CN113774343A

CN113774343A - Novel co-sputtering preparation method of electrochromic doped film

Info

Publication number: CN113774343A
Application number: CN202110912893.7A
Authority: CN
Inventors: 王梦颖; 刁训刚
Original assignee: Beihang University
Current assignee: Beihang University
Priority date: 2021-08-10
Filing date: 2021-08-10
Publication date: 2021-12-10

Abstract

The invention discloses a novel co-sputtering preparation method of an electrochromic doped film, which comprises the following steps: 1. uniformly punching holes on the basic target I by using a bench drill; 2. stacking the doped target II on the basic target I, and combining to be used as a stacking target source; 3. placing the cleaned ITO glass substrate in a cabin of vacuum magnetron sputtering equipment; 4. co-sputtering the stacked target source by adopting a vacuum direct-current magnetron sputtering technology. Through the steps, the electrochromic performance of the doped electrochromic film successfully prepared by the invention has strong dependence on the grain size and the surface appearance of the film, and the film shows good optical modulation amplitude and excellent durability.

Description

Novel co-sputtering preparation method of electrochromic doped film

Technical Field

The invention relates to a novel co-sputtering preparation method of a doped electrochromic film. The electrochromic film can realize the autonomous change of transmittance under the action of an external electric field, can be used in the fields of film supercapacitors, film batteries and the like, and belongs to the technical field of intelligent functional materials.

Background

With the emergence of energy crisis, China pays more attention to energy storage technology, and more recently, "action plan for development of energy storage technology specialty disciplines (2020 and 2024) was issued, which provides guidance for development of energy storage technology. "smart windows" that can save energy by adjusting light intensity according to indoor comfort are receiving increasing attention, and a new generation of active optically controlled electrochromic materials is outstanding among them.

Electrochromism (EC) is a phenomenon of changing color at a persistent and reversible potential through an electrochemical reaction, usually manifested as a significant, reversible, stable change in color and optical properties. Wherein, part of transition metal oxide film is used as common electrochromic material, such as nickel oxide (NiO) and tungsten oxide (WO)₃) Vanadium oxide (V)₂O₅) And the like are receiving much attention because of their low cost and abundant reserves. Further, since electrochromic thin films have occupied a place in the fields of batteries, gas sensors, thin film transistors, capacitors, and the like, researchers have made many studies thereon. Research shows that the electrochromic film is easy to be electrochemically degraded and needs to be optimized.

Doping is a common method, for example, doping of elements such as La, Ag, Mg, Al, Si, V, Nb, W, or Ta in an electrochromic film is studied, and it is found that the doping has positive gain for increasing the optical modulation amplitude and the lifetime of the film. Element doping is proved to improve the charge-discharge reversibility of the electrochromic film electrode, the chemical valence of the base film is greatly influenced, and the electrochromic performance is influenced by the valence change. However, as far as we know, the common doping method adopts a dual-power source/multi-power source sputtering method or an alloy target material method for sputtering, and the methods have the problems of complex operation, high equipment requirement, single doping proportion and the like.

Therefore, a new doping preparation method is imperative to be implemented.

Disclosure of Invention

Objects of the invention

The invention aims to provide a method for preparing an electrochromic film by a novel doping means. The electrochromic performance of the doped electrochromic film prepared by the method has strong dependence on the grain size and the surface appearance of the film, and the film can show good optical modulation amplitude and excellent durability.

(II) technical scheme

The invention aims to provide a novel co-sputtering preparation method of a doped electrochromic film, which comprises the following specific steps:

step 1, uniformly punching holes on a basic target I by using a bench drill;

step 2, stacking the doped target II on the basic target I to form a stacked target source;

step 3, placing the ITO glass substrate in a direct-current magnetron sputtering vacuum chamber;

and 4, co-sputtering the stacked target source by adopting a vacuum direct-current magnetron sputtering technology to prepare the doped electrochromic film.

Wherein, in the step 1, the basic target I is a round target with the diameter of 100 mm;

wherein, the holes punched in the step 1 are uniformly distributed by taking a target center as a center, so that the doping elements can be deposited on the ITO glass substrate;

wherein, in the step 2, the doping target II is a round target with the diameter of 100 mm;

wherein, in the step 2, the stacked target sources need to be assembled together on the target position of the DC magnetron sputtering vacuum chamber;

wherein, in step 3, the ITO glass is purchased from Jun Yiming company in Guangdong, the square resistance of the ITO glass is 15 omega, and the ITO glass is cut into a square with the length of 3cm multiplied by 3 cm;

wherein, in the step 3, the ITO glass substrate needs to be sequentially cleaned in ethanol and deionized water for 20 minutes by an ultrasonic cleaner, and then dried by a vacuum oven at the temperature of 40 ℃;

wherein, in step 3, the distance between the ITO substrate and the target position is kept at about 10 cm;

wherein, in the step 4, the working gas used for sputtering is argon with the purity of 99.99 percent and oxygen with the purity of 99.99 percent;

in step 4, the sputtering step is as follows: vacuumizing, controlling the vacuum degree at 2X 10^-3Pa; then, independently introducing argon/oxygen working gas into the vacuum chamber; before formal sputtering, a baffle plate in front of a magnetron sputtering target position is not taken down, and a stacked target source needs to be pre-sputtered for 5min in a pure argon atmosphere to remove impurities such as oxide on the surface of a metal target; and finally, regulating and controlling the gas flow ratio of oxygen and argon, working power and sputtering time, keeping the gas pressure unchanged in the sputtering process, and depositing the doped electrochromic film on the ITO glass.

(III) the advantages and effects of the invention

1. The invention provides a novel co-sputtering preparation method of a doped electrochromic film, which has simple preparation process and can be prepared in a large area;

2. the doped electrochromic film prepared by the invention has typical electrochromic effect and energy storage effect, and has wider practical application prospect in the field of integrated films;

3. the photoelectric property of the doped electrochromic film can be changed by adjusting the sputtering parameters in the preparation process.

Drawings

FIG. 1 is a schematic view of the preparation method of the present invention

FIG. 2 is a surface topography of a doped electrochromic film prepared in an example

FIG. 3 is an X-ray photoelectron spectrum of the doped electrochromic film prepared in the example

FIG. 4 is an in situ electrochemical test plot of doped electrochromic films prepared by example

FIG. 5 is an in situ optical test chart of doped electrochromic films prepared by example

FIG. 6 is a flow chart of the method of the present invention

The numbers, symbols and codes in the figures are explained as follows:

in FIG. 6, the letters a, b, c, d, e, f, g, h, i, j are the sequence numbers of the small steps of the specific implementation method

Detailed Description

step 1, drilling 6 holes on a basic target I with the diameter of 100mm by using a bench drill, wherein the 6 holes are uniformly distributed on a concentric circle with the center of a target as the center and the radius of 5mm, and the drilled holes have the diameter of 3mm and are far away from the target so that doped elements can be deposited on an ITO glass substrate;

step 2, stacking the doped target II on the base target I, wherein the diameter of the doped target II is 100mm, and combining the doped target II into a stacked target source which needs to be assembled together on a target position of the direct current magnetron sputtering vacuum chamber;

step 3, placing the ITO glass substrate in a direct-current magnetron sputtering vacuum chamber, and keeping the distance between the ITO substrate and a target position at about 10 cm; the ITO glass is purchased from Jun Yiming company in Guangdong, the square resistance of the ITO glass is 15 omega, and the ITO glass is cut into a square with the length of 3cm multiplied by 3 cm; cleaning the ITO glass substrate in ethanol and deionized water for 20 minutes by using an ultrasonic cleaner in sequence, and then drying by using a vacuum oven at the temperature of 40 ℃;

step 4, co-sputtering the stacked target source by adopting a vacuum direct-current magnetron sputtering technology to prepare a doped electrochromic film; the sputtering steps are as follows: vacuumizing, controlling the vacuum degree at 2X 10^-3Pa; then, independently introducing argon/oxygen working gas into the vacuum chamber; before formal sputtering, a baffle plate in front of a magnetron sputtering target position is not taken down, and a stacked target source needs to be pre-sputtered for 5min in a pure argon atmosphere to remove impurities such as oxide on the surface of a metal target; and finally, regulating and controlling the gas flow ratio of oxygen and argon, working power and sputtering time, keeping the gas pressure unchanged in the sputtering process, and depositing the doped electrochromic film on the ITO glass.

In order that the reader will be thoroughly informed of the present invention, a detailed implementation will be provided in the following description. Meanwhile, the above-described embodiments are merely to illustrate the present invention in detail to avoid unnecessary limitations of the present invention.

Examples

The invention provides a novel co-sputtering preparation method of a doped electrochromic film, which comprises the following specific steps:

(1) uniformly punching 6 holes with the diameter of 3mm on a metal target of nickel so that doped elements can be deposited on the ITO glass substrate;

(2) a ceramic target of lanthanum was then stacked on a nickel metal target and co-sputtered as shown in fig. 1. The distance between the target and the substrate was kept at about 10 cm.

(3) Prior to deposition, all ITO glass substrates (having a square resistance of 15 Ω) were cut into a 3cm × 3cm square, and washed in ethanol and deionized water for 20 minutes in sequence with an ultrasonic cleaner, and then dried using a vacuum oven at a temperature of 40 ℃.

(4) Vacuumizing, controlling the vacuum degree at 2X 10^-3Pa; then, independently introducing argon/oxygen working gas into the vacuum chamber, wherein the pressure of the working gas is 2.2 Pa; before formal sputtering, a baffle plate in front of a magnetron sputtering target position is not taken down, and a stacked target source needs to be pre-sputtered for 5min in a pure argon atmosphere to remove impurities such as oxide on the surface of a metal target; finally, regulating and controlling the gas flow ratio of oxygen to argon to be about 1:9, the working power to be 240W and the sputtering time to be 25min, keeping the gas pressure unchanged in the sputtering process, and depositing the doped LaNiO on the ITO glass_xAn electrochromic film.

(5) For doped LaNiO_xThe electrochromic film is subjected to in-situ electrochemical-optical test, namely a self-built test system connecting an electrochemical workstation and a spectrophotometer in series: the electrochemical synchronous test is realized by a three-electrode electrochemical workstation (Shanghai Chenghua CHI660E), and a doped electrochromic film is respectively used as a working electrode, Ag/AgCl is used as a reference electrode, a Pt foil is used as a counter electrode, and a 1M KOH solution is used as an electrolyte; the preparation steps of 1M KOH are as follows: accurately weighing 28g of KOH by using an electronic balance, dissolving by using a small amount of deionized water, transferring to a 500ml beaker, gradually adding the deionized water to 500ml of scale marks, and uniformly stirring by using a magnetic stirrer; the optical synchronization test was measured by an ultraviolet-visible spectrophotometer (Hitachi UV-vis, U-3010, Japan).

Claims

1. A novel co-sputtering preparation method of an electrochromic doped film is characterized by comprising the following steps: the method comprises the following specific steps:

step 1, uniformly punching holes on a basic target I by using a bench drill;

2. The novel co-sputtering preparation method of the doped electrochromic film according to claim 1, characterized in that:

in step 1, the basic target I is a round target with the diameter of 100 mm;

in step 1, the holes are uniformly distributed with the target center as the center, so that the doping elements can be deposited on the ITO glass substrate.

3. The novel co-sputtering preparation method of the doped electrochromic film according to claim 1, characterized in that:

in step 2, the doping target II is a round target with the diameter of 100 mm;

in step 2, the stacked target sources need to be assembled together on the target position of the DC magnetron sputtering vacuum chamber.

4. The novel co-sputtering preparation method of the doped electrochromic film according to claim 1, characterized in that:

in step 3, the ITO glass is purchased from Jun Yiming company in Guangdong, the square resistance of the ITO glass is 15 omega, and the ITO glass is cut into a square with the length of 3cm multiplied by 3 cm;

in step 3, the ITO glass substrate needs to be sequentially cleaned in ethanol and deionized water for 20 minutes by an ultrasonic cleaner, and then dried by a vacuum oven at the temperature of 40 ℃.

In step 3, the distance between the ITO substrate and the target site is maintained at about 10 cm.

5. The novel co-sputtering preparation method of the doped electrochromic film according to claim 1, characterized in that:

in step 4, the working gas used for sputtering is argon with the purity of 99.99 percent and oxygen with the purity of 99.99 percent;

in step 4, the sputtering step is as follows: vacuumizing, controlling the vacuum degree at 2X 10^-3Pa; then, independently introducing argon/oxygen working gas into the vacuum chamber; before formal sputtering, a baffle plate in front of a magnetron sputtering target position is not taken down, and a stacked target source needs to be pre-sputtered for 5min in a pure argon atmosphere to remove impurities such as oxide on the surface of a metal target; finally, adjustControlling the gas flow ratio, the working power and the sputtering time of the oxygen and the argon, keeping the gas pressure unchanged in the sputtering process, and depositing the doped electrochromic film on the ITO glass.