CN115356815A - Optical fiber end surface light-driven micro-gripper and preparation method thereof - Google Patents
Optical fiber end surface light-driven micro-gripper and preparation method thereof Download PDFInfo
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/46—Processes or apparatus adapted for installing or repairing optical fibres or optical cables
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/24—Homopolymers or copolymers of amides or imides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
Abstract
The invention discloses an optical fiber end surface light-driven micro-holder and a preparation method thereof, wherein the optical fiber end surface light-driven micro-holder comprises an optical fiber flexible driving structure and a rigid framework structure; the optical fiber comprises a fiber core and a cladding; the flexible driving structure comprises metal nano particles with light-heat conversion capacity and a thermal response type hydrogel structure, wherein the metal nano particles are embedded in the thermal response type hydrogel structure; the rigid skeleton structure comprises a clamping structure and a supporting structure; when the light-driven micro-gripper is in a water environment below the critical response temperature, the micro-gripper is opened when light is not transmitted, and the micro-gripper is closed after the light is transmitted to the optical fiber.
Description
Technical Field
The invention belongs to the field of micro-nano devices and laser manufacturing, and relates to an optical fiber end surface light-driven micro-holder and a preparation method thereof.
Background
The optical fiber can realize the long-distance lossless transmission of light energy and light signals, and the slender and soft appearance structure of the optical fiber and the convenient and mature manufacturing process thereof have great application value in medical detection and imaging in recent years. By means of internal cavities (such as intestinal tracts, blood vessels and the like) of a human body, the medical instrument based on the optical fiber is beneficial to realizing operations such as intervention and minimally invasive, and the pain of a patient in the operation process is reduced. In order to make the optical fiber have more functions, such as imaging, detection, operation, etc., it is often necessary to integrate a plurality of micro devices at the far end of the optical fiber, i.e., the end face of the optical fiber.
The cross section of the end face of the optical fiber is of a circular structure with the diameter of hundreds of microns, and the overall length-diameter ratio can reach more than 1000. The traditional micro-nano manufacturing process needs a closed processing space (such as electron beam Etching (EBL)) or a planar processing substrate (such as micro-nano photoetching), is difficult to be applied to precise integration and micro-nano manufacturing of the end face of an optical fiber, and the subsequent alignment integration caused by the micro size of a device and the optical fiber is also full of challenges. Particularly, for a holder which is a complex device with a driving structure and a supporting framework, the existing processing technology is difficult to realize the manufacture of a micro-nano device with multiple materials and a rigid-flexible structure.
Disclosure of Invention
In view of the above, the invention discloses an optical fiber end surface light-driven micro-gripper and a preparation method thereof, belonging to the field of micro-processing and comprising the following steps: 1) Preparing a two-photon processable hydrogel; 2) Processing the end face of the optical fiber; 3) A 3D two-photon laser printing temperature response driving structure; 4) 3D two-photon laser printing of a three-dimensional skeleton structure; 5) And reducing the metal particles by the in-situ laser single photon to obtain the multi-material remote optical drive micro-gripper. The invention combines two-photon processing and optical fiber in-situ reduction of metal particles to prepare the micro-holder which can be remotely controlled by light. The micro-gripper prepared by the invention has extremely high biocompatibility and can be used in the biomedical direction.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
an optical fiber end face light driven micro-gripper comprising:
the flexible driving structure comprises metal nano particles with light-heat conversion capacity and a thermal response type hydrogel structure, wherein the metal nano particles are embedded in the thermal response type hydrogel structure;
a rigid skeletal structure comprising a clamping structure and a support structure;
the flexible driving structure is coaxially connected with a fiber core of the optical fiber at the section;
the rigid framework structure is connected with the flexible driving structure;
the flexible driving structure is stimulated by photothermal effect, the metal nano particles absorb light energy, the temperature of the flexible driving structure rises, water molecules in the thermal response type hydrogel structure are separated from the hydrogel, the volume of the flexible hydrogel driving structure is reduced, and the clamping structure is in a closed state;
after the flexible driving structure is stimulated to disappear by photothermal effect, the temperature of the flexible driving structure is reduced to the ambient temperature, water molecules enter the hydrogel again, the volume of the flexible hydrogel driving structure expands, and the clamping structure end is in an open state.
The optical fiber end face light-driven micro-gripper also comprises an optical fiber, wherein the optical fiber comprises a fiber core and a cladding.
The optical fiber is used for light conduction; the thermally responsive hydrogel structure may reversibly expand and contract in response to a temperature stimulus; the rigid skeleton structure does not respond to external stimulation and can be matched with the driving structure to realize the grabbing and releasing of the object.
When the light-driven micro-gripper is in a water environment below the critical response temperature, the micro-gripper is opened when light is not transmitted, and the micro-gripper is closed after the light is transmitted to the optical fiber.
The flexible driving structure is coaxially connected with the fiber core of the optical fiber at the section.
The metal nanoparticles include Au and/or Ag.
The wavelength of the light source for driving the micro-gripper is determined by the absorption spectrum of the metal particles.
The invention also provides a preparation method of the optical fiber end surface light-driven micro-gripper, which comprises the following steps:
1) Dissolving N-isopropyl acrylamide, a cross-linking agent and a photoinitiator in a solvent to prepare a hydrogel solution;
2) Carrying out surface treatment on the end face of the optical fiber;
3) Laser printing of a thermally responsive hydrogel structure: dripping the hydrogel solution prepared in the step 1) on a substrate, suspending the optical fiber above the substrate and immersing the end face of the optical fiber in the hydrogel solution; adjusting laser focus to be positioned at an interface of the optical fiber and hydrogel, importing the drawn model file into software, adjusting printing parameters, controlling a scanning path of the laser to print the hydrogel structure by taking the end face of the optical fiber as a substrate, and preparing the optical fiber with the thermal response type hydrogel structure on the end face;
4) Printing a rigid framework structure: dropping photoresist on the substrate, suspending the optical fiber with the thermal response type hydrogel structure on the end face prepared in the step) 3 above the substrate, and immersing the end face of the optical fiber in the photoresist; adjusting laser focusing to be positioned at the interface of the optical fiber and the hydrogel, importing the drawn model file into software, and adjusting printing parameters to obtain the optical fiber with the end surface having a thermal response type hydrogel structure and a rigid skeleton structure;
5) Soaking the optical fiber with the end surface provided with the thermal response type hydrogel structure and the rigid skeleton structure prepared in the step 4) in a metal salt solution, introducing laser with the central wavelength of 400-550nm into the metal salt solution from the optical fiber after 10-20min, closing the laser after the laser power is 2.0-6.0mW and 1-10s, irradiating the laser emitted from the fiber core on the thermal response type hydrogel structure, absorbing the light energy by metal ions, reducing the metal ions into metal nano particles under the action of a reducing agent, and uniformly distributing the metal nano particles on the thermal response type hydrogel structure.
In the step 5), the metal salt solution is an Au solution or an Ag solution.
And 3D two-photon laser printing is adopted in the laser printing in the step 3) and the step 4).
In the step 1), the cross-linking agent is N, N-methylene-bis-acrylamide; the photoinitiator is phenyl lithium (2, 4, 6-trimethylbenzoyl) phosphonate.
In the step 1), in the hydrogel solution, the mass percent of N-isopropylacrylamide is 45-45wt%, the mass percent of cross-linking agent N, N-methylenebisacrylamide is 4.0-8.4wt%, and the mass percent of photoinitiator phenyl lithium (2, 4, 6-trimethylbenzoyl) phosphonate is 0.5-2wt%.
The surface treatment process in the step 2) is to cut a smooth end face of the optical fiber, soak the optical fiber in a toluene solution of 3- (trimethoxysilyl) propyl methacrylate, and then wash the optical fiber with acetone and deionized water.
In the step 4), the photoresist comprises any one or more of IP-L780, IP-S, IP-Dip and SU-8 photoresist.
The application of the optical fiber end surface light-driven micro-gripper in the field of biomedicine also belongs to the protection scope of the invention.
The key point of the invention is to provide a micro gripper which can remotely and actively control a micron-sized target object. The micro-gripper has the characteristics of multi-material complex structure. The micro-gripper can realize active driving under the synergistic action of the intelligent response material and the metal particles, and then is integrated with the flexible optical fiber to realize remote driving; unlike the prior art compliant driving method, the gripper grasping function needs to be achieved by external force, and the operation range is limited, such as a passive driving method by sidewall constraint or external force applied by a probe. The clamper can realize remote active optical drive; the key point of active driving is to process the intelligent material into a driving structure.
The invention realizes the integrated manufacture of the micro-gripper with a multi-material system on the end face of the optical fiber; the precise integration of the microminiature device at the far end of the optical fiber is realized through a femtosecond laser two-photon three-dimensional integration and a composite manufacturing method of single photon reduction of the end face of the optical fiber, and the multi-functionalization of the optical fiber is realized.
For the composite processing method, it is different from processing techniques such as photolithography, electron beam etching, etc., which are only suitable for manufacturing planar large-area microstructure, and for processing small-sized, non-planar substrates such as optical fiber end faces, it is difficult to achieve precise positioning and three-dimensional secondary integration. The femtosecond laser two-photon processing technology realizes three-dimensional forming of the micro-nano structure by utilizing nonlinear absorption of materials. Meanwhile, the secondary conformal processing of the non-planar substrate can be realized by the flexible positioning capability of the femtosecond laser focus.
In the composite processing method, if single photon reduction generated by light transmission of the optical fiber is changed into external irradiation, in-situ integration of nano particles in the device is difficult to realize. The nano particles exist in the hydrogel material, the hydrogel material exists in the rigid support structure, and due to the complex configuration of the micro-gripper, the secondary integration of the internal material is difficult to realize through an external irradiation mode. However, in the invention, the optical fiber is used for directly transmitting the light energy to the hydrogel flexible driving material on the end face of the fiber core, so that the in-situ reduction of the metal nanoparticles is realized, and the external framework structure is not influenced.
Further, the comparison of the method disclosed by the invention and fiber end face manufacturing processes such as discharging, ablating, melting and the like shows that the manufacturing effect of the multi-material system complex three-dimensional micro-nano device can be achieved only by the femtosecond laser two-photon three-dimensional integration and fiber end face single photon reduction composite manufacturing method disclosed by the invention.
In combination of the above contents, the present invention has the following beneficial effects:
1. by adopting the additive manufacturing method of the optical fiber end face, the invention solves the problem of functionalization of the optical fiber far end and realizes the beneficial effect of optical drive micro-clamping precision operation;
2. by adopting a femtosecond laser and in-situ laser reduction single-two-photon composite processing method, the preparation problem of a multi-material three-dimensional microstructure is solved, and the integrated processing of a micron-scale multi-material three-dimensional device is realized;
3. by adopting the femtosecond laser manufacturing method, the technical problem of accurate integration of the micro-nano device with the special appearance of the end face of the optical fiber is solved, and the micro-gripper on the end face of the optical fiber has the beneficial effects;
3. according to the invention, the in-situ reduction of metal nanoparticles is realized in the flexible driving structure surrounded by the micro-nano three-dimensional rigid skeleton structure by the optical fiber in-situ reduction method, so that the problem of secondary integration of materials in the three-dimensional complex structure is solved;
4. the invention adopts a response type intelligent material as a driving structure, realizes a remote controllable optical active control technology, and solves the problem of poor operability of the compliant micro-gripper;
5. the invention depends on the optical fiber main body to carry out structural design, processing and control on the end surface micro-gripper, realizes the operation of the end surface functional micro-gripper by means of the good flexibility of the optical fiber and the long-distance lossless transmission of optical energy, and is expected to solve the micro-scale operation of tiny cavities and ducts in organisms.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a schematic view of the fiber end face light control micro-gripper opening;
FIG. 2 is a schematic view of a fiber-optic endface light-operated micro-gripper closure;
FIG. 3 is a scanning electron microscope image of silver nanoparticles on a thermally responsive actuated structure;
FIG. 4 is a graph of the repetitive performance characteristics of the optical fiber end face light driven micro-gripper handling bead and opening and closing.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will aid those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any manner. It should be noted that numerous modifications and adaptations can be made by those skilled in the art without departing from the inventive concepts herein. All falling within the scope of the present invention.
Example 1
This example 1 provides an optical fiber end-face light-driven micro-gripper, as shown in fig. 1.
The micro gripper comprises:
an optical fiber comprising a core, a cladding;
the flexible driving structure comprises two functional components, namely metal nano particles with light-heat conversion capability and a thermal response type hydrogel structure, wherein the metal nano particles are embedded in the thermal response type hydrogel structure;
a rigid skeletal structure comprising a clamping structure and a support structure.
The flexible driving structure is coaxially and tightly connected with the fiber core of the optical fiber at the section, the light source can accurately irradiate the end face of the fiber core through the optical fiber and act on the flexible driving structure, the metal nano particles absorb the light energy at the outlet of the fiber core and convert the light energy into heat energy, the thermal response type hydrogel structure deforms due to the temperature rise brought by the metal nano particles, and water molecules in the hydrogel are separated from the hydrogel network structure under the temperature rise state, so that the volume of the flexible hydrogel driving structure is reduced.
Rigid skeleton texture closely links to each other with flexible drive structure, and when the shape changed takes place for flexible drive structure photic thermal effect, can stimulate rigid structure and take place the skew, appears to be the closure state on the clamping structure of extension. Conversely, when the light source is turned off, the photo-thermal nanoparticles no longer generate heat, the flexible driving structure is returned to room temperature, and the water molecules enter the hydrogel again to cause volume expansion, so that the holding structure end is in an open state. The remote optical fiber end surface micro-gripper is opened/closed according to the principle shown in FIG. 2.
Example 2
This example provides the method of making the fiber-optic endface micro-gripper of example 1
The fiber end face micro-holder is prepared by a femtosecond laser single-two-photon integrated manufacturing method, and the specific steps are as follows:
1. optical fiber end face treatment
Selecting a multimode optical fiber with the diameter of 250 mu m, stripping a coating layer to 125 mu m, cutting a flat end face by using an optical fiber cutter, soaking the cut flat end face of the optical fiber in 1mM toluene solution of 3- (trimethoxy silicon-based) propyl methacrylate, washing the end face by using acetone and deionized water after one hour, and improving the adhesive force between the end face of the optical fiber and hydrogel after treatment;
2. femtosecond laser two-photon processing hydrogel driving microstructure
1) Preparation of hydrogel solutions
The reagents used include N-isopropylacrylamide, a crosslinking agent, a photoinitiator, and ethylene glycol. Wherein the cross-linking agent is N, N-methylene-bisacrylamide, and the photoinitiator is phenyl lithium (2, 4, 6-trimethyl benzoyl) phosphonate.
Dissolving 400mg of N-isopropylacrylamide, 40mg of cross-linking agent N, N-methylenebisacrylamide and 10mg of photoinitiator phenyl lithium (2, 4, 6-trimethylbenzoyl) phosphonate in 450 mu L of ethylene glycol, ultrasonically dissolving in a water bath at 60 ℃ for 30-60 min, taking out the solution every 5-10 min, manually shaking to uniformly disperse the solution for assisting in dissolving, and obtaining the hydrogel solution for femtosecond laser processing.
2) The method comprises the steps of selecting 780nm wavelength femtosecond laser as a light source to print a thermal response type hydrogel structure, dripping a hydrogel solution prepared in the step 1) on a substrate, suspending an optical fiber above the substrate by using a clamp, immersing the end face of the optical fiber in the hydrogel solution prepared in the step 1), adjusting laser focusing and positioning to the interface of the optical fiber and the hydrogel, guiding a drawn model file into software, adjusting printing parameters, controlling a scanning path of the laser, and printing the hydrogel structure by taking the end face of the optical fiber as a substrate to obtain the optical fiber with the thermal response type hydrogel structure on the end face. In this embodiment, a 25 × objective lens is used for processing, the laser power of the poly N-isopropylacrylamide (PNIPAM) hydrogel is 85mW, the scanning speed is 30mm/s, the end face of the optical fiber is immersed in deionized water for 10min for development after printing is completed, and the next step of printing is performed after drying;
3. femtosecond laser two-photon integrated three-dimensional rigid skeleton structure
A780 nm wavelength femtosecond laser is still used as a light source, commercial photoresist IP-S is selected, and a three-dimensional rigid skeleton structure is integrated on the end face of the optical fiber with the thermal response type hydrogel structure.
Dropping photoresist on a substrate, suspending the optical fiber processed in the step (2) above the substrate by using a clamp, immersing the end face of the optical fiber in commercial photoresist IP-S, ensuring that the end face of the optical fiber is between hydrogel and the substrate, adjusting laser focusing to be positioned at the interface of the optical fiber and the hydrogel, importing the drawn model file into software, and adjusting printing parameters to obtain the optical fiber of which the end face has a thermal response type hydrogel structure and a rigid framework structure;
processing by using a 25x objective lens, wherein the laser power of IP-S is 29mW, the scanning speed is 100mm/S, and after printing is finished, the whole structure is soaked in Propylene Glycol Methyl Ether Acetate (PGMEA) for 30min and then soaked in Isopropanol (IPA) for 2min for development;
4. optical fiber in-situ single photon reduction metal nano particle
Preparing metal salt solution, adding 0.017g AgNO 3 And dissolving the solid in 1mL of deionized water, adding ammonia water for titration until the solution is just clear, adding 0.017g of sodium citrate, and fully mixing to obtain a silver ammonia solution. Soaking the optical fiber with the end face having thermal response type hydrogel structure and rigid skeleton structure in silver ammonia solution, introducing 405nm wavelength laser into the optical fiber after 10min, turning off the laser after the laser power is 2.0-3.0 mW,1s, directly irradiating the laser emitted from the fiber core on the thermal response type hydrogel structure, and forming Ag metal + The ions absorb light energy, are reduced into silver nanoparticles under the action of a reducing agent sodium citrate, and are uniformly distributed in a thermal response type hydrogel structure, as shown in figure 3. According to the method, the precise integrated preparation of a plurality of material systems on the optical fiber end face structure is realized, the constraint problem of a closed space or plane process in the traditional processing is solved, and the miniaturization and functionalization of medical devices are facilitated.
Example 3
The fiber-end face micro-gripper as described in example 1 relies on the femtosecond laser single-two-photon integration manufacturing method provided by the present invention, and the specific implementation is as follows.
1. And (5) processing the end face of the optical fiber. Selecting a multimode optical fiber with the diameter of 250 mu m, stripping a coating layer to 125 mu m, cutting a flat end face by using an optical fiber cutter, soaking the cut flat end face of the optical fiber in 1mM toluene solution of 3- (trimethoxy silicon-based) propyl methacrylate, washing the end face by using acetone and deionized water after one hour, and improving the adhesive force between the end face of the optical fiber and hydrogel after treatment;
2. the femtosecond laser two-photon processing hydrogel driving microstructure.
1) Preparation of hydrogel solutions
The reagents used include N-isopropylacrylamide, a crosslinking agent, a photoinitiator, and ethylene glycol. Wherein the cross-linking agent is N, N-methylene bisacrylamide, and the photoinitiator is phenyl lithium (2, 4, 6-trimethyl benzoyl) phosphonate.
Dissolving 400mg of N-isopropylacrylamide, 40mg of cross-linking agent N, N-methylenebisacrylamide and 10mg of photoinitiator phenyl lithium (2, 4, 6-trimethylbenzoyl) phosphonate in 450 mu L of ethylene glycol, ultrasonically dissolving in a water bath at 60 ℃ for 30-60 min, taking out the solution every 5-10 min, manually shaking to uniformly disperse the solution for assisting in dissolving, and obtaining the hydrogel solution for femtosecond laser processing.
2) Thermally responsive hydrogel structures
Selecting 780nm wavelength femtosecond laser as a light source to print a thermal response type hydrogel structure, suspending an optical fiber above a substrate by using a clamp, immersing the end face of the optical fiber in the hydrogel solution prepared in the step 1), adjusting laser focusing and positioning to the interface of the optical fiber and the hydrogel, importing a drawn model file into software, adjusting printing parameters, controlling a scanning path of the laser to print the hydrogel structure by taking the end face of the optical fiber as a substrate, and preparing the thermal response type hydrogel structure on the end face of the optical fiber. In this embodiment, a 25 × objective lens is used for processing, the laser power of the poly-N-isopropylacrylamide (PNIPAM) hydrogel is 85mW, the scanning speed is 30mm/s, the end face of the optical fiber is immersed in deionized water for 10min for development after printing is completed, and the optical fiber is dried and then printed in the next step;
3. a femtosecond laser two-photon integrated three-dimensional rigid skeleton structure.
Still using 780nm wavelength femtosecond laser as a light source, selecting a commercial photoresist IP-L780, integrating a three-dimensional rigid skeleton structure on the optical fiber end face with a thermal response type hydrogel structure, suspending the optical fiber processed in the step 2 above the substrate by using a clamp, immersing the optical fiber end face in the commercial photoresist IP-L780, ensuring that the optical fiber end face is between the hydrogel and the substrate, adjusting laser focusing and positioning to the interface between the optical fiber and the hydrogel, introducing a drawn model file into software, adjusting printing parameters, and preparing the three-dimensional rigid skeleton structure. In this example, a 25x objective lens is used for processing, the laser power of the IP-L780 is 34mW, the scanning speed is 100mm/s, the whole structure is soaked in Propylene Glycol Methyl Ether Acetate (PGMEA) for 20min after printing is completed, and then the whole structure is soaked in Isopropanol (IPA) for 2min for development;
4. and (3) carrying out in-situ single photon reduction on the metal nanoparticles by using the optical fiber.
Preparing metal salt solution, adding 0.017g AgNO 3 And dissolving the solid in 1mL of deionized water, adding ammonia water for titration until the solution is just clear, adding 0.017g of sodium citrate, and fully mixing to obtain a silver ammonia solution. Soaking the optical fiber with the end surface provided with the thermal response type hydrogel structure and the rigid framework structure prepared in the step 1-3 in silver ammonia solution, introducing laser with the wavelength of 405nm into the optical fiber after 10min, turning off a laser device after the laser power is 2.0-3.0 mW and 1s, directly irradiating the laser emitted from the fiber core on the thermal response type hydrogel structure by the laser, and enabling the metal Ag to be Ag + The ions absorb the light energy, are reduced into silver nanoparticles under the action of a reducing agent sodium citrate, and are uniformly distributed in the thermal response type hydrogel structure, as shown in fig. 3. According to the method, the precise integrated preparation of a plurality of material systems on the optical fiber end face structure is realized, the constraint problem of a closed space or plane process in the traditional processing is solved, and the miniaturization and functionalization of medical devices are facilitated.
Comparative example 1
This comparative example differs from example 2 in that the drive structure thermally responsive poly N-isopropylacrylamide (PNIPAM) material was replaced with a commercial IP-S photoresist. The obtained device structure meets the design of the micro-gripper, but the micro-gripper cannot realize the closing and opening actions due to the fact that the IP-S cannot respond to external stimulation (namely volume change), and further cannot realize the optical drive clamping function.
Comparative example 2
This comparative example differs from example 2 in that the intercalation of the Ag particles was performed after the micro-gripper preparation was completed without in-situ laser reduction (i.e. without the patented single-two-photon composite processing method). In this case, because the poly-N-isopropylacrylamide (PNIPAM) material is temperature-sensitive, the opening and closing of the micro-gripper can be realized only when the ambient (solution) temperature changes, and this temperature control method can negatively affect the tissue particularly during the medical operation, and compared with the optical drive method, the temperature drive method greatly reduces the universality of the micro-gripper.
Comparative example 3
The difference between the comparative example and the example 2 is that the micro-gripper is prepared on the guide wire, the light energy transmission needs to be considered on the traditional guide wire, the preparation steps of the light-driven micro-gripper are increased, more operation links are introduced, and the device forming design is not facilitated.
Comparative example 4
The comparative example is different from example 2 in that when the optical fiber in-situ single photon reduces the metal nanoparticles, the laser power is increased to 16mW, and after the optical fiber is irradiated for 2s, the laser cannot penetrate through the thermal response type hydrogel structure due to the fact that the flexible driving structure is embedded into too many silver nanoparticles, so that the hydrogel structure cannot contract/expand under the switching of the laser, and accordingly, the micro-gripper cannot be opened or closed.
Performance test
The micro-gripper of example 2 was subjected to operational performance verification. Precise control of the micro-gripper is achieved by remotely controlling the light source switch, as shown in fig. 4. After the light source is turned on, the offset of the holder tip is about 10um, and the device has repeated operation performance and good stability. According to the structural size setting, the grabbing of objects with different sizes can be realized, for example, the diameter range is 5-30 um, and the device has important application value in the aspects of precise medical treatment, minimally invasive surgery and single cell operation.
The foregoing description has described specific embodiments of the present invention. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. An optical fiber endface optically driven microtrip, comprising:
the flexible driving structure comprises metal nano particles with light-heat conversion capacity and a thermal response type hydrogel structure, wherein the metal nano particles are embedded in the thermal response type hydrogel structure;
a rigid skeletal structure comprising a clamping structure and a support structure;
the flexible driving structure is coaxially connected with a fiber core of the optical fiber at the section;
the rigid framework structure is connected with the flexible driving structure;
the flexible driving structure is stimulated by photothermal effect, the metal nano particles absorb light energy, the temperature of the flexible driving structure rises, water molecules in the thermal response type hydrogel structure are separated from the hydrogel, the volume of the flexible hydrogel driving structure is reduced, and the clamping structure is in a closed state;
after the flexible driving structure is stimulated by photothermal effect to disappear, the temperature of the flexible driving structure is reduced to the ambient temperature, water molecules enter the hydrogel again, the volume of the flexible hydrogel driving structure expands, and the clamping structure end is in an opening state.
2. The fiber-optic endface optically driven micro-gripper according to claim 1, wherein the fiber-optic endface optically driven micro-gripper further comprises an optical fiber comprising a core, a cladding.
3. The fiber-optic endface optically driven micro-gripper of claim 1, wherein the flexible driving structure is connected to the fiber core coaxially at a break-out.
4. The fiber-optic endface light-driven micro-gripper of claim 1, wherein said metal nanoparticles comprise Au and/or Ag.
5. A method of making a fiber-optic endface light-driven micro-gripper according to claim 1, comprising the steps of:
1) Dissolving N-isopropyl acrylamide, a cross-linking agent and a photoinitiator in a solvent to prepare a hydrogel solution;
2) Carrying out surface treatment on the end face of the optical fiber;
3) Laser printing of a thermally responsive hydrogel structure: dripping the hydrogel solution prepared in the step 1) on a substrate, suspending the optical fiber above the substrate and immersing the end face of the optical fiber in the hydrogel solution; adjusting laser focus to be positioned at an interface of the optical fiber and hydrogel, importing the drawn model file into software, adjusting printing parameters, controlling a scanning path of the laser to print the hydrogel structure by taking the end face of the optical fiber as a substrate, and preparing the optical fiber with the thermal response type hydrogel structure on the end face;
4) Printing a rigid framework structure: dropping photoresist on the substrate, suspending the optical fiber with the thermal response type hydrogel structure on the end face prepared in the step 3) above the substrate, and immersing the end face of the optical fiber in the photoresist; adjusting laser focus to be positioned at the interface of the optical fiber and the hydrogel, importing the drawn model file into software, and adjusting printing parameters to prepare the optical fiber with the end surface having a thermal response type hydrogel structure and a rigid skeleton structure;
5) Soaking the optical fiber with the end surface provided with the thermal response type hydrogel structure and the rigid skeleton structure prepared in the step 4) in a metal salt solution, introducing laser with the central wavelength of 400-550nm into the metal salt solution by using the optical fiber after 10-20min, closing the laser after the laser power is 2.0-6.0mW and 1-10s, irradiating the laser emitted from the fiber core on the thermal response type hydrogel structure, and reducing the metal ions into metal nano particles under the action of a reducing agent by absorbing light energy and uniformly distributing the metal nano particles in the thermal response type hydrogel structure.
6. The method according to claim 5, wherein in step 5), the metal salt solution is an Au solution or an Ag solution.
7. The method according to claim 5, wherein in step 1), the crosslinking agent is N, N-methylenebisacrylamide; the photoinitiator is phenyl lithium (2, 4, 6-trimethylbenzoyl) phosphonate.
8. The preparation method according to claim 5, characterized in that in the hydrogel solution in step 1), the mass percentage of N-isopropylacrylamide is 25 to 45wt%, the mass percentage of the cross-linking agent N, N-methylenebisacrylamide is 4.0 to 8.4wt%, and the mass percentage of the photoinitiator phenyl lithium (2, 4, 6-trimethylbenzoyl) phosphonate is 0.5 to 2wt%.
9. The method of claim 5, wherein the surface treatment in step 2) is performed by cutting the optical fiber into a flat end surface, soaking the cut optical fiber in a toluene solution of 3- (trimethoxysilyl) propyl methacrylate, and washing the optical fiber with acetone and deionized water.
10. The method according to claim 5, wherein in step 4), the photoresist comprises any one or more of IP-L780, IP-S, IP-Dip and SU-8 photoresist.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023067479A1 (en) * | 2021-10-19 | 2023-04-27 | Khalifa University of Science and Technology | Nanoparticle hydrogels |
| CN116852331A (en) * | 2023-06-09 | 2023-10-10 | 华中科技大学 | Hinge type optical waveguide soft actuator based on multi-core optical fiber |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023067479A1 (en) * | 2021-10-19 | 2023-04-27 | Khalifa University of Science and Technology | Nanoparticle hydrogels |
| CN116852331A (en) * | 2023-06-09 | 2023-10-10 | 华中科技大学 | Hinge type optical waveguide soft actuator based on multi-core optical fiber |
| CN116852331B (en) * | 2023-06-09 | 2024-02-02 | 华中科技大学 | Hinge type optical waveguide soft actuator based on multi-core optical fiber |
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