阅读说明：本技术 一种激光增强三维微区电沉积方法及其对应的装置 (Laser-enhanced three-dimensional micro-area electrodeposition method and corresponding device ) 是由 朱国栋 龚大卫 于 2019-09-11 设计创作，主要内容包括：本发明提供了一种激光增强三维微区电沉积方法,其将激光辐照集成到基于微管的微区电沉积装置中,获得提升的沉积速率。电解液腔体和微管内灌注电解液,经由平移台调控使得微管尖端逼近试样表面,微管尖端液滴在试样表面形成的弯月面、进而限制了液滴在试样表面的扩散,利于电沉积加工精度的控制；通过微管内电解质接正电位、导电试样表面为负电位,使得电沉积过程发生；激光辐照在液滴与试样的接触面上,激光热效应提高电解液中电子转移效率,加速电化学平衡电位向正向偏移并引起液滴内局部涡流搅拌,从而加速了电沉积过程；根据预设图案,协同调控电控平移台运动,实现微管和试样表面的三维相对移动。(the invention provides a laser-enhanced three-dimensional micro-area electrodeposition method, which integrates laser irradiation into a micro-area electrodeposition device based on a micro-tube to obtain an improved deposition rate. Electrolyte is filled in the electrolyte cavity and the microtube, the tip of the microtube approaches the surface of the sample through the regulation and control of the translation table, and the liquid drops at the tip of the microtube form a meniscus on the surface of the sample, so that the diffusion of the liquid drops on the surface of the sample is limited, and the control of the electro-deposition processing precision is facilitated; the electrolyte in the microtube is connected with a positive potential, and the surface of the conductive sample is a negative potential, so that the electrodeposition process occurs; laser is irradiated on the contact surface of the liquid drop and the sample, the laser heat effect improves the electron transfer efficiency in the electrolyte, and accelerates the forward deviation of the electrochemical equilibrium potential and causes local vortex stirring in the liquid drop, thereby accelerating the electrodeposition process; and cooperatively regulating and controlling the motion of the electric control translation stage according to a preset pattern to realize the three-dimensional relative movement of the microtube and the surface of the sample.)

1. a laser-enhanced three-dimensional micro-area electrodeposition method is characterized in that: electrolyte is filled in the electrolyte cavity and the microtube, the tip of the microtube approaches the surface of the sample through the regulation and control of the translation table, and the liquid drops at the tip of the microtube form a meniscus on the surface of the sample, so that the diffusion of the liquid drops on the surface of the sample is limited, and the control of the electro-deposition processing precision is facilitated; the electrolyte in the microtube is connected with a positive potential, and the surface of the conductive sample is a negative potential, so that the electrodeposition process occurs; laser is irradiated on the contact surface of the liquid drop and the sample, the laser heat effect improves the electron transfer efficiency in the electrolyte, and accelerates the forward deviation of the electrochemical equilibrium potential and causes local vortex stirring in the liquid drop, thereby accelerating the electrodeposition process; and cooperatively regulating and controlling the motion of the electric control translation stage according to a preset pattern to realize the three-dimensional relative movement of the microtube and the surface of the sample so as to generate a three-dimensional micro-nano scale pattern.

2. The laser-enhanced three-dimensional micro-area electrodeposition method of claim 1, wherein: selecting a suitable laser light source according to working conditions, wherein the suitable laser light source specifically comprises but is not limited to ultraviolet light, visible light or infrared light; the light beam emitted by the light source is reflected by the reflector and converged by the lens and then is irradiated on the contact surface between the liquid drop at the tip of the microtube and the sample or the contact surface between the liquid drop and the deposited copper layer.

3. The laser-enhanced three-dimensional micro-area electrodeposition method of claim 1, wherein: when the micro-tube approaches the surface of the sample, the approach degree is judged by the aid of an optical microscope, after the tip of the micro-tube is connected with the surface of the sample through the electrolyte liquid drop, a meniscus is formed on two sides of the liquid drop under the action of surface tension due to the hydrophilicity of the surface of the sample, and meanwhile, the meniscus is limited to diffuse along the surface of the sample due to the action of the surface tension of the liquid drop, so that the electro-deposition is guaranteed to have high enough geometric resolution and fine enough machining size.

4. The laser-enhanced three-dimensional micro-area electrodeposition method of claim 1, wherein: the micro-tube is a commercialized capillary tube with various inner diameters ranging from dozens of micrometers to hundreds of micrometers, and specifically comprises but is not limited to materials of metal, common glass and quartz glass; the capillary tube with smaller inner diameter is prepared by drawing one end of the formed capillary tube again, so that the inner diameter of the pipe orifice of the capillary tube for dropping liquid is reduced, and the processing precision of electrodeposition is improved.

5. The laser-enhanced three-dimensional micro-area electrodeposition method of claim 1, wherein: the laser irradiation position keeps relatively static relative to the dropping liquid position of the capillary, and the laser irradiation position moves synchronously with the capillary when the capillary moves; during the electrodeposition process, the dropping position of the capillary and the surface of the sample are relatively moved.

6. the laser-enhanced three-dimensional micro-area electrodeposition method of claim 1, wherein: a micro-injection pump is externally connected in the space, used for containing the electrolyte, of the micro-tube, and the outflow rate of the electrolyte in the capillary tube can be accurately adjusted through adjustment and control of the propelling rate of the injection pump, so that the electrodeposition rate and the machining precision are adjusted and controlled.

7. A laser-enhanced three-dimensional micro-area electrodeposition device is characterized in that: the micro-tube micro-injection machining device comprises an electric control translation table, a displacement controller, an ammeter, a voltage source, a computer, a laser, a micro-tube, an electrolyte cavity, a micro-injection pump, an optical element and a sample placing table, wherein a sample is placed on the sample placing table, a liquid drop outlet of the micro-tube is arranged right above the sample, the electric control translation table and the displacement controller control the micro-tube and the sample placed on the sample placing table to move in relative positions, a liquid inlet at the upper part of the micro-tube is connected with the electrolyte cavity, the injection pump is arranged on the electrolyte cavity, the computer controls the displacement controller to drive the electric control translation table to act, the computer is respectively connected with the ammeter and the voltage source, the ammeter is connected with electrolyte positioned in the micro-tube through a conductor, the ammeter is connected with the anode of the voltage source, and the cathode or the, the laser beam emitted by the laser generates a converged beam through the optical element to be incident on the to-be-processed area of the sample.

8. The laser-enhanced three-dimensional micro-area electrodeposition device according to claim 7, wherein: the electric control translation stage is specifically a one-dimensional translation stage, a two-dimensional translation stage or a three-dimensional translation stage, the electric control translation stage is used for regulating and controlling the movement of a sample or regulating and controlling the movement of a micro tube, when the electric control translation stage is of a split structure, part of the translation stage is connected with the micro tube, part of the translation stage is connected with the sample, and the micro tube and the sample move relatively during working.

9. the laser-enhanced three-dimensional micro-area electrodeposition device according to claim 7, wherein: when the electric control translation stage is used for controlling the movement of a sample, the sample placing stage is the electric control translation stage, the electric control translation stage further comprises a manual translation stage, and in order to facilitate the adjustment of the distance between the micro tube and the sample during working, the three-dimensional manual translation stage is additionally arranged on the electric control translation stage to serve as auxiliary control.

10. The laser-enhanced three-dimensional micro-area electrodeposition device according to claim 7, wherein: when the electric control translation stage is used for controlling the movement of the sample, the electric control translation stage also comprises a deflection stage, the deflection stage is used for adjusting the inclination angle of the sample during working, and the deflection stage is positioned between the translation stage and the sample.

11. the laser-enhanced three-dimensional micro-area electrodeposition device according to claim 7, wherein: the optical element specifically comprises a first plane mirror, a second plane mirror and a lens, wherein laser beams emitted by the laser are reflected by the first plane mirror and then irradiate the second plane mirror, the laser beams are emitted by the second plane mirror and then irradiate the lens, and converged beams emitted by the lens are incident to an area to be processed of the sample.

12. The laser-enhanced three-dimensional micro-area electrodeposition device according to claim 7, wherein: the electrolyte cavity is specifically an injector of various specifications or various containers for containing related electrolyte.

13. the laser-enhanced three-dimensional micro-area electrodeposition device according to claim 7, wherein: the micro tube is specifically a capillary tube made of various materials, a small-diameter outlet is formed by hot stretching of a liquid outlet of the capillary tube, when the capillary tube is made of an insulating material, a conducting wire is inserted into the capillary tube and is connected with the positive electrode of a voltage source, or a conducting coating is deposited on the outer wall of the capillary tube and is connected with the voltage source, so that an external bias can act on electrolyte, and when the capillary tube is made of a conducting material, the capillary tube is directly connected with the positive electrode of the voltage source through a thin conducting wire.

14. The laser-enhanced three-dimensional micro-area electrodeposition device according to claim 7, wherein: the micro-tube is a silicon-based plane micro-tube array which is processed by a micro-electro-mechanical system technology and comprises a plurality of micro-tubes.

Technical Field

The invention relates to the technical field of electrodeposition, in particular to a laser-enhanced three-dimensional micro-area electrodeposition method and a device adopting the method.

Background

the electrodeposition technology is a common coating processing technology in industrial production, and works based on an electrochemical principle, a sample is taken as a cathode and is immersed into a specific electrolyte, and metal ions in the electrolyte are gathered on the surface of the sample and undergo a reduction reaction, so that a metal coating layer is formed on the surface of the sample. The electrodeposition technology has been widely used in various fields such as electronic information, corrosion prevention, decoration, and the like. However, the existing electrodeposition technology has low processing precision and the processing resolution is only about 100 μm. In order to improve the processing precision of the electrodeposition technology, in recent years, a micro-area electrodeposition technology based on a micro-tube is developed, electrolyte is filled into a hollow micro-tube to replace an electroplating bath in the traditional electrodeposition technology, and the distance between a micro-tube nozzle and a sample is regulated and controlled by a precise displacement platform, so that the electrodeposition preparation of micron or even submicron-scale metal wires can be realized. However, this microtube-based micro-area electrodeposition technique has a low deposition rate, typically less than 0.1 μm/s, limiting its application; in addition, the excessively low deposition rate also causes extremely high requirements on the control of the distance between the nozzle and the sample and the relative displacement precision when the system works, so that the displacement control mostly adopts a high-precision (for example, the displacement precision is better than 1nm) piezoelectric displacement table, and the system cost is increased. In conventional electrodeposition techniques, laser-assisted deposition has been demonstrated to increase the electrodeposition rate by up to three orders of magnitude.

disclosure of Invention

in order to solve the problems, the invention provides a laser-enhanced three-dimensional micro-area electrodeposition method, which integrates laser irradiation into a micro-area electrodeposition device based on a micro-tube to obtain an improved deposition rate, further reduces the strict requirement of equipment on the precision of a displacement platform, and reduces the development cost of the equipment.

A laser-enhanced three-dimensional micro-area electrodeposition method is characterized in that: electrolyte is filled in the electrolyte cavity and the microtube, the tip of the microtube approaches the surface of the sample through the regulation and control of the translation table, and the liquid drops at the tip of the microtube form a meniscus on the surface of the sample, so that the diffusion of the liquid drops on the surface of the sample is limited, and the control of the electro-deposition processing precision is facilitated; the electrolyte in the microtube is connected with a positive potential, and the surface of the conductive sample is a negative potential, so that the electrodeposition process occurs; laser is irradiated on the contact surface of the liquid drop and the sample, the laser heat effect improves the electron transfer efficiency in the electrolyte, and accelerates the forward deviation of the electrochemical equilibrium potential and causes local vortex stirring in the liquid drop, thereby accelerating the electrodeposition process; and cooperatively regulating and controlling the motion of the electric control translation stage according to a preset pattern to realize the three-dimensional relative movement of the microtube and the surface of the sample so as to generate a three-dimensional micro-nano scale pattern.

it is further characterized in that:

selecting a suitable laser light source according to working conditions, wherein the suitable laser light source specifically comprises but is not limited to ultraviolet light, visible light or infrared light; a light beam emitted by the light source is reflected by the reflector and converged by the lens and then is irradiated on a contact surface between a liquid drop at the tip of the microtube and a sample or a contact surface between the liquid drop and a deposited copper layer;

When the micro-tube approaches the surface of the sample, the approach degree is judged by the aid of an optical microscope, after the tip of the micro-tube is connected with the surface of the sample through the electrolyte liquid drop, a meniscus is formed on two sides of the liquid drop under the action of surface tension due to the hydrophilicity of the surface of the sample, and the meniscus is limited to diffuse along the surface of the sample due to the action of the surface tension of the liquid drop, so that the electro-deposition is guaranteed to have high enough geometric resolution and fine enough machining size;

the micro-tube is a commercialized capillary tube with various inner diameters ranging from dozens of micrometers to hundreds of micrometers, and specifically comprises but is not limited to materials of metal, common glass and quartz glass; the capillary with smaller inner diameter is prepared by drawing one end of the formed capillary again, so that the inner diameter of a pipe orifice of the capillary for dropping liquid is reduced, and the processing precision of electrodeposition is improved;

The laser irradiation position keeps relatively static relative to the dropping liquid position of the capillary, and the laser irradiation position moves synchronously with the capillary when the capillary moves;

In the electrodeposition process, the dropping position of the capillary and the surface of the sample generate relative movement;

A micro-injection pump is externally connected in the space, used for containing the electrolyte, of the micro-tube, and the outflow rate of the electrolyte in the capillary tube can be accurately adjusted through adjustment and control of the propelling rate of the injection pump, so that the electrodeposition rate and the machining precision are adjusted and controlled.

a laser-enhanced three-dimensional micro-area electrodeposition device is characterized in that: the micro-tube micro-injection machining device comprises an electric control translation table, a displacement controller, an ammeter, a voltage source, a computer, a laser, a micro-tube, an electrolyte cavity, a micro-injection pump, an optical element and a sample placing table, wherein a sample is placed on the sample placing table, a liquid drop outlet of the micro-tube is arranged right above the sample, the electric control translation table and the displacement controller control the micro-tube and the sample placed on the sample placing table to move in relative positions, a liquid inlet at the upper part of the micro-tube is connected with the electrolyte cavity, the injection pump is arranged on the electrolyte cavity, the computer controls the displacement controller to drive the electric control translation table to act, the computer is respectively connected with the ammeter and the voltage source, the ammeter is connected with electrolyte positioned in the micro-tube through a conductor, the ammeter is connected with the anode of the voltage source, and the cathode or the, the laser beam emitted by the laser generates a converged beam through the optical element to be incident on the to-be-processed area of the sample.

It is further characterized in that:

the electric control translation stage is specifically a one-dimensional translation stage, a two-dimensional translation stage or a three-dimensional translation stage, the electric control translation stage is used for regulating and controlling the movement of a sample or regulating and controlling the movement of a micro tube, when the electric control translation stage adopts a split structure, part of the translation stage is connected with the micro tube, part of the translation stage is connected with the sample, and the micro tube and the sample move relatively during working;

When the electric control translation stage is used for controlling the movement of a sample, the sample placing stage is the electric control translation stage, and the electric control translation stage also comprises a manual translation stage;

when the electric control translation stage is used for controlling the movement of the sample, the electric control translation stage also comprises a deflection stage, the deflection stage is used for adjusting the inclination angle of the sample during working, and the deflection stage is positioned between the translation stage and the sample;

the output end of the electrolyte cavity is connected with the micro-tube through an adapter, and the electrolyte cavity is connected with the micro-injection pump through the adapter;

The optical element specifically comprises a first plane mirror, a second plane mirror and a lens, wherein a laser beam emitted by the laser is reflected by the first plane mirror and then irradiates the second plane mirror, the laser beam is emitted by the second plane mirror and then irradiates the lens, and a converged beam emitted by the lens is incident to a to-be-processed area of the sample;

the electrolyte cavity is specifically an injector of various specifications or various containers for containing related electrolyte, and when the electrolyte cavity is used for injecting electrolyte of various specifications, the electrolyte cavity is conveniently connected with a micro-injection pump and a micro-tube;

The micro tube is specifically a capillary tube made of various materials, a small-diameter outlet is formed by hot stretching of a liquid outlet of the capillary tube, when the capillary tube is made of an insulating material, a conducting wire is inserted into the capillary tube and is connected with the positive electrode of a voltage source, or a conducting coating is deposited on the outer wall of the capillary tube and is connected with the voltage source, so that an external bias can act on electrolyte, and when the capillary tube is made of a conducting material, the capillary tube is directly connected with the positive electrode of the voltage source through a thin conducting wire;

The micro-tube is a silicon-based plane micro-tube array which is processed by a micro-electro-mechanical system technology and comprises a plurality of micro-tubes.

After the technical scheme is adopted, the electrolyte is filled in the electrolyte cavity and the micro-tube, the tip of the micro-tube approaches the surface of the sample through the regulation and control of the translation table, and the liquid drop at the tip of the micro-tube forms a meniscus on the surface of the sample, so that the diffusion of the liquid drop on the surface of the sample is limited, and the control of the electro-deposition processing precision is facilitated; the electrolyte in the microtube is connected with a positive potential, and the surface of the conductive sample is a negative potential, so that the electrodeposition process occurs; laser is irradiated on the contact surface of the liquid drop and the sample, the laser heat effect improves the electron transfer efficiency in the electrolyte, and accelerates the forward deviation of the electrochemical equilibrium potential and causes local vortex stirring in the liquid drop, thereby accelerating the electrodeposition process; according to a preset pattern, the movement of the electric control translation stage is cooperatively regulated and controlled, so that the three-dimensional relative movement of the microtube and the surface of the sample is realized, and a three-dimensional micro-nano scale pattern is generated; the laser irradiation is integrated into a micro-area electro-deposition device based on the micro-tube, the improved deposition rate is obtained, the strict requirement of equipment on the precision of a displacement platform is further reduced, and the development cost of the equipment is reduced.

Drawings

FIG. 1 is a schematic structural diagram of an embodiment of the apparatus of the present invention;

FIG. 2 is a schematic view of a meniscus formed on a sample surface by an electrolyte droplet after a tip of a microtube approaches the sample surface;

Fig. 3 is a schematic flow chart of electrodeposition of a copper nanowire on the surface of a conductive sample along the X direction, and for clarity of illustration, contents of electrical connection, computer control and the like are omitted in the diagram. (a: the capillary tip approaches the surface of the sample, the electrolyte liquid drop forms a meniscus on the surface of the sample, b: the electrolyte liquid drop forms a meniscus in the contact surface of the sample under the enhancement effect of laser irradiation, c-d: the copper layer continuously grows along the X direction along with the movement of the X direction electric control translation stage.)

Fig. 4 is a schematic flow chart of the process of electrodepositing the nano copper wire on the surface of the conductive sample along the Z direction (the direction vertical to the surface of the sample), and the contents of electrical connection, computer control and the like are omitted in the diagram for clarity of illustration. (a: the capillary tip approaches the surface of the sample, the electrolyte liquid drop forms a meniscus on the surface of the sample, b: the electrolyte liquid drop forms a meniscus in the contact surface of the sample under the enhancement effect of laser irradiation, c-d: the copper layer continuously grows along the Z direction along with the movement of the Z-direction electric control translation stage.)

The names corresponding to the sequence numbers in the figure are as follows:

the device comprises an electric control translation table 1, a displacement controller 2, an ammeter 3, a voltage source 4, a computer 5, a laser 6, a micro-tube 7, a small-diameter outlet 71, an electrolyte cavity 8, a micro-injection pump 9, a sample 10, electrolyte 11, a laser beam 12, a convergent beam 13, a manual translation table 14, a deflection table 15, a first plane mirror 16, a second plane mirror 17, a lens 18, a thin wire 19, liquid drops 20, deposited copper 21 and copper nanowires 22.

Detailed Description

A laser-enhanced three-dimensional micro-area electrodeposition method comprises the following steps: electrolyte is filled in the electrolyte cavity and the microtube, the tip of the microtube approaches the surface of the sample through the regulation and control of the translation table, and the liquid drops at the tip of the microtube form a meniscus on the surface of the sample, so that the diffusion of the liquid drops on the surface of the sample is limited, and the control of the electro-deposition processing precision is facilitated; the electrolyte in the microtube is connected with a positive potential, and the surface of the conductive sample is a negative potential, so that the electrodeposition process occurs; laser is irradiated on the contact surface of the liquid drop and the sample, the laser heat effect improves the electron transfer efficiency in the electrolyte, and accelerates the forward deviation of the electrochemical equilibrium potential and causes local vortex stirring in the liquid drop, thereby accelerating the electrodeposition process; and cooperatively regulating and controlling the motion of the electric control translation stage according to a preset pattern to realize the three-dimensional relative movement of the microtube and the surface of the sample so as to generate a three-dimensional micro-nano scale pattern.

Selecting a suitable laser light source according to working conditions, wherein the suitable laser light source specifically comprises but is not limited to ultraviolet light, visible light or infrared light; a light beam emitted by the light source is reflected by the reflector and converged by the lens and then is irradiated on a contact surface between a liquid drop at the tip of the microtube and a sample or a contact surface between the liquid drop and a deposited copper layer;

When the micro-tube approaches the surface of the sample, the approach degree is judged by the aid of an optical microscope, after the tip of the micro-tube is connected with the surface of the sample through the electrolyte liquid drop, a meniscus is formed on two sides of the liquid drop under the action of surface tension due to the hydrophilicity of the surface of the sample, and the meniscus is limited to diffuse along the surface of the sample due to the action of the surface tension of the liquid drop, so that the electro-deposition is guaranteed to have high enough geometric resolution and fine enough machining size;

The micro-tube is a commercial capillary tube with an inner diameter of dozens of micrometers to hundreds of micrometers, and specifically comprises but is not limited to materials of metal, common glass and quartz glass; the capillary with smaller inner diameter is prepared by drawing one end of the formed capillary again, so that the inner diameter of a pipe orifice of the capillary for dropping liquid is reduced, and the processing precision of electrodeposition is improved;

The laser irradiation position keeps relatively static relative to the dropping liquid position of the capillary, and the laser irradiation position moves synchronously with the capillary when the capillary moves;

in the electrodeposition process, the dropping position of the capillary and the surface of the sample generate relative movement;

A micro-injection pump is externally connected in the space, used for placing the electrolyte, of the micro-tube, and the outflow rate of the electrolyte in the micro-tube can be accurately adjusted through adjusting and controlling the propelling rate of the injection pump, so that the electrodeposition rate and the machining precision are adjusted and controlled.

a laser-enhanced three-dimensional micro-area electrodeposition device, which is shown in fig. 1: the device comprises an electric control translation table 1, a displacement controller 2, an ammeter 3, a voltage source 4, a computer 5, a laser 6, a micro-tube 7, an electrolyte cavity 8, a micro-injection pump 9, an optical element and a sample placing table, wherein the sample 10 is placed on the sample placing table, a liquid drop outlet of the micro-tube 7 is arranged right above the sample 10, the electric control translation table 1 and the displacement controller 2 control the micro-tube 7 and the sample 10 placed on the sample placing table to move in relative positions, a liquid inlet at the upper part of the micro-tube 7 is connected with the electrolyte cavity 8, the micro-injection pump 9 is arranged on the electrolyte cavity 8, the computer 5 controls the displacement controller 2 to drive the electric control translation table 1 to move, the computer 5 is respectively connected with the ammeter 3 and the voltage source 4, the ammeter 3 is connected with an electrolyte 11 positioned in the micro-tube 7 through a conductor, the ammeter 3 is connected with the anode of the voltage source 4, the laser beam 12 emitted by the laser 6 is transmitted through an optical element to generate a converging beam 13 which is incident on the area to be processed of the sample 10.

The electric control translation stage 1 is specifically a one-dimensional translation stage, a two-dimensional translation stage or a three-dimensional translation stage, the electric control translation stage 1 is used for regulating and controlling the movement of a sample 10 or regulating and controlling the movement of a micro-tube 7, when the electric control translation stage 1 adopts a split type structure, part of the translation stage is connected with the micro-tube 7, part of the translation stage is connected with the sample 10, and the micro-tube 7 and the sample 10 move relatively during working;

When the electric control translation stage 1 is used for controlling the movement of a sample, the sample placing stage is the electric control translation stage 1, the electric control translation stage further comprises a manual translation stage 14, and in order to facilitate the adjustment of the distance between the micro tube 7 and the sample 10 during working, the electric control translation stage is additionally provided with the three-dimensional manual translation stage 14 as an auxiliary control;

When the electric control translation stage 1 is used for controlling the movement of a sample, the electric control translation stage further comprises a deflection stage 15, the deflection stage 15 is used for adjusting the inclination angle of the sample during working, and the deflection stage 15 is positioned between the translation stage and the sample 10;

The output end of the electrolyte cavity 8 is connected with the micro-tube 7 through an adapter, and the electrolyte cavity 8 is connected with the micro-injection pump 9 through the adapter;

The optical element specifically comprises a first plane mirror 16, a second plane mirror 17 and a lens 18, wherein a laser beam 12 emitted by the laser 6 is reflected by the first plane mirror 16 and then irradiates the second plane mirror 17, is emitted by the second plane mirror 17 and then irradiates the lens 18, and a converged beam 13 emitted by the lens 18 is incident on a to-be-processed area of the sample 10;

The electrolyte cavity 8 is embodied as an injector of various specifications or various containers for containing the relevant electrolyte, wherein when the electrolyte cavity 8 is an injector of various specifications, it is conveniently connected with a micro-injection pump and a micro-tube;

The micro tube 7 is a capillary tube made of various materials, a small-diameter outlet 71 is formed by hot stretching of a liquid outlet of the capillary tube, when the capillary tube is made of an insulating material, a conducting wire is inserted into the capillary tube and is connected with the positive electrode of a voltage source, or a conducting coating is deposited on the outer wall of the capillary tube and is connected with the voltage source, so that an external bias can act on electrolyte, and when the capillary tube is made of a conducting material, the capillary tube is directly connected with the positive electrode of the voltage source through a thin conducting wire;

The microtubes 7 may be silicon-based planar microtubes arrays comprising a plurality of microtubes processed by micro-electromechanical systems technology.

A specific embodiment of the device, see fig. 1: according to the requirement of an electrodeposition working principle, an area needing electrodeposition processing on the surface of a sample needs to be conductive, the sample 10 is fixed on X, Y and a Z three-dimensional electric control translation table 1, a deflection table 15 is additionally arranged between the translation table and the sample 10 for adjusting the inclination angle of the sample during working, a three-dimensional manual translation table 14 can be additionally arranged on the electric control translation table 1 for auxiliary control, the micro-tube 7 is a capillary tube, and capillary tubes with different inner diameters are selected according to working requirements; electrolyte 11 is filled in the capillary, the internal capacity of the capillary is limited, so that more efficient electrodeposition is realized, the capillary is communicated with a large electrolyte cavity 8 through an adapter in the design, the electrolyte 11 is filled in the electrolyte cavity 8, the other end of the electrolyte cavity 8 is connected with a micro-injection pump 9 for controlling the outflow rate of liquid drops in the capillary, and the outflow rate of the electrolyte in the capillary can be accurately regulated through regulating the propelling rate of the micro-injection pump 9, so that the electrodeposition rate and the processing precision are regulated;

one end of a thin wire 19 is immersed in the electrolyte 11, the other end of the thin wire is connected with a precise ammeter 3, the ammeter 3 is connected with the positive electrode of a voltage source 4, and the negative electrode or the grounding end of the voltage source 4 is connected with a region to be processed on the surface of the sample 10;

The laser 6 is reflected by the plane mirror and converged by the lens, and then enters the area to be processed of the sample. The first plane mirror 16 and the horizontal plane form an included angle of 45 degrees, the laser 6 is arranged outside the translation table, emergent light of the laser is in the horizontal direction, the emergent light is reflected by the first plane mirror 16 with the included angle of 45 degrees and then vertically and upwards enters the second plane mirror 17, the included angle of the second plane mirror 17 is adjusted as required, and the laser reflected by the second plane mirror 17 is guaranteed to be converged by the lens 18 and then enters a to-be-processed area of the sample 10.

Now, according to the configuration shown in fig. 1, the working flow is described as follows, and for other possible structural configuration changes, the process flow can be changed appropriately according to the actual working conditions, which is not described herein again.

(1) System connection: the ammeter, the voltage source and the displacement controller are connected with the computer, and data acquisition and system control are carried out by the computer. The displacement controller is connected with the electric control mobile station. And after the electrolyte cavity and the micro-tube are mechanically connected through the adapter, electrolyte is injected. The micro-injection pump is mechanically connected with the electrolyte cavity through the adapter. One end of the thin wire is connected with the electrolyte. The ammeter connects the thin wire to the positive input of the voltage source. The negative output (or ground) of the voltage source is electrically connected to the conductive area of the sample to be processed.

(2) Laser beam spot adjustment: and ensuring that the first plane mirror forms an included angle of 45 degrees with the horizontal direction, enabling laser beams output by the laser to enter the first plane mirror along the horizontal direction and enter the second plane mirror after being reflected, adjusting the angle of the second plane mirror and the position of the lens, and ensuring that converged light beams passing through the lens enter the micro-area position of the surface of the sample to be processed.

(3) approaching to the working point: the voltage source applies a constant dc bias to the electrolyte, the magnitude of which is determined by the particular test conditions (electrolyte concentration, electrolyte type, deposition rate, etc.), while the loop current is monitored. When the microtube is far from the sample, the electrolyte drops cannot form an electric circuit between the microtube and the sample, so that the ammeter only displays noise current at the moment. And the distance between the microtube and the sample is approximated to a working point through the cooperative operation of the three-dimensional manual translation stage and the three-dimensional electric control translation stage. The sign of the approach to the operating point can be determined by the current meter displaying the current. When the microtube is close enough to the sample, the electrolyte drops at the end of the microtube are communicated with the electrolyte (and the thin conducting wire) in the microtube and the surface of the sample, so that an electric loop is formed, and at the moment, under the direct-current bias of a voltage source, the ammeter shows considerable current value. Under the action of the DC bias voltage, the electrodeposition process is started. When the micro-tube approaches the surface of the sample, the approach degree is judged by the aid of an optical microscope.

(4) fine adjustment of laser beam spot: the laser beam spot is fine tuned so that the focused spot impinges on the droplet 20 and the sample 10 in contact with the micro-area.

(5) Electrodeposition of a preset pattern: according to a pre-designed electro-deposition pattern (which can be a plane or a three-dimensional structure), the electro-deposition of the pre-designed pattern is realized by cooperatively regulating and controlling the motions (including but not limited to moving distance, moving speed and moving step length) of the X, Y and Z three-dimensional electric control displacement platform.

(6) Separating the microtube from the sample: and after the preset pattern electrodeposition is finished, closing the direct-current bias of the voltage source, interrupting the electrodeposition process and controlling the Z-direction electric control translation stage to move away from the surface of the sample.

the inner diameter of the capillary tube, which is common at present, is large, and is usually larger than 100 μm. With such capillaries having a larger inner diameter, the minimum dimension of the coating line obtained by laser-enhanced micro-area electrodeposition according to the above procedure is usually more than several tens of micrometers (slightly smaller than the inner diameter of the capillary). To further reduce the coating line size and improve the electrodeposition accuracy and resolution of this technique, the capillary may be sharpened. And (3) selecting a common glass capillary or a quartz capillary, and realizing the sharpening of the tip of the capillary by adopting a heating and stretching method. Because the softening temperature of the common glass capillary is low, the common glass capillary can be sharpened by adopting a stretching method after heating and softening by using a resistance wire. The quartz capillary tube has a high melting point and can be prepared by a stretching method after laser focusing, heating and softening. And at present, mature and commercialized needle drawing instruments aiming at common glass capillaries and quartz capillaries are available, and the sharpening treatment of the tips of the capillaries can be conveniently realized. The capillary tip diameter after the sharpening process may be less than 1 μm.

FIG. 2 is a partially enlarged view of the contact area between the capillary tip and the sample during the laser-enhanced micro-area electrodeposition process, so as to illustrate the laser-enhanced micro-area electrodeposition principle of the present invention. The figure shows the capillary tube sharpened at its tip, with a significant conical stretch visible. When the capillary tip is connected to the sample surface via an electrolytic droplet, a meniscus is formed on both sides of the droplet under surface tension due to the hydrophilicity of the sample surface. At the same time, the meniscus is limited to spread along the specimen surface due to the action of the surface tension of the droplets, which ensures a sufficiently high geometric resolution of the electrodeposition and a sufficiently fine processing dimension. The droplet size shown in fig. 2 is slightly larger than the capillary tip size. However, during the relative movement of the capillary and the sample in three dimensions, the meniscus size becomes thin, and when electrodeposition is performed using a low concentration of the electrolyte, it is expected that an electrodeposition pattern slightly smaller than the inner diameter of the capillary tip will be obtained.

The function of the laser in the present invention is explained as follows. As shown in fig. 2, the laser is converged by the lens and then irradiated on the region of the sample to be processed. Although various lasers can be selected according to different electrodeposition conditions (electrolyte components, substrate materials and the like) in actual operation, the wavelength range of the lasers covers ultraviolet, visible and infrared bands, and after the lasers are converged by the lens, the actual converged spot size is larger than the droplet size due to the influence of factors such as light interference, diffraction, lens quality and the like. In the conventional electrodeposition technology, by virtue of excellent localization of laser spots, the conventional laser enhanced electrodeposition technology has higher precision and resolution pattern processing capability than the conventional electrodeposition process without laser irradiation, but also has processing precision and resolution of only about 100 μm due to the limitations of laser beam spot size and the like. However, in the present invention, the size of the focused light spot is larger than the droplet size on the surface of the sample, so the accuracy and resolution of the electrodeposition pattern in the present invention are mainly determined by the droplet size and electrodeposition parameters, and the laser spot size has little influence on the pattern resolution and accuracy. The main contributions of the laser in the present invention are: the laser thermal effect improves the electron transfer efficiency in the electrolyte and accelerates the electrochemical equilibrium potential to shift to the positive direction; laser irradiation creates a pressure gradient in the electrolyte causing local vortex stirring. The electrodeposition rate is greatly improved due to multiple action mechanisms, the electrodeposition efficiency is accelerated, the requirement on the displacement precision of the electric control displacement platform is reduced, and the equipment development cost is reduced.

The configuration of the electric control translation stage and the manual translation stage and the sample and the microtube can be in other various ways according to the actual working requirement, such as: x, Y and Z-direction electric control and manual translation stage can also be connected with the micro-tube to regulate the movement of the micro-tube; and a split design can also be adopted, part of the translation table is connected with the micro-tube, part of the translation table is connected with the sample, and the micro-tube and the sample move coordinately during working. Due to the various combination modes among the translation stage, the microtube and the sample, the invention is not illustrated one by one. The above process flow may be adjusted appropriately according to changes in system configuration.

the positioning of the laser converging beam is particularly important for the laser enhancement effect of the invention. The laser beam converging light spot is always positioned at the contact surface of the liquid drop and the sample or the liquid drop and the copper layer. In the structural configuration shown in fig. 1, the microtube is fixed and the sample moves relative to the microtube during operation, so that the light beam can be ensured to always promote the electrodeposition process by adjusting the irradiation of the converged light beam at the lower end position of the liquid drop. However, in other possible structural configurations, especially when the microtube moves under the control of the electrically controlled translation stage during operation, when the relative movement range of the sample and the microtube is too large, the contact area between the droplet at the tip of the microtube and the sample can exceed the laser spot range, thereby affecting the laser enhancement effect. Therefore, in order to ensure that the light spot is always irradiated on the liquid drop at the tip of the capillary tube when the micro-tube moves, the optical element (such as a reflector, a lens and the like) should move synchronously with the micro-tube, for example, the optical element and the micro-tube are fixed on the same electrically controlled translation stage.

the capillary tube can be made of various materials, including metal capillary tubes, common glass capillary tubes, quartz capillary tubes and plastic capillary tubes. If a conductive metal capillary is used, the thin wire shown in fig. 1 can be directly electrically connected to the metal outer wall of the capillary without being inserted into the electrolyte. For the insulating capillary material, a conductive coating can be deposited on the outer wall of the insulating capillary in advance, and then the thin wire is directly electrically connected with the conductive coating on the outer wall. The capillary can be further subjected to tip sharpening treatment through a hot stretching process, so that the processing precision and the resolution capability of micro-area electrodeposition are improved.

In the configuration shown in fig. 1, the cavity can be an injector of various specifications, and is conveniently connected with an injection pump and a capillary tube; or may be various containers that can contain the relevant electrolyte.

in the configuration shown in fig. 1, the deflection table and the three-dimensional manual translation table are optional and can be selected or selected according to the work requirement. The three-dimensional manual translation stage can also be only configured with one-dimensional or two-dimensional manual translation stage according to the requirement.

In the configuration shown in fig. 1, X, Y and the Z electrically controlled translation stage can be appropriately selected according to the work requirement. For example, if the micro-area electrodeposition is realized only in the horizontal plane, if only the X and Y electric control translation stages are needed, the Z electric control translation stage can be replaced by a Z-direction manual translation stage, so that the approaching operation of the micro-tube and the sample is facilitated.

In the configuration shown in fig. 1, the reflection and convergence paths of the laser beam are not limited to two plane mirrors and one lens. The related optical elements can be increased or decreased according to the needs in actual work. The material of the optical element also needs to be determined according to the performance of the laser light source, such as an ultraviolet light source, and a quartz lens needs to be considered; for infrared laser, a gold mirror, a zinc selenide lens, and the like are considered. If the laser light source is an ultraviolet, infrared or other invisible light source, a coaxial visible light source should be configured at the light source exit as a guiding light beam in order to facilitate adjustment of the converged light beam. During actual adjustment, the visible light source is adjusted and controlled firstly to enable light beams of the visible light source to be converged on the surface to be processed of the sample, and then the laser light source is adjusted finely.

In the configuration shown in fig. 1, the light source is incident from the side and the microtube is in a vertical position. The concentrated beam typically has the greatest thermal effect when incident normal to the sample surface. In actual operation, the included angles among the incident laser beam, the microtube and the sample plane can be adjusted according to requirements.

The first embodiment of the electrodeposition using the apparatus of the first embodiment:

this example illustrates one application of the present invention in terms of electrodeposition of copper nanowires in the X-direction.

the electrolyte is CuSO₄·5H₂The molar concentration of the solute is between 0.01 and 1M according to the requirements of the size and the speed of the deposited nanowire. The capillary (outer diameter 1mm, inner diameter 0.5mm) was subjected to a tip sharpening treatment via a commercial pin puller, after which the capillary tip outer diameter was about 1 μm. Electrolyte is filled into a 10mL glass syringe, the syringe is connected with the capillary tube through an adapter, an electrolyte tube in the syringe is injected into the capillary tube through an injection pump, and micro liquid drops appear at the tip of the stretching section of the capillary tube. The sample is a heavily doped silicon wafer without an oxide layer, and the silicon wafer is rinsed by hydrofluoric acid before electrodeposition. And a 0.1mm thin copper wire is used as one end of a thin wire and inserted into the injector to be electrically contacted with the electrolyte, and the other end of the thin copper wire is sequentially connected with the ammeter, the voltage source and the surface of the sample to form a conductive loop. The rest is assembled as shown in fig. 1, wherein the laser source can be an ArF excimer laser. The voltage source conductively biases the copper by +0.6V while the sample surface is grounded, at which point no effective electrical contact is made due to the far distance of the capillary tip from the sample, at which point the ammeter reading is zero (or very little noise). The sample surface and the tip of the capillary stretching end gradually approach each other through a manual and electric control displacement platform. When the capillary tip droplet contacts the sample surface (fig. 3a), the ammeter shows a considerable current value, which can be of the order of several hundred pA to several tens nA, depending on the electrolyte concentration and bias. At which point electrodeposition begins. Under the enhancement action of the converged laser beam, the deposition rate of copper is improved by orders of magnitude compared with the deposition rate without laser enhancement, and copper 21 is deposited in a micro-area where the liquid is in contact with the surface of the sample (figure 3 b). The copper layer width is limited by the meniscus size and the deposition rate. After a certain time (namely after the thickness of the copper layer reaches an expected value), the X-direction electrically-controlled translation stage translates at a speed of hundreds of nanometers to a few micrometers per second (compared with the speed, when the laser enhancement effect is not provided, the speed of the translation stage is generally limited to about 100nm/s, and the nanowire is easily discontinuous due to the excessively high speed). Moving speed of X-direction electric control translation tablethe degree is chosen so as to ensure that the meniscus formed by the droplet on the surface of the sample moves continuously in the X direction. The electrodeposition process of the sample micro-areas is always enhanced because the converged laser beam is always irradiated at the contact surface of the droplet of the capillary tip and the sample (fig. 3 c-d). The deposited copper nanowires gradually increase in length with the movement of the X-direction translation stage (fig. 3 b-d). And after the length reaches a preset value, removing the direct current bias, and separating the tip of the capillary tube from the surface of the sample, thereby finally realizing the preparation of the X-direction copper nanowire.

A second embodiment of performing electrodeposition using the apparatus of the first embodiment:

This example illustrates the application of the present invention in vertical nanowire growth, using electrodeposition of copper nanowires in a direction perpendicular to the surface of the sample as an example.

The reagents, materials and system configuration used are the same as in the first embodiment. Before the approximation operation, the converged laser spot is adjusted to irradiate the contact surface of the capillary tip liquid drop 20 and the surface of the sample 10. Then, according to example 1, the capillary was approached to the sample surface under positive bias of the copper wire until an observable was detected by the ammeter (fig. 4 a). The electrodeposition process begins and a layer of copper is deposited on the surface of the coupon, forming deposited copper 21 (fig. 4 b). The Z stage is then computer controlled to move slowly in the direction perpendicular to the sample surface at a rate of hundreds of nanometers to microns per second (the speed being chosen so that the meniscus between the droplet and the deposited copper layer is not broken) so that the sample is gradually moved away from the capillary tip. The meniscus is not broken due to the hydrophilic interaction between the droplet 20 and the deposited copper layer, and the electrodeposition process continues under the combined action of the dc bias and the focused light beam, thereby growing copper nanowires 22 in a direction perpendicular to the sample surface (fig. 4 c-d). Fig. 4b-d also show that during the growth of the copper nanowires, the converging light beam is always irradiated at the droplet/copper layer interface. And after the height of the nanowire reaches a preset value, removing the bias voltage, enabling the capillary to be far away from the surface of the sample, and finishing the deposition process.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.