Preparation method and application of visible-near infrared high-transmittance Low-E glass

Abstract

The invention discloses a preparation method and application of visible-near infrared high-transmittance Low-E glass, and belongs to the technical field of building energy conservation, the method comprises the following steps: in a room-temperature mixed atmosphere of hydrogen, oxygen and argon, magnetron sputtering an indium oxide target material on the surface of soda-lime glass to obtain coated glass with a proton-doped indium oxide film layer deposited on the surface; continuously sputtering a silicon dioxide target material in a room-temperature mixed atmosphere to form a silicon dioxide anti-reflection layer, so as to obtain proton-doped indium oxide-based silicon dioxide composite film layer glass; and putting the composite film layer glass into annealing equipment, and carrying out annealing treatment in a nitrogen atmosphere, so as to obtain the Low-E glass with visible-near infrared high transmission property. According to the invention, the mobility and carrier concentration of the oxide are optimized by using a proton doping method, high-selectivity near-red transmission of the oxide-based Low-E film layer is realized, and the oxide-based Low-E film layer has the unique advantages of adjustable intrinsic optical properties of materials, simple film layer structure and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of building energy conservation, and more specifically, relates to a method for preparing visible-near infrared high-transmittance Low-E glass and an application thereof. Background Art

[0002] With economic development and the improvement of living standards, people's requirements for the temperature comfort of building environments are constantly increasing. The huge HVAC energy consumption poses challenges to energy distribution and the development of a low-carbon economy. Windows are important transparent protective structures in buildings, and their lack of radiation management has aggravated the pressure on building energy consumption. Low-E windows can effectively reduce the adverse heat loss caused by the temperature difference between indoors and outdoors by inhibiting the radiation heat exchange of glass, and have extremely high practical application value and development prospects.

[0003] Currently, most Low-E windows are based on metal films, oxide films, metal-oxide composite films, etc. to achieve high long-wave infrared reflection. However, poor spectral selection (low visible light and infrared light transmittance), poor stability, complex preparation and packaging process problems, etc. are the main problems in the field of Low-E films today. This limits the adaptability of Low-E windows to different climate environments, weakens their energy-saving effects (increased lighting and heating energy consumption, etc.), and limits the combined application of Low-E windows with other dynamic sunlight control technologies. Therefore, the ideal Low-E glass should have the characteristics of clear and high transmittance, good weather resistance, etc., especially high spectral selectivity (high visible transmittance, near-infrared adjusted according to climate requirements, and maintaining low emission characteristics).

[0004] The infrared reflection characteristics of transparent Low-E films mainly originate from the interaction between free carriers in the material and the incident electromagnetic waves. Its infrared reflection edge is affected by the plasma resonance frequency and is positively correlated with the carrier density; its emissivity is related to the scattering and absorption behavior of the carriers. The emissivity can be reduced by increasing the carrier mobility to reduce scattering. It is worth noting that this does not have a significant effect on its plasma resonance frequency, but only affects the slope of the reflection edge. Therefore, by appropriately reducing the carrier density of the Low-E material and increasing the carrier mobility, higher near-infrared transmittance can be achieved and low emission properties can be guaranteed. Transparent oxide materials with a wide optical band gap can adjust the above parameters by doping. The currently used Low-E oxide materials In2O3:Sn (ITO) and SnO2:F (FTO) have a high carrier concentration (10 21 cm -3 ), while the mobility is low (μ<50cm 2 V -1 s -1), near-infrared transmittance is limited. Although this low heat gain characteristic is beneficial to window thermal management in hot areas, it is not suitable for areas with cold climates, wasting the heating effect of natural light. Currently, high spectral selectivity is mostly achieved by stack film design, which has a complex structure and lacks relevant high-mobility oxide materials for application in the field of energy-saving windows. Therefore, a method for adjusting the selective transmittance of Low-E film layers based on the intrinsic optical properties of the material is urgently needed.

[0005] The photoelectric properties of oxides can be significantly adjusted by element doping. At present, relevant scientific research has achieved higher mobility by doping In2O3 with Mo. Studies have shown that using Mo doping can achieve lower ionized impurity scattering and higher carrier mobility than Sn at the same doping concentration. There are also studies that doped In2O3 with Ti and increased the substrate temperature, and obtained a film with lower surface roughness than ITO by annealing and optimizing the film preparation process, thereby reducing the adverse effects of crystal interface scattering on mobility. In addition, there are methods such as doping Zr and W. The materials obtained in these works have μ>80cm 2 V -1 s -1 , but they all require higher processing temperatures (>400℃), and the carrier concentration fails to meet the requirements of the near-infrared high-transmittance Low-E window. Compared with doping with other TCO dopants, hydrogen (H proton) has a small ion radius and high reactivity. It is easy to provide electrons or react with elements in TCO to generate oxygen vacancies, optimize the carrier concentration and have little effect on the lattice distortion of the material, which can significantly affect the photoelectric properties of the material. In addition, studies have shown that hydrogen doping is beneficial to increase the grain size during low-temperature annealing crystallization while reducing sub-bandgap defects, reducing grain boundary barriers, and significantly optimizing carrier mobility. Therefore, hydrogen doping has the application potential to achieve the preparation of highly selective Low-E energy-saving glass. Summary of the invention

[0006] In view of the above defects or improvement needs of the prior art, the present invention provides a method for preparing visible-near-infrared high-transmittance Low-E glass and its application, thereby solving the technical problems of the prior art Low-E windows, such as poor spectral selection (low visible light and infrared light transmittance), poor stability and complex preparation process.

[0007] To achieve the above object, according to one aspect of the present invention, a method for preparing visible-near infrared high-transmittance Low-E glass is provided, the method comprising the following steps:

[0008] S1, introducing a mixed gas of hydrogen, oxygen and argon at room temperature, magnetron sputtering an indium oxide target on the surface of soda-lime glass, to obtain a coated glass with a proton-doped indium oxide film layer deposited on the surface;

[0009] S2, continuing to introduce a mixed gas of oxygen and argon at room temperature in step S1, magnetron sputtering a silicon dioxide target on the indium oxide film layer to form a silicon dioxide anti-reflection layer, thereby obtaining a proton-doped indium oxide-based-silicon dioxide composite film glass;

[0010] S3, annealing the composite film layer glass in a nitrogen atmosphere to obtain Low-E glass with high visible-near infrared transmittance.

[0011] Preferably, the method further comprises: before step S1, ultrasonically cleaning the soda-lime glass substrate in sequence using a surfactant, acetone, isopropanol, ethanol and deionized water for 10 minutes, and then placing the substrate in an oven to fully dry.

[0012] Preferably, the step S1 specifically includes the following steps:

[0013] Reduce the ambient pressure to 5×10 -4 Pa or less, and hydrogen, oxygen and argon with a gas pressure of 0.5 Pa and a gas ratio of 0.05:1:6 are introduced;

[0014] An indium oxide target was magnetron sputtered at room temperature using a radio frequency power supply, wherein the power of the magnetron sputtering was 100 W, and formal sputtering was performed after pre-sputtering for 5 minutes, and finally a proton-doped indium oxide film layer was deposited on a dry soda-lime glass substrate.

[0015] Preferably, the step S2 specifically includes the following steps:

[0016] Reduce the ambient pressure to 5×10 -4 Pa, and introduce oxygen and argon with a pressure of 0.7 Pa and a gas ratio of 1:6;

[0017] A silicon dioxide target material was magnetron sputtered at room temperature using a radio frequency power supply, wherein the power of the magnetron sputtering was 200 W, and the formal sputtering was performed after the pre-sputtering for 5 minutes, and finally a silicon dioxide anti-reflection layer was deposited on the coated glass of the proton-doped indium oxide film layer.

[0018] Preferably, the temperature range of the annealing treatment in step S3 is 190° C. to 300° C., and the time range of the annealing treatment is 30 seconds to 10 minutes.

[0019] Preferably, the annealing treatment time is 3 minutes.

[0020] Preferably, the room temperature of the magnetron sputtering is 15°C to 40°C.

[0021] According to another aspect of the present invention, a visible-near infrared high-transmittance Low-E glass is provided.

[0022] According to another aspect of the present invention, there is provided an application of visible-near infrared high-transmittance Low-E glass in energy-saving windows in cold regions.

[0023] In general, the above technical solutions conceived by the present invention can achieve the following beneficial effects compared with the prior art:

[0024] 1. The present invention proposes a method for preparing visible-near infrared high-transmittance Low-E glass and its application, which realizes the high selective infrared transmission of Low-E film by optimizing the key room-temperature coating process, adding an anti-reflection layer, and optimizing the rapid low-temperature annealing process in an inert atmosphere. Compared with the prior art, the present invention uses a room-temperature thin film preparation process and a low-temperature rapid annealing process to obtain a high visible-near infrared transmittance Low-E coated glass, which has unique advantages such as adjustable material spectral characteristics, simple preparation process, and mild processing conditions. In particular, the high visible-near infrared transmittance makes it have the advantage of energy-saving window application in cold regions.

[0025] 2. The present invention proposes a method for preparing visible-near-infrared high-transmittance Low-E glass. The proton doping method is used to improve the carrier mobility of the indium oxide film and optimize the carrier concentration to achieve higher near-infrared transmittance while ensuring low emissivity; the top composite silicon dioxide layer is anti-reflective, which can increase the transmittance of visible light without affecting other spectral characteristics of the film layer.

[0026] 3. The present invention proposes a method for preparing visible-near infrared high-transmittance Low-E glass. The operation process uses magnetron sputtering equipment to prepare a film layer at room temperature, and uses an ultra-fast low-temperature annealing post-treatment process. By adjusting the film sputtering atmosphere, power, annealing temperature, and time, low-E films with different spectral characteristics can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 Schematic diagram of visible-near-infrared high-transmittance Low-E glass prepared by the visible-near-infrared high-transmittance Low-E glass preparation method of the present invention;

[0028] Figure 2 is a scanning electron microscope (SEM) image of a cross section of the visible-near infrared high-transmittance Low-E glass prepared in Example 1 of the present invention;

[0029] Figure 3 and Figure 4 is a spectrum diagram of the visible-near infrared high-transmittance Low-E glass prepared in Example 1 of the present invention;

[0030] Figure 5 This is a simulation experiment effect diagram of applying the visible-near infrared high-transmittance Low-E glass prepared in Example 1 of the present invention to thermal management of energy-saving windows;

[0031] Figure 6and Figure 7 This is a spectrum diagram of the proton-doped indium oxide coated glass prepared in Example 2 of the present invention. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0033] Example 1

[0034] The soda-lime glass substrate was ultrasonically cleaned with surfactant, acetone, isopropanol, ethanol, and deionized water for 10 min each, and then placed in an oven to fully dry. At room temperature, an indium oxide target was magnetron sputtered on the clean glass substrate using a radio frequency power supply. The chamber pressure was reduced to 5×10 -4 Pa, a mixture of hydrogen, oxygen, and argon in a ratio of 0.05:1:6 was introduced, the sputtering pressure was 0.5Pa, the power was 100W, and after 5 minutes of pre-sputtering, the formal sputtering was performed. Then, the silicon dioxide film was sputtered using a radio frequency power supply at room temperature. The chamber pressure dropped to 5×10 -4 Pa, a mixture of oxygen and argon in a ratio of 1:6 was introduced, the sputtering pressure was 0.7Pa, the power was 200W, and after pre-sputtering for 5 minutes, formal sputtering was performed. The obtained proton-doped indium oxide-based silicon dioxide composite film glass was placed in an ultrafast annealing device and subjected to low-temperature heat treatment for 3 minutes in a N2 gas atmosphere. Proton-doped indium oxide-based Low-E glass was obtained.

[0035] Under simulated sunlight (500mW / cm 2 ), the prepared proton-doped indium oxide-based Low-E glass was compared with a blank glass substrate and commercial ITO Low-E glass to conduct light heating and heat preservation experiments; for example, the test cavity was carried out on a foam box with an internal size of 5cm*5cm*5cm. The glass sample was installed at the opening of the foam box and sealed with glass glue on all sides. The outer layer of the glass was covered with a layer of PE film to reduce the interference of non-radiative heat exchange between the model and the environment. After the power of the solar simulator light source stabilizes, the simulator light source baffle is opened to vertically illuminate the center of the glass panel. The light source is 25cm away from the glass. The temperature rise test is carried out during the test. During the test, a thermocouple installed in the center of the foam cavity is used to monitor the temperature change in the cavity.

[0036] Figure 1 The cross-sectional SEM image of the final Low-E composite film layer is shown, from which we can see the double-layer structure of the film and the good bonding between the film and the substrate.

[0037] Figure 2 The figure shows the spectrum comparison of the proton-doped indium oxide-based film and the composite film with the addition of a silicon dioxide anti-reflection layer. It can be seen that the addition of a silicon dioxide layer can effectively reduce film interference, increase the film's transmittance in the sunlight band, and has almost no effect on the long-wave infrared reflection characteristics (Low-E). This shows that the composite film can further optimize the transmittance of glass without affecting the Low-E performance.

[0038] Figure 3 The figure shows the experimental diagram of the heating effect of the glass sample under the solar simulator. It can be seen that the heating rate of IHO under light is significantly higher than that of ITO, which shows that IHO-based Low-E glass has good potential for energy-saving window applications in cold regions.

[0039] Example 2

[0040] The soda-lime glass substrate was ultrasonically cleaned with surfactant, acetone, isopropanol, ethanol, and deionized water for 10 min each, and then placed in an oven to fully dry. At room temperature, an indium oxide target was magnetron sputtered on the clean glass substrate using a radio frequency power supply. The chamber pressure was reduced to 5×10 -4 Pa, a mixture of hydrogen, oxygen and argon in a ratio of 0.05:1:6 was introduced, the sputtering pressure was 0.5Pa, the power was 100W, and the pre-sputtering was performed for 5 minutes before the formal sputtering. Then, the obtained proton-doped indium oxide coated glass was placed in an ultrafast annealing device and treated at 190, 210, 230, 270, and 290°C for 2 minutes in a N2 atmosphere. Proton-doped indium oxide coated glass with different optical properties was obtained.

[0041] Figure 4 The spectra of proton-doped indium oxide coated glass treated with different annealing temperatures are shown in Figure 2. It can be seen that after annealing, the near-infrared transmittance of the film increases with the increase of annealing temperature, and the emissivity remains low. This shows that the proton doping method is beneficial to improve the near-infrared transmittance of the film and maintain its Low-E performance.

[0042] It will be easily understood by those skilled in the art that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing visible-near infrared high-transmittance Low-E glass, characterized in that: The method comprises the following steps: S1, introducing a mixed gas of hydrogen, oxygen and argon at room temperature, magnetron sputtering an indium oxide target on the surface of soda-lime glass, to obtain a coated glass with a proton-doped indium oxide film layer deposited on the surface; S2, continuing to introduce a mixed gas of oxygen and argon at room temperature in step S1, magnetron sputtering a silicon dioxide target on the indium oxide film layer to form a silicon dioxide anti-reflection layer, thereby obtaining a proton-doped indium oxide-based-silicon dioxide composite film layer glass; S3, annealing the composite film layer glass in a nitrogen atmosphere to obtain Low-E glass with high visible-near infrared transmittance.

2. The method for preparing a visible-near infrared high-transmittance Low-E glass according to claim 1, characterized in that: Also includes: Before step S1, the soda-lime glass substrate is ultrasonically cleaned in sequence using a surfactant, acetone, isopropanol, ethanol and deionized water for 10 minutes, and then placed in an oven to be fully dried.

3. The method for preparing a visible-near infrared high-transmittance Low-E glass according to claim 2, characterized in that: The step S1 specifically includes the following steps: Reduce the ambient pressure to 5×10 -4 Pa or less, and hydrogen, oxygen and argon with a gas pressure of 0.5 Pa and a gas ratio of 0.05:1:6 are introduced; An indium oxide target was magnetron sputtered at room temperature using a radio frequency power supply, wherein the power of the magnetron sputtering was 100 W, and formal sputtering was performed after pre-sputtering for 5 minutes, and finally a proton-doped indium oxide film layer was deposited on a dry soda-lime glass substrate.

4. The method for preparing a visible-near infrared high-transmittance Low-E glass according to claim 3, characterized in that: The step S2 specifically includes the following steps: Reduce the ambient pressure to 5×10 -4 Pa, and introduce oxygen and argon with a pressure of 0.7 Pa and a gas ratio of 1:6; A silicon dioxide target material was magnetron sputtered at room temperature using a radio frequency power supply, wherein the power of the magnetron sputtering was 200 W, and the formal sputtering was performed after the pre-sputtering for 5 minutes, and finally a silicon dioxide anti-reflection layer was deposited on the coated glass of the proton-doped indium oxide film layer.

5. The method for preparing a visible-near infrared high-transmittance Low-E glass according to claim 1, characterized in that: The temperature range of the annealing treatment in step S3 is 190° C. to 300° C., and the time range of the annealing treatment is 30 seconds to 10 minutes.

6. The method for preparing a visible-near infrared high-transmittance Low-E glass according to claim 5, characterized in that: The annealing time is 3 minutes.

7. A visible-near infrared high-transmittance Low-E glass prepared by the preparation method according to any one of claims 1 to 6.

8. Application of the visible-near infrared high-transmittance Low-E glass according to claim 7 in energy-saving windows in cold regions.

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