Apparatus and method for patterning nanowire arrays

Abstract

The application relates to a device and a method for patterning and constructing a nanowire array, which comprises an argon gas bottle, a hydrogen gas bottle, a quartz tube, a quartz boat, a vapor deposition raw material sample, a substrate, a syringe pump matched with a syringe, and a container for a noble metal compound solution; an output pipeline of the syringe is connected with an output pipeline of the argon gas bottle, a movable electrode is arranged at an output end of a combined pipeline of the output pipeline of the syringe and the output pipeline of the argon gas bottle and introduced into the quartz tube, the output end of the movable electrode is located above the substrate, and an electrode moving controller is arranged to control directional movement of the movable electrode. The capillary electrode capable of generating micro plasma is assembled on a movable probe capable of moving in two dimensions, so that the nanometer noble metal catalyst is printed on the material surface in one step, the nanowire array is grown in a pattern through the guidance of the catalyst for reuse and the physical vapor deposition technology.

Description

Technical Field

[0001] This invention relates to the fields of additive manufacturing technology and nanowire growth technology, and in particular to a device and method for patterning nanowire arrays. Background Technology

[0002] Semiconductor nanowires are a special type of one-dimensional micro / nanostructure with radial dimensions ranging from 1 to 100 nm and lengths reaching tens of micrometers. This high aspect ratio allows them to perfectly connect the nano and micro worlds, serving not only as basic building blocks for constructing micro / nano functional devices but also as interconnecting wires in device circuits. Furthermore, due to quantum confinement effects existing only in two dimensions, while electrons, holes, and photons can freely transport in a third dimension, semiconductor nanowires possess superior optical, mechanical, electrical, and photoelectric conversion properties compared to traditional bulk semiconductor materials. These advantages make semiconductor nanowires ideal materials for optoelectronic devices, with wide applications in fiber lasers, light-emitting diodes, solar cells, and UV detectors.

[0003] Integrating numerous nanowires into an ordered nanowire array and then growing it over a large area on the device surface in a patterned manner is a good method for nanowire applications.

[0004] Traditional methods for fabricating semiconductor nanowire arrays can be divided into two categories: the "top-down" method, which uses photolithography and etching processes to process materials, and the "bottom-up" method, which manipulates the formation and growth of nanowires under artificially controlled conditions using nanotechnology to obtain the desired structure.

[0005] The "top-down" method has extremely stringent requirements for equipment, manufacturing processes, and operating methods;

[0006] The "bottom-up" approach, which starts at the molecular level, can yield smaller feature sizes.

[0007] Chemical vapor deposition (CVD) is a relatively mature method that has developed over the past few decades. It primarily involves pre-depositing metal nanoparticles on a substrate as catalysts and nucleation sites for semiconductor nanowires, then using a gas-liquid-solid growth mechanism to form nanowires, resulting in nanowires with high purity and excellent crystallinity. However, current techniques cannot directly prepare and precisely arrange metal nanoparticles in specific regions. Typically, a solution containing noble metal nanoparticles is first prepared, the substrate is then immersed in this solution, and after deposition and drying, a catalyst-containing substrate is obtained. This method is not only time-consuming and cumbersome, but also cannot effectively alter the distribution, arrangement, morphology, and size of the catalyst to achieve control over nanowire growth. Consequently, the constructed nanowire arrays are irregular, prone to aggregation, have poor uniformity, and unstable quality. Therefore, there is an urgent need to develop a device and method for directly preparing directionally grown and orderly arranged semiconductor nanowire arrays in specific regions. Summary of the Invention

[0008] To address the shortcomings of existing production technologies, this invention provides a device and method for constructing patterned nanowire arrays with a reasonable structure. It employs a high-precision printing method to obtain nano-precision noble metal catalysts with specified patterns, thereby constructing high-precision nanowire arrays with specific patterns.

[0009] The technical solution adopted in this invention is as follows:

[0010] An apparatus for patterning nanowire arrays includes:

[0011] Argon cylinders, with a mass flow controller connected to their output pipeline.

[0012] The hydrogen cylinder has its output line connected to the argon cylinder's output line, and a quartz tube is connected to the output end. The quartz tube contains a quartz dish, the original vapor-deposited sample, and the substrate.

[0013] The syringe pump is equipped with a syringe and is connected to an external container containing a precious metal compound solution; the syringe's output line is connected to the argon gas cylinder's output line.

[0014] The movable electrode is located at the output end of the combined pipeline of the syringe output line and the argon cylinder output line, and is introduced into the quartz tube. The output end of the movable electrode is located above the substrate.

[0015] The electrode movement controller is connected to the moving electrode and an external computer to control the directional movement of the moving electrode.

[0016] As a further improvement to the above technical solution:

[0017] The upper end of the movable electrode is a metal capillary, and the lower end is a quartz capillary; the metal capillary is connected to a high-voltage electrode of an external AC power source, and the quartz capillary is connected to a counter electrode of an external AC power source.

[0018] A voltage-stabilizing resistor is connected in series between the movable electrode and the external AC power supply.

[0019] The quartz tube is a string-shaped quartz tube. The original sample for vapor deposition is placed in a quartz dish, which is located in the middle of the quartz tube. The substrate is located in the middle between the quartz dish and the end of the quartz tube.

[0020] The opening of the string-shaped quartz tube is provided with a fixed quartz plate and a sliding quartz plate. The sliding quartz plate slides to form an electrode gap between itself and the fixed quartz plate.

[0021] The moving electrode maintains a distance of 1-3 mm from the substrate; the tube length of the moving electrode ranges from 90-120 mm, the inner diameter ranges from 0.06-0.08 mm, and the outer diameter ranges from 1.5-2 mm.

[0022] The length of the quartz tube ranges from 40 to 50 cm; the outer diameter of the quartz tube ranges from 8 to 10 cm; the inner diameter of the tube ranges from 10 to 12 cm; and the width of the opening plane ranges from 4 to 5 cm.

[0023] The length of the metal capillary tube for the movable electrode ranges from 80 to 100 mm, and the length of the quartz capillary tube ranges from 10 to 20 mm; the resistance of the voltage regulator ranges from 10 to 40 kΩ; the length of the fixed quartz plate at the opening of the string-shaped quartz tube ranges from 25 to 35 cm, the length of the sliding quartz plate ranges from 10 to 15 cm, and the sliding range of the sliding quartz plate ranges from 6 to 10 cm.

[0024] A method for constructing patterned nanowire arrays, utilizing the aforementioned equipment for patterned nanowire array construction, includes the following steps:

[0025] A precious metal compound aqueous solution is injected into the syringe; and various pipelines are connected, a printing model is set up, and the movement trajectory of the electrodes is controlled by an external computer.

[0026] Open the output pipeline of the argon cylinder to purge impurities from the argon pipeline and the merging pipeline, and then use a mass flow controller to regulate the argon delivery rate in the pipeline; at the same time, turn on the injection pump to transport the precious metal aqueous solution into the pipeline at a constant rate; the concentration of the precious metal compound aqueous solution is 0.1-1mM.

[0027] Argon gas and a precious metal aqueous solution are mixed and introduced into the capillary tube. The AC power supply is turned on, and an AC current is applied to the moving electrode to break down the argon gas and generate argon plasma. The plasma power is 3-30W.

[0028] After plasma ignition, the input rates of the noble metal compound aqueous solution and argon gas are kept constant. The noble metal ions are rapidly reduced under the action of argon plasma and printed on the substrate surface. The total argon gas flow rate is controlled at 30-100 sccm. The plasma reduction treatment time is 1-20 min.

[0029] As a further improvement to the above technical solution:

[0030] Printing nano-noble metal catalysts in specific areas on the substrate surface;

[0031] After the catalyst printing is completed, remove the moving electrode, push the sliding quartz plate to close the quartz tube, open the argon and hydrogen cylinders, and purge the impurities in the tube.

[0032] The delivery of argon and hydrogen in the pipelines is regulated by mass flow controllers installed on the argon and hydrogen pipelines. The mixed gas is input into the quartz tube at a stable rate, and then the quartz tube is heated and kept at a constant temperature. The sample source gas is patterned and grown into a nanowire array under the guidance of a catalyst by physical vapor deposition. The argon flow rate is regulated within the range of 20-60 sccm, the hydrogen flow rate is regulated within the range of 20-60 sccm, and the temperature range is 800-900℃.

[0033] The manufacturing steps for the movable electrode are as follows:

[0034] A high-voltage AC power electrode is connected to the metal capillary of the moving electrode, and a counter electrode is connected to the quartz capillary. The upper ends of the high-voltage AC power electrode and the counter electrode are insulated. After the insulation treatment, the upper ends of the high-voltage AC power electrode and the counter electrode are welded to the moving device to ensure a relatively insulated connection between the electrode and the moving device.

[0035] The beneficial effects of this invention are as follows:

[0036] This invention features a compact and rational structure, and is easy to operate. Building upon the micro-plasma preparation of noble metal nanomaterials, it rapidly prints noble metal nanocatalysts onto the material surface in a one-step process by assembling capillary electrodes capable of generating micro-plasma onto a two-dimensionally movable probe. Utilizing the guiding effect of a reused catalyst, combined with physical vapor deposition (PVD) technology, a patterned nanowire array is grown. In the catalyst printing stage, this invention uses high-energy electrons with strong reducing properties to replace traditional organic reducing reagents for reducing noble metal ions, thereby further preparing noble metal nanomaterials. This not only significantly shortens the reaction time but also avoids solvation and side reactions caused by solvent involvement, as well as the separation and purification processes.

[0037] This invention, with the assistance of a moving probe, allows noble metal catalysts to be directly printed onto a substrate along a designated path, forming nano-noble metal catalysts with a specified pattern. Simultaneously, due to the strong electric field, the prepared noble metal nanoparticles become charged, and their electrostatic repulsion inhibits particle aggregation, resulting in products with small particle size, good uniformity, and superior catalytic activity. Furthermore, the growth of the nanowires largely depends on the catalyst; therefore, the resulting nanowire array exhibits even better uniformity and smaller diameter.

[0038] The fabrication device in this invention has a positioning function, which enables the printed nanocatalyst array to be patterned with high precision, thereby constructing a nanowire array with a specific pattern.

[0039] The construction method of this invention is low in cost, simple and safe to operate, and semiconductor nanowire arrays with different patterns can be grown by modifying the program; and the morphology of the nanowires can be controlled by adjusting parameters such as printing speed, concentration of precious metal solution, and indoor vapor deposition time. It has the characteristics of high flexibility, strong controllability, high practicality and wide applicability. Attached Figure Description

[0040] Figure 1 This is a schematic diagram of the device structure for patterned nanowire arrays according to the present invention.

[0041] Figure 2 This is a SEM image of the gold nanocatalyst printed according to Example 1 of the present invention.

[0042] Figure 3 This is a super depth-of-field three-dimensional microscope image of cadmium sulfide nanowires prepared according to Example 1 of the present invention.

[0043] Figure 4 This is a super depth-of-field three-dimensional microscope image of cadmium sulfide nanowires prepared according to Example 1 of the present invention.

[0044] Figure 5 This is a SEM image of the cadmium sulfide nanowires prepared in Example 2 of the present invention.

[0045] Figure 6 The XRD pattern of cadmium sulfide nanowires prepared in Example 2 of the present invention.

[0046] Figure 7 The EDX spectrum of cadmium sulfide nanowires prepared in Example 2 of the present invention.

[0047] Figure 8 This is a TEM image of the indium arsenide nanowires prepared in Example 3 of the present invention.

[0048] Figure 9 This is a SEM-Mapping image of the indium arsenide nanowires prepared in Example 3 of the present invention.

[0049] The components include: 1. Argon cylinder; 2. Hydrogen cylinder; 3. Injection pump; 4. Injection syringe; 5. First mass flow controller; 6. First three-way valve; 7. Resistance box; 8. AC power supply; 9. Electrode movement controller; 10. Moving electrode; 11. Quartz tube; 12. Quartz dish; 13. Computer; 14. Second mass flow controller; 15. Third mass flow controller; 16. Second three-way valve. Detailed Implementation

[0050] The specific embodiments of the present invention will now be described with reference to the accompanying drawings.

[0051] like Figure 1As shown, the apparatus for patterning nanowire arrays in this embodiment includes:

[0052] Argon cylinder 1 has a mass flow controller connected to its output pipeline.

[0053] Hydrogen cylinder 2 has its output line connected to the output line of argon cylinder 1, and a quartz tube 11 is connected to the output end. Quartz tube 11 contains a quartz dish 12, the original vapor-deposited sample, and a substrate.

[0054] The syringe pump 3 is connected to a syringe 4, which is connected to an external container containing a precious metal compound solution; the output line of the syringe 4 is connected to the output line of the argon cylinder 1.

[0055] The movable electrode 10 is located at the output end of the combined pipeline of the injection syringe 4 and the argon cylinder 1, and is introduced into the quartz tube 11. The output end of the movable electrode 10 is located above the substrate.

[0056] Electrode movement controller 9 is connected to moving electrode 10 and external computer 13 to control the directional movement of moving electrode 10.

[0057] The upper end of the movable electrode 10 is a metal capillary, and the lower end is a quartz capillary; the metal capillary is connected to the high-voltage electrode of the external AC power supply 8, and the quartz capillary is connected to the counter electrode of the external AC power supply 8.

[0058] A voltage-stabilizing resistor is connected in series between the movable electrode 10 and the external AC power supply 8.

[0059] The quartz tube 11 is a string-shaped quartz tube 11. The original sample for vapor deposition is placed in the quartz dish 12, which is located in the middle of the quartz tube 11. The substrate is located in the middle between the end of the quartz dish 12 and the end of the quartz tube 11.

[0060] The opening of the string-shaped quartz tube 11 is provided with a fixed quartz plate and a sliding quartz plate. The sliding quartz plate slides to form an electrode gap between itself and the fixed quartz plate.

[0061] The movable electrode 10 maintains a distance of 1-3 mm from the substrate; the tube length of the movable electrode 10 ranges from 90-120 mm, the inner diameter ranges from 0.06-0.08 mm, and the outer diameter ranges from 1.5-2 mm.

[0062] The length of the quartz tube 11 ranges from 40 to 50 cm; the outer diameter of the quartz tube 11 ranges from 8 to 10 cm; the inner diameter ranges from 10 to 12 cm; and the width of the opening plane ranges from 4 to 5 cm.

[0063] The length of the metal capillary tube of the movable electrode 10 ranges from 80 to 100 mm, and the length of the quartz capillary tube ranges from 10 to 20 mm; the resistance of the voltage stabilizing impedance ranges from 10 to 40 kΩ; the length of the fixed quartz plate at the opening of the string-shaped quartz tube 11 ranges from 25 to 35 cm, the length of the sliding quartz plate ranges from 10 to 15 cm, and the sliding range of the sliding quartz plate ranges from 6 to 10 cm.

[0064] The method for constructing patterned nanowire arrays in this embodiment utilizes a device for patterned nanowire array construction and includes the following steps:

[0065] A precious metal compound aqueous solution is injected into the syringe 4; and the tubing is connected and the printing model is set up. The movement trajectory of the electrodes is controlled by an external computer 13.

[0066] Open the output pipeline of argon cylinder 1 to purge impurities from the argon pipeline and the merging pipeline, and then use a mass flow controller to regulate the argon delivery rate in the pipeline; at the same time, turn on injection pump 3 to transport the precious metal aqueous solution into the pipeline at a constant rate; the concentration of the precious metal compound aqueous solution is 0.1-1mM.

[0067] Argon gas and the aqueous solution of precious metal are mixed and introduced into the capillary tube. The AC power supply 8 is turned on, and AC current is applied to the moving electrode 10 to break down the argon gas and generate argon plasma; the plasma power is 3-30W.

[0068] After plasma ignition, the input rates of the noble metal compound aqueous solution and argon gas are kept constant. The noble metal ions are rapidly reduced under the action of argon plasma and printed on the substrate surface. The total argon gas flow rate is controlled at 30-100 sccm. The plasma reduction treatment time is 1-20 min.

[0069] Printing nano-noble metal catalysts in specific areas on the substrate surface;

[0070] After the catalyst printing is completed, the moving electrode 10 is removed, the sliding quartz plate is pushed to close the quartz tube 11, the argon cylinder 1 and the hydrogen cylinder 2 are opened, and the impurities in the tube are discharged.

[0071] The delivery of argon and hydrogen in the pipelines is regulated by mass flow controllers installed on the argon and hydrogen pipelines. The mixed gas is input into the quartz tube 11 at a stable rate. The quartz tube 11 is then heated and kept at a constant temperature. The sample source gas is patterned and grown into a nanowire array under the guidance of a catalyst by physical vapor deposition. The argon flow rate is regulated in the range of 20-60 sccm, the hydrogen flow rate is regulated in the range of 20-60 sccm, and the temperature range is 800-900℃.

[0072] The manufacturing steps of the movable electrode 10 are as follows:

[0073] The high-voltage electrode of AC power supply 8 is connected to the metal capillary of the moving electrode 10, and the counter electrode is connected to the quartz capillary. The upper ends of the high-voltage electrode and the counter electrode of AC power supply 8 are insulated. After the insulation treatment, the upper ends of the high-voltage electrode and the counter electrode of AC power supply 8 are welded to the moving device to ensure that the electrodes and the moving device are relatively insulated from each other.

[0074] The specific embodiments of the present invention are as follows:

[0075] The experimental principle of this invention is as follows: Based on the preparation of nano-noble metal materials by micro-plasma, capillary electrodes that can generate micro-plasma are assembled onto a movable probe that can move in two dimensions, thereby rapidly printing nano-noble metal catalysts on the material surface in one step. By utilizing the guiding effect of the reused catalyst and combining it with physical vapor deposition technology, a patterned nanowire array is grown.

[0076] In the catalyst printing stage, this method uses high-energy electrons with strong reducing properties to replace traditional organic reducing agents to reduce noble metal ions, thereby preparing nano-noble metal materials in one step. With the assistance of a moving probe, the product is printed onto the substrate along a specified path to form a nano-noble metal catalyst with a specified pattern.

[0077] The positioning system enables high-precision patterning of the printed nanocatalyst array, thereby constructing nanowire arrays with specific patterns. This method features simple equipment, low cost, and safe operation. By modifying the program, semiconductor nanowire arrays with different patterns can be grown, and the morphology of the nanowires can be controlled by adjusting parameters such as printing speed, noble metal solution concentration, and physical vapor deposition time. The control principle is as follows: by modifying the program, semiconductor nanowire arrays with different patterns can be grown, and the morphology of the nanowires can be controlled by adjusting parameters such as printing speed, noble metal solution concentration, and physical vapor deposition time. This method is highly flexible, controllable, practical, and universal.

[0078] This method uses an aqueous solution of a noble metal compound as a precursor. The precursor solution is mixed with argon gas and introduced into the moving electrode 10 via an injection pump 3 and a microfluidic system. The noble metal catalyst generated by argon plasma treatment is printed onto a rigid or flexible material substrate according to a specified path. Then, nanowires are patterned and grown on the noble metal catalyst using physical vapor deposition technology.

[0079] In one embodiment of the present invention, the noble metal compound solution is one of chloroauric acid aqueous solution, nitrate aqueous solution, and chloroplatinic acid aqueous solution; when the substrate is a rigid material, the material is iron, aluminum, stainless steel, zinc, copper, tin, alloy, glass, silicon wafer, wood board, or quartz; when the substrate is a flexible material, the material is plastic, rubber, polymer, or fabric; and the sample source for the physical vapor deposition process is one of cadmium sulfide, indium arsenide, gallium nitride, indium phosphide, and gallium antimonide.

[0080] The structural design of the construction equipment used in this invention is as follows:

[0081] A first mass flow controller is installed on the output pipeline of the argon gas cylinder;

[0082] An injection pump 3 is installed on the output pipeline of the external precious metal solution container;

[0083] The pipeline connecting the argon gas cylinder and the precious metal aqueous solution is connected to the top of the movable electrode 10.

[0084] The upper end of the movable electrode 10 is a metal capillary, and the lower end is a quartz capillary.

[0085] The movable electrode 10 is disposed in the electrode moving device, which is connected to the computer 13 and is used for the directional movement of the movable electrode 10. The electrode moving device includes an AC power supply 8, a resistance box 7, and an electrode moving controller 9. The electrode moving controller 9 is connected to the movable electrode 10 and controls the directional movement of the movable electrode 10.

[0086] The metal part of the movable electrode 10 is connected to the high-voltage electrode of the AC power supply 8, and the quartz part of the movable electrode 10 is connected to the counter electrode of the AC power supply 8.

[0087] A voltage-stabilizing resistor is connected in series between the movable electrode 10 and the AC power supply 8;

[0088] The substrate is placed at the right 1 / 4 position of the string-shaped quartz tube 11, below the moving electrode 10; the opening plane of the string-shaped quartz tube 11 is composed of a fixed quartz plate and a sliding quartz plate that can be tightly fitted; the physical vapor deposition source sample is placed in a crescent-shaped quartz dish 12, which is placed in the middle of the string-shaped quartz tube 11.

[0089] The manufacturing steps of the movable electrode 10 are as follows:

[0090] The high-voltage electrode of AC power supply 8 is connected to the metal part of the movable electrode 10, and the quartz part is connected to the counter electrode. After the upper end of the movable electrode 10 is insulated, it is welded to the electrode moving device to ensure that the two are relatively insulated.

[0091] Example 1:

[0092] During use, open the valve of argon cylinder 1, set the opening of the connected first mass flow controller 5 to 30 sccm, and maintain this for 1 minute to purge the atmosphere from the pipeline. Add 1 mM chloroauric acid solution to syringe 4, and adjust the injection pump 3 to an input rate of 0.02 mL / min. Plan the movement path in advance using programming software on computer 13 and issue commands to electrode movement controller 9. Once electrode movement controller 9 controls the moving electrode 10 to begin moving, apply high-voltage AC power to the moving electrode 10, adjust the power output, and maintain it at 10W. After plasma ignition, maintain the treatment time for 5 minutes. The chloroauric acid solution mixes with argon gas at the first three-way valve 6 and then enters the plasma treatment area, i.e., the quartz tube 11. Under the action of high-energy electrons, it is reduced to gold nanoparticles and printed onto the substrate. After treatment, turn off the AC power and remove the moving electrode 10.

[0093] Place 3g of cadmium sulfide powder in the center of the quartz dish 12. Push the sliding quartz plate of the quartz tube 11 to close the quartz tube 11. Open the gas valve of the hydrogen cylinder 2. Set the second mass flow controller 14 and the third mass flow controller 15, with openings of 40 sccm and 60 sccm respectively. Raise the temperature of the quartz tube 11 to 800℃ and maintain it for 20 minutes to achieve the effect of patterned growth of nanowire arrays.

[0094] The characterization data of the silicon wafer with patterned nanowire arrays fabricated in this example are as follows: Figures 2-4 As shown, the printed gold nanocatalyst Figure 2 SEM images showed that the gold nanoparticles did not aggregate, had a small particle size, and exhibited good catalytic activity. Super depth-of-field 3D microscopy images clearly showed... Figure 3 The silicon wafer with a mid-line structure and a grown nanowire array has a roughness of approximately 50 μm. (Through...) Figure 5 The SEM images show that the diameter of the nanowire is 50-70 nm, which meets the size requirements for nanowires.

[0095] Example 2:

[0096] The difference between this embodiment and Embodiment 1 is that the solution in the syringe 4 is chloroplatinic acid solution, with a concentration adjusted to 0.05 mM. The opening of the first mass flow controller 5 is adjusted to 50 ccm. The control power supply is 20 W. Figure 6 The characteristic peaks shown in the XRD pattern are consistent with the cadmium sulfide standard card (PDF#41-1049), which corroborates the formation of cadmium sulfide nanowires. Figure 7 The EDX spectrum in the image confirms the presence of sulfur, cadmium, and platinum, which also serves as corroborating evidence.

[0097] Example 3:

[0098] The difference between this embodiment and Embodiments 1 and 2 is that the sample source in the middle of the quartz dish 12 is replaced with indium arsenide powder 5.

[0099] g. The opening degree of both the second mass flow controller 14 and the third mass flow controller 15 is changed to 50ccm, and the time to maintain 900℃ is changed to 30min. For example... Figure 8 The TEM image of indium arsenide nanowires clearly shows the "golden needle mushroom" structure formed by the growth of nanowires guided by the gold catalyst, thus confirming that the nanowire growth is catalytically guided. SEM-mapping images of the indium arsenide nanowires confirm the presence of arsenic, indium, and platinum. These characterizations strongly demonstrate the successful preparation of indium arsenide nanowires.

[0100] This invention employs high-voltage alternating current to generate micro-plasma by utilizing the non-conductive quartz segment and the conductive metal segment. It utilizes the principle of co-catalytic guidance through catalyst and thermal conductivity to construct nano-precious metal catalysts along a designated path. The morphology of the catalyst can be controlled by adjusting the gas flow rate, the type and concentration of the precious metal compound aqueous solution. Through high-precision controllable printing of nano-precious metal catalysts, combined with the catalyst's guiding effect on nanowire growth, patterned nanowire arrays are achieved. Because the catalyst in this invention is prepared directly on the substrate surface, it is simple, efficient, and has a fast reaction rate. Furthermore, due to electrostatic repulsion, the particle size is small and the uniformity is good, resulting in good nanowire uniformity.

[0101] The above description is an explanation of the present invention and not a limitation thereof. The scope of the present invention is defined by the claims. Within the scope of protection of the present invention, any form of modification may be made.

Claims

1. A method for constructing patterned nanowire arrays, characterized in that, Noble metal catalysts are printed directly onto a substrate along a specified path to form nano-noble metal catalysts with a specified pattern. The equipment used in the fabrication method of patterned nanowire arrays includes: Argon cylinder (1), with a mass flow controller connected to its output pipeline, A hydrogen cylinder (2) has its output line connected to the output line of an argon cylinder (1), and a quartz tube (11) is connected to its output end. A quartz dish (12), the vapor-deposited sample, and a substrate are placed inside the quartz tube (11). The syringe pump (3) is connected to a syringe (4) and is connected to an external container containing a precious metal compound solution; the output line of the syringe (4) is connected to the output line of the argon cylinder (1). The movable electrode (10) is located at the output end of the combined pipeline of the syringe (4) output line and the argon cylinder (1) output line, and is introduced into the quartz tube (11). The output end of the movable electrode (10) is located above the substrate. The electrode movement controller (9) is connected to the moving electrode (10) and the external computer (13) to control the directional movement of the moving electrode (10). The method for constructing patterned nanowire arrays includes the following steps: Inject an aqueous solution of a precious metal compound into the syringe (4); connect all the pipelines and set up the printing model; control the movement trajectory of the electrodes through an external computer (13); Open the output pipeline of the argon cylinder (1) to discharge the impurities in the argon pipeline and the merging pipeline, and then use the mass flow controller to regulate the argon delivery rate in the pipeline; at the same time, turn on the injection pump (3) to transport the precious metal aqueous solution into the pipeline at a constant speed; the concentration of the precious metal compound aqueous solution is 0.1-1 mM. Argon gas and precious metal aqueous solution are mixed and enter the capillary tube. The AC power supply (8) is turned on and AC current is applied to the moving electrode (10) to break down the argon gas and generate argon plasma; the plasma power is 3-30 W. After plasma ignition, the input rates of the noble metal compound aqueous solution and argon gas are kept constant. The noble metal ions are rapidly reduced under the action of argon plasma and printed on the substrate surface. The total argon gas flow rate is controlled at 30-100 sccm. The plasma reduction treatment time is 1-20 min. The movable electrode (10) moves along a specified track to print nano-noble metal catalysts in a specific area on the substrate surface; After the catalyst is printed, the moving electrode (10) is removed, the sliding quartz plate is pushed to close the quartz tube (11), the argon cylinder (1) and the hydrogen cylinder (2) are opened, and the impurities in the tube are discharged. The delivery of argon and hydrogen in the pipeline is controlled by mass flow controllers installed on the argon and hydrogen pipelines. The mixed gas is input into the quartz tube (11) at a stable rate. The quartz tube (11) is then heated and kept at a constant temperature. The sample source gas is patterned and grown under the guidance of a catalyst by physical vapor deposition to obtain a nanowire array. The argon flow rate is controlled within the range of 20-60 sccm, the hydrogen flow rate is controlled within the range of 20-60 sccm, and the temperature range is 800-900 ℃.

2. The method for constructing patterned nanowire arrays as described in claim 1, characterized in that: The upper end of the movable electrode (10) is a metal capillary, and the lower end is a quartz capillary; the metal capillary is connected to the high voltage electrode of the external AC power supply (8), and the quartz capillary is connected to the counter electrode of the external AC power supply (8).

3. The method for constructing patterned nanowire arrays as described in claim 1, characterized in that: A voltage-stabilizing resistor is connected in series between the movable electrode (10) and the external AC power supply (8).

4. The method for constructing patterned nanowire arrays as described in claim 1, characterized in that: The quartz tube (11) is a string-shaped quartz tube (11). The vapor-deposited original sample is placed in a quartz dish (12), which is located in the middle of the quartz tube (11). The substrate is located in the middle between the end of the quartz dish (12) and the end of the quartz tube (11).

5. The method for constructing patterned nanowire arrays as described in claim 4, characterized in that: The opening of the string-shaped quartz tube (11) is provided with a fixed quartz plate and a sliding quartz plate. The sliding quartz plate slides to form an electrode gap between itself and the fixed quartz plate.

6. The method for constructing patterned nanowire arrays as described in claim 1, characterized in that: The movable electrode (10) maintains a distance of 1-3 mm from the substrate; the tube length of the movable electrode (10) ranges from 90-120 mm, the inner diameter ranges from 0.06-0.08 mm, and the outer diameter ranges from 1.5-2 mm.

7. The method for constructing patterned nanowire arrays as described in claim 6, characterized in that: The length of the quartz tube (11) ranges from 40 to 50 cm; the outer diameter of the quartz tube (11) ranges from 8 to 10 cm; the inner diameter ranges from 10 to 12 cm; and the width of the opening plane ranges from 4 to 5 cm.

8. The method for constructing patterned nanowire arrays as described in claim 1, characterized in that: The length of the metal capillary tube of the movable electrode (10) ranges from 80. 100 mm, quartz capillary tube length range 10 20 mm; the resistance value of the voltage regulator is 10-40 kΩ; the length of the fixed quartz plate at the mouth of the string-shaped quartz tube (11) is 25-35 cm, the length of the sliding quartz plate is 10-15 cm, and the sliding range of the sliding quartz plate is 6-10 cm.

9. The method for constructing patterned nanowire arrays as described in claim 1, characterized in that, The manufacturing steps of the movable electrode (10) are as follows: The high voltage electrode of AC power supply (8) is connected to the metal capillary of the moving electrode (10), and the counter electrode is connected to the quartz capillary. The upper ends of the high voltage electrode and the counter electrode of AC power supply (8) are insulated. After the insulation treatment, the upper ends of the high voltage electrode and the counter electrode of AC power supply (8) are welded to the moving device to ensure that the electrodes and the moving device are relatively insulated.

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