CN107777659B - The preparation method and its metal break nano-wire array of metal break nano-wire array - Google Patents

Abstract

The invention discloses the preparation method of metal break nano-wire array and its metal break nano-wire arrays, using the etching liquid of heterogeneity and ratio the different characteristic in direction is etched in the substrate of semi-conducting material, produce the nanohole array with different inflection points, again using the precious metal catalyst particle for being deposited on nano-pore bottom as seed layer, the metal material of unlike material is filled in nano-pore by way of centrifuging and being electroplated；Finally use wet etching method remove substrate, to prepare ordered arrangement and with required inflection point metal break nano-wire array.In such a way that centrifugation is electroplated, bending place is avoided to generate notch, improves electroforming rate.

Description

Preparation method of metal breakpoint nanowire array and metal breakpoint nanowire array

technical field

The invention relates to the field of nano-device processing, in particular to a method for preparing a metal inflection point nanowire array and the metal inflection point nanowire array.

Background technique

Metal nanowires have properties such as quantum size effect, surface effect, quantum tunneling effect, and dielectric confinement effect, which will cause them to exhibit macroscopic properties such as light, heat, electricity, magnetism, and force that are different from conventional bulk materials. It has broad application prospects in microelectronic devices, microfluidic devices, sensors, etc. At present, the methods for preparing metal nanowire arrays mainly include: porous alumina template method (AAO membrane), polymer membrane template method, soft template method and external field induction method, etc. Template-assisted methods such as porous alumina template method and polymer membrane template method are easy to damage metal nanowires during template removal; soft template method is complicated in experimental process, easy to pollute the environment, and usually requires complex and expensive equipment, resulting in a sharp increase in cost ; The external field induction method is limited to the preparation of magnetic metal nanowires. Moreover, the existing preparation methods are difficult to prepare an orderly array of metal nanowires with inflection points. The existing prepared metal nanowires are distributed in a non-array and cannot be bent, making microelectronic devices, microfluidic devices, sensors, etc. Technological development is constrained.

Contents of the invention

The purpose of the present invention is to propose a method for preparing a metal inflection point nanowire array with controllable inflection points, orderly arrangement, avoiding gaps at the inflection points, and improving the forming rate of electroplating.

The object of the present invention is to provide a metal inflection point nanowire array with controllable inflection points, orderly arrangement, avoiding gaps at the inflection points, and improving the formation rate of electroplating.

For reaching this purpose, the present invention adopts following technical scheme:

A method for preparing a metal breakpoint nanowire array, comprising the following steps:

Step 1: spin-coat a layer of photoresist on the upper surface of the substrate made of semiconductor material, dry it, cover it with a mask plate with the same size and distribution density as the required nanowires, and place it in a photolithography machine Exposure is carried out, and the exposed photoresist is removed by development; then, the remaining exposed photoresist is removed by plasma etching, and the unexposed photoresist has an array nanohole structure;

In step 2, a layer of titanium film and a layer of gold film are sequentially evaporated on the upper surface of the substrate treated in step 1. Since the unexposed photoresist acts as a mask, the upper surface of the substrate is formed with Sequential arrangement of precious metal lattices;

Step 3, according to the number M of required bending angles of the metal break point nanowire array, prepare M kinds of etching solutions with different compositions and ratios, and select each required bending angle according to the required bending angles of each required bending section. For the etchant of the bending section, the etching time of each required bending section is calculated according to the length of each required bending section. The number of times of etching solution replacement is equal to the number of required bending points. The substrate is put into an etching solution for etching, and a nanohole array with desired bending points is obtained on the substrate;

Step 4, put the substrate treated in step 3 into an electroplating system filled with electroplating solution, the electroplating system is fixed on a centrifugal workbench, and the precious metal catalytic particles deposited at the bottom of the nanopore array are used as a seed layer , under the centrifugal force of the centrifugal workbench, the electroplating layer electroplates the target metal from the bottom of the nanohole array along the bent channels to form the target metal column array;

The rotational speed of the centrifugal table R=A*sinθ, θ is the angle between the axial direction of the electroplated bending section and the normal direction of the substrate, the axial direction of the bending section is along the bending The folding axis points to the direction of the upper surface of the base, the normal direction of the base is the positive direction of the upper surface of the base along the X-axis, and the rotation base A is 1000-10000r/min;

When 90°≤θ≤180°, the position of the base remains unchanged; when 0°≤θ<90°, the base rotates 180° around the central symmetry line of its upper surface;

Step 5, after the electroplating is completed, the substrate is separated from the target array of metal pillars by a wet etching method, so as to obtain an array of metal inflection point nanowires arranged in an orderly manner and having desired inflection lines.

Preferably, the electroplating process of said step 4 is:

In the working chamber of the electroplating system, select a current density of 0.5A/dm ² to 2A/dm ² for electroplating in the electroplating solution;

The plating speed is controlled within the range of 0.8μm/min～1.2μm/min;

The electroplating time corresponding to the bending section = the segment length of the bending section ÷ the electroplating speed;

Electromagnetic stirring of the electroplating solution during the electroplating process;

After the electroplating is finished, the substrate is taken out, washed with distilled water, and then dried with cold air.

Preferably, the etching solution includes hydrofluoric acid, oxidizing agent, water and additives, and the ratio of hydrofluoric acid, oxidizing agent and water is 2:1:2 to 8:1:8;

The additive includes ethylene glycol and glycerol, and the ratio of each component in the additive is adjusted according to the required bending angle.

Preferably, in step three, the etching rate of the substrate is controlled within the range of 0.5 μm/min to 5 μm/min;

The etching time corresponding to the required bent section=the segment length of the required bent section÷the etching speed.

Preferably, in the step 3, after each desired bending section is etched, the substrate is taken out from the etching solution, the substrate is rinsed with deionized water, and the substrate is dried with nitrogen; Then, according to the required bending angle of the next required bending segment, the dried substrate is put into another corresponding etching solution for etching.

Preferably, said step 1 also includes the process of removing oxides from the substrate:

First, the substrate is placed in a mixed hot solution of concentrated sulfuric acid and hydrogen peroxide to remove oxides on the surface of the substrate;

Next, rinse the substrate with deionized water;

Finally, the substrate was dried with nitrogen.

Preferably, in the mixed hot solution, the proportioning ratio of concentrated sulfuric acid and hydrogen peroxide is 1:1;

The temperature of the mixed hot solution is controlled within the range of 20°C to 70°C.

Preferably, the separation process of said step 4 is:

Etching the substrate with a wet etchant until the substrate is completely corroded to obtain the array of metal inflection point nanowires arranged in an orderly manner and having the required inflection lines;

The wet etchant is an alkaline etchant.

Preferably, the target metal has alkali resistance.

Preferably, using the metal breakpoint nanowire array prepared by the method for preparing the metal breakpoint nanowire array, the metal breakpoint nanowire array is formed by orderly arrangement of a plurality of metal breakpoint nanowires, and the metal The breakpoint nanowire has a bent structure.

The preparation method of the metal inflection point nanowire array utilizes the characteristics of different etching directions of different components and proportions of etching solutions in the substrate of semiconductor materials to produce nanohole arrays with different inflection points, and then deposits on The noble metal catalytic particles at the bottom of the nanopores are used as the seed layer, and the nanopores are filled with metal materials of different materials by means of centrifugal electroplating; finally, the substrate is removed by wet etching, so as to prepare orderly arrangements and metals with the required bending lines. Breakpoint nanowire arrays.

The centrifugal electroplating method is used to control the centrifugal force required for electroplating each bent section by controlling the rotational speed of the centrifugal workbench, which is related to the included angle θ of each bent section of the nanohole array. When 90°≤θ≤180°, the electroplated metal grows from right to left along the original electroplated position under the action of centrifugal force, avoiding gaps at the bend and improving the electroplating forming rate.

Description of drawings

The accompanying drawings further illustrate the present invention, but the content in the accompanying drawings does not constitute any limitation to the present invention.

Fig. 1 is a structural diagram of the nanohole array formed on the photoresist after exposure in one of the embodiments of the present invention;

Fig. 2 is a structural view of the upper surface of the substrate of one embodiment of the present invention after vapor-depositing metal;

Fig. 3 is a structure diagram after etching a nanohole array on the substrate of one embodiment of the present invention;

Fig. 4 is a nanopore array structure diagram of one of the embodiments of the present invention;

Fig. 5 is a state diagram of the substrate centrifugal plating target metal according to one embodiment of the present invention;

Fig. 6 is a state diagram of the third required bending section of centrifugal electroplating in one embodiment of the present invention;

Fig. 7 is a state diagram of a notch formed by centrifugal electroplating in one embodiment of the present invention;

Fig. 8 is a first state diagram of the second required bending section of centrifugal electroplating according to one embodiment of the present invention;

Fig. 9 is a second state diagram of the second required bending section of centrifugal electroplating in one embodiment of the present invention;

Fig. 10 is a third state diagram of the second required bending section of centrifugal electroplating according to one embodiment of the present invention;

Fig. 11 is a state diagram of the first required bending section of centrifugal electroplating according to one embodiment of the present invention;

Fig. 12 is a structure diagram of a metal breakpoint nanowire array according to one embodiment of the present invention;

Fig. 13 is a structure diagram of a metal breakpoint nanowire array according to another embodiment of the present invention;

FIG. 14 is another structure diagram of a metal breakpoint nanowire array according to another embodiment of the present invention.

Among them: substrate 1; photoresist 2; nanohole array 11; noble metal lattice 3; noble metal catalytic particles 31; target metal pillar array 4; included angle θ; metal inflection point nanowire array 5; metal inflection point nanowire 51; Notch 6; target metal 7; required bending angle α2; first required bending segment L1; second required bending segment L2; third required bending segment L3.

Detailed ways

The technical solutions of the present invention will be further described below in conjunction with the accompanying drawings and through specific implementation methods.

Embodiment one

The preparation method of the metal breakpoint nanowire array of this embodiment comprises the following steps:

Step 1: spin-coat a layer of photoresist 2 on the upper surface of the substrate 1 made of semiconductor material, dry it, cover it with a mask plate with the same size and distribution density as the required nanowires, and place it on the photolithography Exposure is carried out in the machine, and the exposed photoresist 2 is developed and removed; then, the remaining exposed photoresist 2 is removed by plasma etching, and the unexposed photoresist 2 has an array nanopore structure, as shown in Figure 1 Show;

In step 2, a layer of titanium film and a layer of gold film are sequentially vapor-deposited on the upper surface of the substrate 1 treated in step 1, as shown in FIG. 2 , since the unexposed photoresist 2 acts as a mask, The upper surface of the substrate 1 forms an orderly array of precious metal lattices 3;

Step 3, according to the number M of required bending angles of the metal break point nanowire array, prepare M kinds of etching solutions with different compositions and ratios, and select each required bending angle according to the required bending angles of each required bending section. For the etchant of the bending section, the etching time of each required bending section is calculated according to the length of each required bending section. The number of times of etching solution replacement is equal to the number of required bending points. The substrate 1 is put into an etching solution for etching, and a nanohole array 11 having a desired inflection point is obtained on the substrate 1, as shown in FIGS. 3 and 4 ;

Step 4, put the substrate 1 treated in step 3 into the electroplating system filled with electroplating solution, and the electroplating system is fixed on the centrifugal workbench to deposit the noble metal catalytic particles 31 at the bottom of the nanopore array 11 It is a seed layer, and under the centrifugal force of the centrifugal workbench, the electroplating layer electroplates the target metal 7 from the bottom of the nanohole array 11 along the bent channel to form the target metal column array 4, as shown in FIGS. 5 to 11 ;

The rotational speed of the centrifugal table R=A*sinθ, θ is the angle between the axial direction of the electroplated bent section and the normal direction of the substrate 1, and the axial direction of the bent section is along The axis of the bending section points to the direction of the upper surface of the base 1, the normal direction of the base 1 is the positive direction of the upper surface of the base 1 along the X-axis, and the rotation base A is 1000-10000r/min;

As shown in Figure 8, when 90°≤θ≤180°, the position of the base 1 remains unchanged; as shown in Figure 6, when 0°≤θ<90°, the base 1 wraps around its upper surface The center line of symmetry of is rotated 180°;

Step 5, after the electroplating is completed, the substrate 1 is separated from the target metal column array 4 by wet etching, so as to obtain an ordered array of metal inflection point nanowire arrays 5 with the required bending lines, as shown in FIG. 12 .

The preparation method of the metal inflection point nanowire array utilizes the characteristics of different etching directions of etching solutions in different compositions and proportions in the semiconductor material substrate 1 to manufacture nanohole arrays 11 with different inflection points, and then Using the noble metal catalytic particles 31 as the seed layer, the nanopores are filled with metal materials of different materials by means of centrifugal electroplating; finally, the substrate 1 is removed by wet etching, so as to prepare orderly arranged metal folds with the required bending lines. Dot nanowire array5. The noble metal catalytic particles 31 are evaporated titanium film and gold film.

In the pretreatment, precious metals are used as catalysts, and a layer of titanium film and a layer of gold film are evaporated in sequence to overcome the instability of pretreatment using silver plating solution in the past; by preparing M etching solutions with different components and proportions, according to The required bending angle of the required bending section, changing the composition and proportion of the etching solution to control the viscosity and surface tension of the etching solution, so that the etching direction can be controlled along <100>, <111>, <112 >, <113> etc. to etch the substrate 1 to form finer, adjustable bending angle required bending segments; and the number of required bending points can be controlled by controlling the number of times the etchant is replaced ; Control the segment length of the required bending segment by controlling the etching time each time, so as to realize the preparation of the nanohole array 11 with fully controllable bending angle on the substrate 1 .

Since the nanohole array 11 is a curved hole array with multiple bending points, if it is purely electroplated (that is, the electroplating system is left standing without centrifugal force), it is easy to generate gaps 6 at the bends due to uneven electroplating, and it cannot be electroplated. forming. Therefore, in the step 4, the centrifugal electroplating method is adopted to control the centrifugal force required for electroplating each bending section by controlling the rotation speed of the centrifugal workbench. It is related to the included angle θ of the folded section. And because the direction of the centrifugal force is outward, when 90°≤θ≤180°, as shown in Figure 8 to Figure 10, the electroplated metal grows from right to left under the action of centrifugal force along the original electroplating position. When 0°≤θ<90°, as shown in Figure 6 and Figure 7, the electroplated metal will grow uniformly in all directions, and the nanopores are narrow, which can easily cause local channels to close and form gaps 6, thus making it impossible to electroplate Forming; therefore, when 0°≤θ<90°, the substrate 1 needs to be rotated 180° around the central symmetry line of its upper surface, so that the included angle θ becomes within the range of 90°-180° to avoid bending A gap 6 is generated at the place to improve the electroplating forming rate.

Preferably, the electroplating process of said step 4 is:

In the working chamber of the electroplating system, select a current density of 0.5A/dm ² to 2A/dm ² for electroplating in the electroplating solution; the electroplating speed is controlled within the range of 0.8 μm/min to 1.2 μm/min; the bending section corresponds to The electroplating time=the section length of the bending section÷the electroplating speed; during the electroplating process, the electroplating solution is electromagnetically stirred; after the electroplating, the substrate 1 is taken out, and the substrate 1 is cleaned with distilled water, and then the substrate 1 is dried with cold air .

The current density is controlled within the range of 0.5A/dm ² to 2A/dm ² , and the crystal is delicate and the hardness is appropriate. The electroplating speed is controlled within the range of 0.8 μm/min to 1.2 μm/min, and the deposition speed of the target metal 7 is appropriate. The electroplating time of each bent segment of the nanohole array 11 is determined by its segment length and its electroplating speed. Electromagnetic stirring is performed on the electroplating solution during the electroplating process to make the electroplating more uniform, prevent gaps 6 at the bends, and improve the forming rate of the metal inflection point nanowires. After each bending section is electroplated, the substrate 1 is taken out and cleaned and dried to prevent part of the target metal 7 from remaining in the electroplated bending section and affect the electroplating of the next bending section, and the dried substrate 1 can also be detected The electroplating and forming conditions of the bending section can be detected and repaired in time to avoid subsequent rework.

Preferably, the etching solution includes hydrofluoric acid, oxidizing agent, water and additives, and the ratio of the hydrofluoric acid, oxidizing agent and water is 2:1:2 to 8:1:8; the additives include ethylene glycol Alcohol and glycerin, adjust the proportion of each component in the additive according to the required bending angle. It can be found through experiments that if the ratio of the oxidizing agent in the etching solution is too high, the sidewall of the nanopore will be excessively oxidized, thereby forming a porous structure, and the metal breakpoint nanowire 51 made is easy to break; The ratio is constant. According to the number M of bending angles required by the metal break point nanowire array, the ratio and composition of the additive are changed, and M etching solutions with different compositions and ratios are prepared. The additive can effectively control the etching solution. The viscosity and surface tension of the etching solution can effectively control the bending angle of etching; the number of bending points is controlled by the number of times of etching solution replacement, and the position of the bending point is controlled by the etching time, thus realizing The etched bends are fully controllable.

Preferably, in the third step, the etching speed of the substrate 1 is controlled within the range of 0.5 μm/min to 5 μm/min; the etching time corresponding to the required bending section=the section of the required bending section Long ÷ etch rate. The etching speed is controlled by chemical reaction, and according to the segment length of the required bending segment, the action time of etching each bending segment is calculated, so as to precisely control the length of each bending segment of the nanohole array 11 .

Preferably, in the step 3, after each desired bending section is etched, the substrate 1 is taken out from the etching solution, the substrate 1 is rinsed with deionized water, and the substrate 1 is dried with nitrogen gas. Substrate 1; then, according to the desired bending angle of the next desired bending section, put the dried substrate 1 into another corresponding etching solution for etching. After each required bending section is etched, rinse and dry the substrate 1 to prevent the previous etching solution from remaining on the substrate 1, affecting the etching of the next bending section and causing the bending of the next bending section The angle deviates.

Preferably, the step 1 also includes a process of removing oxides from the substrate 1:

First, the substrate 1 is placed in a mixed hot solution of concentrated sulfuric acid and hydrogen peroxide to remove oxides on the surface of the substrate 1; then, the substrate 1 is rinsed with deionized water; finally, dried with nitrogen The base 1. Through the oxide removal process of the substrate 1, the oxide on the surface of the substrate 1 can be removed, so that the surface of the substrate 1 is clean and has good hydrophilicity.

Preferably, in the mixed hot solution, the ratio of concentrated sulfuric acid to hydrogen peroxide is 1:1; the temperature of the mixed hot solution is controlled within the range of 20°C to 70°C. The ratio of concentrated sulfuric acid to hydrogen peroxide is 1:1 to ensure that the oxides on the surface of the substrate 1 are fully removed. If the temperature is too high, the reaction of concentrated sulfuric acid and hydrogen peroxide will be excessive, and production accidents will occur.

Preferably, the separation process of said step 4 is:

The wet etchant etches the substrate 1 until the substrate 1 is completely corroded to obtain the metal inflection point nanowire array 5 that is ordered and has the required bending lines; the wet etchant is an alkaline etchant.

Preferably, the target metal 7 has alkali resistance.

The target metal 7 is a metal that is not corroded by strong alkali such as gold (Au), silver (Ag), nickel (Ni), platinum (Pt), copper (Cu), and the substrate 1 is silicon or III-V The family of semiconductor materials is a semiconductor material that can be corroded by a strong alkali, so an alkaline etchant is selected as the wet etchant, and the wet etchant only corrodes the substrate 1, but does not corrode the target metal 7, so that when the substrate 1 is completely corroded, it is obtained The metal breakpoint nanowire array 5 arranged in an orderly manner and having required bend lines. The wet etchant may be an alkaline etchant such as KOH or NaOH.

Preferably, using the metal breakpoint nanowire array prepared by the method, as shown in FIGS. The metal inflection point nanowire 51 has a bent structure. The metal inflection point nanowire array 5 has a plurality of metal inflection point nanowires 51 with the same bending shape, and has good macroscopic properties such as light, heat, electricity, magnetism, and force.

Embodiment two

The preparation method of the metal breakpoint nanowire array of this embodiment is as follows:

Step 1: First, place a monocrystalline silicon block with a size of 1cm*1cm*0.035cm (length*width*thickness), p-type doping type, resistivity 1-10Ω/cm, and <100> crystal orientation In the mixed hot solution of concentrated sulfuric acid (mass concentration: 96%) and hydrogen peroxide (mass concentration: 30%) with a volume ratio of 1:1, the mixed hot solution is controlled at 60°C and monocrystalline silicon blocks are soaked in it for 10 Minutes to fully remove the oxide on the surface of the monocrystalline silicon block; then take the monocrystalline silicon block out of the mixed hot solution, rinse it with a large amount of deionized water; dry it in a nitrogen stream to obtain a substrate 1. Next, spin-coat a layer of photoresist 2 with a thickness of about 400 nm on the substrate of the base 1, dry it and place it in a photolithography machine for exposure, and the exposed photoresist 2 is removed by development; Etching for 2 to 3 minutes, remove the remaining exposed photoresist 2, and the unexposed photoresist 2 has an array nanohole structure; then, vapor-deposit 3nm titanium (Ti) and 30nm Ti on the upper surface of the substrate 1 For gold (Au), the evaporation time is about 30 minutes. Since the unexposed photoresist 2 acts as a mask, an orderly array of precious metal lattices 3 can be formed on the upper surface of the substrate 1, as shown in Figures 1 and 2;

Step 2: Preparation of Nanopore Array 11:

Step 21: preparing etching solution.

Prepare etching solution B (prepared from 15ml of deionized water, 2ml of hydrogen peroxide, 10ml of hydrofluoric acid and 15ml of glycerol) according to the required bending angle α2, and add it to a polytetrafluoroethylene container;

Prepare etching solution C (prepared from 20ml of deionized water, 2ml of hydrogen peroxide, and 10ml of hydrofluoric acid), and add it to another polytetrafluoroethylene container;

Step 22: Immerse the substrate 1 obtained in step 1 in the etching solution C, and determine the etching time t1 according to the segment length L1 of the first required bending segment and the etching speed of 3 μm/min. Due to the catalysis of the noble metal catalytic particles 31, the corrosion rate of the substrate 1 below the noble metal catalytic particles 31 is much greater than that of the part without the noble metal catalytic particles 31. In addition, the directional sedimentation of the noble metal catalytic particles 31 results in directional formation along the Z-axis direction. A nano-microchannel with a large aspect ratio in a single direction, that is, forming the first required bending segment L1 on the substrate 1;

Step 23: Take out the substrate 1 obtained after the etching in step 22, rinse it with deionized water, and blow it dry with nitrogen; then, immerse it in the etching solution A, and according to the required bending angle α2, the second required The length of the bent section L2 and the etching speed of 1 μm/min determine the etching time t2. Due to the change of the composition and ratio of the etchant, the viscosity and surface tension of the etchant change, so that the contact position and the etching direction of the noble metal catalytic particles 31 and the substrate 1 change, thus forming an inflection point and forming the second required bend. folding;

Step 24: Take out the substrate 1 obtained after the etching in step 23, rinse it with deionized water, and blow it dry with nitrogen; then, immerse it in the etching solution C, and according to the segment length of the third required bending segment L3 Determine the etching time t3 with an etching speed of 3 μm/min;

Step 25: Take out the substrate 1 that has been etched in step 24, rinse it with deionized water, and dry it with nitrogen gas to obtain a nanohole array 11 with the desired bending line, as shown in FIG. 3 .

Step 3: Prepare target metal post array 4:

The substrate 1 obtained in step 25 is placed in the electroplating system containing the target metal 7 electroplating solution, and the noble metal catalytic particles 31 deposited at the bottom of each nanohole in the nanohole array 11 are used as the seed layer, and the nanopore array of the substrate 1 11 Staged Centrifugal Plating of Target Metals 7 . The electroplating system is fixed on the centrifugal workbench, and the specific electroplating steps are as follows:

Step 31:

Select the current density of 1.3A/ ^dm2 to electroplate the third required bending section L3 of the nanohole array 11 first in the electroplating solution, and the rotation speed of the centrifugal table is zero; the temperature of the electroplating solution is between 20°C and 80°C During the electroplating process, the electroplating solution is stirred to keep the concentration of the electroplating solution uniform; the electroplating time t32 is determined according to the segment length of the third required bending section L3 and the electroplating speed of 1.2 μm/min, and the electroplating Immediately after the end, the substrate 1 was taken out, washed with distilled water and dried with nitrogen, as shown in FIG. 6 .

Step 32:

At this time, if the substrate 1 is placed as shown in Figure 4, that is, the included angle θ of the second required bending section to be plated is <90°, and if it is electroplated according to normal or centrifugal electroplating, the shape shown in Figure 7 will be produced. Notch 6.

Therefore, the entire substrate 1 is rotated 180° with the center line of symmetry on its upper surface as the axis of rotation, so that the included angle θ between the axial direction of the second required bending section L2 to be electroplated and the normal direction of the substrate 1 becomes into the range of 90° to 180°, as shown in Figure 8.

Select the current density of 0.7A/ ^dm2 to electroplate the second required bending section L2 in the electroplating solution, and the rotation speed of the centrifugal table is determined according to the included angle θ of the second required bending section L2. R=A*sinθ, where the range of A is 5000r/min. Utilizing the action of centrifugal force, the electroplating layer is sequentially plated with metal from the bottom of the second required bending section L2 to prevent the gap 6 from being partially closed, especially at the bending point, when the second required bending section L2 is filled by electroplating. The temperature of the electroplating solution is between 20°C and 80°C, preferably 30°C to 60°C; the electroplating solution is stirred during the electroplating process so that the concentration of the electroplating solution is always uniform; according to the segment length and engraving of the second required bending section L2 The electroplating time t22 was determined at an etching rate of 0.9 μm/min. Immediately after the electroplating, the substrate 1 was taken out, washed with distilled water, and dried with nitrogen gas. The electroplating process is shown in Fig. 8 to Fig. 10 .

Step 33:

Select the current density of 1.3A/ ^dm2 to electroplate the first required bending section L1 in the electroplating solution, and the rotation speed of the centrifugal table is zero; the temperature of the electroplating solution is between 20°C and 80°C, preferably 30°C to 60°C; Stir the electroplating solution during the electroplating process so that the concentration of the electroplating solution is always uniform; determine the electroplating time t12 according to the segment length of the first required bending section L1 and the electroplating speed of 1.2 μm/min, and take out the substrate 1 immediately after electroplating , rinsed with distilled water and blown dry with nitrogen, as shown in FIG. 11 , the substrate 1 containing the target metal post array 4 after electroplating is completed.

Step 4: Corroding the substrate 1 with KOH solution as a wet etchant to separate the substrate 1 from the target metal pillar array 4, thereby obtaining a metal inflection point nanowire array 5 arranged in an orderly manner and having the desired inflection line, as shown in Figure 12 shown.

Embodiment Three

According to the method described in Example 2, by changing the etching properties of etching solutions with different components and proportions, nanohole arrays 11 with different numbers of bending points and bending angles are produced on the substrate 1, and then different types of targets are used. The metal 7 is centrifugally plated with the nanohole array 11 to obtain the target metal column array 4, and then the substrate 1 is separated from the target metal column array 4 by wet etching, thereby preparing orderly arranged and bent metal breakpoint nanowires Array 5, as shown in Figure 13 and Figure 14.

The above describes the technical principles of the present invention in conjunction with specific embodiments. These descriptions are only for explaining the principles of the present invention, and cannot be construed as limiting the protection scope of the present invention in any way. Based on the explanations herein, those skilled in the art can think of other specific implementation modes of the present invention without creative efforts, and these modes will all fall within the protection scope of the present invention.

Claims (10)

1. a kind of preparation method of metal break nano-wire array, which is characterized in that include the following steps：

Step 1, one layer photoresist of upper surface spin coating of the substrate made of semi-conducting material, drying, capping and required nano wire Size and distribution density all same mask plate, and be placed in litho machine and be exposed, the photoresist of exposure is gone by development It removes；Then, the remaining photoresist exposed is removed by plasma etching, there is array nano-pore on unexposed photoresist Structure；

One layer of titanium film and one layer of golden film is deposited in the upper surface of the substrate by step 1 processing in step 2 successively, due to Unexposed photoresist plays the role of mask, and the upper surface of the substrate forms the noble metal dot matrix of ordered arrangement；

Step 3 prepares M kinds heterogeneity and ratio according to the required bending angle number M of metal break nano-wire array Etching liquid, and according to the required bending angle of each required bending segment select it is each needed for bending segment etching liquid, by each The segment length of bending segment needed for a calculates the etch period of each required bending segment, and etching fluid exchange number is equal to required inflection point Number performs etching being put into etching liquid by the substrate of step 2 processing, obtains having required bending in the substrate The nanohole array of point；

Step 4 will be put by the substrate of step 3 processing in the electroplating system for filling electroplate liquid, the electroplating system It is fixed on centrifugal work platform, using the precious metal catalyst particle for being deposited on the nanohole array bottom as seed layer, is centrifuging Electroplated layer is formed from the bottom of the nanohole array along the duct plated object metal of bending under the centrifugation force effect of workbench Metal target column array；

Rotary speed the R=A*sin θ, θ of the centrifugal work platform for the axial direction and substrate of the bending segment being electroplated normal direction The axial direction of angle between direction, the bending segment is the direction that upper surface of substrate is directed toward along bending segment axis, the base The normal orientation at bottom is the upper surface of the substrate along X-axis positive direction, and rotation radix A is 1000~10000r/min；

When 90 °≤θ≤180 °, the position of the substrate remains unchanged；As 90 ° of 0 °≤θ ＜, the substrate is around its upper surface Centre symmetry line rotate 180 °；

Step 5 after the completion of plating, makes substrate and the metal target column array detach, to obtain by wet etching method Ordered arrangement and the metal break nano-wire array with required folding line.

2. the preparation method of metal break nano-wire array according to claim 1, which is characterized in that the step 4 Electroplating process is：

In the working chamber of electroplating system, 0.5A/dm is selected²~2A/dm²Current density be electroplated in electroplate liquid；

Electroplating velocity controls in the range of 0.8 μm/min~1.2 μm/min；

Segment length's ÷ electroplating velocities of the corresponding electroplating time=bending segment of bending segment；

Electromagnetic agitation is carried out to electroplate liquid in electroplating process；

The substrate, and the substrate wash with distilled water are taken out after plating, then dry the substrate with cold wind.

3. the preparation method of metal break nano-wire array according to claim 1, it is characterised in that：The etching liquid packet Hydrofluoric acid, oxidant, water and additive are included, the proportioning of the hydrofluoric acid, oxidant and water is hydrofluoric acid 10ml, oxidant 2ml With water 15ml or hydrofluoric acid 10ml, oxidant 2ml and water 20ml；

The additive includes ethylene glycol and glycerine, and each component ratio in the additive is adjusted according to required bending angle.

4. the preparation method of metal break nano-wire array according to claim 1, it is characterised in that：In the step 3 In, the etching speed of the substrate controls in the range of 0.5 μm/min~5 μm/min；

Segment length's ÷ etching speeds of the corresponding etch period=required bending segment of required bending segment.

5. the preparation method of metal break nano-wire array according to claim 1, it is characterised in that：In the step 3 In, often etch one section needed for after bending segment, the substrate is taken out from etching liquid, is rinsed the substrate with deionized water dry Only, nitrogen is used in combination to dry the substrate；Then according to the required bending angle of bending segment needed for next section, by the substrate after drying It is put into corresponding another etching liquid and performs etching.

6. the preparation method of metal break nano-wire array according to claim 1, it is characterised in that：The step 1 is also Removal oxide process including substrate：

First, the substrate is placed in the mixing hot solution of the concentrated sulfuric acid and hydrogen peroxide, removes the oxidation of the substrate surface Object；

Then, the substrate is rinsed well with deionized water；

Finally, the substrate is dried with nitrogen.

7. the preparation method of metal break nano-wire array according to claim 6, it is characterised in that：In the heat of mixing In solution, the concentrated sulfuric acid, hydrogen peroxide proportioning be 1:1；

The temperature of the mixing hot solution controls in the range of 20 DEG C~70 DEG C.

8. the preparation method of metal break nano-wire array according to claim 1, which is characterized in that the step 5 Separation process is：

The substrate is corroded in wet etching agent, until the substrate obtains ordered arrangement and has required bending when being corroded completely The metal break nano-wire array of line；

The wet etching agent is alkaline corrosion agent.

9. the preparation method of metal break nano-wire array according to claim 1, it is characterised in that：The metal target With alkali resistance.

10. being rolled over using metal prepared by the preparation method of the metal break nano-wire array described in claim 1 to 9 any one Point nano-wire array, it is characterised in that：The metal break nano-wire array by a plurality of metal break it is nano thread ordered arrangement and At, and the metal break nano wire has bending structure.