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CN-117156935-B - Preparation method and application of embedded transparent metal micro-grid electrode

CN117156935BCN 117156935 BCN117156935 BCN 117156935BCN-117156935-B

Abstract

The invention discloses a preparation method and application of an embedded transparent metal micro-grid electrode, and uniformly spin-coating positive photoresist on clean transparent conductive glass, and obtaining the patterned photoresist through a photoetching technology. And using the patterned photoresist as a secondary mask, and introducing an ion beam etching process to selectively etch the conductive layer into the patterned groove. The etched sample is directly used for an ion beam sputtering process, and patterned photoresist is used as a three-time mask to sputter metal Cr and metal Ni to fill the patterned groove. Obtaining the embedded transparent metal micro-grid electrode. The method of selectively embedding the non-rare metal micro-grid is adopted, so that the conductivity and mechanical stability of commercial ITO are greatly improved, meanwhile, the introduction of the photoetching technology simplifies the preparation process and reduces the processing cost, and the prepared transparent metal micro-grid electrode has high light transmittance and high conductivity and can meet the requirements of the current novel electrochromic-energy storage device.

Inventors

  • ZHANG YAPENG
  • ZHANG GUANHUA
  • Xiong Yige
  • DUAN HUIGAO

Assignees

  • 湖南大学
  • 湖大粤港澳大湾区创新研究院(广州增城)

Dates

Publication Date
20260512
Application Date
20230803

Claims (10)

  1. 1. The manufacturing method of the embedded transparent metal micro-grid electrode is characterized by comprising the following steps of: (1) Ultrasonically cleaning small-size transparent conductive glass with absolute ethyl alcohol and deionized water in sequence, and then placing the transparent conductive glass in a blast drier for drying; (2) Uniformly spin-coating positive photoresist on the surface of a conductive layer of transparent conductive glass by using a photoresist homogenizing machine, then drying on a drying plate, standing, and cooling to room temperature to obtain transparent conductive glass with photoresist attached on the surface; (3) Covering the customized mask on the transparent conductive glass with the photoresist attached to the surface obtained in the step (2), and placing the transparent conductive glass on an ultraviolet photoetching machine with the illumination power of 20-40 mW/cm 2 and the illumination intensity of 100% -105% for exposure; (4) Placing the transparent conductive glass with the surface photoresist locally modified in the step (3) in a self-made developing solution, developing for 40-60 seconds, taking out, flushing the residual NaOH solution on the surface with deionized water, and blow-drying with a nitrogen gun to obtain the transparent conductive glass with the surface attached with the patterned photoresist, wherein the self-made developing solution is 0.5% NaOH solution; (5) Placing the transparent conductive glass with the patterned photoresist attached to the surface obtained in the step (4) into ion beam etching equipment, selectively etching a patterned groove on a conductive layer of the transparent conductive glass by using an ion beam etching technology, wherein the groove pattern is locally consistent with a customized mask plate, the depth of the groove is consistent with the thickness of the conductive layer, and the transparent conductive glass with the patterned groove on the surface is obtained, wherein the ion beam etching parameters comprise 6.5-7.0A of cathode current, 5-6A of neutralization current, 40-60V of arc electrode voltage, 440-460V of screen grid voltage, 300-310V of acceleration voltage, 1.25 of auxiliary coupling coefficient and 0.3nm/s of sputtering rate; (6) Placing the transparent conductive glass with the patterned grooves on the surface, which is obtained in the step (5), into ion beam sputtering equipment, using patterned photoresist as a mask, and sputtering metal Cr and metal Ni with certain thickness in the patterned grooves by using ion beam sputtering technology to obtain the transparent conductive glass embedded into the metal micro-grid, wherein the main parameters of ion beam sputtering are that the ion source energy is 500eV, the neutralization current is 60-70A, the beam current is 50-60A, and the sputtering rate is 0.143nm/s, and the total thickness of the metal Cr and the metal Ni is consistent with the depth of the grooves; (7) And (3) placing the transparent conductive glass embedded with the metal micro-grid obtained in the step (6) into self-made glue removing solution for ultrasonic cleaning, wherein the self-made glue removing solution is NaOH solution with the concentration of 5%, and washing with deionized water after cleaning is finished to remove photoresist and redundant metal on the surface of the transparent conductive glass, so as to obtain the embedded transparent metal micro-grid electrode.
  2. 2. The method for manufacturing an embedded transparent metal micro-grid electrode according to claim 1, wherein the small-size transparent conductive glass in the step (1) is 1-5 inches.
  3. 3. The method for manufacturing the embedded transparent metal micro-grid electrode according to claim 1, wherein the positive photoresist used in the step (2) is RZJ-390PG-50CP, and parameters of a photoresist homogenizer are set to be that the photoresist is spin-coated for 8-12 s at 400-600 r/min and then spin-coated for 28-32 s at 750-850 r/min, so that the photoresist is spin-coated uniformly and completely.
  4. 4. The method for manufacturing an embedded transparent metal micro-grid electrode according to claim 1, wherein the temperature of the baking plate used in the step (2) is set to be 90-110 ℃, and the baking time is 2-4 min, so that the photoresist is completely cured and photosensitive components in the photoresist are reserved to the maximum extent.
  5. 5. The method for manufacturing the embedded transparent metal micro-grid electrode, as claimed in claim 1, wherein the mask used in the step (3) is a customized mask, and the exposure parameters are that the illumination power is 45-55 mW/cm 2 , the illumination intensity is 100-103%, and the exposure time is 115-125 s.
  6. 6. The method for manufacturing an embedded transparent metal micro-grid electrode according to claim 1, wherein the self-made developing solution used in the step (4) is a 0.5% NaOH solution, and the developing time is 50s.
  7. 7. The method for manufacturing the embedded transparent metal micro-grid electrode according to claim 1, wherein the groove pattern etched in the step (5) by using an ion beam etching technology is locally consistent with a customized mask, the depth of the groove is consistent with the thickness of a conductive layer of transparent conductive glass, and the ion beam etching parameters comprise 6.5-6.8A of cathode current, 5.5-6A of neutralization current, 45-55V of arc electrode voltage, 445-45V of screen electrode voltage, 300-305V of acceleration voltage, 1.25 of auxiliary coupling coefficient and 0.3nm/s of sputtering rate.
  8. 8. The method for manufacturing an embedded transparent metal micro-grid electrode according to claim 1, wherein the bottom metal sputtered by the ion beam in the step (6) is Cr, the sputtering thickness is 3-10 nm, the top metal sputtered by the ion beam is Ni, and the total thickness of the metal Cr and the metal Ni is consistent with the depth of the groove.
  9. 9. The method for manufacturing an embedded transparent metal micro-grid electrode according to claim 1, wherein the self-made photoresist solution used in the step (7) is a NaOH solution with a concentration of 5%, and the solvent is N-methylpyrrolidone.
  10. 10. The method for manufacturing an embedded transparent metal micro-grid electrode according to claim 1, wherein the transparent metal micro-grid electrode is prepared and applied to an electrochromic-energy storage device.

Description

Preparation method and application of embedded transparent metal micro-grid electrode Technical Field The invention relates to preparation of a transparent conductive electrode, in particular to a preparation method of an embedded transparent metal micro-grid electrode for an electrochromic-energy storage device. Background Electrochromic-energy storage devices are new concepts recently introduced in the electrochromic field, and are considered as one of the most promising technologies in the new generation of functional display devices. It is similar to a typical secondary battery in terms of structure and reaction mechanism. The intelligent battery is redesigned, is endowed with a new electrochromic-energy storage integrated function, and can be applied to a new field or used as a standby energy source. Compared with the traditional electrochromic device, the electrochromic-energy storage device can partially recover the energy consumption of the energy storage display device, and has subverted innovative application prospect in the fields of intelligent display, green building and the like. Common electrochromic-energy storage devices generally consist of a multilayer structure comprising an electrochromic layer (containing a redox active material of adjustable optical properties), an ion storage layer (storing the redox active material for charge balancing), an ion transport layer (electrolyte for ion transport) and two transparent conductive electrodes. When a potential difference exists between the two transparent conductive electrodes, ions in the ion storage layer are injected into the electrochromic layer through the ion transmission layer under the action of a space electric field so as to change the optical characteristics of the electrochromic layer, and the charge injection is simultaneously accompanied with the movement of reverse ions or electrons so as to balance the charges in the counter electrode layer. In this process, the conductivity and transmittance of the electrochromic anode have a direct impact on the switching time, optical contrast, and even the coloring efficiency of the electrochromic-energy storage device. At present, the commercial transparent conductive film material widely used In electrochromic-energy storage devices mainly comprises indium doped ITO (i.e. In2O3: sn), and the ITO has higher mechanical strength and good wear resistance and corrosion resistance (except hydrofluoric acid). However, commercial ITO needs to be formed on a transparent substrate, and conventional magnetron sputtering methods have the advantages of high purity, high efficiency, strong binding force, good compactness and uniformity of the film, but cannot meet the performance requirements of high light transmittance (small film thickness) and high conductivity (large film thickness). In order to find a solution with high light transmittance and low sheet resistance transparent electrodes, a metal-based transparent electrode solution was proposed and made a breakthrough in nearly five years, becoming one of the materials that is expected to replace ITO. However, in general, the problems that the metal-based transparent electrode has poor chemical stability, insufficient adhesion to conductive glass, and independent structure cannot be directly applied commercially are still difficult to solve in a short period of time. Disclosure of Invention Transparent electrodes with high light transmittance and low sheet resistance are core components of a new generation of optoelectronic display devices. The conventional commercial transparent electrode mainly comprises indium doped ITO, but has poor conductivity and high brittleness, so that the conventional commercial transparent electrode cannot be applied in a large scale. The invention provides a preparation method and application of an embedded transparent metal micro-grid electrode, which adopts a method of selectively embedding a non-rare metal micro-grid, greatly improves the conductivity and mechanical stability of commercial ITO, simplifies the preparation process and reduces the processing cost by introducing a photoetching technology, and the prepared transparent metal micro-grid electrode has high light transmittance and high conductivity and can meet the requirements of the current novel electrochromic-energy storage device. Firstly, a patterning mask which takes photoresist as a material is designed and processed on the surface of ITO (indium tin oxide) through a photoetching technology, then an ion beam etching technology is used for deeply etching a conductive layer of transparent conductive glass into a groove which is locally consistent with a pattern of a customized mask, and finally, an ion beam sputtering technology is used for sequentially depositing metal Cr and metal Ni in the groove to prepare an embedded transparent metal micro-grid electrode which is used as an electrochromic positive electrode current collector in an electrochromi