CN112194380A - Coated glass and method for producing same - Google Patents

Abstract

The invention discloses coated glass and a manufacturing method thereof: the coated glass comprises a glass substrate and Si sputtered on the surface of the glass substrate in sequence₃N₄Layer, MgF₂Layer, Bi₂Te₃a/TIN composite layer, an ITO layer; wherein, Si₃N₄The thickness of the layer is 15-35 nm, MgF₂The thickness of the layer is 10-30 m and Bi₂Te₃The thickness of the/TIN composite layer is 10-30 nm, and the thickness of the ITO layer is 30-60 nm; the manufacturing method comprises the following steps: s1: surface treatment; s2: magnetron sputtering of Si₃N₄A layer; s3: magnetron sputtering of MgF₂A layer; s4: magnetron sputtering of Bi₂Te₃a/TIN composite layer; s5: and (4) carrying out magnetron sputtering on the ITO layer. The coated glass has excellent mechanical strength, wear resistance and light transmittance, and when the four layers of coatings are applied to various displays, a light source penetrates through different medium layers to be repeatedly refracted and reflected for multiple times due to different refractive indexes of the four layers of coatings.

Description

Coated glass and method for producing same

Technical Field

The invention belongs to the technical field of glass processing, and particularly relates to coated glass and a manufacturing method thereof.

Background

The ITO conductive glass is manufactured by depositing a layer of indium tin oxide film on the basis of soda-lime-based or silicon-boron-based substrate glass by a magnetron sputtering method. ITO is a metal compound with good transparent conductive performance, has the characteristics of forbidden bandwidth, high light transmittance in a visible light spectrum region, low resistivity and the like, is widely applied to the fields of flat panel display devices, solar cells, special function window coatings and other photoelectric devices, and is the only transparent conductive electrode material for various flat panel display devices such as LCDs, PDPs, OLEDs, touch screens and the like at present. The ITO conductive film glass is used as a key basic material of the flat panel display device, and has wider market space along with the continuous updating and upgrading of the flat panel display device.

At present, research on ITO conductive glass mainly focuses on improving the conductivity and reducing the resistance of the ITO conductive glass, the hardness, the wear resistance and the light transmittance of the coated glass are not optimized, the service life of the coated glass is influenced, and meanwhile, the traditional ITO conductive glass is a single dielectric layer and is directly applied to various flat panel displays, so that the problems of non-uniform luminescence or imaging and dazzling of display screens can be caused in the using process.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide coated glass and a manufacturing method thereof.

The technical scheme of the invention is summarized as follows:

coating glass: the coated glass comprises a glass substrate and Si sputtered on the surface of the glass substrate in sequence₃N₄Layer, MgF₂Layer, Bi₂Te₃a/TIN composite layer, an ITO layer; wherein, Si₃N₄The thickness of the layer is 15-35 nm, MgF₂The thickness of the layer is 10-30 m and Bi₂Te₃The thickness of the/TIN composite layer is 10-30 nm, and the thickness of the ITO layer is 30-60 nm.

Preferably, said Si is₃N₄The layer thickness was 70 nm.

Preferably, the MgF₂The layer thickness was 30 nm.

Preferably, the Bi₂Te₃The thickness of the/TIN layer was 20 nm.

Preferably, the thickness of the ITO layer is 45 nm.

The manufacturing method of the coated glass comprises the following steps:

s1: surface treatment: putting the glass substrate into the treatment solution, carrying out ultrasonic treatment for 20min, washing with clear water for 2-3 times, carrying out ultrasonic washing for 10min by using absolute ethyl alcohol, and drying the surface at 80 ℃ to obtain the treated glass substrate;

s2: magnetron sputtering of Si₃N₄Layer (b): placing the glass substrate treated by the S1 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 1 multiplied by 10^-5～3×10^-4Pa, in Si₃N₄Introducing mixed gas of argon and nitrogen into the target material at a flow rate of 35-70 ml/min, wherein the volume ratio of the nitrogen to the argon is 1: (7.5-10), adjusting the working pressure to 0.5-1.2 Pa, controlling the temperature of the glass substrate to 250-400 ℃ and the sputtering power to 140-200W, and forming Si₃N₄A dielectric barrier layer;

s3: magnetron sputtering of MgF₂Layer (b): placing the glass substrate treated by the S2 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 1 multiplied by 10^-5～3×10^-4Pa, in MgF₂Introducing argon with the purity of more than or equal to 99.9 percent into the glass substrate as a target material by using the flow of 35-70 ml/min, adjusting the working pressure to be 0.5-1.2 Pa, controlling the temperature of the glass substrate to be 250-400 ℃ and the sputtering power to be 140-200W, and forming MgF₂An anti-reflection layer;

s4: magnetron sputtering of Bi₂Te₃the/TIN composite layer:

a. preparing a composite target material: bi with the same diameter₂Te₃Respectively cutting the target material and the TIN target material into uniform fan shapes with the uniform specification of 10 equal parts, and taking N parts of fan-shaped Bi₂Te₃The target material is prepared by splicing N1, 2, 3, 4 and 5 with 10-N parts of fan-shaped TIN target material to form Bi₂Te₃a/TIN composite target material;

b. placing the glass substrate processed by the S3 into a radio frequency magnetron sputtering deviceVacuum pumping is carried out until the background vacuum degree is 1 multiplied by 10^-5～3×10^-4Pa, in Bi₂Te₃The method comprises the following steps of taking a/TIN composite target as a target, introducing mixed gas of argon and nitrogen at a flow rate of 35-70 ml/min, wherein the volume ratio of the nitrogen to the argon is 1: (8-13), adjusting the working pressure to 1.2-1.8 Pa, controlling the temperature of the glass substrate to 250-400 ℃ and the sputtering power to 120-180W to form Bi₂Te₃a/TIN composite conductive layer;

s5: magnetron sputtering of an ITO layer: placing the glass substrate treated by the S4 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 1 multiplied by 10^-5～3×10^-4And Pa, using ITO as a target material, introducing argon with the purity of more than or equal to 99.9% by using 35-70 ml/min of gas flow, adjusting the working pressure to be 1.2-1.8 Pa, controlling the temperature of the glass substrate to be 250-400 ℃, and sputtering the glass substrate with the sputtering power of 80-140W to form an ITO conductive layer.

Preferably, the treatment fluid consists of the following components in percentage by mass: 0.5-2% of cocamidopropyl betaine, 1-3% of sodium phytate, 3-7% of sodium carbonate, 2-4% of sodium hydroxide and the balance of deionized water. The invention has the beneficial effects that:

1. the invention is prepared by Si₃N₄Coating layer, compared with conventional SiO₂Barrier layer, Si₃N₄Not only can prevent Na in the glass substrate⁺Out-diffusion and at the same time, shielding Mg²⁺、O^2-、Bi³⁺、Te^2-、Ti⁴⁺、ln³⁺、Sn⁴⁺The diffusion of plasma makes the medium of the coating layer maintain relative stability and endows the glass substrate with higher chemical inertness, and in addition, Si₃N₄The glass has extremely high hardness, and the mechanical strength and the wear resistance of the glass can be obviously improved after the glass is plated; recycling of MgF₂The layer improves optical performance, increases light transmittance and improves luminous effect; and use of Bi₂Te₃the/TIN composite layer and the ITO layer cooperate to reduce the surface resistance of the coated glass and improve the conductivity.

2. The invention utilizes the superposition of four layers of different medium layers, and when the invention is applied to various displays, the light source passes through different medium layers to generate repeated refraction and reflection for a plurality of times due to different refractive indexes of the medium layers, so that the display screen can image more uniformly and the light emission tends to be uniform.

Drawings

FIG. 1 is a flow chart of the manufacturing method of the coated glass of the present invention.

Detailed Description

The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.

Example 1

The manufacturing method of the coated glass comprises the following steps:

s1: surface treatment: putting the glass substrate into the treatment solution, carrying out ultrasonic treatment for 20min, washing with clear water for 2 times, carrying out ultrasonic washing for 10min by using absolute ethyl alcohol, and drying the surface at 80 ℃ to obtain the treated glass substrate;

the treatment fluid consists of the following components in percentage by mass: 0.5% of cocamidopropyl betaine, 1% of sodium phytate, 3% of sodium carbonate, 2% of sodium hydroxide and the balance of deionized water;

s2: magnetron sputtering of Si₃N₄Layer (b): placing the glass substrate treated by the S1 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 5 multiplied by 10^-4Pa, in Si₃N₄Introducing mixed gas of argon and nitrogen into the target material at a flow rate of 35ml/min, wherein the volume ratio of the nitrogen to the argon is 1: 7.5, adjusting the working pressure to 0.5Pa, controlling the temperature of the glass substrate to 250 ℃ and the sputtering power to 140W, and forming Si with the thickness of 15nm₃N₄A dielectric barrier layer;

s3: magnetron sputtering of MgF₂Layer (b): placing the glass substrate treated by the S2 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 5 multiplied by 10^-4Pa, in MgF₂Introducing argon with purity of not less than 99.9% at a flow rate of 35ml/min, adjusting working pressure to 0.5Pa, controlling the temperature of the glass substrate to 250 deg.C, and sputtering at power of 140W to obtain MgF with thickness of 10nm₂An anti-reflection layer;

s4: magnetron sputtering of Bi₂Te₃Composite coating of/TIN：

a. Preparing a composite target material: bi with the same diameter₂Te₃Respectively cutting the target material and the TIN target material into uniform fan shapes with the uniform specification of 10 equal parts, and taking 2 parts of fan-shaped Bi₂Te₃The target material is spliced with 8 parts of fan-shaped TIN target material to form Bi₂Te₃a/TIN composite target material;

b. placing the glass substrate treated by the S3 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 5 multiplied by 10^-4Pa, in Bi₂Te₃the/TIN composite target material is taken as a target material, mixed gas of argon and nitrogen is introduced at the flow rate of 35ml/min, and the volume ratio of the nitrogen to the argon is 1: 8, adjusting the working pressure to be 1.2Pa, controlling the temperature of the glass substrate to be 250 ℃ and the sputtering power to be 120W, and forming Bi with the thickness of 10nm₂Te₃a/TIN composite conductive layer;

s5: magnetron sputtering of an ITO layer: placing the glass substrate treated by the S4 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 5 multiplied by 10^-4And Pa, using ITO as a target material, introducing argon with the purity of more than or equal to 99.9 percent by using the flow of 35ml/min, adjusting the working pressure to be 1.2Pa, controlling the temperature of the glass substrate to be 250 ℃ and the sputtering power to be 100W, and forming an ITO conductive layer with the thickness of 30 nm.

Example 2

The manufacturing method of the coated glass comprises the following steps:

s1: surface treatment: putting the glass substrate into the treatment solution, carrying out ultrasonic treatment for 20min, washing with clear water for 3 times, carrying out ultrasonic washing for 10min by using absolute ethyl alcohol, and drying the surface at 80 ℃ to obtain the treated glass substrate;

the treatment fluid consists of the following components in percentage by mass: 1% of cocamidopropyl betaine, 2% of sodium phytate, 5% of sodium carbonate, 3% of sodium hydroxide and the balance of deionized water;

s2: magnetron sputtering of Si₃N₄Layer (b): placing the glass substrate treated by the S1 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 1 multiplied by 10^-5Pa, in Si₃N₄Introducing mixed gas of argon and nitrogen into the target material at a flow rate of 55ml/min, wherein the volume ratio of the nitrogen to the argonIs 1: 9, adjusting the working pressure to 0.8Pa, controlling the temperature of the glass substrate to 350 ℃ and the sputtering power to 160W, and forming Si with the thickness of 25nm₃N₄A dielectric barrier layer;

s3: magnetron sputtering of MgF₂Layer (b): placing the glass substrate treated by the S2 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 1 multiplied by 10^-5Pa, in MgF₂Introducing argon with purity of not less than 99.9% with flow rate of 55ml/min as target material, adjusting working pressure to 0.8Pa, controlling temperature of glass substrate to 350 deg.C and sputtering power to 160W to form MgF with thickness of 20nm₂An anti-reflection layer;

s4: magnetron sputtering of Bi₂Te₃the/TIN composite layer:

a. preparing a composite target material: bi with the same diameter₂Te₃Respectively cutting the target material and the TIN target material into uniform fan shapes with the uniform specification of 10 equal parts, and taking 3 parts of fan-shaped Bi₂Te₃The target material is spliced with 7 parts of fan-shaped TIN target material to form Bi₂Te₃a/TIN composite target material;

b. placing the glass substrate treated by the S3 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 1 multiplied by 10^-5Pa, in Bi₂Te₃the/TIN composite target material is taken as a target material, mixed gas of argon and nitrogen is introduced at the flow rate of 55ml/min, and the volume ratio of the nitrogen to the argon is 1: 10, adjusting the working pressure to 1.5Pa, controlling the temperature of the glass substrate to 300 ℃ and the sputtering power to 150W, and forming Bi with the thickness of 20nm₂Te₃a/TIN composite conductive layer;

s5: magnetron sputtering of an ITO layer: placing the glass substrate treated by the S4 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 1 multiplied by 10^-5And Pa, using ITO as a target material, introducing argon with the purity of more than or equal to 99.9 percent by using the gas flow of 55ml/min, adjusting the working pressure to be 1.5Pa, controlling the temperature of the glass substrate to be 300 ℃ and the sputtering power to be 120W, and forming an ITO conductive layer with the thickness of 45 nm.

Example 3

The manufacturing method of the coated glass comprises the following steps:

s1: surface treatment: putting the glass substrate into the treatment solution, carrying out ultrasonic treatment for 20min, washing with clear water for 3 times, carrying out ultrasonic washing for 10min by using absolute ethyl alcohol, and drying the surface at 80 ℃ to obtain the treated glass substrate;

the treatment fluid consists of the following components in percentage by mass: 2% of cocamidopropyl betaine, 3% of sodium phytate, 7% of sodium carbonate, 4% of sodium hydroxide and the balance of deionized water;

s2: magnetron sputtering of Si₃N₄Layer (b): placing the glass substrate treated by the S1 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 8 multiplied by 10^-4Pa, in Si₃N₄Introducing mixed gas of argon and nitrogen into the target material at a flow rate of 70ml/min, wherein the volume ratio of the nitrogen to the argon is 1: 10, adjusting the working pressure to 1.2Pa, controlling the temperature of the glass substrate to 400 ℃ and the sputtering power to 200W, and forming Si with the thickness of 35nm₃N₄A dielectric barrier layer;

s3: magnetron sputtering of MgF₂Layer (b): placing the glass substrate treated by the S2 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 8 multiplied by 10^-4Pa, in MgF₂Introducing argon with purity of not less than 99.9% at flow rate of 70ml/min, regulating working pressure to 1.2Pa, controlling glass substrate temperature to 400 deg.C, and sputtering power to 200W to obtain MgF with thickness of 30nm₂An anti-reflection layer;

s4: magnetron sputtering of Bi₂Te₃the/TIN composite layer:

a. preparing a composite target material: bi with the same diameter₂Te₃Respectively cutting the target material and the TIN target material into uniform fan shapes with the uniform specification of 10 equal parts, and taking 2 parts of fan-shaped Bi₂Te₃The target material is spliced with 8 parts of fan-shaped TIN target material to form Bi₂Te₃a/TIN composite target material;

b. placing the glass substrate treated by the S3 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 8 multiplied by 10^-4Pa, in Bi₂Te₃the/TIN composite target material is taken as a target material, mixed gas of argon and nitrogen is introduced at the flow rate of 70ml/min, and the volume ratio of the nitrogen to the argon is 1: 12, adjusting the working air pressure to 1.8Pa, and controlling the temperature of the glass substrateThe temperature is 400 ℃, the sputtering power is 180W, and Bi with the thickness of 30nm is formed₂Te₃a/TIN composite conductive layer;

s5: magnetron sputtering of an ITO layer: placing the glass substrate treated by the S4 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 8 multiplied by 10^-4Pa, using ITO as a target material, introducing argon with the purity of more than or equal to 99.9 percent by using the flow of 70ml/min, adjusting the working pressure to be 1.8Pa, controlling the temperature of the glass substrate to be 400 ℃ and the sputtering power to be 140W, and forming an ITO conductive layer with the thickness of 60 nm.

Comparative example

S1: the operation procedure is the same as that of S1 in example 1;

s2: the operation procedure of sputtering the 65nm ITO layer by using the RF magnetron sputtering technique was the same as that of S5 in example 1.

The following table shows the performance indexes of the coated glass prepared in the examples 1-3 and the comparative example:

examples 1 to 3 preliminary mixing with Si₃N₄Coating layer, compared with conventional SiO₂Barrier layer, Si₃N₄Not only can prevent Na in the glass substrate⁺Out-diffusion and at the same time, shielding Mg²⁺、O^2-、Bi³⁺、Te^2-、Ti⁴⁺、ln³⁺、Sn⁴⁺The diffusion of plasma makes the medium of the coating layer maintain relative stability and endows the glass substrate with higher chemical inertness, and in addition, Si₃N₄The glass has extremely high hardness, and the mechanical strength and the wear resistance of the glass can be obviously improved after the glass is plated; recycling of MgF₂The layer improves optical performance, increases light transmittance and improves luminous effect; and use of Bi₂Te₃the/TIN composite layer and the ITO layer cooperate to reduce the surface resistance of the coated glass and improve the conductivity.

In embodiments 1 to 3, four different dielectric layers are stacked, and since the refractive indexes of the dielectric layers are different, when the light source is applied to various displays, the light source passes through the different dielectric layers to repeatedly refract and reflect for multiple times, so that the display screen can image more uniformly, and the light emission tends to be uniform.

While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.

Claims (7)

1. A coated glass is characterized in that: the coated glass comprises a glass substrate and Si sputtered on the surface of the glass substrate in sequence₃N₄Layer, MgF₂Layer, Bi₂Te₃a/TIN composite layer, an ITO layer; wherein, Si₃N₄The thickness of the layer is 15-35 nm, MgF₂The thickness of the layer is 10-30 m and Bi₂Te₃The thickness of the/TIN composite layer is 10-30 nm, and the thickness of the ITO layer is 30-60 nm.

2. The coated glass according to claim 1, wherein the Si is Si₃N₄The layer thickness was 25 nm.

3. The coated glass according to claim 1, wherein the MgF is₂The layer thickness was 20 nm.

4. The coated glass according to claim 1, wherein the Bi is₂Te₃The thickness of the/TIN layer was 20 nm.

5. The coated glass of claim 1, wherein the thickness of the ITO layer is 45 nm.

6. The method for producing a coated glass according to any one of claims 2 to 5, comprising the steps of:

s1: surface treatment: putting the glass substrate into the treatment solution, carrying out ultrasonic treatment for 20min, washing with clear water for 2-3 times, carrying out ultrasonic washing for 10min by using absolute ethyl alcohol, and drying the surface at 80 ℃ to obtain the treated glass substrate;

s2: magnetron sputtering of Si₃N₄Layer (b): placing the glass substrate treated by the S1 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 1 multiplied by 10^-5～3×10^-4Pa, in Si₃N₄Introducing mixed gas of argon and nitrogen into the target material at a flow rate of 35-70 ml/min, wherein the volume ratio of the nitrogen to the argon is 1: (7.5-10), adjusting the working pressure to 0.5-1.2 Pa, controlling the temperature of the glass substrate to 250-400 ℃ and the sputtering power to 140-200W, and forming Si₃N₄A dielectric barrier layer;

s3: magnetron sputtering of MgF₂Layer (b): placing the glass substrate treated by the S2 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 1 multiplied by 10^-5～3×10^-4Pa, in MgF₂Introducing argon with the purity of more than or equal to 99.9 percent into the glass substrate as a target material by using the flow of 35-70 ml/min, adjusting the working pressure to be 0.5-1.2 Pa, controlling the temperature of the glass substrate to be 250-400 ℃ and the sputtering power to be 140-200W, and forming MgF₂An anti-reflection layer;

s4: magnetron sputtering of Bi₂Te₃the/TIN composite layer:

a. preparing a composite target material: bi with the same diameter₂Te₃Respectively cutting the target material and the TIN target material into uniform fan shapes with the uniform specification of 10 equal parts, and taking N parts of fan-shaped Bi₂Te₃The target material is prepared by splicing N1, 2, 3, 4 and 5 with 10-N parts of fan-shaped TIN target material to form Bi₂Te₃a/TIN composite target material;

b. placing the glass substrate treated by the S3 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 1 multiplied by 10^-5～3×10^-4Pa, in Bi₂Te₃The method comprises the following steps of taking a/TIN composite target as a target, introducing mixed gas of argon and nitrogen at a flow rate of 35-70 ml/min, wherein the volume ratio of the nitrogen to the argon is 1: (8-13) of a first step,adjusting the working pressure to 1.2-1.8 Pa, controlling the temperature of the glass substrate to 250-400 ℃ and the sputtering power to 120-180W to form Bi₂Te₃a/TIN composite conductive layer;

s5: magnetron sputtering of an ITO layer: placing the glass substrate treated by the S4 into a radio frequency magnetron sputtering device, and vacuumizing until the background vacuum degree is 1 multiplied by 10^-5～3×10^-4And Pa, using ITO as a target material, introducing argon with the purity of more than or equal to 99.9% by using 35-70 ml/min of gas flow, adjusting the working pressure to be 1.2-1.8 Pa, controlling the temperature of the glass substrate to be 250-400 ℃, and sputtering the glass substrate with the sputtering power of 80-140W to form an ITO conductive layer.

7. The method for manufacturing coated glass according to claim 6, wherein the treatment liquid comprises the following components in percentage by mass: 0.5-2% of cocamidopropyl betaine, 1-3% of sodium phytate, 3-7% of sodium carbonate, 2-4% of sodium hydroxide and the balance of deionized water.

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