WO2004022665A1

WO2004022665A1 - Two-photon absorption materials

Info

Publication number: WO2004022665A1
Application number: PCT/JP2003/011186
Authority: WO
Inventors: Kenji Kamada; Yoichiro Iwase; Koji Ohta; Koichi Kondo
Original assignee: National Institute Of Advanced Industrial Science And Technology
Priority date: 2002-09-09
Filing date: 2003-09-02
Publication date: 2004-03-18
Also published as: JP4195937B2; AU2003261883A1; JPWO2004022665A1

Abstract

A two-photon absorption material which consists of at least one member selected from the group consisting of compounds represented by the general formulae (1) and (2) and which exhibits a two-photon absorption peak wavelength in a wavelength region within 250nm from the one-photon absorption peak wavelength and has a great two-photon absorption cross-section: (1) (2) wherein R1 and R2 are each independently hydrogen or alkoxy of 1 to 4 carbon atoms; n is an integer of 1 to 3; R3 is alkyl of 1 to 3 carbon atoms; and A- is RSO3- (wherein R is CF3, phenyl, tolyl, or alkyl of 1 to 3 carbon atoms), a halide anion, or ClO4-.

Description

Specification

Two-photon absorption material

Technical field

The present invention relates to a two-photon absorption material useful as a light limiting material, a curing material in two-photon absorption stereolithography, a three-dimensional memory material, a fluorescent dye material in a two-photon fluorescence microscope, and the like.

Background art

Conventionally, in the two-photon absorption material, dye compounds such as rhodamine and coumarin, and compounds such as dichenothiophene derivatives and oligophenylenevinylene derivatives have been used. However, these have a small two-photon absorption cross section indicating the two-photon absorption capacity per molecule, and particularly, the two-photon absorption cross section when using a femtosecond pulsed laser is 200 × ^10-50 cm ⁴ s ■ mo lecul e one ^¹ · photon ^"1 less than what is almost (Stephen Kershaw Pride goes, 'Two-Photon Absorpt i on in' Charac ter izat i on techniques and t abulat ions f or organi c nonl inear opt i cal materi al s ", ed. by Mark G. Kuzyk, Carl W. Dirk, chapter 7, pp. 515-654, Mercel Dekker, Inc. New York, 1988).

When the two-photon absorption cross section of a compound is small, one option is to increase the compound concentration in order to improve the two-photon absorption characteristics as a material. However, the solubility of the compounds is limited and significant improvements in properties are not possible. Also, increasing the concentration is not always an effective method because it may adversely affect other components in the two-photon absorption material. For example, in two-photon absorption stereolithography, three-dimensional memory, etc., the curability of the polymer may be impaired or the fluorescence intensity may be reduced due to concentration quenching. May affect the activity of living tissue.

If the two-photon absorption cross section of the compound is small and its concentration cannot be increased, the laser-peak intensity must be significantly increased if the two-photon absorption properties of the material cannot be improved. As a result, not only is a large-scale laser device required, but the material is easily degraded or even destroyed because of the use of high-intensity energies close to the material. Disclosure of the invention

The present invention has been made in view of the above-mentioned state of the art, and its main purpose is to have a huge two-photon absorption cross-section and to exhibit high two-photon absorption characteristics at a low concentration. It is to provide a new material.

The present inventor has conducted research while paying attention to the current state of the technology as described above, and as a result, a specific acetylene-based compound has a huge two-photon absorption cross section near a one-photon absorption peak, It has been found that it exhibits excellent properties as a two-photon absorption material at low concentrations. That is, the present invention provides the following two-photon absorption material, and application materials and devices using the same for various uses.

1. One-photon ultraviolet of the compound comprising at least one compound selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2)

• A two-photon absorption material that exhibits a two-photon absorption peak wavelength within a wavelength range of 250 nm or less from the visible and near-infrared absorption peak wavelengths;

(Wherein and R ₂ are the same or different and represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, and n represents an integer of 1 to 3;),

(Wherein, R ₂ and eta, the same R ₃ in the above is an alkyl group having 1 to 3 carbon atoms, A one is RS0 ₃ -. (Wherein R, CF _3, phenyl, tolyl or an alkyl group having 1 to 3 carbon atoms), halogen § anion or C10 ₄ - a;)..

2. It is composed of at least one compound selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2), and has one-photon ultraviolet, visible, and near-infrared absorption. Two-photon absorption peak within a wavelength range within 250 nm from the peak wavelength A light limiting material comprising a two-photon absorbing material exhibiting a wavelength;

(Wherein, R ₂ and n are the same as above. R ₃ is an alkyl group having 1 to 3 carbon atoms, A is RSCV (where R is CF ₃ , phenyl, tolyl or 1 carbon atoms. To 3), halogenanion or C1 C.;).

3. It comprises at least one compound selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2), and the compound has one-photon ultraviolet, visible, and near-infrared absorption. Curing material of photocurable resin for stereolithography consisting of a two-photon absorption material that exhibits a two-photon absorption peak wavelength within a wavelength range of 250 nm or less from the peak wavelength;

(Wherein and R ₂ are the same or different and represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, and n represents an integer of 1 to 3).

(Wherein,, R ₂ and n are the same as above. R ₃ is an alkyl group having 1 to 3 carbon atoms, A one is, RS0 ₃ - (wherein R is, CF _3, phenyl, an alkyl group having a tolyl or carbon number 1-3), halogen § anion or cio ₄ - a. ;).

4. It is composed of at least one compound selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2), and has one-photon ultraviolet, visible, and near-infrared absorption. A three-dimensional optical memory material comprising a two-photon absorption material exhibiting a two-photon absorption peak wavelength within a wavelength range of 250 nm or less from the peak wavelength;

(Wherein, and R ₂ are the same or different and each represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, and n represents an integer of 1 to 3.

/ ² (2)

(Wherein, R _{1 ¾} R ₂ and n are the same as above. R ₃ is an alkyl group having 1 to 3 carbon atoms, and A is RSO (where R is CF ₃ , phenyl, tolyl or carbon An alkyl group having a number of 1 to 3), halogen anion or C10 ₄ —;).

5. It is composed of at least one compound selected from the group consisting of the compounds represented by the general formula (1), and has a wavelength within 250 nm from the peak wavelength of one-photon ultraviolet, visible, and near-infrared absorption of the compound. A fluorescent dye material for a scanning two-photon fluorescence microscope, comprising a two-photon absorption material having a peak wavelength of photon absorption and exhibiting fluorescence;

(Wherein and R ₂ are the same or different and represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, and n represents an integer of 1 to 3). 6. A light limiting device in which the light limiting material described in item 2 above is arranged between the light condensing device and the collimating device.

7. Two-photon absorption equipped with a pulse laser generator, a pulse laser collector, a photo-curable monomer collector, and a mechanism for scanning a predetermined focusing position in the photo-curable monomer with a laser beam An optical molding apparatus, wherein the curing material according to item 3 is contained in a photocurable monomer.

8. Pulse laser generating device, pulse laser condensing device, three-dimensional optical memory material, mechanism for scanning a predetermined condensing position of the memory material with one laser beam, and three-dimensional optical memory device including an optical reading device Wherein the three-dimensional memory material comprises at least one compound selected from the group consisting of compounds represented by the following general formula (1), and comprises one photon ultraviolet, visible, near infrared A three-dimensional memory device having a two-photon absorption peak wavelength within a wavelength region within 250 nm from the absorption peak wavelength and exhibiting fluorescence;

9. A pulse laser generator, a pulsed laser condensing device, the three-dimensional optical memory material described in the above item 4, a mechanism for scanning a predetermined condensing position of the memory material with a laser beam, and A three-dimensional optical memory device equipped with a mechanism for detecting a change in refractive index.

10. A pulse laser generator, a pulse laser collector, the fluorescent dye material described in the above item 5, a mechanism for scanning a predetermined focusing position of the fluorescent dye material with a laser beam, and Two-photon fluorescence microscope equipped with a light detection device. The two-photon absorption material of the present invention comprises at least one compound selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following (2). The compound shows a peak wavelength of two-photon absorption in a wavelength range within 250 nm from a peak wavelength of one-photon ultraviolet, visible, and near-infrared absorption.

(Wherein, and R ₂ are the same or different and each represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, and n represents an integer of 1 to 3).

. (Wherein,, R ₂ and n are the same R ₃ in the above is an alkyl group having 1 to 3 carbon atoms, A- is RS0 ₃ - (wherein R is, CF _3, phenyl, tolyl or An alkyl group having 1 to 3 carbon atoms), halogen anion or C10 ₄ —;

In the above general formulas (1) and (2), the alkoxy group having 1 to 4 carbon atoms includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec_butoxy, tert —A straight-chain or branched alkoxy group such as butoxy group, etc. can be exemplified. As the alkyl group having 1 to 3 carbon atoms, a straight-chain or branched chain group such as methyl, ethyl, n-propyl, isopropyl, etc. Can be exemplified. Examples of the halogen anion include F-, CBr ", and Γ.

Specific examples of the compound represented by the general formula (1) and the compound represented by the general formula (2) include compounds represented by the following formulas (3), (4) and (5). it can.

(3)

The above compound can be produced, for example, by the methods described in the following known literatures 1 to 4 and the like. Other compounds can be produced by the same method.

1. Synthesis of diacetylene having St lbazolium group and evaluation of three-dimensional nonlinear optical properties using femtosecond Z-scan method (The 50th Annual Meeting of the Society of Polymer Science, Abstracts vol. 50, p. 728 )

2. Synthesis of diacetylenes containing styrylpyridine derivatives and two-photon absorption properties using the femtosecond Z-scan method (The 50th Symposium on Polymers, Abstracts vol. 50, p. 3318)

3. Synthesis of acetylene derivatives with styrylpyridyl groups and evaluation of two-photon absorption characteristics using the femtosecond Zscan method (Symposium of the 51st Annual Meeting of the Society of Polymer Science, vol. 51, (p. 696)

4. Two-photon absorpt i on proper ty of bis (pyridyl vinyl enephenylene) diacetyl ene der ivat ives (6 ^lh International Conference of Organized Non-inear Ear Optics (IC0N06); Abstracts; Lecture No .: Poster Session I, PS182001.)

The two-photon absorption material of the present invention may be used in the state of being dissolved in an organic solvent such as dimethyl sulfoxide or dimethylformamide, similarly to the compounds used in the above-mentioned known two-photon absorption material, or polymethacrylic acid. It may be used by doping it into a polymer such as methyl, or the compound itself may be used alone. Hereinafter, the present invention will be described in more detail with reference to the drawings.

FIG. 1 is a graph showing an example of the characteristics of the two-photon absorption material according to the present invention. More specifically, the bis (2,5-dimethoxy) used in Example 1 is represented by the following formula (3). It is a graph which shows the result of having investigated the two-photon absorption cross section about -4- (N-methyl -4- pyridyl vinylene) phenyl) butadiin triflate.

The solvent, concentration, measurement conditions for the two-photon extinction coefficient, etc. will be described in detail in Example 1.As is clear from FIG. 1, a remarkable increase in the two-photon absorption cross-sectional area at a wavelength shorter than 650 nm is obtained. giant two-photon absorption cross section of up to ^{^{2400 X 10- 5 ° cm 4 ·}} sec · mo l ecu le one ^¹ · pho t on- ¹ is obtained at a wavelength of 571 nm. This remarkable increase in the two-photon absorption cross section on the short wavelength side occurs near the peak wavelength of one-photon absorption in the visible region of 467 nm, and as shown in Examples 2 and 3 described later, the one-photon absorption always increases. A significant increase in the two-photon absorption cross section near the peak wavelength is obtained.

This property of a large two-photon absorption cross section is obtained in all compounds in the two-photon absorption material of the present invention comprising the compound represented by the general formula (1) and the compound represented by the general formula (2). Yes, all show peak wavelengths of two-photon absorption in a wavelength range within 250 nm from the peak wavelength of one-photon absorption. This is a new characteristic that has not been known before. The two-photon absorption material of the present invention can be effectively used for various uses described later by utilizing such characteristics.

For example, the compound represented by the general formula (1) and the compound represented by the general formula (2) can be used as a light-limiting material in a light-limiting device, a light-curing resin for stereolithography, It can be used effectively as an original optical memory material.

Further, among the compounds used in the present invention, the compound represented by the general formula (1) is a compound exhibiting fluorescence, and in addition to the above-mentioned applications, for example, as a fluorescent dye material in a scanning two-photon fluorescence microscope. Useful. It can also be applied as a three-dimensional memory material using its fluorescence. Hereinafter, various devices using the two-photon absorption material according to the present invention will be described. However, the use of the two-photon absorption material according to the present invention is not limited to these devices, and it goes without saying that excellent effects can be exhibited in other various devices. For simplicity of description, only the main components are shown in the illustrated device, but other known components (not shown) are used in a practical device.

FIG. 2 is a schematic view showing an outline of an example of a light limiting device using the two-photon absorbing material according to the present invention as a light limiting material.

The laser beam that enters from the outside (from the left side in Fig. 2) is collected by the condensing device 1 (lens, concave mirror, etc.) and has extremely high light intensity in the light-limiting material 2, which induces two-photon absorption Then it is absorbed. On the other hand, weak light such as ordinary light passes through the light limiting material without inducing two-photon absorption, and returns to the original optical path by the collimating device 3 (lens, concave mirror, etc.). Then, the light exits the device. Therefore, in this light limiting device, only the strong light is blocked by the device, so that the light detector on the emission side or the naked eye of the observer is protected from the laser beam.

FIG. 3 is a schematic view showing an outline of an example of an optical molding apparatus using the two-photon absorption material according to the present invention as a curing material.

The laser beam is condensed by a pulse laser condensing device 5 (such as an objective lens of a microscope) through a mirror 8 from a pulse laser generating device 4 and a light containing a two-photon absorbing material (hardening material). Focus in the curable monomer 6 resulting in high light intensity and inducing two-photon absorption. Due to this two-photon absorption, a reaction intermediate is generated, and the coexisting monomer is polymerized to form a polymer only near the focal point. As a result, a three-dimensional structure having an arbitrary shape can be formed. When performing fine control of one laser beam, a minute three-dimensional structure can be formed. This stereolithography machine is equipped with a mechanism for scanning a predetermined focusing position with a laser beam, and the focal point of the laser beam in the monomer is moved by moving the stage 7 that supports the photocurable monomer 6. When the mirror 8 is of a fixed type, and when the stage 7 is of a fixed type, the mirror 8 may be of a movable type (such as a galvanometer mirror). Can be.

FIG. 4 is a schematic diagram showing an outline of an example of a three-dimensional memory device using the two-photon absorption material according to the present invention as a three-dimensional optical memory material. This figure is an example of a three-dimensional memory device using the compound represented by the general formula (1) as a three-dimensional optical memory material and utilizing its fluorescence.

In the apparatus shown in FIG. 4, light from the pulse laser generator 4 is condensed by the pulse laser concentrator 5 through the dichroic mirror 10, and is collected in the two-photon absorption material (three-dimensional optical memory material) 9. Focus on the desired spot. At the focus, fluorescence is emitted, which is induced by two-photon absorption. When the laser light intensity is increased to a certain level or more, the two-photon absorbing material 9 in the focal portion is destroyed, and no fluorescence is generated in the portion. By repeatedly performing the light-collecting operation controlled in this manner, a portion that generates fluorescence by laser irradiation and a portion that does not generate fluorescence can be three-dimensionally formed at an arbitrary position. Thus, three-dimensional recording of information becomes possible. The information is read out by irradiating a laser beam weaker than the destructive intensity to the destructive portion and the non-destructive portion, thereby inducing fluorescence by two-photon absorption, collecting the light by the condensing device 5, and collecting the dichroic mirror 10 The light can be separated from the laser light by using the optical detector 11 and detected by an optical reading device such as a photodetector 11. Also in this case, the memory device includes a mechanism for scanning a desired condensing position with a laser beam. As the scanning mechanism, for example, a two-photon absorbing material 9 placed on a stage 7 is moved. Alternatively, one laser beam may be scanned using a movable mirror (such as a galvanometer mirror). FIG. 5 is a schematic diagram showing an outline of an example of a three-dimensional optical memory device utilizing a change in the refractive index generated after two-photon absorption of the two-photon absorption material of the present invention. In this optical memory device, at least one compound selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2) can be used as the optical memory material. In the apparatus of FIG. 5, the method of three-dimensionally recording information may be the same as the apparatus of FIG. That is, the light from the pulse laser generator 4 passes through the dichroic mirror 10 and is condensed by the pulse laser concentrator 5 to focus on a desired location in the two-photon absorption material (three-dimensional optical memory material) 9. Let it tie. Near the focal point, a change in the refractive index of the two-photon absorbing material occurs due to a reaction or thermal transformation that occurs after the two-photon absorption. Controlled like this By repeatedly performing the focused light collection operation, a portion having a three-dimensionally different refractive index can be formed at an arbitrary portion. Thus, three-dimensional recording of information becomes possible. Information can be read out by detecting a change in the refractive index in the optical memory material 9 using, for example, a confocal optical microscope 13. For example, light from the detection light source 14 is condensed by a light condensing device (such as a lens) 15 to irradiate a portion recorded as a change in the refractive index in the optical memory material 9. The emitted light passes through a condenser 17 (a lens or the like) through a condenser device (a lens or the like) 5 and a condenser device (a lens or the like) 16 and then is condensed by a condenser device (a lens or the like) 18. Is detected by the photodetector 11. The change in the refractive index at the recording position can be detected by the photodetector 11 as a change in the amount of light. In this method, by setting the aperture 17 at a focal point (confocal) position corresponding to the focal point in the optical memory material 9, a positional resolution in the depth direction is generated, and three-dimensional recording can be read out. . For example, by moving the stage 7 or moving the aperture 17, horizontal two-dimensional scanning enables horizontal recording and reading. In addition, by moving the stage 7 in the depth direction, reading in the depth direction becomes possible.

FIG. 6 is a schematic diagram showing an outline of an example of a two-photon fluorescence microscope using the two-photon absorption material represented by the general formula (1) as a fluorescent dye material.

The light from the pulse laser generator 4 passes through the dichroic mirror 10 and is condensed by the pulse laser condensing device 5 and is focused in the two-photon absorption material 12 to absorb two photons. Causes the fluorescence induced by The two-photon absorption material 12 placed on the stage 7 is scanned with a laser beam, and the fluorescence intensity at each location is detected by a photodetector such as a photodetector 11, and based on the obtained positional information. A three-dimensional fluorescence image can be obtained by plotting the combination. Also in this case, the two-photon fluorescence microscope is provided with a mechanism for scanning a desired condensing position with a laser beam. As the scanning mechanism, for example, a two-photon absorbing material placed on the stage 7 The laser beam may be scanned using a movable mirror (eg, a galvanometer mirror) or a movable mirror.

As described above, the two-photon absorption material according to the present invention has a large two-photon absorption cross-sectional area, and exhibits high two-photon absorption characteristics at a low concentration. Therefore, according to the present invention, not only can a high-sensitivity two-photon absorption material be obtained, but also the photo-breakdown strength of the material can be improved, and the adverse effect on the properties of other components in the material can be reduced.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a graph showing the relationship between the incident laser wavelength and the two-photon absorption cross-sectional area transmittance of the two-photon absorption material in Example 1, FIG. FIG. 4 is a schematic diagram showing an outline of a two-photon absorption stereolithography device according to the present invention, FIG. 4 is a schematic diagram showing an outline of a three-dimensional memory device utilizing the fluorescence of the two-photon absorption material, and FIG. FIG. 6 is a schematic diagram showing an outline of a three-dimensional memory device using a change in rate, FIG. 6 is a schematic diagram showing an outline of a two-photon fluorescence microscope according to the present invention, and FIG. 7 is an incident laser wavelength and a two-photon absorption material in Example 2. FIG. 8 is a graph showing the relationship between one wavelength of the incident laser and the two-photon absorption cross section of the two-photon absorption material in Example 3. In the figure, 1 is a condensing device, 2 is a two-photon absorbing material, 3 is a collimating device, 4 is a pulse laser generator, 5 is a condensing device, 6 is a two-photon absorbing material, and 7 is a movable or fixed stage. , 8 is a fixed or movable mirror, 9 is a two-photon absorption material, 10 is a dichroic mirror, 11 is a photodetector, 12 is a two-photon absorption material, 13 is a confocal optical microscope, and 14 is detection Reference numeral 15 denotes a light collecting device, 16 denotes a light collecting device, 17 denotes an aperture, and 18 denotes a light collecting device.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1

A dimethyl sulfoxide solution containing 2.0 to 3.0 mol / l of (2,5-dimethoxy-4- (N-methyl-4-pyridylvinylene) phenyl) butadiintriflate represented by the formula (3) In the wavelength range of 570 to 960 nm, a pulse laser with a pulse width of 125 fs was irradiated at a repetition frequency of 1 kHz.

The two-photon extinction coefficient was measured by the open-aperture z-scan method, and the two-photon absorption cross section was calculated considering the concentration. the short wavelength side, an increase of significant two-photon absorption cross section is obtained at a wavelength of 571 nm, up to 2400X 10 one ⁵⁰

A huge two-photon absorption cross section was obtained.

Example 2

For a dimethyl sulfoxide solution containing bis (N_methyl-4-pyridylvinylene-P-phenylene) butane diintriflate represented by the formula (4) in the range of 2.0 to 3, Omol / 1, the wavelength range is 596. At 890890 nm, a single pulse laser with a pulse width of 125 fs was applied at a repetition frequency of 1 kHz.

(Four)

The two-photon extinction coefficient was measured by the open aperture Z-scan method and the concentration was taken into account.The two-photon absorption cross-section was calculated from 650ηπι, which is near the peak wavelength of one-photon absorption in the visible region of 400 nm. At the short wavelength side, a remarkable increase in the two-photon absorption cross section was obtained, and at a wavelength of 596 nm, a huge two-photon absorption cross section of up to 571 X10 " ⁵⁰ cm ⁴ -sec-molecule" ¹ -photon- ¹ was obtained. (See Figure 7).

Example 3

For a dimethylsulfoxide solution containing 2.0 to 3. Omol / 1 of bis (2,5-dimethoxy-4- (4-pyridylvinylene) phenyl) butadiyne represented by the formula (5), in a wavelength range of 579 to 907 nm. A pulse laser with a pulse width of 125 fs was irradiated at a repetition frequency of 1 kHz.

The two-photon extinction coefficient was measured by the open-aperture Z-scan method and the two-photon absorption cross-section was calculated taking into account the concentration.From the 650 nm, which is near the peak wavelength of one-photon absorption in the visible region of 421 nm At the short wavelength side, a remarkable increase in the two-photon absorption cross section was obtained, and at a wavelength of 579 nm, a huge two-photon absorption cross section of up to 600 XIO " ⁵⁰ cm ⁴ -sec-molecule" ¹ -photon " ¹ was obtained. (See Figure 8).

Claims

The scope of the claims

. (Wherein,, R ₂ and n are the same R ₃ in the above is an alkyl group having 1 to 3 carbon atoms, A one is RS0 ₃ - (wherein R is, CF _3, phenyl, tolyl or an alkyl group having 1 to 3 carbon atoms), halogen § anion or C10 ₄ - a;)..

2. It is composed of at least one compound selected from the group consisting of a compound represented by the general formula (1) and a compound represented by the general formula (2), and the compound has one-photon ultraviolet, visible, and near-infrared absorption. A light-limiting material consisting of a two-photon absorption material that exhibits a two-photon absorption peak wavelength within a wavelength range of 250 nm or less from the peak wavelength;

(Wherein and R ₂ are the same or different and each represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, and n represents an integer of 1 to 3). (2)

. (Wherein,, R ₂ and n are the same R ₃ in the above is an alkyl group having 1 to 3 carbon atoms, A one is RS0 ₃ - (wherein R is, CF _3, phenyl, tolyl or An alkyl group having 1 to 3 carbon atoms), halogen anion or C1 (;

(Wherein, and R ₂ are the same or different and represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, and n represents an integer of 3 to 3).

(Wherein,, R ₂ and n are the same R ₃ in the above is an alkyl group having 1 to 3 carbon atoms, A one is RS0 ₃ -. (Wherein R is, CF _3, phenyl, tolyl or an alkyl group having 1 to 3 carbon atoms), halogen § anion or C10 ₄ - a;)..

4. —Consisting of at least one compound selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2), and one-photon ultraviolet • visible / near infrared absorption of the compound Three-dimensional optical memory material consisting of a two-photon absorption material exhibiting a two-photon absorption peak wavelength within a wavelength range of 250 nm from the peak wavelength of

6. A light restricting device in which the light restricting material according to claim 2 is disposed between a light collecting device and a collimating device.

7. Two-photon absorption stereolithography equipped with a pulsed laser generator, a pulsed laser concentrator, a photocurable monomer storage device, and a mechanism for scanning a predetermined condensing position in the photocurable monomer with a laser beam. An optical molding apparatus, wherein the curing material according to claim 3 is contained in a photocurable monomer.

8. Pulse laser generator, pulse laser collector, three-dimensional optical memory material, mechanism for scanning a predetermined focusing position of the memory material with a laser beam, and three-dimensional optical memory including an optical reading device An apparatus, wherein the three-dimensional memory material comprises at least one compound selected from the group consisting of compounds represented by the following general formula (1), and comprises one-photon ultraviolet, visible, near-red light of the compound. A three-dimensional memory device having a two-photon absorption peak wavelength within a wavelength range of 250 nm or less from the external absorption peak wavelength, and being a fluorescent two-photon absorption material;

(In the formula, and R ₂ are the same or different and represent a hydrogen atom or an alkoxy group having 4 to 4 carbon atoms, and n represents an integer of 1 to 3.).

9. A pulsed laser generator, a pulsed laser concentrator, the three-dimensional optical memory material according to claim 4, a mechanism for scanning a predetermined converging position of the memory material with a laser beam, and A three-dimensional optical memory device equipped with a mechanism for detecting a change in refractive index.

10. A pulsed laser generator, a pulsed laser collector, a fluorescent dye material according to claim 5, a mechanism for scanning a predetermined focusing position of the fluorescent dye material with a laser beam, and light. Two-photon fluorescence microscope equipped with a detection device.