TW201940328A - Low-radiation glass coated with aluminum-doped zinc oxide and tin-doped indium oxide and its preparation method - Google Patents

Abstract

This invention discloses a low-radiation glass coated with aluminum-doped zinc oxide and tin-doped indium oxide and its preparation method. The low-radiation glass has a glass base plate, a tin-doped indium oxide layer and an aluminum-doped zinc oxide layer. The preparation method comprises the steps of (1) selecting a glass base plate and a tin-doped indium oxide material as a target material and sputtering the tin-doped indium oxide material onto one side of the glass base plate to obtain a first product; (2) selecting an aluminum-doped zinc oxide material as a target material and depositing the aluminum-doped zinc oxide material onto the first product by sputtering to obtain a second product; and (3) performing a hydrogen plasma annealing step to the second product under a condition of 15-35 torr of hydrogen gas and a plasma power ranging from 400W to 800W to obtain the low-radiation glass coated with aluminum-doped zinc oxide and tin-doped indium oxide of this invention. The low-radiation glass of this invention has a visible light transmittance ranging from 72% to 90 % and a radiation coefficient ranging from 0.1 to 0.26.

Description

Low-emissivity glass with aluminum-doped zinc oxide and tin-doped indium oxide coating and preparation method thereof

This case relates to a low-emissivity glass with aluminum-doped zinc oxide and tin-doped indium oxide coatings and a preparation method thereof.

Glass is a transparent material. Its good light transmission can improve the daylighting rate of the building and reduce the use of electric lights or other lighting devices. However, it is easy to induce skin or eyes when exposed to the ultraviolet rays of sunlight for a long time. Disease, and the infrared radiant heat in the sunlight will also increase the indoor temperature, resulting in the need to adjust the indoor temperature with an air conditioning system, which cannot effectively achieve the purpose of energy saving; therefore, the development of energy-saving glass with high light transmittance and low emissivity is still a related field Important subject. Low-emissivity glass is a thin film with high visible light transmission and high infrared reflection function plated on a glass substrate to isolate heat transfer. The composition of the film is an important key to determine the characteristics of low-emissivity glass.

The Republic of China Patent No. 200838823 (A) is a low-emissive glass, which includes a glass substrate and a low-emissive film; the low-emissive film is formed by alternately superposing a plurality of titanium dioxide film layers and a plurality of silicon dioxide film layers on the surface of the glass substrate. The total number of film layers of the low-emissivity film is 30-40. In the low-emissivity film, the film layer in contact with the glass substrate is a titanium dioxide film layer, and the outermost film layer of the low-emission film is a silicon dioxide film layer; however, the low-emissivity glass of the present invention requires a multi-layer coating layer. Cumbersome and difficult to make.

In addition, the Republic of China Patent No. TW 201505989 (A) is a low-emissivity glass manufacturing method. At least a first dielectric layer is formed on a glass substrate, and a first dielectric layer is deposited on the first dielectric layer by a magnetron sputtering method. An infrared reflective seed layer, and an infrared reflective additional layer is deposited on the infrared reflective seed layer by an ion beam assisted lamination method, and then a second dielectric layer is deposited on the infrared reflective layer. Therefore, the Low-E glass formed by this manufacturing method has The resistance of the block is reduced, the infrared reflection characteristics are improved, the emissivity is reduced, and the processing resistance of the solar control film is enhanced. In addition, the new patent of the Republic of China Patent No. TW M545784 (B) is a silver-containing low-e (Low-E) glass containing a protective coating layer, including a base layer and a functional film layer, and the functional film layer is a silver-containing A multi-layer functional film is formed on the base layer: the silver-containing low-emissivity glass further includes a protective coating layer formed on the outer surface of the silver-containing low-emissivity glass, and is a solvent-soluble coating film or a physically peeling coating film. However, the above-mentioned Low-E glass and silver-containing low-emissivity glass containing a protective coating layer also need to prepare a multilayer coating layer or a functional film layer, which is still cumbersome to produce, and the success rate of preparing multilayer glass is relatively low.

Nowadays, the inventor considers that there are still many shortcomings in the current implementation of low-e glass, so it is a tireless spirit, supplemented by its rich professional knowledge and many years of practical experience, and based on this, Developed the present invention.

This case relates to a low-emissivity glass with an aluminum-doped zinc oxide and a tin-doped indium oxide coating and a method for preparing the same. A tin-doped indium oxide layer and an aluminum-doped zinc oxide layer are sequentially covered thereon. The average visible light transmittance of the low-emissivity glass in this case is between 72% and 90%, and the radiation coefficient is between 0.1 and 0.26. The preparation method includes the steps: First, a glass substrate is taken, a tin-doped indium oxide material is used as a target, a mixed gas containing argon (Ar) and oxygen (O ₂ ) is used as a reaction gas, and the tin-doped indium oxide is deposited by sputtering to One side of the glass substrate to obtain a first product having a tin-doped indium oxide layer; step two, an aluminum-doped zinc oxide material is used as a target material, which contains a mixture of argon (Ar) and oxygen (O ₂ ) The gas is a reaction gas, and aluminum-doped zinc oxide is deposited on the tin-doped indium oxide layer of the first product by a sputtering method to obtain a second product; and step three, the second product is subjected to a hydrogen plasma annealing step. Use hydrogen (H ₂ ) as the working gas at a gas pressure of 15 The hydrogen plasma annealing step is performed under the conditions of -35 torr and plasma power of 400-800 W to obtain a low-emissivity glass with aluminum-doped zinc oxide and tin-doped indium oxide coatings.

In one embodiment, the mixed gas system containing argon and oxygen contains 85% argon and 15% oxygen.

In one embodiment of the present invention, the tin-doped indium oxide material contains 90 wt% of indium oxide (In ₂ O ₃ ) and 10 wt% of stannous oxide (SnO).

In one embodiment of the present invention, the aluminum-doped zinc oxide material contains 98 wt% zinc oxide (ZnO) and 2 wt% alumina (Al ₂ O ₃ ).

In one embodiment of the present invention, the hydrogen plasma annealing step is performed under the conditions of a gas pressure of 25 torr and a plasma power of 600 W.

In one embodiment of the present invention, the average visible light transmittance of the low-emissivity glass coated with aluminum-doped zinc oxide and tin-doped indium oxide is 83.6%, and the radiation coefficient is 0.1.

Accordingly, the present invention provides a low-emissivity glass with aluminum-doped zinc oxide and tin-doped indium oxide coatings capable of improving light transmittance and reducing radiation coefficient, and a method for preparing the same.

In order to enable the reviewing committee to have a more complete understanding of the technical content of this case, the inventor of this case uses the following specific embodiments to explain the overall technical characteristics of this case in detail, and please refer to the accompanying drawings.

This case relates to low-emissivity glass with aluminum-doped zinc oxide and tin-doped indium oxide coatings and a method for preparing the same. Low-emissivity glass with aluminum-doped zinc oxide and tin-doped indium oxide coatings includes a glass substrate, and is located on one side of the glass substrate. The sequence covers a tin-doped indium oxide layer and an aluminum-doped zinc oxide layer. The average visible light transmittance of low-emissivity glass with aluminum-doped zinc oxide and tin-doped indium oxide coating is between 72% and 90%. 0.1-0.26; The visible light transmittance is preferably 83.6%, and the emissivity is preferably 0.1.

The method for preparing low-emissivity glass with aluminum-doped zinc oxide and tin-doped indium oxide coatings includes the following steps: a glass substrate is taken, a tin-doped indium oxide material is used as a target, and argon (Ar) and oxygen are contained A mixed gas of (O ₂ ) is a reaction gas, and a tin-doped indium oxide is deposited on one side of the glass substrate by a sputtering method to obtain a first product having a tin-doped indium oxide layer. Step two, a doped aluminum A zinc oxide material is used as a target material, and the mixed gas containing argon (Ar) and oxygen (O ₂ ) is used as a reaction gas, and an aluminum-doped zinc oxide is deposited on a tin-doped indium oxide layer by a sputtering method to obtain a second Product; and step three, the second product is subjected to a hydrogen plasma annealing step, which uses hydrogen (H ₂ ) as a working gas, and performs the hydrogen power at a gas pressure of 15-35 torr and a plasma power of 400-800 W. The paste annealing step is performed to obtain the low-emissivity glass with aluminum-doped zinc oxide and tin-doped indium oxide coatings. In the preparation method, the mixed gas containing argon and oxygen is preferably a mixed gas containing 85% argon and 15% oxygen, and the preferred composition of the tin-doped indium oxide material is 90 wt% of indium oxide (In ₂ O ₃ ) And 10 wt% of stannous oxide (SnO), aluminum-doped zinc oxide material contains 98 wt% of zinc oxide (ZnO) and 2 wt% of alumina (Al ₂ O ₃ ); In addition, the hydrogen plasma annealing step The preferred operating conditions are a gas pressure of 25 torr and a plasma power of 600 W.

In addition, by the following specific examples, the scope of this case can be further proved, but it is not intended to limit the scope of this case in any form.

1. Preparation of low-e glass coated with aluminum-doped zinc oxide and tin-doped indium oxide

(I) Pretreatment of glass substrate

In this embodiment, a glass slide is used as a glass substrate, and a cleaning step is performed before coating. The brief description is as follows: the substrate is immersed in acetone and washed with ultrasonic vibration for 5 minutes to remove the carbides on the surface of the glass substrate. ; Place the glass substrate in pure water, and then perform ultrasonic vibration cleaning for 5 minutes to remove residual acetone; then immerse the glass substrate in isopropyl alcohol and clean with ultrasonic vibration for 5 minutes; then place the glass substrate in Pure water was subjected to ultrasonic shock cleaning for 5 minutes to remove residual isopropanol; water vapor on the surface of the glass substrate was removed with a nitrogen gun; finally, the glass substrate was washed with alcohol, dried, and placed in a desiccator for later use.

(II) Plating of tin-doped indium oxide layer and aluminum-doped zinc oxide layer

The glass substrate was placed in a horizontal continuous DC magnetron sputtering device, and the tin-doped indium oxide layer and the aluminum-doped zinc oxide layer were plated; the temperature of the glass substrate was normal temperature, and the bottom pressure in the cavity was controlled at 8 X 10 ^-6 torr, the working gas system uses a mixed gas containing 85% argon (Ar) and 15% oxygen (O ₂ ), and the gas flow rate is 80 sccm (standard cubic centimeter per minute). First, tin-doped indium oxide layer was plated. DC power sputtering was used to tin-doped indium oxide on one side of the glass substrate. The target used contained 90 wt% indium oxide (In ₂ O ₃ ) and 10 With a weight percent of stannous oxide (SnO) at a working pressure of 1.6 mtorr and a power of 9 kW, a tin-doped indium oxide layer with a thickness of 250 nm was plated on one side of the glass substrate.

Next, a pulsed DC power supply was used to perform the plating of the aluminum-doped zinc oxide layer. The target used contained 98 wt% zinc oxide (ZnO) and 2 wt% alumina (Al ₂ O ₃ ). Under the conditions of 3 mtorr and power of 2 kW, a 250 nm aluminum-doped zinc oxide was plated on the above-mentioned tin-doped indium oxide layer.

(C), annealing step

The glass substrates doped with tin-doped indium oxide and aluminum-doped zinc oxide were subjected to a hydrogen plasma annealing step; a microwave power supply of 2.45 GHz was used, and the background pressure of the reaction vacuum chamber was first reduced below 10 ^-5 torr After that, hydrogen gas is passed in to perform the annealing step. In the annealing step, the effects of (a) process pressure (hereinafter referred to as "annealing pressure") and (b) microwave power (hereinafter referred to as "annealing power") on the characteristics of the final product are tested: (a) testing When the annealing pressure affects the product characteristics, the annealing step is performed at a hydrogen flow rate of 100 sccm and a power of 600 W for 5 minutes. The working gas pressure is 15 torr, 25 torr, and 35 torr, respectively. (B) Test the annealing power on the product. When the characteristics are affected, the annealing step is performed at a hydrogen flow rate of 100 sccm and a gas pressure of 25 torr for 5 minutes. The plasma power used is 400 W, 600 W, and 800 W, respectively.

After the annealing is completed, a glass substrate coated with a double-layer coating of tin-doped indium oxide layer and aluminum-doped zinc oxide layer can be obtained. Please refer to Table 1 for a schematic diagram of the aluminum-doped zinc oxide and tin-doped indium oxide-coated glass substrate. A tin-doped indium oxide layer (2) is plated on one side of the glass substrate (1), and then an aluminum-doped zinc oxide layer (3) is plated on the tin-doped indium oxide layer (2), and finally an annealing step is performed. In order to obtain a glass substrate with a double-layer coating of aluminum-doped zinc oxide and tin-doped indium oxide (hereinafter referred to as "the double-layer coated glass substrate in this case"). Furthermore, the double-coated glass substrate of this case was analyzed, and the microstructure, light, electricity and radiation characteristics of the products obtained under different processes were compared.

Second, aluminum doped zinc oxide and tin doped indium oxide coated glass substrate characteristics test

(I) Observation of surface morphology

Please refer to the second figure, which is a scanning electron microscope observation photograph of the double-layer coated glass substrate obtained by performing the annealing step under different hydrogen pressure; the surface of the glass substrate that has not been annealed does not have obvious grains, and the annealing step is performed. Obvious grains can be seen on the surface of the obtained glass substrate. When the annealing pressure is increased from 15 torr to 25 torr, the grains on the surface of the glass substrate are more obvious and uniform, but when the annealing pressure is increased to 35 torr, the grain morphology is Change and produce light-colored areas; if the product prepared with an annealing pressure of 35 torr is observed with an optical microscope, part of the glass substrate can be observed to become metallic (not shown in the photo), presumably because the hydrogen plasma caused tin doping in the lower layer of the glass substrate Indium oxide is caused by a metal reduction reaction.

Please refer to the third picture, which is a scanning electron microscope observation photograph of the double-layer coated glass substrate obtained at different annealing powers. It can be found that as the annealing power increases, the crystal agglomeration and growth of the glass substrate surface sheet accelerates, and the surface becomes rough. .

(2) atomic force microscope

The fourth and fifth figures are photos obtained by observing an atomic force microscope with different processes for preparing the double-coated glass substrate of the present case, and calculating the surface roughness of each double-coated glass substrate. The calculation results are shown in Table 1. With Table II. According to the fourth graph and Table 1, as the annealing pressure increases, the average roughness of the surface of the double-coated glass substrate also increases; and according to the fifth graph and Table 2, as the annealing power increases, the double-coated glass The average roughness of the substrate surface will also increase; the increase in roughness on the glass substrate after the annealing step should be due to the energy provided by the annealing step and the crystal grains to grow.

Table I

Table II

(3) X-ray diffraction (XRD)

The sixth figure shows the X-ray diffraction spectrum of the double-coated glass substrate of the present invention prepared with different annealing pressures. Compared to the unannealed double-coated glass substrate, the annealed double-coated glass substrate is either zinc oxide (ZnO ) Or tin-doped indium oxide (ITO) signal is significantly enhanced, and the higher the annealing pressure, the stronger the detected signal of zinc oxide (ZnO) or tin-doped indium oxide (ITO), it is presumed to be zinc oxide It is caused by the grain growth and better crystallinity of tin-doped indium oxide; according to the seventh figure, the hydrogen pressure during annealing can shift the diffraction angle of zinc oxide to a high angle, and it is speculated that it may be more aluminum The position of the zinc atom in the atom replacement lattice is because the radius of the aluminum ion is smaller than the radius of the zinc ion, which makes the crystal width smaller.

The eighth figure is an X-ray diffraction spectrum chart of the double-coated glass substrate of the present invention prepared with different annealing power. Compared to the unannealed glass substrate, the annealed double-coated glass substrate is doped with zinc oxide (ZnO) or doped with zinc oxide (ZnO). The signal of indium tin oxide (ITO) is significantly enhanced, and the higher the annealing power, the higher the signal of zinc oxide or tin-doped indium oxide (ITO); see also Figure 9, the hydrogen plasma power during annealing will also make zinc oxide The diffraction angle is shifted to a high angle. It is speculated that more aluminum atoms may replace the zinc atom positions in the lattice because the aluminum ion radius is smaller than the zinc ion radius, which makes the crystal width smaller.

(IV) Electrical test

This experiment compares the electrical property parameters of the double-layer coated glass substrate made with different annealing pressures or annealing powers, including carrier concentration, carrier mobility, sheet resistance and resistivity. For the test results, see Table 3 and Table 4: The carrier concentration, carrier mobility, and resistance are measured using a Hall measuring instrument (Ecopia HMS-3000 Hall Measurement System), while the chip resistance is measured using a four-point probe. According to Tables 3 and 4, the carrier concentration of the double-layer coated glass substrate after annealing is increased by at least 4 times, the carrier mobility is reduced within 3.3 times, and the resistivity is also significantly reduced. Among them, the annealing pressure is 35 torr. The obtained double-coated glass substrate has the lowest resistivity; however, since the double-coated glass substrate produced by the annealing pressure of 35 torr will exhibit metal reduction, it is not suitable for preparing coated glass substrates with uniform and stable characteristics. The conditions of a pressure of 25 torr and an annealing power of 600 W were taken as the preferred preparation conditions for preparing the double-layer coated glass substrate of the present case.

Table three

Table four

(5) Light property test

In this experiment, a UV / VIS / NIR spectrometer (PerkinElmer LAMBDA 750, PerkinElmer, Waltham, USA) was used to test the double-layer coated glass substrate of this case, which was prepared at different annealing pressures or annealing powers, in the wavelength range of 380 nm-1100 nm. The average visible light transmittance of the spectrum is shown in Tables 5 and 6. According to Tables 5 and 6, after the hydrogen plasma annealing step, the average visible light transmittance of the double-coated glass substrates has been significantly improved, including the annealing pressure. The increase in the average visible light transmittance is more significant. Referring again to the tenth and eleventh graphs, in the wavelength range of 380 nm-1100 nm, as the crystallinity of the double-coated glass substrate changes, the curve of light transmittance gradually flattens with increasing wavelength, representing the Interference changes are reduced.

Table five

Table six

(VI) Radiation coefficient

This experiment uses a radiation coefficient analyzer (Japan Sensor TSS-5X, Japan Sensor, Tokyo, Japan) to measure the radiation coefficient of the double-layer coated glass in this case. The radiation coefficient is used to describe the ability of the object's far-infrared radiation. A lower value indicates the reflection of the object. The far infrared capability is higher. Please refer to Tables 7 and 8 for the measured radiation coefficients of the double-coated glass substrates made in this case for different annealing pressures or annealing powers. According to the test results, the radiation coefficients of the double-coated glass substrates in this case will be obtained after the annealing step. Compared with the resistivity measurement results in Tables 3 and 4, it can be found that the lower the resistivity, the higher the electrical conductivity and the lower the radiation coefficient, which also means that the corresponding far infrared reflectance is higher. Therefore, based on the results of Tables 3, 4 and 7 and 8, the double-layer coated glass substrate processed by the annealing process in this case has lower resistivity, increased conductivity, and lower radiation coefficient, indicating that it can reflect more infrared rays. .

Table seven

Table eight

As can be seen from the above implementation description, compared with the prior art, this case has the following advantages:

1. In this case, low-emissivity glass with aluminum-doped zinc oxide and tin-doped indium oxide coatings. After the annealing step, the grains formed on the glass substrate increase, the surface roughness increases, the sheet resistance and resistivity decrease, and the radiation coefficient also decreases. Indicates that its reflectance to far-infrared rays is improved, so the preparation method in this case can change the properties of the glass substrate and contribute to the development of low-emissivity glass.

2. This case has low-emissivity glass coated with aluminum-doped zinc oxide and tin-doped indium oxide. The use of two layers of coating can achieve the effects of reducing the radiation coefficient and increasing the far-infrared reflectance. Compared with the current common multi-layer coating glass, the manufacturing method It is simpler and can reduce the manufacturing cost and has better economic benefits.

3. In this case, a method for preparing low-emissivity glass with aluminum-doped zinc oxide and tin-doped indium oxide coatings. By using sputtering method and annealing conditions under specific conditions, the emissivity of the prepared low-emissivity glass can be reduced to 0.1, which is in line with CNS. 15833 R2211 has the definition that the low-emissivity coated glass for buildings has an emissivity coefficient of less than 0.2, so the low-emissivity glass produced by the method requested in this case can indeed be applied to building materials.

In summary, the low-emissivity glass with aluminum-doped zinc oxide and tin-doped indium oxide coatings and the preparation method thereof can indeed achieve the expected use effect through the above-disclosed embodiments, and this case has not been disclosed in Before applying, Cheng has fully complied with the provisions and requirements of the Patent Law. I filed an application for an invention patent in accordance with the law, and I urge you to examine it and grant the patent.

However, the above-mentioned description is only a preferred embodiment of this case, and is not intended to limit the scope of protection of this case. Anyone who is familiar with the technology, other equivalent changes or modifications made according to the characteristics of this case, All should be regarded as not departing from the design scope of this case.

(1) ‧‧‧ glass substrate

(2) ‧‧‧ tin-doped indium oxide layer

(3) ‧‧‧Aluminum doped zinc oxide layer

First picture: The structure of the low-emissivity glass with aluminum-doped zinc oxide and tin-doped indium oxide coatings.

Second figure: Scanning electron microscope analysis of low-emissivity glass prepared in this case with different annealing pressures.

Third figure: Scanning electron microscope analysis of low-emissivity glass prepared in this case with different annealing power.

Figure 4: Atomic force microscope analysis of low-emissivity glass prepared in this case with different annealing pressures.

Fifth image: Atomic force microscope analysis of low-emissivity glass prepared in this case with different annealing power.

Figure 6: X-ray diffraction spectrum of low-emissivity glass prepared in this case with different annealing pressures.

Figure 7: X-ray diffraction spectrum of zinc oxide in low-emissivity glass prepared in this case with different annealing pressures.

Figure 8: X-ray diffraction spectrum of low-emissivity glass prepared in this case with different annealing power.

Figure 9: X-ray diffraction spectrum of zinc oxide in low-emissivity glass prepared with different annealing power in this case.

The tenth figure: The light transmittance analysis chart of the low-emissivity glass prepared in this case with different annealing pressures at a light wavelength of 380 nm-1100 nm.

Figure 11: Analysis of the light transmittance of low-emissivity glass prepared in this case with different annealing power at a light wavelength of 380 nm-1100 nm.

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Claims (7)

A method for preparing low-emissivity glass with aluminum-doped zinc oxide and tin-doped indium oxide coatings, comprising: Step 1: taking a glass substrate, using a tin-doped indium oxide material as a target, and containing argon (Ar) A mixed gas with oxygen (O ₂ ) is a reaction gas, and the tin-doped indium oxide material is deposited on one side of the glass substrate by a sputtering method to obtain a first product having a tin-doped indium oxide layer; step two : Using an aluminum-doped zinc oxide material as a target material, the mixed gas containing argon (Ar) and oxygen (O ₂ ) as a reaction gas, depositing the aluminum-doped zinc oxide material to the first product by a sputtering method On the tin-doped indium oxide layer to obtain a second product; and step three: subjecting the second product to a hydrogen plasma annealing step, using hydrogen (H ₂ ) as a working gas at a gas pressure of 15-35 torr The hydrogen plasma annealing step is performed under the conditions of a plasma power of 400-800 W to obtain the low-emissivity glass with aluminum-doped zinc oxide and tin-doped indium oxide coatings. The preparation method according to item 1 of the scope of the patent application, wherein the mixed gas system containing argon and oxygen contains 85% argon and 15% oxygen. The preparation method according to item 1 of the patent application scope, wherein the tin-doped indium oxide material contains 90 wt% of indium oxide (In ₂ O ₃ ) and 10 wt% of stannous oxide (SnO). The preparation method according to item 1 of the scope of the patent application, wherein the aluminum-doped zinc oxide material contains 98 wt% zinc oxide (ZnO) and 2 wt% alumina (Al ₂ O ₃ ). According to the preparation method described in item 1 of the scope of patent application, the hydrogen plasma annealing step is performed under the conditions of a gas pressure of 25 Torr and a plasma power of 600 W. A low-emissivity glass having an aluminum-doped zinc oxide and tin-doped indium oxide coating prepared by the method described in item 1 of the scope of patent application, which comprises a glass substrate, and one side of the glass substrate is sequentially covered with tin-doped The indium oxide layer and an aluminum-doped zinc oxide layer, wherein the low-emissivity glass with aluminum-doped zinc oxide and tin-doped indium oxide coating has an average visible light transmittance of 72% -90%, and an emissivity coefficient of 0.1-0.26 . The low-emissivity glass with aluminum-doped zinc oxide and tin-doped indium oxide coatings described in item 6 of the scope of the patent application has an average visible light transmittance of 83.6% and an emissivity coefficient of 0.1.