KR20160091758A - Metal nanowire, method for synthesizing the metal nanowire, and transparent electrode and organic light emitting diode including the metal nanowire manufactured by the method - Google Patents

Abstract

The present invention provides a metal nanowire having excellent electric conductivity and light scattering effects. As a nanowire including at least two wire parts, the metal nanowire includes an n^th wire part and a (n+1)^th wire part connected to the n^th nanowire. A diameter of the n^th nanowire part and the diameter of the (n+1)^th nanowire are different from each other.

Description

TECHNICAL FIELD [0001] The present invention relates to a metal nanowire, a method of synthesizing the metal nanowire, and a method of manufacturing the same, and a transparent electrode including the metal nanowire and a method of manufacturing the same. BACKGROUND OF THE INVENTION [0002] METHOD}

The present invention relates to a metal nanowire, a method of manufacturing the same, and a light-transmitting electrode including the metal nanowire manufactured thereby and an organic light-emitting device.

Recently, with the rapid development of the display and solar cell fields, the demand for the translucent electrode used therein is also increasing rapidly. Indium Tin Oxide (ITO) is mainly used for the transparent electrode material because of its suitability for mass production technology and applications. However, ITO electrode is not stable against external impact such as thermal shock due to vacuum process Due to problems, development is being made to replace the ITO electrode.

Materials for replacing ITO electrodes include carbon nanotubes (CNT), graphene, zinc oxide (ZnO), poly (3,4-ethylenedioxythiophene (Poly (3, 4-ethylenedioxythiophene, PEDOT), and metal nanowires.

Among them, metal nanowires, especially silver nanowires, have high chemical stability among metals, transparency which is due to the characteristics of silver with very good thermal conductivity and electric conductivity and optical properties due to the very small dimensions of nanowires. And has been spotlighted as an electrode material for manufacturing a conductive film. Such silver nanowires are expected to be used in a variety of fields such as plasma display panels (PDP), optical filters, electromagnetic shielding materials, organic light emitting diodes (OLED), solar cells, liquid crystal displays Screen, EL keypads for mobile phones, and the like.

The metal nanowires can be prepared by a synthetic method known as the so-called polyol method in which the metal salt is reduced to a metal atom by a polyol solvent. (US Patent Publication 2005/0056118) In general, Seeds are formed through a nucleation process, and some of the seeds grow in the same direction in all directions in the solution to form isotropic nanostructures (nanoparticles), and some seeds preferentially grow along the lateral direction To form anisotropic nanostructures (nanotubes, nanowires, nano belts, nanowires, etc.).

The diameter and the length of the metal nanowire are influenced by various parameters of the polyol synthesis method. Conventional polyol synthesis methods include a combination of factors such as kinetic factors, strain and surface energy, and thermal energy during nanowire growth It is difficult to grow the nanowires with a diameter of 50 μm or more. Even if the nanowires are grown with a metal nanowire having a large diameter and a large aspect ratio, the dispersibility is decreased.

In addition, since the metal nanowire used as the light-transmitting electrode needs high electrical conductivity, transparency and flexibility, a surfactant (capping agent) such as polyvinylpyrrolidone (PVP) is used in the synthesis, There is a problem that electrical resistance is increased at a contact point between the electrodes and electrical characteristics are deteriorated.

In addition, due to the small dimension of the metal nanowire, the contact portion between the metal nanowires becomes very narrow, and even if the current density is increased even with a small amount of electric current, the nanowire is heated and the metal nanowire is heated. There is a problem.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems and it is an object of the present invention to provide a metal nanowire having a large diameter and an aspect ratio and having a plurality of bending properties, And to provide a metal nanowire having a structure having appropriate transmittance and haze value when used in light-transmitting electrodes, particularly when used in OLED illumination, organic solar cells, and the like.

Further, the present invention provides a metal nanowire having a large diameter and a large aspect ratio and having a plurality of diameter characteristics, thereby increasing the probability of contact between metal nanowires, preventing increase in sheet resistance, providing excellent electrical conductivity, And to provide a metal nanowire having a structure having appropriate transmittance and haze value when used for illumination, organic solar cells, and the like.

In addition, the present invention provides a core-shell nanowire having metal covering properties, which can prevent sulphation and oxidation to improve reliability, improve light scattering characteristics, and provide a high haze value without significantly lowering electrical conductivity and transmittance To provide a core-shell nanowire having a structure having the structure shown in Fig.

Another object of the present invention is to provide a metal nanowire manufacturing method capable of producing a metal nanowire having a large diameter and an aspect ratio and having a plurality of bending characteristics without producing any by-products other than metal nanowires .

Another object of the present invention is to provide a metal nanowire manufacturing method capable of producing metal nanowires having a large diameter and a large aspect ratio and having a plurality of diameters without producing any by-products other than metal nanowires .

The present invention also provides a method for producing core-shell nanowires capable of synthesizing core-shell nanowires having metal coating properties.

The present invention also provides a transparent electrode having excellent conductivity and excellent transparency and haze suitable for use in OLED illumination, organic solar cells, etc., by incorporating a metal nanowire having a large diameter and a long length and having a plurality of bending properties as a conductor layer. And an organic light emitting element.

Further, the present invention also provides a transparent electrode having excellent conductivity and excellent transparency and haze value suitable for use in OLED illumination by incorporating metal nanowires having a large diameter and a long length and having a plurality of diameter characteristics as a conductor layer. And an organic light emitting element.

In addition, the present invention can prevent sulphidation and oxidation to improve reliability by including core-shell nanowires having metal coating properties as a conductor layer, and can improve light scattering characteristics and improve electrical conductivity and transmittance without significantly deteriorating A transparent electrode having a high haze value and an organic light emitting element.

The present invention relates to a nanowire including at least two wire portions, wherein the nanowire includes an arbitrary n-th wire portion and an (n + 1) -th wire portion connected to the n-th nanowire, The diameter of the wire portion is different from that of the metal nanowire to provide the nanowire.

The present invention also provides a metal wire comprising a first wire portion having a first diameter and a second wire portion having a second diameter formed from the first wire portion and having a first diameter and a second diameter different from each other, Lt; / RTI >

In addition, the present invention provides the metal nanowire wherein the second wire portion is formed at one end or both ends of the first wire portion.

The present invention also provides a metal nanowire having a first diameter of 50 to 100 nm and a second diameter of 150 to 1100 nm.

Also, the present invention provides a metal nanowire having a length of the first wire portion of 40 to 100 m and a length of the second wire portion of 5 to 15 m.

The metal nanowire according to the present invention is a metal nanowire having a structure having a large diameter and an aspect ratio and having a plurality of bending characteristics. The contact point, the contact area or the probability of contact between the metal nanowires increases, so that the sheet resistance is relatively small and the electrical conductivity And a metal nanowire having a light scattering effect can be provided.

Further, the metal nanowire according to the present invention is a metal nanowire having a large diameter and an aspect ratio and having a plurality of diameter characteristics, wherein the contact point, the contact area or the probability of contact between the metal nanowires increases, the sheet resistance is relatively small, It is possible to provide a metal nanowire excellent in light scattering effect.

Further, the metal nanowire according to the present invention is a core-shell nanowire having a metal coating property, which prevents sulphation and oxidation, thereby improving reliability, improving light scattering characteristics, and exhibiting a high haze value without significantly lowering the electric conductivity and transmittance Lt; RTI ID = 0.0 > nanowire. ≪ / RTI >

In addition, the method of manufacturing a metal nanowire according to the present invention is a one-pot synthesis, in which purification of an intermediate product is not required, and by-products other than metal nanowires are not generated, and metal nanowires can be produced with a high yield .

In addition, the method of manufacturing a metal nanowire according to the present invention minimizes volatilization of the reaction mixture by putting all of the reaction mixture into a reaction vessel and reacting under a condition of atmospheric pressure or higher, so that the metal nanowire can be bent into a bending structure without breaking even when the diameter and the aspect ratio are large So that a metal nanowire having a bending characteristic can be manufactured.

In addition, the metal nanowire according to the present invention can control the lateral growth of the metal nanowire by controlling the content of the capping agent in the reaction mixture to produce metal nanowires having a plurality of diameter characteristics.

The method of manufacturing a metal nanowire according to the present invention can be applied not only to a general metal nanowire but also to a metal nanowire having a plurality of bending characteristics and a metal nanowire having a plurality of diameters, Shell nanowires can be fabricated.

Further, by using the metal nanowire having a structure having a large diameter and aspect ratio and having a plurality of bending characteristics according to the present invention as the conductor layer of the light-transmitting electrode, it is possible to obtain an appropriate transmittance in the visible light region and a haze And an organic light emitting device including the same.

Further, by using the metal nanowire having a structure having a large diameter and an aspect ratio and having a plurality of diameter characteristics according to the present invention as the conductor layer of the translucent electrode, particularly when used in OLED lighting, organic solar cells, etc., appropriate transmittance in the visible light region and haze And an organic light emitting device including the same.

Further, by using the core-shell nanowire having the metal compound shell according to the present invention as the conductor layer of the light-transmitting electrode, it is possible to improve the reliability by preventing sulphation and oxidation, and to improve the light scattering property and to increase the electrical conductivity and transmittance It is possible to provide a translucent electrode having a high haze value without deteriorating the organic light emitting device and an organic light emitting device including the same.

FIG. 1 illustrates a metal nanowire having a plurality of bending characteristics including two wire portions according to an embodiment of the present invention,
FIG. 2 illustrates a metal nanowire having a plurality of bending characteristics including n wire portions according to an embodiment of the present invention,
FIG. 3 illustrates a three-dimensional structure of a metal nanowire having a plurality of bending characteristics including n wires according to an embodiment of the present invention,
FIG. 4 illustrates a metal nanowire having a plurality of diameter characteristics including one second wire portion according to another embodiment of the present invention,
FIG. 5 shows a metal nanowire having a plurality of diameter characteristics according to another embodiment of the present invention (FIG. 5A: metal nanowire including a second wire portion at one end, FIG. 5B: A metal nanowire including a two-wire portion),
6 illustrates a wire portion of a metal nanowire having a plurality of bending characteristics according to an embodiment of the present invention,
FIG. 7 illustrates a metal nanowire having a plurality of bending characteristics according to an embodiment of the present invention,
8 illustrates a wire portion of a metal nanowire having a plurality of diameter characteristics according to another embodiment of the present invention,
FIG. 9 illustrates a metal nanowire having a plurality of diameter characteristics according to another embodiment of the present invention,
10 to 13 are conceptual views illustrating a core-shell nanowire structure according to an embodiment of the present invention,
FIG. 14 is a conceptual view illustrating a roll-to-roll continuous process of core-shell nanowires according to an embodiment of the present invention,
15 is a SEM photograph of a silver nanowire according to an embodiment of the present invention,
16 is an SEM photograph of silver nanowires having a plurality of diameter characteristics according to an embodiment of the present invention,
17 and 18 are TEM photographs of silver nanowires having a plurality of bending characteristics according to the present invention,
19 is a TEM photograph of a silver nanowire having a structure without bending,
20 is a graph of transmittance of a transparent electrode including silver nanowires according to Examples 11 to 15 (20a) and Examples 16 to 20 (20a)
21 is a graph of haze value of a transparent electrode containing silver nanowires according to Examples 11 to 15 (21a) and Examples 16 to 20 (21a)
FIGS. 22 and 23 are electron micrographs of core-shell nanowires of Examples 23 to 27 (FIG. 22A: Example 23, FIG. 22B: Example 24, FIG. 6C: Example 25, Example 26, Fig. 23B: Example 27),
24 is a photograph showing that zinc oxide is selectively coated on the nanowire in the core-shell nanowire substrate of Example 25. FIG.
25 is a graph showing sheet resistance values in Examples and Comparative Examples,
FIG. 26 is a graph showing X-ray diffraction peak values of the core-shell nanowires in the examples (FIG. 26A: Example 23, FIG. 26B: Example 24 and FIG. 26C: Example 27)
27 to 29 are diagrams showing light transmittance values of Examples 23 to 27 (FIG. 27A: Example 23, FIG. 27B: Example 24, FIG. 28A: Examples 25 and 28B: 29: Example 27),
Figs. 30 to 32 are diagrams showing haze values in Examples 23 to 27 (Fig. 30A: Example 23, Fig. 30B: Example 24, Fig. 31a: Example 25 and Fig. 31b: 32: Example 27),
FIG. 33 is a graph showing PL (photoluminescence) values of the embodiment (FIG. 33A: Example 23, FIG. 33B: Example 24 and FIG. 33C: Example 25)
34 is a graph showing changes in sheet resistance according to time in Examples 23 to 27,
Figs. 35 and 36 are electron micrographs of core-shell nanowires of Examples 28 to 32 (Fig. 35a: Example 28, Fig. 35b: Example 29, Fig. 35c: Example 30, Fig. Example 31, Fig. 36 (b): Example 32)
37 is a photograph showing that zinc oxide is selectively coated on the nanowire in the produced core-shell nanowire substrate,
38 is a graph showing sheet resistance values in Examples and Comparative Examples,
39 is a graph showing the X-ray diffraction peak value of the core-shell nanowire of the example (FIG. 39A: Example 28, FIG. 39B: Example 29, FIG. 39C: Example 32)
Figs. 40 to 42 are diagrams showing haze values of the embodiment 28 to the embodiment 32 (Fig. 40A: Embodiment 28, Fig. 40b: Embodiment 29, Fig. 41a: Embodiment 30 and Fig. 41b: 42: Example 32),
43 to 45 are diagrams showing light transmittance values of Examples 28 to 32 (FIG. 43A: Example 28, FIG. 43B: Example 29, FIG. 44A: Example 30 and FIG. 44B: 45: Example 32),
46 is a diagram showing changes in sheet resistance according to time in Examples 28 to 32,
FIG. 47 is a graph showing a PL (photoluminescence) value of the embodiment (FIG. 47A: Example 28, FIG. 47B: Example 29 and FIG. 47C: Example 32)

Before describing the present invention in detail, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention, which is defined solely by the appended claims. shall. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise stated.

Throughout this specification and claims, the word "comprise", "comprises", "comprising" means including a stated article, step or group of articles, and steps, , Step, or group of objects, or a group of steps.

On the contrary, the various embodiments of the present invention can be combined with any other embodiments as long as there is no clear counterpoint. Any feature that is specifically or advantageously indicated as being advantageous may be combined with any other feature or feature that is indicated as being preferred or advantageous. Hereinafter, embodiments of the present invention and effects thereof will be described with reference to the accompanying drawings.

(1) metal Nanowire

1) a metal having a plurality of bending characteristics Nanowire

The metal nanowire according to an embodiment of the present invention is a metal nanowire having at least two wire portions (or at least one bent portion) and having a plurality of bending properties. More specifically, the metal nanowire includes at least one wire portion connected by a bending portion, and the (n + 1) th wire portion connected to the nth wire portion by the nth wire portion and the n th bend, The angle? Between the metal nanowires is 0 ° <α <180 °.

For example, in the case of a metal nanowire including two wire portions, as shown in FIG. 1, the first wire portion and the metal wire having a structure in which the second wire portion connected by the first bent portion forms an angle? Wire. As another example, FIG. 2 shows a metal nanowire having a plurality of wire portions.

More specifically, an angle? Between an arbitrary n-th wire section and an n + 1-th wire section connected by the n-th wire section and the n-th bent section is 130??? In the case of synthesizing metal nanowires by a method of manufacturing a metal nanowire having a plurality of bending characteristics according to the present invention, some of the metal nanowires having two wire portions (or one bent portion) Metal nanowires with minor angles are also synthesized, but most of the synthesized metal nanowires have two to four wire portions (or one to three bent portions), wherein the bent angle is in the range of 130 to 170 degrees Lt; / RTI &gt;

The metal nanowire having a plurality of bending characteristics according to the present invention may have a strain to remove stress caused by gravity acting on the growth point of the metal nanowire as the crystal grows during synthesis of the metal nanowire, When the metal nanowire has a bent structure with a predetermined angle in a predetermined direction and has at least one bent portion having the above-mentioned angular range, the contact point between the nanowires, rather than the linear metal nanowire, The contact area or the contact probability is increased, and the electric conductivity is excellent.

The metal nanowire according to an embodiment of the present invention is a two-dimensional or three-dimensional structure. When the metal nanowire has at least three or more wire portions, the plane including any n-th wire portion and the n + The plane including the (n + 1) th wire section and the (n + 2) th wire section is referred to as a B plane, and an angle formed by the B plane with respect to the A plane is -10 ° to 10 °. FIG. 3 illustrates a metal nanowire having a three-dimensional structure according to an embodiment of the present invention.

The diameter of the metal nanowire having a plurality of bending characteristics according to an embodiment of the present invention is 50 to 200 nm and the length is in the range of 40 to 300 탆. Throughout this specification, the term &quot; diameter &quot; refers to the maximum length of the cross section of the metal nanowire, and &quot; length &quot; refers to the maximum length of the longitudinal section of the metal nanowire. In addition, the aspect ratio ranges from 200 to 6,000. The aspect ratio here means the ratio of the length to the diameter of the nanowire.

Since the metal nanowire having a plurality of bending characteristics according to the present invention has a large diameter of 50 to 200 nm, the metal nanowire can be grown in a bent state without breaking even when the stress exceeds a predetermined stress in synthesis. Since the metal nanowire has a long length of 40 to 300 袖 m And has a structure having at least one folded portion. In addition, since it is bent in a certain direction (gravity direction), it has a bent curve structure instead of a zigzag structure when having two or more bent portions.

In addition, the metal nanowires having the above-described diameters, lengths, and aspect ratios are preferable as light-transmitting electrode materials because of their excellent electrical conductivity due to an increase in contact area, compared with smaller-sized metal nanowires.

The metal nanowire according to the present invention may be a metal nanowire such as Ni, Co, Fe, Pt, Au, Ag, Al, Cr, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, W, The nanowire of the metal material. In the case of silver (Ag) nanowires, silver (Ag) has high chemical stability among metals, very good thermal conductivity and electrical conductivity, and transparency which is optical characteristic due to very small dimensions of nanowires, It is preferable to be used as an electrode material for producing a film.

In addition, the metal nanowire according to the present invention, particularly the silver nanowire, can be used for a plasma display panel (PDP), an optical filter, an electromagnetic shielding material, an organic light emitting diode (OLED) Liquid crystal displays, LCDs), touch screens, EL keypads for mobile phones, and the like.

2) Multiple diameter  Metal with characteristics Nanowire

According to another embodiment of the present invention, there is provided a metal nanowire including a first wire portion and a second wire portion extending from the first wire portion, wherein a diameter (first diameter) of the first wire portion is 50 to 100 nm , The length is 40 to 100 占 퐉, the diameter of the second wire portion (second diameter) is 150 to 1100 nm, and the length is 5 to 15 占 퐉. FIG. 4 illustrates a metal nanowire having a plurality of diameter characteristics according to an embodiment of the present invention.

Also, the second diameter of the metal nanowire according to an embodiment of the present invention is 2 to 15 times the first diameter. When the second diameter is less than two times the first diameter, there is a problem of a decrease in the light scattering effect. When the second diameter is more than 15 times, the transmittance is lowered when used in a translucent electrode. More preferably 2 to 5 times.

The second wire portion may be formed at one end or both ends of the first wire portion. At least two second wire portions may be formed at each end of the first wire portion. FIG. 5 shows a metal nanowire having a plurality of diameter characteristics in which a second wire portion is formed at one end (a) or both ends (b) according to an embodiment of the present invention. It is suitable as a translucent electrode material because of its excellent electric conductivity due to an increase in the contact area due to the second wire portion.

The cross section perpendicular to the longitudinal direction of the first wire portion and the second wire portion may be polygonal, and may be, for example, triangular, square, pentagonal or the like, but is not limited thereto.

When the metal nanowire having a plurality of diameter characteristics according to the present invention is used as the conductor layer of the transparent electrode, it has a transmittance of 80% or more and is suitable for use in, for example, OLED illumination.

Further, when metal nanowires having a plurality of diameter characteristics according to the present invention are used as a conductor layer of a transparent electrode, they exhibit a haze value of 1% or more. However, due to the light scattering effect caused by the metal nanowires, The efficiency can be increased.

Generally, metal nanowires having a constant diameter have a low haze value of less than 1% and have almost no light scattering function. However, the metal nanowires having a second wire portion according to the present invention have a light scattering effect and a large haze value.

In general, when the metal nanowire is used for a light-transmitting electrode, the metal nanowire has a large surface area in comparison with a very small weight and volume, The metal nanowires having a plurality of diameter characteristics according to the present invention are excellent in dispersibility and can prevent an increase in resistance per area.

3) a plurality of bending characteristics and a plurality of diameter  Metal with characteristics Nanowire

The metal nanowire having a plurality of bending characteristics according to an embodiment of the present invention further includes a wire portion having multiple diameters. That is, at least one of the wire portions has at least two or more different diameters. Therefore, the wire portion of the metal nanowire according to an embodiment of the present invention includes a wire portion having a single diameter and a wire portion having multiple diameters.

The wire portion having a single diameter has a first diameter of 500 to 200 nm or a diameter of 150 to 1100 nm. The wire portion having multiple diameters has both a first diameter of 50 to 200 nm and a second diameter of 150 to 1100 nm in one wire portion in the case of having two different diameters. One embodiment of a wire portion as shown in Fig. 6 is shown and one embodiment of a possible metal nanowire is shown in Fig.

The second diameter is two to fifteen times the first diameter. When the second diameter is less than 2 times the first diameter, there is a problem of deterioration in the effect of light scattering. When the second diameter is more than 15 times, the transmittance is lowered when used in a light transmitting electrode. More preferably 2 to 5 times.

The wire portion including the second diameter is mainly included at the end of the metal nanowire, but is not limited thereto. A wire portion having multiple diameters may be formed at the position of any wire portion depending on the amount of the capping agent in the synthesis of the metal nanowire.

In another aspect, the metal nanowire having a plurality of diameter characteristics according to an embodiment of the present invention is a wire portion in which at least one of the wire portions has at least one bent portion. Referring to Fig. 6, the wire portion having the first diameter or the wire portion having the second diameter may be in a straight line shape, or may have a bent portion.

And in the case of a wire portion having a bending portion, the bending angle alpha is formed within a range of 130 to 170 degrees. In the case of including two wire portions, one embodiment of the wire portion as shown in Fig. 8 is shown and one embodiment of the metal nanowire as shown in Fig. 9 is shown.

4) Core-shell with metal coating properties Nanowire

The core-shell nanowire according to one embodiment of the present invention comprises a nanowire core and a metal compound shell coated on the nanowire core.

The nanowire core may be a conductive metal nanowire, for example a silver (Ag) nanowire. The metal nanowires can be used without limitation, but the metal nanowires having a plurality of bending characteristics, the metal nanowires having a plurality of diameter characteristics, the plurality of bending characteristics, and the plurality of diameters It is preferable to use a metal nanowire having the characteristics of

The nanowire core is not limited, but it is preferable that the shape of the cross section perpendicular to the nanowire length direction is polygonal. For example, the nanowire core may be a triangle, a rectangle, a pentagon, or a hexagon. When the nanowire core is polygonal, the metal compound shell is preferably coated with a structure in which the light scattering property is further increased.

The nanowire core may have a diameter in the range of 30 to 200 nm and a length in the range of 10 to 300 탆. When the nanowire core is a metal nanowire having a plurality of bending characteristics according to the present invention, the diameter may be in the range of 50 to 200 nm, and the length may be in the range of 40 to 300 μm. When the nanowire core is a metal nanowire having a plurality of diameter characteristics according to the present invention, the first diameter may be in the range of 50 to 100 nm, the second diameter may be in the range of 150 to 1100 nm, and the length of the first wire portion may be 40 [ 100 mu m, and the length of the second wire portion may be in the range of 5 mu m to 15 mu m.

The metal compound shell is coated surrounding the nanowire core. The metal compound shell is not limited, but is preferably transparent, and may comprise a transparent conductive metal oxide, nitride, or sulfide component. In one example, the transparent conductive metal compound The shell may be made, including ZnO, SiO2, SnO _2, TiO _2, AlN, GaN, BN, InN, ZnS, CdS, ZnSe, ZnTe, CdSe, at least one of the compounds consisting of carbon and , And a component such as a dopant may be added for conductivity. The transparent conductive metal compound shell may be composed of one component or may be in the form of an alloy of several components. Further, the transparent conductive metal compound shell may be a single layer or a multi-layer structure.

Conventionally, it has been common that the nanowire should have a small light scattering from an optical point of view and that the haze value should be small when the conductive layer is formed of nanowires. However, an embodiment of the present invention contemplates a core-shell nanowire capable of increasing the light scattering and increasing the haze value.

In one embodiment of the present invention, the core-shell structure is introduced to increase the light scattering of the nanowire, and the light scattering effect is remarkably increased by introducing a specific protruding structure, which was not previously available in the structure of the shell.

As one example, the metal compound shell may be a structure having a plurality of protruding structures that are narrowed as they are away from the nanowire core in a cross-sectional view perpendicular to the longitudinal direction of the nanowire. The protruding structure is not limited, but may be in the range of three to six. In this case, "protruding structure that narrows as the distance from the nanowire core" is exceptional. Even if there is a region that is widened away from the nanowire core, a protrusion of a shape that becomes narrower as more than 70% Structure. &Lt; / RTI &gt;

As another example, the metal compound shell may have a plurality of polygonal shapes in a cross-sectional view perpendicular to the nanowire length direction. But the polygonal shape may be in the range of three to six. Here, the &quot; polygonal shape &quot; is a broad sense including not only a case where the vertical cross-section is exactly polygonal but also a case where it is universally recognized as a shape similar to a polygon.

As another example, the metal compound shell may be a plurality of stripe pattern structures formed long in the nanowire length direction. Although not limited, the stripe pattern structure may be in the range of three to six.

As a specific example, Figures 10-13 illustrate a core-shell nanowire structure according to one embodiment of the present invention. As shown in the figure, the metal compound shell 20 is coated on the nanowire core 10. The metal compound shell 20 may be in the form of aggregated metal compound particles. The diameter (e) of the metal compound particles 21 is not limited, but may be in the range of 10 to 100 nm.

As shown in FIG. 10, the metal compound shell 20 has four triangular shapes in a cross-sectional view perpendicular to the longitudinal direction of the nanowire, and four stripe pattern structures Lt; / RTI &gt;

Alternatively, as shown in FIG. 11, the metal compound shell 20 has five triangular shapes in cross section perpendicular to the longitudinal direction of the nanowire, and five stripe- (FIG. 11A), and may have six triangular shapes, but may be six stripe pattern structures elongated in the nanowire length direction (FIG. 11B).

12, the metal compound shell 20 has five trapezoidal shapes in a cross-sectional view perpendicular to the longitudinal direction of the nanowire, and five stripe- Pattern structure. It is possible to manufacture a triangular or trapezoidal shape by changing the process conditions for forming the metal compound shell. For example, a trapezoidal structure can be created when coating under insufficient conditions, such as reducing the time or reducing the amount of precursor in process conditions for forming a triangular structure (see FIG. 13).

When the side adjacent to the nanowire core 10 in the polygon is a base line d, the length of the base line d is preferably in the range of 40 nm to 200 nm and the height c is preferably in the range of 10 nm to 200 nm. If the height is less than the above range, the light scattering effect is poor. If the height is out of the above range, light loss due to light absorption may be caused.

The length (a) of the core-shell nanowire is not limited, but is preferably in the range of 10 μm to 200 μm. The ratio (c / a) of the length (a) of the core- The 0.02 range is good for me. It is also preferable that the ratio (maximum diameter / a) of the length (a) of the core-shell nanowire to the maximum diameter on the cross-sectional view perpendicular to the longitudinal direction of the core-shell nanowire is within the range of 0.0001 to 0.06. It is preferable to scatter various light wavelengths through the above structure.

The core-shell nanowire having the above structure may have a haze value measured by coating on a transparent substrate on a transparent substrate with a good light scattering property at a wavelength of 550 nm of 3% or more, more preferably 20% or more at a wavelength of 550 nm . A haze value of more than 60% can be obtained as shown in the following experimental example.

In addition, the sheet resistance value is as good as 60 (Ω / □) or less, and the uncoated nanowire is not significantly deteriorated compared to the uncoated wire, and the sheet resistance value may be better. Further, it can be seen that the light transmittance value is very excellent in the range of 70 to 98% at a wavelength of 550 nm (excluding the substrate absorption).

When the core-shell nanowire having the metal coating property according to the present invention is used as the conductor layer of the transparent electrode, it has a transmittance of 80% or more and is suitable for use in, for example, OLED illumination.

In addition, when the core-shell nanowire according to the present invention is used as a conductor layer of a light-transmitting electrode, it exhibits a haze value of 1% or more, but has a light extracting function due to the light scattering effect, The efficiency can be increased.

Generally, when a metal nanowire is used for a light-transmitting electrode, the metal nanowire has a large surface area compared to a very small weight and volume, The core-shell nanowire according to the present invention has excellent dispersibility and can prevent an increase in the resistance per unit area.

(2) metal Nanowire  Manufacturing method

1) a metal having a plurality of bending characteristics Nanowire  Manufacturing method

A method of manufacturing a metal nanowire having a plurality of bending characteristics according to an embodiment of the present invention is a method of putting all the reaction mixture into a reaction vessel together and proceeding a synthesis reaction under a condition of atmospheric pressure or higher, Wire can be manufactured.

A manufacturing method according to an embodiment of the present invention is a method of synthesizing metal nanowires having a diameter of 50 to 200 nm and a length of 40 to 300 m, And a metal nanowire having a structure having at least two or more wire portions connected to each other through at least one bent portion can be manufactured.

In addition, as one-pot synthesis, there is no need to purify an intermediate product, and metal nanowires having a plurality of bending properties at a high yield can be produced without by-products other than metal nanowires.

More specifically, the present invention includes a step (S10) of preparing a reaction mixture containing a metal salt, a capping agent, a reducing solvent and a catalyst, and a step (S20) of synthesizing metal nanowires into a metal nanowire by reacting the reaction mixture into a reaction vessel And the metal nanowires having a large diameter and aspect ratio and having a plurality of bending characteristics are synthesized by controlling the content of the reaction mixture, the reaction temperature, the reaction pressure, and the reaction time.

The reaction mixture preparing step S10 is a step of preparing a reaction mixture by adding metal salts, a reducing solvent for reducing a metal salt to a metal, a capping agent for growing a reduced metal into a wire form, and a catalyst in a specific ratio, .

The metal salt is a compound consisting of a metal cation and an organic or inorganic anion. For example, the metal cation is at least one selected from the group consisting of Ni, Co, Fe, Pt, Au, Ag, Al, Cr, Cu, Mg, Mn, Mo, , a cation of metal containing Ti, W, U, V, Zr, Ge, etc., organic or inorganic anion is ^{_{[NO 3] -, [ClO}} 4] -, [BF 4] -, [PF 6] -, ^{_{[CH 3 COO] -, [}} CF 3 SO 3] - an organic or inorganic anion, such as _{^{-, [SO 4] 2-,}} [CH3COCH = COCH3]. When the ionization degree of the metal salt is similar, two or more metal salts may be used in combination. It is preferable to use a silver salt composed of a silver cation (Ag +) and an organic or inorganic anion.

The metal salt is dissolved by a reducing solvent and decomposed into metal cations and organic or inorganic anions. The decomposed metal cations are reduced to crystallize or grow into nanowires.

The metal salt is mixed at 0.03 mol / l to 0.4 mol / l. When the molar concentration is less than 0.03 mol / l, the amount of metal nanowires is rapidly decreased. When the molar concentration is more than 0.4 mol / l, there is a problem that the wires are agglomerated due to excessive production. More preferably 0.05 mol / l to 0.10 mol / l.

The reductive solvent is a polar solvent in which a metal salt, a catalyst, and a capping agent are dissolved. For example, a solvent such as a diol, a polyol, or a glycol having at least two hydroxyl groups in the molecule is used. The reducing solvent functions as a reducing agent to reduce the metal salt to form a metal. Specific examples thereof include ethylene glycol, propylene glycol and glycerol, and more specifically, at least one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerin, glycerol and diethyl glycol.

The capping agent refers to a chemical agent that preferentially interacts with and adheres to the lateral surface of the growing nanowire such that the cross-sectional surface of the nanowire can be crystallized. That is, the capping agent interacts more strongly with the side surface than interacts with the cross-sectional surface to passivate the side surface, while the cross-sectional surface can be further crystallized to produce nanowires.

As the capping agent, a surface-adhering polymer such as polyvinylpyrrolidone (PVP), polyvinylalcohol (PVA), polyacrylamide (PAM) and polyacrylic acid (PAA) is used.

The capping agent is mixed with 0.5 to 3.0 parts by weight based on 28 parts by weight of the reducing solvent. If the amount of the metal nanowires is less than 0.5 parts by weight, the diameter of the generated metal nanowires may increase. If the amount of the metal nanowires exceeds 3.0 parts by weight, the length of the metal nanowires may be shortened. More preferably 2.0 to 3.0 parts by weight.

 The catalyst is a salt additive comprising ionically cations and anions and is separated into ions in polar solvents such as water, alcohols, diols and polyols. In this case, the cation may be an organic substance or an inorganic substance, and the anion is generally an inorganic substance and includes a halogen ion (Cl-, Br-, F-, etc.). The anisotropic nanostructures are preferentially grown by the catalyst, whereby a relatively high yield of nanowires can be obtained.

The catalyst includes at least one of a compound in which one or more cations and anions are mainly ion-bonded and a hydrate thereof. The cations of Al, NH4, Sb, As, Ba, Bi, Cd, Ca, Cr, Co, Cu, Fe, H, Pb, Mg, Hg, Ni, K, Ag, Na, anions are _{C 2 H 3 O 2, Br} , CO 3, Cl, CrO 4, OH, I, NO 3, O, C 2 O 4, PO 4, SIO 3, SO 4, S, and / or SO 3 Of anions.

The catalyst is mixed with 10 ^-5 mol / l to 10 ^-2 mol / l. In the case of less than 10 ^-5 mol / l, the generation of metal nanowires is lowered due to the decrease of initial nucleation. When the concentration exceeds 10 ^-2 mol / l, large aggregation occurs, or surplus catalyst interferes with anisotropic growth of metal nanowires The diameter becomes larger and the generation of spherical particles increases.

In the metal nanowire synthesis step (S20), the reaction mixture is reacted together in the reaction mixture in the reaction vessel so that the metal salt is reduced, and the crystal is grown from the generated nucleation site through metal cations to metal nanowires . The metal nanowires having a large diameter and a large aspect ratio and having a plurality of bending characteristics are synthesized by controlling the reaction mixture and the reaction temperature and the reaction time. The diameter, length, and bending characteristics of the metal nanowires synthesized according to the reaction conditions can be controlled.

The reaction temperature of the metal nanowire synthesis step is 110 to 150 ° C. If the temperature is less than 110 ° C, the synthesis time of the metal nanowires is prolonged and the production amount is decreased. If the temperature is higher than 150 ° C, the metal nanowires are agglomerated due to an abrupt reaction rate increase.

The reaction time of the metal nanowire synthesis step is 3 to 12 hours. When the time is less than 3 hours, there is a problem that the length of the nanowire is shortened due to a short growth time. When the time exceeds 12 hours, there is a problem that nanowires are agglomerated due to an excessive reaction.

In the metal nanowire synthesis step, the reaction mixture is put together in a reaction vessel, and the reaction pressure is made to be higher than the normal pressure to synthesize the metal nanowire. This increases the pressure and increases the vaporization point, thereby minimizing the volatilization of the reaction solution and maintaining the solution composition. As a result, the length of the metal nanowires becomes 1.5 times longer than in the conventional case. Examples of the method for increasing the pressure include a method of sealing the reaction vessel, a method of injecting the inert gas into the reaction vessel, and the like.

The reaction pressure of the metal nanowire synthesis step is higher than the normal pressure and is made at 1 to 5 atm. More preferably at a pressure of 1 to 3 atm.

When the composition of the metal nanowire is changed, there is a problem that the length of the synthesized metal nanowire varies. However, when the reaction vessel is sealed and reacted, the composition can be kept constant by preventing the influx of the component into the atmosphere during the reaction So that a metal nanowire having a constant length can be obtained.

In addition, if necessary, additives can be further mixed and synthesized. For example, stabilizers such as antioxidants, dispersants, thickeners, and the like may be further mixed, but the present invention is not limited thereto. For example, HCl or HNO ₃ may be mixed in an amount of 0.01 to 1 part by weight based on the total weight of the mixed catalyst so that the length of the generated metal nanowires may be prolonged.

After the step of synthesizing the metal nanowires, the metal nanowires are cooled to room temperature, washed with acetone, ethanol or the like, and then purified to obtain metal nanowires having a large diameter and an aspect ratio and having a plurality of bending properties.

In the case of manufacturing the metal nanowire through the manufacturing method according to an embodiment of the present invention, metal nanowires having a plurality of diameter characteristics together with metal nanowires having a plurality of bending characteristics can be synthesized.

2) Multiple diameter  Metal with characteristics Nanowire  Manufacturing method

The method of manufacturing a metal nanowire having a plurality of diameters in accordance with an embodiment of the present invention is a method of putting all the reaction mixture into a reaction vessel together and proceeding the synthesis reaction under a condition of atmospheric pressure or higher, By controlling the reaction time, metal nanowires having a plurality of diameter characteristics can be produced.

A manufacturing method according to an embodiment of the present invention is a metal nanowire including at least two wire portions and includes an n + 1 wire portion connected to an arbitrary n-th wire portion and an n-th wire portion, The n-th diameter and the (n + 1) -th diameter of the (n + 1) -th wire portion are used to synthesize different metal nanowires. The metal nano- Nanowires can be synthesized.

In addition, as one-pot synthesis, there is no need to purify an intermediate product, and metal nanowires having a plurality of bending properties at a high yield can be produced without by-products other than metal nanowires.

More specifically, the present invention includes a step (S11) of preparing a reaction mixture containing a metal salt, a capping agent, a reducing solvent and a catalyst, and a step (S21) of synthesizing metal nanowires into a metal nanowire by reacting the reaction mixture into a reaction vessel And the metal nanowires having a large diameter and a large aspect ratio and having a plurality of diameter characteristics are synthesized by controlling the content of the reaction mixture, the reaction temperature, the reaction pressure, and the reaction time.

In the reaction mixture preparing step (S11), a metal salt, a reducing solvent for reducing a metal salt to a metal, a capping agent for growing a reduced metal into a wire form, and a catalyst are put in a reaction vessel together at a specified ratio and mixed at room temperature to prepare a reaction mixture .

The metal salt is a compound consisting of a metal cation and an organic or inorganic anion. For example, the metal cation is at least one selected from the group consisting of Ni, Co, Fe, Pt, Au, Ag, Al, Cr, Cu, Mg, Mn, Mo, , a cation of metal containing Ti, W, U, V, Zr, Ge, etc., organic or inorganic anion is ^{_{[NO 3] -, [ClO}} 4] -, [BF 4] -, [PF 6] -, ^{_{[CH 3 COO] -, [}} CF 3 SO 3] - an organic or inorganic anion, such as _{^{-, [SO 4] 2-,}} [CH3COCH = COCH3]. When the ionization degree of the metal salt is similar, two or more metal salts may be used in combination. It is preferable to use a silver salt composed of a silver cation (Ag +) and an organic or inorganic anion.

The metal salt is dissolved by a reducing solvent and decomposed into metal cations and organic or inorganic anions. The decomposed metal cations are reduced to crystallize or grow into nanowires.

The metal salt is added in an amount of 0.03 mol / l to 0.4 mol / l. When the molar concentration is less than 0.03 mol / l, the amount of metal nanowires is rapidly decreased. When the molar concentration is more than 0.4 mol / l, there is a problem that the wires are agglomerated due to excessive production. More preferably 0.05 mol / l to 0.10 mol / l.

The reductive solvent is a polar solvent in which a metal salt, a catalyst, and a capping agent are dissolved. For example, a solvent such as a diol, a polyol, or a glycol having at least two hydroxyl groups in the molecule is used. The reducing solvent functions as a reducing agent to reduce the metal salt to form a metal. Specific examples thereof include ethylene glycol, propylene glycol and glycerol, and more specifically, at least one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerin, glycerol and diethyl glycol.

The capping agent refers to a chemical agent that preferentially interacts with and adheres to the lateral surface of the growing nanowire such that the cross-sectional surface of the nanowire can be crystallized. That is, the capping agent interacts more strongly with the side surface than interacts with the cross-sectional surface to passivate the side surface, while the cross-sectional surface can be further crystallized to produce nanowires.

As the capping agent, a surface-adhering polymer such as polyvinylpyrrolidone (PVP), polyvinylalcohol (PVA), polyacrylamide (PAM) and polyacrylic acid (PAA) is used.

The capping agent is mixed in 0.05 to 1.0 part by weight with respect to 28 parts by weight of the reducing solvent. When the amount of the metal nanowires is less than 0.05 part by weight, the diameter of the produced metal nanowires increases. When the amount of the metal nanowires exceeds 1.0 part by weight, the length of the metal nanowires is rapidly shortened. More preferably 0.05 to 0.5 parts by weight.

The catalyst is a salt additive comprising ionically cations and anions and is separated into ions in polar solvents such as water, alcohols, diols and polyols. In this case, the cation may be an organic substance or an inorganic substance, and the anion is generally an inorganic substance and includes a halogen ion (Cl-, Br-, F-, etc.). The anisotropic nanostructures are preferentially grown by the catalyst, whereby a relatively high yield of nanowires can be obtained.

The catalyst includes at least one of a compound in which one or more cations and anions are mainly ion-bonded and a hydrate thereof. As cations, Al, NH4, Sb, As, Ba, Bi, Cd, Ca, Cr, Co, Cu, Fe, H, Pb, Mg, Hg, Ni, K, Ag, Na, It will include the _{C 2 H 3 O 2, Br} , CO 3, Cl, CrO 4, OH, I, NO 3, O, C 2 O 4, PO 4, SIO 3, SO 4, S, and / or SO 3 .

The catalyst is mixed with 10 ^-5 mol / l to 10 ^-2 mol / l. In the case of less than 10 ^-5 mol / l, the generation of metal nanowires is lowered due to the decrease of initial nucleation. When the concentration exceeds 10 ^-2 mol / l, large aggregation occurs, or surplus catalyst interferes with anisotropic growth of metal nanowires The diameter becomes larger and the generation of spherical particles increases.

In the metal nanowire synthesis step (S21), the reaction mixture is reacted with the reaction mixture in the reaction vessel, thereby reducing the metal salt. The metal nanowires are synthesized by growing the crystals into metal nanowires through metal cations from the generated nucleation site The metal nanowires having a large diameter and a large aspect ratio and having a plurality of diameter characteristics are synthesized by controlling the reaction mixture and the reaction temperature and the reaction time. The diameter, length and diameter characteristics of the metal nanowires synthesized according to the reaction conditions can be controlled.

The reaction temperature of the metal nanowire synthesis step is 110 to 150 ° C. If the temperature is less than 110 ° C, the synthesis time of the metal nanowires is prolonged and the production amount is decreased. If the temperature is higher than 150 ° C, the metal nanowires are agglomerated due to an abrupt reaction rate increase.

The reaction time of the metal nanowire synthesis step is 3 to 12 hours. When the time is less than 3 hours, there is a problem that the length of the nanowire is shortened due to a short growth time. When the time exceeds 12 hours, there is a problem that nanowires are agglomerated due to an excessive reaction. More preferably 4 to 6 hours. In this case, a metal nanowire having a high haze value of 7% or more can be synthesized.

In the metal nanowire synthesis step, the reaction mixture is put together in a reaction vessel, and the reaction pressure is made to be higher than the normal pressure to synthesize the metal nanowire. This increases the pressure and increases the vaporization point, thereby minimizing the volatilization of the reaction solution and maintaining the solution composition. As a result, the length of the metal nanowires becomes 1.5 times longer than in the conventional case. Examples of the method for increasing the pressure include a method of sealing the reaction vessel, a method of injecting the inert gas into the reaction vessel, and the like.

When the composition of the metal nanowire is changed, there is a problem that the length of the synthesized metal nanowire varies. However, when the reaction vessel is sealed and reacted, the composition can be kept constant by preventing the influx of the component into the atmosphere during the reaction So that a metal nanowire having a constant length can be obtained.

In addition, if necessary, additives can be further mixed and synthesized. For example, stabilizers such as antioxidants, dispersants, thickeners, and the like may be further mixed, but the present invention is not limited thereto. For example, HCl or HNO 3 may be mixed in an amount of 0.01 to 1 part by weight based on the total weight of the mixed catalyst so that the length of the generated metal nanowires may be increased.

After the step of synthesizing the metal nanowires, the metal nanowires are cooled to room temperature, washed with acetone, ethanol or the like, and purified to obtain metal nanowires having a large diameter and an aspect ratio and having a plurality of diameter characteristics.

By making the content of the capping agent smaller than that in the conventional polyol synthesis method but increasing the reaction time, a capping agent which interferes with the lateral growth of the metal nanowire is sufficiently present at the beginning of the synthesis reaction to form a first wire portion having a first diameter And the diameter of the metal nanowires is increased as the side growth is increased by decreasing the amount of the capping agent at the end of the synthesis reaction, thereby forming the second wire portion having the second diameter. Thereby forming a metal nanowire having a structure including a first wire portion and a second wire portion extending from the first wire portion.

When the metal nanowire is manufactured through the manufacturing method according to an embodiment of the present invention, metal nanowires having a plurality of bending characteristics together with metal nanowires having a plurality of diameter characteristics can be synthesized.

3) Core-shell with metal coating properties Nanowire  Manufacturing method

A method of manufacturing a core-shell nanowire including a metal compound shell according to an embodiment of the present invention includes the steps of preparing a nanowire core on a substrate, contacting a precursor solution for forming a metal compound shell on the nanowire core, And absorbing at the nanowire core relative to the substrate supply higher growth energy to form a metal compound shell in the nanowire core. After the step of forming the metal compound shell, a washing and a nitrogen drying step may be further included.

First, a nanowire core is prepared on the substrate. The nanowire core can be fabricated by growing directly on top of the substrate. Alternatively, the metal nanowires synthesized by the manufacturing method including the manufacturing method according to the present invention can be applied onto the substrate and prepared. The substrate is not limited and may be a translucent substrate. Further, it may be a substrate provided with a separate layer such as a conductive film or a conductive pattern.

Next, a precursor solution for forming a metal compound shell is brought into contact with the nanowire core. Contact methods can vary. For example, it may be a method of applying a precursor solution to a nanowire core substrate so that the nanowire core is evenly and precisely contacted by the precursor solution.

The precursor solution is not limited to a solvent but distilled water can be used. The precursor solution includes a metal organic compound or a derivative thereof, which is a precursor of a metal compound. The concentration of the metal organic compound contained in the precursor solution is not limited, but is preferably in the range of 0.0001 mol / l to 1 mol / l. If it is less than the above range, the projecting structure may be insignificant, and if it exceeds the above range, the metal compound may be unnecessarily coated on the substrate.

The precursor solution may further include a growth promoter. The growth promoter is not limited, but a basic compound or an amine-based compound may be preferably selected. Examples thereof include sodium hydroxide, potassium hydroxide, ammonia water, diphenylamine, diaramine, diisocyanate, monoethylenediamine, esbetaphenylamine, chlorophenylamine and the like. The content of the growth promoter is preferably in the range of 0.0001 mol / l to 1 mol / l per 1 mol of the metal organic compound contained in the precursor solution. If it is less than the above range, the growth rate is slow, and if it exceeds the above range, the formation of the projecting structure may be incomplete, and a metal compound may be formed on the substrate.

Next, the metallic compound shell is coated on the nanowire core by supplying growth energy. The metal organic salt is reduced through growth energy to form a metal compound shell. As the growth energy to be used, it is preferable to select an energy having a higher absorption rate in the nanowire core than the substrate to suppress generation of a metal compound on the substrate unnecessarily. For example, electromagnetic waves including at least one of ultraviolet rays, visible rays, and infrared rays (IR) can be supplied as growth energy. It is preferable to supply growth energy emitted from a light source selected from among xenon, halogen, UV, laser, and infrared lamps, and more preferably, a xenon lamp can be used. It is preferable to irradiate xenon light in the range of 50W to 1000W with a xenon lamp. However, more power may be used depending on the manufacturing area.

Or may be energy that causes molecular vibrations and is preferably microwave energy. The microwave energy is preferably energy in the range of 50 to 200W. However, more power may be used depending on the manufacturing area.

The supply of the growth energy is not limited, but is preferably within the range of 10 seconds to 5 minutes. However, it may take more time depending on the manufacturing area.

Next, after the metal compound shell is formed, it may be subjected to washing and nitrogen drying steps. The washing is not limited, but it is preferable to wash with alcohol such as ethanol, and it is preferable to dry using nitrogen.

On the other hand, a nanowire core including a metal compound shell without a substrate may be produced. That is, the method includes preparing a nanowire core, contacting a precursor solution for forming a metal compound shell to the nanowire core, and supplying growth energy absorbed in the nanowire core to form a metal compound shell on the nanowire core The core-shell nanowires including the metal compound shell can be separately obtained through the manufacturing method including the steps of: The contacting may be performed by impregnating the nanowire core into a reaction vessel containing the precursor solution.

On the other hand, as shown in Fig. 14, the core-shell nanowire including the metal compound shell can be manufactured by the roll-to-roll continuous process. As an example, the nanowire core is first coated on the flexible substrate using the nanowire injector 40 while moving the flexible substrate using the roller 30. [ Thereafter, it is passed through a dryer (50) and dried. Thereafter, the precursor solution for forming the metal compound shell is applied to the applicator 60 so as to sufficiently contact the nanowire core. Then, growth energy is applied through a growth energy irradiator 70 to coat the metal compound shell on the nanowire core. Thereafter, the substrate is washed and dried with a washing / drying machine 80, and finally a substrate coated with a core-shell nanowire core including a metal compound shell by a roll-to-roll process can be manufactured.

(3) Translucency  Electrode and organic light emitting element

The present invention provides a transparent electrode 300 using metal nanowires or core-shell nanowires according to an embodiment of the present invention and an organic light emitting device 1000 using the same. Throughout this specification, when a member is &quot; on &quot; another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.

The transparent electrode 300, which is an embodiment of the present invention, includes a conductive layer 31 provided on a transparent substrate 200 and a transparent electrode layer 320 formed on the conductive layer. The conductor layer 310 includes metal (or core-shell) nanowires 311 according to the present invention, and metal particles 312 or metal oxide particles 313.

The nanowires 311 included in the conductor layer 310 use metal (or core-shell) nanowires having any of the above-described characteristics, that is, any one of a plurality of bending characteristics, a plurality of diameter characteristics, do. Also, a metal (or core-shell) nanowire fabricated by the above-described manufacturing method is used.

The metal particles 312 or the metal oxide 313 included in the conductor layer 310 may be any conductive material. More typically, a metal such as Ag, Au, Cu, Pt, Fe, Ni, Cb, Zn, Ti, (Cr), aluminum (Al), palladium (Pd), and oxides thereof, but is not limited thereto.

Silver (Ag) is preferably used. Silver (Ag) reflects light as a metal and reflects light to the second electrode 500, for example, an aluminum (Al) metal electrode in the organic light emitting diode 600 although the transmittance is low. This is because light loss inside the device is reduced.

The translucent substrate 200 may be formed of a polyester resin such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), or polyarylate, a polysulfone resin such as polysulfone or polyethersulfone (PES) A cellulose derivative such as a polyether ketone resin such as a ketone (PEK) or a polyetheretherketone (PEEK), a polycarbonate resin, a polyolefin acrylic resin, a styrene resin, a cellulose triacetate (TAC) &Lt; / RTI &gt; or a mixture thereof.

The substrate may be a silicon substrate, a silicon on insulator (SOI) substrate, a gallium arsenide substrate, a silicon germanium (SiGe) substrate, a ceramic substrate, a quartz substrate, or a glass substrate for illumination. .

The light transmitting electrode layer 320 is not limited as long as it is transparent and can provide conductivity, but it is preferably made of ITO (Indium Tin Oxide), ATO (Antimony Tin Oxide), IZO (Indium Zinc Oxide) ), AZO (ZnO-Al2O3: aluminum-doped zinc oxide), GZO (ZnO-Ga2O3: gallium-doped zinc oxide), graphene and the like can be used.

The light transmitting electrode layer 320 is formed on the conductor layer 310 in a flat or curved shape. When winding be formed, La Rλa the cycle of bending and, when referred to the height Ra of the winding, the height of the winding for the period of the winding ratio, i.e., Ra / Rλa is 10 ^- is preferably less than ^3. The translucent electrode layer 320 enhances the light scattering effect and can protect the nanowires 311 and the metal particles 312 or the metal oxide particles 313. [

The organic light emitting device 1000 includes the organic light emitting layer 600 provided between the first electrode 400 and the second electrode 500 and between the first electrode 400 and the second electrode 500, to provide.

The first electrode 400 uses a translucent electrode including metal (or core-shell) nanowires of various sizes and large aspect ratios according to the present invention.

The organic light emitting layer 600 is provided between the first electrode 400 and the second electrode 500 and emits light by electrical driving of the first electrode and the second electrode. The organic light emitting layer 600 includes a light emitting layer 610 and a stacked structure including at least one selected from a hole injecting layer 620, a hole transporting layer 630, an electron transporting layer 640, and an electron injecting layer 650. . The material capable of forming the light emitting layer 610 is a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transporting layer 630 and the electron transporting layer 640, Materials with good quantum efficiency are preferred.

The second electrode 500 may be formed of a metal having a small work function and having a small work function and an alkaline earth metal and a metal of the third periodic table, that is, silver (Ag), magnesium (Mg), aluminum (Al), platinum (Pt), palladium ), Gold (Au), nickel (Ni), neodymium (Nd), iridium (Ir), chromium (Cr), lithium (Li), calcium (Ca) or an alloy thereof. no.

The first electrode 400 and the second electrode 500 are formed on the transparent substrate 200, the first electrode 400 according to the present invention, the second electrode 500 facing the first electrode 400, and the second electrode 500 An organic light emitting device 1000 including an organic light emitting layer 600 disposed between the organic light emitting device 1000 and the organic light emitting device 1000; And an encapsulating substrate (2000).

The sealing substrate 2000 is provided on the second electrode 500 to cover the organic light emitting device 1000 and prevents oxygen and moisture from penetrating into the organic light emitting device 1000 due to the sealing substrate 2000 And so on.

In the organic light emitting device used for illumination, the importance of internal light extraction efficiency becomes more important, and the translucent electrode according to the present invention includes the metal (or core-shell) nanowire according to the present invention to increase the electrical conductivity, And an organic light emitting device having a haze value and reducing loss due to total reflection of light generated in the organic light emitting diode due to a difference in refractive index and causing scattering and improving internal light extraction efficiency.

Example

One) Example  1 to Example  10 - metal having a plurality of bending characteristics Nanowire

Example  One

A reaction mixture was prepared by mixing 0.1 mol / l AgNO ₃ , 28 g EG (99.5%), ₃ g PVP (Mw ~ 360,000), and 1X10 ^-3 mol / l FeCl ₃ . The reaction mixture was put in a single vessel, sealed, and reacted at 130 캜 for 5 hours at 1 atm to obtain silver nanowires having a plurality of bending properties.

Example 2

A reaction mixture was prepared by mixing 0.1 mol / l AgNO ₃ , 28 g EG (99.5%), ₃ g PVP (Mw ~ 360,000), and 1X10 ^-3 mol / l FeCl ₃ . The reaction mixture was put into a single vessel, sealed, and reacted at 3 atm and 130 ° C for 5 hours to obtain silver nanowires having a plurality of bending properties.

Example 3

A reaction mixture was prepared by mixing 0.1 mol / l AgNO ₃ , 28 g EG (99.5%), ₃ g PVP (Mw ~ 360,000), and 1X10 ^-3 mol / l FeCl ₃ . The reaction mixture was put into a single vessel, sealed, and reacted at 5 atm and 130 ° C for 5 hours to obtain silver nanowires having multiple bending properties.

Example 4

Silver nanowires having a plurality of bending characteristics were obtained in the same manner as in Example 2 except that FeCl ₃ 5X10 ^-3 mol / l was mixed and the reaction time was 1 hour.

Example 5

Silver nanowires having a plurality of bending characteristics were obtained in the same manner as in Example 2 except that FeCl ₃ 5X10 ^-3 mol / l was mixed and the reaction time was changed to 6 hours.

Example 6

Silver nanowires having a plurality of bending properties were obtained in the same manner as in Example 2 except that FeCl ₃ 5X10 ^-3 mol / l was mixed and the reaction time was changed to 12 hours.

Example 7

Silver nanowires having a plurality of bending characteristics and a plurality of diameter characteristics were obtained in the same manner as in Example 2 except that the reaction temperature was changed to 110 캜.

Example 8

Silver nanowires having a plurality of bending properties and a plurality of diameter characteristics were obtained in the same manner as in Example 2 except that the reaction temperature was set to 150 캜.

Example 9

Silver nanowires having a plurality of bending characteristics were obtained in the same manner as in Example 2 except that 0.8 g of PVP (Mw ~ 360,000) was mixed.

Example 10

Silver nanowire having a plurality of bending properties was obtained in the same manner as in Example 2 except that 1.5 g of PVP (Mw ~ 360,000) was mixed.

2) Example  11 - Example  22 - plural diameter  Metal with characteristics Nanowire

Example  11

A reaction mixture was prepared by mixing 0.2 mol / l AgNO ₃ , 28 g EG (99.5%), 0.1 g PVP (Mw ~ 360,000), and 1X10 ^-3 mol / l FeCl ₃ . The reaction mixture was put in a single vessel, sealed, and reacted at 130 캜 for 3 hours at 1 atm to obtain silver nanowires having a plurality of diameter characteristics.

Example 12

Silver nanowires having a plurality of diameter characteristics were obtained in the same manner as in Example 11 except that the reaction time was changed to 4 hours.

Example 13

Silver nanowires having a plurality of diameter characteristics were obtained in the same manner as in Example 11 except that the reaction time was changed to 5 hours.

Example 14

Silver nanowires having a plurality of diameter characteristics were obtained in the same manner as in Example 11 except that the reaction time was changed to 6 hours.

Example 15

Silver nanowires having a plurality of diameter characteristics were obtained in the same manner as in Example 11 except that the reaction time was changed to 7 hours.

Example 16

A reaction mixture was prepared by mixing 0.1 mol / l AgNO ₃ , 28 g EG (99.5%), 0.05 g PVP (Mw ~ 360,000), and 5X10 ^-3 mol / l FeCl ₃ . The reaction mixture was put in a single vessel, sealed, and reacted at 3 atm at 130 캜 for 3 hours to obtain silver nanowires having a plurality of diameter characteristics.

Example 17

Silver nanowires having a plurality of diameter characteristics were obtained in the same manner as in Example 16 except that the reaction time was changed to 4 hours.

Example 18

Silver nanowires having a plurality of diameter characteristics were obtained in the same manner as in Example 16 except that the reaction time was changed to 5 hours.

Example 19

Silver nanowires having a plurality of diameter characteristics were obtained in the same manner as in Example 16 except that the reaction time was changed to 6 hours.

Example 20

Silver nanowires having a plurality of diameter characteristics were obtained in the same manner as in Example 16 except that the reaction time was changed to 7 hours.

Example 21

A reaction mixture was prepared by mixing 0.1 mol / l AgNO ₃ , 28 g EG (99.5%), 0.1 g PVP (Mw ~ 360,000), and 1X10 ^-3 mol / l FeCl ₃ . The reaction mixture was placed in a single vessel, sealed, and reacted at 3 atm at 110 DEG C for 12 hours to obtain silver nanowires having a plurality of diameter characteristics and a plurality of bending properties.

Example 22

A reaction mixture was prepared by mixing 0.1 mol / l AgNO ₃ , 28 g EG (99.5%), 0.05 g PVP (Mw ~ 360,000), and 1X10 ^-3 mol / l FeCl ₃ . The reaction mixture was put in a single vessel, sealed, and reacted at 3 atm and 150 ° C for 12 hours to obtain silver nanowires having a plurality of diameter characteristics and a plurality of bending properties.

3) Comparative Examples 1 to 7

Comparative Example 1

A reaction mixture was prepared by mixing 0.1 mol / l AgNO ₃ , 28 g EG (99.5%), ₃ g PVP (Mw ~ 360,000), and 1X10 ^-3 mol / l FeCl ₃ . The reaction mixture was placed in a single vessel and reacted at 130 캜 for 5 hours at 1 atm without sealing to obtain silver nanowires.

Comparative Example 2

A reaction mixture was prepared by mixing 0.15 mol / l AgNO ₃ , 28 g EG (99.5%), ₃ g PVP (Mw ~ 360,000), and 1X10 ^-3 mol / l FeCl ₃ . The reaction mixture was placed in a single vessel and reacted at 130 캜 for 5 hours at 1 atm without sealing to obtain silver nanowires.

Comparative Example 3

A reaction mixture was prepared by mixing 0.1 mol / l of AgNO ₃ , 28 g of EG (99.5%), ₃ mol / l of PVP (Mw ~ 360,000) and 1 mol of FeCl ₃ ^-5 mol / l. The reaction mixture was charged in a single vessel and reacted at 130 캜 for 5 hours at 3 atm without sealing to obtain silver nanowires.

Comparative Example 4

A reaction mixture was prepared by mixing 0.1 mol / l AgNO ₃ , 28 g EG (99.5%), ₃ g PVP (Mw ~ 360,000) and FeCl ₃ 5X10 ^-5 mol / l. The reaction mixture was charged in a single vessel and reacted at 130 캜 for 5 hours at 3 atm without sealing to obtain silver nanowires.

Comparative Example 5

A reaction mixture was prepared by mixing 0.1 mol / l AgNO ₃ , 28 g EG (99.5%), ₃ g PVP (Mw ~ 360,000), and 1X10 ^-4 mol / l FeCl ₃ . The reaction mixture was charged in a single vessel and reacted at 130 캜 for 5 hours at 3 atm without sealing to obtain silver nanowires.

Comparative Example 6

A reaction mixture was prepared by mixing 0.1 mol / l AgNO ₃ , 28 g EG (99.5%), 0.5 g PVP (Mw ~ 360,000), and 1X10 ^-3 mol / l FeCl ₃ . The reaction mixture was poured into a single vessel, sealed, and reacted at 3 atm at 130 DEG C for 2 hours to obtain silver nanowires.

Comparative Example 7

A reaction mixture was prepared by mixing 0.1 mol / l AgNO ₃ , 28 g EG (99.5%), 1 g PVP (Mw ~ 360,000) and 1X10 ^-3 mol / l FeCl ₃ . The reaction mixture was placed in a single vessel, sealed, and reacted at 130 ° C for 1 hour at 3 atm to obtain silver nanowires.

Reaction mixture preparation step Silver nanowire synthesis step Sealed
Metal salt
[mol / l] menstruum
[g] Capping agent
[g] catalyst
[mol / l] Reaction pressure
[ATM] Reaction time
[hr] Reaction temperature
[° C] Example 1 0.1 28 3 1X10 ^-3 One 5 130 O Example 2 0.1 28 3 1X10 ^-3 3 5 130 O Example 3 0.1 28 3 1X10 ^-3 5 5 130 O Example 4 0.1 28 3 5X10 ^-3 3 One 130 O Example 5 0.1 28 3 5X10 ^-3 3 6 130 O Example 6 0.1 28 3 5X10 ^-3 3 12 130 O Example 7 0.1 28 3 1X10 ^-3 3 5 110 O Example 8 0.1 28 3 1X10 ^-3 3 5 150 O Example 9 0.1 28 0.8 1X10 ^-3 3 5 130 O Example 10 0.1 28 1.5 1X10 ^-3 3 5 130 O Example 11 0.2 28 0.1 1X10 ^-3 One 3 130 O Example 12 0.2 28 0.1 1X10 ^-3 One 4 130 O Example 13 0.2 28 0.1 1X10 ^-3 One 5 130 O Example 14 0.2 28 0.1 1X10 ^-3 One 6 130 O Example 15 0.2 28 0.1 1X10 ^-3 One 7 130 O Example 16 0.1 28 0.05 5X10 ^-3 3 3 130 O Example 17 0.1 28 0.05 5X10 ^-3 3 4 130 O Example 18 0.1 28 0.05 5X10 ^-3 3 5 130 O Example 19 0.1 28 0.05 5X10 ^-3 3 6 130 O Example 20 0.1 28 0.05 5X10 ^-3 3 7 130 O Example 21 0.1 28 0.1 1X10 ^-3 3 12 110 O Example 22 0.1 28 0.05 1X10 ^-3 3 12 150 O Comparative Example 1 0.1 28 3 1X10 ^-3 One 5 130 X Comparative Example 2 0.15 28 3 1X10 ^-3 One 5 130 X Comparative Example 3 0.1 28 3 1X10 ^-5 3 5 130 X Comparative Example 4 0.1 28 3 5X10 ^-5 3 5 130 X Comparative Example 5 0.1 28 3 1X10 ^-4 3 5 130 X Comparative Example 6 0.1 28 0.5 1X10 ^-3 3 2 130 O Comparative Example 7 0.1 28 One 1X10 ^-3 3 One 130 O

4) Example  23 - Example  32 Core-shell with metal coating properties Nanowire

Example 23

Zinc acetate dehydrate was added to distilled water to a concentration of 0.001 mol / l, and 0.001 mol / l of hexamethylenediamine was added to prepare a precursor solution. Thereafter, the precursor solution was applied to a substrate such as silver nanowire (manufacturer, product name, etc.) and then irradiated with a white light source for 5 minutes. After completion of the reaction, the substrate was washed with ethanol and dried with nitrogen to obtain a core- .

Example 24

The procedure of Example 19 was repeated except that the concentration of zinc acetate dehydrate was changed to 0.01 mol / l and the addition amount of hexamethylenediamine was changed to 0.01 mol / l.

Example 25

The procedure of Example 19 was repeated except that the concentration of zinc acetate dehydrate was changed to 0.10 mol / l and the addition amount of hexamethylenediamine was changed to 0.10 mol / l.

Example 26

The procedure of Example 19 was repeated except that the concentration of zinc acetate dehydrate was changed to 0.50 mol / l and the addition amount of hexamethylenediamine was changed to 0.50 mol / l.

Example 27

The procedure of Example 19 was repeated except that the concentration of zinc acetate dehydrate was changed to 1.00 mol / l and the amount of hexamethylenediamine to be added was changed to 1.00 mol / l.

Example 28

Zinc nitrate was added to distilled water to a concentration of 0.001 mol / l, and 0.001 mol / l of hexamethylenediamine was added to prepare a precursor solution. Thereafter, the precursor solution was applied onto the substrate to which the silver nanowire according to Example 1 was applied. The microwave was then applied for 30 seconds under 1000 W conditions. After completion of the reaction, the resultant was washed with ethanol and dried with nitrogen to prepare core-shell nanowires.

Example 29

The procedure of Example 28 was repeated except that the concentration of zinc nitrate was changed to 0.01 mol / l and the addition amount of hexamethylenediamine was changed to 0.01 mol / l.

Example 30

The procedure of Example 28 was repeated except that the concentration of zinc nitrate was changed to 0.10 mol / l and the addition amount of hexamethylenediamine was changed to 0.10 mol / l.

Example 31

The procedure of Example 28 was repeated except that the concentration of zinc nitrate was changed to 0.50 mol / l and the addition amount of hexamethylenediamine was changed to 0.50 mol / l.

Example 32

The procedure of Example 28 was repeated except that the concentration of zinc nitrate was changed to 1.00 mol / l and the amount of hexamethylenediamine was changed to 1.00 mol / l.

Comparative Examples 8 to 12

Silver nanowire substrates before zinc oxide coating of Examples 23 to 27 were used as Comparative Examples 8 to 12, respectively.

Comparative Examples 13 to 17

Silver nanowire substrates before zinc oxide coating of Examples 28 to 32 were used as Comparative Examples 13 to 17, respectively.

Test Example

One) diameter , Length and aspect ratio measurements

Table 2 shows the results of measuring the diameter and length of the silver nanowires synthesized according to each of the examples and the comparative examples, and the aspect ratio, which is the ratio of the length to the first diameter.

The first diameter (nm) The second diameter (μm) The third diameter (μm) Length (μm) Aspect ratio Example 1 80 100 1250 Example 2 100 150 1500 Example 3 120 230 1917 Example 4 60 60 1000 Example 5 150 120 800 Example 6 200 230 1150 Example 7 90 0.3-0.9 0.2-0.6 100 1111 Example 8 150 0.4-1.2 0.4-1.0 130 867 Example 9 200 100 500 Example 10 150 100 667 Example 11 50 0.01-0.1 70 1400 Example 12 60 0.02-0.13 100 1667 Example 13 80 0.03-0.15 140 1750 Example 14 80 0.025-0.2 0.025-0.1 150 1875 Example 15 90 0.1-0.3 0.1-0.3 160 1778 Example 16 60 0.03-0.1 50 833 Example 17 70 0.06-0.2 70 1000 Example 18 80 0.1-0.2 0.08-0.15 100 1250 Example 19 100 0.15-0.35 0.08-0.2 120 1200 Example 20 130 0.2-0.5 0.1-0.5 150 1154 Example 21 90 0.3-0.9 0.2-0.6 100 1111 Example 22 150 0.4-1.2 0.4-1.0 130 867 Comparative Example 1 60 40 667 Comparative Example 2 80 40 500 Comparative Example 3 50 15 300 Comparative Example 4 55 20 364 Comparative Example 5 60 30 500 Comparative Example 6 150 30 200 Comparative Example 7 100 30 300

As shown in Table 2, it can be seen that the silver nanowires according to the embodiment of the present invention have larger diameter and longer length than the silver nanowires according to the comparative example, and the aspect ratio has a value more than 1000 in most cases.

It is also understood that the silver nanowires according to Examples 7, 8 and Examples 11 to 22 have a plurality of diameter characteristics such as the second diameter and the third diameter, unlike the silver nanowires according to the comparative example having a single diameter have.

2) Surface scanning electron microscopy (Scanning Electron Microscopy, SEM ) analysis

FIG. 15 is a photograph of a surface of a silver nanowire according to an embodiment of the present invention measured by SEM (Scanning Electron Microscopy). The diameter distribution 15a of the silver nanowires prepared as shown in Fig. 15 is D1 (124.47 nm), D2 (81.48 nm), D3 (84.42 nm), D4 (85.93 nm) The length distribution 15b is D1 (194.79 m), D2 (182.86 m), D3 (100.14 m), and D3 D4 (193.74 m), D5 (111.31 m), D6 (243.61 m), D7 (95.14 m) and D8 (123.00 m).

FIG. 16 is a photograph of a silver nanowire having a plurality of diameter characteristics according to the present invention measured by SEM (Scanning Electron Microscopy). It can be seen that a second wire portion having a second diameter connected to the first wire portion having the first diameter is formed as shown in FIG.

3) Transmission Electron Microscope (Transmission Electron Microscope, TEM ) analysis

FIGS. 17 and 18 are TEM (Transmission Electron Microscope) photographs of a silver nanowire having a plurality of bending characteristics according to the present invention. The shape of the nanowires bent in a certain direction can be confirmed. FIG. 19 shows a TEM photograph of a silver nanowire having a structure without bending as a comparative example.

Table 3 shows the number of bending portions of the silver nanowires having a plurality of bending characteristics according to the present invention and the average value of the bending angle.

The first diameter (nm) The second diameter (μm) The third diameter (μm) Length (μm) Number of folds (pieces) Bending angle (°) Example 1 80 100 2 155 Example 2 100 150 2 110 Example 3 120 230 3 87 Example 4 60 60 One 150 Example 5 150 120 2 155 Example 6 200 230 2 160 Example 7 90 0.3-0.9 0.2-0.6 100 2 150 Example 8 150 0.4-1.2 0.4-1.0 130 2 160 Example 9 200 100 2 155 Example 10 150 100 2 155 Example 11 50 0.01-0.1 70 Example 12 60 0.02-0.13 100 Example 13 80 0.03-0.15 140 Example 14 80 0.025-0.2 0.025-0.1 150 Example 15 90 0.1-0.3 0.1-0.3 160 Example 16 60 0.03-0.1 50 Example 17 70 0.06-0.2 70 Example 18 80 0.1-0.2 0.08-0.15 100 Example 19 100 0.15-0.35 0.08-0.2 120 Example 20 130 0.2-0.5 0.1-0.5 150 Example 21 90 0.3-0.9 0.2-0.6 100 2 150 Example 22 150 0.4-1.2 0.4-1.0 130 2 160 Comparative Example 1 60 40 Comparative Example 2 80 40 Comparative Example 3 50 15 Comparative Example 4 55 20 Comparative Example 5 60 30 Comparative Example 6 150 30 Comparative Example 7 100 30

As shown in Table 3, unlike the silver nanowires according to the embodiments of the present invention, the silver nanowires according to the comparative examples have two or three folds, It can be seen that the silver nanowires according to Examples 21 and 22 have a plurality of bending characteristics together with a plurality of diameter characteristics.

Experimental Example

1) Electrical conductivity ( Sheet resistance ) Measure

Using a 4-point probe, the translucent substrate containing silver nanowires according to each of the examples and the comparative examples was measured 15 times and the sheet resistance was calculated as an average value. Table 4 shows the average sheet resistance and standard deviation of the translucent electrode containing silver nanowires according to the present invention measured five times in the sheet resistance test.

Sheet resistance
(Ω / □) Standard Deviation Example 1 25 7.5 Example 2 21 6.3 Example 3 40 12 Example 4 80 24 Example 5 82 24.6 Example 6 42 12.6 Example 7 27 8.1 Example 8 37 11.1 Example 9 29 8.7 Example 10 42 12.6 Example 11 108 20.4 Example 12 97 18.9 Example 13 68 16.7 Example 14 54 13.9 Example 15 40 12.2 Example 16 115 31.1 Example 17 110 29.7 Example 18 48 7.3 Example 19 43 9.7 Example 20 35 8.3 Example 21 27 8.1 Example 22 37 11.1 Comparative Example 1 58 17.4 Comparative Example 2 75 22.5 Comparative Example 3 73 21.9 Comparative Example 4 90 27 Comparative Example 5 120 36 Comparative Example 6 160 48 Comparative Example 7 180 54

As shown in Table 4, the translucent electrode including the silver nanowire according to the embodiment exhibited a sheet resistance of at least 21? / ?, a maximum of 115? / ?, and an average of 54.9? /? In the case of the light transmitting electrode including the nanowire, the sheet resistance was at least 58 Ω / □, a maximum of 180 Ω / □, and an average of 108 Ω / □. Thus, it can be seen that silver nanowires according to the present invention prevent an increase in sheet resistance and exhibit excellent electrical conductivity.

2) Transmittance and Hayes  Measure

The transmittance and haze of the transparent electrode containing silver nanowires according to Examples and Comparative Examples were measured and shown in Table 5, and Examples 11 to 15 (20a) and Examples 16 to 20 (20a ), And FIG. 21 is a graph showing the transmittance of the transparent electrode including the silver nanowires according to Examples 11 to 15 (21a) and Examples 16 to 20 (21a) Value graph.

Permeability
(%) Hayes
(%) Example 1 88.3 1.2 Example 2 88.2 1.5 Example 3 88.6 2.2 Example 4 88.8 1.2 Example 5 88.7 1.8 Example 6 88.5 2 Example 7 87.2 10.2 Example 8 87.7 17.4 Example 9 88.3 1.2 Example 10 88.2 1.5 Example 11 86.7 4.5 Example 12 84 8.4 Example 13 85.9 6.1 Example 14 86.9 4.8 Example 15 85.8 6.6 Example 16 85.4 5.9 Example 17 83.2 9.1 Example 18 85.5 7.3 Example 19 82.1 11.2 Example 20 84.3 7.4 Example 21 87.2 10.2 Example 22 87.7 17.4 Comparative Example 1 89.9 1.2 Comparative Example 2 88.7 1.5 Comparative Example 3 89.3 1.3 Comparative Example 4 89.3 1.4 Comparative Example 5 88.2 1.7 Comparative Example 6 87.1 2 Comparative Example 7 87.7 1.6

A haze value of 1% or less is required when used in a display device, but a haze value of 1% or more, more preferably 5% or more is required in the case of being used for an OLED illumination (an internal light extraction layer) or an organic solar battery, As shown in Table 5, the transmittance of the translucent electrode including the silver nanowire according to the embodiment shows a transmittance similar to that of the comparative example, and the haze value is comparable to that of the comparative example, or 10% or more Value, indicating that it has properties suitable for use in OLED illumination (an internal light extraction layer) or an organic solar cell.

3) Example  23 to 27 and Comparative Example  8 to 12 Experimental Example

Electron micrographs of the core-shell nanowires of Examples 23 to 27 are shown in Figs. 22 and 23. Fig. As shown in the figure, it can be confirmed that the metal compound shell is formed in a plurality of stripe pattern structures formed long in the nanowire length direction.

FIG. 24 is a photograph showing that zinc oxide is selectively coated on the nanowire in the prepared core-shell nanowire substrate. As shown, it can be confirmed that zinc oxide is selectively coated on the nanowire position.

The sheet resistance values of the examples are shown in Fig. It can be seen that the same level of surface resistance appears before the nanowire coating, and that the sheet resistance value is better when the metal oxide shell is coated.

The X-ray diffraction peak values of the core-shell nanowires of the examples are shown in Fig. It can be confirmed that the metal oxide peak is formed. As the amount of the coating increases, the intensity of the metal oxide peak further increases.

The light transmittance values of Examples 23 to 27 are shown in Figs. 27 to 29. It can be confirmed that the light transmittance value is very excellent.

The haze values of Examples 23 to 27 are shown in Figs. 30 to 32. Fig. As the coating amount of the metal oxide shell is increased, the haze value is greatly increased.

The PL (photoluminescence) value of the example is shown in Fig.

The sheet resistance change values of Examples 23 to 27 over time are shown in Fig. It can be seen that the sheet resistance according to the time is generally maintained.

4) Example  28 to 32 and Comparative Example  13 to 17 Experimental Example

Electron microscopic photographs of the core-shell nanowires of Examples 28 to 32 are shown in Figs. 35 and 36. Fig. As shown in the figure, it can be confirmed that the metal compound shell is formed in a plurality of stripe pattern structures formed long in the nanowire length direction.

FIG. 37 is a photograph showing that zinc oxide is selectively coated on the nanowire in the prepared core-shell nanowire substrate. As shown, it can be confirmed that zinc oxide is selectively coated on the nanowire position.

The sheet resistance values of Examples and Comparative Examples are shown in Fig. It can be seen that the same level of surface resistance appears before the nanowire coating, and that the sheet resistance value is better when the metal oxide shell is coated.

The X-ray diffraction peak value of the core-shell nanowire of the example is shown in Fig. It can be confirmed that the metal oxide peak is formed. As the amount of the coating increases, the intensity of the metal oxide peak further increases.

The haze values of Examples 28 to 32 are shown in Figs. 40 to 42. Fig. As the coating amount of the metal oxide shell is increased, the haze value is greatly increased.

The light transmittance values of Examples 28 to 32 are shown in Figs. 43 to 45. Fig. It can be confirmed that the light transmittance value is very excellent.

The sheet resistance change values of Examples 28 to 32 over time are shown in Fig. It can be seen that the sheet resistance according to the time is generally maintained.

The PL (photoluminescence) value of the example is shown in Fig.

The features, structures, effects, and the like illustrated in the above-described embodiments can be combined and modified in other embodiments by those skilled in the art to which the embodiments belong. Therefore, it should be understood that the present invention is not limited to these combinations and modifications.

Claims (16)

A nanowire comprising at least two wire portions,
And an (n + 1) -th wire portion connected to the n-th nanowire,
And the diameter of the n-th wire part and the diameter of the (n + 1) th wire part are different from each other.
A first wire portion having a first diameter and a second wire portion having a second diameter extending from the first wire portion,
Wherein the first diameter and the second diameter are different from each other.
3. The method of claim 2,
And the second wire portion is formed at one end or both ends of the first wire portion.
3. The method of claim 2,
The first diameter is 50 to 100 nm,
And the second diameter is 150 to 1100 nm.
3. The method of claim 2,
The length of the first wire portion is 40 to 100 탆,
And the length of the second wire portion is 5 to 15 占 퐉.
3. The method of claim 2,
Wherein the first wire portion and the second wire portion have a polygonal cross-section perpendicular to the longitudinal direction.
The method according to claim 6,
And the cross section perpendicular to the longitudinal direction of the first wire portion is a square or pentagon.
8. The method according to any one of claims 1 to 7,
The metal nanowire may be a metal nanowire including at least one metal selected from the group consisting of Ni, Co, Fe, Pt, Au, Ag, Al, Cr, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, W, Metal nanowires, which are nanowires of a selected metal material.
9. The method according to any one of claims 1 to 8,
Wherein at least one of the wire portions has at least one fold.
10. The method of claim 9,
Wherein a bent angle (?) Of the wire portion having the bend is 130 °??? 170 °.
8. The method according to any one of claims 1 to 7,
Wherein the metal nanowire further comprises a metal compound shell formed on the metal nanowire.
12. The method of claim 11,
Wherein the metal compound shell is a transparent conductive metal compound.
12. The method of claim 11,
Wherein the metal compound shell has a plurality of polygonal shapes in a cross-sectional view perpendicular to a longitudinal direction of the metal nanowires.
14. The method of claim 13,
Wherein the polygonal shape on the cross section is in the range of 3 to 6,
Wherein a side of the polygon adjacent to the metal nanowire is referred to as a base, the length d of the base is in the range of 40 nm to 200 nm, and the height c is in the range of 10 nm to 200 nm.
14. The method of claim 13,
Wherein the ratio (c / a) of the length (a) of the metal nanowire to the height (c) of the polygon is in the range of 0.00006 to 0.02.
14. The method of claim 13,
Wherein the ratio (f / a) of the length (a) of the metal nanowires to the maximum diameter (f) on the cross section perpendicular to the longitudinal direction of the metal nanowires is within the range of 0.0001 to 0.06.

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