TW201833635A - Glass substrate for display and method for manufacturing glass substrate for display provides a glass substrate for stripping the electrified display - Google Patents

Abstract

The invention provides a glass substrate for stripping the electrified display and a manufacturing method of the glass substrate. The invention discloses a glass substrate for a display. The glass substrate is characterized in the average fluorine concentration (mol%) of 0 to 10 nm formed on the surface of the glass, which is opposite to the surface of the semiconductor element forming surface of the glass substrate, is set to be F0 to 10 nm. When the average fluorine concentration of 100 to 400 nm formed from the surface of the glass is set as F100 to 400 nm, F0-10 nm/F100-400 nm ≥ 3, and the surface roughness Ra of the glass surface opposite to the surface of the semiconductor element forming surface is 0.3 nm or more.

Description

Glass substrate for display and manufacturing method of glass substrate for display

The present invention relates to a glass substrate for a display and a method for manufacturing a glass substrate for a display.

In a flat panel display (FPD), a substrate in which a transparent electrode, a semiconductor element, or the like is formed on a glass substrate is used. For example, in a liquid crystal display (LCD), a transparent electrode, a TFT (Thin Film Transistor), or the like is formed on a glass substrate as a substrate. The formation of transparent electrodes, semiconductor elements, and the like on a glass substrate is performed in a state where the glass surface of the glass substrate opposite to the semiconductor element formation surface is fixed on the adsorption table by vacuum adsorption. However, when a glass substrate on which a transparent electrode, a semiconductor element, or the like is formed is peeled off from an adsorption stage, the glass substrate is charged, and electrostatic destruction of a semiconductor element such as a TFT occurs. In order to suppress the occurrence of peeling and charging, the surface of the glass substrate connected to the side of the adsorption table is subjected to a surface roughening treatment to reduce the contact area between the glass substrate and the adsorption table. As a method of surface roughening treatment, for example, a method of chemically treating the surface of a glass substrate by an atmospheric piezoelectric slurry process is known (Patent Document 1). [Prior Art Literature] [Patent Literature] [Patent Literature 1] International Publication No. 2010/128673

[Problems to be Solved by the Invention] However, in the previous method, the difference between the work function of the glass substrate and the adsorption table was not taken into consideration, and thus the generation of peeling and charging was not sufficiently suppressed, which may cause electrostatic destruction of the semiconductor element. The present invention has been made in view of the above-mentioned problems, and provides a glass substrate for a display that is less prone to peeling and charging when peeled from a suction table, and a method for manufacturing the same. [Technical means to solve the problem] The present invention provides a glass substrate for a display, which is characterized in that a fluorine concentration (mol%) of 0 to 10 nm in depth is formed from a glass surface on the opposite side of the glass substrate from the semiconductor element formation surface. The average value is set to F _{0-10 nm} , and the average value of the fluorine concentration (mol%) at a depth of 100 to 400 nm from the glass surface is set to F _{100-400 nm} , F _{0-10 nm} / F _{100- 400 nm} ≧ 3, and the surface roughness Ra of the glass surface on the opposite side of the semiconductor element formation surface is 0.3 nm or more. In addition, the present invention provides a method for manufacturing a glass substrate for a display, which is characterized by having a procedure for supplying a gas containing hydrogen fluoride (HF) to one surface of a sheet glass to be transported in a heat treatment device, and one surface of the above sheet glass. The glass surface on the opposite side of the semiconductor element formation surface of the glass substrate, the HF concentration of the HF-containing gas is 0.5 to 30 vol%, and the glass surface temperature when the HF-containing gas is supplied is 500 to 900 ° C. [Effects of the Invention] When the glass substrate for a display of the present invention is peeled off from an adsorption stage, it is unlikely to be charged with peeling.

[Glass substrate for display] Hereinafter, a glass substrate for a display according to an embodiment of the present invention will be described. As for the glass substrate for a display of this embodiment, the glass composition is not particularly limited, and may be a wide range of glass compositions such as soda lime silicate glass, aluminosilicate glass, borosilicate glass, and alkali-free glass. Generally speaking, with regard to contact charging, it is easy to occur if the difference in work function between substances is large. The so-called work function refers to the minimum amount of energy required to take out the electrons inside the solid to the outside, which is exactly the amount of energy required to take out into the vacuum. Charges are generated by the migration of a substance with a smaller electron self-work function to a larger substance. The glass substrate is charged due to the difference in work function between the glass substrate and the adsorption table. Therefore, in order to reduce the charge amount of the glass substrate, the inventors of the present application paid attention to the work function of the glass substrate. However, a method for measuring the work function of a glass substrate has not been established. Through intensive research, the inventors of the present application found that the difference between the fluorine atom concentration near and inside the glass substrate is related to the difference between the work functions of the glass substrate and the adsorption table. That is, by increasing the concentration of fluorine atoms having a high anion conductivity near the surface of the glass substrate, the energy level changes, and the work function of the glass substrate is changed. It is generally believed that the charge of a glass substrate depends on the difference between the work function of the glass substrate and the adsorption table (contact charging characteristics of high-resistance insulating glass, Hiroshi Kitabayashi, Zhiji Fujii, Electricity Theory A, Vol. 2, No. 2, 179-184, 2005 This difference is narrowed by allowing fluorine atoms to penetrate into the vicinity of the surface of the glass substrate. Regarding the glass substrate for a display of this embodiment, the average value of the fluorine concentration (mol%) at a depth of 0 to 10 nm from the glass surface of the glass substrate on the side opposite to the semiconductor element formation surface is set to F _{0-10 nm} , When the average value of the fluorine concentration (mol%) at a depth of 100 to 400 nm from the glass surface is set to F _{100-400 nm} , F _{0-10 nm} / F _{100-400 nm} ≧ 3. Thereby, the difference between the work function of the glass substrate and the adsorption stage becomes small, and peeling and charging of the glass substrate can be suppressed. Here, the reason why the fluorine concentration near the surface of the glass substrate is set to the above-mentioned F _{0-10 nm} , and the fluorine concentration inside the glass substrate is set to the above-mentioned F _{100-400 nm} is as follows. The contact-charged electron migration mainly occurs in a region with a depth of 0 to 10 nm from the surface of the glass substrate, and is controlled by the interaction between this region and a region with a depth of 100 to 400 nm. The F _{0-10 nm} and F _{100-400 nm} are measured by X-ray photoelectron spectroscopy (XPS). The glass substrate for a display of this embodiment is preferably F _{0-10 nm} / F _{100-400 nm} ≧ 5, and more preferably F _{0-10 nm} / F _{100-400 nm} ≧ 10. If the difference in fluorine atom concentration between the vicinity of the surface of the glass substrate and the inside of the glass substrate is too large, the haze will be deteriorated, which is unfavorable. F _{0-10 nm} / F _{100-400 nm} ≦ 150 can suppress the deterioration of haze, so it is better, more preferably F _{0-10 nm} / F _{100-400 nm} ≦ 100. In addition, the greater the surface roughness of the glass surface, the smaller the contact area between the glass substrate and the adsorption stage, and the less likely it is to cause the migration of electrons, so the peeling and charging of the glass substrate can be suppressed (contact charging characteristics of high-resistance insulating glass, Beilin Hongjia, Zhikui Fujii, Electrics A, Vol. 125, No. 2, 179-184, 2005). Regarding the glass substrate for a display of this embodiment, the surface roughness Ra of the glass surface of the glass substrate on the side opposite to the semiconductor element formation surface is 0.3 nm or more. Thereby, the difference between the work function of the glass substrate and the adsorption stage becomes small, and peeling and charging of the glass substrate can be suppressed. The surface roughness Ra is measured using an atomic force microscope (AFM). The surface roughness Ra is preferably 0.7 nm or more. However, if the surface roughness Ra is too large, a large defect may be generated on the glass surface, which may cause a reduction in the strength of the glass substrate. In the case where the surface roughness Ra is 5 nm or less, no large defects are generated on the glass surface, and there is no risk of reducing the strength of the glass substrate, so it is preferable. The surface roughness Ra is more preferably 2 nm or less. As for the glass substrate for a display of this embodiment, it is preferable that the peeling charge amount measured by the procedure described in the following examples is -10 kV or more. This prevents electrostatic damage to the semiconductor element formed on the glass substrate for a display. The peeling charge amount is more preferably -7 kV or more, and even more preferably -5 kV or more. If the irradiation light energy obtained by the photoelectron yield spectroscopy (PYS) measurement and the square root of the photoelectron emission quantity are plotted, the square root of the photoelectron emission quantity at the time point when the irradiation light energy reaches a certain value is urgent. increase. The energy of the irradiated light which becomes the threshold at this time is a work function. If the irradiation energy is further increased, the square root of the number of photoelectron emission will increase linearly. Through intensive research, the inventors of the present application found that there is a correlation between the slope of the linear increase and the peeling charge of the glass substrate. Regarding the glass substrate for a display of this embodiment, it is preferable that the irradiation light energy obtained by the photoelectron yield spectrum analysis (PYS) measurement is set to X (eV), and the square root of the number of photoelectron emission is set to Y At this time, the slope ΔY / ΔX of Y when X is 5.5 to 6.0 eV is 10 or more. The work function of the glass substrate is less than 5.5 eV. A region where X is 5.5 to 6.0 eV is a region where Y linearly increases. The slope ΔY / ΔX approximately represents the state density of the electrons at 5.5 to 6.0 eV. It is considered that the larger the slope ΔY / ΔX, the more difficult it becomes for the glass substrate to receive electrons, and the less likely it is to be charged. The glass substrate for a display of this embodiment is more preferably ΔY / ΔX ≧ 20, and more preferably ΔY / ΔX ≧ 50. The size of the glass substrate for a display of this embodiment is not particularly limited, and large glass substrates are suitable because they suppress the peeling and charging of the glass substrate. Specifically, it is preferably 2500 mm × 2200 mm or more, and more preferably 3130 mm × 2880 mm or more. The thickness of the plate is also not particularly limited, and a thin glass substrate is suitable because it can suppress the peeling and charging of the glass substrate. Specifically, it is preferably 1.0 mm or less, more preferably 0.75 mm or less, and still more preferably 0.45 mm or less. The glass substrate for a display of this embodiment is preferably an alkali-free glass. The alkali-free glass is preferably expressed in terms of mass percentages based on the following oxides and contains 50 to 73% of SiO ₂ , 10.5 to 24% of Al ₂ O ₃ , 0.1 to 12% of B ₂ O ₃ , and 0 to 8%. MgO, 0 to 14.5% CaO, 0 to 24% SrO, 0 to 13.5% BaO, 0 to 5% ZrO ₂ , and the total amount of MgO, CaO, SrO, and BaO (MgO + CaO + SrO + BaO) is 8 to 29.5% . The alkali-free glass is preferably expressed in terms of mass percentages based on the following oxides and contains 58 to 66% of SiO ₂ , 15 to 22% of Al ₂ O ₃ , and 5 to 12% of B ₂ O ₃ , 0 to 8 % Of MgO, 0 to 9% of CaO, 3 to 12.5% of SrO, 0 to 2% of BaO, and the total amount of MgO, CaO, SrO, and BaO (MgO + CaO + SrO + BaO) is 9 to 18%. The alkali-free glass is preferably expressed in terms of mass percentages of the following oxide standards and contains 54 to 73% of SiO ₂ , 10.5 to 22.5% of Al ₂ O ₃ , 0.1 to 5.5% of B ₂ O ₃ , and 0 to 8 % MgO, 0-9% CaO, 0-16% SrO, 0-2.5% BaO, and the total amount of MgO, CaO, SrO, and BaO (MgO + CaO + SrO + BaO) is 8-26%. [Manufacturing method of glass substrate for display] Next, a configuration example of a manufacturing method of the glass substrate for display of the present invention will be described. FIG. 1 is an explanatory diagram of a method for manufacturing a glass substrate for a display according to an embodiment of the present invention, and is a schematic diagram showing a configuration example of a heat treatment apparatus. In the heat treatment apparatus 60 shown in FIG. 1, the plate glass 20 is carried in the direction of the arrow. The transport mechanism is not particularly limited, and it is, for example, a transport roller (not shown). The heat treatment apparatus 60 and the heat treatment apparatus 62 described below include heaters (not shown). Here, the lower surface 22 of the plate glass 20 is a semiconductor element formation surface in a glass substrate for a display, and the upper surface 24 of the plate glass 20 is a glass surface on the opposite side of the semiconductor element formation surface. As described above, when forming a semiconductor element It is fixed on the adsorption table by vacuum adsorption. The heat treatment apparatus 60 shown in FIG. 1 has an injector 70. The gas blown from the supply port 71 of the injector 70 to the upper surface 24 of the plate glass 20 moves in the flow path 74 which is a forward direction or a reverse direction with respect to the moving direction of the plate glass 20 and flows out to the exhaust port 75. The injector 70 shown in FIG. 1 is a dual-flow type injector in which the flow direction of the gas from the supply port 71 to the exhaust port 75 is equally divided into a forward direction and a reverse direction with respect to the moving direction of the plate glass 20. FIG. 2 is a schematic diagram showing another configuration example of the heat treatment apparatus. The heat treatment apparatus 62 shown in FIG. 2 has an injector 80. The injector 80 is a single-flow type injector. The single-flow type injector refers to an injector in which the flow direction of the gas from the supply port 81 to the exhaust port 85 is fixed to be either the forward direction or the reverse direction with respect to the moving direction of the plate glass 20. The flow direction 84 of the injector 80 shown in FIG. 2 from the supply port 81 to the exhaust port 85 of the gas is positive with respect to the moving direction of the plate glass 20. However, the flow direction of the gas from the supply port 81 to the exhaust port 85 may be opposite to the moving direction of the plate glass 20. In the method for manufacturing a glass substrate for a display of the present invention, a gas containing hydrogen fluoride (HF) is supplied to the upper surface 24 of the plate glass 20 from the supply ports 71 and 81 of the injectors 70 and 80. Thereby, the fluorine concentration near the glass surface on the opposite side of the semiconductor element formation surface becomes higher than the fluorine concentration inside the glass substrate, the difference in work function between the glass substrate and the adsorption table becomes smaller, and peeling and charging of the glass substrate can be suppressed . In the method for manufacturing a glass substrate for a display of the present invention, the glass surface temperature when the gas containing HF is supplied, that is, the temperature of the upper surface 24 of the plate glass 20 is set to 500 to 900 ° C. By setting the glass surface temperature to 500 ° C or higher, the following effects are exhibited. The fluorine invades near the glass surface, and the fluorine concentration near the glass surface becomes higher than the fluorine concentration inside the glass substrate. The glass surface temperature is more preferably 550 ° C or higher, and even more preferably 600 ° C or higher. In addition, by setting the glass surface temperature to 900 ° C or lower, the following effects are exhibited. The surface roughness Ra of the glass surface is suppressed from becoming too large, and a uniform surface shape is formed. The glass surface temperature is more preferably 850 ° C or lower, and even more preferably 800 ° C or lower. In the method for manufacturing a glass substrate for a display of the present invention, an inert gas such as nitrogen (N ₂ ) or a rare gas is used for the gas containing HF from the viewpoint of preventing the corrosion of the heat treatment devices 60, 62, and the injectors 70 and 80. The gas is used as a carrier gas and is supplied to the upper surface 24 of the plate glass 20 in the form of a mixed gas with the carrier gas. The HF concentration of the HF-containing gas supplied from the supply ports 71 and 81 of the injectors 70 and 80 is set to 0.5 to 30 vol%. By setting the HF concentration to 0.5 vol% or more, the following effects are exhibited. The fluorine invades near the glass surface, and the fluorine concentration near the glass surface becomes higher than the fluorine concentration inside the glass substrate. The HF concentration is more preferably 2 vol% or more, and even more preferably 4 vol% or more. In addition, by setting the HF concentration to 30 vol% or less, the following effects are exhibited. It is possible to suppress the occurrence of defects on the glass surface due to the reaction between the glass surface and HF, and to suppress the decrease in the strength of the glass substrate. The HF concentration is more preferably 26 vol% or less, and still more preferably 22 vol% or less. The distance D between the supply ports 71 and 81 of the injectors 70 and 80 and the upper surface 24 of the plate glass 20 is preferably 5 to 50 mm. The distance D is more preferably 8 mm or more. The distance D is more preferably 30 mm or less, and further preferably 20 mm or less. By setting the distance D to 5 mm or more, even if the plate glass 20 is vibrated due to, for example, an earthquake, contact between the upper surface 24 of the plate glass 20 and the injectors 70 and 80 can be avoided. On the other hand, by setting the distance D to 50 mm or less, it is possible to suppress the gas from diffusing inside the device, and allow a sufficient amount of gas to reach the upper surface 24 of the plate glass 20 for the required amount of gas. The distance L in the moving direction of the plate glass 20 of the injectors 70 and 80 is preferably 100 to 500 mm. The distance L is more preferably 150 mm or more, and further preferably 200 mm or more. The distance L is more preferably 450 mm or less, and further preferably 400 mm or less. By setting the distance L to 100 mm or more, the supply ports 71 and 81 and the exhaust ports 75 and 85 can be provided. Particularly preferably, the distance L of the injector 70 is 150 mm or more, and the distance L of the injector 80 is 100 mm or more. On the other hand, by setting the distance L to 500 mm or less, the heat loss of the plate glass 20 caused by the injectors 70 and 80 can be suppressed, and the output of a plurality of heaters can be suppressed. The distance in the width direction of the plate glass 20 of the injectors 70 and 80 is preferably the distance above the product area having the plate glass 20 in that direction. When the manufacturing method of the glass substrate for a display of the present invention is implemented online, the distance is preferably 3000 mm or more, and more preferably 4000 mm or more. The flow velocity (linear velocity) of the HF-containing gas is preferably 20 to 300 cm / s. By setting the flow velocity (linear velocity) to 20 cm / s or more, the gas flow of the gas containing HF is stable, and the glass surface can be treated uniformly. The flow velocity (linear velocity) is more preferably 50 cm / s or more, and still more preferably 80 cm / s or more. When the method for manufacturing a glass substrate for a display of the present invention is implemented on-line as described below, by setting the flow velocity (linear velocity) to 300 cm / s or less, it is possible to suppress the presence of gas in the slow cooling device. In a diffused state, a sufficient amount of gas reaches the top surface of the glass ribbon. The flow velocity (linear velocity) is more preferably 250 cm / s or less, and still more preferably 200 cm / s or less. The manufacturing method of the glass substrate for a display of the present invention can be implemented on-line or off-line. The "on-line processing" in this specification refers to a case where the method of the present invention is applied in a slow cooling process of slow cooling a glass ribbon formed by a float method or a down-draw method. On the other hand, the "off-line treatment" refers to a case where the method of the present invention is applied to a sheet glass that is formed and cut to a desired size. Therefore, the sheet glass in this specification includes not only sheet glass that is formed and cut to a desired size, but also glass ribbons formed by a float method or a down-draw method. The method for manufacturing a glass substrate for a display of the present invention is preferably implemented on-line for the following reasons. In the case of offline processing, additional steps are required, while in the case of online processing, no additional steps are required, so processing can be performed at low cost. In addition, in the case of off-line processing, a gas containing HF is wound between the glass substrates to the semiconductor element formation surface of the glass substrate. In contrast, in the case of on-line processing of a glass ribbon, the swirling of the gas containing HF can be suppressed. For example, the manufacturing process of plate glass for display glass substrates has the following steps: a melting step, which fuses glass raw materials to make molten glass; a forming step, which shapes the molten glass obtained in the above melting step into a ribbon shape A glass ribbon is made; and a slow cooling step, which is a slow cooling of the glass ribbon obtained in the above-mentioned forming step. Examples of the forming step include a float forming step performed by a float method and a down forming step performed by a down method. When the manufacturing method of the glass substrate for a display of this invention is implemented online, in the said slow cooling process, the top surface of a glass ribbon is supplied with the gas containing HF. FIG. 3 is an explanatory view of a method for manufacturing a glass substrate for a display according to an embodiment of the present invention, and is a schematic cross-sectional view showing a float glass manufacturing apparatus. The float glass manufacturing apparatus 100 shown in FIG. 3 includes a melting device 200 that melts glass raw material 10 to produce molten glass 12 and a molding device 300 that shapes molten glass 12 supplied from the melting device 200 into The ribbon is formed into a glass ribbon 14; and a slow cooling device 400 for slow cooling the glass ribbon 14 formed in the molding device 300. The melting device 200 includes a melting tank 210 that contains the molten glass 12 and a burner 220 that forms a flame above the molten glass 12 that is contained in the melting tank 210. The glass raw material 10 put into the melting tank 210 is slowly melted into the molten glass 12 by the radiant heat from the flame formed by the burner 220. The molten glass 12 is continuously supplied from the melting tank 210 to the forming apparatus 300. The molding apparatus 300 includes a bath 320 that accommodates molten tin 310. The molding apparatus 300 forms the glass ribbon 14 by flowing the molten glass 12 continuously supplied onto the molten tin 310 into a band shape by flowing on the molten tin 310 in a specific direction. The ambient temperature in the forming apparatus 300 becomes gradually lower from the inlet to the outlet of the forming apparatus 300. The ambient temperature in the molding apparatus 300 is adjusted by a heater (not shown) or the like provided in the molding apparatus 300. The glass ribbon 14 is cooled while flowing in a specific direction, and is pulled up from the molten tin 310 in a region downstream of the bath 320. The glass ribbon 14 pulled up from the molten tin 310 is transferred to the slow cooling device 400 by a lift roller 510. The slow cooling device 400 slow-cools the glass ribbon 14 formed in the forming device 300. The slow cooling device 400 includes, for example, a slow cooling furnace (Lehr) 410 with a heat insulation structure, and a plurality of conveying rollers 420, which are arranged in the slow cooling furnace 410 and convey the glass ribbon 14 in a specific direction. The ambient temperature in the slow cooling furnace 410 gradually decreases from the inlet to the outlet of the slow cooling furnace 410. The ambient temperature in the slow cooling furnace 410 is adjusted using a heater 440 or the like provided in the slow cooling furnace 410. The glass ribbon 14 carried out from the exit of the slow cooling furnace 410 is cut to a specific size by a cutter and shipped as a product. Before shipment as a product, at least one of the two surfaces of the glass substrate may be polished and the glass substrate may be cleaned as necessary. Furthermore, when the manufacturing method of the glass substrate for a display of the present invention is implemented online, the glass surface of the glass substrate opposite to the semiconductor element formation surface corresponds to the top surface of the glass ribbon 14, and the semiconductor element formation surface corresponds to the glass ribbon. Underside of 14. In the method for manufacturing a glass substrate for a display of the present invention, by making the fluorine concentration near the glass surface on the opposite side of the semiconductor element formation surface higher than the fluorine concentration inside the glass substrate, the function of the glass substrate and the adsorption stage is improved. The difference in the functions becomes smaller, and the peeling and charging of the glass substrate is suppressed. Therefore, when polishing is performed, it is preferable to polish only the bottom surface of the glass ribbon 14. The semiconductor element formation surface of the glass substrate was polished with a polishing tool while supplying a cerium oxide aqueous solution. During grinding, a part of the cerium oxide aqueous solution was spirally wound onto the glass surface of the glass substrate on the side opposite to the semiconductor element formation surface, and became a slurry residue. The glass substrate is cleaned, for example, by shower cleaning, slurry cleaning using a disc brush, and rinsing. Slurry cleaning is performed by supplying a slurry (e.g., cerium oxide aqueous solution, calcium carbonate aqueous solution) on the glass surface of the glass substrate on the side opposite to the surface on which the semiconductor element is formed, and grinding with a disc brush to remove residues remaining on the semiconductor element Sludge residue on the glass surface on the opposite side. Since the float glass manufacturing apparatus 100 shown in FIG. 3 implements the manufacturing method of the glass substrate for a display of the present invention on-line, injectors 70 and 80 are provided above the glass ribbon 14 in the slow cooling apparatus 400 and used. The injectors 70 and 80 supply a gas containing hydrogen fluoride (HF) to the top surface of the glass ribbon 14. In addition, when the heat treatment apparatuses 60 and 62 shown in FIGS. 1 and 2 implement the manufacturing method of the glass substrate for a display of this invention on line, it corresponds to the slow cooling apparatus 400 shown in FIG. In FIG. 3, the injectors 70 and 80 are installed in the slow cooling device 400. However, regarding the float glass manufacturing device according to another embodiment of the present invention, the glass surface temperature when a gas containing HF is supplied When the temperature is 500 to 900 ° C, the injector may be installed in the molding apparatus 300. [Examples] Examples and comparative examples of the present invention will be specifically described below. The present invention is not limited to these descriptions. (Experimental Example 1) In Experimental Example 1, the manufacturing method of the glass substrate for a display of the present invention was carried out offline. In Experimental Example 1, the following alkali-free glass plate (520 mm × 410 mm × thickness 0.5 mm) was prepared, which contained SiO ₂ : 59.5%, Al ₂ O ₃ : 17%, B ₂ O ₃ : 8%, and MgO: 3.3%, CaO: 4%, SrO: 7.6%, BaO: 0.1%, ZrO ₂ : 0.1%, and MgO + CaO + SrO + BaO: 15%, the remaining amount is unavoidable impurities, and the total content of alkali metal oxides is 0.1% the following. A gas containing HF is supplied from the injector 70 of the heat treatment apparatus shown in FIG. 1 to the upper surface of the alkali-free glass plate. FIG. 4 is a diagram showing the relationship between the slit width (a), the processing length (b), and the processing width (c) of the injector in Experimental Example 1. FIG. In Experimental Example 1, the a (mm), b (mm), c (mm), and the flow rate (L / min), processing time (sec), and linear velocity (mm / sec) of the gas containing HF are set. The conditions are shown in Table 1 below. The distance D between the supply port 71 of the injector 70 and the upper surface of the plate glass 20 is set to 10 mm. The glass surface temperature (referred to as the temperature in Table 2) and the HF concentration (vol%) when the gas containing HF was supplied were set to the conditions shown in Table 2 below. In Table 2, Examples 1 and 2 are comparative examples, and Examples 3 and 4 are examples. After supplying the gas containing HF, the glass surface temperature was kept at the same temperature for 5 minutes, and then cooled to normal temperature in 30 minutes. Then, the evaluation shown below was performed. [F concentration (F _{0-10 nm} , F _{100-400 nm} ) near and inside the glass substrate] The F _{0-10 nm} and F _{100-400 nm were} measured according to the following procedure. The glass substrate obtained by the above procedure was cut into a width of 10 mm × length of 10 mm, and an X-ray photoelectron spectroscopy device (manufactured by ULVAC-PHI Corporation, ESCA5500) was used to measure the depths of 0, 2, 5, and 5 from the glass surface of the glass substrate. 7. F concentration (mol%) at 10 nm. The measured values of the F concentration at the depths of 0, 2, 5, 7, and 10 nm were averaged to calculate the average value of the F concentration at the depth of 0 to 10 nm, F 0 to 10 _nm . The grinding from the surface of the glass substrate to a depth of 10 nm is performed by sputtering etching using a C ₆₀ ion beam. The X-ray photoelectron spectroscopy device (manufactured by ULVAC-PHI, ESCA5500) was used to measure the depth from the glass surface of the glass substrate to 100, 101, 112, 123, 134, 145, 156, 167, 178, 189, 200, 211, F concentration (mol%) of 222, 266, 310, 354, 398, 400 nm. The measured values of the F concentration at a depth of 100 to 400 nm are averaged, and the average value of the F concentration at a depth of 100 to 400 nm is calculated as F _{100 to 400 nm} . The relationship between the depth from the surface of the glass plate and the fluorine concentration in the glass plate in Example 4 is shown in FIG. 5. [Average surface roughness Ra of glass surface] The glass substrate obtained by the above procedure was cut into a width of 5 mm × length 5 mm, and the average surface roughness Ra (arithmetic average surface) of the glass surface of the glass substrate was measured by the following method. Roughness Ra (JIS B0601-2013)). The glass surface of the glass substrate was observed using an atomic force microscope (product name: SPI-3800N, manufactured by Seiko Instruments). The cantilever system uses SI-DF40P2. The observation system uses dynamic force mode to scan 5 μm × 5 μm in the scanning area at a scanning rate of 1 Hz (the number of data in the area: 256 × 256). Based on this observation, the average surface roughness Ra of each measurement point is calculated. The calculation software system uses software (software name: SPA-400) attached to the atomic force microscope. [Peeling Charge of Glass Substrate] The peeling charge of the glass substrate obtained by the above procedure was measured by the following method. After the glass substrate having a width of 410 mm × a length of 520 mm × a thickness of 0.5 mm was brought into contact with a vacuum adsorption table made of SUS304, the adsorption and release of the glass substrate was repeated for 110 cycles. Thereafter, the glass substrate was peeled from the vacuum adsorption stage using a jack pin. A surface potentiometer (product name: MODEL 341B, manufactured by TREK JAPAN) was used to measure the change in the surface potential of the glass substrate up to 5 cm from the vacuum adsorption stage. The peak value of the measurement result was set as the peeling charge amount. [PYS measurement (ΔY / ΔX)] In Example 4, the photoelectron yield spectroscopy (PYS) measurement was performed by the following procedure, and the slope (ΔY / ΔX). Prepare a glass substrate with a width of 20 mm × length of 20 mm × thickness of 0.5 mm. The ultraviolet irradiation surface is a glass surface on the glass substrate, which is opposite to the semiconductor element formation surface. The photoelectron emission amount on the irradiation surface was measured using an atmospheric photoelectron spectrometer AC-5 (manufactured by Riken Keiki Co., Ltd.). The irradiation ultraviolet intensity was set to 2000 nW. The ultraviolet rays are irradiated in units of 0.1 eV within a range of irradiation light energy X of 4.2 to 6.2 eV. The optoelectronic counting time is set to 5 seconds per 0.1 eV. A graph showing the relationship between the irradiation light energy X and the square root Y of the number of photoelectron emission in Example 4 is shown in FIG. 6 (a). FIG. 6 (b) is an enlarged view of FIG. 6 (a) when the irradiation light energy X is 5.5 to 6.0 eV. The slope ΔY / ΔX is calculated by linearly approximating the tracing plot when X is 5.5 to 6.0 eV by the least square method. (Experimental Example 2) In Experimental Example 2, the manufacturing method of the glass substrate for a display of the present invention was implemented on-line. In Experimental Example 2, a float glass glass manufacturing apparatus 100 shown in FIG. 3 was used to manufacture an alkali-free glass plate having a thickness of 0.5 mm and containing SiO ₂ : 59.5%, Al ₂ O ₃ : 17%, and B ₂ O. ₃ : 8%, MgO: 3.3%, CaO: 4%, SrO: 7.6%, BaO: 0.1%, ZrO ₂ : 0.1%, and MgO + CaO + SrO + BaO: 15%. The remaining amount is an inevitable impurity, which is an alkali metal oxide. The total content is 0.1% or less. After the glass raw material 10 is melted using the melting device 200 to prepare a molten glass 12, the molten glass 12 is supplied to a molding device 300, and the molten glass 12 is shaped into a ribbon shape to obtain a glass ribbon 14. After the glass ribbon 14 is withdrawn from the exit of the forming apparatus 300, it is slowly cooled in the slow cooling apparatus 400. In a position where the temperature of the glass ribbon 14 in the slow cooling device 400 is 500 ° C., an injector 70 having a distance L in the moving direction of the glass ribbon 14 of 300 mm is set. FIG. 4 is a diagram showing the relationship between the slit width (a), the processing length (b), and the processing width (c) of the injector in Experimental Example 2. FIG. In Experimental Example 2, the a (mm), b (mm), c (mm), and the flow rate (L / min), processing time (sec), and linear velocity (mm / sec) of the gas containing HF are set. The conditions are shown in Table 1 below. The distance D between the supply port 71 of the injector 70 and the upper surface of the plate glass 20 is set to 10 mm. The glass surface temperature (referred to as the temperature in Table 3) and the HF concentration (vol%) when the gas containing HF was supplied were set to the conditions shown in Table 3 below. In Table 3, Example 11 is a comparative example, and Examples 12 and 13 are examples. The obtained glass plate was evaluated by the same procedure as in Experimental Example 1. The relationship between the depth from the surface of the glass plate and the fluorine concentration in the glass plate in Example 11 is shown in FIG. 5. The graphs showing the relationship between the irradiation light energy X and the square root Y of the number of photoelectron emission in Examples 11 and 13 are shown in Figs. 6 (a) and 6 (b). [Table 1] [Table 2] [table 3] In Examples 1, 2, and 11 where F _{0-10 nm} / F _{100-400 nm} <3 or Ra less than 0.3 nm, the peeling charge did not reach -10 kV. In contrast, in Examples 3, 4, 12, and 13 in which F _{0-10 nm} / F _{100-400 nm} ≧ 3 and Ra was 0.3 nm or more, the peeling charge was suppressed to be -10 kV or more. In addition, in Example 11, ΔY / ΔX <10, whereas in Examples 4, 12 and 13, ΔY / ΔX ≧ 10. In the above, the present invention has been described in detail with reference to specific embodiments. However, it is apparent to practitioners that various changes or modifications can be made without departing from the spirit and scope of the present invention. This application is based on Japanese Patent Application No. 2017-029636 filed on February 21, 2017, and the contents are incorporated herein by reference.

10‧‧‧Glass Raw Materials

12‧‧‧ molten glass

14‧‧‧glass ribbon

20‧‧‧ plate glass

22‧‧‧ lower surface

24‧‧‧ Top surface

60, 62‧‧‧ heat treatment equipment

70, 80‧‧‧ injector

71, 81‧‧‧ supply port

74, 84‧‧‧ stream

75, 85‧‧‧ exhaust port

100‧‧‧ float glass manufacturing equipment

200‧‧‧ melting device

210‧‧‧ melting tank

220‧‧‧ burner

300‧‧‧forming device

310‧‧‧ Molten Tin

320‧‧‧ bath

400‧‧‧ Slow cooling device

410‧‧‧ Slow cooling furnace

420‧‧‧ transporting roller

440‧‧‧heater

510‧‧‧Lifting roller

D‧‧‧distance

L‧‧‧ Distance

FIG. 1 is an explanatory diagram of a method for manufacturing a glass substrate for a display according to an embodiment of the present invention, and is a schematic diagram showing a configuration example of a heat treatment apparatus. FIG. 2 is an explanatory diagram of a method for manufacturing a glass substrate for a display according to an embodiment of the present invention, and is a schematic diagram showing another configuration example of a heat treatment apparatus. 3 is an explanatory diagram of a method for manufacturing a glass substrate for a display according to an embodiment of the present invention, and is a schematic cross-sectional view showing a float glass manufacturing apparatus. FIG. 4 is a diagram showing the relationship between the slit width (a), the processing length (b), and the processing width (c) of the injector in the embodiment. Fig. 5 is a graph showing the relationship between the depth from the surface of the glass plate and the fluorine concentration in the glass plate in Examples (Examples 4 and 11). FIG. 6 (a) is a graph showing the relationship between the irradiated light energy X and the square root Y of the number of photoelectron emission in the example. FIG. 6 (b) is an enlarged view of FIG. 6 (a) when the irradiation light energy X is 5.5 to 6.0 eV.

Claims (6)

A glass substrate for a display, characterized in that an average value of a fluorine concentration (mol%) at a depth of 0 to 10 nm from a glass surface on a side of the glass substrate opposite to a surface on which a semiconductor element is formed is set to F _{0-10 nm} , When the average value of the fluorine concentration (mol%) at a depth of 100 to 400 nm from the glass surface is set to F _{100-400 nm} , F _{0-10 nm} / F _{100-400 nm} ≧ 3, and the same as the above semiconductor device The surface roughness Ra of the glass surface on the opposite side of the formation surface is 0.3 nm or more. For example, the glass substrate for display of claim 1 has a peeling charge of -10 kV or more. For example, the glass substrate for a display according to claim 1 or 2, wherein the irradiation light energy obtained by the photoelectron yield spectroscopy (PYS) measurement is set to X (eV), and the square root of the number of photoelectron emission is set to Y In this case, the slope ΔY / ΔX of the Y when the X is 5.5 to 6.0 eV is 10 or more. A manufacturing method of a glass substrate for a display is characterized in that it has a procedure for supplying a gas containing hydrogen fluoride (HF) to one surface of a sheet glass to be transported in a heat treatment device, and one surface of the sheet glass is a glass substrate The glass surface on the opposite side of the semiconductor element formation surface has a HF concentration of the HF-containing gas of 0.5 to 30 vol%, and a glass surface temperature when the HF-containing gas is supplied is 500 to 900 ° C. The method for manufacturing a glass substrate for a display according to claim 4, comprising: a melting step of melting glass raw materials to produce molten glass; and a forming step of forming the molten glass obtained in the above melting step into a ribbon To form a glass ribbon; and a slow cooling step, which is to slowly cool the glass ribbon obtained in the forming step; and to supply a gas containing HF to the top surface of the glass ribbon in the slow cooling step. The method for manufacturing a glass substrate for a display according to claim 4 or 5, wherein the forming step is a floating method forming step.