KR102453324B1 - Electrochromic structure complex and electrochromic device - Google Patents

Abstract

The present invention relates to an electrochromic composite structure and an electrochromic device, and more particularly, to an electrochromic composite structure and an electrochromic device that impart additional functions to the electrochromic properties of an electrochromic material film.
An electrochromic composite structure according to an embodiment of the present invention includes an electrochromic material film forming a matrix of a continuous phase; and a plurality of metal nanoparticles dispersed in the electrochromic material layer.

Description

Electrochromic structure complex and electrochromic device

The present invention relates to an electrochromic composite structure and an electrochromic device, and more particularly, to an electrochromic composite structure and an electrochromic device that impart additional functions to the electrochromic properties of an electrochromic material film.

In electrochromic, an oxidation or reduction reaction occurs in an electrochromic material by an external electric field, and through this, a color change effect is visually generated. Electrochromic devices generally have a structure in which an electrochromic layer (or working electrode), an electrolyte (layer), and an ion storage layer (or counter electrode) are sequentially stacked between transparent electrodes on both sides, and electrochromic by electrochemical reaction The optical properties of the layer and the ion storage layer can be changed reversibly.

Conventionally, organic electrochromic materials have been mainly used for fast response speed and various colors, but organic materials have poor environmental durability and are not suitable for application to external environments. The electrochromic technology using inorganic materials is being developed for application to windows).

Conventional inorganic electrochromic materials have advantages of good environmental durability and large transmittivity variation, but also have disadvantages such as low response speed and impossible to implement various colors. In addition, since the conventional electrochromic device absorbs light in a discolored state of the electrochromic layer to reduce transmittance, it also absorbs light from the display light source, which is not greatly helpful in improving the visibility of the display.

Accordingly, there is a need for a technology for forming an electrochromic layer capable of realizing various colors while using an inorganic material with a fast response speed, and an electrochromic layer capable of adjusting the reflectance is required.

Korean Patent Publication No. 2003-0037100

The present invention provides an electrochromic composite structure and an electrochromic device in which the reflectance of the electrochromic material film is improved and the reflectance can be adjusted according to an applied voltage.

An electrochromic composite structure according to an embodiment of the present invention includes an electrochromic material film forming a matrix of a continuous phase; and a plurality of metal nanoparticles dispersed in the electrochromic material layer.

The electrochromic material layer may include a metal oxide of a metal different from the metal constituting the plurality of metal nanoparticles.

The total mass of the plurality of metal nanoparticles may be 0.01 to 10% of the total mass of the metal oxide.

The average particle diameter of the plurality of metal nanoparticles may be 10 to 200 nm.

A particle diameter deviation of the plurality of metal nanoparticles may be ±10% based on the average particle diameter.

The plurality of metal nanoparticles is gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), iridium (Ir), rhodium (Rh), ruthenium (Ru), osmium (Os) ) may be made of any one metal or an alloy of two or more.

The plurality of metal nanoparticles may include: a plurality of first nanoparticles having a first average particle diameter; and a plurality of second nanoparticles having a second average particle diameter different from the first average particle diameter.

The plurality of second nanoparticles may reflect light having a wavelength different from that of the plurality of first nanoparticles.

An electrochromic device according to another embodiment of the present invention includes first and second electrodes provided to correspond to each other; an electrochromic composite structure according to an embodiment of the present invention formed on the first electrode; an ion storage layer formed on the second electrode to correspond to the electrochromic composite structure; and an electrolyte layer provided between the electrochromic composite structure and the ion storage layer, wherein reflectivity of the electrochromic composite structure may be adjusted according to voltages applied to the first and second electrodes.

The electrochromic composite structure may have a reflectance in a discoloration state of 40 to 90%.

In the method for manufacturing an electrochromic composite structure according to another embodiment of the present invention, the electrochromic composite structure according to an embodiment of the present invention may be prepared by sputtering in an oxidizing atmosphere.

and co-sputtering a target region made of a metal or metal oxide included in the electrochromic material layer and a target region made of a metal of the metal nanoparticles.

The co-sputtering process may be performed by applying power to the metal or metal oxide target at least twice as high as that of the metal target of the metal nanoparticles.

and sputtering an alloy target of a metal included in the electrochromic material layer and a metal of the metal nanoparticles.

The sputtering of the alloy target may be performed by sputtering an alloy target containing a metal included in the electrochromic material film in a weight ratio of at least twice that of the metal of the metal nanoparticles.

The process of heat-treating the electrochromic composite structure deposited by the sputtering; may include.

The heat treatment of the electrochromic composite structure may be performed at a temperature of 150 to 500 °C.

In the electrochromic composite structure according to an embodiment of the present invention, a plurality of metal nanoparticles are dispersed in an electrochromic material film constituting a matrix of a continuous phase, and reflectivity can be improved by excellent reflectance of the metal nanoparticles. In addition, the reflectance can be adjusted by controlling the absorptivity of the plurality of metal nanoparticles according to a localized surface plasmon (LSP) according to an applied voltage. In addition, various colors can be implemented depending on the size of the metal nanoparticles, the response speed can be improved by the excellent electrical conductivity of the metal nanoparticles, the color change characteristics of the electrochromic material film and the surface plasmon resonance of the metal nanoparticles By simultaneously implementing the (Surface Plasmon Resonance; SPR) effect, it is possible to control the transmittance change according to the wavelength while having a large transmittivity change range.

In addition, the electrochromic composite structure contains metal nanoparticles with excellent electrical conductivity, so that the shielding rate of (near) infrared rays can be improved, and accordingly, when applied to windows of automobiles, buildings, etc., it is possible to provide a thermal insulation effect. may be

On the other hand, in the electrochromic device including the electrochromic composite structure, the reflectance can be adjusted according to the voltage applied to the first and second electrodes by the local surface plasmon (LSP) of the plurality of metal nanoparticles, and the color is changed (colored). ) state, the reflectance may be 40 to 90%, so that when applied to a transparent display, the visibility of the display may be improved.

1 is a schematic perspective view showing an electrochromic composite structure according to an embodiment of the present invention.
2 is an electron microscope image of an electrochromic composite structure according to an embodiment of the present invention.
3 is a schematic cross-sectional view showing an electrochromic device according to another embodiment of the present invention.
4 is a schematic cross-sectional view showing a display device to which an electrochromic element is applied according to another embodiment of the present invention.
5 is a flowchart illustrating a method for manufacturing an electrochromic composite structure according to another embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in a variety of different forms, only these embodiments allow the disclosure of the present invention to be complete, and the scope of the invention to those of ordinary skill in the art completely It is provided to inform you. In the description, the same reference numerals are assigned to the same components, and the sizes of the drawings may be partially exaggerated in order to accurately describe the embodiments of the present invention, and the same reference numerals refer to the same elements in the drawings.

1 is a schematic perspective view showing an electrochromic composite structure according to an embodiment of the present invention.

Referring to FIG. 1 , an electrochromic composite structure 100 according to an embodiment of the present invention includes an electrochromic material film 110 forming a continuous-phase matrix; and a plurality of metal nanoparticles 120 dispersed in the electrochromic material film 110 .

The electrochromic material layer 110 may be formed of an electrochromic material, and may form a continuous matrix. In the electrochromic material layer 110 , oxidation or reduction reaction may occur in the electrochromic material by an external electric field, and thus a color change effect may occur visually.

The plurality of metal nanoparticles 120 may have excellent electrical conductivity and may be dispersed in the electrochromic material layer 110 . When the plurality of metal nanoparticles 120 are dispersed in the electrochromic material film 110 , the response speed of the electrochromic material film 110 may be improved due to the excellent electrical conductivity of the plurality of metal nanoparticles 120 . . Accordingly, even if an inorganic electrochromic material is used as the electrochromic material, it is possible to solve the problem that the response speed of discoloration/discoloration is low in the prior art. In addition, the plurality of metal nanoparticles 120 have a low emissivity due to their excellent electrical conductivity, so that the shielding rate of infrared rays (Infrared Ray; IR) including near infrared rays (NIR) may be high, and accordingly, The (near) infrared shielding rate of the electrochromic composite structure 100 can be improved, and when the electrochromic composite structure 100 is applied to a window such as a car or a building, an excellent thermal insulation effect can be provided .

In addition, the plurality of metal nanoparticles 120 may have a surface plasmon resonance (SPR) characteristic. Surface plasmon resonance (SPR) refers to a state of surface plasmon (SP) in which electrons in a material vibrate collectively by being excited by light incident on a flat surface of a material (eg, metal). In this case, the surface plasmon generated from the nano (meter) sized metal structure (or particle) is called Localized Surface Plasmon Resonance (LSPR). For example, a nanomaterial with a size similar to or smaller than the wavelength of light that generates surface plasmon (SP) has a localized surface plasmon (SP) generated by limiting the propagation of surface plasmon (SP) to the nanomaterial. ; LSP) is observed. These localized surface plasmons (LSPs) can have two important effects: First, a strong electric field may be formed on the surface of the nanomaterial, and second, light absorption of the nanomaterial may be maximized at the natural frequency (ie, resonant frequency) of the nanomaterial. Through this, it is possible to control the change in transmittivity according to the wavelength of light according to the natural frequency of the nanomaterial. Therefore, the electrochromic composite structure 100 according to the present invention simultaneously realizes the discoloration characteristics of the electrochromic material film 110 and the surface plasmon resonance (SPR) effect (or characteristics) of the metal nanoparticles 120, so that the transmittance change width is increased. It is possible to control the change in transmittance according to the wavelength of light while being large, and it is also possible to control the transmittance of visible light (line) and near-infrared (NIR) according to voltage.

In addition, since the absorption wavelength of the light causing resonance of the plurality of metal nanoparticles 120 is in the visible ray region, a special color may be displayed according to the size of the metal nanoparticles 120 , and Various colors can be realized by adjusting (or controlling) the size.

Here, the electrochromic material layer 110 may include a metal oxide of a metal different from the metal constituting the plurality of metal nanoparticles 120 . For example, the metal oxide is tungsten (W), titanium (Ti), niobium (Nb), molybdenum (Mo), tin (Sn), bismuth (Bi), vanadium (V), nickel (Ni), iridium ( Ir), antimony (Sb), tantalum (Ta), chromium (Cr), manganese (Mn), may be an oxide of one or more metals selected from cobalt (Co). That is, the electrochromic material layer 110 may be an inorganic electrochromic material, and may have an advantage of good environmental durability and a large transmittance change range. The inorganic electrochromic material has a disadvantage in that the response speed of decolorization/discoloration is low, but in the electrochromic composite structure 100 according to the present invention, a plurality of metal nanoparticles 120 having excellent electrical conductivity are included in the electrochromic material film 110 . Dispersion and excellent electrical conductivity of the plurality of metal nanoparticles 120 may improve the response speed of decolorization/discoloration. Therefore, in the present invention, an inorganic electrochromic material such as the metal oxide can be used as the electrochromic material of the electrochromic material film 110, and thus, the environmental durability is good, the transmittance change is large, and it can have a fast response speed. It may be easy to apply to an external environment such as a windshield and/or a window of a vehicle.

In addition, the inorganic electrochromic material such as the metal oxide has the disadvantage that it is impossible to implement various colors because it can implement only transparent and a single color, but in the present invention, various colors can be implemented depending on the size of the metal nanoparticles 120, It is possible to solve the conventional problem that only a single color can be realized due to the use of an electrochromic material.

2 is an electron microscope image of an electrochromic composite structure according to an embodiment of the present invention.

Referring to FIG. 2 , the total mass of the plurality of metal nanoparticles 120 may be 0.01 to 10% of the total mass of the metal oxide. That is, in the electrochromic composite structure 100 , a mass ratio between the plurality of metal nanoparticles 120 and the metal oxide may be 1:10 to 10,000. When the total mass of the plurality of metal nanoparticles 120 exceeds 10% of the total mass of the metal oxide and the number of the plurality of metal nanoparticles 120 is too large, the electrochromic composite structure 100 may become opaque, , the electrochromic composite structure 100 has a low transmittance even in a bleached state as well as in a colored state, so it may be difficult to secure a front view, and accordingly, an external view such as a windshield or window of a vehicle It becomes unsuitable for use where securing is required. On the other hand, when the total mass of the plurality of metal nanoparticles 120 is less than 0.01% of the total mass of the metal oxide and the plurality of metal nanoparticles 120 becomes too small, the gap between the plurality of metal nanoparticles 120 This inevitably becomes too wide, and the excellent electrical conductivity of the plurality of metal nanoparticles 120 is not provided in the entire (or overall) electrochromic composite structure 100 , and excellent electricity of the plurality of metal nanoparticles 120 is not provided. Since the effect of conductivity is insignificant, the response speed of the electrochromic material film 110 cannot be improved, and the portion of the electrochromic composite structure 100 where the plurality of metal nanoparticles 120 is not provided is widened, so that the plurality of metal nanoparticles It is also not possible to provide a thermal insulation effect by the particles (120).

And the average particle diameter of the plurality of metal nanoparticles 120 may be 10 to 200 nm. The metal nanoparticles 120 may exhibit a special color according to particle size, and various colors may be realized by controlling the average particle diameter of the plurality of metal nanoparticles 120 in the range of 10 to 200 nm. When the average particle diameter of the plurality of metal nanoparticles 120 is smaller than 10 nm, the electrical conductivity of the plurality of metal nanoparticles 120 does not affect the electrochromic material film 110 , so that the electrochromic material film 110 is formed. The response speed cannot be improved, and the distance between the plurality of metal nanoparticles 120 is too wide or the plurality of metal nanoparticles 120 are concentrated (or concentrated) on a specific part(s), so that the plurality of metal nanoparticles ( It is difficult to evenly disperse the 120 ) in the electrochromic material film 110 . When the plurality of metal nanoparticles 120 are not evenly dispersed, the electrochromic composite structure 100 cannot be uniformly (or entirely) discolored, and the discoloration color is partially changed.

On the other hand, when the average particle diameter of the plurality of metal nanoparticles 120 is greater than 200 nm, the metal intrinsic color of the plurality of metal nanoparticles 120 (eg, gold Au is gold, silver (Ag) exhibits a silver color (silver, etc.) and the reflectance is increased to decrease the transmittance of the electrochromic composite structure 100, and even in a discolored state of the electrochromic material film 110, a plurality of metal nanoparticles (120), the unique color of the metal appears. When the transmittance (or transparency) of the electrochromic composite structure 100 is lowered and the electrochromic composite structure 100 is opaque, it is difficult to secure the front view. When it is not suitable for the following, and the metal-specific color of the plurality of metal nanoparticles 120 appears even in the discolored state of the electrochromic material film 110 , the (unique) color of the plurality of metal nanoparticles 120 is Interference makes it unsuitable for use as a backplane of a panel bonding type (OLED/EC) transparent display or a screen of a projection type transparent display.

Here, the particle diameter deviation of the plurality of metal nanoparticles 120 may be ±10% with respect to the average particle diameter. Since the plurality of metal nanoparticles 120 exhibit a special color according to the particle diameter, when the particle diameter deviation of the plurality of metal nanoparticles 120 is large, the plurality of metal nanoparticles 120 exhibit different colors according to the particle diameter. and a different color may appear for each portion where the metal nanoparticles 120 of each particle diameter are located. As a result, the electrochromic composite structure 100 may not be uniformly discolored as a whole, and the discoloration may be partially changed.

Accordingly, by limiting the particle size deviation of the plurality of metal nanoparticles 120 to ±10% around the average particle diameter, the plurality of metal nanoparticles 120 can exhibit the same color, and the electrochromic composite structure 100 ) to achieve uniform discoloration as a whole.

And the plurality of metal nanoparticles 120 are gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), iridium (Ir), rhodium (Rh), ruthenium (Ru), It may be made of any one metal or an alloy of two or more of osmium (Os). The plurality of metal nanoparticles 120 may be made of a noble metal, and may be made of a metal having excellent electrical conductivity, and hardly oxidize or oxidize because chemical reactions such as oxidation do not occur. It may be made of a metal capable of maintaining excellent electrical conductivity even when the device is turned on. Through this, it is possible to prevent or suppress oxidation of the plurality of metal nanoparticles 120 by reacting with external oxygen (O ₂ ).

For example, the electrochromic composite structure 100 may be prepared by sputtering in an oxidizing atmosphere, and a plurality of metal nanoparticles 120 in the electrochromic material film 110 may be dispersed using a metal. While sputtering the metal target of the nanoparticles 120 , the metal of the metal nanoparticles 120 may be oxidized, and electrical conductivity of the oxidized metal nanoparticles 120 may be reduced or lost. In addition, the oxidized metal nanoparticles 120 may lose their metallicity, so that reflectivity may be lowered, and a special color may not be exhibited according to a particle diameter.

In addition, precious metals such as gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), iridium (Ir), rhodium (Rh), ruthenium (Ru), and osmium (Os) are chemically Although it hardly reacts and has a unique color with a beautiful luster, a special color may be exhibited depending on the particle size at a nano size of 10 to 200 nm.

For example, silver (Ag) exhibits a red color at a particle size of less than 40 nm and a blue color at a particle size of 40 to 50 nm. In addition, gold (Au) exhibits a red color at a particle diameter of 20 nm or less, but as the distance between the nanoparticles gets closer, the nanoparticles interact with each other to gradually change to a deep purple color, and the electrochromic composite structure In order to make the discoloration color of 100 uniform as a whole, the plurality of metal nanoparticles 120 may be spaced apart from each other, and may be arranged spaced apart from each other at a predetermined (or substantially uniform) distance. Depending on the type of metal, the color may be different depending on the size.

In addition, surface plasmon (SP) is generated on the surface of a metal having a negative dielectric function, and noble metals such as gold (Au), silver (Ag), copper (Cu), etc. are easy to emit electrons by external stimuli and have negative dielectric properties. It is the metal(s) with a constant. In particular, gold (Au) or silver (Ag) is representative, gold (Au) shows excellent surface stability, and silver (Ag) shows the sharpest surface plasmon resonance (SPR) peak.

Accordingly, in the present invention, as the plurality of metal nanoparticles 120 , gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), iridium (Ir), rhodium (Rh), ruthenium (Ru), osmium (Os) using any one of metal or an alloy of two or more of the plurality of metal nanoparticles 120 is a special color according to the particle size without reducing or losing the electrical conductivity of the metal nanoparticles 120 , and may have surface plasmon resonance (SPR) characteristics.

The plurality of metal nanoparticles 120 may include a plurality of first nanoparticles having a first average particle diameter; and a plurality of second nanoparticles having a second average particle diameter different from the first average particle diameter. The plurality of first nanoparticles may have a first average particle diameter, and a particle diameter deviation may be ±10% with respect to the first average particle diameter, and may exhibit a first color according to the first average particle diameter. have.

The plurality of second nanoparticles may have a second average particle diameter different from the first average particle diameter, and a particle diameter deviation may be ±10% with respect to the second average particle diameter, and the second average particle diameter Accordingly, a second color different from the first color may be displayed.

That is, the plurality of second nanoparticles may reflect light having a wavelength different from that of the plurality of first nanoparticles, and thus may exhibit different colors from the plurality of first nanoparticles. Through this, a third color may be represented by synthesizing (or mixing) the first color of the plurality of first nanoparticles and the second color of the plurality of second nanoparticles. By mixing (or synthesizing) the discoloration color and the third color, the discoloration color of the electrochromic composite structure 100 may be expressed as gray or dark gray.

When the electrochromic composite structure 100 is used in a display device 300 such as a transparent display, the electrochromic composite structure 100 has a red (Red) series, blue (Blue) series, or green (Green) series discoloration color. The red (R), green (G), and blue (B) light sources of red (R), green (G) and/or blue (B) colors representing images of various colors when having ) may be buried in the discoloration color, so that the sharpness of the image may be lowered, and the visibility of the display may be lowered. Accordingly, in the present invention, the plurality of metal nanoparticles 120 is formed of a plurality of the first nanoparticles, the second nanoparticles, etc. having various average particle diameters including the first average particle diameter and the second average particle diameter. (n-th) discoloration of the electrochromic composite structure 100 by mixing the synthetic color (or mixed color) by the plurality of metal nanoparticles 120 and the discoloration color of the electrochromic material film 110 by composing the (n-th) nanoparticles The color may be expressed in gray or dark gray, and when the electrochromic composite structure 100 is applied to the display device 300 , the sharpness of an image and the visibility of the display may be improved.

On the other hand, when the discoloration color of the electrochromic material film 110 is too dark, the color of the plurality of metal nanoparticles 120 is buried in the discolored color of the electrochromic material film 110 and the mixed color (or synthetic color) does not come out. Therefore, the electrochromic material film 110 may be formed of a non-stoichiometric metal oxide to lower the color density of the electrochromic material film 110 . In this case, oxygen may be increased in the stoichiometric ratio (ratio) of the metal oxide. For example, the metal oxide may have a composition of WO _3±x (0 < x ≤ 0.5).

3 is a schematic cross-sectional view showing an electrochromic device according to another embodiment of the present invention.

An electrochromic device according to another embodiment of the present invention will be described in more detail with reference to FIG. 3 , but matters overlapping with those described above with respect to the electrochromic composite structure according to an embodiment of the present invention will be omitted.

The electrochromic device 200 according to another embodiment of the present invention includes first and second electrodes 210 and 220 provided to correspond to each other; The electrochromic composite structure 100 according to an embodiment of the present invention is formed on the first electrode 210; an ion storage layer 230 formed on the second electrode 220 to correspond to the electrochromic composite structure 100; and an electrolyte layer 240 provided between the electrochromic composite structure 100 and the ion storage layer 230 .

The first and second electrodes 210 and 220 may be provided to correspond to each other, may supply electric charge to the electrochromic composite structure 100 , and may be transparent electrodes. For example, the first and second electrodes 210 and 220 may include indium tin oxide (ITO), fluor doped tin oxide (FTO), aluminum doped zinc oxide (AZO), galium doped zinc oxide (GZO), and antimony doped tin oxide (ATO). Oxide), IZO (Indium doped Zinc Oxide), NTO (Niobium doped Titanium Oxide), ZnO (Zinc Oxide), OMO (Oxide/Metal/Oxide) and CTO (Cesium Tungsten Oxide) at least one transparent conductive compound, conductivity It may include a polymer, silver (Ag) nanowire, or metal mesh, but is not limited thereto. Also, the first and second electrodes 210 and 220 may have a structure in which two or more conductive materials are stacked in a plurality of layers. A method of forming the first and second electrodes 210 and 220 is not particularly limited, and a known method may be used without limitation. For example, the method of forming the first and second electrodes 210 and 220 may be prepared by forming an electrode material including transparent conductive oxide particles in a thin film form on a substrate 10 such as transparent glass through a sputtering process. .

Here, a working electrode on which the electrochromic composite structure 100 is formed among the first and second electrodes 210 and 220 may be the first electrode 210 , and a counter electrode on which the ion storage layer 230 is formed. (counter electrode) may be the second electrode 220 .

The electrochromic composite structure 100 may be the electrochromic composite structure 100 according to an embodiment of the present invention, and may be formed on the first electrode 210 . The method of forming the electrochromic composite structure 100 is not particularly limited, and may be mainly formed by deposition, and the electrochromic composite structure 100 may be formed in a thin film form through sputtering. In addition, the electrochromic composite structure 100 is colored or bleached due to the oxidation or reduction reaction of the electrochromic material depending on the voltage applied to the first and second electrodes 210 and 220 . can happen Since the detailed description of the electrochromic composite structure 100 has been described above in detail with respect to the electrochromic composite structure 100 according to an embodiment of the present invention, it will be omitted.

The ion storage layer 230 may be formed on the second electrode 220 to correspond to the electrochromic composite structure 100 , and the color development characteristics are complementary to the electrochromic material included in the electrochromic composite structure 100 . It may contain an electrochromic material. Here, the complementary color characteristic refers to a case in which the types of reactions in which the electrochromic material can be colored are different from each other. (100) can be used. As the electrochromic material having complementary color development properties is included in the electrochromic composite structure 100 and the ion storage layer 230, respectively, the coloring and/or discoloration of the electrochromic composite structure 100 and the ion storage layer 230 is reduced. can be done simultaneously. For example, the coloring of the electrochromic composite structure 100 by the reduction reaction and the coloring of the ion storage layer 230 by the oxidation reaction may be simultaneously made, and in the opposite case, the electrochromic composite structure 100 and the ions The discoloration of the storage layer 230 may be simultaneously performed. Accordingly, coloring and discoloration of the entire electrochromic device 200 can be simultaneously performed, and such coloring and discoloration depend on the polarity of the voltage applied to the electrochromic device 200 (that is, to the first and second electrodes). may be alternated accordingly.

On the other hand, the ion storage layer 230 is nickel (Ni), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), rhodium (Rh), iridium (Ir), vanadium (V), tungsten (W) and may be made of an oxide of one or more metals selected from aluminum (Al), but is not particularly limited thereto.

The electrolyte layer 240 may be provided between the electrochromic composite structure 100 and the ion storage layer 230 , and may be configured to provide electrolyte ions involved in the electrochromic reaction. Here, the electrolyte ions are inserted into the electrochromic composite structure 100, and monovalent cations (eg, H ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ or Cs ⁺ ) can be The type of electrolyte used in the electrolyte layer 240 is not particularly limited, and a liquid electrolyte, a gel polymer electrolyte, or an inorganic solid electrolyte may be used without limitation, and monovalent cations (ie, H ⁺ , Li ⁺ , Na ⁺ , K The specific composition of the electrolyte used in the electrolyte layer 240 is not particularly limited as long as it can include a compound capable of providing ⁺ , Rb ⁺ or Cs ⁺ ), but an inorganic solid electrolyte is preferred for excellent environmental durability and deposition characteristics. can do.

For example, the electrolyte layer 240 may be formed of an inorganic solid electrolyte, and may include tantalum oxide, tungsten oxide, molybdenum oxide, antimony oxide, niobium oxide, chromium oxide, cobalt oxide, titanium oxide, tin oxide, nickel oxide, and aluminum. Zinc oxide optionally alloyed, zirconium oxide, aluminum oxide, silicon oxide optionally alloyed with aluminum, silicon nitride optionally alloyed with aluminum or boron, boron nitride, aluminum nitride, oxides of vanadium optionally alloyed with aluminum and tin It may include at least one layer based on a material selected from zinc oxide, and at least one of these oxides may be optionally hydrogenated or nitrided. Here, the electrolyte layer 240 may be tantalum oxide (Ta ₂ O ₅ ), and may be deposited by sputtering a target made of tantalum (Ta) in an oxidizing atmosphere.

In addition, the reflectivity of the electrochromic composite structure 100 may be adjusted according to voltages applied to the first and second electrodes 210 and 220 . In the electrochromic composite structure 100 , a plurality of metal nanoparticles 120 are dispersed in the electrochromic material film 110 , and thus the reflectance of the electrochromic composite structure 100 due to the excellent reflectivity of the plurality of metal nanoparticles 120 . This can be improved, and the light absorptivity of the plurality of metal nanoparticles 120 according to the local surface plasmon (LSP) is adjusted (or controlled) according to the voltage applied to the first and second electrodes 210 and 220 . This allows you to control (or adjust) reflectivity as well as transmittivity.

Here, the reflectance of the electrochromic composite structure 100 may be in a range of 40 to 90%. Through this, when the electrochromic device 200 is applied to the display device 300 such as a transparent display, the visibility of the display can be improved.

4 is a schematic cross-sectional view showing a display device to which an electrochromic element is applied according to another embodiment of the present invention, FIG. 4 (a) shows a projection type transparent display, and FIG. 4 (b) is a panel bonding type (OLED/EC) ) indicates a transparent display.

Referring to FIG. 4 , the electrochromic device 200 according to another embodiment of the present invention may be applied to the display device 300 , and the display device 300 according to another embodiment of the present invention is another embodiment of the present invention. The electrochromic device 200 according to the embodiment; may include. The electrochromic device 200 may have a reflectivity of 40 to 90% in a discolored state of the electrochromic composite structure 100 . Here, the display device 300 may be a projection type transparent display as shown in Fig. 4(a), or a panel bonding type (OLED/EC) transparent display as shown in Fig. 4(b).

When the display device 300 is a projection-type transparent display as shown in FIG. 4( a ), the electrochromic device 200 is formed on a windshield or window 310 of a vehicle, etc., and an image is projected from the display light source unit 320 ( Or it can be used as a projected screen (screen). In this case, the display device 300 may further include a driving unit 330 for controlling the electrochromic device 200 and/or the display light source unit 320 .

When the display device 300 is a panel bonding type (OLED/EC) transparent display as shown in FIG. 4(b) , the electrochromic device 200 is a display light source unit 320 such as a display panel rear (or rear) It may serve as a light-shutter and may be used as a backplane for improving visibility of the display.

Conventionally, in order to improve the visibility of a display in a transparent display, a variable transmittance element such as PDLC (Polymer Dispersed Liquid Crystal), SPD (Suspended Particle Display), EC (ElectroChromic), etc. is applied, and PDLC, SPD and conventional EC (or electric Although the color-changing element) can reduce the transmittance through discoloration, PDLC and SPD mainly scatter light in the discolored state to lower the transmittance, and the conventional EC absorbs light in the discolored state to reduce transmittance. It doesn't help much to improve. In particular, when PDLC, SPD, and conventional EC are used as the screen of a projection type transparent display, the PDLC or SPD scatters even the light projected on the screen or the conventional EC absorbs light that can be recognized by being reflected on the screen. As this is reduced, the visibility of the display becomes poor. In addition, when PDLC, SPD, and the conventional EC are used as the backplane of the panel bonding type (OLED/EC) transparent display, the light incident from the display light source unit 320 is reflected in the display direction (or the display direction) to provide visibility of the display. does not fulfill the role of the backplane to improve Therefore, it cannot be reflected in the display direction. As a result, the visibility of the display is inevitably poor.

However, in the present invention in which the electrochromic composite structure 100 is configured by dispersing a plurality of metal nanoparticles 120 in the electrochromic material film 110 , not only the excellent reflectivity of the plurality of metal nanoparticles 120 itself but also the electrochromic material The electrochromic composite structure 100 may have a reflectivity of 40 to 90% in a discolored state by adjusting the reflectance according to the voltage applied to the first and second electrodes 210 and 220 of the composite structure 100 . Accordingly, when the electrochromic device 200 according to the present invention is applied to the display device 300, the light projected (or incident) from the display light source unit 320 can be effectively reflected to improve the visibility of the display, and the transparency of the display can be improved. Visibility of the display may be maximized.

In addition, in the electrochromic device 200 of the present invention, an image can be formed (or formed well) due to the high reflectivity of the plurality of metal nanoparticles 120 , and within the electrochromic material film 110 . The reflection direction of light can be controlled according to the incident direction by the surface plasmon resonance (SPR) of the plurality of distributed metal nanoparticles 120 , and the light incident from the display light source unit 320 at a predetermined angle (only) may be reflected in the display direction. Accordingly, the visibility of the display may be further improved, and the visibility of the transparent display may be maximized.

5 is a flowchart illustrating a method of manufacturing an electrochromic composite structure according to another embodiment of the present invention. 5(b) shows sputtering of an alloy target of metal and metal nanoparticles included in the electrochromic material film.

A method of manufacturing an electrochromic composite structure according to another embodiment of the present invention will be described in more detail with reference to FIG. 5. The electrochromic composite structure according to an embodiment of the present invention and an electrochromic device according to another embodiment of the present invention In relation to the above-described parts and overlapping matters will be omitted.

In the method for manufacturing an electrochromic composite structure according to another embodiment of the present invention, the electrochromic composite structure 100 according to an embodiment of the present invention may be manufactured by sputtering in an oxidizing atmosphere.

The electrochromic composite structure 100 according to an embodiment of the present invention can be manufactured by sputtering in an oxidizing atmosphere, and the electrochromic composite structure 100 can be simply formed through sputtering, , since the electrochromic composite structure 100 is densely formed, the environmental durability of the electrochromic composite structure 100 may be excellent. In addition, by forming the electrochromic composite structure 100 through sputtering, it may be effective to deposit the electrochromic composite structure 100 over a large area.

In addition, the electrochromic composite structure 100 as well as the ion storage layer 230 and the electrolyte layer 240 are made of an inorganic material such as metal oxide, and the electrochromic composite structure 100, the electrolyte layer 240, and the ions are formed through sputtering. All of the storage layer 230 and the like may be continuously formed in the form of a thin film, and an all-solid-state electrochromic device 200 may be manufactured.

For example, the electrochromic material film 110 of the electrochromic composite structure 100 may be made of a metal oxide, and a metal oxide target made of a metal oxide or a metal target made of a metal of a metal oxide is sputtered in an oxidizing atmosphere to obtain a metal. The electrochromic material film 110 made of oxide may be deposited. In addition, a plurality of metal nanoparticles 120 may be dispersed in the electrochromic material film 110 through sputtering in an oxidizing atmosphere, and the plurality of metal nanoparticles 120 may not be oxidized in an oxidizing atmosphere by sputtering. Thus, the plurality of metal nanoparticles 120 may be made of a noble metal that hardly causes a chemical reaction such as oxidation. Accordingly, it is possible to prevent the reduction or loss of electrical conductivity of the metal nanoparticles 120 due to oxidation or loss of metallicity, thereby reducing reflectance and preventing a special color from being exhibited according to the particle size.

The method for manufacturing an electrochromic composite structure according to another embodiment of the present invention includes a process of co-sputtering a metal or a metal oxide included in the electrochromic material film 110 and a metal of the metal nanoparticles 120 ( S110); may include.

A target region made of a metal or metal oxide included in the electrochromic material layer 110 and a target region made of a metal of the metal nanoparticles 120 may be co-sputtered ( S110 ). Through this, the electrochromic composite structure 100 may be manufactured. For example, a target region made of a metal or a metal oxide included in the electrochromic material layer 110 and a target region made of a metal of the metal nanoparticles 120 are co-sputtered to form electricity on the first electrode 210 . The electrochromic composite structure 100 in which the plurality of metal nanoparticles 120 are dispersed in the color-changing material film 110 may be formed (or deposited). Here, in the co-sputtering, a target made of a metal or a metal oxide included in the electrochromic material film 110 and a target made of a metal of the metal nanoparticles 120 may be respectively prepared to perform sputtering with a plurality of targets, The sputtering may be performed as a single target having a region (or a portion) of a metal or a metal oxide included in the electrochromic material layer 110 and a region made of the metal of the metal nanoparticles 120 by dividing the region.

The co-sputtering process (S110) is performed on the metal (eg, W) or metal oxide (eg, WO ₃ ) target of the metal nanoparticles 120 in the metal (eg, Ag) target 2 It can be performed by applying a power that is more than twice as high. In the electrochromic composite structure 100 according to the present invention, the electrochromic material film 110 forms a continuous matrix, and the plurality of metal nanoparticles 120 must be dispersed in the electrochromic material film 110 in the matrix. To this end, the metal target of the metal nanoparticles 120 (or the target made of the metal of the metal nanoparticles) on the metal or metal oxide target (or the target made of metal or metal oxide included in the electrochromic material film) ) can be co-sputtered by applying a power (or voltage) that is twice as high as that of the

When the power applied to the metal or metal oxide target is lower than twice the power applied to the metal target of the metal nanoparticles 120, the metal nanoparticles 120 are formed in a bulk form in the middle. As a result, the electrochromic material film 110 does not form a continuous phase and does not have a matrix form, and the plurality of metal nanoparticles 120 are also prevented from being dispersed in the matrix of the electrochromic material film 110 .

In this case, the discoloration of the electrochromic material film 110 is not effectively achieved, and the electrical conductivity of each part varies according to the distance from the metal nanoparticles 120 , so that the electrochromic material film 110 is discolored/discolored according to the location of the electrochromic material film 110 . response speed may vary.

Accordingly, in the present invention, the electrochromic material film 110 forms a continuous matrix and forms a matrix by co-sputtering the metal or metal oxide target by applying a power twice or more higher than that of the metal target of the metal nanoparticles 120 . The metal nanoparticles 120 may form (or manufacture) the electrochromic composite structure 100 dispersed in the matrix of the electrochromic material film 110 , and as the electrochromic material film 110 is effectively discolored, electricity The response speed of the color-changing material layer 110 may be improved.

Meanwhile, the power applied to the metal or metal oxide target may not exceed 20 times the power applied to the metal target of the metal nanoparticles 120 , and the power applied to the metal or metal oxide target is the metal nanoparticle 120 . When the particle 120 is greater than 20 times the power applied to the metal target, the power is too high, so it is not easy to apply high power to the metal or metal oxide target, and the electrochromic material film 110 is too densified. The plurality of metal nanoparticles 120 may not be dispersed (or penetrated) in the electrochromic material film 110 and may be attached only to the surface of the electrochromic material film 110 .

The method for manufacturing an electrochromic composite structure according to another embodiment of the present invention includes a step (S120) of sputtering an alloy target of a metal included in the electrochromic material film 110 and a metal of the metal nanoparticles 120; can

An alloy target of a metal included in the electrochromic material film 110 and a metal of the metal nanoparticles 120 may be sputtered (S120). Through this, the electrochromic composite structure 100 may be manufactured. For example, the electrochromic material film 110 on the first electrode 210 by sputtering the alloy target made of an alloy of the metal included in the electrochromic material film 110 and the metal of the metal nanoparticles 120 . ) may form an electrochromic composite structure 100 in which a plurality of metal nanoparticles 120 are dispersed.

The process of sputtering the alloy target (S120) is a metal (for example, W) may be carried out by sputtering the containing alloy target. That is, the alloy target may contain the metal included in the electrochromic material film 110 in a weight ratio of more than twice that of the metal of the metal nanoparticles 120, and in the alloy target, the electrochromic material film 110 The weight (or weight) of the metal contained in ) may be more than twice the weight of the metal of the metal nanoparticles 120 . In the electrochromic composite structure 100 according to the present invention, the electrochromic material film 110 forms a continuous matrix, and a plurality of metal nanoparticles 120 must be dispersed in the electrochromic material film 110 matrix. To form (or manufacture) the electrochromic composite structure 100 by sputtering the alloy target containing the metal included in the electrochromic material film 110 in a weight ratio of at least twice that of the metal of the metal nanoparticles 120 to can do.

When the weight of the metal included in the electrochromic material film 110 in the alloy target is lower than twice the weight of the metal of the metal nanoparticles 120, the metal nanoparticles 120 are formed in the electrochromic material film ( 110) is interposed in the middle of the electrochromic material film 110 in the form of a lump, does not form a continuous phase and does not have a matrix form, and the plurality of metal nanoparticles 120 are also in the matrix of the electrochromic material film 110. cannot be dispersed.

In this case, the discoloration of the electrochromic material film 110 is not effectively achieved, and the electrical conductivity of each part varies according to the distance from the metal nanoparticles 120 , so that the electrochromic material film 110 is discolored/discolored according to the location of the electrochromic material film 110 . response speed may vary.

Accordingly, in the present invention, the electrochromic composite structure 100 is formed by sputtering the alloy target containing the metal included in the electrochromic material film 110 in a weight ratio of at least twice that of the metal of the metal nanoparticles 120 . By doing so, the electrochromic material film 110 forms a continuous matrix and a plurality of metal nanoparticles 120 can form the electrochromic composite structure 100 in which the electrochromic material film 110 is dispersed in the matrix, As the color change of the color-changing material film 110 is effectively performed, the response speed of the electro-chromic material film 110 may be improved.

Meanwhile, in the alloy target, the weight of the metal included in the electrochromic material film 110 may not exceed 20 times the weight of the metal of the metal nanoparticles 120 , and the electrochromic material film in the alloy target If the weight of the metal contained in 110 is greater than 20 times the weight of the metal of the metal nanoparticles 120, the weight of the alloy target is too large, so it is not easy to drive the sputtering device for sputtering the alloy target In addition, the density of the electrochromic material film 110 is too high, so that the plurality of metal nanoparticles 120 cannot penetrate (or disperse) in the electrochromic material film 110 , and the electrochromic material film 110 . It can be attached only to the surface of

The method for manufacturing an electrochromic composite structure according to the present invention may include a step (S200) of heat-treating the electrochromic composite structure 100 deposited by the sputtering process (S200).

The electrochromic composite structure 100 deposited by the sputtering may be heat-treated (S200). The plurality of metal nanoparticles 120 dispersed through the sputtering has a particle diameter (or size) of less than 10 nm, which is too small, or the particle diameter deviation between the plurality of metal nanoparticles 120 is ± Exceeding 10% may be too large. Accordingly, by heat-treating the electrochromic composite structure 100 deposited by the sputtering, the plurality of metal nanoparticles 120 dispersed through the sputtering are agglomerated to increase the average particle diameter of the plurality of metal nanoparticles 120 to 10 to 200 nm, and the particle diameter deviation of the plurality of metal nanoparticles 120 may be made ± 10% based on the average particle diameter.

The process (S200) of heat-treating the electrochromic composite structure 100 may be performed at a temperature of 150 to 500 °C. When the heat treatment temperature is higher than 500° C., the average particle diameter of the plurality of metal nanoparticles 120 exceeds 200 nm, so that transparency of the electrochromic composite structure 100 may be reduced. On the other hand, when the heat treatment temperature is lower than 150 ℃, the average particle diameter of the plurality of metal nanoparticles 120 does not become 10 nm, or the metal nanoparticles 120 whose particle diameter does not become 10 nm may increase, A particle diameter deviation between the metal nanoparticles 120 may exceed ±10% with respect to the average particle diameter. In this case, the electrical conductivity of the plurality of metal nanoparticles 120 does not affect the electrochromic material film 110, so that the response speed of the electrochromic material film 110 is not improved, or the metal nanoparticles of each particle diameter ( Different colors appear for each portion where 120 is located, thereby preventing uniform discoloration of the electrochromic composite structure 100 as a whole.

Therefore, in the present invention, by heat treatment of the electrochromic composite structure 100 deposited by the sputtering at a temperature of 150 to 500 ℃, the electrochromic material film 110 by the excellent electrical conductivity of the plurality of metal nanoparticles 120 In addition to improving the response speed, the plurality of metal nanoparticles 120 may exhibit the same color, and the electrochromic composite structure 100 may be uniformly discolored as a whole.

As such, in the present invention, a plurality of metal nanoparticles are dispersed in the electrochromic material film constituting the matrix of the continuous phase, so that the reflectance can be improved by the excellent reflectivity of the metal nanoparticles, and the local surface plasmon (LSP) according to the applied voltage ) by controlling the light absorptivity of a plurality of metal nanoparticles according to the reflectance can be adjusted. In addition, various colors can be realized depending on the size of the metal nanoparticles, the response speed can be improved by the excellent electrical conductivity of the metal nanoparticles, and the discoloration characteristics of the electrochromic material film and the surface plasmon resonance (SPR) of the metal nanoparticles. By implementing the effect at the same time, the transmittance change according to the wavelength can be controlled while the transmittance change is large. In addition, the electrochromic composite structure includes metal nanoparticles having excellent electrical conductivity, and thus the shielding rate of infrared rays including near-infrared rays can be improved, and accordingly, when applied to windows of automobiles, buildings, etc., it may provide an insulating effect. . On the other hand, in the electrochromic device including the electrochromic composite structure, the reflectance can be adjusted according to the voltage applied to the first and second electrodes by the local surface plasmon (LSP) of the plurality of metal nanoparticles, and in a discolored state The reflectance may be 40 to 90%, so that when applied to a transparent display, the visibility of the display may be improved.

Although preferred embodiments of the present invention have been illustrated and described above, the present invention is not limited to the above-described embodiments, and common knowledge in the field to which the present invention pertains without departing from the gist of the present invention as claimed in the claims It will be understood by those having the above that various modifications and equivalent other embodiments are possible therefrom. Accordingly, the technical protection scope of the present invention should be defined by the following claims.

10: substrate 100: electrochromic composite structure
110: electrochromic material film 120: metal nanoparticles
200: electrochromic element 210: first electrode
220: second electrode 230: ion storage layer
240: electrolyte layer 300: display device
310: windshield or window 320: display light source unit
330: driving unit

Claims (17)

an electrochromic material film formed of an electrochromic material capable of discoloration through oxidation or reduction reaction by an external electric field to form a continuous matrix; and
Including; a plurality of metal nanoparticles dispersed in the electrochromic material film;
The electrochromic material layer includes a metal oxide of a metal different from the metal constituting the plurality of metal nanoparticles as the electrochromic material,
The total mass of the plurality of metal nanoparticles is 0.01 to 10% of the total mass of the metal oxide electrochromic composite structure. delete delete The method according to claim 1,
The average particle diameter of the plurality of metal nanoparticles is 10 to 200 nm electrochromic composite structure. 5. The method according to claim 4,
The particle size deviation of the plurality of metal nanoparticles is ± 10% with respect to the average particle size of the electrochromic composite structure. The method according to claim 1,
The plurality of metal nanoparticles is gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), iridium (Ir), rhodium (Rh), ruthenium (Ru), osmium (Os) ) of any one metal or an electrochromic composite structure made of two or more alloys. The method according to claim 1,
The plurality of metal nanoparticles,
a plurality of first nanoparticles having a first average particle diameter; and
The electrochromic composite structure comprising a plurality of second nanoparticles having a second average particle diameter different from the first average particle diameter. 8. The method of claim 7,
The plurality of second nanoparticles is an electrochromic composite structure for reflecting light of a wavelength different from that of the plurality of first nanoparticles. first and second electrodes provided to correspond to each other;
The electrochromic composite structure of any one of claims 1 and 4 to 8 formed on the first electrode;
an ion storage layer formed on the second electrode to correspond to the electrochromic composite structure; and
Including; an electrolyte layer provided between the electrochromic composite structure and the ion storage layer;
The electrochromic composite structure is an electrochromic device whose reflectance is adjusted according to the voltage applied to the first and second electrodes. 10. The method of claim 9,
The electrochromic composite structure has a color change state reflectance of 40 to 90%. 9. A method for manufacturing an electrochromic composite structure, wherein the electrochromic composite structure of any one of claims 1 and 4 to 8 is prepared by sputtering in an oxidizing atmosphere. 12. The method of claim 11,
The electrochromic composite structure manufacturing method comprising a; co-sputtering a target region made of a metal or metal oxide included in the electrochromic material film and a target region made of the metal of the metal nanoparticles. 13. The method of claim 12,
The co-sputtering process is an electrochromic composite structure manufacturing method performed by applying power to the metal or metal oxide target at least twice as high as that of the metal target of the metal nanoparticles. 12. The method of claim 11,
A method of manufacturing an electrochromic composite structure comprising a; sputtering an alloy target of the metal included in the electrochromic material film and the metal of the metal nanoparticles. 15. The method of claim 14,
The process of sputtering the alloy target is an electrochromic composite structure manufacturing method performed by sputtering an alloy target containing a metal included in the electrochromic material film in a weight ratio of at least twice that of the metal of the metal nanoparticles. 12. The method of claim 11,
An electrochromic composite structure manufacturing method comprising a; heat treatment of the electrochromic composite structure deposited by the sputtering. 17. The method of claim 16,
The process of heat-treating the electrochromic composite structure is an electrochromic composite structure manufacturing method performed at a temperature of 150 to 500 ℃.

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