Optical storage medium, super-resolution information reading method and device based on medium, and super-resolution information writing method and device based on medium

Abstract

An optical storage medium, a super-resolution information reading method and device based on said medium, and a super-resolution information writing method and device based on said medium. The mole fractions of components of the optical storage medium are as follows: 0.1%-5% of a photoinitiator, 0.1%-5% of an aggregation-induced emission dye, 0.1%-5% of a metal ion compound, and 85%-99.7% of a monomer. The information writing method comprises: using a solid light beam having a wavelength λ1 to irradiate an optical storage medium, so as to enhance the fluorescence intensity of an irradiated area; using a hollow light beam having a wavelength λ2 to irradiate a surrounding area around the irradiated area of the solid light beam, so as to quench the fluorescence intensity of the surrounding area; and using fluorescence contrast record information of the irradiated area and the surrounding area to form an information record point the size of which is smaller than a diffraction limit. The super-resolution writing and the stimulated emission depletion microscopy technology-based super-resolution reading solve the problems that conventional reading and writing methods cannot break through a diffraction limit, the material transmittance is low, the number of three-dimensional record layers is limited, etc., and the optical storage density and capacity are greatly improved.

Description

Optical storage medium and super-resolution information reading and writing method and device based on the medium Technical Field

[0001] The present invention relates to the field of optical storage technology, and in particular to an optical storage medium and a super-resolution information reading and writing method and device based on the medium. Background Art

[0002] With the advent of the Fourth Industrial Revolution, centered around smart manufacturing, and the rapid development of the internet, the Internet of Things, cloud computing, and artificial intelligence, data volumes are exploding. Currently, information storage methods, primarily based on magnetic storage technology, suffer from short lifespans and high energy consumption. Especially with the surge in data volumes, the resulting loss of storage media and power consumption will inevitably significantly increase data storage costs. Optical storage, on the other hand, offers the advantage of long-term "offline" operation and a lifespan of up to 50 years. During this lifespan, it consumes less than 1% of the power of a hard disk system, enabling secure, long-term, energy-efficient data storage with resistance to electromagnetic interference and tamper-proof properties. However, traditional optical storage systems are limited by the optical diffraction limit, resulting in a recording point size of approximately half the wavelength. In the process of writing information, when the distance between adjacent recording points is less than the scale of optical diffraction, the writing of the second recording point will affect the writing of the first recording point, and the writing of the two adjacent points will overlap, and the contrast between the writing area and the non-writing area is very low, resulting in the two recording points being unable to be distinguished (Applied Physics Letters, 2008, 92(9): 90-93 and Optics Express, 2013, 21(9): 10831-10840). In the process of reading information, due to the restriction of the optical diffraction limit, it is impossible to distinguish the super-resolution recording points, and thus it is impossible to complete the super-resolution reading. Therefore, the limitation of the optical diffraction limit makes it extremely difficult for optical storage to write or read information in the super-resolution size dimension, and it is impossible to further improve the total storage capacity, which limits its application in the big data era. Super-resolution optical storage technology based on green fluorescent protein and diarylethene dyes uses three laser beams to write super-resolution information: two writing beams and one quenching beam. Super-resolution recording is achieved through the quenching principle. Both the writing and reading processes require pre-treatment of the medium to maintain the stability of the quenched state of the recorded information. Furthermore, the storage system requires a high degree of three-dimensional overlap for all three beams, making the system complex and the quenching-based super-resolution effect less than ideal. In particular, using green fluorescent protein as the storage medium suffers from a short storage lifespan (see CN108877844B and Nature, 2011, 478(7368):204-208).

[0003] In addition to expanding the recording point size beyond the diffraction limit and reducing it to super-resolution dimensions, optical storage systems can also expand their architecture from traditional and common single-layer optical storage to three-dimensional multi-layer storage, fully utilizing the previously unused 99.99% of the storage medium volume. Existing traditional optical storage based on reflective readout has a maximum of six recording layers, resulting in limited storage capacity improvements (see Wikipedia Contributors. Blu-ray [EB / OL]. (2019-02). https: / / en.wikipedia.org / wiki / Blu-ray). While fluorescent three-dimensional optical storage, based on the high specificity and accuracy of fluorescence signal readout, can effectively improve the volume utilization of the storage medium, it is limited by the transmittance of the medium material and the inter-layer crosstalk problem of multi-layer writing (see Light: Science & Applications, 2014, 3(e177):1-11), preventing the use of more storage layers to increase total storage capacity. Moreover, fluorescent three-dimensional optical storage by combining polymers with fluorescent dyes (The Journal of Chemical Physics, 1957, 27(3):758-763, Small, 2008, 4(1):134-142 and Journal of Physical Chemistry A, 2009, 113(49):13633-13644) mostly uses conventional fluorescent dyes, which have the problem of aggregation-induced quenching. For example, pyrene, rhodamine and coumarin can emit strong fluorescence in solution. As the degree of aggregation increases, their fluorescence is quenched, resulting in the loss of the fluorescence readout signal at the recording point, which limits the development of fluorescent three-dimensional multilayer optical storage based on polymers.

[0004] As can be seen from the above-mentioned optical storage technologies, existing methods are limited by the optical diffraction limit and cannot further reduce the size of the recording point, resulting in low total storage capacity. Fluorescent three-dimensional optical storage based on fluorescence signal readout is limited by the transmittance of the medium material, the inter-layer crosstalk of multi-layer writing, and the characteristics of conventional fluorescent dyes that are easily aggregated and quenched. As a result, the number of recording layers can be increased only to a limited extent, and the total storage capacity cannot be significantly increased. In the existing technology, especially in optical storage media based on polymer materials, some technologies also require the material to be heated first, and then the storage medium is formed into an information recording point by irradiating it with a laser of a single wavelength. This process is complicated and the size of the information recording point is limited by the diffraction limit (see CN1662967A). In addition, during the information recording point writing process, only a solid laser of one wavelength can be used to irradiate the storage medium to cause aggregation-induced emission, and a second wavelength of hollow laser cannot be used to suppress aggregation-induced emission in the storage medium in the surrounding area irradiated by the first solid laser beam, so that information records with a size smaller than the diffraction limit cannot be formed (see CN110527523A); during the information reading process, only confocal imaging technology with single wavelength excitation can be used to read the information, and the principle of stimulated emission depletion microscopy technology based on stimulated emission of excited state electrons is not realized to achieve super-resolution reading, and the recording points of information records smaller than the diffraction limit cannot be distinguished. However, the method of using a high-power single-beam wavelength laser to quench the central area of ​​the information recording point and using a dark spot as the recording point can only achieve super-resolution size recording in the case of a single recording point. It does not solve the mutual influence between two or more adjacent recording points, cannot reduce the distance between two or more recording points, and cannot effectively improve the total storage capacity (see CN114621395A). Moreover, according to this method, the interlayer spacing is greater than 2μm and cannot be reduced any further.

[0005] Summary of the Invention

[0006] In response to the above-mentioned defects of the prior art, the purpose of the present invention is to provide an optical storage medium and a super-resolution information reading and writing method and device based on the medium, which can simultaneously realize super-resolution writing of dual-beam wavelength laser and super-resolution reading based on the principle of stimulated emission depletion microscopy technology, solve the problems that traditional reading and writing methods cannot break through the diffraction limit, the number of three-dimensional recording layers is limited, and the transmittance of fluorescent three-dimensional storage medium materials is low, increase the number of storage recording layers, improve storage capacity and density, and have great application value in the field of fluorescent three-dimensional super-resolution optical storage.

[0007] To achieve the above objectives, the technical solutions of the present invention are as follows:

[0008] The present invention provides an optical storage medium, the components of which include a photoinitiator, a monomer, a metal ion compound and an aggregation-induced luminescence dye, wherein the molar amount of each component in the material is as follows: the photoinitiator is 0.1% to 5%, the aggregation-induced luminescence dye is 0.1% to 5%, the metal ion compound is 0.1% to 5%, and the monomer is 85% to 99.7%.

[0009] Furthermore, the optical storage medium improves the fluorescence contrast of the information recording point by combining the metal ion compound with the aggregation-induced luminescence dye.

[0010] The present invention also provides a method for writing super-resolution information based on the above optical storage medium, comprising:

[0011] A solid light beam with a wavelength of λ1 is used to illuminate the optical storage medium, causing the irradiated area to produce an aggregation-induced emission effect, thereby enhancing the fluorescence intensity.

[0012] irradiating the surrounding area of ​​the solid beam irradiation area with a hollow light beam of wavelength λ2, so that the surrounding area produces an aggregation-induced emission suppression effect and suppresses the fluorescence intensity;

[0013] Information is recorded by utilizing the fluorescence contrast between the irradiated area and the surrounding area to form information recording spots with a size smaller than the diffraction limit.

[0014] Preferably, the center positions of the solid light beam and the hollow light beam coincide with each other in three-dimensional space.

[0015] Preferably, the fluorescence contrast between the information recording point and the area without information recording is greater than 10:1.

[0016] Preferably, the size of the information recording spot is smaller than the diffraction limit λ1 / 2NA, where NA is the numerical aperture of the objective lens.

[0017] Preferably, the metal ion compound includes Li + ions, Zn 2+ ions, Yb 3+ ions, Zr 4+ ion or Mg 2+ A compound containing one or more ions that is readily soluble in an organic solvent.

[0018] Preferably, the optical storage medium has a single-photon absorption range of 200nm to 400nm and a two-photon absorption range of 400nm to 800nm.

[0019] Preferably, the aggregation-induced emission dye includes one or more of tetraphenylethylene, hexaphenylsiloxane, and distyryl anthracene.

[0020] Preferably, the monomers include one or more of 1,6-hexanediol diacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, di-trimethylolpropane tetraacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, and dipentaerythritol pentaacrylate.

[0021] Preferably, the photoinitiator comprises IRGACURE-250, IRGACURE-907, IRGACURE-184, IRGACURE-369, IRGACURE-819, IRGACURE-1173, IRGACURE-784, IRGACURE-ITX, IRGACURE-DETC, or a mixture thereof.

[0022] Preferably, the optical storage medium is attached to a substrate and pre-cured using UV.

[0023] The present invention also provides a method for super-resolution reading of information based on an optical storage medium, characterized in that the method comprises the following steps:

[0024] A solid light beam with a wavelength of λ3 and a hollow light beam with a wavelength of λ4 are used to irradiate the optical storage medium, wherein the optical storage medium is doped with aggregation-induced luminescence dye. The solid light beam with a wavelength of λ3 causes spontaneous radiation of ground state electrons to an excited state, and the hollow light beam with a wavelength of λ4 causes stimulated radiation of excited state electrons. The fluorescence enhancement signal generated by aggregation induction is collected to read out the information recording point; wherein the wavelength λ4 is greater than the wavelength λ3.

[0025] On the other hand, the present invention provides an information writing device based on an optical storage medium, comprising an optical path module and a control module;

[0026] The optical path module is configured to form a solid light beam with a wavelength of λ1 and a hollow light beam with a wavelength of λ2, and to irradiate the solid light beam with a wavelength of λ1 onto an optical storage medium, causing the irradiated area to produce an aggregation-induced emission effect and enhance the fluorescence intensity, wherein the optical storage medium is doped with an aggregation-induced emission dye; irradiate the hollow light beam with a wavelength of λ2 onto an area surrounding the irradiated area of ​​the solid light beam, causing the surrounding area to produce an aggregation-induced emission effect that suppresses the fluorescence intensity; and record information using the fluorescence contrast between the irradiated area and the surrounding area to form an information recording point with a size smaller than the diffraction limit.

[0027] The control module is used to control the displacement of the objective lens or the optical storage medium in the z direction to adjust the focusing positions of the solid light beam and the hollow light beam in the optical storage medium.

[0028] Furthermore, the optical path module includes a first writing laser module, a first lens, a first pinhole, a second lens, a first dichroic mirror, a second writing laser module, a third lens, a second pinhole, a fourth lens, a vortex phase plate, a second dichroic mirror and an objective lens;

[0029] The first writing laser module emits a continuous light beam with a wavelength range of 200nm to 400nm or a pulsed laser beam with a wavelength range of 400nm to 800nm, which passes through the first lens, the first aperture, the second lens, and the first dichroic mirror and enters the objective lens to be focused into a solid light beam with a wavelength of λ1 and enters the optical storage medium;

[0030] The second writing laser module emits a beam of continuous light or pulsed laser with a wavelength range of 500nm to 800nm, which passes through a third lens, a second pinhole, a fourth lens and a vortex phase plate to form a hollow light beam with a wavelength of λ2, and then passes through a second dichroic mirror and a first dichroic mirror to enter the objective lens and is focused together with the solid light beam with a wavelength of λ1 to the same position of the optical storage medium, wherein the focal planes of the solid light beam and the hollow light beam coincide in space, and the center positions of the solid light beam and the hollow light beam coincide in three-dimensional space;

[0031] The present invention also provides an information super-resolution readout device based on an optical storage medium, including a readout optical path module for forming a double light beam, wherein the double light beam is a solid light beam with a wavelength of λ3 and a hollow light beam with a wavelength of λ4. The double light beam is used to irradiate the optical storage medium, utilizing the spontaneous radiation of ground state electrons to an excited state caused by the solid light beam with a wavelength of λ3, and the stimulated radiation of excited state electrons by the hollow light beam with a wavelength of λ4, collecting the fluorescence enhancement signal induced by aggregation to read the information recording point; wherein the wavelength λ4 is greater than the wavelength λ3.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] 1. The present invention relates to a method and apparatus for super-resolution information writing to an optical storage medium based on aggregation-induced emission dyes. The method and apparatus can simultaneously achieve super-resolution writing using two laser beams, achieving a contrast ratio of greater than 10:1 between the emitted fluorescence intensity of recorded and unrecorded areas. The transmittance of the storage medium is greater than 80% within the wavelength range of the system's readout light, enabling three-dimensional fluorescence storage recording with more than 10 or even 100 layers, with a layer spacing of 1.5 μm or less. This effectively addresses the issues of existing optical storage systems, where single-point size and track spacing are limited by the optical diffraction limit, as well as the low volume utilization efficiency of the storage medium.

[0034] 2. The present invention relates to an optical storage medium that enhances the fluorescence contrast of information writing recording points by combining a metal ion compound with an aggregation-induced luminescence dye;

[0035] 3. The present invention provides an optical storage medium, wherein the medium material can be quickly formed into a disk on a substrate by a spin coating process, thereby realizing large-scale rapid production.

[0036] 4. The present invention provides a method and apparatus for super-resolution information reading and writing of optical storage media based on aggregation-induced luminescence dyes. This method utilizes dual laser beams for super-resolution writing and stimulated emission depletion microscopy for super-resolution reading. The super-resolution writing and reading principles employed by the present invention are completely different from those employed in methods based on green fluorescent protein and diarylethene thin film media, which require the introduction of permanent quenching light. Multiple laser beams are used to repeatedly modulate the bright and dark states of the storage medium, allowing super-resolution storage and recording to occur in dark spots (see CN108877844B and Nature, 2011, 478(7368):204-208). The present invention utilizes two beams of writing light to modulate the fluorescence intensity enhanced by the aggregation-induced luminescence effect in the illuminated area. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] FIG1 is a schematic diagram of recording super-resolution optical storage using the optical storage medium of the present invention;

[0038] FIG2 is a schematic diagram of the optical path of a dual-beam laser super-resolution information writing device at a super-resolution scale according to the present invention;

[0039] 3 is a schematic diagram of the optical path of a dual-beam super-resolution information readout device based on an optical storage medium according to the present invention;

[0040] FIG4 shows the reading result of 35-layer 3D optical storage recording with a layer spacing of 1.5 μm in Example 1 of the present invention;

[0041] FIG5 is a diagram showing the reduction of the information recording spot size under different powers of the suppression beam in Example 3 of the present invention;

[0042] FIG6 is a graph comparing the results of single-beam non-super-resolution readout and dual-beam stimulated emission depletion microscopy super-resolution readout in Example 3 of the present invention;

[0043] FIG7 is a cross-sectional view of a 100-layer three-dimensional optical storage recording with a layer spacing of 1 μm in Example 3 of the present invention;

[0044] FIG8 is a diagram showing the transmittance of the optical storage medium material in Example 3 of the present invention. DETAILED DESCRIPTION

[0045] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0046] Please refer to Figure 1, which is a schematic diagram of super-resolution optical storage recording using an optical storage medium according to the present invention. The present invention utilizes an optical storage medium that achieves super-resolution writing and reading of information. The optical storage medium is first cured under ultraviolet light and then cured again under writing light. Specifically, the writing light is a solid beam with a wavelength of λ1, which further enhances the degree of polymerization of the optical storage medium, restricts the rotational motion of the aggregation-induced luminescence dye molecules in the material, and improves the efficiency of aggregation-induced luminescence. It also increases the coplanarity between the side benzene rings and the central silicon ring of the aggregation-induced luminescence dye molecules, enhancing the conjugation of the dye molecules, achieving a red shift in the emission spectrum, and improving the fluorescence contrast between the written and non-written areas. The suppression light is a hollow beam with a wavelength of λ2. The hollow beam with a wavelength of λ2 illuminates the area surrounding the area illuminated by the solid beam with a wavelength of λ1, suppressing aggregation-induced luminescence in the surrounding area. This results in enhanced fluorescence intensity in the center of the optical storage medium's writing light-illuminated area and suppressed fluorescence intensity in the periphery. Information is recorded using the fluorescence contrast between the center and periphery (preferably, a fluorescence contrast greater than 10:1), forming an information recording spot. At the same time, the size of a single information recording point can be smaller than the diffraction limit (λ1 / 2NA), where NA is the numerical aperture of the objective lens in the optical storage system. Preferably, the centers of the suppression light and the write light coincide in three dimensions, a prerequisite for achieving super-resolution information recording point size and track spacing.

[0047] The specific process of curing the optical storage medium for the first time includes the following steps:

[0048] (1) placing a photoinitiator, an aggregation-induced emission dye, a metal ion compound, and 85% to 99.7% of a monomer in a molar ratio of 0.1% to 5% in an acetone solution, mixing by ultrasonication, and then baking in an oven to remove all of the acetone solution to obtain an optical storage medium material;

[0049] (2) mixing the optical storage medium material in step (1) with an organic solvent of tetrafluoropropanol or acetone in a certain proportion, and dripping the mixture onto a substrate rotating at a low speed (rotation speed of 200 rpm to 600 rpm); then increasing the rotation speed of the substrate to 800 rpm to 2000 rpm, allowing the solution to flow outward along the radial direction on the substrate until it is evenly distributed on the substrate; finally, increasing the rotation speed of the substrate to 4800 rpm to 6500 rpm, and completely volatilizing and removing the mixed organic solvent;

[0050] (3) Using an ultraviolet curing lamp to expose the optical storage medium material evenly distributed on the substrate and perform the first pre-curing to obtain a solid storage medium film, namely, a UV pre-cured optical storage medium.

[0051] Please refer to Figure 2, which is a schematic diagram of the optical path of the dual-beam laser super-resolution information writing device of the present invention at the super-resolution scale. The optical path module of the dual-beam laser super-resolution writing device includes a first writing laser module 101, a first lens 102, a first aperture 103, a second lens 104, a first dichroic mirror 105, a second writing laser module 201, a third lens 202, a second aperture 203, a fourth lens 204, a vortex phase plate 205, a second dichroic mirror 206, and an objective lens 106. The first writing laser module 101 emits a beam of continuous light or pulsed laser with a wavelength range of 200nm to 400nm or 400nm to 800nm, which passes through the first lens 102, the first pinhole 103, the second lens 104, and the first dichroic mirror 105 and enters the objective lens 106 to be focused into a solid light beam with a wavelength of λ1 to the optical storage medium; the second writing laser module 201 emits a beam of continuous light or pulsed laser with a wavelength range of 500nm to 800nm, which passes through the third lens 202, the second pinhole 203, the fourth lens 204 and the vortex phase plate 205 to form a hollow light beam with a wavelength of λ2, and then passes through the second dichroic mirror 206 and the first dichroic mirror 105 to enter the objective lens 106, and is focused to the same position of the optical storage medium together with the solid light beam with a wavelength of λ1, and the center positions of the hollow light beam with a wavelength of λ2 and the solid light beam with a wavelength of λ1 coincide in three-dimensional space. The dual-beam laser super-resolution writing system also includes a control module for controlling the displacement of the objective lens or optical storage medium in the z-direction, thereby adjusting the focal position of the laser beam in the optical storage medium. Specifically, the control module can be represented by a displacement mobile platform 107, which carries the optical storage medium. Optionally, a fifth lens 108 and a camera 109 are placed in sequence in the opposite direction of the first dichroic mirror 105 and the objective lens 106 to form confocal imaging to observe the information writing in real time. As a result, the dual-beam laser super-resolution writing device has a simple optical path design, effectively reducing system complexity.

[0052] Please refer to Figure 3, which is a schematic diagram of the optical path of the dual-beam super-resolution information readout device based on an optical storage medium of the present invention. The optical path of the dual-beam laser readout device is as follows: the first laser beam S01 (wavelength λ3) passes through the dichroic mirror S03 and enters the objective lens S04 to be focused on the optical storage medium S05; the second laser beam S02 (wavelength λ4) passes through the vortex phase plate S06 to form an annular hollow suppression beam (annular hollow light spot), then passes through the dichroic mirror S07 and enters the objective lens S04 to be focused on the optical storage medium S05. The signal is collected by lens S08 to the weak light detector S09 for super-resolution readout of the information recording point, where the wavelength λ4 is greater than the wavelength λ 3；The dual light beams S01 and S02 are focused onto the storage medium S05, i.e. irradiated onto the optical storage medium; the solid light beam with wavelength λ3 causes the ground state electrons to spontaneously radiate to the excited state, and the hollow light beam with wavelength λ4 stimulates the excited state electrons to radiate, and the fluorescence enhancement signal induced by aggregation is collected to read the information recording point.

[0053] The present invention uses an optical storage medium, the components of which include a photoinitiator, a monomer, a metal ion compound, and an aggregation-induced luminescence dye. In a specific embodiment, the molar amount of each component in the material is as follows: 0.1% to 5% of the photoinitiator, 0.1% to 5% of the aggregation-induced luminescence dye, 0.1% to 5% of the metal ion compound, and 85% to 99.7% of the monomer. By way of example, the aggregation-induced luminescence dye includes one or more of tetraphenylethylene, hexaphenylsiloxane, and diphenylanthracene. More specifically, the monomer includes one or more of 1,6-hexanediol diacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, di-trimethylolpropane tetraacrylate, tris(2-hydroxyethyl)isocyanuric acid triacrylate, and dipentaerythritol pentaacrylate. By way of example, the metal ion compound includes one or more of Li + ions, Zn 2+ ions, Yb 3+ ions, Zr 4+ ion or Mg 2+ One or more compounds soluble in organic solvents containing ions. The photoinitiator can be selected according to actual needs and is compatible with the laser wavelength, for example, one or more selected from IRGACURE-250, IRGACURE-907, IRGACURE-184, IRGACURE-369, IRGACURE-819, IRGACURE-1173, IRGACURE-784, IRGACURE-ITX, and IRGACURE-DETC.

[0054] Example 1

[0055] 97% analytically pure trimethylolpropane triacrylate, 1% IRGACURE-ITX, and 1% tetraphenylethylene were mixed and dissolved in acetone, and 1% metal ion compound (Li + ions, Zn 2+ ions, Yb 3+ ions, Zr 4+ ion or Mg 2+ ionic compound), ultrasonically dissolve it completely, and then heat or vacuum treat to remove the acetone to obtain the preparation of the optical storage medium material.

[0056] The optical storage medium material is mixed with an organic solvent of tetrafluoropropanol or acetone in a certain proportion and dropped onto a substrate rotating at a low speed (rotation speed of 300 rpm); the rotation speed of the substrate is then increased to 1600 rpm, so that the solution flows outward along the radial direction on the substrate until it is evenly distributed on the substrate; finally, the rotation speed of the substrate is increased to 5500 rpm, the mixed organic solvent is completely volatilized and removed, and the optical storage medium material evenly distributed on the substrate is exposed by a UV curing lamp and pre-cured for the first time to obtain a solid storage medium film; a dual-beam laser super-resolution writing system is set to irradiate the solid storage medium film, and the first writing laser module 101 emits a beam of writing light (pulsed laser with a wavelength range of 515 nm), which passes through the first lens 102, the first lens 103 and the second lens 104 in sequence. The pinhole 103, second lens 104, and first dichroic mirror 105 enter the objective lens 106 and focus into a solid writing beam (solid spot) into the optical storage medium material; the second writing laser module 201 emits a beam of suppression light (continuous light with a wavelength range of 639nm), which passes through the third lens 202, second pinhole 203, fourth lens 204, and vortex phase plate 205 to form a ring-shaped hollow suppression beam (ring-shaped hollow spot). It then passes through the second dichroic mirror 206 and the first dichroic mirror 105 and enters the objective lens 106, where it is focused together with the solid writing beam onto the same position on the optical storage medium material. The three-dimensional distributions of the two writing laser beams are highly overlapped, and the position of the laser acting on the material is controlled by the displacement moving platform 107, forming a localized second solidification, as shown in Figure 2. Optionally, a fifth lens 108 and a camera 109 are placed on the opposite side of the second dichroic mirror 206 from the objective lens 106 to form a real-time imaging system to observe the writing of information. After the information is written, a dual-beam super-resolution laser super-resolution readout system is set up. The first beam of pulsed laser S01 with a wavelength of 405nm passes through the dichroic mirror S03 and enters the objective lens S04 to be focused on the storage medium S05; the second beam of continuous light S02 with a wavelength of 520nm passes through the vortex phase plate S06 to form an annular hollow suppression beam (annular hollow light spot), and then passes through the dichroic mirror S07 to enter the objective lens S04 to be focused on the storage medium S05. The signal is collected by lens S08 to the S09 weak light detector for super-resolution readout of the information recording point, as shown in Figure 3. The power density of the writing beam and the suppression light power density are 2.85GW / cm 2 and 0.05MW / cm 2 Using metal-doped optical storage media, information was written and read out in 35 layers with a layer spacing of 1.5 microns, as shown in Figure 4. The fluorescence contrast of information recording points without metal ion doping and with different metal ion compounds is shown in Table 1.

[0057] Table 1

[0058] Example 2

[0059] 94% analytically pure dipentaerythritol pentaacrylate, 1.5% IRGACURE-ITX, and 3% hexaphenylthiole were mixed and dissolved in acetone, and 1.5% metal ion compound (Li + ions, Zn 2+ ions, Yb 3+ ions, Zr 4+ ion or Mg 2+ After the acetone is fully dissolved by ultrasonic treatment, it is heated or vacuum-treated to remove the acetone, thereby obtaining the optical storage medium material. The fluorescence contrast of the information recording point is compared with the optical storage medium material without the addition of the ionic compound.

[0060] The optical storage medium material is mixed with an organic solvent, tetrafluoropropanol or acetone, in a certain proportion and dropped onto a substrate rotating at a low speed (rotation speed of 300 rpm); the rotation speed of the substrate is then increased to 1600 rpm, so that the solution flows outward along the radial direction on the substrate until it is evenly distributed on the substrate; finally, the rotation speed of the substrate is increased to 5500 rpm, the mixed organic solvent is completely volatilized and removed, and the optical storage medium material evenly distributed on the substrate is exposed by a UV curing lamp and pre-cured for the first time to obtain a solid storage medium film; a dual-beam laser super-resolution writing system is set to irradiate the solid storage medium film, and the first writing laser module 101 emits a beam of writing light (pulse light with a wavelength range of 515 nm), which passes through the first lens 102, the first lens 103, and the second lens 104 in sequence. The pinhole 103, second lens 104, and first dichroic mirror 105 enter the objective lens 106 and focus into a solid writing beam (solid spot) into the optical storage medium material; the second writing laser module 201 emits a beam of suppression light (continuous light with a wavelength range of 639nm), which passes through the third lens 202, second pinhole 203, fourth lens 204, and vortex phase plate 205 to form a ring-shaped hollow suppression beam (ring-shaped hollow spot). It then passes through the second dichroic mirror 206 and the first dichroic mirror 105 and enters the objective lens 106, where it is focused together with the solid writing beam onto the same position on the optical storage medium material. The three-dimensional distributions of the two writing laser beams are highly overlapped, and the position of the laser acting on the material is controlled by the displacement moving platform 107, forming a localized second solidification, as shown in Figure 2. Optionally, a fifth lens 108 and a camera 109 are placed on the opposite side of the second dichroic mirror 206 from the objective lens 106 to form a real-time imaging system to observe the writing of information. After the information is written, a dual-beam super-resolution laser super-resolution readout system is set up. The first beam of pulsed laser S01 with a wavelength of 480nm passes through the dichroic mirror S03 and enters the objective lens S04 to be focused on the storage medium S05; the second beam of continuous light S02 with a wavelength of 592nm passes through the vortex phase plate S06 to form an annular hollow suppression beam (annular hollow light spot), and then passes through the dichroic mirror S07 to enter the objective lens S04 to be focused on the storage medium S05. The signal is collected by lens S08 to the S09 weak light detector for super-resolution readout of the information recording point, as shown in Figure 3. The writing beam power density and the suppression light power density are 2.85GW / cm 2 and 0.05MW / cm 2 The fluorescence contrast of the information recording points is shown in Table 2.

[0061] Table 2

[0062] Example 3

[0063] Take 93% analytically pure dipentaerythritol pentaacrylate, 3% IRGACURE-ITX, 2% Zr 4+ The ionic compound and 2% hexaphenylthiole are mixed and dissolved in acetone, and after being fully dissolved by ultrasonic treatment, the acetone is removed by heating or vacuum treatment to obtain the preparation of the optical storage medium material.

[0064] The optical storage medium material is mixed with an organic solvent, tetrafluoropropanol or acetone, in a certain proportion and dropped onto a substrate rotating at a low speed (rotation speed of 400 rpm); the rotation speed of the substrate is then increased to 1700 rpm, so that the solution flows outward along the radial direction on the substrate until it is evenly distributed on the substrate; finally, the rotation speed of the substrate is increased to 4800 rpm, the mixed organic solvent is completely volatilized and removed, and the optical storage medium material evenly distributed on the substrate is exposed by a UV curing lamp and pre-cured for the first time to obtain a solid storage medium film; a dual-beam laser super-resolution writing system is set to irradiate the solid storage medium film, and the first writing laser module 101 emits a beam of writing light (pulsed laser with a wavelength range of 515 nm), which passes through the first lens 102, the first lens 103, and the second lens 104 in sequence. The pinhole 103, second lens 104, and first dichroic mirror 105 enter the objective lens 106 and focus into a solid writing beam (solid spot) into the optical storage medium material; the second writing laser module 201 emits a beam of suppression light (continuous light with a wavelength range of 639nm), which passes through the third lens 202, second pinhole 203, fourth lens 204, and vortex phase plate 205 to form a ring-shaped hollow suppression beam (ring-shaped hollow spot). It then passes through the second dichroic mirror 206 and the first dichroic mirror 105 and enters the objective lens 106, where it is focused together with the solid writing beam onto the same position on the optical storage medium material. The three-dimensional distributions of the two writing laser beams are highly overlapped, and the position of the laser acting on the material is controlled by the displacement moving platform 107, forming a localized second solidification, as shown in Figure 2. Optionally, a fifth lens 108 and a camera 109 are placed on the opposite side of the second dichroic mirror 206 from the objective lens 106 to form a real-time imaging system to observe the writing of information. After the information is written, a dual-beam super-resolution readout system is set up, in which the first pulse laser S01 with a wavelength of 480nm passes through the dichroic mirror S03 and enters the objective lens S04 to be focused on the storage medium S05; the second continuous light S02 with a wavelength of 592nm passes through the vortex phase plate S06 to form an annular hollow suppression beam (annular hollow light spot), and then passes through the dichroic mirror S07 to enter the objective lens S04 to be focused on the storage medium S05. The signal is collected by the lens S08 to the S09 weak light detector for super-resolution readout of the information recording point, as shown in Figure 3. As shown in Figure 5, when the writing light power density is 2.14GW / cm 2 When the power density of the suppression light is increased, the recording spot size gradually becomes smaller. When the power density of the suppression light reaches 0.4 MW / cm2 The minimum single spot size can reach 54nm. Under the same write power density, a comparison of dual-beam super-resolution readout with a track pitch of 112nm was conducted using single-beam and dual-beam writing. Figure 6 shows that at a track pitch of 112nm, only dual-beam super-resolution writing can distinguish two super-resolved recording spots. A multilayer recording experiment with 100 layers and a 1μm interlayer spacing was conducted, with the cross-sectional results shown in Figure 7. Furthermore, the optical storage medium material has high transmittance, exceeding 80% within the wavelength range of 430nm to 700nm, as shown in Figure 8.

[0065] Example 4

[0066] Take 99.7% analytically pure pentaerythritol tetraacrylate, 0.1% IRGACURE-ITX, 0.1% Mg 2+ The ionic compound and 0.1% hexaphenylthiole are mixed and dissolved in acetone, ultrasonicated until the mixture is fully dissolved, and then heated or vacuum treated to remove the acetone to obtain the preparation of the optical storage medium material.

[0067] The optical storage medium material is mixed with an organic solvent, tetrafluoropropanol or acetone, in a certain proportion and dropped onto a substrate rotating at a low speed (rotation speed of 400 rpm); the rotation speed of the substrate is then increased to 1700 rpm, so that the solution flows outward along the radial direction on the substrate until it is evenly distributed on the substrate; finally, the rotation speed of the substrate is increased to 4800 rpm, the mixed organic solvent is completely volatilized and removed, and the optical storage medium material evenly distributed on the substrate is exposed by a UV curing lamp and pre-cured for the first time to obtain a solid storage medium film; a dual-beam laser super-resolution writing system is set to irradiate the solid storage medium film, and the first writing laser module 101 emits a beam of writing light (pulsed laser with a wavelength range of 515 nm), which passes through the first lens 102, the first lens 103, and the second lens 104 in sequence. The pinhole 103, second lens 104, and first dichroic mirror 105 enter the objective lens 106 and focus into a solid writing beam (solid spot) into the optical storage medium material; the second writing laser module 201 emits a beam of suppression light (continuous light with a wavelength range of 639nm), which passes through the third lens 202, second pinhole 203, fourth lens 204, and vortex phase plate 205 to form a ring-shaped hollow suppression beam (ring-shaped hollow spot). It then passes through the second dichroic mirror 206 and the first dichroic mirror 105 and enters the objective lens 106, where it is focused together with the solid writing beam onto the same position on the optical storage medium material. The three-dimensional distributions of the two writing laser beams are highly overlapped, and the position of the laser acting on the material is controlled by the displacement moving platform 107, forming a localized second solidification, as shown in Figure 2. Optionally, a fifth lens 108 and a camera 109 are placed on the opposite side of the second dichroic mirror 206 from the objective lens 106 to form a real-time imaging system to observe the writing of information. After the information is written, a dual-beam super-resolution readout system is set up. The first beam of pulsed laser S01 with a wavelength of 480nm passes through the dichroic mirror S03 and enters the objective lens S04 to be focused on the storage medium S05; the second beam of continuous light S02 with a wavelength of 592nm passes through the vortex phase plate S06 to form an annular hollow suppression beam (annular hollow light spot), and then passes through the dichroic mirror S07 to enter the objective lens S04 to be focused on the storage medium S05. The signal is collected by lens S08 to the S09 weak light detector for super-resolution readout of the information recording point. When the writing light power density and the suppression power density are 2.90GW / cm 2 and 0.1MW / cm 2 When the recording was completed, a track pitch of 165nm and a multi-layer recording of 45 layers with a layer pitch of 1.2μm were achieved.

[0068] Example 5

[0069] Take the molar amount of 85% analytically pure pentaerythritol tetraacrylate, 5% IRGACURE-DETC, 5% Mg 2+The ionic compound and 5% of diphenylethylene are mixed and dissolved in acetone, ultrasonicated until the mixture is fully dissolved, and then heated or vacuum treated to remove the acetone, thereby obtaining the preparation of the optical storage medium material.

[0070] The optical storage medium material is mixed with an organic solvent of tetrafluoropropanol or acetone in a certain proportion and dropped onto a substrate rotating at a low speed (rotation speed of 400 rpm); the rotation speed of the substrate is then increased to 1700 rpm, so that the solution flows outward along the radial direction on the substrate until it is evenly distributed on the substrate; finally, the rotation speed of the substrate is increased to 4800 rpm, the mixed organic solvent is completely volatilized and removed, and the optical storage medium material evenly distributed on the substrate is exposed by a UV curing lamp and pre-cured for the first time to obtain a solid storage medium film; a dual-beam laser super-resolution writing system is set to irradiate the solid storage medium film, and the first writing laser module 101 emits a beam of writing light (pulsed laser with a wavelength range of 800 nm) which passes through the first lens 102, the first lens 103 and the second lens 104 in sequence. The pinhole 103, second lens 104, and first dichroic mirror 105 enter the objective lens 106 and focus into a solid writing beam (solid spot) into the optical storage medium material; the second writing laser module 201 emits a beam of suppression light (continuous light with a wavelength range of 532nm), which passes through the third lens 202, second pinhole 203, fourth lens 204, and vortex phase plate 205 to form a ring-shaped hollow suppression beam (ring-shaped hollow spot). It then passes through the second dichroic mirror 206 and the first dichroic mirror 105 and enters the objective lens 106, where it is focused together with the solid writing beam onto the same position on the optical storage medium material. The three-dimensional distributions of the two writing laser beams are highly overlapped, and the position of the laser acting on the material is controlled by the displacement moving platform 107, forming a localized second solidification, as shown in Figure 2. Optionally, a fifth lens 108 and a camera 109 are placed on the opposite side of the second dichroic mirror 206 from the objective lens 106 to form a real-time imaging system to observe the writing of information. After the information is written, a dual-beam super-resolution readout system is set up. The first beam of pulsed laser S01 with a wavelength of 410nm passes through the dichroic mirror S03 and enters the objective lens S04 to be focused on the storage medium S05; the second beam of continuous light S02 with a wavelength of 480nm passes through the vortex phase plate S06 to form an annular hollow suppression beam (annular hollow light spot), and then passes through the dichroic mirror S07 to enter the objective lens S04 to be focused on the storage medium S05. The signal is collected by lens S08 to the S09 weak light detector for super-resolution readout of the information recording point. When the writing light power density and the suppression power density are 2.85GW / cm 2 and 0.33MW / cm 2 When the track pitch is 155nm, recording with a track pitch of 155nm and a multi-layer recording with a layer pitch of 45 layers of 1.3μm are achieved.

[0071] The above-described embodiments merely illustrate the implementation methods of the present invention. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art may make various modifications and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. An optical storage medium, comprising a photoinitiator, a monomer, a metal ion compound and an aggregation-induced emission dye, wherein the molar amount of each component in the material is as follows: 0.1% to 5% of the photoinitiator, 0.1% to 5% of the aggregation-induced emission dye, 0.1% to 5% of the metal ion compound, and 85% to 99.7% of the monomer.

2. A method for writing super-resolution information to an optical storage medium according to claim 1, characterized in that: include: A solid light beam with a wavelength of λ1 is used to illuminate the optical storage medium, so that the irradiated area produces an aggregation-induced emission effect and enhances the fluorescence intensity; Using a hollow light beam with a wavelength of λ2 to irradiate the surrounding area of ​​the solid light beam irradiation area, so that the surrounding area produces an aggregation-induced emission inhibition effect and suppresses the fluorescence intensity; Information is recorded by utilizing the fluorescence contrast between the irradiated area and the surrounding area to form information recording spots with a size smaller than the diffraction limit.

3. The super-resolution information writing method according to claim 2, characterized in that: The center positions of the solid light beam and the hollow light beam coincide with each other in three-dimensional space.

4. The super-resolution information writing method according to any one of claims 2 to 3, characterized in that: The fluorescence contrast between the information recording point and the area without information recording is greater than 10:

1.

5. The super-resolution information writing method according to any one of claims 2 to 3, characterized in that: The size of the information recording point is smaller than the diffraction limit λ1 / 2NA, where NA is the numerical aperture of the objective lens.

6. The optical storage medium according to claim 1, wherein The metal ion compound includes Li + Ion, Zn 2+ Ion, Yb 3+ Ion, Zr 4+ Ion or Mg 2+ A compound of one or more ions that is readily soluble in an organic solvent.

7. The optical storage medium according to claim 6, characterized in that The aggregation-induced emission dye includes one or more of tetraphenylethylene, hexaphenylsiloxane, and distyryl anthracene; the monomer includes one or more of 1,6-hexanediol diacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, di-trimethylolpropane tetraacrylate, tris(2-hydroxyethyl)isocyanuric acid triacrylate, and dipentaerythritol pentaacrylate; the photoinitiator includes one or more mixtures of IRGACURE-250, IRGACURE-907, IRGACURE-184, IRGACURE-369, IRGACURE-819, IRGACURE-1173, IRGACURE-784, IRGACURE-ITX, and IRGACURE-DETC.

8. The optical storage medium according to claim 1, wherein The optical storage medium is attached to a substrate and pre-cured using UV.

9. The optical storage medium according to claim 8, characterized in that The optical storage medium is prepared by the following method: (1) placing a photoinitiator having a molar ratio of 0.1% to 5%, an aggregation-induced emission dye having a molar ratio of 0.1% to 5%, a metal ion compound having a molar ratio of 0.1% to 5%, and a monomer having a molar ratio of 85% to 99.7% in an acetone solution, mixing the mixture by ultrasound, and then baking the mixture in an oven to remove all the acetone solution, thereby obtaining an optical storage medium material; (2) mixing the optical storage medium material in step (1) with an organic solvent of tetrafluoropropanol or acetone in a certain proportion, and dropping the mixture onto a substrate rotating at a low speed (rotation speed of 200 rpm to 600 rpm); then increasing the rotation speed of the substrate to 800 rpm to 2000 rpm, so that the solution flows outward along the radial direction on the substrate until it is evenly distributed on the substrate, and finally increasing the rotation speed of the substrate to 4800 rpm to 6500 rpm to completely volatilize and remove the mixed organic solvent; (3) Using an ultraviolet curing lamp, the optical storage medium material evenly distributed on the substrate is exposed and a first pre-curing is performed to obtain a solid storage medium film.

10. A super-resolution information readout method based on an optical storage medium, characterized in that: The method comprises the following steps: A solid light beam with a wavelength of λ3 and a hollow light beam with a wavelength of λ4 are used to irradiate the optical storage medium, wherein the optical storage medium is doped with aggregation-induced luminescence dye, and the solid light beam with a wavelength of λ3 causes spontaneous radiation of ground state electrons to an excited state, and the hollow light beam with a wavelength of λ4 causes stimulated radiation of excited state electrons, and the fluorescence enhancement signal generated by aggregation induction is collected to read out the information recording point; wherein the wavelength λ4 is greater than the wavelength λ3.

11. A super-resolution information writing device based on an optical storage medium, characterized in that: It includes an optical path module and a control module; The optical path module is used to form a solid light beam with a wavelength of λ1 and a hollow light beam with a wavelength of λ2, and irradiate the solid light beam with a wavelength of λ1 on an optical storage medium, so that the irradiated area produces an aggregation-induced emission effect and enhances the fluorescence intensity, wherein the optical storage medium is doped with an aggregation-induced emission dye; irradiate the hollow light beam with a wavelength of λ2 on an area surrounding the irradiated area of ​​the solid light beam, so that the surrounding area produces an aggregation-induced emission effect that inhibits the fluorescence intensity; and record information using the fluorescence contrast between the irradiated area and the surrounding area to form an information recording point with a size smaller than the diffraction limit; A control module is used to control the displacement of the objective lens or the optical storage medium in the z direction to regulate the solid light beam and The focusing position of the hollow light beam in the optical storage medium.

12. The information writing device according to claim 11, characterized in that: The optical path module includes a first writing laser module, a first lens, a first pinhole, a second lens, a first dichroic mirror, a second writing laser module, a third lens, a second pinhole, a fourth lens, a vortex phase plate, a second dichroic mirror and an objective lens; The first writing laser module emits a beam of continuous light with a wavelength range of 200nm to 400nm or a pulsed laser with a wavelength range of 400nm to 800nm, which enters the objective lens through the first lens, the first pinhole, the second lens, and the first dichroic mirror and is focused into a solid light beam with a wavelength of λ1 to the optical storage medium; The second writing laser module emits a beam of continuous light or pulsed laser with a wavelength range of 500nm to 800nm, which forms a hollow light beam with a wavelength of λ2 through the third lens, the second pinhole, the fourth lens and the vortex phase plate, and then enters the objective lens through the second dichroic mirror and the first dichroic mirror, and is focused to the same position of the optical storage medium together with the solid light beam with a wavelength of λ1. The center positions of the solid light beam and the hollow light beam coincide in three-dimensional space.

13. A super-resolution information reading device based on an optical storage medium, characterized in that: It comprises a readout optical path module, which is used to form a double light beam, wherein the double light beam is a solid light beam with a wavelength of λ3 and a hollow light beam with a wavelength of λ4, wherein the optical storage medium is doped with aggregation-induced luminescence dye, and the double light beam is used to irradiate the optical storage medium, and spontaneous radiation of ground state electrons to excited state caused by the solid light beam with a wavelength of λ3 is used, and stimulated radiation of excited state electrons is performed by the hollow light beam with a wavelength of λ4, and the fluorescence enhancement signal generated by aggregation induction is collected to read out the information recording point; wherein the wavelength λ4 is greater than the wavelength λ3.

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