RIKEN Review No.

49 (November, 2009): Focused on Ultrafast Optical Sciences

3D optical data storage

Satoshi Wada,∗1 Andong Xia,∗2 and Hideo Tashiro∗1
∗1
Fundamental Technology Development Division, Advanced Engineering Center, RIKEN
∗2
National Synchrotron Radiation Laboratory, University of Science and Technology of China

A new approach for multilayered optical data storage is demonstrated here. in this technology we
find that photo-oxidation may increase the fluorescence intensity of molecule by two-photon excitation in
a wide wavelength region (780–910 nm) from a 100 fs Ti:sapphire laser. The proposed scheme encodes the
digital bits by photo-oxidation of induced by two-photon excitation, and reads the increase in fluorescence
from the oxidation area. The high-fluorescence signal can easily be distinguished as bit 1, and the low-
fluorescence signal, as bit 0. This change in the fluorescence intensity could be used to encode information
for read-only memory.

Introduction ple with a spot size of 15 µm diamater through an objective

Successful isolation and purification of macroscopic quanti-
ties of fullerene clusters have generated in a huge amount
of interest in the physical and chemical properties of these
carbon structures. Fullerenes are now anticipated to have
a number of applications in future nano-photonics science
and technology.1–4) Recently, we successfully demonstrated
the three-dimensional (3D) optical data storage and
read from the enhanced fluorescence of the photo-oxidation5)
products.
The highly symmetric π-electron density distribution of the
icosahedral cage may considerably enhance the two-
photon absorption of powerful femtosecond pulse light.6)
We further note that the fluorescence is also enhanced in
ambient air after two-photon irradiation in a wide wavelength
region (780 nm–910 nm) from 100 fs Ti:sapphire laser. There-
fore, the two-photon-induced photo-oxidation of C60 may also
be a subject of interest for application to 3D optical data
storage. In this review, we introduce a new approach for
multilayered optical data storage in -doped polystyrene
film. The proposed scheme encodes the digital bits by photo-
oxidation of C60 induced by two-photon excitation in a wide
wavelength region. We report that the fluorescence inten-
sity. -doped polystyrene film is significantly increased
in areas that have been exposed to a sufficient dose from the
100 fs, 82 MHz Ti:sapphire laser. This change in the fluo-
rescence intensity could be used to encode information for
read-only memory (ROM). The fluorescence properties and
photo-oxidation induced by two-photon ex-
citation have been investigated.
Experimental
The investigated films were prepared as described else-
where.5) The C60 -doped polystyrene film with porous struc-
ture was coated to a thickness of about 200 µm on a micro-
scope slide glass in air at room temperature. A mode-locked
Ti:sapphire laser pumped by an argon ion laser was used
for two-photon excitation, which was focused onto the sam-
(10 x, NA 0.25). Typical intensity of the laser at the focal
point is 3.5 GW/cm2 . This objective served as both the fo-
cusing lens and fluorescence collecting lens. The pulse width,
continuously monitored by an intensity autocorrelator, was
about 100 fs, and the pulse repetition rate was 82 MHz as
measured with a fast photodiode. The Ti:sapphire laser was
used not only for fluorescence measurement but also for
photo-oxidation . The C60 -doped polystyrene film was
mounted upon a computer-controlled programmable X-Y-Z
translation stage. This stage permits precise (1 µm) linear
translation of the sample with a maximum displacement of
2.5 cm in all directions, and a wide range of velocities. The
data writing processes in the film were performed in air by
keeping the Ti:sapphire laser beam focused at a fixed position
and moving the sample through the focused beam point by
point. The irradiation dwell time per exposed point was also
controlled by a computer. We obtained the photo-oxidation
points in the sample. To read these points, the film was then
sealed carefully with a cover slide glass and wax in a N2 envi-
ronment such that further photo-oxidation of C60 was blocked
to enable nondestructive reading. Fluorescence was detected
through an emission band-pass filter (D680/32) in order to
receive fluorescence wavelengths between 664 nm and 696 nm.
Results and discussion
ithas a complex absorption band structure extending from
400 nm to 650 nm.7) The two-photon-induced fluorescence
from C60 is extremely weak, but the relative fluorescence
spectral distributions from one- and two-photon-excitation
are very similar (data not shown). This suggests that the
same excited states are reached regardless of the excitation
mode. Figure 1 shows the two-photon excitation fluorescence
spectra of C60 -doped polystyrene film under Ti:sapphire laser
irradiation (910 nm, 100 fs, 82 MHz, and 50 mW) in air. We
find that the fluorescence signal is weak with a broad peak
at about 730 nm before extended laser irradiation of the
sample in air, and after 30 s irradiation in air, the fluores-
cence intensity increases 3-fold with a peak shift to about
715 nm. The enhancement of the fluorescence might

52

Fig. 1. Fluorescence spectra of C60 doped polystyrene film under
100 fs, 82 MHz, 50 mW Ti:sapphire laser irradiation at 910 nm,
for different exposure times of (a) 0 s and (b) 30 s.
result from the decrease in symmetry of the oxidized C60
in the polystyrene induced by two-photon excitation. Fig-
ure 2 shows the irradiation time dependence of the fluores-
cence intensity of C60 -doped polystyrene film in air at dif-
ferent excitation wavelengths. Similar to the case of one-
photon excitaion, the relative fluorescence intensities at var-
ious excitation wavelengths show a rapid increase followed
by a slow decay with the irradiation time. The finding that
the photo-oxidation rate of C60 , under irradiation at the same
power is much faster at a shorter wavelength than at a longer
Fig. 2. Irradiation time dependence of the fluorescence intensities in
the wavelength region between 664 nm and 696 nm for C60 -doped
polystyrene film in an air environment with an irradiation power
of about 50 mW at various wavelengths. (a) 830 nm, (b) 880 nm,
and (c) 910 nm.
Fig. 3. (a) Fluorescence intensity vs distance along the X-direction in the X–Y plane. (b) Fluorescence intensity vs distance along the
Z-direction in the X–Z plane. The exposure time for each point is marked above the peak. Fluorescence was observed in the wavelength
region between 664 nm and 696 nm.
wavelength was unexpected. In fact, UV light is highly effi-
cient for C60 photo-oxidation.8) In the one-electron descrip-
tion the one-photon excitation of C60 between the highest oc-
cupied molecular orbital-lowest unoccupied molecular orbital
(HOMO-LUMO) is strongly dipole-forbidden due to the cen-
trosymmetric structure of the molecule, while the third-order
optical polarizibility is always allowed. Two-photon excita-
tion is a third order effect in nonlinear optics. After photo-
oxidation, some higher excited singlet states are also reached
with greater probability by two-photon excitation in the near
UV region than in visible region. This may be the reason why
the photo-oxidation rate is higher at 830 nm than at 910 nm
at the same excitation power. However, the changes of the
fluorescence intensity induced by two-photon excitation can
be blocked in an air-free environment, and nondestructive
reading becomes possible for two-photon excitation.5, 9)
When the oxidized areas in C60 -doped polystyrene films are
exposed to a reading laser beam, the fluorescence becomes
much stronger than in the non-oxidation areas, and the high-
fluorescence signals can easily be distinguished as bit 1 and
the low-fluorescence signals from nonoxidation areas, as bit
0. This change in fluorescence intensity could be used to
encode information for read-only memory. Figure 3 shows a
demonstration of this 3D optical data storage. Seven points
in the sample were selected along the X-direction on the same
line in the X–Y plane with the desired distances from one
another by moving the computer-controlled, and another six
points were chosen along the Z-direction on the same line
in the X–Y plane in the same manner as before. All the
points were irradiated with focused 880 nm, 100 fs, 82 MHz,
50 mW Ti:sapphire laser for different durations. The recorded
bit data was read nondestructively with a low two-photon
excitation power of about 30 mW at 880 nm after the film
was sealed carefully with a cover slide glass and wax in a
N2 environment to block photo-oxidation. For reading these
data, the sample stage was scanned at a rate of 50 µm/s along
both X- and Z-directions. The results for the 3D data storage
in C60 -doped polystyrene film are shown in Figs. 3 (a) and
(b), where (a) represents the data written in the X–Y plane
and (b), that in the X–Z plane. We obtained the FWHM of
about 5 µm for one point in the X–Y plane, and FWHM of
about 12 µm for one point in the X–Z plane.
The oxidation of C60 was very sensitive to light with energy
higher than its LUMO. For two-photon induced fluorescence
of C60 , the excitation rate for the process is proportional to
the square of the incident intensity, and excitation is hence
53
confined to the focal volume, where the excitation intensity References
is extremely high. C60 molecules could reach the excited 1)
state by simultaneously absorbing two photons; this simul-
taneous absorption may also result in the photo-oxidation of
C60 . The oxidation area was confined to the focal volume, 2)
therefore it is possible to increase the data storage density by 3)
two-photon-induced photo-oxidation. We did not attempt
4)
any optimization to obtain high-density storage, due to the
limitation of the experimental configuration used.
5)
6)
Summary
We demonstrated 3D optical data storage with photo- 7)
oxidation of C60 pumped by the fs Ti:sapphire laser. How-
ever, the writing speed of our demonstration experiment is
still much too slow for practical use. Recently, we noted 8)
that some polymer composites with C60 as the photosensi-
tizer could produce highly efficient optical property changes
under both one-and two-photon excitation with very fast re- 9)
sponse times of several microseconds. Thus, very fast writing
can be achieved with such a memory system.
54
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