本發明是有關於一種高耐熱性的玻璃，例如是有關於一種用以在高溫下製作發光二極體（Light Emitting Diode，LED）用半導體結晶（semiconductor crystal）的玻璃基板。The present invention relates to a glass with high heat resistance, for example, relates to a glass substrate for making semiconductor crystals for Light Emitting Diodes (LEDs) at high temperatures.
對於用於LED等的半導體結晶而言，已知在越高的溫度下成膜，則半導體特性越會提高。For semiconductor crystals used in LEDs and the like, it is known that the higher the temperature at which the film is formed, the more the semiconductor characteristics will be improved.
在所述用途中一般使用高耐熱性的藍寶石（sapphire）基板。在其他用途中，當在高溫（例如700℃以上）下使半導體結晶成膜時，亦使用藍寶石基板。 [現有技術文獻] [專利文獻]Generally, a highly heat-resistant sapphire (sapphire) substrate is used for such applications. In other applications, a sapphire substrate is also used when forming a semiconductor crystal film at a high temperature (for example, 700° C. or higher). [Prior art literature] [Patent Document]
[專利文獻1]日本專利特開平11-243229號公報[Patent Document 1] Japanese Patent Laid-Open No. 11-243229
[發明所欲解決之課題] 而且近年來，正積極地研究使面積大的半導體結晶成膜的技術。認為該技術亦有望用於大型顯示器（display）的面發光光源。[Problem to be Solved by the Invention] In addition, in recent years, a technique of forming a large-area semiconductor crystal into a film has been actively studied. It is believed that this technology is also expected to be used as a surface-emitting light source for large displays.
然而，對於藍寶石基板而言，難以實現大面積化，不適合於所述用途。However, a sapphire substrate is difficult to achieve a large area, and is not suitable for such applications.
若使用玻璃基板來代替藍寶石基板，則認為可使基板實現大面積化，但以往的玻璃基板由於耐熱性不充分，故而容易在高溫的熱處理中產生熱變形。If a glass substrate is used instead of a sapphire substrate, it is considered that the substrate can be enlarged in area, but conventional glass substrates are not sufficiently heat resistant, and thus tend to be thermally deformed during high-temperature heat treatment.
而且，若欲使以往的玻璃基板的耐熱性提高，則玻璃基板的熱膨脹係數會不當地降低，從而難以與半導體結晶的熱膨脹係數匹配，在製作出半導體結晶後，玻璃基板容易翹曲，或半導體膜容易產生裂紋（crack）。進而，若欲使玻璃基板的耐熱性提高，則耐失透性會降低，從而難以成形為平板形狀的玻璃基板。Moreover, if the heat resistance of the conventional glass substrate is to be improved, the thermal expansion coefficient of the glass substrate will be unduly lowered, making it difficult to match the thermal expansion coefficient of the semiconductor crystal. After the semiconductor crystal is produced, the glass substrate is easy to warp, or the semiconductor The film is prone to cracks. Furthermore, when trying to improve the heat resistance of a glass substrate, devitrification resistance will fall, and it will become difficult to shape it into a flat glass substrate.
本發明是鑒於所述情況而成的發明，其技術課題在於創作耐熱性與熱膨脹係數高且能成形為平板形狀之玻璃。The present invention was made in view of the above circumstances, and its technical problem is to create glass that has high heat resistance and thermal expansion coefficient and can be formed into a flat plate shape.
[解決課題之手段] 本發明人反覆地進行各種實驗後，結果發現藉由將玻璃組成限制於規定範圍，能夠解決所述技術課題，從而提出了本發明。即，本發明的玻璃的特徵在於：以莫耳%計，含有55%～80%的SiO2、11%～30%的Al2O3、0～3%的B2O3、0～3%的Li2O+Na2O+K2O、5%～35%的MgO+CaO+SrO+BaO作為玻璃組成，且應變點（strain point）高於700℃。此處，「Li2O+Na2O+K2O」是指Li2O、Na2O及K2O的總量。「MgO+CaO+SrO+BaO」是指MgO、CaO、SrO及BaO的總量。此處，「應變點」是指基於美國材料試驗學會（American Society for Testing and Materials，ASTM）C336的方法進行測定所得的值。MEANS TO SOLVE THE PROBLEM As a result of repeated various experiments, the present inventors found that the said technical subject can be solved by limiting a glass composition to a predetermined range, and came up with this invention. That is, the glass of the present invention is characterized by containing 55% to 80% of SiO2 , 11% to 30% of Al2 O3 , 0 to 3% of B2 O3 , and 0 to 3% in mole %. % Li2 O+Na2 O+K2 O, 5%-35% MgO+CaO+SrO+BaO as the glass composition, and the strain point (strain point) is higher than 700°C. Here, "Li2 O+Na2 O+K2 O" means the total amount of Li2 O, Na2 O and K2 O. "MgO+CaO+SrO+BaO" means the total amount of MgO, CaO, SrO, and BaO. Here, the "strain point" refers to a value measured based on the method of American Society for Testing and Materials (ASTM) C336.
本發明的玻璃於玻璃組成中將Al2O3的含量限制為11莫耳%以上，將B2O3的含量限制為3莫耳%以下，且將Li2O+Na2O+K2O的含量限制為3莫耳%以下。藉此，應變點顯著地上升，從而能夠大幅度地提高玻璃基板的耐熱性。In the glass composition of the present invention, the content of Al2 O3 is limited to 11 mol % or more, the content of B2 O3 is limited to 3 mol % or less, and Li2 O+Na2 O+K2 The content of O is limited to 3 mol % or less. Thereby, the strain point rises remarkably, and the heat resistance of a glass substrate can be improved significantly.
而且，本發明的玻璃在玻璃組成中含有5莫耳%～25莫耳%的MgO+CaO+SrO+BaO。藉此，能夠使熱膨脹係數上升，且能夠提高耐失透性。Furthermore, the glass of the present invention contains 5 mol% to 25 mol% of MgO+CaO+SrO+BaO in the glass composition. Thereby, thermal expansion coefficient can be raised, and devitrification resistance can be improved.
第二，本發明的玻璃的B2O3的含量較佳為不足1莫耳%。Second, the B2 O3 content of the glass of the present invention is preferably less than 1 mol%.
第三，本發明的玻璃的Li2O+Na2O+K2O的含量較佳為0.2莫耳%以下。Thirdly, the content of Li2 O+Na2 O+K2 O in the glass of the present invention is preferably 0.2 mol % or less.
第四，本發明的玻璃的莫耳比（MgO+CaO+SrO+BaO）/Al2O3較佳為0.5～5。此處，「（MgO+CaO+SrO+BaO）/Al2O3」是將MgO、CaO、SrO及BaO的總量除以Al2O3的含量所得的值。Fourth, the molar ratio (MgO+CaO+SrO+BaO)/Al2 O3 of the glass of the present invention is preferably 0.5-5. Here, "(MgO+CaO+SrO+BaO)/Al2 O3 " is a value obtained by dividing the total amount of MgO, CaO, SrO, and BaO by the content of Al2 O3 .
第五，本發明的玻璃的莫耳比MgO/（MgO+CaO+SrO+BaO）較佳為不足0.5。此處，「MgO/（MgO+CaO+SrO+BaO）」是將MgO的含量除以MgO、CaO、SrO及BaO的總量所得的值。Fifth, the glass of the present invention preferably has a molar ratio MgO/(MgO+CaO+SrO+BaO) of less than 0.5. Here, "MgO/(MgO+CaO+SrO+BaO)" is a value obtained by dividing the content of MgO by the total amount of MgO, CaO, SrO, and BaO.
第六，本發明的玻璃的30℃～380℃的溫度範圍內的熱膨脹係數較佳為40×10-7/℃以上。此處，「30℃～380℃的溫度範圍內的熱膨脹係數」是指利用膨脹計（dilatometer）進行測定所得的平均值。Sixth, the thermal expansion coefficient of the glass of the present invention in the temperature range of 30°C to 380°C is preferably 40×10-7 /°C or higher. Here, "the thermal expansion coefficient in the temperature range of 30 degreeC - 380 degreeC" means the average value measured by the dilatometer.
第七，本發明的玻璃的應變點較佳為800℃以上。Seventh, the strain point of the glass of the present invention is preferably 800° C. or higher.
第八，本發明的玻璃的（在高溫黏度102.5dPa·s時的溫度-應變點）較佳為900℃以下。此處，「在高溫黏度102.5dPa·s時的溫度」是指利用鉑球提拉法進行測定所得的值。Eighth, the glass of the present invention (temperature-strain point at a high temperature viscosity of 102.5 dPa·s) is preferably 900°C or lower. Here, "the temperature at which the high-temperature viscosity is 102.5 dPa·s" refers to a value measured by the platinum ball pulling method.
第九，本發明的玻璃在高溫黏度102.5dPa·s的黏度時的溫度較佳為1750℃以下。Ninth, the temperature of the glass of the present invention is preferably below 1750°C when the high temperature viscosity is 102.5 dPa·s.
第十，本發明的玻璃較佳為平板形狀。Tenth, the glass of the present invention is preferably in the shape of a flat plate.
第十一，本發明的玻璃較佳為用作用以使半導體結晶成長的基板。Eleventh, the glass of the present invention is preferably used as a substrate for growing semiconductor crystals.
本發明的玻璃以莫耳%計，含有55%～80%的SiO2、11%～30%的Al2O3、0～3%的B2O3、0～3%的Li2O+Na2O+K2O、5%～35%的MgO+CaO+SrO+BaO作為玻璃組成。如上所述，以下說明對各成分的含量進行限制的理由。再者，在各成分的說明中，下述的%的表達是指莫耳%。The glass of the present invention contains 55% to 80% of SiO2 , 11% to 30% of Al2 O3 , 0 to 3% of B2 O3 , and 0 to 3% of Li2 O+ in mole %. Na2 O+K2 O, 5% to 35% MgO+CaO+SrO+BaO are used as the glass composition. As mentioned above, the reason for limiting content of each component is demonstrated below. In addition, in description of each component, the following expression of % means mole %.
SiO2的適當的下限範圍為55%以上、58%以上、60%以上、65%以上，尤其為68%以上，適當的上限範圍較佳為80%以下、75%以下、73%以下、72%以下、71%以下，尤其為70%以下。若SiO2的含量過少，則容易產生由包含Al2O3的失透結晶引起的缺陷，並且應變點容易降低。而且，高溫黏度會降低，從而液相黏度容易降低。另一方面，若SiO2的含量過多，則熱膨脹係數會不當地降低，而且高溫黏度會升高，熔融性降低，進而容易產生包含SiO2的失透結晶等。The appropriate lower limit range ofSiO2 is more than 55%, more than 58%, more than 60%, more than 65%, especially more than 68%, and the appropriate upper limit range is preferably less than 80%, less than 75%, less than 73%, and less than 72%. % or less, 71% or less, especially 70% or less. When the content of SiO2 is too small, defects due to devitrified crystals containing Al2 O3 are likely to occur, and the strain point is likely to decrease. Furthermore, the high-temperature viscosity decreases, and the liquid phase viscosity tends to decrease. On the other hand, if the content ofSiO2 is too high, the coefficient of thermal expansion will decrease unduly, and the high-temperature viscosity will increase, the meltability will decrease, and devitrification crystals containingSiO2 will easily occur.
Al2O3的適當的下限範圍為11%以上、12%以上、13%以上、14%以上，尤其為15%以上，適當的上限範圍為30%以下、25%以下、20%以下、18%以下、17%以下，尤其為16%以下。若Al2O3的含量過少，則應變點容易降低，或高溫黏性升高，熔融性容易降低。另一方面，若Al2O3的含量過多，則容易產生包含Al2O3的失透結晶。The appropriate lower limit of Al2 O3 is 11%, 12%, 13%, 14%, especially 15%, and the appropriate upper limit is 30%, 25%, 20%, 18% % or less, 17% or less, especially 16% or less. When the content of Al2 O3 is too small, the strain point tends to decrease, or the high-temperature viscosity increases, and the meltability tends to decrease. On the other hand, when the content of Al2 O3 is too large, devitrified crystals containing Al2 O3 are likely to be generated.
就兼顧高應變點與高耐失透性的觀點而言，莫耳比SiO2/Al2O3較佳為2～6、3～5.5、3.5～5.5、4～5.5、4.5～5.5，尤其為4.5～5。再者，「SiO2/Al2O3」是將SiO2的含量除以Al2O3的含量所得的值。From the viewpoint of both high strain point and high devitrification resistance, the molar ratio SiO2 /Al2 O3 is preferably 2-6, 3-5.5, 3.5-5.5, 4-5.5, 4.5-5.5, especially 4.5-5.In addition, "SiO2 /Al2O3 " is the value obtained by dividing the contentofSiO2 by the content ofAl2O3 .
B2O3的適當的上限範圍為3%以下、1%以下、不足1%，尤其為0.1%以下。若B2O3的含量過多，則應變點有可能會大幅度地降低。The appropriate upper limit range of B2 O3 is 3% or less, 1% or less, less than 1%, especially 0.1% or less. When the content of B2 O3 is too high, the strain point may be significantly lowered.
Li2O+Na2O+K2O的適當的上限範圍為3%以下、1%以下、不足1%、0.5%以下，尤其為0.2%以下。若Li2O+Na2O+K2O的含量過多，則玻璃上所形成的半導體結晶的特性有可能會變差。再者，Li2O、Na2O及K2O的適當的上限範圍分別為3%以下、1%以下、不足1%、0.5%以下、0.3%以下，尤其為0.2%以下。The appropriate upper limit range of Li2 O+Na2 O+K2 O is 3% or less, 1% or less, less than 1%, 0.5% or less, especially 0.2% or less. When the content of Li2 O+Na2 O+K2 O is too large, the properties of the semiconductor crystal formed on the glass may deteriorate. In addition, the appropriate upper limit ranges of Li2 O, Na2 O, and K2 O are respectively 3% or less, 1% or less, less than 1%, 0.5% or less, 0.3% or less, especially 0.2% or less.
MgO+CaO+SrO+BaO的適當的下限範圍為5%以上、7%以上、9%以上、11%以上、13%以上，尤其為14%以上，適當的上限範圍為35%以下、30%以下、25%以下、20%以下、18%以下、17%以下，尤其為16%以下。若MgO+CaO+SrO+BaO的含量過少，則液相溫度會大幅度地上升，玻璃中容易產生失透結晶，或高溫黏性升高，熔融性容易降低。另一方面，若MgO+CaO+SrO+BaO的含量過多，則應變點容易降低，而且容易產生包含鹼土類元素的失透結晶。The appropriate lower limit range of MgO+CaO+SrO+BaO is 5% or more, 7% or more, 9% or more, 11% or more, 13% or more, especially 14% or more, and the appropriate upper limit range is 35% or less, 30% Less than 25%, less than 20%, less than 18%, less than 17%, especially less than 16%. If the content of MgO+CaO+SrO+BaO is too small, the liquidus temperature will rise significantly, devitrification crystals will easily occur in the glass, or the high-temperature viscosity will increase, and the meltability will easily decrease. On the other hand, if the content of MgO+CaO+SrO+BaO is too large, the strain point will tend to fall, and devitrified crystals containing alkaline earth elements will tend to occur.
MgO的適當的下限範圍為0%以上、1%以上、2%以上、3%以上、4%以上，尤其為5%以上，適當的上限範圍為15%以下、10%以下、8%以下，尤其為7%以下。若MgO的含量過少，則熔融性容易降低，或包含鹼土類元素的結晶的失透性容易升高。另一方面，若MgO的含量過多，則會助長包含Al2O3的失透結晶析出而導致液相黏度降低，或導致應變點大幅度地降低。再者，MgO雖具有使熱膨脹係數上升的效果，但在鹼土類氧化物中，MgO的效果最小。The appropriate lower limit range of MgO is 0% or more, 1% or more, 2% or more, 3% or more, 4% or more, especially 5% or more, and the appropriate upper limit range is 15% or less, 10% or less, 8% or less, Especially less than 7%. When there is too little content of MgO, meltability will fall easily, or the devitrification property of the crystal|crystallization containing an alkaline-earth element will become high easily. On the other hand, if the content of MgO is too high, the precipitation of devitrified crystals including Al2 O3 will be promoted, resulting in a decrease in liquid phase viscosity, or a significant decrease in strain point. In addition, although MgO has the effect of increasing the thermal expansion coefficient, the effect of MgO is the smallest among alkaline earth oxides.
CaO的適當的下限範圍為2%以上、3%以上、4%以上、5%以上、6%以上，尤其為7%以上，適當的上限範圍為20%以下、15%以下、12%以下、11%以下、10%以下，尤其為9%以下。若CaO的含量過少，則熔融性容易降低。另一方面，若CaO的含量過多，則液相溫度會上升，玻璃中容易產生失透結晶。再者，CaO與其他鹼土類氧化物相比較，不使應變點降低而改善液相黏度的效果或提高熔融性的效果大，而且使熱膨脹係數上升的效果比MgO更大。The appropriate lower limit range of CaO is 2% or more, 3% or more, 4% or more, 5% or more, 6% or more, especially 7% or more, and the appropriate upper limit range is 20% or less, 15% or less, 12% or less, Below 11%, below 10%, especially below 9%. When there is too little content of CaO, meltability will fall easily. On the other hand, when there is too much content of CaO, a liquidus temperature will rise, and devitrification crystal|crystallization will generate|occur|produce easily in glass. Furthermore, compared with other alkaline earth oxides, CaO has a greater effect of improving the liquid phase viscosity or improving the meltability without lowering the strain point, and has a greater effect of increasing the thermal expansion coefficient than MgO.
SrO的適當的下限範圍為0%以上、1%以上，尤其為2%以上，適當的上限範圍為10%以下、8%以下、7%以下、6%以下、5%以下，尤其為4%以下。若SrO的含量過少，則應變點容易降低。另一方面，若SrO的含量過多，則液相溫度會上升，玻璃中容易產生失透結晶，而且熔融性容易降低。進而，在與CaO共存的情況下，若SrO的含量增多，則存在耐失透性降低的傾向。再者，SrO與MgO或CaO相比較，使熱膨脹係數上升的效果更大。The appropriate lower limit range of SrO is 0% or more, 1% or more, especially 2% or more, and the appropriate upper limit range is 10% or less, 8% or less, 7% or less, 6% or less, 5% or less, especially 4% the following. When there is too little content of SrO, a strain point will fall easily. On the other hand, if the content of SrO is too large, the liquidus temperature will rise, devitrification crystals will easily occur in the glass, and the meltability will tend to decrease. Furthermore, when it coexists with CaO, when content of SrO increases, there exists a tendency for devitrification resistance to fall. Furthermore, SrO has a greater effect of raising the thermal expansion coefficient than MgO or CaO.
BaO的適當的下限範圍為0%以上、3%以上、4%以上、5%以上、6%以上、7%以上，尤其為8%以上，適當的上限範圍為15%以下、12%以下、11%以下，尤其為10%以下。若BaO的含量過少，則應變點或熱膨脹係數容易降低。另一方面，若BaO的含量過多，則液相溫度會上升，玻璃中容易產生失透結晶。而且，熔融性容易降低。再者，BaO在鹼土類金屬氧化物中，使熱膨脹係數或應變點上升的效果最大。The appropriate lower limit range of BaO is 0% or more, 3% or more, 4% or more, 5% or more, 6% or more, 7% or more, especially 8% or more, and the appropriate upper limit range is 15% or less, 12% or less, Below 11%, especially below 10%. When the content of BaO is too small, the strain point and the coefficient of thermal expansion tend to decrease. On the other hand, when there is too much content of BaO, a liquidus temperature will rise, and devitrification crystal|crystallization will generate|occur|produce easily in glass. Furthermore, meltability tends to decrease. Furthermore, BaO has the greatest effect of increasing the thermal expansion coefficient or strain point among alkaline earth metal oxides.
就提高耐失透性的觀點而言，莫耳比MgO/CaO的下限範圍較佳為0.1以上、0.2以上、0.3以上，尤其為0.4以上，上限範圍較佳為2以下、1以下、0.8以下、0.7以下，尤其為0.6以下。再者，「MgO/CaO」是指將MgO的含量除以CaO的含量所得的值。From the viewpoint of improving devitrification resistance, the lower limit range of the molar ratio MgO/CaO is preferably 0.1 or more, 0.2 or more, 0.3 or more, especially 0.4 or more, and the upper limit range is preferably 2 or less, 1 or less, and 0.8 or less. , 0.7 or less, especially 0.6 or less. In addition, "MgO/CaO" means the value which divided the content of MgO by the content of CaO.
就提高耐失透性的觀點而言，莫耳比BaO/CaO的下限範圍較佳為0.2以上、0.5以上、0.6以上、0.7以上，尤其為0.8以上，上限範圍較佳為5以下、4.5以下、3以下、2.5以下，尤其為2以下。再者，「BaO/CaO」是指將BaO的含量除以CaO的含量所得的值。From the viewpoint of improving devitrification resistance, the lower limit range of the molar ratio BaO/CaO is preferably 0.2 or more, 0.5 or more, 0.6 or more, 0.7 or more, especially 0.8 or more, and the upper limit range is preferably 5 or less and 4.5 or less , 3 or less, 2.5 or less, especially 2 or less. In addition, "BaO/CaO" means the value which divided the content of BaO by the content of CaO.
鑒於應變點與熔融性的平衡，莫耳比（MgO+CaO+SrO+BaO）/Al2O3的下限範圍較佳為0.5以上、0.6以上、0.7以上，尤其為0.8以上，上限範圍較佳為5.0以下、4.0以下、3.0以下、2.0以下、1.5以下、1.2以下，尤其為1.1以下。In view of the balance between strain point and melting property, the lower limit range of the molar ratio (MgO+CaO+SrO+BaO)/Al2 O3 is preferably 0.5 or more, 0.6 or more, 0.7 or more, especially 0.8 or more, and the upper limit range is better 5.0 or less, 4.0 or less, 3.0 or less, 2.0 or less, 1.5 or less, 1.2 or less, especially 1.1 or less.
莫耳比MgO/（MgO+CaO+SrO+BaO）較佳為0.6以下、不足0.5、0.4以下、0.3以下、0.2以下，尤其為0.1以下。MgO是使應變點大幅度地降低的成分，其在MgO的含量少的區域中，使應變點降低的效果顯著。藉此，較佳為鹼土類金屬氧化物中的MgO的含有比例少。The molar ratio MgO/(MgO+CaO+SrO+BaO) is preferably 0.6 or less, less than 0.5, 0.4 or less, 0.3 or less, 0.2 or less, especially 0.1 or less. MgO is a component that greatly lowers the strain point, and the effect of lowering the strain point is remarkable in an area where the content of MgO is small. Accordingly, it is preferable that the content ratio of MgO in the alkaline earth metal oxide is small.
7×[MgO]+5×[CaO]+4×[SrO]+4×[BaO]較佳為100%以下、90%以下、80%以下、70%以下、65%以下，尤其為60%以下。鹼土類金屬元素均具有使應變點降低的效果，但元素的離子半徑越小，則其影響越大。藉此，若以不使離子半徑小的鹼土類元素的比例增大的方式，對7×[MgO]+5×[CaO]+4×[SrO]+4×[BaO]的上限範圍進行限制，則能夠優先提高應變點。再者，[MgO]是指MgO的含量，[CaO]是指CaO的含量，[SrO]是指SrO的含量，[BaO]是指BaO的含量。而且，「7×[MgO]+5×[CaO]+4×[SrO]+4×[BaO]」是指7倍的[MgO]、5倍的[CaO]、4倍的[SrO]及4倍的[BaO]的總量。7×[MgO]+5×[CaO]+4×[SrO]+4×[BaO] is preferably 100% or less, 90% or less, 80% or less, 70% or less, 65% or less, especially 60% the following. All alkaline earth metal elements have the effect of lowering the strain point, but the smaller the ionic radius of the element, the greater the effect. In this way, the upper limit of 7×[MgO]+5×[CaO]+4×[SrO]+4×[BaO] is limited so as not to increase the proportion of alkaline earth elements with small ionic radii , the strain point can be increased preferentially. In addition, [MgO] means the content of MgO, [CaO] means the content of CaO, [SrO] means the content of SrO, and [BaO] means the content of BaO. Moreover, "7×[MgO]+5×[CaO]+4×[SrO]+4×[BaO]" means 7 times [MgO], 5 times [CaO], 4 times [SrO] and 4 times the total amount of [BaO].
21×[MgO]+20×[CaO]+15×[SrO]+12×[BaO]較佳為200%以上、210%以上、220%以上、230%以上、240%以上、250%以上，尤其為300%～1000%。鹼土類金屬元素均具有提高熔融性的效果，但元素的離子半徑越小，則其影響越大。藉此，若以不使離子半徑小的鹼土類元素的比例增大的方式，對21×[MgO]+20×[CaO]+15×[SrO]+12×[BaO]的下限範圍進行限制，則能夠優先提高熔融性。然而，若21×[MgO]+20×[CaO]+15×[SrO]+12×[BaO]過大，則應變點有可能會降低。再者，「21×[MgO]+20×[CaO]+15×[SrO]+12×[BaO]」是指21倍的[MgO]、20倍的[CaO]、15倍的[SrO]及12倍的[BaO]的總量。21×[MgO]+20×[CaO]+15×[SrO]+12×[BaO] is preferably 200% or more, 210% or more, 220% or more, 230% or more, 240% or more, 250% or more, In particular, it is 300% to 1000%. Alkaline earth metal elements all have the effect of improving the meltability, but the smaller the ionic radius of the element, the greater the effect. In this way, the lower limit of 21×[MgO]+20×[CaO]+15×[SrO]+12×[BaO] is limited so as not to increase the proportion of alkaline earth elements with small ionic radii , the meltability can be preferentially improved. However, if 21×[MgO]+20×[CaO]+15×[SrO]+12×[BaO] is too large, the strain point may decrease. Furthermore, "21×[MgO]+20×[CaO]+15×[SrO]+12×[BaO]" means 21 times [MgO], 20 times [CaO], and 15 times [SrO] And 12 times the total amount of [BaO].
除了所述成分以外，亦可將以下的成分導入至玻璃組成中。In addition to the above components, the following components may also be introduced into the glass composition.
ZnO是提高熔融性的成分，但若玻璃組成中大量地含有該ZnO，則玻璃容易失透，而且應變點容易降低。藉此，ZnO的含量較佳為0～5%、0～3%、0～0.5%、0～0.3%，尤其為0～0.1%。ZnO is a component that improves the meltability, but if the glass composition contains a large amount of ZnO, the glass is likely to be devitrified and the strain point is likely to be lowered. Accordingly, the content of ZnO is preferably 0-5%, 0-3%, 0-0.5%, 0-0.3%, especially 0-0.1%.
ZrO2是提高楊氏模量（Young's modulus）的成分。ZrO2的含量較佳為0～5%、0～3%、0～0.5%、0～0.2%，尤其為0～0.02%。若ZrO2的含量過多，則液相溫度會上升，鋯石（zircon）的失透結晶容易析出。ZrO2 is a component that increases Young's modulus. The content of ZrO2 is preferably 0-5%, 0-3%, 0-0.5%, 0-0.2%, especially 0-0.02%. If the content of ZrO2 is too high, the liquidus temperature will rise, and devitrified crystals of zircon (zircon) will easily precipitate.
TiO2是降低高溫黏性而提高熔融性的成分，並且是抑制曝曬作用（solarization）的成分，但若玻璃組成中大量地含有該TiO2，則玻璃容易著色。藉此，TiO2的含量較佳為0～5%、0～3%、0～1%、0～0.1%，尤其為0～0.02%。TiO2 is a component that lowers high-temperature viscosity to improve meltability, and is a component that suppresses solarization. However, when the glass composition contains a large amount of TiO2 , the glass tends to be colored. Accordingly, the content of TiO2 is preferably 0-5%, 0-3%, 0-1%, 0-0.1%, especially 0-0.02%.
P2O5是提高耐失透性的成分，但若玻璃組成中大量地含有該P2O5，則玻璃容易分相而變得乳白，而且耐水性有可能會大幅度地降低。藉此，P2O5的含量較佳為0～5%、0～4%、0～3%、0～不足2%、0～1%、0～0.5%，尤其為0～0.1%。P2 O5 is a component that improves the devitrification resistance, but if the glass composition contains a large amount of this P2 O5 , the glass is likely to phase-separate and become opalescent, and there is a possibility that the water resistance may be significantly lowered. Accordingly, the content of P2 O5 is preferably 0 to 5%, 0 to 4%, 0 to 3%, 0 to less than 2%, 0 to 1%, 0 to 0.5%, especially 0 to 0.1%.
SnO2是在高溫區域中具有良好的澄清作用的成分，並且是使高溫黏性降低的成分。SnO2的含量較佳為0～1%、0.01%～0.5%、0.01%～0.3%，尤其為0.04%～0.1%。若SnO2的含量過多，則SnO2的失透結晶容易析出。SnO2 is a component that has a good clarification effect in a high-temperature region, and is a component that lowers high-temperature viscosity. The content of SnO2 is preferably 0-1%, 0.01%-0.5%, 0.01%-0.3%, especially 0.04%-0.1%. When the content of SnO2 is too large, devitrified crystals of SnO2 are easily precipitated.
如上所述，對於本發明的玻璃而言，較佳為添加SnO2作為澄清劑，但只要不損害玻璃特性，則亦可添加直至1%為止的CeO2、SO3、C、金屬粉末（例如Al、Si等）作為澄清劑。As mentioned above, it is preferable to add SnO2 as a clarifying agent to the glass of the present invention, but CeO2 , SO3 , C, metal powder (such as Al, Si, etc.) as clarifiers.
As2O3、Sb2O3、F、Cl亦作為澄清劑而有效地發揮作用，本發明的玻璃並不排除含有該些成分，但就環境的觀點而言，該些成分的含量分別較佳為不足0.1%，尤其為不足0.05%。As2 O3 , Sb2 O3 , F, and Cl also function effectively as clarifiers, and the glass of the present invention does not exclude the inclusion of these components, but from an environmental point of view, the contents of these components are relatively low. It is preferably less than 0.1%, especially less than 0.05%.
在包含0.01%～0.5%的SnO2的情況下，若Rh2O3的含量過多，則玻璃容易著色。再者，Rh2O3有可能會從鉑製造容器混入。Rh2O3的含量較佳為0～0.0005%，更佳為0.00001%～0.0001%。In the case of containing 0.01% to 0.5% of SnO2 , if the content of Rh2 O3 is too large, the glass will be easily colored. Furthermore, Rh2 O3 may be mixed in from the platinum manufacturing container. The content of Rh2 O3 is preferably from 0 to 0.0005%, more preferably from 0.00001% to 0.0001%.
SO3是作為雜質而從原料混入的成分，但若SO3的含量過多，則會在熔融或成形過程中產生被稱為再沸（reboil）的氣泡，從而有可能使玻璃中產生缺陷。SO3的適當的下限範圍為0.0001%以上，適當的上限範圍為0.005%以下、0.003%以下、0.002%以下，尤其為0.001%以下。SO3 is a component mixed from the raw material as an impurity, but if the content of SO3 is too high, bubbles called reboil will be generated during melting or forming, which may cause defects in the glass. The appropriate lower limit range of SO3 is 0.0001% or more, and the appropriate upper limit range is 0.005% or less, 0.003% or less, 0.002% or less, especially 0.001% or less.
稀土類氧化物（Sc、Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等的氧化物）的含量較佳為不足2%、1%以下、不足0.5%，尤其為不足0.1%。特別是La2O3+Y2O3的含量較佳為不足2%、不足1%、不足0.5%，尤其為不足0.1%。La2O3的含量較佳為不足2%、不足1%、不足0.5%，尤其為不足0.1%。若稀土類氧化物的含量過多，則批次成本（batch cost）容易增加。再者，「Y2O3+La2O3」為Y2O3與La2O3的總量。The content of rare earth oxides (oxides of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, etc.) is preferably less than 2%, Less than 1%, less than 0.5%, especially less than 0.1%. In particular, the content of La2 O3 +Y2 O3 is preferably less than 2%, less than 1%, less than 0.5%, especially less than 0.1%. The content of La2 O3 is preferably less than 2%, less than 1%, less than 0.5%, especially less than 0.1%. If the content of the rare earth oxide is too high, the batch cost will easily increase. In addition, "Y2 O3 +La2 O3 " is the total amount of Y2 O3 and La2 O3 .
本發明的玻璃較佳為具有以下的特性。The glass of the present invention preferably has the following properties.
密度較佳為3.20 g/cm3以下、3.00 g/cm3以下、2.90 g/cm3以下，尤其為2.80 g/cm3以下。若密度過高，則難以實現電子元件的輕量化。The density is preferably 3.20 g/cm3 or less, 3.00 g/cm3 or less, 2.90 g/cm3 or less, especially 2.80 g/cm3 or less. If the density is too high, it will be difficult to reduce the weight of electronic components.
30℃～380℃的溫度範圍中的熱膨脹係數較佳為40×10-7/℃以上、42×10-7/℃以上、44×10-7/℃以上、46×10-7/℃以上，尤佳為48×10-7/℃～80×10-7/℃。若30℃～380℃的溫度範圍中的熱膨脹係數過低，則半導體結晶（例如氮化物半導體結晶）與玻璃基板的熱膨脹係數不匹配，玻璃基板容易翹曲，或半導體結晶容易產生裂紋。The thermal expansion coefficient in the temperature range of 30°C to 380°C is preferably 40×10-7 /°C or higher, 42×10-7 /°C or higher, 44×10-7 /°C or higher, 46×10-7 /°C or higher , preferably 48×10-7 /°C to 80×10-7 /°C. If the thermal expansion coefficient in the temperature range of 30° C. to 380° C. is too low, the thermal expansion coefficients of semiconductor crystals (for example, nitride semiconductor crystals) and the glass substrate will not match, and the glass substrate will easily warp, or the semiconductor crystal will easily crack.
應變點較佳為超過700℃、750℃以上、780℃以上、800℃以上、810℃以上、820℃以上，尤佳為830℃～1000℃。若應變點過低，則無法使熱處理溫度實現高溫化，難以提高半導體結晶的半導體特性。The strain point is preferably higher than 700°C, higher than 750°C, higher than 780°C, higher than 800°C, higher than 810°C, higher than 820°C, particularly preferably 830°C to 1000°C. If the strain point is too low, the heat treatment temperature cannot be increased, making it difficult to improve the semiconductor characteristics of the semiconductor crystal.
本發明的SiO2-Al2O3-RO（RO是指鹼土類金屬氧化物）系玻璃一般難以熔融。因此，熔融性的提高成為課題。若提高熔融性，則由氣泡、異物等引起的不良率會降低，因此，能夠大量且廉價地供給高品質的玻璃基板。另一方面，若高溫黏度過高，則難以利用熔融步驟來促進除氣。藉此，在高溫黏度102.5dPa·s時的溫度較佳為1750℃以下、1700℃以下、1680℃以下、1670℃以下、1650℃以下，尤其為1630℃以下。再者，在高溫黏度102.5dPa·s時的溫度相當於熔融溫度，該溫度越低，則熔融性越優異。The SiO2 -Al2 O3 -RO (RO means alkaline earth metal oxide)-based glass of the present invention is generally difficult to melt. Therefore, improvement of meltability becomes a subject. If the meltability is improved, the defective rate due to air bubbles, foreign matter, etc. will be reduced, and thus a large amount of high-quality glass substrates can be supplied at low cost. On the other hand, if the high-temperature viscosity is too high, it is difficult to promote degassing by the melting step. Accordingly, the temperature at high temperature viscosity of 102.5 dPa·s is preferably below 1750°C, below 1700°C, below 1680°C, below 1670°C, below 1650°C, especially below 1630°C. Furthermore, the temperature at a high-temperature viscosity of 102.5 dPa·s corresponds to the melting temperature, and the lower the temperature, the better the meltability.
就兼顧高應變點與低熔融溫度的觀點而言，（在102.5dPa·s時的溫度-應變點）較佳為900℃以下、850℃以下，尤其為800℃以下。From the viewpoint of achieving both a high strain point and a low melting temperature, (temperature-strain point at 102.5 dPa·s) is preferably 900°C or lower, 850°C or lower, especially 800°C or lower.
在成形為平板形狀的情況下，耐失透性變得重要。若考慮到本發明的SiO2-Al2O3-RO系玻璃的成形溫度，則液相溫度較佳為1450℃以下、1400℃以下，尤其為1300℃以下。而且，液相黏度較佳為103.0dPa·s以上、103.5dPa·s以上，尤其為104.0dPa·s以上。再者，「液相溫度」是指將通過30目（mesh）（500 μm）的標準篩且殘留於50目（300 μm）的標準篩的玻璃粉末放入至鉑舟皿（platinum boat）中，在溫度梯度爐中保持24小時，對結晶析出時的溫度進行測定所得的值。「液相黏度」是指利用鉑球提拉法對液相溫度下的玻璃的黏度進行測定所得的值。When forming into a flat plate shape, devitrification resistance becomes important. Considering the forming temperature of the SiO2 -Al2 O3 -RO glass of the present invention, the liquidus temperature is preferably 1450°C or lower, 1400°C or lower, especially 1300°C or lower. Furthermore, the liquid phase viscosity is preferably at least 103.0 dPa·s, at least 103.5 dPa·s, especially at least 104.0 dPa·s. Furthermore, "liquidus temperature" refers to putting glass powder that passed through a 30 mesh (500 μm) standard sieve and remained on a 50 mesh (300 μm) standard sieve into a platinum boat , the value obtained by measuring the temperature at the time of crystallization in a temperature gradient furnace for 24 hours. The "liquidus viscosity" refers to a value obtained by measuring the viscosity of glass at the liquidus temperature by the platinum ball pulling method.
本發明的玻璃能利用各種成形方法成形。例如，能利用溢流下拉（overflow down draw）法、流孔下拉（slot down draw）法、再拉（redraw）法、浮式法、碾平（roll out）法等使玻璃基板成形。再者，若利用溢流下拉法使玻璃基板成形，則容易製作表面平滑性高的玻璃基板。The glass of the present invention can be formed by various forming methods. For example, the glass substrate can be shaped by an overflow down draw method, a slot down draw method, a redraw method, a float method, a roll out method, or the like. Furthermore, if the glass substrate is shaped by the overflow down-draw method, it is easy to produce a glass substrate with high surface smoothness.
在本發明的玻璃為平板形狀的情況下，其板厚較佳為1.0 mm以下、0.7 mm以下、0.5 mm以下，尤其為0.4 mm以下。板厚越小，則越容易使電子元件輕量化。另一方面，板厚越小，則玻璃基板越容易撓曲，但本發明的玻璃由於楊氏模量或比楊氏模量（specific Young's modulus）高，故而不易產生由撓曲引起的不良情況。再者，能利用成形時的流量或板提拉速度等來調整板厚。When the glass of the present invention is in the form of a plate, the plate thickness is preferably not more than 1.0 mm, not more than 0.7 mm, not more than 0.5 mm, especially not more than 0.4 mm. The smaller the plate thickness, the easier it is to reduce the weight of electronic components. On the other hand, the smaller the plate thickness, the easier the glass substrate is to bend, but the glass of the present invention has a higher Young's modulus or higher specific Young's modulus, so it is less likely to cause defects caused by bending . Furthermore, the plate thickness can be adjusted by utilizing the flow rate during forming, the plate pulling speed, and the like.
對於本發明的玻璃而言，若使β-OH值降低，則能夠提高應變點。β-OH值較佳為0.45/mm以下、0.40/mm以下、0.35/mm以下、0.30/mm以下、0.25/mm以下、0.20/mm以下，尤其為0.15/mm以下。若β-OH值過大，則應變點容易降低。再者，若β-OH值過小，則熔融性容易降低。藉此，β-OH值較佳為0.01/mm以上，尤其為0.05/mm以上。In the glass of the present invention, if the β-OH value is lowered, the strain point can be increased. The β-OH value is preferably 0.45/mm or less, 0.40/mm or less, 0.35/mm or less, 0.30/mm or less, 0.25/mm or less, 0.20/mm or less, especially 0.15/mm or less. When the β-OH value is too large, the strain point tends to decrease. Furthermore, when the β-OH value is too small, the meltability tends to decrease. Accordingly, the β-OH value is preferably at least 0.01/mm, especially at least 0.05/mm.
可列舉以下的方法作為使β-OH值降低的方法。（1）選擇含水量低的原料。（2）添加使玻璃中的水分量減少的成分（Cl、SO3等）。（3）使爐內環境中的水分量降低。（4）在熔融玻璃中進行N2起泡。（5）採用小型熔融爐。（6）加快熔融玻璃的流量。（7）採用電熔融法。The following method can be mentioned as a method of reducing a (beta)-OH value. (1) Choose raw materials with low water content. (2) Add components (Cl, SO3 , etc.) that reduce the moisture content in the glass. (3) Reduce the moisture content in the furnace environment. (4)N2 bubbling in molten glass. (5) Use a small melting furnace. (6) Speed up the flow of molten glass. (7) The electric melting method is adopted.
此處，「β-OH值」是指使用傅立葉轉換紅外光譜儀（Fourier Transform Infrared Spectrometer，FT-IR）測定玻璃的透射率，且使用下述的式子而求出的值。 β-OH值=（1/X）log（T1/T2） X：玻璃壁厚（mm） T1：3846 cm-1的參照波長下的透射率（%） T2：3600 cm-1附近的羥基吸收波長下的最小透射率（%） [實施例]Here, the "β-OH value" refers to a value obtained by measuring the transmittance of glass using a Fourier Transform Infrared Spectrometer (Fourier Transform Infrared Spectrometer, FT-IR) and using the following formula. β-OH value=(1/X)log(T1 /T2 ) X: Glass wall thickness (mm) T1 : Transmittance (%) at reference wavelength of 3846 cm-1 T2 : 3600 cm-1 Minimum transmittance (%) at nearby hydroxyl absorption wavelength [Example]
以下，基於實施例來詳細地說明本發明。再者，以下的實施例僅為例示。本發明完全不限定於以下的實施例。Hereinafter, the present invention will be described in detail based on examples. In addition, the following embodiment is only an illustration. The present invention is not limited to the following examples at all.
表1～表4表示本發明的實施例（試樣No.1～No.63）。Tables 1 to 4 show Examples (sample No. 1 to No. 63) of the present invention.
[表1]
[表2]
[表3]
[表4]
以如下方式製作各試樣。首先，將以成為表中的玻璃組成的方式對玻璃原料進行調配而成的玻璃配合料（glass batch）放入至鉑坩堝中，以1600℃～1750℃熔融24小時。在熔解玻璃配合料時，使用鉑攪拌器（stirrer）進行攪拌，使該玻璃配合料均質化。其次，使熔融玻璃流出至碳板上而成形為平板形狀。對於所獲得的各試樣，評價密度ρ、熱膨脹係數α、應變點Ps、退火點Ta、軟化點Ts、在高溫黏度104.0dPa·s時的溫度、在高溫黏度103.0dPa·s時的溫度、在高溫黏度102.5dPa·s時的溫度、液相溫度TL、液相黏度logηTL。Each sample was prepared as follows. First, glass batches prepared by preparing glass raw materials so as to have the glass compositions in the table were put into platinum crucibles and melted at 1600° C. to 1750° C. for 24 hours. When melting the glass batch, stirring was performed using a platinum stirrer to homogenize the glass batch. Next, the molten glass is flowed onto a carbon plate to form a flat plate shape. For each sample obtained, density ρ, coefficient of thermal expansion α, strain point Ps, annealing point Ta, softening point Ts, temperature at high temperature viscosity of 104.0 dPa·s, temperature at high temperature viscosity of 103.0 dPa·s Temperature, temperature at high temperature viscosity of 102.5 dPa·s, liquidus temperature TL, liquidus viscosity logηTL.
密度ρ是藉由眾所周知的阿基米德（Archimedes）法進行測定所得的值。Density ρ is a value measured by the well-known Archimedes method.
熱膨脹係數α是在30℃～380℃的溫度範圍內，利用膨脹計進行測定所得的平均值。The thermal expansion coefficient α is an average value measured with a dilatometer in a temperature range of 30°C to 380°C.
應變點Ps、退火點Ta、軟化點Ts是依據ASTM C336或ASTM C338進行測定所得的值。The strain point Ps, the annealing point Ta, and the softening point Ts are values measured in accordance with ASTM C336 or ASTM C338.
在高溫黏度104.0dPa·s時的溫度、在高溫黏度103.0dPa·s時的溫度、在高溫黏度102.5dPa·s時的溫度是利用鉑球提拉法進行測定所得的值。The temperature at high temperature viscosity of 104.0 dPa·s, the temperature at high temperature viscosity of 103.0 dPa·s, and the temperature at high temperature viscosity of 102.5 dPa·s are values measured by the platinum ball pulling method.
液相溫度TL是粉碎各試樣，將通過30目（500 μm）的標準篩且殘留於50目（300 μm）的標準篩的玻璃粉末放入至鉑舟皿中，在溫度梯度爐中保持24小時後取出鉑舟皿，在玻璃中看到失透（失透結晶）時的溫度。液相黏度logηTL是利用鉑球提拉法對液相溫度TL下的玻璃的黏度進行測定所得的值。The liquidus temperature TL is to pulverize each sample, put the glass powder that passes through a 30 mesh (500 μm) standard sieve and remains on a 50 mesh (300 μm) standard sieve into a platinum boat, and keep it in a temperature gradient furnace The temperature at which the platinum boat is taken out after 24 hours and devitrification (devitrification crystals) is seen in the glass. The liquidus viscosity logηTL is a value obtained by measuring the viscosity of glass at the liquidus temperature TL by the platinum ball pulling method.
β-OH值是根據所述式子而計算出的值。The β-OH value is a value calculated from the above formula.
表1～表4表明：試樣No.1～No.63的應變點與熱膨脹係數高，具備能成形為平板形狀的耐失透性。藉此，認為試樣No.1～No.63適合作為用以使半導體結晶（例如氮化物半導體結晶，尤其為氮化鎵系半導體結晶）在高溫下結晶成長的基板。 [產業上之可利用性]Tables 1 to 4 show that samples No. 1 to No. 63 have high strain points and thermal expansion coefficients, and have devitrification resistance capable of being formed into a flat plate shape. Accordingly, it is considered that samples No. 1 to No. 63 are suitable as substrates for crystal growth of semiconductor crystals (for example, nitride semiconductor crystals, especially gallium nitride-based semiconductor crystals) at high temperatures. [Industrial availability]
本發明的玻璃的應變點與熱膨脹係數高，具備良好的耐失透性。藉此，本發明的玻璃除了適合於用以在高溫下製作半導體結晶的基板以外，亦適合於有機發光二極體（Organic Light Emitting Diode，OLED）顯示器、液晶顯示器等顯示器用基板，尤其適合作為由低溫多晶矽（Low Temperature Poly Silicon，LTPS）、以氧化物薄膜電晶體（Thin Film Transistor，TFT）進行驅動的顯示器用基板。The glass of the present invention has a high strain point and a high coefficient of thermal expansion, and has good resistance to devitrification. Thereby, the glass of the present invention is not only suitable for substrates used to make semiconductor crystals at high temperatures, but also suitable for display substrates such as organic light emitting diode (Organic Light Emitting Diode, OLED) displays, liquid crystal displays, etc., especially suitable as A substrate for displays driven by low temperature polysilicon (Low Temperature Poly Silicon, LTPS) and oxide thin film transistors (Thin Film Transistor, TFT).
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| JP2015-164475 | 2015-08-24 |
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| TW202235390Atrue TW202235390A (en) | 2022-09-16 |
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| TW109131014ATWI768463B (en) | 2015-04-03 | 2016-04-01 | Glass |
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| TW105110469ATWI706923B (en) | 2015-04-03 | 2016-04-01 | glass |
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| TW105110469ATWI706923B (en) | 2015-04-03 | 2016-04-01 | glass |
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