WO2003034142A1 - Element optique et procede permettant de fabriquer cet element - Google Patents
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- WO2003034142A1 WO2003034142A1 PCT/JP2002/010794 JP0210794W WO03034142A1 WO 2003034142 A1 WO2003034142 A1 WO 2003034142A1 JP 0210794 W JP0210794 W JP 0210794W WO 03034142 A1 WO03034142 A1 WO 03034142A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/3523—Non-linear absorption changing by light, e.g. bleaching
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/257—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/258—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of reflective layers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/3515—All-optical modulation, gating, switching, e.g. control of a light beam by another light beam
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2203/00—Function characteristic
- G02F2203/26—Pulse shaping; Apparatus or methods therefor
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
- G11B2007/24318—Non-metallic elements
- G11B2007/24328—Carbon
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
- G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers
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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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/742—Carbon nanotubes, CNTs
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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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/753—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc. with polymeric or organic binder
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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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/21—Circular sheet or circular blank
Definitions
- the present invention relates to an optical element capable of controlling light in a communication wavelength range by utilizing the saturable absorption function of a single-walled carbon nanotube, and a method for manufacturing the same.
- Carbon nanotubes discovered in recent years are tubular materials. Ideally, a sheet-like structure of carbon hexagonal mesh (graph ensheet) is parallel to the axis of the tube to form a tube. This tube may be multiplexed.
- the carbon nanotubes are theoretically expected to exhibit metallic or semiconducting properties depending on how the hexagonal network made of carbon is connected and the thickness of the tube, and are expected to be future functional materials. .
- a carbon hexagonal mesh graphent is a carbon nanotube in which a tube is formed in parallel with the axis of the tube. (In the present invention, the carbon nanotube is defined in the narrow sense. ).
- carbon nanotubes in a narrow sense are further classified, and those having a structure of one hexagonal mesh tube are single-walled carbon nanotubes (hereinafter simply referred to as “carbon nanotubes”).
- S WNT single-layer hexagonal mesh tubes
- those composed of multi-layer hexagonal mesh tubes are multi-walled carbon nanotubes (hereinafter simply referred to as
- MWN T Metal-nitride-Nitride-Nitride-Nitride-Nitride-Nitride-Nitride-Nitride-Nitride-Nitride-Nitride-Nitride-Nitride-Nitride-Nitride-Nitride-Nitride-Nitride-Nitride-Nitride-Nitride-Nitorous .
- Attempts to improve the characteristics of electroluminescent devices by using high-efficiency field electron emission characteristics are at a stage near practical use (K. Matsumo toetal. Ex tended Abstractsofthe 200 0 State Devicesand Materials (2000) pp. 100-101, etc.).
- the optical applications of SWNTs have not been sufficiently studied.
- SWNT is known to have an absorption in the communication wavelength region (1.2 to 2 tm) 1.
- an optical element according to the present invention is characterized in that it has a thin film in which single-walled carbon nanotubes are laminated, and uses its saturable absorption function.
- a dispersion is prepared by dispersing a single-walled carbon nanotube in a dispersion medium, and the dispersion is spray-coated on an object to form a thin film. It is characterized by the following. BRIEF DESCRIPTION OF THE FIGURES
- Figure 1 is a graph showing the absorption characteristics of the SWNT thin film in the infrared region, with the horizontal axis plotting the light energy applied to the SWNT thin film and the vertical axis plotting the absorbance of the SWNT thin film. It is.
- FIG. 2 is a graph in which the portion of the absorption band with the lowest energy in the graph of FIG. 1 is extracted, and the horizontal axis is replaced with the light wavelength.
- FIG. 3 is a schematic configuration diagram for explaining the Z-scan method.
- FIG. 4 is a graph showing the results of measuring the saturable absorption of SWNT thin films by the Z-scan method.
- FIG. 5 is a schematic configuration diagram showing an outline of an experiment in which the optical element of the present invention was operated as a transmittance-change optical switch.
- FIG. 6 is a schematic cross-sectional view showing an embodiment of an optical element having the function of a saturable absorbing mirror.
- FIG. 7 is a graph for explaining the principle of waveform shaping when the optical element of the present invention is used as a waveform shaper having a waveform shaping function.
- the horizontal axis represents time, and the vertical axis represents light of an incident light pulse. This is a plot of strength.
- FIG. 8 is a schematic sectional view showing an embodiment of an optical element having the function of a super-resolution optical disc.
- carbon nanotubes There are two types of carbon nanotubes: single-walled carbon nanotubes, each of which has a single tube of carbon hexagonal mesh structure, and multi-walled carbon nanotubes, which are composed of multi-walled (multi-walled) tubes.
- a single-walled carbon nanotube having a high saturable absorption function is used.
- the diameter of the SWNT to be used is preferably 1.0 to 1.6 nm.
- the optical element of the present invention utilizes the light absorption of the pseudo one-dimensional exciton accompanying the interband transition, which is caused by the one-dimensional fan-hobe singularity of SWNT found in the 1.5 m band.
- the wavelength of this absorption varies greatly with the diameter of the SWNT. This is because the energy gap of SWNT is proportional to the reciprocal of the diameter.
- the basic absorption of the 1.5 band SWNTs other than this absorption is not so large, so even if various types of SWNTs are mixed, the function can be exhibited. This is because if a considerable amount of SWNTs exhibiting the absorption at the wavelength to be used is mixed, appropriate light absorption can be expected, and other SWNTs do not significantly affect the absorption.
- the diameter distribution is significantly widened, the light absorption by SWNTs other than the SWNT concerned (this is the tail absorption of ⁇ plasmon in the ultraviolet, so there is no saturable absorption effect) will have a significant effect, and the obtained optical In some cases, the performance of the device may be significantly deteriorated. Therefore, it is desirable that the diameter distribution of the SWNT used is as sharp as possible, centering on a tube having absorption at the wavelength.
- the method for producing the SWNTs used is not particularly limited, and includes a pyrolysis method using a catalyst (a method similar to a vapor phase growth method), an arc discharge method, and laser evaporation. Any of the conventionally known manufacturing methods such as a method may be employed. As described above, in the present invention, it is desired to use SWNT having a sharp diameter distribution. Currently, the laser evaporation method and the arc discharge method achieve a sharp diameter distribution. However, the SWNT of the arc discharge method contains a large amount of catalytic metal (which does not naturally contribute to the operation of the device), and it is difficult to purify it to high purity.
- SWNT by a laser evaporation method.
- CVD method chemical vapor deposition
- mixed rods of graphite powder and fine powders of nickel and cobalt were prepared.
- This mixed rod was heated to 1250 by an electric furnace under an argon atmosphere of 665 hPa (500 Torr), and irradiated with a second harmonic pulse of a 350 mJZPu 1 se Nd: YAG laser to obtain carbon and metal.
- the single-walled carbon nanotubes were produced by evaporating the fine particles (the above-mentioned production operation A).
- the above manufacturing method is only a typical example, and the kind of the metal, the kind of the gas, the temperature of the electric furnace, the wavelength of the laser, and the like may be changed.
- fabrication methods other than the laser evaporation method such as chemical vapor deposition (CVD), arc discharge, pyrolysis of carbon monoxide, and organic molecules in fine pores
- CVD chemical vapor deposition
- arc discharge pyrolysis of carbon monoxide
- organic molecules in fine pores Single-wall carbon nanotubes prepared by other methods such as a template method of inserting and thermally decomposing, a fullerene / metal co-evaporation method, etc. may be used.
- SWNT samples obtained by various methods contain more or less impurities as they are. In order to obtain an optical element with good performance, it is desirable to purify the SWNT sample.
- the purification method is not particularly limited.
- the SWNT sample by the laser evaporation method (production operation A) using the above-described NiCo fine metal particles is purified by the following procedure. I can.
- dispersion in ethanol is performed as a pretreatment for preparing a pure water dispersion. After dispersion, filtration is performed.
- Hydrogen peroxide solution is added to the obtained pure water dispersion to adjust the total amount of hydrogen peroxide (by volume) to 15%.
- the pure water dispersion to which the hydrogen peroxide solution was added was heated at 100 ° C. for 3 hours with a reflux device for reflux operation in order to burn the amorphous carbon as an impurity contained therein. Do. Then, filtration is performed.
- the substrate is washed with dilute hydrochloric acid in order to remove the NiCo metal fine particles.
- the SWNT sample is dispersed in dilute hydrochloric acid and stirred. Then, filtration is performed.
- the residue is washed with aqueous sodium hydroxide for the purpose of neutralizing residual hydrochloric acid and removing by-products by acid treatment.
- the SWNT sample is dispersed in an aqueous sodium hydroxide solution and stirred. Then, filtration is performed.
- SWNTs with extremely high purity can be produced (purification operation B in all of the above steps 1 to 10).
- the operation performed by the inventor of the present invention resulted in high-purity SWNT having a purity of 90% or more and containing almost no metal fine particles.
- Any method can be used as long as it can be purified to the same purity. For example, it is possible to burn amorphous carbon by heating it carefully in the air, or to purify it using diluted nitric acid or concentrated nitric acid.These methods are applied to the purification of SWNT used in the present invention. No problem.
- the optical element of the present invention can be obtained by forming a thin film in which the above SWNTs are laminated.
- the method for forming such a thin film is not particularly limited, as long as it is a method for forming a thin film in which SWNTs are finally laminated. Examples include a membrane method and a polymer dispersion method. Hereinafter, these thin film forming methods will be described.
- the spray method is a method of forming a thin film by using a dispersion obtained by dispersing the SWNT in a dispersion medium and spray-coating the dispersion.
- a dispersion is prepared by dispersing the purified SWNT in an appropriate dispersion medium.
- the dispersion medium that can be used include alcohol, dichloroethane, and dimethylformamide.Dichloroethane and dimethylformamide are preferable because they have very good dispersibility and the obtained thin film has good film quality.
- alcohol is preferable because of its high volatility. Examples of such alcohol include methanol, ethanol, isopropyl alcohol (IPA), and n-propyl alcohol, and among them, ethanol is particularly preferable.
- additives such as a surfactant can be used as necessary.
- a surfactant those generally used as a dispersant are preferably used.
- those having a polarity those having a functional group which can be chemically bonded to SWNT, and the like are preferable.
- the concentration of the carbon nanotubes in the dispersion is not particularly limited, but is preferably in the range of 1 to 2 mg / m1 when ethanol is used as the dispersion medium.
- the apparatus used for stirring is not particularly limited, and is a stirring blade type stirring apparatus. Examples thereof include an apparatus, a kneader, a roll mill, and an ultrasonic disperser. Among them, an ultrasonic disperser is preferable.
- the dispersion obtained as described above is spray-coated on a predetermined object to be coated.
- the method of spraying is not particularly limited, and it can be performed by a known device, conditions, and the like. For example, it can be performed by an air brush. At this time, since SWNT in a dispersion medium such as ethanol is easily aggregated, it is also effective to apply ultrasonic waves to the reservoir of the airbrush to disperse.
- the temperature of the object to be coated is increased by simultaneously blowing hot air with a drier or directly heating the object to be heated all day long so that the sprayed solution evaporates instantaneously.
- the purified SWNT is dispersed in a dispersion medium similar to the spray method such as dimethylformamide at a concentration of about 0.4 to 0.5 mg Zm1, and a 50% by mass aqueous sodium hydroxide solution is added thereto. About 1% by mass (external addition).
- a pair of electrodes is inserted into this dispersion at a distance of about 1 cm, and a DC voltage is applied between both electrodes. The voltage is preferably about 20 V.
- SWNT migrates to the positive electrode surface, deposits and forms a film. That is, in this method, the positive electrode is the object to be coated.
- the polymer dispersion method is a method in which purified SWNT is dispersed in a solution of a polymer such as polystyrene in an organic solvent, and the solution is applied to the surface of the object to be coated by any means such as a spinner. According to this method, a uniform film can be obtained, which is an effective method. However, there is a drawback that the chemical stability of SWNT deteriorates depending on the polymer used. Any polymer can be used as long as it can form a film.
- Polystyrene or the like, which has little effect on WNT, is preferred.
- the organic solvent one that can dissolve the polymer to be used may be appropriately selected.
- the concentration of the polymer in the organic solvent solution may be appropriately adjusted depending on the suitability for application, and the concentration of SWNT may be appropriately adjusted according to the desired amount of SWNT in the SWNT thin film.
- the SWNT manufacturing equipment It is also effective to insert an object to be coated, such as a substrate, into the SWNT manufacturing equipment and directly collect SWNT on the surface of the object to be coated.
- the amorphous carbon which is an impurity, is removed by oxidation in air, and the metal catalyst is removed by high-temperature sublimation heating in vacuum.
- the transmittance at the target wavelength should be about 0.1 to 10% in order for the SWNT thin film to exhibit a sufficient saturable absorption function. It is more preferable that the content be about 1%.
- Substrates on which the SWNT thin film is formed include substrates such as glass substrates and quartz substrates, optical materials and optical elements.
- a substrate is used as an object to be coated, an optical element using the saturable absorption function itself of the SWNT thin film to be formed can be manufactured.
- an optical material or an optical element is used as an object to be coated, it is possible to manufacture an optical element in which a saturable absorption function of a formed SWNT thin film is added to these optical functions. Specific objects to be coated will be described in each embodiment described later.
- the SWNT thin film obtained as described above exhibits multiple absorption bands in the infrared region.
- the absorption band with the lowest energy is located near 1.2 to 2 xm, which is the communication wavelength range, and the absorption peak wavelength is about 1.78 zm. Therefore, the optical element having the SWNT thin film formed thereon utilizes the saturable absorption function of the film, It can operate in the communication wavelength range.
- the SWNT thin film when used as a saturable absorbing material in the communication wavelength region, it is considered that the SWNT thin film has the following characteristics as compared with the semiconductor material.
- the cost of the semiconductor device can be kept extremely low.
- SWNT is relatively inexpensive in raw materials compared to other semiconductor materials, and can be mass-produced.
- a quantum structure forming process by a vacuum process such as a semiconductor quantum well is not required, it is only necessary to form a thin film directly on the surface of an object to be coated such as a substrate, so that the manufacturing is simple and the yield is good. From these facts, it is expected that optical devices can be manufactured at several orders of magnitude lower cost than semiconductor materials.
- the optical element can easily be provided with a saturable absorption function.
- a SWNT thin film on the surface of a reflecting mirror (mirror body)
- a conventional semiconductor material was used, it was necessary to form a quantum well layer directly on a reflector by a vacuum process.
- an existing optical element is used. Not only can manufacturing costs be significantly reduced, but it is also possible to form a saturable absorbing film in areas where film formation has been difficult to date, thereby creating new optical elements. It is possible.
- SWNT is composed of only a strong bond called sp 2 conjugate bond of carbon atom, and it has extremely high durability and light resistance because it has high electrical conductivity and heat hardly accumulates. Sex is expected.
- SWNT is stable in air and does not burn to about 500 Can be used under warm conditions. In vacuum, the structure does not change up to 1600, so it can be used at higher temperatures.
- the saturable absorption function of the SWNT thin film formed by the present invention was verified as follows by actually forming the SWNT thin film.
- SWNTs manufactured by the laser evaporation method (manufacturing operation A) using the above-described NiCo fine metal particles and purified by the above-described purification operation B were used.
- a liquid in which 1 to 2 mg of the above SWNT was dispersed in 5 ml of ethanol with an ultrasonic disperser was sprayed on the surface of the quartz substrate to form a SWNT thin film.
- the temperature of the quartz substrate was raised by simultaneously blowing hot air with a dryer, so that the sprayed solution was instantaneously evaporated.
- the obtained SWNT thin film is black, and the horizontal axis represents the light energy applied to the SWNT thin film, and the vertical axis represents the absorbance of the SWNT thin film. It showed multiple absorption bands.
- Figure 2 shows a graph in which the portion of the absorption band with the lowest energy is extracted and the horizontal axis is replaced by the light wavelength. As shown in Fig. 2, the lowest energy absorption band was located around 1.5 to 2 xm, and the absorption peak wavelength was 1.78 / m. From the Raman spectrum and the STM observation, it is estimated that the diameter of SWNT is distributed in the range of 1.2 to 1.6 nm.
- the saturable absorption function of the SWNT thin film was measured by a method called Z-scan method.
- Saturable absorption is a type of third-order nonlinear optical effect, in which a large amount of electrons are excited to the upper level under irradiation of a strong laser beam that matches the absorption wavelength, and electron excitation in this state is suppressed. This is a phenomenon in which absorption is temporarily reduced.
- FIG. 3 is a schematic configuration diagram for explaining the Z-scan method.
- the laser beam L is made incident on the lens 3 via a filter such as the UV power filter 1 and the ND filter 2, and a substantially intermediate point (focus X) between the lens 3 and the light receiver 5 To collect light.
- the sample 4 to be measured is moved from the lens 3 side to the light receiver 5 along the traveling direction of the laser light L.
- the focal point X is 0 (zero) with respect to the position Z of the sample 4 and the position on the lens 3 side from the focal point X is represented by — (minus), and the position on the light receiver 5 side is represented by + (plus),
- the decrease in absorbance due to absorption saturation was estimated from the increase in transmittance near the focal point X.
- a femtosecond laser beam was used as the laser light source, and the measurement wavelength was adjusted to 1.78 m, which is the absorption peak of the SWNT thin film, using an optical parametric ampli? Er (OPA).
- Fig. 4 shows a graph of the measured results.
- the horizontal axis represents the sample position (Z)
- the thickness of the SWNT film assuming 1 00 nm, is about 1 0- 6 esu when estimating the nonlinear optical constant from the incident light intensity.
- the figure of merit is about one order of magnitude lower than that of semiconductor quantum wells (QW), which is currently the main material for optical switching devices, and is a very promising value as a material that can be easily thinned from a solution dispersion state. is there.
- QW semiconductor quantum wells
- the Chi wave are possible SWNT as simple thinning, non-linear optical constant of the phthalocyanine are known as organic nonlinear optical material having a high nonlinearity is 1 0_ 1 ⁇ 1 0- 12 esu . This confirms that SWNT is very promising as a saturable absorber in the infrared region.
- FIG. 5 shows the outline of such an experiment.
- reference numeral 10 denotes an optical element having an optical switching function, which is formed by forming a SWNT thin film 11 on the surface of a glass substrate 12.
- the control light wavelength and the signal light wavelength were both set to 1.78 / m, and the change in the amount of transmitted light with and without the control light was measured with a power meter as the light receiver 5.
- the control light and signal light were produced by converting the wavelength of femtosecond laser light using OPA.
- the pulse width was 200 fs and the repetition period was 1 kHz.
- the optical element of the present embodiment can be used as an optical element (optical switch) having an optical switching function in the 1.2 to 2.0 m band.
- the surface of a glass substrate 12 is coated with a silver (Ag) mirror layer 14 on an Ag coat mirror (optical element).
- the SWNT thin film 11 was formed in the same manner as described in>, and an optical element having a saturable absorbing mirror function was manufactured.
- the dependence of the reflected light intensity on the irradiation light intensity was measured.
- an increase in the reflected light intensity was observed near the irradiation light intensity exceeding 1 O ⁇ JZ cm 2 'pulse, and the reflected light intensity was increased.
- the irradiation light intensity was about twice as large as 10 J Zcm 2 ⁇ pu 1 se.
- the optical element of the present embodiment can be used as an optical element having a saturable absorbing mirror function in the 1.2 to 2.0 m band.
- a SWNT thin film having a saturable absorption function When a SWNT thin film having a saturable absorption function is used, it is possible to form an optical element having a waveform shaping function that shortens the time width of an incident light pulse.
- the configuration of the optical element is basically the same as that of “(1) Optical switch”.
- the principle of waveform shaping when the optical element of the present invention is used as a waveform shaper having a waveform shaping function will be described.
- Fig. 7 shows a graph for this. In the graph of FIG. 7, the horizontal axis is time, and the vertical axis is the light intensity of the incident light pulse.
- the optical element of the present invention When viewed on the time axis, the optical element of the present invention has a low transmittance near the low light intensity at the front and rear ends of the pulse, and has a high transmittance near the high light intensity at the center of the pulse. As a result, the pulse transmitted through the SWNT thin film is cut (including reduced) at the front and rear ends of the pulse, and has a shorter time width than the original pulse.
- Waveform shaping experiments were performed with an infrared OPA system.
- infrared light with a pulse width of 4 to 6 ns and a repetition of 1 OHz can be oscillated.
- the output light having a wavelength of 1.78 rn. 3 mW was condensed to about 50NT ⁇ on the SWNT thin film and measured.
- a time width reduction of about 30% compared to the original pulse width was observed. This confirms that the SWNT thin film functions as a waveform shaper. Therefore, the optical element of the present embodiment can be used as an optical element having a waveform shaping function in the 1.2 to 2.0 am band.
- FIG. 8 is a schematic sectional view showing an optical element of the present invention having a function of a super-resolution optical disc for realizing super-resolution by reducing a spatial beam diameter.
- a pit 23 is formed on one surface of a substrate 21 made of a plastic material such as a polycarbonate resin, an acrylic resin, or a polyolefin resin, and pits 23 are formed thereon.
- a reflective layer 22 made of a metal such as gold, silver, aluminum, platinum, or copper, or an alloy containing these, is provided.
- the surface of the optical disk 25 on which the protective layer 24 is provided on the substrate 21 side hereinafter referred to as the “recording surface”.
- the “recording surface” refers to the irradiation beam
- the SWNT thin film 11 is formed on the surface. Note that the layer configuration of the optical disk 25 is not limited to that shown in FIG.
- the laser beam has a Gaussian beam pattern
- the light intensity is higher at the center than at the periphery. Therefore, when the SWNT thin film 11 is formed on the recording surface of the optical disk 25, when the laser light is irradiated from the recording surface side, the saturable absorption function of the SWNT thin film 11 causes a part of the center of the irradiation beam to be irradiated. Only light is transmitted. By this effect, it is possible to form a spot smaller than the beam focusing limit on the recording surface of the optical disk 25.
- An optical disk having such a function is referred to as a super-resolution optical disk, and the verification of the saturable absorption function of the SWNT thin film described above>
- the effect of reducing the beam diameter was observed for the optical element (super-resolution optical disk) shown.
- Irradiation was performed using the infrared ⁇ PA system used in the waveform shaping experiment.
- the output light having a wavelength of 1.788 m was condensed on the surface of the SWNT thin film 11, observed with a beam profiler, and compared with the original condensed beam diameter.
- a change in the beam pattern appeared near the irradiation light intensity exceeding 1 mW, and only the brightness at the center of the beam selectively increased.
- the beam diameter could be reduced to about 60% in radius compared to the original beam diameter. From this, it was confirmed that the SWNT thin film functions as a material for a super-resolution optical disc. Therefore, the optical element of the present embodiment can be used as an optical element having the function of a super-resolution optical disk.
- the active element such as an optical switch capable of actively controlling the signal light by the external control light, and the signal light itself.
- a passive element such as a saturable absorption mirror whose signal light is passively controlled can be arbitrarily manufactured.
- the four embodiments of the optical element of the present invention utilizing the saturable absorption function of the SWNT thin film have been described.
- the present invention is not limited to the embodiments described here. It covers all optical devices fabricated using the saturable absorption function of T thin film by resonance excitation. Industrial applicability
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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US10/492,751 US6936322B2 (en) | 2001-10-18 | 2002-10-17 | Optical element, and manufacturing method thereof |
KR1020047004976A KR100619773B1 (ko) | 2001-10-18 | 2002-10-17 | 광학 소자 및 그 제조 방법 |
EP02801591A EP1445647A4 (en) | 2001-10-18 | 2002-10-17 | OPTICAL ELEMENT AND MANUFACTURING METHOD THEREFOR |
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JP2001/320383 | 2001-10-18 | ||
JP2001320383A JP4306990B2 (ja) | 2001-10-18 | 2001-10-18 | 非線形光学素子 |
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WO2003034142A1 true WO2003034142A1 (fr) | 2003-04-24 |
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PCT/JP2002/010794 WO2003034142A1 (fr) | 2001-10-18 | 2002-10-17 | Element optique et procede permettant de fabriquer cet element |
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US (1) | US6936322B2 (ja) |
EP (1) | EP1445647A4 (ja) |
JP (1) | JP4306990B2 (ja) |
KR (1) | KR100619773B1 (ja) |
CN (1) | CN1325990C (ja) |
WO (1) | WO2003034142A1 (ja) |
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Also Published As
Publication number | Publication date |
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CN1571941A (zh) | 2005-01-26 |
EP1445647A1 (en) | 2004-08-11 |
US6936322B2 (en) | 2005-08-30 |
EP1445647A4 (en) | 2007-05-23 |
US20050069669A1 (en) | 2005-03-31 |
KR100619773B1 (ko) | 2006-09-08 |
JP2003121892A (ja) | 2003-04-23 |
JP4306990B2 (ja) | 2009-08-05 |
CN1325990C (zh) | 2007-07-11 |
KR20040048934A (ko) | 2004-06-10 |
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