CN117215048A - Preparation method and application of substrate for electrowetting display - Google Patents

Preparation method and application of substrate for electrowetting display Download PDF

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Publication number
CN117215048A
CN117215048A CN202311001983.6A CN202311001983A CN117215048A CN 117215048 A CN117215048 A CN 117215048A CN 202311001983 A CN202311001983 A CN 202311001983A CN 117215048 A CN117215048 A CN 117215048A
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substrate
electrowetting display
preparation
electrolyte
molybdate
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CN202311001983.6A
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孙海玲
舒畅
蒋洪伟
袁冬
唐彪
周国富
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Guangxian Technology Guangdong Co ltd
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Guangxian Technology Guangdong Co ltd
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Abstract

The invention discloses a preparation method and application of a substrate for electrowetting display, and belongs to the technical field of electrowetting display. The preparation method provided by the invention comprises the steps of taking a substrate semi-finished product as an anode and molybdate solution as electrolyte for electrolytic repair treatment; the semi-finished substrate comprises a valve metal electrode and an insulating hydrophobic layer which are overlapped, and the insulating hydrophobic layer is contacted with the electrolyte in the electrolytic repair treatment process. When the substrate prepared by the preparation method is applied to electrowetting display, gas is hardly generated, and the service life and performance of the substrate are further improved. The invention also provides application of the preparation method.

Description

Preparation method and application of substrate for electrowetting display
Technical Field
The invention relates to the technical field of electrowetting display, in particular to a preparation method and application of a substrate for electrowetting display.
Background
Electrowetting refers to changing the surface tension between a liquid and a solid by adjusting the potential applied between the liquid-solid electrodes, thereby changing the contact angle between the two. The discovery and development history of electrowetting includes the following phases: in 1875, scientists Lippmann observed that a capillary drop phenomenon occurs when a voltage is applied between mercury and electrolyte, and a well-known Lippmann-Young equation was proposed. In 1993, scientist Berge introduced a dielectric layer (between liquid and solid electrodes) in the electrowetting model to try to eliminate electrolysis, which was called electrowetting-on-dielectric (EWOD). Under the action of the voltage V, the contact angle of the liquid drop satisfies the electrowetting equation:
wherein epsilon is the dielectric constant of the dielectric layer, d is the thickness of the dielectric layer, and gamma sv Gamma, the interfacial tension between the oil and the dielectric layer sl Gamma, the interfacial tension between water and the dielectric layer lv Is the interfacial tension between water and oil.
The dielectric layer of current EWOD systems is relatively thick (10 -6 m) whose performance is limited by the dielectric film thickness, which requires higher voltages to achieve significant changes in contact angle according to the above equation. In order to obtain large contact angle variations, practical EWOD systems require that a hydrophobic coating be also provided between the dielectric layer and the liquid. That is, in a conventional electrowetting substrate, a solid electrode, a dielectric layer, a hydrophobic layer, and a liquid are sequentially stacked.
An important field of application of electrowetting technology is electrowetting display, in which the wetting effect of the surface can be changed by voltage regulation, and thus the droplets can be manipulated. Thus, with voltage regulation, a pixel modulator can be built up on the surface of the electrowetting display device. When the different pixels are activated independently to create an image, the oil is colored in one color, thereby forming a display function.
The preparation of a typical electrowetting limiting device comprises the following steps: (1) autonomously designing a substrate, cutting and cleaning; (2) coating a functional material and modifying the surface; (3) Preparing a pixel grid by a photoetching process, gluing, pre-baking, aligning, exposing, middle-baking, developing and post-baking; (4) Performing photoetching post-treatment, namely initially hydrophobic, changing the surface of the material into hydrophilic after surface modification, and changing the material into hydrophobic after photoetching modification; (5) filling and packaging ink; (6) cutting into samples, and modularizing. That is, the electrowetting display device includes a substrate, and ink encapsulated by the substrate.
When the electrowetting display device is in use, the following problems exist: mibus found that the electrolyte/dielectric contact exhibited significant asymmetry in breakdown characteristics in that the cathode bias resulted in a low voltage breakdown, while at the anode bias, high electric field ion conduction began before breakdown occurred. These phenomena can be explained by the electrochemical reactions that occur at the surface, where the cathodic process can lead to dissolution and failure of the oxide (dielectric) and the anodic process can lead to additional oxide growth before breakdown. Under the condition of a conventional ITO electrode, pinholes of a dielectric layer can lead to electrochemical reaction (water electrolysis).
To solve the above technical problem, m.d. dndsa presents an electrowetting system with dielectric breakdown protection, specifically selecting valve metal (a type of metal with a wide passivation voltage range) as anode, then further coating 300nm of xylene-C dielectric (er=3.1) on the electrode coated substrate using a special coating system laboratory coater, and then dip-coating the Parylene-C sample on the surface of the anode dielectric layer with 30nm Dupont Teflon AF1600 layers as a hydrophobic layer. The substrate thus produced shows practically instantaneous self-healing (within 100 milliseconds) after dielectric breakdown under DC and certain ac wetting conditions, the principle being to use the anodized metal oxide to reduce leakage current. The oxidation products block the pinholes so that the droplets do not generate bubbles (no electrolyzed water) during the subsequent electrowetting process.
However, there are still a number of problems associated with the use of the substrate provided by the above solution in electrowetting displays: during the repair process, bubbles are still inevitably generated within 100 milliseconds, and the electrowetting display system is closed, and the generated bubbles have a very adverse effect on the performance and safety of the electrowetting display system. Thus, there is still a need to develop a substrate for an electrowetting display device that does not generate bubbles during use.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides the preparation method of the substrate for the electrowetting display, which can effectively avoid the process that the substrate is corroded to generate gas when the substrate is applied to the electrowetting display, thereby prolonging the service life and improving the performance of the substrate.
The invention also provides application of the preparation method.
According to an embodiment of the first aspect of the present invention, there is provided a method for manufacturing a substrate for electrowetting display, the method comprising performing electrolytic repair treatment with a substrate semi-finished product as an anode and a molybdate solution as an electrolyte;
the semi-finished substrate comprises a valve metal electrode and an insulating hydrophobic layer which are overlapped, and the insulating hydrophobic layer is contacted with the electrolyte in the electrolytic repair treatment process.
The preparation method provided by the embodiment of the invention has at least the following beneficial effects:
(1) In the prior art, if the gas is prevented from being separated out in the use process of the substrate as far as possible, the thought of optimizing the material selection is generally adopted; limited to the properties of the raw materials, this concept is more limited.
The research of the invention discovers that micropores are inevitably formed in the dielectric layer or the hydrophobic layer in the process of preparing the substrate, the main sites of the occurrence of later electrolytic water are also micropores remained in the process of preparing, in particular the hydrophobic layer which cannot be defaulted, the substrate is composed of organic polymers, and the substrate has good ductility and also means that the geometrical space is easy to be heated or stress creep to cause hole defects. Therefore, the invention creatively carries out electrolytic self-repairing treatment on the semi-finished substrate before the use of the substrate, so that gas can not be generated in the use process of the substrate, and further, the gas can not be stored in the closed space of the electrowetting display device, and the reliability of the electrowetting limiting device can be obviously improved by the substrate.
(2) In the electrolytic restoration treatment adopted by the invention, the electrolyte containing molybdenum salt is adopted, and molybdenum is typical blunting metal, so that the valve metal electrode is oxidized in the pores of the insulating hydrophobic layer to generate a corresponding oxide passivation film, thereby achieving the restoration purpose. And the surface of the substrate obtained by repairing does not comprise a bare valve metal electrode (no obvious weak position), so that the breakdown of an insulating hydrophobic layer can be obviously avoided, and the failure of the substrate in the application process of electrowetting display can be further avoided.
(3) In the prior art, there is a technical scheme that an oxide passivation layer is directly arranged between a valve metal electrode and an insulating hydrophobic layer, but basically any preparation method at the present stage can not meet the requirement of no pore, for example, when the valve metal oxide is generated on the valve metal electrode by an anodic oxidation method, pores are inevitably generated at weak positions of thickness due to self-limiting thickness of an oxide film and large-area oxidation. Thus, when the substrate is used in an electrowetting display device, the electrolyte of the electrowetting display device still penetrates and contacts the electrodes of the substrate and breaks the electrodes of the substrate. The preparation provided by the invention is used for controllably repairing the pores on the insulating hydrophobic layer, and has the advantages of stronger specificity and better repairing effect.
(4) The preparation method provided by the invention can realize self-repairing of the substrate by simple electrolysis, has mild conditions and simple operation, and is expected to be popularized and applied on a large scale.
According to some embodiments of the invention, the material of the insulating hydrophobic layer comprises a Fluoropolymer (FP).
According to some embodiments of the invention, the thickness of the insulating hydrophobic layer is 500-1000 nm. For example, it may be about 800nm.
According to some embodiments of the invention, the method of preparing the insulating hydrophobic layer includes applying a slurry including a fluoropolymer to the valve metal electrode surface and drying.
According to some embodiments of the invention, the method of coating comprises at least one of spray coating, knife coating, curtain coating, spin coating, and dip coating.
When the preparation method of the insulating hydrophobic layer comprises spin coating, the rotation speed of the spin coating is 1200-1500 rpm. For example, it may be about 1400rpm. The spin coating time is 50-70 s. For example, it may be about 65 seconds.
According to some embodiments of the invention, the concentration of molybdate in the electrolyte is 0.5 to 2moL/L. Therefore, the effect of electrolytic repair treatment can be improved, and the original pores in the insulating hydrophobic layer in the obtained substrate are blocked by the oxide of the valve metal electrode.
According to some embodiments of the invention, the electrolyte has a pH of about 7. No intervention is typically required.
According to some embodiments of the invention, the molybdate comprises at least one of sodium molybdate, potassium molybdate, ammonium molybdate, and calcium molybdate.
According to some embodiments of the invention, the potential of the anode is 0.5-1.0V during the electrolytic repair process. The electrolytic repair treatment is a constant pressure oxidation process. The current through the valve metal electrode/electrolyte increases dramatically and then decays exponentially as the insulating oxide layer on the interface increases. The final thickness of the oxide layer is proportional to the anodic oxidation voltage, and the slope (anodic oxidation ratio) is also different according to the concentration and composition of the electrolyte. In general, large current densities, such as dielectric breakdown of electrowetting systems, can form dense non-conductive oxide layers in less than one second. Therefore, by adjusting the above-mentioned potential, the final thickness of the oxide layer obtained after oxidation of the valve metal electrode can be precisely controlled. In the above potential range, in the obtained substrate, the original pores in the insulating hydrophobic layer are blocked by the oxide of the valve metal electrode.
According to some embodiments of the invention, the treatment duration of the electrolytic repair treatment is greater than or equal to 200 seconds. For example, the time period may be specifically 5 minutes to 2 hours. And more specifically may be about 1 hour.
According to some embodiments of the invention, the electrolytic repair treated cathode comprises a solid metal. For example, it may be specifically at least one of stainless steel, silver and platinum. Tests prove that different types of cathodes have no obvious influence on the performance of the obtained substrate, so that stainless steel is often selected from the aspect of economy.
According to some embodiments of the invention, the valve metal electrode comprises at least one of titanium, niobium, tungsten, bismuth, tantalum, zirconium, hafnium, and aluminum. In particular to a simple substance of metal, a laminated structure of two or more metals, or an alloy structure of two or more metals.
The oxides of the valve metals have high dielectric constants, so that even if the oxides exist in the pores of the dielectric hydrophobic layer, the oxides can still play a dielectric role without negatively affecting the electrowetting performance of the substrate.
According to some embodiments of the invention, the valve metal electrode is made of aluminum. Therefore, the material cost of the substrate can be reduced, and the difficulty of electrolytic repair treatment in the preparation method can be reduced.
According to some embodiments of the invention, the valve metal electrode is made of titanium.
When the valve metal electrode is made of titanium, the electrochemical process possibly occurring in the electrolytic repair process is as follows
Equation (anode): ti+2H 2 O==TiO 2 +4H + +4e -
Equation (cathode): 4H (4H) + +4e - ==2H 2 ↑。
Thus, the electrolytic repair process is complete with all possible reactions.
According to an embodiment of the second aspect of the present invention there is provided the use of the method of manufacture as described in the manufacture of an electrowetting display device.
The preparation of the electrowetting display device adopts all the technical schemes of the preparation method of the embodiment, so that the electrowetting display device has at least all the beneficial effects brought by the technical schemes of the embodiment. In particular, the resulting electrowetting display device has excellent reliability and a long lifetime.
According to some embodiments of the invention, the electrowetting display device comprises the substrate, an electrolyte and a packaging structure; the electrolyte is positioned in a closed space surrounded by the substrate and the packaging structure.
The insulating hydrophobic layer of the substrate is in direct contact with the electrolyte.
According to some embodiments of the invention, a side surface of the substrate in contact with the electrolyte is provided with a pixel cell.
According to some embodiments of the invention, the preparation of the electrowetting display device comprises the steps of:
s1, sequentially carrying out surface modification, pixel grid preparation and secondary modification on the surface of a substrate;
s2, filling, packaging and post-treatment of the ink.
According to some embodiments of the invention, in step S1, the surface modification is a hydrophilic modification. Because the material of the pixel wall of the pixel grid is hydrophilic, the hydrophilic modification is carried out so as to facilitate the preparation of the pixel grid. The hydrophilic modification method comprises reactive ion etching.
According to some embodiments of the invention, in step S1, the pixel grid is prepared by photolithography, which specifically includes sequentially performing photoresist coating, pre-baking, alignment, exposure, mid-baking, developing, and post-baking. The exposure and the development are matched with each other, photoresist in the pixel grid can be removed, and photoresist in the frame position of the pixel grid is reserved.
According to some embodiments of the invention, in step S1, the secondary modification comprises a hydrophobic modification performed sequentially. I.e. the hydrophilic surface is adjusted to a hydrophobic surface to facilitate the later electrowetting control.
In step S2, the ink filling refers to filling the ink into the pixel grid.
According to some embodiments of the invention, in step S2, the post-processing includes sequentially performing encapsulation, dicing, and modularity.
According to some embodiments of the invention, the electrowetting display device comprises a reflective electrofluidic display. In contrast to other types of electrowetting display devices, the reflective electrofluidic display is hydrophobic in all areas except the pixel wall, enabling an electrowetting response.
The term "about" as used herein, unless otherwise specified, means that the tolerance is within + -2%, for example, about 100 is actually 100 + -2%. Times.100.
Unless otherwise specified, the term "between … …" in the present invention includes the present number, for example "between 2 and 3" includes the end values of 2 and 3.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
fig. 1 is a schematic diagram of a working mechanism of a substrate having no self-repairing function and a self-repairing function in the conventional technology.
FIG. 2 is a schematic diagram showing the mechanism of electrolytic repair treatment in example 1 of the present invention.
Fig. 3 is a schematic view showing a process for manufacturing an electrowetting display device in example 2 of the present invention.
FIG. 4 is an apparent graph of the electrowetting display device obtained in example 2 of the present invention after aging.
FIG. 5 is an apparent graph of the electrowetting display device of comparative example 1 after aging.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
In the description of the present invention, the descriptions of the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Example 1
The substrate for electrowetting display is prepared by the method, and the specific process is as follows:
referring to the structure of FIG. 2, in this example, electrolytic repair treatment was performed for 1 hour using a substrate semi-finished product as an anode, stainless steel as a cathode, a sodium molybdate aqueous solution of 0.5mol/L as an electrolyte, and an anode potential of +0.5V.
Wherein, the semi-finished substrate is composed of a valve metal electrode (Ti) and an insulating hydrophobic layer which are overlapped; the insulating hydrophobic layer is made of fluorine-containing polymer (AF (Teflon 1600)). The surface of one side of the insulating hydrophobic layer is in direct contact with the electrolyte. The setting method is spin coating, the rotating speed is 1400rpm, and the duration is 65s.
During the electrolytic repair process, hydrogen ions flow to the cathode and hydroxide ions flow to the anode, while a voltage source provides a constant voltage. The hydrogen ion cathode combines to produce hydrogen gas, and the hydroxide ion reacts with Ti to produce anodic titanium oxide. The anodization process blocks the current very quickly so that bubbles stop generating. The hydrogen gas formed in the electrolytic remediation process directly enters the air. At the valve metal electrode/oxide interface, the high electric field drives the mobile and hydroxyl ions to continue to react with the anode inside the oxide and continue the titania growth.
The preparation flow of this example is shown in FIG. 3.
Example 2
The present example provides an electrowetting display device, the preparation process is shown in fig. 3, and the specific steps are as follows:
s1, sequentially carrying out surface modification, pixel grid preparation and secondary modification on the surface of a substrate; wherein,
the surface modification is hydrophilic modification by reactive ion etching.
The preparation method of the pixel grid is a photolithography method, and specifically comprises the steps of photoresist coating, pre-baking, alignment, exposure, intermediate baking, development and post-baking which are sequentially carried out.
The secondary modification includes hydrophobic modification.
S2, filling, packaging and post-treatment of the ink. Wherein, the post-treatment comprises the steps of packaging, cutting and modularizing sequentially.
Comparative example 1
This example produced an electrowetting display device, which differs from example 2 in particular in that:
the substrate semifinished product used in example 1 was directly used as a substrate. I.e. without electrolytic self-repair treatment.
Test case
The reliability of the electrowetting display devices obtained in example 2 and comparative example 1 was tested in this example by aging in an aging tester for 24 hours and observing whether bubbles are generated in the electrowetting display device, the aging condition being 50 ℃ and 50% relative humidity; 17.87V square wave voltage (duty cycle 50%) at a frequency of 5Hz. The results show that:
the electrowetting display device obtained in example 2 did not generate bubbles visible to the naked eye, whereas comparative example 1 generated a large amount of bubbles, thereby affecting the display performance of the electrowetting display device. The specific test results are shown in fig. 4 to 5.
Therefore, the preparation method provided by the invention remarkably avoids gas generation in the use process by carrying out advanced electrolytic repair treatment on the substrate, and prolongs the service life and the operation stability of the electrowetting display device comprising the substrate compared with the substrate in comparative example 1 or the substrate in the prior art (shown in figure 1).
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.

Claims (10)

1. The preparation method of the substrate for electrowetting display is characterized by comprising the steps of taking a substrate semi-finished product as an anode and molybdate solution as electrolyte for electrolytic repair treatment;
the semi-finished substrate comprises a valve metal electrode and an insulating hydrophobic layer which are overlapped, and the insulating hydrophobic layer is contacted with the electrolyte in the electrolytic repair treatment process.
2. The method of claim 1, wherein the valve metal electrode comprises at least one of titanium, niobium, tungsten, bismuth, tantalum, zirconium, hafnium, and aluminum.
3. The method according to claim 1, wherein the concentration of molybdate in the electrolyte is 0.5 to 2moL/L; and/or the molybdate comprises at least one of sodium molybdate, potassium molybdate, ammonium molybdate and calcium molybdate.
4. The method according to claim 1, wherein the potential of the anode is 0.5 to 1.0V during the electrolytic repair treatment.
5. The method according to claim 1, wherein the electrolytic repair treatment is carried out for a period of time of 200s or more.
6. Use of a method according to any one of claims 1 to 5 for the preparation of an electrowetting display device.
7. The use according to claim 6, wherein the electrowetting display device comprises the substrate, an electrolyte and a packaging structure; the electrolyte is positioned in a closed space surrounded by the substrate and the packaging structure.
8. The use according to claim 7, wherein the preparation of the electrowetting display device comprises the steps of:
s1, sequentially carrying out surface modification, pixel grid preparation and secondary modification on the surface of a substrate;
s2, filling, packaging and post-treatment of the ink.
9. The use according to claim 8, wherein in step S1, the secondary modification comprises a hydrophobic modification.
10. Use according to any of claims 6-9, wherein the electrowetting display device comprises a reflective electrofluidic display.
CN202311001983.6A 2023-08-08 2023-08-08 Preparation method and application of substrate for electrowetting display Pending CN117215048A (en)

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Application Number Priority Date Filing Date Title
CN202311001983.6A CN117215048A (en) 2023-08-08 2023-08-08 Preparation method and application of substrate for electrowetting display

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