CN107324648B - Alkali-free low softening point glasses and compositions, and methods thereof - Google Patents
Alkali-free low softening point glasses and compositions, and methods thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 175
- 239000000203 mixture Substances 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 19
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 8
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 8
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 238000004093 laser heating Methods 0.000 claims description 4
- 239000011368 organic material Substances 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 29
- 239000000758 substrate Substances 0.000 description 15
- 239000011787 zinc oxide Substances 0.000 description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 10
- 239000000395 magnesium oxide Substances 0.000 description 7
- 230000006378 damage Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000000156 glass melt Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910016006 MoSi Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/841—Self-supporting sealing arrangements
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
Alkali-free low softening point glass compositions are presented herein. The glass composition contains SiO2、B2O3、ZnO、Al2O3And CuO, and SrO and MgO as optional additives. The glass composition is alkali-free and produces a glass having a softening point from about 600 ℃ to about 700 ℃ and a temperature from about 35x 10 at 50 ℃ to 300 ℃‑7/° c to about 55x10‑7Coefficient of linear expansion (CTE) at/° C. The glass can be used to seal Organic Light Emitting Diode (OLED) displays to extend the life of the organic materials used to make the diodes.
Description
Technical Field
The present disclosure relates to alkali-free low softening point glasses and compositions, and methods of making and using the same. The glass can be used to seal Organic Light Emitting Diode (OLED) displays to extend the life of the organic materials used to make the diodes.
Background
The new generation of organic light emitting diodes has attracted public attention because they are self-emitting, ultra-thin, flexible, fast-responding, and energy efficient. One of the biggest technical challenges faced during the development of OLED technology is the limited lifetime of the organic materials used to fabricate the diodes. However, this problem is addressed when researchers find that OLEDs can be encapsulated in low softening point glasses to provide advantages over traditional thin film encapsulation and back cover encapsulation. For example, OLEDs encapsulated in low softening point glasses have excellent water resistance and gas barrier properties.
However, the use of low softening point glasses has created a different set of challenges. Generally, low softening point glasses contain SiO2-B2O3-ZnO、Bi2O3-B2O3Vanadate, phosphate and alkali glass systems. Bismuthates and vanadates are relatively expensive and phosphate glasses lack chemical stability. Compared with Bi2O3-B2O3Vanadate, phosphate and alkali glass systems, SiO2-B2O3The ZnO glass system has a higher softening point. The lowest softening point glass contains a large amount of alkali metal oxide to lower the softening point. However, a large amount of alkali metal oxide will increase the thermal expansion coefficient and decrease the weatherability of the glass composition. At the same time, alkali metal ions may tend to migrate or diffuse into other materials during high temperature heat treatment. In general, OLED glass substrates are alkali-free and have a low melting pointCoefficient of Thermal Expansion (CTE) (α ═ 30x10-7/° c to 38x10-7/° c), excellent heat resistance (strain point temperatures above 650 ℃), high mechanical stability, and high softening point (above 900 ℃). Therefore, there is a need for glasses for sealing such OLED glass substrates having low coefficients of thermal expansion and low softening points. Furthermore, there is a need for glasses that can be treated by partial laser heating methods to protect the organic materials of electronic components from thermal damage.
Disclosure of Invention
An alkali-free, low softening point glass is presented. The alkali-free, low softening point glass can be used to seal an OLED glass substrate to extend the life of organic materials contained in the OLED glass substrate.
According to several exemplary embodiments, the alkali-free, low softening point glass has a composition comprising:
from about 6.0 wt% to about 28.0 wt% SiO2；
From about 20.0 wt% to about 45.0 wt% of B2O3；
From about 25.0 wt% to about 48.0 wt% ZnO;
from about 0.0 wt% to about 15.0 wt% Al2O3；
From about 3.0 wt% to about 15.0 wt% CuO;
from about 0.0 wt% to about 10.0 wt% SrO; and
from about 0.0 wt% to about 5.0 wt% MgO.
According to several exemplary embodiments, the alkali-free, low softening point glass has a composition characterized by:
SiO in an amount of from 8.0 wt% to 30.0 wt%2+Al2O3，
B in a proportion of from 0.1 to 1.5% by weight2O3/ZnO, and
(SiO) in a proportion of wt.% of from 0.2 to 1.52+Al2O3)/B2O3。
According to several exemplary embodiments, the glass has a composition comprising:
from about 6.0 wt% to about 28.0 wt%, from about 8.0 wt% to about 28.0 wt%, or from about 8.0 wt% to about 19.0% SiO2；
From about 20.0 wt% to about 45.0 wt%, or from about 23.0 wt% to about 42.0 wt% of B2O3；
From about 25.0 wt% to about 48.0 wt%, or from about 27.0 wt% to about 48.0 wt% ZnO;
from about 0.0 wt% to about 15.0 wt%, or from about 2.0 wt% to about 11.0 wt% Al2O3；
From about 3.0 wt% to about 15.0 wt%, or from about 3.0 wt% to about 10.0 wt% CuO;
from about 0.0 wt% to about 10.0 wt%, or from about 0.5 wt% to about 10.0 wt% SrO; and
from about 0.0 wt% to about 5.0 wt%, or from about 0.5 wt% to about 5 wt% MgO.
According to several exemplary embodiments, the alkali-free, low softening point glass has a composition characterized by:
SiO in an amount of from 8.0 wt.% to 30.0 wt.%, or from 9.0 wt.% to about 28.0 wt%2+Al2O3，
B in a proportion of from 0.1 to 1.5, or from 0.5 to 1.1, wt%2O3/ZnO, and
(SiO) in a proportion of wt.% from 0.2 to 1.5, or from 0.2 to 1.22+Al2O3)/B2O3。
According to several exemplary embodiments, the alkali-free, low softening point glass has an absorption coefficient greater than about 2/mm at wavelengths from about 800nm to about 1400 nm.
According to several exemplary embodiments, the alkali-free, low softening point glass has a composition that includes less than about 1000ppm (parts per million) of alkali metals.
According to several exemplary embodiments, the alkali-free, low softening point glass has a softening point of from about 600 ℃ to about 700 ℃.
Brief description of the drawings
The following drawings are directed to the disclosed embodiments and should not be considered limiting.
FIG. 1 is a UV-VIS plot of compositions represented by example 1 in Table 3, wherein "T%" is percent transmission, "R%" is percent reflection, and "A" is absorption.
Detailed Description
When used in describing a single numeral, the term "about" is intended to encompass a range of ± 5%. When applied to a range, the term "about" means that the range includes from-5% of the numerical lower limit and + 5% of the numerical upper limit, unless the lower limit is 0. For example, a range from about 100 ℃ to about 200 ℃ includes a range from 95 ℃ to 210 ℃. However, when the term "about" modifies a percentage, such as wt%, then the term is ± 1% of the exponential or numerical boundary unless the lower limit is less than 1. Thus, a range of about 5-10% includes 4-11%, and a range of about 0-5% includes 0-6%.
The term "alkali-free" or "alkali free" refers to glass compositions that include less than about 1000ppm alkali metal, including alkali metal contained in oxides. Alkali metals include lithium, sodium, potassium, rubidium, cesium, francium.
The term "low softening point" refers to glass compositions having a softening point of from about 600 ℃ to about 700 ℃. The term "softening point" refers to a glass sample viscosity of 10 as measured by ASTM C-338 fiber lengthening7 . 6The temperature of poise.
All measurements are in metric units, unless otherwise indicated.
Unless otherwise stated, the terms "wt%" or "weight percent" of a composition of a glass composition refer to the weight percent of the composition relative to the weight of the glass composition. One skilled in the art will appreciate that the sum of the wt% must add up to 100 wt% and must not exceed 100.0 wt%.
According to several exemplary embodiments, the alkali-free, low softening point glass has a composition including SiO as a glass network forming composition2Which is almost entirely of [ SiO ]4]Present, and necessary to provide a low coefficient of thermal expansion glass. According to several embodiments, the SiO of the glass composition2The content is from about 6.0 wt% to about 28.0 wt%, from about 8.0 wt% toAbout 28.0 wt%, or from about 8.0 wt% to about 19.0 wt%. If SiO of the glass composition2When the content is reduced to less than 6.0 wt%, it becomes difficult to form glass from the composition. On the contrary, if SiO of the glass composition2The content is increased to more than 28.0 wt%, the softening point of the glass is increased to an excessively high degree and damage to the OLED substrate may be caused when the OLED substrate is sealed using the glass composition.
According to several exemplary embodiments, the alkali-free, low softening point glass has a composition comprising B as a glass network forming composition2O3Which is represented by [ BO3]And [ BO ]4]There is a reduction in the coefficient of thermal expansion of the glass and an increase in the structural integrity of the glass. At the same time, B2O3Can reduce the viscosity and softening point of the glass and accelerate the clarification. According to several exemplary embodiments, B of the glass composition2O3The amount is from about 20.0 wt% to about 45.0 wt%, or from 23.0 wt% to about 42.0 wt%. However, if B in the glass composition2O3If the amount exceeds 45 wt%, the stability of the glass is lowered and the thermal expansion coefficient is increased to an excessively high degree. If B of the glass composition2O3When the content is reduced to less than 20.0 wt%, the softening point of the glass may increase to an excessively high degree and may cause damage to the OLED substrate when the glass composition is used to seal the OLED substrate.
According to several example embodiments, the alkali-free, low softening point glass has a composition that includes ZnO as a glass network modifier. In the glass composition, the content of ZnO tends to lower the softening point of the glass and to be able to finely adjust the thermal expansion coefficient of the glass to a desired range. According to several exemplary embodiments, the ZnO content of the glass composition is from about 25.0 wt% to about 48 wt%, or from about 27.0 wt% to about 48.0 wt%. However, if the ZnO content of the glass composition is increased to 48.0 wt% or more, it is difficult to form glass from the composition. If the ZnO content of the glass composition is reduced below 25.0 wt%, the ability to fine tune the glass' coefficient of thermal expansion to the desired range is affected and the softening point of the glass is increased to an undesirable extent.
According to several exemplary embodiments, the alkali-free, low softening point glass has a composition that includes Al as an intermediate to the glass network2O3Which is [ AlO ]4]Are present. Containing Al in the glass composition2O3The viscosity of the glass can be increased, the possibility of devitrification of the glass is reduced, and the stability of the glass is increased. According to several exemplary embodiments, the Al of the glass composition2O3The amount is from 0 wt% to about 15.0 wt%, or from about 2.0 wt% to about 11 wt%. If Al of the glass composition2O3At levels greater than 15.0 wt%, the softening point of the glass may increase to too high a level and may cause damage to the OLED substrate when the glass composition is used to seal the OLED substrate.
According to several exemplary embodiments, the alkali-free, low softening point glass has a composition that includes CuO as a colorant. According to several exemplary embodiments, the addition of CuO to the glass composition may allow the glass to efficiently absorb light of a long wavelength, which is suitable for a laser heating glass sealing process. However, CuO can also change the softening point of the glass. According to several exemplary embodiments, the CuO content in the glass composition is from about 3.0 wt% to about 15 wt%, or from about 3.0 wt% to about 10.0 wt%. If the CuO content of the glass composition is less than 3.0 wt%, the glass may become difficult to absorb the laser irradiation wavelength necessary in the laser heating glass sealing process. However, if the CuO content in the glass composition is increased to more than 15.0 wt%, it is difficult to form glass from the composition. According to several exemplary embodiments, the alkali-free, low softening point glass has a high laser radiation absorption capacity with an absorption coefficient greater than 2/mm at wavelengths from about 800nm to 1400 nm.
According to several exemplary embodiments, the alkali-free, low softening point glass has a composition that includes SrO as an optional additive. The inclusion of SrO in the glass composition can lower the softening point of the glass, reduce the occurrence of devitrification of the glass, and lower the liquefaction temperature of the glass. According to several exemplary embodiments, the SrO content in the glass composition is from about 0.0 wt% to about 10.0 wt%, or from about 0.5 wt% to about 10.0 wt%. If the SrO content in the glass composition is more than 10 wt%, the density of the glass will be too high to make the glass too heavy, and the thermal expansion coefficient of the glass will be too high, which may cause stress to adversely affect the sealing effect of the glass when the glass composition is used to seal an OLED.
According to several exemplary embodiments, the alkali-free, low softening point glass has a composition that includes MgO as an optional additive that may facilitate glass fining. According to several embodiments, the MgO content in the glass composition is from about 0.0 wt% to about 5.0 wt%, or from about 0.5 wt% to about 5.0 wt%. If the content of MgO in the glass composition is more than 5.0 wt%, the thermal expansion coefficient of the glass will be too high, and stress will be generated when the glass composition is used to seal an OLED, thereby adversely affecting the sealing effect of the glass.
According to several exemplary embodiments, the alkali-free, low softening point glass has a composition characterized as having from 8.0 wt.% to 30.0 wt.%, or from 9.0 wt.% to 28.0 wt.% SiO2And Al2O3Aggregate content. According to several exemplary embodiments, SiO2And Al2O3Has an aggregate content of more than 8.0 wt.% such that the glass has a temperature range of from 50 ℃ to 300 ℃ of less than 55x10-7Coefficient of thermal expansion/° c. However, if SiO2And Al2O3With aggregate content of more than 30.0 wt%, the glass may have a softening point of more than 700 ℃, which may cause damage to the OLED substrate when the glass composition is used to seal the OLED substrate.
According to several exemplary embodiments, the alkali-free, low softening point glass has a composition characterized by having a B of from 0.5 to 1.5, or from 0.5 to 1.12O3Wt% ratio of/ZnO. If B is present in the glass composition2O3The wt% ratio of/ZnO of less than 0.5 wt% will result in a glass having a too high coefficient of thermal expansion, which will cause stress to adversely affect the sealing effect of the glass when the glass composition is used to seal an OLED. If B is present in the glass composition2O3Wt% ratio of/ZnOAbove 1.5 wt%, the stability of the glass may be degraded and crystallization of the oxide material in the glass composition may occur.
According to several exemplary embodiments, the alkali-free, low softening point glass has a composition characterized by a wt% ratio of (SiO) of from 0.2 to 1.5, or from 0.2 to 1.22+Al2O3)/B2O3. If in the glass composition (SiO)2+Al2O3)/B2O3The wt% ratio of (B) is less than 0.2 wt%, it becomes difficult to form glass from the composition. On the contrary, (SiO) in the glass composition2+Al2O3)/B2O3With a wt% ratio of more than 1.5 wt%, the glass may have a softening point of more than 700 ℃, which may result in damage to the OLED substrate when the glass composition is used to seal the OLED substrate.
According to several exemplary embodiments, a method for making alkali-free low softening point glass is provided. According to several example embodiments, the method comprises:
weighing and mixing the raw materials;
softening the raw materials to form a homogeneous glass melt; and
cooling or water quenching the glass melt.
According to several exemplary embodiments of the methods for making alkali-free low softening point glasses described above, the glass composition is melted at about 1100 ℃ for up to about 12 hours, up to about 6 hours, or up to about 4 hours.
According to several exemplary embodiments of the methods for making alkali-free low softening point glasses described above, the glass composition is annealed at a temperature of 450 ℃ for about 2 hours, then cooled at a rate of about 1.0 ℃ per hour until the glass reaches 400 ℃, and then allowed to cool to room temperature (or about 21 ℃).
According to several exemplary embodiments of the alkali-free low softening point glass described above, the glass is a substrate for sealing an Organic Light Emitting Diode (OLED). According to several exemplary embodiments of the alkali-free, low softening point glasses described above, the glasses are used to produce touch displays, including mobile phones, tablets, ATM machines, and other electronic devices that incorporate touch displays.
The following examples are illustrative of the above compositions and methods.
Example (b):
preparation of test samples
An alkali-free low softening point glass composition comprising the composition shown in table 1 below was prepared as follows:
TABLE 1
| Oxide compound | Mass percent (wt%) |
| SiO2 | 6.0 |
| B2O3 | 40.2 |
| ZnO | 35.0 |
| Al2O3 | 2.8 |
| CuO | 4.0 |
| SrO | 7.3 |
| MgO | 4.7 |
The batches shown in table 2 were weighed and mixed before being added to a 2 liter plastic container. The batch material used is of chemical grade quality.
TABLE 2
| Batch of raw materials | Batched weight (gm) |
| Sand | 15.01 |
| Boric acid | 179.40 |
| Zinc oxide | 88.50 |
| Aluminum hydroxide | 10.71 |
| Copper oxide | 10.10 |
| Strontium carbonate | 26.26 |
| Magnesium oxide | 11.77 |
The particle size of the sand is between 0.045 and 0.25 mm. The raw materials were mixed using a tumbler to produce a homogeneous batch and destroy soft aggregates. The mixed batch was transferred from the plastic container to an 800 ml platinum rhodium crucible for glass melting. The platinum rhodium crucible was placed in an alumina backing and loaded into a high temperature furnace equipped with a MoSi heating assembly operating at a temperature of 1000 ℃. The furnace temperature was gradually increased to 1100 ℃ and the platinum rhodium crucible and its backing were maintained at this temperature for 1 to 3 hours. While maintaining the temperature at 1100 ℃, the glass was stirred to accelerate bubble elimination and glass fining. The molten batch material was then poured from a platinum rhodium alloy crucible onto a stainless steel plate to form a glass cake, thereby forming a glass sample. While the glass cake was still hot, it was transferred to an annealer, held at a temperature of 450 ℃ for two hours, and then cooled to 400 ℃ at a rate of 1 ℃/min. The samples were then allowed to cool naturally to room temperature (21 ℃) to achieve more consistent test results.
The results for the compositions shown in table 1 above are shown in the fields indicated in "example 1" in table 3 below. Other compositions shown in table 3 and represented by "example 2" to "example 8" were prepared in the same manner as the composition represented by the above example 1.
TABLE 3
Definition of symbols and measurement of physical properties
Physical properties of the glass samples were measured and are listed in table 3. The figure is a UV-VIS plot of the composition represented by example 1 in table 3, where "T%" is percent transmission, "R%" is percent reflection, and "a" is absorption.
The definitions of each symbol used in table 3 are shown below:
α: coefficient of Thermal Expansion (CTE) is the amount of change in the linear dimension from 50 to 300 ℃ as measured by ASTM-228 dilatometer;
beta: absorption coefficient at wavelength 810nm calculated from the following equation
β＝-log10[T/(1-R2)]/t,
Where β represents the absorption coefficient, T represents the proportion of light passing through the thickness (T) of the sample, and R refers to the reflectivity ratio.
While the invention has been described with reference to certain embodiments, those skilled in the art will recognize that the invention can be practiced with modification within the spirit and scope of the claims.
Any spatial reference terms, such as "up", "down", "between", "bottom", "vertical", "horizontal", "oblique", "up", "down", "side-by-side", "left-to-right", "up-down", "left", "right-to-left", "up-to-down", "down-to-up", "top", "bottom-top", "top-bottom", etc., are used for illustrative purposes only and do not limit the specific orientation or position of the above structure.
The invention has been described with respect to certain embodiments. It is within the spirit and scope of the present application that modifications or variations may occur to those skilled in the art upon reading this disclosure. It will be appreciated that a number of modifications, variations and alternatives are included in the foregoing disclosure and, in some instances, some features of the invention will be employed without a corresponding use of the other features. It is therefore to be understood that the appended claims may be interpreted broadly, in a manner consistent with the scope of the invention.
Claims (12)
1. An alkali-free low-softening-point glass with a composition, wherein the glass is composed of the following compositions in percentage by mass:
from 6.0 to 28.0 wt% SiO2；
From 20.0 to 45.0 wt% of B2O3；
From 25.0 wt% to 48.0 wt% ZnO;
from 0.0 wt% to 15.0 wt% Al2O3；
From 3.0 wt% to 15.0 wt% CuO;
from 0.0 wt% to 10.0 wt% SrO; and
from 0.0 to 5.0 wt% MgO;
SiO in an amount of from 8.0 wt% to 30.0 wt%2+Al2O3，
B in a proportion of from 0.5 to 1.5% by weight2O3/ZnO, and
(SiO) in a proportion of wt.% of from 0.2 to 1.52+Al2O3)/B2O3
The glass has a softening point of from 600 ℃ to 700 ℃;
the glass has a temperature of from 50 ℃ to 300 ℃ of from 40 x10-7From/° C to 48X 10-7Coefficient of Thermal Expansion (CTE)/DEG C;
the glass has an absorption coefficient of greater than 2/mm at a wavelength of from 800nm to 1400 nm;
the glass has a composition having less than 1000 parts per million of alkali metal; the glass is used for laser heating and sealing the organic light-emitting diode display.
2. The glass of claim 1, wherein the glass has an SiO comprising from 8.0 wt% to 28.0 wt%2The composition of (1).
3. The glass of claim 1, wherein the glass has an SiO comprising from 8.0 wt% to 19.0 wt%2The composition of (1).
4. The glass of claim 1, wherein the glass has a B content comprising from 23.0 wt% to 42.0 wt%2O3The composition of (1).
5. The glass of claim 1, wherein the glass has a composition comprising from 27.0 wt% to 48.0 wt% ZnO.
6. The glass of claim 1, wherein the glass has an Al content comprising from 2.0 wt% to 11.0 wt%2O3The composition of (1).
7. The glass of claim 1, wherein the glass has a composition comprising from 3.0 wt% to 10.0 wt% CuO.
8. The glass of claim 1, wherein the glass has a composition comprising from 0.5 wt% to 10.0 wt% SrO.
9. The glass of claim 1, wherein the glass has a composition comprising from 0.5 wt% to 5.0 wt% MgO.
10. The glass of claim 1, wherein the glass has a composition characterized by having:
SiO in an amount of from 9.0 wt% to 28.0 wt%2+Al2O3。
11. The glass of claim 1, wherein the glass has a composition characterized by having:
b in a proportion of from 0.5 to 1.5% by weight2O3/ZnO。
12. The glass of claim 1, wherein the glass has a composition characterized by having:
(SiO) in a proportion of wt.% of from 0.2 to 1.52+Al2O3)/B2O3。
Priority Applications (3)
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| CN201610272853.XA CN107324648B (en) | 2016-04-28 | 2016-04-28 | Alkali-free low softening point glasses and compositions, and methods thereof |
| TW105114593A TWI702195B (en) | 2016-04-28 | 2016-05-11 | Alkali-free, low softening point glass and compositions and methods thereof |
| PCT/CN2017/081120 WO2017186044A1 (en) | 2016-04-28 | 2017-04-19 | Alkali-free, low softening point glass and compositions and methods thereof |
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| CN201610272853.XA CN107324648B (en) | 2016-04-28 | 2016-04-28 | Alkali-free low softening point glasses and compositions, and methods thereof |
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| US6586087B2 (en) * | 1999-12-30 | 2003-07-01 | Corning Incorporated | Articles sealed with glass |
| CN101139165A (en) * | 2006-08-18 | 2008-03-12 | 康宁股份有限公司 | Boro-silicate glass frits for hermetic sealing of light emitting device displays |
| CN101179113A (en) * | 2006-11-07 | 2008-05-14 | 康宁股份有限公司 | Hermetic seal for light emitting display device, method, and apparatus |
| CN101256969A (en) * | 2007-02-28 | 2008-09-03 | 康宁股份有限公司 | Seal for light emitting display device and method |
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|---|---|---|---|---|
| US6897610B1 (en) * | 1999-04-28 | 2005-05-24 | Matsushita Electric Industrial Co., Ltd. | Plasma display panel |
| JP3389243B1 (en) * | 2001-07-03 | 2003-03-24 | 松下電器産業株式会社 | Plasma display panel and method of manufacturing the same |
| JP2003246643A (en) * | 2002-02-27 | 2003-09-02 | Asahi Glass Co Ltd | Glass powder, fired body and method of producing glass powder |
| DE60318517T2 (en) * | 2002-04-24 | 2009-07-23 | Central Glass Co., Ltd., Ube | Lead-free low-melting glass |
| CN100506729C (en) * | 2003-07-18 | 2009-07-01 | 旭硝子株式会社 | Non-lead glass, glass powder for covering electrodes and plasma display device |
| DE102005001078A1 (en) * | 2005-01-08 | 2006-07-20 | Schott Ag | Glass powder, in particular biologically active glass powder and process for the production of glass powder, in particular biologically active glass powder |
| KR20080024086A (en) * | 2006-09-12 | 2008-03-17 | 주식회사 휘닉스피디이 | Glass powder for covering electrode of display device |
| KR100952750B1 (en) * | 2007-12-28 | 2010-04-13 | 주식회사 휘닉스피디이 | Lead free dielectric powder composition for display device and display device comprising same |
| CN101565276A (en) * | 2009-06-01 | 2009-10-28 | 贵阳晶华电子材料有限公司 | Glass powder for PDP barrier |
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- 2016-04-28 CN CN201610272853.XA patent/CN107324648B/en active Active
- 2016-05-11 TW TW105114593A patent/TWI702195B/en active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6586087B2 (en) * | 1999-12-30 | 2003-07-01 | Corning Incorporated | Articles sealed with glass |
| CN101139165A (en) * | 2006-08-18 | 2008-03-12 | 康宁股份有限公司 | Boro-silicate glass frits for hermetic sealing of light emitting device displays |
| CN101179113A (en) * | 2006-11-07 | 2008-05-14 | 康宁股份有限公司 | Hermetic seal for light emitting display device, method, and apparatus |
| CN101256969A (en) * | 2007-02-28 | 2008-09-03 | 康宁股份有限公司 | Seal for light emitting display device and method |
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| TWI702195B (en) | 2020-08-21 |
| CN107324648A (en) | 2017-11-07 |
| TW201738191A (en) | 2017-11-01 |
| WO2017186044A1 (en) | 2017-11-02 |
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