KR102230604B1 - Method of manufacturing light-sensitive photochromic device and the device thereof - Google Patents

Abstract

Therefore, the technical problem to be solved by the present invention is that it provides improved transparency and can be electrochromic by an external light source to improve the quality of the smart window, and at the same time, the grain crystallinity can be easily adjusted and the phase purity. It is to provide a photosensitive automatic color conversion device with improved discoloration characteristics due to improved (phase purity).

Description

TECHNICAL FIELD The method of manufacturing light-sensitive photochromic device and the device thereof

The present invention relates to a light-sensitive autochromic device and a method of manufacturing the same, and more particularly, to provide improved transparency and self-discoloration by an external light source, thereby improving the quality of a smart window, and at the same time making particle crystals. The present invention relates to a light-sensitive autochromic device having improved color change characteristics by easily controlling the property and improving phase purity, and a method of manufacturing the same.

Recently, a smart window technology that can improve energy efficiency and satisfy both sensitivity and functionality is attracting great attention.

Smart window refers to an active control technology that can reduce energy loss and provide a comfortable environment to consumers by controlling the amount of light entering from the outside, and a base technology that can be commonly applied to various industrial fields such as transportation, information display, and architecture. It can be called this.

Depending on the driving method, these smart windows include a head-up display (HUD), a chromatic display (CD), a suspended particle display (SPD), and a polymer/liquid composite film (Polymer/Liquid). crystal composites film).

Here, electrochromism among the discoloration methods refers to a phenomenon in which the transmittance or color of light is changed when a voltage is applied from the outside. The characteristics of such an electrochromic device are that the operating voltage is less than 1.5V, the photochromic efficiency is high, and since it has a memory effect even in an open circuit state, there is no need to continuously apply voltage.

9 shows the internal structure of a conventional electrochromic device, in which a tungsten oxide (WO ₃ ) electrochromic layer is on a transparent conductor as a working electrode, and an ion storage layer is located on the transparent conductor as a counter electrode, and an electrolyte is interposed therebetween. It has an intervening electrochemical structure.

In general, as the electrochromic layer in the working electrode, a material in which coloration occurs when a cathodic reaction occurs, and a material in which bleaching occurs when an anodic reaction occurs may be used.

In addition, in the case of the ion storage layer of the counter electrode, it simply stores or exports ions regardless of the reduction or oxidation reaction, and the ion storage layer, on the other hand, is colored in the case of oxidation reaction opposite to the working electrode and decolorized in case of reduction reaction. In this case, it is possible to use a material that is colored or decolorized together with the working electrode to improve the contrast characteristics of the device. Representative examples of such materials include nickel oxide (NiOs), iridium oxide (IrOs), and vanadium oxide ( VOs) and the like.

As such, electrochromic devices are sometimes developed as hybrid types with low-voltage power sources such as solar cells because their operating voltage (less than 1.5V) is much lower than other display devices such as LEDs and liquid crystal display devices. In the case of the case, it has been fabricated in a hybrid form with an electrochromic device using a pn junction solar cell (or Si solar cell).

However, since Si is opaque, it is not easy to manufacture a solar cell with a thickness of at least 100 nm or less to make it semi-transparent, and it has a problem of facilitating a short circuit of the solar cell and increasing the manufacturing cost. Still had the problem of low permeability.

Therefore, the first technical problem to be solved by the present invention is that it provides improved transparency and can be electrochromic by an external light source to improve the quality of the smart window, and at the same time, it is possible to easily adjust the grain crystallinity. It is to provide a photosensitive automatic color change device with improved color change characteristics due to improved phase purity.

In addition, the second technical problem to be solved by the present invention is that it provides improved transparency and can be electrochromic by an external light source to improve the quality of the smart window, and at the same time, the grain crystallinity can be easily adjusted and It is to provide a method of manufacturing a photosensitive automatic color change device with improved color change characteristics due to improved phase purity.

In order to solve the above-described first technical problem, the present invention is an electrochromic layer stacked on one of the opposed first and second substrates, wherein an electrolyte is interposed between the electrochromic layer, and the electrochromic layer is titanium. It provides a method of manufacturing a photosensitive automatic color change device comprising (Ti) doped tungsten oxide.

According to an embodiment of the present invention, the electrochromic layer may include a titanium coupling agent.

According to another embodiment of the present invention, the titanium coupling agent may be 1 to 50 parts by weight based on 100 parts by weight of the tungsten oxide precursor.

According to another embodiment of the present invention, the titanium coupling agent may use tetraisopropyl di (dioctyl phosphate) titanate, which may be provided in a powder form or in a liquid form dispersed in a solvent. (Dioctyl phosphate) titanate, isopropyl dioleyl (dioctyl phosphate) titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl trioleyl titanate, isopropyl tristearyl titanate At least one selected from the group consisting of nate, isopropyl tri(dodecylbenzenesulfonate) titanate, isopropyl tri(dioctylpyrrophosphate) titanate, di(dioctylpyrrophosphate) ethylene titanate have.

According to another embodiment of the present invention, the toilet discoloration layer may be coated in the form of a solution or gel and then subjected to a thermal curing process.

According to another embodiment of the present invention, a metal oxide layer may be coated on the electrochromic layer.

According to another embodiment of the present invention, the metal oxide layer may be subjected to an additional thermal curing process.

According to another embodiment of the present invention, the crystal structure of the toilet discoloration layer after the thermal curing process may be cubic.

According to another embodiment of the present invention, the electrochromic layer may be discolored by internal electromotive force generated by light sensitization rather than external power.

According to another embodiment of the present invention, a pre-drying step may be further included in the thermal curing process.

According to another embodiment of the present invention, the solvent in the form of a solution or a gel may be anhydrous ethanol.

In order to solve the second technical problem described above, the present invention is an electrochromic layer stacked on one of the opposed first and second substrates, wherein an electrolyte is interposed between the electrochromic layer, and the electrochromic layer is titanium. It provides a photosensitive autochromic device containing (Ti) doped tungsten oxide.

According to an embodiment of the present invention, the electrochromic layer may include a titanium coupling agent.

According to another embodiment of the present invention, the titanium coupling agent may be 1 to 50 parts by weight based on 100 parts by weight of tungsten oxide.

According to another embodiment of the present invention, the crystal structure of the toilet discoloration layer may be cubic.

According to another embodiment of the present invention, the electrochromic layer may be discolored by internal electromotive force generated by light sensitization rather than external power.

Therefore, according to the present invention, it is possible to improve the quality of the smart window by providing improved transparency and self-discoloration by an external light source, and at the same time, it is possible to easily control particle crystallinity and phase purity. Can improve the discoloration properties.

1 is a cross-sectional view of a photosensitive automatic color change device according to an embodiment of the present invention,
2 is a light transmittance graph according to Example 1 of the present invention,
3 is an actual photograph showing the degree of discoloration/discoloration according to Example 1 of the present invention,
4 is a light transmittance graph according to Example 2 of the present invention,
5 is an actual photograph showing the degree of discoloration/discoloration according to Example 2 of the present invention,
6 is a light transmittance graph according to a comparative example of the present invention,
7 is an actual photograph showing the degree of discoloration/discoloration according to a comparative example of the present invention,
8 is an XRD measurement graph for the electrochromic layers of Examples and Comparative Examples of the present invention (Example 1 = TC 0.25, Example 2 = TC 0.5, Example 3 = TC 0.75, Comparative Example TC 0),
9 is a scanning surface microscope (SEM) photographs of the surfaces and cross sections of Examples and Comparative Examples of the present invention,
10 is a cross-sectional view showing the internal structure of a conventional electrochromic device.

Hereinafter, the present invention will be described in detail.

However, it should be noted that the technical terms used in the present invention are only used to describe specific embodiments and are not intended to limit the present invention.

In addition, the technical terms used in the present invention should be interpreted as generally understood by those of ordinary skill in the technical field to which the present invention belongs, unless otherwise defined in the present invention, and is excessively comprehensive. When the technical term used in the present invention is an incorrect technical term that does not accurately express the idea of the present invention, it should not be interpreted in the meaning of a person or construed as an excessively reduced meaning. It should be replaced and understood, and the general terms used in the present invention should be interpreted as defined in the dictionary or according to the context before and after, and should not be interpreted as an excessively reduced meaning, and the singular number used in the present invention The expression of the expression includes a plurality of expressions unless clearly defined otherwise in the context, and in the present invention, terms such as "consisting of" or "comprising" necessarily include all of the various elements or various steps described in the present invention. It should not be construed as, and some of the components or some steps may not be included, or it should be construed as that it may further include additional components or steps. If it is determined that the detailed description may obscure the subject matter of the present invention, the detailed description will be omitted.

1 is a cross-sectional view of a photosensitive automatic color change device according to an embodiment of the present invention, FIG. 2 is a light transmittance graph according to Example 1 of the present invention, and FIG. 3 is a decolorization/discoloration diagram according to Example 1 of the present invention. It is an actual photograph showing the degree, Figure 4 is a light transmittance graph according to the second embodiment of the present invention, Figure 5 is an actual photograph showing the degree of discoloration / discoloration according to the second embodiment of the present invention, Figure 6 is It is a light transmittance graph according to a comparative example of the present invention, FIG. 7 is an actual photograph showing the degree of discoloration/discoloration according to the comparative example of the present invention, and FIG. 8 is an XRD measurement of the electrochromic layer of the examples and comparative examples of the present invention. It is a graph (Example 1 = TC 0.25, Example 2 = TC 0.5, Example 3 = TC 0.75, Comparative Example TC 0), Fig. 9 is a surface scanning microscope ( SEM) photo, refer to this.

The method of manufacturing a photosensitive autochromic device according to the present invention is an electrochromic layer 220 stacked on one of the opposing first substrate 100 and the second substrate 200, with an electrolyte ( 300) is interposed, and the electrochromic layer includes titanium (Ti) doped tungsten oxide.

As the first and second substrates 100 and 200, a transparent glass substrate or a polymer substrate may be used to generally have transparency as a glass material or a polymer material, but depending on the application to which the electrochromic device is applied, in some cases, it is translucent. Or it can be used as an opaque substrate.

In addition, the electrochromic layer 220 may include a titanium precursor powder and a titanium coupling agent, wherein a peroxo-tungstic acid (PTA) powder may be used as the titanium precursor powder, and titanium As the coupling agent, it is used to improve the electrochromic function of the electrochromic device according to the present invention and to improve crystallinity and phase purity, and preferably tetraisopropyl di(dioctylphosphate) titanate may be used, It may be provided in the form of a powder or a liquid dispersed in a solvent, in addition to tetraisopropyl di (dioctyl phosphate) titanate, isopropyl dioley (dioctyl phosphate) titanate, isopropyl tri (dioctyl phosphate) tie Tanate, isopropyl trioleyl titanate, isopropyl tristearyl titanate, isopropyl tri(dodecylbenzenesulfonate) titanate, isopropyl tri(dioctylpyrrophosphate) titanate, di( At least one selected from the group consisting of dioctyl pyrophosphate) ethylene titanate may be selected, and such a coupling agent is a tetraalkoxide titanate hydrolyzed in an ethanol solvent (e.g., titanium(IV) isopropoxide, titanium(IV) ) Unlike butoxide, alkyl phosphate is bonded to prevent hydrolysis, so it has excellent storage stability of the solution.

When heat treatment is performed by adding crystalline titanium dioxide powder to the PTA with particle powder having a particle diameter of 10 to 100 nm, it is possible to form a heterogeneous reducing discoloration material in which crystalline titanium dioxide is dispersed in amorphous tungsten oxide. In this case, the discoloration is mainly _{operated by amorphous WO 3} , and it is known that crystalline titanium dioxide forms an electric path smoothly for the transfer of electrons and lithium ions, where the PTA is WO ₃ .xH ₂ O ₂ .yH ₂ O can be expressed as 0.05=<x<<=1.0, 3<=y<=4. That is, if the average particle diameter of the titanium dioxide powder is less than 10 nm, dispersion in the PTA solution may be difficult, and if it exceeds 100 nm, the transmittance of the final reduced color change layer may decrease due to the scattering effect.

On the other hand, the titanium coupling agent may be 1 to 50 parts by weight based on 100 parts by weight of the tungsten oxide precursor powder. If it is less than 1 part by weight, a very dense thin film is formed to reduce the movement of electrolyte ions, thereby reducing the color change rate and discoloration. The range can be reduced, and on the contrary, when it exceeds 50 parts by weight, it is possible to raise the problem of lowering the color change rate and the color change range by forming an _{amorphous WO 3 and forming a dense thin film.}

Here, the toilet discoloration layer is preferably coated in the form of a solution or gel and then subjected to a thermal curing process, and tungsten oxide may be changed to crystalline by the thermal curing process, Such Crystalline can be confirmed by powdery X-ray diffraction spectroscopy (XRD), particularly in a cubic phase, and thermal curing is preferably 400 to 500°C, but if it is less than 400°C, amorphous WO ₃ can be produced. Conversely, if it exceeds 500°C, it may cause a limitation problem on the substrate and an unexpected change in the crystal structure of _{the WO 3 layer due to the ions eluted from the substrate, resulting in deterioration of quality.}

In addition, the thermal curing process there is a first, after forming the WO ₃ layer can proceed more heat treatment after applying the layer of metal oxide (e.g., TiO ₂₎ above to form a cubic crystalline WO _3, which the WO ₃ If the metal oxide (TiO ₂ ) is applied after application and heat treatment is performed at the same time, there may be a fair benefit, but there may be cases where the desired cubic WO ₃ cannot be obtained due to additionally doped metal (Ti) of the metal oxide. .

This additional thermal curing process is also preferably 400 to 500°C. If it is less than 400°C, _{it may be a problem that amorphous WO 3} is generated instead of the desired crystalline phase. Conversely, if it exceeds 500°C, limitations on the substrate and from the substrate It may cause an unexpected change in the crystal structure of _{the WO 3} layer due to the eluted ions (metal ions, for example, Ti of _{TiO 2 ), resulting in deterioration of quality.}

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Here, during the thermal curing process, in particular, pre-drying may be performed in the previous step, which has the purpose of removing the solvent already present in the coating layer, and is performed at a temperature of 90 to 120°C, if less than 90°C, There may be a problem in that the solvent is not completely removed. Conversely, when the temperature exceeds 120° C., the solvent rapidly evaporates and cracks or pinholes may be generated in the coating layer.

One feature of the electrochromic layer is that the electrochromic layer is discolored by internal electromotive force generated by light sensitization, not by external power, which is reduced by _{WO 3} due to the resistance of the conductive substrate in the case of electrochromic using the _{WO 3 layer alone.} To reduce the color change layer, a voltage higher than the required voltage must be applied. Also, as the area increases, the color change rate decreases significantly due to the increase of the sheet resistance of the conductive substrate. However, when the color change layer and the photosensitive layer are stacked, the transfer distance of charges is minimized. The speed of discoloration is greatly improved, and the voltage for discoloration may also be significantly lowered.

In addition, in order to use the tungsten oxide of the present invention in a solution or gel form, alcohols having a low carbon number (methanol, ethanol, propanol, isopropanol, or mixtures thereof) may be used as a solvent, and alcohols having a low carbon number It has a low evaporation temperature of 120℃ or less, so it can be easily removed in the pre-drying step.

Meanwhile, the magnetically driven electrochromic device 1000 according to the present invention may be structurally implemented in various embodiments, and the accompanying drawings will be specified and described.

1 and 2, in the photosensitive automatic color conversion device 1000 according to an embodiment of the present invention, an electrochromic layer 220 and a metal oxide layer 120 to which the ligand 130 is adsorbed are stacked in order. And a second substrate 200 disposed to face the first substrate 100 and to interpose the electrolyte 300 therebetween.

Since the description of the electrochromic layer 220 has been previously described, it will be replaced with the description.

The ligand 130 has a dictionary meaning of an atom or group of atoms that forms a coordination bond while providing an electron pair to a central metal atom in a complex compound, but in the present invention, a compound that acts as an electron donor in the metal oxide layer is included. As such, 2,3-Salicylic acid, 2,3-Pyrazine dicarboxylic acid, Rosmarinic acid, Citric acid, Boric acid , 3-Methylsalicylic acid, 4-Methyl salicylic acid, 5-Methyl salicylic acid, 4-Aminosalicylic acid, 2-hydro Roxynicotinic acid (2-Hydroxynicotinic acid), 3-hydroxypicolinic acid (3-Hydroxypicolinic acid), 2-hydroxy-1-naphthoic acid (2-Hydroxy-1-naphthoic acid), 3-hydroxy-2- Naphthoic acid (3-Hydroxy-2-naphthoic acid), 3-hydroxy-2-methyl-4-quinolinecarboxylic acid (3-Hydroxy-2-methyl-4-quinolinecarboxylic acid), 2-hydroxy-3-isopropyl Benzoic acid (2-Hydroxy-3-isopropylbenzoic acid), 2-hydroxy-5- (1H-pyrrol-1-yl) benzoic acid (2-Hydroxy-5- (1H-pyrrol-1-yl) benzoic acid), 2 -Hydroxy-6-methylpyridine-3-carboxylic acid (2-Hydorxy-6-methylpyridine-3-carboxylic acid), 2-(4-hydroxyphenylazo)benzoic acid (2-(4-Hydroxyphenylazo)benzoic acid), 1-Hydroxy-2-naphthoic acid, 4-hydroxy-7-trifluoromethyl-3-quinolinecarboxylic acid (4-Hydroxy-7-trifluoromethyl-3-quinolinecarboxyli c acid), 3-hydroxy-2-quinoxaline carboxylic acid, 9-hydroxy-9-fluorene carboxylic acid (9-Hydroxy-9-fluorene carboxylic acid), 4' -(Diphenylamino)-4-hydroxy-[1,1'-biphenyl]-3-carboxylic acid (4'-(Diphenylamino)-4-hydroxy-[1,1'-biphenyl]-3-carboxylic acid ) Or 4-(4-(diphenylamino)styryl)-2-hydroxybenzoic acid (4-(4-(Diphenylamino)styryl)-2-hydroxybenzoic acid).

The first substrate 100 may be a plate made of a transparent material and may be flat as well as curved with a certain curvature, and may be a transparent polymer material as well as a glass material, such as PET, PEN, PC, PP, PI, or TAC. The same material can be selectively used as needed.

On the other hand, the electrochromic layer 220 is stacked on the first substrate, and the electrochromic layer causes coloration during a reduction reaction and causes bleaching during an oxidation reaction. A mixture of peroxo-tungstic acid (PTA) is used, the detailed description of which has been previously mentioned, and is thereby replaced.

Such an electrochromic layer 220 can be applied to various applications. For example, when used as a window, it is colored by a reduction reaction in the daytime, so that the cooling and heating costs can be reduced in summer or winter, as well as the building itself. In the case of decorating or displaying a specific color or image, it can be used in a variety of mixed configurations.

In addition, in the electrochromic layer, the metal oxide layer 120 has electrical conductivity and is provided to secure the adsorption and durability of the ligand 130, titanium dioxide (TiO ₂ ), zinc oxide (ZnO), and tin oxide (SnO). ₂ ), niobium oxide (Nb ₂ O ₅ ), etc. can be used.

Meanwhile, the second substrate 200 is disposed opposite to the first substrate, and the electrolyte 300 is interposed therein, and the second substrate is a flat plate made of a transparent material, as well as being curved with a certain curvature. It may be a (curved) material, as well as a glass material, as a transparent polymer material, and a material such as PET, PEN, PC, PP, PI, or TAC may be selectively used as needed.

On the other hand, the electrolyte 300 interposed between the first substrate 100 and the second substrate 200 is a bromide-based compound (Br composite) that secures transparency, and is a lithium bromide, sodium bromide, potassium bromide, quaternary A liquid electrolyte in which at least one selected from the group consisting of ammonium salt, imidazolium salt, and pyridinium salt is mixed with an organic solvent may be used, and a lithium salt may be dissolved in the bromide-based compound.

In addition, the electrolyte may be included as a lithium salt in the form of a combination of ClO ₄ , BF ₄ , PF ₆ , OTf (trifluoromethanesulfonate), TFSI (CF ₃ SO ₂ ) ₂ N), and B(CN) ₄ functional groups, and oxidation As a reducing material, metal ions such as Co(III)/Co(II) and Fc/Fc ⁺ can be mixed and used in an organic solvent.

Here, the organic solvent is not particularly limited as long as the electrolyte is smoothly subjected to oxidation and reduction reactions, but is selected from the group of organic solvents consisting of nitrile, lactone, sulfone, carbonate, pyrrolidone and amide. At least one of which may be included as a solvent, and at least one selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, tetrahydrofuran and gamma-butyrolactone is each or mixed Can be used.

Meanwhile, as the electrolyte of the present invention, at least one selected from the group of ionic liquid electrolytes consisting of imidazolium, pyrrolidium, and pyridinium may be used, and a gel electrolyte may be used, examples of which include silica, titania, and A metal oxide such as zirconia may include nanoparticles having an average particle size of 10 to 500 nm.

Manufacturing Example 1

A transparent glass substrate was prepared as a first substrate, and tetraisopropyl di (dioctyl phosphate) titanate (KH401) and tungstic acid (PTA) were added to the first substrate, respectively, 0.25 g, 3.1 g, and 8 g of ethanol as a solvent. The mixture was applied by a doctor blade coating method, pre-dried at 100°C for 30 minutes, and then heat treated at 450°C. Next, titanium dioxide oxide was applied, heat-treated at 450°C, and then a ligand (0.3mM 5-methyl salicylic acid solution) was adsorbed to prepare a cathode electrode having a thickness of 300 nm.

Manufacturing Example 2

It was carried out in the same manner as in Example 1, except that 0.5 g of tetraisopropyl di(dioctylphosphate) titanate (KH401) was used.

Manufacturing Example 3

It was carried out in the same manner as in Example 1, except that 0.75 g of tetraisopropyl di(dioctylphosphate) titanate (KH401) was used.

Comparative Production Example

A transparent glass substrate was prepared as a first substrate, and a tungstic acid solution (36% by weight solution, solvent ethanol) was applied to the first substrate, followed by heat treatment at 450° C. for 30 minutes. Thereafter, titanium dioxide oxide was applied, heat-treated at 450° C., and a ligand (0.3 mM 5-methyl salicylic acid solution) was adsorbed to prepare a cathode electrode having a thickness of 300 nm.

Examples 1 to 3, Comparative Example

After making the cathode electrodes of Preparation Examples 1 to 3 and Comparative Preparation Examples and the second substrate, which is a transparent glass substrate, face each other, a thermoplastic polymer layer having a thickness of about 60 μm made of SURLYN (manufactured by Du Pont) was formed with the opposite edges. The first substrate and the second substrate are interposed inside, put in an oven at 130° C. for 2 minutes to attach and seal the two electrodes, and a fine hole penetrating the second substrate is formed to form a fine hole between the two electrodes. An electrolyte solution in which 1.0 M LiI was dissolved in 3-methoxypropionitrile solvent was injected into the space, and then the outside of the hole was sealed with an adhesive to prepare a photosensitive automatic color change device according to the present invention and a comparative example color change device.

Experimental Example 1

For the previously prepared Examples 1 to 3 and Comparative Examples, the transmittance was first measured, and the photosensitive autochromic element was exposed for 5 minutes under the solar condition (AM 1.5) of a xenon lamp corrected using a standard solar cell to electrochromic. The discoloration and transmittance of the device were measured and tested, and are shown in Table 1 below.

division Transmittance(%)
(Cathode electrode)* Transmittance(%)
(Second electrode) ^* Transmittance during coloring of electrochromic element (%) ^* Transmittance during decolorization of electrochromic element (%) ^* Transmittance change rate (%) ^** Example 1 (tc-0.25) 75.3% 91.29% 15.83% 59.67% 43.84% Example 2
(tc-0.50) 74.9% 91.29% 55.84% 65.48% 9.64% Example 3
(tc-0.75) 75.2% 91.29% 52.02% 67.00% 14.98% Comparative example
(tc-0.00) 73.4% 91.29% 32.86% 62.08% 29.22%

^* Tvis: Average transmittance in the range of 380nm ~ 780nm

^** △OD = Log(Tvis(bleaching)/Tvis(coloring))

In addition, referring to Table 1 and FIGS. 2, 3, 4, 5, and 6, it can be seen that the transmittance of the photosensitive autochromic device according to the embodiment is improved by 20 to 500% compared to the comparative example.

Experimental Example 2

In order to confirm the monoclinic crystallinity of the tungsten oxide particles for Examples 1 to 3 and Comparative Examples, X-ray diffraction analysis (XRD) was performed (mechanism used: Dmax-2500pc manufactured by Rigaku).

Referring to FIG. 8, Examples 1 to 3 according to the present invention mainly have a cubic crystal phase in the case of _{pure tungsten oxide (WO 3) in which Ti is not doped with respect to the comparative example (powder diffraction file (PDF) reference} While a small amount of unidentified crystal phase is visible, as in the example of the present invention, by adding an appropriate amount of the titanium coupling agent (Example 1), the same cubic phase of _{pure WO 3 is shown.} At the same time, it can be seen that the unidentified crystal phase seen in the _{pure WO 3 sample disappears, thereby improving the characteristic value.} It can also be seen that the addition of a higher amount of titanium coupling agent rather _{interferes with the crystallization of WO 3} to form an amorphous thin film layer and lowers the discoloration characteristic value.

Experimental Example 3

In order to observe the surface and cross-sectional images of the coating films for Examples 1 to 3 and Comparative Examples, a surface scanning microscope photograph was taken (mechanism used: FE-SEM is a Hitachi S-4700 model).

Referring to FIG. 9, in Examples 1 to 3 according to the present invention, it can be seen that in the case of pure tungsten oxide (WO ₃ ) not doped with Ti, a crack is formed on the surface. It can be seen through SEM that crystals of various sizes that do not have a specific shape are arranged very closely.

These cracks are known to degrade the characteristic values of the final device.

In the case of Example 1, it was confirmed that the WO3 thin film was uniformly coated without cracking, and it was found that crystals of a more uniform shape were formed. Seems to improve. When more titanate coupling agent was added, it was confirmed that, as a result of XRD, _{the crystallization of WO 3} was prevented, increasing the amorphous state of WO 3, forming a more dense thin film, and at the same time forming unidentified heterogeneous crystals on the surface. .

First substrate 100, metal oxide layer 120,
Ligand 130, second substrate 200,
Electrochromic layer 220, electrolyte 300,
Auto color conversion device 1000

Claims (16)

As an electrochromic layer stacked on one of the opposed first and second substrates, an electrolyte is interposed between the electrochromic layer, and the electrochromic layer includes titanium (Ti) doped tungsten oxide,
Is reduced to form a color transfer material color change after heat treatment of yiseonghyeong (heterogenous) that are distributed to the titanium (Ti) a crystalline titanium dioxide powder in the tungsten sanhwamulneun 10 to 100㎚ particle doped in the tungsten oxide is in an amorphous amorphous WO ₃ The crystalline titanium dioxide forms an electric path for the transfer of electrons and lithium ions.
The electrochromic layer includes a titanium coupling agent, wherein the titanium coupling agent is 1 to 50 parts by weight based on 100 parts by weight of a tungsten oxide precursor,
The titanium coupling agent may use tetraisopropyl di (dioctyl phosphate) titanate, which may be provided in a powder form or in a liquid form dispersed in a solvent, in addition to isopropyl dioleyl (dioctyl phosphate) titanate, Optical characterized in that it is at least one selected from the group consisting of isopropyl trioleyl titanate, isopropyl tristearyl titanate, isopropyl tri(dodecylbenzenesulfonate) titanate, and ethylene titanate A method of manufacturing a responsive automatic color conversion device.
delete delete delete The method of claim 1,
The method of manufacturing a light-sensitive automatic color conversion device, wherein the electrochromic layer is coated in a solution or gel form and then subjected to a thermal curing process.
The method of claim 5,
A method of manufacturing a photosensitive automatic color conversion device, characterized in that coating a metal oxide layer on the electrochromic layer.
◈ Claim 7 was abandoned upon payment of the set registration fee. The method of claim 6,
The method of manufacturing a light-sensitive automatic color conversion device, characterized in that the metal oxide layer undergoes an additional thermal curing process.
◈ Claim 8 was abandoned upon payment of the set registration fee. The method of claim 5,
The method of manufacturing a photosensitive automatic color conversion device, characterized in that the crystal structure of the electrochromic layer after the thermal curing process is cubic.
The method of claim 1,
The method of manufacturing a photosensitive automatic color conversion device, wherein the electrochromic layer is discolored by internal electromotive force generated by light sensitization, not by external power.
◈ Claim 10 was abandoned upon payment of the set registration fee. The method of claim 5,
According to another embodiment of the present invention, a method of manufacturing a light-sensitive automatic color conversion device, further comprising a pre-drying step during the thermal curing process.
◈ Claim 11 was abandoned upon payment of the set registration fee. The method of claim 5,
The method of manufacturing a light-sensitive automatic color conversion device, characterized in that the solvent in the form of a solution or a gel is alcohol.
Tungsten oxide doped with titanium (Ti) manufactured by the manufacturing method of claim 1 is laminated on one of the first substrate and the second substrate opposite to the electrochromic layer, and the electrochromic layer and the first substrate or the second substrate are A photosensitive automatic color conversion device characterized in that an electrolyte is interposed therebetween.
The method of claim 12,
The photosensitive automatic color conversion device, characterized in that the electrochromic layer contains a titanium coupling agent.
The method of claim 13,
The titanium coupling agent is a photosensitive automatic color conversion device, characterized in that 1 to 50 parts by weight based on 100 parts by weight of tungsten oxide.
◈ Claim 15 was abandoned upon payment of the set registration fee. The method of claim 14,
The photosensitive automatic color conversion device, characterized in that the crystal structure of the electrochromic layer is cubic.
The method of claim 15,
The photosensitive automatic color conversion device, wherein the electrochromic layer is discolored by internal electromotive force generated by light sensitization, not by external power.

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