Patent Application
20080254373
1. Field of the Invention
The present invention concerns glasses for the storage of holographic data and the related manufacturing methods. More particularly, the present invention concerns silver ion-exchanged silicate glass articles that include photo-darkenable-refractive (PDR) and photo-bleachable-refractive (PBR) glass plates.
2. Description of Related Art
Holographic data storage has been an active field of research and development worldwide for more than 40 years. The concepts of holographic data storage is based on storing in a suitable medium a large number of images, each consisting of a large array of picture elements or pixels.
In its simplest form, holographic data storage involves causing each pixel to become either bright or dark to encode a binary 1 or 0. Each image or page of data is stored in an optically sensitive material as an interference pattern formed by the interaction of a data-bearing light beam (that is, the information light beam) with a reference light beam.
A large number of data pages can be independently stored and read back within a single common volume of materials by using multiplexing techniques, such as wavelength multiplexing (changing the recording laser wavelength), angular multiplexing (changing the angle between the data-bearing light beam and reference beam), peristrophic multiplexing (physically rotating the hologram with the axis of rotation being perpendicular to the surface of the photosensitive recording film every time a new hologram is stored), and shift multiplexing (slightly displacing the recording medium and optics relative to each other such that holograms are partially overlapped). Because an entire page of data, consisting of megabits of data, is stored in or read out of the storage medium in parallel, the data rate can be quite large in principle, in the order of gigabits per second.
Advancement in holographic system technology were disclosed, among others, in U.S. Pat. No. 6,909,529 “Method and Apparatus for Phase Correlation Holographic Drive,” issued on Jun. 21, 2005 to K. R. Curtis; U.S. Pat. No. 6,995,882 “Apparatus for Recording Optical Information,” issued on Feb. 7, 2006 to H. Horimai; and U.S. Pat. No. 7,002,891 “Apparatus and Method for Recording and Reproducing Information to and from an Optical Storage Medium,” issued on Feb. 21, 2006 also to H. Horimai. In spite of the advancements disclosed in the above documents, holographic data-storage technologies remain limited primarily by the properties of the storage medium.
In particular, materials for holographic recording in high density optical storage applications require a combination of properties that include a high dynamic range, dimensional stability, high diffraction efficiency, high sensitivity, optical clarity (including low light scattering and absorption), long hologram lifetime, high speed (that is, a short time constant to build up a photo-refractive grating), a high optical quality (including homogeneous bulk refractive index and optical flatness), resistance to erasure during reading, and wavelengths for writing, reading and erasing that match practical and available laser wavelengths such as wavelengths of semiconductor diode lasers. Candidates materials for holographic optical storage include LiNbO3 doped with Fe, Sr1-x, Bax Nb2O6 (SBN) doped with Ce or Cr, BaTiO3 undoped or doped with Rh, photorefractive polymers such as DuPont's HRF-150 photopolymer film, and photochromic films. Each of these material groups has its own strengths and weakness.
Among the above mentioned properties, optical quality is very important. When single crystals are employed, a common cause of poor optical quality is the presence of striations introduced in crystal growth processes, which causes scattering, that leads to interpixel interference in the recorded hologram as well as noise during readout of data. Bulk refractive index inhomogeneities lead to wave-front distortions that limit the ability to image high-resolution data patterns through the storage medium, thus data density. Even though the optical quality of LiNbO3 may currently be the best available among the candidate ferroelectric photorefractive materials, the images transmitted through a LiNbO3 single crystal are still significantly poorer than those formed through an optical glass plate.
The utility of photopolymers for data storage is generally limited by volume shrinkage and by the substantial amount of scattering and/or bulk refractive index inhomogeneity. Due to the high absorption losses usually observed in photochromic films, useful sample thickness is limited.
Based on the foregoing, a silicate glass plate of high optical quality that has a homogeneous bulk refractive index and that is optically flat would be a suitable candidate as a holographic recording material, provided that the combination of the other above listed properties is also attained.
U.S. Pat. No, 4,160,654, issued on Jul. 10, 1979 to Bartholomew, Mach and Wu, discloses a method of making a transparent, essentially colorless glass body, which exhibits thermoplastic properties and photosensitivity to ultraviolet radiation, and in which at least a surface portion contains Ag+ ions. This method includes the steps of melting a batch for an anhydrous glass body that essentially consists, in mole percent on oxide basis, of about 3-25% Na2O and/or K2O, 50-95% SiO2, zero to 25% of at least one oxide selected from the group consisting of BaO, B2O3, CaO, PbO, and ZnO, zero to 35% MgO, zero to 20% Al2O3, zero to 10% Li2O, and about 0.1-3% of a halide selected from the group consisting of F−, Cl−, Br−, and I−; and of contacting the anhydrous glass body in thickness dimensions no greater than about 5 mm with an aqueous solution environment containing Ag+ ions and having a pH less than about 4. The oxidation state of the glass is controlled both in the batch composition and in the aqueous solution environment; in particular, the oxidation state of the aqueous solution environment is controlled by including an oxidizing agent therein. Such a contact is made at a temperature in excess of 100° C. and at a pressure in excess of 20 psi for a period of time sufficient to hydrate at least a surface portion of the glass body, to attain an amount of absorbed H2O effective for imparting thermoplastic properties to the surface portion having been hydrated, and to cause the replacement of Na+ and/or K+ ions with Ag+ ions in the hydrated glass. The proportion of Na+ and/or K+ ions in the hydrated glass is lower with a corresponding increase in Ag+ ions.
The thermoplastic properties of the photosensitive hydrated glasses according to the '654 patent have an adverse effect on dimensional stability. Since dimensional instability leads to Bragg detuning or rotations in the Bragg angles of recorded holograms, the silver-containing glasses of the '654 patent are not suitable for use as a holographic recording material.
U.S. Pat. No. 4,297,417, issued on Oct. 27, 1981 to Wu, discloses photosensitive colored glasses that exhibit alterable photo-anisotropic effects, and U.S. Pat. No. 4,191,547, issued on Mar. 4, 1980 also to Wu, discloses a method of making the same. Further, U.S. Pat. No. 4,296,479, issued on Oct. 20, 1981 to Wu, discloses a method for optical recording in photo-dichroic glass surfaces (the same glass surfaces as disclosed in U.S. Pat. No. 4,297,417). In particular, the '417 patent describes a photosensitive storage medium for storing optical information, which utilizes photo-anisotropic effects and which comprises a photosensitive colored glass article that exhibits alterable photo-anisotropic effects and that consists of a body portion and of an integral hydrated surface layer of a thickness of about 1-500 microns including Ag—AgCl-containing crystals therein. At least a portion of that hydrated surface layer exhibits photo-dichroic and birefringent properties when exposed to colored, linearly polarized bleaching light, and that body portion consists essentially, in mole-percent on oxide basis, of about 70-82% SiO2, 10-17% Na2O and/or K2O, 5-15% ZnO, 0.5-5% Al2O3 and 0.1-3% Cl. That said surface layer contains instead about 1-8% by weight H2O and about 2-20% by weight Ag, the proportion of Na+ and/or K+ ions in said surface layer being less with a corresponding increase in Ag+ ions. The Ag portion of those crystals is present as a layer on the surface of the crystals and/or is contained within the crystals.
A photo-dichroic glass surface is a bit-by-bit write-erasable storage medium. The write state (i.e.,1 bit) is accomplished by exposing the photo-dichroic glass surface to a write beam that includes a linearly polarized red light, and the erased state (i.e., zero bit) is accomplished by utilizing an erasing beam, which is the write beam whose polarization direction has been rotated about 45°. The mode of reading the stored image or data is done with a bit-by-bit extinction read mode between a pair of crossed polarizers. The read signal is obtained bit-by-bit via transmission of the read beam through a sequence of elements consisting of a polarizer, recorded bit in the photo-dichroic glass surface, and an analyzer, which is a second polarizer whose polarization direction is 90° from the first polarizer. This read mode utilizing the photo-anisotropic effects is not compatible with the requirement of holographic recording and retrieval, and the photosensitive colored glasses exhibiting alterable photo-anisotropic effects were demonstrated to be useful only as a write-erasable bit-by-bit recording material.
U.S. Pat. Nos. 4,670,306, issued on Jun. 2, 1987 to Wu, and U.S. Pat. No. 5,078,771, issued on Jan. 7, 1992 also to Wu, the contents of which are incorporated herein by reference, disclose a High Energy Beam Sensitive (HEBS) glass and a Laser Direct Write (LDW) glass prepared from HEBS glass by uniformly darkening the HEBS-glass with a flood electron beam. LDW-glass is a suitable candidate as a bit-by-bit optical recording material. Focused laser beam writing with a visible laser wavelength results in the ionization of atomic silver in LDW-glass and in converting the silver particles and/or specks in LDW-glass to silver ions, thus reverting the e-beam darkened glass layer at heat erased spots to transparent HEBS-glass. Therefore, an optical data bit with excellent contrast can be recorded in the LDW-glass plate. An experimental characterization of the LDW-glass plate for optical disk data storage is disclosed in “Characterization of Erasable Inorganic Photochromic Media for Optical Disk Data Storage” by X. Huang et al and C. Wu in J. Applied Physics, Vol. 83, No. 7, pages 3795-3799, published in April 1998. The optical recording of data is based on a heat erasure mode of recording that uses a focused laser beam to record data bit by bit. Since the e-beam darkened areas in a LDW-glass layer are heat erased at a temperature above about 200° C., heat spread from the recording bits to the surrounding bits causes the LDW-glass plate of U.S. Pat. No. 5,078,771 not to be a suitable candidate for holographic recording material.
U.S. Pat. No. 6,586,141, issued on Jul. 1, 2003 to Efimov et al, discloses a method of forming diffractive optical elements and holographic optical elements in photosensitive silicate glasses doped with silver, cerium, fluorine, and bromine. This process employs a photo-thermo-refractive (PTR) glass of high purity exposed to the ultraviolet (UV) radiation of a He—Cd laser at 325 nm wavelength, followed by thermal development at temperatures from 480° C. to 580° C. for a time duration of up to several hours. Absolute diffraction efficiency up to 95% was observed for 1 mm thick gratings. Maximum spatial frequency recorded in the PTR glass was about 10,000 mm−1, and no decreasing of diffraction efficiency were detected at low spatial frequencies. However, due to the requirement of post-exposure thermal development steps, PTR glasses are not useful as a direct-read-after-write optical information recording medium for use in an optical system for recording and reproduction of information utilizing holography.
In one embodiment, the present invention relates to a method of forming a volume phase hologram that includes the steps of making a photo-darkenable-refractive (PDR) glass plate having at least one photosensitive glass layer of a silver ion-exchanged holographic recording (SIHR) glass, and of exposing the photosensitive glass layer of the PDR glass plate to the darkening-light radiation of laser write beams, causing the volume phase hologram to be formed in the photosensitive glass layer of the PDR glass plate. The SIHR glass has a base glass composition that has been ion-exchanged in an aqueous ion-exchange solution containing silver ions, such to cause the photosensitive glass layer of the PDR glass plate to show a change in refractive index upon exposure to the darkening-light radiation without any post-exposure step that involves either a physical or chemical treatment.
In another embodiment, the present invention relates to a base glass composition that consists essentially, in mole percent of the oxide basis, of about 10-23% of one or more alkali metal oxides, about 4-18% ZnO, about 0.5-12% MgO, about 0.5-10% Al2O3, about 0.2-3.5% Cl, and about 54-78% SiO2.
In still another embodiment, the base glass composition consists essentially, in mole percent of the oxide basis, of about 8-28% of one or more alkali metal oxides such as Li2O, Na2O, and K2O, zero to about 24% ZnO, zero to about 10% Al2O3, zero to about 12% MgO, zero to about 8% ZrO2, zero to about 10% CaO, zero to about 20% PbO, zero to about 15% B2O3, zero to about 30% P2O5, zero to about 4% TiO2, about 0.1-9% Cl, zero to about 3% total of F, Br, and I, and about 50 to 86% SiO2. The acid-durability-and-glass-network-strengthener (ADAGNS) is ZnO, ZrO2, Al2O3, MgO, TiO2, or PbO and is in an amount of about 5 to 35% in mole percent of the oxide basis, and the base glass composition has a concentration of the ADAGNS effective to render the photosensitive glass layer free of any thermoplastic property that may adversely affect the dimensional stability of the photosensitive glass layer for multiplex recording or for reproducing information utilizing holography. In still another embodiment, a base glass composition contains at least 4% of ZnO in mole percent of the oxide basis. In still another embodiment, the glass composition contains at least 2% of MgO in mole percent of the oxide basis. In still another embodiment, the base glass composition contains at least 0.5% of Al2O3 in mole percent of the oxide basis.
The photosensitive glass layer has a thickness of SIHR glass that ranges from about 5 to more than 500 micrometers and that is not limited by high absorption losses at selected read wavelengths, because the wavelength λp of at least one prominent absorption peak of atomic silver clusters is shifted to a shorter wavelength as exposure dosage of the darkening-light radiation on the SIHR glass increases.
The aqueous ion-exchange solution contains at least one oxidizing agent, preferably HNO3 and a metal nitrate such as AgNO3, LiNO3, NaNO3, KNO3, Zn(NO3)2, among others. The aqueous ion exchange solution is acidic.
The laser write beams, in a photo energy darkening mode of recording that utilizes holography, have a wavelength selected from within a spectral range of about 250 nm to about 550 nm, and the photosensitive glass layer of the PDR glass plate is exposed using exposure dosages to the darkening-light radiation of the laser write beams that range from about 10 mJ/cm2 to about 20,000 mJ/cm2. The exposure dosage that is required to form the volume phase hologram is reduced by optimizing the concentration of MgO in the base glass composition.
The PDR glass plate can be utilized in an optical information recording medium for use in a holographic optical disc drive. The photosensitive glass layer of the PDR glass plate is a hologram layer in the optical information recording medium. The laser write beams consist of an information light beam and a reference light beam. Information light in the information light beam is reconstructed using a laser read beam that has a wavelength selected from about 500 nm to about 1100 nm. Preferably, the photosensitive glass layer of the PDR glass plate is optimized to have essentially no darkening as well as no bleaching sensitivity at the wavelength and/or at the intensity level of the laser read beam, and also is optimized to have a sufficiently large value of the refractive index change at the wavelength of the laser read beam for multiplex reproduction of the information light utilizing holography. Further, the photosensitive glass layer of the PDR glass plate is optimized to have a sufficiently low value of optical density at the wavelength of the laser read beam for multiplex reproduction of the information light utilizing holography. The optical density at the wavelength of the laser read beam has a sufficiently low value, because the composition of the SIHR glass is optimized and balanced to have the wavelength λp of at least one prominent absorption peak of atomic silver clusters shifted to a shorter wavelength as the exposure dosage of the darkening-light radiation on the SIHR glass is increased. One of the preferred laser read beam has a wavelength of about 780 nm.
The present invention also relates to a method of forming a volume phase hologram comprising the step of making a photo-bleachable-refractive (PBR) glass plate that has at least one photosensitive glass layer of a silver ion-exchanged holographic recording (SIHR) glass, and of exposing the photosensitive glass layer of the PBR glass plate to the bleaching-light radiation of laser write beams to form the volume phase hologram in the photosensitive glass layer of the PBR glass plate. The SIHR glass has a base glass composition that has been ion exchanged in an aqueous ion-exchange solution containing silver ions, and the SIHR glass has been darkened uniformly at least in lateral (that is, x, y) dimensions (which are perpendicular to the depth dimension z of ion exchange reaction) with darkening-light radiation, causing the photosensitive glass layer of the PBR glass plate to show a refractive index change upon exposure to bleaching-light radiation without any post-exposure steps, such as a physical or a chemical treatment. The uniformity of darkening of the SIHR glass along z direction with darkening-light radiation is predetermined by selecting the wavelength of the darkening radiation. Using a darkening radiation shorter than about 254 nm, the depth of the darkened SIHR glass layer is limited by the penetration depth of UV light due to attenuation by the SIHR glass. On the other hand, using a darkening radiation longer than about 365 nm, a substantially constant darkening along z direction is achieved. A uniformly darkened photosensitive glass layer of a larger thickness is obtained using a longer wavelength of the darkening-light radiation.
In one embodiment, a base glass composition consists essentially, in mole percent of the oxide basis, of about 10-23% of one or more alkali metal oxides, about 4-18% ZnO, zero to about 4% MgO, about 0.5-10% Al2O3, about 0.2 to 3.5% Cl, and about 54 to 78% SiO2. In another embodiment, the base glass composition consists essentially, in mole percent of the oxide basis, of about 8-28% of one or more alkali metal oxides such as Li2O, Na2O, and K2O, zero to about 24% ZnO, zero to about 10% Al2O3, zero to about 12% MgO, zero to about 8% ZrO2, zero to about 10% CaO, zero to about 20% PbO, zero to about 15% B2O3, zero to about 30% P2O5, zero to about 4% TiO2, about 0.1-9% Cl, zero to about 3% total of F, Br, and I, and 50 to 86% SiO2, provided that the amount of an acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of ZnO, ZrO2, Al2O3, MgO, TiO2, and PbO is about 5% to 35%, and that the base glass composition has a concentration of the ADAGNS effective to render the photosensitive glass layer free of any thermoplastic property that may adversely affect the dimensional stability of the photosensitive glass layer for multiplex recording or for reproducing information utilizing holography.
In still another embodiment, a base glass composition contains at least about 4% of ZnO in mole percent of the oxide basis, and in yet another embodiment, the base glass composition contains at least about 0.5% total of Al2O3, ZrO2, and TiO2 in mole percent of the oxide basis.
The darkening-light radiation is provided by an ultraviolet lamp and has wavelengths within a spectral range of about 250 nm to about 450 nm. The photosensitive glass layer which is a darkened SIHR glass has a thickness ranging from about 5 to more than 500 micrometer. In particular, the thickness of the SIHR glass is not limited by high absorption losses at selected read wavelengths, because the wavelength λp of at least one prominent absorption peak of atomic silver clusters is shifted to a shorter wavelength as exposure dosage of the darkening-light radiation on the SIHR glass is increased.
The aqueous ion exchange solution contains at least one oxidizing agent, preferably HNO3 and a metal nitrate such as AgNO3, LiNO3, NaNO3, KNO3, Zn(NO3)2, among others. The aqueous ion exchange solution is acidic.
The laser write beams in photo energy bleaching mode of recording utilizing holography have a wavelength selected from within a spectral range of about 500 nm to about 750 nm. In photo energy bleaching mode of recording utilizing holography, the photosensitive glass layer of the PBR glass plate is exposed using exposure dosages of the bleaching-light radiation of the laser write beams that range from about 10 mJ/cm2 to about 5,000 mJ/cm2.
The PBR glass plate is utilized in an optical information recording medium for use in a holographic optical disc drive. The photosensitive glass layer of the PBR glass plate is a hologram layer in the optical information recording medium. The laser write beams consist of an information light beam and a reference light beam. Information light in the information light beam is reconstructed using a laser read beam that has a wavelength ranging from about 500 nm to about 1100 nm.
In one embodiment, the photosensitive glass layer of the PBR glass plate is balanced and/or optimized to have essentially no darkening and no bleaching sensitivity at the wavelength and/or at an intensity level of the laser read beam, and also to have a sufficiently large value of the refractive index change at the wavelength of the laser read beam for multiplex reproduction of the information light utilizing holography. Further, the photosensitive glass layer of the PBR glass plate is optimized to have a sufficiently low optical density value at the wavelength of the laser read beam for multiplex reproduction of the information light utilizing holography, because the composition of the SIHR glass is balanced and/or optimized to have the wavelength λp of at least one prominent absorption peak of atomic silver clusters shifted to a shorter wavelength as the exposure dosage of the darkening-light radiation on the SIHR glass is increased. The laser read beam may operate at the wavelength of the laser write beams and has a fraction of the intensity of the reference light beam.
The present invention also relates to an optical information recording medium that comprises a photo-bleachable-refractive (PBR) glass plate having at least one photosensitive glass layer of a silver ion-exchanged holographic recording (SIHR) glass, which includes a base glass composition that has been ion-exchanged in an aqueous ion-exchange solution containing silver ions. The SIHR glass is darkened uniformly at least in the lateral (x, y) dimensions (that is, perpendicular to thickness dimension of the photosensitive glass layer) with darkening-light radiation, so that the photosensitive glass layer of the PBR glass plate shows a change in refractive index change upon exposure to a bleaching-light radiation without any post-exposure steps, such as a physical or a chemical treatment. In one embodiment, the base glass composition consists essentially, in mole percent of the oxide basis, of about 10-23% of one or more alkali metal oxides, about 4-18% ZnO, zero to about 4% MgO, about 0.5-10% Al2O3, about 0.2 to 3.5% Cl, and about 54-78% SiO2. In another embodiment, the base glass composition consists essentially, in mole percent of the oxide basis, of about 8-28% of one or more alkali metal oxides selected from the group consisting essentially of Li2O, Na2O, and K2O, zero to about 24% ZnO, zero to about 10% Al2O3, zero to about 12% MgO, zero to about 8% ZrO2, zero to about 10% CaO, zero to about 20% PbO, zero to about 15% B2O3, zero to about 30% P2O5, zero to about 4% TiO2, about 0.1-9% Cl, zero to about 3% total of F, Br, and I, and 50 to 86% SiO2, provided that the amount of an acid-durability-and-glass-network-strengthener (ADAGNS), selected from the group consisting of ZnO, ZrO2, Al2O3, MgO, TiO2, and PbO, is about 5 to 35%, and that the base glass composition has a concentration of the ADAGNS effective to render the photosensitive glass layer free of any thermoplastic property that may adversely affect the dimensional stability of the photosensitive glass layer for multiplex recording or for reproducing information utilizing holography. In another embodiment, the base glass composition contains at least-about 4% of ZnO in mole percent of the oxide basis. In still another embodiment, the base glass composition contains at least about 0.5% total of Al2O3, ZrO2, and TiO2 in mole percent of the oxide basis.
The darkening-light radiation is from an ultraviolet lamp and has wavelengths within a spectral range of about 250 nm to about 450 nm. The photosensitive glass layer, which is a darkened SIHR glass, has a thickness of about 5 or more micrometers. The thickness of the SIHR glass is not limited by high absorption losses at selected read wavelengths, because the wavelength λp of at least one prominent absorption peak of atomic silver clusters is shifted to a shorter wavelength as exposure dosage of the darkening-light radiation on the SIHR glass increases.
The aqueous ion exchange solution contains at least one oxidizing agent, preferably selected from the group consisting of HNO3 and nitrates of metals that include AgNO3, LiNO3, NaNO3, KNO3, Zn(NO3)2, as well as other metal nitrates. The aqueous ion exchange solution is acidic.
The optical information recording medium is used in an optical system such as a holographic optical disc drive for multiplex recording or for reproducing of information utilizing holography. In a photo energy bleaching mode of recording utilizing holography, the photosensitive glass layer of the PBR glass plate is exposed using exposure dosages of the bleaching-light radiation of laser write beams that range from about 10 mJ/cm2 to about 5,000 mJ/cm2 and that have a wavelength selected from within a spectral range of about 500 nm to about 750 nm; for example, the laser write beams may have a wavelength of 650 nm.
The photosensitive glass layer of the PBR glass plate is a hologram layer in the optical information recording medium. The laser write beams consist of an information light beam and a reference light beam. Information light in the information light beam is reconstructed using a laser read beam that has a wavelength selected from about 500 nm to about 1100 nm; for example, the laser read beam can have a wavelength of about 780 nm. In one embodiment, the photosensitive glass layer of the PBR glass plate is balanced and/or optimized to have essentially no darkening as well as no bleaching sensitivity at the wavelength and/or at the intensity level of the laser read beam, and also to have a sufficiently large value of the refractive index change at the wavelength of the laser read beam for multiplex reproduction of the information light utilizing holography. The photosensitive glass layer of the PBR glass plate is also optimized to have a sufficiently large transmittance value at the wavelength of the laser read beam for multiplex reproduction of the information light utilizing holography. The optical density at the wavelength of the laser read beam has a sufficiently low value, because the composition of the SIHR glass is balanced and/or optimized to have the wavelength λp of at least one prominent absorption peak of atomic silver clusters shifted to a shorter wavelength as the exposure dosage of the darkening-light radiation on the SIHR glass increases. The laser read beam can have the wavelength of the laser write beams and has a fraction of the intensity of the reference light beam. Additionally, the optical information recording medium may include a reflecting film.
The present invention also relates to an optical information recording medium that comprises a photo-darkenable-refractive (PDR) glass plate having at least one photosensitive glass layer of a silver ion-exchanged holographic recording (SIHR) glass. The SIHR glass has a base glass composition that has been ion-exchanged in an aqueous ion-exchange solution containing silver ions, causing the photosensitive glass layer of the PDR glass plate to exhibit a refractive index change upon exposure to darkening-light radiation without any post-exposure steps, such as a physical or a chemical treatment.
In one embodiment, the base glass composition consists essentially, in mole percent of the oxide basis, of about 10-23% of one or more alkali metal oxides, about 4-18% ZnO, about 0.5-12% MgO, about 0.5-10% Al2O3, about 0.2 to 3.5% Cl, and about 54 to 78% SiO2. In another embodiment, the base glass composition consists essentially, in mole percent of the oxide basis, of about 8-28% of one or more alkali metal oxides such as Li2O, Na2O, and K2O, zero to about 24% ZnO, zero to about 10% Al2O3, zero to about 12% MgO, zero to about 8% ZrO2, zero to about 10% CaO, zero to about 20% PbO, zero to about 15% B2O3, zero to about 30% P2O5, zero to about 4% TiO2, about 0.1-9% Cl, zero to about 3% total of F, Br, and I, and 50-86% SiO2, provided that the amount of an acid-durability-and-glass-network-strengthener (ADAGNS), selected from the group consisting of ZnO, ZrO2, Al2O3, MgO, TiO2, and PbO, is about 5 to 35%, and that the base glass composition has a concentration of the ADAGNS effective to render the photosensitive glass layer free of any thermoplastic property that may adversely affect the dimensional stability of the photosensitive glass layer for multiplex recording or reproduction of information utilizing holography. In still another embodiment, the base glass composition contains at least 4% of ZnO in mole percent of the oxide basis. In yet another embodiment, the base glass composition contains at least 2% of MgO in mole percent of the oxide basis. In a further embodiment, the base glass composition contains at least 0.5% of Al2O3 in mole percent of the oxide basis.
The photosensitive glass layer has a thickness of SIHR glass of about 5 or more micrometers. The thickness of the SIHR glass is not limited by high absorption losses at selected read wavelengths, because the wavelength λp of at least one prominent absorption peak of atomic silver clusters is shifted to a shorter wavelength as exposure dosage of the darkening-light radiation on the SIHR glass increases. The aqueous ion exchange solution contains at least one oxidizing agent, preferably selected from the group consisting of HNO3 and nitrates of metals that include AgNO3, LiNO3, NaNO3, KNO3, Zn(NO3)2, and other metal nitrates. The aqueous ion-exchange solution is acidic.
The optical information recording medium is used in an optical system such as a holographic optical disc drive for multiplex recording or reproduction of information utilizing holography. In a photo energy darkening mode of recording utilizing holography, the photosensitive glass layer of the PDR glass plate is exposed by using exposure dosages of the darkening-light radiation of laser write beams that range from about 10 mJ/cm2 to about 20,000 mJ/cm2. The exposure dosage that is required to form the volume phase hologram is reduced by optimizing the concentration of MgO in the base glass composition.
The laser write beams in photo energy darkening mode of recording utilizing holography have a wavelength selected from within a spectral range of about 250 nm to about 550 nm; for example, the laser write beams may have a wavelength of about 405 nm. The photosensitive glass layer of the PDR glass plate is a hologram layer in the optical information recording medium. The laser write beams consist of an information light beam and a reference light beam. Information light in the information light beam is reconstructed using a laser read beam that has a wavelength selected from about 500 nm to about 1100 nm; for example, the laser read beam may have a wavelength of about 780 nm. In one embodiment, the photosensitive glass layer of the PDR glass plate is balanced and/or optimized to have essentially no darkening as well as no bleaching sensitivity at the wavelength and/or at an intensity level of the laser read beam, and also to have a sufficiently large value of the refractive index change at the wavelength of the laser read beam for multiplex reproduction of the information light utilizing holography. In addition, the photosensitive glass layer of the PDR glass plate is also optimized to have a sufficiently large transmittance value at the wavelength of the laser read beam for multiplex reproduction of the information light utilizing holography, because the composition of the SIHR glass is optimized to have the wavelength λp of at least one prominent absorption peak of atomic silver clusters shifted to a shorter wavelength as the exposure dosage of the darkening-light radiation on the SIHR glass increases.
The optical information recording medium may also include a reflecting film.
The use of volume diffractive optical elements as angular selector, spatial filter, attenuator, switcher, modulator, beam splitter, beam sampler, beam deflectors controlled by positioning of grating matrix, by a small-angle master deflector or by spectral scanning, selector of particular wavelengths (notch filter, add/drop element, spectral shape former (gain equalizer), spectral sensor (wavelength meter/wavelocker), angular sensor (pointing locker), Bragg spectrometer (spectral analyzer), transversal and longitudinal mode selector in laser resonator were described n U.S. Pat. No. 6,673,497, issued on Jun. 6, 2004 to Efimov et al, which is incorporated herein by reference.
a-5g illustrate the function Δn(Δλ, Dp) vs. Δλ, wherein in
a illustrates the function ΔD(λ) vs. λ, wherein the difference OD spectrum ΔD(λ) is D(λ) of spectral curve B of
b illustrates the function ΔD(λ) vs. λ, wherein the difference OD spectrum ΔD(λ) is D(λ) of spectral curve C of
a illustrates the propagation directions of laser write beams that is interferenced within a photosensitive glass layer of either a PDR glass plate or a PBR glass plate to form a phase volume transmitting diffractive grating.
a depicts a portion of optical elements in a prior art holographic optical disc drive.
Detailed descriptions of embodiments of the invention are provided herein. It is to be understood, however, that the present invention may be embodied in various forms. Therefore, the specific details disclosed herein are not to be interpreted as limiting, but rather as a representative basis for teaching one skilled in the art how to employ the present invention in virtually any detailed system, structure, or manner.
The present invention concerns glasses for the storage of holographic data and for making computer-generated holograms therein, and the related manufacturing methods. More particularly, the present invention concerns silver ion-exchanged silicate glass articles that include photo-darkenable-refractive (PDR) and photo-bleachable-refractive (PBR) glass plates.
In one embodiment, a PDR glass plate has at least one photosensitive glass layer of a silver ion-exchanged holographic recording (SIHR) glass, in which a base glass composition has been ion-exchanged in an aqueous ion-exchange solution containing silver ions. This process causes the photosensitive glass layer of the PDR glass plate to show a refractive index change upon exposure to darkening-light radiation without any post-exposure step such as a physical or a chemical treatment, because the exposure to the darkening-light radiation causes formation of atomic silver cluster species in the SIHR glass.
In another embodiment, a PBR glass plate has at lease one photosensitive glass layer of a silver ion-exchanged holographic recording (SIHR) glass, in which a base glass composition has been ion-exchanged in an aqueous ion-exchange solution containing silver ions. The SIHR glass is then uniformly darkened with darkening-light radiation. This process causes the photosensitive glass layer of the PBR glass plate to show a refractive index change upon exposure to bleaching-light radiation without any post-exposure step such as a physical or a chemical treatment, because the exposure to the bleaching light radiation causes transformation of at least a portion of one silver cluster species into another silver cluster species within the uniformly darkened SIHR glass.
An optical information recording medium constructed in accordance with the principles of the present invention includes a PDR glass plate, in which the SIHR glass of the PDR glass plate is optimized for multiplex recording and for reproducing information that utilizes holography using darkening light radiation as recording beams.
Another optical information recording medium constructed in accordance with the principles of the present invention includes a PBR glass plate, in which the SIHR glass of the PBR glass plate is optimized for multiplex recording and for reproducing information that utilizes holography using bleaching light radiation as recording beams.
In one embodiment, SIHR glasses according to the present invention are produced through the ion-exchange of Ag+ ions for Li+, Na+ and/or K+ ions in a parent/base glass composition within a Li2O, Na2O, and/or K2O—ZnO—Cl—SiO2 silicate glass composition, most preferably in an acidic aqueous solution of silver salt, for example, AgNO3. Upon ion-exchange most or all of the silver in the SIHR glass remains in the ionic state until exposure to darkening radiation, and such exposure results in the instantaneous formation of silver color centers and/or atomic silver species. The darkening radiation is selected from the group consisting of darkening-light radiation and high energy electron beams. One or more distinct types of aggregation of atomic silver cluster species may exist in a darkened SIHR glass, for example, either one or two types of atomic silver cluster species may exist in the darkened SIHR glass having been exposed to a darkening-light radiation or to an electron beam with more than about 5 kV accelerating voltage. In general, the darkening-light radiation of a SIHR glass is the light radiation that has a wavelength or a wavelength range selected from the spectral range of UV light, near UV light, blue light, and green light.
The photosensitive glass layer of a PDR glass plate is a silver ion-exchanged glass layer consisting of a SIHR glass, and the photosensitive glass layer of a PBR glass plate is a silver ion-exchanged glass layer consisting of a uniformly darkened SIHR glass.
A method of preparing a base glass or the parent anhydrous glass useful for preparing a SIHR glass comprises the steps of:
Oxides and salts may be used in the preparation of the pre-melt batch, for example, oxides, halide salts, nitrate salts, carbonate salts, bicarbonate salts, silicate salts and other similar materials. Preferably, the glass melt is stirred during the melting step to form a uniform glass composition. Prior to cooling, the glass melt may be formed into a glass article, such as a glass sheet or plate. As is known in the art of silicate glass making, the glass article may be annealed at an annealing temperature TA and cooled down slowly from TA, so that it is absent of any stress birefringence and can be cut, ground and polished without breakage due to thermal stress.
The base glass composition is defined herein as the composition of a pre-melt batch.
To obtain a maximum Cl concentration in the base glass, the base glass composition is compounded with an excess of Cl-containing salts. During melting, some Cl will evaporated off, but the resulting melt and the cooled glass will be saturated or super saturated with respect to Cl. Cl saturation can be increased by performing the melt under a partial or complete Cl or chloride atmosphere. In one embodiment, the melting is done in an atmosphere containing at least a partial pressure of chlorine or chlorides.
The surface of the glass articles formed from the melt after cooling and annealing can be ground and polished to any desired surface figure or to a surface of any desired optical quality. If the glass article is a glass sheet or plate, the major opposing surfaces of the glass sheet can be ground to form a plate or sheet of the desired uniform thickness and then polished to form smooth, planar surfaces.
Volatilization of halides can be quite high during melting, particularly where temperatures in the upper extreme of the melting range are employed. Thus, halide losses of more than 20% are common. Besides being essential ingredients, halides also are a fining agent for the glass melts.
It will be appreciated that large melts of glass can be made in pots or continuous melting units in accordance with known commercial glass making practice. Where glass of optical quality is to be produced from commercial continuous melting tanks, the melt will be stirred in accordance with conventional practice. Volatilization of halides in such commercial melting practices can be held below 50% and, with proper care, below 10%. Retention of halides can be further increased by melting in a halogen-containing atmosphere.
A base glass compositions suitable for preparing a SIHR glass comprises, in mole percent, about 8-28% of one or more alkali metal oxides, 3-24% ZnO, 0.2-3% Cl, 50-89% SiO2, and up to about 12% MgO. Preferably the composition contains at least 0.5% MgO, and most preferably contains at least 2% MgO in the SIHR glass of a PDR glass plate, and the composition contains less than about 4% MgO in the SIHR glass of a PBR glass plate.
The base glass composition also preferably contains at least one of the following constituents, in mole percent: zero-about 10% CaO, zero-about 8% ZrO2, zero-about 10% Al2O3, zero-about 4% TiO2, zero-about 10% SrO, zero-about 20%, PbO, zero-about 20% BaO, zero-about 30% P2O5, zero-about 15% B2O3 and/or zero-about 4% F, Br, I or a mixture thereof. Further, the base glass composition preferably contains an amount of an acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of ZnO, ZrO2, Al2O3, MgO, TiO2, and PbO from about 5% to about 35%. Still further, the base glass most preferably contains about 5 to 20% of ZnO, Al2O3, ZrO2 or a mixture thereof as ADAGNS. The concentration of ADAGNS in the glass composition is sufficient to prevent SIHR glass from being excessively hydrated and/or to prevent SIHR glass from becoming water soluble, and/or to maintain the optical quality surface of the glass plate during the ion-exchange process of producing the SIHR glass. The base glass composition of a SIHR glass is so designed that the SIHR glass is absent of excessive hydration, which excessive hydration may impart an undesirable thermoplastic property to the SIHR glass.
One base glass composition includes, in mole percent, about 2%-about 20% ZnO, zero-about 10% Al2O3, and about 1.2-about 12% MgO. Another base glass composition includes, in mole percent, about 3%-about 10% MgO and about 60%-about 82% SiO2.
Suitable alkali metal oxides are Li2O, Na2O, K2O, Rb2O, and Cs2O, with Li2O, Na2O and K2O being preferred for the base glass. The base glass composition may contain at least two of the alkali metal oxides selected from Li2O, Na2O, and K2O; for example, the base glass composition may contain about 10 to about 20 mole percent of Li2O, Na2O, K2O or of a mixture thereof, and about 1 to 3 mole percent Cl.
The total quantity of constituents in the base glass composition of a pre-melt batch shall equal 100 mole percent. All mole percents are based on a mole percent oxide basis except for Cl, F, Br, and I, which are based on a mole percent element basis.
Although the constituents of the anhydrous base glass compositions are identified as specific chemical oxides or elements pursuant to the practice of the glass art, it is to be understood that such identification is for convenience only, in accordance with the practice of the glass art. As those skilled in the glass art will recognize, the chemical structure and coordination of all cations in glass are not known at present with complete certainty.
One base glass composition useful for preparing a SIHR glass comprises, in mole percent, about 12-24% Li2O, Na2O, K2O or a mixture thereof, zero to about 10% MgO, about 4-14% ZnO, about 0.5-5% Al2O3, about 0.4-3% Cl, and about 65-75% SiO2. The base glass composition may include, in mole percent, zero-about 10% ZrO2, zero-about 15% CaO, zero-about 15% SrO, zero-about 15% BaO, zero-about 15% PbO, zero-about 35% B2O3, and/or zero-about 3% F, Br, I or a mixture thereof.
A preferred base glass composition for preparing SIHR glass articles comprises, in mole percent, about 13-24% of a mixture of Li2O, Na2O and K2O; about zero-8% MgO; about 6.5-9.5ZnO; about 1-2% Al2O3; about 0.7-3% Cl and about 69-72% SiO2. The base glass composition may also contain an amount of Cl equivalent to the Cl saturation value of the melt of the base glass composition.
It has been found that the base glass composition has a significantly adverse effect on the properties of the SIHR glass if the glass batch is contaminated with certain impurities, such as a carbon containing substance or a thermal reducing agent that affect the oxidation state of the glass melt.
It has been determined that the production of a SIHR glass article exhibiting darkening sensitivity to UV radiation and to longer wavelengths involves a complex combination of relationships among the various components of the base glass composition, the ingredients of the ion-exchange solution, and the conditions of the ion-exchange reactions. Nevertheless, there exists a very wide range of glass compositions in the field of alkali metal zinc silicate glasses that are suitable as a base for the products manufactured according to the present invention. The sensitivity to actinic radiation of SIHR glasses is strongly dependent upon the ingredients of the aqueous ion-exchanged solution, in particular, upon the concentrations of the silver ion and hydrogen ion.
The SIHR glass are prepared by treating a glass article having a base glass composition with a silver salt-containing material at a temperature sufficient to generate an ion-exchange reaction between the silver ions in the silver salt-containing material and the alkali metal ions in the base glass composition. The ion-exchange reaction is continued for a period of time sufficient to have the ion-exchange reaction proceed to a depth of at least 5 micrometer into the surface of the glass article to produce an ion-exchanged glass article, for example, a PDR glass plate, having a body portion composed of the base glass composition and an integral ion-exchanged surface glass layer that is the photosensitive glass layer composed of the SIHR glass.
The SIHR glass contains, in addition to a high concentration of ionic silver, silanol and/or water species in a concentration greater than about 0.01% by weight H2O. The concentration of the alkali metal oxides in the SIHR glass is less than the concentration of the alkali metal oxides in the base glass composition. The thickness of the body portion may be reduced to zero when the ion-exchange process is allowed to proceed throughout the thickness dimension, in particular when the glass article is in a plate form of less than about 1 mm thickness.
Hydration and/or an exchange of H+ and/or H3O+ ions for alkali metal ions in the base/parent glass article is expected to take place when the ion-exchange reactions are carried out in an aqueous solution containing Ag+ ions. The base glass compositions are designed so that the SIHR glass does not contain an excessive concentration of water species, because an excessive concentration of water species would impart thermoplastic properties to the hydrated glass and would have an adverse effect on the dimensional stability of the SIHR glass for use as a holographic recording material. Therefore, the base glass composition of a SIHR glass is designed and selected so that there is no thermal plastic properties in the SIHR glass layer. One SIHR glass embodiment contains less than about 2% by weight H2O. Another SIHR glass embodiment contains less than about 1% by weight H2O.
In cases where other ingredients such as cupric and/or cuprous oxide or gold oxide are included in an aqueous ion-exchange solution, additional reactions that exchange the alkali metal ions in the surface layer of the parent silicate glass with the other cations in the aqueous solution are also expected to take place, but to a lesser extent than with the Ag+ ion.
The ion-exchange reactions can be carried out as follows. The glass articles are immersed into an aqueous ion-exchange solution containing Ag+ ions and other ingredients, and the glass articles together with the aqueous solution are sealed in an autoclave and heated to a temperature sufficient to effect an ion-exchange reaction between the silver ions in the aqueous solution and the alkali metal ions in the glass article, usually above about 200° C. Reaction temperature is held for a duration of more than about 1 minute, and when a desired thickness of the ion-exchanged glass layer is obtained, the autoclave is cooled down to about room temperature. Thereafter, the glass articles having a photosensitive glass layer of SIHR glass are removed from the autoclave and washed with distilled water.
The concentration of silver ions in the aqueous ion-exchange solution according to the principles of the present invention is found to range from less than 10−3 mole/liter up to the concentration of a saturated AgNO3 aqueous solution, while the concentration of hydrogen ion/hydronium ion can range from 10−6 to more than 3 moles per liter of the aqueous ion-exchange solution. The optimum concentration of silver ions in the aqueous ion-exchange solution, in general, increases with the concentration of hydrogen ion in the aqueous solution for preparing SIHR glasses. The hydrogen ions are added to the aqueous ion-exchange solution in the form of one or more acids, such as HNO3, H2SO4, acetic acid, and the like.
The concentration of Ag+ ions in the SIHR glass can be varied from less than 1% up to more than 30% by weight of Ag2O through various combinations of the concentrations of Ag+ ions and H+ ions in the aqueous ion-exchange solution, and of the temperature and duration of the ion-exchange reaction. One way to ensure a large concentration of Ag+ ions within the SIHR glass is to utilize an aqueous ion-exchange solution having a large concentration of Ag+ ions, that is, greater than about 100 g AgNO3/liter of the aqueous solution. Another way to ensure a large concentration of Ag+ ions within the SIHR glass is to employ an aqueous ion-exchange 150° C. up to the softening point of the SIHR glass on the surface of the parent glass article and/or up to the strain point of the anhydrous base glass are operable. The temperature and duration of the ion-exchange reaction in combination with the choice of a base glass composition determines solution having a large mole ratio of [Ag+]:[H+], that is, in excess of 10, which is readily obtainable by buffering the aqueous solutions at a pH value selected from 2 to 5 with a buffering agent.
Cuprous oxide can be advantageously added to the aqueous ion-exchanged solution to cause the solution to buffer at a desirable pH, particularly in the pH range of 1 to 3, and most effectively in the pH range of 2 to 3. It also has been determined that the inclusion of cuprous and/or cupric ions in the aqueous ion-exchange solution can have some effect on the light radiation exposure-induced coloration of the SIHR glass articles.
Ion-exchange temperatures in excess of the rate of depth penetration of the ion-exchange reaction into the body portion of the glass article. A depth of penetration ranging from 5 to 200 micrometer is obtained in about 10 minutes to about 24 hours of ion-exchange at a temperature selected from about 200° C. to about 370° C., using a base glass composition such as the exemplary compositions listed in Table 1.
As a matter of convenience, the ion-exchange reactions of the present invention will preferably be carried out in an autoclave, because such an apparatus permits a relatively easy control of the ion-exchange temperature, pressure, and atmosphere. To prevent the water in the aqueous ion-exchange solution from evaporating off during the ion-exchange reaction when conducted at elevated temperatures, the pressure of the autoclave can be maintained at the saturated vapor pressure of the ion-exchange solution or higher. Very high pressures can be utilized, although they are not required. Inert and/or oxidizing gases including N2, air, O2 and Ar can be advantageously added, usually at room temperature, to the vapor phase above the aqueous ion-exchange solution in the autoclave.
The filling factor, which is herein defined as the fractional volume of the autoclave occupied by the aqueous ion-exchange solution at room temperature, is another ion-exchange reaction parameter. The maximum allowable filling factor, which is herein defined as the filling factor at which the volume of the vapor phase in the autoclave diminishes at the ion-exchange temperature, should never be approached for safety reasons. However, when the filling factor is kept excessively below the maximum allowable filling factor, the concentration of the ingredients in the aqueous ion-exchange solution at elevated temperatures can be significantly different from the concentration at room temperature.
A large number of base glass compositions were melted and formed into glass plates, then ground and polished to 2 mm thickness. The glass plates were ion-exchanged in an acidic aqueous solution containing Ag+ ions to produce SIHR glass plates. Table 1 records the base glass compositions of SIHR glass plates No. 1 to No. 20. The thickness of SIHR glass layer increased with ion-exchange time duration. SIHR glass layers of about 100 μm were produced in about 2 to 64 hours depending on the base glass composition, in particular on the concentration of alkali metal oxides. The maximum thickness of the photosensitive glass layer of SIHR glass was limited to about 600 μm for many of the base glass compositions, due to dissolution, due to surface deterioration, or due to crystallization resulting from the concurrent hydration process during the silver ion-exchange in an aqueous solution.
Each of the base glass compositions of Table 1 contains one or more alkali metal oxides selected from the group consisting of Li2O, Na2O, and K2O. When a base glass plate is immersed in an acidic aqueous solution containing Ag+ ions, alkali metal ions in the silicate glass network diffuse out of the silicate glass network and facilitate the diffusion of Ag+ ions and H+ ions into the silicate glass network. This phenomenon is referred to herein as a silver ion-exchange reaction. Upon the silver ion-exchange reaction, at least some, and preferably most or all of the silver ions in the SIHR glass are present in the form of silver-alkali-halide (AgX)m(MX)n complex nano crystals or nanophases that are about 10 nanometers (i.e. 100 Å) or less in each dimension within the cavity of the SiO4 tetrahedron silicate glass network, wherein M represents an alkali ion, and X represents a halide such as chloride. The water species that is present in the glass network and/or is present in the interphase between the silver halide containing nanocrystals/nanophases and the silicate glass matrix and/or is present as an impurity in the silver halide containing nanocrystals/nanophases, is believed to function as electron traps or hole traps in various photo-reactions of the nanocrystals/nanophases discussed herein.
In general, an alkali silicate glass containing no other cations such as Zn++ in the base glass composition may either crystallize or dissolve in the aqueous ion-exchange solution when soaked in the aqueous solution at the ion-exchange temperatures described herein for a certain amount of time. Therefore, each of the glass compositions of Table 1 contains a suitable concentration of an acid-durability-and-glass-networks-strengthener (ADAGNS) selected from ZnO, Al2O3, ZrO2, TiO2, and PbO or a mixture thereof, in order to ensure that the SIHR glass contains a uniform and desirable concentration of water species in the glass network of the silver ion rich SIHR glass. The base glass composition of a SIHR glass has a concentration of ADAGNS effective to render the SIHR glass free of any thermoplastic properties that may adversely affect the dimensional stability of the photosensitive glass layer for multiplex recording or reproduction of information utilizing holography. A particularly effective ADAGNS is ZnO. The base glass composition of a SIHR glass article preferably contains at least about 4% ZnO on the mole percent oxide basis.
Exemplary glass compositions 1 and 2 of Table 1 were ion-exchanged at 300° C. for six hours in an aqueous solution containing 200 g AgNO3+36.7 cc of 16N HNO3/liter of the solution to produce PDR glass plates No. 1A and No. 2A respectively. The thickness of the photosensitive glass layer, that is, the ion-exchanged surface glass layer of the PDR glass plates No. 1A and No. 2A was 80.5 and 79.4 micrometers respectively. Both plates No. 1A and 2A are clear glass plates, and are colorless and retain the optical quality surface and the bulk index homogeneity of the base anhydrous glass plates. It is herein defined that “clear” glass plate means, when examined under intense light illumination, for example, from a slide-projection lamp in a dark room, the glass plate is clear and transparent just like a high quality optical glass and there is no observable haziness indicating no scatter centers of any size larger than about 10 nanometer. PDR glass plates contain a high concentration of silver ions present in the form of AgCl containing complex nanocrystals/nanophases that are less than about 10 nanometers in each dimension and do not scatter light in the uv and visible spectral range.
The optical density spectra Do(λ) of PDR glass plate No. 1A having two ion-exchanged surface glass layers, that is, having two photosensitive glass layers of SIHR glass corresponding to two surfaces of a glass plate, are shown as spectral curve Do in
When SIHR glass was formed by silver ion-exchange of a base glass composition in an acidic aqueous solution, H+and/or H3O+ ions entered into the glass network and silanol groups formed in the glass network. The formation of the silanol groups in a silicate glass is referred to as hydration of glass. SIHR glass was hydrated and a moving boundary type concentration profile formed; namely, the error function type concentration profile, which commonly exists as a result of a diffusion process, does not exist in a photosensitive glass layer of the SIHR glass. When water species are among the diffusing species in glass, the diffusion of water species (i.e. H+ and/or H3O+) and Ag+ ions through a hydrated layer is accompanied by an instantaneous and irreversible immobilization of the diffusing species at the boundary surface. The moving boundary type diffusion profile of Ag+ in a photosensitive glass layer of the SIHR glass is characterized by an essentially constant concentration of Ag+ ions throughout the thickness dimension of the photosensitive glass layer. The Ag+ ions in the SIHR glass have a constant concentration profile along the depth dimension of diffusion because the diffusion coefficient of Ag+ ions in the hydrated glass layer is orders of magnitude larger than that in the anhydrous base glass.
The concentration of Ag+ ions is essentially constant throughout the thickness dimension of the photosensitive glass layer, and the thickness of the photosensitive glass layer is readily measured by observing the boundary line between the SIHR glass and the anhydrous base glass in the cross section of a PDR glass plate under a microscope. The Do value of
PDR glass plates were darkened through exposure to a darkening-light radiation without any post-exposure development or fixing step. Wavelengths of practical and readily available darkening-light sources include 254 nm, 365 nm, 405 nm, 436 nm, and 442 nm. In plate 1A, the observed darkening-light radiation exposure induced optical density spectra D(λ), see spectral curves A, B, and C of
In general, either one of the two atomic silver cluster species may be dominant in concentration in a SIHR glass of different glass compositions. Elementary silver atoms and/or clusters of silver atoms are formed within or on the surface of the silver-alkali-halide containing or silver chloride containing complex nanocrystals/nanophases during exposure of SIHR glass to darkening-light radiation, at exposure temperatures that are, in general, at or near room temperatures. The formation of these atomic silver cluster species is believed to involve a movement of electrons, such as delocalization of electrons among a group of silver atoms, and that there is likely to be no diffusion of silver ions or silver atoms as a result of the exposure at or near room temperatures to the darkening-light radiation.
The broad absorption bands in D(λ) spectra of PDR glass plates are absorption bands of atomic silver species in various stable states of coagulation. Since the coagulation of silver atoms are due only to delocalization of electrons, it is possible that two distinct silver species in a SIHR glass are monoatomic species of silver color centers in which an electron is delocalized due to a static force field surrounding a silver atom, and polyatomic silver clusters consisting of two or more silver atoms. Because the monoatomic silver color centers and the polyatomic silver clusters are of molecular dimensions, they do not scatter light in the visible and UV spectral ranges.
SIHR glass has a uniform refractive index and does not scatter light propagating therethrough before and after being darkened with darkening-light radiation selected from the UV, blue light, and longer wavelengths. The absorption bands in D(λ) spectra of SIHR glasses are due to excitation of transition dipoles of delocalized electrons of elementary silver atoms and/or clusters of silver atoms, and there exists no attenuation of light due to scattering.
Portions of PDR plate No. 1A were exposed to darkening-light radiation at the mercury I line at 365 nm wavelength at an intensity level of 23.18 mw/cm2. The optical density spectra D(λ) of darkened areas that have been exposed to 2.51 joule/cm2, 10.9 joule/cm2 and 78 joule/cm2 of light radiation at 365 nm are represented by curves A, B, and C of
As shown in
Dp (curve C of
The transmittance at read wavelengths can be further increased by selecting a SIHR glass that has a darkening-light exposure induced absorption band at shorter wavelengths.
The high absorption losses at read wavelengths, which are usually observed in prior art photochromic films and which limit their useful sample thickness, are circumvented in PDR as well as PBR glass plates because of blue shifting λp with increasing exposure dosage of darkening light radiation for selected compositions of SIHR glasses. This phenomenon, shown in
Certain chemical elements added in the glass melt batch of the parent/base glass composition of a SIHR glass can cause the silver ion-exchanged PDR glass plates to become more sensitive to darkening-light radiation, requiring a lesser exposure dosage to produce a desired darkening-light radiation exposure induced optical density in a PDR glass article, and/or to become sensitive to darkening-light radiation of longer wavelengths. A particularly effective chemical element for increasing the sensitivity to darkening-light exposure of the silver chloride containing nanocrystals/nanophases is magnesium, i.e. MgO in the parent/base glass melt batch.
When MgO was added to the glass melt batch of a base glass composition of a PDR glass article, the darkening light exposure-induced optical density, as well as the accompanying change in refractive index, increased exceptionally. Namely, the sensitivity of a SIHR glass to darkening mode of recording of information light utilizing holography increases with the addition of MgO as a batch ingredient in the glass melt batch.
Curves A and B of
Glass composition No. 18 of Table 1, containing 5.26 mole percent of MgO, was ion-exchanged at 310° C. for 50 minutes to produce a 10 μm photosensitive glass layer of PDR glass plate No. 18A. Plate No. 18A, having a SIHR glass layer of 10 μm, was exposed in three areas A, B, and C to an exposure dosage of 10 joule/cm2 with darkening-light radiation having wavelengths of 365 nm, 405 nm, and 442 nm respectively. The optical density spectra D(λ) of the exposure darkened area A, area B, and area C of plate No. 18A are exhibited
The darkening-light radiation at 365 nm, at 405 nm, or at 442 nm may be used as write beams to record holograms in the photosensitive glass layer of the SIHR plate. It is shown below that the read wavelength for holographic reconstruction is preferably at a wavelength longer than about 750 nm, for example, 785 nm, or 830 nm, or 900 nm.
Δn(λ, Dp) of SIHR glasses due to exposure-induced change in the oxidation state of silver from silver ions to clusters of elementary silver atoms is discussed in the section “Δn between Darkened and Undarkened Areas.”
The darkening-light exposure-induced changes in refractive index |Δn| at 785 nm read-wavelength for each of the three areas A, B, and C of plate No. 18A are 6.73×10−3, 3.65×10−3, or 2.11×10−3 respectively. These values of |Δn| at 785 nm are readily found from the |Δn| vs. Dp plot of
The dynamic range, that is, the refractive index change, Δn of e.g. 1.1×10−2 at a read beam wavelength indicates that a large number of high efficiency holograms can be recorded in the same volume of a SIHR glass layer. Preferably, the thickness of the SIHR glass layer is more than about 10 μm, e.g. 50 to 200 μm. When a number of holograms are recorded in a 100 μm thickness of SIHR glass of base glass composition 18 with the sum of the multiplexed hologram recording dosage of 10 Joule/cm2 at 365 nm write wavelength, the Dp value resulting from the multiplexed hologram recording with darkening write beams is expected to be about 9.54. As is further elaborated in the paragraphs below, such a large value of Dp is acceptable in holographic reconstruction, provided the wavelength of the read beam is so chosen that the optical density at read wavelength is sufficiently low, e.g., less than 1.0 and preferably less than 0.3. Since a refractive index change of 10−5 at a read wavelength is adequate for holographic reconstruction, the minimum write dosage of darkening-light radiation to form one volume phase hologram in a PDR glass plate is about 10 to 100 mJ/cm2.
Glass composition No. 3 of Table 1 was ion-exchanged at 260° C. for 6 hours to produce PDR glass plate No. 3A having a photosensitive glass layer of 130 μm thickness. Plate No. 3A was exposed in 3 areas A, B, and C to a dosage of 4, 20, and 60 Joule/cm2 respectively with darkening-light radiation at 365 nm wavelength. The optical density spectra D(λ) of the exposure darkened areas A, B, and C are exhibited in
As shown in the spectral curves of
Scattering noise in holographic reconstruction due to bulk inhomogeneity is a serious disadvantage of many prior art holographic recording materials. Nevertheless, SIHR glasses are silicate glasses and can be mass produced in very good optical quality using conventional optical glass melting processes. Due to a very low noise in holographic reconstruction, a large value of signal to noise ratio can be expected, and the required index change between 1 bit and 0 bit within a digital hologram is less than about 10−5. A digital hologram having index modulation of 10−5 can be produced in a PDR glass plate using an exposure dosage of more than about 10 millijoule/cm2 at a write beam wavelength of 365 nm, or about 30 mJ/cm2 at a write wavelength of 405 nm.
Areas of PDR glass plate No. 1A represented by spectral curves D0, A, B, and C of
HEBS-glasses are High Energy Beam Sensitive glasses, as disclosed in U.S. Pat. Nos. 4,670,366 and 5,078,771 to Wu, the contents of which are incorporated herein by reference. A HEBS-glass plate is a silver ion-exchanged glass plate that is sensitive to electron beams with more than about 10 KeV of kinetic energy and that is inert to light radiation of UV, visible and longer wavelengths. Silver halide containing nanocrystals/nanophases in HEBS-glasses are sensitive to and darkenable with high energy electron beams having kinetic energy of more than about 10 KeV, and are insensitive to UV light and longer wavelength, because a large energy band gap exists between the valence band and the conduction band of the silver halide containing nanocrystals/nanophases in a silicate glass matrix of HEBS-glass compositions. On the other hand, the silver halide containing nanocrystals/nanophases in a silicate glass matrix of SIHR glasses have a small energy band gap between their valence band and conduction band, therefore, SIHR glasses are sensitive to and darkenable with UV light and longer wavelength. The energy band gap of silver halide containing nanocrystals/nanophases in a HEBS-glass is increased by the addition of a transition metal oxide, TiO2 in particular in the base glass composition of HEBS-glasses, as discussed in the '366 patent. On the other hand, the energy band gap of silver halide containing nanocrystals/nanophases in SIHR glasses is decreased by the addition of MgO in the base glass composition of SIHR glasses.
The darkening radiation exposure-induced spectral absorption bands in both a HEBS-glass plate and a PDR glass plate are caused by elementary silver atoms and/or clusters of silver atoms. This is expected to cause an accompanying increase or change in the refractive index Δn(λ) in the exposure darkened area. According to the Kramers Kronig dispersion relationship, the accompanying index change Δn(λ) is dependent primarily on the strength of the absorption band per unit thickness of a HEBS-glass or a SIHR glass and is independent of whether the darkening radiation is a light radiation or an electron beam. Exposure-induced Δn(λ) value due to a change in the oxidation state of silver from silver ions to clusters of elementary silver atoms is calculated from measured data of phase advance in a HEBS-glass plate. The calculated dispersion spectra Δn(λ) corresponding to an exposure-darkened level, which is defined by a Dp value of a HEBS-glass plate, is applicable qualitatively to SIHR glasses for the purpose of estimating the Δn(λ, Dp) values discussed herein.
a-5g show the difference in refractive index Δn between darkened and undarkened areas of a silver ion-exchanged glass that includes SIHR glasses and HEBS-glasses, as a function of Δλ, wherein Δλ=λ−λp. The peak optical density value Dp of an e-beam exposure-darkened area having a silver ion-exchanged surface glass layer of 10 micrometer thickness is a variable parameter in
The graphical representation Δn(λ, Dp) vs. Δλ of
a-5g were calculated from wavefront phase advance of an e-beam darkened HEBES-glass plate having a silver ion-exchanged surface glass layer of 10 μm thickness. The wavefront phase advance was measured by an interferometric method, see for example, “Measurement of wavefront phase delay and optical density in apodized coronographic mask materials” by Peter G. Halverson et. al in Technique and Instrumentation for Detection of Exoplanets II, edited by Danien R. Coulter, Proceedings of SPIE Vol. 5905.
a-5g are utilized herein to predict qualitatively the change in refractive index of a SIHR glass which has been exposed to darkening-light radiation to result in exposure induced optical density spectra having Dp values found in
In
a-5g are utilized to predict |Δn| values at holographic write or read wavelengths of a SIHR glass layer whose absorption spectra have been measured. The |Δn| value at any chosen wavelength of a SIHR glass having a Dp value of 1.2, 1.75, 2.35, 2.85, 3.35, 3.38 and 4.25 per 10 μm thickness of the SIHR glass layer is readily found in
For example, by setting λp=620 nm, Δn values of plate No. 18A at wavelengths of 405 nm, 785 nm, 830 nm, and 900 nm are found in
It is shown in
The absorption band of pre-darkened SIHR glass was found to shift along the wavelength coordinate, when a uniformly darkened area of a pre-darkened SIHR glass layer was bleached with a bleaching-light radiation. For example, when a pre-darkened SIHR glass layer of a PBR glass plate was bleached with a red light laser beam, λp of the PBR glass plate was shifted from 700 nm to 520 nm.
The change in refractive index Δn between unexposed area and exposure-darkened areas differs as λp is shifted from e.g. 700 nm to 520 nm. The change in Δn value at a given wavelength, arising from λp being shifted e.g. from 700 nm to 520 nm upon laser light bleaching, is referred to herein as Δ(Δn). Example of Δ(Δn) values are discussed immediately below.
Referring to
By setting λp=520 nm in
The Δ(Δn) value at 633 nm is equal to 0.00823, which is 0.00235−(−0.00588). The Δ(Δn) value at 785 nm is equal to 0.00794, which is (−0.00441)−(−0.01235). The Δ(Δn) value at 830 nm is equal to 0.00765 which is (−0.00647)−(−0.0142).
The Δ(Δn) values of a PBR glass plate having Dp values of 1.75, 2.35, 2.85, 3.35, 3.8 and 4.25 were derived from
One or more types of silver clusters were formed in the pre-darkened SIHR glass layer of a PBR glass plate. The darkening-light radiation of SIHR glasses includes light radiation having wavelengths selected from ultraviolet, blue light and green light. It is postulated herein that the absorption bands which peaked at λp1 and λp2 (see
It was observed that the spectral hole burning of one of the absorption bands, e.g. the λp2 band may be accompanied by a spectral growth of other absorption bands, for example, the λp1 band and vice versa. This phenomenon is herein referred to as photo-adaptation.
The bleaching-light radiation which is most effective in causing the spectral hole burning and/or photo-adaptation of a PBR glass plate is in the wavelength range of red light including, among others, 633 nm of a HeNe laser, 647 nm from an ArKr mixed gas laser, and 650 nm of a diode laser, and may also include green light. It has also been observed that when a photosensitive glass layer of a PBR glass plate, that is, a layer uniformly darkened to, for example, blue colored SIHR glass, is bleached with a red light laser, the area exposed to the red laser light turns red in color instantaneously, and without any post exposure processing step, and that when the red colored area is later bleached with a green light laser, the area exposed to the green laser light turns green in color instantaneously. The green colored area is reversed to red color when it is later bleached with a red light laser. Blue, red, and green colored areas in a PBR glass plate are permanently stable in room lighting conditions.
Glass composition No. 8 of Table 1 was ion-exchanged at 340° C. for 4 hours to produce an ion-exchanged glass plate No 8A that is colorless and clear and that has a SIHR glass layer of 78 μm thickness. Two areas (each being 0.25″×2″) of plate No. 8A was uniformly darkened with UV 365 nm darkening-light radiation from Spectroline Black-Ray Lamp Model B-100 at an intensity level of 7 mW/cm2 for 20 and 10 minutes to form PBR glass plate 8A-light blue area and PBR plate 8A-lighter blue area respectively. These two UV darkened areas in the PBR glass plate 8A appear light blue and lighter blue in color and have a Dp value of 1.20 and 0.72 respectively. In other words, there are two photosensitive glass layers in the PBR glass plate 8A, one being the light blue area and the other being the lighter blue area. Curve A of
A portion of each of the light blue and the lighter blue areas was bleached with a 15 mW plane, polarized 633 nm, red laser beam having a beam cross section of 1.5 mm diameter from a HeNe laser. Red light bleached areas, each being 0.25″×0.5″, were produced by raster exposures of 5 second pulses of the plane polarized HeNe laser beam, 15 mWatt in a 1.5 mm diameter spot, at 0.34 mm grid spacing, on the light blue and the lighter blue areas of plate No. 8A. Both of the 0.25″×0.5″ areas that were exposed to red polarized red light turn into red colors. Light red and lighter red areas were produced from the original light blue and lighter blue areas of the photosensitive glass layers of the PBR plate respectively. The red colored areas so produced in plate No. 8A are plane polarized.
Curve B of
Examining the transformation of spectral curve A to curve B of
Because the polarizers used to polarize the probing beams in the measurement of spectral curves B and curve C of
Examining the transformation of spectral curve A to curve C of
The sum of negative areas in the integrals ∫ΔD(λ)dλ contributed from negative values of ΔD(λ) in the spectral curves of
The phenomenon discussed in the paragraphs immediately above also were observed in the corresponding spectral curve A of the lighter blue area and in the corresponding spectral curves B and C of the lighter red bleached area of the PBR plate No. 8A.
It was determined experimentally that when the intensity of a bleaching write beam is increased by a factor of 10, the required duration of write beam exposure pulse to produce the same extent of bleaching is reduced by a factor of 25. In other words, the sensitivity of the photosensitive glass layer of the PBR glass plate increases by a factor of 2.5 when the write beam intensity is increased by a factor of 10.
The red laser light bleached areas of a PBR glass plate is permanently stable in room lighting conditions and is also permanently stable in ambient atmosphere at 0 to 100% humidity levels.
Diminishing certain species of silver clusters with a simultaneous creation of other silver cluster species results in the photo adaptation phenomenon also referred to herein as color adaptation. Photo adaptation is manifested as a spectral change, for example from spectral curve A of the light blue color area of plate 8A to the spectral curve B and C of the light red color area, see
The changes in Δn value, Δ(Δn), arising from λp being shifted from 700 nm to 520 nm are shown as a function of Dp value in
Δ(Δn) values larger than 10−3 indicate that the dynamic range of refractive index modulation can support multiplex recording and reconstruction of information light utilizing holography. Namely, a number of high efficiency holograms can be recorded in the same volume of a PBR glass plate using a photo-energy bleaching mode of recording. In one embodiment, the thickness of the photosensitive glass layer is more than about 10 μm, for example, 100 to 200 μm.
A periodical pattern of Δ(Δn) was produced in a photosensitive glass layer of a PBR glass plate by the interference of two red laser beams launched on the flat surface of the PBR glass plate.
Holographic recording and reconstruction were carried out using the PBR glass plate No. 8A as the optical information recording medium. Volume holographic gratings resulting from interference of two plane waves, an object beam (that is, an information beam) and a reference beam were recorded in the light blue area having a Dp value of 1.2 and also were recorded in the lighter blue area with a Dp value of 0.72 in the PBR glass plate No. 8A, which had a photosensitive glass layer of 78 μm thickness. Both the object and the reference beams were the output of a single HeNe laser without spatial filtering, and each was about 10 mW on the glass surface, and also was of about 1.5 mm beam diameter with a Gaussian intensity profile. Volume holographic gratings of different exposure durations were recorded in the light blue areas and also in the lighter blue areas under room lighting conditions. Among the various recording durations that were utilized, the results of read back signal are discussed below for the reconstruction of information light from the volume holographic gratings recorded with exposure durations of 5 sec and 1 sec.
Reconstruction of information light utilizing holography was demonstrated by reducing the reference beam intensity to 0.1 milliwatt (without the information beam), with the wavelength of the read beam being that of the write beam at 633 nm. Signal to noise ratio of the reconstructed information beam were 53 and 32 from the gratings recorded in the light blue area using exposure durations 5 sec and 1 sec respectively, and the signal to noise ratio were 46 and 42 from the gratings recorded in the lighter blue area with exposure durations of 5 sec and 1 sec respectively.
The little increase in signal to noise ratio of the reconstructed information light with an exposure duration exceeding about 1 second in the lighter blue area may imply that an exposure dosage of 1.698 joule/cm2, corresponding to a 1 sec exposure duration in the hologram recording, nearly bleached and effected photo adaptation to a saturation state in the lighter blue areas and that a Δ(Δn) value of 6.93×10−3 at 785 nm, is obtained corresponding to the saturation state of photo adaptation in the lighter blue area.
A large number of reads, equivalent to 1010 reads, were demonstrated by having read beam on continuously for 42 days.
The simple experiment of recording and reconstructing information light utilizing the holography described above demonstrated the index modulation in photo energy bleaching mode of recording in a PBR glass plate. It is noted that the signal to noise of the reconstructed information light can readily be improved at least in the following aspects:
Recording beams were not spatial filtered and have a Gaussian intensity profile, that is, not a preferred flat top beam.
The optical set up was not on a vibration isolation table that would adequately filter out vibrations for better hologram recordings.
Holographic recordings were performed under room lighting conditions, moreover, during holographic reconstruction stray light level was simply minimized by covering the optical set-up with a cover made of a large cardboard box without covering the bulky sized He—Ne laser, and a 0.5″ diameter opening on the cardboard box enabled the passage of the laser beam to enter the optical set up. The stray light level within a would-be optimized holographic recording system such as a holographic optical disc drive, would readily be improved by orders of magnitude.
A holographic optical disc drive for recording data in a photosensitive glass layer of a PBR glass plate includes at least one light source for generating a reference beam and an information beam. The reference beam is preferably a red laser beam of constant phase. The holographic drive includes a photosensitive glass layer of a PBR glass plate as an optical information recording medium in a path of the reference beam and in a path of the information beam. The holographic optical information recording medium may also include a data reflective surface, produced by coating a reflective surface on a plane beneath the photosensitive glass layer of the PBR glass plate. For example, a reflective film is coated on the back surface (i.e. second surface) of the PBR glass plate.
In a holographic optical disc drive such as those described in U.S. Pat. Nos. 6,909,529 and 6,995,882, which are incorporared herein by reference, the reference beam and the information beam interfere in the holographic medium to create a hologram only after at least one of the reference beam and the information beam have reflected off the data reflective surface. The prior art holographic optical disc drive of the '882 patent is depicted in
In the above described holographic optical disc drive, one may use a 200 mW diode laser at, for example, a 650 nm wavelength to record a hologram of 0.1 mm diameter on a PBR glass plate by using a surface power of 20 mW each of an information beam and of a reference beam (i.e. 20% efficiency on disc from laser output). The intensity of the recording beam is increased by a factor of 450, that is, (20/10)(1.5/0.1)2, from that of the exemplary holographic recording experiment described above. It was determined experimentally that the sensitivity of the bleaching mode of recording in a PBR glass plate increases by a factor of 2.5 when the intensity of the red bleaching beam is increased by a factor of 10.
Based on the above described non-linear effect of the write beam intensity on the bleaching sensitivity, the bleaching sensitivity is increased by a factor of 11.37 due to the increase in intensity level by a factor of 450. Therefore, a sum of 149 mJ/cm2 (that is, 1.698/11.37) total exposure dosage can effectively record multiple holograms within the same volume of the lighter blue area in the photosensitive glass layer of the PBR plate No. 8A. The required energy density to record a single hologram is thus less than about 15 mJ/cm2, since more than 10 holograms can be recorded with a dynamic range in index modulation Δ(Δn) of, for example, 6.93×10−3 at a read wavelength of 785 nm.
Holographic recording medium 05 of
Structure (a) of
Structure (b) of
Structure (c) of
Structure (d) of
In performed experiments, the stability of red laser light bleached areas in room lighting conditions indicated that the intensity of the recording beam exceeded a certain intensity threshold. Therefore, reproduction of information light can be done using a read beam at the recording wavelength with a reduced intensity from that of the recording beams, or using a read beam at whose wavelength the photosensitive glass layer has no bleaching and no darkening sensitivity, and/or has a more favorable intensity threshold, and/or has a lower optical density value (i.e. has a higher transmittance value), and/or has a larger Δ(Δn) value.
One application of a PDR glass plate and/or a PBR glass plate having a volume phase hologram recorded therein is to provide a volume diffractive optical element or as a volume holographic optical element.
The use of a volume diffractive optical elements as an angular selector, spatial filter, attenuator, switcher, modulator, beam splitter, beam sampler, beam deflector (controlled by the positioning of a grating matrix, small-angle master deflector, or spectral scanning), selector of particular wavelengths, notch filter, add/drop element, spectral shape former (gain equalizer), spectral sensor (wavelength meter/wavelocker), angular sensor (pointing locker), Bragg spectrometer (spectral analyzer), or as a transversal and longitudinal mode selector in a laser resonator was described in U.S. Pat. No. 6,673,497, issued on Jun. 6, 2004 to Efimov et al, which is incorporated herein by reference.
Instead of using two laser write beams to record an interference pattern in the photosensitive glass layer to produce a diffractive optical element and/or a holographic optical element, a diffractive optical element and/or a holographic optical element in either a PDR glass plate or a PBR glass plate can be produced as a computer-generated hologram (CGH) using a laser beam or an electron beam pattern generator to write on the photosensitive glass layer of a PDR or a PBR glass plate. Moreover, CGHs can be mass-produced in a PBR or a PDR glass plate using a gray scale photomask. The gray scale optical density pattern of a CGH can either be written using an electron beam pattern generator in a HEBS glass plate, or using a laser beam pattern generator in a Laser Direct Write (LDW) glass plate to generate a HEBS-glass gray scale photomask or a LDW-glass gray scale photomask respectively.
The fabrication of HEBS-glass gray scale photomasks and LDW-glass gray scale photomasks was disclosed in U.S. Pat. No. 6,562,523, issued on May 13, 2003 to Wu et al, which is incorporated herein by reference. CGHs in a PDR glass plate can be mass produced by exposing a PDR glass plate to a spatially modulated gray scale intensity pattern of the darkening-light radiation, formed by passing a plane wave of darkening-light radiation through a gray scale photomask containing the gray scale mask pattern of the CGH. Similarly, CGHs in a PBR glass plate can be mass produced by exposing a PBR glass plate to a spatially modulated gray scale intensity pattern of the bleaching-light radiation, formed by passing a plane wave of bleaching-light radiation through a gray scale photomask containing the gray scale mask pattern of the CGH.
Computer-generated holograms (CGHs) are used in a number of important optical technology application areas such as diffractive optics devices/diffractive optical elements, holographic optical elements, optical interconnect devices for high speed parallel processors, invariant correlation filters for object detection and recognition, optical processing and computing, optical testing, image and information displays, beam forming, and beam scanning. An overview of CGH applications and CGH fabrication methods and devices that is employed to fabricate CGHs, was discussed in an article “CGH Fabrication Techniques and Facilities” by J. N. Cederquist et al in SPIE Vol. 884 Computer Generated Holography II (1988). The content of this article is incorporated herein by reference.
A method of forming a computer-generated hologram (CGH) according to the present invention includes the steps of:
In another embodiment, a method of forming a computer-generated hologram (CGH) according to the present invention includes the step of:
The bleaching-light radiation may be an interference pattern of an information beam and a reference beam, or may be a spatially modulated gray scale intensity pattern of the bleaching-light radiation written bit-by-bit on the PBR glass plate, or the entire gray scale intensity pattern being formed by passing a plane wave of bleaching-light radiation through a gray scale photomask. Such gray scale photomask may be a HEBS glass gray scale photomask, a LDW glass gray scale photomask, or another gray scale photomasks. The CGH can be used as a diffractive optical element or as a holographic optical element. The diffractive optical element or the holographic optical element may be a beam splitter, a spectral shape former, a beam sampler, an angular selector, a spatial filter, an attenuator, a switcher, a modulator, a beam deflector, a selector of particular wavelengths, a spectral sensor, an angular sensor, or a Bragg spectrometer.
One product of the present invention is a volume holographic optical element that includes a photo-bleachable-refractive (PBR) glass plate having at least one photosensitive glass layer of a SIHR glass, which has a base glass composition that has been ion-exchanged in an aqueous ion-exchange solution containing silver ions, and which has been darkened uniformly at least in lateral (x, y) dimensions (that is, perpendicular to the depth dimension z of ion exchange reaction) with darkening-light radiation, causing the photosensitive glass layer of the PBR glass plate to show a refractive index change upon exposure to bleaching-light radiation without any post-exposure step such as a physical or a chemical treatment; and that also includes appropriate devices for forming the volume holographic optical element in the PBR glass. The volume holographic optical element is formed either by exposing the PBR glass plate to the interference pattern of two laser write beams, or is produced as a CGH using either a laser beam pattern generator or an electron beam pattern generator to write bit-by-bit on the PBR glass plate, or is produced using a gray scale photomask. The volume holographic optical element may be a beam splitter, a spectral shape former, a beam sampler, an angular selector, a spatial filter, an attenuator, a switcher, a modulator, a beam deflector, a selector of particular wavelengths, a spectral sensor, an angular sensor, or a Bragg spectrometer.
Another product of the present invention is a volume holographic optical element that includes a photo-darkenable-refractive (PDR) glass plate having at least one photosensitive glass layer of a SIHR glass, which has a base glass composition that has been ion-exchanged in an aqueous ion-exchange solution containing silver ions, causing the photosensitive glass layer of the PDR glass plate to show a refractive index change upon exposure to darkening-light radiation without any post-exposure step such as a physical or a chemical treatment; and that includes appropriate devices for forming the volume holographic optical element in the PDR glass. The volume holographic optical element is formed either by exposing the PDR glass plate to the interference pattern of two laser write beams, or is produced as a CGH using either a laser beam pattern generator or an electron beam pattern generator to write bit-by-bit on the PDR glass plate, or is produced using a gray scale photomask. The volume holographic optical element may be a beam splitter, a spectral shape former, a beam sampler, an angular selector, a spatial filter, an attenuator, a switcher, a modulator, a beam deflector, a selector of particular wavelengths, a spectral sensor, an angular sensor, or a Bragg spectrometer.
Optical density patterns in a PDR glass plate and in a PBR glass plate were transformed into gray scale height profiles of surface relief with a chemical etching step. Differential etch rates among various optical density levels are a manifestation of different concentrations of elemental silver species in the SIHR glass matrix. The chemical etching is selected from wet chemical etching in aqueous solution containing HF, and dry chemical etching using fluorine containing gas such as CH3F.
Three dimensional microstructures including refractive micro optical elements such as microlens arrays and diffractive micro elements such as fresnel lenses can be mass produced economically using a PDR or a PBR glass plate.
In one embodiment of the present invention, a three dimensional microstructure according to the present invention includes the steps of:
One application of a PBR glass plate is as an optical information recording medium; similarly, an application of a PDR glass plate is as an optical information recording medium.
Such an optical information recording medium may be employed as a holographic recording material. Moreover, the optical information recording medium can also be employed as a gray scale bit-by-bit recording material to store data bits with gray levels or a gray scale image and/or pattern, in which each bit may have an optical density level of 2 or more gray scale levels. A large number of gray scale levels can be utilized because of the very large dynamic range of photo induced optical density change and/or refractive index change in a PDR glass plate.
The gray scale image and/or pattern having data bits with gray levels in a PDR or a PBR glass plate can be mass produced via use of a gray scale photomask including a HEBS-glass gray scale photomask, a LDW-glass gray scale photomask, or other types of photomask.
While the invention has been described in connection with the above described embodiments, it is not intended to limit the scope of the invention to the particular forms set forth, but on the contrary, it is intended to cover such alternatives, modifications, and equivalents as may be included within the scope of the invention. Further, the scope of the present invention fully encompasses other embodiments that may become obvious to those skilled in the art and the scope of the present invention is limited only by the appended claims.
