KR20180096518A - Glass substrate for display, and method for manufacturing substrate for display - Google Patents

Abstract

Provided are a glass substrate for a display which is difficult to generate delamination charging in delaminating from an absorption stage, and a manufacturing method thereof. When the average value of fluorine density (mol%) in the depth of 0-10 nm from the glass substrate opposite to a semiconductor device formation surface of the glass substrate is F0-10 nm, and the average value of the fluorine density (mol%) in the depth of 100-400 nm from the glass surface is F100-400 nm, the glass substrate for a display has F0-10 nm/F100-400 nm >= 3, and has the surface roughness Ra of the glass substrate opposite to the semiconductor device formation surface higher than or equal to 0.3 nm.

Description

TECHNICAL FIELD [0001] The present invention relates to a glass substrate for a display, and a method for manufacturing a glass substrate for a 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 as a substrate. 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 is used as a substrate.

The formation of transparent electrodes, semiconductor elements and the like on the glass substrate is carried out in a state where the glass surface on the opposite side of the semiconductor element formation surface of the glass substrate is fixed on the absorption stage by vacuum suction. However, when a glass substrate on which a transparent electrode, a semiconductor element, or the like is formed is peeled off from the adsorption stage, the glass substrate is charged and electrostatic destruction of semiconductor elements such as TFTs occurs.

In order to suppress the occurrence of peeling electrification, the surface of the glass substrate on the side in contact with the adsorption stage is roughened to reduce the contact area between the glass substrate and the adsorption stage. As a method of roughening treatment, for example, a method of chemically treating the surface of a glass substrate in an atmospheric plasma process is known (Patent Document 1).

International Publication No. 2010/128673

However, in the conventional method, since the difference in work function between the glass substrate and the adsorption stage is not considered, the occurrence of peeling electrification is not sufficiently suppressed, and the electrostatic destruction of the semiconductor element occurs in some cases.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and provides a glass substrate for display which is less prone to peeling electrification when peeling off from the adsorption stage, and a method of manufacturing the same.

In the present invention, 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 _defined as F 0 - 10 nm, when the to the average value of the fluorine concentration (mol%) by _{F 100-400nm, F 0-10nm / F 100-400nm} ≥3 , and not less than the surface roughness Ra of the glass surface opposite to the semiconductor element formation surface 0.3nm And a glass substrate for a display.

In addition, the present invention is a method for producing a glass substrate for a display having a procedure for supplying a gas containing hydrogen fluoride (HF) to one surface of a plate glass conveyed in a heat treatment apparatus,

One surface of the plate glass is a glass surface opposite to the semiconductor element formation surface of the glass substrate,

The HF-containing gas has an HF concentration of 0.5 to 30 vol%

Wherein the glass surface temperature at the time of supplying the HF-containing gas is 500 to 900 占 폚.

In the glass substrate for a display of the present invention, peeling electrification hardly occurs when peeling off from the adsorption stage.

Fig. 1 is an explanatory diagram of a manufacturing method of a glass substrate for a display according to an embodiment of the present invention, and is a schematic diagram showing an example of the structure of a heat treatment apparatus.
Fig. 2 is an explanatory diagram of a manufacturing method of a glass substrate for a display according to an embodiment of the present invention, and is a schematic diagram showing another structural example of the heat treatment apparatus. Fig.
Fig. 3 is an explanatory diagram of a manufacturing method of a glass substrate for a display according to an embodiment of the present invention, and is a cross-sectional view showing an outline of a float glass production 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.
5 is a graph showing the relationship between the depth from the surface of the glass plate in Examples (Example 4 and Example 11) and the fluorine concentration in the glass plate.
6A is a graph showing the relationship between the irradiation light energy X in the embodiment and the square root Y of the photoelectron emission number, and FIG. 6B is a graph showing the relationship between the irradiation light energy X in the range of 5.5 to 6.0 eV Fig. 6 (a) is an enlarged view of Fig.

[Glass substrate for display]

Hereinafter, a display glass substrate according to an embodiment of the present invention will be described.

The glass composition for display of the present embodiment is not particularly limited and may be a wide glass composition such as soda lime silicate glass, aluminosilicate glass, borosilicate glass, and alkali-free glass.

Generally, contact charging is likely to occur if the difference in work function between the materials is large. Work function refers to the minimum amount of energy required to extract electrons in a solid, out of solid, even into a vacuum. Electrons move from a material having a small work function to a material having a large work function, thereby causing charging. In the glass substrate, electrification occurs due to a difference in work function from the adsorption stage.

Therefore, the present inventors have focused on the work function of the glass substrate in order to reduce the charge amount of the glass substrate. However, a method of measuring the work function of the glass substrate is not established.

The inventors of the present invention have studied extensively and found that the difference in fluorine atom concentration between the vicinity of the surface and the inside of the glass substrate is related to the difference in work function between the glass substrate and the adsorption stage.

That is, the energy level is changed by increasing the concentration of fluorine atoms having a high electronegativity to the vicinity of the surface of the glass substrate, and the work function of the glass substrate changes.

The charge amount of the glass substrate is generally determined by the difference in work function between the glass substrate and the adsorption stage (contact charging characteristics of the high-resistance insulating glass, etc.), etc., ) A, Vol. 125, No. 2, pp. 179-184, 2005), it is considered that the difference is caused by the infiltration of fluorine atoms into the vicinity of the surface of the glass substrate.

A glass substrate for a display of the present embodiment, the average value of the fluorine concentration (mol%) of the semiconductor element forming surface of the glass substrate and the depth is from 0 to 10nm from the glass surface on the side opposite to the F _0-10nm, and the glass surface F 0 - 10 _nm / F 100 - 400 nm? 3, when the average value of the fluorine concentration (mol%) at a depth of 100 to 400 nm is F _{100-400 nm} .

As a result, the difference in work function between the glass substrate and the adsorption stage is reduced, and peeling electrification of the glass substrate can be suppressed.

The reason why the fluorine concentration in the vicinity of the surface of the glass substrate is set to be F 0 - 10 _nm and the fluorine concentration in the glass substrate is set to F _{100 - 400 nm} is as follows.

The movement of electrons in the contact charging mainly occurs in a region of 0 to 10 nm in depth from the surface of the glass substrate and is controlled by the interaction of the region with the region of 100 to 400 nm in depth.

Further, the F _{0-10 nm} and F _{100-400 nm} are measured by X-ray photoelectron spectroscopy (XPS).

In the glass substrate for a display of the present embodiment, F _{0-10 nm} / F _{100-400 nm?} 5 is preferable, and F _{0-10 nm} / F _{100-400 nm?} 10 is more preferable.

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 excessively large, the haze is deteriorated.

F _{0-10 nm} / F _{100-400 nm? 150} is preferable because deterioration of haze can be suppressed, and F _{0-10 nm} / F _{100-400 nm? 100} is more preferable.

In addition, the larger the surface roughness of the glass surface, the smaller the contact area between the glass substrate and the adsorption stage and the less the migration of electrons becomes, so that the peeling electrification of the glass substrate can be suppressed (the contact charging property , Kitabashihiro Yoshi, Fujiharuhisa, Transferred A, Vol. 125, No. 2, pp. 179-184, 2005).

In the glass substrate for a display of the present embodiment, the surface roughness Ra of the glass surface on the side opposite to the semiconductor element formation surface of the glass substrate is 0.3 nm or more.

As a result, the difference in work function between the glass substrate and the adsorption stage is reduced, and peeling electrification of the glass substrate can be suppressed.

The surface roughness Ra is measured by an atomic force microscope (AFM).

The surface roughness Ra is preferably 0.7 nm or more.

However, if the surface roughness Ra is excessively large, a large defect occurs on the glass surface, and the strength of the glass substrate may be lowered. The surface roughness Ra of 5 nm or less is preferable because it does not cause large defects on the glass surface and there is no possibility that the strength of the glass substrate is lowered. The surface roughness Ra is more preferably 2 nm or less.

The glass substrate for display of the present embodiment preferably has a peeling electrification amount of -10 kV or more as measured by the procedure described in the later-described embodiment.

Thereby, the electrostatic breakdown of the semiconductor element formed on the glass substrate for display is prevented.

The amount of peeling charge is more preferably -7 kV or more, and more preferably -5 kV or more.

Plotting the irradiation energy obtained by the photoelectron spectroscopy (PYS) measurement and the square root of the photoelectron emission number, the square root of the photoelectron emission number is abruptly increased at the point when the irradiation light energy reaches a certain value . At this time, the irradiated light energy as a threshold value is a work function. When the irradiation energy is further increased, the square root of the photoelectron emission number linearly increases.

As a result of intensive studies, the present inventors have found that there is a correlation between the slope of the linear increase and the peeling electrification amount of the glass substrate.

The glass substrate for a display of the present embodiment is characterized in that X is 5.5 to 6.0 eV when X (eV) is the irradiated light energy obtained by the photoelectron quantity spectroscopy (PYS) measurement and Y is the square root of the photoelectron emission number It is preferable that the slope? Y /? X of Y of 10 or more is 10 or more. The work function of the glass substrate is less than 5.5 eV. The region where X is 5.5 to 6.0 eV is a region where Y linearly increases.

The slope? Y /? X approximately represents the state density of electrons at 5.5 to 6.0 eV. The larger the slope? Y /? X, the more difficult it is for the glass substrate to receive electrons and become difficult to charge.

The display glass substrate of the present embodiment is more preferably? Y /? X? 20 and more preferably? Y /? X? 50.

The size of the glass substrate for display of the present embodiment is not particularly limited, but is suitable for a large glass substrate because it suppresses peeling electrification of the glass substrate. Specifically, it is preferably 2500 mm x 2200 mm or larger, and more preferably 3130 mm x 2880 mm or larger.

The thickness of the plate is not particularly limited, but it is suitable for a thin glass substrate because it suppresses peeling electrification of the glass substrate. Specifically, it is preferably 1.0 mm or less, more preferably 0.75 mm or less, and further preferably 0.45 mm or less.

The display glass substrate of the present embodiment is preferably an alkali-free glass. The alkali-free glass, to a weight percentage display of the oxide basis, 50 to 73%, Al ₂ O ₃ of 10.5 to 24%, B ₂ O ₃ from 0.1 to 12%, the MgO 0 to 8% of SiO _2, CaO (MgO + CaO + SrO + BaO) of 0 to 14.5%, 0 to 24% of SrO, 0 to 13.5% of BaO and 0 to 5% of ZrO ₂ , 8 to 29.5%.

Further, the alkali-free glass, in weight percentages shown below oxide basis, 58 to 66% of SiO _2, Al ₂ O ₃ of 15 to 22%, B ₂ O ₃ 5 to 12%, the MgO 0 to 8% , MgO, CaO, SrO and BaO in an amount of 9 to 18% (MgO + CaO + SrO + BaO), CaO in an amount of 0 to 9%, SrO in an amount of 3 to 12.5% and BaO in an amount of 0 to 2% desirable.

Further, the alkali-free glass, in weight percentages shown below oxide basis, 54 to 73% of SiO _2, to 22.5% of _{Al 2 O 3 10.5, B 2} O 3 0.1 to 5.5%, the MgO 0 to 8% , MgO, CaO, SrO and BaO in an amount of 8 to 26% (MgO + CaO + SrO + BaO), 0 to 9% of CaO, 0 to 16% of SrO and 0 to 2.5% of BaO desirable.

[Manufacturing method of glass substrate for display]

Next, a structural example of a manufacturing method of a glass substrate for a display of the present invention will be described.

Fig. 1 is an explanatory diagram of a manufacturing method of a glass substrate for a display according to an embodiment of the present invention, and is a schematic diagram showing an example of the structure of a heat treatment apparatus.

In the heat treatment apparatus 60 shown in Fig. 1, the plate glass 20 is conveyed in the direction of the arrow. The conveying means is not particularly limited, but is, for example, a conveying roll not shown. The heat treatment apparatus 60 and the heat treatment apparatus 62 described later include a heater (not shown).

Here, the lower surface 22 of the plate glass 20 is the semiconductor element formation surface of the glass substrate for display, the upper surface 24 of the plate glass 20 is the glass surface opposite to the semiconductor element formation surface, , And when the semiconductor element is formed, it is fixed on the adsorption stage by vacuum adsorption.

The heat treatment apparatus 60 shown in FIG. 1 has an injector 70. The gas injected from the supply port 71 of the injector 70 to the upper surface 24 of the plate glass 20 moves the forward or reverse flow path 74 with respect to the moving direction of the plate glass 20, ).

The injector 70 shown in Fig. 1 is an injector of both flow types in which the flow of gas from the supply port 71 to the discharge port 75 is equally divided in the forward direction and the reverse direction with respect to the moving direction of the plate glass 20.

2 is a schematic diagram showing another structural example of the heat treatment apparatus. The heat treatment apparatus 62 shown in FIG. 2 has an injector 80. The injector 80 is an injector of one flow type. The one flow type injector is an injector in which the flow of gas from the supply port 81 to the discharge port 85 is fixed to either the forward direction or the reverse direction with respect to the moving direction of the plate glass 20. The injector 80 shown in Fig. 2 has a forward flow of the gas flow 84 from the supply port 81 to the exhaust port 85 with respect to the moving direction of the plate glass 20. However, the present invention is not limited to this, and the flow of the gas from the supply port 81 to the exhaust port 85 may be reversed with respect to the moving direction of the plate glass 20.

In the method of 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 .

As a result, the fluorine concentration in the vicinity of the glass surface on the opposite side of the semiconductor element formation surface becomes higher than the fluorine concentration in the glass substrate, and the difference in work function between the glass substrate and the adsorption stage becomes small, have.

In the method for producing a glass substrate for a display according to the present invention, the glass surface temperature at the time of supplying a gas containing HF, that is, the temperature of the upper surface 24 of the glass plate 20 is 500 to 900 캜. By setting the glass surface temperature at 500 占 폚 or higher, the following effects are exhibited.

Fluorine invades into the vicinity of 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 DEG C or more, and more preferably 600 DEG C or more.

Further, by setting the glass surface temperature to 900 占 폚 or less, the following effects are exhibited.

The surface roughness Ra of the glass surface is prevented from becoming excessively large, and a uniform surface shape is formed.

The glass surface temperature is more preferably 850 DEG C or less, and further preferably 800 DEG C or less.

In the method for manufacturing the glass substrate for a display of the present invention, a gas containing HF is, from the point of view of preventing corrosion of equipment, such as injectors 70 and 80 of the thermal processing apparatus (60, 62), nitrogen (N ₂₎ or inert gas Is used as the carrier gas, and is supplied to the upper surface 24 of the plate glass 20 as a mixed gas with these carrier gases.

The HF concentration of the HF-containing gas supplied from the supply ports 71 and 81 of the injectors 70 and 80 is 0.5 to 30 vol%. By setting the HF concentration to 0.5 vol% or more, the following effects are exhibited.

Fluorine invades into the vicinity of 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 still more preferably 4 vol% or more.

Further, 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 formed by the reaction of HF with the glass surface and to suppress the decrease of 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 openings 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. Further, the distance D is more preferably 30 mm or less, further preferably 20 mm or less. By making the distance D 5 mm or more, contact between the upper surface 24 of the plate glass 20 and the injectors 70 and 80 can be avoided even if the plate glass 20 vibrates due to an earthquake or the like. On the other hand, by setting the distance D to 50 mm or less, the gas can be prevented from diffusing inside the device, and a sufficient amount of gas can reach the upper surface 24 of the plate glass 20 with respect to the desired gas atmosphere.

The distance L of the injectors 70 and 80 in the moving direction of the plate glass 20 is preferably 100 to 500 mm. The distance L is more preferably 150 mm or more, and still more preferably 200 mm or more. The distance L is more preferably 450 mm or less, and further preferably 400 mm or less. When the distance L is 100 mm or more, the supply ports 71 and 81 and the exhaust ports 75 and 85 can be formed. In particular, the distance L of the injector 70 is preferably 150 mm or more, and the distance L of the injector 80 is preferably 100 mm or more. On the other hand, by setting the distance L to 500 mm or less, it is possible to suppress the heat amount of the plate glass 20 by the injectors 70, 80, and thus the output of a plurality of heaters can be suppressed.

It is preferable that the distance in the width direction of the plate glass 20 of the injectors 70 and 80 is longer than the product area in the corresponding direction of the plate glass 20. [ When the method for producing a glass substrate for a display according to the present invention is carried out as online processing, it is preferably at least 3000 mm, more preferably at least 4000 mm.

The flow rate (linear velocity) of the gas containing HF is preferably 20 to 300 cm / s. By setting the flow velocity (linear velocity) to 20 cm / s or more, the air flow of the gas containing HF is stabilized, 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.

Further, as will be described later, when the process for producing a glass substrate for a display according to the present invention is carried out as on-line treatment, the flow velocity (linear velocity) is set to 300 cm / s or less to suppress diffusion of gas inside the gradual cooling apparatus A sufficient amount of gas can reach 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 may be performed as online processing or as offline processing. The " on-line processing " in the present specification refers to a case where the method of the present invention is applied in the slow cooling process in which the glass ribbon formed by the float method or the down-draw method is slowly cooled. On the other hand, " offline processing " refers to the case where the method of the present invention is applied to a plate glass which is formed and cut to a desired size. Therefore, the plate glass in this specification includes a glass ribbon formed by a float method or a down-draw method in addition to a plate glass which is molded and cut to a desired size.

It is preferable to carry out the process for producing a glass substrate for a display of the present invention as an online process for the following reasons.

If the process is offline, it is necessary to increase the process. On the other hand, if the process is on-line, there is no need to increase the process, and the process can be performed at low cost. Further, in the case of off-line processing, while the gas containing HF is transferred between the glass substrates to the semiconductor element formation surface of the glass substrate, the on-line treatment of the glass containing HF can be suppressed have.

A production process of a plate glass such as a glass substrate for display includes a melting process in which a glass raw material is melted to be melted glass, a molding process in which a molten glass obtained in the melting process is formed into a strip to form a glass ribbon, And a slow cooling step of slowly cooling the obtained glass ribbon. Examples of the forming step include a float forming step by the float method and a down-draw forming step by the down-draw method.

In the case where the process for producing a glass substrate for a display of the present invention is carried out as on-line treatment, a gas containing HF is supplied to the top surface of the glass ribbon in the slow cooling process.

Fig. 3 is an explanatory diagram of a manufacturing method of a glass substrate for a display according to an embodiment of the present invention, and is a sectional view schematically showing a float glass production apparatus.

A float glass manufacturing apparatus 100 shown in Fig. 3 comprises a melting apparatus 200 for melting a glass raw material 10 to form a molten glass 12 and a molten glass 12 supplied from the dissolving apparatus 200 And a slow cooling device 400 for slowly cooling the glass ribbon 14 formed in the molding device 300. The cooling device 400 includes a cooling device 400 for cooling the glass ribbon 14 formed by the molding device 300,

The melting apparatus 200 includes a melting vessel 210 for receiving the molten glass 12 and a burner 220 for forming a flame above the molten glass 12 accommodated in the melting vessel 210. The glass raw material 10 charged into the melting vessel 210 is gradually dissolved in 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 molding apparatus 300.

The molding apparatus 300 has a bath 320 for receiving the molten tin 310. The molding apparatus 300 forms the glass ribbon 14 by forming a molten glass 12 continuously flowing on the molten tin 310 in a strip shape by flowing the molten glass 12 in a predetermined direction on the molten tin 310. The temperature of the atmosphere in the molding apparatus 300 is lowered from the entrance to the exit of the molding apparatus 300. The atmospheric temperature in the molding apparatus 300 is adjusted by a heater (not shown) or the like installed in the molding apparatus 300. The glass ribbon 14 is cooled while flowing in a predetermined direction and is pulled up from the molten tin 310 in the region downstream of the bathtub 320. The glass ribbon 14 pulled up from the molten tin 310 is conveyed to the slow cooling device 400 by the lift-out roll 510.

The gradual cooling apparatus 400 slowly softens the glass ribbon 14 formed in the molding apparatus 300. The slow cooling apparatus 400 includes a slow cooling furnace 410 having a heat insulating structure and a plurality of transport rolls 420 disposed in the annealing furnace 410 for transporting the glass ribbon 14 in a predetermined direction, . The ambient temperature in the annealing furnace 410 is lowered from the inlet to the outlet of the annealing furnace 410. The ambient temperature in the annealing furnace 410 is adjusted by the heater 440 or the like installed in the annealing furnace 410. The glass ribbon 14 taken out from the exit of the gradual cooling path 410 is cut to a predetermined size by a cutter and shipped as a product.

At least one of both surfaces of the glass substrate may be polished and the glass substrate may be cleaned before shipment as a product, if necessary. The glass substrate for a display according to the present invention has a glass surface opposite to the semiconductor element formation surface of the glass substrate corresponding to the top surface of the glass ribbon 14, Corresponds to the bottom surface of the glass ribbon 14.

In the method of manufacturing a glass substrate for a display of the present invention, the fluorine concentration near the glass surface on the opposite side of the semiconductor element formation surface is made higher than the fluorine concentration inside the glass substrate, so that the difference in work function between the glass substrate and the absorption stage is reduced , It is preferable to polish only the bottom surface of the glass ribbon 14 in the case of performing polishing because the peeling electrification of the glass substrate is suppressed. The semiconductor element formation surface of the glass substrate is polished by a polishing tool while supplying a cerium oxide aqueous solution. At the time of polishing, a part of the aqueous cerium oxide solution flows into the glass surface on the side opposite to the semiconductor element formation surface of the glass substrate, and becomes a slurry residue.

The glass substrate is cleaned by, for example, shower cleaning, slurry cleaning using a disc brush, or shower rinsing. The slurry cleaning is carried out by polishing with a disc brush while supplying a slurry (for example, a cerium oxide aqueous solution or an aqueous solution of calcium carbonate) to the glass surface on the side opposite to the semiconductor element formation surface of the glass substrate, Remove the remaining slurry residue from the glass surface.

The float glass manufacturing apparatus 100 shown in Fig. 3 is arranged so that the injectors 70, 70 are disposed above the glass ribbon 14 in the gradual cooling apparatus 400 to perform the on- And the gas containing hydrogen fluoride (HF) is supplied to the top surface of the glass ribbon 14 by using the injectors 70 and 80. [ The heat treatment apparatuses 60 and 62 shown in Figs. 1 and 2 correspond to the gradual cooling apparatus 400 shown in Fig. 3 when the manufacturing method of the glass substrate for a display of the present invention is carried out as online processing.

3, the injectors 70 and 80 are provided in the gradual cooling apparatus 400. However, the float glass manufacturing apparatus according to another embodiment of the present invention is not limited to the glass surface temperature when supplying the gas containing HF The injector may be provided in the molding apparatus 300. In this case,

[Example]

Hereinafter, examples and comparative examples of the present invention will be described in detail. The present invention is not limited to these descriptions.

(Experimental Example 1)

In Experimental Example 1, a method of manufacturing a glass substrate for a display of the present invention was performed as offline processing.

In Experimental Example _{1, SiO 2: 59.5%,} Al 2 O 3: 17%, B 2 O 3: 8%, MgO: 3.3%, CaO: 4%, SrO: 7.6%, BaO: 0.1%, ZrO 2: Alkali glass plate (520 mm x 410 mm x thickness 0.5 mm) containing 0.1% of MgO + CaO + SrO + BaO: 15%, the balance being inevitable impurities and a total content of alkali metal oxides of 0.1% Respectively. From the injector 70 of the heat treatment apparatus shown in Fig. 1, a gas containing HF was supplied to the upper surface of the alkali-free glass plate. 4 is a graph 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 flow rate (L / min), the processing time (sec), and the linear velocity (mm / sec) of the gas including a (mm), b (mm), c The conditions shown in Table 1 were used.

The distance D between the supply port 71 of the injector 70 and the upper surface of the plate glass 20 was set to 10 mm.

The glass surface temperature (described as temperature in Table 2) and the HF concentration (vol%) at the time of supplying the gas containing HF were set as shown in Table 2 below. In Table 2, Examples 1 and 2 are Comparative Examples, and Examples 3 and 4 are Examples.

After the supply of the gas containing HF, the glass surface temperature was maintained at the same temperature for 5 minutes, and then cooled to room temperature over 30 minutes.

Thereafter, the following evaluations were carried out.

[F concentration (F 0 - 10 _nm , F _{100 - 400 nm} ) in the vicinity of the surface and inside of the glass substrate]

F _{0-10 nm} and F _{100-400 nm} were measured in the following procedure.

The glass substrate obtained by the above procedure was cut into a 10 mm width × 10 mm length and the F concentration (mol%) at 0, 2, 5, 7 and 10 nm from the glass surface of the glass substrate was measured with an X-ray photoelectron spectroscope ESCA 5500, manufactured by Alabai Pty.). The measured values of the F concentration at depths 0, 2, 5, 7 and 10 nm were _averaged to calculate the average value F _0-10 nm of the F concentration at the depth of 0 to 10 nm. Grinding from the surface of the glass substrate to a depth of 10 nm was sputter-etched by a C ₆₀ ion beam.

The F concentration in the depth of 100, 101, 112, 123, 134, 145, 156, 167, 178, 189, 200, 211, 222, 266, 310, 354, 398, (mol%) was measured by an X-ray photoelectron spectroscopy apparatus (ESCA5500, manufactured by Alabai Pty. Ltd.). The measured values of the F concentration at a depth of 100 to 400 nm were averaged to calculate an average value F _100-400 nm of the F concentration at a depth of 100 to 400 nm.

The relationship between the depth from the surface of the glass plate in Example 4 and the fluorine concentration in the glass plate is shown in Fig.

[Average surface roughness Ra of the glass surface]

The glass substrate obtained by the above procedures was cut to a width of 5 mm and a length of 5 mm, and the average surface roughness Ra (arithmetic mean surface roughness Ra (JIS B0601-2013)) of the glass surface of the glass substrate was measured by the following method. The glass surface of the glass substrate was observed using an atomic force microscope (product name: SPI-3800N, manufactured by Seiko Instruments Inc.). The cantilever used SI-DF40P2. Observation was performed at a scan rate of 1 Hz (number of data in the area: 256x256) using a dynamic force mode for a scan area of 5 占 퐉 占 5 占 퐉. Based on this observation, the average surface roughness Ra at each measurement point was calculated. The calculation software used software (software name: SPA-400) attached to the atomic force microscope.

[Peeling electrification amount of glass substrate]

The amount of peeling electrification of the glass substrate obtained in the above procedure was measured by the following method. A glass substrate having a width of 410 mm, a length of 520 mm and a thickness of 0.5 mm was brought into contact with a vacuum adsorption stage made of SUS304, and then the adsorption and release of the glass substrate were repeated for 110 cycles. Thereafter, the glass substrate was peeled off from the vacuum adsorption stage using a lift pin. The change in surface potential until the glass substrate was lifted 5 cm apart from the vacuum adsorption stage was measured with a surface electrometer (product name: MODEL341B, manufactured by Trek Japan). The peak value of the measurement result was taken as the peeling electrification amount.

[PYS measurement (? Y /? X)]

With respect to Example 4, photoelectron quantity spectroscopy (PYS) measurement was performed in the following procedure, and the slope (Y /? X) of the irradiated light energy X and the square root Y of the photoelectron emission number was obtained.

A glass substrate having a width of 20 mm, a length of 20 mm and a thickness of 0.5 mm was prepared. The irradiation surface of the ultraviolet ray was a glass surface opposite to the semiconductor element formation surface of the glass substrate. The number of photoelectron emission on the irradiation surface was measured using an atmospheric photoelectron spectroscopic analyzer AC-5 (manufactured by Riken Keiki Co., Ltd.). The ultraviolet intensity of the irradiation was 2000 nW. The ultraviolet rays were irradiated in the range of 4.2 eV to 6.2 eV in the unit of 0.1 eV. The counting time of the photoelectron was set to 5 seconds per 0.1 eV.

A graph showing the relationship between the irradiation light energy X in Example 4 and the square root Y of the photoelectron emission number is shown in Fig. 6 (a). 6 (b) is an enlarged view of FIG. 6 (a) in which the irradiation light energy X is 5.5 to 6.0 eV. The slope DELTA Y / DELTA X was calculated by linearly approximating plots with X in the range of 5.5 to 6.0 eV by the least squares method.

(Experimental Example 2)

In Experimental Example 2, a method for producing a glass substrate for a display of the present invention was carried out as online processing.

In Experimental Example 2, 59.5% of SiO ₂ , 17% of Al ₂ O ₃ , 8% of B ₂ O ₃ , 3.3% of MgO, CaO: 4%, SrO: 7.6%, BaO: 0.1%, ZrO 2: containing 0.1%, MgO + CaO + SrO + BaO: is 15%, the balance being an inevitable impurities, 0.1 volume content of the sum of alkali metal oxides Alkali glass plate having a thickness of 0.5 mm or less.

The molten glass 12 is melted into the molten glass 12 in the dissolving apparatus 200 and then the molten glass 12 is supplied to the molding apparatus 300 to form the molten glass 12 into a belt shape, The ribbon 14 was obtained. After the glass ribbon 14 is drawn out from the outlet of the molding apparatus 300, the glass ribbon 14 is slowly cooled in the gradual cooling apparatus 400.

An injector 70 having a distance L of 300 mm in the moving direction of the glass ribbon 14 was provided at a position where the temperature of the glass ribbon 14 in the gradual cooling apparatus 400 was 500 ° C.

4 is a graph showing the relationship between the slit width (a), the processing length (b), and the processing width (c) of the injector in Experimental Example 2.

In Experimental Example 2, the flow rate (L / min), the processing time (sec), and the linear velocity (mm / sec) of the gas including a (mm), b (mm), c The conditions shown in Table 1 were used.

The distance D between the supply port 71 of the injector 70 and the upper surface of the plate glass 20 was set to 10 mm.

In addition, the glass surface temperature (described as temperature in Table 3) and the HF concentration (vol%) at the time of supplying a gas containing HF were set as 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 in the same manner as in Experimental Example 1. [ The relationship between the depth from the surface of the glass plate in Example 11 and the fluorine concentration in the glass plate is shown in Fig.

6A and 6B are graphs showing the relationship between the irradiation light energy X in Examples 11 and 13 and the square root Y of the photoelectron emission number.

In Examples 1, 2 and 11 in which F _{0-10 nm} / F _{100-400 nm} <3, or Ra is less than 0.3 nm, the peeling electrification amount is less than -10 kV. On the other hand, in Examples 3 and 4 and Examples 12 and 13 in which F _{0-10 nm} / F _{100-400 nm?} 3 and Ra was 0.3 nm or more, the amount of peeling electrification was suppressed and was -10 kV or more. In Example 11, ΔY / ΔX ≧ 10, whereas Example 4, Example 12, and 13 were ΔY / ΔX≥10.

Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

The present application is based on Japanese Patent Application No. 2017-029636 filed on February 21, 2017, the content of which is incorporated herein by reference.

10: Glass raw material
12: molten glass
14: Glass ribbon
20: Plate glass
22: When you
24: upper surface
60, 62: heat treatment apparatus
70, 80: injector
71, 81: supply port
74, 84: Euro
75, 85: Exhaust port
100: Float glass manufacturing apparatus
200: dissolution apparatus
210:
220: Burner
300: forming device
310: molten tin
320: Bathtub
400: slow cooling device
410: slow cooling
420: conveying roll
440: Heater
510: Lift-out roll

Claims (6)

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 _defined as F 0 - 10 nm and the fluorine concentration the average value of (mol%) wherein at least when a _{F 100-400nm, F 0-10nm / F 100-400nm} ≥3 , and the semiconductor device forming surface and the surface roughness Ra of the glass surface opposite 0.3nm A glass substrate for a display. The glass substrate for display according to claim 1, wherein the amount of peeling charge is -10 kV or more. The method according to claim 1 or 2, wherein, when X (eV) is the irradiation light energy in the photoelectron quantity spectroscopy (PYS) measurement and Y is the square root of the photoelectron emission number, X is 5.5 to 6.0 eV Wherein the Y slope? Y /? X of Y is 10 or more. A process for producing a glass substrate for a display having a process of supplying a gas containing hydrogen fluoride (HF) to one surface of a glass plate conveyed in a heat treatment apparatus,
One surface of the plate glass is a glass surface opposite to the semiconductor element formation surface of the glass substrate,
The HF-containing gas has an HF concentration of 0.5 to 30 vol%
Wherein the glass surface temperature at the time of supplying the HF-containing gas is 500 to 900 占 폚. The method according to claim 4, further comprising: a melting step of melting the glass raw material to obtain a molten glass; a molding step of molding the molten glass obtained in the melting step into a strip to form a glass ribbon; And has a slow cooling step,
In the slow cooling step, a gas containing HF is supplied to the top surface of the glass ribbon. The method of manufacturing a glass substrate for a display according to claim 4 or 5, wherein the forming step is a float forming step.

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