TWI700257B - Thermal insulation and self-cleaning glass and manufacturing method thereof - Google Patents

Abstract

The present invention discloses a thermal insulation and self-cleaning glass and a manufacturing method thereof. The thermal insulation and self-cleaning glass comprises a glass substrate, an aluminum-doped zinc oxide layer and a titanium oxide layer sequentially coated on one side of the glass substrate. The manufacturing method comprises the steps of coating an aluminum-doped zinc oxide layer onto one side of a glass substrate, coating a titanium layer on the aluminum-doped zinc oxide layer, performing a thermal oxidation process for oxidation of the titanium layer to form a titanium oxide layer, and performing an annealing process to obtain the thermal insulation and self-cleaning glass of the present invention. The thermal insulation and self-cleaning glass has an average visible light transmittance of more than 85%, a radiation coefficient of less than 0.2 and a contact angle of less than 6°.

Description

Glass with heat insulation and self-cleaning and its manufacturing method

The invention relates to a heat-insulating and self-cleaning glass and a manufacturing method thereof. The heat-insulating and self-cleaning glass has good heat-insulating and self-cleaning effects.

Because of its good light transmission, glass materials are one of the commonly used building materials to improve the lighting conditions of buildings. However, in recent years, air pollution has become more serious. Maintaining the cleanliness of building glass and cleaning the glass are also Self-cleaning glass is a kind of glass material that is easy to maintain the cleanliness of the glass surface. The glass surface is usually treated with special treatment, such as covering a nano material, so that it will be catalyzed by sunlight to decompose organic pollutants attached to the surface. And it can also improve the hydrophilicity or hydrophobicity of the glass surface, so that the inorganic dust attached to the surface can be easily removed.

The Republic of China Patent Publication No. TW 201345859(A) is a method for preparing self-cleaning glass, which uses chemical vapor deposition to deposit and form a titanium dioxide film on a glass substrate to produce self-cleaning glass. In addition, the Chinese Patent Publication No. CN 106746713(A) is a method for preparing titanium dioxide thin film self-cleaning glass, which uses a sol-gel method to plate a multi-layer titanium dioxide coating on a glass plate, and then undergo heat treatment to complete the hydrophilic Self-cleaning glass with high performance and photocatalytic activity. However, the existing self-cleaning glass cannot have both heat insulation performance and self-cleaning performance.

Nowadays, in view of the shortcomings of the existing self-cleaning glass, the inventor has worked tirelessly with his rich professional knowledge and years of practical experience to improve, and developed the present invention accordingly. .

The present invention relates to a heat-insulating and self-cleaning glass and a manufacturing method thereof. The prepared glass has good heat-insulating and self-cleaning effects.

The heat-insulating and self-cleaning glass of the present invention includes a glass substrate, and one side of the glass substrate is sequentially covered with an aluminum-doped zinc oxide layer and a titanium oxide (TiOx) layer, which has heat-insulating and self-cleaning The best characteristics of glass can reach an average visible light transmittance higher than 85%, and the emissivity is not more than 0.2.

The manufacturing method of the heat-insulating and self-cleaning glass of the present invention includes: Step 1. Sputtering an aluminum-doped zinc oxide layer on a glass substrate, wherein the thickness of the aluminum-doped zinc oxide layer is between 300~ 800nm; Step two, deposit a titanium metal (Ti) layer on the aluminum-doped zinc oxide layer by evaporation; Step three, perform a thermal oxidation step to oxidize the titanium metal layer and produce a titanium monoxide (TiOx) layer , Wherein the thickness of the titanium oxide layer is between 80-150 nm; and step four, an annealing step is performed to obtain the heat-insulating and self-cleaning glass of the present invention.

In an embodiment of the present invention, the thickness of the aluminum-doped zinc oxide layer is 500 nm.

In an embodiment of the present invention, the thickness of the titanium oxide layer is 100 nm.

In an embodiment of the present invention, the annealing step is a vacuum annealing step.

In one embodiment of the present invention, the vacuum annealing step is performed at 400-600°C for 30-45 minutes under vacuum.

In an embodiment of the present invention, the annealing step is a hydrogen plasma annealing step.

In an embodiment of the present invention, the hydrogen plasma annealing step is performed for 1 to 10 minutes under the conditions of a hydrogen flow rate of 80 to 120 sccm, a gas pressure of 30 to 40 Torr, and a plasma power of 400 to 800 W.

In an embodiment of the present invention, the contact angle of the heat-insulating and self-cleaning glass is not greater than 6°.

Thereby, the method for manufacturing heat-insulating and self-cleaning glass of the present invention has low emissivity and small contact angle, and has the effects of heat insulation and self-cleaning; in addition, the present invention has heat insulation The self-cleaning glass also has good visible light transmittance, which is very suitable for the application of building materials, especially the building materials of green buildings.

1: glass substrate

2: Al-doped zinc oxide layer

3: Titanium oxide layer

Figure 1: The schematic diagram and electron microscope photograph of the heat-insulating and self-cleaning glass of the present invention.

Figure 2: Microscopic photo of the surface topography of heat-insulating and self-cleaning glass without treatment, 300℃ thermal oxidation treatment and different annealing steps.

Figure 3: Microscopic photo of the surface topography of heat-insulated and self-cleaning glass without treatment, 400℃ thermal oxidation treatment and different annealing steps.

Figure 4: Microscopic photo of the surface morphology of heat-insulating and self-cleaning glass without treatment, 500℃ thermal oxidation treatment and different annealing steps.

Figure 5: A micrograph of the surface roughness of heat-insulating and self-cleaning glass affected by annealing treatment.

Figure 6: Photographs of contact angle analysis of heat-insulating and self-cleaning glass affected by annealing treatment.

Figure 7: Analysis of visible light transmittance of the heat-insulating and self-cleaning glass of the present invention.

Figure 8: X-ray diffraction analysis diagram of the glass with heat insulation and self-cleaning of the present invention.

The purpose of the present invention and its structural and functional advantages will be described in conjunction with specific embodiments as shown in the following figures, so that the examiner can have a deeper and specific understanding of the present invention.

The invention relates to a heat-insulating and self-cleaning glass and a manufacturing method thereof. The prepared glass has both good heat-insulating and self-cleaning effects.

The manufacturing method of the heat-insulating and self-cleaning glass of the present invention includes: Step 1: Sputtering an aluminum-doped zinc oxide layer on the glass substrate, wherein the thickness of the aluminum-doped zinc oxide layer is 300~800nm , Preferably 500nm; step two, deposit a titanium metal (Ti) layer on the aluminum-doped zinc oxide layer by evaporation; step three, perform a thermal oxidation step to oxidize the titanium metal layer and produce titanium monoxide The thickness of the titanium oxide layer is between 80-150nm, preferably 100nm; and step four, an annealing step is performed to obtain the low emissivity self-cleaning glass of the present invention, the annealing step can be a vacuum annealing step or Hydrogen plasma annealing step; the average visible light transmittance of the produced heat-insulating and self-cleaning glass can reach 85%, the emissivity is not more than 0.2, and the contact angle is not more than 6°.

In addition, the following specific examples can further prove the scope of practical application of the present invention, but it is not intended to limit the scope of the present invention in any form.

1. Manufacturing of heat-insulating and self-cleaning glass

(1) Plating aluminum-doped zinc oxide layer

The glass substrate used in this embodiment is a borosilicate glass substrate. Before plating, the borosilicate glass substrate is cleaned with acetone, isopropanol and pure water in sequence with an ultrasonic vibration cleaning machine, and then a nitrogen gun is used to blow Moisture on the surface of the dry borosilicate glass substrate.

Place the borosilicate glass substrate in a linear continuous sputtering machine to plate the aluminum-doped zinc oxide layer; the temperature of the glass substrate is normal temperature, the bottom pressure in the cavity is controlled at 1 X 10 ^-5 torr, and the working gas system is used Argon gas (Ar), gas flow rate is 440sccm (standard cubic centimeter per minute); using aluminum-doped zinc oxide as the target, under the conditions of working pressure 3 X 10 ^-3 torr and power 2kW, sputtered by DC magnetron In this way, an aluminum-doped zinc oxide layer is plated on one side of the glass substrate, and the thickness of the aluminum-doped zinc oxide layer is 500 nm; later, the aluminum-doped zinc oxide layer is referred to as AZO layer for short.

(Two), plating titanium metal layer

Next, use electron gun evaporation method to deposit a titanium metal layer on the aluminum-doped zinc oxide layer; the electron gun output power of the electron gun evaporation system is 8kw, the rotating speed of the turntable is 6rpm, so that the titanium material is vaporized and sublimated, and adhered On the AZO layer; the thickness of the plated titanium metal layer is 100nm, and the product obtained here is called "Ti/AZO glass".

(3) Thermal oxidation treatment

Then, the above-mentioned Ti/AZO glass is subjected to thermal oxidation treatment, the temperature of thermal oxidation is 300℃, 400℃ and 500℃, the thermal oxidation time is 10 minutes, the oxygen flow rate is 100sccm, and the heating rate is 25℃/sec. The titanium metal layer is oxidized into a titanium oxide layer (hereinafter referred to as TiOx layer), and the obtained product is called "TiOx/AZO glass".

Please refer to Table 1, for the analysis of Ti/AZO glass without thermal oxidation, and TiOx/AZO glass treated with different thermal oxidation temperatures, the atomic percentages (Atomic(%)) contained therein; according to Table 1, on each coated glass The proportion of titanium atoms in TiOx/AZO glass will not change significantly due to thermal oxidation treatment, but the proportion of oxygen atoms in TiOx/AZO glass after thermal oxidation treatment has increased significantly, from 48.91% of Ti/AZO glass to TiOx/AZO glass More than 80%, and the proportion of oxygen atoms tends to increase as the thermal oxidation temperature increases.

(4) Annealing steps

The TiOx/AZO glass is processed in an annealing step to complete the preparation of the heat-insulating and self-cleaning glass of the present invention. The annealing steps used are the vacuum annealing step and the hydrogen plasma annealing step, which are described as follows: If the vacuum annealing step is used, the TiOx/AZO glass is placed in a vacuum reactor and heated at 400°C in a vacuum environment1 After hours, the product obtained is referred to as "TiOx/AZO-VA glass"; the vacuum annealing step provides heat energy to repair the crystal structure or rearrange the crystal lattice and repair the defects of the film.

If the hydrogen plasma annealing step is used, place the TiOx/AZO glass in the reaction vacuum chamber, and reduce the background pressure of the reaction vacuum chamber to below 10 ^-5 torr, and then add hydrogen. The hydrogen flow rate is 100sccm and the working pressure It is 35torr, and the plasma power is 600W for 1 minute. The product obtained is referred to as "TiOx/AZO-PA glass". The hydrogen plasma annealing step uses high-density plasma and hydrogen treatment to take away the oxygen adsorbed on the surface of the crystal grains to increase the carrier concentration and conductivity of the processed object.

2. Testing the properties of heat-insulating and self-cleaning glass

(1) Analysis of surface topography.

Please refer to Figure 1 (A), which is a structural diagram of the heat-insulating and self-cleaning glass of this case. The heat-insulating and self-cleaning glass of the present invention includes a glass substrate (1) and an aluminum-doped zinc oxide layer (2) It is arranged on the glass substrate (1), and the titanium monoxide layer (3) is arranged on the aluminum-doped zinc oxide layer (2); please refer to the first figure (B) again, which is a cross-section of a specific embodiment of the present invention observed with a microscope In the figure, Glass is a glass substrate (1), AZO is an aluminum-doped zinc oxide layer (2) with a thickness of 500 nm, and TiOx is a titanium oxide layer (3) with a thickness of 100 nm.

Please refer to the second to fourth diagrams, which are the analysis diagrams of the influence of thermal oxidation temperature and different annealing steps on the surface microstructure of the coated glass. The scanning electron microscope (Scanning Electron Microscope) is used to observe the surface microstructure of the coated glass.

Please refer to the second figure. The second figure (A) is the Ti/AZO glass without thermal oxidation and annealing steps, and the second figure (B) is the TiOx/AZO glass which has been thermally oxidized at 300℃ but without the annealing step. The second picture (C) is the TiOx/AZO-VA glass that has been thermally oxidized at 300°C and undergoes a vacuum annealing step, and the second picture (D) is the TiOx/AZO glass that has been thermally oxidized at 300°C and has undergone a hydrogen plasma annealing step. -PA glass; according to the second figure, there is no obvious agglomeration and dense material on the surface of the coated glass.

Please refer to the third figure. The third figure (A) is the Ti/AZO glass without thermal oxidation and annealing steps, and its surface particles are uniformly distributed; the third figure (B) is the thermal oxidation treatment at 400℃ but no annealing step TiOx/AZO glass has agglomerated crystal grains on its surface; the third image (C) is a TiOx/AZO-VA glass that has been thermally oxidized at 400°C and has undergone a vacuum annealing step, and its surface crystals have also agglomerated; and The third image (D) shows the TiOx/AZO-PA glass that has been thermally oxidized at 400°C and undergoes a hydrogen plasma annealing step. The surface grains are relatively small and become fine grains.

Please refer to the fourth figure. The fourth figure (A) is the Ti/AZO glass without thermal oxidation and annealing steps, and its surface particles are uniformly distributed; the fourth figure (B) is the thermal oxidation treatment at 500°C without annealing The surface of the TiOx/AZO glass has agglomeration; the fourth picture (C) is the TiOx/AZO-VA glass that has been thermally oxidized at 500°C and has undergone a vacuum annealing step. The surface crystals have also agglomerated. ; And the fourth figure (D) is a TiOx/AZO-PA glass that has been thermally oxidized at 500° C. and has undergone a hydrogen plasma annealing step. The surface grains are small and become fine grains.

(2) Roughness analysis

Please refer to Table 2. For the influence of different thermal oxidation temperatures and different annealing steps on the average surface roughness (Ra) of the film, the average surface roughness (Ra) of the film was observed and measured by scanning probe microscopes ( Ra);

Please refer to the fifth figure (A) for the Ti/AZO glass without thermal oxidation, with an average surface roughness of 3.72nm; the fifth figure (B) for the TiOx/AZO glass thermally oxidized at 500℃, with an average surface The roughness increased to 7.22nm; the fifth figure (C) shows the TiOx/AZO-VA glass thermally oxidized at 500°C and vacuum annealed. Compared with TiOx/AZO glass, the average surface roughness is slightly reduced to 6.96nm; And the fifth figure (D) shows the TiOx/AZO-PA glass thermally oxidized at 500°C and annealed with hydrogen plasma. Compared with the TiOx/AZO glass, the average surface roughness is significantly reduced to 3.28nm.

(Three), contact angle analysis

Please refer to Table 3, in order to use a contact angle measuring instrument to measure the influence of thermal oxidation temperature and annealing steps on the size of the contact angle; contact angle refers to the angle formed by contacting the solid surface at the liquid and gas interface, and is used for measurement The degree of adhesion of the liquid surface to the solid surface determines whether the surface is hydrophilic or hydrophobic. The smaller the contact angle, the hydrophilic surface. In this test, the contact angle of each sample is measured at the same time after no UV light is irradiated and UV light is irradiated for 1 hour. According to Table 3, the group of thermal oxidation treatment at 300℃, the group without annealing treatment and the group with vacuum annealing treatment, the sample The contact angle is significantly reduced after UV irradiation, which means that UV irradiation can trigger the hydrophilicity of the TiOx/AZO film, and the hydrogen plasma annealing step treatment group, regardless of UV irradiation, the contact angle is about 7° , Which means that the sample after hydrogen plasma annealing treatment has high hydrophilicity. The above-mentioned UV irradiation reduces the contact angle. It can also be observed in the thermal oxidation treatment group at 400℃ and 500℃. However, the contact angle of the sample after the hydrogen plasma treatment step is significantly lower than that before the UV light is irradiated. For the other two groups, the contact angle will drop again after irradiating UV light.

See also the sixth figure. The sixth figure (A) is the contact angle photo of the TiOx/AZO glass without annealing treatment, and the sixth figure (B) is the contact angle of the TiOx/AZO glass after being irradiated with UV light for 1 hour. In the photo, it can be observed that the contact angle of TiOx/AZO glass drops significantly after UV irradiation. The sixth figure (C) is a photo of the contact angle of TiOx/AZO-VA glass after vacuum annealing treatment, and the sixth figure (D) is a photo of the contact angle of TiOx/AZO-VA glass after being irradiated with UV light for 1 hour. It can be observed that after UV irradiation, the contact angle of TiOx/AZO-VA glass decreases significantly. The sixth image (E) is a photo of the contact angle of the TiOx/AZO-PA glass after hydrogen plasma treatment, and the sixth image (F) is a photo of the contact angle of the TiOx/AZO-PA glass after being irradiated with UV light for 1 hour. The contact angle of TiOx/AZO-PA glass that has not been irradiated by UV is significantly lower than that of TiOx/AZO glass and TiOx/AZO-VA glass. After UV irradiation, the contact angle of TiOx/AZO-PA glass will decrease again.

(4) Visible light transmittance and transmittance spectrum analysis

Please refer to Table 4, in order to use UV/VIS/NIR spectrometer to analyze the average light transmittance of each sample in the visible light band (400-800nm); according to Table 4, the average light transmittance of the sample without thermal oxidation treatment The lowest, the average visible light transmittance of the sample after thermal oxidation treatment has increased significantly, and as the temperature of the thermal oxidation treatment increases, the average visible light transmittance of the sample will also increase. This phenomenon indicates that the titanium metal is thin The structure of the layer is indeed transformed from a metal material to a ceramic material (TiOx) after thermal oxidation; in the group of thermal oxidation treatment at 500°C, the average light transmittance of visible light is the highest when the hydrogen plasma annealing step is used. Reach 85.2%. In addition, please refer to the seventh figure again, which is the light transmittance analysis graph for different wavelengths of visible light; among them, the Ti/AZO glass that has not been thermally oxidized has a relatively low visible light transmittance; and it has been thermally oxidized at 500°C. The visible light transmittance of the group, whether or not after annealing step, has been greatly improved.

(5) Crystallinity analysis

Please refer to the eighth figure again, which is an X-ray diffraction analyzer (X-ray diffraction) to measure the crystallinity analysis of the film; the eighth figure (A) is the X-ray diffraction analyzer (X-ray diffraction) quantity The crystallinity spectrum of the film was measured. The eighth image (B) is a partial enlarged view of the eighth image (A) on the zinc oxide (ZnO) crystal plane (002) front. After the Ti/AZO glass is thermally oxidized to form TiOx/AZO glass, the peak of the zinc oxide (ZnO) crystal plane (002) moves to a higher angle, and the TiOx/AZO-PA glass processed by the hydrogen plasma annealing step , The (002) peak of the ZnO crystal plane moves to a higher angle; the phenomenon of the (002) peak of the ZnO crystal plane shifts, indicating that the distance between the ZnO crystal planes is reduced, which may be related to the hydrogen plasma annealing step. The phenomenon that aluminum (Al) ions replace zinc (Zn) ions in TiOx/AZO films is related; because zinc (Zn) ions have an ionic radius of 0.74Å, which is similar to the ionic radius of aluminum (Al) ions of 0.50Å, if aluminum occurs The phenomenon of ions replacing zinc ions will reduce the lattice spacing of the TiOx/AZO film.

(6) Analysis of electrical property parameters and radiation coefficient

Please refer to Table 5, for TiOx/AZO glass without annealing treatment or TiOx/AZO glass after annealing treatment, its electrical property parameters and emissivity analysis results, including measurement of conductive film Carrier concentration, carrier mobility and resistivity, and sheet resistance. Please refer to Table 5. In the detection of carrier concentration, the hydrogen plasma annealing group has the highest carrier concentration, and the second annealing treatment group has significantly higher carrier mobility than the non-annealing treatment group. In the test results of electrical resistance, the electrical resistivity of the vacuum annealing group was significantly lower than that of the untreated group by 75%, and the electrical resistivity of the hydrogen plasma annealing group was the lowest among the three groups, compared with the untreated group It is reduced by 78%. The possible reason for this decrease in resistivity is that after annealing treatment, aluminum ions replace zinc ions, and aluminum ions will provide free electrons, which reduces the resistivity of the TiOx/AZO film. According to X in Figure 8 Optical diffraction analysis graph, TiOx/AZO glass formed by thermal oxidation, TiOx/AZO-VA glass after vacuum annealing, and TiOx/AZO-PA glass after hydrogen plasma treatment, (002) peak and (103) The peak position shifts to a high angle, which also implies that impurity atoms replace base atoms.

(7) Analysis of radiation coefficient

Table 6 shows the emissivity analysis results of each glass processed by thermal oxidation at 500℃, without annealing step or after annealing step. This test was performed with an emissivity analyzer (Japan Sensor TSS-5X, Japan Sensor, Tokyo, Japan) Measurement, emissivity is used to describe the ability of an object to radiate far infrared rays. The lower the value, the higher the ability of the object to reflect far infrared rays. According to Table 6, after annealing treatment, the emissivity of the tested samples has decreased significantly, and the decrease rate is 60%; In the Hagen-Rubens relation, the emissivity will decrease as the resistivity decreases. Combined with the test results in Table 5, the resistivity of those who have undergone the annealing step is significantly lower than that of those without annealing.

From the above implementation description, it can be seen that the heat-insulating and self-cleaning glass produced by the present invention has both good hydrophilicity and low emissivity, and can indeed meet the current requirements for self-cleaning glass and heat-insulating glass.

In summary, the heat-insulating and self-cleaning glass of the present invention and the manufacturing method thereof can indeed achieve the expected use effect through the embodiments disclosed above, and the present invention has not been disclosed before the application, sincerely Has fully complied with the provisions and requirements of the Patent Law. If you file an application for a patent for invention in accordance with the law, you are kindly requested to review and grant a quasi-patent.

However, the above-mentioned descriptions are only preferred embodiments of the present invention, and are not intended to limit the scope of protection of the present invention. Those familiar with the art will make other equivalent changes based on the characteristics of the present invention. Any modification or modification should be regarded as not departing from the design scope of the present invention.

1: glass substrate

2: Al-doped zinc oxide layer

3: Titanium oxide layer

Claims (9)

A method for manufacturing heat-insulating and self-cleaning glass includes: Step 1: Sputtering an aluminum-doped zinc oxide layer on a glass substrate, wherein the thickness of the aluminum-doped zinc oxide layer is between 300~ 800nm; Step 2: Deposit a titanium metal (Ti) layer on the aluminum-doped zinc oxide layer by evaporation; Step 3: Perform a thermal oxidation step to oxidize the titanium metal layer and generate a titanium monoxide layer, The thickness of the titanium oxide layer is between 80 and 150 nm; and step 4: performing an annealing step to obtain the heat-insulating and self-cleaning glass. The method for manufacturing heat-insulating and self-cleaning glass according to claim 1, wherein the thickness of the aluminum-doped zinc oxide layer is 500 nm. The method for manufacturing a heat-insulating and self-cleaning glass according to claim 1, wherein the thickness of the titanium oxide layer is 100 nm. The method for manufacturing heat-insulating and self-cleaning glass according to claim 1, wherein the annealing step is a vacuum annealing step. The method for manufacturing heat-insulating and self-cleaning glass according to claim 4, wherein the vacuum annealing step is performed under vacuum at 400-600°C for 30-45 minutes. The method for manufacturing low emissivity self-cleaning glass according to claim 1, wherein the annealing step is a hydrogen plasma annealing step. The method for manufacturing heat-insulating and self-cleaning glass according to claim 6, wherein the hydrogen plasma annealing step is under the conditions of a hydrogen flow rate of 80~120sccm, a gas pressure of 30~40 Torr, and a plasma power of 400~800W, Act for 1~10 minutes. A heat-insulating and self-cleaning glass prepared by the manufacturing method described in claim 1, comprising a glass substrate, and covering one side of the glass substrate with an aluminum-doped zinc oxide layer and titanium monoxide (TiOx ) Layer, wherein the average visible light transmittance of the heat-insulating and self-cleaning glass is higher than 85%, and the emissivity is not more than 0.2. For the heat-insulating and self-cleaning glass described in claim 8, the contact angle is not more than 6°.

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