A meniscus-confined electrochemical deposition device based on a sealed nozzle electrode and a microstructure preparation method

Abstract

The application discloses a meniscus confined electrochemical deposition device based on a sealed nozzle electrode and a microstructure preparation method, which comprises an air pressure liquid supply module, a sealed nozzle electrode assembly, a motion positioning module, a cathode bearing module, an electrochemical deposition module and an online monitoring module. The sealed nozzle electrode assembly integrates a platinum wire anode, a glass capillary nozzle, a T-shaped three-way plug valve, a liquid supply channel and a composite sealing structure. During preparation, a meniscus liquid bridge is established between the nozzle and the conductive substrate through a contact-back-off mode, deposition is carried out under a constant current condition, and the nozzle is synchronously pulled up, and the deposition state is monitored and adjusted in combination with a liquid bridge image and a deposition voltage. The application can improve the sealing reliability and the liquid bridge construction stability of the nozzle electrode, and can enhance the online monitoring and adjustment capability of the microstructure deposition process.

Description

Technical Field

[0001] This invention relates to the fields of micro-nano additive manufacturing and electrochemical deposition technology, and in particular to a curved liquid surface confined electrochemical deposition device and microstructure preparation method based on a sealed nozzle electrode. Background Technology

[0002] Meniscus confined electrochemical deposition is a fabrication method that utilizes a microscale electrolyte bridge formed between a micro-nozzle and a conductive substrate to confine the electrochemical reaction to a localized area. The relative movement between the nozzle and the deposited structure enables the additive manufacturing of metal microstructures. This method features high material utilization, requires no mask, and can fabricate micron- or nanoscale metal structures.

[0003] In meniscus-confined electrochemical deposition, the installation position of the electrode inside the nozzle, the continuity of electrolyte supply, the sealing of the pipeline, the relative position between the nozzle and the conductive substrate, and the stability of the liquid bridge in the meniscus all affect the deposition process. Existing experimental setups typically consist of a liquid supply mechanism, micro-nozzles, a motion platform, a power supply, and observation devices, all built separately. The lack of a unified structural connection and positioning benchmark between these modules easily leads to problems such as electrode misalignment inside the nozzle, gas or liquid leakage in the pipeline, fluctuations in the liquid supply, and difficulty in repositioning after nozzle replacement.

[0004] Furthermore, establishing liquid bridges on curved surfaces typically requires manual control of the nozzle or substrate proximity, making it difficult to stably reproduce the bridge gaps. The continuous growth of the deposited structure also alters the distance between the nozzle and the deposition interface; if the nozzle pull-up speed does not match the deposition growth rate, it can easily lead to excessive stretching of the liquid bridge, nozzle contact with the deposition structure, or liquid bridge breakage. When judging the deposition state solely through microscopic images, it is also difficult to promptly identify anomalies such as insufficient local ion supply, concentration polarization, or dendrite initiation. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide a curved surface confined electrochemical deposition device and a microstructure preparation method based on a sealed nozzle electrode, which can improve the sealing reliability of the nozzle electrode and the stability of liquid bridge construction, and enhance the online monitoring and regulation capability of the microstructure deposition process.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: a meniscus-confined electrochemical deposition device based on a sealed nozzle electrode, comprising a liquid supply module, a sealed nozzle electrode assembly, a motion positioning module, a cathode support module, an electrochemical deposition module, and an online monitoring module; The liquid supply module is connected to the sealed nozzle electrode assembly (4) and is used to deliver electrolyte to the nozzle outlet of the sealed nozzle electrode assembly (4); the sealed nozzle electrode assembly (4) includes a glass capillary nozzle (49), a three-way stopcock valve (46), a platinum wire (44) and a conductive connecting wire (41). The platinum wire (44) is arranged along the axial direction of the glass capillary nozzle (49), and the lower end of the platinum wire (44) is located near the outlet of the glass capillary nozzle (49). The motion positioning module is used to adjust and drive the movement of the sealed nozzle electrode assembly (4), and the cathode support module is used to install the conductive substrate (7) and adjust the distance between the conductive substrate (7) and the glass capillary nozzle (4). The electrochemical deposition module is electrically connected to the platinum wire (44) and the conductive substrate (7) respectively. A curved liquid bridge is formed between the glass capillary nozzle (49) and the conductive substrate (7). The online monitoring module is used to observe the curved liquid bridge and the deposition structure (13) and record the electrical signals during the deposition process.

[0007] In a preferred embodiment, the sealed nozzle electrode assembly (4) is provided axially with a first combined connecting pipe (43), a three-way stopcock valve (46), a second combined connecting pipe (48), and a glass capillary nozzle (49). The lateral interface of the three-way stopcock valve (46) is connected to the liquid supply module. The two ends of the three-way stopcock valve (46) are respectively connected to the first combined connecting pipe (43) and the second combined connecting pipe (48). The platinum wire (44) passes through the three-way stopcock valve (46) and the second combined connecting pipe (48) to reach the glass capillary nozzle (49). The lower end of the platinum wire (44) does not extend out of the glass capillary nozzle outlet. The upper end of the platinum wire (44) is connected to one end of a conductive connecting wire (41). The other end of the conductive connecting wire (41) passes through the first combined connecting pipe (43) and is connected to an external wire (410).

[0008] In a preferred embodiment, the sealed nozzle electrode assembly (4) further includes epoxy resin sealant (42); the epoxy resin sealant (42) is provided at the positions where the conductive connecting wire (41) extends out of the first combined connecting tube (43), at the positions where the platinum wire (44) extends out of both ends of the three-way stopcock valve (46), and at the positions where the platinum wire (44) extends out of both ends of the second combined connecting tube (48).

[0009] In a preferred embodiment, the motion positioning module includes a three-dimensional displacement platform (5), a stepper motor (6), and a controller (1); the controller (1) is connected to the stepper motor (6), the stepper motor (6) is connected to the three-dimensional displacement platform (5), and the three-dimensional displacement platform (5) is connected to the sealed nozzle electrode assembly (4).

[0010] In a preferred embodiment, the cathode support module is specifically a substrate lifting platform (8), including a coarse adjustment lifting mechanism and a fine adjustment lifting mechanism, for adjusting the height of the conductive substrate (7).

[0011] In a preferred embodiment, the online monitoring module includes a CCD microscope (9) and a display (10); the CCD microscope (9) is connected to the display (10).

[0012] In a preferred embodiment, the electrochemical deposition module is specifically a DC voltage / current source meter (11) with constant current output and voltage recording function; the external wire (410) is connected to one end of the DC voltage / current source meter (11), and the other end of the DC voltage / current source meter (11) is connected to the conductive substrate (7) through a wire.

[0013] In a preferred embodiment, the liquid supply module includes a two-stage gas pressure control device (2) and a copper sulfate electrolyte storage bottle (3); the copper sulfate electrolyte storage bottle (3) is connected to the sealed nozzle electrode assembly (4) via a pipeline.

[0014] The present invention also provides a method for preparing microstructures by meniscus confined electrochemical deposition using a meniscus confined electrochemical deposition device based on a sealed nozzle electrode, comprising the following steps: Step 1: Deliver the electrolyte to the vicinity of the outlet of the glass capillary nozzle (49) and adjust the relative position of the glass capillary nozzle (49) and the conductive substrate (7); Step 2: Make the conductive substrate (7) come into contact with the electrolyte at the outlet of the glass capillary nozzle (49) to form a liquid bridge, and then make the conductive substrate (7) retreat in a direction away from the glass capillary nozzle (49) to establish a stable curved liquid bridge. Step 3: Using a platinum wire (44) as the anode and a conductive substrate (7) as the cathode, electrochemical deposition is carried out under constant current conditions, and the glass capillary nozzle (49) is driven to move along the deposition growth direction. Step 4: Observe the liquid bridge and deposition structure on the curved surface, record the deposition voltage, and adjust the relative position of the glass capillary nozzle (49) and the conductive substrate (7) according to the liquid bridge morphology and deposition voltage.

[0015] In a preferred embodiment, when the meniscus shows a significant tendency to stretch, shift, or break, or when the deposition voltage shows an abnormal increase or sudden change, the constant current output and / or nozzle movement are paused, and a stable meniscus is re-established by adjusting the position of the nozzle or conductive substrate.

[0016] Compared with the prior art, the present invention has the following beneficial effects: The present invention integrates the liquid supply channel, platinum wire anode and capillary nozzle into a sealed nozzle electrode assembly, and adopts a combination of threaded sealing and sealant to improve the sealing performance and installation stability of the nozzle electrode.

[0017] This invention achieves position adjustment between the nozzle and the conductive substrate through a motion positioning module and a cathode support module, and establishes a liquid bridge using a contact-retraction method, which helps to improve the repeatability of constructing liquid bridges on curved liquid surfaces.

[0018] This invention can drive the nozzle to move along the microstructure growth direction during the deposition process, reducing the risk of excessive stretching of the liquid bridge or contact between the nozzle and the deposited structure.

[0019] This invention uses a combination of microscopic images and deposition voltage to monitor the deposition state, which facilitates timely identification of liquid bridge instability and abnormal deposition, thereby improving the controllability of the microstructure preparation process. Attached Figure Description

[0020] Figure 1 This is a schematic diagram of the overall structure of the confined electrochemical deposition device for the meniscus of the present invention; Figure 2 This is a schematic diagram of the overall structure of the sealed nozzle electrode assembly of the present invention; Figure 3 This is a partial enlarged view of the tip of the sealed nozzle electrode assembly of the present invention; Figure 4 This is a schematic diagram showing the relative positions of the glass capillary nozzle, the curved liquid bridge, and the conductive substrate of the present invention. Figure 5 This is a flowchart of the method for preparing microstructures by confined electrochemical deposition of the meniscus according to the present invention; Figure 6 and Figure 7 These are typical experimental images of microstructures prepared using the apparatus of this invention. Detailed Implementation

[0021] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0022] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of this application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.

[0023] It should be noted that the terminology used herein is for the purpose of describing particular implementations only and is not intended to limit the exemplary implementations according to this application; as used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise; furthermore, it should be understood that when the terms “comprising” and / or “including” are used in this specification, they indicate the presence of features, steps, operations, devices, components and / or combinations thereof.

[0024] like Figure 1-7 As shown, the sealed nozzle electrode assembly 4 is fixed to the three-dimensional displacement platform 5, and the glass capillary nozzle 49 is positioned vertically downwards. The three-dimensional displacement platform 5 is connected to the stepper drive mechanism 6, which is controlled by the controller 1.

[0025] ITO conductive glass is used as the conductive substrate 7 and fixed to the substrate lifting platform 8. The substrate lifting platform 8 includes a coarse adjustment knob and a fine adjustment knob for controlling the vertical movement of the conductive substrate 7.

[0026] A CCD microscope 9 is positioned on one side of the glass capillary nozzle 49 and the conductive substrate 7, and its focal length is adjusted so that the nozzle outlet and the meniscus formation area are within a clear field of view. A microscopic imaging device 9 is also positioned on one side of the glass capillary nozzle 49 and the conductive substrate 7, and its focal length is adjusted so that the nozzle outlet and the meniscus formation area are within a clear field of view. The microscopic imaging device 9 is connected to a display 10 for real-time display and storage of experimental images.

[0027] The positive terminal of the DC voltage / current source meter 11 is connected to the copper wire 410, and the negative terminal is connected to the ITO conductive glass. The secondary pneumatic control device 2 is connected to the T-type three-way stopcock valve 46 via the infusion tube 3.

[0028] like Figure 2 and Figure 3 As shown, the sealed nozzle electrode assembly 4 includes, from bottom to top along the axial direction, a glass capillary nozzle 49, a second combined connecting pipe 48, a second threaded connector 47, a T-type three-way stopcock valve 46, a first threaded connector 45, a first combined connecting pipe 43, and a copper wire 41.

[0029] Platinum wire 44 is selected as the anode and is sequentially passed through the first combined connecting pipe 43, the first threaded connector 45, the T-type three-way stopcock valve 46, the second threaded connector 47, and the second combined connecting pipe 48, with its lower end extending into the lower part of the inner cavity of the glass capillary nozzle 49. The lower end of the platinum wire 44 is positioned close to the outlet of the glass capillary nozzle 49, but does not enter the narrowing channel at the nozzle tip, to avoid clogging the nozzle outlet and to ensure that the electrolyte can be smoothly delivered to the nozzle outlet.

[0030] The upper end of the platinum wire 44 is in close contact with the copper wire 41 to form an electrical connection. The copper wire 41 extends from the upper end of the first combined connecting tube 43 and is welded to the external wire 410, which is used to connect to the positive terminal of the DC voltage / current source meter 11. The welding and wire lead-out positions are fixed and sealed with epoxy resin sealant 42 to prevent axial or radial displacement of the platinum wire and to improve the stability of the conductive connection.

[0031] The side port of the T-type three-way stopcock valve 46 is used as the electrolyte inlet and connected to the infusion tube 3. Polytetrafluoroethylene sealing tape is wrapped around each threaded connection position; the assembly gap between the glass capillary nozzle 49 and the second combined connecting tube 48, as well as other non-threaded connection gaps, are fully filled with epoxy resin sealant 42, which forms a sealant layer after curing.

[0032] In this embodiment, the platinum wire diameter is 0.05 mm, and the inner diameter of the glass capillary nozzle outlet is approximately 15 μm. These specific dimensions can also be adjusted according to the target microstructure size and liquid supply requirements.

[0033] Prepare a copper sulfate electrolyte solution and add it to the storage container of the supply module. Activate the secondary pressure control device 2 to allow the copper sulfate electrolyte solution in the storage bottle 3 to enter the sealed nozzle electrode assembly 4. When the copper sulfate electrolyte tip moves close to the outlet of the glass capillary nozzle 49 and has not yet dripped naturally, reduce the supply pressure to maintain a stable electrolyte level at the nozzle outlet.

[0034] The horizontal position of the glass capillary nozzle 49 is adjusted using the three-dimensional displacement platform 5 so that the nozzle outlet is located in the center of the observation area of ​​the CCD microscope 9. The position of the ITO conductive glass is adjusted using the substrate lifting stage 8 so that it is directly below the nozzle outlet.

[0035] The contact-retraction method is used to establish the liquid bridge 12 on the curved surface: First, the conductive substrate 7 is slowly raised by the substrate lifting platform 8 so that it comes into contact with the electrolyte at the outlet of the glass capillary nozzle 49; after observing that a liquid bridge is formed between the nozzle and the conductive substrate 7, the conductive substrate 7 is retracted downwards by a suitable distance, thereby forming a stable liquid bridge 12 on the curved surface.

[0036] After the liquid bridge 12 is established, check the connection status of the electrodes and wires. Set the DC voltage / current source meter 11 to constant current mode and apply a constant current between the platinum wire 44 and the conductive substrate 7 to reduce copper ions in the electrolyte on the surface of the conductive substrate 7 and form deposited microstructures 13.

[0037] In this embodiment, the constant current is set to 2μA, 3μA, 4μA, or 5μA. During the deposition process, the stepping drive mechanism 6 drives the glass capillary nozzle 49 to move vertically upward at a speed of 146 nm / s, so that a liquid bridge connection is maintained between the nozzle outlet and the top of the deposition structure.

[0038] The CCD microscope 9 acquires real-time data on the morphology of the meniscus liquid bridge 12 and the deposition structure 13, while the DC voltage / current source meter 11 records the deposition voltage simultaneously. When the meniscus liquid bridge 12 is observed to be excessively stretched, significantly offset, or showing a tendency to break, the stepping drive mechanism 6 and / or constant current output are paused, and the relative position of the glass capillary nozzle 49 and the conductive substrate 7 is adjusted via the three-dimensional displacement platform 5 or the substrate lifting platform 8. After the meniscus liquid bridge 12 stabilizes, the deposition process is restarted. When the deposition voltage shows an abnormally rapid increase or abrupt change, the deposition is paused, and the liquid bridge status and deposition structure morphology are checked.

[0039] In this embodiment, the deposition time is 30 minutes. Deposition is stopped prematurely if rapid dendrite growth, liquid bridge breakage, or contact between the deposited structure and the nozzle occurs during the deposition process.

Claims

1. A meniscus-confined electrochemical deposition apparatus based on a sealed nozzle electrode, characterized in that, It includes a liquid supply module, a sealed nozzle electrode assembly, a motion positioning module, a cathode support module, an electrochemical deposition module, and an online monitoring module; The liquid supply module is connected to the sealed nozzle electrode assembly (4) and is used to deliver electrolyte to the nozzle outlet of the sealed nozzle electrode assembly (4); the sealed nozzle electrode assembly (4) includes a glass capillary nozzle (49), a three-way stopcock valve (46), a platinum wire (44) and a conductive connecting wire (41). The platinum wire (44) is arranged along the axial direction of the glass capillary nozzle (49), and the lower end of the platinum wire (44) is located near the outlet of the glass capillary nozzle (49). The motion positioning module is used to adjust and drive the movement of the sealed nozzle electrode assembly (4), and the cathode support module is used to install the conductive substrate (7) and adjust the distance between the conductive substrate (7) and the glass capillary nozzle (4). The electrochemical deposition module is electrically connected to the platinum wire (44) and the conductive substrate (7) respectively. A curved liquid bridge is formed between the glass capillary nozzle (49) and the conductive substrate (7). The online monitoring module is used to observe the curved liquid bridge and the deposition structure (13) and record the electrical signals during the deposition process.

2. The meniscus-confined electrochemical deposition apparatus based on a sealed nozzle electrode according to claim 1, characterized in that, The sealed nozzle electrode assembly (4) is arranged axially in sequence as a first combined connecting pipe (43), a three-way stopcock valve (46), a second combined connecting pipe (48), and a glass capillary nozzle (49). The side interface of the three-way stopcock valve (46) is connected to the liquid supply module. The two ends of the three-way stopcock valve (46) are respectively connected to the first combined connecting pipe (43) and the second combined connecting pipe (48). The platinum wire (44) passes through the three-way stopcock valve (46) and the second combined connecting pipe (48) to reach the glass capillary nozzle (49). The lower end of the platinum wire (44) does not extend out of the glass capillary nozzle outlet. The upper end of the platinum wire (44) is connected to one end of a conductive connecting wire (41). The other end of the conductive connecting wire (41) passes through the first combined connecting pipe (43) and is connected to an external wire (410).

3. The meniscus-confined electrochemical deposition apparatus based on a sealed nozzle electrode according to claim 1, characterized in that, The sealed nozzle electrode assembly (4) also includes epoxy resin sealant (42); the epoxy resin sealant (42) is provided at the positions where the conductive connecting wire (41) extends out of the first combined connecting tube (43), the positions where the platinum wire (44) extends out of both ends of the three-way stop valve (46), and the positions where the platinum wire (44) extends out of both ends of the second combined connecting tube (48).

4. The meniscus-confined electrochemical deposition apparatus based on a sealed nozzle electrode according to claim 1, characterized in that, The motion positioning module includes a three-dimensional displacement platform (5), a stepper motor (6), and a controller (1); the controller (1) is connected to the stepper motor (6), the stepper motor (6) is connected to the three-dimensional displacement platform (5); the three-dimensional displacement platform (5) is connected to the sealed nozzle electrode assembly (4).

5. The meniscus-confined electrochemical deposition apparatus based on a sealed nozzle electrode according to claim 1, characterized in that, The cathode support module is specifically a substrate lifting platform (8), which includes a coarse adjustment lifting mechanism and a fine adjustment lifting mechanism for adjusting the height of the conductive substrate (7).

6. The meniscus-confined electrochemical deposition apparatus based on a sealed nozzle electrode according to claim 1, characterized in that, The online monitoring module includes a CCD microscope (9) and a display (10); the CCD microscope (9) is connected to the display (10).

7. The meniscus-confined electrochemical deposition apparatus based on a sealed nozzle electrode according to claim 1, characterized in that, The electrochemical deposition module is specifically a DC voltage / current source meter (11) with constant current output and voltage recording function; the external wire (410) is connected to one end of the DC voltage / current source meter (11), and the other end of the DC voltage / current source meter (11) is connected to the conductive substrate (7) through a wire.

8. The meniscus-confined electrochemical deposition apparatus based on a sealed nozzle electrode according to claim 1, characterized in that, The liquid supply module includes a two-stage gas pressure control device (2) and a copper sulfate electrolyte storage bottle (3); the copper sulfate electrolyte storage bottle (3) is connected to the sealed nozzle electrode assembly (4) through a pipeline.

9. A method for preparing meniscus-confined electrochemical deposition microstructures using a meniscus-confined electrochemical deposition apparatus based on a sealed nozzle electrode as described in any one of claims 1 to 8, characterized in that, Includes the following steps: Step 1: Deliver the electrolyte to the vicinity of the outlet of the glass capillary nozzle (49) and adjust the relative position of the glass capillary nozzle (49) and the conductive substrate (7); Step 2: Make the conductive substrate (7) come into contact with the electrolyte at the outlet of the glass capillary nozzle (49) to form a liquid bridge, and then make the conductive substrate (7) retreat in a direction away from the glass capillary nozzle (49) to establish a stable curved liquid bridge. Step 3: Using a platinum wire (44) as the anode and a conductive substrate (7) as the cathode, electrochemical deposition is carried out under constant current conditions, and the glass capillary nozzle (49) is driven to move along the deposition growth direction. Step 4: Observe the liquid bridge and deposition structure on the curved surface, record the deposition voltage, and adjust the relative position of the glass capillary nozzle (49) and the conductive substrate (7) according to the liquid bridge morphology and deposition voltage.

10. The method for preparing a meniscus-confined electrochemical deposition microstructure based on a sealed nozzle electrode according to claim 9, characterized in that, When the meniscus shows obvious stretching, displacement or breakage, or when the deposition voltage rises or changes abruptly, the constant current output and / or nozzle movement are paused, and a stable meniscus is re-established by adjusting the position of the nozzle or conductive substrate.

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