Femtosecond laser plating probe and micro-nano localized deposition device based on femtosecond laser

Abstract

This invention relates to a femtosecond laser deposition probe and a micro / nano localized deposition device based on a femtosecond laser, which relates to the field of nanofabrication, specifically to the field of surface metallization process equipment technology and the field of probe technology used in this process. It solves the problems of existing probes being unable to simultaneously excite electrochemical reactions and conduct laser light, and the high optical path transmission loss in existing deposition devices. The probe comprises multiple parallel single-mode silica optical fibers, each fiber having a tapered end and its outer surface covered with a metal layer. The laser emitted by the femtosecond laser transmission system in the deposition device is guided by the fiber probe (301) to the surface metallization processing area within the movable reaction pool system (4), and the end of the fiber probe (301) also serves as the working electrode for the chemical reaction within the movable reaction pool system (4). The femtosecond laser deposition probe is suitable for systems combining laser and chemical reactions.

Description

Technical Field

[0001] This invention relates to the field of nanofabrication, specifically to the field of surface metallization process technology and the probe technology used in the process. Background Technology

[0002] In the field of micro-nano manufacturing, high-precision localized deposition technology is key to realizing the fabrication of three-dimensional micro-nano metal structures. However, when applying electrochemical deposition to the micro-nano scale, traditional techniques face severe challenges: first, the low current density in the micro-area leads to low deposition efficiency; second, the nanometer-level precise control of the distance between the electrode and the deposition substrate is difficult, resulting in poor deposition localization and structural consistency; and third, the grains of the deposited layer tend to be coarse, affecting the mechanical properties of the micro-nano structures.

[0003] Femtosecond laser deposition is a surface metallization process that uses femtosecond lasers as the core energy source or auxiliary means to achieve surface metallization at the micro-nano scale.

[0004] The femtosecond laser-assisted local deposition technology utilizes the ultra-short pulse width and ultra-high peak power of the femtosecond laser, which has no obvious thermal effect during the processing and is a cold photon source. It can precisely control the light field environment of the micro-area and provide additional energy for chemical conversion reactions or electrochemical reduction reactions.

[0005] For the aforementioned laser-assisted micro / nano localized deposition technology, traditional metal microelectrode probes are used as electrodes for electrodeposition, and then micro-glass tube probes or optical fibers are used to transfer laser energy, combining the optical path with the electrodeposition process. In practical applications, however, metal microelectrode probes are prone to surface passivation, difficult to reduce in size, and cannot conduct laser light, resulting in limited functionality. While micro-glass tube probes or optical fibers can achieve precise positioning through laser energy transfer, they are themselves insulators and cannot act as electrodes to initiate electrochemical reactions. They cannot form effective electrical or chemical interfaces with the deposition system, making it difficult to directly stimulate localized deposition reactions.

[0006] Therefore, in the existing femtosecond laser-assisted local deposition technology, the laser system and the deposition system cannot accurately and efficiently transmit external laser energy to the deposition micro-area, and the laser system and the deposition system cannot cooperate effectively. Summary of the Invention

[0007] This invention solves the problems in the prior art where the probe cannot simultaneously excite the electrochemical reaction and conduct the laser, as well as the large optical path conduction loss in existing deposition devices.

[0008] Option 1: The femtosecond laser plating probe of the present invention includes multiple single-mode silica optical fibers arranged in parallel to each other; the single-mode silica optical fibers are divided into a clamping region and a detection region along the axial direction, and the end of the detection region of the single-mode silica optical fiber is tapered; the outer surface of the single-mode silica optical fiber is covered with a metal layer; and an insulating plating layer is also provided outside the surface metal layer of the clamping region of the single-mode silica optical fiber.

[0009] In a further optimized design, a gap is left between any two adjacent single-mode quartz optical fibers in the multiple single-mode quartz optical fibers.

[0010] In a further optimized scheme, the multiple single-mode silica optical fibers are arranged in a multi-layered circular ring with one single-mode silica optical fiber as the center, or the multiple single-mode silica optical fibers are arranged in a rectangular pattern.

[0011] In a further optimized scheme, the metal layer is a single-material metal layer or a composite metal layer composed of multiple metal material layers, and the thickness of the metal layer is 0.5-12μm.

[0012] The scheme is further optimized so that the radius of curvature of the cone at the end of the detection area is between 5 and 10 μm.

[0013] Option 2: The micro-nano localized deposition device based on femtosecond laser described in this invention includes: an optical platform, a femtosecond laser transmission system, an optical fiber probe, a movable reaction cell system, an adapter, an optical fiber coupler, and a gantry device;

[0014] The femtosecond laser transmission system and the gantry device are fixed on the optical platform; the movable reaction cell system is placed on the optical platform and located below the gantry device; the fiber optic probe is fixed on the gantry device, and its lower part can extend into the movable reaction cell system; the femtosecond laser transmission system is used to generate femtosecond lasers and transmit the femtosecond lasers to the inside of the fiber optic probe through an adapter and a fiber optic coupler; a three-electrode system is set inside the movable reaction cell system, and the detection area of ​​the fiber optic probe is the working electrode of the three-electrode system.

[0015] Further optimized, the femtosecond laser transmission system includes a laser, a beam expander, a first reflector, an optical climbing frame, a first climbing frame reflector, a second climbing frame reflector, and a second reflector; the optical climbing frame is used to support the first climbing frame reflector and the second climbing frame reflector.

[0016] The laser generates a femtosecond laser beam, which is reflected by a reflector to a beam expander. After being expanded by the beam expander, the beam passes sequentially through a climbing frame reflector, a climbing frame reflector, and a second reflector before being emitted into the adapter.

[0017] In a further optimized design, the micro / nano localized deposition device also includes a probe fixing device, which comprises: an upper limiting plate, a lower limiting plate, an organic substrate, a test circuit board, a protective shell, and a mounting baffle. Both the upper and lower limiting plates have limiting holes, and an optical fiber probe sequentially passes through these holes. The upper limiting plate is positioned above the protective shell near the optical fiber coupler, and the lower limiting plate is positioned below the protective shell near the detection area of ​​the optical fiber probe. Both the organic substrate and the test circuit board have probe through-holes, and the detection area of ​​the optical fiber probe is sequentially inserted into these through-holes. The end of the optical fiber probe extends below the test circuit board. The organic substrate, test circuit board, and mounting baffle are positioned below the protective shell, with the organic substrate embedded inside the test circuit board, and the mounting baffle fixedly connected to the bottom of the test circuit board.

[0018] Further optimization of the scheme: the movable reaction cell system includes an electrolytic cell and a three-axis moving platform; the three-axis moving platform is used to drive the electrolytic cell to move in three dimensions; the electrolytic cell is equipped with an auxiliary electrode and an Ag / AgCl reference electrode; the auxiliary electrode, the Ag / AgCl reference electrode and the detection area of ​​the fiber optic probe constitute the three-electrode system of the electrolytic cell.

[0019] In a further optimized design, the device also includes a tuning fork, which faces away from the fiber optic probe and is fixedly mounted on a baffle, with its lower surface located within the horizontal plane of the probe's detection end.

[0020] The beneficial effects of this invention compared to the prior art are as follows:

[0021] The fiber optic probe of the coupling tuning fork of the present invention has multiple functions: it can serve as a precise mechanical positioning unit and as a high-efficiency femtosecond laser energy transmission channel, so that the energy can directly act on the deposition micro-area, and the laser system and the deposition system can be closely integrated and mutually supportive.

[0022] Based on the fiber optic probe described in this invention, a femtosecond laser and a fiber optic probe can be integrated into a single unit to obtain the femtosecond laser-based micro / nano localized deposition device claimed in this invention. In this device, the transient high-frequency alternating electric field introduced by the femtosecond laser through the fiber optic probe can significantly increase the local current density of the deposition micro-region, thereby increasing the deposition rate by more than 35% compared to traditional processes and providing more energy sources for metal ion reduction. Simultaneously, the transient alternating electric field can promote the formation of nanocrystals within the microstructure, increasing the tensile strength of the deposited structure by more than 45% and the compressive strength by more than 38%, significantly optimizing the mechanical properties.

[0023] In the femtosecond laser-based micro-nano localized deposition device of the present invention, the detection and control of the distance between the probe and the deposition substrate are achieved through a variety of technical means. Specifically, through the collaborative design of the tuning fork and the fiber coupler, combined with the precise positioning of the upper and lower limiting plates, the control accuracy of the distance between the probe and the deposition substrate reaches ±0.1μm, which solves the problem of poor localization in traditional deposition processes, and the size error of the deposition structure is ≤±0.5μm.

[0024] The femtosecond laser-based micro / nano localized deposition device of this invention adopts a modular integrated design. It utilizes a femtosecond laser transmission system to generate and emit the femtosecond laser, and a movable reaction cell system to work in conjunction with it. This movable reaction cell system can be flexibly adapted to various localized deposition processes such as electrochemical deposition and chemical conversion deposition according to actual needs. A femtosecond laser deposition probe connects the femtosecond laser transmission system and the movable reaction cell system. The femtosecond laser deposition probe serves as the optical waveguide of the femtosecond laser transmission system and also as the working electrode of the three-electrode system in the movable reaction cell system, achieving precise coordination between laser and chemical conversion. The device has a compact structure and high stability.

[0025] The femtosecond laser deposition probe described in this invention is suitable for systems combining laser and chemical reactions. The femtosecond laser-based micro / nano localized deposition device described in this invention is suitable for the field of nanofabrication. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of the matrix fiber probe in the femtosecond laser plating probe of the present invention;

[0027] Figure 2 This is an axial cross-sectional view of the structure described in Embodiment 2;

[0028] Figure 3 This is a schematic diagram of the overall structure of the micro / nano localized deposition device based on a nickel-plated fiber probe according to the present invention.

[0029] Figure 4 for Figure 3 Enlarged view of the upper part of the device shown;

[0030] Figure 5 for Figure 3 A schematic diagram of the assembly structure of the movable reaction tank system, the three-axis moving platform, the fiber optic probe device, the adapter, and the fiber optic coupler in the device shown.

[0031] Figure 6 for Figure 3 A schematic diagram of the fiber optic probe device in the illustrated apparatus.

[0032] Figure 7 for Figure 3A schematic diagram of the assembly structure of the fiber optic probe device, adapter, fiber optic coupler and three-axis moving platform in the device shown.

[0033] Figure 8 for Figure 3 A schematic diagram of the internal structure of the three-axis moving platform in the device shown.

[0034] Figure 9 for Figure 3 A schematic diagram of the optical path in the device shown.

[0035] Reference numerals in the attached figures: Optical platform 1, Laser 201, Beam expander 202, Reflector 1 203, Optical climbing frame 204, Climbing frame reflector 1 2041, Climbing frame reflector 2 2042, Reflector 2 205, Fiber optic probe 301, Upper limit plate 3021, Lower limit plate 3022, Organic substrate 303, Test circuit board 304, Protective shell 305, Pin hole 3051, Step hole 3052, Mounting baffle 306, Tuning fork 307, Movable reaction cell system 4, Ag / AgCl reference electrode 402, Electrolytic cell 403, Three-axis moving platform 404, Adapter 6, Fiber optic coupler 7, Gantry device 8, and Power supply unit 9. Detailed Implementation

[0036] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0037] In the description of this invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing the invention and for simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0038] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0039] Furthermore, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0040] It should be noted that some of the accompanying drawings are in a very simplified form and are not to scale, and are only used to facilitate and clearly illustrate the purpose of the embodiments of the present invention.

[0041] Implementation Method 1: See Figure 1 and 2 This embodiment describes a femtosecond laser-coated probe, comprising multiple single-mode silica optical fibers arranged parallel to each other; each single-mode silica optical fiber is divided into a clamping region and a detection region along its axial direction, and the end of the detection region of each single-mode silica optical fiber is tapered; the outer surface of each single-mode silica optical fiber is covered with a metal layer; and an insulating coating is further disposed outside the surface metal layer of the clamping region of the single-mode silica optical fiber.

[0042] The fiber probe described in this embodiment has a metal layer coated on the outer surface of the single-mode quartz fiber, enabling the fiber probe to transmit both optical and electrical signals. In the field of electrochemical deposition, the fiber probe achieves precise positioning of the laser heat source by conducting laser light, and due to its conductivity, it can be used as the working electrode of a three-electrode system to participate in chemical reactions during the electrochemical deposition process.

[0043] The fiber optic probe described in this embodiment is divided into a clamping region and a detection region along its axial direction. In practical applications, the large-area conductivity of the probe can lead to uncontrollable deposition positions, thus hindering micro-machining. Therefore, in this embodiment, an insulating coating is provided outside the metal layer on the surface of the clamping region of the fiber optic probe. A SiO2 insulating layer can be deposited on the surface to avoid the problem of uncontrollable deposition positions and achieve precise micro-machining. The SiO2 insulating layer can be achieved using the existing PECVD method.

[0044] A preferred embodiment of the single-mode silica optical fiber described herein is to use an existing optical fiber with a cladding diameter of 125 μm.

[0045] Implementation Method Two: See Figure 2This embodiment describes an optimized design of the femtosecond laser-coated probe described in Embodiment 1. In this embodiment, a gap is left between any two adjacent single-mode silica fibers.

[0046] The optical fiber probe described in this embodiment has a gap between adjacent single-mode silica fibers. A preferred embodiment of the gap is that the gap is designed to be less than one-third of the diameter of the single-mode silica fiber.

[0047] The gap is used to ensure the metal plating process during the fiber optic probe processing, and to cooperate with the upper and lower limiting plates to make each fiber more firmly fixed. At the same time, it can reduce or even avoid optical coupling crosstalk between adjacent fibers, ensuring that the laser can be accurately transmitted to their respective needle tip outlets.

[0048] In practical applications, multiple single-mode silica optical fibers are spaced at equal intervals to achieve uniform transmission of laser energy in the chemical reaction region.

[0049] Implementation Method 3: See Figure 1 and 2 This embodiment describes an optimized design of the femtosecond laser-deposited probe described in Embodiment 1. In this embodiment, the multiple single-mode silica fibers are arranged in a multi-layered circular ring around a single single-mode silica fiber (see [link to previous embodiment]). Figure 2 (as shown), or, the multiple single-mode quartz optical fibers are arranged in a rectangular pattern (see...). Figure 1 (As shown).

[0050] This embodiment limits the arrangement of multiple single-mode quartz optical fibers. In practical applications, the arrangement can be designed according to the regional requirements of the chemical deposition reaction. The arrangement shape is not limited to the circle or rectangle described in this embodiment, but can also be a triangle, a polygon, or even arranged in a row.

[0051] Implementation Method 4: This implementation method is an optimized design of the femtosecond laser-coated probe described in Implementation Method 1. In this implementation method, the metal layer is a metal layer of a single material or a composite metal layer composed of multiple metal material layers stacked together, and the thickness of the metal layer is 5.5-11μm.

[0052] In the optical fiber probe described in this embodiment, the material of the metal layer coated on the single-mode quartz fiber can be selected according to the deposition process requirements. It can be a composite of multiple metal coatings or a single metal coating. The thickness of the metal layer is designed according to actual needs, and can generally be 5.5-11μm.

[0053] The metal layer in this embodiment can be prepared using existing processing techniques. For example, the processing technique employs quartz optical fiber pretreatment, electroless nickel plating, and electrochemical copper plating, including:

[0054] Pretreatment: The fiber bundle is sequentially subjected to processes such as deprotection, degreasing, roughening, heat treatment, sensitization and activation, and degumming to construct a palladium catalytic active layer on the surface of each single-mode quartz fiber;

[0055] Electroless nickel plating: The pretreated optical fiber bundle is plated with nickel on the palladium catalyst layer to form a nickel plating layer with a thickness of 0.5-1μm.

[0056] Electrochemical copper plating: When the nickel plating layer on the surface of the optical fiber bundle is not satisfactory for use, electrochemical copper plating can be performed on the basis of the nickel plating layer, with a thickness of 5-10μm.

[0057] Insulation coating: After chemical nickel plating, an insulation coating is applied to the surface metal layer of the clamping area in the single-mode quartz fiber of the fiber bundle.

[0058] The following is a specific operating method for the above processing technology:

[0059] Remove the protective layer: Immerse the fiber bundle in concentrated sulfuric acid at room temperature for 10 minutes, take it out, wash it with water, and then immerse it for 3 minutes to remove the surface siloxane resin protective layer.

[0060] Degreasing: Use an acidic degreasing solution containing 100 mL / L sulfuric acid and 5 g / L sodium dodecyl sulfate. Soak at room temperature for 5 minutes, then rinse with deionized water until a uniform water film forms on the surface.

[0061] Roughening: Immerse in a fluorine-containing weak corrosive solution, which contains ammonium fluoride at a concentration of 30 g / L and hydrochloric acid at a concentration of 10 ml / L, soak at room temperature for 10 minutes, wash with water and then blow dry with nitrogen;

[0062] Heat treatment: Keep warm in a 100℃ oven for 10 minutes to remove the surface water film;

[0063] Sensitization and activation: Immerse in colloidal palladium activation solution, which contains palladium chloride at a concentration of 0.25 g / L, stannous chloride at a concentration of 4 g / L, concentrated hydrochloric acid at a concentration of 10 ml / L, and sodium chloride at a concentration of 250 g / L, and soak for 5 min at a temperature of 30°C.

[0064] Degelatinization: Immerse in 50 g / L sodium hydroxide solution, soak at room temperature for 1 min, and rinse with deionized water;

[0065] Electroless nickel plating: The pretreated fiber probe 301 is immersed in an alkaline electroless nickel plating solution with a pH of 8.5-9.5, containing nickel sulfate (25 g / L), sodium hypophosphite (25 g / L), ammonium chloride (30 g / L), sodium citrate (15 g / L), triethanolamine (100 g / L), and thiourea (0.3 mg / L). The solution is kept at 40-50°C for 15-25 minutes to deposit an electroless nickel plating layer with a thickness of 0.5-1 μm and a phosphorus content of 5-7%.

[0066] Electrochemical copper plating: Using a chemically nickel-plated optical fiber bundle as the cathode and a pure copper sheet as the anode, the copper is immersed in an acidic copper plating solution. The solution contains: copper sulfate at a concentration of 200 g / L, sulfuric acid at a concentration of 50 mL / L, chloride at a concentration of 50 mg / L, and brightener at a concentration of 2 g / L. The pH of the solution is 1.5-2.0. Electroplating is performed for 15-20 minutes at a cathode current density of 1-1.2 A / dm² under conditions of 25-30℃ to form a dense copper functional layer. The thickness of the dense copper functional layer is 5-10 μm, covering the surface of the chemically nickel-plated layer, forming a composite metal layer with both high adhesion and high conductivity.

[0067] After the composite metal layer is fabricated, the clamping area of ​​the optical fiber bundle is covered with a SiO2 insulating layer; the insulating layer can be fabricated using the existing PECVD method. Following this process, the fabrication of probe 301 is completed, wherein the outer surface of the probe area used for connection with the organic substrate 303 is a composite conductive layer.

[0068] Implementation Method 5: This implementation method is an optimized design of the femtosecond laser plating probe described in Implementation Method 1. In this implementation method, the radius of curvature of the cone at the end of the detection area is between 5 and 10 μm.

[0069] Implementation Method Six: See Figure 3 , 4 Section 5 describes this embodiment. This embodiment describes a micro / nano localized deposition device based on a femtosecond laser. The device includes: an optical platform 1, a femtosecond laser transmission system, an optical fiber probe 301, a movable reaction cell system 4, an adapter 6, an optical fiber coupler 7, and a gantry device 8.

[0070] The femtosecond laser transmission system and the gantry device 8 are fixed on the optical platform 1; the movable reaction cell system 4 is placed on the optical platform 1 and located below the gantry device 8; the fiber optic probe 301 is fixed on the gantry device 8, and its lower part can extend into the movable reaction cell system 4; the femtosecond laser transmission system is used to generate femtosecond lasers and transmit the femtosecond lasers to the inside of the fiber optic probe 301 through the adapter 6 and the fiber optic coupler 7; a three-electrode system is provided inside the movable reaction cell system 4, and the detection area of ​​the fiber optic probe 301 is the working electrode in the three-electrode system.

[0071] The device described in this embodiment employs a femtosecond laser transmission system. In existing technologies, electrochemical deposition devices often use nanosecond or picosecond lasers for assisted deposition, but these result in a large heat-affected zone, which can easily lead to diffusion in the deposition area and degradation of the substrate material. This invention utilizes a femtosecond laser, a typical representative of ultrafast lasers, which features ultrashort pulse widths and ultra-high peak power. The processing process has no significant thermal effect, and as a cold photon source, it allows for precise control of the micro-area light field environment, providing additional energy for chemical conversion reactions or electrochemical reduction reactions.

[0072] In actual use, the device described in this embodiment emits a laser through a femtosecond laser transmission system and reflects the laser beam onto the fiber coupler 7, which then transmits the laser to the fiber probe 301. The fiber probe 301 has light-guiding properties, which in turn transmits the laser to the movable reaction pool system 4 to achieve deposition.

[0073] Implementation Method Seven: See Figure 3 , 4 Section 9 describes this embodiment. This embodiment is an optimized design of the femtosecond laser-based micro / nano localized deposition device described in Embodiment 6. In this embodiment, the femtosecond laser transmission system includes a laser 201, a beam expander 202, a first reflector 203, an optical climbing frame 204, a first climbing frame reflector 2041, a second climbing frame reflector 2042, and a second reflector 205; the optical climbing frame 204 is used to support the first climbing frame reflector 2041 and the second climbing frame reflector 2042.

[0074] The laser 201 generates a femtosecond laser beam, which is reflected by a reflector 203 to a beam expander 202. After being expanded by the beam expander 202, the beam passes sequentially through a climbing frame reflector 2041, a climbing frame reflector 2042, and a reflector 205 before being emitted into the adapter 6.

[0075] The operation process of the femtosecond laser transmission system described in this embodiment during actual use is as follows:

[0076] When preparing for deposition, turn on the laser 201 and adjust the power to 0.5W (minimum power setting). Adjust the optical path through the fiber coupler 7 to focus the laser onto the needle tip inlet of the fiber probe 301.

[0077] During the deposition process, the laser 201 is adjusted to 5-15W (actual processing power).

[0078] After deposition is complete, turn off laser 201.

[0079] Implementation Method 8: See Figure 6 , 7 This embodiment is an optimized design of the femtosecond laser-based micro / nano localized deposition device described in Embodiment 6. In this embodiment, the micro / nano localized deposition device further includes a probe fixing device, which comprises: an upper limit plate 3021, a lower limit plate 3022, an organic substrate 303, a test circuit board 304, a protective shell 305, and a mounting baffle 306. Both the upper limit plate 3021 and the lower limit plate 3022 are provided with limiting holes. An optical fiber probe 301 sequentially passes through the limiting holes of the upper limit plate 3021 and the lower limit plate 3022. The upper limit plate 3021 is positioned above the protective shell 305, adjacent to the optical fiber coupler 7. The lower limit plate 3021... The mounting plate 3022 is disposed below the protective shell 305, adjacent to the detection area of ​​the fiber optic probe 301; both the organic substrate 303 and the test circuit board 304 are provided with probe through holes, and the detection area of ​​the fiber optic probe 301 is sequentially inserted into the probe through holes of the organic substrate 303 and the test circuit board 304, with the end of the fiber optic probe 301 extending to the bottom of the test circuit board 304; the organic substrate 303, the test circuit board 304, and the mounting baffle 306 are disposed below the protective shell 305, wherein the organic substrate 303 is embedded inside the test circuit board 304, and the mounting baffle 306 is fixedly connected to the bottom of the test circuit board 304.

[0080] The assembly method of the probe fixing device described in this embodiment is as follows:

[0081] The detection area of ​​the fiber optic probe 301 was rinsed with isopropanol and then dried with nitrogen.

[0082] The fiber optic probe 301 is sequentially installed through the lower limiting plate 3022, the test circuit board 304, the organic substrate 303, the protective shell 305, and the upper limiting plate 3021. The conductive contact points between the fiber optic probe 301 and the organic substrate 303 are fixedly connected using conductive silver paste, and the gaps are filled with silicone sealant to ensure reliable connection and effective signal transmission. The organic substrate 303 is embedded above the test circuit board 304. The protective shell 305 covers the lower limiting plate 3022, the organic substrate 303, and the test circuit board 304, and is fixedly connected to the test circuit board 304. The mounting baffle 306 is located at the lower part of the test circuit board 304 and is fixedly connected to any side plate of the protective shell 305. The probe fixing device is then connected to the fiber optic coupler 7 via the adapter 6, and the fiber optic coupler 7 is fixed to the gantry device 8. The electrical signal output terminal of the test circuit board 304 is connected to the working electrode interface of the power supply unit 9.

[0083] The protective shell 305 and the test circuit board 304 are fixedly connected by a threaded connection. A pin hole 3051 and a stepped hole 3052 are respectively provided on the protective shell 305 and the test circuit board 304. The bolt is threaded into the stepped hole 3052. The pin is inserted into the pin hole 3051 to lock the protective shell 305 and the test circuit board 304. Furthermore, the end of the bolt is embedded in the stepped hole 3052 to ensure the flatness of the surface of the protective shell 305.

[0084] The light probe 301 has a detection area extending downwards from the upper surface of the organic substrate 303, and its surface is a metal layer.

[0085] Implementation Method Nine: See Figure 8 This embodiment describes an optimized design of the femtosecond laser-based micro / nano localized deposition device described in Embodiment Six. In this embodiment, the movable reaction cell system 4 includes an electrolytic cell 403 and a three-axis moving platform 404. The three-axis moving platform 404 is used to drive the electrolytic cell 403 to move in three dimensions. The electrolytic cell 403 is internally equipped with an auxiliary electrode and an optional Ag / AgCl reference electrode 402. The auxiliary electrode, the Ag / AgCl reference electrode 402, and the detection area of ​​the fiber optic probe 301 constitute the three-electrode system of the electrolytic cell 403.

[0086] In this embodiment, the mobile reaction tank system 4 is controlled by an existing power supply unit 9 for controlling the reaction tank system during the electrochemical deposition process.

[0087] In actual operation: the deposition solution is injected into the electrolytic cell 403, and then the electrolytic cell 403 is slowly raised by controlling the three-axis moving platform 404. During the raising process, the distance between the tip of the fiber optic probe 301 and the surface of the deposition substrate is calibrated in real time to a range of 2μm to 5μm. The control method can be achieved using existing technology.

[0088] In order to observe the internal state of the electrolytic cell 403 in real time, a miniature light source can be installed in the electrolytic cell 403 to provide background illumination in practical applications. At this time, the image information inside the electrolytic cell 403 can be clearly captured by the camera device and transmitted to the computer screen, so that the operator can clearly observe the position of the spot formed by the femtosecond laser at the needle tip, and then set the process parameters.

[0089] When performing electrochemical deposition, the deposition parameters are set on the control software of the power supply unit 9: the deposition voltage is set to 0.6V to 1.0V (relative to the Ag / AgCl reference electrode), and the deposition current range is set to 8mA to 12mA.

[0090] When chemical conversion deposition is carried out, reaction monitoring parameters are set on the control software of power supply unit 9: the solution temperature in electrolytic cell 403 is maintained at 40℃ to 50℃ by an external thermostat, and the solution pH value is monitored and maintained at 8.5-9.5.

[0091] After setting the parameters, adjust the output power of laser 201 to the range of 5W to 15W required for actual processing, and begin deposition.

[0092] After deposition is complete, the three-axis moving platform 404 drives the moving reaction tank system 4 to descend and move away from the probe fixing device until the deposited part can be removed. The deposited part is then removed and its surface is rinsed with isopropanol and deionized water in sequence to complete the processing.

[0093] Implementation Method 10: See Figure 7 and 8 This embodiment is an optimized design of the femtosecond laser-based micro / nano localized deposition device described in Embodiment Six. In this embodiment, the device further includes a tuning fork 307, which faces away from the fiber optic probe, is fixedly mounted on the baffle 306, and its lower surface is located in the horizontal plane where the probe end of the fiber optic probe is located.

[0094] The device described in this embodiment is equipped with a tuning fork 307, which is made of quartz material and has a natural resonant frequency of 32.768kHz. It is the core component for precise control of the interpole spacing and can provide real-time feedback on the distance information between the probe and the deposition substrate by the resonant frequency disturbance caused by the change in spacing.

[0095] The tuning fork 307 is fixed to the mounting baffle 306. Theoretically, the lower surface of the tuning fork 307 should be located in the horizontal plane where the detection end of the light probe 301 is located. In practical applications, there is an error in the detection of the tuning fork, which should be within ±0.01mm. In practical applications, the tuning fork 307 is set on the mounting baffle 306 to ensure that it does not obstruct the imaging light path.

[0096] In existing technologies, position monitoring in the field of electrochemical deposition often employs the current feedback method. However, in practice, the current feedback method often relies on specific redox pairs in the reaction medium, and its deposition is often limited to large flat surfaces, making predictions inaccurate for rough, porous, and heterogeneous surfaces. The tuning fork monitoring device described in this invention, on the other hand, senses the extremely weak interaction force between the probe tip and the deposition substrate by monitoring minute changes in the tuning fork's resonant frequency, thereby calculating the distance. This overcomes the limitations of existing technologies regarding the deposition substrate and solution, making it applicable to a wider range of deposition scenarios.

Claims

1. A femtosecond laser-coated probe, characterized in that: The femtosecond laser-coated probe includes multiple single-mode silica optical fibers arranged parallel to each other; the single-mode silica optical fibers are divided into a clamping region and a detection region along the axial direction, and the end of the detection region of the single-mode silica optical fiber is tapered; the outer surface of the single-mode silica optical fiber is covered with a metal layer; and an insulating coating is also provided outside the surface metal layer of the clamping region of the single-mode silica optical fiber.

2. The femtosecond laser deposition probe according to claim 1, characterized in that: In the multiple single-mode silica optical fibers, a gap is left between any two adjacent single-mode silica optical fibers.

3. The femtosecond laser deposition probe according to claim 1, characterized in that: The multiple single-mode silica optical fibers are arranged in a multi-layered circular ring with one single-mode silica optical fiber as the center, or the multiple single-mode silica optical fibers are arranged in a rectangular pattern.

4. The femtosecond laser deposition probe according to claim 1, characterized in that: The metal layer is a single-material metal layer or a composite metal layer composed of multiple metal material layers stacked together, and the thickness of the metal layer is 5.5-11 μm.

5. The femtosecond laser deposition probe according to claim 1, characterized in that, The radius of curvature of the cone at the end of the detection area is between 5 and 10 μm.

6. A micro / nano localized deposition device based on femtosecond laser, characterized in that: The device includes: an optical platform (1), a femtosecond laser transmission system, an optical fiber probe (301), a movable reaction cell system (4), an adapter (6), an optical fiber coupler (7), and a gantry device (8). The femtosecond laser transmission system and the gantry device (8) are fixed on the optical platform (1); the movable reaction cell system (4) is placed on the optical platform (1) and located below the gantry device (8); the fiber probe (301) is fixed on the gantry device (8), and its lower part can extend into the movable reaction cell system (4); the femtosecond laser transmission system is used to generate femtosecond lasers and transmit the femtosecond lasers to the inside of the fiber probe (301) through the adapter (6) and the fiber coupler (7); the movable reaction cell system (4) is provided with a three-electrode system, and the detection area of ​​the fiber probe (301) is the working electrode in the three-electrode system; The fiber optic probe (301) is the femtosecond laser plating probe as described in any one of claims 1 to 5.

7. The micro / nano localized deposition device based on femtosecond laser according to claim 6, characterized in that: The femtosecond laser transmission system includes a laser (201), a beam expander (202), a first reflector (203), an optical climbing frame (204), a first climbing frame reflector (2041), a second climbing frame reflector (2042), and a second reflector (205); the optical climbing frame (204) is used to support the first climbing frame reflector (2041) and the second climbing frame reflector (2042). The laser (201) generates a femtosecond laser beam, which is reflected by a reflector (203) to a beam expander (202). After being expanded by the beam expander (202), the beam passes through a climbing frame reflector (2041), a climbing frame reflector (2042), and a reflector (205) in sequence before being emitted into the adapter (6).

8. The micro / nano localized deposition device based on femtosecond laser according to claim 6, characterized in that: The micro / nano localized deposition device further includes a probe fixing device, which comprises: an upper limit plate (3021), a lower limit plate (3022), an organic substrate (303), a test circuit board (304), a protective shell (305), and a mounting baffle (306). Both the upper limit plate (3021) and the lower limit plate (3022) are provided with limiting holes. An optical fiber probe (301) passes sequentially through the limiting holes of the upper limit plate (3021) and the lower limit plate (3022). The upper limit plate (3021) is positioned above the protective shell (305) near the optical fiber coupler (7), and the lower limit plate (3022) is positioned below the protective shell (305) near the optical fiber coupler (7). The detection area of ​​the fiber optic probe (301) is located near the test area of ​​the organic substrate (303) and the test circuit board (304). Probe through holes are provided on both the organic substrate (303) and the test circuit board (304). The detection area of ​​the fiber optic probe (301) is inserted into the probe through holes of the organic substrate (303) and the test circuit board (304) in sequence. The end of the fiber optic probe (301) extends to the bottom of the test circuit board (304). The organic substrate (303), the test circuit board (304) and the mounting baffle (306) are located below the protective shell (305). The organic substrate (303) is embedded inside the test circuit board (304), and the mounting baffle (306) is fixedly connected to the bottom of the test circuit board (304).

9. The micro / nano localized deposition device based on femtosecond laser according to claim 6, characterized in that: The movable reaction pool system (4) includes an electrolytic cell (403) and a three-axis moving platform (404); the three-axis moving platform (404) is used to drive the electrolytic cell (403) to move in three dimensions. The electrolytic cell (403) is provided with an auxiliary electrode and an Ag / AgCl reference electrode (402). The detection areas of the auxiliary electrode, the Ag / AgCl reference electrode (402) and the optical fiber probe (301) constitute the three-electrode system of the electrolytic cell (403).

10. The micro / nano localized deposition device based on femtosecond laser according to claim 6, characterized in that: The device also includes a tuning fork (307), which faces away from the fiber optic probe (301) and is fixedly mounted on the baffle (306), and its lower surface is located in the horizontal plane where the detection end of the fiber optic probe (301) is located.

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