KR100205533B1 - Manufacturing method of color glass - Google Patents

Abstract

The present invention relates to a method of producing colored glass by forming an oxide film and a reflective film on the surface of the glass in vacuum, and more particularly, to form an oxide film on the glass by evaporating metal indium in an atmosphere of oxygen gas in vacuum. It relates to a method for producing colored glass.

Description

Manufacturing method of colored glass

1 is a schematic diagram of an apparatus for illustrating the present invention.

* Explanation of symbols for main parts of the drawings

1: vacuum chamber 2: evaporation source

3: shutter 4: substrate

5: heating apparatus 5 ': substrate holder

6: gas inlet

The present invention relates to a method for producing a colored glass by forming an oxide film and a reflective film on the surface of the glass in a vacuum, and more particularly, by forming an oxide film on the glass by evaporating the metal indium in the atmosphere of oxygen gas in a vacuum. It relates to a method for producing colored glass.

Colored glass is applied to the window of various buildings, the glass for automobiles, etc., and is utilized. When applied to windows, besides simply colored glass, there are selective light transmitting membranes and anti-reflective coatings for energy saving.

In glass for automobiles, colored glass such as a blue mirror or an elomirror is used for the purpose of preventing strong light reflection.

The specific color of the glass by the oxide film is due to interference caused when light is reflected from the front and back sides of the transparent thin film, respectively. Two factors play a role in determining the nature of the interference, one for the optical path difference and the other for phase shift. Considering these two things, the condition under which the intensity of interference generated by the thin film is maximized is as shown in Equation (I) below.

Where n is the refractive index of the thin film, d is the thickness of the thin film, and λ is the wavelength of light. Therefore, by properly adjusting the refractive index and thickness of the thin film it is possible to reflect the light of the desired color.

Wet and sputtering methods are mainly used to manufacture conventional colored glass. In recent years, however, wet methods have gradually disappeared due to pollution problems, and most of them use sputtering methods (Japanese Patent No. 3287758). Sputtering is a method of manufacturing a metal oxide into a target shape and then discharging argon gas in a vacuum chamber so that the argon ions strongly strike the target, thereby removing the evaporation material from the target and coating the substrate. However, this method has a disadvantage in that the production cost is increased because the oxide must be formed in advance.

An object of the present invention to solve the above problems is to provide a method for producing an oxide film using oxygen gas while using a metal other than the evaporation material oxide.

Hereinafter, the present invention will be described in detail.

The present invention has been made in a conventional vacuum deposition apparatus. 1 is a schematic diagram of an apparatus for explaining the method of the present invention. The apparatus consists of an evaporation source 2, a substrate holder and heating device 5, a shutter 3, and a gas inlet 6 in the vacuum chamber 1. As the evaporation source 2, a conventional resistance heating evaporation source, an electron beam evaporation source, or the like can be used. Since the metals used in the present invention have a low melting point and low reactivity, a resistance heating evaporation source was used. Meanwhile, the glass substrate used in the present invention used a transparent glass substrate to which no other material was added. Since the reflective layer is required for coloring, the glass substrate was coated with a material such as aluminum or silver.

First, the glass substrate is sufficiently pretreated in the air. Pretreatment was mainly performed using an ultrasonic cleaning method using an organic solvent. In particular, glass products require a lot of stains after pretreatment. In the present invention, a method of finally removing the stain using a breaking alcohol was used.

The pre-treated glass substrate 4 is mounted on the substrate holder 5 'and the vacuum chamber 1 is evacuated using a vacuum pump (not shown). When the vacuum degree of the vacuum chamber 1 is 10 ⁻⁵ Torr or less, when argon gas is injected to clean the substrate 4 and a negative voltage is applied to the substrate 4, a glow discharge is generated, which is present in the glow discharge region. Argon ions are accelerated to the substrate to clean the substrate 4.

The substrate 4 may not be cleaned separately, but should be performed only when the contamination of the substrate is severe.

The next step is to heat the substrate. Heating of the substrate was used for three purposes. One is to remove impurities such as hydrates and organic matter remaining on the substrate, and the second is to activate the substrate to improve the adhesion between the film and the substrate. Finally, it is intended to increase the formation energy of oxide, which is one of the important parts of the present invention. In other words, it is to improve the overall characteristics of the oxide by controlling the crystallization and stoichiometry of the oxide. In the present invention, the temperature control of the substrate used a substrate heating apparatus 5 equipped with a halogen lamp. The temperature of a board | substrate is suitable for 200-400 degreeC, for the following reason. This is because when the substrate temperature is 200 ° C. or less, crystallization of indium oxide does not sufficiently occur, and the color of the film is not uniform, and when the temperature becomes 400 ° C. or more, the film formation efficiency is remarkably decreased by redevaporation of indium oxide. When the substrate temperature rises and stabilizes to a desired temperature, the gas is injected through the gas introduction port 6 to supply power to the evaporation source to evaporate the metal. When the evaporation rate reaches a constant state, the shutter is opened to form an oxide film having a desired thickness. The pressure of the oxygen gas is preferably limited to 1 × 10 ^{-4 to} 5 × 10 ^-3 Torr, for the following reasons. If not due to the pressure of the oxygen gas is 1 × 10 ^-4 Torr or less to the film out of components of the oxygen uneven color, 5 × 10 ^-3 Torr or more when As is remarkably lowered by the evaporation rate of the gas scattering film characteristics It is because also falls. The evaporation rate of the metal is preferably limited to 1-5 kPa per second, for the following reason. This is because when the evaporation rate of the metal is 1 kPa or less, the evaporation rate is low and the efficiency of film formation is lowered. When the evaporation rate of the metal is 5 kPa or more, the metal component in the film is excessive and the film becomes black.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1

An evaporation source 2 was installed in a vacuum chamber 1 of a conventional vacuum evaporator, and oxygen gas was injected through a gas inlet 6 to prepare an oxide film on aluminum coated glass (Corning # 2947) as a reflective layer. By opening the vacuum chamber (1) installing the pre-pre-treated glass through the ultrasonic cleaning such as the substrate holder 5 and using the following into the evaporation source by selecting the evaporation material as indium, oil rotary pump and a booster pump to ^10-2 Torr Initial exhaust was performed. A diffusion pump was then used to evacuate to less than 10 ^-5 Torr. After the desired vacuum degree was obtained, glow discharge cleaning was performed by applying a voltage of about 500 V to the substrate in an argon gas atmosphere to remove impurities present in the substrate and to clean the substrate. After the substrate was cleaned and the vacuum degree again became 10 ⁻⁵ Torr or less, the temperature of the substrate was adjusted to 300 ° C. using the substrate heating apparatus 5. After the temperature of the substrate 4 is stabilized, oxygen gas is injected through the gas inlet 6 to adjust the oxygen pressure of the vacuum chamber 1 to 3 × 10 ^-4 Torr, and then flow a 300 mA current into the evaporation source 2. An oxide film was prepared on the glass substrate 4 by setting the evaporation rate to 1 Pa and opening the shutter 3. In the present Example, the thickness of the oxide film was manufactured at 746 kPa by Formula (I) to make red colored glass. After forming the oxide film, the color of the film was visually observed, and the characteristics and state of the film were measured using a scanning electron microscope and an OZ electron spectrometer, and the results are shown in Table 1 below.

Example 2

Except that the substrate temperature was 400 ℃ was carried out in the same manner as in Example 1, and the characteristics of the color and film in the same manner as in Example 1 to observe the characteristics shown in Table 1 below.

Example 3

The substrate temperature was set to 200 ° C. and the thickness of the oxide film was adjusted to 670 kPa, except that it was manufactured in the same manner as in Example 1, and the characteristics of the color and film were observed in the same manner as in Example 1 It described in 1.

Example 4

Oxygen gas pressure was adjusted to 1 × 10 ^-3 Torr and the thickness of the oxide film was adjusted to 552 kPa, which was carried out in the same manner as in Example 1, and the color and film characteristics were the same as in Example 1. It was observed and described in Table 1 below.

Example 5

Tin was used as the evaporation material, except that the evaporation rate was 3 kV / s, the oxygen gas pressure was 5 × 10 ^-4 Torr, and the thickness of the oxide film was adjusted to 963 kPa to produce purple color. In the same manner as in Example 1, the color and the properties of the coating were observed in Table 1 below.

Example 6

The same process as in Example 1 was carried out except that tin was used as the evaporation material and the thickness of the oxide film was adjusted to 1176 Å to produce green color. It described in 1. If it is.

Comparative Example 1

Except that the evaporation rate of 0.5 dl / s was carried out in the same manner as in Example 1, and the characteristics of the color and the film in the same manner as in Example 1 were described in Table 1 below.

Comparative Example 2

Except that the evaporation rate was 10 Å / s was carried out in the same manner as in Example 1, and the characteristics of the color and film in the same manner as in Example 1 to observe the characteristics shown in Table 1 below.

Comparative Example 3

Except that the substrate temperature was set to 100 ℃ was carried out in the same manner as in Example 1, and the characteristics of the color and the film in the same manner as in Example 1 are shown in Table 1 below.

Comparative Example 4

Oxygen gas pressure was carried out in the same manner as in Example 1, except that the pressure was 7 × 10 ^-3 Torr, and the characteristics of color and film were observed in the same manner as in Example 1, and are shown in Table 1 below.

Comparative Example 5

Except that the oxygen gas pressure was 5 × 10 ^-5 Torr was carried out in the same manner as in Example 1, in the same manner as in Example 1 to observe the characteristics of the color and film are shown in Table 1 below.

From the results in Table 1, the evaporation rate of the metal is 1-5 kPa per second, which is the evaporation rate range of the metal of the present invention, and the pressure of oxygen gas is 1 × 10, which is the pressure range of the oxygen gas of the present invention. 5 x 10 In case of Thor, a dense film having a uniform color was formed, but in other cases, a black film or a color was uneven.

According to the manufacturing method of the colored glass of the present invention, it is not necessary to prepare the metal oxide in the target shape in advance, which saves time, the process is simple, and can be easily used for the colored glass by producing a film having excellent coloring characteristics, and the effect of cost reduction There is.

Claims (2)

In the method of manufacturing colored glass that produces color using the characteristic of the oxide film, that is, the interference color, the colored film is manufactured by heating the glass substrate and injecting oxygen gas at the same time while evaporating the metal in a vacuum. Way. The method of claim 1, wherein the heating temperature of the glass substrate is 200 to 400 ℃, the evaporation rate of the metal is 1 to 5 kPa per second, the pressure of the oxygen gas is 1 × 10 ^{-4 to} 5 × 10 ^-3 Torr The manufacturing method of the colored glass characterized by the above-mentioned.