Low melting point glass powder and its composite with electronic device

Abstract

A low-melting glass powder and a composite thereof and an electronic device, the low-melting glass powder comprising, in terms of molar amounts, 20-50 parts of V2O5, 20-40 parts of ZnO, 5-20 parts of BaCO3, 10-30 parts of TeO2, 0-10 parts of Al2O3, 0-15 parts of Bi2O3, and 0-10 parts of Nb2O5. The glass powder and the composite thereof provided by the present application have excellent thermal properties (Tg, Tx), a low coefficient of thermal expansion, and excellent fracture toughness, have excellent hermeticity as sealing glass, and the composition glass of the present application does not contain Pb and P, has good environmental friendliness and stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of electronic materials, in particular to a low-melting point glass powder and a composite thereof and an electronic device. BACKGROUND

[0002] An organic light-emitting diode (OLED) is a device that generates electroluminescence by using a multilayer organic thin film structure. It is a self-luminous display without a backlight and liquid crystals, and only needs a low driving voltage. It can be made into a thin film and has a fast response speed, thus meeting the requirements of consumers for display technology, and has a significant advantage in the application of flat panel displays. The market industrialization process is currently high.

[0003] However, the OLED screen also has its inherent defects. Since organic matter is used as a luminescent material, it is prone to aging. In addition, the device electrode is usually made of a metal material with high activity, which is prone to react with water and oxygen, resulting in black spots in the luminescent area, which gradually increases with time, affecting the stability and life of the device. Therefore, it is very important to isolate water and oxygen for OLED devices. The current solution in the industry is to add a sealing material around the display panel as a water and oxygen barrier.

[0004] In view of the need for electrical insulation and weather resistance, metal and organic sealing materials are excluded, and inorganic materials are preferred. Similarly, high-temperature sealing processes can damage other electronic components, so using low-melting point glass (Frit) as a sealing material can solve all the above problems.

[0005] Frit has a thermal softening bonding function, and the melting point is significantly lower than that of ordinary glass, usually below 600°C. It can realize mutual bonding and sealing between metals, ceramics, glass, and chips, and has a high bonding strength. In addition, Frit is superior to metal solder in electrical insulation performance and chemical stability, and is superior to organic polymer materials in airtightness and heat resistance. Therefore, low-temperature glass has a wide range of applications in microelectronic packaging, sensors, lasers, and display fields.

[0006] Domestic and foreign enterprises have conducted a large amount of research on low-temperature sealing glass formulations, mechanisms, and composition optimization. At present, it is mainly divided into the following categories: 1. borate glass; 2. phosphate glass; 3. bismuth-based glass; 4. vanadium-based glass.

[0007] Among them, borate is an early non-crystalline low-melting point glass that is commonly used. It usually contains PbO. This type of glass has good wettability and flowability, and good airtightness. However, the mechanical properties of the sealing layer are relatively poor, and due to environmental protection restrictions, it is not suitable for end electronic products.

[0008] The phosphate system low-melting-point glass usually needs to increase Al2O3, B2O3, SnO, ZnO, ZrO, etc. Oxides, there is a phosphorus-oxygen double bond on the phosphate [PO4] tetrahedron, which makes one of the apexes of the tetrahedron change, and the phosphate glass has a layered structure. Adding different oxides in the multinary phosphate will cause different chemical reactions, which will break the layered chain structure or produce cross-linked structure. The chemical stability of the phosphate system glass needs to be focused on.

[0009] The addition of SiO2, B2O3, ZnO, etc. Oxides in Bi2O3 can form glass, but the cost of bismuth oxide is high, and the expansion coefficient and Tg are also relatively high. The softening point is usually higher than 350℃, and the working temperature is higher than 450℃.

[0010] For vanadate system low-melting-point glass, V2O5 itself cannot be glassified, but by adding other oxides such as ZnO, P2O5, TeO2, SiO2, BaO, etc. Covalent bond is generated to shorten the molecular bond, thereby reducing Tg and realizing a sealing temperature below 450℃. However, the existing vanadate system low-melting-point glass material has a high Tg and poor fracture toughness, which needs to be improved. SUMMARY

[0011] According to the first aspect, in an embodiment, a low-melting-point glass powder is provided, which comprises, in terms of molar amounts, 20-50 parts of V2O5, 20-40 parts of ZnO, 5-20 parts of BaCO3, 10-30 parts of TeO2, 0-10 parts of Al2O3, 0-15 parts of Bi2O3, and 0-10 parts of Nb2O5.

[0012] According to the second aspect, in an embodiment, a composite is provided, comprising the low-melting-point glass powder of any one of the first aspect.

[0013] According to the third aspect, in an embodiment, a slurry is provided, which comprises the low-melting-point glass powder of any one of the first aspect, or the composite of any one of the second aspect, and an organic carrier.

[0014] According to the fourth aspect, in an embodiment, an electronic device is provided, comprising the low-melting-point glass powder of any one of the first aspect, or the composite of any one of the second aspect.

[0015] In an embodiment, the glass powder provided by the present application has excellent thermal performance (Tg, Tx), low thermal expansion coefficient, and excellent fracture toughness. As a sealing glass, it has excellent air tightness, and the composition glass of the present application does not contain Pb, P, has good environmental protection and stability. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 The test results of the glass performance of Examples 1-12 are shown in Table 1.

[0017] Figure 2 Structure diagram of electronic device.

[0018] Label explanation:

[0019] 1. First substrate

[0020] 2. Second substrate

[0021] 3. Sealing device

[0022] 4. Sample

[0023] 5. Laser DETAILED DESCRIPTION

[0024] The application will be further described below in connection with specific embodiments and with reference to the attached drawings. In the following embodiments, many specific details are described in order to provide a more thorough understanding of the application. However, it will be apparent to one skilled in the art that the application can be practiced without some or all of these details. In some instances, well-known features, operations or constructions have not been described in detail in order to avoid obscuring the application. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the application. However, it will be apparent to one skilled in the art that the application can be practiced without some or all of these specific details. In other instances, well-known structures have not been described in detail in order to avoid unnecessarily obscuring the application.

[0025] In addition, the features, operations or structures described in the specification can be combined in any suitable manner in various embodiments. Also, various steps or acts in a method described in the specification can be performed in a different sequence from the one described, or can be performed concurrently, unless otherwise specified or required. Thus, the various sequences and / or orderings of steps or acts in the specification are illustrative only and are not mandatory, unless otherwise specified or required.

[0026] The serial numbers of components in the specification, such as "first", "second", etc., are only used to distinguish the described objects, and do not have any sequence or technical meaning.

[0027] In the specification, "room temperature" refers to 23°C ± 2°C.

[0028] According to the first aspect, in an embodiment, a low melting point glass powder is provided, which comprises, in terms of molar amounts, 20-50 parts of V2O5, 20-40 parts of ZnO, 5-20 parts of BaCO3, 10-30 parts of TeO2, 0-10 parts of Al2O3, 0-15 parts of Bi2O3, and 0-10 parts of Nb2O5.

[0029] In one embodiment, the low melting point glass powder comprises, in terms of molar amounts, 40-44 parts of V2O5, 15-35 parts of ZnO, 8-10 parts of BaCO3, 18-25 parts of TeO2, 2.5-5 parts of Al2O3, 0-5 parts of Bi2O3, and 1-5 parts of Nb2O5.

[0030] In one embodiment, the low melting point glass powder comprises, in terms of molar amounts, 40-44 parts of V2O5, 17-35 parts of ZnO, 10 parts of BaCO3, 18-25 parts of TeO2, 2.5-3.3 parts of Al2O3, 0-5 parts of Bi2O3, and 1-5 parts of Nb2O5.

[0031] In one embodiment, the low melting point glass powder comprises, in terms of molar amounts, 40-44 parts of V2O5, 20-35 parts of ZnO, 10 parts of BaCO3, 18-25 parts of TeO2, 2.5-3.3 parts of Al2O3, 5 parts of Bi2O3, and 2-5 parts of Nb2O5.

[0032] In one embodiment, the low melting point glass powder comprises, in terms of molar amounts, 44 parts of V2O5, 35 parts of ZnO, 10 parts of BaCO3, 18 parts of TeO2, 3.3 parts of Al2O3, 5 parts of Bi2O3, and 2 parts of Nb2O5.

[0033] In one embodiment, the low melting point glass powder has a glass transition temperature Tg lower than (i.e., ≤) 350°C.

[0034] In one embodiment, the low melting point glass powder has a sintering temperature lower than (i.e., ≤) 450°C.

[0035] In one embodiment, the low melting point glass powder is prepared by mixing raw materials, melting, and quenching.

[0036] In one embodiment, the melting temperature can be 1000-1300°C.

[0037] In one embodiment, the low melting point glass powder has a D50≤3 μm.

[0038] In one embodiment, the low melting point glass powder has a D90<5 μm.

[0039] In one embodiment, the low melting point glass powder further comprises a colorant. The colorant can be used to color the glass powder, and dark colors are advantageous for absorbing laser light.

[0040] In one embodiment, the low melting point glass powder further comprises, in terms of molar amounts, 0-20 parts of a colorant.

[0041] In one embodiment, the low melting point glass powder further comprises, in terms of molar amounts, 4-15 parts of a colorant.

[0042] In one embodiment, the colorant comprises an oxide.

[0043] In an embodiment, the oxide comprises at least one of CuO, MnO, Fe2O3.

[0044] In an embodiment, the solid resulting from sintering of the low melting point glass powder has a fracture toughness value of > 0.20 MPa*m1 / 2. Including but not limited to 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, 1.00 MPa*m1 / 2, and the like.

[0045] In an embodiment, the solid resulting from sintering of the low melting point glass powder has a fracture toughness value of > 0.20 MPa*m1 / 2.

[0046] In an embodiment, the solid resulting from sintering of the low melting point glass powder has a fracture toughness value of > 0.25 MPa*m1 / 2.

[0047] In an embodiment, the solid resulting from sintering of the low melting point glass powder has a fracture toughness value of > 0.30 MPa*m1 / 2.

[0048] In an embodiment, the solid resulting from sintering of the low melting point glass powder has a fracture toughness value of > 0.35 MPa*m1 / 2.

[0049] In an embodiment, the solid resulting from sintering of the low melting point glass powder has a fracture toughness value of 0.30 to 0.90 MPa*m1 / 2.

[0050] In an embodiment, the solid resulting from sintering of the low melting point glass powder has a fracture toughness value of 0.30 to 0.80 MPa*m1 / 2.

[0051] In an embodiment, the solid resulting from sintering of the low melting point glass powder has a fracture toughness value of 0.40 to 0.80 MPa*m1 / 2.

[0052] In an embodiment, the solid resulting from sintering of the low melting point glass powder has a fracture toughness value of 0.21 to 0.75 MPa*m1 / 2.

[0053] In an embodiment, the solid resulting from sintering of the low melting point glass powder has a fracture toughness value of 0.25 to 0.75 MPa*m1 / 2.

[0054] In an embodiment, the solid resulting from sintering of the low melting point glass powder has a fracture toughness value of 0.27 to 0.75 MPa*m1 / 2.

[0055] In an embodiment, the solid resulting from sintering of the low melting point glass powder has a fracture toughness value of 0.30 to 0.75 MPa*m1 / 2.

[0056] In one embodiment, the solid resulting from sintering of the low melting point glass powder has a fracture toughness value of 0.35 to 0.75 MPa*m1 / 2.

[0057] In one embodiment, the solid resulting from sintering of the low melting point glass powder has a fracture toughness value of 0.37 to 0.75 MPa*m1 / 2.

[0058] In one embodiment, the fracture toughness value can be tested by a microhardness tester or an indenter, among others. The indenter includes, but is not limited to, a micro indenter, a nano indenter, among others.

[0059] In one embodiment, the solid resulting from sintering of the low melting point glass powder has a coefficient of thermal expansion of < 12 x 10 -6 / °C. Included, but not limited to, 8.0 x 10 -6 / °C, 8.1 x 10 -6 / °C, 8.2 x 10 -6 / °C, 8.3 x 10 -6 / °C, 8.4 x 10 -6 / °C, 8.5 x 10 -6 / °C, 8.6 x 10 -6 / °C, 8.7 x 10 -6 / °C, 8.8 x 10 -6 / °C, 8.9 x 10 -6 / °C, 9.0 x 10 -6 / °C, 9.1 x 10 -6 / °C, 9.2 x 10 -6 / °C, 9.3 x 10 -6 / °C, 9.4 x 10 -6 / °C, 9.5 x 10 -6 / °C, 9.6 x 10 -6 / °C, 9.7 x 10 -6 / °C, 9.8 x 10 -6 / °C, 9.9 x 10 -6 / °C, 10.0 x 10 -6 / °C, 10.1 x 10 -6 / °C, 10.2 x 10 -6 / °C, 10.3 x 10 -6 / °C, 10.4 x 10 -6 / °C, 10.5 x 10 -6 / °C, 10.6 x 10 -6 / °C, 10.7 x 10 -6 / °C, 10.8 x 10 -6 / °C, 10.9 x 10 -6 / °C, 11.0 x 10-6 / °C, 11.1 x 10 -6 / °C, 11.2 x 10 -6 / °C, 11.3 x 10 -6 / °C, 11.4 x 10 -6 / °C, 11.5 x 10 -6 / °C, 11.6 x 10 -6 / °C, 11.7 x 10 -6 / °C, 11.8 x 10 -6 / °C, 11.9 x 10 -6 / °C, 12.0 x 10 -6 / °C, and so on.

[0060] In one embodiment, the coefficient of thermal expansion of the solid sintered from the low melting point glass powder is ≤ 11.2 x 10 -6 / °C.

[0061] In one embodiment, the coefficient of thermal expansion of the solid sintered from the low melting point glass powder is 9.0 x 10 -6 / °C to 12.0 x 10 -6 / °C.

[0062] In one embodiment, the coefficient of thermal expansion of the solid sintered from the low melting point glass powder is 9.5 x 10 -6 / °C to 12.0 x 10 -6 / °C.

[0063] According to the second aspect, in one embodiment, there is provided a composite comprising the low melting point glass powder of any one of the first aspect.

[0064] In one embodiment, the composite further comprises a low CTE filler.

[0065] In one embodiment, the coefficient of thermal expansion of the low CTE filler is ≤ 3.0 x 10 -6 / °C.

[0066] In one embodiment, the low CTE filler comprises, but is not limited to, at least one of silica, cordierite, eucryptite, zirconium phosphate type filler. That is, a low coefficient of thermal expansion ceramic filler.

[0067] In one embodiment, the zirconium phosphate type filler comprises, but is not limited to, at least one of zirconium phosphate, zirconium oxyphosphate, zirconium tungstophosphate, zirconium niobophosphate, zirconium tantalophosphate.

[0068] In one embodiment, the content of the low CTE filler in the composite is 0 to 40 wt%.

[0069] In one embodiment, the content of the low melting point glass powder in the composite is ≥ 60 wt%.

[0070] In an embodiment, the composite has a coefficient of thermal expansion ≤ 6.0 x 10 -6 / °C.

[0071] According to the third aspect, in an embodiment, there is provided a paste comprising the low melting point glass powder of any one of the first aspect, or the composite of any one of the second aspect, and an organic carrier.

[0072] In an embodiment, the content of the composite in the paste is 50-80 wt%.

[0073] In an embodiment, the composite has a D50≤ 3 pm, and a D90< 5 pm.

[0074] In an embodiment, the organic carrier comprises an organic substance and / or a binder;

[0075] In an embodiment, the organic carrier mainly comprises a high-boiling organic substance, including but not limited to at least one of dimethyl carbonate, propylene carbonate, butyl carbitol acetate, terpineol, ethylene glycol, ethylene glycol ethyl ether acetate, tributyl citrate, dibutyl phthalate, lecithin, and the like.

[0076] In an embodiment, the organic carrier comprises at least one of dimethyl carbonate, propylene carbonate, butyl carbitol acetate, terpineol, ethylene glycol, ethylene glycol ethyl ether acetate, tributyl citrate, dibutyl phthalate, lecithin, carboxymethyl cellulose, ethyl cellulose, carboxypropyl cellulose, and the like.

[0077] In an embodiment, the content of the organic carrier in the paste is 20-50 wt%.

[0078] According to the fourth aspect, in an embodiment, there is provided an electronic device comprising the low melting point glass powder of any one of the first aspect, or the composite of any one of the second aspect. The composite comprising the low melting point glass powder is mainly used for packaging the electronic device, which includes but is not limited to a display screen, specifically an OLED screen, and the like. The composite comprising the low melting point glass powder is mixed with the organic carrier to form a paste, which is coated on the electronic device by screen printing or the like, and then sintered or laser fused to obtain the electronic device comprising the low melting point glass powder or the composite thereof.

[0079] In an embodiment, the paste of any one of the third aspect is coated on the electronic device, and after fusion, the electronic device comprising the low melting point glass powder of any one of the first aspect, or the composite of any one of the second aspect is obtained. The paste coated on the electronic device forms a dense product on the electronic device after fusion, which serves as a water and oxygen barrier layer and plays a sealing role.

[0080] In an embodiment, the method of fusion includes but is not limited to sintering and / or laser fusion. In an embodiment, sintering can be performed first, followed by laser fusion.

[0081] In one embodiment, the present application provides a P-free vanadium-based low-melting glass, and a composite and paste containing the low-melting glass and electronic devices, which can achieve a Tg lower than 350℃ and a working temperature lower than 450℃. The glass has good sealing performance and good fracture toughness.

[0082] In one embodiment, the present application provides a low-melting glass and a composite containing the low-melting glass and a paste thereof:

[0083] The low-melting glass formula contains, in terms of molar amount, 20-50 parts of V2O5, 20-40 parts of ZnO, 5-20 parts of BaCO3, 10-20 parts of TeO2, 0-10 parts of Al2O3, 0-15 parts of Bi2O3, 0-10 parts of Nb2O5, and 0-20 parts of a colorant.

[0084] The above raw material powders are weighed according to the formula amount, preliminarily mixed using a crucible, then melted and quenched at 1000-1300℃, and the quenched material is dried and broken to an appropriate particle size, for example, D50≤3μm and D90<5μm, to obtain a low-melting glass powder.

[0085] The ceramic filler has a low expansion coefficient and includes, but is not limited to, one or more combinations of silica, cordierite, petalite, and zirconium phosphate type (zirconium phosphate, zirconium oxyphosphate, zirconium phosphate tungstate, zirconium phosphate niobate, and zirconium phosphate tantalate). The mass percentage of the ceramic filler in the composite is 0-40%.

[0086] The ceramic filler is mixed with the low-melting glass powder to obtain a composite containing the above glass and filler.

[0087] The above low-melting glass, composite of ceramic filler, and organic carrier are mixed to obtain a paste.

[0088] The mass ratio of glass to ceramic filler (inorganic component) in the paste is 50-80%.

[0089] The organic carrier includes one or more than two of dimethyl carbonate, propylene carbonate, butyl carbitol acetate, terpineol, ethylene glycol, ethylene glycol ethyl ether acetate, tributyl citrate, dibutyl phthalate, lecithin, carboxymethyl cellulose, ethyl cellulose, and carboxypropyl cellulose.

[0090] In one embodiment, the low-melting glass and paste thereof provided by the present application are P-free, have good water resistance, a low Tg (lower than 350℃), and a sintering temperature (Tw) lower than 450℃.

[0091] In the present application, the glass preparation process is a conventional and general process, which can be easily understood by those skilled in the art, and therefore the detailed operation process and safety precautions will not be described in detail in the specific implementation.

[0092] In the present application, the components used in the formula of the glass frit are all commercially available oxide raw material powders.

[0093] In the present application, the glass powder refers to the glass frit (oxide raw material powder) after the conventional glass preparation process, which is processed to a certain particle size and has uniform material.

[0094] The low-melting point glass of the present application refers to a glass with a glass transition temperature Tg lower than 350℃ and a sintering temperature lower than 450℃.

[0095] The low-melting point glass frit composition of the present application is a V2O5-ZnO-BaCO3-TeO2-Al2O3-Bi2O3-Nb2O5+(CuO-Mn O-Fe2O3) component system, and each component has a specific ratio.

[0096] In terms of molar amount, the low-melting point glass powder contains 20-50 parts of V2O5, 20-40 parts of ZnO, 5-20 parts of BaCO3, 10-20 parts of TeO2, 0-10 parts of Al2O3, 0-15 parts of Bi2O3, 0-10 parts of Nb2O5, and 0-20 parts of colorant.

[0097] Hereinafter, the role and content of each component in the glass frit composition of the present application are described.

[0098] V2O5

[0099] In the present application, V2O5 is the main glass former, and reacts with ZnO to destroy V bonds, reduce Tg, and form covalent bonds to improve the bonding force with other molecules in the glass.

[0100] ZnO

[0101] In the present application, ZnO is the main glass former, which is beneficial to improve the flowability of the glass and the fracture toughness of the glass, but if the content is too high, it will significantly increase the Tg of the glass.

[0102] BaCO3

[0103] In the present application, BaCO3 is a glass additive that can improve the mechanical strength and chemical stability of the glass, and reduce the glass melting viscosity, but if the content is too high, it will increase the brittleness of the glass.

[0104] TeO2

[0105] In the present application, TeO2 can form glass and increase the strength and stability of the glass, but if the content is too low, the effect is limited, and if the content is too high, it will increase the CTE.

[0106] Al2O3

[0107] In the present application, Al2O3 as a glass additive can reduce the crystallization tendency of the glass and the thermal expansion coefficient of the glass, but if the content is too high, it will increase the Tg and the melting viscosity of the glass, which is not conducive to the glass quenching process.

[0108] Bi2O3

[0109] In the present application, Bi2O3 as a network modifier is conducive to improving the stability of the glass, but if the content is too high, it will increase the Tg and decrease the Tx, and the sintering process is easy to crystallize and reduce the glass flowability.

[0110] Nb2O5

[0111] In the present application, Nb2O5 as a glass additive can further increase the network density of the glass, thereby increasing the strength of the glass and improving the stability of the glass.

[0112] CuO, MnO, Fe2O3

[0113] In the present application, the three components have similar effects, which can adjust the color of the glass and increase the laser absorption rate of the glass in the infrared waveband 800-850 nm, so that lower power melting sealing can be realized. Similarly, the content of the three components cannot be too high, and the total amount is best in the range of 5-15%, too high will lead to an increase in Tg.

[0114] The glass of the above formula has excellent thermal performance (Tg, Tx), low thermal expansion coefficient (5.0*10 -6 / ℃ to 8.0*10 -6 / ℃), excellent water resistance, excellent air tightness as a sealing glass, and the composition glass of the present application does not contain Pb, P, has good environmental protection and stability.

[0115] Detailed embodiments of the present application:

[0116] I. Glass powder preparation

[0117] The process of preparing the glass material into a low-melting-point glass powder is as follows:

[0118] 1. Weigh the corresponding raw material components to prepare a low-melting-point glass powder. In terms of molar amount, the low-melting-point glass powder contains 20-50 parts of V2O5, 20-40 parts of ZnO, 5-20 parts of BaCO3, 10-30 parts of TeO2, 0-10 parts of Al2O3, 0-15 parts of Bi2O3, 0-10 parts of Nb2O5, and 0-20 parts of a colorant.

[0119] The raw material composition is mixed thoroughly, loaded into a crucible, heated to melt at a temperature ranging from 1000 to 1300°C under an atmosphere, and held for 1 hour, and then quenched to obtain glass fragments. After heating to melt and holding for 1 hour, a portion of the sample is cooled to room temperature to obtain a frit, which is used as a pre-reserved sample for testing the coefficient of thermal expansion (CTE) and the fracture toughness value (K 1c ) of the frit. After quenching, a sample is taken from the glass fragments for testing the glass transition temperature (Tg) and the crystallization onset temperature (Tx).

[0120] The glass fragments are further processed into glass powder with a particle size D max of about 5 μm by a mechanical crushing process, such as ball milling, sand milling, jet milling, etc.

[0121] The pre-reserved molten glass in the quenching process is annealed to obtain a dense block, which can be used for testing the coefficient of thermal expansion.

[0122] II. Low-expansion composite powder

[0123] A low-expansion filler (i.e., a low-CTE filler) is added to the low-melting-point glass powder to prepare a composite powder, which includes but is not limited to one or more combinations of silicon oxide, cordierite, petalite, and zirconium phosphate (zirconium phosphate, zirconium oxyphosphate, zirconium tungstophosphate, zirconium niobophosphate, and zirconium tantalophosphate).

[0124] The composite powder has a coefficient of thermal expansion lower than 6.0*10 -6 / °C, and a particle size D max of the composite powder is less than 5 μm.

[0125] III. Preparation of slurry

[0126] The slurry is prepared by uniformly mixing the composite powder and an organic carrier.

[0127] The organic carrier mainly includes one or more than two of high-boiling-point organic substances and / or binders, such as dimethyl carbonate, propylene carbonate, butyl carbitol acetate, terpineol, ethylene glycol, ethylene glycol ethyl ether acetate, tributyl citrate, dibutyl phthalate, lecithin, carboxymethyl cellulose, ethyl cellulose, and carboxypropyl cellulose.

[0128] The main function of the organic carrier is to adjust the viscosity and thixotropy of the slurry, so that the slurry can be stored stably and fine lines can be obtained in the printing process.

[0129] Examples 1 to 12

[0130] The preferred examples of the present application are described, and the skilled person in the art can fully understand and implement the detailed process, so the process itself is not described in detail.

[0131] 1. Preparation of glass frit

[0132] The glass frits of Examples 1-12 were prepared according to Table 1.

[0133] 2. Performance test

[0134] The glass preparation process reserved samples, respectively, test the glass transition temperature (Tg), the crystallization start temperature (Tx), the coefficient of thermal expansion (CTE), the fracture toughness value (K 1c ).

[0135] The performance of the slurry is mainly determined by the glass powder, and the filler only changes the coefficient of thermal expansion, which is an inert filler and will not soften below 500°C, so the filler has almost no effect on the Tg of the slurry and the sintered slurry. The organic carrier is used for printing into a thin film, and after subsequent sintering, the organic carrier will be removed under high temperature conditions, and the product almost does not contain the organic carrier.

[0136] The test results are shown in Table 1 and Figure 1 , and the test methods of each item are as follows.

[0137] 1) Tg, Tx: Use differential scanning calorimeter NETSCH DSC214, the heating rate is 10°C / min, the test range is 65-580°C, and Tg, Tx is measured.

[0138] 2) CTE: Use thermal mechanical analyzer NETSCH TMA 402F3, the heating rate is 5°C / min, the test range is 25-250°C, and the coefficient of thermal expansion is measured.

[0139] 3) K 1c : Take the glass frit, embed it by epoxy resin, grind it, and polish it to obtain a smooth and flat section sample, use nanoindentation instrument to form a rhombus indentation and crack on the surface of the frit by external load, and calculate the fracture toughness value K 1c of the material combined with the modulus of the material.

[0140] Table 1 Examples 1-12 (the content of each component is in mol)

[0141] Examples 1# 2# 3# 4# 5# 6# 7# 8# 9# 10# 11# 12# V2O5 40 42 42 42 44 44 44 44 44 44 44 44 ZnO 20 20 30 40 15 15 15 17 17 17 35 35 BaCO3 10 15 15 15 8 8 8 10 10 10 10 10 TeO2 25 20 20 20 18 18 18 20 20 20 18 18 Al2O3 2.5 0 0 0 3 4 5 3 3 3 3.3 3.3 Bi2O3 5 6 6 6 0 0 0 0 0 0 5 7 [Nb2O5] 5 0 0 0 1 1 1 1 1 1 2 2 CuO 3 0 0 0 4 4 4 4 4 5 7 7 MnO2 3 3 3 3 0 0 0 0 2.5 5 0 0 Fe2O3 3 3 3 3 1 1 1 0 2.5 5 3 3 Tg (°C) 337 355 371 379 317 322 323 320 334 345 345 356 Tx (°C) / 553 560 577 / / / / / / / / CTE (*10 -6 / ℃) 11.2 10.8 10.5 10.2 10.4 10.0 10.1 11.0 10.4 9.9 9.9 9.7 K 1c (MPa*m^1 / 2)]]> 0.37 0.72 0.79 0.72 0.23 0.25 0.25 0.21 0.26 0.27 0.75 0.84

[0142] " / " indicates that the test range is 65-580°C, and no crystallization occurs.

[0143] It can be seen that Examples 1, 5-10 can reduce Tg to below 350°C, and have better fracture toughness.

[0144] Example 11 has the highest fracture toughness in addition to reducing Tg relative to other formulations.

[0145] 3. Adjust the expansion coefficient of composite materials

[0146] Zirconium phosphate was selected as a filler to reduce the composite's thermal expansion coefficient. A glass powder: filler powder mass ratio of 80:20 was used. A small amount of the composite powder was compacted into a 15 mm diameter, 3 mm thick button sample. The glass powder was then fired at 80°C above its glass transition temperature (Tg) for 30 minutes. The sample was then polished on both sides and the thermal expansion coefficient (CTE) was measured at a heating rate of 5°C / min over a test range of 25°C to 250°C. The composite's thermal expansion coefficient can be adjusted by adjusting the type and amount of filler.

[0147] 4. Slurry preparation

[0148] The slurry is prepared using the composite powder with the above-mentioned CTE performance meeting the standard.

[0149] First, prepare an organic carrier. Take 3wt% ethyl cellulose, slowly add a mixed solution of 85wt% ethylene glycol ethyl ether acetate and 12wt% dibutyl phthalate, stir for 2 hours under 80℃ insulation conditions, and obtain an organic carrier. The main function of the organic carrier is to adjust the viscosity and thixotropy of the slurry, ensure that the subsequent slurry can be stored stably, and obtain fine lines through the silk screen process.

[0150] The composite powder and the organic carrier are premixed, with the mass of the composite powder accounting for 75% of the total mass of the mixture and the mass of the organic carrier accounting for 25% of the total mass of the mixture. After premixing, they are evenly mixed by a double planetary stirrer, and then further rolled by a three-roll mill. Finally, vacuum degassing treatment is performed to obtain a low-melting-point glass slurry.

[0151] A low-melting-point glass paste is screen-printed around the perimeter of a transparent first substrate (1). The film is then dried at 150°C for 30 minutes and fired at a temperature approximately 50-100°C above its Tg point, achieving a film thickness of 5-15μm. Components that are sensitive to high temperatures are located on the second substrate (2). Therefore, the first substrate (1) is sintered first, removing organic materials during the sintering process. After the panels are joined, they are partially sealed with a laser, a process that acts as a secondary melting step.

[0152] like Figure 2 As shown, the second substrate 2 is stacked on the first substrate 1 with precise alignment, the sealing device 3 is located between the first substrate 1 and the second substrate 2, and the sample 4 is a composite material sintered with a low-melting-point glass paste. Then, a semiconductor laser 5 (wavelength of about 810 nm) is used for welding from the side where the first substrate 1 is located. The laser path is the low-melting-point glass silk-screened firing film. The low-melting-point glass is melted again to completely bond the first substrate 1 and the second substrate 2, achieving water and oxygen isolation inside.

[0153] The above application of specific examples to the present invention is described, is only used to help understand the present invention, and does not limit the present invention. For the skilled in the art to which the present invention belongs, according to the idea of the present invention, several simple deductions or substitutions can be made.

Claims

1. A low-melting-point glass powder, characterized in that: The low-melting-point glass powder is composed, by mole, of 40 to 44 parts of V2O5, 20 to 40 parts of ZnO, 10 to 15 parts of BaCO3, 18 to 25 parts of TeO2, 0 to 10 parts of Al2O3, 5 to 15 parts of Bi2O3, 0 to 10 parts of Nb2O5, and 0 to 20 parts of a colorant, wherein the colorant comprises an oxide, and the oxide comprises at least one of CuO, MnO, and Fe2O3; the fracture toughness value of a solid obtained by sintering the low-melting-point glass powder is ≥0.30 MPa·m^1 / 2.

2. The low-melting-point glass powder according to claim 1, wherein Calculated by mole, the low-melting-point glass powder comprises 40-44 parts of V2O5, 20-35 parts of ZnO, 18-25 parts of TeO2, 2.5-5 parts of Al2O3, and 1-5 parts of Nb2O5.

3. The low-melting-point glass powder according to claim 1, wherein Calculated by mole, the low-melting-point glass powder comprises 40-44 parts of V2O5, 20-35 parts of ZnO, 10 parts of BaCO3, 18-25 parts of TeO2, 2.5-3.3 parts of Al2O3, and 1-5 parts of Nb2O5.

4. The low-melting-point glass powder according to claim 1, wherein Calculated by mole, the low-melting-point glass powder comprises 40 to 44 parts of V2O5, 20 to 35 parts of ZnO, 10 parts of BaCO3, 18 to 25 parts of TeO2, 2.5 to 3.3 parts of Al2O3, 5 parts of Bi2O3, and 2 to 5 parts of Nb2O5.

5. The low-melting-point glass powder according to claim 1, wherein Optionally, the glass transition temperature Tg of the low-melting-point glass powder is ≤350°C.

6. The low-melting-point glass powder according to claim 1, wherein Optionally, the sintering temperature of the low-melting-point glass powder is ≤450°C.

7. The low-melting-point glass powder according to claim 1, wherein The low-melting-point glass powder has a D50 of ≤3 μm.

8. The low-melting-point glass powder according to claim 1, wherein The low-melting-point glass powder has a D90 value less than 5 μm.

9. The low-melting-point glass powder according to claim 1, wherein The low-melting-point glass powder contains 4 to 15 parts of a colorant by mole.

10. The low-melting-point glass powder according to claim 1, wherein The fracture toughness value of the solid obtained by sintering the low-melting-point glass powder is ≥0.35 MPa·m^1 / 2.

11. The low-melting-point glass powder according to claim 1, wherein The fracture toughness of the solid obtained by sintering the low-melting-point glass powder is 0.30-0.90 MPa·m^1 / 2.

12. The low-melting-point glass powder according to claim 1, wherein The fracture toughness of the solid obtained by sintering the low-melting-point glass powder is 0.30-0.80 MPa·m^1 / 2.

13. The low-melting-point glass powder according to claim 1, wherein The fracture toughness of the solid obtained by sintering the low-melting-point glass powder is 0.40-0.80 MPa·m^1 / 2.

14. The low-melting-point glass powder according to claim 1, wherein The thermal expansion coefficient of the solid obtained by sintering the low-melting-point glass powder is ≤12.0×10 -6 / ℃.

15. The low-melting-point glass powder according to claim 1, wherein The thermal expansion coefficient of the solid obtained by sintering the low-melting-point glass powder is ≤11.2×10 -6 / ℃.

16. The low-melting-point glass powder according to claim 1, wherein The thermal expansion coefficient of the solid obtained by sintering the low-melting-point glass powder is 9.0×10 -6 ~12.0×10 -6 / ℃.

17. The low-melting-point glass powder according to claim 1, wherein The thermal expansion coefficient of the solid obtained by sintering the low-melting-point glass powder is 9.5×10 -6 ~12.0×10 -6 / ℃.

18. A composite, characterized in that The method comprises the low-melting-point glass powder according to any one of claims 1 to 17.

19. The composite according to claim 18, wherein The composite also includes a low CTE filler.

20. The composite according to claim 19, wherein The thermal expansion coefficient of the low CTE filler is ≤3.0×10 -6 / ℃.

21. The composite according to claim 19, wherein The low CTE filler includes at least one of silicon oxide, cordierite, eucryptite, and zirconium phosphate fillers.

22. The composite according to claim 21, wherein The zirconium phosphate type filler includes at least one of zirconium phosphate, zirconyl phosphate, zirconium tungstate phosphate, zirconium niobate phosphate, and zirconium tantalum phosphate.

23. The composite according to claim 19, wherein The content of the low CTE filler in the composite is 0-40 wt %. The composite according to claim 18 , wherein the content of the low-melting-point glass powder in the composite is ≥ 60 wt %.

25. The composite material according to claim 18, wherein the thermal expansion coefficient of the solid obtained by sintering the composite material is ≤ 6.0×10 -6 / ℃.

26. A slurry, characterized in that The slurry comprises the low-melting-point glass powder according to any one of claims 1 to 17, or the composite according to any one of claims 18 to 25, and an organic vehicle.

27. The slurry according to claim 26, wherein The content of the composite in the slurry is 50-80 wt %.

28. The slurry according to claim 27, wherein The D50 of the composite is ≤ 3 μm.

29. The slurry according to claim 27, wherein The D90 of the composite was < 5 μm.

30. The slurry according to claim 26, wherein The organic carrier includes at least one of dimethyl carbonate, propylene carbonate, butyl carbitol acetate, terpineol, ethylene glycol, ethylene glycol ethyl ether acetate, tributyl citrate, dibutyl phthalate, lecithin, carboxymethyl cellulose, ethyl cellulose, and carboxypropyl cellulose.

31. The slurry according to claim 26, wherein The content of the organic carrier in the slurry is 20-50 wt %.

32. An electronic device, characterized in that: The method comprises the low-melting-point glass powder according to any one of claims 1 to 17, or the composite according to any one of claims 18 to 25.

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