WO2006098296A1

WO2006098296A1 - Optical storage medium making use of oligothiophene

Info

Publication number: WO2006098296A1
Application number: PCT/JP2006/304952
Authority: WO
Inventors: Tamejiro Hiyama; Masaki Shimizu; Yukio Kawanami; Hirohisa Kanbara; Yuhei Mori; Takashi Kurihara; Masafumi Adachi; Yutaka Sasaki; Seiji Akiyama
Original assignee: Kyoto University; Nippon Telegraph And Telephone Corporation; Pioneer Corporation; Mitsubishi Chemical Corporation; Rohm Co., Ltd.
Priority date: 2005-03-14
Filing date: 2006-03-14
Publication date: 2006-09-21
Also published as: JP4623515B2; TW200705090A; JP2006293292A

Abstract

A highly efficient two-stage-excited hologram memory or other optical storage medium making use of a compound, such as an oligothiophene compound, that although being high in the efficiency of generation of singlet excited state and triplet excited state, is not apt to immediately induce a chemical reaction involving a structural change, etc.; and an organic composition for production of optical storage medium wherein an organic mixture constituting this optical storage medium is contained. There is provided an optical storage medium of organic mixture characterized by having not only a two-stage-excited energy donor capable of being excited to a singlet excited state by irradiation with a first exciting light, subsequently being transferred to the lowest triplet excited state by intersystem crossing and thereafter being excited to a higher triplet excited state by irradiation with a second exciting light but also an energy acceptor capable of receiving energy from the energy donor and feeding the energy to a chemical reaction.

Description

Specification

Optical storage media using oligothiophene

Technical field

[0001] The present invention relates to an organic composition comprising a two-stage excited energy donor via a highly excited triplet state, an energy acceptor that receives energy from the energy donor, and an organic composition. The present invention relates to an optical storage medium having an organic mixture power produced by using the same.

Background art

[0002] As a holographic memory, a one-step excitation type holographic memory, that is, by simultaneously irradiating an object beam carrying data on an optical storage medium and a reference beam to form interference fringes of these two beams, this interference A hologram memory is known in which the intensity distribution of fringes is stored as data, and then diffracted light is generated by irradiating the optical memory medium with reference light, and data is reproduced from the diffracted light.

[0003] When an optical storage medium such as this hologram memory has a layer structure, the recording layer is usually a single layer, and there is a limit to meet the recent demand for large capacity storage. One effective method for overcoming such a limit is to stack a plurality of recording layers.

[0004] However, in the case of using a laminate in which a plurality of recording layers are laminated, it is difficult to realize the case of the one-step excitation type. That is, when recording data on a plurality of recording layers, first, as shown in FIG. 7 (a), a single storage layer al is irradiated with reference light and object light to store the data. Subsequently, as shown in FIG. 7 (b), the other storage layer a2 is irradiated with reference light and object light to record other data. At this time, as shown in FIGS. 7 (a) and 7 (b), the object light passes not only the layer a2 but also other layers including the layer al. At this time, there arises a problem that the data of the layer in which the data of the layer al and the like are stored is erased. Furthermore, the same applies to data reproduction. As shown in Fig. 7 (c), when data in one layer is reproduced, the reproduction light erases data in the other layer.

[0005] As a promising technique for solving this problem, there is a method of applying a two-stage excitation type optical storage medium via a highly excited triplet state as shown in FIG. In the example of hologram memory For example, as shown in FIG. 8 (a), when the first excitation light (= gate light) is irradiated, only that layer becomes the lowest triplet excited state and recording becomes possible. By irradiating (= reference light + object light), it becomes a highly excited triplet excited state, and interference fringes due to two-beam interference are fixed in the medium as a structural change (refractive index change), resulting in optical storage Is performed. On the other hand, as shown in Fig. 8 (b), the layer that has not been irradiated with the first excitation light is not in a state that can be memorized to the lowest triplet excited state. Even if it is irradiated with (body light), triplet excited state is not obtained, so two-beam interference does not occur and optical storage is not performed. For this reason, even if there is already stored data, the layer not irradiated with the first excitation light is not erased.

That is, in the two-stage excitation type, irradiation with both the first excitation light and the second excitation light is necessary for optical recording. As shown in FIG. It is the first time to irradiate the object light on which data is loaded and the reference light that interferes with this object light and generates interference fringes after being excited to the recordable triplet excited state. The donor can be in a higher triplet excited state, and optical recording is possible.

[0007] On the other hand, even if only the object light and the reference light are irradiated without irradiating the gate light, as shown in FIG. 8 (b), the energy donor is in the lowest triplet excited state that can be recorded. Since it cannot be excited, optical recording is impossible, and data is not erased in the layer not irradiated with the gate light.

[0008] Biacetyl (butane 2, 3 dione, see Non-Patent Document 1) and force rubazole (9H force) are used as organic materials for such a two-stage excitation type hologram memory via a highly excited triplet state. Luvazole, see Non-Patent Document 2) is known.

In the methods described in Non-Patent Documents 1 and 2, when biacetyl or force rubazole is excited to a highly excited triplet excited state (T 1), a structural change occurs, and as a result, It is described that the interference fringes formed by the reference light are fixed as a change in the refractive index in the medium, so that the hologram can be recorded and reproduced.

[0010] Since these biacetyls and force rubazoles have low efficiency, the diffraction efficiency of the reference light, which is an index indicating the hologram memory's reproduction efficiency, is 1%. For this purpose, a thickness of at least 200 xm is required. For this reason, biacetyl and As long as strong rubazole is used, it is difficult to realize a thin film type optical storage medium with a practical thickness of several meters per meter.

By the way, as a method for improving the diffraction efficiency, there are a method of increasing the intensity of the light source and a method of increasing the light density by shortening the focal length of the condensing lens. However, according to these methods, the above-mentioned biacetyl and force rubazole had a problem that the necessary gate light irradiation intensity becomes too high and photodamage occurs.

On the other hand, oligothiophene compounds (see Non-Patent Document 3) are known as organic materials that generate highly excited triplet states.

[0013] Non-Patent Document 1: Opt. Lett., 7, 177 (1982) (Chr. Brauchle et al)

Non-Patent Document 2: Opt. Lett., 6, 159 (1981) (G. C. Bjorklund et al) Non-Patent Document 3: J. Phys. Chem., 100, 18683 (1996) (R. S. Becker et al) Disclosure of the Invention

Problems to be solved by the invention

However, when using an oligothiophene compound, a highly excited triplet excited state

Even if excited by (T), it cannot be expected that a chemical reaction such as a structural change will immediately occur from there, and optical recording cannot be performed as it is.

That is, as described in Non-Patent Document 3, the oligothiophene compound is conventionally predicted by theory or the like to have high generation efficiency of a singlet excited state or a triplet excited state. However, chemical reactions such as structural changes are unlikely to occur immediately, and cannot be applied to optical storage media such as hologram memory.

Therefore, the present invention uses a compound such as an oligothiophene compound that has high generation efficiency of a singlet excited state or a triplet excited state, but hardly causes a chemical reaction such as a structural change immediately. An object of the present invention is to provide an optical storage medium such as a highly efficient two-stage excitation type hologram memory, and an organic composition for forming an organic mixture constituting the optical storage medium.

Means for solving the problem

[0017] In the present invention, the first excitation light irradiation is excited to a singlet excited state, and then a transition to the lowest triplet excited state is made by intersystem crossing, followed by second excitation light irradiation. Characterized in that it has a two-stage excitation type energy donor excited to a higher triplet excited state and an energy acceptor that receives energy from the energy donor and donates powerful energy to a chemical reaction. By using an optical storage medium having an organic mixture power, the above-mentioned problems have been solved.

The invention's effect

[0018] Since the present invention uses a specific energy donor and energy acceptor, energy is transferred from the energy donor excited to the triplet excited state to the energy acceptor, and the passed energy is used for a chemical reaction. Can be provided. Thus, energy can be appropriately supplied to the chemical reaction, optical recording can be performed more reliably, and an optical storage medium such as a highly efficient two-stage excitation type hologram memory can be provided.

[0019] Further, when an oligothiophene compound is used as an energy donor, this compound has high generation efficiency of a singlet excited state or a triplet excited state. Therefore, when a hologram memory is produced using this compound, High diffraction efficiency can be obtained, and the memory medium can be made into a practical number / m thin film.

[0020] Further, the application of the present invention is not limited to the hologram memory, and is not usually adapted to interference fringes at any spot (= dot) inside the medium through the two-step excitation process by light irradiation. This can also be applied to the case where the refractive index change is caused at low power. In this case, it can be realized with two beams of the first excitation light and the second excitation light. For example, it is possible to cause a refractive index change at an arbitrary spot where two beams overlap with a three-dimensional medium. It becomes possible.

Brief Description of Drawings

[0021] [Fig. 1] Schematic diagram of energy-excited states, showing the energy acceptance relationship between energy donors and energy acceptors.

[Fig.2] Diagram showing manufacturing process of optical storage media by blade coating method and thermocompression bonding method

[Fig. 3] Schematic diagram showing a transient absorption measurement device that measures the excitation energy of a compound.

[Fig.4] Schematic diagram showing the method of hologram experiment

[Figure 5] Graph showing the results of the hologram experiment (percentage of diffracted light generated for one hour)

[Figure 6] Graph showing the results of the hologram experiment (comparison with the conventional material biacetyl) [Fig. 7] Schematic diagram showing the problems of conventional one-step excitation memory

[Figure 8] Schematic diagram of the energy excitation state showing the relationship between data recording and photoexcitation

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the optical storage medium of the present invention will be described in detail with a focus on application to a hologram memory. The present invention is directed to an optical storage medium comprising an organic composition containing a predetermined energy donor and an energy acceptor, and an organic mixture prepared using the organic composition.

[0023] The energy donor refers to a compound that has high generation efficiency of a singlet excited state and a triplet excited state, such as an oligothiophene compound, but is unlikely to cause a chemical reaction such as a structural change immediately. The generation efficiency of the singlet excited state or the triplet excited state is high, and the compound is high in the efficiency of being excited to the singlet excited state by the first excitation light irradiation. It refers to a two-stage excitation type compound that has high efficiency for intersystem crossing to a state and high efficiency for excitation to a higher triplet excited state by irradiation with second excitation light.

[0024] The energy acceptor refers to a compound that receives energy from the energy donor and is in a lowest triplet excited state and can easily donate energy to a chemical reaction. That is, since the energy level of the triplet excited state of the energy acceptor is about the same or slightly smaller than the energy level of the triplet excited state of the energy donor, the energy acceptor of the energy acceptor becomes easy. A compound that can donate most of the obtained energy to the chemical reaction is preferable.

[0025] An example of the energy accepting relationship between the energy donor and the energy acceptor can be shown in FIG. First, by providing the energy donor with the first excitation light that is the gate light, the energy donor is changed from the ground state (S 1) to the singlet excited state (S 1), etc.

0 1 Next, the transition to the lowest triplet excited state (τ) occurs at the intersystem crossing. Then, by applying the second excitation light (in the case of a hologram, object light and reference light), a higher triplet excited state (τ) is obtained.

[0026] Next, energy is transferred (ET) from the energy donor in the triplet excited state (T) to the energy acceptor. As a result, the energy donor is in the ground state (S)

On the other hand, the energy acceptor becomes the lowest triplet excited state (τ) etc. And Does the energy acceptor donate the obtained energy to the chemical reaction and return to the ground state (S)?

0

Or the reaction product.

[0027] In order to exert such a state, the S — T excitation energy of the energy donor

0 n

And the absolute value of the difference between the S — T excitation energy of the energy acceptor is 0 to 1.5 eV

0 1

0 to 1. OeV is preferred. 1. If it is greater than 5 eV, energy transfer tends to not be successful. It should be noted that the S — T excitation energy of the energy donor

0 n

The difference that is larger than the S-T excitation energy of the container falls within the above range.

0 1

preferable.

[0028] When the energy donor and the energy acceptor as described above are used, a structural change (= refractive index change) occurs due to a chemical reaction by the energy obtained by the energy acceptor.

As a result, optical recording is performed.

[0029] Next, an energy donor and an energy acceptor constituting the optical storage medium will be described. The energy donor and energy acceptor are not particularly limited as long as they can exhibit the above functions. However, among them, there are preferable energy donors and energy acceptors, and examples thereof will be described here.

[0030] Examples of the preferable energy donor include an oligothiophene compound represented by any one of the following formulas (11 :!) to (14).

[0031] [Chemical 11]

(1 -2)

[0032] In the formulas (11 :!) to (14), X to X, X to X, X to X, and X to X are water.

1 6 7a 7b 8a 8d 9a 9f Elementary atoms, alkyl groups, groups in which some carbon atoms of alkyl groups are replaced with silicon atoms, halogens, hydroxyl groups, alkyloxy groups, aryloxy groups, dialkylamino groups and the like can be mentioned. And the above-mentioned X to X, X to χ, X to Χ, X

1 6 7a 7b 8a 8d 9a

˜x may be the same or different.

9f

[0033] Of these, oligothiophene compounds as shown in the following formula (2) are more preferable. The compound represented by the formula (2) is a compound represented by the formula (13) or the formula (14), and x = x = x = x = x = x = x = x = x = x = x = x = x = x = x =

2 3 4 5 8a 8b 8c 8d 9a 9b 9c 9d 9e 9f A hydrogen atom, X represents Si (R) (R) (R), and X represents Si (R) (R) (R). Also, R to R are hydrogen atom, alkyl group, halogen, hydroxyl group, alkyloxy group, aryl

1 6

A group selected from an oxy group and a dialkylamino group; Furthermore, R to R are the same.

1 6

But it's different. Furthermore, n represents 4 or 5.

[Chemical 12]

[0035] Specific examples of the oligothiophene compound represented by the above formula (2) include compounds represented by the following formulas (2— :!) to (2-5).

[0036] [Chemical 13]

[0037] [Chemical 14]

[0038] [Chemical 15]

(2-3)

[0039] [Chemical 16]

[0041] Furthermore, among the oligothiophene compounds represented by the formula (2), R to R force S

16, an alkyl group having 1 to 2 carbon atoms, an alkyl group having 6 to 10 carbon atoms, an aryleno group, an alkenyl group, an alkynyl group, an alkoxy group, a pyridinole group, or a compound having a thiophenone ring is used as the energy donor. In particular, R ~ R, R ~

1 3 4

For each of R, at least one of them is an alkyl group having 6 to 10 carbon atoms, an aryl group,

6

A compound showing an alkenyl group, an alkynyl group, an alkoxy group, a pyridinole group or a thiophene ring is more preferred. Specific examples thereof include compounds represented by the above formulas (2-2) to (2-5).

[0042] The ability to introduce alkyl groups via silicon atoms is known to contribute to solubility, for example, J. Mater. Chem., 10, 1471–1507, (2000). However, in the case of oligothiophene with a limited conjugated molecular length, the effect becomes even more apparent.

That is, when pentathiophene is substituted with η-decyl groups at both ends of the molecule (a compound represented by the following formula (2-5) ′) and when substituted with decyldimethylsilyl groups ( In the above formula (compound represented by 2_5)), the latter can dissolve 3-4 orders of magnitude and weight of the former in the same solvent.

[0044] Specifically, a compound represented by the following formula (2_5) 'has a solubility in chloroform of less than 0.05 mg / ml, a solubility in toluene of less than 0.05 mgZml, and In contrast, the compound represented by the formula (2-5) has a solubility in chloroform of 200 mgZml or more, a solubility in toluene of 300 mgZml or more, and a solubility in hexane. Indicates 100 mg / ml or more.

[0045] [Chemical 18]

[0046] When the trioctylsilyl group is substituted, the oligothiophene can be liquefied even at a temperature close to room temperature, and an amorphous medium having a concentration of 100% can be formed. Such a compound can be used, for example, as an optical recording medium or a non-linear optical medium by enclosing it in a hollow chiral container.

[0047] Thus, substitution of the alkylsilyl group allows other low-molecular compounds to be dissipated near the oligothiophene site by allowing the substituted compound to be dispersed in the matrix at a high concentration. Inclusive molecular interactions that can be selectively placed into can be expressed. As will be described later, in the 5, 5 "" bis (decinoledimethylsilyl) pentathiophene represented by the formula (2-5) and the azide compound represented by the formula (3-2), Near-neighbor placement is possible, and it is possible to achieve high-efficiency optical writing that cannot be achieved with other combinations.

[0048] The oligothiophene-based compound has a singlet excited state (S) and a triplet excited state (T).

The 1 n production rate is usually 1 digit or more, preferably 2 digits or more, and more preferably 3 digits or more, compared to biacetyl, which is conventionally known as a compound that can be excited in two steps. Among them, the compound represented by the general formulas (1 D to ₄₎ has a production rate several thousand times higher than that of biacetyl, and is particularly preferably used as the energy donor of the present invention.

[0049] Next, the energy acceptor is not particularly limited as long as it is a compound that receives energy from the energy donor and is in the lowest triplet excited state and can easily donate energy to a chemical reaction. Among these, preferred energy acceptors include azide compounds represented by the following formula (3).

[0050] [Chemical 19]

[0051] In the formula (3), Y represents an alkyl group, a halogen, an azide group, a sulfonyl group, an aryl group, a hydroxy acid A group having at least one group selected from a group and an alkoxy group, or a hydrogen atom;

Specific examples of such azide compounds include azide compounds represented by the following formula (3-1) or (3-2).

[Chemical 20]

[0054] When the azide-based compound is in a triplet excited state, the reaction shown in the following reaction formula <1> occurs to generate triplet nitrene and nitrogen molecules. This triplet nitrene then undergoes chemical reactions such as coupling reactions, addition reactions to double bonds, and hydrogen abstraction reactions. For this reason, when an energy acceptor composed of the azide compound is used, triplet nitrene causes a structural change in the polymer compound that disperses the energy donor and the energy acceptor in the irradiated portion. Due to this, the force S for generating a change in refractive index is positive.

[0055] [Chemical 22]

(-Ns) * ^ R-F + z <1>

[0056] When calculated using density functional theory, S — of the oligothiophene compound

0

The excitation energies of T are 3.65eV (when 340nm, n = 2) and 3.05eV (when 407nm, n = 3), while the excitation energy of S — T of the azide compound is 3. 64e V (340 nm, for compound (3-1)), 3.47 eV (357 nm, for compound (3-2)). Although there are some high and low numerical values, these compounds can be used in combination as an energy donor and energy acceptor.

By the way, it is important that the optical storage medium is uniform and excellent in flatness. For example, in a hologram experiment, when the surface of the medium is not flat or striae occur inside the medium, the beam of the object beam and the reference beam hardly overlap each other. This is because the interference fringes created by this phenomenon are difficult to fix as a refractive index change in the medium. Therefore, as shown in FIG. 2, a method for producing an optical storage medium uniformly and flatly by combining the blade coating method and the thermocompression bonding method will be described.

[0058] First, the above-mentioned energy donor and energy acceptor are mixed and dispersed at a predetermined ratio to obtain an organic composition which is a solution for an optical storage medium. Each of the energy donor and energy acceptor may be a single compound or a mixture of two or more compounds.

[0059] The energy donor and the solvent for dispersing the energy acceptor are not particularly limited as long as the energy donor and the energy acceptor have sufficient solubility and do not damage the material of the substrate. It is not limited. Preferable examples of this solvent include tetrahydrofuran (THF), xylene, monochrome benzene, toluene, mesitylene and the like.

[0060] Further, as the polymer compound in which the energy donor and the energy acceptor are dispersed, polymethylmetatalylate (PMMA), cyanoacrylate, optical cycloolefin polymer (manufactured by Nippon Zeon Co., Ltd .: trade name) ZEONEX).

Next, as shown in FIG. 2 (a), the optical storage medium solution is dropped onto the substrate. And figure

2 As shown in FIG. 2 (b), a sweeping process is performed in which the optical storage medium solution is flattened by sweeping the substrate with a blade that maintains a constant distance from the substrate (see FIG. 2 (c)). )). Next, after such sweeping, the solvent is removed by heating (Fig. 2 (d)), and then the obtained medium is peeled from the substrate (Fig. 2 (e)). Next, a heating process is performed in which the obtained medium is sandwiched between two substrates and heated under pressure (FIG. 2 (f)). Thereafter, by peeling the medium from the substrate (FIG. 2 (g)), a thin film type optical storage medium with improved flatness can be produced. When the obtained optical storage medium is thin, a plurality of sheets such as two are stacked and thermally compressed in the same manner as in the method of FIG. As a result, a thick-film optical storage medium is obtained (FIG. 2 (h)). After the step of FIG. 2 (c), the step of FIG. 2 (f) may be performed by placing the substrate on the medium without performing the steps of FIG. 2 (d) and (e).

[0062] In addition to the blade coating method described above, a coating method such as a spin coating method, a spray method, a wire bar method, or a U method may be used as a method for applying the optical storage medium solution to the substrate. Can do.

Example

Hereinafter, the present invention will be described more specifically with reference to examples.

Example 1 (Production of oligothiophene compound)

[Production of compound represented by formula (2-1)]

Compound represented by formula (2-1) (5, 5 '"' bis (t-butyldimethylsilyl) 2, 2 ':

5 ', 2 ": 5", 2 "': 5" ', 2' '' '—kincatiophene) production method and compound data are shown.

[0065] [1] Production of 2 tributylstannyl-5 (t-butyldimethylsilyl) thiophene

In an argon atmosphere, 0 · 74 g (8.8 mmol) of thiophene (Aldrich) in 18 ml of tetrahydrofuran was dissolved in a solution kept at −30 ° C., 5.8 ml (8.8 mmol, Hexane solution) was added dropwise. After stirring the mixed solution at the same temperature for 2 hours, 1.4 g (9. Immol) of t_butylchlorodimethylsilane (manufactured by Aldrich) was added, and the mixture was further stirred at the same temperature for 1 hour. To this mixed solution, butyl lithium 6. Oml (9. lm mol, hexane solution) was added dropwise and stirred at the same temperature for 2 hours. Then, 2.8 g (8.8 mmol) of chlorotributyltin (manufactured by Aldrich) was added. In addition, the mixture was further stirred at the same temperature for 1 hour. The mixed solution was stirred overnight at room temperature, diluted with jetyl ether, and poured into vigorously stirred ice-cold saturated brine. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 5. lg of a crude product.

170. This crude product. By performing Kugelrohr distillation at C, 0.3 Torr, 2.6 g of 2_tributylstannyl-5- (t-butyldimethylsilyl) thiophene was obtained. Yield is 60%.

[0066] [2] Production of compound represented by formula (2-1)

To 4 ml of toluene, add 2 tributylstannyl-5- (t-butyldimethylsilyl) 0.59 g (0.80 mmol) of ophen, 5, 5 ,,-dibromo-2,2 ': 5', 2,-terthiophene (Aldrich) 0 · 16 g (0.4 mmol) and tetrakis (triphenylphosphine) A solution in which 46 mg (0.040 mmol) of palladium (0) (manufactured by Aldrich) was mixed was heated and stirred at 120 ° C. for 18 hours in an oil bath under an argon atmosphere.

The reaction solution was concentrated under reduced pressure to remove toluene, and the residue was washed with dry ethyl acetate and extracted with dichloromethane. The dichloromethane solution was concentrated to obtain 0.1 llg (0.17 mmol) of an orange powder of the compound represented by the formula (2-1). The yield was 42%.

[0067] The ¹ H_NMR, ¹³ C_NMR, and MS spectra of the obtained compound are as follows.

'H-NMR (200MHz, CDCI) σ 7.24 (AB, J = 3.5Hz, 2H), 7.14 (AB, J =

Three

3.5Hz, 2H), 7.10 (AB, J = 3.8Hz, 2H), 7.07 (AB, J = 3.8Hz, 2H) 7.07 (s, 2H), 0.94 (s, 18H), 0.31 (s, 12H) ppm

^{[0068] - 13 C-NMR} (50MHz, CDCI) σ 141.98, 137.09, 136.29, 135.89, 135

Three

.83, 135.66, 124.77, 124.34, 124.26, 124. 18, 26.42, 17.02—4.8 3ppm

[0069] -FAB-LRMS for C H S Si: 641 ([M + H] +, 60), 640 (M +, 100), 583

32 40 5 2

([M-tBu] ⁺ , 25)

[0070] Further, the dry ethyl acetate layer used in the washing was concentrated, and the resulting residue was washed with dry acetonitrile to give 5,5'-bis (t-butyldimethylsilyl) -2,2'-bithiphene. · 006 8 g (0.017 mmol) of yellow powder was obtained. The yield was 43%.

[0071] ¹ H-NMR and MS spectra of the obtained compound are as follows.

'H-NMR (200MHz, CDCI) σ 7.25 (AB, J = 3.5Hz, 2H), 7.13 (AB, J =

Three

3.5Hz, 2H), 7.13 (AB, J = 3.5Hz, 2H) 0.95 (s, 18H), 0.30 (s, 12H) pp m

[0072] -FAB-LRMS for C H S Si: 396 ([M + 2] +, 4), 395 ([M + l] +, 7), 39

30 34 2 2

4 (M +, 13), 379 ([M_Me] +, 1), 337 ({M_t_Bu} +, 14)

[0073] [Production of compound represented by formula (2-2)]

Compound represented by formula (2-2) (5, 5 '"' _ bis (dimethylphenylsilyl) 1 2, 2 ': 5', 2": 5 ", 2"': 5 "', 2 Manufacturing method and compound data of Show.

[0074] [1] Production of 2-tributylstannyl-5- (dimethylfuelsilyl) thiophene

Under an argon atmosphere, 1.9 ml of butyllithium (5.Ommol, hexane solution) was added dropwise to a solution kept at -30 ° C by dissolving 0.42 g (5.Ommol) of thiophene in 10 ml of tetrahydrofuran. After stirring this mixed solution at the same temperature for 2 hours, 0.88 g (5.2 mmol) of Kokuguchi dimethylvinylsilan (manufactured by Aldrich) was added, and the mixture was further stirred at the same temperature for 1 hour. To this mixed solution, 2.4 ml (6.2 mmol, hexane solution) of butyllithium was added dropwise and stirred at the same temperature for 2 hours. Then, 2.0 g (6. Ommol) of chlorotributyltin was added. Stir at temperature for 1 hour. The mixed solution was stirred overnight at room temperature, diluted with jetyl ether, and poured into ice-cooled saturated brine that was vigorously stirred. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 2.9 g of a crude product.

200 of this crude product. Kugelrohr distillation at C, 0.3 Torr gave 2_tributylstannyl-5- (dimethylphenylsilyl) thiophene 1 · 6 g. The yield was 64%.

[0075] [2] Production of compound represented by formula (2-2)

To 8 ml of toluene, 0 · 81 g (l.6 mmol) of 2-tributylstannyl-5- (dimethylphenylsilyl) thiophene was added, and 5, 5 "—dib-mouthed 2, 2, ': 5', 2" — A solution in which 0. 32 g (0.8 mmol) of terthiophene and 92 mg (0.080 mmol) of tetrakis (triphenylphosphine) palladium (0) were mixed was heated and stirred at 120 ° C. for 18 hours in an oil bath under an argon atmosphere. The reaction solution was concentrated under reduced pressure to remove toluene, and the residue was washed with dry ethyl acetate and extracted with dichloromethane. The dichloromethane solution was concentrated to obtain 0.31 g (0.46 mmol) of an orange powder of the compound represented by the formula (2-2). The yield was 57%.

[0076] ¹ H_NMR, ¹³ C_NMR, and MS spectra of the obtained compound are as follows.

• 'H-NMR (200MHz, CDC1) σ 7.55—7.62 (m, 4Η), 7.35—7.43 (m, 6

Three

H), 7.24 (AB, J = 3.6 Hz, 2H), 7.16 (AB, J = 3.6 Hz, 2H), 7.09 (AB, J = 3.8 Hz, 2H) 7.07 (s, 2H), 7. 06 (AB, J = 3. 8Hz, 2H), 0. 61 (s, 12H) ppm [0077] - 13 C-NMR (50MHz, CDC1) σ 142. 72, 137. 95, 137. 93, 136. 37, 136

Three

07, 136. 04, 135. 97, 133. 85, 129. 41, 127. 88, 125. 04, 124. 55, 12 4. 34, 124. 29, —1. 22ppm

[0078] [Production of compound represented by formula (2-3)]

Compound represented by formula (2-3) (5, 5, ..., bis (trioctylsilyl) -2, 2,: 5, 2 ": 5", 2 "': 5"', 2 " "—Kinkachiobean) production method and compound data are shown.

[0079] [1] Production of 2_tributylstannyl _ 5_ (trioctylsilyl) thiophene

Under an argon atmosphere, 0.42 g (5 Ommol) of thiophene was dissolved in 10 ml of tetrahydrofuran, and 3.3 ml (5 mmol, hexane solution) of butyllithium was added dropwise to a solution kept at -30 ° C. After the mixed solution was stirred at the same temperature for 2 hours, 1.9 g (5.2 mmol) of chlorotrioctylsilane (manufactured by Aldrich) was added and further stirred at the same temperature for 1 hour. To this mixed solution, 3.4 ml (5.2 mmol, hexane solution) of butyllithium was added dropwise and stirred at the same temperature for 2 hours. Then, 1.9 g (5.2 mmol) of chlorotributyltin was added, and the same solution was added. Stir at temperature for 1 hour. The mixed solution was stirred overnight at room temperature, diluted with jetyl ether, and poured into ice-cooled saturated brine that was vigorously stirred. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 3.7 g of a crude product.

This crude product was subjected to Kugelrohr distillation at 250 ° C. and 0.3 Torr to obtain 2.3 g of 2-tributylstannyl-5- (trioctylsilyl) thiophene. The yield was 63%.

[0080] [2] Production of compound represented by formula (2-3)

To 6 ml of toluene, 0.90 g (l. 22 mmol) of 2-tributylstannyl-5- (trioctylsilyl) thiophene, 5, 5 ,,-dibromo-2,2 ': 5', 2, ...- terthiophene A solution in which 0.25 g (0.61 mmol) and tetrakis (triphenylphosphine) palladium (0) 70 mg (0.061 mmol) were mixed was heated and stirred at 120 ° C. for 18 hours in an oil bath under an argon atmosphere.

The residue from which volatile components were removed by vacuum distillation at 120 ° C and 0.3Τοιτ was purified by volume exclusion chromatography, and 0.26 g (0.22 mmol) of an orange oily substance represented by the formula (2-3) was obtained. )Obtained. Yield 37. /. Met.

[0081] The ¹ H_NMR, ¹³ C_NMR, and MS spectra of the obtained compound are as follows.

'H-NMR (200MHz, CDCI) σ 7. 24 (AB, J = 3.5Hz, 2H), 7. 12 (AB, J =

Three

3.5 Hz, 2H), 7.10 (AB, J = 3.8Hz, 2H), 7.07 (AB, J = 3.8Hz, 2H), 7.0 7 (s, 2H), 1.22— 1.46 (m, 72H), 0.76— 0.96 (m, 30H) ppm

^{[0082] - 13 C-NMR} (50MHz, CDCI) σ 141.85, 137.61, 136.48, 135.97, 135

Three

.66, 135.34, 124.84, 124.31, 124.26, 124. 16, 33.69, 31.94, 29.2 8, 29.21, 23.73, 22.70, 14.13, 13.37ppm

[0083] -FAB-LRMS for C H S Si: 1146 ([M + H] +, 87), 1145 (M +, 100),

68 112 5 2

1033 ([M—Oct + H] +, 10), 1032 ([M—Oct] +, 10)

[0084] As a by-product, 5, 5,, ',,, _bis (trioctylsilyl) _2, 2': 5 ', 2 ": 5", 2 "': 5" \ 2 " ": 5" ", 2" ": 5" "', 2" "": 5 "" ", 2,,,,, --Otathiophene 0.077g (0.055mmol) of red pasty solid was obtained . The yield was 18%.

[0085] The ¹ H_NMR and MS spectra of the obtained compound are as follows.

'H-NMR (200MHz, CDCI) σ 7.23 (AB, J = 3.5Hz, 2H), 7.12 (AB, J =

Three

3.5Hz, 2H), 7.07 (br s, J = 3.8Hz, 12H) 1.22— 1.46 (m, 72H), 0.76 -0.96 (m, 30H) ppm

^{[0086] - 13 C-NMR} (50MHz, CDCI) σ 141.71, 137.62, 136.50, 136.12, 135

Three

.79, 135.63, 135.49, 135.25, 124.81, 124.29, 124.12, 33.75, 32. 01, 31.66, 29.34, 29.28, 23.81, 22.78, 22.74, 14.22, 13.49 ppm [0087] -FAB-LRMS for CHS Si: 1391 ( [M + H] +), 1390 (M +)

80 118 8 2

[0088] [Production of compounds represented by formula (2-4) and formula (2-5)]

A compound represented by formula (2-4) (5,5 ′ ′ ′ monobis (decyldimethylsilyl) quaterthiophene) and a compound represented by formula (2-5) (5,5 ′ ′ ′ ′-bis The production method and compound data of (decinoledimethylsilyl) pentathiophene) are shown.

[0089] [1] Manufacture of decinoredimethyl (2'_chenyl) silane (compound represented by the following formula (4_1))

[Chemical 23]

(4-1)

Si (Me) ₂ C ₁₀ H ₂₁ [0090] Thiophene (1.68 g, 20. Ommol) dissolved in anhydrous THF (40 mL) was cooled to 20 ° C and butynolethium (13. OmL, 20. Ommol, 1.6 M in hexanes) was added to it for 30 minutes. It was dripped slowly. The mixed solution was warmed to room temperature and stirred for 1 hour. Again, after the solution was cooled to 20 ° C., a THF solution (10 mL) of black-decyldimethylsilane (4.70 g, 20. Ommol) was quickly added. The solution was warmed to room temperature and stirred overnight, and then 50 mL of an aqueous salt ammonium solution was added. The aqueous phase was extracted three times with 10 mL of jetyl ether, and the combined organic phases were washed with 150 mL of saturated brine. The organic phase is dried over anhydrous magnesium sulfate and concentrated using an evaporator. The resulting crude product is purified by silica gel chromatography (solvent hexane) to yield the desired product (5.03 g) in 89% yield. . / Obtained at ₀

[0091] TLC R value, H-NMR ¹³ C_NMR, IR, MS spectrum of the obtained compound

f

Is as follows.

• TLC: R = 0.85 (hexanes).

f

[0092] • 'H-NMR (400MHz, CDC1): σ = 0.31 (s, 6H), 0.77 (dd, J = 9.2, J = 6.

Three

4Hz, 2H), 0. 87 (t, J = 6.6 Hz, 3H

), 1.21—1.41 (m, 16H), 7.06 (dd, J = 3. 8, J = 3.2 Hz, 1H), 7.27 (d, J = 3.2 Hz, 1H) , 7. 60 (d, J = 3.8Hz, lH) ppm.

[0093] • ¹³ C—NMR (100 MHz, CDC1): σ = — 1. 81, 14. 13, 16. 61, 22. 69, 23.

Three

76, 29. 29, 29. 34, 29. 58, 29. 65, 31. 92, 33. 49, 128. 02, 130. 33, 13 4. 10, 139. 21 ppm.

[0094] • IR (KBr): 3076, 2922, 2853, 1499, 1465, 1407, 1250, 1213, 1082, 99 1, 810, 704cm— ¹ .

FAB-MS: m / z = 283/282 (5/34, M +).

[0095] [2] Production of 2-decyldimethylsilyl-5-tributylstannylthiophene (compound represented by the following formula (4-2))

[Chemical 24]

[0096] A decyldimethyl (2′-cenyl) silane (compound represented by the formula (41)) (2.82 g, 10. Ommol) obtained in the above-described method (30 mL) was added at 0 ° After cooling to C, butinorelithium (6.25 mL, 10. Ommol, 1.6 M in hexanes) was added dropwise thereto for 15 minutes. The suspension was warmed to room temperature and stirred for 1 hour. The yellow reaction solution was cooled to 0 ° C. and chlorotributylstannane (3.26 g, 10. Ommol) was added quickly. The mixture was warmed to room temperature and stirred overnight, and then 50 mL of a saturated aqueous solution of ammonium chloride was added to stop the reaction. The aqueous phase was extracted 3 times with 50 mL of jetyl ether, and the combined organic phase was washed with 50 mL of saturated brine and dried over anhydrous magnesium sulfate. The organic solvent was concentrated by an evaporator, and the obtained yellow crude product (5.44 g, 9.52 mmol, 95%) was directly used for the next coupling reaction without purification.

[0097] The ¹ H_NMR, ¹³ C_NMR, IR, and MS spectra of the obtained compound are as follows.

[0098]-'H-NMR (400MHz, CDC1): σ = 0.30 (s, 6H), 0.71— 0.97 (m, 14H),

Three

0. 99- 1. 21 (m, 6H), 1. 28— 1. 42 (m, 22H), 1. 44— 1.66 (m, 6H), 7. 1 6-7. 20 (m, 1H), 7.39 (bs, lH) ppm.

^{[0099] - 13 C-NMR} (100MHz, CDC1): σ = - 1. 63, 10. 84, 13. 66, 14. 13, 16.

Three

78, 17. 51, 22. 70, 23. 83, 27. 27, 28. 96, 29. 32, 29. 35, 29. 68, 31. 9 3, 33. 53, 134. 87, 136. 09 , 142. 13, 144. 97 ppm.

[0100] -IR (KBr): 2955, 2922, 2853, 1466, 1250, 1200, 1105, 837, 769cm " ¹ .

M + — C H).

4 9

[0101] [3] Production of compound represented by formula (2-4)

5, 5 _ Dibromo-1,2,2 '_bithiophene (311 mg, 960 mmol) in anhydrous toluene 15 mL was carefully degassed with argon, then 2 _decyldimethylsilyl _ 5 _tributylstannyl obtained by the above method Thiophene (a compound represented by the formula (4-2)) (1.65 g, 2.88 mmol) was calorie-free. Pd (PPh) (65.4 mg, 144 mmol, 15 mol%) was calorie free

3 4

The reaction solution was then heated at 120 ° C. for 24 hours. After the solvent was distilled off under reduced pressure, the crude product was washed with acetonitrile. The remaining solid was dissolved in 10 mL dichloromethane and filtered. B Silica gel was added to the liquid to adsorb the product, and then the solvent was distilled off under reduced pressure to obtain silica gel carrying the product. This was packed in a column tube, and the product was purified using a hexane / dichloromethane mixed solvent to obtain the desired product as a yellow solid (551 mg, yield 79%).

[0102] Mp of the obtained compound (melting point. The solvent in parentheses indicates the recrystallization solvent of the crystal used for the melting point measurement.), R value of TLC, 'H-NMR, ¹³ C_NMR, IR, MS SPET

f

The rules are as follows.

[0103] -Mp: 70 ° C (hexanes / dichloromethane).

TLC: R = 0.70 (hexanes: dich 丄 ormethane = 7: 丄

f

[0104] -'H-NMR (400MHz, CDCI): σ = 0.31 (s, 12H), 0.78 (dd, J = 9.2, J = 6

Three

.4Hz, 4H), 0.88 (t, J = 6.6Hz, 6H), 1.22-1.42 (m, 32H), 7.06 (d, J = 3.8Hz, 2H), 7.09 (d, J = 3.8Hz, 2H) , 7.13 (d, J = 3.4Hz, 2H), 7.23 (d, J = 3.4Hz, 2H) ppm.

^{[0105] - 13 C-NMR} (100MHz, CDCI): σ = - 1.92, 14.13, 16.49, 22.69, 23.

Three

79, 29.29, 29.35, 29.59, 29.66, 31.92, 33.47, 124.21, 124.39, 12 4.93, 134.98, 135.91, 136.30, 139.30, 141.98 ppm.

[0106] -IR (KBr): 3057, 2957, 2920, 2851, 1425, 1257, 1070, 984, 835, 802, 789cm " ¹ .

[0107] [4] Production of compound represented by formula (2-5)

5, 5 "'Follow the same procedure as for bis (decyldimethylsilyl) quaterthiophene (compound of formula (2-4)), 5, 5' '_ dibromo_2, 2': 5 ', 2 It was synthesized from __tatiophene and 2_decyldimethylsilyl_5-tributylstannylthiophene (compound represented by the formula (4-2)) as a bright orange solid with a yield of 76%.

[0108] Mp, TLC R value, H— NMI ^ ¹³ C_NMR, IR, MS of the obtained compound

f

The tuttle is as follows.

[0109] · Μρ .: 101-103 ° C (hexanes / dichloromethane).

• TLC: R = 0.5 (hexanes: dichlormethane = 1). [0110]-'H-NMR (400MHz, CDC1): σ = 0.32 (s, 12H), 0.79 (dd, J = 9. 2, 6. 4

Three

Hz, 4H), 0. 89 (t, J = 6. 6Hz, 6H), 1. 21— 1. 41 (m, 32H), 7. 07 (s, 2H), 7. 07 (d, J = 3.2Hz, 2H), 7.10 (d, J = 3.2Hz, 2H), 7.14 (d, J = 3.4Hz, 2H), 7.23 (d, J = 3.4Hz, 2H) ppm.

^{[0111] - 13 C-NMR} (100MHz, CDC1): σ = - 1. 93, 14. 13, 16. 48, 22. 69, 23.

Three

74, 29. 29, 29. 35, 29. 59, 29. 65, 31. 92, 33. 47, 124. 23, 124. 32, 12 4. 40, 124. 95, 134. 98, 135. 75 , 135. 97, 136. 41, 139. 34, 141. 93 pp m.

[0112] -IR (KBr): 3059, 2955, 2920, 2851, 1442, 1427, 1250, 1070, 988, 837, 791cm— ^1.- FAB-MS: m / z = 810/809/808/807 ( 14/19/26/3, M +).

[0113] (Example 2) [Excitation energy of oligothiophene compound and azide compound] Using the transient absorption measuring apparatus shown in Fig. 3, the energy donor of the compound represented by the formula (2-3) Measure T-T absorption and measure phosphorescence when falling to T force S

1 n 1 0

It was. In this device, the second harmonic or the third harmonic obtained through the second harmonic generator (SHG) or third harmonic generator (THG) of the Q switch YAG laser is used as pump light. In addition, using xenon lamp light as probe light, thiophene with TT absorption can measure TS (phosphorescence). Measurement result, T

I n 1 0 1

T absorption is 650nm, T-S enenoregi is 820nm; ^ IJ clear, n 1 0

From these, it was found that S-T enenoregi was 360 nm. Normal absorption spectrum

0 n

Torr measurements also showed that the S-S absorption was 405 nm.

0 1

[0114] Next, the S-T energy of the Tonolene solution of the compound represented by the compound (3-1) which is an energy acceptor and the compound represented by (3-2) (manufactured by Toyo Gosei Co., Ltd.) is measured. Figure 3

0 1

Measurements were made using the equipment shown. As a result, it was found that the compound (3-1) was 440 nm and the compound (3-2) was 500 nm.

From these results, it was experimentally confirmed that a suitable energy acceptor for the thiophene compound represented by the formula (2_3) is an azide compound represented by the formula (3-1) or the formula (3-2). It was done. Of course, for thiophene compounds, the side chain shape is slightly different. However, the energy level force will not be significantly different from the current measurement value.

For example, even when thiophene represented by the formula (2-1) is used, an azide compound represented by the formula (3-1) or the formula (3-2) can be used as an energy acceptor.

[0115] (Example 3) [Fabrication of optical storage medium]

As an energy donor, a compound represented by the formula (2_ 1) (5, 5 "" -bis (t-butyldimethylsilyl)-2, 2 ': 5', 2 ": 5", 2 "': 5 A thin film suitable for optical experiments was fabricated using “', 2” “—kinkathiophene) and DZDS with BAP-P as the energy acceptor.

[0116] First, thiophene (concentration: 0.1 wt%) and azide DZDS (concentration: 0.4 wt%) or BAP-P (concentration: 0.4 wt%) were mixed with the solvent tetrahydrofuran (THF) (concentration: 5.6 wt%). Heat and dissolve, and add a mixed solution of optical cycloolefin polymer (manufactured by Nippon Zeon Co., Ltd .: trade name ZEONEX, concentration 37.6 wt%) and mesitylene (concentration 56.3 wt%). Then, the solution was heated again and dissolved to prepare an optical storage medium solution (organic composition) used in the step of FIG. 2 (a).

[0117] Here, THF was used as a solvent for dissolving pentathiophene of formula (2-1) and azide DZDS or BAP-P (THF can be dissolved at room temperature), but in addition, four solvents ( It was confirmed that it can also be dissolved under heating in (xylene, monochlorobenzene, toluene, mesitylene). Of these four solvents, mesitylene was the best and had the greatest transparency when the solution returned to room temperature after heating. As a polymer that disperses pentathiophene of formula (2-1) and azide, polymethylmethalate (PMMA) cyanoacrylate was investigated, and as a result, optical cycloolefin polymer (Japan) Zeon Co., Ltd. (trade name: Zeonetas) was found to be optimal. However, PMMA cancyanacrylate can be a good dispersion medium if the side chain of pentathiophene is chemically modified to increase solubility.

[0118] Mesitylene was the most suitable solvent for dissolving optical cycloolefin polymer (product name: Zeonex, manufactured by Nippon Zeon Co., Ltd.), and pentathiophene and azide DZDS of formula (2-1) Alternatively, since mesitylene was also suitable as a solvent for dissolving BAP-P, an optical cycloolefin polymer (made by Nippon Zeon Co., Ltd .: trade name ZEONEX) added to the THF solution of pentathiophene and azide of formula (2-1) ) Mesitylene as solvent of the solution used. This mixed solution also had transparency and uniformity suitable for optical experiments when it returned to room temperature.

[0119] Figure 2 (b) (c) This substrate was used as a substrate for creating a flat solution for an optical storage medium by sweeping the substrate with a blade that keeps the distance from the substrate constant. In the example, an ordinary glass slide glass was used, but the present invention is not limited to this, and any glass substrate may be used as long as the surface of the quartz substrate and the like itself is flat.

[0120] In the step shown in Fig. 2 (d), the solvent (THF, mesitylene) was removed by beta-treating in an oven at 90 ° C for 60 minutes. The concentration of each component after beta is 0.3 wt% for thiophene, 1. Owt% for both DZ DS or BAP-P, and 98 for optical cycloolefin polymer (Nippon ZEON Co., Ltd .: trade name ZEONEX). It became 7wt%. If the beta time was 90 ° C and 60 minutes, the amount of residual solvent could be reduced to a level that would not interfere with optical experiments. Since the distance between the blade and the substrate can be arbitrarily changed, the film thickness after film formation can be controlled by this distance.

[0121] Although the film having undergone Fig. 2 (d) has uniformity without sufficient striae for optical memory experiments, there was a problem in flatness. In this example, the medium was peeled off from the slide glass. A thermocompression bonding process (Fig. 2 (f)) was held in which a 100 ° C heating was maintained for 30 minutes under pressure.

[0122] When sandwiching with a vise, a glass slide was pasted on both sides of the film, and a sandwich medium was sandwiched between the glass slides. The vise pressure was set to a level just before the slide glass was broken. The pressure to be applied was varied within this range, and several trials were conducted. As a result, the thickness and quality of the produced film were not greatly affected. It was confirmed that even with pressure, the film thickness and film quality were almost constant. The beta shown in Fig. 2 (f) was performed by putting the sampnore into a baking furnace with a vise sandwiched between them.

[0123] In the case of the DZDS and BAP-P solutions, the film when reaching Fig. 2 (g) is the film when the distance between the blade and the substrate in Figs. 2 (b) and (c) is 500 μm. Both thicknesses were 170 μm. The film quality was confirmed not only to show no striae but also to have a flatness on the surface of the medium that sufficiently contributed to the hologram experiment described later.

[0124] In the case where the produced optical storage medium is thin, for example, two samples having undergone FIG. 2 (g) If they are stacked and thermally compressed in the same manner as in FIG. 2 (f), a thick optical storage medium can be obtained (FIG. 2 (h)). Using the DZDS and BAP-P solutions, a film with a film thickness of 170 / m was fabricated, and two of them were stacked and thermocompression bonded. As a result, an optical memory thin film with a film thickness of 250 μm could be obtained. . The beta temperature was 100 ° C and this was done for 90 minutes. Even in this process, it was confirmed that the film quality had not only striae, but also had flatness sufficiently contributing to the hologram experiment of Example 4.

[0125] In this example, it was confirmed from the state of Fig. 2 (c) that it is possible to perform a hot pressing process in which the medium is not peeled off from the slide glass. If another slide glass is attached to the medium on the side not attached to the slide glass, and then the process shown in FIG. 2 (f) and subsequent steps, a medium having exactly the same film quality and film thickness can be produced. It was.

[Example 4] [Hologram experiment]

Using the medium obtained in Example 3, a hologram experiment was conducted with the system shown in FIG. 4, and the time dependence of the diffraction efficiency was measured. In the hologram experiment, the obtained medium (thickness 250 μΐη) was placed at the position of Sample in Fig. 4 and irradiated with gate light (Gate Laser) for the first excitation. Next, using a holographic laser as the second excitation laser, a beam splitter (BS) is used for reference light and object light (Object

light) and each medium was irradiated.

In this configuration, interference fringes generated by the object light and the reference light, which are the second excitation light, are fixed in the memory medium as the refractive index change in the area in the memorizable state first excited by the gate light. By measuring the ratio of the reference light diffracted from the fixed interference fringes, it is possible to know the potential as an optical storage medium.

In this example, a GaN laser (continuous light) with a wavelength of 410 nm was used for the first excitation light, and a semiconductor laser (continuous light) with a wavelength of 660 nm was used for the second excitation light. The angle between the object beam and the reference beam was 2 degrees. The spot size of incident light was 250 xm. The intensity of the incident light was 0.10 W / cm ^{2 for} the first excitation light, and 20 W / cm ² for the second excitation light for both the reference light and the object light.

In the configuration in FIG. 4, the diffraction efficiency is measured by temporarily blocking the object light during the measurement and measuring the ratio of the reference light diffracted by the interference fringes generated in the memory medium. That power S. Figure 5 shows the results of measuring the time dependence of the diffraction efficiency. This is a graph in which the amount of reference light passing through the sample is measured, and then the ratio of the diffracted light (Efficiency η (%)) is measured, and the time dependence thereof is plotted. In the figure, (1) indicates the case where the first excitation light is blocked and the second excitation light (both reference light and object light) is incident, and (2) indicates that the first excitation light is incident. The figure shows the case where both light and second excitation light (both reference light and object light) are input. From the experimental results, it was found that the diffraction efficiency increased in proportion to the square of the irradiation time in the case of (2), while the diffraction efficiency did not increase in the state of (1). When the first excitation light was irradiated and only either the object light or the reference light of the second excitation light was irradiated, no increase in diffraction efficiency was observed. Only when three beams of the first excitation (gate) light and the second excitation light (both reference light and object light) are applied to the sample, interference fringes are generated and diffraction of the object light is observed. This result indicates that interference fringes were formed in the optical storage medium of the present invention through a two-step excitation process.

In addition, the results here show that the energy level investigated in Example 2 is correct, and that the above-described interference transfer fringes due to structural changes caused by the energy transfer from thiophene to azide can be formed. It proves that the inventors' idea is correct.

[0130] The absolute value of the diffraction efficiency in Fig. 5 is as small as about 0.01%. The power or optical power density of the laser light source used in this example (= can be increased or decreased depending on the focal length of the condenser lens). This can be improved by changing the focal length of the force condensing lens using a higher intensity laser to a shorter focal length. The pentathiophene film has sufficient light resistance.

FIG. 6 shows the results of normalizing and plotting the diffraction efficiency (experimental results) of the conventional material biacetyl in accordance with the experimental conditions such as the irradiation light intensity in FIG. In biacetyl, the wavelength of the first excitation light is 410 nm, which is the same as that of thiophene, and the wavelength of the second excitation light is 830 nm. This is based on energy level differences. The thickness of the biacetyl film was 500 μm. Biacetyl was prepared by enclosing a biacetyl solution in a quartz cell with an optical path length of 500 xm. For the dispersion medium of biacetyl, use of cyanoacrylate, via The concentration of cetyl was 10 wt%.

[0132] Figure 6 shows that the potential of thiophene is about two orders of magnitude higher than that of biacetyl, considering that the concentration of thiophene in the media produced this time is 1/30 times that of biacetyl and the difference in film thickness. Yes. That is, in this example, a medium having a thiophene concentration of 0.3 wt% was produced, but an optical storage medium was produced by setting the thiophene concentration to the same level as that of biacetyl (and increasing the azide concentration accordingly) In addition, if the film thickness is equivalent to that of thiophene, the efficiency of the actually obtained medium is more than two orders of magnitude.

[0133] Therefore, if thinning is performed using a medium in which thiophene is dispersed at a high concentration, for example, even in a thinned medium considered to be impossible with biacetyl, that is, a medium thinned to several zm order, Practical diffracted light can be observed.

[0134] In Example 4, the state in which the structural change (refractive index change) based on light irradiation occurs in the optical storage medium through the two-step excitation process is shown in the area excited by the first excitation light (gate light). Although the observation light was observed by the phenomenon that the reference light was diffracted by the interference fringes generated by the two-beam interference between the object light as the second excitation light and the reference light, it passed through the two-step excitation process intended by the present invention. The optical storage medium is not limited to this, and the second excitation light may be one. As shown in Fig. 8, the lowest triplet state that can be recorded by the first excitation is obtained, and even if only one second excitation light is irradiated there, the structural change (refractive index change) occurs. If the change caused by the irradiation of the second excitation light is read by irradiating another light and observing the change in transmittance, etc., optical storage and reproduction can be performed. In Example 4, the appearance of structural change (refractive index change) was only confirmed by observation of diffracted light.

[0135] Therefore, in the three-dimensional optical storage medium, if the first excitation light and the second excitation light are irradiated, the structural change (refractive index change) occurs only in the overlapping portion of the two. In any form of 3D media, for example, a DVD storage layer with multiple layers, optical storage can be performed without the problem of data erasure as in the one-step excitation process described in Fig. 7. It becomes.

[Example 5]

Experiments similar to Example 3 were performed using thiophene represented by the formulas (2_4) and (2_5) (concentration and film thickness are the same as in Example 3). ,spin An optically good thin film was also produced by the coating method. In the spin coating method, pentathiophene was dissolved in mesitylene and DZDS was added and dissolved under heating. A mesitylene solution of an optical cycloolefin polymer (manufactured by ZEON CORPORATION: trade name ZEONEX) was added and dissolved therein, and a thin film was prepared with a spin counter. The rotation speed of the spin coater was 1500 rpm. The prepared spin coat thin film was 0.3 wt% of thiophene represented by the formulas (2-4) and (2-5), 1.0 wt% of DZDS, an optical cycloolefin polymer (manufactured by Nippon Zeon Co., Ltd.). : Product name ZEONEX) is 98.7 wt. /. Met. Both film thicknesses were 45 μm.

[Example 6]

A hologram experiment similar to that in Example 4 was performed using the film prepared according to Example 5 using the thiophene represented by the formula (2_5). As a result of using a medium manufactured by the same method as in Example 3 (the optical system including the applied wavelength is the same), similar hologram diffraction could be observed. Next, in the experiment using the spin coat thin film, although the signal intensity decreased corresponding to the decrease in the film thickness, the produced thin film had sufficient light resistance. As a result, it was possible to obtain results having the same efficiency as in FIGS. However, for materials with a large absorption coefficient of the first excitation light, such as thiophene, the physical thickness and the effective length become closer as the physical thickness of the medium decreases (the effective length decreases as the physical thickness decreases). Does not decrease). For this reason, the results examined in this example show that the difference in physical thickness between the 170 μm medium produced by the same method as in Example 3 and the spin coat thin film of 45 μm is about twice that expected. It was possible to obtain a large diffraction efficiency. That is, the result of the spin coat thin film of this example is based on the thiophene film of the present invention, in addition to the conclusion of the thick film produced by the method of Example 3, and the thiophene thin film even when the thickness force is in the S micron unit. It supported that practical hologram diffraction could be realized by the medium.

[0138] Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.

This application is based on Japanese patent applications filed on March 14, 2005 (Japanese Patent Application No. 2005-071431) and Japanese patent applications filed on November 28, 2005 (Japanese Patent Application No. 2005-342). 451), which is incorporated by reference in its entirety.

Claims

Claims Excited to the singlet excited state by irradiation with the first excitation light, then transitioned to the lowest triplet excited state by intersystem crossing, and then to the higher triplet excited state by irradiation with the second excitation light. A light comprising an organic mixture characterized by comprising: a two-stage excitation type energy donor excited by an electron; and an energy acceptor for receiving energy from the energy donor and donating energetic energy to a chemical reaction. Storage medium. 2. The optical storage medium according to claim 1, wherein the optical storage medium is an oligothiophene compound represented by the energy donor force S, the following formulas (11) to (14).

[Chemical 1]

X2 X3 X9a X¾ X9o X9d Xge A9f 4 Χδ (In the formulas (11 :!) to (14), X to X, X to Χ, X to ,, and X to Χ are hydrogen fields.

1 6 7a 7b 8a 8d 9a 9f Group, alkyl group, group in which some carbon atoms of alkyl group are replaced with silicon atom, group having halogen, hydroxyl group, alkyloxy group or aryloxy group, or dialkylamino group power Represents a group. X to x, X to x, X to x, X to χ are

1 6 7a 7b 8a 8d 9a 9f may be the same or different. )

[3] The optical storage medium according to [2], wherein the energy donor is an oligothiophene compound represented by the following formula (2).

[Chemical 2]

In the formula (2), R to R are a hydrogen atom, an alkyl group, a halogen, a hydroxyl group, an alkyl group.

1 6

A group having a xyl group or an aryloxy group, or a group selected from dialkylamino groups; R to R may be the same or different. N is 4 or 5

1 6

Show. )

[4] R to R are alkyl groups having 1 to 2 carbon atoms, alkyl groups having 6 to 10 carbon atoms, aryl

1 6

4. The optical storage medium according to claim 3, selected from a group, an alkenyl group, an alkynyl group, an alkoxy group, a pyridinole group, and a thiophene ring.

[5] The optical storage medium according to [3], wherein the energy donor is an oligothiophene compound represented by any one of the following formulas (2_ :!) to (2-5).

[Chemical 3]

[Chemical 4]

[Chemical 5]

(octy Ds— SS i— (octy l) ₃ (2-3)

[Chemical 6]

[Chemical 7]

6. The optical storage medium according to claim 1, wherein the energy acceptor is an azide compound represented by the following formula (3).

[Chemical 8]

(In Formula (3), Y represents a group having at least one group selected from an alkyl group, a halogen, an azide group, a sulfonyl group, an aryl group, a hydroxyl group and an alkoxy group, or a hydrogen atom. The )

7. The optical storage medium according to claim 6, wherein the energy acceptor is represented by the following formula (3-1) or (3-2).

[Chemical 9]

[8] A solution for an optical storage medium in which the energy donor according to any one of claims 1 to 5 and the energy acceptor according to claim 6 or 7 are dispersed is dropped on a substrate, and thereafter A thin film type including a sweeping step of flattening the optical storage medium solution by sweeping the substrate with a blade that maintains a constant distance from the substrate, and a heating step of increasing the flatness by heating under pressure. A method for manufacturing an optical storage medium.

[9] Excited to singlet excited state by first excitation light irradiation, then transitioned to triplet excited state by intersystem crossing, then excited to higher triplet excited state by second excitation light irradiation An organic composition for producing an optical storage medium, comprising: a two-stage excitation type energy donor, and an energy acceptor that receives energy from the energy donor and chemically imparts energetic energy. .