the realization
of freestandipg metal nano embedded polymer film and demonstrates their optical
iimiting capability, serving as a step toward the development of optical power limiters.
STATEMENT OF THE INVENTION
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Accordingly, the present invention relates to a polymeric film embedded with silver nano
particles whekein the size of silver particles is in the range of 3 to 10 nm.
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.%ISOt,h e preynt invention relates to method for preparing a polymeric film embedded with
silver nano pbticle, said method comprising the steps ol;
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a. preparing aqueous solution of polymer at a temperature in the range of 60 to 7 0 ' ~
and subsequently c&ling the same up to 30°c,'
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b. mixing aqueous solution of step (a) with solution of silver nitrate in a ratio in the
range of 0.015 to 0.25, stirring the same for 5 to 15 minutes and obtaining the
solution mixture,
c. applying the solution mixture on a substrate, annealing the solution misture on the
substrate at a temperature in the range of 100 to 1 6 0 ' ~ for time in the
range of 1 to 3 hrs, thereby generating a polymeric film embedded with silver
nano particle.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 Bacterial growth reflected in the increase of optical density (at 600 nin) of thc bacterial
suspension (in LB broth) with time; control, samples treated with the films (a) Ag-PVA(1) (b)
Ag-PVA(I1) and (c) Ag-PVA(II1) for different periods of times, 10, 30 and 60 min.
Figure 2 Bacterial growth reflected in the increase of optical density (at 600 nm) of the bacterial
suspension (in LB broth) with time; control, sample treated with PVA film, and samples treated
with one Ag-PVA(II1) film in multiple uses are shown.
:Figure 3 Absorption spectra of the. same Ag-PVA (111) film before and after multiple uses for 30
rnin each in the bacterial suspension (in LB broth). Inset shows the integrated intensity in each
case, normalized to the starting value.
Figure 4 AFlM images of the same Ag-PVA (111) film (a> before use and after use .for 30 11iin
cach in the bacterial suspension (in LB broth) (b) first (c) second and (d) third time. Magnified
images of the same films are shown in (e), (0, (g) and (h) respectively.
Figure 5 Photographs of petri plates (after 12 h.incubation) spread with ultrapure water samples
containing E. coli. (105 CFU); untreated (C) and treated for 15 min with the same Ag-PVA (Ill)
tilm in multiple uses (1 - 20) are shown.
Figure 6 Absorption spectra of the Ag-PVA (111) films before and after multiple uses for 15 min
each in ultrapure water samples containing 105 CFU of E. coli (the number of uses is indicated
on the plot).
Figure 7 AFM images of the Ag-PVA (111) film before and after multiple uses for 15 mi11 each in
ultrapure water samples containing 105 CFU of E. coli (the number of uses is indicated on the
images). mul5ple uses (Fig. 7). The lower concentration of bacteria present in this study and the
absence of LB broth and bacteria growth process therein, might be the reasons for the film
morphclogy remaining unaffected. This experiment shows that even with fairly large bacterial
concentratiohs, Ag-PVA film .is very effective as reusable antibacterial agent for water
purification. i
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Figure 8 photographs of petri plates spread with ordinary tap water - 15 ml each of untreated
sample (C) And samples treated for 5 min with the same Ag-PVA (111) film coated glass rod in
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multiple used. upto 2 1 times - and incubated for 12 h.
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Figure 9 ~ h c l t o ~ r a o~fh pse tri plates spread with ordinary tap water - untreated samplc (C) and
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200 ml and b 0 ml samples treated for 5 min each with Ag-PVA (Ill) film coated on glass rod -
and incubated for 12 h.
Figure 10 showing three kinds of AgN03-PVA films, prepared by spin coating.
Figure 11 shbwing TEM image of the Ag-PVA films with (a) x=0.029 and (b) x = 0.058.
Figure 12 showing colour online (a) Electronic absorption spectra of PVA and Ag-PVA films
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coated on g l ~ sO. p en apercture Z-scan traces of (b) glass and PVA on glass and Ag-PVA lilnis
on glass with (c) x=0,029 and (d) x=0.058 for different input intensities(I,,) fenitosecond laser
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pulses. ~
Figure 13 shlawing colour online Output vs input intensity plots of Ag-PVA films on glass for
femtosecond laser pulses.
Figure 14 shb~ wing closed aperture Z-scan traces of Ag-PVa films on glass, with (a) x-0.029 and
[b) x=0.058,1 for femtosecond laser pulses.with input intensity, 1,,=0.62 T W / C I ~ ~T~he.
transmittance is normalized and divided by the corresponding open aperture values.
Figure 15 showing colour online photographs of freestanding films of Ag-PVA(PVA/Ag-
PVAIPVA), hansparency of the films is demonstrated by placing them on wire framcs abovc a
paper on whiLh the corresponding value of x is printed.
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Figure 16 &wing colour online (a) Electronic absorption spectra of freestanding PVA and Ag-
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PVA films. Open specture Z-scan traces of freestanding (b) PVA films and Ag-I'Va films with
98% alone were chosen since they showed low solubility in
water at room temperature. This also implied that the aqueous solutions of PVA had to be
prepared in water at 60-70oC, and then cooled to room temperature (-30oC) before mixing with
the solution of silver nitrate.
Antibacterial action of Ag-PVA was examined on Escherichia coli (NCIM No. 293 1, A'SCC No.
25922); control experiments were conducted in all cases. The effective concentration of silver
used in all the experiments is < 6 ppm. Approximately 107 - 108 CFU of E. coli was inoculated
in 15 ml Lur-a-Bertani (LB) broth. Ag-PVA film coated on 6 crn2 quartz plate was immersed in
this and shaken at 37OC for 10, 30 and 60 min in different runs; the plate was removed
immediately after the run. Following this, the bacterial growth was monitored for up to 12 11 by
measuring the optical density at 600 nrn. The main results are collected in Fig. 11. Fig. 1 la - c
shows that, vihen the films are shaken in the broth for 10 mi'n, the bacterial growth suppres.sion is
more effective with Ag-PVA (11) and Ag-PVA (111). However, when shaken for 30 min or more,
the effective inhibition of bacterial growth is achieved with Ag-PVA (I) and Ag-PVA (TIT) Ag'
s' PVA(II1) pr&duces the maximum bacterial .growth inhibition at 10 h. Based on the strongest
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, effects obserr~ed, the inventors have chosen Ag-PVA(I1T) for further antibacterial experinients
discussed below. The main aspect investigated in the following experiments is the reusability of
the Ag-PVA tilms; three types of situations were studied.
I. Bacteria introduced in LB Brotlz
Approximately 107 - 108 CFU of E. coli was inoculated in 15 ml LB broth. Ag- PVA (111) film
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coated on a 6 cm2 quartz plate was immersed in this and shaken at 370C Sor 30 min; tlic plate
was immediately removed. Following this, the bacterial growth was monitored for up to 12 11 by
measuring th':: optical density at 600 nm. The main results collected in Fig. 12 indicatc cfrcctivc
inhibition of Sacterial growth for up to 8 h in the first two uses of the film and for up to 4 h in tlie
third use of the same film. The changes in the absorption spectra after the reuses arc shown in the
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Fig. 13; it is interesting to note that the change in intensity up to third reuse is < 10%. 'l'lie
applicants h ~exeam ined the film morphology before and after the reuses, using atomic forcc
microscopy (Fig. 14). The films show formation of pits, typically - 30-100 nm in diamctcr Cram
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thc second reuse onwards. This could be a reason for the degradation of antibacterial activity.
The applicants have carried out control experiments in which LB broth alonc was used with no
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bacteria inoc~latedT. he films were found to be unaffected after multiple reuses.
2. ~ a c t b iIan troduced in Ultrapure Water
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In the previous experiments, the inventors have used very large concentrations (CFU/niI) of
bacteria, which are typically much higher than that encountered in ordinary drinking water. 111
spite of this, !the inventors have observed the bactericidal action of Ag-PVA films. The applicants
have now considered slightly lower concentration of bacteria. Approximately 105 CI'U of 12. coli
was inoculaizd in 15 ml of ultrapure water (Millipore). Ag- PVA(II1) film coated on a 6 cm2
quartz plate -i?las immersed in this and shaken at 370C for 15 min. The test was repeated using
the same f i b 20 times in new samples of bacteria-containing water. Subsequent to each
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treatment, thi water sample was plated on LB agar Petri plates and incubated for 12 h at 37oC.
The bacterid colonies formed u7ere observed under a microscope. Control sample of water
showed > 450 bacterial colonies whereas not a single colony was detected in the experimental
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samples from up to the 20th reuse of the Ag-PVA film (Fig.15). Absorptioi~ spectra of tlie l7lm
were monitoled throughout the experiment. Selected spectra of the films upto twenty reuse are
collected in !he Fig. 16. There is very little variation of the spectrum and its intensity obscrved
even after twenty reuses.
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3. Bactiria Introduced in Ordinary Water
The AFM im,ages of the film surface show no appreciable change through the Ordinary tap watcr
(possibly containing a range of nonpathogenic and pathogenic bacteria) was treated by stirring
with Ag-PV4 (111) coated glass rods for 5 min at 370C. With 15 ml fresh samples of watcr, thc
test was repeated 2 1 times using the same rod. The effective concentration of silver prcscnt in thc
films, in the& experiments is - 0.4 ppm. While the control showcd a bactcrial count oC - 250
CFUlml, the 15 min treated ones showed tremendous reduction; the samplc subjected to thc 20th
reuse of the same rod showed 5 30CFUlml (Fig. 18). Similar results were obtaincd wit11 a singlc
treatment o f t 200 - 250 ml water (Fig. 19).
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The differed experiments described above demonstrate the antibacterial capability of silver
nanoparticle.s in Ag-PVA (111) film. Two general possibilities can be considered: (i) bacteria
1 coming into d.ontact with the silver nanoparticles inside the Ag- PVA film and (ii) silver leaching
out from the film into the bacterial medium. The spectroscopy and'microscopy experiments
suggest that the Ag-PVA films are strongly affected only when inserted in thc L13 broth
containing large initial concentrations of bacteria (107-108 CFU) which grow hrthcr during
incubation. rb view of the pit formation observed, leaching of silver from thc film is quitc
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possible; pakick aggregation may also occur. The pit formation could facilitate contact of
bacteria witk the nanoparticles inside the film. In the case of water samples with lower
concentratio4 of bacteria (105 CFU), even though the films are intact, bactericidal action is still
observed. be minor decrease in the absorption spectral intensities suggests that the
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nanoparticles! are mildly affected. One possibility is that the films swell when submerged in the
aqueous medium allowing bacterial contact with the nanoparticles; particle aggregation may
result from this. Another possibility is that the film swelling induces controlled leaching of the
nanoparticles and consequent bactericidal action.
The applican!s report the optical limiting in the nanosecond time scale by silver nano particlcembedded
pc/ly (vinyl alcohol) film layered over polystyrene (Ag-PVAIPS) supported on glass.
It was demhstrated that films typically a few micrometers thick show characteristics
3 , - comparable to colloidal silver with path lengths of a few millimeters. Nonlinear absorption in the
nanosecond regime, of AgIAu-PVA films typically 100 pm thick, has also been reported. 'rhe
inventors now investigated the nonlinear absorption/refraction and optical limiting of
femtosecond laser pulses by Ag-PVA coated directly on glass and more importantly, as
freestanding films with the trilayer structure, PVAIAg-PVAIPVA.
The films with optimal concentrations of Ag show efficient responses and are quite stable
against the high power laser irradiation. Unlike the case with nanosecond laser pulses, the high .
intensities associated with the femtosecond laser pulses can cause the substrates on which tlie
films are coated to produce their own nonlinear responses. Open and closed aperture %-scan
experiments on the freestanding films allowed unambiguous estimation of the nonlinear
absorption cross sections and nonlinear refraction due to the nanoparticles without the
complications arising from the contribution of the glass substrate.
Ag-PVA shows large nonlinear absorption 2.2 cm/GW and nonlinear refractive index
. (n2=1.20) (10-12 esu). Significantly, the n2 dominated by electronic responses has a positivc
sign; experiments in the nanosecond domain revealed contrasting behavior, with ~iegative
nonlinearity possibly arising due to thermal contributions. The Ag- PVA films show nearly 90%
linear transmission coupled with efficient optical limiting for femtosecond pulses; tlie
freestanding nature of these composite films is a significant development from the point of view
of device applications.
,. . 1 he advantages of the disclosed invention are thus attained in an economical, practical, and facile
manner. While preferred aspects and example configurations have been shown and described, it
is to be understood that various further modifications and additional conl7gurations will be
apparent to those skilled in the art. It is intended that the specific embodiments and
configurations herein disclosed are illustrative of the preferred and best modes for practicing tlie
invention, and should not be interpreted as limitations on the scope.of the invention.
WORKING EXAMPLES
'C A. Film preparing
Required weight of silver nitrate (AgN03) dissolved in 1.0 ml water was mixed with 0.4 rnl of a
solution of polyvinyl alcohol (Aldrich, average molecular weight =13-23 kDa, % hydrolysis=86)
in water (2.4 g PVA in 8 ml water) to prepare different compositions designated using the
AgIPVA weight ratio x (for example, 5.5 mg of AgN03 gives x=0.029). The solution mixture
was stiired fc.r 5 min at 27-30 "C.
Millipore MilliQ purified water was used in all operations. The glass substrate was
cleaned by sonication with isopropyl alcohol, methanol, and finally acetone for 10 min cacli. 'l'lie
substrate required for fabricating freestanding films of Ag-PVA and san~plesf or transmission
electron microscopy (TEM) studies was prepared by spin coating a few drops of a solution of
polystyrene, (average molecular weight=280 kDa) in toluene (1 g PS in 8 ml toluene) on glass,
using a Laurell Technologies Corporation model WS- 400B-6NPP/LITIZ/8K photoresist spinner,
at 1000 rpm for 10 s followed by drying in a hot air oven at 85-90 "C for 15-20 min.
Three kinds of AgN03-PITA films were prepared by spin coating at 6000 rpm Sor 10 s:
(i) AgN03-PVA solution on glass substrate,
(ii) AgN03-PVA solution on PSIglass substrate, and
{iii) F'VA, AgN03-PVA, and PVA solutions in succession on PSIglass substrate (schenie
10).
The film coated plates were heated in a hot air oven at 130 "C for 60 niin to generate tlie
silver nanoparticles in situ inside the PVA matrix. Sample prepared using procedurc (i) is
referred to in the text as Ag-PVh film on glass. Samples from procedures (ii) and (iii) werc
immersed in toluene taken in a Petri dish to dissolve the PS layer and release free films. 'l'he frcc
Ag-PVA film obtained via procedure (ii) was used directly for TEM imaging. Thc film obtaincd
via procedur~ (iii) is referred to in the text as freestanding Ag-PVA or PVAIAg-PVAIPVA lil~ii.
Thicknesses of the films were measured using an Ambios Technology XP-1 profilomctcr. 'I'hc
values estimated for the different films are as follows. Ag-PVA on glass of (0.5 )m; Ag-PVAIPS
on glass of (5.5)m; freestanding PVAIAg-PVAIPVA of (1O)m.
H. Spectroscopy and microscopy
Electronic absorption spectra of the Ag-PVA films coated on glass or freestanding wcre recorded
on a Shimadzu model UV-3101 UV-vis spectrometer. Ag-PVA films prepared following
P' procedure (ii) described above were placed directly on a 100 mesh copper grid and exaniined . in a
TECNAI G2 5EI F12 transmission electron microscope at an accelerating voltage of 120 kV.
C. Nonlinear optical studies
A Tisapphire laser (800 nm, -110 fs, I kHz) and frequency doubled Nd: YAG (yttrium
aluminum garnet) lasers (532 nm, 6 ns, 10 Hz) were used as the excitation sourccs for tlic
nonlinear optical studies. Open and closed aperture %-scan measurements were carried out by
moving the sample across the foc.us of the laser beam using a computer controlled translation
I stage; the scans were repeated several times to ensure reproducibility of the data. Femtosecond
'(nanosecond) pulse laser was focused using a lens of 80 mm (60 mm) focal length; the bean1
waist was 2'7.1 pm (13.5 pm) at focus leading to peak intensity in the range of (0.1 5-1.73)
TWIcm2 (0.03-0.28 GWIcmZ), i.e., fluences in the range of 0.02-0.19 J lcm2' (0.18-1 7 1 lcm2). ,
l'he input intensity could be varied using calibrated neutral density filters; closed aperture
experiments used an aperture of diameter of 1 or 2 mm after the sample. The transmitted output
was col1ecte.j using a calibrated fast photodiode (FND 100) and processed using a data
acquisition system consisting of a lock-in amplifier or boxcar averager, adc and computer. The
films were st3ble at all the intensities reported in the paper. Optical limiting studies were carried
out using f /LO geometry (using 8 cm focal length lens and a beam diameter of 0.2 cm) with the
femtosecond pulse laser in the same input fluence/intensity'range as noted above.
111. RESULTS AND DISCUSSION
Ag-PVA films spin coated on glass substrate were fabricated with four different compositions
(x=0.029, 0.058, 0.087, and 0.1 16). In this invention the inventors present the studies on .films
with x=0.02? and 0.058, since they showed superior damage thresholds conipared to the films
with higher content of silver; TEM images of the films are shown in Fig. 1 . A uniform
distribution of silver nanoparticles is observed with particle sizes ranging froni 5 to 10 nni. The
density of p~rticlesin creases with the value of x.18 Figure 2(a) shows the electronic absorption
spectra recorded for the different films. The intensity of the plasmon peak increases with
increasing si ,ver content.
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Plots of the transmittance versus scan position for the open aperture %-scan studies using the ~
femtosecon; pulse laser are shown in Figs. 12(b)-12(d). Control experiment on glass and plain ~
PVA coated on glass showed weak nonlinear absorption, possibly resulting from the large (I
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mm) interaction length of glass involved, since both show nearly identical response. With
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comparable hnd higher input laser power, Ag-PVA films coated on glass exhibit strong nonlinear
absorption. Films with x00.06 show perceptible damage at input intensity exceeding (1.3
Tw/crn2). st;ldies on silver nanoparticles in the form of suspensions and doped in glass matrices
indicated saturable absorption; this could be due to longer lifetimes of the surface plasm011 state
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in these endronments. The applicants have attempted to fit the Z-scan curves of the Ag-PVA
films using ltnodels for nonlinear absorption. However, the fitting was not very satisfactory,
possibly bedause of the non-negligible effect of the glass substrate at these high laser powcrs.
Results of the optical limiting experiments are collected. in Fig. 3. The films show high lincar
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transmittany (87%) at low laser intensity. The plots of output versus input intensity indicatc
appreciable I
Optical limiting with a threshold (1112) of 1.62 Tw/crn2 and output clamped at 0.70 Tw/cm2 (1112
is defined & the input intensity at which the transmittance reduces to half of the linear
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transmhtance). The dynamic range estimated as the ratio of the damage and limiting thresholds is
1 . I . The ability of these polymer films to sustain high laser power is of practical intcrcst. 'flic
contribution' from nonlinear refraction was assessed using closed aperture %-scan cxpcrimcnts
The kduced transmittance before focus and increased transmittance after focus indicate
that Ag-PvA possesses positive nonlinearity for refraction in the femtosecond regi~iic.'f liennal
buildup wo$d typically lead to negative non-linearity; the positive nonlinearity of the lilnis
with the fedosecond pulses. Traces of the transmittance of the Ag-PVA films coated 011 glass,
observed even with 1 kHz repetition rate therefore suggests that the responses are dominated by
electronic ekects. As in the case of the open aperture %-scan curves, theoretical fitting of thc
closed apertlre data is not dependable; the value of nonlinear refractive index obtaincd is
divided by
1 comparable ti2 that of glass alone.
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the corresponding values in the open aperture experiment so as to reveal the effcct of
nonlinear rekaction alone, are shown in Fig. 14.
? Experiments using nanosecond laser pulses revealed interesting contrast with the nonlinear
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response for femtosecond pulses. Open and closed aperture %-scan experiments
with the nanosecond laser pulses were carried out on pure PVA on glass as well as Ag-PVA
films on glass with two different c.ompositions.
PVA film did not show any detectable nonlinear absorption or refraction with the nanosecond
pulses. Ag-PVA films, however, showed appreciable nonlinear absorption and the closed
aperture experiment clearly revealed a negative nonlinearity. The latter is a consequence of
resonant abs~ptiona t 532 nrn and considerable thermal effects operative with the longer laser
pulses in the nanosecond regime. These experiments reaffirm that the strong positive nonlinear
response of rlg-PVA films to femtosecond laser pulses arises primarily due to electronic effects.
I-Towever, as noted above, the %-scan experiments on the films supported on glass substrates do
not permit an accurate evaluation of the nonlinear susceptibility of the Ag- PVA films. 'I'hc
reason for this is the following: the glass substrate, in spite of its weaker nonlinear susceptibility
compared to Ag-PVA, is a couple of orders of magnitude thicker than the polymer film and
hence e:xerts a comparable or even overwhelming impact on the total nonlinear response for the
femtosecond pulses.
In order to unambiguously demonstrate the nonlinear absorption, quantitatively estiniatc
the nonlinear susceptibility, and project the potential advantage from the point of view of device
applicarions, the applicants have fabricated freestanding films of Ag-PVA having no glass
substrate and carried out the nonlinear optical studies on them. As noted earlier, these I'llms were
prepared by successively spin coating PVA, AgN03-PVA, and PVA and generating the Ag
nanoparticles by thermal treatment. Photographs of the lop m thick freestanding films are shown
in Fig. 5. l'he larger thickness of these films precluded direct TEM imaging. I2lectronic
absorption spectra of the freestanding films are shown in Fig. 16(a); the plasmon absorption
peaks are quite similar to those observed in the supported films, suggesting that the nanoparticles
are similar in size. Data from the open aperture %-scan experiments using femtosecond lascr
pulses are provided in Fig.16. Pure PVA film of comparable thickness (10 pm) does not show
any nonlinear absorption Fig. 16(b); once again proving that the weak absorption seen in Fig.
2(b) is due to the glass substrate.
On the other hand, the freestanding films of Ag-PVA show appreciable nonlinear
sbsorption similar to that observed in the glass supported films [Figs. 16( c) and 16(d):(. The data
+T were fined t( the equation for the transmittivity TOzO, taking into account the spatial extent ofa
Gaussian beah,
zo is the Rayleigh range for the beam with intensity Ioo at focus, L is the thickness of the film,
i
and f3 is a boss nonlinear absorption coefficient. The value of f3 is found to increase linearly
with 109 with a small but nonzero intercept, suggesting that it is likely to arise horn an
association Gth two and three photon absorptions, leading to reverse saturable absorption.
!
At thb highest input fluence of 1.22 TWIcm2, .the values of P are found to be 2.0 and 2.2
cmIGW, respectively, for films with x =0.029 and 0.058.
-She plots 04 output versus input intensity (Fig. 7) indicate a limiting threshold (1112) of 1.4
TWIcm2, output clamped at 0.70 TWIcm2, and dynamic range of 1.'2 for the fill11 with ~ 0 . 0 2 9 ;
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similar characteristics are observed in the case of x=0.058 as well. It may be noted that the linear
transmittance of the freestanding films is higher than that of the glass supported ones;
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transparency of the film with x =0.029 is quite significant. The silver nanoparticle- embedded
films k e cpile stable for several months under ambient conditions; the stability of the material
' 1
under laser itradiation is indicated by reproducible responses in %-scan experinients repeated
several times for up to 10 min, keeping the peak intensities below the damage threshold. Closed
sperture %-scan experiments using femtosecond laser pulses .on the freestanding fi111is of Ag-
PVA confirm that they exhibit positive nonlinearity (Fig. 18). More importantly, these %-scan
I . [races allow ;:he direct estimation of the nonlinear refractive index n2 and the real part of the
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rhird order susceptibility x3 of the Ag-PVA films. The data were fitted to the equation
where Avo is the phase change. The values of Avo estimated for Ag-PVA filnis with ~ 0 . 0 2 9
and 0.058 are very similar, -0.39 and -0.41, respectively. Based on the preparing proccdure, the
active layer jf Ag-PVA in the freestanding PVAIAg-PVAIPVA films is likely to be l p111 thick.
Even though:SEM and TEM images of the film cross sections support this, in spite of several
attempts we were unable to establish the thickness of the Ag-PVA layer unambiguously with
corroborating elemental composition or electron diffraction data.
Therefore, the inventors have used the full thickness (10 urn) of the PVA/Ag- PVA/PVA films in
the estimation of n2 and X even though the contribution of the PVA layer is negligible. Hence
the values we report are likely to be the lower bounds for these materials. It is notable that even
then they are comparable to the nonlinear susceptibility for silver nano particles in colloidal films
on silicon substrates. The freestanding films which exhibit strong nonlinear response and optical
limiting capability are highly advantageous from an application point of view.
WE CLAIM
1 . A polymeric film embedded with silver nano particles wherein the size of silver particles
is in th? range of 3 to 10 nm.
2. The polymeric film as claimed in claim 1, comprising nonlinear absorption, positive non
linear refraction and efficient optical limiting in the femtosecond regime.
3. The polymeric film as claimed in claim 1, wherein the polymer is selected from the group
of bio-compatible and bio-degradable polymer.
4. The film as claimed in claim 1, wherein the polymer is poly vinyl alcohol.
5. 'She film as claimed in claim 1, having antibacterial properties for utilization in
purification of drinking water.
6. A met!od for preparing a polymeric film embedded with silver nano particle, said
method comprising the steps of;
d. preparing aqueous solution of polymer at a temperature in the rangc of 60 to 7 0 " ~
and subsequently cooling the same up to 30°c,
e. mixing aqueous solution of step (a) with solution of silver nitrate in a ratio in the
range of 0.015 to 0.25, stirring the same for 5 to 15 minutes and obtaining the
solution mixture,
f. applying the solution mixture on a substrate, annealing the solution mixhre on the
substrate at a temperature in the range of 100 to 1 6 0 ' ~ for time period in the
range of 1 to 3 hrs, thereby generating a polymeric film embedded with silver
nano particle.
7. "l'he method as claimed in claim 6, wherein in step (a) the polymer is selected from the
group of bio-compatible and bio-degradable polymer.
8. The method as claimed in claim 6, wherein in step (a) the polymer is poly (vinyl alcohol)
(PVA). ,
9. The method as claimed in claim 6, wherein in step (a) the ,poly (vinyl alcohol) having
average molecular weight in the range of 20 to 300 KDa and extent of hydrolysis is in the
range of 70 to 99.5 %.
I .' ,
I
I
7 10. The method as claimed in claim 6, wherein in step (b) the mixing of aqueous solution of
i
step (a:) with solution of silver nitrate in a ratio 0.029 or 0.058 and stirring the same for 10
minutes.
11. The mzthod as claimed in claim 6, wherein in step (c) substrate are quartz plate or glass
rod.
12. The method as claimed in claim 6, wherein in step (c) applying the solution niisture
either Dn quartz plate by spin coating or on glass rod by dip coating,
13. The method as claimed in claim 6, wherein in step (c), annealing results in .y~/u
generztion of silver nano particle.
14. The rethod as claimed in claim 6, wherein in the particle size of nano particles is in tllc
range of 3 to 10 nrn.
15. A polymeric film embedded with silver nano particles and a mcthod for preparing the
same substantially describsd with reference to the forgoing examples and figures.