KR20120129447A - Silver nanowire having protuberance and Method for preparing the same - Google Patents

Abstract

PURPOSE: A silver nanowire with projections and a manufacturing method thereof are provided to obtain high manufacturing yield by reducing the production ratio of byproducts such as metal particles. CONSTITUTION: A method for manufacturing a silver nanowire with projections the steps of heating and inducing reaction of polyol, a dispersion stabilizing agent, a silver precursor, bronsted acid, and a halogen ion donor and rapidly cooling the reactant.

Description

Silver nanowires with protuberances and method for manufacturing same {Silver nanowire having protuberance and Method for preparing the same}

The present invention relates to a silver nanowire having a projection and a method for producing the same.

In recent years, as the demand for thin-film TVs increases, development of displays such as liquid crystal plasma, organic electroluminescence (organic EL), field emission, and the like has been made.

In addition to the above-described display, the transparent electrode is applied as an essential member in other forms of display. In addition to the touch panel, a mobile phone, an electronic paper, a solar cell, and an electroluminescent element, the transparent electrode is applied as an essential member that cannot be omitted.

Although various transparent electrodes are known, in particular, ITO (Indium Tin Oxide) has a good balance between light transmittance and conductivity, and is easy to form fine electrode patterns by wet etching using an acid solution. It is used as a transparent electrode for engineering purposes.

However, the conductive oxide represented by ITO or the like forms a transparent conductive film on the surface of the substrate by a vacuum process such as a sputtering method. Since the oxide transparent conductive film is formed by a vacuum process such as a sputtering method, expensive equipment is required and continuous production is difficult.

In order to solve such a problem, the method of forming a transparent conductive film is proposed by apply | coating the composition containing a conductive oxide and a conductive polymer. However, in such a method, it is difficult to obtain sufficient conductivity, and there is a problem in that performance is particularly poor when applied to a touch screen, an organic EL element, or a solar cell.

As another transparent electrode, the transparent electrode which formed the mesh structure by the metal pattern represented by the electromagnetic shielding film of a plasma display is mentioned, for example, and it is a metal nanowire or a metal. A transparent electrode made of a fine mesh using a nanostructure may be used.

Conventionally, a template method has been mainly used as a method for manufacturing metal nanowires. These template methods were based on carbon nanotubes, porous silica or alumina, surfactants, or block copolymers, but all are complex processes requiring a large number of processes or reaction times of several tens of hours. In addition, the length and thickness of the metal nanowires obtained are nonuniform and have disadvantages that are insufficient for use in the transparent conductive film. A template method using carbon nanotubes is disclosed, for example, in Japanese Patent Laid-Open No. 2004-269987.

In addition to the template method, an electron beam irradiation method (see, for example, Japanese Patent Application Laid-Open No. 2002-67000) and an ultraviolet irradiation method (for example, Japanese Patent Application Laid-Open No. 2007-239055) have been proposed. As it is disadvantageous and has a non-uniform shape and thickness, it is difficult to use a transparent electrode requiring high light transmittance.

In recent years, the method of manufacturing a metal nanowire by the chemical reduction method which is simple in operation is researched, and the polyol method is especially actively researched especially.

The preparation of silver nanostructures by a method called "polyol process" or "polyol method" is known in the literature, for example by Wiley et al. , Shape-Controlled Synthesis of Metal Nanostructures The case of Silver, Chem. Eur. J. , 11: 454-463 (2005) and Wiley et al., Polyol Synthesis of Silver Nanoparticles: Use of Chloride and Oxygen to Promote the Formation of Single-Crystal, Truncated Cubes and Tetrahedrons, Nano Letters , 4 (9): 1733-1739 (2004). Also

In general, the polyol process is a solution-based method. According to early literature, silver containing solutions are produced by mixing silver compounds with polyol solvents. Here, the silver compound may be an inorganic salt such as silver nitrate (AgNO ₃ ) or an organic salt such as silver acetate. The silver compound is reduced to silver metal by the polyol method. These silver metals are silver metals that form silver nanostructures [Ref. Ducamp-Sanguesa et al., Synthesis and Characterization of Fine and Monodisperse Silver Particles of Uniform Shape, Journal of Solid State Chemistry , 100: 272-280 ( 1992). In typical polyol synthesis, silver atoms (which produce metals that form nanostructures) are obtained by reducing AgNO ₃ with ethylene glycol (EG), as shown in Schemes 1 and 2 below:

Scheme 1

2HOCH ₂ CH ₂ OH → 2CH ₃ CHO + 2H ₂ O

Scheme 2

2Ag ⁺ + 2CH ₃ CHO → CH ₃ CHO? OHCCH ₃ + 2Ag + 2H ⁺

In general, polyols are used not only as solvents for silver compounds but also as reaction solvents. According to early literature, polyols are also used as reducing agents to reduce silver compounds to silver metals. The production of silver is controlled by the rate of silver (I) reduction (increasing with temperature) [Ducamp-Sanguesa et al., Journal of Solid State Chemistry , 100: 272-280 (1992) at page 274, col . 2]. As such, the polyol process is typically performed at elevated temperatures, although the reaction is known to occur at ambient temperature in the presence of poly (vinylpyrrolidone) (PVP). Carotenuto et al., Eur. Phys. J. B , 16: 11-17 (2000) at page 12, col. 2 and US Published Patent Application No. US 2007/0034052 A1 to Vanheusden et al. published on Feb. 15, 2007 at paragraph 38].

In early experiments, the polyol method involves mixing the silver compound with the polyol and heating it (US Pat. No. 4,539,041) or dissolving the silver compound in the polyol and mixing the solution with a portion of the heated polyol [Ducamp-Sanguesa et al. al., Journal of Solid State Chemistry , 100: 272-280 (1992). In either case, the combined reactants were heated until metals were formed (metallic precipitates or powders). Then, the metal was separated by filtration.

One problem observed in the early experiments of the polyol method was that metal particles could sinter (aggregate into larger metal particles). However, it has been found that the phenomenon of sintering (agglomeration into large metal particles) in the polyol process can be minimized or inhibited by the use of organic protecting agents [Ducamp-Sanguesa et al., Journal of Solid State Chemistry , 100: 272-280 (1992) at page 275, col. 2]. As such an organic protecting agent, polyvinylpyrrolidone (PVP) is usually used.

In addition, US Patent Publication No. 2008/0003130 discloses a method for synthesizing silver nanoparticles of various forms through a polyol method characterized in that it comprises a halogen compound, which is mainly limited to the production of particles of a single crystal form. There is a disadvantage that it is not suitable for making nanowires for transparent electrodes requiring high light transmittance.

The present invention has been made to solve the problems of the prior art, and an object of the present invention is to provide a silver nanowire of a novel structure that can be used, for example, a conductive transparent electrode.

Another object of the present invention is to provide a method for producing silver nanowires having high yields of silver nanowires and / or protrusions by reducing the production rate of metal particles generated by incidentality and ensuring reproducibility.

In order to achieve the above and other objects, the present invention provides a silver nanowire having a projection of a silver component. Silver nanowires with protrusions according to the invention comprise, for example, silver nanowires of at least 1 μm to 50 μm and protrusions in the range of 5 nm to 100 nm in diameter. The protrusions formed on the surface of the silver nanowire may have a diameter of 100 nm or more by an additional reaction. Such protrusions may be formed in at least one end of the silver nanowire and / or a plurality of protrusions on the surface of the silver nanowire (see FIG. 12). The silver nanowires with protrusions according to the present invention are not limited to the exemplary description as described above, but should be understood to also include various types of protrusion portions formed by additional processes (see Examples 7 and 8).

Silver nanowires having the projections as described above are prepared by the method of the present invention, such a method according to the present invention,

(a) heating the polyol, optionally a dispersion stabilizer, a silver precursor, Bronsted acid and a halogen ion donor;

(b) rapid cooling the heating reactant from step (a).

In step (a), the polyol serves to reduce the silver compound (from the silver precursor) to the silver metal. The polyol used in the present invention simultaneously serves as a solvent for dissolving the silver precursor and serves to reduce the silver compound to silver metal (polyol process). Polyols are polyfunctional alcohols having two or more hydroxyl groups (-OH) in the molecule, and are largely divided into ether polyols and ester polyols. Etherpolyols are prepared by adding propylene oxide (PO) or ethylene oxide (EO) to an initiator with two or more activated hydrogens (-OH, NH ₂ ), and ester polyols are dehydration polymerized dihydric or polyfunctional alcohols on polyacids. Can be prepared. Polyols used in the present invention include glycols and diols having two or more hydroxyl groups, in addition to ethylene glycol or diethylene glycol etherified propylene glycol, dipropylene glycol, polyethylene glycol and glycerol having three hydroxyl groups, 4 Pentaerythritol having two hydroxyl groups, including, but not limited to. In the present invention, ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, glycerol and polyethylene glycol are particularly preferably used.

In the present invention, a dispersion stabilizer is used as necessary. There is no restriction | limiting in particular as such a dispersion stabilizer, Especially water-soluble polymers, such as polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, polyacrylic acid, poly (diallyldimethylammonium chloride), starch, are used suitably.

In the present invention, silver nitrate, silver acetate, silver chloride, silver bromide, silver iodide and silver fluoride may be used as the silver precursor. In an embodiment of the present invention, silver nitrate is used as the silver precursor.

In the present invention, particularly, brested acid is used as an acid capable of generating H ⁺ ions. In the examples of the present invention, only nitric acid (HNO ₃ ) is shown as an acid capable of generating H ⁺ ions, but those skilled in the art will be able to consider various Bronsted acids capable of generating H ⁺ ions. will be.

In addition, in the present invention, a halogen ion donor capable of donating a halogen ion is used. Representative non-limiting examples of such halogen ion donors may be mentioned NaCl, NaBr, KCl, KBr, NH ₄ Cl, ZnCl ₂ . These halogen ion donors may be used alone, but two or more halogen ion donors may be mixed and used.

Further, in the present invention, in the step (a), with respect to 100 parts by weight of the polyol, the dispersion stabilizer is 0.1 to 20 parts by weight, the silver precursor is 0.1 to 10 parts by weight, the Bronsted acid is 0.00001 to 0.1 parts by weight The halogen ion donor is used in an amount of 0.001 to 5 parts by weight.

When the dispersion stabilizer is less than 0.1 part by weight, the produced silver nanoparticles may not be sufficiently stabilized to form uniform silver nanoparticles, and when the dispersion stabilizer is more than 20 parts by weight, the polyol may not be completely dissolved in the polyol and the viscosity is too high, making the process difficult. There is a disadvantage, the growth of the resulting nanoparticles is delayed to form nanoparticles in the form of amorphous particles.

When the silver precursor is less than 0.1 parts by weight, the number of silver nanoparticles produced is low, resulting in low process yield. When the silver precursor is more than 10 parts by weight, the silver nanowires are thick and mixed with various types of nanoparticles. There is a disadvantage that the yield is lowered.

When the Bronsted acid is less than 0.00001 parts by weight, amorphous silver nanoparticles are formed, and when the amount is greater than 0.1 parts by weight, amorphous particles are mixed, resulting in a lowered yield.

When the halogen ion donor is less than 0.001 parts by weight, silver nanoparticles in the form of particles are mixed, so that the yield of silver nanowires is lowered. When the halogen ion donor is more than 5 parts by weight, amorphous particles and thick silver nanowires are mixed in the yield. There is a disadvantage of deterioration.

In addition, the heating in step (a) is carried out in a temperature range of 100 ℃ to 200 ℃.

Rapid cooling in the step (b) is carried out when the absorption coefficient of the silver nanowire at 600nm wavelength / the absorption coefficient of the silver nanoparticles at 600nm wavelength has a value between 1 and 5, which will be described later. In this case, the rapid cooling method may be variously considered, and may be easily performed by, for example, ice water or ethanol solvent.

The solution used in the embodiment of the present invention may be obtained by separately preparing a solution I and a solution II as follows, or may be prepared all at once without dividing the solution I and solution II. In the following, only the general method for preparing the solution I and the solution II and then preparing the solution is described, but the present invention should not be construed as being limited to this general method.

Preparation of Solution I

Solution I is prepared by adding the dispersion stabilizer to the polyol and then stirring until the dispersion stabilizer is completely dissolved.

Preparation of Solution II

Solution II is prepared by adding a silver precursor to the polyol and stirring until the silver precursor is completely dissolved. The polyol used at this time serves as a solvent for dissolving the silver compound and serves to reduce the silver compound to silver.

Preparation of Silver Nanowires with Projections

After mixing the prepared solution I and solution II, Bronsted acid (eg HNO ₃ ) is added. Thereafter, the resulting mixture is reacted at a temperature range of 100 ° C. to 200 ° C., preferably 130 ° C. to 190 ° C. for a predetermined time (eg, 5 minutes to 20 minutes), and then a halogen ion donor is added thereto. The reaction proceeds further. At this time, the reaction time by the halogen ion donor is suitable for 10 minutes or more, preferably 15 to 30 minutes. Here, the order of adding Bronsted acid and a halogen ion donor may change. The reactants produced by cooling means such as ice water are then rapidly cooled. In the present invention, the reaction was further progressed by Bronsted acid and the halogen ion donor so that unreacted Ag ions and Ag atoms remain in the solution, and the lowering of the reaction temperature was then performed by the silver nanowires produced in the reaction solution. This is to create small silver nanowires on the surface. That is, at high temperatures, the ostwalt ripening effect causes the growth of the large silver nanowires, which are more thermodynamically stable, consume the smaller silver particles. At this time, if the reaction rate is reduced by dropping the reaction temperature, the growth of the silver nanowires is slowed, and the unreacted silver ions and silver atoms remaining in the solution may undergo secondary growth on the surface of the silver nanowires.

Absorption coefficient of silver nanowires at 600 nm / absorbance coefficient of silver nanoparticles at 600 nm is ~ 1, the extinction coefficient of silver nanowires at 600 nm / absorption coefficient of silver nanoparticles at 600 nm when the reaction is complete, preferably ~ 10 value, preferably -5, More preferably, the value of about -4 is shown.

In order to synthesize the silver nanowires having protrusions, the absorption coefficient of silver nanowires at 600 nm / the absorption coefficient of silver nanoparticles at 600 nm is 1 to 10, more preferably 1 to 5, even more preferably 1 to 4 values. It can be obtained by slowing down the reaction rate when

In addition, after the step (b) to control the size of the projections of the silver nanowire having the projections, (c) injecting a silver precursor to the reactant rapidly cooled from the step (b) to further react. It may include.

The further reaction in step (c) may be carried out at 0 ^o C to 200 ^o C. Reducing agent component remains in the reactant rapidly cooled in the step (b) to reduce the silver precursor irrespective of the reaction temperature and can increase the temperature of the reactant in order to specifically increase the reaction rate. In addition, a reducing agent may be additionally introduced from the outside to induce a reduction reaction.

According to the method according to the present invention, the reproducibility is excellent, and the silver nanowires can be selectively grown, so that the yield of the silver nanowires produced is very high.

In addition, the silver nanowire according to the present invention can be used as a transparent electrode because of excellent conductivity and light transmittance.

Moreover, since absorption by silver protrusion occurs separately, it is possible to apply a biosensor by attaching a substance capable of reacting with a specific substance on the protrusion (for example, an antigen antibody reaction). (Silver nanowire sensor with protrusion)

In addition, the silver nanowire contact by the protrusion and the anti-slip between the silver nanowires can be improved to improve the entanglement between the silver nanowires, it is expected that the silver nanowire resistance can be reduced.

1 is a scanning electron micrograph of silver nanowires prepared in Example 1. FIG.
Figure 2 is a scanning electron micrograph of the silver nanowires prepared in Example 2.
Figure 3 is a scanning electron micrograph of the silver nanowires prepared in Example 3.
Figure 4 is a scanning electron micrograph of the silver nanowires prepared in Example 4.
FIG. 5 is a scanning electron micrograph of silver nanowires prepared in Example 7. FIG.
Figure 6 is a scanning electron micrograph of the silver nanowires prepared in Example 8.
FIG. 7 is a scanning electron micrograph of silver nanowires having protrusions prepared in Comparative Example 1. FIG.
8 is a scanning electron micrograph of silver nanowires having protrusions prepared in Comparative Example 2. FIG.
9 is a scanning electron micrograph of silver nanowires prepared through Comparative Example 3. FIG.
10 is a scanning microscope picture of silver nanowires prepared through Comparative Example 4. FIG.
FIG. 11 shows normalized absorbance spectra of silver nanoparticles according to the reaction time of Example 7.
12 is a diagram illustrating one example of silver nanowires having projections of a silver component according to the present invention.

Hereinafter, the present invention is described in more detail by the following examples. The following examples are only for illustrating the present invention, and the present invention is not limited to the following examples. The following examples and comparative examples were performed five times or more in the same manner, and the data listed in Table 1 describes the ranges of the minimum and maximum values of the examples and comparative examples performed five or more times. In addition, the average value should be understood as the average value of the minimum and maximum values listed in Table 1.

Example 1

Put 100 mL of ethylene glycol (one solvent in polyol) into a 200 mL round bottom flask, add 14 g of polyvinylpyrrolidone (dispersion stabilizer), and stir until the polyvinylpyrrolidone is completely dissolved at room temperature. Solution I "was prepared. In addition, 100 mL of ethylene glycol was added to a 200 mL round bottom flask, 6 g of silver nitrate (AgNO ₃ ) was added, followed by stirring until the silver nitrate was completely dissolved at room temperature to prepare " Solution II ". Then, I and II were added to a 1 L round bottom flask with a stirrer, and then 0.1 g of nitric acid was added at room temperature. (The nitric acid may be added after dipping the reactor in an oil bath of 160 ° C.) Then, the reactor was immersed in an oil bath preset to 160 ° C., and then stirring was started. After 10 minutes, 0.1 g of sodium chloride was added to the reactor, followed by further reaction for 50 minutes to prepare silver nanowires. At this time, the order of adding sodium chloride and nitric acid may be changed. In this embodiment, solution I and solution II were performed separately, but may be performed all at once without separation between solution I and solution II. The results are shown in Table 1 below and FIG. 1.

Example 2

Silver nanowires were prepared in the same manner as in Example 1, except that the amount of sodium chloride was changed from 0.1 g to 0.01 g. The results are shown in Table 1 below and FIG. 2.

Example 3

Silver nanowires were prepared in the same manner as in Example 1, except that the amount of nitric acid was changed from 0.1 g to 0.01 g. The results are shown in Table 1 below and FIG. 3.

Example 4

Silver nanowires were prepared in the same manner as in Example 1, except that the reaction temperature was changed from 160 ° C to 140 ° C. The results are shown in Table 1 below and FIG. 4.

Example 5

Silver nanowires were prepared in the same manner as in Example 1, except that the reaction temperature was changed from 160 ° C to 180 ° C. The results are shown in Table 1 below.

Example 6

Silver nanowires were prepared in the same manner as in Example 1, except that 0.1 g of ammonium chloride was used instead of 0.1 g of sodium chloride. The results are shown in Table 1 below.

Example 7

Preparation of Silver Nanowires with Projections

Put 100 mL of ethylene glycol (one solvent in polyol) into a 200 mL round bottom flask, add 7 g of polyvinylpyrrolidone (dispersion stabilizer), and stir until the polyvinylpyrrolidone is completely dissolved at room temperature. Solution I "was prepared. In addition, 100 mL of ethylene glycol was added to a 200 mL round bottom flask, and 3 g of silver nitrate was added, followed by stirring until the silver nitrate was completely dissolved at room temperature to prepare " Solution II ". Then, I and II were added to a 1 L round bottom flask with a stirrer, and then 0.1 g of nitric acid was added at room temperature. (Nitric acid may be added after dipping the reactor in an oil bath of 160 ° C.) After that, the reactor was immersed in an oil bath preset to 160 ° C., and then stirring was started. After 10 minutes, 0.1 g of sodium chloride was added to the reactor, followed by further reaction for 20 minutes, and then immersed in iced water and cooled to room temperature (a solvent such as ethanol may be added to temporarily lower the reaction temperature). Silver nanowires were prepared. At this time, the order of adding sodium chloride and nitric acid may be changed. In this example, the reaction proceeded for 30 minutes (to proceed with the reaction for 10 minutes after adding nitric acid and sodium chloride for 20 minutes) to leave unreacted Ag ions and Ag atoms in the solution The lowering of the reaction temperature is to cause small silver nanowires to be generated on the surface of the silver nanowires generated in the reaction solution. That is, at high temperatures, the ostwalt ripening effect causes the growth of the large silver nanowires, which are more thermodynamically stable, consume the smaller silver particles. At this time, if the reaction rate is reduced by dropping the reaction temperature, the growth of the silver nanowires is slowed, and the unreacted silver ions and silver atoms remaining in the solution may undergo secondary growth on the surface of the silver nanowires. In this embodiment, solution I and solution II were performed separately, but may be performed all at once without separation between solution I and solution II. The results are shown in Table 1 below and FIG. 1. The results are shown in FIG.

Example 8

Preparation of Silver Nanowires with Projections

Silver nanowires were prepared in the same manner as in Example 7, except that the cooling process was performed by adding 200 mL of ethanol instead of dipping in ice water. The results are shown in FIG.

Comparative Example 1

Silver nanowires were prepared in the same manner as in Example 1, except that nitric acid and sodium chloride were not added. The results are shown in Table 1 below and FIG. 7.

Comparative Example 2

Silver nanowires were prepared in the same manner as in Example 1, except that sodium chloride was not added. The results are shown in Table 1 below and FIG. 8.

Comparative Example 3

Silver nanowires were prepared in the same manner as in Example 1, except that nitric acid was not added. The results are shown in Table 1 below and FIG. 9.

Comparative Example 4

(Comparison with Example 7 and / or 8)

Silver nanowires were prepared in the same manner as in Example 7, except that the reaction at 160 ° C. was performed for 1 hour without a cooling process. The results are shown in FIG.

shape Length (㎛) Diameter (nanometer) Example 1 Narrow 30-50 100-130 Example 2 Narrow 30-50 70-130 Example 3 Narrow 20-50 50-100 Example 4 Narrow 30-50 40-100 Example 5 Narrow 20-60 70-130 Example 6 Narrow 10-50 60-140 Example 7 Nanowire with protrusion 5-30 100-200 Example 8 Nanowire with protrusion 5-30 100-400 Comparative Example 1 rectangle - 50-70 Comparative Example 2 rectangle - 100-300 Comparative Example 3 Nanowire, spherical, cube, equilateral triangular pyramid - ~ 100 Comparative Example 4 Narrow 5-30 100-400

Normalized absorbance spectrum of silver nanoparticles with reaction time (FIG. 11)

FIG. 11 shows normalized absorbance spectra of silver nanoparticles according to the reaction time of Example 7. Samples of the same volume were taken and the absorbance spectra were measured and the absorbance spectra normalized. When the silver nanowires are generated, absorption occurs at a wavelength of 500 nm or more, and when the reaction is completed, the absorption spectrum is saturated. That is, silver nanowires having protrusions can be obtained by quenching or slowing down the reaction between red and blue lines. In the absorption spectrum shown in FIG. 11, black indicates that it is still in the form of silver nanoparticles, red indicates that silver nanowires start to be produced (nanowires are generated when absorption near 350 nm peaks), and yellow green indicates silver nanowire growth + Unreacted indicates the presence of ions and silver atoms, and blue indicates the end of the reaction.

Absorption coefficient of silver nanowires at 600 nm / absorbance coefficient of silver nanoparticles at 600 nm is ~ 1, the extinction coefficient of silver nanowires at 600 nm / absorption coefficient of silver nanoparticles at 600 nm when the reaction is complete, preferably ~ 10 value, preferably -5, More preferably, the value of about -4 is shown.

Therefore, in order to synthesize the silver nanowires having protrusions, the absorption coefficient of silver nanowires at 600 nm / the absorption coefficient of silver nanoparticles at 600 nm is 1 to 10, more preferably 1 to 5, even more preferably 1 to 4 It can be obtained by slowing down the reaction rate when it has a value.

Conductive Transparent Electrode Manufacturing

The silver nanowires prepared in Examples 4 and 7 were centrifuged, redispersed by adding ethanol, and then again centrifuged to recover the silver nanowires. The washing process was repeated three times to recover pure silver nanowires, and then redispersed in 20 mL of ethanol to prepare a silver nanowire coating solution. After dropping the prepared silver nanowire coating solution on a glass substrate, a conductive transparent electrode was prepared by a bar coater. The wire resistance of the prepared conductive transparent electrode was 40 to 50 Ω / cm and the transmittance was 80 to 85%.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as defined in the following claims. It can be understood that it is possible.

Claims (13)

Silver nanowires with protrusions on the surface. (a) heating the polyol, dispersion stabilizer, silver precursor, Bronsted acid and halogen ion donor; And
(b) a method of producing silver nanowires with projections on the surface, including rapidly cooling the heating reactants from step (a). The method of claim 2, wherein in step (a), the dispersion stabilizer is 0.1 to 20 parts by weight, the silver precursor is 0.1 to 10 parts by weight, and the Bronsted acid is 0.00001 to 0.1 parts by weight based on 100 parts by weight of the polyol. And wherein the halogen ion donor is used in an amount of 0.001 to 5 parts by weight. The method of claim 2, wherein the heating in step (a) is carried out in a temperature range of 100 ℃ to 200 ℃. The method of claim 2, wherein the rapid cooling in the step (b) is performed when the absorption coefficient of the silver nanowire at 600nm wavelength / the absorption coefficient of the silver nanoparticles at 600nm wavelength has a value between 1 and 5. How to. 6. The process of claim 5, wherein the rapid cooling is performed in ice water or ethanol solvent. The method according to any one of claims 2 to 6, wherein the polyol is one, or a mixture of two or more selected from the group consisting of ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, glycerol and polyethylene glycol. How to feature. The dispersion stabilizer according to any one of claims 2 to 6, wherein the dispersion stabilizer is selected from the group consisting of polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, polyacrylic acid, poly (diallyldimethylammonium chloride) and starch. 1 or 2 or more mixtures. The method according to any one of claims 2 to 6, wherein the silver precursor is silver nitrate, silver acetate, silver chloride, silver bromide, silver iodide and silver fluoride, or a mixture thereof. 7. The halogen ion donor according to any one of claims 2 to 6, wherein the halogen ion donor is one or a mixture of two or more selected from the group consisting of NaCl, NaBr, KCl, KBr, NH ₄ Cl and ZnCl ₂ . How to. The method according to any one of claims 2 to 7, further comprising, after step (b), (c) injecting a silver precursor into the rapidly cooled reactant from step (b) to further react. How to feature. Silver nanowires with protrusions prepared according to the method of any one of claims 2 to 7. A conductive electrode formed by including a silver nanowire having a projection according to claim 1.

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