KR101599191B1 - Electrochromic material, electrochromic thim film element and display device comprising the same - Google Patents

Abstract

The present invention relates to a compound, an electrochromic material comprising the same, and a display device comprising the same. The compound, the electrochromic thin film element comprising the same, and the display device comprising the same have excellent memory performance, enable electrochemical switching, have a simple manufacturing process to have high competitiveness in aspects of manufacturing and costs, and enable mass production of the material and the display comprising the same. Also, high definition of the inside and outside is obtained to apply the same to a transparent display, a smart phone, and a tablet PC.

Description

TECHNICAL FIELD [0001] The present invention relates to an electrochromic material, and an electrochromic thin film device including the electrochromic material, and a display device including the electrochromic material,

The present invention relates to an electrochromic material, an electrochromic thin film device including the electrochromic material, and a display device including the electrochromic material.

The electrochromic phenomenon refers to a phenomenon in which the color reversibly changes in the direction of the electric field when a voltage is applied. The material of the electrochromic material is a material which can reversibly change the optical characteristics of the material by the electrochemical oxidation or reduction reaction. do. Therefore, the color can be selectively controlled by adjusting the applied voltage and current direction. Electrochromic materials include metal oxides such as tungsten, iridium, nickel, and vanadium; organic materials such as viols and quinones; and conductive polymers such as polythiophenes, polyanilines, and polypyrroles. In particular, electrochromic devices incorporating conductive polymers can display various colors by changing their molecular structure, and have advantages of low operating voltage, light weight, memory, and simple manufacturing process, Have been studied extensively.

However, when a thin film is formed using an electrochromic material such as a metal oxide such as tungsten, iridium, nickel, or vanadium, it is difficult to form a large-area thin film, has a slow response speed, have.

In addition, the electrochromic materials of organic materials such as viologen have a fast response speed, but the response speed is slow without pretreatment, and the electrochromic material is dissolved in the electrolyte solution. In the state of power-off, the coloring material is freely diffused, There is a problem that there is no memory effect in the colored state.

In addition, in the case of electrochromic materials such as polythiophene, polyaniline and polypyrrole, the memory effect is reduced due to the movement of charge due to the use of the liquid electrolyte. In order to solve this problem, when a sol-gel type electrolyte is used There is a problem that the response speed is slow.

Korea Patent Publication No. 2012-0090353

The present invention can produce a thin film having excellent memory performance and having various absorptions according to oxidation and reduction states generated by electrochemical switching using a compound capable of electrochromatography at a low voltage, In addition to the absorption control, the transparent thin film is implemented through switching in the room, and an energy-saving electrochromic thin film device and a display device due to excellent memory performance are provided.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound capable of electrochromatography at a low voltage, an electrochromic thin film device including the same, and a display device including the same,

A compound represented by the following formula (1) can be provided.

[Chemical Formula 1]

In Formula 1,

X is S, O, Se, Te or NR '

Y and Z are each independently S, O, Se or CR'R "

R ₁ and R ₂ each independently represent -R _a -R _b ,

R _a is a single bond or an alkylene group having 1 to 10 carbon atoms,

R _b is hydrogen, OR ', SR', NR'R ", Br, I, F or Cl,

R 'and R " are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms,

m is from 0 to 4,

n is from 5 to 10,000.

Further, as an example of the above-described electrochromic thin film device,

Electrodes disposed at regular intervals;

An electrochromic thin film formed on one surface of at least one of the electrodes, the electrochromic thin film comprising the compound according to the present invention and controlling the degree of absorption of incident light incident from an external light source;

An electrolyte layer formed between oppositely disposed electrodes;

And a power source electrically connected to the oppositely disposed electrodes to apply a voltage,

It is possible to provide an electrochromic thin film device that maintains a discolored state or a colored state for at least 1 hour after the power supply is shut off.

Further, a display device including the electrochromic thin film device can be provided.

The compound according to the present invention, the electrochromic thin film device including the same, and the display device including the same are excellent in memory performance, can be electrochemically switched, can be easily manufactured, And mass production of displays containing the same. In addition, it can exert high clarity both in the outside and inside, and can be applied to transparent displays, smart phones and tablet PCs.

1 and 2 are schematic views of an electrochromic thin film device according to an embodiment of the present invention in one embodiment.
Figs. 3 to 6 are schematic views of a display device including an electrochromic thin film device according to the present invention, in each embodiment.
FIG. 7 is a photograph showing coloring, decoloring, and memory performance of the electrochromic thin film device according to an embodiment of the present invention.
8 is a graph showing the memory performances of the electrochromic thin film devices manufactured in Examples 2 and 7.
FIG. 9 is a graph comparing the memory performances of the electrochromic thin film devices manufactured in Examples and Comparative Examples.
FIGS. 10 and 11 are photographs and light transmittance graphs showing the feasibility of implementing an optoelectronic dual mode device of an electrochromic thin film device according to an embodiment of the present invention.

The present invention relates to a compound capable of electrochromatography at a low voltage, an electrochromic thin film device including the same, and a display device including the same.

Specifically, the electrochromic material according to the present invention can control the oxidation voltage according to the introduction of the functional group of the electron donor and the acceptor, and can form an electrochromic thin film using the functional group. The electrochromic material can be formed into a thin film having excellent memory effect which maintains coloring and decoloring for a long time through a solution process. The electrochromic material can be formed into various shapes by mixing various structures of monomers and two or more monomers to control the band gap of the electrochromic thin film Colors can be implemented.

As an example of a compound according to the present invention,

A compound represented by the following formula (1) can be provided.

[Chemical Formula 1]

In Formula 1,

X is S, O, Se, Te or NR '

Y and Z are each independently S, O, Se or CR'R "

R ₁ and R ₂ each independently represent -R _a -R _b ,

R _a is a single bond or an alkylene group having 1 to 10 carbon atoms,

R _b is hydrogen, OR ', SR', NR'R ", Br, I, F or Cl,

R 'and R " are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms,

m is from 0 to 4,

n is from 5 to 10,000.

At this time, the alkyl group may mean a functional group derived from a linear or branched saturated hydrocarbon.

Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 1,1-dimethylpropyl group, , 2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, 2-ethylpropyl group, n-hexyl group, Methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2- Dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 2-methylpentyl group and 3-methylpentyl group.

As one example, the compound of Formula 1 may include at least one of the following Formulas 2 to 4.

(2)

(3)

 [Chemical Formula 4]

In the above Chemical Formulas 2 to 4,

Each X is independently S, O, Se, Te or NR '

Y and Z are each independently S, O, Se or CR'R "

R ₃ to R ₈ each independently represent -R _a -R _b ,

R _a is a single bond or an alkylene group having 1 to 10 carbon atoms,

R _b is hydrogen, OR ', SR', NR'R ", Br, I, F or Cl,

R 'and R'R " are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms,

n is independently from 5 to 10,000.

For example, compound monomers having the structure of Formula 2 may be represented by the following Structures 2-1 to 2-6.

<Structure 2-1> <Structure 2-2> <Structure 2-3>

<Structure 2-4> <Structure 2-5> <Structure 2-6>

Further, for example, the compound monomer having the structure of Formula 3 may be represented by the following Structures 3-1 to 3-29.

<Structure 3-1> <Structure 3-2> <Structure 3-3>

<Structure 3-4> <Structure 3-5> <Structure 3-6>

<Structure 3-7> <Structure 3-8> <Structure 3-9>

<Structure 3-10><Structure3-11><Structure3-12>

<Structure 3-13> <Structure 3-14> <Structure 3-15>

<Structure 3-16> <Structure 3-17> <Structure 3-18>

<Structure 3-19> <Structure 3-20> <Structure 3-21>

<Structure 3-22> <Structure 3-23> <Structure 3-24>

<Structure 3-25> <Structure 3-26> <Structure 3-27>

<Structure 3-28> <Structure 3-29>

Further, for example, the compound monomer having the structure of the formula (4) can be represented by the following structures 4-1 to 4-6.

<Structure 4-1> <Structure 4-2> <Structure 4-3>

<Structure 4-4> <Structure 4-5> <Structure 4-6>

Specifically, among the substituent definitions of the above formulas (2) to (4)

X is S,

Y and Z are O,

R ₃ and R ₄ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms,

R ₅ and R ₆ are each independently _{- (CH 2) l -OR '} , - (CH 2) l -F, - (CH 2) l -Br, - (CH 2) l -I or - (CH ₂ ) _l- Cl,

R ₇ and R ₈ are each _{independently, - (CH 2) l -OR} ', - (CH 2) l -F, - (CH 2) l -Br, - (CH 2) l -I or - (CH ₂ ) _l- Cl,

R 'each independently represents hydrogen or an alkyl group having 1 to 10 carbon atoms,

l is 0 to 10,

Each n may independently be 5 to 10,000.

At this time, the compound according to the present invention may include two or more types of the above-mentioned formulas (2) to (4). As one example, the compound may be a compound including at least one compound represented by the general formula (2) and a compound represented by the general formulas (3) and (4). As another example, the compound may be a compound including at least one compound represented by the general formula (3) and a compound represented by the general formulas (2) and (4). As another example, the compound may be a compound containing at least one compound represented by the general formula (4) and a compound represented by the general formulas (2) and (3).

As another example, the compound of Formula 1 may include one or more structures of Formula 6 and Formula 7 in addition to Formula 5 below.

[Chemical Formula 5]

[Chemical Formula 6]

 (7)

In the above formulas 5 to 7,

R &lt; ₉ &gt; is Br or I,

R ₁₀ is OR 'or I,

R ₁₁ And R ₁₂ are each independently OR 'or Br,

R ₁₃ and R ₁₄ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms,

R 'is hydrogen or an alkyl group having 1 to 10 carbon atoms,

n is from 5 to 10,000.

The K repeating structure of K (K is an arbitrary integer between 5 and 10000) repeating structure of formula (1) is at least one of X, Y, Z, R ₁ and R ₂ Can be different.

For example, one or more of the monomers derived from the compounds represented by the above formulas (2) to (4) may be connected to each other to represent a compound according to the present invention.

At this time, when a compound is formed from a plurality of monomers, the monomers constituting the compound may have different structures from each other. The combination of monomers constituting the compound is not particularly limited as long as it does not deviate from the structure of the formula (1).

As an example, each monomer making up a compound may form a different structure.

As another example, it is possible to form a structure in which a plurality of monomers of the first structure (A) are connected to each other and a plurality of second structures (B) have. In this case, the first structure and the second structure are arbitrary structures in which at least one of X, Y, Z, R ₁ and R ₂ is different from the definition of the formula (1), and the first structure and the second structure are, for example, It is only described, but other structures may be included.

The oxidation voltage of the compounds according to the invention may be from 0.5 to 1 V on the Ag / AgCl basis. By controlling the oxidation voltage of the compound to the above range, the absorption of various wavelengths can be controlled by controlling the oxidation and reduction through the low voltage switching, and the device manufactured using the device can realize high memory performance. For example, the oxidation voltage may be between-0.3 and 0.75 V or between 0.2 and 0.72 V.

The present invention can provide an electrochromic thin film device comprising the above compound. As one example of the electrochromic thin film device,

Electrodes disposed at regular intervals;

An electrochromic thin film formed on one surface of at least one of the electrodes, the electrochromic thin film comprising a compound according to the present invention and controlling the degree of absorption of incident light incident from an external light source;

An electrolyte layer formed between oppositely disposed electrodes;

And a power source electrically connected to the oppositely disposed electrodes to apply a voltage,

It is possible to provide an electrochromic thin film device that maintains a discolored state or a colored state for at least 1 hour after the power supply is shut off.

Specifically, the electrochromic thin film device can provide an electrochromic thin film having excellent memory performance by maintaining a discolored state or a colored state for at least 1 hour after the power is shut off. This can be applied to an energy saving electronic device, a smart window, or the like. For example, electronic devices can be applied to a variety of applications such as low-voltage displays with low power consumption, organic memory, optical element filters, and flexible devices. In the case of smart windows, a large amount of energy is consumed Environment-friendly buildings, cars, airplanes, etc. For example, the memory performance may be maintained for 1 to 600 hours, 180 to 500 hours, or 200 to 500 hours.

The at least one electrode of the oppositely disposed electrodes may further comprise a layer containing an organic, inorganic or organic hybrid on one side.

For example, the organic material may include a nitroxide radical and a phenoxyl radical.

In addition, the inorganic material may include TiO ₂ , SnO ₂ , Sn: Mo, and ATO (Antimony Tin Oxide).

In addition, the oil-and-inorganic hybrid can simultaneously contain organic and inorganic materials.

In the organic-inorganic hybrid, examples of the organic material include tri (pentachlorophenyl) methyl, diphenylpicryl hydrazyl, 2,4,6-tri-t-butyl 2,4,6-tri-t-butylphenoxyl, 2,2,6,6-tetramethyl-1-piperidinyloxy and Poly (2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate)), and the like .

By further forming a layer containing an organic material, an inorganic material, or an organic-inorganic hybrid on the electrode disposed opposite to the electrochromic layer as described above, the existing applied voltage can be further lowered and the repeatability can be increased.

In the electrochromic thin film device, the rate of change of the transmittance after 5 seconds of power application may be 50% or more. For example, the rate of change of the transmittance of the electrochromic thin film device after 5 seconds of power application may be 50 to 85%, 55 to 75%, or 70 to 75%. It can be seen that the electrochromic thin film device according to the present invention has a good reaction rate through the rate of change of the transmittance in the above range.

In the above-mentioned electrochromic thin film device, the electrochromic thin film may include the compound according to the present invention described above.

The electrochromic thin film may further comprise, in addition to the compound according to the present invention, an oxidizing agent, a monomer, an additive and a solvent. Examples of the oxidizing agent include iron (III) p-toluenesulfonate hexahydrate (Iron (III) p-toluenesulfonate hexahydrate), iron (III) chloride hexahydrate Iron (III) chloride hexahydrate and iron (III) chloride. Examples of the additive include pyridine, poly (propylene glycol) block copolymer and poly (ethylene glycol) Block copolymer and the like, and the solvent may include methanol, ethanol, butanol, and the like.

The electrochromic thin film may exhibit various oxidation states depending on the composition. Specifically, a thin film having various absorptions can be produced according to the content of the compound, the oxidizing agent, the monomer, the additive, and the solvent,

As a result, the electrochromic thin film can exhibit a reversible color change by electrochemical oxidation and reduction by voltage application.

The method of forming the electrochromic thin film is not limited to a specific process. For example, the electrochromic thin film may be formed by a conventional method such as electrochemical polymerization, vapor polymerization, chemical polymerization, and electrochemical polymerization, In the case of the electrochromic material according to the present invention, which can be subjected to a solution process, the electrochromic material may be dissolved in a solvent and formed by a method such as spin coating, spray coating, dip coating, bar coating or inkjet printing. Through the solution process, the electrochromic thin film can be formed on various substrates. For example, in forming thin films on glass, wafers, plastic, metal foil or flexible substrates.

For example, the thickness of the electrochromic thin film may be 130 to 200 nm, 150 to 200 nm, or 170 to 200 nm. The thickness of the electrochromic thin film may be, for example, . At this time, the thickness control may be controlled by spin coating and the composition of the solution.

The electrochromic thin film may have an oxidized state changed by electrochemical switching. The electrochromic coloration refers to a phenomenon in which the color reversibly changes in the direction of the electric field when a voltage is applied. Specifically, when electrochemical coloring is applied, an electrochemical redox reaction of a substance takes place in the direction of the electric field, and at this time, a change in the absorbance of the accompanying material is reversibly observed in the visible light region. For example, what is colored in a reduced state and discolored in an oxidized state is referred to as cathodic coloration, and is referred to as anodic coloration when discolored in a reduced state and colored in an oxidized state. As described above, the electrochromic thin film can exhibit a color change by a method of causing redox through electrochemical switching.

The electrodes disposed opposite to each other at the predetermined intervals of the electrochromic thin film elements may be transparent electrodes and may be in the form of two electrodes or three electrodes. For example, the two electrodes may mean an electrode system using two electrodes including a counter electrode and a working electrode, and the three electrodes may be three electrodes including a counter electrode, a reference electrode, and a working electrode, May refer to the electrode system used.

The electrochromic thin film may be in a patterned form. For example, fine patterns can be formed on a glass or flexible substrate in a number ranging from nano size to micro size. For example, the patterned electrochromic thin film may have a grating in which a discoloring portion having an electrical activity at regular intervals and a non-discoloring portion having no electrical activity are alternately displayed. The size of the grating may be 1 nm to 50 탆. For example, the size of the grating may be 100 nm to 50 탆, 1 탆 to 50 탆, 5 탆 to 30 탆, or 5 탆 to 15 탆. For example, photolithography using a photoresist pattern and e-beam lithography can be used as the method of forming the pattern, but the method is not particularly limited. For example, In the case of the electrochromic material according to the present invention which can be processed, the electrochromic material can be formed by an imprinting method, a micromolding in capillaries process, a holography method, or a photo-patterning method. have. However, the present invention does not exclude that the electrochromic thin film is not patterned.

The electrolyte layer can cause charge transfer of the electrolyte and doping or dedoping of the electrolyte into the electrochromic thin film upon application of a voltage.

At this time, the electrolyte layer may include an ionic liquid electrolyte, and the kind of the ionic liquid electrolyte is generally used in the art, and is not particularly limited.

Specifically, the ionic liquid electrolyte can form an electrolyte layer by using a solution in which an electrolytic salt is dissolved, by injecting it or by vacuum entry. In this instance, the electrolyte salt is not particularly limited, for _{example, n-Bu 4 NClO 4,} n-Bu 4 NPF 6, NaBF 4, LiClO 4, LiPF 6, LiBF 4, LiN (SO 2 C 2 F 5 ) ₂ , LiCF ₃ SO ₃ , C ₂ F ₆ LiNO ₄ S ₂ and K ₄ Fe (CN) ₆ , and the like. The electrolytic salt may be a single compound or a mixture of two or more compounds. Specifically, the electrolyte solution may contain 0.001 to 10 M of an electrolyte salt. For example, the electrolyte salt may comprise 0.001 to 5 M, 0.01 to 5 M, 0.1 to 1 M, or 0.1 to 0.5 M, and may contain 1 M of solvent. Within this range, it is possible to realize high electrochromicity and to prevent the problem of elution of the compound in the solution.

The electrolyte layer may further include a photochromic material. For example, the photochromic material may be at least one of a dye and a pigment. At least one of the dye and the pigment may include 0.001 to 1 part by weight based on 100 parts by weight of the total of the electrolyte layer. The dye and the pigment are not particularly limited, and azo dyes such as azo dye may include one or more of dyes, nitro dyes, nitroso dyes, anthraquinone dyes, acridine dyes, indigo dyes and azine dyes. have. By further including a photochromic material in the electrolyte layer, it is possible to realize an optical / electrical dual mode dual color changing device.

The electrolyte layer may further include an additive for charge balance. For example, the additive for charge balancing may include 0.001 to 0.5 M, and the additive is not particularly limited and may include, for example, at least one of metallocene, amine oxide and a derivative thereof.

Also, the electrolyte layer may include a solvent, and the solvent is not particularly limited and may be, for example, dichloromethane, chloroform, acetonitrile, ethylene carbonate (EC), propylene carbonate (PC), tetrahydrofuran THF) and butylene carbonate can be used.

The electrochromic thin film device 100 according to the present invention can be described with reference to FIG. Referring to FIG. 1, the oppositely disposed electrodes may refer to a transparent electrode 170 and a counter electrode 180, respectively. The electrochromic thin film 160 formed between the electrodes, the electrolyte layer 130, and the power source 190 ). Specifically, the opposed electrodes may be formed by forming transparent substrates 110 and 150 and conductive films 120 and 140 on one surface of the transparent substrate, respectively.

In the electrochromic thin film device, incident light incident from an external high light source is absorbed by the electrochromic thin film, and a voltage is applied to electrodes disposed opposite to each other by a power source. This is because charge transfer and electrochromism Doping and de-doping into a thin film can be performed to realize electrochromism.

The counter electrode structure of the counter electrode of the electrochromic thin film device may be variously changed in design. As one example, the counter electrode upper layer structure 200 may be formed as a planar transistor type as shown in FIG. More specifically, the conductive films 220 and 240 are formed on the transparent substrates 210 and 250 and the transparent substrate 220 in the form of FIG. 2, and the electrochromic thin film 230 is formed therebetween. The power source 260 may be formed on the upper transparent substrate.

In addition, the present invention can include a display device including an electrochromic thin film device. The display device may include a liquid crystal display (LCD), a cathode ray tube (CRT), a plasma display panel (PDP), a field emission display (FED), and an organic light emitting diode (OLED) Computers, laptops, navigation, smart phones, tablet PCs, e-books, and wrist watches. For example, the display device may be a transparent display device.

Specifically, the display device includes a display panel; Touch panel; And a protective substrate,

The electrochromic thin film element may be formed between the touch panel and the protective substrate.

For example, an external light source may be incident on the display device, and the external light source may penetrate the electrode and the electrolyte layer to reach the electrochromic thin film. At this time, the absorption of the light source can be controlled through the electrochromic thin film. Specifically, the absorbance of the light source can be controlled from 80% to 5% depending on the state of oxidation or reduction. Here, the absorption degree of 100% means that the light is completely blocked. As a result, electrochromism can be exhibited through the change of the oxidation state depending on the thickness of the thin film and the applied voltage. Therefore, the display device including the electrochromic thin film according to the present invention can achieve clearer and clearer images by adjusting external light by a simple method. The display device can be shown in FIG. 3, the display device includes a display panel 300, a touch panel 310, an electrochromic thin film element layer 320, a protective substrate 330, a photosensor 340 and a voltage unit 350 .

The electrochromic thin film device may be formed on a protective substrate of a display device. In addition, the external light can be adjusted by the above-described method to realize a high definition of the display. The display device can be shown in FIG. 4, the display device includes a display panel 400, a touch panel 410, a protection substrate 430, an electrochromic thin film element layer 420, a photosensor 440, and a voltage unit 450 .

In one embodiment, the electrochromic thin film device may be included in a display device that does not include a touch panel, for example, as shown in FIGS. 5 and 6. 5 includes a photosensor 540 and a voltage unit 550 in the form of a sequentially stacked display panel 500, an electrochromic thin film element layer 520 and a protective substrate 530. 6 includes a photosensor 640 and a voltage unit 650 in the form of a sequentially stacked display panel 600, a protective substrate 630 and an electrochromic thin film element layer 620.

The display device can be used indoors or outdoors. For example, devices such as smart phones, tablet PCs, navigation and e-books can be used indoors and outdoors variably. At this time, the display device according to the present invention can solve the problem of sharpness and visibility, which is a problem when used outdoors, by using the electrochromic thin film device.

In the display device, the electrochromic thin film device adjusts the absorption of external light in an outdoor environment where there is a light source from the outside, thereby causing discoloration of the thin film, and discoloration of the thin film may not occur in the room. Specifically, the electrochromic thin film device can exhibit electrochromism by controlling the absorption of external light.

 As one example, the electrochromic thin film formed between the touch panel and the protective substrate of the display device or above the protective substrate may exhibit electrochromism by controlling the absorption of external light. For example, the degree of absorption of the light source can be controlled by adjusting the oxidation state through voltage switching, thereby maintaining the inherent characteristics of the transparent electrode in the room, and achieving high clarity and visibility in the outdoor environment.

As another example, photochromism can be induced through the photochromic material contained in the electrolyte layer in the electrochromic thin film device. Specifically, photo-discoloration can be induced in a desired color by absorbing sunlight outdoors in a discolored or colored state. Accordingly, it is possible to realize a display device in which the color varies in an outdoor environment in which sunlight is present and in a room in which no sunlight is present. Thus, it is possible to maintain the inherent characteristics of the transparent electrode in the room, and realize high clarity and visibility in the outdoor.

Best Mode for Carrying Out the Invention Hereinafter, the present invention will be described in more detail with reference to examples and drawings based on the above description. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

Manufacturing example  1: monomer synthesis

The following Monomer of Structure 1 was synthesized through the following Reaction Scheme 1. NMR and oxidation voltage measurement results of the monomers thus prepared are described below.

[Reaction Scheme 1]

&Lt; 1 &gt; H NMR (250 MHz, CDCl3); [delta] 6.50 (s, 2H); 4.04 (s, 4 H); 3.62 (s, 2H); 3.45 (s, 2H); 3.37 (s, 3 H)

Oxidation voltage (based on Ag / AgCl): 0.27 V

Manufacturing example  2: monomer synthesis

The following Monomer of Structure 2 was synthesized through the following Reaction Scheme 2. NMR and oxidation voltage measurement results of the monomers thus prepared are described below.

 [Reaction Scheme 2]

&Lt; 1 &gt; H NMR (250 MHz, CDCl3); [delta] 6.50 (s, 2H); 4.10 (s, 4H); 3.61 (s, 4H)

Oxidation voltage (based on Ag / AgCl): 0.72 V

Manufacturing example  3: monomer synthesis

The following Monomer of Structure 3 was synthesized through the following Reaction Scheme 3. NMR and oxidation voltage measurement results of the monomers thus prepared are described below.

 [Reaction Scheme 3]

&Lt; 1 &gt; H NMR (250 MHz, CDCl3); [delta] 6.50 (s, 2H); 4.04 (s, 4 H); 3.62 (s, 4H); 3.37 (s, 6H)

Oxidation voltage (based on Ag / AgCl): 0.03 V

Manufacturing example  4: monomer synthesis

The monomers of structure 4 below were synthesized through a known technique [Nature Materials 2008, 7, 795-799]. The results of measurement of the oxidation voltage of the prepared monomers are described below.

Oxidation voltage (based on Ag / AgCl): 0.74 V

Manufacturing example  5: monomer synthesis

2,3-dihydrothio [3,4-b] [1,4] dioxin monomer of Structure 5 below was synthesized. The results of measurement of the oxidation voltage of the prepared monomers are described below.

Oxidation voltage (based on Ag / AgCl): - 0.3 V

Manufacturing example  6: monomer synthesis

2-hexyl-2,3-dihydrothio [3,4-b] [1,4] dioxin monomer of Structure 6 below was synthesized. The results of measurement of the oxidation voltage of the prepared monomers are described below.

Oxidation voltage (based on Ag / AgCl): 0.1 V

Example  1 to 7: Manufacture of electrochromic thin film

The monomers prepared in the above Production Example were polymerized to form an electrochromic thin film. The content of the monomer and the thickness of the formed film are shown in Table 1 below.

Structure 1 (g) Structure 2 (g) Structure 3 (g) Structure 4 (g) Structure 5 (g) Thin film thickness (nm) Example 1 0.05 - - - - 170 Example 2 - 0.06 - - - 175 Example 3 - 0.03 0.02 - - 220 Example 4 - 0.03 0.04 - - 210 Example 5 - 0.03 0.06 - - 200 Example 6 - - 0.04 - - 170 Example 7 - - - 0.06 - 180

Comparative Example

An electrochromic thin film was formed using a known PEDOT conductive polymer (J. Braz. Chem. Soc., Vol.10, No. 5, 394, 1999.).

Experimental Example  1: Measurement of response speed

The response speed of the electrochromic thin films prepared in Examples 1 to 7 was measured. Specifically, the rate of change of transmittance was measured at a wavelength showing the maximum transmittance difference after elapse of 5 seconds after voltage application.

Transmittance change rate (%) Example 1 73 Example 2 75 Example 3 55 Example 4 74 Example 5 79 Example 6 60 Example 7 72

Referring to Table 2, it was confirmed that a high transmittance difference can be realized within a short time when the electrochromic material according to the present invention is used to form an electrochromic thin film. Specifically, it was confirmed that the maximum difference in transmittance was 79% in the case of Example 5 including the monomers of Structure 2 and Structure 3.

Experimental Example  2: coloration of the electrochromic thin film device, Decoloration  And Memory Performance Verification

An electrochromic thin film device was fabricated by forming an electrolyte layer using the electrochromic thin film and the ionic liquid electrolyte prepared in Example 2 above. (A) coloring, (b) decolorization and (c) memory performance were confirmed for the thus prepared electrochromic thin film device. The results are shown in FIG. 7, respectively. Accordingly, it was confirmed that the electrochromic thin film device according to the present invention can realize coloring, decoloring, and memory performance.

Experimental Example  3: Check memory performance of electrochromic thin film device

The electrochromic thin film devices were prepared using the electrochromic thin films prepared in Examples 2 and 7. Specifically, the electrochromic thin film device according to the present invention uses an ionic liquid electrolyte as an electrolyte layer, and the memory performance of the electrochromic thin film device thus manufactured is measured. Specifically, memory performance for coloring and decoloring was measured through electrochromic switching followed by a change in transmittance over time under an open circuit. The measurement results are shown in Fig. 8, the electrochromic thin film was formed using the compound according to the present invention. In Examples 2 and 7 in which the oxidation voltage was high, the applied voltage was shut off and the colored state was maintained even after a lapse of 1 hour or more . Thus, excellent memory performance of the electrochromic thin film device according to the present invention can be confirmed.

Experimental Example  4: Memory performance comparison of electrochromic thin film device

An electrochromic thin film device was fabricated using the electrochromic thin film prepared in Example 2 and Comparative Example. Specifically, the electrochromic thin film device according to the present invention uses an ionic liquid electrolyte as the electrolyte layer, and the ionic liquid electrolyte is not used in the comparative example.

The memory effect of the electrochromic thin film device was measured. Specifically, memory performance for coloring and decoloring was measured through electrochromic switching followed by a change in transmittance over time under an open circuit. The measurement results are shown in Fig. 9 below.

9, in the case of Example 2 in which the electrochromic material according to the present invention was used to form an electrochromic thin film and an electrolyte layer was formed using an ionic liquid electrolyte, In the comparative example in which the electrochromic thin film was formed by using the PEDOT polymer and the electrolyte layer was formed without using the ionic liquid electrolyte, the transmittance was remarkably changed within 30 minutes I could confirm.

Thus, excellent memory performance of the electrochromic thin film device according to the present invention can be confirmed.

Experimental Example  5: Optical / electric dual mode dual coloring device performance experiment

The electrochromic thin film, the ionic liquid electrolyte and the electrolyte layer to which the photochromic material was added were formed to prepare an electrochromic thin film device. At this time, a red dye (FIG. 10) and a Blue dye (FIG. 11) were added as a photochromic material at a concentration of 10 wt% to prepare an electrochromic thin film device.

10 and 11 (a), the electrochromic thin film device according to the present invention exhibits electrochromic characteristics in a colored state (b, 2b) when a voltage is applied through electrochemical switching in a decolored state (a, 2a) . In addition, photochromism was induced by irradiating UV light on the upper side of the dot line of the electrochromic thin film device. Specifically, it was confirmed that the device with photochromic (c, 2c) in the decolored state and the photochromic (d, 2d) device in the colored state.

Further, the photochromic electrochromic thin film device was exposed to visible light. As a result, it was confirmed that the electrochromic thin film which had been photo-discolored returned to the original discolored state (a ', 2a') and the colored state (b ', 2b').

The light transmission spectrum for each of the above states can be confirmed through (b) in FIGS. 10 and 11.

As a result, it was confirmed that the optical / electrical dual mode color conversion device can be realized.

100: electrochromic device
110, 150, 210, 250: transparent substrate
120, 140, 220, 240: conductive film
130: electrolyte layer
160, 230: electrochromic thin film
190, 260: Power
170: transparent electrode
180: counter electrode
200: upper electrode structure of counter electrode
300, 400, 500, 600: Display panel
310, 410: Touch panel
320, 420, 520, 620: an electrochromic thin film element layer
330, 430, 530, 630:
340, 440, 540, 640: Light sensor
350, 450, 550, 650:

Claims (14)

A compound represented by the formula (1):
[Chemical Formula 1]

In Formula 1,
X is S, O, Se, Te or NR '
Y and Z are each independently S, O, Se or CR'R &quot;
R ₁ and R ₂ each independently represent -R _a -R _b ,
R _a is a single bond or an alkylene group having 1 to 10 carbon atoms,
R _b is hydrogen, SR ', NR'R ", Br, I, F, or Cl,
R 'and R &quot; are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms,
m is from 0 to 4,
n is from 5 to 10,000.
The method according to claim 1,
Wherein the compound represented by Formula 1 comprises at least one of the following Formulas 2 to 4:
(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 2 to 4,
Each X is independently S, O, Se, Te or NR '
Y and Z are each independently S, O, Se or CR'R &quot;
R ₃ to R ₈ each independently represent -R _a -R _b ,
R _a is a single bond or an alkylene group having 1 to 10 carbon atoms,
R _b is hydrogen, SR ', NR'R ", Br, I, F, or Cl,
R 'and R'R &quot; are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms,
n is independently from 5 to 10,000.
3. The method of claim 2,
Among the substituent definitions of formulas (2) to (4)
X is S,
Y and Z are O,
R ₃ and R ₄ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms,
And _{(CH 2) l -Cl, -} R 5 and R ₆ are each independently _{- (CH 2) l -F,} - (CH 2) l -Br, - (CH 2) l -I or
And _{(CH 2) l -Cl, -} R 7 and R ₈ are each independently _{- (CH 2) l -F,} - (CH 2) l -Br, - (CH 2) l -I or
R 'each independently represents hydrogen or an alkyl group having 1 to 10 carbon atoms,
l is 0 to 10,
and n is each independently from 5 to 10,000.
3. The method of claim 2,
Wherein the compound comprises at least two structures of the following formulas (2) to (4).
The method according to claim 1,
The K repeating structure of K (K is an arbitrary integer between 5 and 10000) repeating structure of formula (1) is at least one of X, Y, Z, R ₁ and R ₂ Lt; / RTI &gt;
The method according to claim 1,
Wherein the oxidation voltage is from 0.5 to 1 V on an Ag / AgCl basis.
Electrodes disposed at regular intervals;
An electrochromic thin film formed on one surface of at least one of the electrodes, the electrochromic thin film comprising a compound according to any one of claims 1 to 6, which regulates the degree of absorption of incident light incident from an external light source;
An electrolyte layer formed between oppositely disposed electrodes;
And a power source electrically connected to the oppositely disposed electrodes to apply a voltage,
An electrochromic thin film device which keeps a coloring or coloring state for 1 hour or more after the power supply is cut off.
8. The method of claim 7,
Wherein at least one of the electrodes disposed opposite to each other further comprises a layer including an organic material, an inorganic material, or an organic-inorganic hybrid on one side.
8. The method of claim 7,
Wherein the rate of change of the transmittance after 5 seconds of power application is 50% or more.
8. The method of claim 7,
Wherein the electrochromic thin film has a thickness of 130 to 220 nm.
8. The method of claim 7,
Wherein the electrochromic thin film has a patterned shape.
8. The method of claim 7,
Wherein the electrolyte layer comprises an ionic liquid electrolyte.
8. The method of claim 7,
Wherein the electrolyte layer further comprises a photochromic material.
A display device comprising the electrochromic thin film element according to claim 7.

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