Alumina ceramic composite colloidal tungsten metallization paste, preparation method and application thereof

Abstract

The application provides an alumina ceramic composite colloidal tungsten paste and a preparation method and application thereof. According to mass percentage, the tungsten paste comprises 70-90% conductive metal tungsten powder, 1-15% inorganic bonding phase, 5-25% organic carrier A, and 1-10% organic carrier B. The organic carrier A comprises 10-25% organic binder, 5-40% plasticizer, 5-90% solvent, and 1-5% modified montmorillonite. The organic carrier B comprises 5-20% organic binder, 10-60% plasticizer, and 5-90% solvent. The modified montmorillonite is polyether polyol modified montmorillonite. The application improves the flowability, thixotropy and printing resolution of the paste by compounding the organic carrier A and the organic carrier B, and the sintering matching with the ceramic substrate is good, the flatness is high, the adhesion is strong, and the paste can meet the requirements of other multilayer ceramic processes such as lamination, layering, green cutting and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high-temperature co-fired ceramic slurry, in particular, especially relates to an alumina ceramic composite colloidal tungsten metallization slurry and a preparation method and application thereof. BACKGROUND

[0002] With the rapid development of electronic technology, high-temperature co-fired ceramic technology has gained widespread attention in the fields of materials science and electronic engineering. As a high-precision technology in high-temperature co-fired ceramic manufacturing, electrostatic chuck realizes stable clamping with precise electrostatic adsorption, significantly improves processing precision and production efficiency, and reduces waste rate, providing solid technical support for the research and production of high-performance chips.

[0003] In recent years, domestic electrostatic chucks have made significant progress in technological innovation and market application. The new generation of electrostatic chuck patents involve high-performance electrode design, intelligent control system and application of new wear-resistant materials, significantly enhancing clamping force and stability. The introduction of intelligent control technology makes real-time monitoring and simplified operation possible, meeting the needs of the microelectronics and optoelectronics industries for high precision. In addition, with the rapid development of the semiconductor and precision machining markets, domestic electrostatic chucks gradually replace imported products, enhancing the industry's self-control capability. With the booming development of 5G communication, the Internet of Things and smart devices, the demand for high-performance domestic chip materials is increasing, further promoting the innovation and progress of electrostatic chuck technology and setting higher industry requirements.

[0004] The key to electrostatic chuck manufacturing lies in the co-firing process of ceramic and conductive slurry. During this process, the interface reaction and material diffusion between ceramic and metal slurry need to be effectively controlled to ensure good matching between ceramic material and slurry. Therefore, the interface layer must be consistent in terms of densification rate, sintering shrinkage and thermal expansion rate, etc., to reduce the risk of defects such as layer cracking, warping and cracking, so as to obtain an electrostatic chuck with low sintering surface roughness, good slurry adhesion and stable sheet resistance.

[0005] Conductive tungsten paste is widely used in electronic devices and sensors due to its excellent electrical conductivity and high-temperature resistance. However, in practical applications, conductive tungsten paste faces problems such as stability and dispersion, which have a significant impact on its performance and reliability. First, the stability of conductive tungsten paste is insufficient, especially during long-term storage or transportation, the paste is prone to stratification and precipitation. This not only leads to uneven composition of the paste, affecting the electrical conductivity, but also may cause inconsistencies in the quality of finished products during production. In addition, tungsten particles in conductive tungsten paste often exhibit aggregation, resulting in poor dispersion. This aggregation causes uneven electrical paths, thereby reducing the overall performance of electrodes or sensors. Second, as the high-temperature sintering process progresses, the oxidation and aggregation of tungsten particles become more prominent, further affecting the performance of conductive tungsten paste. These problems need to be addressed to promote the widespread application of conductive tungsten paste in electrostatic chuck manufacturing. Therefore, in-depth research on the stability and dispersion of conductive tungsten paste will provide important support for the performance improvement of high-temperature ceramic materials and the development of new electronic devices. SUMMARY

[0006] To solve the above problems, the present application provides an alumina ceramic composite colloidal metal tungsten paste, which not only solves the problems of insufficient adhesion and unstable electrical conductivity in common printed tungsten paste on the market, but also ensures that the conductor tungsten paste has good printing performance.

[0007] The first aspect of the present application provides an alumina ceramic composite colloidal metal tungsten paste, characterized in that it comprises, by mass percentage: 70% to 90% of conductive metal tungsten powder, 1% to 15% of inorganic bonding phase, 5% to 25% of organic carrier A, and 1% to 10% of organic carrier B.

[0008] The organic carrier A comprises 10% to 25% of organic binder, 5% to 40% of plasticizer, 5% to 90% of solvent, and 1% to 5% of modified montmorillonite.

[0009] The organic carrier B comprises 5% to 20% of organic binder, 10% to 60% of plasticizer, and 5% to 90% of solvent.

[0010] The modified montmorillonite is polyether polyol modified montmorillonite.

[0011] The particle size of the conductive metal tungsten powder is 0.5 μm to 2.5 μm.

[0012] The polyether polyol in the polyether polyol modified montmorillonite is selected from one or more of PTMEG-1000, PEG-2000, PEG-4000, PEG-6000, or PEG-8000, and is further preferably PEG-4000 or PEG-6000.

[0013] The amount of the polyether polyol modified montmorillonite is preferably 2% to 3%.

[0014] The organic binder in the organic carrier A is composed of one or more mixtures of acrylic resin, phenolic resin, and epoxy resin.

[0015] The organic binder in the organic carrier B is composed of one or more mixtures of ethyl cellulose, polyvinyl alcohol, and polyvinyl butyral.

[0016] The inorganic bonding phase is composed of 92% to 99% Al2O3 powder and 1% to 8% sintering aid.

[0017] The organic solvent is selected from one or more mixtures of methanol, ethanol, acetone, benzyl alcohol, diethylene glycol butyl ether acetate, ethylene glycol diacetate, terpineol, and butyl carbitol.

[0018] The second aspect of the present application provides a preparation method of the above-mentioned alumina ceramic composite colloidal metalized tungsten slurry, comprising the following steps:

[0019] (1) Preparation of the inorganic bonding phase: Al2O3 powder and sintering aid are weighed according to the proportion, then are placed in a ball mill tank, an appropriate amount of dispersant and pure water are added, and ball milling is performed for 2 to 6 hours. After the ball milling is completed, the slurry is poured into a tray, vacuum freeze drying is performed by using a vacuum freeze dryer, and after the freeze drying, the powder is sieved through a 200 to 300 mesh sieve network by using vibration, and is ready for use.

[0020] (2) Preparation of the organic carrier A: organic binder, modified montmorillonite, plasticizer, and solvent are weighed according to the proportion. The solvent and the plasticizer are first added to a stirring dissolving container and are stirred uniformly. The heating temperature is set to 50°C to 100°C, the stirring speed is set to 150 r / min to 500 r / min, the organic binder and the modified montmorillonite are added while stirring, until they are completely dissolved and dispersed uniformly, and the mixture is cooled and sealed for storage.

[0021] (3) Preparation of the organic carrier B: organic binder, plasticizer, and solvent are weighed according to the proportion, and are added to a stirring dissolving container. The solvent and the plasticizer are first added and are stirred uniformly. The heating temperature is set to 50°C to 100°C, the stirring speed is set to 150 r / min to 500 r / min, the organic binder is added while stirring, until it is completely dissolved and dispersed uniformly, and the mixture is cooled and sealed for storage.

[0022] (4) Preparation of the conductive metal tungsten powder mixture: the inorganic bonding phase obtained in step (1) and the conductive tungsten powder are weighed according to the proportion, and are placed in a ball mill tank. An appropriate amount of dispersant and acetone are added to the ball mill tank, and ball milling is performed for 4 hours to 24 hours. The organic carrier A in step (2) is weighed according to the proportion, and is placed in the ball mill tank. Ball milling is performed again for 2 to 6 hours.

[0023] (5) Preparation of the metalized tungsten slurry: After the mixture after the ball milling in step (4) is passed through a 100-200 mesh screen, it is loaded into a vacuum stirrer, heated and stirred, with the heating temperature set at 50-100°C, and the ball milling medium such as acetone is removed by reduced pressure distillation, to obtain a uniform tungsten slurry;

[0024] (6) The organic carrier B in step (3) is weighed according to the proportion, added to the tungsten slurry obtained in step (5), and uniformly stirred in a high-shear stirrer, with the stirring speed being 500-10000 r / min and the stirring time being 0.5-1 h; the mixed slurry is then rolled by a three-axis slurry roller multiple times, with the roller spacing gradually reduced until the desired printing viscosity is reached, to obtain the desired composite colloidal metalized tungsten slurry electronic paste for printing.

[0025] The third aspect of the present application provides an application of the above-mentioned alumina ceramic composite colloidal metalized tungsten slurry in an electrostatic chuck.

[0026] Compared with the prior art, the present application has the following advantages:

[0027] The present application improves the flowability, thixotropy and printing resolution of the alumina ceramic composite colloidal metalized tungsten slurry by compounding the organic carrier A and the organic carrier B, has good sintering matching with the ceramic substrate, high flatness, strong adhesion, and can meet the requirements of laminating, laminating, green cutting and other multi-layer ceramic process requirements. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 Screen printing pattern of the composite colloidal metalized tungsten slurry prepared for Example 12

[0029] Figure 2 Screen printing pattern of the composite colloidal metalized tungsten slurry prepared for Example 8

[0030] Figure 3 Screen printing pattern of the composite colloidal metalized tungsten slurry prepared for Comparative Example 3 DETAILED DESCRIPTION

[0031] Hereinafter, the specific embodiments of the present application will be described in detail, but the present application is not limited to the embodiments including the following examples, and various modifications can be made within the scope of the purpose of the invention and without departing from the spirit of the invention.

[0032] In each of the following examples, unless otherwise specifically stated, the raw material reagents or processing techniques used are commercially available raw materials or conventional processing techniques commonly used in the art.

[0033] The first aspect of the present application provides an alumina ceramic composite colloidal metalized tungsten paste, characterized by comprising, in percentage by mass: 70-90% of conductive metal tungsten powder, 1-25% of inorganic bonding phase, 5-15% of organic carrier A, and 1-10% of organic carrier B.

[0034] The organic carrier A comprises 10-25% of organic binder, 5-40% of plasticizer, 5-90% of solvent, and 1-5% of modified montmorillonite.

[0035] The organic carrier B comprises 5-20% of organic binder, 10-60% of plasticizer, and 5-90% of solvent.

[0036] The modified montmorillonite is polyether polyol modified montmorillonite. The long chain of polyether polyol forms a hydrophilic protective layer on the surface of the montmorillonite, which can reduce the particle agglomeration in the paste. As a high-efficiency thixotropic agent, the polyether polyol modified montmorillonite enables the paste to quickly restore high viscosity after printing in the process of screen printing, prevents pattern diffusion deformation, and guarantees high-precision pattern transfer.

[0037] The present application simultaneously uses the organic carrier A and the organic carrier B, mainly solves the core problems of process stability, dispersibility, and adhesion that cannot be considered by a single carrier through functional complementation. The organic carrier A dominates the printing morphology control and sintering structure strengthening through thixotropy and high-temperature stability; and the organic carrier B optimizes the process adaptability and adhesion through fluidity and interfacial wettability.

[0038] In the embodiment of the present application, the particle size of the conductive metal tungsten powder is 0.5-2.5 μm.

[0039] <Modified Montmorillonite>

[0040] In the embodiment of the present application, the preparation method of the modified montmorillonite comprises: weighing 1-20 g of dry montmorillonite and adding it into a solvent, ultrasonicating at 50-100 ℃ for 10-90 min (power 200-500 W), then adding 0.01-5 g of polyether polyol, stirring at 50-100 ℃ for 2-10 h under nitrogen protection; obtaining a mixed solution; centrifuging and washing the mixed solution to neutral, vacuum drying, and grinding, screen sieving, and vacuum drying the obtained modified montmorillonite for 12 h for standby.

[0041] In the embodiment of the present application, the polyether polyol is selected from one or more of PTMEG-1000, PEG-2000, PEG-4000, PEG-6000, or PEG-8000.

[0042] In the embodiment of the present application, the amount of the polyether polyol is 1-5% of the mass of the montmorillonite.

[0043] <Inorganic bonding phase>

[0044] In the present application, the inorganic bonding phase comprises: 92% to 99% of Al2O3 powder, 1% to 8% of sintering aid.

[0045] The sintering aid comprises: rare earth oxide and alkali metal oxide. Preferably, the rare earth oxide is Y2O3, the alkali metal oxide is MgO, and the sintering aid further comprises talc powder, and the content of each component of the sintering aid is 0.25% to 2.5% of Y2O3, 0.3% to 5.5% of MgO, and 0.05% to 1.5% of talc powder.

[0046] Preparation method: after the Al2O3 powder and the sintering aid are weighed according to the proportion and are loaded into a ball mill tank, an appropriate amount of dispersant and pure water are added, and ball milling is performed for 2 to 6 hours. After the ball milling is completed, the slurry is poured into a tray, and vacuum freeze drying is performed using a vacuum freeze dryer. After freeze drying, the powder is sieved through a 200 to 300 mesh sieve network using vibration, and is ready for use.

[0047] The present application adopts vacuum freeze drying technology. For spherical or spherical-like alumina powder, good particle morphology is of great importance to the overall bulk density and dispersibility of the slurry. Since micro cracks inevitably exist on the surface of alumina particles during ball milling dispersion, the present application solves the problem of alumina crystal rupture during the high-temperature drying process of the common slurry preparation process in the market, and improves the overall dispersibility and adhesion of the slurry.

[0048] <Organic carrier A>

[0049] In the embodiment of the present application, the organic binder in the organic carrier A comprises one or more mixtures of acrylic resin, phenolic resin, and epoxy resin. The above resins have low cracking temperature and low carbon residue rate during sintering, and improve the conductivity and interface reliability.

[0050] In the embodiment of the present application, the plasticizer comprises one or more mixtures of dibutyl phthalate, di-n-butyl adipate, dioctyl phthalate, and dioctyl succinate.

[0051] In the embodiment of the present application, the organic solvent is selected from one or more mixtures of methanol, ethanol, acetone, benzyl alcohol, diethylene glycol butyl ether acetate, ethylene glycol diacetate, terpineol, and butyl carbitol.

[0052] Preparation method: the organic binder, modified montmorillonite, plasticizer and solvent are weighed according to the proportion, the solvent and plasticizer are first added to the stirring dissolving container and stirred uniformly, the heating temperature is set to 50-100 DEG C, the stirring speed is 150-500 r / min, the organic binder and modified montmorillonite are added while stirring until they are completely dissolved and uniformly dispersed, and the mixture is cooled and sealed for storage.

[0053] <Organic carrier B>

[0054] In the embodiment of the application, the organic binder in the organic carrier B comprises one or more mixtures of ethyl cellulose, polyvinyl alcohol and polyvinyl butyral.

[0055] In the embodiment of the application, the plasticizer comprises one or more mixtures of dibutyl phthalate, di-n-butyl adipate, dioctyl phthalate and dioctyl succinate.

[0056] In the embodiment of the application, the organic solvent is selected from one or more mixtures of methanol, ethanol, acetone, benzyl alcohol, diethylene glycol butyl ether acetate, ethylene glycol diacetate, terpineol and butyl carbitol.

[0057] Preparation method: the organic binder, plasticizer and solvent are weighed according to the proportion and added to the stirring dissolving container, the solvent and plasticizer are first added and stirred uniformly, the heating temperature is set to 50-100 DEG C, the stirring speed is 150-500 r / min, the organic binder is added while stirring until it is completely dissolved and uniformly dispersed, and the mixture is cooled and sealed for storage.

[0058] The second aspect of the application provides a preparation method of an alumina ceramic composite colloidal tungsten metallization slurry, comprising the following steps:

[0059] (S1) Preparation of conductive tungsten powder mixture: the inorganic binder phase and conductive tungsten powder are weighed according to the proportion and placed in a ball mill tank, then an appropriate amount of dispersant and acetone are added to the ball mill tank and ball milled for 4-24 h; then the organic carrier A is weighed according to the proportion and placed in the ball mill tank, and ball milled again for 2-6 h;

[0060] (S2) Preparation of metallized tungsten slurry: after the mixture in step (S1) is ball milled, it is passed through a 100-200 mesh screen and loaded into a vacuum stirrer, heated and stirred, the heating temperature is set to 50-100 DEG C, and the ball milling medium such as acetone is removed by reduced pressure distillation to obtain a uniform tungsten slurry;

[0061] (S3) according to the proportion of organic carrier B, added to the tungsten slurry obtained in step (S2) after high shear mixer fast stirring uniform, the stirring speed is 500r / min~10000r / min, stirring time is 0h~1h;Again the mixed slurry is rolled by three shafts and is rolled by three shafts, gradually reduces the roll spacing, until the required printing viscosity, gets the required printing composite colloidal metallized tungsten slurry electronic paste.

[0062] Examples

[0063] The application will be described in detail below with specific embodiments. In the following examples, unless otherwise specified, the raw materials or processing techniques used are commercially available or conventional processing techniques in the art.

[0064] <Preparation of modified montmorillonite>

[0065] Preparation Example 1

[0066] 10g of dry sodium-based montmorillonite was weighed into 200mL of N,N-dimethylformamide (DMF), and ultrasonic treatment was carried out at 80°C for 30min (power 300W), then 0.5g of PTMEG-1000 was added, and stirring was carried out at 80°C for 4h under nitrogen protection; a mixed solution was obtained; the mixed solution was washed by centrifugation until neutral, and vacuum drying was carried out at 80°C for 12h, and the obtained modified montmorillonite was ground, sieved with a 300 mesh sieve, and vacuum dried for 12h for standby, i.e. modified montmorillonite A.

[0067] Preparation Example 2

[0068] 10g of dry sodium-based montmorillonite was weighed into 200mL of N,N-dimethylformamide (DMF), and ultrasonic treatment was carried out at 80°C for 30min (power 300W), then 0.5g of PEG-2000 was added, and stirring was carried out at 80°C for 4h under nitrogen protection; a mixed solution was obtained; the mixed solution was washed by centrifugation until neutral, and vacuum drying was carried out at 80°C for 12h, and the obtained modified montmorillonite was ground, sieved with a 300 mesh sieve, and vacuum dried for 12h for standby, i.e. modified montmorillonite B.

[0069] Preparation Example 3

[0070] 10g of dry sodium-based montmorillonite was weighed into 200mL of N,N-dimethylformamide (DMF), and ultrasonic treatment was carried out at 80°C for 30min (power 300W), then 0.5g of PEG-4000 was added, and stirring was carried out at 80°C for 4h under nitrogen protection; a mixed solution was obtained; the mixed solution was washed by centrifugation until neutral, and vacuum drying was carried out at 80°C for 12h, and the obtained modified montmorillonite was ground, sieved with a 300 mesh sieve, and vacuum dried for 12h for standby, i.e. modified montmorillonite C.

[0071] Preparation Example 4

[0072] 10 g of dry Na-montmorillonite was weighed into 200 mL of deionized water, and ultrasonic treatment was carried out at 80°C for 60 min (power 300 W), then 0.5 g of PEG-6000 was added, and stirring was carried out at 80°C for 2 h under nitrogen protection; a mixed solution was obtained; the mixed solution was washed to neutral by centrifugation, vacuum dried at 80°C for 12 h, and the obtained modified montmorillonite was ground, sieved through a 300-mesh screen, and vacuum dried for 12 h, ready for use, namely modified montmorillonite D.

[0073] Preparation Example 5

[0074] 10 g of dry Na-montmorillonite was weighed into 200 mL of deionized water, and ultrasonic treatment was carried out at 80°C for 60 min (power 300 W), then 0.5 g of PEG-8000 was added, and stirring was carried out at 80°C for 2 h under nitrogen protection; a mixed solution was obtained; the mixed solution was washed to neutral by centrifugation, vacuum dried at 80°C for 12 h, and the obtained modified montmorillonite was ground, sieved through a 300-mesh screen, and vacuum dried for 12 h, ready for use, namely modified montmorillonite E.

[0075] <Preparation of metalized tungsten slurry>

[0076] Example 1

[0077] The composition of the metalized tungsten slurry: by mass percentage, 90% of conductive metal tungsten powder, 4% of inorganic bonding phase, 5% of organic carrier A, and 1% of organic carrier B.

[0078] The particle size of the conductive metal tungsten powder is 1.5 μm-2 μm;

[0079] The inorganic bonding phase includes: 95% of Al2O3 powder and 5% of sintering aid (1% of Y2O3, 3.5% of MgO, and 0.5% of talc powder).

[0080] The organic carrier A: by mass percentage, 15% of acrylic resin organic binder, 25% of dioctyl phthalate, 58% of terpineol, and 2% of modified montmorillonite C.

[0081] The organic carrier B: by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate, and 20% of ethylene glycol diacetate.

[0082] Example 2

[0083] The composition of the metalized tungsten slurry: by mass percentage, 70% of conductive metal tungsten powder, 5% of inorganic bonding phase, 20% of organic carrier A, and 5% of organic carrier B.

[0084] The particle size of the conductive metal tungsten powder is 1.5-2 μm;

[0085] The inorganic bonding phase comprises 95% Al2O3 powder and 5% sintering aids (1% Y2O3, 3.5% MgO and 0.5% talc powder).

[0086] The organic carrier A comprises, by mass percentage, 15% acrylic resin organic binder, 25% dioctyl phthalate, 58% terpineol and 2% modified montmorillonite C.

[0087] The organic carrier B comprises, by mass percentage, 10% ethyl cellulose organic binder, 25% dibutyl phthalate, 45% diethylene glycol butyl ether acetate and 20% ethylene glycol diacetate.

[0088] Example 3

[0089] The metallized tungsten slurry comprises, by mass percentage, 80% conductive metal tungsten powder, 5% inorganic bonding phase, 10% organic carrier A and 5% organic carrier B.

[0090] The particle size of the conductive metal tungsten powder is 1.5-2 μm;

[0091] The inorganic bonding phase comprises 95% Al2O3 powder and 5% sintering aids (1% Y2O3, 3.5% MgO and 0.5% talc powder).

[0092] The organic carrier A comprises, by mass percentage, 15% acrylic resin organic binder, 25% dioctyl phthalate, 58% terpineol and 2% modified montmorillonite C.

[0093] The organic carrier B comprises, by mass percentage, 10% ethyl cellulose organic binder, 25% dibutyl phthalate, 45% diethylene glycol butyl ether acetate and 20% ethylene glycol diacetate.

[0094] Example 4

[0095] The metallized tungsten slurry comprises, by mass percentage, 80% conductive metal tungsten powder, 5% inorganic bonding phase, 5% organic carrier A and 10% organic carrier B.

[0096] The particle size of the conductive metal tungsten powder is 1.5-2 μm;

[0097] The inorganic bonding phase comprises 95% Al2O3 powder and 5% sintering aids (1% Y2O3, 3.5% MgO and 0.5% talc powder).

[0098] The organic carrier A: 15% of acrylic resin organic binder, 25% of dioctyl phthalate, 58% of terpineol, 2% of modified montmorillonite C by mass percentage;

[0099] The organic carrier B: 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate by mass percentage.

[0100] Example 5

[0101] The tungsten metallization slurry composition: 80% of conductive metal tungsten powder, 5% of inorganic bonding phase and 10% of organic carrier A by mass percentage; 5% of organic carrier B.

[0102] The particle size of the conductive metal tungsten powder is 1.5 μm-2 μm;

[0103] The inorganic bonding phase includes: 95% of Al2O3 powder and 5% of sintering aid (1% of Y2O3, 3.5% of MgO and 0.5% of talc powder).

[0104] The organic carrier A: 15% of acrylic resin organic binder, 25% of dioctyl phthalate, 58% of terpineol, 2% of modified montmorillonite A by mass percentage;

[0105] The organic carrier B: 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate by mass percentage.

[0106] Example 6

[0107] The tungsten metallization slurry composition: 80% of conductive metal tungsten powder, 5% of inorganic bonding phase and 10% of organic carrier A by mass percentage; 5% of organic carrier B.

[0108] The particle size of the conductive metal tungsten powder is 1.5 μm-2 μm;

[0109] The inorganic bonding phase includes: 95% of Al2O3 powder and 5% of sintering aid (1% of Y2O3, 3.5% of MgO and 0.5% of talc powder).

[0110] The organic carrier A: 15% of acrylic resin organic binder, 25% of dioctyl phthalate, 58% of terpineol, 2% of modified montmorillonite B by mass percentage;

[0111] The organic carrier B: 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate by mass percentage.

[0112] Example 7

[0113] The composition of the metallized tungsten slurry: by mass percentage, 80% of conductive metal tungsten powder, 5% of inorganic bonding phase, 10% of organic carrier A; 5% of organic carrier B.

[0114] The particle size of the conductive metal tungsten powder is 1.5 μm-2 μm;

[0115] The inorganic bonding phase includes: 95% of Al2O3 powder, 5% of sintering aid (1% of Y2O3, 3.5% of MgO, 0.5% of talc powder).

[0116] The organic carrier A: by mass percentage, 15% of acrylic resin organic binder, 25% of dioctyl phthalate, 58% of terpineol, 2% of modified montmorillonite D;

[0117] The organic carrier B: by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0118] Example 8

[0119] The composition of the metallized tungsten slurry: by mass percentage, 80% of conductive metal tungsten powder, 5% of inorganic bonding phase, 10% of organic carrier A; 5% of organic carrier B.

[0120] The particle size of the conductive metal tungsten powder is 1.5 μm-2 μm;

[0121] The inorganic bonding phase includes: 95% of Al2O3 powder, 5% of sintering aid (1% of Y2O3, 3.5% of MgO, 0.5% of talc powder).

[0122] The organic carrier A: by mass percentage, 15% of acrylic resin organic binder, 25% of dioctyl phthalate, 58% of terpineol, 2% of modified montmorillonite E;

[0123] The organic carrier B: by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0124] Example 9

[0125] The composition of the metallized tungsten slurry: by mass percentage, 80% of conductive metal tungsten powder, 5% of inorganic bonding phase, 10% of organic carrier A; 5% of organic carrier B.

[0126] The particle size of the conductive metal tungsten powder is 1.5-2 μm;

[0127] The inorganic bonding phase comprises 95% Al2O3 powder and 5% sintering aids (1% Y2O3, 3.5% MgO and 0.5% talc powder).

[0128] The organic carrier A comprises, by mass percentage, 10% acrylic resin organic binder, 10% dioctyl phthalate, 78% terpineol and 2% modified montmorillonite C.

[0129] The organic carrier B comprises, by mass percentage, 5% ethyl cellulose organic binder, 15% dibutyl phthalate, 60% diethylene glycol butyl ether acetate and 20% ethylene glycol diacetate.

[0130] Example 10

[0131] The metalized tungsten slurry comprises, by mass percentage, 80% conductive metal tungsten powder, 5% inorganic bonding phase, 10% organic carrier A and 5% organic carrier B.

[0132] The particle size of the conductive metal tungsten powder is 1.5-2 μm;

[0133] The inorganic bonding phase comprises 95% Al2O3 powder and 5% sintering aids (1% Y2O3, 3.5% MgO and 0.5% talc powder).

[0134] The organic carrier A comprises, by mass percentage, 25% acrylic resin organic binder, 20% dioctyl phthalate, 53% terpineol and 2% modified montmorillonite C.

[0135] The organic carrier B comprises, by mass percentage, 20% ethyl cellulose organic binder, 5% dibutyl phthalate, 45% diethylene glycol butyl ether acetate and 20% ethylene glycol diacetate.

[0136] Example 11

[0137] The metalized tungsten slurry comprises, by mass percentage, 80% conductive metal tungsten powder, 5% inorganic bonding phase, 10% organic carrier A and 5% organic carrier B.

[0138] The particle size of the conductive metal tungsten powder is 1.5-2 μm;

[0139] The inorganic bonding phase comprises 95% Al2O3 powder and 5% sintering aids (1% Y2O3, 3.5% MgO and 0.5% talc powder).

[0140] The organic carrier A: 15% of acrylic resin organic binder, 25% of dioctyl phthalate, 59% of terpineol, 1% of modified montmorillonite C by mass percentage;

[0141] The organic carrier B: 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate by mass percentage.

[0142] Example 12

[0143] The tungsten metallization slurry composition: 80% of conductive metal tungsten powder, 5% of inorganic bonding phase, 10% of organic carrier A and 5% of organic carrier B by mass percentage.

[0144] The particle size of the conductive metal tungsten powder is 1.5 μm-2 μm;

[0145] The inorganic bonding phase includes: 95% of Al2O3 powder, 5% of sintering aid (1% of Y2O3, 3.5% of MgO and 0.5% of talc powder).

[0146] The organic carrier A: 15% of acrylic resin organic binder, 25% of dioctyl phthalate, 57% of terpineol, 3% of modified montmorillonite C by mass percentage;

[0147] The organic carrier B: 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate by mass percentage.

[0148] Example 13

[0149] The tungsten metallization slurry composition: 80% of conductive metal tungsten powder, 5% of inorganic bonding phase, 10% of organic carrier A and 5% of organic carrier B by mass percentage.

[0150] The particle size of the conductive metal tungsten powder is 1.5 μm-2 μm;

[0151] The inorganic bonding phase includes: 95% of Al2O3 powder, 5% of sintering aid (1% of Y2O3, 3.5% of MgO and 0.5% of talc powder).

[0152] The organic carrier A: 15% of acrylic resin organic binder, 25% of dioctyl phthalate, 56% of terpineol, 4% of modified montmorillonite C by mass percentage;

[0153] The organic carrier B: 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate by mass percentage.

[0154] Example 14

[0155] The composition of the metallized tungsten slurry: 80% of conductive metal tungsten powder, 5% of inorganic bonding phase, 10% of organic carrier A; 5% of organic carrier B.

[0156] The particle size of the conductive metal tungsten powder is 1.5 μm-2 μm;

[0157] The inorganic bonding phase includes: 95% of Al2O3 powder, 5% of sintering aid (1% of Y2O3, 3.5% of MgO, 0.5% of talc powder).

[0158] The organic carrier A: 15% of acrylic resin organic binder, 25% of dioctyl phthalate, 55% of terpineol, 5% of modified montmorillonite C by mass percentage;

[0159] The organic carrier B: 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate by mass percentage.

[0160] Example 15

[0161] The composition of the metallized tungsten slurry: 80% of conductive metal tungsten powder, 5% of inorganic bonding phase, 10% of organic carrier A; 5% of organic carrier B.

[0162] The particle size of the conductive metal tungsten powder is 1.5 μm-2 μm;

[0163] The inorganic bonding phase includes: 95% of Al2O3 powder, 5% of sintering aid (1% of Y2O3, 3.5% of MgO, 0.5% of talc powder).

[0164] The organic carrier A: 15% of epoxy resin organic binder, 25% of dioctyl phthalate, 58% of terpineol, 2% of modified montmorillonite C by mass percentage;

[0165] The organic carrier B: 10% of polyvinyl butyral organic binder, 25% of dibutyl phthalate, 25% of benzyl alcohol and 40% of ethylene glycol diacetate by mass percentage.

[0166] Example 16

[0167] The composition of the metallized tungsten slurry: 80% of conductive metal tungsten powder, 5% of inorganic bonding phase, 10% of organic carrier A; 5% of organic carrier B.

[0168] The particle size of the conductive metal tungsten powder is 1.5 μm-2 μm;

[0169] The inorganic bonding phase comprises: 95% of Al2O3 powder, 5% of sintering aid (1% of Y2O3, 3.5% of MgO, 0.5% of talc powder).

[0170] The organic carrier A comprises, by mass percentage, 15% of phenolic resin organic binder, 25% of dioctyl phthalate, 58% of terpineol, and 2% of modified montmorillonite C.

[0171] The organic carrier B comprises, by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate, and 20% of ethylene glycol diacetate.

[0172] Comparative Example 1

[0173] The metalized tungsten slurry comprises, by mass percentage, 80% of conductive metal tungsten powder, 5% of inorganic bonding phase, and 10% of organic carrier A.

[0174] The conductive metal tungsten powder has a particle size of 1.5 μm to 2 μm.

[0175] The inorganic bonding phase comprises: 95% of Al2O3 powder, 5% of sintering aid (1% of Y2O3, 3.5% of MgO, 0.5% of talc powder).

[0176] The organic carrier A comprises, by mass percentage, 15% of acrylic resin organic binder, 25% of dioctyl phthalate, and 60% of terpineol.

[0177] The organic carrier B comprises, by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate, and 20% of ethylene glycol diacetate.

[0178] Comparative Example 2

[0179] The metalized tungsten slurry comprises, by mass percentage, 80% of conductive metal tungsten powder, 5% of inorganic bonding phase, and 15% of organic carrier A.

[0180] The conductive metal tungsten powder has a particle size of 1.5 μm to 2 μm.

[0181] The inorganic bonding phase comprises: 95% of Al2O3 powder, 5% of sintering aid (1% of Y2O3, 3.5% of MgO, 0.5% of talc powder).

[0182] The organic carrier A comprises, by mass percentage, 15% of acrylic resin organic binder, 25% of dioctyl phthalate, 58% of terpineol, and 2% of modified montmorillonite C.

[0183] Comparative Example 3

[0184] The composition of the metallized tungsten paste: by mass percentage, 80% of conductive metal tungsten powder, 5% of inorganic bonding phase, and 15% of organic carrier B.

[0185] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0186] The inorganic bonding phase includes 95% of Al2O3 powder and 5% of sintering aid (1% of Y2O3, 3.5% of MgO, and 0.5% of talc powder).

[0187] The organic carrier B: by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate, and 20% of ethylene glycol diacetate.

[0188] Performance test:

[0189] <Printing performance test of composite colloidal metallized tungsten paste>

[0190] The metallized tungsten paste obtained in each of Examples 1-16 and Comparative Examples 1-3 is mixed uniformly and without air bubbles, and is used after standing for at least 5 minutes. The viscosity and thixotropic index are tested by using a BROOKFIELD-DV2T type viscometer, a No. 14 rotor, and a rotor barrel, at a constant temperature of 25°C, at 1 RPM, 10 RPM, and 30 RPM, and the thixotropic index = viscosity (1 RPM) / viscosity (10 RPM). The metallized tungsten paste obtained in each of Examples 1-16 and Comparative Examples 1-3 is printed as a printing test sample by using a screen printing process, and each of the metallized tungsten pastes is printed on an electrostatic chuck alumina green sheet, and the printing performance of the paste is observed by using a high-power microscope, and the results are shown in Table 1.

[0191] Table 1: Printing performance test results of composite colloidal metallized tungsten paste

[0192]

[0193] Among them, the effect level of printing visual appearance: clear pattern, good resolution > clear pattern > clear pattern, slight mesh > complete pattern > complete pattern, slight mesh > complete pattern, obvious overflow.

[0194] <Sintering matching test of composite colloidal metallized tungsten paste>

[0195] Sintering matching verification of the paste: the metallized tungsten paste obtained in Examples 1-16 and Comparative Examples 1-3 was printed on the surface of a 96% Al2O3 white porcelain green tape with a thickness of 0.6 mm and a size of 100x100 mm, and printed in a square pattern with a size of 20x20 mm. After drying, the green tape was placed in an atmosphere sintering furnace and sintered at 1500-1600°C for 2 h under a wet hydrogen atmosphere. After sintering, the test sample was removed, and the roughness of the printed surface was measured using a bench roughness meter.

[0196] Paste adhesion test: the metallized tungsten paste obtained in Examples 1-16 and Comparative Examples 1-3 was sintered to form a sintered piece, and a nickel layer was plated on the sintered piece. The thickness of the nickel layer was 5-7 μm. The maximum tensile force that the soldered surface could withstand was measured using the hanging weight method. The maximum tensile force that the lead could withstand when bent at 90° was measured. 2

[0197] Sheet resistance test of the paste: the metallized tungsten paste obtained in Examples 1-14 and Comparative Examples 1-3 was printed on the surface of a 96% Al2O3 white porcelain green tape with a thickness of 0.6 mm and a size of 100x100 mm, and printed in a square pattern with a size of 20x20 mm. After drying, the green tape was placed in an atmosphere sintering furnace and sintered at 1500-1600°C for 2 h under a nitrogen-hydrogen atmosphere. After sintering, the test sample was removed, and the sheet resistance of the paste was measured using a four-probe sheet resistance tester.

[0198] The results of the sintering matching test of the composite colloidal metallized tungsten paste are shown in Table 2.

[0199]

[0200] As shown in Tables 1 and 2, when the polyether polyol is selected from PEG-4000 or PEG-6000 in Examples 3, 5-8, the thixotropic index, printing performance, adhesion, sheet resistance, and other comprehensive effects of the prepared composite colloidal metallized tungsten paste are good. In addition, by comparing Examples 3, 11-14, it can be found that the amount of modified montmorillonite is preferably 2%-3%.

[0201] The above description is merely preferred specific embodiments of the present application. The scope of the present application is not limited to the above description, and simple changes or equivalent replacements within the scope of the present application disclosed herein can be made by those skilled in the art, and all such changes and replacements fall within the scope of the present application.​

Claims

1. An alumina ceramic composite colloidal metallized tungsten paste, characterized by, By mass percentage, it comprises: 70% to 90% conductive metal tungsten powder, 1% to 15% inorganic adhesive phase, 5% to 25% organic carrier A, 1% to 10% organic carrier B; The organic carrier A comprises: 10% to 25% organic binder, 5% to 40% plasticizer, 5% to 90% solvent and 1% to 5% modified montmorillonite; The organic carrier B comprises: 5% to 20% organic binder, 10% to 60% plasticizer and 5% to 90% solvent; The organic binder in the organic carrier A comprises: one or more mixtures of acrylic resin, phenolic resin and epoxy resin; The organic binder in the organic carrier B comprises: one or more mixtures of ethyl cellulose, polyvinyl alcohol and polyvinyl butyral; The modified montmorillonite is polyether polyol modified montmorillonite.

2. The alumina ceramic composite colloidal metallized tungsten paste of claim 1, wherein, The conductive metal tungsten powder has a particle size of 0.5 μm to 2.5 μm.

3. The alumina ceramic composite colloidal metallized tungsten paste of claim 1, wherein, The polyether polyol in the polyether polyol modified montmorillonite is selected from one or more of PTMEG-1000, PEG-2000, PEG-4000, PEG-6000 or PEG-8000.

4. The alumina ceramic composite colloidal metallized tungsten paste of claim 1, wherein, The polyether polyol in the polyether polyol modified montmorillonite is selected from PEG-4000 or PEG-6000.

5. The alumina ceramic composite colloidal metallized tungsten paste of claim 1, wherein, The amount of the polyether polyol modified montmorillonite is 2% to 3%.

6. The alumina ceramic composite colloidal tungsten metallized slurry according to any one of claims 1-5, characterized in that, The inorganic adhesive phase comprises: 92% to 99% Al2O3 powder and 1% to 8% sintering aid.

7. The alumina ceramic composite colloidal tungsten metallized slurry according to any one of claims 1-5, characterized in that, The solvent is selected from one or more mixtures of methanol, ethanol, acetone, benzyl alcohol, diethylene glycol butyl ether acetate, ethylene glycol diacetate, terpineol and butyl carbitol.

8. A method of preparing the alumina ceramic composite colloidal metallized tungsten paste according to claim 1, characterized by, The method comprises the following steps: (1) Inorganic adhesive phase preparation: Al2O3 powder and sintering aid are weighed in proportion, then are put into a ball mill tank, an appropriate amount of dispersant and pure water are added, and ball milling is carried out for 2 to 6 hours. After ball milling, the slurry is poured into a tray, and vacuum freeze drying is carried out by using a vacuum freeze dryer. After freeze drying, the powder is sieved through a 200 to 300 mesh sieve by using vibration, and is ready for use; (2) Preparation of organic carrier A: organic binder, modified montmorillonite, plasticizer and solvent are weighed in proportion. The solvent and plasticizer are first added to a stirring dissolving container and are stirred uniformly. The heating temperature is set to 50 to 100 DEG C, and the stirring speed is set to 150 to 500 r / min. The organic binder and modified montmorillonite are added while stirring, until they are completely dissolved and dispersed uniformly. The mixture is cooled and sealed for storage; (3) Preparation of organic carrier B: organic binder, plasticizer and solvent are weighed in proportion, and are added to a stirring dissolving container. The solvent and plasticizer are first added and are stirred uniformly. The heating temperature is set to 50 to 100 DEG C, and the stirring speed is set to 150 to 500 r / min. The organic binder is added while stirring, until it is completely dissolved and dispersed uniformly. The mixture is cooled and sealed for storage; (4) Preparation of the conductive tungsten powder mixture: the inorganic binder phase and the conductive tungsten powder obtained in step (1) are weighed according to the proportion, and then placed in a ball mill tank, and an appropriate amount of dispersant and acetone are added to the ball mill tank and ball milled for 4h-24h; then the organic carrier A in step (2) is weighed according to the proportion and placed in the ball mill tank, and ball milled again for 2h-6h; (5) Preparation of the metallized tungsten paste: the mixture after ball milling in step (4) is passed through a 100-200 mesh screen and then loaded into a vacuum stirrer, heated and stirred, the heating temperature is set to 50-100°C, and the ball milling medium such as acetone is removed by vacuum distillation to obtain a uniform tungsten paste; (6) The organic carrier B in step (3) is weighed according to the proportion and added to the tungsten paste obtained in step (5) and then rapidly stirred in a high-shear stirrer to form a mixed slurry, wherein the stirring speed is 500-10000r / min and the stirring time is 0.5-1h; the mixed slurry is then rolled by a three-axis slurry roller multiple times, and the roller spacing is gradually reduced until the desired printing viscosity is reached to obtain the desired printing composite colloidal metallized tungsten paste electronic paste.

9. Use of the alumina ceramic composite colloidal metallized tungsten paste according to any one of claims 1-7 in an electrostatic chuck.

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