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Applied Physics A
DOI: 10.1007/s00339-005-3372-4
t. gleitsmann
t.m. bernhardtu
l. woste
Luminescence properties
of femtosecond-laser-activated silver oxide
nanoparticles embedded in a biopolymer matrix
Institut fr Experimentalphysik, Freie Universitt Berlin, Arnimallee 14, 14195 Berlin, Germany
Introduction
of the matrix in this respect might be assigned to a stabilizing effect on the electronic as well as on the geometric cluster
structure (caging effect) [3, 6].
Readily prepared through UV-light-induced reduction of
silver oxide thin films, atomic silver clusters have also been
identified as the origin of strong visible luminescence observed in this new photosensitive material [8, 9]. In similar
silver oxide thin films, electroluminescence of atomic silver clusters at nanoscale break junctions has been employed
for single-nanocluster quantum optoelectronic logic operations [10]. With respect to advanced optical data-storage applications, the UV-light-induced formation of luminescent
clusters on silver oxide was proposed to enable local multilevel writing followed by read out via fluorescence excitation
in the visible [8]. However, very fast data writing and read out
are necessary for the utilization of this system as an efficient
storage medium. Even more important, the written data have
to be long-time stable and inert against the read-out process
itself. These prerequisites have been recently met by employing a focused femtosecond (fs) near-infrared laser for spatially
resolved and fast photoactivation. In contrast, for read out
low-power Ar+ /Kr+ laser excitation was used, which does
not generate fluorescent structures itself [11]. With this approach it was possible to write diffraction-limited structures
which could be read out through fluorescence excitation without degradation even after months.
In particular, with respect to the activation sensitivity and
the luminescence intensity, the interaction of the photoactive
silver oxide material with the surrounding environment has
been found to be very crucial in previous experiments [9].
Silver oxide in vacuum, for example, showed an order of
magnitude lower activation rate compared to that in air at
atmospheric pressure, whereas the fluorescence intensity increased in nitrogen or argon atmospheres [9]. This interface
influence is also well known from the photoactivation of photographic silver halide materials, in which a similar process of
light-induced silver cluster generation gives rise to the latent
image [12], which is in turn stabilized by a surrounding transparent matrix. The biopolymer gelatin is the classical matrix
for photosensitive materials. It consists of a polymeric collagen structure. Collagen itself is not a homogeneous substance,
but consists of a whole family of proteins. Similar in all collagen types is the triple-helical structure. The macromolecular
network undergoes coagulation under partial hydrolysis, de-
126
Experimental
Schematic illustration of the experimental arrangement. (a) Activation (writing) by scanning with focused fs-laser pulses (800 nm) over
a square on the sample surface. (b) Excitation (read out) of fluorescence
by subsequent scanning of the activated region with blue (488 nm) or green
(568 nm) light from an Ar+ /Kr+ laser. The luminescence light passes
through long-pass filters (LP1) and is detected by a photomultiplier (PM).
The lower part shows a perspective view of an image of a pure Ag2 O
nanoparticle film acquired in this way and digitized to an 8-bit false-color
intensity scale. The nine squares were individually written by 10-min activation at powers ranging from 0.6 to 6.5 MW/cm2 (from upper left to lower
right corners). Alternatively, filtered light of a mercury lamp is used to record
real-color fluorescence images with a color digital camera (D). A dichroic
mirror (DM) in combination with long-pass filters (LP2) is used to separate
excitation light from fluorescence light in this case
FIGURE 1
objective. Finally, the photons were detected by a photomultiplier to yield an 8-bit gray-scale image.
The micrograph shown in the lower part of Fig. 1 was obtained in this way from a pure silver oxide nanoparticle film.
Nine squares (40 40 m2 each) were individually activated
over 10 min with different fs-laser powers, resulting in different luminescence intensities. To block scattered excitation
light and to bracket the spectral range of the fluorescence,
long-pass filters were used in front of the photomultiplier.
In contrast to the pure silver oxide particle films, luminescence from previously activated gelatin matrix embedded
Ag2 O nanoparticles could already be excited with a weak
mercury (Hg) lamp. Real-color fluorescence images of the
activated structures under filtered Hg-lamp excitation were
recorded in this case directly with a Samsung UCA-3 color
digital camera (detector D in Fig. 1). This detector was also
used to obtain microscopic images of the samples in reflection
of unfiltered, unfocused radiation from an externally mounted
tungsten lamp (not shown in Fig. 1).
3
GLEITSMANN et al.
127
no apparent formation of areas of metallic silver could be detected [11]. This is in contrast to the matrix embedded Ag2 O
nanoparticle films, as will be described below.
3.1
3.2
Microscopic structure
of luminescent silver oxide nanoparticle films
FIGURE 2 (a) Topographic AFM image of a pure silver oxide thin film
showing several agglomerations of nanoparticles with a size of a few 100 nm.
(b)(d) Evolution of the fluorescence at the periphery of a similar aggregate
of Ag2 O nanoparticles as in (a). Activation times were 12, 22, and 60 min for
(b)(d), respectively (Pact = 6.5 MW/cm2 , 32 32 m2 total activated area,
ecx = 568 nm of Ar+ /Kr+ laser, photomultiplier detection yielding a falsecolor image). The fluorescence images were recorded with the same low
signal amplification to avoid photomultiplier saturation at high fluorescence
intensity. The length scale is the same in all images
Femtosecond-laser-induced activation
of biopolymer matrix embedded
silver oxide nanoparticles
FIGURE 3 Single lines (total length: 500 m) written with the activating fs laser into a gelatin matrix embedded silver oxide nanoparticle film.
Line width: 4 m. Activation power Pact = 12.7 MW/cm2 . Scan frequency:
1 kHz. False-color images: 568-nm Ar+ /Kr+ -laser excitation, recorded with
the photomultiplier. (a) Activation time: 0.1 s. Note that fluorescence is only
observed along the scan line (dashed) at the laser turning point region.
(b) Activation times: A: 1 s; B:2 s; C: 4 s
128
Figure 4 shows the absorbance of a gelatin matrix embedded sliver oxide nanoparticle film in the wavelength range between 250 and 900 nm. Trace A was obtained
from a luminescent film. The sample was activated to yield
maximum visible fluorescence from a 1 mm2 activated area.
Trace B was obtained from a non-activated area of the same
sample. The increase in absorbance around 300 nm can be
attributed to the absorption of the gelatin matrix itself, as evidenced from spectra taken of a pure gelatin film (not shown).
The maximum at 265 nm in spectra A and B most likely originates from silver oxide nanoparticles, because a pure silver
oxide thin film also exhibits an absorbance maximum at this
wavelength as can be seen from trace D in the inset of Fig. 4.
Trace C results from the difference of traces A and B. This
spectrum exhibits maxima at 290 nm and 425 nm, as well as
a shoulder around 610 nm.
Silver clusters with a diameter between 5 and 50 nm display a plasmon absorption resonance at about 410 nm [15, 16].
This plasmon peak shifts to longer wavelength under the influence of the dielectric gelatin matrix and also as a function
of the matrix filling factor [1618]. A new peak in the optical
spectrum around 400 nm has also been observed after thermal
annealing of silver oxide thin films and it has been assigned to
the formation of nanometer-sized silver clusters [19].
Absorption spectra of silver clusters in photosensitive
glass display, in addition to this plasmon absorption, a peak
around 300-nm wavelength which has been attributed to a molecular absorption of very small, not yet metallic, silver clusters [16]. Also, atomic silver clusters with one to four atoms
that are stabilized by encapsulation in an organic matrix material exhibit distinct absorption bands at 424 and 520 nm [20].
These bands are found to coincide with the electronic transitions calculated and observed for small silver clusters, in
particular Ag2 and Ag3 , in this spectral region [21, 22].
Thus, the absorbance spectrum (trace C in Fig. 4) clearly
identifies the fs-laser-activated generation of nanometer-sized
silver particles exhibiting the plasmon absorption around
400 nm. However, it furthermore provides indications of the
initial formation of atomic silver clusters consisting of only
a few atoms which are expected to be responsible for the observed luminescence properties of the activated silver oxide
nanoparticle films.
3.4
Luminescence characterization
FIGURE 5 Series of lines written with the focused fs-laser into a gelatin
embedded Ag2 O nanoparticle film. (a) Image recorded in reflection of an
unfocused tungsten lamp with the color digital camera showing the microscopic structure of the film after activation. Note the apparent formation of
metallic silver at the laser turning point on the left-hand side. (b) False-color
fluorescence image: Ar+ /Kr+ -laser (ecx = 568 nm)-excited fluorescence,
recorded with the photomultiplier after long-pass filtering (LP 590). (c)
Real-color fluorescence image: Hg-lamp (ecx = 546 nm)-excited fluorescence, recorded with the color digital camera after long-pass filtering (LP
590, transmitted wavelength trans > 590 nm). (d) Real-color fluorescence
image: Hg-lamp (ecx = 363366 nm)-excited fluorescence, recorded with
the color digital camera after long-pass filtering (LP 430, transmitted wavelength trans > 430 nm)
GLEITSMANN et al.
129
Exposure-time-dependent
spatial luminescence distribution
As distinct from the previously investigated fslaser-activated pure silver oxide nanoparticle films [11], luminescence from the fs-laser-activated areas of gelatin polymer
matrix embedded silver oxide particle films can already be
excited with light from a weak mercury lamp. Activated sam-
130
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