1. Field of the Invention
The disclosure relates generally to optical data storage and, more specifically, to the use of photochromic and fluorescent components in high capacity optical memories.
2. Description of the Related Art
Present optical memories rely on multilayer structures to store large numbers of bits. Referring to
The polycarbonate layer 14 interposed between the aluminum coating 16 and the light source must be transparent to the reading wavelength to allow the incident beam to reach the aluminum mirror 16. This limitation restricts the storage capacity of CDs to a single layer of pits and bumps. In an effort to enhance the volume of recordable information, semi-reflective overlayers have been introduced in digital versatile disks (DVDs). These media can have up to two storing and overlapping layers per disk face and, therefore, extend their capacity in the direction normal to the disk surface. Nonetheless, data storage in three dimensions cannot be implemented in full with this technology. As a result, a number of strategies for the development of three-dimensional optical storage media have been actively pursued in recent years.
Photochromic molecules have been investigated as candidates for use with high-capacity optical memories. The photochromic molecules have the ability to switch from colorless to colored forms in response to optical stimulations, and this switching ability can be used to store binary digits (i.e., 0 and 1). The stored information can be retrieved optically following diverse protocols. For example, the covalent attachment of a fluorescent label to a photochromic switch enables the written data to be read by measuring the emission intensity. This method, however, often requires a multi-step synthetic procedure for the integration of fluorescent and photochromic fragments into the same molecular skeleton.
Embodiments of the invention address deficiencies of the art in respect to storage devices and provide a novel and non-obvious optical storage device. The optical storage medium has a multilayer structure that includes a photochromic layer having a thermally-stable photochromic compound, and a fluorescent layer having a fluorescent compound. The photochromic compound is transformable between a first form and a second form. The fluorescent compound has an excitation wavelength centered in a region that is not substantially absorbed by the second form of the photochromic compound, and an emission wavelength that is absorbed by the first form and not absorbed by the second form.
In certain aspects of the optical storage medium, the excitation wavelength is centered in a region that is not substantially absorbed by the first form of the photochromic compound. The photochromic compound may be selected from the group consisting of azulenes, azobenzenes, stilbenes, fulgides, diarylethenes, and spiropyrans. Also, the first form of the photochromic compound may be merocyanine and the second form may be spiropyran. The fluorescent compound may be benzofurazan.
In other aspects of the invention, an optical storage reading/recording device for reading/recording data on an optical storage medium is provided. The optical storage reading/recording device includes a fluorescing light source emitting light having a first wavelength, a transforming light source emitting light having a second wavelength; and a detector sensitive to light having a third wavelength. A fluorescent layer of the optical storage medium emits light having the third wavelength upon exposure to the first wavelength. The photochromic layer of the optical storage device includes a photochromic compound transformable between a first form and a second form upon exposure to light having the second wavelength.
Additional aspects of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The aspects of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
The accompanying drawings, which are incorporated in and constitute part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention. The embodiments illustrated herein are presently preferred, it being understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown, wherein:
A optical storage device according to the invention is disclosed in
Although not limited in this manner, the optical storage medium 100 may be formed by respectively coating first and second substrates 112, 122, with the photochromic layer 110 and the fluorescent layer 120. The substrates 112, 122 can then be sandwiched together to form the optical storage medium 100.
The photochromic layer 110 includes a photochromic component. Photochromism is defined as a reversible transformation in a chemical species between two forms having different absorption spectra by irradiation, and thus, the photochromic component has two forms having different absorption spectra. As used herein, the photochromic component includes a first form and a second form. In the first form (also referred to as the colored state), the photochromic component substantially absorbs in a wavelength emitted by a fluorescent component of the fluorescent layer 120. In the second form (also referred to as the colorless state), the photochromic component does not substantially absorb in a wavelength emitted by the fluorescent component of the fluorescent layer 120.
As illustrated in
A second light source 140 is used to illuminate the photochromic layer 110 to induce the interconversion between the colorless and colored forms of the photochromic component of the photochromic layer. The colorless and colored form of the photochromic component may be selected so as to be transparent at the wavelength used to excite the fluorescent component. In this manner, the fluorescent layer 120 can be excited without affecting the photochromic component 130, whereas the photoinduced interconversion of the photochromic component of the photochromic layer 110 may be used to modulate the light emitted from the fluorescent layer 120.
A third light source may be included, which for purposes of discussion may be considered to be included within the second light source 140, although the optical storage device 200 is not limited in this manner. The third light source is used to illuminate the photochromic layer 110 to reverse the effect of the second light source 140. Thus, while the second light source 140 may induce interconversion from the colorless form to the colored form (or vice-versa), the third light source may induce interconversion from the colored form to the colorless form (or vice-versa).
If the photochromic component of the photochromic layer 110 is thermally stable, then the second light source 140 can write binary digits into the photochromic layer 110, where the bits will remain stored. The first light source 130, in combination with the detector 150, can then read the bits at any point in time thereby resulting in all-optical storage medium 100 in which data can be written, read and erased relying exclusively on optical signals. Examples of a thermally-stable photochromic compound include a diarylethene or a furylfulgide.
If the photochromic component of the photochromic layer 110 is thermally unstable, then the amplitude of the optical signal propagating from the first light source 130 to the detector 150 can be modulated by switching on and off the second light source 140. This result is an all-optical inverter in which an optical input from the second light source 140 gates an optical output from the first light source 130.
The optical storage medium 100 is not limited in the manner in which the photochromic layer 110 is formed. In certain aspects, organic photochromes may be trapped in a rigid polymer matrices following, for example, evaporation or spin-coating procedures. The encaged dopants may retain their photochromic properties, and thin films of the resultant material may be deposited on a variety of supports/substrates.
Although not limited the following list, the photochromic component of the photochromic layer 110 may be selected from azulenes, azobenzenes, stilbenes, fulgides, diarylethenes and spiropyrans. For purposes of the following examples, studies were based on the reversible photoisomerization of spiropyrans. Referring to
Referring to Table 1, following spin-coating procedures, the photochromic dopant of spiropyran was trapped within five different polymer films deposited on quartz plates. The amount of dopant in each polymer matrix is about 3.6% in weight relative to the polymer. The five polymer matrices are polymethylmethacrylate (PMMA), polystyrene (PS), polyethylmethacrylate-polymethylmethacrylate (PEMA-PMMA), poly-1-butylmethacrylate-poly-n-butylmethacrylate (PiBMA-PnBMA) and poly-n-butylmethacrylate (PnBMA). The photochromic layers 110 were prepared from dichloromethane solutions of spiropyran (3 mg mL-1) and one of the polymers (95 mg mL-1). Aliquots of these solutions were spin-coated on quartz plates at 480 rpm for 12 seconds.
Using surface profilometry, the thickness of the films was determined to range between about 2 and about 5 μm. Although the absorption spectra of these polymer films do not reveal significant absorbance in the visible region, the characteristic visible absorption band of merocyanine developed in all materials upon irradiation at a wavelength of 341 nm.
Tg is the glass transition temperature of the polymer matrix. The dipole moment of the polymer is represented by μ, and the values listed for the two copolymers PEMA-PMMA and PiBMA-PnBMA are the averages of the values of the constituent polymers. The wavelength of the visible absorption band of merocyanine is represented by λ. The absorbance raise constant for the photoinduced coloration (341 nm, 8 μW cm-2) is kUV, the absorbance decay constant for thermal decoloration is represented by kDark, and the absorbance decay constant for the photoinduced decoloration (562 nm, 320 μW cm-2) is represented by kVIS.
Referring to
Under continuous irradiation at 341 nm, the absorbance at λ increases exponentially with the irradiation time for all the doped polymers, and the absorbance decreases gradually when the light source is turned off or if the irradiation wavelength is changed to 562 nm. It is noted that all of the doped polymers retain a residual absorbance at λ after reaching thermal equilibrium. By contrast, the absorbance at λ is negligible at the photostationary state obtained after irradiation at 562 nm.
The absorbance at λ of either one of the above photochromic films can be modulated efficiently by switching the irradiation wavelength between ultraviolet and visible regions.
The absorbance changes for all coloration and decoloration steps fit respectively monoexponential raise and decay profiles. The associated raise (kUV) and decay (kDark and kVIS) constants for coloration are listed in Table 1. The coloration raise and decay constants decrease monotonically as the glass transition temperature (Tg) of the polymer matrix increases, with the exception of PS. The deviation of PS from this trend may be a result of its lower μ.
Referring to Table 2, the relative influence of the rigidity and polarity of the medium on the coloration and decoloration steps is further demonstrated from the values of kUV, kDark and kVIS determined in four solvents. The initial concentration of spiropyran in each solvent is 1×10-4 M.
All three constants (kUV, kDark, and kVIS) increase as the μ of the solvent decreases. The coloration and decoloration constants in the polymer matrixes with low Tg are similar to those constants in solvents with high μ. The coloration rates (kUV, kDark and kVIS) of PnBMA, which has a relative low Tg of only 15° C., are comparable to the coloration rates of MeCN and DMF, which have a relatively high dipole moment μ greater than 3.8 D. For this reason, in certain aspects of the optical storage medium 100, this polymer matrix is used for the photochromic layer 110 illustrated in
The optical storage medium 100 is not limited in the manner in which the fluorescent layer 120 is formed. For example, a fluorescent compound may be evaporated onto or spin-coated onto a substrate 122. The fluorescent component within the fluorescent layer 120 of the optical storage device 110 is not limited as to a particular fluorescent compound. However, in certain aspects of the optical storage medium 100, an excitation wavelength of the fluorescent compound is centered in a region that is not substantially absorbed by either the first form or the second form of the photochromic compound within the photochromic layer 110. Also, the emission wavelength of fluorescent compound is absorbed by the first form of the photochromic compound but not absorbed by the second form of the photochromic compound. Under these conditions, an exciting beam can travel substantially unaffected through the photochromic layer 110 to the fluorescent layer 120 and the emitted light from the fluorescent layer 120 can propagate through the photochromic layer 110 and back to the detector 150 only when the photochromic layer is in the colorless state. Although not limited in this manner, the fluorescent compound may include benzofurazan (
Similar to the procedures described with regard to the polychromic component, polymethylmethacrylate (PMMA) films containing this benzofurazan were spin-coated onto quartz slides to obtain a film having a thickness of about 1 μm. The fluorescent layer 120 was prepared from dichloromethane solutions of benzofurazan (0.2 mg mL-1) and PMMA (100 mg mL-1). Aliquots of this solution was spin-coated on quartz plates at 1000 rpm for 5 seconds.
Referring to
The photostationary state (e.g., about 85%) is reached in about 360 seconds. When the second light source 140 is turned off, the colored merocyanine reverts partially to the colorless merocyanine, and the detected intensity increases from 85 to 91% in about 520 seconds. The photostationary state is again reached in about 660 if the ultraviolet source is turned on again, as spiropyran switches back to merocyanine. In this manner, the intensity of the fluorescence output can be switched from high to low values by turning the ultraviolet input from off to on and vice-versa. In operation, binary digits can be encoded in the input (off=0, on=1) and output (low=0, high=1) under a positive logic convention, and output is 0 when the input is 1 and vice-versa. The detected emission intensity is high (binary 1) when the input is off (binary 0), and the detected emission intensity is low (binary 0) when the input is on (binary 1). The inverse relation between the input and output bits corresponds to a NOT function.
A change in irradiation wavelength from 341 nm (ultraviolet) to 562 nm (visible) switches the photochromic compound from one photostationary state to the other in about 830 seconds. The photoinduced re-isomerization from merocyanine to spiropyran results in an increase of detected intensity to 98%; and thus, the photoinduced fluorescence recovery is significantly more efficient than the corresponding thermal process, which is in full agreement with the absorbance changes observed for the photoinduced and thermal decoloration of the five polymers in Table 1. Only partial decoloration occurs in the dark (see
If the visible source is turned off after reaching the photostationary state, a fraction of spiropyran isomerizes to merocyanine. Thermal equilibrium is reestablished, and the detected intensity drops to 94% in about 370 seconds. In this manner, the intensity of the fluorescence output can be switched from low to high values by turning the visible input from on to off and vice-versa. In this manner, the light emitted by the fluorescent layer 120 can be exploited to read the state of the photochromic layer 110. Additionally, the fluorescence reading does not alter the state of the photochromic switch.
Although merocyanine absorbs the light emitted by benzofurazan, the number of absorbed photons is not sufficiently high to significantly alter the ratio between spiropyran and merocyanine. The fluorescence trace for this step was constructed by reading the state of the system 210 times over an interval of 1260 seconds. As shown, the detected intensity decreases over time, which indicates an increase in the concentration of the absorbing state merocyanine. Despite the merocyanine having absorbed 210 times the fluorescence of benzofurazan, its concentration increases rather than decreases since the emitted light is too weak for the photoinduced decoloration to overcome the opposing thermal decoloration.
The photoinduced changes in fluorescence intensity illustrated in
Although not limited in this manner, a determination may be made that an intensity value above the logic threshold corresponds to a binary 1, and any intensity value below the logic threshold corresponds to a binary 0. For example, an ultraviolet input can switch the state of the system from 1 (a) to 0(b). If the input is turned off, the intensity increases. However, the intensity still remains below the logic threshold, even after reaching thermal equilibrium (c), which still corresponds to a binary 0. In this manner, the binary 0 written optically in the photochromic layer 110 is stored by the optical storage device 200.
The bit can be erased by illuminating the photochromic film 110 with a visible input. Under these conditions, the detected intensity raises above the logic threshold, and the bit is switched from a binary 0 back to binary 1. If the visible input is turned off after reaching the photostationary state (a), the detected intensity returns gradually to the value at thermal equilibrium (c), and it has been determined, using the above described configuration of materials, that it takes about 670 seconds to reach the logic threshold. Therefore, the binary 1 is stored only for a relatively short retention time. This limitation, however, can be overcome by replacing spiropyran within the photochromic layer 110 with a thermally-stable photochromic compound, for example, a diarylethene or a furylfulgide.
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/US2006/013203 | 4/6/2006 | WO | 00 | 10/4/2007 |
Number | Date | Country | |
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60669222 | Apr 2005 | US |