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WO2014050308A1 - Élément optique de diffraction et procédé et dispositif de production d'élément optique de diffraction - Google Patents

Élément optique de diffraction et procédé et dispositif de production d'élément optique de diffraction Download PDF

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Publication number
WO2014050308A1
WO2014050308A1 PCT/JP2013/070992 JP2013070992W WO2014050308A1 WO 2014050308 A1 WO2014050308 A1 WO 2014050308A1 JP 2013070992 W JP2013070992 W JP 2013070992W WO 2014050308 A1 WO2014050308 A1 WO 2014050308A1
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WIPO (PCT)
Prior art keywords
optical element
diffractive optical
polymer material
material layer
dye
Prior art date
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Ceased
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PCT/JP2013/070992
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English (en)
Japanese (ja)
Inventor
佐々木俊央
望月英宏
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Fujifilm Corp
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Fujifilm Corp
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Publication of WO2014050308A1 publication Critical patent/WO2014050308A1/fr
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Ceased legal-status Critical Current

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/18—Diffraction gratings
    • G02B5/1847—Manufacturing methods
    • G02B5/1857—Manufacturing methods using exposure or etching means, e.g. holography, photolithography, exposure to electron or ion beams
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
    • G03F7/2053—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
    • G03H1/024—Hologram nature or properties
    • G03H1/0244—Surface relief holograms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/04—Processes or apparatus for producing holograms
    • G03H1/08—Synthesising holograms, i.e. holograms synthesized from objects or objects from holograms
    • G03H1/0891—Processes or apparatus adapted to convert digital holographic data into a hologram
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H2224/00—Writing means other than actinic light wave
    • G03H2224/06—Thermal or photo-thermal means
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H2260/00—Recording materials or recording processes
    • G03H2260/30—Details of photosensitive recording material not otherwise provided for
    • G03H2260/33—Having dispersed compound
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H2260/00—Recording materials or recording processes
    • G03H2260/50—Reactivity or recording processes
    • G03H2260/61—Producing material deformation

Definitions

  • the present invention relates to a diffractive optical element that can be used as an image display device, a security element, an optical filter element, and the like, and a manufacturing method and a manufacturing apparatus of the diffractive optical element.
  • Patent Document 1 a method for manufacturing a diffractive optical element
  • Patent Document 2 a method of manufacturing a diffractive optical element by forming a fine uneven shape by laser ablation by irradiating the surface of a polymer material with laser light.
  • the diffractive optical element according to one embodiment of the present invention includes a polymer material layer, and the polymer material layer is dispersed in the polymer material and the polymer material layer, or the polymer material layer And a dye which is covalently bonded to a molecular material, and a diffractive optical element pattern having dot-like openings and / or convex portions is arranged at the interface of the polymer material layer.
  • the dye contained in the polymer material layer absorbs laser light, thereby giving energy to the polymer material layer with high efficiency and opening the interface at the polymer material layer. It is also possible to form a diffractive optical element pattern by forming convex portions. Therefore, it is not necessary to perform etching, and it can be easily manufactured in a short irradiation time. Further, since the openings and / or convex portions are formed by deforming the interface rather than peeling the material as in laser ablation, it is possible to form a diffractive optical element pattern that can be finely controlled in gradation. .
  • the opening referred to in the present invention may be a bottomed recess or may penetrate the polymer material layer.
  • the dye may include a one-photon absorption dye.
  • the dye contains a one-photon absorption dye, it can be processed with a low energy laser such as a semiconductor laser.
  • the dye may include a multiphoton absorbing dye.
  • a diffractive optical element having high transmittance in the visible wavelength region can be obtained.
  • the diffractive optical element described above can have a support that supports the polymer material layer. By providing the support, it is possible to reduce the cost by thinning the polymer material layer.
  • the diffractive optical element described above preferably includes a cover layer on the side where the openings and / or convex portions of the polymer material layer are arranged.
  • the cover layer is provided on the side where the openings and / or convex portions are arranged, the functions of the diffractive optical element can be maintained by protecting the openings and / or convex portions.
  • a multi-value diffractive optical element pattern is formed by the plurality of types of openings and / or projections. It can be set as a structure. By configuring the multi-value diffractive optical element pattern in this way, it is possible to enhance the function of the diffractive optical element, such as removing unnecessary diffraction images. In order to change the depth or height of the opening and / or the convex portion, it is only necessary to adjust the irradiation time of the laser beam. Therefore, a highly functional diffractive optical element can be easily manufactured. it can.
  • the dye has an absorption wavelength band of mainly 450 nm or less and a light transmittance of a wavelength of 450 to 800 nm of 50% or more. That is, the dye mainly absorbs light in a wavelength region of 450 nm or less, whereby a diffractive optical element that is relatively colorless (highly transmissive in the visible wavelength region) can be obtained.
  • a method for manufacturing a diffractive optical element comprising: preparing a polymer material layer having a polymer material in which a dye is dispersed or a polymer material having a dye covalently bonded; Dot-shaped openings and / or protrusions that form a diffractive optical element pattern at the interface by irradiating laser light having a wavelength that is absorbed by the dye in the vicinity to deform the interface and performing this irradiation at the interface in a predetermined pattern It is characterized by forming.
  • the irradiation time of the laser beam for forming one opening or convex portion is 120 ⁇ sec or less.
  • the diffractive optical element can be manufactured at high speed.
  • the reflected light from the interface is detected by the sensor during the irradiation of the laser light, and the focal position of the laser light is adjusted to a predetermined position based on the output signal of the sensor.
  • the focal position based on the reflected light from the interface it is possible to obtain a diffractive optical element with desired performance by aligning the size of the opening or the recess.
  • a diffractive optical element manufacturing apparatus for forming a diffractive optical element pattern on a polymer material layer having a polymer material in which a dye is dispersed or a polymer material to which a dye is covalently bonded.
  • the diffractive optical element manufacturing apparatus includes a light source that emits laser light having a wavelength that is absorbed by the dye, a deflector that deflects the laser light emitted from the light source, and a laser beam deflected by the deflector as a polymer material.
  • An image forming optical system for forming an image near the interface of the layer, and a control device for controlling the output of the light source and the deflector.
  • the control device is a dot that forms a diffractive optical element pattern at the interface of the polymer material layer.
  • the output of the light source is changed in synchronism with the scanning of the laser beam on the interface of the polymer material layer by controlling the deflector so as to form an opening and / or a convex portion.
  • an optical diffractive element can be manufactured by changing the output of a light source while scanning a laser beam with a deflector and forming an opening and / or a convex portion at the interface of the polymer material layer. it can. Further, since the diffractive optical element pattern is formed at the interface by scanning the laser beam on the interface, it is not necessary to use a mask as in the prior art. Furthermore, in this manufacturing apparatus, since the diffractive optical element pattern is formed by scanning the laser beam on the interface with a deflector, it is not necessary to move the polymer material layer during processing. The manufacturing apparatus irradiates the polymer material layer containing the dye with laser light to form openings and / or projections, so that the output of the laser light can be reduced and the processing can be performed at high speed. .
  • the imaging optical system includes an objective lens and at least two condenser lenses.
  • the irradiation time of the laser light for forming one opening or convex portion is 120 ⁇ sec or less.
  • the diffractive optical element can be manufactured at high speed.
  • the imaging optical system preferably includes an objective lens, and the objective lens preferably has a numerical aperture of 0.13 or more.
  • the objective lens preferably has a numerical aperture of 0.13 or more.
  • the manufacturing apparatus described above further includes a sensor that detects the laser light reflected at the interface, and the control apparatus controls the imaging optical system based on the output signal of the sensor to adjust the focal position of the laser light to a predetermined position. It is desirable to be configured as follows.
  • the size of the opening or the concave portion is made uniform, and a diffractive optical element having a desired performance can be obtained.
  • the wavelength of the laser light emitted from the light source is preferably 450 nm or less.
  • a dye that does not absorb much visible light can be used as a dye, so that the diffractive optical element can be made relatively colorless.
  • a transport device that moves the polymer material layer relative to the laser beam.
  • a plurality of diffractive optical elements can be continuously manufactured by moving the polymer material layer by the transport device.
  • the diffractive optical element can be easily manufactured in a short time.
  • a diffractive optical element pattern is formed at the interface by scanning the interface with laser light, so that it is not necessary to use a mask as in the prior art.
  • the diffractive optical element pattern is formed by scanning the laser beam on the interface with the deflector, and therefore it is not necessary to move the polymer material layer during processing.
  • FIG. 5 is a simulation result of a reproduced image using the (a) design original image, (b) phase pattern, and (c) (b) phase pattern in the diffractive optical element of Example 1 displaying an image as a diffraction image.
  • . 2 is a laser microscope image of the diffractive optical element of Example 1.
  • FIG. 17 is a laser microscope image of the diffractive optical element of Example 1 in which a part of the visual field in FIG. 16 is enlarged.
  • 2 is a cross-sectional profile of a concave portion of the diffractive optical element of Example 1.
  • 2 is a reproduced image using the diffractive optical element of Example 1.
  • FIG. It is the reproduction
  • 4 is an atomic force microscope image of the diffractive optical element of Example 3.
  • FIG. 10 is a cross-sectional profile of a convex portion of a diffractive optical element of Example 3.
  • the diffractive optical element E of the present invention is a diffractive optical element pattern formed by forming fine dot-shaped openings and / or convex portions in a predetermined range of a sheet-like member.
  • the pattern area PA on which the diffractive optical element pattern is formed has a square as an example, but the shape of the pattern area PA is not particularly limited.
  • the diffractive optical element E an element that obtains a diffracted image that becomes a predetermined image by applying a laser beam is exemplified.
  • the diffractive optical element E is arranged in the order of the reproduction laser L2, the diffractive optical element E, and the screen SC, and emits the reproduction laser light LB2 from the reproduction laser L2.
  • the laser beam LB2 for use is passed through the pattern area PA to obtain the diffracted light DB.
  • the diffracted light DB displays a predetermined image by irradiating the pattern region PA with the reproduction laser beam LB2.
  • the diffractive optical element E can also be used as shown in FIG.
  • the reproducing laser L2, the screen SC, and the diffractive optical element E are arranged in this order, and the hole SC1 is formed in the screen SC. Then, the reproducing laser beam LB2 emitted from the reproducing laser L2 is applied to the pattern area PA of the diffractive optical element E through the hole SC1. In this way, the reproduction laser beam LB2 is diffracted by the diffractive optical element pattern while being reflected at the interface where the diffractive optical element pattern of the diffractive optical element E is formed, and displays a predetermined image on the screen SC. be able to.
  • the diffractive optical element E As shown in FIG. 4, the diffractive optical element E according to the first embodiment has a structure composed of two layers in which a polymer material layer 20 is provided on a support 10.
  • the support 10 is a member for supporting the polymer material layer 20.
  • the material of the support 10 is not particularly limited, but is made of a material that can transmit the reproducing laser beam LB2 of the reproducing laser L2 as an example because the reproducing laser beam LB2 is transmitted therethrough.
  • the support 10 may be a member that is opaque to the reproduction laser beam LB2.
  • the support 10 may be a metal plate, and the surface of the support 10 on the polymer material layer 20 side may be used as a reflection surface.
  • the thickness of the support 10 is not particularly limited as long as it has sufficient mechanical properties to support the polymer material layer 20, and may be a film of about 1 mm or less, for example, about 1 mm or more. A plate-like member may be used.
  • the polymer material layer 20 has a diffractive optical element pattern formed by dot-like openings and / or convex portions (hereinafter, sometimes referred to as “lattice points”) at the interface, here the interface 21 with the air layer. It is a layer to be formed.
  • a plurality of recesses 31 are formed as an example of the opening.
  • the concave portions 31 in FIG. 4 are dot-like when viewed in plan, and all have substantially the same depth and diameter.
  • the diffractive optical element pattern is designed according to a desired reproduced image, and is, for example, a pattern like the laser microscope image of FIGS.
  • the polymer material layer 20 has a dispersed dye or a dye covalently bonded to the polymer material in the polymer material layer 20.
  • the dye When the dye is covalently bonded to the polymer material, it prevents the precipitation and elution of the dye due to long-term storage, and can reduce the time-dependent change in optical properties such as transmittance and reflectance, and has excellent long-term storage
  • a diffractive optical element can be constructed.
  • the dye herein can include a one-photon absorbing dye and / or a multi-photon absorbing dye.
  • a one-photon absorption dye When a one-photon absorption dye is included, it can be processed with a low energy laser such as a semiconductor laser.
  • a multiphoton absorbing dye when a multiphoton absorbing dye is included, the diffractive optical element E1 having high transparency in the visible wavelength region can be configured.
  • the one-photon absorption dye is preferably a one-photon absorption compound that does not have a linear absorption band at the wavelength of the reproduction laser beam LB2, and the multiphoton absorption dye does not have a linear absorption band at the wavelength of the reproduction laser light LB2.
  • a multiphoton absorbing compound is preferred.
  • the absorptance (one-photon absorptance) of the polymer material layer 20 with respect to laser light (recording laser light) for forming lattice points is desirably 5% or more per 1 ⁇ m thickness, and is 10% or more. Is more desirable.
  • the higher the absorptance the faster the temperature of the polymer material can be increased when the recording laser light is irradiated, the diffractive optical element E1 can be formed in a short time, and a low energy laser light source is used. be able to.
  • the formation method of the polymer material layer 20 is not particularly limited, but the polymer material layer 20 can be formed by spin coating or blade coating using a solution obtained by dissolving a dye material and a polymer material in a solvent.
  • a solvent As the solvent at this time, dichloromethane, chloroform, methyl ethyl ketone (MEK), acetone, methyl isobutyl ketone (MIBK), toluene, hexane, or the like can be used.
  • Polymer materials used for the polymer material layer 20 include polyvinyl acetate (PVAc), polymethyl methacrylate (PMMA), polyethyl methacrylate, polybutyl methacrylate, polybenzyl methacrylate, polyisobutyl methacrylate, polycyclohexyl methacrylate, polycarbonate (PC ), Polystyrene (PS), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), and the like.
  • the range of the molecular weight Mw of the polymer material (or polymer material to which a dye is covalently bonded) in the polymer material layer 20 is preferably 10,000 to 1,000,000.
  • the molecular weight Mw can be measured by gel permeation chromatography (GPC).
  • the glass transition point Tg of the polymer material is preferably 60 ° C. or higher, and more preferably 100 ° C. or higher.
  • the glass transition point Tg of the polymer material is preferably 300 ° C. or lower in order to realize high-speed processing of lattice points.
  • the dye dispersed in the polymer material or the dye covalently bonded to the polymer material is a methine dye (cyanine dye, hemicyanine dye, styryl dye, oxonol dye, merocyanine dye, etc.) as long as it is a one-photon absorption dye.
  • Macrocyclic dyes phthalocyanine dyes, naphthalocyanine dyes, porphyrin dyes, etc.
  • azo dyes including azo metal chelate dyes
  • arylidene dyes complex dyes, coumarin dyes, azole derivatives, triazine derivatives, benzotriazole derivatives, benzophenone derivatives, phenoxy Sazine derivatives, phenothiazine derivatives, 1-aminobutadiene derivatives, cinnamic acid derivatives, quinophthalone dyes, and the like
  • azo dyes including azo metal chelate dyes
  • arylidene dyes complex dyes
  • coumarin dyes coumarin dyes
  • azole derivatives triazine derivatives
  • benzotriazole derivatives benzophenone derivatives
  • phenoxy Sazine derivatives phenothiazine derivatives
  • 1-aminobutadiene derivatives 1-aminobutadiene derivatives
  • triazine derivatives, benzotriazole derivatives, and benzophenone derivatives are ultraviolet absorbing dyes, the absorption wavelength band is mainly 450 nm or less, and the light transmittance at a wavelength of 450 to 800 nm is 50% or more. Therefore, when these dyes are used, light in a wavelength region of 450 nm or less is mainly absorbed, so that a relatively colorless diffractive optical element E1 can be configured.
  • the dye compound is not particularly limited as long as it does not have a linear absorption band at the wavelength of the reproduction laser beam LB2.
  • the dye compound is represented by the following general formula (1). Examples thereof include compounds having a structure.
  • X and Y each represent a substituent having a Hammett's sigma para value ( ⁇ p value) of zero or more, which may be the same or different, and n represents an integer of 1 to 4.
  • R represents a substituent, which may be the same or different, and m represents an integer of 0 to 4.
  • X and Y are those having a positive ⁇ p value in the Hammett formula, so-called electron-withdrawing groups, and preferably, for example, a trifluoromethyl group, a heterocyclic group, a halogen atom, a cyano group Nitro group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, carbamoyl group, acyl group, acyloxy group, alkoxycarbonyl group, etc., more preferably trifluoromethyl group, cyano group, acyl group, acyloxy group, Or an alkoxycarbonyl group, and most preferably a cyano group or a benzoyl group.
  • an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a carbamoyl group, an acyl group, an acyloxy group, and an alkoxycarbonyl group are further added for various purposes in addition to imparting solubility to a solvent. It may have a substituent, and preferred examples of the substituent include an alkyl group, an alkoxy group, an alkoxyalkyl group, and an aryloxy group.
  • n is preferably 2 or 3, most preferably 2. As n becomes 5 or more, linear absorption comes out on the longer wavelength side, and non-resonant two-photon absorption recording using recording light in a wavelength region shorter than 700 nm becomes impossible.
  • R represents a substituent, and the substituent is not particularly limited, and specific examples include an alkyl group, an alkoxy group, an alkoxyalkyl group, and an aryloxy group.
  • Specific examples of the compound having the structure represented by the general formula (1) are not particularly limited, but compounds represented by the following chemical structural formulas D-1 to D-21 can be used.
  • polymer material to which the dye is covalently bonded for example, a compound represented by the following general formula (2) can be used.
  • Y represents a substituent in which both Hammett's sigma para value ( ⁇ p value) has a value of zero or more, and X also represents the same kind of substituent.
  • N represents an integer of 1 to 4
  • R1, R2, and R3 represent substituents, which may be the same or different
  • l represents 1 or more
  • m represents an integer of 0 to 4.
  • the concave portion 31 can be formed by condensing and irradiating the recording material laser beam on the polymer material layer 20, and the diffractive optical element E1 can be manufactured.
  • the dye contained in the polymer material layer 20 is made to absorb the recording laser light, whereby energy can be given to the polymer material layer 20 with high efficiency, and the diffractive optical element E1 can be manufactured in a short time.
  • the diffractive optical element E1 can be manufactured in a short time because etching is not necessary at the time of manufacture.
  • the recess 31 is formed by deforming the interface rather than peeling the material as in laser ablation, a fine and gradation-controllable optical element pattern can be formed. Further, by supporting the polymer material layer 20 on the support 10, the polymer material layer 20 can be thinned, and the cost can be reduced.
  • the diffractive optical element E2 of the second embodiment includes a support 10 and a polymer material layer 20, and lattice points on the opposite side of the polymer material layer 20 from the support 10 are arranged.
  • a cover layer 41 is provided on the provided side.
  • the cover layer 41 is for protecting the shape of the lattice points mechanically or chemically.
  • the configuration of the cover layer 41 is not particularly limited as long as the lattice points are not adversely affected.
  • the cover layer 41 can be provided by applying and curing an ultraviolet curable resin.
  • the cover layer 41 may be configured by attaching a film (such as polycarbonate) with an adhesive.
  • the diffractive optical element E2 of the second embodiment has a lattice point constituted by a convex portion 32. Whether the lattice point is an opening or a convex portion is determined by the absorption energy (output, irradiation time and absorption rate) of the polymer material layer 20 when the recording laser beam is irradiated. If it is large, it tends to be an opening.
  • the cover layer 41 protects the lattice points and can be stored for a long time.
  • the lattice points are preferably formed after the cover layer 41 is provided. By doing so, the shape of the lattice points is not disturbed when the cover layer 41 is provided, and the presence of air or the like between the cover layer 41 and the polymer material layer 20 can be suppressed.
  • the diffractive optical element E ⁇ b> 3 has a form in which the lattice point is a hole 33 penetrating the polymer material layer 20 with respect to the first embodiment.
  • Such holes 33 may be formed by thinly forming the polymer material layer 20 and exposing the polymer material layer 20 with large energy when forming lattice points. Even if such holes 33 are used as lattice points, the function of the diffractive optical element can be exhibited as in the first embodiment, and it can be manufactured easily and in a short time.
  • the dye of the polymer material layer 20 absorbs a lot of light in the visible wavelength region (for example, 50% or more).
  • the reproduction laser beam LB2 can be passed through the hole 33, and the diffracted light of the light that has passed through the hole 33 can be used.
  • the diffractive optical element E4 according to the fourth embodiment is obtained by eliminating the support 10 from the first embodiment, and instead of providing the support 10, the thickness of the polymer material layer 20 is increased. And the shape of the diffractive optical element E4 is maintained.
  • the polymer material layer 20 may be a film of about 1 mm or less or a plate-shaped member of about 1 mm or more.
  • the manufacturing process can be simplified by omitting the support.
  • the diffractive optical element E5 according to the fifth embodiment is different from the first embodiment in that the diffractive optical element E5 has lattice points on the inner interface on the support side instead of the interface with the air of the polymer material layer 20.
  • a recess 31 is formed.
  • an adhesive that is a layer softer than the polymer material layer 20 for example, having a low glass transition point Tg) between the support 10 and the polymer material layer 20 so that the inner interface is easily deformed.
  • Layer 42 is interposed.
  • the recording laser beam may be condensed and irradiated near the inner interface.
  • the lattice points may be convex when viewed from the polymer material layer 20 (may project from the polymer material layer 20).
  • the shape of the lattice points can be changed without providing the cover layer 41 separately. Can be protected.
  • the diffractive optical element E6 is different from the first embodiment in that a reflective layer 43 is provided on the outer surface of the polymer material layer 20.
  • the reflective layer 43 may be a metal thin film, or may be a layer made of a material having a refractive index significantly different from that of the polymer material layer 20.
  • the diffractive optical element E6 having such a configuration, as indicated by an arrow in FIG. 9, the reproducing laser beam LB2 is reflected by the reflective layer 43, and the reproducing laser beam LB2 is incident on the diffractive optical element E6.
  • a reproduced image can be formed.
  • the reproduction laser beam LB2 is irradiated from the outside (upper side of the drawing) of the reflective layer 43, but the reproduction laser beam LB2 is irradiated from the opposite side (lower side of the drawing). I do not care.
  • the diffractive optical element E7 according to the seventh embodiment is different from the first embodiment in that the grating point is not limited to the concave portion 31 having a constant depth, but different depths, for example, the concave portion 31.
  • the deep concave portions 31B are mixed and arranged. In order to make the depths of the recesses different, it is only necessary to make the irradiation time of the recording laser light different during manufacture. When the recording laser light is irradiated for a short time, a shallow concave portion is formed, and when irradiated for a long time, a deep concave portion is formed.
  • the concave portions 31 and the concave portions 31B having different depths when there are the concave portions 31 and the concave portions 31B having different depths, when the reproduction laser beam LB2 is diffracted at each lattice point during use, the optical path length of the diffracted light is different at each lattice point.
  • the diffraction angle which is the traveling direction determined by the interference of the reproduction laser beam LB2 diffracted by a plurality of lattice points, can be adjusted.
  • the multi-valued diffraction grating using the concave portion 31 and the concave portion 31B can give variations to the image, such as fading the inverted image or the secondary diffraction image.
  • the recesses 31 and the recesses 31B having two kinds of depths are mixed in the lattice point is illustrated here, the recesses having three or more kinds of depths may be mixed.
  • the diffractive optical element E8 according to the eighth embodiment is obtained by arranging not only the concave portions 31 but also the convex portions 32 in the lattice points in the first embodiment.
  • the concave portion 31 and the convex portion 32 are present, as in the seventh embodiment, when the reproduction laser beam LB2 is diffracted at each lattice point during use, the optical path length of the light diffracted at each lattice point is set. Since the difference is made, it is possible to adjust the diffraction angle, which is the traveling direction determined by the interference of the reproduction laser beam LB2 diffracted by a plurality of lattice points. For this reason, the multi-valued diffraction grating using the concave portion 31 and the convex portion 32 can give variations to the image, such as fading the inverted image or the secondary diffraction image.
  • a structured diffraction grating may be configured.
  • a diffractive optical element pattern may be formed.
  • diffractive optical element E Although various forms of the diffractive optical element E have been described above, the features of the diffractive optical elements E can be applied in combination with each other.
  • the manufacturing apparatus 50 mainly includes a recording laser 51 as a light source, a deflector 52, a stage 57, an imaging optical system 60, and a control device 59.
  • the recording laser 51 is a laser that emits the recording laser beam LB1, and is preferably a semiconductor laser.
  • the wavelength of the recording laser beam LB1 is a wavelength that is absorbed by the dye in the polymer material layer 20 (one-photon absorption and / or multiphoton absorption), and the wavelength of the reproducing laser beam LB2 used when the diffractive optical element E is used. It is desirable to be different from the wavelength. Accordingly, since the diffractive optical element E is suppressed from being heated by the reproducing laser beam LB2 during reproduction, the reproducing laser beam LB2 having a large output can be used during reproduction. In particular, when the diffractive optical element E for image display is manufactured, it is desirable that the diffractive optical element E has high transparency in the visible wavelength range. Therefore, the recording laser 51 has a wavelength of 450 nm or less. It is desirable that the laser beam LB1 is emitted.
  • the recording laser 51 is preferably a short wavelength laser capable of reducing the spot size of the recording laser beam LB1, and in particular, 400 to 410 nm.
  • the semiconductor laser may be preferable.
  • the recording laser 51 may have an output with an average power of 10 mW or more, more preferably 100 mW or more. Note that, when a multiphoton absorption dye is used as the dye in the polymer material layer 20, a wavelength without linear absorption is used, so that it is easy to make a diffractive optical element E that is particularly highly transparent in the visible wavelength region.
  • the deflector 52 is a device that deflects the traveling direction of the recording laser light emitted from the recording laser 51, and a galvanometer mirror, a polygon mirror, a resonant mirror, or the like can be used. Alternatively, the deflector 52 may employ an electro-optic element (EO element) to deflect the traveling direction of the recording laser beam LB1.
  • EO element electro-optic element
  • the deflector 52 may deflect the recording laser beam LB1 in at least one direction. However, in the case of using a deflector that deflects in two directions, such as a biaxial galvanometer mirror, the material EM of the diffractive optical element E placed on the stage 57 (with no lattice points recorded) is not moved. A diffractive optical element pattern can be manufactured.
  • the stage 57 may be configured so that the material EM can be conveyed in a direction orthogonal to the one direction.
  • the stage 57 is a table on which the material EM is placed.
  • the stage 57 may be one that does not move while the material EM is fixed, but as shown in FIG. 13, it is desirable that the stage 57 is a transport stage configured to transport the material EM in one direction.
  • the transport stage 570 includes a winding roller 571 that winds the strip-shaped material EM and an unwinding roller 572 that transports the material EM while stretching the material EM between the winding roller 571 and the unwinding roller 572. It is.
  • the material EM is transported, and the deflector 52 scans the recording laser beam LB1 in a direction that intersects at least the transport direction of the transport stage 570 (for example, a direction orthogonal thereto).
  • the deflector 52 may deflect the recording laser beam LB1 only in the direction intersecting the transport direction of the transport stage 570, or in the direction intersecting the transport direction of the transport stage 570 and in the transport direction. It may be deflected in both directions.
  • the transport stage 570 is stopped while the one row of diffractive optical elements E is manufactured, and the transport stage 570 is operated each time the one row of diffractive optical elements E is manufactured to transport the material EM for one row. Good.
  • the imaging optical system 60 includes a first condenser lens 61, a second condenser lens 62, and an objective lens 63.
  • the first condenser lens 61 and the second condenser lens 62 are both lenses having the same focal length f, and constitute a so-called 4f optical system.
  • the reflecting surface of the deflector 52 is disposed in the vicinity of the focal position on the front side of the first condenser lens 61.
  • the objective lens 63 is a condensing lens that forms an image of the recording laser beam LB1 that has passed through the second condensing lens 62 in the vicinity of the interface of the polymer material layer 20, and is disposed at the focal position of the second condensing lens 62. ing.
  • the objective lens 63 is provided with a focus actuator 63A.
  • the objective lens 63 is preferably an f ⁇ lens that is corrected so that the image height is proportional to the deflection angle in the scanning range.
  • the objective lens 63 preferably has a numerical aperture of 0.13 or more. Thereby, the recording laser beam LB1 can be condensed to form fine lattice points.
  • the recording laser beam LB1 having a predetermined beam diameter deflected by the deflector 52 passes through the first condenser lens 61 and is deflected.
  • the image is once formed at an intermediate point between the first condenser lens 61 and the second condenser lens 62 in parallel with the traveling direction of the non-recording laser beam LB1.
  • the same beam diameter and the same deflection angle as when exiting the deflector 52 are obtained.
  • the recording laser beam LB1 is narrowed down by the objective lens 63 at the focal position on the rear side so as to form an image in a minute spot shape on the image plane IM.
  • the recording laser beam LB1 deflected by the deflector 52 can be scanned along the interface of the polymer material layer 20 with a simple configuration.
  • the 4f optical system having the simplest configuration is illustrated.
  • the space between the biaxial reflecting mirrors of the deflector 52 with the 4f optical system, the aberration of the condensed spot in the laser scanning range is illustrated. It is also possible to make the imaging optical system 60 smaller by reducing the above-mentioned or by adopting an aspheric lens.
  • a PBS (polarized beam splitter) 54 and a quarter wavelength plate 55 are arranged in this order.
  • a light receiving element 53 (sensor) for focusing is disposed on the side of the PBS 54.
  • the PBS 54 is an optical element that reflects and separates light of a specific polarization, passes the recording laser light LB1 emitted from the recording laser 51 and advances it toward the quarter wavelength plate 55, and 1 / It fulfills the function of reflecting the light returned from the four-wavelength plate 55 and advancing it toward the light receiving element 53.
  • the quarter-wave plate 55 is an optical element that converts linearly polarized light into circularly polarized light and converts the circularly polarized light into linearly polarized light in a direction corresponding to the rotation direction, and the recording laser beam LB1 travels toward the deflector 52.
  • the direction of polarized light differs by 90 ° between when reflected from the material EM and then returned from the deflector 52.
  • the control device 59 receives the signal from the light receiving element 53, controls the focus actuator 63A, and functions to adjust the focus of the recording laser beam LB1 near the interface of the polymer material layer 20 in the material EM. This focus adjustment is performed by adjusting the relative distance between the objective lens 63 and the polymer material layer 20 so that the intensity of the reflected light is maximized, or by one-dimensional or two-dimensional gain obtained by scanning the recording laser beam LB1. The contrast of the three-dimensional light intensity profile can be maximized, or a so-called astigmatism method can be used.
  • the control device 59 operates the deflector 52 to scan the recording laser beam LB1 along the polymer material layer 20, and controls the output of the recording laser 51 based on the exposure data stored in advance.
  • the output of the recording laser beam LB1 is modulated.
  • the mechanical laser is controlled to block the recording laser beam LB1, or preferably the electro-optic modulation element (EOM) is controlled for high-speed modulation.
  • the recording laser beam LB1 may be modulated by deflecting it.
  • This synchronization can be performed, for example, by detecting a part of the recording laser beam LB1 deflected by the deflector 52 with a sensor (not shown). Then, by controlling one or both of the irradiation time and the irradiation intensity of the recording laser beam LB1 for each portion where the lattice point at the interface of the polymer material layer 20 is to be formed, the size of the lattice point and the depth of the opening are controlled. Or the height of the convex portion can be adjusted.
  • the irradiation time of the laser beam for forming one lattice point is preferably 120 ⁇ sec or less.
  • a diffractive optical element can be manufactured at high speed.
  • the diffractive optical element E having 250,000 lattice points can be manufactured in about 1 minute.
  • a method for manufacturing the diffractive optical element E using the manufacturing apparatus 50 as described above will be described.
  • the material EM before recording lattice points is placed on the stage 57.
  • the deflector 52 is operated, and the output of the recording laser 51 is modulated based on the exposure data stored in advance in synchronization with the operation of the deflector 52.
  • the recording laser beam LB1 passes from the recording laser 51 through the PBS 54 and the quarter wavelength plate 55 to the deflector 52, is deflected by the deflector 52, and enters the imaging optical system 60.
  • the deflected recording laser beam LB1 passes through the first condenser lens 61, the second condenser lens 62, and the objective lens 63, and in the vicinity of the interface of the polymer material layer 20 of the material EM.
  • the image is formed into fine dots.
  • a focal point is imaged at a position corresponding to the deflection angle.
  • a part of the laser light reflected at the interface of the polymer material layer 20 returns in the order of the imaging optical system 60, the deflector 52, and the quarter wavelength plate 55, and the direction of polarization is rotated by 90 ° with respect to the direction.
  • the controller 59 adjusts the focus of the recording laser beam LB1 to a predetermined position by controlling the focus actuator 63A based on the signal received by the light receiving element 53.
  • the recording laser beam LB1 when the recording laser beam LB1 is condensed and irradiated near the interface of the polymer material layer 20 while scanning the polymer material layer 20 with the deflector 52, the dye absorbs the recording laser beam LB1.
  • the temperature of the portion of the polymer material layer 20 irradiated with the recording laser beam LB1 is efficiently raised, and the interface is deformed. Specifically, an opening or a convex portion is formed by thermal expansion due to heating and rapid cooling after the irradiation of the recording laser beam LB1 is stopped.
  • the height and width of the convex portion increase as the irradiation energy increases, and when the irradiation energy increases, an opening is formed by the high-temperature molten material moving from the center of the convex shape to the periphery during cooling. At this time, when the thickness of the polymer material layer 20 is thin, a hole penetrating the polymer material layer 20 is formed. Thus, an opening or a convex portion can be formed at the interface of the polymer material layer 20.
  • dot-like lattice points constituting a diffractive optical element pattern can be formed at the interface of the polymer material layer 20. That is, a desired diffractive optical element pattern can be formed in a desired pattern area PA.
  • the diffractive optical element pattern can be calculated so as to obtain a laser intensity distribution that forms a desired reproduced image, for example, by a method disclosed in “Digital Diffractive Optics” Maruzen Publishing, 2005 or the like.
  • a desired diffractive optical element pattern can be designed easily and at high speed by a computer. Divide the phase distribution of the designed diffraction grating surface into multiple pixels, quantize the amount of phase change required for each pixel, and record the laser light according to the size of the minute aperture and the size of the irregularities that are actually processed What is necessary is just to determine the irradiation energy of LB1.
  • the simplest method of quantizing the phase change amount is to use a binary pattern of processed and unprocessed binary, and the phase difference between the processed pixel and the unprocessed pixel is half the wavelength used. It is desirable to be minutes. By making the quantization gradation a finer step, it is possible to suppress higher-order diffracted light and make the diffraction pattern closer to the design. Usually, it is desirable to divide into steps of 4 to 8 gradations, more preferably 16 to 32 gradations.
  • the diffractive optical element pattern is formed by deforming the interface of the polymer material layer 20, the diffractive optical can be easily performed without requiring development. Element E can be manufactured. Further, since the lattice point is formed by irradiating the polymer material layer 20 containing the dye with the recording laser light LB1 having a wavelength that is absorbed by the dye, the output of the recording laser light LB1 can be reduced, and the processing is performed at high speed. Can do. Furthermore, since the manufacturing method of this embodiment forms openings and / or protrusions by deforming the interface rather than peeling the material as in laser ablation, the diffractive optical element can be finely controlled in gradation. A pattern can be formed.
  • the imaging optical system 60 is an optical system including the objective lens 63 and the two condenser lenses 61 and 62, a fine optical diffraction element pattern reduced with a simple configuration is formed. be able to.
  • the control device 59 controls the objective lens 63 based on the output signal of the light receiving element 53 to adjust the focal position of the recording laser beam LB1 to a predetermined position.
  • a high-performance diffractive optical element E can be obtained.
  • the manufacturing apparatus 50 includes the transport stage 570, it is possible to continuously manufacture the plurality of diffractive optical elements E by moving the polymer material layer 20 by the transport stage 570.
  • Example 1 is an example in which a diffractive optical element pattern that displays a character image of “ABC” is composed of a binary binary pattern.
  • azo metal complex dye compound A having the following structure and polymethyl methacrylate (Mw: 100,000 produced by Sigma-Aldrich) were dissolved in methyl ethyl ketone at a mass ratio of 45:55 to prepare a coating solution having a solid content concentration of 3% by mass.
  • Compound A was synthesized by the method described in JP 2010-100029 A.
  • This coating solution was applied by spin coating on a triacetyl cellulose film having a thickness of 100 ⁇ m serving as a support to form a polymer material layer.
  • the diffractive optical element pattern to be processed into the polymer material layer was designed by being divided into 250 ⁇ 250 pixel minute areas by the IFTA method, and a binary binary pattern of pixels to be processed and pixels not to be processed was used.
  • FIG. 15A shows the original image
  • FIG. 15B shows the diffractive optical element pattern for reproducing the image of FIG. 15A calculated by the IFTA method.
  • FIG. 15C shows a simulation result obtained by reproducing the diffractive optical element pattern shown in FIG.
  • the diffractive optical element pattern of FIG. 15B was processed into a 0.5 mm ⁇ 0.5 mm scanning area (pattern forming region) of the polymer material layer by the same manufacturing apparatus as in the above-described embodiment.
  • a biaxial galvanometer mirror was used as the deflector, and a 405 nm semiconductor laser was used as the recording laser beam.
  • the laser intensity during processing was 2.8 mW on the surface of the polymer material layer.
  • the polymer material layer is fixed on a stage movable in the optical axis direction of the recording laser beam and two orthogonal axes, and can be adjusted to an appropriate position for processing the diffractive optical element pattern.
  • the objective lens an infinity objective lens (magnification ⁇ 20) having an NA (numerical aperture) of 0.6 and a focal length of 10 mm is used, and the two condenser lenses constituting the 4f optical system are convex lenses having a focal length of 100 mm. It was used.
  • the irradiation time of the recording laser light per pixel was 50 ⁇ sec.
  • the recording laser beam was raster scanned at a scanning rate of 20 Hz, and a 0.5 mm ⁇ 0.5 mm scanning area was processed in about 20 seconds in consideration of the transfer time of control data and the delay required for timing synchronization.
  • the pitch of the lattice points was 2 ⁇ m.
  • a 0.5-mm square pattern formation region was irradiated with a He—Ne laser having a wavelength of 633 nm so as to pass through the diffractive optical element as shown in FIG.
  • the designed letters “ABC” are displayed by a diffraction pattern. That is, it was confirmed that a desired diffractive optical element was produced.
  • Example 2 is an example in which a diffractive optical element pattern that displays a character image of “ABC” is composed of binary and ternary diffractive optical element patterns.
  • TINUVIN 326 manufactured by BASF
  • polymethyl methacrylate manufactured by Sigma-Aldrich Mw: 100,000
  • This coating solution was spin-coated on a glass slide serving as a support to form a polymer material layer having a thickness of 1 ⁇ m.
  • the diffractive optical element pattern to be processed into a polymer material is designed by dividing it into a minute area of 250 ⁇ 250 pixels by the IFTA method, and quantized with two types of binary and ternary values.
  • the diffractive optical element pattern was calculated.
  • the letters “ABC” in the original image were inverted.
  • the polymer material layer was exposed using the same apparatus and conditions as in Example 1. In the case of binary values, the recording exposure time of each pixel was set to 0 and 30 ⁇ sec, and in the case of ternary values, it was set to 0.14 ⁇ sec and 30 ⁇ sec.
  • the image shown in FIG. 20 is displayed on the screen, and in the case of ternary values, the image shown in FIG. 21 is displayed on the screen, and in each case, the pattern predicted by the simulation calculation is displayed.
  • the inverted characters “ABC” in the first-order diffraction image could be suppressed.
  • Example 3 In Example 3, a two-photon absorption dye was used as a dye, and a diffractive optical element was manufactured using a pulse laser as a light source.
  • the polymer two-photon absorption compound B having the following structure was dissolved in methyl ethyl ketone to prepare a coating solution having a solid concentration of 9% by mass.
  • the obtained coating solution was spin-coated on a glass slide serving as a support to form a polymer material layer having a thickness of 1 ⁇ m.
  • a pulse laser having a wavelength of 405 nm, a pulse width of 2.0 ps, and a repetition rate of 76 MHz was used.
  • the pulse intensity was controlled using an electro-optic modulator (EOM) in the optical path.
  • EOM electro-optic modulator
  • the objective lens an infinite objective lens having a NA of 0.85 (magnification ⁇ 60) was used.
  • the pulse laser was set so that the peak power on the surface of the polymer material layer was 60 W, and the number of irradiation pulses was controlled by EOM so that dots with an interval of 300 nm were formed.

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PCT/JP2013/070992 2012-09-27 2013-08-02 Élément optique de diffraction et procédé et dispositif de production d'élément optique de diffraction Ceased WO2014050308A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0798870B2 (ja) * 1987-12-11 1995-10-25 帝人株式会社 高分子の光加工方法
JP2005099416A (ja) * 2003-09-25 2005-04-14 Fuji Photo Film Co Ltd ホログラム記録方法及びホログラム記録材料
JP2007057622A (ja) * 2005-08-22 2007-03-08 Ricoh Co Ltd 光学素子及びその製造方法、光学素子用形状転写型の製造方法及び光学素子用転写型
WO2007043451A1 (fr) * 2005-10-05 2007-04-19 Pioneer Corporation Système d’enregistrement/de reproduction d’hologramme
JP2007212485A (ja) * 2006-02-07 2007-08-23 Ricoh Co Ltd 光学素子、マルチビーム光源ユニット、光走査装置及び画像形成装置
WO2009050857A1 (fr) * 2007-10-15 2009-04-23 Fujifilm Corporation Procédé de formation d'une partie concave, procédé de fabrication d'un produit concavo-convexe, procédé de fabrication d'un élément électroluminescent et procédé de fabrication d'un élément optique
JP2011095465A (ja) * 2009-10-29 2011-05-12 Toppan Printing Co Ltd 表示体

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0798870B2 (ja) * 1987-12-11 1995-10-25 帝人株式会社 高分子の光加工方法
JP2005099416A (ja) * 2003-09-25 2005-04-14 Fuji Photo Film Co Ltd ホログラム記録方法及びホログラム記録材料
JP2007057622A (ja) * 2005-08-22 2007-03-08 Ricoh Co Ltd 光学素子及びその製造方法、光学素子用形状転写型の製造方法及び光学素子用転写型
WO2007043451A1 (fr) * 2005-10-05 2007-04-19 Pioneer Corporation Système d’enregistrement/de reproduction d’hologramme
JP2007212485A (ja) * 2006-02-07 2007-08-23 Ricoh Co Ltd 光学素子、マルチビーム光源ユニット、光走査装置及び画像形成装置
WO2009050857A1 (fr) * 2007-10-15 2009-04-23 Fujifilm Corporation Procédé de formation d'une partie concave, procédé de fabrication d'un produit concavo-convexe, procédé de fabrication d'un élément électroluminescent et procédé de fabrication d'un élément optique
JP2011095465A (ja) * 2009-10-29 2011-05-12 Toppan Printing Co Ltd 表示体

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