Transparent titanium-based high-refractive-index micro-nano optical component and preparation method thereof

Abstract

The invention discloses a transparent titanium-based high-refractive-index micro-nano optical component. The transparent titanium-based high-refractive-index micro-nano optical component comprises a transparent titanium-based high-refractive-index photosensitive resin material with graphical performance, the photosensitive resin material can be formed at a time through light induction, the refractive index in the visible light and near-infrared range is larger than 1.8, and the transmittance is larger than 80%. The photosensitive resin material comprises a resin matrix material and organic modified titanium-based high-refractive-index nanocrystalline particles uniformly dispersed in the resin matrix material. Wherein the organic modified titanium-based high-refractive-index nanocrystalline particles account for not less than 70% of the photosensitive resin material in proportion, and the particle size is not greater than 30 nanometers. The photosensitive resin can form a planar or three-dimensional micro-nano structure through single-photon, two-photon and multi-photon photopolymerization induction, micro-nano optical and photonics devices with the one-time forming characteristic are achieved, and the design and manufacturing process difficulty of the micro-nano optical and photonics devices is greatly reduced.

Description

Technical Field

[0001] This invention belongs to the field of optical chip manufacturing, specifically relating to a micro / nano optical component made of a transparent titanium-based high-refractive-index photosensitive resin with optical patterning properties and its fabrication method. Background Technology

[0002] High-refractive-index optical materials, due to their high refractive index, can significantly reduce the physical thickness of devices while achieving the same optical path difference, thus driving the development of thinner and lighter devices. Especially in micro-nano optical and photonic components oriented towards lightweight design, their micro-nano unit structures typically have a large aspect ratio. If traditional high-refractive-index materials are used for fabrication, complex multi-step processes are often required, which significantly increases the difficulty of device fabrication.

[0003] Optical resins, as common optical materials, are relatively easy to process and mold. Especially some photosensitive resin monomers can be molded in one step through photoinduced curing. However, the refractive index of common optical resins is generally low (usually around 1.5), which limits their application in micro-nano optics and photonic devices. Currently, there are two main methods to improve the refractive index of optical resins: one is through substituent modulation, that is, introducing polarizable groups or atoms with high molar refractive index into the polymer. However, this method is complex and easily leads to decreased transparency and darkening of the material in the visible light range, as well as unsatisfactory processing performance, thus limiting its application in the optical and optoelectronic fields. The second method is the inorganic-organic composite method, which directly dops high-refractive-index nanoparticles such as TiO2, ZnO, and ZrO2 into an organic polymer matrix to improve the overall refractive index. However, with the increase of doping amount, the material often exhibits problems such as decreased light transmittance, deteriorated processing performance, and increased structural inhomogeneity.

[0004] Therefore, developing a resin material that combines high transparency, high refractive index, and photosensitive properties, and on this basis, developing corresponding micro-nano optical elements and their efficient fabrication methods, has significant scientific research value and application prospects. Summary of the Invention

[0005] The purpose of this application is to overcome the above-mentioned shortcomings of the prior art and provide a design and manufacturing scheme for micro-nano optical components based on one-time molding technology of transparent titanium-based high refractive index photosensitive resin. The transparent titanium-based high refractive index photosensitive resin with patterning properties can be induced to form planar or three-dimensional optical microstructures by single-photon, two-photon, and multi-photon photopolymerization, directly realizing one-time molding of micro-nano optical devices, which greatly reduces the difficulty of design and manufacturing process of micro-nano optical components.

[0006] To achieve the aforementioned objectives, this application provides a transparent titanium-based high-refractive-index micro / nano optical component. The micro / nano optical component comprises a transparent titanium-based high-refractive-index photosensitive resin material with patterning properties. The photosensitive resin material can be photo-induced into a single molding process, exhibiting a refractive index greater than 1.8 and a transmittance greater than 80% in the visible and near-infrared ranges. The transparent titanium-based high-refractive-index photosensitive resin material comprises a resin matrix material and organically modified titanium-based high-refractive-index nanocrystalline particles uniformly dispersed within the resin matrix material. The organically modified titanium-based high-refractive-index nanocrystalline particles account for no less than 70% of the transparent titanium-based high-refractive-index photosensitive resin material, and their particle size is no greater than 30 nanometers. It should be noted that the visible light range is 400–750 nm, and the near-infrared range is 750–3000 nm, as is known in the art. This invention does not limit the specific visible and near-infrared wavelength ranges; preferably, the visible and near-infrared ranges are 400–2000 nm.

[0007] This invention constructs a novel micro / nano optical component based on a transparent titanium-based high-refractive-index photosensitive resin with optical patterning properties. This micro / nano optical component can be manufactured into corresponding micro / nano optical and photonic devices using a photo-induced photopolymerization one-step molding technology. The titanium-based high-refractive-index nanocrystalline particles have a high surface charge energy, readily adsorbing hydroxyl or hydroxyl groups, allowing for good dispersion in an aqueous system. However, photosensitive resins are generally oil-phase materials; when the surface charge energy is high, the nanoparticles tend to aggregate, forming large-diameter clusters or large particles. When the particle size exceeds 40 nanometers, significant scattering occurs, resulting in a white liquid. Only by controlling the particle size can a highly transparent material system be obtained. This requires synthesizing small-diameter nanoparticles, especially when the particle mass ratio reaches 70 wt% or more, resulting in a transparent resin material with even higher requirements for particle size and dispersibility. This invention innovatively involves simultaneously performing surface organic modification on the synthesized nanocrystalline particles to form an organic layer, preventing further aging and growth of small particles and particle agglomeration in the oil phase. This optimizes the selection of photosensitive resin specifications, resulting in uniform dispersion of titanium-based high-refractive-index nanocrystalline particles within the photosensitive resin with high homogeneity. The technical solution of this invention achieves highly efficient dispersion of high-concentration, small-particle-size particles in photosensitive resin, offering significant design freedom. The effective refractive index of the transparent titanium-based high-refractive-index photosensitive resin can be controlled by adjusting the concentration of nanocrystalline particles.

[0008] Preferably, the organically modified titanium-based high-refractive-index nanocrystalline particles comprise a nanocrystalline particle core and an organically modified layer coating the nanocrystalline particle core; the thickness of the organically modified layer is 0.1 nm to 10 nm. This thickness of organic layer is sufficient to precisely and efficiently alter the surface energy, hydrophilicity / hydrophobicity, and charge properties of the nanoparticles through its terminal functional groups. For example, it can stably disperse hydrophilic nanocrystalline particles in photosensitive resins. Simultaneously, this thickness has minimal interference with the physical properties of the nanocrystalline particles.

[0009] Preferably, the organically modified titanium-based high-refractive-index nanocrystalline particles have a particle size of no more than 10 nanometers, and the nanocrystalline particles include, but are not limited to, single nanocrystalline particles formed from any one of titanium dioxide, titanium pentoxide, titanium monoxide, and titanium nitride, or core-shell structured nanocrystalline particles formed from any two or more of them. With a particle size of no more than 10 nanometers, dispersed in the photosensitive resin, they can achieve good transparency and high refractive index.

[0010] Preferably, the preparation of the organically modified titanium-based high-refractive-index nanocrystalline particles includes: preparing a titanium-based precursor dispersion, and modifying the surface of the titanium-based nanocrystalline particles using a surfactant or coupling agent to obtain an organically modified titanium-based high-refractive-index nanocrystalline particle dispersion solution. The surfactant mainly provides dispersion and wetting through physical adsorption, improving the dispersion performance of the nanocrystalline particles in the photosensitive resin; the coupling agent can attach hydrophobic alkyl chains to the surface of the hydrophilic nanocrystalline particles, enabling them to be stably dispersed in the photosensitive resin.

[0011] More preferably, the surfactant includes one or two of ionic surfactants and nonionic surfactants; the coupling agent includes any one of silane coupling agents, titanate coupling agents, and aluminate coupling agents, or any composite coupling agent formed by two or more of them.

[0012] More preferably, the preparation of the transparent titanium-based high-refractive-index photosensitive resin material includes: adding a photosensitive resin monomer solution to the organically modified titanium-based high-refractive-index nanocrystalline particle dispersion solution, dispersing it evenly, and then adding other raw materials to react and obtain the final product. In some embodiments of the present invention, the other raw materials include any one or more of photoinitiators, photosensitizers, and polymerization inhibitors. This preparation method fully utilizes the design function of the surface of the organically modified titanium-based high-refractive-index nanocrystalline particles, achieving "in-situ" and "pre-dispersion" of nanocrystalline particles in the resin matrix at an early stage before the photosensitive resin is formed, thereby solving the most critical problem, namely, the dispersion and interface issues.

[0013] Preferably, the titanium-based precursor includes any one of titanium tetrachloride, titanium oxysulfate, tetrabutyl titanate, tetraethyl titanate, and tetraisopropyl titanate, or a composite titanium-based precursor formed by any two or more of these. The titanium-based precursor is a crucial first step in the preparation of titanium-based nanomaterials, directly affecting the feasibility of the synthesis route, the phase, morphology, purity, and properties of the product. The aforementioned titanium-based precursor is suitable for the sol-gel method, which provides a high degree of control over the size of the nanocrystals formed.

[0014] In some embodiments of the present invention, the micro-nano optical device further includes a substrate; the substrate is any one of a quartz substrate, a borosilicate substrate, a sapphire substrate, a transparent conductive oxide glass substrate, and a silicon substrate, and the substrate material thickness is above 130 micrometers and below 500 micrometers.

[0015] The present invention also provides a method for fabricating the transparent titanium-based high-refractive-index micro / nano optical component, comprising the following steps: S1. Using titanium precursors and combining the sol-gel method under acidic conditions, a transparent titanium-based high-refractive-index nanoparticle alcohol dispersion was obtained. S2. Surface modification of transparent titanium-based high-refractive-index nanocrystalline particles is carried out by surfactants or coupling agents to obtain surface-modified nanocrystalline particles; S3. By means of physical and / or chemical methods, the surface-modified titanium-based high-refractive-index nanocrystalline particles are dispersed in a photosensitive organic polymer monomer material with patterning properties, and after adding other raw materials and reacting, a transparent titanium-based high-refractive-index photosensitive resin material is obtained. S4. Obtain planar micro / nano optical components based on transparent titanium-based high-refractive-index photosensitive resin through photo-induced one-time molding using ultraviolet lithography or laser direct writing technology; or obtain three-dimensional micro / nano optical components based on transparent titanium-based high-refractive-index photosensitive resin through ultrafast high-energy pulsed laser direct writing technology.

[0016] The above preparation method synthesizes transparent titanium-based high-refractive-index nanocrystalline particles through the sol-gel method. After surface modification, these particles are combined with photosensitive organic polymers to construct a transparent titanium-based high-refractive-index photosensitive resin with patterning properties. This photosensitive resin can be induced to form planar or three-dimensional micro-nano structures by single-photon, two-photon, or multi-photon photopolymerization, realizing micro-nano optical and photonic devices with one-time molding characteristics. This greatly reduces the difficulty of designing and manufacturing micro-nano optical and photonic devices.

[0017] The principle behind the one-time molding of the aforementioned transparent titanium-based high-refractive-index photosensitive resin is that the photosensitive resin material and the surface-modified nanocrystalline particles can undergo a photochemical reaction under the action of an external light field. This photochemical reaction can induce the one-time molding of the transparent titanium-based high-refractive-index photosensitive resin, and based on the focused beam direct writing technology, it can further realize one-time molding of planar or three-dimensional micro-nano optical and photonic components.

[0018] Preferably, in step S3, the surface-modified titanium-based high-refractive-index nanocrystalline particles are dispersed in a photosensitive organic polymer monomer material with patterning properties by physical and / or chemical methods, other raw materials are added, and then the mixture is stirred and dissolved to obtain a reaction solution. 30 to 200 microliters of the reaction solution are dropped onto a substrate, dried and cured to obtain a solid photosensitive resin material that can be used for subsequent planar or stereolithography.

[0019] In this invention, the photosensitive organic polymer material is preferably a photosensitive acrylate polymer material with high transparency, low shrinkage, and low yellowing. Meanwhile, the high-refractive-index TiO2 nanoparticles strongly scatter and absorb ultraviolet light; therefore, the selection of the photoinitiator is crucial, with TPO, ITX, and diaryliodonium salts being preferred.

[0020] In this invention, the dispersion is carried out by physical and / or chemical methods. Physical methods include ball milling / sand milling, high-speed shear dispersion, three-roll milling, ultrasonic dispersion, etc.; chemical methods include in-situ polymerization, that is, in-situ polymerization is initiated on the surface of nanocrystalline particles to grow polymer "brushes" and generate extremely strong steric hindrance and compatibility.

[0021] Compared with the prior art, this application has the following technical effects: 1. This invention innovatively modifies the surface of synthesized titanium-based nanocrystalline particles to form an organic layer, avoiding particle agglomeration in the oil phase, reducing the dispersion size of the nanocrystalline particles, and enabling the titanium-based high-refractive-index nanocrystalline particles to be uniformly dispersed in the photosensitive resin with high uniformity.

[0022] 2. The technical solution of the present invention can obtain high-concentration small-particle-size titanium-based particles in photosensitive resin with high design freedom. The effective refractive index of titanium-based high-refractive-index photosensitive resin can be controlled by the concentration of small-particle-size titanium-based particles.

[0023] 3. The photosensitive resin of the present invention can be induced by single-photon, two-photon, or multi-photon photopolymerization to form planar or three-dimensional micro-nano structures, realizing micro-nano optical and photonic devices with one-time molding characteristics, which greatly reduces the design and manufacturing process difficulty of micro-nano optical and photonic devices. Attached Figure Description

[0024] Figure 1 This is a schematic diagram of the transparent titanium-based high-refractive-index photosensitive resin of the present invention; Figure 2 The dispersion curve of the transparent titanium-based high-refractive-index photosensitive resin of the present invention is shown. Figure 3 This is a transmittance curve of the transparent titanium-based high-refractive-index photosensitive resin of the present invention. Figure 4 This is a scanning electron microscope image of the planar diffraction grating based on transparent titanium-based high-refractive-index photosensitive resin of the present invention. Figure 5 This is a scanning electron microscope image of the three-dimensional wood stacking structure based on transparent titanium-based high-refractive-index photosensitive resin of the present invention. Figure 6 These are microscopic and scanning electron microscope images of the Fresnel zone plate based on transparent titanium-based high-refractive-index photosensitive resin of the present invention. Figure 7 This is a focused light field diagram of the Fresnel zone plate based on transparent titanium-based high-refractive-index photosensitive resin of the present invention; Figure 8 This is a transmission electron microscope image of the titanium-based high-refractive-index nanocrystalline particles in this invention. Detailed Implementation

[0025] To enable those skilled in the art to better understand the present invention, the present invention will now be further described in conjunction with specific embodiments.

[0026] In the following description, the embodiments of this application are for illustrative purposes and not for limiting purposes, so as to provide a thorough understanding of the embodiments. However, those skilled in the art will understand that the embodiments of this application can also be implemented in other embodiments without these specific details. In other cases, detailed descriptions of well-known preparation methods have been omitted so as not to obscure the description of the embodiments of this application with unnecessary details. Unless otherwise specified, the raw materials used in the following embodiments are all commercially available.

[0027] It should also be understood that the term "and / or" as used in the specification of embodiments of this application and the appended claims refers to any combination and all possible combinations of one or more of the associated listed items, and includes such combinations. The terms "comprising," "including," "having," and variations thereof all mean "including but not limited to," unless otherwise specifically emphasized. "A plurality" means two or more.

[0028] This section only introduces content related to the inventive points; other details can be obtained from relevant technologies and will not be described in detail here. The following embodiments only illustrate several implementation methods of this application, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of this patent application. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

[0029] In a preferred embodiment of the present invention, see [reference needed]. Figure 1 The transparent titanium-based high-refractive-index photosensitive resin with optical patterning properties is arranged sequentially from the outer layer to the core as organic polymer material 11, organic modified layer 22, and titanium-based high-refractive-index nanocrystalline particles 33. It is then formed into a thin film structure on the substrate 00 in a single step under the action of an external light field. Furthermore, through structural design, a planar structure can be formed on the substrate 00 in a single step (see reference). Figure 4 Or refer to the three-dimensional structure Figure 5 .

[0030] Specifically, the optoelectronic functional device may include a substrate 00, an organic polymer material 11, an organic modification layer 22, and titanium-based high-refractive-index nanocrystal particles 33, wherein the organic polymer material 11, the organic modification layer 22, and the titanium-based high-refractive-index nanocrystal particles 33 constitute a transparent titanium-based high-refractive-index photosensitive resin with optical patterning properties for micro-nano optical and photonic components.

[0031] Furthermore, the substrate 00 is preferably a fused silica sheet.

[0032] Furthermore, the organic polymer material 11 includes photosensitive organic polymer materials or organic polymer materials formed by any one or more of photoinitiators, photosensitizers, and polymerization inhibitors, including photosensitive organic polymer materials, and the material can be used alone or in combination.

[0033] Furthermore, the coating thickness of the organic modified layer 22 is 0.1-10 nanometers, and the components include, but are not limited to, any one of the following coupling agents: ionic surfactants, nonionic surfactants, silane coupling agents, titanate coupling agents, and aluminate coupling agents, or any composite coupling agent formed by two or more of them.

[0034] Furthermore, the titanium-based high-refractive-index nanocrystalline particles have a particle size of less than 30 nanometers, and the materials include, but are not limited to, any one or more of titanium dioxide, titanium pentoxide, titanium monoxide, and titanium nitride forming a core-shell morphology. (See also...) Figure 8 Its particle size is around 4 nanometers.

[0035] Furthermore, the preferred proportion of the titanium-based high-refractive-index nanocrystalline particles 33 in the transparent titanium-based high-refractive-index photosensitive resin with optical patterning properties is 70%-80%, and more preferably 90% or higher.

[0036] The specific implementation method is as follows: Example 1: A transparent titanium-based high-refractive-index micro / nano optical component is fabricated using the following steps: (1) In an environment with extremely low water content (the water content in a glove box is generally less than 0.1 ppm), take an appropriate amount of anhydrous ethanol in a flat-bottomed flask and stir it on a magnetic stirrer; (2) Slowly add an appropriate amount of titanium tetrachloride, the titanium precursor, into anhydrous ethanol solution; (3) After the titanium tetrachloride / ethanol solution is cooled to room temperature, deionized water is added dropwise, stirred and aged for 6 h to obtain titanium dioxide sol; (4) Add an appropriate amount of silane coupling agent KH-570 dropwise to this sol, and adjust the pH of the reaction solution with anhydrous acetic acid to keep the pH under acidic conditions. Protect from light and age for 36 h. (5) Evaporate the solvent to half of the original volume at 80℃, add an equal volume of n-butanol, and continue to evaporate to 1 / 3 of the original volume to obtain the surface-modified TiO2 gel. At this time, the gel is a pale yellow-green liquid. (6) A certain amount of silyl methacrylate / n-butanol mixture was dropped into TiO2 gel and magnetically stirred at 80°C for 1 h to make it uniformly dispersed. The amount was determined by the mass ratio of TiO2 / photosensitive organic polymer. (7) When the volume of the mixed liquid evaporates to 1 / 3 of the original volume, a transparent alcoholic solution of titanium-based high refractive index photosensitive resin is obtained (refrigerated at 5°C). (8) Add 1 wt% of the free radical photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) to the above-mentioned transparent titanium-based high-refractive-index photosensitive resin alcohol solution. After dissolution, take 30-200 μL and drop it onto a substrate (such as a quartz substrate, cover glass, silicon wafer, etc.). Bake at 100°C for 10 min to obtain a solid photosensitive resin thin film structure (or photoresist) that can be used for subsequent planar or stereolithography. The titanium-based high-refractive-index nanocrystal particles have a particle size of 6 nm and account for 72% of the total concentration. The organic modification layer has a coating thickness of 0.4 nm. The performance of the thin film structure is tested, and its dispersion curve is obtained (see figure). Figure 2 For pass rate reference Figure 3 From the dispersion curve Figure 2 and transmittance curve Figure 3It is evident that when the proportion of titanium-based high-refractive-index nanocrystalline particles exceeds 70%, the small-diameter nanoparticles remain uniformly dispersed without agglomeration into large particles. The photo-induced one-step forming of the thin film structure exhibits a refractive index greater than 1.8 within the range of 400-2000 nm, and a transmittance greater than 80%, meeting the requirements for transparent titanium-based high-refractive-index micro / nano optical components. This further demonstrates that the present invention achieves highly efficient dispersion of high-concentration small-diameter titanium-based particles in photosensitive resin.

[0037] (9) Obtain planar micro-nano optical components based on transparent titanium-based high-refractive-index photosensitive resin through photo-induced one-time molding by ultraviolet lithography or laser direct writing technology.

[0038] Example 2: This embodiment of a micro / nano optical device based on a transparent titanium-based high-refractive-index photosensitive resin with optical patterning properties includes a substrate 00 (fused silica), an organic polymer material 11 (epoxy acrylate monomer and diaryl iodine salt PAG-20102), an organic modification layer 22 (silane coupling agent KH-560), and titanium-based high-refractive-index nanocrystalline particles 33 (titanium dioxide nanocrystals). The device structure is selected as follows: the titanium dioxide nanocrystal particles have a particle size of 5 nanometers and account for 70% of the total density; the organic modification layer 22 has a coating thickness of 0.4 nanometers; the ratio of epoxy acrylate monomer to diaryl iodine salt PAG-20102 in the organic polymer material 11 is 99:1; a microscale wood-like stacked structure is formed in one step by two-photon photopolymerization induced by a high-energy pulsed laser.

[0039] This embodiment is achieved by the following preparation method: (1) Using titanium tetrachloride, a titanium precursor, and combined with the sol-gel method under acidic conditions, a transparent titanium-based high refractive index nanoparticle alcohol dispersion was obtained. (2) The transparent titanium-based high refractive index nanocrystalline particles were surface modified by surfactant KH-560 to obtain surface-modified nanocrystalline particles. (3) By means of physical and chemical methods, high-concentration titanium-based high-refractive-index nanocrystal particles after surface modification are dispersed in a photosensitive organic polymer material with patterning properties to obtain a transparent titanium-based high-refractive-index photosensitive resin material. (4) A microscale wood stacking structure based on transparent titanium-based high refractive index photosensitive resin was obtained in one step by ultrafast high-energy pulsed laser direct writing technology.

[0040] Example 3: This embodiment utilizes a transparent titanium-based high-refractive-index photosensitive resin with optical patterning properties to create micro / nano optical components. The components include a substrate 00 (fused silica), an organic polymer material 11 (pentaerythritol triacrylate, isopropylthioxanthone), an organic modification layer 22 (silane coupling agent KH-570), and titanium-based high-refractive-index nanocrystalline particles 33 (titanium dioxide nanocrystals). The device structure is as follows: the titanium dioxide nanocrystal particles have a particle size of 5 nm, accounting for 70% of the total density; the organic modification layer 22 has a coating thickness of 0.5 nm; the ratio of pentaerythritol triacrylate to isopropylthioxanthone in the organic polymer material 11 is 97:3; and a microscale Fresnel zone sheet is formed in a single step through two-photon photopolymerization induced by a high-energy pulsed laser. Microscopic and scanning electron microscope images are available in the reference [reference needed]. Figure 6 For optical focusing effects, please refer to [reference needed]. Figure 7 .Depend on Figure 7 It can be seen that the Fresnel zone plate based on transparent titanium-based high refractive index photosensitive resin (refractive index of 1.95@633 nm at 70% specific gravity) is relatively compact in the focused light field, with a smaller focal spot size and higher focused energy at the focal spot, which is consistent with the design theory that high refractive index micro-nano optical elements have better light field control effect.

[0041] This embodiment is achieved by the following preparation method: (1) Using titanium tetrachloride, a titanium precursor, and combined with the sol-gel method under acidic conditions, a transparent titanium-based high refractive index nanoparticle alcohol dispersion was obtained. (2) The transparent titanium-based high refractive index nanocrystalline particles were surface modified by surfactant KH-570 to obtain surface-modified nanocrystalline particles. (3) By means of physical and chemical methods, high-concentration titanium-based high-refractive-index nanocrystal particles after surface modification are dispersed in a photosensitive organic polymer material with patterning properties to obtain a transparent titanium-based high-refractive-index photosensitive resin material. (4) A microscale Fresnel zone sheet based on transparent titanium-based high refractive index photosensitive resin was obtained by ultrafast high-energy pulsed laser direct writing technology.

[0042] Based on the disclosure and teachings of the foregoing specification, those skilled in the art can make changes and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and changes to the present invention should also fall within the protection scope of the claims of the present invention. Furthermore, although some specific terms are used in this specification, these terms are only for convenience of explanation and do not constitute any limitation on the present invention.

Claims

1. A transparent titanium-based high-refractive-index micro / nano optical component, characterized in that, The micro / nano optical components include a transparent titanium-based high-refractive-index photosensitive resin material with patterning properties; the photosensitive resin material can be formed in one step by light induction, and has a refractive index greater than 1.8 and a transmittance greater than 80% in the visible and near-infrared range; The transparent titanium-based high-refractive-index photosensitive resin material includes a resin matrix material and organically modified titanium-based high-refractive-index nanocrystalline particles uniformly dispersed within the resin matrix material; wherein the organically modified titanium-based high-refractive-index nanocrystalline particles account for no less than 70% of the transparent titanium-based high-refractive-index photosensitive resin material, and the particle size is no greater than 30 nanometers.

2. The transparent titanium-based high-refractive-index micro / nano optical component as described in claim 1, characterized in that, The organically modified titanium-based high-refractive-index nanocrystalline particles include a nanocrystalline particle core and an organically modified layer covering the nanocrystalline particle core; the thickness of the organically modified layer is 0.1 nanometers to 10 nanometers.

3. The transparent titanium-based high-refractive-index micro / nano optical component as described in claim 1, characterized in that, The particle size of the organically modified titanium-based high-refractive-index nanocrystalline particles is no greater than 10 nanometers, and the nanocrystalline particles include, but are not limited to, single nanocrystalline particles formed by any one of titanium dioxide, titanium pentoxide, titanium monoxide, and titanium nitride, or core-shell structured nanocrystalline particles formed by any two or more of them.

4. The transparent titanium-based high-refractive-index micro / nano optical component as described in claim 1, characterized in that, The preparation of the organically modified titanium-based high-refractive-index nanocrystalline particles includes: preparing a titanium-based precursor dispersion, and modifying the surface of the titanium-based nanocrystalline particles with a surfactant or coupling agent to obtain an organically modified titanium-based high-refractive-index nanocrystalline particle dispersion.

5. The transparent titanium-based high-refractive-index micro / nano optical component as described in claim 4, characterized in that, The preparation of transparent titanium-based high refractive index photosensitive resin material includes: adding a photosensitive resin monomer solution to the organic modified titanium-based high refractive index nanocrystalline particle dispersion, dispersing it evenly, and then adding other raw materials to react and obtain the material.

6. The transparent titanium-based high-refractive-index micro / nano optical component as described in claim 4, characterized in that, The surfactant includes one or two of ionic surfactants and nonionic surfactants; the coupling agent includes any one of silane coupling agents, titanate coupling agents, and aluminate coupling agents, or any composite coupling agent formed by two or more of them. And / or, The titanium-based precursor includes any one of titanium tetrachloride, titanium oxysulfate, tetrabutyl titanate, tetraethyl titanate, and tetraisopropyl titanate, or any composite titanium-based precursor formed by two or more of them.

7. The transparent titanium-based high-refractive-index micro / nano optical component as described in claim 5, characterized in that, The other raw materials include any one or two or more of the following: photoinitiator, photosensitizer, and polymerization inhibitor.

8. The transparent titanium-based high-refractive-index micro / nano optical component as described in claim 1, characterized in that, The micro-nano optical components also include a substrate; the substrate is any one of a quartz substrate, a borosilicate substrate, a sapphire substrate, a transparent conductive oxide glass substrate, and a silicon substrate, and the substrate material thickness is above 130 micrometers and below 500 micrometers.

9. The method for fabricating the transparent titanium-based high-refractive-index micro / nano optical component according to claim 1, characterized in that, Includes the following steps: S1. Using titanium precursors and combining the sol-gel method under acidic conditions, a transparent titanium-based high-refractive-index nanoparticle alcohol dispersion was obtained. S2. Surface modification of transparent titanium-based high-refractive-index nanocrystalline particles is carried out by surfactants or coupling agents to obtain surface-modified nanocrystalline particles; S3. By means of physical and / or chemical methods, the surface-modified titanium-based high-refractive-index nanocrystalline particles are dispersed in a photosensitive organic polymer monomer material with patterning properties, and after adding other raw materials and reacting, a transparent titanium-based high-refractive-index photosensitive resin material is obtained. S4. Obtain planar micro / nano optical components based on transparent titanium-based high-refractive-index photosensitive resin through photo-induced one-time molding using ultraviolet lithography or laser direct writing technology; or obtain three-dimensional micro / nano optical components based on transparent titanium-based high-refractive-index photosensitive resin through ultrafast high-energy pulsed laser direct writing technology.

10. The method for fabricating transparent titanium-based high-refractive-index micro / nano optical components as described in claim 9, characterized in that, In step S3, the surface-modified titanium-based high-refractive-index nanocrystalline particles are dispersed in a photosensitive organic polymer monomer material with patterning properties through physical and / or chemical methods. Other raw materials are added, and then the mixture is stirred and dissolved to obtain a reaction solution. 30 to 200 microliters of the reaction solution are dropped onto a substrate, dried and cured to obtain a solid photosensitive resin material that can be used for subsequent planar or stereolithography.

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