TW202314005A - Method for preparing electrochromic ion storage film including performing a co-sputtering treatment with a vanadium pentoxide target material and a cobalt target material - Google Patents

Abstract

A method for preparing an electrochromic ion storage film comprises setting a vanadium pentoxide target material and a cobalt target material in an environment containing an argon gas and an oxygen gas to perform radio frequency co-sputtering treatment, so as to form a layer of electrochromic ion storage film on a substrate. The pressure of the environment is controlled at 0.005 torr. The content ratio of the argon gas to the oxygen is controlled within a range. The radio frequency power of the vanadium pentoxide target is controlled at a first power and the radio frequency power of the cobalt target is controlled at a second power. The ratio of the second power to the first power is between 0.158 and 0.175. The invention can improve and optimize a color contrast and a color change rate of the electrochromic ion storage film.

Description

Preparation method of electrochromic ion storage membrane

The invention relates to a preparation method of an electrochromic ion storage membrane, in particular to a preparation method of an electrochromic ion storage membrane using cobalt doped on a vanadium pentoxide thin film.

Electrochromic devices are widely used, for example, in non-emissive information displays, energy-saving smart windows, car sunroofs, and anti-glare rearview mirrors. The conventional electrochromic device comprises a glass substrate, a transparent conductive layer, an electrochromic layer, an electrolyte layer, an ion storage layer, a transparent conductive layer, and a glass substrate from top to bottom.

Among them, the thin film of vanadium pentoxide has semiconductor characteristics, and is a mixed conductive material for ion and electron conduction, so it can be used as a cathode material for lithium-ion batteries and an electrochromic material. The structure is a layered structure, which is conducive to ion transmission and has good The reversibility of lithium ion implantation and extraction makes vanadium pentoxide can be used as the intercalation host of many alkali metal ions, organic compounds and polymers, and it can be judged that vanadium pentoxide thin film may be suitable as an excellent ion storage layer. material, but thin films of vanadium pentoxide also suffer from several disadvantages, such as poor color contrast and low discoloration rates.

Therefore, the present inventor proposes a method for preparing an electrochromic ion storage film in order to improve the color contrast and coloring rate of the ion storage layer prepared using a thin film of vanadium pentoxide.

The preparation method of the electrochromic ion storage membrane comprises a radio frequency co-sputtering step.

In the radio frequency co-sputtering step, a vanadium pentoxide target and a cobalt target are placed in an environment containing an argon gas and an oxygen gas to perform a radio frequency co-sputtering process to form a layer of electrochromic ions on a substrate storage film, wherein the pressure of the environment is controlled at 5x10 ^-3 torr, the content ratio of the argon and the oxygen is controlled within a range, and the radio frequency power of the vanadium pentoxide target is controlled at a first power, the cobalt The radio frequency power of the target is controlled at a second power, and the ratio of the second power to the first power is between 0.158 and 0.175.

Further, the first power is 120W, and the second power is between 19W and 21W.

Further, the range is that the oxygen accounts for 8.65% to 9.55% of the total amount of the argon and the oxygen formed.

Further, the substrate is indium tin oxide glass.

Further, before the pressure of the environment is controlled at 5x10 ^-3 torr, a mechanical pump is used to evacuate the environment until the pressure of the environment is 4x10 ^-2 torr, and then a high vacuum oil diffusion pump is used to evacuate the air to the environment. The pressure is up to 5x10 ^-5 torr, and then the argon and the oxygen are introduced to control the pressure of the environment at 5x10 ^-3 torr.

Further, the preparation method of the electrochromic ion storage film also includes a cleaning step before the radio frequency co-sputtering step, the cleaning step is to immerse the substrate in an acetone solution and vibrate it with ultrasonic waves for 5 minutes, and then the substrate Soak in pure water and vibrate with ultrasonic waves for 5 minutes, then soak the substrate in an isopropanol solution and vibrate with ultrasonic waves for 5 minutes, then soak the substrate in pure water and vibrate with ultrasonic waves for 5 minutes, and finally The substrate was quickly blown dry with high-pressure nitrogen.

According to the above-mentioned technical features, the following effects can be achieved:

1. In the preparation method of the electrochromic ion storage film, by adjusting the radio frequency power of the vanadium pentoxide target at the first power, the radio frequency power of the cobalt target at the second power, and the second power The ratio of the first power ratio is between 0.158 and 0.175 to control the amount of cobalt doped in the vanadium pentoxide film. Compared with the vanadium pentoxide film not doped with cobalt, the electrochromic ion storage film The color contrast and color change rate are indeed improved and optimized.

2. By adjusting the content of the oxygen in the total working gas of the argon and the oxygen to between 8.65% and 9.55%, the color contrast and color change rate of the electrochromic ion storage film are also improved.

Based on the above technical features, the main effects of the method for preparing the electrochromic ion storage membrane of the present invention will be clearly presented in the following examples.

Referring to the first figure, it is an embodiment of the preparation method of the electrochromic ion storage membrane of the present invention. The preparation method of the electrochromic ion storage membrane includes a cleaning step S01 and a radio frequency co-sputtering step S02.

The cleaning step S01 is to immerse a substrate in an acetone solution and oscillate with ultrasonic waves for 5 minutes to remove grease and organic matter on the surface of the substrate, and then immerse the substrate in pure water and oscillate with ultrasonic waves for 5 minutes to remove the The acetone solution remaining on the substrate, then soak the substrate in an isopropanol solution and oscillate it with ultrasonic waves for 5 minutes, then immerse the substrate in pure water and oscillate it with ultrasonic waves for 5 minutes, and finally quickly remove it with high-pressure nitrogen gas The substrate was blown dry. In this example, the substrate is indium tin oxide glass.

In the RF co-sputtering step S02, the substrate is first placed in a cavity, and the cavity is first evacuated by a mechanical pump to an ambient pressure of 4x10 ^-2 torr, and then evacuated by a high-vacuum oil-type diffusion pump. gas to the ambient pressure to 5x10 ^-5 torr, and then feed the working gas, argon and oxygen, so that the pressure of the environment is controlled at 5x10 ^-3 torr, and the oxygen accounts for 8.65% to 8.65% of the total amount of the argon and the oxygen 9.55%, the optimum is 9.1%. In this example, the argon flow is fixed at 22.0 sccm, and the oxygen flow is fixed at 2.2 sccm. A vanadium pentoxide target and a cobalt target are placed in the cavity for radio frequency co-sputtering treatment to form an electrochromic ion storage film on the substrate, and the radio frequency power of the vanadium pentoxide target is controlled At a first power, the radio frequency power of the cobalt target is controlled at a second power, and the ratio of the second power to the first power is between 0.158 and 0.175. In this example, the first power is 120 W and the second power is between 19 W and 21 W, optimally 20 W

When the electrochromic ion storage film undergoes reduction discoloration (coloring) by applying a voltage, lithium ions (Li ⁺ ) and electrons in the electrolyte move into the electrochromic ion storage film, so that the electrochromic ion storage film forms Li _x V ₂ O ₅ , and the vanadium pentoxide of the electrochromic ion storage membrane is reduced from V ⁵⁺ to V ⁴⁺ . When the electrochromic ion storage film is oxidatively discolored (decolorized) by applying a voltage, the lithium ions and electrons originally in the electrochromic ion storage film will move out and return to the electrolytic liquid, making the vanadium pentoxide The film is reoxidized from V ⁴⁺ to V ⁵⁺ . The reaction formula is as follows.

V ₂O ₅+ Li ⁺+ xe ^-(氧化反應)           Li _xV ₂O ₅(還原反應)

V ₂ O ₅ + Li ⁺ + xe ^- (oxidation reaction) Li _x V ₂ O ₅ (reduction reaction)

The inventors conducted multiple experiments on adjusting the radio frequency power of the cobalt target, and confirmed that doping cobalt into the vanadium pentoxide thin film will indeed affect the color contrast and discoloration rate of the electrochromic ion storage film.

Referring to Figures 2 to 10 and Table 1, the chamber is first evacuated to an ambient pressure of 5x10 ^-5 torr, and the flow rate of the argon gas is fixed at 22.0 sccm and the flow rate of the oxygen gas is fixed at 2.2 sccm, so that the chamber The pressure of the body is controlled at 5x10 ^-3 torr, the RF power of the vanadium pentoxide target is fixed at 120 W, and the RF power of the cobalt target is controlled at 0 W, 10 W, 20 W, 30 W, 50 W, 9 states of 70 W, 90 W, 110 W, and 120 W, and after 3 hours of deposition of the electrochromic ion storage film, a total of 9 test pieces were produced.

The 9 test pieces were measured using an ultraviolet-visible light spectrometer (SEMSO-3000 photoelectrochemical simultaneous measurement system) to measure the light transmittance of the test pieces at three visible light wavelengths of 550nm, 600nm, and 650 nm , the range of discoloration is represented by the difference in transmittance. The transmittance of these test pieces will decrease during the coloring process, and the transmittance will increase if the color removal process is carried out. Therefore, the greater the transmittance difference, the more obvious the range of discoloration. The formula for the difference in penetration is shown below. Among them, ∆T represents the difference in transmittance, T _bleach represents the transmittance of decolorization, and T _color represents the transmittance of coloring.

∆T = T _bleach - T _color

It can be seen from the experiment that when the RF power of the cobalt target is controlled at 10 W, 20 W, and 30 W, the range of discoloration changes significantly. However, when the RF power of the cobalt target is controlled at 50 W, In the three visible wavelengths of 550nm, 600nm, and 650 nm, the range of variation is significantly reduced, and after the RF power of the cobalt target is controlled at 70 W, the range of variation in the spectrum is reduced even more. When the RF power of the cobalt target In the state of 90 W~120 W, the spectral color change transmittance basically does not change. Therefore, a small amount of cobalt is doped in the vanadium pentoxide film to change the color range, but excessive doping will make the vanadium pentoxide film lose the color change function, but the RF power of the cobalt target is controlled at 20 W , the lithium ion migration caused by the electrochromic ion storage film is the best in the discoloration effect, that is, the range of the transmittance difference is the best in all conditions.

With reference to the eleventh figure to the thirteenth figure, the 9 test pieces are measured by the ultraviolet-visible light spectrometer (SEMSO-3000 photoelectrochemical simultaneous measurement system), and the measurement of the test pieces in the full spectrum wavelength The light transmittance, and the voltage applied to each test piece for reductive discoloration (coloring) and oxidative discoloration (decolorization) are the light transmittance at -3.0 V and +3.0 V respectively. The changes in the spectral range are similar to the changes in the three visible light wavelengths of 550nm, 600nm, and 650 nm, that is, when the RF power of the cobalt target is controlled at 20 W, the lithium ion migration caused by the electrochromic ion storage film is also The color change effect is the best, that is, the change of the transmittance is the best among all conditions. This case only reveals that the RF power of the cobalt target is controlled at 0 W, 20 W, and 90 W. Table I The light transmittance difference (∆T) of visible light wavelength (nm)/RF power of cobalt target 0W 10W 20W 30W 50W 70W 90W 110W 120W 550nm ∆T(%) 6.47 9.08 13.86 9.4 2.01 2.07 0.91 0.21 0.04 600nm ∆T(%) 10.51 10.97 15.78 10.11 3.14 2.28 0.46 0.08 0.14 650nm ∆T(%) 15.49 14.12 19.21 10.10 2.66 3.05 1.22 0.17 0.09

Referring to the fourteenth figure, the inventor further carried out the coloring and decolorization process on these 9 kinds of test pieces, and the voltages applied to each test piece for reductive discoloration (coloring) and oxidative discoloration (decolorization) were respectively -3.0 V and +3.0V. When the RF power of the cobalt target is controlled at 20 W, the coloring rate and decolorization rate of the electrochromic ion storage film are the fastest.

The inventors conducted multiple experiments on adjusting the oxygen content in the whole gas, and confirmed that adjusting the oxygen content will also affect the color contrast and color change rate of the electrochromic ion storage film.

Referring to Figures 15 to 18 and Table 2, the cavity is first evacuated to ambient pressure to 5x10 ^-5 torr, and the flow rate of the argon gas is fixed at 22.0 sccm, and the flow rate of the oxygen gas is controlled at 1.1 sccm, 1.47 sccm, 2.2 sccm, and 4.4 sccm, that is, the content of oxygen in the whole gas is 4.76%, 6.25%, 9.1%, and 16.67%, so that the pressure of the cavity is controlled at 5x10 ^-3 torr, The radio frequency power of the vanadium pentoxide target was fixed at 120 W, the radio frequency power of the cobalt target was controlled at 20 W, and the electrochromic ion storage film was deposited after 3 hours, and a total of 4 test pieces were produced.

The four test pieces were also measured using a UV-visible spectrometer (SEMSO-3000 photoelectrochemical simultaneous measurement system) to measure the light of these test pieces at three visible wavelengths of 550 nm, 600 nm, and 650 nm. penetration rate. It can be seen from the experiment that in the RF co-sputtering process, a small amount of oxygen and argon are introduced into the working gas, and the light transmittance of the electrochromic ion storage film is improved to a certain extent. When the working gas contains When the percentage of oxygen increased to 9.09%, the difference between light transmittance and light transmittance was effectively improved, but when the percentage of oxygen in the working gas was raised to 16.67%, the difference between light transmittance and light transmittance value decreased instead. Therefore, when the oxygen content of the working gas is 9.09%, the light transmittance difference range is the best among all conditions. Table II Difference in light transmittance (∆T) of visible light wavelength (nm)/percentage of oxygen content 4.76% 6.25% 9.09% 16.67% 550nm ∆T(%) 8.47 8.53 13.86 5.82 600nm ∆T(%) 7.39 7.73 15.78 6.21 650nm ∆T(%) 6.24 5.91 18.60 4.42

Referring to Figure 19, the inventor further carried out the coloring and decolorization process on the four test pieces, and the voltages applied to each test piece for reductive discoloration (coloring) and oxidative discoloration (decolorization) were -3.0 V and + 3.0V. When the oxygen content percentage of the working gas is 9.09%, the coloring rate and decoloring rate of the electrochromic ion storage membrane are the fastest.

In summary, in the preparation method of the electrochromic ion storage film, by adjusting the radio frequency power of the vanadium pentoxide target at the first power, the radio frequency power of the cobalt target at the second power, and the The ratio of the second power ratio to the first power is between 0.158 and 0.175 to control the amount of cobalt doped in the vanadium pentoxide film. Compared with the vanadium pentoxide film not doped with cobalt, the electrochromic The color contrast and discoloration rate of the ion storage film are indeed improved and optimized, and the electrochromic ion is stored by adjusting the content of the oxygen in the total working gas of the argon and the oxygen to 8.65% to 9.55%. The color contrast and rate of color change of the film are also improved.

Based on the description of the above-mentioned embodiments, it is possible to fully understand the operation of the present invention, use and the effect that the present invention produces, but the above-mentioned embodiments are only preferred embodiments of the present invention, and should not be used to limit the implementation of the present invention. The scope, that is, the simple equivalent changes and modifications made according to the patent scope of the present invention and the content of the description of the invention, all fall within the scope of the present invention.

S01: Cleaning step S02: RF co-sputtering step

[FIG. 1] is a flowchart illustrating an embodiment of the method for producing the electrochromic ion storage membrane of the present invention. [The second figure] is an experimental diagram illustrating the penetration of the electrochromic ion storage film when the radio frequency power of the vanadium pentoxide target is controlled at 120 W and the radio frequency power of the cobalt target is controlled at 0 W. Transmittance difference. [The third figure] is an experimental diagram, illustrating the penetration of the electrochromic ion storage film when the radio frequency power of the vanadium pentoxide target is controlled at 120 W and the radio frequency power of the cobalt target is controlled at 10 W. Transmittance difference. [Figure 4] is an experimental diagram illustrating the penetration of the electrochromic ion storage film when the radio frequency power of the vanadium pentoxide target is controlled at 120 W and the radio frequency power of the cobalt target is controlled at 20 W. Transmittance difference. [Figure 5] is an experimental diagram illustrating the penetration of the electrochromic ion storage film when the radio frequency power of the vanadium pentoxide target is controlled at 120 W and the radio frequency power of the cobalt target is controlled at 30 W. Transmittance difference. [Figure 6] is an experimental diagram illustrating the penetration of the electrochromic ion storage film when the radio frequency power of the vanadium pentoxide target is controlled at 120 W and the radio frequency power of the cobalt target is controlled at 50 W. Transmittance difference. [Figure 7] is an experimental diagram illustrating the penetration of the electrochromic ion storage film when the radio frequency power of the vanadium pentoxide target is controlled at 120 W and the radio frequency power of the cobalt target is controlled at 70 W. Transmittance difference. [Figure 8] is an experimental diagram illustrating the penetration of the electrochromic ion storage film when the radio frequency power of the vanadium pentoxide target is controlled at 120 W and the radio frequency power of the cobalt target is controlled at 90 W. Transmittance difference. [Figure 9] is an experimental diagram illustrating the penetration of the electrochromic ion storage film when the radio frequency power of the vanadium pentoxide target is controlled at 120 W and the radio frequency power of the cobalt target is controlled at 110 W. Transmittance difference. [Figure 10] is an experimental diagram illustrating the penetration of the electrochromic ion storage film when the radio frequency power of the vanadium pentoxide target is controlled at 120 W and the radio frequency power of the cobalt target is controlled at 120 W. Transmittance difference. [Figure 11] is an experimental diagram, illustrating that the preparation of the electrochromic ion storage film is under the condition that the radio frequency power of the vanadium pentoxide target is controlled at 120 W, and the radio frequency power of the cobalt target is controlled at 0 W. Penetration without redox and with redox. [Figure 12] is an experimental diagram, illustrating that the preparation of the electrochromic ion storage film is under the condition that the radio frequency power of the vanadium pentoxide target is controlled at 120 W, and the radio frequency power of the cobalt target is controlled at 20 W. Penetration without redox and with redox. [Figure 13] is an experimental diagram, illustrating that the preparation of the electrochromic ion storage film is under the condition that the radio frequency power of the vanadium pentoxide target is controlled at 120 W, and the radio frequency power of the cobalt target is controlled at 90 W. Penetration without redox and with redox. [Figure 14] is an experimental diagram illustrating the relationship between the electrochromic ion storage film and the control of the radio frequency power of the cobalt target and the discoloration rate in the preparation of the electrochromic ion storage film. [Fig. 15] is an experimental diagram illustrating the difference in transmittance of the electrochromic ion storage membrane when the oxygen content is controlled at 4.76%. [Figure 16] is an experimental diagram illustrating the difference in transmittance when the oxygen content of the electrochromic ion storage membrane is controlled at 6.25%. [Figure 17] is an experimental diagram illustrating the difference in transmittance when the electrochromic ion storage membrane is prepared when the oxygen content is controlled at 9.09%. [Figure 18] is an experimental diagram illustrating the difference in transmittance of the electrochromic ion storage membrane when the oxygen content is controlled at 16.67%. [Figure 19] is an experimental figure illustrating the relationship between oxygen content control and discoloration rate in the preparation of the electrochromic ion storage membrane.

S01: Cleaning step

S02: RF co-sputtering step

Claims (6)

A method for preparing an electrochromic ion storage film, comprising: setting a vanadium pentoxide target material and a cobalt target material in an environment containing an argon gas and an oxygen gas to perform radio frequency co-sputtering treatment, so that on a substrate An electrochromic ion storage film is formed, wherein the pressure of the environment is controlled at 5x10 ^-3 torr, the content ratio of the argon gas to the oxygen is controlled within a certain range, and the radio frequency power of the vanadium pentoxide target is controlled within a certain range. The first power, the radio frequency power of the cobalt target is controlled at a second power, and the ratio of the second power to the first power is between 0.158 and 0.175. The method for preparing an electrochromic ion storage membrane according to Claim 1, wherein the first power is 120W, and the second power is between 19W and 21W. The method for preparing an electrochromic ion storage membrane according to claim 1, wherein the range is that the oxygen accounts for 8.65% to 9.55% of the total amount of the argon and the oxygen formed. The method for preparing an electrochromic ion storage film according to claim 1, wherein the substrate is indium tin oxide glass. The preparation method of the electrochromic ion storage membrane as described in Claim 1, wherein, before the pressure of the environment is controlled at 5x10 ^-3 torr, a mechanical pump is used to pump air until the pressure of the environment is 4x10 ^-2 torr , and then use a high vacuum oil diffusion pump to evacuate the environment to a pressure of 5x10 ^-5 torr, and then introduce the argon and oxygen to control the pressure of the environment at 5x10 ^-3 torr. The preparation method of the electrochromic ion storage film as described in Claim 1 further includes: soaking the substrate in an acetone solution and vibrating it with ultrasonic waves for 5 minutes before performing radio frequency co-sputtering treatment, and then soaking the substrate in Vibrate with ultrasonic waves in pure water for 5 minutes, then soak the substrate in an isopropanol solution and vibrate with ultrasonic waves for 5 minutes, then soak the substrate in pure water and vibrate with ultrasonic waves for 5 minutes, and finally use high pressure Nitrogen quickly blows the substrate dry.

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