A high-energy beam processing method and device based on a hydroxyl-containing short peptide solid material

Abstract

The application discloses a high-energy beam processing method and device based on a hydroxyl-containing short peptide solid material. A hydroxyl-containing short peptide solid material is used as a hydroxyl-containing short peptide solid substrate; the hydroxyl-containing short peptide solid substrate is fixed on a processing platform; a high-energy beam carried by the processing platform is used to locally irradiate the hydroxyl-containing short peptide solid substrate; processing parameters of the high-energy beam are regulated, so that a local modification of an irradiation area of the hydroxyl-containing short peptide solid substrate subjected to local irradiation is caused, and an optical functional area is formed in the hydroxyl-containing short peptide solid material. The side chain hydroxyl in the hydroxyl-containing short peptide molecule is used to participate in the formation of an intermolecular hydrogen bond network, which is beneficial to dispersing local energy input and relieving structural damage around a processing area in a high-energy beam local irradiation process, so that local processing of the hydroxyl-containing short peptide solid material and preparation of a short peptide micro-nano optical device are realized.

Description

Technical Field

[0001] This invention relates to the field of biointegrated optics and functional biomaterial micro / nano fabrication technology, specifically to a high-energy beam fabrication method and device based on hydroxyl-containing short peptide solid materials. Background Technology

[0002] Biointegrated optics is an important interdisciplinary field between photonics and life sciences. Its core lies in constructing light transmission, light modulation, light response, or biosensor devices using materials with biocompatibility, biodegradability, or biointerface compatibility. Current integrated optical devices are mostly fabricated using silicon, silicon dioxide, silicon nitride, lithium niobate, semiconductor materials, or synthetic polymer materials. While these materials possess mature processing technologies and excellent optical properties, they still have shortcomings in areas such as biointerface compatibility, flexible adaptation, low-temperature processing, and biodegradable applications.

[0003] Short peptide materials possess well-defined molecular structures, strong self-assembly capabilities, designable functional groups, and favorable biorelevant properties, making them promising candidates for applications in biophotonic materials and bio-integrated devices. Hydroxyl-containing short peptide materials, due to the presence of hydroxyl functional groups, can form solid-state materials through hydrogen bonding and ordered intermolecular assembly, potentially exhibiting structural stability and functional properties suitable for optical devices. However, these materials differ significantly from traditional inorganic optical materials in terms of thermal response, mechanical properties, and energy deposition behavior. Existing photolithography, wet etching, plasma etching, or mechanical processing methods struggle to simultaneously achieve processing precision, material structure preservation, and device functionality.

[0004] High-energy beam fabrication technology, characterized by its non-contact, localized, and high spatial resolution, is suitable for constructing micro- and nano-structures and functional regions. However, a systematic approach is currently lacking for high-energy beam fabrication methods, parameter control, and applications in bio-integrated optical devices for hydroxyl-containing short peptide solid materials. Therefore, it is necessary to propose a high-energy beam fabrication method and device suitable for hydroxyl-containing short peptide solid materials to achieve localized modification, patterning, structural characterization, or optical functional construction of such materials, and to expand their applications in the field of bio-integrated optics. Summary of the Invention

[0005] To address the problems existing in the background technology, the present invention aims to provide a high-energy beam processing method and device based on hydroxyl-containing short peptide solid materials, breaking through the traditional understanding that organic short peptides cannot withstand high-energy beam processing, and solving the problems of insufficient processing precision of existing bio-based optical materials, easy damage to material structure during processing, difficulty in achieving local controllable modification, and difficulty in constructing bio-integrated optical devices.

[0006] The technical solution adopted in this invention is: I. A high-energy beam processing method based on hydroxyl-containing short peptide solid materials (1) Prepare hydroxyl-containing short peptide solid substrates using hydroxyl-containing short peptide solid materials; (2) Fix the hydroxyl-containing short peptide solid substrate onto the processing platform and determine the processing area; (3) The hydroxyl-containing short peptide solid substrate is locally irradiated using the high-energy beam of the processing platform; (4) Adjust the processing parameters of the high-energy beam to locally modify the irradiated area of ​​the hydroxyl-containing short peptide solid substrate, and form an optical functional structure - a special structure region in the hydroxyl-containing short peptide solid material.

[0007] In step (1), the amino acid sequence of the short peptide in the hydroxyl-containing short peptide solid material adopts an amino acid residue containing a hydroxyl side chain. The amino acid residue containing the hydroxyl side chain is one or more of tyrosine residue, serine residue or threonine residue. The hydroxyl-containing short peptide solid material is one or more of short peptide glassy material, short peptide crystal material, short peptide microwire, short peptide nanowire, and short peptide nanotube.

[0008] The aforementioned hydroxyl-containing short peptide self-assembled solid substrate is one or a combination of two of the following: glycine-tyrosine-serine-tyrosine-glycine (GYSYG) crystal and tyrosine pentapeptide (YYYYY) glass material. Specifically, the hydroxyl-containing short peptide solid substrate is formed by the self-assembly of hydroxyl-containing short peptide molecules, wherein the hydroxyl-containing short peptide molecules are composed of 2 to 10 amino acid residues linked by peptide bonds, and wherein the hydroxyl-containing short peptide molecules contain at least two amino acid residues with side chain hydroxyl groups.

[0009] In step (1), the preparation method of the hydroxyl-containing short peptide solid substrate is one or a combination of drop coating, spin coating, casting, scraping coating, spraying, solution evaporation, cooling crystallization, antisolvent diffusion, gas phase method, gas phase induced crystallization method, self-assembly method, template-assisted assembly method, hydrothermal method, and solvothermal method.

[0010] In step (3), the local irradiation of the hydroxyl-containing short peptide solid material by the high-energy beam specifically refers to the local irradiation of the surface, near-surface region, or interior region of the hydroxyl-containing short peptide solid material by the high-energy beam; the high-energy beam is one or more of the following combinations: femtosecond laser, picosecond laser, nanosecond laser, continuous laser, focused ion beam, electron beam, plasma beam, and X-ray beam; the near-surface region refers to the region extending from the surface of the hydroxyl-containing short peptide solid material to the interior of the material from 0.1 μm to 50 μm; for short peptide films with a thickness of less than 50 μm, the near-surface region is the region extending from the surface to the interior and not exceeding the thickness of the film.

[0011] In step (3), the processing region of the hydroxyl-containing short peptide solid substrate is locally modified by adjusting the processing parameters of the high-energy beam. Specifically, when the high-energy beam is a femtosecond laser, the processing parameters include one or more of the following: center wavelength, pulse width, repetition frequency, single pulse energy, average power, beam spot size, focusing position, scanning speed, scanning path, scanning interval, number of processing layers, and interlayer spacing; wherein the center wavelength is 500 nm to 1030 nm, the pulse width is 50 fs to 500 fs, the repetition frequency is 1 kHz to 1 MHz, the single pulse energy is 10 nJ to 5 μJ, the average power is 0.1 mW to 100 mW, the beam spot size is 0.5 μm to 10 μm, the scanning speed is 0.1 mm / s to 20 mm / s, the scanning interval is 0.1 μm to 10 μm, the number of processing layers is 1 to 100 layers, and the interlayer spacing is 0.1 μm to 10 μm.

[0012] When the high-energy beam is a focused ion beam, the processing parameters include one or more of the following: accelerating voltage, ion beam current, beam spot size, dwell time, scanning path, scanning interval, number of scans, and irradiation dose; wherein the accelerating voltage is 5 kV to 30 kV, the ion beam current is 1 pA to 100 pA, the beam spot size is 5 nm to 100 nm, the dwell time is 0.1 μs to 10 μs, the scanning interval is 5 nm to 100 nm, and the number of scans is 1 to 20.

[0013] When the high-energy beam is a femtosecond laser, the femtosecond laser is focused by an objective lens on the processing platform onto the surface, near-surface region, or internal region of the hydroxyl-containing short peptide solid material for localized irradiation. This causes localized modification of the irradiated region of the hydroxyl-containing short peptide solid substrate, resulting in changes in refractive index, amorphization, densification, or morphology of the processed region, forming an optical functional structure in the hydroxyl-containing short peptide solid material. The localized irradiation method is one or more combinations of point scanning, line scanning, surface scanning, and layer-by-layer scanning, and the optical functional structure is one or more combinations of waveguide structure, three-dimensional pattern, and micro / nano structure.

[0014] When the high-energy beam is a focused ion beam, the focused ion beam is focused onto the surface, near-surface region, or cross-sectional region of the hydroxyl-containing short peptide solid material for localized irradiation, causing localized modification of the irradiated area of ​​the hydroxyl-containing short peptide solid substrate to form patterned etching, thereby forming an optical functional structure in the hydroxyl-containing short peptide solid material; the localized irradiation method adopts a patterned scanning method, and the patterned etching structure is one or more combinations of trenches, hole arrays, grating structures, relief structures, three-dimensional patterns, and micro / nano structures.

[0015] The local modification is one or more of the following: morphological change, etching, ablation, carbonization, crosslinking, densification, molecular rearrangement, crystal structure change, amorphization, refractive index change, light absorption change, luminescence property change, surface energy change, or electrical property change.

[0016] II. A short peptide micro / nano optical device based on hydroxyl-containing short peptide solid material The short peptide micro / nano optical device, fabricated using the above processing method, includes a hydroxyl-containing short peptide solid material host and a high-energy beam processing region formed on the surface, near-surface region, interior, or cross-section of the hydroxyl-containing short peptide solid material host. The high-energy beam processing region is used to constitute an optical functional structure. The morphology of the hydroxyl-containing short peptide solid material host is one or more combinations of glassy, ​​crystalline, polycrystalline, thin film, microwire, nanowire, nanotube, fiber, bulk, and composite solid.

[0017] The short peptide micro / nano optical device structure is one or more of the following: waveguide structure, grating structure, trench structure, aperture array, relief structure, optical storage region, and sensing region. The high-energy beam processing region is used to form an optical functional structure, which includes one or more of the following: waveguide structure, grating structure, trench structure, aperture array, relief structure, micro / nano structure, or three-dimensional patterned structure.

[0018] III. An application of short peptide micro / nano optical devices based on hydroxyl-containing short peptide solid materials Applications in the fabrication of bio-integrated optical devices, biosensors, optical information storage devices, micro-nano optical devices, flexible photonic devices, biodegradable photonic devices, and bio-interface light-modulating devices.

[0019] This invention utilizes the intermolecular hydrogen bond network formed by the side chain hydroxyl groups in hydroxyl-containing short peptide molecules to disperse local energy input and reduce structural damage during high-energy beam local irradiation, thereby achieving controllable local modification of hydroxyl-containing short peptide solid materials and the construction of micro-nano optical structures.

[0020] Compared with the prior art, the present invention has the following beneficial effects: First, this invention uses hydroxyl-containing short peptide solid materials as the processing target, and takes advantage of their well-defined molecular structure, abundant hydrogen bonding, strong self-assembly ability and good biological relevance to provide a new material system for bio-integrated optical devices.

[0021] Second, the present invention uses high-energy beams for local processing, which has the advantages of non-contact processing, strong spatial selectivity, high processing accuracy and flexible pattern design, and can form controllable micro-nano structures on the surface or inside of hydroxyl-containing short peptide solid materials.

[0022] Third, the present invention can achieve local modification, removal, crosslinking, carbonization, densification or refractive index control by adjusting the high-energy beam parameters, thereby obtaining different functional regions, which are suitable for optical transmission, optical control, biosensing and interface integration.

[0023] Fourth, the present invention can reduce the damage to the structure and function of short peptide materials caused by traditional wet etching, machining or high temperature processes, which is beneficial to maintaining the biocompatibility and optical function of the materials.

[0024] Fifth, this invention utilizes the side chain hydroxyl groups in hydroxyl-containing short peptide molecules to participate in the formation of an intermolecular hydrogen bond network, which is beneficial for dispersing local energy input and alleviating structural damage around the processing area during high-energy beam local irradiation, thereby realizing the local processing of hydroxyl-containing short peptide solid materials and the fabrication of short peptide micro-nano optical devices. Attached Figure Description

[0025] Figure 1 This is a schematic diagram of the process for high-energy beam processing of hydroxyl-containing short peptide solid materials according to the present invention; Figure 2 Microscopic optical image of the GYSYG single crystal prepared in Example 1 of this invention; Figure 3 Microscopic optical image of the YYYYY short peptide glass surface ridge waveguide beam splitter prepared in Example 2 of the present invention; Figure 4 This is a microscopic optical image of the YYYYY short peptide glass micro / nano pattern prepared in Example 3 of the present invention; Figure 5 The image shows the SEM topography of the GYSYG single-crystal surface waveguide interferometer prepared in Example 4 of this invention. Figure 6 This is a comparison of the Raman spectra of the YYYYY short peptide glass material before and after high-energy beam processing in an embodiment of the present invention; Figure 7 The image shows the SEM morphology of the FFF short peptide crystal without side chain hydroxyl groups in Comparative Example 1 after femtosecond laser processing. Detailed Implementation

[0026] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0027] A high-energy beam processing method based on hydroxyl-containing short peptide solid materials according to the present invention is as follows: (1) A hydroxyl-containing short peptide solid material is used as the hydroxyl-containing short peptide solid substrate; In step (1), the amino acid sequence of the short peptide in the hydroxyl-containing short peptide solid material is an amino acid residue containing a hydroxyl side chain; the hydroxyl-containing short peptide solid material is one or more of the following: short peptide glassy material, short peptide crystal material, short peptide microwire, short peptide nanowire, and short peptide nanotube.

[0028] In step (1), the preparation method of the hydroxyl-containing short peptide solid substrate is one or a combination of drop coating, spin coating, casting, scraping coating, spraying, solution evaporation, cooling crystallization, anti-solvent diffusion, gas phase method, gas phase induced crystallization method, self-assembly method, template-assisted assembly method, hydrothermal method, and solvothermal method.

[0029] (2) Fix the solid substrate containing hydroxyl short peptides onto the processing platform; (3) Local irradiation of solid substrates containing hydroxyl short peptides was carried out using a high-energy beam from the processing platform; In step (3), the local irradiation of the hydroxyl-containing short peptide solid material by the high-energy beam is specifically as follows: the high-energy beam irradiates the surface, near-surface region or internal region of the hydroxyl-containing short peptide solid material; the high-energy beam is one or more of the following combinations: femtosecond laser, picosecond laser, nanosecond laser, continuous laser, focused ion beam, electron beam, plasma beam, and X-ray beam.

[0030] (4) Adjust the processing parameters of the high-energy beam to locally modify the irradiated area of ​​the solid substrate containing hydroxyl short peptides, and form an optical functional structure in the solid material containing hydroxyl short peptides.

[0031] In step (4), the processing parameters include one or more of the following: energy, power, beam spot size, focusing position, scanning speed, scanning path, scanning spacing, pulse width, repetition frequency, dwell time, number of processing layers, interlayer spacing, or irradiation dose; the optical functional structure is a combination of one or more of the following: waveguide structure, three-dimensional pattern, and micro / nano structure.

[0032] When a femtosecond laser is used in the high-energy beam, the femtosecond laser is focused onto the surface, near-surface region, or internal region of the hydroxyl-containing short peptide solid material for localized irradiation. This causes localized modification of the irradiated area of ​​the hydroxyl-containing short peptide solid substrate, forming an optical functional structure in the hydroxyl-containing short peptide solid material. The localized irradiation method can be one or a combination of point scanning, line scanning, surface scanning, and layer-by-layer scanning. The optical functional structure can be one or a combination of waveguide structure, three-dimensional pattern, and micro / nano structure. When a focused ion beam is used in the high-energy beam, the focused ion beam is focused onto the surface, near-surface region, or cross-sectional region of the solid material containing hydroxyl peptides for localized irradiation, causing localized modification of the irradiated area of ​​the solid substrate containing hydroxyl peptides, forming an optical functional structure in the solid material containing hydroxyl peptides; the localized irradiation method adopts a patterned scanning method, and the optical functional structure is one or more combinations of trenches, hole arrays, grating structures, relief structures, three-dimensional patterns, and micro / nano structures.

[0033] Local modification includes one or more of the following: morphological change, etching, ablation, carbonization, crosslinking, densification, molecular rearrangement, crystal structure change, amorphization, refractive index change, light absorption change, luminescence property change, surface energy change, or electrical property change.

[0034] Short peptide micro / nano optical devices based on hydroxyl-containing short peptide solid materials are fabricated using the above-mentioned processing methods. The short peptide micro / nano optical devices include a hydroxyl-containing short peptide solid material host and a high-energy beam processing region formed on the surface, near-surface region, interior or cross-section of the hydroxyl-containing short peptide solid material host. The high-energy beam processing region is the optical functional structure. The morphology of the hydroxyl-containing short peptide solid material host is one or more combinations of glassy state, crystal, polycrystalline, thin film, microwire, nanowire, nanotube, fiber, and bulk.

[0035] The structure of short peptide micro / nano optical devices can be one or more of the following: waveguide structure, grating structure, trench structure, aperture array, and relief structure.

[0036] Applications in the fabrication of bio-integrated optical devices, biosensors, optical information storage devices, micro-nano optical devices, flexible photonic devices, biodegradable photonic devices, and bio-interface light-modulating devices.

[0037] More specifically, the high-energy beam micro / nano fabrication method includes the following steps: (1) Preparation of a solid substrate for self-assembly of hydroxyl-containing short peptides; (2) Construct a high-energy beam direct writing processing platform, which includes at least a high-energy beam emission source, a high-precision three-dimensional moving platform and a computer control system; import the model image of the target micro-nano optical device into the computer control system, and convert the model image into a path program by the computer control system; (3) The parameters of the high-energy beam emitted by the high-energy beam emission source are adjusted by the computer control system, and the hydroxyl-containing short peptide self-assembled solid substrate is placed on a high-precision three-dimensional moving platform. (4) According to the path program, drive the high-precision three-dimensional moving platform to move, so that the high-energy beam focus moves relative to the hydroxyl-containing short peptide self-assembled solid substrate according to the predetermined trajectory specified by the path program, thereby constructing a preset micro-nano optical structure on the surface or inside of the hydroxyl-containing short peptide self-assembled solid substrate.

[0038] In step (1), the amino acid sequence of the short peptide in the self-assembled solid substrate containing hydroxyl-containing short peptides includes at least one amino acid residue with a hydroxyl side chain; the self-assembled solid substrate containing hydroxyl-containing short peptides is one or a combination of short peptide single crystals and short peptide glasses; the short peptide single crystal is a glycine-tyrosine-serine-tyrosine-glycine (GYSYG) short peptide single crystal material with long-range ordered arrangement, and the short peptide glass is a pentatyrosine (YYYYY) short peptide glass material with long-range disorder and isotropic characteristics. Specifically, the solid substrate containing hydroxyl-containing short peptides is formed by the self-assembly of hydroxyl-containing short peptide molecules, which are composed of 2 to 10 amino acid residues linked by peptide bonds, and each hydroxyl-containing short peptide molecule contains at least two amino acid residues with hydroxyl side chains.

[0039] Short peptide crystals were prepared by solution gradient cooling, while short peptide glass was prepared by drop coating and spin coating.

[0040] In step (2), the high-energy beam direct writing processing platform is one or more of the following: an ultrafast femtosecond laser direct writing processing system and a focused ion beam (FIB) etching processing system; the model image of the target micro-nano optical device includes a three-dimensional structural design model and a two-dimensional surface pattern of the target micro-nano optical device; the path program is used to control the high-energy beam focus generated by the high-energy beam direct writing processing platform to perform precise scanning on or inside the surface of the short peptide solid substrate.

[0041] When using a focused ion beam (FIB) etching system, the system employs a liquid metal ion source, and the accelerating voltage and ion beam current are adjusted according to the material damage threshold.

[0042] When using an ultrafast femtosecond laser direct writing system, the center wavelength of the femtosecond laser is between 500nm and 1030nm, the pulse width is limited to between 100 and 300 femtoseconds, and the single pulse energy is controlled within the range of 50nJ to 500nJ, so as to utilize its ultrafast characteristics to suppress the negative impact of thermal diffusion on the surrounding sensitive hydrogen bond network.

[0043] When the high-energy beam is a femtosecond laser, the processing parameters are one or more of the following: femtosecond laser single pulse energy, average power, beam spot size, focusing position, scanning speed, scanning path, scanning interval, pulse width, repetition frequency, number of processing layers, or layer interval. When the high-energy beam is a focused ion beam, the processing parameters are one or more of the following: focusing ion beam acceleration voltage, ion beam current, beam spot size, residence time, scanning path, scanning spacing, or irradiation dose.

[0044] In step (3), the high-energy beam emission source parameters include the energy density of the emitted high-energy beam, pulse duration, ion beam current size, and scanning speed.

[0045] The computer control system coordinates and regulates the energy density, pulse duration, or ion beam magnitude of the high-energy beam, as well as the scanning speed. It utilizes the high-density hydrogen bond network between short peptide molecules in the self-assembled solid substrate containing hydroxyl peptides, constructed by hydroxyl groups, as an energy dissipation and structural buffering mechanism. The energy density or physical stripping force injected by the high-energy beam onto the self-assembled solid substrate containing hydroxyl peptides is controlled so that the energy density or physical stripping force is within a critical range. This critical range is sufficient to induce permanent changes in the physical or chemical properties of local areas in the self-assembled solid substrate containing hydroxyl peptides or to cause material stripping, but is below the threshold that would cause macroscopic thermal cracking, fragmentation along cleavage planes, or large-area carbonization of the substrate.

[0046] The solid substrate for self-assembly of hydroxyl-containing short peptides is divided into a functional reserved region and a non-functional reserved region. The functional reserved region is used to construct micro-nano optical structures, while the non-functional reserved region is used to detect whether the parameters of the high-energy beam regulated in step (3) are correct.

[0047] Whether the parameters of the high-energy beam are correctly controlled is specifically as follows: Before the high-energy beam focus moves relative to the self-assembled solid substrate containing hydroxyl short peptides in step (4) along the predetermined trajectory specified in the path program, i.e. before the formal processing of the device, a processing parameter window establishment step is performed: by systematically changing the high-energy beam energy parameters and scanning speed, test lines are written in the non-functional reserved area using the high-energy beam. Subsequently, the non-functional reserved area is observed using a scanning electron microscope or atomic force microscope. Based on the edge sharpness, sidewall roughness, and presence or absence of thermal damage signs of the test lines, the correctness of the high-energy beam parameters is determined, thereby clarifying safe and effective processing parameters.

[0048] If the test structure has clear edges, low sidewall roughness, and no obvious thermal damage is observed, then the corresponding parameters are determined as processing parameters; otherwise, adjust the high-energy beam parameters and retest.

[0049] A short peptide micro / nano optical device is fabricated using the above-mentioned processing method. Specifically, the short peptide micro / nano optical device is a functional microstructure integrally fabricated on a single hydroxyl-containing short peptide solid substrate using high-energy beam local forming technology.

[0050] Short peptide micro-nano optical devices are a combination of one or more of the following composite optical structures: embedded optical waveguide structures that are completely embedded inside a crystal and guide light by refractive index difference; ridge waveguide structures that are fabricated on a surface; and micro-nano relief structures that are fabricated on a substrate surface and modulate the light field through contour changes.

[0051] Short peptide micro-nano optical devices are ridge-shaped optical waveguide structures fabricated using high-energy beam processing on the surface of GYSYG short peptide single crystals. The ridge width of the ridge-shaped optical waveguide structure is 2 μm to 10 μm, and the ridge height is 1 μm to 5 μm. Short peptide micro-nano optical devices are used to achieve low-loss transmission of optical signals in the communication band.

[0052] Short peptide micro-nano optical devices are ridge-shaped optical waveguide structures fabricated by high-energy beam processing on the surface of YYYYY short peptide glass. The ridge width of the ridge-shaped optical waveguide structure is 2 μm to 15 μm, and the ridge height is 1 μm to 10 μm. Short peptide micro-nano optical devices are used to achieve low-loss confinement and transmission of optical signals in amorphous flexible optical networks.

[0053] The high-energy beam processing method provided by this invention is applicable to hydroxyl-containing short peptide solid materials. Because the short peptide material contains hydroxyl side chains, the hydroxyl groups can participate in the formation of intermolecular hydrogen bond networks. During localized high-energy beam irradiation, this helps to disperse local energy input and alleviate structural damage around the processing area, thereby reducing the risk of crack propagation, thermal damage, or large-area carbonization around the processing area. Furthermore, it facilitates the formation of waveguide structures, three-dimensional patterns, micro / nano structures, or optical functional regions on the surface, near-surface region, or inside the short peptide solid material.

[0054] In a preferred embodiment, the hydroxyl-containing short peptide solid material is a glycine-tyrosine-serine-tyrosine-glycine (GYSYG) short peptide single crystal. This short peptide single crystal contains serine and tyrosine residues, which can participate in hydrogen bonding through hydroxyl groups and, combined with the ordered molecular arrangement within the crystal, provide a stable solid material basis for high-energy beam local processing.

[0055] In another preferred embodiment, the hydroxyl-containing short peptide solid material is a pentatyrosine (YYYYY) short peptide glass. This short peptide glass is an amorphous solid material with isotropic characteristics and can be used to prepare flexible or amorphous short peptide optical structures.

[0056] Before fabricating the target device, processing parameter windows can be tested in the non-functional reserved area of ​​the hydroxyl-containing short peptide solid material. Specifically, by changing parameters such as high-energy beam energy, power, scanning speed, ion beam current, or irradiation dose, test lines or test arrays are formed in the non-functional reserved area. The morphology, edge sharpness, sidewall roughness, and thermal damage of the test structure are then observed using an optical microscope, scanning electron microscope, or atomic force microscope to determine the parameter range suitable for fabricating the target device.

[0057] Example 1: Preparation of GYSYG pentapeptide single crystals by solution evaporation method Weigh 10.0 mg of GYSYG pentapeptide powder and add it to 1.0 mL of deionized water. Sonicate the solution at room temperature for 10 min and then shake for 10 min to ensure complete dissolution, yielding a GYSYG pentapeptide solution with a concentration of 10.0 mg / mL. Filter the obtained GYSYG pentapeptide solution through a 0.22 μm microporous membrane to remove insoluble impurities, obtaining a clear GYSYG pentapeptide filtrate.

[0058] Add 500 μL of the GYSYG pentapeptide filtrate to a clean glass sample vial, and place the container in an environment of 25 ℃ and relative humidity of 40% to 60% for static crystallization. During crystallization, the solvent decreases slowly through evaporation, and the GYSYG pentapeptide molecules gradually self-assemble to form single crystals. After standing for 3 days, GYSYG pentapeptide single crystals are obtained at the bottom or sidewall of the container.

[0059] The obtained GYSYG pentapeptide single crystals were removed from the mother liquor and quickly rinsed once with a small amount of deionized water to remove residual mother liquor from the crystal surface. They were then dried at 25 °C for 12 h to obtain dried GYSYG pentapeptide single crystals. The obtained GYSYG pentapeptide single crystals exhibited a plate-like morphology, with a size of approximately 100 μm to 500 μm. The crystal surface was intact and transparent, making them suitable for subsequent femtosecond laser processing or focused ion beam processing. The microscopic optical image of the obtained GYSYG pentapeptide single crystals is shown below. Figure 2 As shown.

[0060] Example 2: Preparation of YYYYY short peptide glass film by drop coating Weigh 100.0 mg of YYYYY short peptide powder and add it to 1.0 mL of deionized water. Sonicate the solution at room temperature for 10 min and then shake for 10 min to ensure complete dissolution, resulting in a YYYYY short peptide solution with a concentration of 100.0 mg / mL. Filter the obtained YYYYY short peptide solution through a microporous membrane with a pore size of 0.22 μm to obtain a clear YYYYY short peptide filtrate.

[0061] A quartz sheet with dimensions of 10 mm × 10 mm was selected as the substrate. The substrate was ultrasonically cleaned in acetone, isopropanol, ethanol, and deionized water for 10 min each, and then dried with nitrogen. The dried substrate was then subjected to plasma cleaning for 2 min to improve the surface cleanliness and solution spreadability.

[0062] Take 10 μL of the YYYYY short peptide filtrate and drop it onto the substrate surface, allowing it to spread naturally and cover the target area of ​​the substrate surface. Place the substrate after drop coating in an environment of 25 ℃ and relative humidity of 40% to 60% to dry for 12 h, allowing the solvent to gradually evaporate, and the YYYYY short peptide molecules to form a glassy film on the substrate surface.

[0063] The resulting YYYYY short peptide glass film has a coverage area of ​​approximately 10 mm × 10 mm and a thickness of approximately 5 μm to 10 μm, with a continuous and smooth surface. The obtained YYYYY short peptide glass film can be used as a solid-state material containing hydroxyl-containing short peptides for subsequent femtosecond laser processing or focused ion beam processing.

[0064] Example 3: Femtosecond laser fabrication of ridge waveguide beam splitters and micro / nano patterns on YYYYY short peptide glass surface The YYYYY short peptide glass film prepared in Example 2 was fixed on a three-dimensional precision displacement platform. It was processed using a femtosecond laser processing system with a center wavelength of 1030 nm, a pulse width of 290 fs, a repetition rate of 25 kHz, an average power of 15.6 mW, and a single pulse energy of 0.62 μJ. The microscope objective used had a magnification of 20x and a numerical aperture of 0.40. The overall process for high-energy beam processing of hydroxyl-containing short peptide solid materials is as follows: Figure 1 As shown.

[0065] A femtosecond laser is focused onto the surface or near-surface region of a YYYYY short peptide glass film using a microscope objective. The scanning path is set to a straight line, a Y-branch, or an array pattern, with a scanning speed of 5 mm / s, a scanning interval of 2 μm, and 1 to 3 scans. By controlling a three-dimensional precision displacement platform to move along a preset path, the femtosecond laser focal point forms a continuous localized modification region in the YYYYY short peptide glass film along the preset path.

[0066] In fabricating the surface-ridged waveguide beamsplitter, a femtosecond laser scans the input straight waveguide, the beam-splitting region, and the output waveguide path according to a pre-defined sequence. After localized irradiation by the femtosecond laser, differences in morphology, refractive index, density, or optical absorption are formed between the processed and unprocessed areas of the YYYYY short peptide glass film, thus creating the surface-ridged waveguide beamsplitter. The resulting surface-ridged waveguide beamsplitter has a single waveguide width on the order of micrometers, a beam-splitting angle of approximately 8°, a beam-splitting region length of approximately 500 μm, and an overall structural length of approximately 2 mm. The microscopic optical image of the resulting YYYYY short peptide glass surface-ridged waveguide beamsplitter is shown below. Figure 3 As shown.

[0067] In fabricating micro / nano patterns, a femtosecond laser scans along a pre-defined linear array or grid pattern path at a scanning speed of 1 mm / s, a scanning spacing of 2 μm, and 1 to 3 scans. After processing, a patterned structure consisting of multiple locally modified lines is formed on the surface of the YYYYY short peptide glass film. The overall size of the resulting pattern is on the order of millimeters to centimeters, while the local linewidths can be on the order of micrometers. The resulting pattern's microscopic optical image is shown below. Figure 4 As shown.

[0068] Example 4: Fabrication of a GYSYG pentapeptide single-crystal surface waveguide interferometer using focused ion beam The GYSYG pentapeptide single crystal prepared in Example 1 was fixed on the sample stage of a focused ion beam processing system. Before processing, the surface of the GYSYG pentapeptide single crystal was gently blown with nitrogen to remove surface particles; optionally, a gold conductive layer with a thickness of about 5 nm was deposited on the sample surface to reduce charge accumulation.

[0069] A focused ion beam (FIB) was used to pattern the surface of a GYSYG pentapeptide single crystal. The FIB source was a liquid metal ion source with Ga+ ions, an accelerating voltage of 30 kV, an ion current of 10 pA, a spot size of approximately 10 nm, a residence time of 1 μs, a scanning interval of 20 nm, and 1 to 5 scans. The etched area size was 10 μm × 10 μm.

[0070] According to a preset waveguide interferometer pattern, a focused ion beam is controlled to scan along a preset path to form grooves, etching lines, or relief structures on the surface of a GYSYG pentapeptide single crystal. The waveguide interferometer includes an input end, a beam splitting region, two interference arms, and an output end; wherein the input end has a width of 500 nm, the interference arm width is 500 nm, the distance between the two interference arms is 2 μm, and the interference region length is 10 μm. After processing, a difference in morphology, refractive index, or light absorption is formed between the processed and unprocessed areas on the GYSYG pentapeptide single crystal surface, thus constituting a surface waveguide interferometer structure. The SEM morphology image of the obtained GYSYG pentapeptide single crystal surface waveguide interferometer is shown below. Figure 5 As shown.

[0071] Example 5: Device performance and material structure characterization The YYYYY short peptide glass surface ridge waveguide beam splitter and micro / nano pattern prepared in Example 3, and the GYSYG pentapeptide single crystal surface waveguide interferometer prepared in Example 4 were characterized.

[0072] The overall morphology and pattern integrity of the processed area are observed using an optical microscope with a magnification of 20x or 50x. The micro-nano structure morphology of the processed area is observed using a scanning electron microscope with an accelerating voltage of 3 kV and a working distance of 4 mm. Optionally, the surface height and roughness of the processed area are tested using an atomic force microscope with a scanning area of ​​20 μm × 20 μm.

[0073] Raman spectroscopy was used to analyze the molecular vibrational characteristics of YYYYY short peptide glass material before and after high-energy beam processing. The excitation wavelength used in the Raman test was 532 nm, the laser power was 1 mW, the integration time was 10 s, and the scanning range was 500 cm⁻¹ to 3600 cm⁻¹. Tests were conducted on the unprocessed region and the femtosecond laser-processed region, respectively, and the Raman spectra of the YYYYY short peptide glass material before and after femtosecond laser processing were compared, as shown in the figure. Figure 6 As shown. By Figure 6 It is evident that the main Raman characteristic peaks of the processed region compared to the unprocessed region can still be observed, and there are changes in peak intensity or peak shape. This indicates that femtosecond laser processing did not completely destroy the main molecular vibrational characteristics of the YYYYY short peptide glass material, but at the same time caused local modification in the processed region.

[0074] For the waveguide device, a 1310 nm laser was used as the input light source, and the light was coupled to the waveguide input end through a microscope objective. The output light signal was detected at the waveguide output end using a CCD camera or optical power meter. The test results show that the fabricated short peptide waveguide structure has a continuous waveguide morphology and can be used for the construction of short peptide micro / nano optical structures.

[0075] For micro / nano patterned devices, microscopic imaging or surface morphology testing was used to evaluate the pattern quality. The test results showed that the prepared micro / nano patterns had clear pattern boundaries, continuous structural morphology, and good structural integrity, indicating that this method is suitable for the controllable local fabrication of hydroxyl-containing short peptide solid materials and the fabrication of short peptide micro / nano optical devices.

[0076] Comparative Example 1: Comparison of femtosecond laser processing of FFF short peptide crystals without side chain hydroxyl groups Weigh 10.0 mg of FFF short peptide powder and add it to 1.0 mL of hexafluoroisopropanol. Sonicate the solution at room temperature for 10 min and then shake for 10 min to ensure complete dissolution of the FFF short peptide, yielding an FFF short peptide solution with a concentration of 10.0 mg / mL. Filter the obtained FFF short peptide solution through a microporous membrane with a pore size of 0.22 μm to remove insoluble impurities, obtaining a clear FFF short peptide filtrate.

[0077] Add 500 μL of the FFF short peptide filtrate to a clean glass sample vial, and place the container in an environment of 25 ℃ and relative humidity of 40% to 60% for static crystallization. During crystallization, the solvent decreases slowly through evaporation, and the FFF short peptide molecules gradually self-assemble to form crystals. After standing for 3 days, FFF short peptide crystals are obtained at the bottom or sidewall of the container.

[0078] The obtained FFF short peptide crystals were removed from the mother liquor and quickly rinsed once with a small amount of hexafluoroisopropanol to remove residual mother liquor from the crystal surface. They were then dried at 25 °C for 12 h to obtain dried FFF short peptide crystals. The obtained FFF short peptide crystals exhibited a plate-like morphology with a size of approximately 100 μm to 500 μm.

[0079] The obtained FFF short peptide crystal was fixed on a three-dimensional precision displacement platform and processed using the same femtosecond laser processing system as in Example 3. The femtosecond laser had a center wavelength of 1030 nm, a pulse width of 290 fs, a repetition rate of 25 kHz, an average power of 15.6 mW, a single pulse energy of 0.62 μJ, and a microscope objective with a magnification of 20x and a numerical aperture of 0.40. The femtosecond laser was focused onto the surface or near-surface region of the FFF short peptide crystal through the microscope objective at a scanning speed of 5 mm / s, a scanning interval of 2 μm, and a scanning number of 1 to 3 times.

[0080] The morphology of the processed area was observed using scanning electron microscopy (SEM) after processing. The results showed that under the aforementioned femtosecond laser processing conditions, the processed area of ​​the FFF short peptide crystal exhibited poor continuity of processing lines, rough edges, localized ablation, cracks, or structural damage. In contrast, the hydroxyl-containing YYYYY short peptide glass film in Example 3 was able to form continuous locally modified lines and patterned structures. This result indicates that the intermolecular hydrogen bond network formed by the side-chain hydroxyl groups in the hydroxyl-containing short peptide molecule is beneficial for dispersing local energy input and reducing structural damage around the processed area. The SEM morphology of the FFF short peptide crystal without side-chain hydroxyl groups after femtosecond laser processing is shown below. Figure 7 As shown.

[0081] The above are merely specific embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A high-energy beam processing method based on hydroxyl-containing short peptide solid materials, characterized in that: (1) A solid substrate containing hydroxyl-containing short peptides was prepared using a solid material containing hydroxyl-containing short peptides; The hydroxyl-containing short peptide solid substrate is formed by the self-assembly of hydroxyl-containing short peptide molecules, and the hydroxyl-containing short peptide molecules contain at least two amino acid residues with side chain hydroxyl groups. (2) Fix the hydroxyl-containing short peptide solid substrate onto the processing platform; (3) The hydroxyl-containing short peptide solid substrate is locally irradiated using the high-energy beam of the processing platform; (4) Adjust the processing parameters of the high-energy beam to locally modify the irradiated area of ​​the hydroxyl-containing short peptide solid substrate, thereby forming an optical functional structure in the hydroxyl-containing short peptide solid material.

2. The high-energy beam processing method based on hydroxyl-containing short peptide solid materials according to claim 1, characterized in that: In step (1), the amino acid sequence of the hydroxyl-containing short peptide solid material is an amino acid residue containing a hydroxyl side chain, wherein the amino acid residue containing the hydroxyl side chain is one or more of tyrosine residues, serine residues or threonine residues.

3. The high-energy beam processing method based on hydroxyl-containing short peptide solid materials according to claim 2, characterized in that: The hydroxyl-containing short peptide solid material is one of glycine-tyrosine-serine-tyrosine-glycine short peptide single crystal and tyrosine pentapeptide YYYYY glass; The hydroxyl-containing short peptide solid material is in one or more of the following forms: short peptide glassy material, short peptide crystal material, short peptide microwire, short peptide nanowire, and short peptide nanotube.

4. The high-energy beam processing method based on hydroxyl-containing short peptide solid materials according to claim 2, characterized in that: In step (1), the preparation method of the hydroxyl-containing short peptide solid substrate is one or a combination of solution evaporation method, cooling crystallization method, antisolvent diffusion method, and gas phase method.

5. The high-energy beam processing method based on hydroxyl-containing short peptide solid materials according to claim 1, characterized in that: In step (3), the local irradiation of the hydroxyl-containing short peptide solid material by the high-energy beam specifically means that the high-energy beam irradiates the surface, near-surface region, or internal region of the hydroxyl-containing short peptide solid material; the high-energy beam is one of femtosecond laser and focused ion beam.

6. The high-energy beam processing method based on hydroxyl-containing short peptide solid materials according to claim 5, characterized in that, When the high-energy beam is a femtosecond laser, the processing parameters include: a center wavelength of 500 nm to 1030 nm, a pulse width of 50 fs to 500 fs, a repetition frequency of 1 kHz to 1 MHz, a single pulse energy of 10 nJ to 5 μJ, an average power of 0.1 mW to 100 mW, a beam size of 0.5 μm to 10 μm, a scanning speed of 0.1 mm / s to 20 mm / s, a scanning interval of 0.1 μm to 10 μm, a number of processing layers of 1 to 100 layers, and an interlayer spacing of 0.1 μm to 10 μm. When the high-energy beam is a focused ion beam, the processing parameters include: an accelerating voltage of 5 kV to 30 kV, an ion beam current of 1 pA to 100 pA, a beam spot size of 5 nm to 100 nm, a dwell time of 0.1 μs to 10 μs, a scanning interval of 5 nm to 100 nm, and 1 to 20 scans.

7. The high-energy beam processing method based on hydroxyl-containing short peptide solid materials according to claim 5, characterized in that: When the high-energy beam uses a femtosecond laser, the femtosecond laser is focused onto the surface, near-surface region, or internal region of the hydroxyl-containing short peptide solid material for localized irradiation, causing localized modification of the irradiated area of ​​the hydroxyl-containing short peptide solid substrate and forming an optical functional structure in the hydroxyl-containing short peptide solid material; the localized irradiation method is one or more of point scanning, line scanning, surface scanning, and layer-by-layer scanning, and the optical functional structure is one or more of waveguide structure, three-dimensional pattern, and micro / nano structure. When the high-energy beam is a focused ion beam, the focused ion beam is focused onto the surface, near-surface region, or cross-sectional region of the hydroxyl-containing short peptide solid material for localized irradiation, causing localized modification of the irradiated region of the hydroxyl-containing short peptide solid substrate, forming an optical functional region in the hydroxyl-containing short peptide solid material; the localized irradiation method employs a patterned scanning method, and the optical functional structure is one or more combinations of trenches, aperture arrays, grating structures, three-dimensional patterned structures, and micro / nano structures.

8. The high-energy beam processing method based on hydroxyl-containing short peptide solid materials according to claim 1, characterized in that: The local modification is one or more of the following: morphological change, carbonization, crosslinking, densification, molecular rearrangement, crystal structure change, refractive index change, light absorption change, luminescence property change, surface energy change, or electrical property change.

9. A short peptide micro / nano optical device based on a hydroxyl-containing short peptide solid material, characterized in that: The short peptide micro / nano optical device is prepared by any of the processing methods described in claims 1-8. It includes a solid material body containing hydroxyl short peptides and a high-energy beam processing region formed on the surface, near-surface region, and interior of the solid material body containing hydroxyl short peptides. The high-energy beam processing region is used to form an optical functional structure. The solid material body containing hydroxyl short peptides is in one or more combinations of glassy state, crystal, thin film, microwire, nanowire, nanotube, fiber, and bulk material.

10. A short peptide micro / nano optical device based on a hydroxyl-containing short peptide solid material according to claim 9, characterized in that: The short peptide micro / nano optical device structure is one or more of the following: waveguide structure, grating structure, trench structure, aperture array, and relief structure.

11. An application of a short peptide micro / nano optical device based on a hydroxyl-containing short peptide solid material as described in any one of claims 9-10, characterized in that: Applications in the fabrication of bio-integrated optical devices, biosensors, optical information storage devices, micro-nano optical devices, flexible photonic devices, biodegradable photonic devices, and bio-interface light-modulating devices.

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