CN102690056A - A formula of glass substrate used for flat panel display - Google Patents
A formula of glass substrate used for flat panel display Download PDFInfo
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- CN102690056A CN102690056A CN2012100952123A CN201210095212A CN102690056A CN 102690056 A CN102690056 A CN 102690056A CN 2012100952123 A CN2012100952123 A CN 2012100952123A CN 201210095212 A CN201210095212 A CN 201210095212A CN 102690056 A CN102690056 A CN 102690056A
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Abstract
The invention provides a formula of a glass substrate used for a flat panel display. The formula comprises, by mole, 63.0 to 73.0% of SiO2, 3.0 to 12.5% of Al2O3, 3.0 to 12.5% of B2O3, 3.5 to 10.0% of MgO, 1.0 to 10.0% of CaO, 0.01 to 4.0% of SrO, and 0.04 to 0.15% of SnO. The stannous oxide SnO, which is the clarificant in this formula, is a matter easy to obtain and is known to be harmless. The MgO has the capabilities to reduce the high temperature viscosity without reduced strain point, to enable the glass easy to melt and to reduce the capability of glass crystallization. By the glass substrate produced by the formula in the invention, it is possible to achieve the following technical indexes of thermal expansion coefficient of 28~37*10-7/degree centigrade at the temperature of 50 to 350 degree centigrade, strain point above 680 degree centigrade, density below 2.40g/cm3, liquidus temperature below 1100 degree centigrade, liquidus viscosity above 250000 poise, and invisible bubble with diameter more than 0.1mm in every kilo of glass substrate.
Description
Technical field
The invention belongs to glass and make the field; The making prescription that relates to the base plate glass of using on the flat-panel monitor LCD; Particularly be suitable for prescription as the base plate glass of active-matrix formula liquid-crystal display (AMLCD also claims TFT-LCD), Organic Light Emitting Diode (OLED) and low temperature polycrystalline silicon LTPS TFT-LCD.
Background technology
Show the fast development of industry along with the plane; Demand to various display devices constantly increases; Show liquid-crystal display (LTPS TFT-LCD) device that (AMLCD), Organic Light Emitting Diode (OLED) and application of cold temperature polysilicon are technological such as active matrix liquid crystal, these display devices are all based on using thin film semiconductor material to produce thin film transistor (TFT) technology.At present; TFT can be divided into non-crystalline silicon (a-Si) TFT, polysilicon (p-Si) TFT and silicon single crystal (SCS) TFT; Wherein non-crystalline silicon (a-Si) TFT is the technology that present main flow TFT-LCD uses, and the ME of polysilicon (p-Si) TFT is divided into high temperature polysilicon technology and low temperature polycrystalline silicon technology.The performance of polysilicon (p-Si) TFT is superior to non-crystalline silicon (a-Si) TFT, mainly shows as: high electron mobility, big electric current, littler component size.The amorphous silicon technology of using at present is ripe, and flat-panel display device attenuate, efficient, low cost are had in low temperature polycrystalline silicon (LTPS) the technology fast development of advantage.
Very sophisticated at present TFT-LCD display device, what mainly use is non-crystalline silicon (a-Si) TFT technology, the treatment temp in procedure for producing can be accomplished below 600 degree.And for active matrix OLED (AMOLED); Because OLED is the electric current driving electronic device, it needs high drive current, and present non-crystalline silicon (a-Si) technology mainly is applicable to the TFT-LCD of driven; Its drive current is lower; Can not satisfy the requirement of AMOLED, and LTPS polysilicon (p-Si) TFT has high drive current and electronic mobility, can satisfy the requirement of AMOLED drive current to drive current.The time of response that while LTPS polysilicon (p-Si) TFT can improve indicating meter, improve the brightness of indicating meter, and can directly on glass substrate, make up circuit of display driving, can make more frivolous display device.
LTPS polysilicon (p-Si) TFT need repeatedly handle under comparatively high temps in the processing procedure process, and this just proposes higher requirement to the base plate glass performance, and its strain point should be high as much as possible, preferably is higher than 650 ℃, more preferably is higher than 670 ℃, 720 ℃.The coefficient of expansion of glass substrate need be close with the coefficient of expansion of silicon simultaneously, reduce stress and destruction as far as possible, so the preferred thermal linear expansion coefficient of base plate glass is 28 ~ 39 * 10
-7/ ℃ between.For the ease of producing, reduce production costs, the glass of using as display base plate should have lower temperature of fusion and liquidus temperature.
Be used for the glass substrate that the plane shows; Need to form nesa coating, insulating film, semi-conductor (polysilicon, amorphous silicon etc.) film and metallic membrane on bottom base plate glass surface through technology such as sputter, chemical vapor deposition (CVD)s; Form various circuit and figure through photoetch (Photo-etching) technology then, if glass contains alkalimetal oxide (Na
2O, K
2O, Li
2O), alkalimetal ion diffuses into deposited semiconductor material in heat treatment process, infringement semiconductor film characteristic, and therefore, glass is answered the alkali-free MOX, and first-selected is with SiO
2, Al
2O
3, B
2O
3And alkaline earth metal oxide RO (RO=Mg, Ca, Sr, Ba) etc. is the alkaline earth Boroalumino silicate glasses of principal constituent.At present along with the popularizing fast of portable electric appts (like notebook computer, smart mobile phone, PDA), requirements at the higher level have been proposed for the lightweight of accessory.Thus the composition of glass substrate is had higher requirement, to guarantee to adapt to the needs of modern liquid crystal displays.Glass substrate must have following properties: the tool chemical resistant properties; Thermal expansivity must be close with the silicon of thin film transistor; Improve strain point of glass, to reduce thermal shrinking quantity; Has less density, so that carry and hand.
In the course of processing of glass substrate, base plate glass is a horizontal positioned, and glass has to a certain degree sagging, sagging degree to be directly proportional with the density of glass, to be inversely proportional to the Young's modulus of glass under the deadweight effect.Along with the development of substrate manufacturing towards large size, slimming direction, the sagging of sheet glass must draw attention in the manufacturing.Therefore should design composition, make base plate glass have alap density and high as far as possible Young's modulus.
In order to obtain still non-alkali glass, utilize clarification gas, the gas that produces when from glass melt, expelling glass reaction; When homogenizing fusing, need to utilize once more the clarification gas that produces in addition, increase the alveolar layer footpath; Make its come-up, take out the small bubble of participating in thus.
, be used as the viscosity height of the glass melt of glass for flat panel display substrate, need with higher temperature fusing.In the glass substrate of this kind, cause vitrifying reaction at 1300 ~ 1500 degree usually, deaeration under the high temperature more than 1500 degree, homogenize.Therefore, in finings, being widely used to produce the As of clarification gas in wide TR (1300 ~ 1700 degree scope)
2O
3But, As
2O
3Toxicity very strong, when the processing of the manufacturing process of glass or cullet, might contaminate environment with bring healthy problem, its use is restricted.Once attempted clarifying the substitute for arsenic clarification with antimony.Yet there is the problem that causes environment and healthy aspect in antimony itself.Though Sb
2O
3Toxicity unlike As
2O
3Such high, but Sb
2O
3Remain deleterious.And compare with arsenic, the temperature that antimony produces clarification gas is lower, and the validity of bubble of removing this kind glass is lower.
Summary of the invention
The object of the present invention is to provide the more perfectly design of components of flat-panel screens glass substrate of a kind of environmentally friendly, performance, even provide a kind of finings not use As
2O
3And/or Sb
2O
3, there is not the prescription of the glass substrate that becomes surface imperfection yet, designed a kind of prescription of glass basal plates of flat panel display, the glass substrate compliance with environmental protection requirements of utilizing this prescription to make does not contain As
2O
3, Sb
2O
3And compound, this glass does not contain heavy metal barium and compound thereof simultaneously, has higher strain point, has higher transmittance, has lower temperature of fusion, has lower liquidus temperature, has lower density, meets FPD industry development trend.
The technical scheme that the present invention adopts is: a kind of prescription of glass basal plates of flat panel display, and key is: the molar percentage of each moity is respectively in the prescription of above-mentioned glass substrate:
SiO
2 63.0~73.0%，
Al
2O
3 3.0~12.5%，
B
2O
3 3.0~12.5%，
MgO 3.5~10.0%，
CaO 1.0~10.0%，
SrO 0.01~4.0%，
SnO 0.04~0.15%。
The invention has the beneficial effects as follows: 1, finings tin protoxide SnO; SnO is the material that obtains easily, and the harmful character of known nothing, when using it as glass fining agent separately; The TR of higher generation clarification gas is arranged, be fit to the elimination of this kind glass blister; 2, MgO has under the situation that does not reduce strain point and reduces high temperature viscosity, makes glass be easy to fusing.The earth alkali metal resultant is introduced the bigger network-modifying ion Mg of strength of electric field more after a little while in the alkali-free silicate glass
+, in structure, produce the local accumulation effect easily, the short range order scope is increased.Introduce more Al in this case
2O
3, B
2O
3Deng oxide compound, with [AlO
4], [BO
4] when state exists,, attracted the subnetwork outer cationic because these polyhedrons have negative electricity, make the degree of gathering, the crystallization ability drop of glass; , network more when earth alkali metal resultant fracture relatively under the serious situation, adds intermediate oxide MgO, and the silicon-oxy tetrahedron that can make fracture connects again and makes the devitrification of glass ability drop; 3, the glass substrate by means of glass ingredient prescription provided by the invention production can reach following technical indicator through detecting: the thermal expansivity at 50～350 degree is 28～37 * 10
-7/ ℃; Strain point is more than 680 ℃, and density is less than 2. 40g/cm
3, liquidus temperature is lower than 1100 degree, and liquidus viscosity is greater than 250000 pools, and the bubbles number of bubble diameter in＞0.lmm is invisible in the per kilogram glass substrate.
Embodiment
A kind of prescription of glass basal plates of flat panel display, importantly: the molar percentage of each moity is respectively in the prescription of above-mentioned glass substrate:
SiO
2 63.0~73.0%，
Al
2O
3 3.0~12.5%，
B
2O
3 3.0~12.5%，
MgO 3.5~10.0%，
CaO 1.0~10.0%，
SrO 0.01~4.0%，
SnO 0.04~0.15%。
SiO
2Preferred molar percentage be 63 ~ 68.23%.
The preferred molar percentage of MgO is 3.5 ~ 6.5%.
The preferred molar percentage of SnO is 0.08 ~ 0.09%.
Al
2O
3Preferred molar percentage be 10.34 ~ 11.48%.
B
2O
3Preferred molar percentage be 6.49 ~ 11.5%.
The preferred molar percentage of SrO is 2.5 ~ 3.72%.
The present invention is when implementing; Be after the raw material that will include the corresponding oxide molar per-cent of above-mentioned each glass substrate component earlier evenly mixes; With the mixing raw material melt-processed, stir the discharge bubble and make the glass metal homogenizing again, then its temperature is reduced to the needed glass substrate forming TR of moulding with the platinum rod; Pass through annealing theory; Produce the thickness of the glass substrate of flat-panel screens needs, the glass substrate to moulding carries out simple cold work again, and the basic physical property of glass substrate is tested becomes specification product at last.
In the present invention, SiO
2Molar percentage be 63.0～73.0%.Improve SiO
2Content helps the glass lightweight, and thermal expansivity reduces, and chemical resistant properties increases, but the high temperature viscosity rising is unfavorable for fusion like this, and general kiln is difficult to satisfy, so confirm SiO
2Content be 63.0～73.0%.
Al
2O
3Mole percent level be 3.0～12.5 %, in order to improve the intensity of glass structure, high-load A1
2O
3Help increasing of strain point of glass, bending strength, but the crystallization phenomenon appears in too high glass easily, so A1
2O
3Mole percent level confirm as 3.0～12.5 %.
B
2O
3Mole percent level be 3.0～12.5 %, B
2O
3Effect more special, it can generate glass separately, also is a kind of good fusing assistant, B under the high temperature melting condition
2O
3Be difficult to form [BO
4], can reduce high temperature viscosity, B has the free oxygen of capturing to form [BO during low temperature
4] trend, structure is tending towards closely, improve the low temperature viscosity of glass, prevent the generation of crystallization phenomenon.But too much B
2O
3Strain point of glass is reduced, so B
2O
3Mole percent level confirm as 3.0～12.5 %.
The effect of aluminum oxide and boron oxide is to influence glass viscosity and melting temperature (Tm).
MgO has under the situation that does not reduce strain point and reduces high temperature viscosity, makes glass be easy to fusing.The earth alkali metal resultant is introduced the bigger network-modifying ion Mg of strength of electric field more after a little while in the alkali-free silicate glass
+, in structure, produce the local accumulation effect easily, the short range order scope is increased.Introduce more Al in this case
2O
3, B
2O
3Deng oxide compound, with [AlO
4], [BO
4] when state exists,, attracted the subnetwork outer cationic because these polyhedrons have negative electricity, make the degree of gathering, the crystallization ability drop of glass; , network more when earth alkali metal resultant fracture relatively under the serious situation, adds intermediate oxide MgO, and the silicon-oxy tetrahedron that can make fracture connects again and makes the devitrification of glass ability drop.Therefore when adding MgO, to note and Al
2O
3,B
2O
3The cooperation ratio.Its mole percent level is 3.5 ~ 10.0%.If MgO is greater than 10.0%, the glass endurance can variation, the easy devitrification of glass simultaneously.
The molar content of CaO is 1.0～10.0 %, fusion and the adjustment glass ware forming property of quicklime in order to promote glass.If calcium oxide content is less than 1%, can't reduce the viscosity of glass, content is too much, and crystallization can appear in glass easily, and also amplitude variation is big greatly for thermal expansivity, and is unfavorable to successive process.So the molar content of CaO confirms as 1.0～10.0%.
The molar content of SrO is 0.01～4.0 %, and strontium oxide is as fusing assistant and prevent that crystallization from appearring in glass, if content is too much, glass density can be too high, causes the quality of product overweight.So the molar content of SrO is confirmed as 0.01～4.0 %.
Among the present invention, can also be added with the finings of 0.04～0.15 % in the glass composition, wherein finings is tin protoxide SnO, and finings when fusing as glass or defrother are to improve the fusion quality of glass.If content is too much, can cause the glass substrate devitrification, so its addition is no more than 0.15%.
Provide the specific embodiment that each component measures with molar percentage in the prescription below:
Table 1
| Form (molar percentage) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| SiO 2 | 63.0 | 63.59 | 66.14 | 65.32 | 64.91 | 68.77 | 68.11 |
| Al 2O 3 | 11.48 | 8.07 | 11.26 | 9.66 | 8.71 | 12.22 | 10.94 |
| B 2O 3 | 11.27 | 10.9 | 7.79 | 9.58 | 10.47 | 6.49 | 9.26 |
| MgO | 4.36 | 7.85 | 7.91 | 6.3 | 5.33 | 7.21 | 6.39 |
| CaO | 8.86 | 8.57 | 6.81 | 9.05 | 10.0 | 4.60 | 4.59 |
| SrO | 0.95 | 1.34 | 0.01 | 0.01 | 0.49 | 0.62 | 0.62 |
| SnO | 0.08 | 0.04 | 0.08 | 0.08 | 0.09 | 0.09 | 0.09 |
| Thermal expansivity ( 50-350) /×10 -7/℃ | 31.5 | 32.2 | 31.9 | 33.1 | 34.6 | 30.2 | 30.4 |
| Temperature of fusion/℃ | 1655 | 1613 | 1651 | 1627 | 1634 | 1680 | 1660 |
| The glass liquidus temperature/℃ | 1070 | 1060 | 1070 | 1050 | 1080 | 1070 | 1070 |
| Strain point/℃ | 687 | 680 | 691 | 680 | 681 | 714 | 706 |
| Density/g/cm 3 | 2.387 | 2.394 | 2.389 | 2.387 | 2.390 | 2.387 | 2.367 |
| Young's modulus/GPa | 76 | 75 | 77 | 78 | 77 | 83 | 81 |
| Transmitance/% | 92.5 | 92.0 | 93.2 | 92.4 | 91.9 | 93.0 | 92.7 |
Table 2
| Form (molar percentage) | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 |
| SiO 2 | 67.68 | 67.79 | 68.23 | 69.6 | 73 | 72.85 | 68.21 |
| Al 2O 3 | 5.56 | 12.44 | 10.34 | 8.85 | 9.64 | 12.5 | 3 |
| B 2O 3 | 11.76 | 10.07 | 12.5 | 9.25 | 6.12 | 3.0 | 11.50 |
| MgO | 7.81 | 4.14 | 4.12 | 6.5 | 3.5 | 6.98 | 10.0 |
| CaO | 4.60 | 2.38 | 1.0 | 3.44 | 3.73 | 3.40 | 4.83 |
| SrO | 2.50 | 3.09 | 3.72 | 2.49 | 4.0 | 1.12 | 2.38 |
| SnO | 0.09 | 0.09 | 0.09 | 0.09 | 0.01 | 0.15 | 0.08 |
| Thermal expansivity ( 50-350) /×10 -7/℃ | 35.5 | 30.0 | 31.1 | 31.8 | 30.4 | 28.1 | 36.7 |
| Temperature of fusion/℃ | 1608 | 1649 | 1646 | 1655 | 1656 | 1689 | 1601 |
| The glass liquidus temperature/℃ | 1090 | 1050 | 1060 | 1050 | 1080 | 1100 | 1050 |
| Strain point/℃ | 682 | 680 | 682 | 689 | 683 | 731 | 680 |
| Density/g/cm 3 | 2.395 | 2.394 | 2.382 | 2.393 | 2.379 | 2.391 | 2.392 |
| Young's modulus/GPa | 75 | 76 | 77 | 75 | 79 | 85 | 75 |
| Transmitance/% | 92.0 | 92.6 | 93.1 | 92.5 | 92.0 | 92.8 | 93.2 |
Can know that by above embodiment MgO is at preferred molar percentage at 3.5 ~ 6.5% o'clock, successfully realize under the situation that does not reduce strain point, having reduced temperature of fusion that temperature of fusion is stabilized in 1608 ~ 1651 ℃ the interval.The preferred molar percentage of SnO is 0.08 ~ 0.09%, and the transmittance of glass is stabilized in 92.0 ~ 93.2% the interval in this is interval.
Claims (7)
1. the prescription of a glass basal plates of flat panel display, it is characterized in that: the molar percentage of each moity is respectively in the prescription of above-mentioned glass substrate:
SiO
2 63.0~73.0%，
Al
2O
3 3.0~12.5%，
B
2O
3 3.0~12.5%，
MgO 3.5~10.0%，
CaO 1.0~10.0%，
SrO 0.01~4.0%，
SnO 0.04~0.15%。
2. the prescription of a kind of glass basal plates of flat panel display according to claim 1 is characterized in that: SiO
2Preferred molar percentage be 63 ~ 68.23%.
3. the prescription of a kind of glass basal plates of flat panel display according to claim 1, it is characterized in that: the preferred molar percentage of MgO is 3.5 ~ 6.5%.
4. the prescription of a kind of glass basal plates of flat panel display according to claim 2, it is characterized in that: the preferred molar percentage of SnO is 0.08 ~ 0.09%.
5. the prescription of a kind of glass basal plates of flat panel display according to claim 1 is characterized in that: Al
2O
3Preferred molar percentage be 10.34 ~ 11.48%.
6. the prescription of a kind of glass basal plates of flat panel display according to claim 1 is characterized in that: B
2O
3Preferred molar percentage be 6.49 ~ 11.5%.
7. the prescription of a kind of glass basal plates of flat panel display according to claim 1, it is characterized in that: the preferred molar percentage of SrO is 2.5 ~ 3.72%.
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|---|---|---|---|
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|---|---|---|---|
| CN201210095212.3A CN102690056B (en) | 2012-04-01 | 2012-04-01 | A kind of formula of glass substrate of flat-panel monitor |
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| CN102690056A true CN102690056A (en) | 2012-09-26 |
| CN102690056B CN102690056B (en) | 2015-09-16 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211300A (en) * | 2013-08-27 | 2014-12-17 | 东旭集团有限公司 | Formula of glass substrate with high modular ratio |
| CN104276754A (en) * | 2013-08-27 | 2015-01-14 | 东旭集团有限公司 | Silicate glass substrate for flat-panel display |
| CN106746601A (en) * | 2016-12-30 | 2017-05-31 | 东旭集团有限公司 | Composition, glassware and purposes for preparing glass |
| CN109613218A (en) * | 2018-12-10 | 2019-04-12 | 彩虹（合肥）液晶玻璃有限公司 | Material side's test method and system |
| CN110746111A (en) * | 2019-09-29 | 2020-02-04 | 彩虹显示器件股份有限公司 | Glass substrate and application thereof as glass substrate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6992030B2 (en) * | 2002-08-29 | 2006-01-31 | Corning Incorporated | Low-density glass for flat panel display substrates |
| CN1787039A (en) * | 2004-12-06 | 2006-06-14 | 株式会社日立制作所 | Flat-panel display |
-
2012
- 2012-04-01 CN CN201210095212.3A patent/CN102690056B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6992030B2 (en) * | 2002-08-29 | 2006-01-31 | Corning Incorporated | Low-density glass for flat panel display substrates |
| CN1787039A (en) * | 2004-12-06 | 2006-06-14 | 株式会社日立制作所 | Flat-panel display |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211300A (en) * | 2013-08-27 | 2014-12-17 | 东旭集团有限公司 | Formula of glass substrate with high modular ratio |
| CN104276754A (en) * | 2013-08-27 | 2015-01-14 | 东旭集团有限公司 | Silicate glass substrate for flat-panel display |
| CN106746601A (en) * | 2016-12-30 | 2017-05-31 | 东旭集团有限公司 | Composition, glassware and purposes for preparing glass |
| US11319241B2 (en) | 2016-12-30 | 2022-05-03 | Tunghsu Group Co., Ltd. | Composition for preparing glass, glass article and use thereof |
| CN109613218A (en) * | 2018-12-10 | 2019-04-12 | 彩虹（合肥）液晶玻璃有限公司 | Material side's test method and system |
| CN110746111A (en) * | 2019-09-29 | 2020-02-04 | 彩虹显示器件股份有限公司 | Glass substrate and application thereof as glass substrate |
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|---|---|
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Effective date of registration: 20160425 Address after: 215300 Suzhou Development Zone, Kunshan, No. 167 Qianjin Road, the middle of the building (International Building), room 1, 1517 Patentee after: Dong Xu (Kunshan) display material Co., Ltd. Address before: 050021 No. 94, Huitong Road, Hebei, Shijiazhuang Patentee before: Tungsu Group Co., Ltd. |