CN113121117A - Glass powder suitable for OLED packaging and preparation method and application thereof - Google Patents
Glass powder suitable for OLED packaging and preparation method and application thereof Download PDFInfo
- Publication number
- CN113121117A CN113121117A CN202010026806.3A CN202010026806A CN113121117A CN 113121117 A CN113121117 A CN 113121117A CN 202010026806 A CN202010026806 A CN 202010026806A CN 113121117 A CN113121117 A CN 113121117A
- Authority
- CN
- China
- Prior art keywords
- glass
- low
- melting
- devitrifying
- glass frit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C03C12/00—Powdered glass; Bead compositions
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- 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)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses glass powder suitable for OLED packaging and a preparation method and application thereof. The composition of the basic glass powder in the non-devitrification low-melting-point glass powder comprises the following components: bi2O3 50～90wt%，B2O35-25 wt%, ZnO 3-20 wt%, and less than 10wt% of MgO or SiO2、Al2O3、Na2O、K2O、Li2O、SrO、BaO、CaO、Nd2O3、Sm2O3、Sb2O3At least one additive of (a).
Description
Technical Field
The invention belongs to the field of low-temperature OLED precision packaging glass, and particularly relates to low-melting-point glass powder free of crystallization in a sealing process, and a preparation method and a use method thereof.
Background
Organic Light-Emitting Diode (OLED) displays have become an important technology for commercial flat panel displays, and have the advantages of self-luminescence, wide viewing angle, almost infinite contrast, low power consumption, and very high response speed, compared with LED displays. However, the electrodes and the organic light emitting materials thereof in the conventional OLED display are liable to react with moisture, oxygen, etc. permeated in the air, resulting in deterioration of performance and reduction of lifetime, so that effective hermetic encapsulation is performed to prevent permeation of moisture, oxygen, dust, and rays in the air, and to ensure that the elements are protected from external mechanical stress, which is very important for the lifetime of the OLED. At present, OLED sealing modes are mainly divided into three major categories, namely light-cured resin, metal welding or brazing and low-melting-point glass sealed by laser. Photocuring resins have good mechanical properties, but are relatively expensive and in many cases do not prevent oxygen and moisture from diffusing into the OLED display; metal welding or soldering is very complex in process, and can obtain good sealing by a plurality of layers of films, and the problems of short circuit and the like of a lead sealed in the OLED display can be caused; the laser sealing of the low-melting-point glass has the advantages of good sealing effect, simple process and the like. The requirements for OLED sealing glass performance include: (a) in order to ensure that the organic light-emitting diode material is not damaged by high temperature, the glass has low sealing temperature (400-500 ℃); (b) the Coefficient of Thermal Expansion (CTE) of the glass substrate is matched, and the CTE of the glass is 8-9 ppm/DEG C; (c) good chemical stability, etc.
The glass with low melting point at present hasLead glass, vanadate glass, bismuthate glass and phosphate glass, wherein lead can volatilize into the air in the production process of the lead glass, and a large amount of lead-containing waste is generated, so that the lead-free low-melting-point glass is greatly harmful to people and the environment, and the development and the production of the lead-free low-melting-point glass become the mainstream of development. Chinese patent CN201410143646.5 reports V with controllable softening temperature lower than 450 ℃ and thermal expansion coefficient between 4.9 ppm/DEG C and 12.5 ppm/DEG C2O5-ZnO-B2O3Low melting point glass, but expensive and toxic TeO is added to improve the water resistance and chemical resistance of the glass2(1 to 10 mol%). Phosphate glass is a lead-free low-temperature sealing glass which is studied earlier, such as U.S. Pat. No. 5,5246890, Japanese patent JP2003146691, Chinese patent CN95103974.1 and the like, but the phosphate glass is difficult to industrialize due to the disadvantages of generally high thermal expansion coefficient, poor chemical stability and the like.
Compared with the glass system, the bismuthate glass has the advantages of small toxicity, small thermal expansion coefficient and good chemical stability, and becomes a star material in a low-temperature sealing glass material. Japanese patent laid-open No. 2006143480 discloses a Bi2O3-B2O3The glass component and the sealing material adopting the component comprise the following components: bi2O3 30～60mol％、B2O3 10～35mol％、WO30.1-5 mol%, the glass has the defects of over high CTE (more than 11 ppm/DEG C) and easy crystallization in the sealing process. Two disclosures of Zhang Teng of Fuzhou university on low temperature Bi2O3-B2O3ZnO sealing glasses are also devitrifying glasses (CN201610965868.4 and CN 201610967745.5). U.S. Pat. No. 2006/01058981 reports a low melting Bi that does not devitrify upon heat treatment2O3-B2O3-ZnO sealing glass of Bi2O3 70～90wt％、B2O3 2～12wt％、B2O31～20wt％、0.1～5wt％Al2O3、0～5wt％CuO、0～5wt％CeO2、0～0.2wt％Fe2O3The glass of the system is added with a large amount of Al2O3So as to obviously improve the sealing temperature of the glass. In the sealing process, if the crystallization phenomenon occurs, the glass sealing temperature is increased, and sealing failure can be caused, and at present, many researches only focus on the softening temperature and the thermal expansion coefficient of glass, and the influence of the crystallization process in sealing on the sealing effect is often ignored.
Disclosure of Invention
Aiming at the possible crystallization phenomenon of the low-melting-point bismuthate glass in the sealing process, the invention provides the glass powder which is not crystallized and is suitable for OLED packaging, and the preparation method and the use method thereof.
In a first aspect, the present invention provides a non-devitrifying low-melting glass frit, wherein the base glass frit comprises: bi2O3 50～90wt％，B2O35-25 wt%, ZnO 3-20 wt%, and less than 10wt% of MgO or SiO2、Al2O3、Na2O、K2O、Li2O、SrO、BaO、CaO、Nd2O3、Sm2O3、Sb2O3At least one additive of (a).
The non-devitrifying low-melting-point glass powder is Bi2O3、B2O3ZnO is used as a main component, and also comprises one or more compounds for inhibiting glass crystallization, stabilizing the glass structure and increasing the glass forming capability. By adjusting the main component Bi in the glass2O3、B2O3The mass percentage of ZnO reduces the glass transition temperature and the softening temperature of the glass, and the possibility of realizing low-temperature sealing is reached; and then a certain amount of compounds with stable glass structure and glass forming capacity are added to achieve the purposes of not only preventing glass from crystallizing, but also properly adjusting the thermal expansion coefficient of the glass, and finally the obtained glass powder can be used for low-temperature packaging of electronic components such as OLED and the like.
Preferably, the base glass frit comprises the following components in percentage by mass:
Bi2O3：50～90wt％；
B2O3：5～25wt％；
ZnO：3～20wt％；
MgO、SiO2、Al2O3at least one of: 0.5-5 wt%;
Na2O、K2o and Li2At least one of O: 0.5-5 wt%;
at least one of SrO, BaO and CaO: 0.5-5 wt%;
Nd2O3、Sm2O3and Sb2O3At least one of: 0.5 to 5 wt%.
Preferably, the colorant is a calcined material obtained by keeping the temperature of iron-based oxide and cobalt-based oxide at 700-1000 ℃ for 2-8 hours, wherein the molar ratio of the iron-based oxide to the cobalt-based oxide is 1: (0.5 to 2); preferably, the cobalt-based oxide is CoO, Co2O3Or Co3O4The iron-based oxide comprises FeO and Fe2O3Or Fe3O4At least one of them.
Preferably, the filler comprises a ceramic filler and/or a glass filler with a thermal expansion coefficient of-8.6-1 ppm/DEG C, and the content of the filler is less than 10wt% of the mass of the basic glass powder.
Preferably, the ceramic filler comprises at least one of cordierite and beta-eucryptite, and the glass filler comprises at least one of quartz glass powder and eucryptite glass powder.
Preferably, the median particle diameter D50 of the base glass powder, the colorant and the filler is 2-4 μm.
Preferably, the expansion coefficient of the non-devitrifying low-melting-point glass powder is 9-10 ppm/DEG C, the glass transition temperature is 360-400 ℃, the softening temperature is 400-440 ℃, and the packaging temperature is 450-510 ℃.
In a second aspect, the present invention provides a method for non-devitrifying low melting point glass frits comprising the steps of:
s1: weighing raw materials of basic glass powder, adding water, ball-milling for 0.5-2 hours, and drying at 110-200 ℃ for 3-12 hours to obtain a mixture;
s2: heating the mixture obtained in the step S1 to 900-1100 ℃ at a speed of 1-10 ℃/min, melting for 0.5-2 hours, and cooling the molten glass obtained by melting to obtain glass fragments;
s3: and ball-milling the glass fragments obtained in the step S2, or the glass fragments, the coloring agent and the filler for 0.5-6 hours to obtain the non-devitrification low-melting-point glass powder.
In a third aspect, the present invention provides a method for encapsulating an OLED using the above non-devitrifying low melting point glass frit, comprising the steps of:
s1: uniformly mixing non-devitrifying low-melting-point glass powder with an organic solvent to form glass slurry;
s2: pretreating a glass substrate to be packaged;
s3: coating the glass slurry on the glass substrate pretreated in the step S2;
s4: heating the glass substrate coated with the glass slurry in the step S3 to 450-550 ℃ at a speed of 1-5 ℃/min, and preserving heat for 0.5-2 hours, so as to remove organic matters in the glass slurry and vitrify the low-melting glass;
s5: and (3) placing the OLED element into the glass substrate lamination, and packaging through a laser, namely completing the packaging of the OLED element.
Preferably, the glass powder solid content of the glass paste in the step S1 is 75-85 wt%.
Preferably, the organic solvent in step S1 includes one or more of alcohols, ketones, and benzenes.
The invention has the following remarkable advantages:
(1) by adjusting the main component Bi in the glass2O3、B2O3The mass percentage of ZnO reduces the glass transition point and the softening point of the glass, and reaches the possibility of realizing low-temperature sealing;
(2) the total percentage of the added oxides or compounds with the functions of stabilizing the glass structure and increasing the glass forming ability is less than 10wt%, so that the crystallization phenomenon of the glass in the heat treatment process can be inhibited, the thermal expansion coefficient of the glass can be properly adjusted, and the characteristic of low melting point of the glass is also preserved;
(3) the added colorant and the filler are less than 15 wt% relative to the total amount of the glass, so that the low-melting-point glass is ensured to be matched with the glass substrate in laser absorption capacity and thermal expansion coefficient, and the low-melting-point characteristic of the glass is also preserved;
(4) the low-melting-point glass does not contain toxic components such as Pb, Cr, V, Te and the like, and has simple preparation process, economy and environmental protection.
Drawings
FIG. 1 is a flow chart of the preparation of low melting point glass frit;
FIG. 2 is a flow chart of low melting point glass frit encapsulation of OLED devices;
FIG. 3 is a photograph of a low melting point glass paste obtained by the preparation;
FIG. 4 is a DSC curve of examples 1 to 3, 5 and comparative examples 1 to 2;
FIG. 5 is an XRD pattern of example 2 and comparative example 1 untreated and incubated at 550 ℃ for 2 h;
FIG. 6 is a SEM image of a cross section of the laser-sealed steel sheets obtained in example 2, comparative example 1 and comparative example 2.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The invention provides a non-devitrifying low-melting point glass powder, which is prepared from Bi2O3、B2O3ZnO is used as a main component, and also comprises one or more compounds for inhibiting glass crystallization, stabilizing the glass structure and increasing the glass forming capability. In some embodiments, the composition of the base glass frit in the non-devitrifying, low melting point glass frit comprises: bi2O3 50～90wt％，B2O35-25 wt%, ZnO 3-20 wt%, and less than 10wt% of MgO or SiO2、Al2O3、Na2O、K2O、Li2O、SrO、BaO、CaO、Nd2O3、Sm2O3、Sb2O3At least one additive of (a).
In some embodiments, the present invention is directed to a non-devitrifying, low melting glass frit comprising a base glass frit comprising, in mass percent: bi2O3：50～90wt％；B2O3：5～25wt％；ZnO：3～20wt％；MgO、SiO2、Al2O3At least one of: 0.5-5 wt%; na (Na)2O、K2O and Li2At least one of O: 0.5-5 wt%; at least one of SrO, BaO and CaO: 0.5-5 wt%; nd (neodymium)2O3、Sm2O3And Sb2O3At least one of: 0.5 to 5 wt%.
Bi and Pb are located at adjacent positions in the periodic table, and have many similar properties such as high polarizability, high refraction and dispersion ratios, and similar viscosity, characteristic temperature, coefficient of linear expansion (CET) and the like according to the diagonal line and the adjacent principle. Bi2O3SiO capable of being combined with glass forming body2、B2O3Or P2O5The components are co-melted and have a relatively wide glass forming range even when only 1 wt% of SiO is used2Or B2O3When present, glass is also readily formed. In addition, the bismuthate low-temperature sealing glass is not easy to recover in the melting process, is harmless to the environment and human bodies, and belongs to environment-friendly glass, so that the bismuthate glass is the best substitute of lead acid salt glass.
Bi in the invention2O3The composition range of (A) is 50 to 90 wt%. When the content is less than 50 wt%, the softening point of the glass cannot be sufficiently lowered, and the sealing effect cannot be expected; when the content is more than 90 wt%, a part of Bi may be caused due to an excessively large content2O3Is reduced to precipitate Bi metal, is not easy to form glass, and causes an excessively large thermal expansion coefficient. Further preferably, the Bi2O3The composition range is 70-85 wt%.
B2O3Is one of the most basic oxides in many low-melting glasses and is also an important network former in the glass, and can accelerate glass homogenization, reduce the viscosity of the glass and reduce crystallization capacity at high temperature so as to enable the glass to be formed more easily. After the glass is formed, it can improve the thermal stability, chemical stability and fluidity of the glass, and reduce the viscosity of the glassLow coefficient of expansion and surface tension of the glass. In the invention B2O3The composition range of (A) is 5 to 25 wt%. When the content thereof is less than 5% by weight, it cannot function as a co-solvent to accelerate the fining of the glass and to reduce the crystallization ability of the glass; and when the content is more than 25% by weight, B is contained in the glass during melting2O3The water vapor is volatilized, so that a devitrified skin is formed on the surface of molten glass due to the reduction of volatilization, and the glass is formed by BO3]The trihedron increases, the thermal expansion coefficient of the glass increases instead, and the softening point temperature of the glass increases significantly. Further preferably, said B2O3The composition range is 10-20 wt%.
ZnO is an important glass network regulating oxide, can reduce the softening point of glass, regulate the thermal expansion coefficient and improve the chemical stability, the thermal stability and the refractive index of the glass. The composition range of ZnO in the invention is 3-20 wt%. When the content is less than 3%, glass is not easily formed, and the thermal expansion coefficient of the glass is obviously increased; when the content is more than 20% by weight, the softening point temperature of the glass is increased, the fluidity of the glass is deteriorated, and the crystallization is liable to occur. Further preferably, the ZnO composition range is 5-15 wt%.
MgO、SiO2And Al2O3The addition of one or more of the above components can reduce the crystallization tendency of the glass, increase the stability, mechanical strength, refractive index and the like of the glass, and is used for adjusting the thermal expansion coefficient and sealing temperature of the glass, but the addition amount is not easy to be excessive, and the softening temperature of the glass can be increased. The total addition amount of the additive is 0.5-5 wt%, preferably 0.5-3 wt%.
Alkali metal oxide (Na)2O、K2O、Li2One or more of O) can increase the solubility of the glass during melting, lower the melting temperature, and lower the softening temperature of the glass. The total addition amount of the additive is 0.5-5 wt%, preferably 0.5-5 wt%.
One or more of SrO, BaO, CaO may increase the fluidity of the glass in the low temperature region. However, the addition amount is not too large, and the softening temperature of the glass is increased. The total addition amount of the additive is 0.5-5 wt%, preferably 0.5-3 wt%.
Nd2O3、Sm2O3And Sb2O3The glass refining agent can be used as a clarifying agent in the glass melting process, and can improve the uniformity of the glass in the low-temperature melting process. Meanwhile, the crystallization tendency of the glass can be inhibited, and the thermal stability of the glass is improved. The content of the two components is 0.5-5 wt% in total. When the content is less than 0.5 wt%, the effect of inhibiting glass crystallization cannot be achieved; when the content is more than 5%, the viscosity of the glass is increased, and the glass is not easily formed. Further preferably, Nd is added to the glass composition of the present invention in a total amount ranging from 0.5 to 3 wt%2O3、Sb2O3At least one of (1).
In order to further improve the properties of the glass frit, the glass frit may further comprise a colorant, the colorant content being < 5 wt.%.
The colorant can be an iron-based oxide and a cobalt-based oxide according to a molar ratio (1-2): (1-2) keeping the temperature of the mixture at 700-1000 ℃ for 2-8 hours to obtain a calcined material. The iron-based oxide comprises FeO and Fe2O3Or Fe3O4At least one of Co-based oxide and Co-based oxide2O3Or Co3O4。
In some embodiments, the glass frit may further comprise a ceramic filler and/or a glass filler having a coefficient of thermal expansion of-8.6 to 1 ppm/DEG C, the filler content being < 10 wt%. The ceramic filler may include at least one of cordierite and beta-eucryptite, and the glass filler may include at least one of quartz glass frit and eucryptite glass frit.
In the invention, the median particle size D50 of the base glass powder, the colorant and the filler can be 2-4 μm. Preferably, the particle size of the filler may be 2 to 3 μm.
The expansion coefficient of the glass powder is 9-10 ppm/DEG C, the glass transition temperature is 360-400 ℃, the softening temperature is 400-440 ℃, and the packaging temperature is 450-510 ℃.
The non-devitrification low-melting-point glass powder can inhibit the devitrification phenomenon of glass in the heat treatment process, can also properly adjust the thermal expansion coefficient of the glass, and simultaneously preserves the low-melting-point characteristic of the glass.
The glass powder has the characteristic of no crystallization in the heat treatment process, the glass transition temperature is lower than 400 ℃, and the glass powder can be completely vitrified at the temperature of below 550 ℃ after a proper amount of coloring agent and filler are added; the packaging of the OLED device is completed by combining and modulating the low-melting-point glass powder into slurry, screen printing the slurry on a glass substrate, glue discharging and vitrifying at 450-550 ℃, laser sealing and the like. The invention comprehensively provides a preparation method and application of the low-melting-point glass for OLED packaging, and the low-melting-point glass has the advantages of simple and easily obtained raw materials, no toxic components, low cost and simple and feasible process, and achieves the practical and industrialized conditions.
The method for preparing and using the low-melting-point glass powder for sealing the OLED in the specific embodiment comprises the following steps:
(1) respectively weighing raw materials corresponding to the components, adding water, and then carrying out ball milling for 0.5-2 hours: water: the mass ratio of the raw materials is (2-4): (2-3): (1) discharging, and drying for 6-12 hours at 110-150 ℃ to obtain a mixture; in the raw materials for preparing the glass powder, the B source can be H with the purity of more than 99 percent3BO3The Na source, the K source, the Li source, the Sr source, the Ba source and the Ca source can be one of carbonate and nitrate with the purity of more than 99 percent, and the rest raw materials can be introduced by oxides with the purity of more than 99 percent;
(2) heating the mixture in the step (1) to 900-1100 ℃ at a speed of 1-10 ℃/min, melting for 0.5-2 hours, and cooling the molten glass to obtain glass fragments; the cooling mode is rapid cooling, for example, water quenching;
(3) mixing the glass fragments, the coloring agent and the filler (or the coloring agent and the filler can be omitted) in the step (2) in a mass ratio of 1: (1-5 wt%): (3-10 wt%) ball milling for 0.5-6 hours, adding absolute ethyl alcohol as a dispersion medium, and mixing: grinding balls: the mass ratio of the absolute ethyl alcohol is (2-4): (2-3): (1) drying for 6-12 hours at 100-130 ℃, and sieving with a 120-200 mesh sieve after drying to form glass powder with the particle size of 2-4 microns;
(4) mixing the glass powder in the step (3) with an organic solvent, and performing ball milling for 1-3 hours to form glass slurry with the solid content of the glass powder being 75-85 wt%; the organic solvent can be one or more of alcohols, ketones and benzene organic solvents, wherein the benzene organic solvent is preferably xylene;
(5) ultrasonically cleaning a glass substrate to be sealed in acetone or alcohol for 30-60 minutes, and drying the glass substrate in a constant-temperature air blast drying oven at the temperature of 80-110 ℃ for 30-60 minutes;
(6) coating the glass slurry on the glass substrate pretreated in the step (5);
(7) putting the glass substrate coated in the step (6) into a muffle furnace, heating to 450-550 ℃ at a heating rate of 1-5 ℃/min, preserving heat for 0.5-2 hours, removing organic matters in the glass slurry and vitrifying the low-melting-point glass;
(8) and (5) placing the OLED component into the glass substrate lamination with the low-melting-point glass layer obtained in the step (7), and packaging by using a semiconductor laser, namely completing the packaging of the OLED component.
In the above method, the coating of the glass paste is not limited by its coating manner. The application may be screen printing. The mesh number of the silk screen is preferably 80-200 meshes.
In the method, the rotation speed of the ball milling is preferably 300 to 600 r/min.
In the step (8), the wavelength of the laser is 810 +/-10 nm, and the output power is 10-20W.
In the process of ball milling of the glass powder, one or more of silane coupling agent, stearate, PVB alcohol solution with the weight percent of 2-12 and PVA water solution with the weight percent of 3-10 which are less than 10wt% of the total weight of the glass powder can be added. In addition, an auxiliary agent such as a plasticizer or a binder may be added to the organic solvent.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
(1) According to the glass mixture ratio of example 1 in table 1, the total mass is 1000g, and the corresponding raw materials are calculated and weighed: bi2O3627.18g、H3BO3 210.33g、ZnO 90.44g、Na2CO3 24.91g、Nd2O3 13.58g、MgO 15.37g、BaCO318.17g, adding the prepared materials into 2000g of deionized water, and performing planetary ball milling for 1 hour to obtain the following materials: the mass ratio of the grinding balls is 4:1, discharging, and drying in a drying oven at a constant temperature of 150 ℃ for 12 hours to obtain a mixture;
(2) placing the mixture obtained in the step (1) in an alumina crucible, heating to 1000 ℃ at a speed of 3 ℃/min, preserving heat for 1.5 hours, and then quenching and cooling the molten glass obtained by melting to obtain glass fragments;
(3) using Fe3O4、Co2O3According to a molar ratio of 1: 1 and keeping the temperature at 1000 ℃ for 4 hours after mixing to obtain a calcined material as a coloring agent. The filler uses self-made quartz glass powder with the particle size of 5 um. Adding the glass fragments obtained in the step (2) into an alumina ceramic pot according to the ratio of 100 wt% of the glass fragments to 3 wt% of the colorant to 7.5 wt% of the quartz glass powder, adding absolute ethyl alcohol as a dispersion medium, and mixing the following materials: grinding balls: the mass ratio of the absolute ethyl alcohol is 1:4:1, after ball milling for 4 hours, drying for 4 hours in a constant temperature drying oven at 110 ℃, and after drying, sieving with a 120-mesh sieve to obtain glass powder with D50 being approximately equal to 2.5 +/-0.5 um for later use;
(4) mixing the glass powder obtained in the step (3) with xylene to form slurry according to the solid content of 80 wt%, and uniformly dispersing for 1 hour by adopting planetary ball milling to obtain glass slurry;
(5) ultrasonically cleaning the surface of a glass substrate to be sealed in acetone for 45 minutes, and drying the glass substrate in a constant-temperature air-blast drying oven at 100 ℃ for 60 minutes;
(6) printing the glass slurry on the peripheral edge of the treated glass substrate in the step (5) by a 200-mesh screen;
(7) putting the glass substrate printed in the step (6) into a muffle furnace, heating to 510 ℃ at the heating rate of 2.5 ℃/min, preserving heat for 1 hour, removing organic matters in the glass slurry, and removing glue and vitrifying the low-melting-point glass;
(8) the OLED element was placed in (7) to obtain a glass substrate laminate having a low-melting glass layer and was encapsulated by a semiconductor laser of wavelength 810nm at an output power of 14.85W.
Example 2
The difference from example 1 is that: calculating and weighing each corresponding raw material by taking the total mass as 1000 g: bi2O3696.68g、H3BO3 170.53g、ZnO 81.57g、Na2CO3 14.15g、Sb2O3 10.76g、MgO 7.45g、Al2O318.85 g. The OLED element was encapsulated in the same manner as in example 1.
Example 3
The difference from example 1 is that: calculating and weighing each corresponding raw material by taking the total mass as 1000 g: bi2O3652.38g、H3BO3 229.21g、ZnO 71.13g、Na2CO3 12.89g、SrCO3 25.52g、Sb2O38.87 g. The OLED element was encapsulated in the same manner as in example 1.
Example 4
The difference from example 1 is that: calculating and weighing each corresponding raw material by taking the total mass as 1000 g: bi2O3671.52g、H3BO3 186.22g、ZnO 78.74g、Na2CO3 14.98g、Sb2O3 8.76g、MgO 22.26g、Nd2O317.52 g. The OLED element was encapsulated in the same manner as in example 1.
Example 5
The difference from example 1 is that: calculating and weighing each corresponding raw material by taking the total mass as 1000 g: bi2O3713.43g、H3BO3 155.06g、ZnO 57.7g、Na2CO3 5.83g、BaCO3 36.18g、SiO2 13.83g、Al2O317.97 g. The OLED element was encapsulated in the same manner as in example 1.
Comparative example 1
And embodiments thereof1, the difference lies in that: calculating and weighing each corresponding raw material by taking the total mass as 1000 g: bi2O3675.35g、H3BO3236.51g and ZnO 88.14 g. The OLED element was encapsulated in the same manner as in example 1.
Comparative example 2
Since the import from abroad is directly the glass slurry, the glass preparation method is omitted. The preparation and use method of the low-temperature glass for sealing the OLED comprises the following steps:
(1) carrying out surface ultrasonic cleaning and drying pretreatment on the glass substrate by adopting the method of the embodiment 1;
(2) printing the glass slurry on the periphery of the glass substrate processed in the step (1) by a 200-mesh screen printing method;
(3) putting the glass substrate printed in the step (2) into a muffle furnace, heating to 480 ℃ at the heating rate of 2.5 ℃/min, preserving heat for 1 hour, removing organic matters in the glass slurry, and removing glue and vitrifying the low-melting-point glass;
(4) the OLED cells were placed in (3) a glass substrate stack already having a low-melting glass layer and encapsulated by a 810nm wavelength semiconductor laser at an output of 13.95W.
TABLE 1 test tables for the proportions and properties of examples 1 to 5 and comparative examples 1 to 2
Fig. 1 shows a flow chart of the preparation of the low melting point glass paste, and it can be seen from the chart that the preparation process of the glass paste is simple and is applicable to industrialization.
FIG. 4 shows DSC curves of examples 1 to 5 and comparative examples 1 to 2, and it can be seen that no crystallization peak is detected in the DSC curves of examples 1 to 5, and no crystallization peak is detected in the inlet glass frit (i.e., comparative example 2), but a significant crystallization peak appears in comparative example 1. In addition, it can be seen that the glass transition temperatures of examples 1-5 are slightly higher than that of comparative example 2, which is an imported glass frit.
FIG. 5 shows XRD patterns of example 2 and comparative example 1 without heat treatment and after heat-holding at 550 ℃ for 2 hours, and it can be seen from the graphs that example 2 does not precipitate a crystal phase during the heat treatment, while comparative example 1 apparently precipitates a crystal phase.
FIG. 6 shows SEM images of cross sections of example 2, comparative example 1 and comparative example 2 after laser sealing, and it can be seen that the sealing cross section of example 2 and comparative example 2 after laser sealing is neat, and a small amount of bubbles exist in the sealing glass; in contrast, comparative example 1 had a rough sealing interface and the glass was apparently unmelted.
Claims (10)
1. The non-devitrifying low-melting-point glass powder is characterized in that the composition of a base glass powder in the non-devitrifying low-melting-point glass powder comprises the following components: bi2O3 50～90wt%，B2O35-25 wt%, ZnO 3-20 wt%, and less than 10wt% of MgO or SiO2、Al2O3、Na2O、K2O、Li2O、SrO、BaO、CaO、Nd2O3、Sm2O3、Sb2O3At least one additive of (a).
2. The devitrification-free low melting point glass frit of claim 1, wherein the base glass frit comprises the following components in mass percent:
Bi2O3：50～90wt%；
B2O3：5～25wt%；
ZnO：3～20wt%；
MgO、SiO2、Al2O3at least one of: 0.5-5 wt%;
Na2O、K2o and Li2At least one of O: 0.5-5 wt%;
at least one of SrO, BaO and CaO: 0.5-5 wt%;
Nd2O3、Sm2O3and Sb2O3At least one of: 0.5 to 5 wt%.
3. The non-devitrifying, low melting point glass frit according to claim 1 or 2, wherein the non-devitrifying, low melting point glass frit further comprises a colorant and a filler in addition to the base glass frit; the content of the colorant is 5wt% or less of the mass of the base glass frit.
4. The devitrification-free low-melting-point glass frit as claimed in claim 3, wherein the colorant is a calcined material obtained by maintaining iron-based oxide and cobalt-based oxide at 700-1000 ℃ for 2-8 hours, wherein the molar ratio of iron-based oxide to cobalt-based oxide is 1: (0.5 to 2); preferably, the cobalt-based oxide is CoO, Co2O3Or Co3O4The iron-based oxide comprises FeO and Fe2O3Or Fe3O4At least one of them.
5. The devitrification-free low melting point glass frit according to claim 3 or 4, wherein the filler comprises a ceramic filler and/or a glass filler having a thermal expansion coefficient of-8.6 to 1ppm/° C, and the filler content is 10wt% or less based on the mass of the glass frit.
6. The non-devitrifying, low melting point glass frit according to claim 5, wherein said ceramic filler comprises at least one of cordierite, β -eucryptite and said glass filler comprises at least one of quartz glass frit, eucryptite glass frit.
7. The non-devitrifying, low melting point glass frit according to any one of claims 3 to 6, wherein the median particle diameter D50 of the base glass frit, the colorant and the filler is 2 to 4 μm.
8. The non-devitrifying low melting point glass frit according to any one of claims 1 to 7, wherein the non-devitrifying low melting point glass frit has an expansion coefficient of 9 to 10ppm/° C, a glass transition temperature of 360 to 400 ℃, a softening temperature of 400 to 440 ℃, and a sealing temperature of 450 to 510 ℃.
9. A method for producing the non-devitrifying, low-melting-point glass frit according to any one of claims 1 to 8, characterized by comprising: the method comprises the following steps:
s1: weighing raw materials of basic glass powder, adding water, ball-milling for 0.5-2 hours, and drying at 110-200 ℃ for 3-12 hours to obtain a mixture;
s2: heating the mixture obtained in the step S1 to 900-1100 ℃ at a speed of 1-10 ℃/min, melting for 0.5-2 hours, and cooling the molten glass obtained by melting to obtain glass fragments;
s3: and ball-milling the glass fragments obtained in the step S2, or the glass fragments, the coloring agent and the filler for 0.5-6 hours to obtain the non-devitrification low-melting-point glass powder.
10. A method for encapsulating an OLED by using the non-devitrifying low-melting-point glass powder as claimed in any one of claims 1 to 8, comprising the steps of: non-viable cells
S1: uniformly mixing non-devitrifying low-melting-point glass powder with an organic solvent to form glass slurry;
s2: pretreating a glass substrate to be packaged;
s3: coating the glass slurry on the glass substrate pretreated in the step S2;
s4: heating the glass substrate coated with the glass slurry in the step S3 to 450-550 ℃ at a speed of 1-5 ℃/min, and preserving heat for 0.5-2 hours, so as to remove organic matters in the glass slurry and vitrify the low-melting glass;
s5: and (3) placing the OLED element into the glass substrate lamination, and packaging through a laser, namely completing the packaging of the OLED element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010026806.3A CN113121117B (en) | 2020-01-10 | 2020-01-10 | Glass powder suitable for OLED packaging and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010026806.3A CN113121117B (en) | 2020-01-10 | 2020-01-10 | Glass powder suitable for OLED packaging and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113121117A true CN113121117A (en) | 2021-07-16 |
| CN113121117B CN113121117B (en) | 2022-09-06 |
Family
ID=76771522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010026806.3A Active CN113121117B (en) | 2020-01-10 | 2020-01-10 | Glass powder suitable for OLED packaging and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113121117B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113735446A (en) * | 2021-09-30 | 2021-12-03 | 北京北旭电子材料有限公司 | Glass powder and preparation method thereof |
| CN114409251A (en) * | 2022-02-18 | 2022-04-29 | 广州市儒兴科技股份有限公司 | Lead-free glass powder and preparation method and application thereof |
| CN114590999A (en) * | 2022-01-20 | 2022-06-07 | 广西科技大学 | Low-melting-point lead-free glass powder and preparation method thereof |
| CN115286253A (en) * | 2022-08-09 | 2022-11-04 | 中建材玻璃新材料研究院集团有限公司 | Preparation method of low-melting-point sealing glass powder for micro electronic mechanical system |
| CN115305035A (en) * | 2021-05-08 | 2022-11-08 | 深圳市首骋新材料科技有限公司 | Glass cement for OLED sealing, OLED element packaging method and OLED device |
| CN115745661A (en) * | 2022-11-29 | 2023-03-07 | 浙江安防职业技术学院 | Sealing method for end face of tubular ceramic membrane |
| CN115772005A (en) * | 2021-09-06 | 2023-03-10 | 长春理工大学 | Preparation method of lead-free glass powder for silver paste of solar cell |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1656033A (en) * | 2002-03-29 | 2005-08-17 | 松下电器产业株式会社 | Bismuth glass composition, and magnetic head and plasma display panel including the same as sealing member |
| CN101602573A (en) * | 2009-07-21 | 2009-12-16 | 中国计量学院 | A kind of bismuthate lead-free sealing glass material with low melting point and preparation method thereof |
| CN101723589A (en) * | 2008-10-29 | 2010-06-09 | 珠海彩珠实业有限公司 | Lead-free glass powder with low melting point for sealing PDP and preparation method thereof |
| CN102066280A (en) * | 2009-07-23 | 2011-05-18 | 旭硝子株式会社 | Method and apparatus for manufacturing glass member provided with sealing material layer and method for manufacturing electronic device |
| KR20130132005A (en) * | 2012-05-25 | 2013-12-04 | 순천향대학교 산학협력단 | Low melting temperature glass compositions for laser-based sealing |
| CN105731803A (en) * | 2016-02-26 | 2016-07-06 | 中国建筑材料科学研究总院 | Copper sealing glass powder, preparation method and application thereof, and electrodes of battery |
-
2020
- 2020-01-10 CN CN202010026806.3A patent/CN113121117B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1656033A (en) * | 2002-03-29 | 2005-08-17 | 松下电器产业株式会社 | Bismuth glass composition, and magnetic head and plasma display panel including the same as sealing member |
| CN101723589A (en) * | 2008-10-29 | 2010-06-09 | 珠海彩珠实业有限公司 | Lead-free glass powder with low melting point for sealing PDP and preparation method thereof |
| CN101602573A (en) * | 2009-07-21 | 2009-12-16 | 中国计量学院 | A kind of bismuthate lead-free sealing glass material with low melting point and preparation method thereof |
| CN102066280A (en) * | 2009-07-23 | 2011-05-18 | 旭硝子株式会社 | Method and apparatus for manufacturing glass member provided with sealing material layer and method for manufacturing electronic device |
| KR20130132005A (en) * | 2012-05-25 | 2013-12-04 | 순천향대학교 산학협력단 | Low melting temperature glass compositions for laser-based sealing |
| CN105731803A (en) * | 2016-02-26 | 2016-07-06 | 中国建筑材料科学研究总院 | Copper sealing glass powder, preparation method and application thereof, and electrodes of battery |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115305035A (en) * | 2021-05-08 | 2022-11-08 | 深圳市首骋新材料科技有限公司 | Glass cement for OLED sealing, OLED element packaging method and OLED device |
| CN115772005A (en) * | 2021-09-06 | 2023-03-10 | 长春理工大学 | Preparation method of lead-free glass powder for silver paste of solar cell |
| CN113735446A (en) * | 2021-09-30 | 2021-12-03 | 北京北旭电子材料有限公司 | Glass powder and preparation method thereof |
| CN114590999A (en) * | 2022-01-20 | 2022-06-07 | 广西科技大学 | Low-melting-point lead-free glass powder and preparation method thereof |
| CN114409251A (en) * | 2022-02-18 | 2022-04-29 | 广州市儒兴科技股份有限公司 | Lead-free glass powder and preparation method and application thereof |
| CN115286253A (en) * | 2022-08-09 | 2022-11-04 | 中建材玻璃新材料研究院集团有限公司 | Preparation method of low-melting-point sealing glass powder for micro electronic mechanical system |
| CN115286253B (en) * | 2022-08-09 | 2024-04-16 | 中建材玻璃新材料研究院集团有限公司 | Preparation method of low-melting-point sealing glass powder for micro electronic mechanical system |
| CN115745661A (en) * | 2022-11-29 | 2023-03-07 | 浙江安防职业技术学院 | Sealing method for end face of tubular ceramic membrane |
| CN115745661B (en) * | 2022-11-29 | 2023-09-08 | 浙江安防职业技术学院 | Sealing method for end face of tubular ceramic membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113121117B (en) | 2022-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113121117B (en) | Glass powder suitable for OLED packaging and preparation method and application thereof | |
| KR102005286B1 (en) | Tellurate joining glass having processing temperatures ≤ 420 °C | |
| US9469562B2 (en) | Glass substrate with sealing material layer, organic EL device using same, and manufacturing method for electronic device | |
| US8697242B2 (en) | Glass member provided with sealing material layer, electronic device using it and process for producing the electronic device | |
| WO2011108115A1 (en) | Lead-free glass material for organic-el sealing, organic el display formed using same, and process for producing the display | |
| WO2011122218A1 (en) | Sealing material and paste material using same | |
| US20140023803A1 (en) | Airtight member and its production process | |
| US20130287989A1 (en) | Glass member provided with sealing material layer electronic device using it and process for producing the electronic device | |
| CN111302629B (en) | Glass composition, glass powder, sealing material, glass paste, sealing method, sealed package, and organic electroluminescent element | |
| JP6269991B2 (en) | Glass substrate with sealing material layer | |
| CN114212995B (en) | Preparation method of OLED sealing solder | |
| JP2022538801A (en) | Compositions, pastes and methods | |
| JPWO2001090012A1 (en) | Glass composition and glass-forming material containing the composition | |
| CN109320071B (en) | Aluminosilicate glass composition, aluminosilicate glass, and preparation method and application thereof | |
| JP5516194B2 (en) | Light heat sealing glass, glass member with sealing material layer, electronic device and method for producing the same | |
| CN112551902A (en) | Low-melting-point glass powder containing alkaline earth metal and preparation method and application thereof | |
| JP2008308393A (en) | Lead-free low softening point glass, lead-free low softening point glass composition, lead-free low softening point glass paste, and fluorescent display tube | |
| KR101028340B1 (en) | Frit composition having softening characteristics at low temperature | |
| KR101008201B1 (en) | Lead-free frit composition for flat display panel sealing | |
| CN113165957B (en) | Glass powder and packaging material using same | |
| JP2021066647A (en) | Glass composition, glass powder, sealing material, glass paste, sealing method, sealing package and organic electroluminescence element | |
| JP6075599B2 (en) | Method for producing glass substrate with sealing material layer | |
| KR101095002B1 (en) | The manufacturing methods of low temperature and low dielectric constant transparent dielectric layer and paste for soda-lime glass substrate in Plasma Display Panel | |
| CN118221349A (en) | High-performance electronic glass substrate with high strain point and low thermal expansion coefficient and preparation method thereof | |
| WO2010113838A1 (en) | Colored lead-free glass for sealing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |