Titanium nitride ceramic electronic paste, preparation method thereof and ceramic electrode

Abstract

This invention relates to the field of electronic materials technology, specifically disclosing a titanium nitride ceramic electronic paste, its preparation method, and a ceramic electrode. The titanium nitride ceramic electronic paste is prepared from the following components by mass percentage: 50%–80% titanium nitride powder, 10%–50% organic components, 0.5%–5% solid binder phase, and 0–5% additives. This invention uses titanium nitride powder as the functional phase. The physicochemical properties of titanium nitride are similar to those of the ceramic substrate. It is bonded to the ceramic substrate via high-temperature sintering, resulting in sintering shrinkage behavior that is more closely similar to that of the ceramic substrate. This reduces the difficulty of sintering and matching with the ceramic substrate, effectively reducing stress and defects during co-firing, and improving bonding strength and process stability. The paste provided by this invention also has comprehensive advantages such as low cost, excellent dispersibility, good stability, high temperature resistance, and corrosion resistance, and has broad application prospects in the high-end electronics field.

Description

Technical Field

[0001] This invention relates to the field of electronic materials technology, and in particular to a titanium nitride ceramic electronic paste, its preparation method, and a ceramic electrode. Background Technology

[0002] Electronic pastes represent a crucial direction in the development of advanced electronic materials. They allow for the formation of circuit patterns on the surface of multilayer co-fired ceramics using screen printing or additive manufacturing, followed by high-temperature sintering to achieve electrical connectivity. Traditional electronic pastes utilize precious metals such as silver, copper, and gold, or high-melting-point metals like tungsten and molybdenum. However, metal conductor electronic pastes present challenges such as high cost, difficulty in sintering with ceramic substrates, poor adhesion, and poor high-temperature and corrosion resistance. Summary of the Invention

[0003] Based on this, the purpose of this invention is to provide a titanium nitride ceramic electronic paste, its preparation method, and a ceramic electrode. This titanium nitride ceramic electronic paste can be bonded to a ceramic substrate by high-temperature sintering, exhibiting excellent comprehensive performance and is expected to become an important development direction for future electronic pastes.

[0004] To achieve the above objectives, the present invention adopts the following technical solution:

[0005] This invention provides a titanium nitride ceramic electronic paste, which is prepared from the following components by mass percentage: 50%~80% titanium nitride powder, 10%~50% organic components, 0.5%~5% solid binder phase, and 0~5% additives.

[0006] This invention uses titanium nitride powder as the functional phase. The physicochemical properties of titanium nitride are similar to those of the ceramic substrate. It is bonded to the ceramic substrate via high-temperature sintering, resulting in sintering shrinkage behavior that more closely resembles that of the ceramic substrate. This reduces the difficulty of sintering and effectively decreases stress and defects during co-firing, improving bonding strength and process stability. The slurry provided by this invention also possesses comprehensive advantages such as low cost, excellent dispersibility, good stability, high-temperature resistance, and corrosion resistance, making it promising for applications in high-end electronics.

[0007] As a further improvement to the above-mentioned solution of the present invention, the D50 of the titanium nitride powder is 500nm~10μm.

[0008] As a further improvement to the above-described scheme of the present invention, the organic component includes an organic solvent and a polymer resin. The organic solvent is selected from at least one of methanol, ethanol, ethyl acetate, isopropanol, butyl acetate, toluene, xylene, trimethylbenzene, turpentine, terpineol, dibutyl phthalate, diethylene glycol butyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether acetate, propylene glycol methyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide. The polymer resin is selected from at least one of polyethylene oxide, epoxy resin, ethyl cellulose resin, polyvinyl alcohol resin, polyacrylic acid resin, polycarbonate resin, and polyurethane resin.

[0009] As a further improvement to the above-described scheme of the present invention, the solid binder phase is at least one of a non-glassy inorganic compound and a glass.

[0010] As a further improvement to the above-described scheme of the present invention, the silicon-based glass is selected from at least one of Ca-Al-Si-based glass, B-Si-based glass, and Ca-B-Si-based glass.

[0011] As a further improvement to the above-described scheme of the present invention, the additive is at least one of a dispersant, a leveling agent, and a thixotropic agent.

[0012] This invention also provides a method for preparing the titanium nitride ceramic electronic paste as described above, comprising the following steps: Preparation of titanium nitride powder: Initial titanium nitride powder of a certain particle size is placed in a ball mill container, and grinding fluid and grinding balls are added according to a certain formula ratio, followed by ball milling for a certain period of time. After milling, titanium nitride powder is obtained by sieving. During the milling process, the particle size of the processed titanium nitride powder is measured using a laser particle size analyzer. Then, by optimizing and improving the grinding formula ratio and milling time, the particle size of the titanium nitride powder is controlled within the required range (500nm~10μm, preferably 1μm). Preparation of organic components: One or more solvents are added to the same container in a certain formula ratio and mechanically stirred to form an organic solvent; one or more polymer resin materials are added to the organic solvent in a ratio of 4~50wt%, and then dissolved by mechanical stirring under a certain temperature condition to form a transparent organic component without obvious insoluble substances; Preparation of solid binder phase: One or more oxides are uniformly mixed together according to a certain formula ratio to form a non-glassy inorganic compound mixture system; one or more glasses are uniformly mixed together according to a certain formula ratio to form a glass component; the non-glassy inorganic compound mixture system and the glass component are weighed and placed in the same grinding container according to a certain formula ratio, and grinding media and grinding liquid are added according to a certain ratio. They are then uniformly mixed together through grinding for a certain time to form a powdery solid binder phase with a certain particle size distribution (400nm~15μm, preferably 800nm); Titanium nitride powder, organic components, solid binder phase, and additives are mixed evenly in proportion to form an initial slurry mixing system; the initial slurry mixing system is rolled to form titanium nitride ceramic electronic slurry.

[0013] The present invention also provides a ceramic electrode prepared using the titanium nitride electronic paste as described above.

[0014] As a further improvement to the above-mentioned solution of the present invention, the method for preparing the ceramic electrode includes the following steps: forming a circuit pattern (line resolution ≥ 50 μm) on a ceramic green sheet by means of screen printing or additive manufacturing of the titanium nitride ceramic electronic paste, and sintering to obtain the ceramic electrode.

[0015] As a further improvement to the above-mentioned solution of the present invention, the sintering atmosphere is an inert atmosphere and the temperature is ≥1800℃.

[0016] Compared with the prior art, the present invention has the following beneficial effects: This invention uses titanium nitride powder as the functional phase. The physicochemical properties of titanium nitride are similar to those of the ceramic substrate. It is bonded to the ceramic substrate via high-temperature sintering, resulting in sintering shrinkage behavior that more closely resembles that of the ceramic substrate. This reduces the difficulty of sintering and effectively decreases stress and defects during co-firing, improving bonding strength and process stability. The slurry provided by this invention also possesses comprehensive advantages such as low cost, excellent dispersibility, good stability, high-temperature resistance, and corrosion resistance, making it promising for applications in high-end electronics.

[0017] This invention provides a new approach and method for all-ceramic multilayer co-fired material systems, which can realize the relevant preparation process and is compatible with the existing high-temperature co-fired ceramic system process without the need for large-scale upgrades. Attached Figure Description

[0018] Figure 1 A photograph of the titanium nitride ceramic electronic paste prepared in Example 1 of this invention; Figure 2 This is a schematic diagram of the printing effect of titanium nitride ceramic electronic paste in Embodiment 1 of the present invention. Detailed Implementation

[0019] To facilitate understanding of the present invention, a more comprehensive description will be given below with reference to specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of the present invention.

[0020] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of this invention is for the purpose of describing particular embodiments only and is not intended to limit the invention. Furthermore, unless otherwise specified, methods not specifically describing conditions or steps are conventional methods, and the reagents and materials used are commercially available.

[0021] Example 1 This embodiment proposes a titanium nitride ceramic electronic paste, the preparation method of which includes the following five steps (1)-(4): (1) Titanium nitride powder treatment: Weigh 100g of titanium nitride ceramic powder, 150g of anhydrous ethanol and 150g of grinding balls and add them to a ball mill jar. Process the powder at a ball milling speed of 100r / min for 2h, then filter and dry to obtain titanium nitride ceramic powder with a particle size of 1μm.

[0022] (2) Preparation of organic components: Weigh 200g of toluene and 200g of terpineol and place them in a beaker. Stir mechanically for 1 hour to obtain an organic solvent. Weigh 30g of polyvinyl alcohol and add it to 170g of organic solvent. Heat and stir at 65℃ for 4 hours to fully dissolve the solvent and obtain organic mixture A. Weigh 24g of ethyl cellulose and add it to 176g of toluene. Heat and stir at 50°C for 4 hours to fully dissolve the cellulose and obtain organic mixture B. Weigh 100g of organic mixture system A and 100g of organic mixture system B, heat and stir at 50℃ to mix thoroughly, and obtain organic components.

[0023] (3) Preparation of solid binder phase: Weigh 100g of calcium carbonate, 50g of aluminum oxide and 52g of silicon dioxide, mix them evenly with mechanical stirring and place them in a crucible, heat to 1400℃, and then quench in water to obtain the initial glass mixture system A. Weigh 150g of initial glass mixture A, 225g of pure water and 225g of grinding balls and add them to a ball mill jar. Process the mixture at a ball milling speed of 200r / min for 1h, then filter and dry to obtain glass mixture powder A. Weigh out 40g of magnesium oxide, 113g of yttrium oxide and 52g of silicon dioxide, mix them evenly with mechanical stirring and place them in a crucible, heat to 1400℃, and then quench in water to obtain the initial glass mixture system B; Weigh 150g of initial glass mixture B, 225g of anhydrous ethanol and 225g of grinding balls and add them to a ball mill jar. Process the mixture at a ball milling speed of 200r / min for 1h, then filter and dry to obtain glass mixture powder B. Weigh 100g of glass mixture powder A, 100g of glass mixture powder B, 200g of anhydrous ethanol and 200g of grinding balls and place them in a ball mill jar. Process the mixture at a ball milling speed of 200r / min for 1h, then filter and dry to obtain a powdery solid binder phase with a particle size of 800nm.

[0024] (4) Preparation of titanium nitride ceramic electronic paste: Weigh 70g of titanium nitride powder, 25g of organic components, 4g of solid binder phase, and 1g of organosilicon ether dispersant. Mix them mechanically at 200 rpm for 10 minutes to obtain an initial titanium nitride electronic paste mixture system. Then, place the obtained initial titanium nitride electronic paste mixture system in a three-roll mill and roll it for 30 minutes to obtain a titanium nitride ceramic electronic paste, as shown below. Figure 1 As shown.

[0025] The titanium nitride ceramic electronic paste prepared in this embodiment was used to screen print circuit patterns on a ceramic green sheet. The printed patterns are shown below. Figure 2 As shown; then the green ceramic sheet with the pattern is dried, stacked and pressed to obtain the sample to be fired; the sample to be fired is placed in an atmosphere sintering furnace, nitrogen gas is introduced, the temperature is increased from room temperature to 600℃ at 2℃ / min and held for 2h, then increased to 1800℃ at 2℃ / min and held for 2h, then decreased to 500℃ at 2℃ / min, and then naturally cooled to room temperature to obtain a multilayer ceramic electrode. After testing, the sheet resistance of the multilayer ceramic electrode prepared in this embodiment is 0.051Ω / .

[0026] Example 2 This embodiment proposes a titanium nitride ceramic electronic paste, the preparation method of which includes the following five steps (1)-(4): (1) Titanium nitride powder treatment: Weigh 100g of initial titanium nitride powder, 100g of anhydrous ethanol and 100g of grinding balls and add them to a ball mill jar. Process the powder at a ball milling speed of 100r / min for 1h, then filter and dry to obtain titanium nitride powder A with a particle size of about 2.5μm. Weigh 100g of initial titanium nitride powder, 100g of anhydrous ethanol and 100g of grinding balls and add them to a ball mill jar. Process the powder at a ball milling speed of 400r / min for 1h, then filter and dry to obtain titanium nitride powder B with a particle size of 1μm.

[0027] (2) Preparation of organic components: Weigh 100g of N,N-dimethylacetamide and 100g of terpineol and place them in a beaker. Stir mechanically for 2 hours to obtain an organic solvent. Weigh 24g of polyurethane and add it to 176g of organic solvent. Heat and stir at 50°C for 4 hours to fully dissolve the polyurethane and obtain organic mixture A. Weigh 40g of ethyl cellulose and add it to 160g of toluene. Heat and stir at 50℃ for 4 hours to fully dissolve the cellulose and obtain organic mixture B. Weigh 100g of organic mixture system A and 100g of organic mixture system B, heat and stir at 50℃ to mix thoroughly, and obtain the organic components.

[0028] (3) Preparation of solid binder phase: Weigh 100g of calcium carbonate, 62g of boric acid and 52g of silicon dioxide, mix them evenly with mechanical stirring and place them in a crucible, heat to 1400℃, and then quench in water to obtain the initial glass mixture system. Weigh 150g of initial glass mixture A, 150g of anhydrous ethanol and 150g of grinding balls and add them to a ball mill jar. Process the mixture at a ball milling speed of 200r / min for 1h, then filter and dry to obtain glass mixture powder. Weigh 50g of lithium fluoride, 104g of silicon dioxide, 80g of pure water and 80g of grinding balls and add them to a ball mill jar. Process the mixture at a ball milling speed of 200r / min for 1h, then filter and dry to obtain an inorganic mixture system. Weigh 100g of glass mixture powder, 100g of inorganic mixture, 200g of pure water and 200g of grinding balls and place them in a ball mill jar. Process the mixture at a ball milling speed of 200r / min for 1h to obtain a powdery solid binder phase with a particle size of 800nm.

[0029] (4) Preparation of titanium nitride ceramic electronic paste: Weigh 36g of titanium nitride powder A, 44g of titanium nitride powder B, 16g of organic components, 3.5g of solid binder phase, and 0.5g of organosilicon ether dispersant, and mechanically mix them at 200r / min for 10min to obtain 100g of initial titanium nitride ceramic electronic paste mixture system; place the initial titanium nitride ceramic electronic paste mixture system in a three-roll mill and roll it for 30min to obtain titanium nitride ceramic electronic paste.

[0030] The titanium nitride ceramic electronic paste prepared in this embodiment was used to screen print circuit patterns onto a ceramic green sheet. The green sheet with the pattern was then dried, stacked, and pressed to obtain a sample for firing. The sample was placed in an atmosphere sintering furnace, argon gas was introduced, and the temperature was increased from room temperature to 600°C at 2°C / min and held for 2 hours. Then, the temperature was increased to 1850°C at 2°C / min and held for 2 hours. Finally, the temperature was decreased to 400°C at 2°C / min and allowed to cool naturally to room temperature, resulting in a multilayer ceramic electrode. Testing showed that the sheet resistance of the multilayer ceramic electrode prepared in this embodiment was 0.063 Ω / min. .

[0031] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0032] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A titanium nitride ceramic electronic paste, characterized in that, It is prepared from the following components by mass percentage: 50%~80% titanium nitride powder, 10%~50% organic components, 0.5%~5% solid binder phase, and 0~5% additives.

2. The titanium nitride ceramic electronic paste according to claim 1, characterized in that, The D50 of the titanium nitride powder is 500 nm to 10 μm.

3. The titanium nitride ceramic electronic paste according to claim 1, characterized in that, The organic component includes an organic solvent and a polymer resin. The organic solvent is selected from at least one of methanol, ethanol, ethyl acetate, isopropanol, butyl acetate, toluene, xylene, trimethylbenzene, turpentine, terpineol, dibutyl phthalate, diethylene glycol butyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether acetate, propylene glycol methyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide. The polymer resin is selected from at least one of polyethylene oxide, epoxy resin, ethyl cellulose resin, polyvinyl alcohol resin, polyacrylic acid resin, polycarbonate resin, and polyurethane resin.

4. The titanium nitride ceramic electronic paste according to claim 1, characterized in that, The solid binder phase is at least one of a non-glassy inorganic compound and a glass.

5. The titanium nitride ceramic electronic paste according to claim 4, characterized in that, The glass is selected from at least one of Ca-Al-Si based glass, B-Si based glass, and Ca-B-Si based glass.

6. The titanium nitride ceramic electronic paste according to claim 1, characterized in that, The additive is at least one of a dispersant, a leveling agent, and a thixotropic agent.

7. A method for preparing titanium nitride ceramic electronic paste as described in any one of claims 1-6, characterized in that, It includes the following steps: Titanium nitride powder, organic components, solid binder phase, and additives are mixed evenly in proportion to form an initial slurry mixing system; the initial slurry mixing system is rolled to form titanium nitride ceramic electronic slurry.

8. A ceramic electrode, characterized in that, It is prepared using the titanium nitride ceramic electronic paste as described in any one of claims 1-6.

9. The ceramic electrode according to claim 8, characterized in that, Its preparation includes the following steps: forming circuit patterns on a ceramic green sheet by screen printing or additive manufacturing of the titanium nitride ceramic electronic paste, and sintering to obtain a ceramic electrode.

10. The ceramic electrode according to claim 8, characterized in that, The sintering atmosphere is an inert atmosphere, and the temperature is ≥1800℃.

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