WO2014092026A1 - ガラス及びガラス基板 - Google Patents
ガラス及びガラス基板 Download PDFInfo
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- WO2014092026A1 WO2014092026A1 PCT/JP2013/082882 JP2013082882W WO2014092026A1 WO 2014092026 A1 WO2014092026 A1 WO 2014092026A1 JP 2013082882 W JP2013082882 W JP 2013082882W WO 2014092026 A1 WO2014092026 A1 WO 2014092026A1
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- 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
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
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- 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
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- 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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
Definitions
- the present invention relates to glass and a glass substrate, and specifically relates to a glass and a glass substrate suitable for an organic EL (OLED) display and a liquid crystal display. Further, the present invention relates to a glass and a glass substrate suitable for an oxide TFT, a low temperature p-Si • TFT (LTPS) driven display.
- OLED organic EL
- LTPS low temperature p-Si • TFT
- glass substrates have been widely used as substrates for flat panel displays such as liquid crystal displays, hard disks, filters and sensors.
- OLED displays have been actively developed for reasons such as self-emission, high color reproducibility, high viewing angle, high-speed response, and high definition, and some have already been put into practical use. Has been.
- the display of a mobile device such as a smartphone has a small area, it is required to display a large amount of information. Therefore, an ultra-high-definition screen is required and a moving image is displayed. I need it.
- an OLED display or a liquid crystal display driven by LTPS is suitable.
- An OLED display emits light when a current flows through an OLED element constituting a pixel.
- a material having low resistance and high electron mobility is used as the driving TFT element.
- an oxide TFT typified by IGZO (indium, gallium, zinc oxide) has attracted attention.
- An oxide TFT has low resistance and high mobility, and can be formed at a relatively low temperature.
- Conventional p-Si TFTs, especially LTPS form elements on a large-area glass substrate due to the instability of excimer lasers used when polycrystallizing amorphous Si (a-Si) films.
- the TFT characteristics are likely to vary, and screen display unevenness is likely to occur in TV applications.
- an oxide TFT has been attracting attention as an effective TFT forming material when it is formed on a glass substrate having a large area, and thus has attracted attention as a powerful TFT forming material.
- Glass substrates used for high-definition displays have many required characteristics. In particular, the following characteristics (1) to (5) are required.
- the alkali component in the glass is large, alkali ions are diffused into the semiconductor material on which the film is formed during the heat treatment, and the characteristics of the film are deteriorated. Therefore, the content of alkali components (particularly, Li component and Na component) is small or not substantially contained.
- Various chemicals such as acid and alkali are used in the photolithography etching step. Therefore, it has excellent chemical resistance.
- the glass substrate is heat-treated at several hundred degrees Celsius in steps such as film formation and annealing. When the glass substrate is thermally contracted during the heat treatment, pattern deviation or the like is likely to occur. Therefore, heat shrinkage is difficult, especially the strain point is high.
- the thermal expansion coefficient is close to that of a member (for example, a-Si, p-Si) formed on a glass substrate.
- the thermal expansion coefficient is 30 to 40 ⁇ 10 ⁇ 7 / ° C.
- the thermal shock resistance is also improved.
- the Young's modulus (or specific Young's modulus) is high in order to suppress problems caused by the bending of the glass substrate.
- the following properties (6) and (7) are required for glass.
- (6) Excellent meltability in order to prevent melting defects such as bubbles, blisters and striae.
- (7) Excellent devitrification resistance to avoid generation of foreign matter in the glass substrate.
- the present invention has been made in view of the above circumstances, and its technical problem is that the glass satisfies the above required characteristics (1) to (7) and is suitable for OLED displays and liquid crystal displays driven by LTPS and oxide TFT elements. And to create a glass substrate. Specifically, it is to create a glass and a glass substrate having a low alkali component, a low density and a low thermal expansion coefficient, a high strain point and a Young's modulus, and excellent in devitrification resistance, meltability, moldability, and the like. .
- the present inventors have found that the above technical problem can be solved by regulating the glass composition within a predetermined range, and propose the present invention. That is, the glass of the present invention has a glass composition in terms of mass% of SiO 2 58 to 70%, Al 2 O 3 16 to 25%, B 2 O 3 3 to 8%, MgO 0 to 5%, CaO 3 to 13%, SrO 0-6%, BaO 0-6%, ZnO 0-5%, ZrO 2 0-5%, TiO 2 0-5%, P 2 O 5 0-5% To do.
- the present inventors have used SiO 2 —Al 2 O 3 —B 2 O 3 —RO (RO: alkaline earth metal oxide, MgO + CaO + SrO + BaO) glass as a glass that satisfies the above required characteristics (1) to (7). If the content of SiO 2 is controlled to 58% or more, the content of Al 2 O 3 to 16 to 25%, and the content of B 2 O 3 to 3 to 8%, high strain point and good resistance It has been found that chemical properties can be compatible. It has also been found that if the contents of SiO 2 , Al 2 O 3 , B 2 O 3 and RO are optimized, Young's modulus, devitrification resistance and the like are improved. Furthermore, it has been found that if the contents of B 2 O 3 , MgO and CaO are optimized, the meltability, moldability, resistance to devitrification and the like are improved.
- RO alkaline earth metal oxide
- the glass of the present invention has a glass composition, in mass%, SiO 2 58 ⁇ 70% , Al 2 O 3 16 ⁇ 25%, B 2 O 3 3 ⁇ 8%, MgO 0 ⁇ 5%, CaO 3-13%, SrO 0-6%, BaO 0-6%, ZnO 0-5%, ZrO 2 0-5%, TiO 2 0-5%, P 2 O 5 0-5%, In particular, it is characterized by containing no Li component or Na component, a density of 2.43 to 2.52 g / cm 3 , and a strain point of 680 ° C. or higher.
- substantially does not contain refers to the case where the content of the explicit component is 0.1% or less (preferably 0.05% or less), for example, “substantially contains no Li component. "" Refers to the case where the content of the Li component is 0.1% or less (preferably 0.05% or less). “Density” can be measured by the well-known Archimedes method. “Strain point” refers to a value measured based on the method of ASTM C336.
- the glass of the present invention contains substantially no Li component or Na component, a density of 2.43 to 2.52 g / cm 3 , a thermal expansion coefficient of 30 to 40 ⁇ 10 ⁇ 7 / ° C., Young's modulus is 75 GPa or more, strain point is 680 ° C. or more and less than 740 ° C., temperature at 10 5.0 dPa ⁇ s is 1250 ° C. or less, temperature at 10 2.5 dPa ⁇ s is 1650 ° C. or less, liquid viscosity (liquidus viscosity) ) Is 10 5.0 dPa ⁇ s or more.
- thermal expansion coefficient refers to an average thermal expansion coefficient measured in a temperature range of 30 to 380 ° C., and can be measured, for example, with a dilatometer.
- Young's modulus refers to a value measured by a dynamic elastic modulus measurement method (resonance method) based on JIS R1602.
- Tempoture at 10 5.0 dPa ⁇ s can be measured by, for example, a platinum ball pulling method.
- Tempoture at 10 2.5 dPa ⁇ s can be measured by, for example, a platinum ball pulling method.
- Liquid phase viscosity refers to the viscosity of glass at the liquid phase temperature (liquidus temperature), and can be measured by, for example, a platinum ball pulling method. “Liquid phase temperature” is obtained by passing the standard sieve 30 mesh (500 ⁇ m) and putting the glass powder remaining in 50 mesh (300 ⁇ m) into a platinum boat and holding it in a temperature gradient furnace for 24 hours, then removing the platinum boat, The temperature at which devitrification (crystal foreign matter) is observed in the glass.
- the glass composition of the present invention has a glass composition of mass% by weight of SiO 2 59-67%, Al 2 O 3 17-22%, B 2 O 3 4-7%, MgO 0-4%, CaO. 3-12%, SrO 0-5%, BaO 0.1-5%, ZnO 0-5%, ZrO 2 0-5%, TiO 2 0-5%, P 2 O 5 0-5%, SnO 2 It is preferable that 0 to 5% is contained and substantially no Li component or Na component is contained.
- the glass of the present invention has a glass composition, in mass%, SiO 2 60 ⁇ 65% , Al 2 O 3 17 ⁇ 20%, B 2 O 3 4 ⁇ 7%, MgO 0 ⁇ 3%, CaO 4-10%, SrO 0-5%, BaO 0.1-5%, ZnO 0-1%, ZrO 2 0-1%, TiO 2 0-1%, P 2 O 5 0-3%, SnO 2 It is preferable that it contains 0.01 to 1% and substantially does not contain a Li component or a Na component.
- the glass substrate of the present invention includes any one of the above glasses.
- the glass substrate of the present invention is preferably used for an OLED display.
- the glass substrate of the present invention is preferably used for a liquid crystal display.
- the glass substrate of the present invention is preferably used for an oxide TFT-driven display.
- the preferable upper limit content of SiO 2 is 70%, 68%, 66%, 65%, or 64%, and the preferable lower limit content is 58%, 59%, 60%, or 61%.
- the most preferable content range is 61 to 64%.
- a preferable upper limit content of Al 2 O 3 is 25%, 23%, 22%, 21%, or 20%, and a preferable lower limit content is 17%, 17.5%, or 18%. The most preferable content range is 18 to 20%.
- B 2 O 3 is a component that works as a flux and lowers viscosity to improve meltability.
- the content of B 2 O 3 is preferably 3 to 8%, 3 to 7%, or 4 to 7%.
- B 2 O 3 content is too small, it does not act sufficiently as a flux, the BHF resistance and crack resistance tends to decrease. Also, the liquidus temperature tends to increase.
- the content of B 2 O 3 is too large, the strain point, heat resistance, acid resistance tends to decrease. In particular, when the content of B 2 O 3 is 7% or more, the tendency becomes remarkable. Further, when the content of B 2 O 3 is too large, reduced Young's modulus, easily bending of the glass substrate is increased.
- the mass ratio Al 2 O 3 / B 2 O 3 is preferably 1 to 5, 1.5 to 4.5, 2 to 4, or 2.5 to 3.5. It is.
- MgO is a component that improves the meltability by lowering the high temperature viscosity without lowering the strain point. MgO has the effect of reducing the density most in RO, but when introduced excessively, the liquidus temperature tends to rise. Further, MgO is a component that easily reacts with BHF or hydrofluoric acid to form a product. This reaction product may adhere to the element on the surface of the glass substrate or adhere to the glass substrate, and may cause the element or the glass substrate to become cloudy. Therefore, the content of MgO is preferably 0 to 5%, more preferably 0 to 4%, still more preferably 0 to 3%, and most preferably 0 to 2.5%.
- CaO like MgO, is a component that significantly improves meltability by lowering the high temperature viscosity without lowering the strain point. If the content of CaO is too large, devitrification is likely to occur and the BHF resistance is lowered, and the reaction product adheres on the surface of the glass substrate or adheres to the glass substrate. Or the glass substrate may become cloudy.
- the preferable upper limit content of CaO is 12%, 11%, 10.5%, or 10%, and the preferable lower limit content is 3%, 3.5%, or 4%. The most preferable content range is 4 to 10%.
- SrO is a component that enhances chemical resistance and devitrification resistance. However, if the ratio is excessively increased in RO, the meltability tends to decrease and the density and thermal expansion coefficient easily increase. Therefore, the SrO content is preferably 0 to 6%, 0 to 5%, or 0 to 4.5%.
- BaO is a component that enhances chemical resistance and devitrification resistance, but if its content is too large, the density tends to increase. Moreover, BaO has a poor effect of improving the meltability in RO. Since the SiO 2 —Al 2 O 3 —B 2 O 3 —RO glass according to the present invention is generally difficult to melt, the melting property is improved from the viewpoint of supplying a high-quality glass substrate at a low cost and in large quantities. Therefore, it is very important to reduce the defect rate due to bubbles, foreign matters and the like. Therefore, the BaO content is preferably 0 to 6%, 0.1 to 5%, or 0.5 to 4%.
- MgO, SrO, and BaO have the property of improving crack resistance compared to CaO. Therefore, the content of MgO + SrO + BaO (total amount of MgO, SrO and BaO) is preferably 2% or more, 3% or more, or more than 3%. However, when there is too much content of MgO + SrO + BaO, a density and a thermal expansion coefficient will rise easily. Therefore, the content of MgO + SrO + BaO is preferably 9% or less or 8% or less.
- the RO content is preferably less than 15% or less than 14%, and the preferred range is less than 2 to 13%.
- the mass ratio CaO / (MgO + SrO + BaO) is preferably 0.7 or more, 0.8 or more, 0.9 or more, or 1 or more, and the mass ratio CaO / MgO is Preferably they are 2 or more, 3 or more, 4 or more, or 5 or more.
- ZnO is a component that improves meltability and BHF resistance. However, if its content is too large, the glass tends to be devitrified or the strain point is lowered, making it difficult to ensure heat resistance. . Therefore, the ZnO content is preferably 0 to 5%, or 0 to 1%.
- ZrO 2 is a component that enhances chemical durability. However, when the amount of ZrO 2 is increased, devitrification of ZrSiO 4 tends to occur.
- the preferable lower limit content of ZrO 2 is 1%, 0.5%, 0.3%, 0.2%, or 0.1%, and 0.005% or more may be introduced from the viewpoint of chemical durability. preferable. The most preferable content range is 0.005 to 0.1%.
- ZrO 2 may be introduced from a raw material or may be introduced by elution from a refractory.
- TiO 2 has the effect of lowering the high-temperature viscosity to increase the meltability and the chemical durability, but when the amount introduced is excessive, the ultraviolet transmittance tends to decrease.
- the content of TiO 2 is preferably 3% or less, 1% or less, 0.5% or less, 0.1% or less, 0.05% or less, or 0.03% or less. If a very small amount of TiO 2 is introduced (for example, 0.001% or more), an effect of suppressing coloring by ultraviolet rays can be obtained.
- P 2 O 5 is a component that increases the strain point and is a component that can suppress precipitation of devitrified crystals of alkaline earth aluminosilicates such as anorthite. However, when P 2 O 5 is contained in a large amount, the glass is likely to undergo phase separation.
- the content of P 2 O 5 is preferably 0 to 5%, 0 to 3%, 0 to 2%, 0 to 1%, or 0 to 0.5%.
- metal powder such as As 2 O 3 , Sb 2 O 3 , SnO 2 , SO 3 , Fe 2 O 3 , CeO 2 , F 2 , Cl 2 , C, Al, Si, or the like can be used. .
- the total content is preferably 3% or less.
- As 2 O 3 and Sb 2 O 3 are environmentally hazardous chemicals, so it is desirable not to use them as much as possible.
- the contents of As 2 O 3 and Sb 2 O 3 are less than 0.3%, less than 0.1%, less than 0.09%, less than 0.05%, less than 0.03%, and less than 0.01%, respectively. , Less than 0.005% or less than 0.003%.
- SnO 2 functions as a fining agent for reducing bubbles in the glass and has an effect of maintaining a relatively high ultraviolet transmittance when coexisting with Fe 2 O 3 or FeO.
- the preferable upper limit content of SnO 2 is 0.5%, 0.4%, or 0.3%, and the preferable lower limit content is 0.01%, 0.05%, or 0.1%.
- the most preferable content range is 0.1 to 0.4%.
- Fe 2 O 3 conversion refers to a value obtained by converting the total Fe amount to the Fe 2 O 3 amount regardless of the valence.
- Rh 2 O 3 may be mixed from a platinum production container.
- the content of Rh 2 O 3 is preferably 0 to 0.0005%, more preferably 0.00001 to 0.0001%.
- SO 3 is a component mixed from the raw material as an impurity, but if the content of SO 3 is too large, bubbles called reboil may be generated during melting and molding, which may cause defects in the glass. is there.
- the preferable upper limit content of SO 3 is 0.005%, 0.003%, 0.002%, or 0.001%, and the preferable lower limit content is 0.0001%.
- the most preferable content range is 0.0001% to 0.001%.
- Iron is a component mixed from the raw material as an impurity, but if the iron content is too large, the ultraviolet transmittance may be lowered. When the ultraviolet transmittance is lowered, there is a possibility that a defect may occur in a photolithography process for manufacturing a TFT or a liquid crystal alignment process using ultraviolet rays. Therefore, the preferable upper limit content of iron is 0.001% in terms of Fe 2 O 3 , and the preferable lower limit content is 0.05% and 0.04% in terms of Fe 2 O 3. , 0.03%, or 0.02%. The most preferable content range is 0.001% to 0.02%.
- Cr 2 O 3 is a component mixed from the raw material as an impurity.
- the content of Cr 2 O 3 is too large, light is incident from the end face of the glass substrate and the inside of the glass substrate is inspected by scattered light. When it is performed, light transmission is less likely to occur, which may cause a defect in the foreign matter inspection. In particular, this problem is likely to occur when the substrate size is 730 mm ⁇ 920 mm or more.
- the thickness of the glass substrate is small (e.g. 0.5mm or less, 0.4 mm or less, or 0.3mm or less), since the light incident from the glass substrate end face is reduced, regulating the content of Cr 2 O 3 The significance of doing is increased.
- the preferable upper limit content of Cr 2 O 3 is 0.001%, 0.0008%, 0.0006%, 0.0005%, or 0.0003%, and the preferable lower limit content is 0.00001%.
- the most preferable content range is 0.00001 to 0.0003%.
- alkali components particularly Li components and Na components (for example, Li 2 O, Na 2 O)
- Li components and Na components for example, Li 2 O, Na 2 O
- a preferable glass composition range can be obtained by combining preferable ranges of components.
- particularly preferable glass composition ranges are as follows. (1) As a glass composition, by mass%, SiO 2 59 to 67%, Al 2 O 3 17 to 22%, B 2 O 3 4 to 7%, MgO 0 to 4%, CaO 3 to 10%, SrO 0 -5%, BaO 0.1-5%, ZnO 0-5%, ZrO 2 0-5%, TiO 2 0-5%, P 2 O 5 0-5%, SnO 2 0-5% , Substantially free of Li component and Na component.
- the density is preferably 2.52 g / cm 3 or less, 2.51 g / cm 3 or less, 2.50 g / cm 3 or less, 2.49 g / cm 3 or less, or 2.48 / cm 3 or less.
- the density is preferably 2.43 g / cm 3 or more, 2.44 g / cm 3 or more, or 2.45 g / cm 3 or more.
- the thermal expansion coefficient is preferably 30 to 40 ⁇ 10 ⁇ 7 / ° C., 32 to 39 ⁇ 10 ⁇ 7 / ° C., 33 to 38 ⁇ 10 ⁇ 7 / ° C., or 34 to 37. ⁇ 10 -7 / ° C. In this way, it becomes easy to match the thermal expansion coefficient of a member (for example, a-Si, p-Si) formed on the glass substrate.
- a member for example, a-Si, p-Si
- a large-area glass substrate for example, 730 ⁇ 920 mm or more, 1100 ⁇ 1250 mm or more, or 1500 ⁇ 1500 mm or more
- a thin glass substrate for example, a plate thickness of 0.5 mm.
- 0.4 mm or less, or 0.3 mm or less tends to be used.
- the specific Young's modulus is preferably 30.0 GPa / g ⁇ cm ⁇ 3 or more, 30.5 GPa / g ⁇ cm ⁇ 3 or more, 31.0 GPa / g ⁇ cm ⁇ 3 or more, or 31.5 GPa / g ⁇ cm ⁇ 3. That's it.
- the Young's modulus is preferably 75 GPa or more, or 76 GPa or more.
- the process temperature of LTPS used in ultra-high-definition mobile displays is about 400-600 ° C.
- the strain point is preferably 680 ° C. or higher, 690 ° C. or higher, or 700 ° C. or higher.
- oxide TFTs have been fabricated by a temperature process of 300 to 400 ° C. equivalent to a-Si. However, if annealing is performed at a higher heat treatment temperature than before, more stable device characteristics can be obtained. I understand.
- the heat treatment temperature is about 400 to 600 ° C., and a glass substrate having a low heat shrinkage is required for this application.
- the heat shrinkage value is preferably 30 ppm or less, 25 ppm or less, 23 ppm or less, 22 ppm or less, or 21 ppm or less. In this way, even if heat treatment is performed in the LTPS manufacturing process, problems such as pixel pitch deviation are less likely to occur. If the heat shrinkage value is too small, the productivity of the glass tends to decrease. Therefore, the heat shrinkage value is preferably 5 ppm or more, or 8 ppm or more. In addition to increasing the strain point, the heat shrinkage value can also be reduced by reducing the cooling rate during molding.
- molten glass flows down the surface of a wedge-shaped refractory (or a refractory coated with a platinum group metal), joins at the lower end of the wedge, and is formed into a plate shape.
- a ribbon-shaped molten glass is caused to flow down from a platinum group metal pipe having a slit-shaped opening, cooled, and formed into a plate shape. If the temperature of the molten glass in contact with the molding apparatus is too high, the molding apparatus will be deteriorated, and the productivity of the glass substrate will be easily lowered. Therefore, the temperature at the high temperature viscosity of 10 5.0 dPa ⁇ s is preferably 1300 ° C.
- the temperature at a high temperature viscosity of 10 5.0 dPa ⁇ s corresponds to the temperature of the molten glass at the time of molding.
- the SiO 2 —Al 2 O 3 —B 2 O 3 —RO glass according to the present invention is generally difficult to melt. For this reason, improvement of meltability becomes a problem.
- the temperature at a high temperature viscosity of 10 2.5 dPa ⁇ s is preferably 1650 ° C. or lower, 1640 ° C. or lower, 1630 ° C. or lower, 1620 ° C. or lower, or 1610 ° C. or lower.
- the temperature at a high temperature viscosity of 10 2.5 dPa ⁇ s corresponds to the melting temperature, and the lower this temperature, the better the meltability.
- Devitrification resistance is important when molding by the downdraw method or the like.
- the liquidus temperature is preferably 1250 ° C. or lower, 1230 ° C. or lower, 1220 ° C. or lower, 1210 ° C. or lower, It is 1200 degrees C or less, or 1190 degrees C or less.
- the liquid phase viscosity is preferably 10 5.0 dPa ⁇ s or more, 10 5.2 dPa ⁇ s or more, 10 5.3 dPa ⁇ s or more, 10 5.4 dPa ⁇ s or more, 10 5.5 dPa ⁇ s or more, or 10 5.6 dPa ⁇ s or more. That's it.
- a transparent conductive film, an insulating film, a semiconductor film, a metal film, etc. are formed on a glass substrate used for a high-definition display. Furthermore, various circuits and patterns are formed by a photolithography etching process. In these film forming process and photolithography etching process, the glass substrate is subjected to various chemical treatments. For example, in a TFT type active matrix liquid crystal display, an insulating film or a transparent conductive film is formed on a glass substrate, and a large number of amorphous silicon or polycrystalline silicon TFTs (thin film transistors) are formed on the glass substrate by a photolithography etching process.
- the glass and glass substrate of the present invention are preferably formed by an overflow downdraw method.
- the overflow down draw method is a method of forming a glass substrate by overflowing molten glass from both sides of a wedge-shaped refractory and drawing the overflowed molten glass downward at the lower end of the wedge shape.
- the surface to be the surface of the glass substrate is not in contact with the refractory, and is formed in a free surface state. Therefore, an unpolished glass substrate having a good surface quality can be manufactured at low cost, and the area can be easily increased and the thickness can be reduced.
- the material of the refractory used in the overflow downdraw method is not particularly limited as long as it can realize desired dimensions and surface accuracy.
- the method of applying a force when performing downward stretch molding is not particularly limited.
- a method may be adopted in which a heat-resistant roll having a sufficiently large width is rotated and stretched in contact with glass, or a plurality of pairs of heat-resistant rolls are contacted only near the end face of the glass. It is also possible to adopt a method of stretching by stretching.
- a glass substrate can be formed by a downdraw method (slot down method, redraw method, etc.), a float method, or the like.
- the plate thickness is not particularly limited, but is preferably 0.5 mm or less, 0.4 mm or less, 0.35 mm or less, or 0.3 mm or less.
- the smaller the plate thickness the easier it is to reduce the weight of the device.
- the smaller the plate thickness the easier the glass substrate bends.
- board thickness can be adjusted with the flow rate at the time of glass manufacture, a board drawing speed, etc.
- the ⁇ -OH value is preferably 0.5 / mm or less, 0.45 / mm or less, 0.4 / mm or less, or 0.35 / mm or less. If the ⁇ -OH value is too large, the strain point tends to decrease. If the ⁇ -OH value is too small, the meltability tends to be lowered. Therefore, the ⁇ -OH value is preferably 0.01 / mm or more, or 0.05 / mm or more.
- the following methods may be mentioned.
- a component (Cl, SO 3 or the like) that reduces the amount of water in the glass is added.
- (4) N 2 bubbling is performed in molten glass.
- Adopt a small melting furnace. Increase the flow rate of the molten glass. (7) An electric melting method is adopted.
- ⁇ -OH value refers to a value obtained by measuring the transmittance of glass using FT-IR and using the following equation.
- ⁇ -OH value (1 / X) log (T 1 / T 2 )
- X Glass wall thickness (mm)
- T 1 Transmittance (%) at a reference wavelength of 3846 cm ⁇ 1
- T 2 Minimum transmittance (%) in the vicinity of a hydroxyl group absorption wavelength of 3600 cm ⁇ 1
- the glass and glass substrate of the present invention are preferably used for OLED displays. OLEDs are generally being marketed, but cost reduction by mass production is strongly desired. Since the glass and the glass substrate of the present invention are excellent in productivity and can be easily increased in area and thinned, it is possible to satisfy such a demand accurately.
- Tables 1 to 3 show examples of the present invention (sample Nos. 1 to 30).
- Each sample was produced as follows. First, a glass batch in which glass raw materials were prepared so as to have the glass composition in the table was placed in a platinum crucible and melted at 1600 ° C. for 24 hours. In melting the glass batch, the mixture was stirred and homogenized using a platinum stirrer. Next, the molten glass was poured out on a carbon plate and formed into a plate shape.
- the density is a value measured by the well-known Archimedes method.
- the thermal expansion coefficient is an average thermal expansion coefficient measured with a dilatometer in a temperature range of 30 to 380 ° C.
- the Young's modulus refers to a value measured by a dynamic elastic modulus measurement method (resonance method) based on JIS R1602, and the specific Young's modulus is a value obtained by dividing Young's modulus by density.
- strain point and softening point are values measured based on the method of ASTM C336.
- the temperature at a high temperature viscosity of 10 5.0 dPa ⁇ s and 10 2.5 dPa ⁇ s is a value measured by a platinum ball pulling method.
- each sample was pulverized, passed through a standard sieve 30 mesh (500 ⁇ m), and the glass powder remaining on 50 mesh (300 ⁇ m) was placed in a platinum boat and held in a temperature gradient furnace for 24 hours.
- the temperature at which devitrification (crystal foreign matter) was observed in the glass was taken as the liquidus temperature.
- the viscosity of the glass at the liquidus temperature was measured by the platinum ball pulling method, and this was taken as the liquidus viscosity.
- a 30 mm ⁇ 160 mm ⁇ 0.5 mm sample was cut out from the glass substrate, and the thermal shrinkage value of each sample was measured in the following manner.
- FIG. 1a After two linear marks M1 and M2 are entered at predetermined intervals in a predetermined portion of the glass substrate 25, the glass substrate 25 is oriented in a direction perpendicular to the mark M as shown in FIG.
- the glass plate piece 25a and the glass plate piece 25b were obtained by parting. Then, only the glass plate piece 25a was heated from normal temperature to 500 ° C.
- the glass plate pieces 25a subjected to heat treatment and the glass plate pieces 25b not subjected to heat treatment are aligned and fixed with the adhesive tape T, and the marks M1, M2 of the glass plate pieces 25a
- the amount of deviation from the marks M1 and M2 of the glass plate piece 25b was measured, and the heat shrinkage value was calculated based on the following mathematical formula 1.
- Equation 1 l 0 is the distance between the marks M on the glass substrate 25
- l 1 is the distance between the mark M1 on the glass plate piece 25a and the mark M1 on the glass plate piece 25b
- l 2 is the glass plate piece. This is the distance between the mark M2 of 25a and the mark M2 of the glass plate piece 25b.
- Sample No. Each of 1 to 30 has a density of 2.43 to 2.52 g / cm 3 , and the glass substrate can be reduced in weight.
- the thermal expansion coefficient of 30 ⁇ 40 ⁇ 10- 7 / °C , strain point is less than 740 ° C. 680 ° C. or higher, the heat shrinkage value is also small.
- the Young's modulus is 75 GPa or more and the specific Young's modulus is 30 GPa / (g / cm 3 ) or more, so that bending and deformation hardly occur.
- the temperature at a high temperature viscosity of 10 5.0 dPa ⁇ s is 1250 ° C. or lower, the temperature at 10 2.5 dPa ⁇ s is 1650 ° C.
- the liquidus temperature is 1300 ° C. or lower, and the liquid phase viscosity is 10 5.0 dPa ⁇ s or higher. Therefore, it has excellent meltability and moldability and is suitable for mass production. Furthermore, chemical resistance is also excellent.
- the glass and glass substrate of the present invention have few alkali components, low density and thermal expansion coefficient, high strain point and Young's modulus, and are excellent in devitrification resistance, meltability, moldability and the like. Therefore, the glass and glass substrate of the present invention are suitable for displays such as OLED displays and liquid crystal displays, and are suitable for displays driven by LTPS and oxide TFTs.
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- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
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Abstract
Description
(2)フォトリソグラフィーエッチング工程では、種々の酸、アルカリ等の薬液が使用される。よって、耐薬品性に優れていること。
(3)成膜、アニール等の工程で、ガラス基板は数100℃に熱処理される。熱処理の際に、ガラス基板が熱収縮すると、パターンズレ等が発生し易くなる。よって、熱収縮し難いこと、特に歪点が高いこと。
(4)熱膨張係数が、ガラス基板上に成膜される部材(例えば、a-Si、p-Si)に近いこと。例えば、熱膨張係数が30~40×10-7/℃であること。なお、熱膨張係数が40×10-7/℃以下であると、耐熱衝撃性も向上する。
(5)ガラス基板の撓みに起因する不具合を抑制するために、ヤング率(又は比ヤング率)が高いこと。
(6)泡、ブツ、脈理等の溶融欠陥を防止するために、溶融性に優れていること。
(7)ガラス基板中の異物発生を避けるために、耐失透性に優れていること。
(1)ガラス組成として、質量%で、SiO2 59~67%、Al2O3 17~22%、B2O3 4~7%、MgO 0~4%、CaO 3~10%、SrO 0~5%、BaO 0.1~5%、ZnO 0~5%、ZrO2 0~5%、TiO2 0~5%、P2O5 0~5%、SnO2 0~5%を含有し、実質的にLi成分、Na成分を含有しない。
(2)ガラス組成として、質量%で、SiO2 60~65%、Al2O3 17~20%、B2O3 4~7%、MgO 0~3%、CaO 4~10%、SrO 0~5%、BaO 0.1~5%、ZnO 0~1%、ZrO2 0~1%、TiO2 0~1%、P2O5 0~3%、SnO2 0.01~1%を含有し、実質的にLi成分、Na成分を含有しない。
β-OH値 = (1/X)log(T1/T2)
X:ガラス肉厚(mm)
T1:参照波長3846cm-1における透過率(%)
T2:水酸基吸収波長3600cm-1付近における最小透過率(%)
25a ガラス板片
25b ガラス板片
M マーク
M1 マーク
M2 マーク
Claims (9)
- ガラス組成として、質量%で、SiO2 58~70%、Al2O3 16~25%、B2O3 3~8%、MgO 0~5%、CaO 3~13%、SrO 0~6%、BaO 0~6%、ZnO 0~5%、ZrO2 0~5%、TiO2 0~5%、P2O5 0~5%を含有することを特徴とするガラス。
- ガラス組成として、質量%で、SiO2 58~70%、Al2O3 16~25%、B2O3 3~8%、MgO 0~5%、CaO 3~13%、SrO 0~6%、BaO 0~6%、ZnO 0~5%、ZrO2 0~5%、TiO2 0~5%、P2O5 0~5%を含有し、実質的にLi成分、Na成分を含有せず、密度が2.43~2.52g/cm3であり、且つ歪点が680℃以上であることを特徴とするガラス。
- 実質的にLi成分、Na成分を含有せず、密度が2.43~2.52g/cm3、熱膨張係数が30~40×10-7/℃、ヤング率が75GPa以上、歪点が680℃以上で且つ740℃未満、105.0dPa・sにおける温度が1250℃以下、102.5dPa・sにおける温度が1650℃以下、液相粘度が105.0dPa・s以上であることを特徴とするガラス。
- ガラス組成として、質量%で、SiO2 59~67%、Al2O3 17~22%、B2O3 4~7%、MgO 0~4%、CaO 3~12%、SrO 0~5%、BaO 0.1~5%、ZnO 0~5%、ZrO2 0~5%、TiO2 0~5%、P2O5 0~5%、SnO2 0~5%を含有し、実質的にLi成分、Na成分を含有しないことを特徴とする請求項1~3の何れか一項に記載のガラス。
- ガラス組成として、質量%で、SiO2 60~65%、Al2O3 17~20%、B2O3 4~7%、MgO 0~3%、CaO 4~10%、SrO 0~5%、BaO 0.1~5%、ZnO 0~1%、ZrO2 0~1%、TiO2 0~1%、P2O5 0~3%、SnO2 0.01~1%を含有し、実質的にLi成分、Na成分を含有しないことを特徴とする請求項1~4の何れか一項に記載のガラス。
- 請求項1~5の何れか一項に記載のガラスを備えることを特徴とするガラス基板。
- OLEDディスプレイに用いることを特徴とする請求項6に記載のガラス基板。
- 液晶ディスプレイに用いることを特徴とする請求項6に記載のガラス基板。
- 酸化物TFT駆動のディスプレイに用いることを特徴とする請求項6に記載のガラス基板。
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US14/441,280 US9598307B2 (en) | 2012-12-14 | 2013-12-06 | Glass and glass substrate |
CN201380047108.XA CN104619663B (zh) | 2012-12-14 | 2013-12-06 | 玻璃和玻璃基板 |
KR1020157000459A KR101639226B1 (ko) | 2012-12-14 | 2013-12-06 | 유리 및 유리 기판 |
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JP6037117B2 (ja) | 2016-11-30 |
KR20150031267A (ko) | 2015-03-23 |
KR101639226B1 (ko) | 2016-07-13 |
US20150315065A1 (en) | 2015-11-05 |
US9598307B2 (en) | 2017-03-21 |
TW201433557A (zh) | 2014-09-01 |
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