WO2019172442A1 - 無アルカリガラス基板 - Google Patents

無アルカリガラス基板 Download PDF

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Publication number
WO2019172442A1
WO2019172442A1 PCT/JP2019/009467 JP2019009467W WO2019172442A1 WO 2019172442 A1 WO2019172442 A1 WO 2019172442A1 JP 2019009467 W JP2019009467 W JP 2019009467W WO 2019172442 A1 WO2019172442 A1 WO 2019172442A1
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Prior art keywords
glass substrate
glass
less
alkali
content
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PCT/JP2019/009467
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English (en)
French (fr)
Japanese (ja)
Inventor
邦雄 増茂
和孝 小野
史朗 谷井
未央 徳永
小林　大介
Original Assignee
Ａｇｃ株式会社
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Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Priority to CN202211424319.8A priority Critical patent/CN115611510A/zh
Priority to JP2020504067A priority patent/JP7136184B2/ja
Priority to KR1020207024935A priority patent/KR102674809B1/ko
Priority to CN202211426784.5A priority patent/CN115636584A/zh
Priority to CN201980017599.0A priority patent/CN111867992B/zh
Publication of WO2019172442A1 publication Critical patent/WO2019172442A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00—Shaping glass in contact with the surface of a liquid
    • C03B18/02—Forming sheets
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00—Shaping glass in contact with the surface of a liquid
    • C03B18/02—Forming sheets
    • C03B18/20—Composition of the atmosphere above the float bath; Treating or purifying the atmosphere above the float bath
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium

Definitions

  • the present invention relates to a glass substrate suitable for forming a thin film transistor (TFT) or the like.
  • TFT thin film transistor
  • a borosilicate glass substrate (so-called alkali-free glass substrate) containing almost no alkali metal component is used as a glass substrate for various displays, particularly when a thin film such as a TFT is formed on a glass substrate. This is because when a glass substrate containing a large amount of an alkali metal component is used, the alkali metal component in the glass deteriorates the film characteristics and causes a decrease in the reliability of the TFT.
  • the glass substrate for display is also required to have a high strain point and high acid resistance.
  • Patent Document 1 describes a method of melting glass by containing alkali metal oxide in an alkali-free glass in an amount of 200 to 2000 ppm and using heating by a burner combustion flame and heating by energizing molten glass. ing.
  • a float method is known as a method for forming glass into a plate shape.
  • molten glass that is continuously supplied onto molten metal (for example, simply “bath”) in a float bath (hereinafter referred to simply as “bath”) is flowed over the molten metal and formed into a plate shape. To do.
  • the glass ribbon formed on the molten metal is then conveyed using a roller. In that case, it is known that the part which contacts a roller tends to be damaged.
  • Patent Document 2 As a method of preventing such scratches, sulfurous acid gas (SO 2 gas) is sprayed on the back surface of the glass substrate and reacted with an alkali metal (for example, sodium) present in the glass to form sodium sulfate on the back surface of the glass substrate.
  • an alkali metal for example, sodium
  • Patent Document 3 describes a method in which sodium tetraborate or the like is sprayed on the surface of the display substrate glass and then sulfurous acid gas is sprayed.
  • Patent Document 2 cannot be applied to the production of an alkali-free glass substrate in which the amount of alkali metal present in the glass is extremely small.
  • the method of patent document 3 is applicable also to an alkali free glass substrate, since two types of gases are sprayed on the surface of a glass ribbon, a process is complicated and an apparatus also becomes complicated.
  • the present invention has been made in view of the above problems, and has an object to provide a high-quality alkali-free glass substrate that is less likely to deteriorate the reliability of the TFT due to an alkali metal component, has few scratches, and is excellent in productivity. To do.
  • the present inventors have found that the strain point and the average thermal expansion coefficient at 50 to 350 ° C. are within a predetermined range, have a specific composition, and Na 2 O on the surface of at least one glass substrate.
  • the present inventors have found that the above problem can be solved by a glass substrate whose amount is 20 mass ppm or more less than the amount of Na 2 O inside the glass substrate, and completed the present invention.
  • the present invention is an alkali-free glass having a strain point of 650 ° C. or higher and an average coefficient of thermal expansion of 30 ⁇ 10 ⁇ 7 to 45 ⁇ 10 ⁇ 7 / ° C. at 50 to 350 ° C.
  • the alkali-free glass substrate of the present invention has a specific composition, and the amount of Na 2 O on the surface of at least one glass substrate is 20 mass ppm or less less than the amount of Na 2 O inside the glass substrate. The damage of the TFT due to the alkali metal component can be suppressed.
  • FIG. 1 is a diagram illustrating an example of a signal intensity ratio profile of 23 Na + and 30 Si + in the thickness direction of a glass substrate.
  • FIG. 2 is a diagram showing an example of a Na 2 O content profile near the glass substrate surface.
  • FIG. 3 is a conceptual diagram showing a glass manufacturing apparatus using a float process.
  • FIG. 4 shows an example of the relationship between the variation amount of the threshold voltage in the reliability test of the TFT formed on the glass substrate surface and the amount of Na 2 O on the glass substrate surface.
  • FIG. 5 is a schematic diagram of a TFT element.
  • the glass composition is expressed in terms of mass% based on oxide in principle, and “%” and “ppm” used for the glass composition in the present specification are “mass%”, “ It means “ppm by mass”.
  • non-alkali glass refers to a glass in which the content of alkali metal components such as lithium, sodium, and potassium is 5000 ppm or less in terms of oxide.
  • glass ribbon refers to a molten glass formed into a plate shape. The glass ribbon is cooled and cut to become a glass substrate.
  • the “bottom surface” is the surface of the glass ribbon or glass substrate manufactured by the float process that is in contact with the molten metal in the float bath.
  • the “top surface” is a surface facing the bottom surface.
  • the Na 2 O content of the glass substrate is obtained by pulverizing the glass substrate, thermally decomposing the obtained glass powder with sulfuric acid, nitric acid and hydrofluoric acid, and then concentrating until white sulfuric acid smoke is generated.
  • a constant volume solution dissolved in dilute nitric acid is obtained, and the Na concentration in the constant volume solution is determined by ICP mass spectrometry [unit: mass ppm].
  • the “Na 2 O content inside the glass substrate” is equal to the Na 2 O content of the glass substrate determined by the above method.
  • Na 2 O content on the surface of the glass substrate is a standard value obtained by cutting out a part of the glass substrate to be evaluated and etching it about 10 ⁇ m (specifically 8 to 12 ⁇ m) from the surface using a 5% hydrogen fluoride aqueous solution.
  • the sample is obtained from a Na content profile obtained by a time-of-flight secondary ion mass spectrometry (TOF-SIMS) method using C 60 sputtering described later. Specifically, determined from Na content profile of the glass, the average content of Na 2 O depth in the region of 0.30 ⁇ m from 0.25 ⁇ m from the surface and the content of Na 2 O of the glass substrate surface.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • FIG. 1 is a signal intensity ratio profile of 23 Na + and 30 Si + in the thickness direction of the glass substrate obtained by the following procedure. That is, five small pieces were cut out from the present glass substrate, and the surface of each of the four pieces was etched using a 5% hydrogen fluoride aqueous solution. By changing the etching time for the five small pieces, 1 ⁇ m, 3 ⁇ m, 5 ⁇ m, and 10 ⁇ m were etched from the glass substrate surface, respectively. The etching thickness was measured using a micrometer.
  • FIG. 1 shows a plot of the signal intensity ratio of 23 Na + and 30 Si + measured for each piece by time-of-flight secondary ion mass spectrometry (TOF-SIMS) using C 60 sputter. .
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • the signal intensity ratio between 23 Na + and 30 Si + indicates a profile of Na content. It can be considered. From FIG. 1, in the region from the glass substrate surface to a depth of about 5 ⁇ m, the Na content is smaller than that of the deeper portion, but at a depth of about 10 ⁇ m or more, the Na content is It turns out that it does not fluctuate.
  • a part of the glass substrate to be evaluated is cut out and etched from the surface by using a 5% aqueous hydrogen fluoride solution about 10 ⁇ m (specifically, 8 to 12 ⁇ m).
  • a 5% aqueous hydrogen fluoride solution about 10 ⁇ m (specifically, 8 to 12 ⁇ m).
  • Na 2 O as a standard sample for quantification of Na 2 O
  • the Na content profile near the glass substrate surface is measured by measuring the signal intensity ratio of 23 Na + to 30 Si + with respect to the sputtering time for an unetched glass substrate. A method is mentioned.
  • the signal intensity ratio of 23 Na + and 30 Si + obtained for the standard sample is the Na 2 O content obtained by IPC mass spectrometry. Equivalent to. Therefore, the signal intensity ratio can be converted into the Na 2 O content using the value. Further, after the TOF-SIMS measurement, a surface shape measuring device (e.g. manufactured by Veeco; Dektak150) Measurement of the shaved depth C 60 sputtering using, can convert the sputtering time to depth from the glass surface.
  • a surface shape measuring device e.g. manufactured by Veeco; Dektak150
  • Na 2 O content profile as shown in FIG. 2 is obtained.
  • the average Na 2 O content of the region of 0.30 ⁇ m depth from the surface is from 0.25 ⁇ m to Na 2 O of the glass surface.
  • the “ ⁇ -OH value” of a glass substrate is obtained by the following method.
  • the infrared transmittance of the glass substrate was measured using an infrared spectrophotometer, the minimum value of the transmittance at a wave number of 3500 to 3700 cm ⁇ 1 was I a [unit:%], and the transmittance at a wave number of 4000 cm ⁇ 1 was I If b [unit:%] and the thickness of the glass substrate is d [unit: mm], the ⁇ -OH value is ⁇ (log (I a / I b )) / d [unit: mm ⁇ 1 ].
  • Glass substrate manufacturing method First, in order to help understanding of the present invention, a method for producing a glass substrate by a float method will be described as one embodiment of a method for producing an alkali-free glass substrate of the present invention (hereinafter also referred to as “the glass substrate of the present invention”). The manufacturing method of the glass substrate of this invention is not limited to this.
  • FIG. 3 is a conceptual diagram which shows the example of the glass manufacturing apparatus by a float glass process.
  • molten glass 4 is obtained by putting the glass raw material prepared and mixed in accordance with a desired glass composition into melting furnace 3.
  • the temperature of the melting furnace 3 may be appropriately adjusted depending on the glass raw material used, and is, for example, about 1400 ° C. to 1600 ° C.
  • a glass ribbon is formed by continuously flowing molten glass 4 from melting furnace 3 onto the molten tin surface of float bath 2 filled with molten tin 1.
  • the glass ribbon formed on the molten metal is transported to the slow cooling furnace 6 by the transport roller 5 and gradually cooled. However, the glass ribbon is in a period from when the glass ribbon leaves the float bath 2 until it contacts the transport roller 5. It is preferable to blow the SO 2 gas against the bottom surface of the.
  • the sodium sulfate has an effect of preventing the glass ribbon from being damaged by the contact between the glass ribbon and the transport roller 5 and can be easily removed by washing with water, so that the quality of the glass substrate is not affected. .
  • the glass substrate of the present invention which is an alkali-free glass substrate having a low Na 2 O content
  • the glass substrate of the present invention which is an alkali-free glass substrate having a low Na 2 O content
  • the conditions of the upstream and downstream temperatures of the float bath 2, the residence time of the molten glass 4, and the dissolved oxygen concentration in the molten tin 1 include the following (1) to (4).
  • the temperature on the upstream side of the float bath 2 is preferably 1400 ° C. to 900 ° C., more preferably 1300 ° C. to 1000 ° C., and further preferably 1250 ° C. to 1100 ° C.
  • the temperature on the upstream side of the float bath 2 indicates the temperature of the upstream glass ribbon and can be measured with a radiation thermometer.
  • the temperature on the downstream side of the float bath 2 is preferably 600 ° C. to 850 ° C., more preferably 650 ° C.
  • the temperature on the downstream side of the float bath 2 indicates the temperature of the downstream glass ribbon and can be measured with a radiation thermometer.
  • the residence time of the molten glass 4 is preferably 5 minutes to 60 minutes, more preferably 10 minutes to 40 minutes, and even more preferably 15 minutes to 30 minutes.
  • the dissolved oxygen concentration in the molten tin 1 is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 3 ppm or less, and most preferably 0 ppm.
  • the dissolved oxygen concentration in the molten tin 1 can be measured with a tin oxygen concentration meter (Redox).
  • the amount of Na 2 O on the glass surface on the bottom surface side is smaller than the amount of Na 2 O inside the glass, specifically, 20 ppm by mass or more, 40 ppm by mass.
  • the content is preferably less, more preferably 90 mass ppm or less.
  • the temperature of the heat treatment at the time of manufacturing the TFT is 400 ° C. to 500 ° C., but the temperature of the glass ribbon when blowing the SO 2 gas is about 600 ° C. to 750 ° C., which is higher than the temperature of the heat treatment at the time of manufacturing the TFT. . Therefore, by blowing SO 2 gas, Na ions existing at a position deeper than the depth at which Na ions in the glass substrate diffuse during the heat treatment during TFT manufacturing can be reacted with SO 2 and removed. .
  • the glass ribbon carried by the transport roller 5 is slowly cooled in the slow cooling furnace 6 to obtain the glass substrate of the present invention.
  • the temperature of the slow cooling furnace 6 is not particularly limited, for example, it can be set to 550 to 750 ° C. on the upstream side of the slow cooling furnace 6 and 200 to 300 ° C. on the downstream side, as in the conditions of a general float process.
  • the glass substrate of the present invention has a SiO 2 content of 54 to 66%, an Al 2 O 3 content of 10 to 25%, a B 2 O 3 content of 0.1 to 12%, MgO, CaO, and SrO in terms of mass% based on oxide. and one or more components selected from the group consisting of BaO contain 7-25% in total, Na 2 O and containing 150-2000 mass ppm, Na 2 O amount of at least one glass surface of the inner glass Na less than 20 ppm by weight from 2 O amount.
  • SiO 2 is an essential component of alkali-free glass.
  • the content of SiO 2 in the glass substrate of the present invention is 54% or more, preferably 57% or more, and more preferably 58% or more.
  • the viscosity of the glass becomes high when the content of SiO 2 becomes large, the temperature T 4 which is a temperature T 2 and 10 4 dPa ⁇ s glass viscosity becomes 10 2 dPa ⁇ s is increased, the devitrification temperature rises To do. Therefore, the content of SiO 2 in the glass substrate of the present invention is 66% or less, preferably 63% or less, more preferably 62% or less.
  • the content of Al 2 O 3 in the glass substrate of the present invention is 10% or more, preferably 14% or more, and more preferably 15% or more.
  • the content of Al 2 O 3 in the glass substrate of the present invention is 25% or less, preferably 21% or less, and more preferably 18% or less.
  • the content of B 2 O 3 in the glass substrate of the present invention is 0.1% or more, preferably 0.5% or more, more preferably 1% or more, and further preferably 2% or more. In particular, 3% or more is preferable and 5% or more is more preferable from the viewpoint of preventing haze from being generated by etching using buffered hydrofluoric acid.
  • the content of B 2 O 3 in the glass substrate of the present invention is 12% or less, preferably 11% or less, more preferably 9% or less. Further, when it is desired to increase the strain point, it is preferably 7% or less, more preferably 5% or less, and further preferably 3% or less.
  • MgO, CaO, SrO and BaO are not essential, but these components have the effect of lowering the viscosity of the glass and maintaining chemical durability. Therefore, the total content of these components in the glass substrate of the present invention is 7% or more, preferably 9% or more, and more preferably 12% or more.
  • the total content of these components in the glass substrate of the present invention is 25% or less, preferably 21% or less, and more preferably 18% or less.
  • MgO is a component having a relatively small effect of increasing the thermal expansion coefficient of glass among alkaline earth oxides. It is also a component that can increase the Young's modulus while keeping the glass density low.
  • the content of MgO is preferably 1% or more, more preferably 2% or more, and further preferably 3% or more.
  • the MgO content is preferably 10% or less, more preferably 8% or less, and even more preferably 6% or less.
  • CaO is a component that can increase the Young's modulus without increasing the thermal expansion coefficient and density too much.
  • the content of CaO is preferably 2% or more, and more preferably 3% or more.
  • the CaO content is preferably 15% or less, more preferably 10% or less, and even more preferably 6% or less.
  • SrO has an effect of decreasing the viscosity without increasing the devitrification temperature of the glass, and it is preferable to contain 6% or more.
  • the SrO content is preferably 15% or less, more preferably 10% or less, and even more preferably 9% or less.
  • BaO is a component that lowers the viscosity.
  • the BaO content is preferably 5% or less, more preferably 1% or less because the coefficient of thermal expansion can be reduced by lowering the BaO content.
  • the content is preferably 0.5% or less, and more preferably substantially not contained.
  • the Na 2 O content is 2000 mass ppm or less, preferably 1000 mass ppm or less, more preferably 800 mass ppm or less.
  • the Na 2 O content of the glass is 150 mass ppm or more, preferably 300 mass ppm or more, and more preferably 500 mass ppm or more.
  • the glass substrate of the present invention by decreasing least 20 mass ppm from Na 2 O content of the glass substrate to Na 2 O of the glass substrate surface in at least one major surface, a wound surface of the glass substrate Can be reduced.
  • the amount of Na 2 O on the glass substrate surface in at least one main surface is 20 mass ppm or less, preferably 40 mass ppm or more, more preferably 90 mass, less than the amount of Na 2 O inside the glass substrate. It shall be less than ppm.
  • the glass substrate of the present invention by setting the Na 2 O content in the above-described range, a decrease in the reliability of the TFT when the TFT is formed on the glass substrate is prevented, but this particularly affects the reliability of the TFT. It is Na 2 O present on the surface of the glass substrate. Therefore, in the glass substrate of the present invention, at least in the one principal surface, a Na 2 O of the glass substrate surface by less than Na 2 O content of the glass substrate, further suppressing a decrease in reliability of the TFT be able to.
  • FIG. 4 shows the amount of variation in threshold voltage and Na on the surface of the glass substrate when a low-temperature polysilicon thin film transistor (LTPS-TFT) is formed on the surface of the bottom surface of the glass substrate and a positive bias is applied. It is the figure which showed the relationship of 2 O content.
  • LTPS-TFT low-temperature polysilicon thin film transistor
  • this LTPS-TFT structure is a standard top gate coplanar structure, and the source drain region is formed by ion implantation of boron to form a p-channel TFT.
  • the polysilicon film is crystallized by irradiating an amorphous silicon film having a thickness of 50 nm obtained by a plasma CVD method with a XeCl excimer laser (wavelength 308 nm).
  • LTPS-TFTs are characterized by being more strongly affected by the Na 2 O content on the glass substrate surface because they are processed at a higher temperature than amorphous silicon TFTs, which are currently the mainstream.
  • the amount of Na 2 O on the glass substrate surface on at least one main surface is preferably 500 ppm by mass or less, more preferably 300 ppm by mass or less, and further preferably 250 ppm by mass or less.
  • the glass substrate of the present invention is alkali-free glass, it is known that alkali metal oxides are inevitably mixed as impurities in the glass raw material.
  • Na 2 O occupies most of the alkali metal oxide mixed as an impurity from the raw material, but it may contain Li 2 O and K 2 O.
  • the total amount of alkali metal oxides including Na 2 O is 5000 ppm by mass or less, preferably 2000 ppm by mass or less, more preferably 1000 ppm by mass or less, and even more preferably 800 ppm by mass or less.
  • the glass substrate of the present invention may contain SO 3, SnO 2, ZrO 2 or the like.
  • the glass substrate of the present invention has a strain point of 650 ° C. or higher, and an average coefficient of thermal expansion at 50 to 350 ° C. is 30 ⁇ 10 ⁇ 7 to 45 ⁇ 10 ⁇ 7 / ° C.
  • the strain point of the glass substrate of the present invention is 650 ° C. or higher, preferably 660 ° C. or higher, and more preferably 670 ° C. or higher.
  • the strain point of the glass substrate of the present invention is preferably 800 ° C. or lower, more preferably 750 ° C. or lower, and further preferably 730 ° C. or lower.
  • the strain point can be measured using a fiber drawing method according to the method defined in JIS R3103-2 (2001).
  • the average thermal expansion coefficient of the glass substrate of the present invention at 50 to 350 ° C. is 30 ⁇ 10 ⁇ 7 to 45 ⁇ 10 ⁇ 7 / °C.
  • the average thermal expansion coefficient at 50 to 350 ° C. of the glass substrate of the present invention is preferably 33 ⁇ 10 ⁇ 7 / ° C. or more, and more preferably 35 ⁇ 10 ⁇ 7 / ° C. or more. Further, it is preferably 42 ⁇ 10 ⁇ 7 / ° C. or less, and more preferably 40 ⁇ 10 ⁇ 7 / ° C. or less.
  • the average coefficient of thermal expansion can be measured using a thermal dilatometer according to the method specified in ASTM E831.
  • the density of the glass substrate of this invention is not specifically limited, 3.0 g / cm ⁇ 3 > or less is preferable from a viewpoint of implement
  • the glass substrate of the present invention is easy to dissolve because the temperature T 2 at which the viscosity ⁇ is 10 2 poise (dPa ⁇ s) is relatively low.
  • the temperature T 2 is preferably 1800 ° C. or less, more preferably 1750 ° C. or less, further preferably 1700 ° C. or less, and particularly preferably 1680 ° C. or less from the viewpoint of solubility.
  • the glass substrate of the present invention is suitable for float forming because the temperature T 4 at which the viscosity ⁇ is 10 4 poise (dPa ⁇ s) is relatively low.
  • the temperature T 4 is preferably 1350 ° C. or less, more preferably 1325 ° C. or less, still more preferably 1300 ° C. or less, and particularly preferably 1290 ° C. or less from the viewpoint of float moldability.
  • the temperature T 2 and the temperature T 4 in accordance with the method specified in ASTM C965-96, can be measured using a rotational viscometer.
  • the Young's modulus of the glass substrate of the present invention is preferably 70 GPa or more, and more preferably 75 GPa or more.
  • the Young's modulus can be measured by an ultrasonic pulse method according to the method defined in JIS Z2280 (1993).
  • the photoelastic constant of the glass substrate of the present invention is preferably 33 nm / MPa / cm or less. Due to the birefringence of the glass substrate due to stress generated during the manufacturing process of the liquid crystal display panel and the liquid crystal display device, a phenomenon in which the black display becomes gray and the contrast of the liquid crystal display decreases may be observed.
  • the photoelastic constant is more preferably 32 nm / MPa / cm or less, and still more preferably 30 nm / MPa / cm or less.
  • the photoelastic constant of the glass substrate of the present invention is preferably 21 nm / MPa / cm or more, and more preferably 23 nm / MPa / cm or more, considering the ease of securing other physical properties.
  • the photoelastic constant is measured by a disk compression method at a measurement wavelength of 546 nm.
  • the relative dielectric constant of the glass substrate of the present invention is preferably 5.0 or more, more preferably 5.5 or more, and even more preferably 5.7 or more.
  • the relative dielectric constant can be measured by the method described in JIS C-2141 (1992).
  • the ⁇ -OH value of the glass substrate of the present invention can be appropriately selected according to the required characteristics of the glass substrate. From the viewpoint of increasing the strain point of the glass substrate, the ⁇ -OH value is preferably low. Specifically, beta-OH value is preferably 0.50 mm -1 or less, more preferably 0.45 mm -1 or less, more preferably 0.40 mm -1 or less.
  • the ⁇ -OH value can be adjusted by various conditions during melting of the raw material, for example, the amount of water in the glass raw material, the water vapor concentration in the melting kiln, the residence time of the molten glass in the melting kiln, and the like.
  • TFT manufacturing method Next, in order to help understanding of the present invention, a manufacturing method of the TFT element 10 using a glass substrate will be described by taking a top gate coplanar type LTPS-TFT manufacturing method shown in FIG. 5 as an example.
  • the use of the glass substrate is not limited to this.
  • a barrier film 12 is formed on one main surface of the glass substrate 11.
  • the barrier film 12 is made of, for example, silicon oxide, silicon oxynitride, silicon nitride, or alumina, but may be omitted.
  • an amorphous silicon layer is formed as a semiconductor on the barrier film 12 (or the glass substrate 11).
  • amorphous silicon is crystallized by laser annealing to obtain a polysilicon layer 13.
  • Laser annealing is performed, for example, by a method of irradiating an excimer laser with a wavelength of 308 nm.
  • the polysilicon layer 13 is patterned into a predetermined shape. The patterning is performed by, for example, photolithography and an etching method. Subsequently, an insulating film and a conductive film are formed.
  • This insulating film is made of, for example, silicon oxide, silicon oxynitride, silicon nitride, or alumina, and later becomes the gate insulating film 14a.
  • the thickness of the insulating film is, for example, 30 to 600 nm.
  • the conductive film is made of, for example, a metal such as chromium, molybdenum, aluminum, copper, silver, or an alloy containing them, and is later patterned to form the gate electrode 15.
  • the thickness of the conductive film is, for example, 30 to 600 nm.
  • a process of reducing the electrical resistance value (low resistance process) is performed on the portion of the polysilicon layer 13 protruding from the gate electrode 15.
  • the resistance reduction process is performed by a method such as ion implantation of B (boron) ions into the polysilicon layer 13, for example.
  • the implanted ions are activated by the heat treatment. This heat treatment may be performed at 450 to 600 ° C. for 10 to 60 minutes, for example.
  • an interlayer insulating film 14b is formed.
  • the interlayer insulating film 14b is made of, for example, silicon oxide, silicon oxynitride, silicon nitride, alumina, or the like.
  • the interlayer insulating film 14 b is patterned so that part of the protruding portion of the polysilicon layer 13 is exposed on both sides of the gate electrode 15.
  • the source electrode 16 and the drain electrode 17 are formed. These electrodes are formed, for example, by forming a conductive film made of a metal such as chromium, molybdenum, aluminum, copper, silver, or an alloy containing them, and then patterning the conductive film.
  • a metal such as chromium, molybdenum, aluminum, copper, silver, or an alloy containing them
  • the passivation film 18 is made of, for example, silicon oxide, silicon oxynitride, silicon nitride, or alumina.
  • the thickness is, for example, 30 to 600 nm.
  • the TFT element 10 can be manufactured as described above.
  • the use of the glass substrate of this invention is not specifically limited, It is useful as a glass substrate for displays, such as a liquid crystal display device.
  • the glass raw material was melted and molded by the float process to obtain the glass substrates of Examples 1 to 5.
  • the SO 2 gas was sprayed onto the bottom surface of the glass ribbon between the time when the glass ribbon left the float bath and the time when the glass ribbon contacted the transport roller in the float process.
  • the composition of the obtained glass substrate is shown in Table 1 in terms of mass% based on oxide.
  • Example 1 is manufactured under the conventional manufacturing conditions, Examples 2 and 3 are manufactured so that the water vapor concentration in the float bath is slightly high, and Examples 4 and 5 are in the float bath. It was manufactured with a higher water vapor concentration.
  • the content of these components is It was determined from the blending amount of the glass raw material.
  • the obtained glass substrate is pulverized, the obtained glass powder is thermally decomposed with sulfuric acid, nitric acid and hydrofluoric acid, and then concentrated until white smoke of sulfuric acid is produced.
  • a constant volume solution dissolved in nitric acid was obtained, and the Na concentration in the constant volume solution was determined by ICP mass spectrometry [unit: mass ppm].
  • the measurement conditions were Target Rh, tube voltage was 50 KV, and tube current was 60 mV.
  • the optical conditions were an attenuator 1/1 and a slit S4, a spectral crystal Ge, and a detector PC.
  • a calibration curve was prepared using several standard samples, and the sulfate amount of each sample was measured using the calibration curve. The results of S amount measurement for each sample are shown in Table 2 below.
  • Example 1 As a result of evaluating the ease of scratching of each sample, strong scratches occurred in Example 1, and no scratches occurred in Examples 2 to 5.
  • Example 1 since the amount of sulfate produced was small, the result was easily damaged. That is, the glass substrate of Example 1 the difference between the Na 2 O content and the glass substrate inside the Na 2 O content of the glass substrate surface is less than 20, scratched for production of sodium sulphate in the bottom surface the surface is insufficient It was easy and there was a quality control problem.
  • the glass substrates of Examples 2 and 3 were hardly scratched because sodium sulfate was formed on the bottom surface.
  • the glass substrates of Examples 4 and 5 were more difficult to be damaged because a large amount of sodium sulfate was formed on the bottom surface.
  • the glass substrate in any of Examples 2 to 5 has a sufficiently small amount of surface Na 2 O, it is considered that there is little deterioration in TFT characteristics when a TFT is formed on the bottom surface. Since the substrate has a particularly small amount of surface Na 2 O, it is considered that the degradation of TFT characteristics is particularly small.

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