TWI755408B - Manufacturing method of glass plate with dielectric multilayer film and glass plate with film - Google Patents

Abstract

The present invention provides a method for producing a dielectric multilayer film-attached glass plate, which is less stained and capable of suppressing deterioration of optical properties, and a film-attached glass plate. The method for manufacturing a glass plate with a dielectric multilayer film according to the present invention is characterized by comprising the steps of: forming a dielectric multilayer film 3 on the glass plate 2; The step of manufacturing the glass plate 10 with the film by oxidizing the silicon oxide film 7, and the step of reducing the thickness of the silicon oxide film 7 by alkali cleaning.

Description

Manufacturing method of glass plate with dielectric multilayer film and glass plate with film

The present invention relates to a manufacturing method of a glass plate with a dielectric multilayer film and a glass plate with the film.

Heretofore, a glass plate with a dielectric multilayer film provided with a dielectric multilayer film on a glass plate has been used. The above-mentioned dielectric multilayer films are used as optical functional films such as antireflection films, infrared reflection films, bandpass filters, and mirror surfaces. For example, in the following Patent Document 1, a dielectric multilayer film in which high-refractive-index material layers such as tantalum oxide and titanium oxide and low-refractive-index material layers such as silicon oxide are alternately laminated is formed on a glass plate. In most cases, the outermost layer of the dielectric multilayer film is generally formed with a silicon oxide layer which also serves as a protective layer. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 7-209516

THE PROBLEM TO BE SOLVED BY THE INVENTION However, in some cases, alkaline cleaning is performed in order to remove the contamination on the film-forming surface of the glass plate on which the dielectric multilayer film is formed. If the alkaline cleaning is performed, the dirt will be removed, but the outermost silicon oxide layer will be dissolved by the alkaline solution, and the thickness of the outermost layer will be reduced, and the desired optical properties may not be obtained. An object of the present invention is to provide a method for producing a dielectric multilayer film-attached glass sheet and a film-attached glass sheet capable of suppressing the deterioration of optical properties with less contamination. [Technical Means for Solving the Problem] The method for producing a glass plate with a dielectric multilayer film of the present invention is characterized by comprising the steps of forming a dielectric multilayer film on the glass plate, and forming a thickness of the dielectric multilayer film on the glass plate. A step of manufacturing a glass plate with a film with a silicon oxide film below 30 nm, and a step of reducing the thickness of the silicon oxide film by alkali cleaning. In the step of manufacturing the glass plate with the film, it is preferable to form the silicon oxide film so that the thickness may be 1 nm or more. Preferably, the silicon oxide film is substantially completely removed by alkaline cleaning. Preferably, the outermost layer of the dielectric multilayer film contains tantalum oxide. Dielectric multilayer films and silicon oxide films can also be formed on the two main surfaces of the glass plate, respectively. The film-attached glass plate of the present invention is characterized by comprising a glass plate, a dielectric multilayer film provided on the glass plate, and a silicon oxide film with a thickness of 30 nm or less provided on the dielectric multilayer film. Preferably, the outermost layer of the dielectric multilayer film contains tantalum oxide. A dielectric multilayer film and a silicon oxide film can also be respectively provided on the two main surfaces of the glass plate. [Effects of the Invention] According to the present invention, there can be provided a method for producing a dielectric multilayer film-attached glass sheet and a film-attached glass sheet which can suppress the deterioration of optical properties with less contamination.

Hereinafter, preferred embodiments will be described. However, the following embodiments are merely examples, and the present invention is not limited to the following embodiments. In addition, in each drawing, the same code|symbol may be attached|subjected to the member which has substantially the same function, and it may be referred. FIG. 1 is a schematic cross-sectional view for explaining a method of manufacturing a glass plate with a dielectric multilayer film according to an embodiment of the present invention. In FIG. 1, the glass plate 10 with a film before the following alkali washing is shown. As shown in FIG. 1 , the film-attached glass plate 10 of this embodiment includes a glass plate 2 , a dielectric multilayer film 3 provided on the glass plate 2 , and a thickness 30 provided on the dielectric multilayer film 3 . Silicon oxide film 7 below nm. The glass plate 2 has the 1st main surface 2a and the 2nd main surface 2b which mutually oppose. In the present embodiment, the dielectric multilayer film 3 is provided on the first main surface 2 a of the glass plate 2 . As the glass constituting the glass plate 2 , for example, SiO ₂ -B ₂ O ₃ -RO (R is Mg, Ca, Sr, or Ba)-based glass, SiO ₂ -B ₂ O ₃ -R' ₂ O (R' is Li, Na or Ka) series glass, SiO ₂ -B ₂ O ₃ -RO-R' ₂ O series glass, SnO-P ₂ O ₅ series glass, TeO ₂ series glass or Bi ₂ O ₃ series glass and the like. Although it does not specifically limit as thickness of the glass plate 2, For example, it can be set as 0.1 mm - 1.1 mm. The dielectric multilayer film 3 is constituted by alternately laminating high-refractive-index layers and low-refractive-index layers. The high refractive index layer can be formed of, for example, niobium oxide, titanium oxide, tantalum oxide, lanthanum oxide, yttrium oxide, tungsten oxide, bismuth oxide, zirconium oxide, or the like. The low refractive index layer can be formed of, for example, silicon oxide or the like. The number of layers constituting the dielectric multilayer film 3 is not particularly limited. The number of layers constituting the dielectric multilayer film 3 is preferably 3 or more, and preferably 50 or less. The film thickness per layer of the high refractive index layer and the low refractive index layer is not particularly limited, but is preferably 1 nm or more, more preferably 1.5 nm or more, more preferably 180 nm or less, more preferably 150 nm or less . In the dielectric multilayer film 3 in this embodiment, the silicon oxide layer 4 is formed as the low refractive index layer, the niobium oxide layer 5 is formed as the first high refractive index layer, and the tantalum oxide layer 6 is formed as the second high refractive index layer. . Specifically, the silicon oxide layer 4 and the niobium oxide layer 5 are alternately formed on the glass plate 2 , and the tantalum oxide layer 6 is formed on the outermost layer. The dielectric multilayer film 3 in the present embodiment is formed as an antireflection film, and the number of layers constituting the dielectric multilayer film 3 is preferably 3 to 25 layers. A silicon oxide film 7 with a thickness of 30 nm or less is provided on the dielectric multilayer film 3 . At least a part of the silicon oxide film 7 is removed by the following alkali cleaning. By removing at least a part of the silicon oxide film 7, the dirt adhering to the silicon oxide film 7 can be removed. The thickness of the silicon oxide film 7 is preferably a thickness that does not adversely affect the optical properties of the dielectric multilayer film 3 when the silicon oxide film 7 remains in the alkali cleaning. From this viewpoint, in the present invention, the thickness of the silicon oxide film 7 is set to be 30 nm or less, preferably within the range of 1 to 20 nm, and more preferably within the range of 5 to 15 nm. If the thickness of the silicon oxide film 7 is too thin, there is a case where the dirt cannot be sufficiently removed by alkali cleaning. Hereinafter, the method of manufacturing the glass plate 1 with the dielectric multilayer film shown in FIG. 2 is demonstrated. First, the film-attached glass plate 10 shown in FIG. 1 is produced. As shown in FIG. 1 , a dielectric multilayer film 3 is formed on the glass plate 2 . The dielectric multilayer film 3 is formed by alternately laminating low-refractive-index layers and high-refractive-index layers. In this embodiment, silicon oxide layers 4 and niobium oxide layers 5 are alternately formed on the glass plate 2 , and a tantalum oxide layer 6 is formed on the silicon oxide layer 4 as the outermost layer. The formation method of each layer is not specifically limited, For example, it can be formed by a sputtering method. A silicon oxide film 7 with a thickness of 30 nm or less is formed on the dielectric multilayer film 3 , that is, on the tantalum oxide layer 6 . The method for forming the silicon oxide film 7 is not particularly limited, and for example, it can be formed by a sputtering method. The film-attached glass plate 10 can be produced in the manner described above. Next, alkali cleaning is performed on the glass plate 10 with a film. The cleaning solution used for the alkali cleaning is not particularly limited as long as it can remove the silicon oxide film 7 on the surface. Generally, a cleaning solution containing an aqueous sodium hydroxide solution as the main component is used. The concentration of sodium hydroxide can be preferably used, for example, in an amount of 1.0 to 5.0% by mass. In addition, in the case of alkali cleaning, the temperature of the cleaning solution is preferably about 40 to 80°C. By reducing the thickness of the silicon oxide film 7 by removing at least the surface of the silicon oxide film 7 by alkaline cleaning, the dirt adhering to the silicon oxide film 7 can be removed. The dielectric multilayer film-attached glass plate 1 shown in FIG. 2 can be produced in the manner described above. In this embodiment, the silicon oxide film 7 is substantially completely removed, and the tantalum oxide layer 6 under the silicon oxide film 7 is exposed. Furthermore, the so-called complete removal of the silicon oxide film 7 means that the thickness of the silicon oxide film 7 is less than 0.5 nm. The layer under the silicon oxide film 7 is preferably resistant to alkaline cleaning. The tantalum oxide layer 6 has excellent chemical resistance and is resistant to alkaline cleaning. Therefore, the tantalum oxide layer 6 can suppress the dissolution of the dielectric multilayer film 3 caused by alkali cleaning, and can thereby exhibit desired optical properties. In this embodiment, the silicon oxide film 7 is substantially completely removed, but it may not necessarily be substantially completely removed. The silicon oxide film 7 may remain after the alkali cleaning as long as it is a thickness that does not adversely affect the optical properties of the dielectric multilayer film 3, for example, 0.5 nm to 3 nm. Furthermore, the alkali cleaning time is preferably adjusted so as to end when the silicon oxide film 7 is substantially removed. When the alkali cleaning time is too long, the thickness of the outermost layer of the dielectric multilayer film 3 may become thinner. In the case where the dielectric multilayer film 3 is removed by alkaline washing, the thickness of the removed dielectric multilayer film 3 is preferably more than 0 nm and 3 nm or less. In this embodiment, the tantalum oxide layer 6 is formed only on the outermost high-refractive index layer of the dielectric multilayer film 3, but at least a part or all of the niobium oxide layer 5 may be replaced with the tantalum oxide layer 6 to form a dielectric layer. Electrical multilayer film 3 . In addition, the dielectric multilayer film 3 may be formed by replacing the tantalum oxide layer 6 as the outermost high refractive index layer with the niobium oxide layer 5 . Furthermore, at least one or more layers selected from the group consisting of titanium oxide, lanthanum oxide, yttrium oxide, tungsten oxide, bismuth oxide, zirconium oxide, and the like may be used as the high refractive index layer. In this embodiment, the dielectric multilayer film 3 is provided on the first main surface 2a, but may be provided on the second main surface 2b. That is, the dielectric multilayer film 3 may be provided only on one principal surface of the first principal surface 2a and the second principal surface 2b, or may be provided on both principal surfaces. Hereinafter, the present invention will be described in further detail based on specific examples. The present invention is not limited at all to the following examples, and can be implemented with appropriate modifications within the scope of not changing the gist of the present invention. (Example 1) The glass plate 10 with a film shown in FIG. 1 was produced. Specifically, silicon oxide layers 4 and niobium oxide layers 5 are alternately formed on the glass plate 2 , and a tantalum oxide layer 6 is formed on the silicon oxide layer 4 as the outermost layer. Regarding the number of layers of the dielectric multilayer film 3, five silicon oxide layers 4, four niobium oxide layers 5, and one tantalum oxide layer 6 are formed. A silicon oxide film 7 is formed on the tantalum oxide layer 6 . Each layer is formed by sputtering. The thickness of the silicon oxide film 7 was set to 10 nm. The size of the glass plate 2 is 28.3 mm×34.3 mm. The number of samples produced was 16. The produced glass plate 10 with the film is alkali-washed. A 3 mass % sodium hydroxide aqueous solution was used as a cleaning solution, and the temperature of the cleaning solution was set to 60°C. The silicon oxide film 7 is substantially completely removed by alkaline cleaning. The adhesion of dirt was observed with the naked eye on the dielectric multilayer film-attached glass plate 1 obtained by alkali-washing the film-attached glass plate 10 . As a result, 1 out of 16 stains adhered. Therefore, the generation ratio of fouling adhesion was 1/16. (Comparative Example 1) A film-attached glass plate 10 was produced in the same manner as in Example 1 except that the silicon oxide film 7 was not formed, and alkali cleaning was performed. The adhesion of dirt was observed in the same manner as in Example 1 with respect to the glass plate 1 with the dielectric multilayer film attached after the alkali cleaning. As a result, 11 out of 16 had dirt adhered. Therefore, the generation ratio of fouling adhesion was 11/16. According to the present invention, by forming a silicon oxide film with a thickness of 30 nm or less on the dielectric multilayer film, the silicon oxide film can be easily removed by alkaline cleaning. In addition, since the silicon oxide film does not affect the optical properties of the dielectric multilayer film, even if alkali cleaning is performed, the optical properties can be suppressed from deteriorating.

1‧‧‧Glass Plate with Dielectric Multilayer Film 2‧‧‧Glass Plate 2a‧‧First Main Surface 2b‧‧‧Second Main Surface 3‧‧‧Dielectric Multilayer Film 4‧‧‧Oxidation Silicon Layer 5‧‧‧Niobium Oxide Layer 6‧‧‧Tantalum Oxide Layer 7‧‧‧Silicon Oxide Film 10‧‧‧Glass Plate with Film

FIG. 1 is a schematic cross-sectional view for explaining a method for producing a glass plate with a dielectric multilayer film according to an embodiment of the present invention. 2 is a schematic cross-sectional view for explaining a method for producing a glass plate with a dielectric multilayer film according to an embodiment of the present invention.

2‧‧‧glass plate

2a‧‧‧First main face

2b‧‧‧Second main side

3‧‧‧Dielectric multilayer film

4‧‧‧Silicon oxide layer

5‧‧‧Niobium oxide layer

6‧‧‧Tantalum oxide layer

7‧‧‧Silicon oxide film

10‧‧‧Glass plate with film

Claims (5)

A method for manufacturing a glass plate with a dielectric multilayer film, comprising the steps of forming a dielectric multilayer film on the glass plate, and forming a silicon oxide film with a thickness of 30 nm or less on the above-mentioned dielectric multilayer film to manufacture a glass plate with a dielectric multilayer film. The step of forming a glass plate with a film, and the step of reducing the thickness of the above-mentioned silicon oxide film by alkali washing, wherein the outermost layer of the above-mentioned dielectric multilayer film includes tantalum oxide. The method of manufacturing a glass plate with a dielectric multilayer film according to claim 1, wherein in the step of manufacturing the glass plate with the film, the silicon oxide film is formed so as to have a thickness of 1 nm or more. The method for producing a glass plate with a dielectric multilayer film according to claim 1, wherein the silicon oxide film is substantially completely removed by the alkali cleaning. The method for producing a glass plate with a dielectric multilayer film according to claim 2, wherein the silicon oxide film is substantially completely removed by the alkali cleaning. The method for producing a glass plate with a dielectric multilayer film according to any one of claims 1 to 4, wherein the dielectric multilayer film and the silicon oxide film are respectively formed on both principal surfaces of the glass plate.

Images