WO2000054112A1 - Nouveau materiau d'enregistrement holographique - Google Patents

Nouveau materiau d'enregistrement holographique Download PDF

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Publication number
WO2000054112A1
WO2000054112A1 PCT/EP2000/001500 EP0001500W WO0054112A1 WO 2000054112 A1 WO2000054112 A1 WO 2000054112A1 EP 0001500 W EP0001500 W EP 0001500W WO 0054112 A1 WO0054112 A1 WO 0054112A1
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Prior art keywords
recording material
particularly preferably
material according
dye
alkyl
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PCT/EP2000/001500
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German (de)
English (en)
Inventor
Thomas Bieringer
Horst Berneth
Johannes Eickmans
Rainer Hagen
Serguei Kostromine
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Bayer Aktiengesellschaft
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Priority to AU31599/00A priority Critical patent/AU3159900A/en
Priority to JP2000604276A priority patent/JP2002539476A/ja
Priority to EP00909245A priority patent/EP1166187A1/fr
Priority to CA002366846A priority patent/CA2366846A1/fr
Priority to KR1020017011356A priority patent/KR20020002401A/ko
Publication of WO2000054112A1 publication Critical patent/WO2000054112A1/fr

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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
    • G11B7/244—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 organic materials only
    • G11B7/245—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 organic materials only containing a polymeric component
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/106—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an azo dye
    • 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
    • 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
    • G03H2001/026—Recording materials or recording processes
    • 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
    • G03H2001/026—Recording materials or recording processes
    • G03H2001/0264—Organic recording material
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H2240/00—Hologram nature or properties
    • G03H2240/20—Details of physical variations exhibited in the hologram
    • G03H2240/26—Structural variations, e.g. structure variations due to photoanchoring or conformation variations due to photo-isomerisation
    • 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
    • G11B7/004—Recording, reproducing or erasing methods; Read, write or erase circuits therefor
    • G11B7/0065—Recording, reproducing or erasing by using optical interference patterns, e.g. holograms
    • 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

Definitions

  • the present invention relates to a recording material for a holographic volume memory, its production and use for the recording of volume holograms.
  • Holography is a process in which objects can be imaged in suitable storage materials by the interference of two coherent light beams (signal wave and reference wave) and these images can be read out again with light (reading beam) (D. Gabor, Nature 151, 454 (1948), NH Farath, Advances in Holography, Vol. 3, Marcel Decker (1977), HM Smith, Holographie Recording Materials, Springer (1977)).
  • signal and reference wave By changing the angle between the signal and reference wave on the one hand and the holographic storage material on the other hand, numerous holograms can be inserted into one and the same sample position
  • the light from a laser is generally used as the coherent light source.
  • Various materials are described as storage material, e.g. B. inorganic crystals such as LiNbO 3 (for example), organic polymers (for example M. Eich, JH Wendorff, Makromol. Chem., Rapid Commun. 8, 467 (1987), JH Wendorff, M. Eich, Mol. Cryst. Liq. Cryst. 169, 133
  • Stabilities of the registered hologram A multiple description is generally only possible to a limited extent, since when a new hologram is written in, the hologram already written in is overwritten and thus deleted. This applies in particular to inorganic crystals that are subjected to extensive temperature treatment in order to compensate for these stability problems.
  • Photo- polymers show the problem of shrinkage, which has a negative effect on the holographic imaging properties.
  • the invention accordingly relates to a recording material for a holographic volume memory, containing at least one dye which changes its spatial arrangement when a hologram is written in, and optionally at least one shape-anisotropic grouping, characterized in that it allows two or more holograms to be recorded at a sample position.
  • the at least one dye changes its spatial arrangement in such a way that it can no longer be excited by the electromagnetic radiation or changes its absorption behavior, in particular its Sensitivity to the actinic light reduced, preferably between 10% and 100%, particularly preferably between 50% and 100% and very particularly preferably between 90 and 100%, in each case based on the sensitivity before the writing of the first hologram.
  • the dye can also reduce its absorption behavior, in particular its sensitivity to actinic light, by folding in the direction perpendicular to the direction of polarization of the actinic light and its longitudinal axis of the molecule making an angle between 10 ° and 90 °, preferably between, with the direction of polarization of the actinic light 50 ° and 90 ° is particularly preferably between 75 ° and 90 ° and very particularly preferably between 85 ° and 90 °.
  • This change in the excitation behavior with regard to electromagnetic radiation when the hologram is written in can be calibrated in that the dye changes its spatial arrangement in the polymeric or oligomeric organic, amorphous material.
  • Materials of this type can be used to prevent the holograms previously written into this material from being unacceptably reduced, completely damaged or even completely overwritten when a hologram is written.
  • an unacceptable weakening means that the remaining information can no longer be resolved in relation to the background noise.
  • the information is stored holographically. For this purpose, two polarized, coherent beams are brought to interference on the sample.
  • the polarization of the light is perpendicular to the plane of incidence, the light can no longer be excited by aligning its longitudinal axis in the plane spanned by the two writing beams (plane of incidence).
  • the information (hologram) written into these dyes during this writing process is against when writing a next hologram
  • the molecular longitudinal axis can be determined, for example, on the basis of the molecular shape by molecular modeling (eg CERIUS 2 ).
  • the reorientation of the dyes after exposure to actinic light results, for example, from investigations on polarized absorption spectroscopy: A sample previously exposed to actinic light is placed between 2 polarizers in a UV / VIS spectrometer (e.g. CARY 4G, UV / VIS spectrometer) examined in the spectral range of absorption of the dyes. When the sample is rotated around the sample normal and a suitable polarizer position, for example in the crossed state, the reorientation of the dyes follows from the intensity profile of the extinction as a function of the sample angle and can thus be clearly determined.
  • multiplexing methods for writing multiple holograms such as angle multiplexing, wavelength division multiplexing, phase multiplexing, shift multiplexing, peristrophic multiplexing and others.
  • a measure of the sensitivity to actinic light is holographic
  • the sensitivity is defined as the slope of the root of the diffraction efficiency according to the deposited energy, normalized to the thickness of the
  • the invention relates to a recording material for a holographic volume memory that has an optical density ⁇ 2, preferably ⁇ 1, particularly preferably ⁇ 0.3 at the wavelength of the writing laser. In this way it can be ensured that the actinic light leads to homogeneous illumination of the entire storage medium and a thick hologram can be generated.
  • the optical density can be determined with commercial UV / VIS spectrometers (e.g. CARY, 4G, UV / VIS spectrometer).
  • the recording material according to the invention is a material which has an irradiated thickness of> 0.1 mm, particularly 0.5 mm, preferably> 1 mm and very particularly preferably not greater than 5 cm.
  • the grouping that interacts with the electromagnetic radiation is a dye.
  • the material according to the invention consequently contains at least one dye.
  • the electromagnetic radiation is preferably laser light, preferably in the wavelength range between 390 to 800 ⁇ m, particularly preferably in the range 400 to 650 nm, very particularly preferably in the range from 510 to 570 nm.
  • the recording material is no longer exposed to two interfering beams as in writing, but only one beam, the reading beam.
  • the wavelength of the reading beam is preferably longer than that of the signal and reference waves, for example 70 to 500 nm longer. Reading with the
  • the wavelength of the write laser is also possible and will be used in particular for the commercial use of holographic volume memories.
  • the energy of the reading beam is reduced during the reading process either by reducing the exposure intensity or the exposure time, or by reducing the exposure intensity and the exposure time.
  • optical density of the recording material according to the invention is set by the following two parameters
  • Dyes with low extinction coefficients are, for example, dyes with a non-polar and / or less polarizable structure. Such dyes can, for example, come from the classes of anthraquinone, stilbene, azastilbene, azo or methine dyes. Azo dyes are preferred. Azo dyes with an absorption maximum of the ⁇ * band which is less than or equal to 400 nm, very particularly preferably less than 400 nm, are particularly preferred.
  • azo dyes have the following structure of formula (I) wherein
  • R 1 and R 2 independently of one another represent hydrogen or a nonionic substituent
  • Rl can additionally mean -Xl'-R ⁇
  • n and n independently of one another represent an integer from 0 to 4, preferably 0 to 2,
  • X 1 and X 2 mean -X '-R 3 or X 2' -R 4 ,
  • R, R, R and R independently of one another for hydrogen, C, - to C 20 alkyl, C 3 - bis
  • X 1 -R " 'and X 2' -R 4 represent hydrogen. Halogen, cyan, nitro, CF, or CC1 3 can be.
  • R 6 and R 7 independently of one another are hydrogen, halogen, C 1 -C 20 -alkyl, C 1 -C 20 alkoxy, C 3 -C 10 cycloalkyl, C 2 -C 20 alkenyl or C 6 - Stand up to C I0 aryl.
  • Nonionic substituents are to be understood as halogen, cyano, nitro, C, - bis
  • the alkyl, cycloalkyl, alkenyl and aryl radicals may in turn by up to 3 radicals from the series halogen, cyano, nitro, C, - to C 20 - alkyl, C, - to C 20 alkoxy, C 3 - to C 10 -cycloalkyl, C 2 - to C 20 alkenyl or C 6 - to C, 0- aryl may be substituted and the alkyl and alkenyl radicals may be straight-chain or branched.
  • Halogen is to be understood as meaning fluorine, chlorine, bromine and iodine, in particular fluorine and chlorine.
  • the recording material according to the invention is preferably polymeric or oligomeric organic, amorphous material, particularly preferably a side chain polymer, likewise particularly preferably a block copolymer and / or a graft polymer.
  • the main chains of the side chain polymer come from the following basic structures: polyacrylate, polymethacrylate, polysiloxane, polyurea, polyurethane, polyester or cellulose. Polyacrylate and polymethacrylate are preferred.
  • the block copolymers consist of several blocks, at least one of which contains the copolymer systems described above.
  • the other blocks consist of unfunctionalized polymer scaffolds that do the job of dilution of the functional block for setting the required optical density.
  • the extension of the functional block is below the light wavelength, preferably in the range of less than 200 nm, particularly preferably less than 100 nm.
  • the block copolymers are polymerized, for example, via free-radical or anionic polymerization or via other suitable polymerization processes, possibly followed by a polymer-analogous reaction or by a combination of these methods.
  • the uniformity of the systems is in a range less than 2.0, preferably less than 1.5.
  • the molecular weight of the block copolymers obtained by radical polymerization has values in the range of 50,000; values greater than 100,000 can be set by anionic polymerization.
  • the dyes in particular the azo dyes of the formula (I), are covalently bonded to these polymer skeletons, generally via a spacer.
  • X ' the azo dyes of the formula (I)
  • i stands for an integer from 0 to 4, where for i> 1 the individual Q 1 can have different meanings,
  • T 1 stands for - (CH 2 ) p -, where the chain can be interrupted by -O-, -NR 9 -, or -OSiR 10 2 O-,
  • S 1 stands for a direct bond, -O-, -S- or -NR 9 -,
  • p represents an integer from 2 to 12, preferably 2 to 8, in particular 2 to 4,
  • R 9 represents hydrogen, methyl, ethyl or propyl
  • R 10 represents methyl or ethyl
  • R 5 to R 8 have the meaning given above.
  • Preferred dye monomers for polyacrylates or methacrylates then have the formula (II)
  • R represents hydrogen or methyl
  • X 1 is hydrogen, halogen or C to C 4 alkyl, preferably hydrogen, and
  • Dye monomers of the formula (IIb) are also suitable if they are present in the polymer in an amount of ⁇ 10 mol%, preferably ⁇ 5 mol%, particularly preferably ⁇ 1 mol%,
  • X 4 means cyano or nitro
  • Particularly preferred monomers of the formula (IIb) are, for example
  • the polymeric or oligomeric organic amorphous material according to the invention can, in addition to the dyes, for example of the formula (I). lormanisotropic groupings wear. These are also covalently bonded to the polymer frameworks, usually via a spacer.
  • Shape anisotropic groupings have, for example, the structure of the formula (III)
  • A represents O, S or NC, to C 4 alkyl
  • X 4 stands for X 4 -R 1J ,
  • R ⁇ R 8 and R ⁇ independently of one another for hydrogen, C, - to C 20 -alkyl, C 3 - to C 10 -cycloalkyl, C 2 - to C 20 -alkenyl, C 6 - to C, 0 -aryl.
  • X 4 -R 13 can stand for hydrogen, halogen, cyan, nitro, CF 3 or CC1 3 ,
  • R 6 and R 7 independently of one another are hydrogen, halogen, C r to C 20 alkyl,
  • q, r and s independently of one another represent an integer from 0 to 4, preferably 0 to 2,
  • j represents an integer from 0 to 4, where the individual Q 'may have different meanings for j> 1,
  • T 2 stands for - (CH 2 ) p -, where the chain can be interrupted by -O-, -NR 9 -, or -OSiR 10 2 O-,
  • S 2 stands for a direct bond, -O-, -S- or -NR 9 -,
  • p represents an integer from 2 to 12, preferably 2 to 8, in particular 2 to 4,
  • R 9 represents hydrogen, methyl, ethyl or propyl
  • R 10 represents methyl or ethyl.
  • Preferred monomers with such shape-anisotropic groupings for polyacrylates or methacrylates then have the formula (IV)
  • R represents hydrogen or methyl
  • Particularly preferred shape-anisotropic monomers of the formula (IV) are, for example:
  • alkyl, cycloalkyl, alkenyl and aryl radicals can in turn be substituted by up to 3 radicals from the series halogen, cyano, nitro, C r to C 20 alkyl, C 1 -C 20 alkoxy,
  • C 3 to C 10 cycloalkyl, C 2 to C 20 alkenyl or C 6 to C 10 aryl can be substituted and the alkyl and alkenyl radicals can be straight-chain or branched.
  • Halogen is to be understood as meaning fluorine, chlorine, bromine and iodine, in particular fluorine and chlorine.
  • the oligomers or polymers according to the invention can also contain building blocks which are used primarily to lower the percentage content of functional building blocks, in particular of dye building blocks. In addition to this task, they can also be used for other properties
  • Oligo- or polymers may be responsible, e.g. B. the glass transition temperature, liquid crystallinity, film-forming property, etc.
  • such monomers are acrylic or methacrylic acid esters of the formula (V) wherein
  • R represents hydrogen or methyl
  • R ' represents optionally branched C, -, alkyl or an at least one further acrylic unit containing group - to C twentieth
  • Polyacrylates and polymethacrylates according to the invention then preferably contain, as repeating units, those of the formulas (VI), preferably those of the formulas (VI) and (VII) or of the formulas (VI) and (VIII) or of the formulas (VI), (VII) and (VIII)
  • the quantitative ratio between VI, (Via, b), VII and VIII is arbitrary.
  • the concentration of VI (via, b) is preferably between 0.1 and 100%, based on the respective mixture, depending on the absorption coefficient of VI (via, b).
  • the ratio between VI (Via, b) and VII is between 100: 0 and 1:99, preferably between 100: 0 and 30:70, very particularly preferably between 100: 0 and 50:50.
  • the dyes of the formula (I) or the dye monomers of the formula (II) have a short-wave main absorption band ( ⁇ - ⁇ * band) and a longer-wave secondary absorption band (n- ⁇ * band).
  • the molar extinction coefficient ⁇ of this n- ⁇ * band is in the range 400 to 5,000 * 10 3 cnr / mol.
  • the polymers and oligomers according to the invention preferably have glass transition temperatures T. of at least 40 ° C.
  • the glass transition temperature can for example according to B. Vollmer, Grundriß der Makromolekularen Chemie, pp. 406-410, Springer-Verlag, Heidelberg 1962.
  • the polymers and oligomers according to the invention have a weight average molecular weight of 5,000 to 2,000,000, preferably from 8,000 to
  • Graft polymers are prepared by free-radical attachment of dye monomers of the formulas (II) or (Ila) or (Ilb) and, if appropriate, additionally of formanisotropic monomers of the formula (IV) and / or if appropriate additionally of monomers of the formula (V) to oligomeric or polymeric basic systems .
  • Such basic systems can be a wide variety of polymers, e.g. Polystyrene, poly (meth) acrylates, starch, cellulose, peptides.
  • the radical linkage can take place by irradiation with light or by using radical-generating reagents, e.g. Tert.-butyl hydroperoxide, dibenzoyl peroxide, azodisobutyronitrile, hydrogen peroxide / iron (II) salts.
  • interaction forces occur between the side groups of the repeating units of the formula (VI), (Via, b) or between those of the formulas (VI), (Via, b) and (VII), which are sufficient for the photo-induced configuration change of the side groups of the Formula ( ⁇ ; I).
  • (Via, b) a rectified - so- mentioned cooperative - reorientation of the other side groups ((VI), (Via, b) and / or (VII)).
  • optical anisotropy can be induced in the optically isotropic amorphous photochromic polymers (An to 0.4).
  • Polarized light is used as the light, the wavelength of which lies in the range of the absorption band, preferably in the range of the long-wave n- ⁇ * band of the repeating units of the formula (VI).
  • the polymers and oligomers can be prepared by methods known from the literature, for example according to DD 276 297, DE-A 3 808 430, Macromolecular Chemistry 187, 1327-1334 (1984), SU 887 574, Europ. Polym. 18, 561 (1982) and Liq. Cryst. 2, 195 (1987).
  • Films, foils, plates and cuboids can be produced without the need for complex orientation processes using external fields and / or surface effects. They can be applied to substrates by spin coating, dipping, pouring or other technologically easy-to-control coating processes, by pressing or flowing between two transparent plates or simply prepared as a self-supporting material by pouring or extruding. Such films, foils. Plates and cuboids can be produced by abrupt cooling, ie by a cooling rate of> 100 K / min, or by rapid removal of the solvent from liquid-crystalline polymers or oligomers which contain structural elements in the sense described. Preferred is a manufacturing process of the holographic volume storage in which a step by a conventional injection molding process is included in the range up to 300 ° C, preferably up to 220 ° C, particularly preferably 180 ° C.
  • the layer thickness is> 0.1 mm, preferably> 0.5 mm, particularly preferably> 1 mm.
  • a particularly preferred preparation process for layers in the millimeter range is the injection molding process.
  • the polymer melt is pressed through a nozzle into a shaping holder, from which it can be removed after cooling.
  • a preferred method of producing the recording material or the polymer according to the invention comprises a process in which at least one monomer is polymerized without further solvent, preferably free-radically polymerizing, and particularly preferably initiated by free-radical initiators and / or UV light and / or thermally.
  • the process is carried out at temperatures between 20 ° C. and 200 ° C., preferably between 40 ° C. and 150 ° C., particularly preferably 50 ° C. and 100 ° C. and very particularly preferably around 60 ° C.
  • AIBN is used as the radical starter.
  • Monomers understood which are preferably olefinically unsaturated monomers, particularly preferably based on acrylic acid and methacrylic acid, very particularly preferably methyl methacrylate.
  • the proportion of the monomers of the formula (II) in the copolymers is preferably 0.1 to 99.9% by weight, particularly preferably 0.1 to 50% by weight, very particularly preferably 0.1 to 5% by weight and in the best case 0.5 to 2% by weight.
  • the method of holographic data storage is, for example, in LASER
  • the polymer films described above are irradiated by two coherent laser beams of a wavelength which produces the required light-induced reorientations.
  • One beam, the object beam contains the optical information to be stored, for example the intensity curve, which results from the passage of a light beam through a two-dimensional, checkerboard-like pixel structure (data page).
  • the object beam is brought to interference on the storage medium with the second laser beam, the reference beam, which is generally a flat or circular wave.
  • the resulting interference pattern is memorized in the storage medium as a modulation of the optical constant (refractive index and / or absorption coefficient). This modulation penetrates the entire irradiated area, in particular the thickness of the optical constant (refractive index and / or absorption coefficient). This modulation penetrates the entire irradiated area, in particular the thickness of the optical constant (refractive index and / or absorption coefficient). This modulation penetrates the entire irradiated area, in particular the thickness of the optical constant (refractive index and
  • the modulated storage medium functions as a kind of diffraction grating for the reference beam.
  • the intensity distribution resulting from the diffraction corresponds to the intensity distribution which started from the object to be stored, so that it can no longer be distinguished whether the light comes from the object itself or whether it results from the diffraction of the reference beam.
  • Different multiplexing methods are used to store different holograms at a sample position: wavelength division multiplexing, shift multiplexing, phase multiplexing, peristrophic multiplexing and / or angle multiplexing and / or others.
  • angle multiplexing you change the angle between the storage medium in which a hologram was saved at the current angles and the reference beam. After a certain change in angle, the original hologram (Bragg-Mismatch) disappears: the incident reference beam can no longer be deflected from the storage medium to reconstruct the object.
  • the angle from which this occurs depends crucially on the thickness of the storage medium (and on the modulation of the optical constants generated in the medium): the thicker the medium, the smaller the angle by which the reference steel has to be changed.
  • the polymer systems described in this patent now have the great advantage that when a subsequent hologram is written, the information of the previous holograms deposited in the storage medium is not deleted, and that more than three holograms, preferably more than 50, particularly preferably more than 100, are very particularly preferred more than 500 and most preferably more than 1000 holograms can be written at one location on the storage medium.
  • the objects to be stored are data pages that are transmitted by a
  • Liquid crystal displays are generated. These data pages have 256 x 256 pixels, preferably 512 x 512 pixels, particularly preferably 1024 x 1024 data pixels.
  • Another object of the invention is a recording material for a holographic volume storage consisting of a polymeric or oligomeric organic, amorphous material, the at least one with electromagnetic Radiation interacting grouping and optionally contains at least one shape-anisotropic grouping, characterized in that it has an optical density ⁇ 2, preferably ⁇ 1, very particularly preferably ⁇ 0.3.
  • the recording material can be used as a self-supporting film, or preferably in a multilayer structure for data storage.
  • This multilayer structure is, for example, a sandwich in which the actual recording medium is surrounded by at least one substrate.
  • the substrate can be transparent media with high optical quality, for example glass plates, quartz plates or plates made of polycarbonate.
  • High optical quality is understood to mean that the scattering efficiency, ie the quotient between light scattered on this sandwich and the incident light, is not less than 10 "4 , preferably not less than 10 " 5 , very particularly preferably not less than 10 "6 .
  • the sample can be exposed to the beam of a HeNe laser and detected using a CCD camera.
  • Toluene sulfonic acid and 10 g hydroquinone are refluxed in 150 ml chloroform with stirring.
  • the water formed during the reaction is separated on the water separator.
  • the reaction mixture is diluted with 150 ml of chloroform, washed several times with 100 ml of water and dried over Na 2 SO 4 .
  • the desiccant is filtered off, and the chloroform is distilled off on a rotary evaporator to two thirds.
  • the yield is 28 g (45% of theory).
  • the dispersion was diluted 1:10 with water, spread on a glass plate and dried.
  • the transparent, slightly yellow film on the glass plate was irradiated with polarized light, cold light lamp KL 500 from Schott, (spot diameter 6 mm) for 10 min. Between the crossed polarizers, the illuminated spot could be seen brightly in a dark environment.
  • Example 3 Production of holographic materials by polymerisation in block
  • a copolymer with 10 mol% of the azo dye is produced analogously. Analogously, copolymer becomes 1 mol% of the monomer:
  • the polymer from Example 3 is applied from a solution by means of spin coating to a 150 ⁇ m thick glass substrate.
  • the layer thickness at the measuring point located centrally on the substrate is 600 nm.
  • the height of the refractive index n of the polymer layer is determined for the three spatial directions x, y (layer plane) and z (layer normal) using the prism coupling method.
  • the base of a prism is brought into close contact with the polymer layer.
  • the angles at which the polarized light from a laser couples into the layer and passes through it in a waveguide fashion provide information about its refractive index at the light wavelength. Every coupling is evident as a signal dip at a detector in reflection.
  • the refractive index in the direction of polarization can be determined.
  • the values for n x and n v can be determined.
  • the value for n 7 can be determined. To do this, one of the both spatial directions x or y coincide with the plane of incidence.
  • the value of the refractive index of the direction chosen in this way (n x or r- y ) is included in the calculation.
  • the refractive indices n x , ri y and n- are determined on the sample before, during and after several exposures and deletions.
  • the light intensity is 200 mW / cm 2 .
  • the light is linearly polarized in the x direction.
  • the orientation anisotropy induced in this way in the xy plane is deleted with polarization in the y direction.
  • the level of the refractive index of each spatial direction is a measure of the average number of chromophores oriented in this direction, because it conches with the inducible polarization and this is mainly due to the high molecular ones
  • n ⁇ and n v are originally identical, there is a macroscopically isotropic distribution in the xy plane.
  • the smaller value for n z indicates the planar molecular orientation, which was created by the manufacturing process.
  • the first exposure successively leads to an orientation distribution with a reduced number of chromophores. the in x Direction.
  • the depletion of this direction takes place in equal parts on a statistical average in favor of the other two spatial directions y and z, as can be seen from the increasing values for n-. and n z .
  • a birefringence ⁇ .-n x in the film level can be almost completely deleted.
  • the number of chromophores oriented in the z direction increases with each new exposure or deletion process.
  • the polymer from Example 3 is in the form of granules. It is placed on a glass support and heated to approx. 180 ° C. The polymer melts at this temperature. There are spacers on the glass substrate, e.g. made of Mylar film or glass fibers and another cover glass. This sandwich glass-polymer-glass creates layers in the range from 20 to 1000 ⁇ m.
  • An SHG Nd: YAG laser (532 nm) serves as the writing source.
  • In the beam path of the object beam is a spatial light modulator that creates a data mask of 1024 x 1024 pixels.
  • the intensity ratio of the reference to the object beam is 7: 1, the total power density falling on the sample is 200 mW / cm 2 .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Holo Graphy (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne de nouveaux matériaux d'enregistrement holographique entrant dans le domaine des polymères photoadressables.
PCT/EP2000/001500 1999-03-08 2000-02-24 Nouveau materiau d'enregistrement holographique WO2000054112A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AU31599/00A AU3159900A (en) 1999-03-08 2000-02-24 Holographic recording material
JP2000604276A JP2002539476A (ja) 1999-03-08 2000-02-24 ホログラフィック記録材料
EP00909245A EP1166187A1 (fr) 1999-03-08 2000-02-24 Nouveau materiau d'enregistrement holographique
CA002366846A CA2366846A1 (fr) 1999-03-08 2000-02-24 Nouveau materiau d'enregistrement holographique
KR1020017011356A KR20020002401A (ko) 1999-03-08 2000-02-24 홀로그래피 기록 재료

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19910247A DE19910247A1 (de) 1999-03-08 1999-03-08 Neues holographisches Aufzeichnungsmaterial
DE19910247.3 1999-03-08

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Publication Number Publication Date
WO2000054112A1 true WO2000054112A1 (fr) 2000-09-14

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JP (1) JP2002539476A (fr)
KR (1) KR20020002401A (fr)
AU (1) AU3159900A (fr)
CA (1) CA2366846A1 (fr)
DE (1) DE19910247A1 (fr)
TW (1) TWI261153B (fr)
WO (1) WO2000054112A1 (fr)

Cited By (7)

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Publication number Priority date Publication date Assignee Title
WO2001026105A1 (fr) * 1999-10-01 2001-04-12 Bayer Aktiengesellschaft Procede de mise en memoire optique numerique de donnees
WO2002015178A1 (fr) * 2000-08-11 2002-02-21 Tesa Scribos Gmbh Memoire de donnees holographique
WO2003029311A1 (fr) * 2001-09-27 2003-04-10 Bayer Aktiengesellschaft Materiau d'enregistrement optique reinscriptible presentant une bonne solubilite
US7018684B2 (en) * 2000-05-31 2006-03-28 Bayer Aktiengesellschaft Block copolymers for optical data storage
US7501210B2 (en) 2002-06-07 2009-03-10 Fuji Xerox Co., Ltd. Photo-responsive high-molecular compound, photo-responsive high-molecular composition, dicarboxylic acid monomer, polyester, optical recording medium and optical record reproducing device
US7951922B2 (en) 2004-08-13 2011-05-31 National Institute Of Advanced Industrial Science And Technology Photoresponsive heterocyclic azo compound, method for producing the same, and optical information recording medium
US8168764B2 (en) 2006-07-11 2012-05-01 Nitto Denko Corporation Polyfunctional compound, optical recording material, optical recording medium, optical recording/reproducing apparatus, optical waveguide material, and photo-alignment film material

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JP4649158B2 (ja) * 2004-09-30 2011-03-09 富士フイルム株式会社 ホログラム記録方法
US7897296B2 (en) 2004-09-30 2011-03-01 General Electric Company Method for holographic storage
JP4888766B2 (ja) 2006-07-11 2012-02-29 日東電工株式会社 多官能化合物の製造方法
KR100927853B1 (ko) 2006-11-24 2009-11-23 주식회사 엘지화학 컬러필터용 이색성 염료, 이를 포함하는 컬러필터 형성조성물, 및 이로 제조된 컬러필터 어레이 기판
WO2024005139A1 (fr) * 2022-06-30 2024-01-04 三菱ケミカル株式会社 Procédé de production d'élément optique

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DE19703132A1 (de) * 1997-01-29 1998-07-30 Bayer Ag Photoadressierbare Seitengruppenpolymere mit hoher induzierbarer Doppelbrechung
WO1998051721A1 (fr) * 1997-05-15 1998-11-19 Bayer Aktiengesellschaft Homopolymeres a birefringence photoinductible elevee

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DE4339862A1 (de) * 1993-03-30 1994-10-06 Agfa Gevaert Ag Flächenhafte Gebilde aus Seitengruppenpolymeren
US5496670A (en) * 1993-08-30 1996-03-05 Riso National Laboratory Optical storage medium
DE4431823A1 (de) * 1994-09-07 1996-03-14 Bayer Ag Verfahren zur Verstärkung von Information in photoadressierbaren Seitenkettenpolymeren
DE19703132A1 (de) * 1997-01-29 1998-07-30 Bayer Ag Photoadressierbare Seitengruppenpolymere mit hoher induzierbarer Doppelbrechung
WO1998051721A1 (fr) * 1997-05-15 1998-11-19 Bayer Aktiengesellschaft Homopolymeres a birefringence photoinductible elevee

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001026105A1 (fr) * 1999-10-01 2001-04-12 Bayer Aktiengesellschaft Procede de mise en memoire optique numerique de donnees
JP2003511807A (ja) * 1999-10-01 2003-03-25 バイエル アクチェンゲゼルシャフト データをディジタル的及び光学的に記憶する方法
JP5002104B2 (ja) * 1999-10-01 2012-08-15 バイエル アクチェンゲゼルシャフト データをディジタル的及び光学的に記憶する方法
US7018684B2 (en) * 2000-05-31 2006-03-28 Bayer Aktiengesellschaft Block copolymers for optical data storage
WO2002015178A1 (fr) * 2000-08-11 2002-02-21 Tesa Scribos Gmbh Memoire de donnees holographique
WO2003029311A1 (fr) * 2001-09-27 2003-04-10 Bayer Aktiengesellschaft Materiau d'enregistrement optique reinscriptible presentant une bonne solubilite
US7214451B2 (en) 2001-09-27 2007-05-08 Bayer Aktiengesellschaft Rewriteable optical recording material having good solubility
US7501210B2 (en) 2002-06-07 2009-03-10 Fuji Xerox Co., Ltd. Photo-responsive high-molecular compound, photo-responsive high-molecular composition, dicarboxylic acid monomer, polyester, optical recording medium and optical record reproducing device
US7951922B2 (en) 2004-08-13 2011-05-31 National Institute Of Advanced Industrial Science And Technology Photoresponsive heterocyclic azo compound, method for producing the same, and optical information recording medium
US8168764B2 (en) 2006-07-11 2012-05-01 Nitto Denko Corporation Polyfunctional compound, optical recording material, optical recording medium, optical recording/reproducing apparatus, optical waveguide material, and photo-alignment film material
CN102690215A (zh) * 2006-07-11 2012-09-26 日东电工株式会社 多官能化合物、光记录材料、光记录介质、光记录再生装置、光波导材料及光取向膜材料

Also Published As

Publication number Publication date
JP2002539476A (ja) 2002-11-19
TWI261153B (en) 2006-09-01
EP1166187A1 (fr) 2002-01-02
CA2366846A1 (fr) 2000-09-14
KR20020002401A (ko) 2002-01-09
AU3159900A (en) 2000-09-28
DE19910247A1 (de) 2000-09-28

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