WO2012133920A1 - 固体色素レーザー媒質およびその製造方法 - Google Patents
固体色素レーザー媒質およびその製造方法 Download PDFInfo
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- WO2012133920A1 WO2012133920A1 PCT/JP2012/059278 JP2012059278W WO2012133920A1 WO 2012133920 A1 WO2012133920 A1 WO 2012133920A1 JP 2012059278 W JP2012059278 W JP 2012059278W WO 2012133920 A1 WO2012133920 A1 WO 2012133920A1
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- polydimethylsiloxane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
- H01S3/16—Solid materials
- H01S3/168—Solid materials using an organic dye dispersed in a solid matrix
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0004—Coated particulate pigments or dyes
- C09B67/0008—Coated particulate pigments or dyes with organic coatings
- C09B67/0013—Coated particulate pigments or dyes with organic coatings with polymeric coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
- C09B67/0085—Non common dispersing agents
- C09B67/009—Non common dispersing agents polymeric dispersing agent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/05—Construction or shape of optical resonators; Accommodation of active medium therein; Shape of active medium
- H01S3/06—Construction or shape of active medium
- H01S3/0619—Coatings, e.g. AR, HR, passivation layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/0007—Applications not otherwise provided for
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/05—Construction or shape of optical resonators; Accommodation of active medium therein; Shape of active medium
- H01S3/08—Construction or shape of optical resonators or components thereof
- H01S3/08018—Mode suppression
- H01S3/08022—Longitudinal modes
- H01S3/08031—Single-mode emission
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/09—Processes or apparatus for excitation, e.g. pumping
- H01S3/091—Processes or apparatus for excitation, e.g. pumping using optical pumping
- H01S3/094—Processes or apparatus for excitation, e.g. pumping using optical pumping by coherent light
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/4998—Combined manufacture including applying or shaping of fluent material
Definitions
- the present invention relates to a solid dye laser medium and a method for producing the same.
- a dye laser using a dye as a medium has an advantage that an oscillation wavelength can be selected depending on the dye used, and is widely used industrially.
- a medium in which a dye is dissolved in an organic solvent is used for the dye laser.
- a solid dye laser in which a dye is added to a solid medium such as glass or polymer has been proposed because of its excellent handleability ( Non-patent documents 1 to 4).
- the conventional solid dye laser has a short service life, it is suitable for a single use application such as a biochip, but has a problem that it is not suitable for a use requiring a long life such as environmental sensing or optical communication.
- an object of the present invention is to provide a solid dye laser medium having excellent durability.
- the inventors of the present invention have studied the short service life of the conventional solid dye laser, and as a result, found that the cause is that the dye in the portion irradiated with the excitation light is deteriorated. Therefore, in a solid dye laser medium, the durability of the solid dye laser cannot be improved if the dye circulation can be performed so that the deteriorated dye existing in the portion irradiated with the excitation light can be replaced with an undegraded dye. I got the idea of a heel. As a result of intensive studies, it has been found that the circulation of the dye can be achieved by using polydimethylsiloxane having a nanoporous structure as a solid medium.
- polydimethylsiloxane is very difficult to simply dissolve a polar dye molecule to a concentration capable of laser oscillation, and is difficult to use as a laser medium as it is. Therefore, by selecting a dye that is easily dissolved in polydimethylsiloxane and devising its dissolution method, laser oscillation was made possible. Furthermore, the present inventors have completed the present invention by finding a device for improving the solubility of a dye having a poor solubility.
- a solid dye laser medium comprising polydimethylsiloxane and a dye dissolved in the polydimethylsiloxane
- a method for producing a solid dye laser medium comprising: (3) a step of dissolving a pigment in silicone oil to obtain a solution; Mixing the solution with a liquid dimethylsiloxane oligomer to obtain a composition; Applying the composition onto a substrate to form a coating film; and polymerizing or crosslinking the oligomer in the coating film to form poly
- the present invention can provide a solid dye laser medium having excellent durability.
- a solid dye laser medium is a member capable of lasing including a solid medium and a dye dissolved in the solid medium.
- the solid medium is a medium that can maintain its shape at the temperature at which the laser is used (usually 20 to 100 ° C.). In the present invention, it is solid polydimethylsiloxane.
- the dye is an organic dye capable of lasing.
- the polydimethylsiloxane polydimethylsiloxane, - (CH 3) is a polymer with 2 Si-O-repeating units.
- the polydimethylsiloxane used in the present invention is solid at room temperature.
- Such polydimethylsiloxane can be formed by polymerizing or crosslinking a liquid dimethylsiloxane oligomer (hereinafter also simply referred to as “oligomer”) which is a precursor of polydimethylsiloxane.
- oligomer liquid dimethylsiloxane oligomer
- the dimethylsiloxane oligomer is a dimer to decamer, preferably a dimer to tetramer of the above repeating unit, and is liquid at room temperature. The polymerization and crosslinking will be described in detail later.
- the solid dye laser medium of the present invention provides a laser having excellent durability because the dye circulates in the medium, but the dye circulation is affected by the spatial density of polydimethylsiloxane.
- This spatial density can be mainly adjusted by adding silicone oil, which will be described later, but has a high correlation with the crosslinking density and the molecular weight of the polymer.
- the spatial density is highly correlated with the hardness, and the durometer A hardness at 25 ° C. of the polydimethylsiloxane used in the present invention is preferably 60 or less.
- a dye that dissolves in polydimethylsiloxane is used.
- the dye an organic dye that is usually used in the art and that dissolves in polydimethylsiloxane can be used.
- the dye concentration in the solid dye laser medium is preferably 2 mmol / L or more, and more preferably 3 mmol / L or more in order to obtain an output.
- the upper limit of the dye concentration is selected in consideration of output and cost, but is usually preferably 200 mmol / L or less.
- the solubility of the dye in polydimethylsiloxane has a correlation with the polarity of the dye molecule, and since polydimethylsiloxane is nonpolar, the dye used in the present invention is preferably nonpolar. From such a viewpoint, a pyromethene dye is preferable in the present invention.
- the pyromethene dye is a dye having a skeleton represented by the following formula (1).
- R 1 to R 6 are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 7 and R 8 are halogen atoms.
- R 1 and R 5 are t-butyl groups
- R 2 , R 4 , R 6 and R 9 are methyl groups
- R 3 is a hydrogen atom
- R 7 and R 8 are fluorine atoms
- R 3 is a hydrogen atom
- R 7 and R 8 are fluorine atoms
- PM597 dye is preferable as a dye used in the present invention because it can be dissolved in dimethylsiloxane at the highest concentration.
- the concentration is 3 mmol / L, which is usually slightly higher than 2 mmol / L necessary for obtaining laser oscillation. It is difficult to dissolve PM650 as it is to a lower limit concentration capable of laser oscillation, and other pyromethene dyes cannot be dissolved to a concentration necessary for laser oscillation as they are.
- the silicone oil described later when the silicone oil described later is used, the solubility of the pigment having low solubility can be improved.
- Silicone oil may further contain silicone oil. Silicone oil can greatly improve the solubility of the dye in polydimethylsiloxane. Silicone oil is a general term for silicon compounds that are liquid at room temperature.
- the silicone oil used in the present invention has a lower viscosity than the polydimethylsiloxane precursor described above, and dimethyl Those having siloxane in the skeleton are preferred. Those having a diglycidyl ether group (PDMS-DGE oil), an ethoxy group, or a propoxy group at the terminal are preferred because the solubility of the dye is further increased.
- silicon-containing (meth) acrylates such as 3-trimethoxysilyl (meth) arylate, silicon-containing alkylamines such as N- [3- (trimethylsilyl) propyl] ethylenediamine, or (3-glycidyloxypropyl) trimethoxy Epoxy group-containing trialkoxysilane such as silane may be used.
- These silicone oils may exist in a state of reacting with the above-mentioned polydimethylsiloxane.
- the polydimethylsiloxane Since the polydimethylsiloxane is swollen by the silicone oil, the spatial density of the polydimethylsiloxane is lowered. Therefore, the dye molecules can easily move in the polydimethylsiloxane. Therefore, the addition of silicone oil is particularly effective when using large pigment molecules.
- silicone oil may promote the generation of impurities due to excitation light for laser oscillation, which may reduce the laser oscillation characteristics or its sustainability. Therefore, it is necessary to determine the amount of silicone oil used in consideration of the balance between the required dye concentration and impurity generation. For example, when PDMS-DGE oil is used, sufficient laser oscillation can be obtained even if PDMS-DGE oil is used up to 1 volume part with respect to 1 volume part of polydimethylsiloxane, but usually 1 volume part of polydimethylsiloxane is used. On the other hand, the silicone oil is preferably 1 part by volume or less.
- Whether the solid dye laser medium of the present invention contains silicone oil can be determined by the presence of a functional group derived from silicone oil, hardness, spatial density, and the like.
- FIG. 1 is a diagram showing an outline of a solid dye laser medium of the present invention.
- 10 is a solid dye laser medium
- 12 is a polydimethylsiloxane solid medium
- 120 is a cavity in a nanoporous structure in polydimethylsiloxane
- 14 is a dye
- an arrow indicates the movement of the dye.
- the polydimethylsiloxane solid medium 12 used in the present invention has a so-called nanoporous structure having a nano-sized cavity 120 formed by, for example, a polydimethylsiloxane chain having a spring shape inside.
- the dye 14 used in the present invention can move one after another through the solid medium 12 through the cavity 120. For this reason, even if the dye is deteriorated by the irradiation of the excitation light, if the irradiation of the excitation light is stopped and the solid dye laser medium 10 is allowed to stand, the deteriorated dye moves to another portion with time and is irradiated with light. A new dye 14 is brought into the portion. That is, dye circulation occurs and the performance as a laser is restored.
- the polydimethylsiloxane chain is flexible, the polydimethylsiloxane itself is solid at room temperature, but the cavities 120 have motility to further promote dye circulation.
- the solid dye laser medium of the present invention has extremely excellent durability as compared with the conventional solid dye laser medium.
- the solid dye laser medium of the present invention is preferably produced by the following production method. Hereinafter, the manufacturing method will be described.
- the first production method comprises a step of obtaining a solution by dissolving a dye in a nonpolar solvent having a dielectric constant of 5 or less, and mixing the solution with a liquid dimethylsiloxane oligomer (oligomer) to prepare a composition.
- a step of removing the nonpolar solvent in the composition a step of applying a composition from which the solvent has been removed to form a coating film on a substrate, and a coating film from which the solvent has been removed. Polymerizing or cross-linking the oligomer to give polydimethylsiloxane.
- each step will be described.
- a solution is obtained by dissolving the aforementioned dye in a nonpolar solvent having a dielectric constant of 5 or less.
- a nonpolar solvent having a dielectric constant of 5 or less is used in this step in consideration of compatibility with a liquid dimethylsiloxane oligomer.
- the dielectric constant is a value defined by the ratio of the capacitance of a capacitor containing a nonpolar solvent as a dielectric and the capacitance of the same capacitor using a vacuum as a dielectric, and is an index representing polarity in an organic solvent. That is, the lower the dielectric constant, the lower the polarity of the organic solvent.
- the dielectric constant of an organic solvent is a value measured at 20 ° C. or 25 ° C. under atmospheric pressure, and is described in “Solvent Handbook” (Kodansha Co., Ltd.).
- Nonpolar solvents having a dielectric constant of 5 or less used in the present invention include toluene (about 2.4), benzene (about 2.3), and hexane (about 2.0).
- the solvent used here is removed by evaporation in a later step. However, if the solvent is removed by heating at 100 ° C. or higher, there is a possibility of deteriorating the dye or the like.
- the slightly remaining solvent may photochemically react with the dye molecules during laser operation and change the molecular properties.
- toluene is most preferred because it does not adversely affect the dye molecules.
- the amount of the nonpolar solvent is selected so as to achieve this concentration and to minimize the addition amount of the nonpolar solvent. .
- Most nonpolar solvents evaporate during the process, so there is essentially no effect on the dye concentration in the solid dye laser medium, but residual nonpolar solvents can change dye properties or degrade dyes. There is a possibility of accelerating. From this point of view, it is preferable to use a non-polar solvent as much as possible and use it at a saturation concentration that maximizes the dye concentration.
- composition Preparation Step the solution is mixed with a liquid dimethylsiloxane oligomer to obtain a composition.
- the mixing mass ratio of the solution and the oligomer is selected so as to achieve the dye concentration when the solid dye laser medium is used.
- the volume ratio is preferably in the range of 1: (0.01 to 0.5), but more preferably as small as possible.
- Mixing may be performed using an electric stirrer or the like. Mixing may be performed by heating, but it is preferable to perform the mixing at room temperature in consideration of deterioration of the pigment.
- Solvent removal step In this step, the nonpolar solvent is removed from the composition by evaporation.
- the composition may be heated to promote evaporation, but it is preferable to evaporate at room temperature and under reduced pressure because the dye may be deteriorated.
- the time required for removal may be adjusted as appropriate.
- Solidifying agent mixing step In this step, a cross-linking agent or a curing accelerator for forming a solid polydimethylsiloxane by reacting an oligomer with the composition (hereinafter collectively referred to as "solidifying agent"). ) Is added.
- solidifying agent known solidifying agents can be used. Examples thereof include alkoxysilanes such as ethyl silicate and tin-based curing accelerators.
- the amount of the crosslinking agent or curing accelerator used may be a normal amount.
- the solidifying agent mixing step can be omitted when the dimethylsiloxane oligomer is sufficiently reacted without using a solidifying agent in the subsequent solidifying step.
- Coating film formation process the said composition is apply
- a known substrate such as a glass plate or a plastic film can be used.
- a known method such as casting (molding), bar coating, drawing with a dispenser, or spin coating can be used.
- the oligomer in a composition is made to react and solid polydimethylsiloxane is formed.
- the dimethylsiloxane oligomer is a 2 to 10, preferably 2 to 4 mer of — (CH 3 ) 2 Si—O— units, and is liquid at room temperature.
- a dimethylsiloxane oligomer has a functional group capable of addition reaction or crosslinking reaction in the molecule. Accordingly, this step can be carried out by subjecting dimethylsiloxane oligomers to addition polymerization to increase the molecular weight, cross-linking oligomers, or addition polymerization and cross-linking of oligomers.
- the solidification reaction may be performed by heating the dried coating film at 50 to 100 ° C. or at room temperature. Moreover, you may perform simultaneously removing further the solvent which remained by the solvent removal process by decompressing this process.
- a solid dye laser medium is obtained, and the thickness is preferably 5 to 200 ⁇ m.
- the second production method comprises a step of dissolving a pigment in silicone oil to obtain a solution, a step of mixing the solution with liquid dimethylsiloxane oligomer to obtain a composition, and the composition on a substrate.
- each step will be described.
- Solution preparation step In this step, a solution is obtained by dissolving the aforementioned dye in the aforementioned silicone oil.
- the amount of silicone oil is adjusted by the balance between the degree of improvement in the solubility of the dye and the oscillation characteristics when used as a medium. As described above, 1 volume per 1 part by volume of polydimethylsiloxane when used as a medium. An amount of less than or equal to parts is preferred. Further, when the solubility of the dye is low, it is preferable to use a nonpolar solvent in the same manner as in the first production method.
- Solidification process This process is also as described in the first method.
- the silicone oil in which the dye is dissolved and the dimethylsiloxane oligomer may not react with each other, or may be added to each other to form polydimethylsiloxane.
- the third production method comprises a step of preparing polydimethylsiloxane, a step of obtaining a dye-containing medium by dissolving a dye in a medium that does not swell the polydimethylsiloxane, and contacting the medium with the polydimethylsiloxane. And diffusing the dye into the polydimethylsiloxane.
- a step of preparing polydimethylsiloxane a step of obtaining a dye-containing medium by dissolving a dye in a medium that does not swell the polydimethylsiloxane, and contacting the medium with the polydimethylsiloxane. And diffusing the dye into the polydimethylsiloxane.
- polydimethylsiloxane preparation step In this step, polydimethylsiloxane may be prepared by an arbitrary method. However, as described above, it is preferable to prepare a dimethylsiloxane oligomer by adding a solidifying agent and solidifying it.
- Dye-containing medium preparation step In this step, the above-mentioned dye is dissolved in a medium that does not swell polydimethylsiloxane to prepare a dye-containing medium.
- the medium that does not swell polydimethylsiloxane is a solvent that cannot penetrate into nonpolar polydimethylsiloxane because of its high polarity, or a liquid or solid substance that cannot penetrate into polydimethylsiloxane because of its high molecular weight.
- the former include water or alcohols having 1 to 3 carbon atoms, and examples of the latter include uncured dimethylsiloxane oligomer or polydimethylsiloxane.
- the dye-containing medium can be prepared by dispersing or dissolving the dye in water.
- the concentration of the dye in the medium is preferably higher than the concentration desired to be introduced into the polydimethylsiloxane. Specifically, when it is desired to introduce 5 ⁇ 10 ⁇ 3 mol / liter of dye into polydimethylsiloxane, the dye concentration in the dye-containing medium is preferably higher.
- the composition obtained through the solution preparation step, the composition preparation step, and the solvent removal step of the first production method is used as the dye-containing medium.
- the dye-containing medium can be used.
- the solid dye laser medium obtained by the 1st manufacturing method can be used as a dye containing medium, for example.
- the dye-containing medium and polydimethylsiloxane are brought into contact with each other to diffuse the dye into the polydimethylsiloxane.
- the dye-containing medium is a liquid, it can be carried out by immersing polydimethylsiloxane in the medium or applying the medium to polydimethylsiloxane.
- dye containing medium is solid, it is preferable to make the said medium and a part of polydimethylsiloxane contact.
- the temperature of the medium at the time of contact is not limited, but is preferably room temperature (23 ° C.) to 100 ° C., more preferably 25 to 80 ° C., and further preferably 50 to 75 ° C.
- the contact time may be adjusted as appropriate, but is preferably 3 to 24 hours. The higher the temperature of the medium, the shorter the contact time.
- the dye since it is possible to avoid that the dye reacts with the solidifying agent, there is an advantage that even a dye that may react with the solidifying agent and deteriorate may be used. Further, in the first and second methods, the dye may be deteriorated when a high temperature of about 150 to 200 ° C. is required when solidifying the dimethylsiloxane oligomer in which the dye is dissolved. This can be avoided.
- the solid dye laser of the present invention includes the above-described solid dye laser medium, an excitation light source, and resonance means.
- the excitation light source is a light source for exciting the dye, and for example, a known light source such as an Nd: YAG laser can be used.
- the resonance means is means for creating a standing wave of light such as a pair of mirrors.
- the resonance means corresponds to a diffraction grating in a DFB laser (distributed feedback laser).
- FIG. 2 is a diagram showing an example of a DFB laser using the solid dye laser medium of the present invention.
- (A) shows the oscillating DFB laser.
- Reference numeral 10 denotes a solid dye laser medium
- 20 denotes a substrate
- 30 denotes excitation light
- 40 denotes output light.
- a diffraction grating provided on the upper surface of the solid dye laser medium 10 is not shown.
- (B) shows the laser immediately after oscillation, and 16 shows a portion where the dye has deteriorated by irradiation with the excitation light 30.
- (C) shows the DFB laser in which the deteriorated portion 16 is recovered by the dye circulation after leaving the laser immediately after oscillation for a while.
- the deteriorated portion 16 can be recovered by allowing it to stand overnight at room temperature, but when the solid dye laser medium 10 is heated, the molecular motion of polydimethylsiloxane is activated, so that recovery is also promoted.
- the heating temperature is preferably 30 to 80 ° C.
- the heating time is preferably 1 to 12 hours.
- the solid dye laser of the present invention can be produced by arranging a known resonance means and an excitation light source in a known manner on the solid dye laser medium obtained by the first production method described above.
- a known resonance means and an excitation light source in a known manner on the solid dye laser medium obtained by the first production method described above.
- an uppermost layer having a refractive index of about 0.01 to 0.1 is formed on a solid dye laser medium with a thickness of 1 to 5 microns, and then an ultraviolet laser beam It is possible to manufacture by forming a diffraction pattern having a desired laser oscillation wavelength on the above-mentioned uppermost layer by interference exposure using the above.
- the solid dye laser of the present invention can be produced by arranging a known resonance means and an excitation light source by a known method on the solid dye laser medium obtained by the second or third production method described above.
- FIG. 7 shows the concept of such a solid dye laser with a dye tank.
- 100 is an excitation region of a solid dye laser medium
- 102 is a solid dye laser medium as a dye tank
- 104 is a solid dye laser medium as an exchange cartridge
- a substrate and the like are omitted.
- the fresh dye is solidified from the dye tank 102 in contact with the excitation region 100 of the solid dye laser medium. It can be carried to the excitation region 100 of the dye laser medium.
- the fresh dye can be removed from the solid dye laser medium by bringing the replacement cartridge 104 into contact with the excitation region 100 of the solid dye laser medium. It can also be carried to the excitation region 100.
- the volume of the dye tank 102 and the exchange cartridge 104 is preferably larger than the volume of the excitation region 100 of the solid dye laser medium in order to increase the amount of molecules that can be exchanged.
- the volume of the dye tank or the exchange cartridge is preferably 10 to 100,000 with respect to the excitation region of one volume part of the solid dye laser medium.
- Example 1 Production of solid dye laser using toluene Pyromethene 597 (PM597, manufactured by Exciton) as a dye was dissolved in toluene to prepare a saturated concentration (100 to 130 mmol / L) solution.
- the above dye solution is mixed with a dimethylsiloxane oligomer (SIM-360, manufactured by Shin-Etsu Chemical Co., Ltd.), which is a precursor of polydimethylsiloxane, at a mixing ratio of 40: 1 (volume ratio), and stirred sufficiently for 2 days to be sufficiently uniform. After the dispersion, this was further heated at 72 ° C. to evaporate toluene, and the final dye concentration was adjusted to 3 mmol / L.
- SIM-360 dimethylsiloxane oligomer
- a 2 cm ⁇ 2 cm mold was placed on the glass substrate, and the composition was cast into a cavity of this mold to form a coating film. This was heated at 72 ° C. for solidification to form polydimethylsiloxane from a dimethylsiloxane oligomer. The time required for solidification was one day. After solidification, the mold was removed to obtain a solid dye laser medium having a film thickness of 50 to 100 ⁇ m.
- a semi-polymerized polymer of polytrifluoroethyl methacrylate was spin-coated, and then heated and polymerized at 72 ° C. to form a polytrifluoroethyl methacrylate layer having a thickness of 2 to 5 ⁇ m.
- a refractive index type DFB structure having a laser oscillation wavelength of 580 nm was formed on the polytrifluoroethyl methacrylate layer by using interference exposure with Ar + laser second high wavelength (SHG): 244 nm as an ultraviolet laser.
- the DFB laser manufactured in this way was irradiated with a second high wavelength of 532 nm of Nd: YAG laser as excitation light under conditions of a pulse energy of 28 ⁇ J and a repetition frequency of 100 Hz (first excitation cycle).
- the excitation light was applied to a certain part of the solid dye laser medium.
- Fig. 3 shows the spectrum during laser oscillation. Single mode oscillation with a wavelength of 582.5 nm was observed. The spectral width was 0.11 nm.
- the first excitation cycle was terminated.
- the portion irradiated with the excitation light was decolorized.
- the DFB laser was allowed to stand at room temperature, and the DFB laser was recovered by dye circulation (first recovery cycle).
- the output intensity was measured by irradiating excitation light again after being allowed to stand for 250 minutes, the output intensity was recovered to about 88% of the initial output.
- the measurement of the output intensity was repeated after leaving the DFB laser for a certain time.
- the result is shown in FIG. FIG. 4 reveals that the degree of recovery is saturated by leaving the DFB laser at room temperature for about 9 hours, and the output intensity after recovery reaches almost 100%.
- the second excitation cycle was performed again under the same excitation conditions (pulse energy 28 ⁇ J, repetition frequency 100 Hz) as the first excitation cycle.
- the durability was evaluated by the number of shots at which the output intensity in the second excitation cycle was 50% of the initial intensity of the first excitation cycle, that is, the half-value intensity. As a result, the durability of the DFB laser obtained in this example was 5.2 ⁇ 10 5 shots.
- the time constant defined as the time when the tangent at the rising portion reaches the saturation point (1.0 au) was 124 minutes.
- a solid dye laser medium is formed by arranging a mold having a side of 2 cm on a glass substrate. Actually, however, the length of the side is set to 0.1 mm to 100 cm and the solid dye laser medium is used. It is possible to form, that is, to form a large area solid dye laser medium.
- Example 2 A DFB laser was produced in the same manner as in Example 1 except that silicone oil (KF-1065, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of toluene and the process of removing toluene was not performed.
- silicone oil KF-1065, manufactured by Shin-Etsu Chemical Co., Ltd.
- FIG. 5 is a photograph of the DFB laser obtained in this example after the first excitation cycle and a photograph after the first recovery cycle (after standing for 12 hours). From FIG. 5, it is clear that the decolorized portion observed after the first excitation cycle has disappeared after the first recovery cycle, and dye circulation has occurred.
- FIG. 6 shows that in the first to third excitation cycles, the output intensity decreased with each cycle.
- the durability determined in the same manner as in Example 1 was 55000 shots.
- the output intensity recovered (increased) by the first recovery cycle but the recovery amount was 67% of the minimum intensity of the first excitation cycle.
- the recovery in the second recovery cycle was 72% of the minimum intensity of the second excitation cycle.
- the degree of recovery in the first and second recovery cycles was saturated at 9 hours, and the time constants were 120 minutes and 128 minutes, respectively.
- the laser of Example 1 is considered to be superior to the laser of Example 2 in terms of durability and degree of recovery because it does not contain silicone oil.
- Example 3 Except that SIM-260 (manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the dimethylsiloxane oligomer, CAT-260 (manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the solidifying agent, and the solidification time is 72 ° C. for 3 days In the same manner as in Example 1, a solid dye laser medium was produced and evaluated. As a result, it was confirmed that laser oscillation was obtained.
- SIM-260 manufactured by Shin-Etsu Chemical Co., Ltd.
- CAT-260 manufactured by Shin-Etsu Chemical Co., Ltd.
- the pigment when the pigment is dissolved in polydimethylsiloxane using silicone oil as in Example 2, the pigments of PM650, PM605, PM567 and PM597 can be dissolved to a concentration capable of laser oscillation.
- Example 4 A solid dye laser medium was manufactured and evaluated in the same manner as in Example 2 using PM650, PM605, and PM567 as the dye. As a result, it was confirmed that laser oscillation was obtained.
- Example 5 1 part by volume of a solidifying agent (CAT-360, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with 10 parts by volume of a dimethylsiloxane oligomer (SIM-360, manufactured by Shin-Etsu Chemical Co., Ltd.) which is a precursor of polydimethylsiloxane.
- a 2 cm ⁇ 2 cm mold was placed on the glass substrate, and a dimethylsiloxane oligomer composition was cast into the cavity of this mold to form a coating film. This was heated at 72 ° C. for solidification to form polydimethylsiloxane from a dimethylsiloxane oligomer. The time required for solidification was one day. After solidification, the mold was removed to obtain a polydimethylsiloxane molded product having a film thickness of 100 ⁇ m.
- Pyromethene 597 (PM597, manufactured by Exciton) as a pigment was dissolved in toluene to prepare a saturated concentration (100 to 130 mmol / L) solution.
- the above dye solution is mixed with a dimethylsiloxane oligomer (SIM-360, manufactured by Shin-Etsu Chemical Co., Ltd.), which is a precursor of polydimethylsiloxane, at a mixing ratio of 40: 1 (volume ratio), and stirred sufficiently for 2 days to be sufficiently uniform. After the dispersion, this was further heated at 72 ° C. to evaporate toluene, and the final dye concentration was adjusted to 3 mmol / L to obtain a dye-containing medium.
- SIM-360 dimethylsiloxane oligomer
- FIG. 8 shows a mode in which the medium and the polydimethylsiloxane molded product are brought into contact with each other.
- 50 is a polydimethylsiloxane molded product
- 60 is a dye-containing medium.
- the dye-containing medium 60 is placed in a container, the temperature of the medium is kept at 25 ° C., and is brought into contact with one end of the polydimethylsiloxane molded product 50 for 24 hours to diffuse the dye into the polydimethylsiloxane.
- a solid dye laser medium was produced. A laser was produced and evaluated in the same manner as in Example 2 using the medium. As a result, it was confirmed that laser oscillation was obtained.
- Example 6 A solid dye laser medium was produced and evaluated in the same manner as in Example 5 except that the temperature of the medium at the time of contact was 75 ° C. As a result, it was confirmed that laser oscillation was obtained.
- FIG. 9 shows an image obtained by observing the solid dye laser medium obtained in Examples 5 and 6 under ultraviolet illumination. From FIG. 9, it can be seen that the dye diffuses more quickly when the temperature of the solution is higher.
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Abstract
Description
(1)ポリジメチルシロキサンと、当該ポリジメチルシロキサン中に溶解した色素とを含む、固体色素レーザー媒質;
(2)誘電率が5以下の非極性溶媒に色素を溶解して溶液を得る工程、
前記溶液を液状のジメチルシロキサンオリゴマーに混合して組成物を得る工程、
前記組成物中の前記非極性溶媒を除去する工程、および
基材の上に前記組成物を塗布して塗布膜を形成する工程、
前記塗布膜中の前記オリゴマーを重合または架橋してポリジメチルシロキサンを形成する工程、
を含む、固体色素レーザー媒質の製造方法;
(3)シリコーンオイルに色素を溶解して溶液を得る工程、
前記溶液を液状のジメチルシロキサンオリゴマーに混合して組成物を得る工程、
基材の上に前記組成物を塗布して塗布膜を形成する工程、および
前記塗布膜中の前記オリゴマーを重合または架橋してポリジメチルシロキサンを形成する工程、
を含む、固体色素レーザー媒質の製造方法;
(4)ポリジメチルシロキサンを準備する工程、
前記ポリジメチルシロキサンを膨潤させない媒体に色素を溶解して、色素含有媒体を得る工程、
前記媒体と前記ポリジメチルシロキサンとを接触させて、当該色素を当該ポリジメチルシロキサン中に拡散する工程、
を含む、固体色素レーザー媒質の製造方法。
固体色素レーザー媒質とは、固体媒体と固体媒体に溶解した色素とを含むレーザー発振可能な部材である。固体媒体とはレーザーが使用される温度(通常は20~100℃)において形状を保つことができる媒体であり、本発明においては固体のポリジメチルシロキサンである。色素とはレーザー発振しうる有機色素である。以下、各成分等について説明する。
ポリジメチルシロキサンとは、−(CH3)2Si−O−を繰り返し単位とするポリマーである。
本発明においてはポリジメチルシロキサン中に溶解する色素を用いる。色素としては、当該分野で通常使用される有機色素であってポリジメチルシロキサン中に溶解する色素を使用できる。固体色素レーザー媒質中の色素濃度は、2mmol/L以上が好ましく、出力を得るためには3mmol/L以上であることがより好ましい。色素濃度の上限は、出力やコストを考慮して選択されるが、通常は、200mmol/L以下が好ましい。ポリジメチルシロキサンに対する色素の溶解性は色素分子の極性と相関があり、ポリジメチルシロキサンは非極性であるので、本発明で用いる色素も非極性であることが好ましい。このような観点から、本発明においてはピロメテン系色素が好ましい。ピロメテン系色素とは下記式(1)で表される骨格を有する色素である。
本発明の固体色素レーザー媒質はシリコーンオイルをさらに含んでいてもよい。シリコーンオイルにより、ポリジメチルシロキサンに対する色素の溶解性を大きく向上させられる。シリコーンオイルとは、室温で液体のケイ素化合物の総称である。
本発明の固体色素レーザー媒質は優れた耐久性を有する。その理由は以下のように考えられる。図1は本発明の固体色素レーザー媒質の概要を示す図である。図1において10は固体色素レーザー媒質、12はポリジメチルシロキサンの固体媒体、120はポリジメチルシロキサン内のナノポーラス構造における空洞、14は色素、矢印は色素の動きを示す。本発明で用いるポリジメチルシロキサンの固体媒体12は、内部にポリジメチルシロキサン鎖がスプリング状の形状になること等によって形成されるナノサイズの空洞120を有する、いわゆるナノポーラス構造を有する。本発明で使用する色素14はこの空洞120を介して固体媒体12中を次々と移動しうる。このため、励起光の照射により色素が劣化しても励起光の照射を中止して固体色素レーザー媒質10を放置すると、この劣化した色素は時間経過とともに他の部分へ移動し、光照射された部分には新たな色素14が運び込まれる。すなわち、色素循環が起こりレーザーとしての性能が回復する。さらにポリジメチルシロキサン鎖は柔軟であるため、室温ではポリジメチルシロキサン自体は固体であるものの空洞120は運動性を有しており色素循環をより一層促進する。従来の固体色素レーザー媒質において用いられるガラス等の固体媒体はナノポーラス構造を有していないので本発明の固体色素レーザー媒質のような色素循環が生じない。よって、本発明の固体色素レーザー媒質は従来の固体色素レーザー媒質に比べて極めて優れた耐久性を有する。
本発明の固体色素レーザー媒質は以下の製造方法によって製造されることが好ましい。以下、製造方法について説明する。
第一の製造方法は、誘電率が5以下の非極性溶媒に色素を溶解して溶液を得る工程、前記溶液を液状のジメチルシロキサンオリゴマー(オリゴマー)に混合して組成物を得る工程、前記組成物中の前記非極性溶媒を除去する工程、基材の上に前記溶媒を除去した組成物を塗布して塗布膜を形成する工程、および前記溶媒が除去された塗布膜中のオリゴマーを重合または架橋してポリジメチルシロキサンとする工程、を含む。以下、各工程について説明する。
本工程では、誘電率が5以下の非極性溶媒に前述の色素を溶解して溶液を得る。一般にポリジメチルシロキサンは極性が低いので、液状のジメチルシロキサンオリゴマーとの相溶性を考慮して、本工程では誘電率が5以下の非極性溶媒を用いる。誘電率は非極性溶媒を誘電体として含むコンデンサの容量と、真空を誘電体とする同じコンデンサの容量との比で定義される値であり、有機溶媒においては極性を表す指標となる。すなわち、誘電率が低いほど極性の低い有機溶媒となる。通常、有機溶媒の誘電率は20℃または25℃大気圧下で測定された値であり、「溶剤ハンドブック」(株式会社講談社)に記載されている。本発明で使用する誘電率が5以下の非極性溶媒としては、トルエン(約2.4)、ベンゼン(約2.3)、ヘキサン(約2.0)が含まれる。ここで使用する溶媒は、後の工程で蒸発により除去されるが、100℃以上で加熱して溶媒を除去すると色素等を劣化させる恐れがあるので、室温で揮発しやすいことが好ましい。さらに、わずかに残留した溶媒はレーザー動作時に色素分子と光化学反応して分子特性を変化させる可能性がある。本発明においては、色素分子に悪影響を与えにくいトルエンが最も好ましい。
本工程では、前記溶液を液状のジメチルシロキサンオリゴマーに混合して組成物を得る。前記溶液とオリゴマーとの混合質量比は、前述の固体色素レーザー媒質としたときの色素濃度を達成できるように選択される。その体積比は1:(0.01~0.5)の範囲が好ましいが、できるだけ少ないことがより好ましい。混合は電動撹拌機等を用いて行なってよい。混合は加熱して行なってもよいが、色素の劣化等を考慮すると室温で行なうことが好ましい。
本工程では前記組成物から前記非極性溶媒を蒸発させて除去する。蒸発を促進するために組成物を加熱してもよいが、色素が劣化する恐れがあるため室温でかつ減圧下にて蒸発させることが好ましい。除去に要する時間は適宜調整してよい。
本工程では、前記組成物に、オリゴマーを反応させて固体のポリジメチルシロキサンを形成するための架橋剤または硬化促進剤(以下これらを総称して「固化剤」ともいう)を添加する。本発明においては公知の固化剤が使用できるが、その例には、エチルシリケート等のアルコキシシランおよびスズ系硬化促進剤が含まれる。架橋剤または硬化促進剤の使用量は通常の量としてよい。固化剤を混合すると、重合または架橋反応が開始する。反応は1~12時間程度で完了するが、反応の進行とともに組成物の流動性が低下するので、反応開始後は流動性があるうちに速やかに次工程に移行する必要がある。
本工程では、基材の上に前記組成物を塗布して塗布膜を形成する。基材としては、ガラス板またはプラスチックフィルム等の公知の基材を使用できる。塗布膜の形成には注型(モールディング)、バーコート、ディスペンサーによる描画、またはスピンコート等の公知の方法を使用できる。
本工程では、組成物中のオリゴマーを反応させて、固体のポリジメチルシロキサンを形成する。前述のとおり、ジメチルシロキサンオリゴマーとは、−(CH3)2Si−O−単位の2~10好ましくは2~4量体であり、室温で液状である。通常、ジメチルシロキサンオリゴマーは付加反応または架橋反応可能な官能基を分子内に有する。従って、本工程は、ジメチルシロキサンオリゴマー同士を付加重合させて高分子量化する、またはオリゴマー同士を架橋する、あるいはオリゴマー同士を付加重合かつ架橋させることで実施できる。より硬度の高いポリジメチルシロキサンを得るためには、前記オリゴマーを付加重合かつ架橋させることが好ましい。さらに、前記固化剤混合工程において固化剤が添加されていると、反応をより速やかに行なうことができる。
第二の製造方法は、シリコーンオイルに色素を溶解して溶液を得る工程、前記溶液を液状のジメチルシロキサンオリゴマーに混合して組成物を得る工程、基材の上に前記組成物を塗布して塗布膜を形成する工程、および前記塗布膜中のオリゴマーを重合または架橋してポリジメチルシロキサンとする工程、を含む。以下、各工程について説明する。
本工程では、前述のシリコーンオイルに前述の色素を溶解して溶液を得る。シリコーンオイルの量は、色素の溶解性向上の度合いと媒質としたときの発振特性とのバランスによって調整されるが、前述のとおり、媒質としたときにポリジメチルシロキサン1体積部に対して1体積部以下となる量が好ましい。また、色素の溶解性が低い場合は、第一の製造方法と同様に非極性溶媒を併用することが好ましい。
本工程は、第一の方法において説明したとおりである。ただし色素の前述シリコーンオイルへの溶解度は、第一の製造方法で述べた非極性溶媒への溶解度よりもそれよりも低く、かつシリコーンオイルは蒸発しないので最終的な固体色素レーザー媒質にも残存する。従って、色素のシリコーンオイル溶液と前述のオリゴマーとの混合比率は、第一の製造方法における色素の非極性溶媒溶液とオリゴマーとの混合比率とは大きく異なる。本工程においては、最終的な固体色素レーザー媒質における色素濃度およびシリコーンオイル濃度を勘案して調整される。
前記溶液調製工程で非極性溶媒を用いた場合は、第一の製造方法で説明したとおりに、溶媒を除去する。
これらの工程は、第一の方法において説明したとおりである。
本工程も第一の方法で説明したとおりである。本方法においては、色素を溶解したシリコーンオイルとジメチルシロキサンオリゴマーとは反応しなくてもよいし、互いに付加反応してポリジメチルシロキサンを形成してもよい。
第三の製造方法は、ポリジメチルシロキサンを準備する工程、前記ポリジメチルシロキサンを膨潤させない媒体に色素を溶解して色素含有媒体を得る工程、前記媒体と前記ポリジメチルシロキサンを接触させて、当該色素を当該ポリジメチルシロキサン中に拡散する工程、を含む。以下、各工程について説明する。
本工程では、任意の方法でポリジメチルシロキサンを準備してよいが、前述のとおり、ジメチルシロキサンオリゴマーに固化剤を添加して固化して調製することが好ましい。
本工程では、前述の色素を、ポリジメチルシロキサンを膨潤させない媒体に溶解して色素含有媒体を調製する。ポリジメチルシロキサンを膨潤させない媒体とは、極性が高いために非極性のポリジメチルシロキサン中に侵入できない溶媒、または分子量が大きいためにポリジメチルシロキサン中に侵入できない液体または固体の物質である。前者の例としては、水または炭素数1~3のアルコール等が挙げられ、後者の例としては未硬化のジメチルシロキサンオリゴマー、またはポリジメチルシロキサンが挙げられる。
本工程では、前記色素含有媒体とポリジメチルシロキサンとを接触させて、色素を当該ポリジメチルシロキサン中に拡散する。前記色素含有媒体が液体の場合は、当該媒体にポリジメチルシロキサンを浸漬する、または前記媒体をポリジメチルシロキサンに塗布する等により行なうことができる。また、前記色素含有媒体が固体の場合は、当該媒体とポリジメチルシロキサンの一部を接触させることが好ましい。
本発明の固体色素レーザーは、前述の固体色素レーザー媒質、励起用光源、および共振手段を備える。励起用光源とは、色素を励起するための光源であり、例えばNd:YAGレーザー等の公知の光源を使用できる。共振手段とは一対のミラー等の光の定在波を作り出すための手段である。共振手段は、DFBレーザー(分布帰還型レーザー)においては回折格子に相当する。
本発明の固体色素レーザーは、前述の第一の製造方法で得た固体色素レーザー媒質に、公知の共振手段および励起用光源を、公知の方法で配置することにより製造できる。例えば、DFBレーザーとする場合は、固体色素レーザー媒質の上に、屈折率0.01から0.1ほど高くなるような最上部層を厚さ1~5ミクロンで形成し、次に紫外レーザー光等を用いた干渉露光などで、所望のレーザー発振波長となるような回折パターンを前述最上部層に形成することにより製造できる。
色素としてピロメテン597(PM597、エキシトン社製)をトルエンに溶解させ飽和濃度(100~130mmol/L)溶液を調製した。ポリジメチルシロキサンの前駆体であるジメチルシロキサンオリゴマー(SIM−360、信越化学工業株式会社製)に混合比40:1(体積比)で前述の色素溶液を混合し、二日間撹拌して十分均一に分散させた後、これをさらに72℃で加熱してトルエンを蒸発させ、最終的な色素濃度が3mmol/Lとなる様に調整した。
トルエンの代わりにシリコーンオイル(KF−1065、信越化学工業株式会社製)を用い、トルエンを除去する工程を行なわなかった以外は、実施例1と同様にしてDFBレーザーを製造した。
ジメチルシロキサンオリゴマーとして、SIM−260(信越化学工業株式会社製)を使用し、固化剤としてCAT−260(信越化学工業株式会社製)を使用し、固化時間を72℃で3日とした以外は、実施例1と同様にして固体色素レーザー媒質を製造し、評価した。その結果、レーザー発振を得ることを確認した。
以下の色素を用いて、実施例1および2と同様にしてポリジメチルシロキサン(PDMS)に溶解できる最大濃度を検討した。結果を表1に示す。
ピロメテン系色素(エキシトン社製)
PM650:赤
PM605:橙
PM597:橙
PM580:茶
PM567:黄
PM556:黄
ローダミン系色素(エキシトン社製)
Rh6G:桃
クマリン系色素(エキシトン社製)
C456:白
色素として、PM650、PM605およびPM567を用い、実施例2と同様にして固体色素レーザー媒質を製造し、評価した。その結果、レーザー発振を得ることを確認した。
ポリジメチルシロキサンの前駆体であるジメチルシロキサンオリゴマー(SIM−360、信越化学工業株式会社製)10体積部に固化剤(CAT−360、信越化学工業株式会社製)を1体積部混合した。ガラス基板の上に2cm×2cmの型枠を配置し、この型の空洞部分にジメチルシロキサンオリゴマー組成物を注型して塗布膜を形成した。これを72℃で加熱して固化を行い、ジメチルシロキサンオリゴマーからポリジメチルシロキサンを形成した。固化に要した時間は1日であった。固化後、型枠を取り外して膜厚が100μmのポリジメチルシロキサン成形物を得た。
接触時の媒体の温度を75℃にした以外は、実施例5と同様にして固体色素レーザー媒質を製造し、評価した。その結果、レーザー発振を得ることを確認した。
100 固体色素レーザー媒質の励起領域
102 色素タンク
104 交換カートリッジ
12 ポリジメチルシロキサンの固体媒体
120 ポリジメチルシロキサン内のナノポーラス構造における空洞
14 色素
16 色素が劣化した部分
20 基板
30 励起光
40 出力光
50 ポリジメチルシロキサン成形物
60 色素含有媒体
Claims (10)
- ポリジメチルシロキサンと、当該ポリジメチルシロキサン中に溶解した色素とを含む、固体色素レーザー媒質。
- 前記色素がピロメテン系色素である、請求項1に記載の媒質。
- シリコーンオイルをさらに含む、請求項1に記載の媒質。
- 誘電率が5以下の非極性溶媒に色素を溶解して溶液を得る工程、
前記溶液を液状のジメチルシロキサンオリゴマーに混合して組成物を得る工程、
前記組成物中の前記非極性溶媒を除去する工程、
基材の上に前記溶媒を除去した組成物を塗布して塗布膜を形成する工程、および
前記溶媒が除去された塗布膜中の前記オリゴマーを重合または架橋してポリジメチルシロキサンを形成する工程、を含む、固体色素レーザー媒質の製造方法。 - シリコーンオイルに色素を溶解して溶液を得る工程、
前記溶液を液状のジメチルシロキサンオリゴマーに混合して組成物を得る工程、
基材の上に前記組成物を塗布して塗布膜を形成する工程、および
前記塗布膜中の前記オリゴマーを重合または架橋してポリジメチルシロキサンを形成する工程、
を含む、固体色素レーザー媒質の製造方法。 - ポリジメチルシロキサンを準備する工程、
前記ポリジメチルシロキサンを膨潤させない媒体中に色素を溶解して、色素含有媒体を得る工程、
前記媒体と前記ポリジメチルシロキサンを接触させて、当該色素を当該ポリジメチルシロキサン中に拡散する工程、
を含む、固体色素レーザー媒質の製造方法。 - 請求項1に記載の固体色素レーザー媒質、
励起用光源、および
共振手段、
を備える、色素レーザー。 - 誘電率が5以下の非極性溶媒に色素を溶解して溶液を得る工程、
前記溶液を液状のジメチルシロキサンオリゴマーに混合して組成物を得る工程、
前記組成物中の前記非極性溶媒を除去する工程、
基材の上に前記溶媒が除去された組成物を塗布して塗布膜を形成する工程、
前記溶媒が除去された塗布膜中の前記オリゴマーを重合または架橋してポリジメチルシロキサンとし、固体色素レーザー媒質を形成する工程、および
前記媒質に、共振手段および励起用光源を配置する工程、
を含む、色素レーザーの製造方法。 - シリコーンオイルに色素を溶解して溶液を得る工程、
前記溶液を液状のジメチルシロキサンオリゴマーに混合して組成物を得る工程、
基材の上に前記組成物を塗布して塗布膜を形成する工程、
前記塗布膜塗中の前記オリゴマーを重合または架橋してポリジメチルシロキサンとし、固体色素レーザー媒質を形成する工程、および
前記媒質に、共振手段および励起用光源を配置する工程
を含む、色素レーザーの製造方法。 - ポリジメチルシロキサンを準備する工程、
前記ポリジメチルシロキサンを膨潤させない媒体に色素を溶解して、色素含有媒体を得る工程、
前記媒体と前記ポリジメチルシロキサンを接触させて、当該色素を当該ポリジメチルシロキサン中に拡散して固体色素レーザー媒質を形成する工程、
前記媒質に、共振手段および励起用光源を配置する工程
を含む、色素レーザーの製造方法。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US9448169B2 (en) | 2013-09-20 | 2016-09-20 | Kyushu University, National University Corporation | Light measuring apparatus, light measuring method, filter member, and method of making filter member |
CN114188814A (zh) * | 2021-12-23 | 2022-03-15 | 河北科技大学 | 一种hof复合激光染料及制备方法 |
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US11952496B1 (en) | 2023-05-02 | 2024-04-09 | King Saud University | Liquid and solid state laser from 7H-pyrano[2,3-B:4,5-B′]diquinoline derivatives using energy transfer mechanism |
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JPH11246661A (ja) * | 1998-03-04 | 1999-09-14 | Nippon Steel Corp | 透光性無機・有機ハイブリッド |
JP2002264244A (ja) * | 2001-03-08 | 2002-09-18 | Asahi Glass Co Ltd | フォトクロミック膜付き基体とその製造方法 |
JP2005506438A (ja) * | 2001-10-25 | 2005-03-03 | ザ・ビクトリア・ユニバーシテイ・オブ・マンチエスター | 光安定化有機材料 |
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2012
- 2012-03-29 JP JP2013507848A patent/JP5907569B2/ja not_active Expired - Fee Related
- 2012-03-29 WO PCT/JP2012/059278 patent/WO2012133920A1/ja active Application Filing
- 2012-03-29 US US14/008,315 patent/US9048628B2/en not_active Expired - Fee Related
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JPH09124794A (ja) * | 1995-11-06 | 1997-05-13 | Dow Corning Asia Ltd | 有機光機能材を含有するポリシロキサン樹脂組成物及びそれから得られる透明な光機能素子 |
JPH11246661A (ja) * | 1998-03-04 | 1999-09-14 | Nippon Steel Corp | 透光性無機・有機ハイブリッド |
JP2002264244A (ja) * | 2001-03-08 | 2002-09-18 | Asahi Glass Co Ltd | フォトクロミック膜付き基体とその製造方法 |
JP2005506438A (ja) * | 2001-10-25 | 2005-03-03 | ザ・ビクトリア・ユニバーシテイ・オブ・マンチエスター | 光安定化有機材料 |
JP2009516162A (ja) * | 2005-11-11 | 2009-04-16 | モレキュラー・ビジョン・リミテッド | マイクロ流体装置 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US9448169B2 (en) | 2013-09-20 | 2016-09-20 | Kyushu University, National University Corporation | Light measuring apparatus, light measuring method, filter member, and method of making filter member |
CN114188814A (zh) * | 2021-12-23 | 2022-03-15 | 河北科技大学 | 一种hof复合激光染料及制备方法 |
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JP5907569B2 (ja) | 2016-04-26 |
US9048628B2 (en) | 2015-06-02 |
JPWO2012133920A1 (ja) | 2014-07-28 |
US20140294032A1 (en) | 2014-10-02 |
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