CN113782249B - Low-cost chip resistor paste - Google Patents
Low-cost chip resistor paste Download PDFInfo
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- CN113782249B CN113782249B CN202111336763.XA CN202111336763A CN113782249B CN 113782249 B CN113782249 B CN 113782249B CN 202111336763 A CN202111336763 A CN 202111336763A CN 113782249 B CN113782249 B CN 113782249B
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- chip resistor
- ruthenium oxide
- copper sulfide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/003—Thick film resistors
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/18—Printed circuits structurally associated with non-printed electric components
Abstract
The invention discloses a chip resistor paste which comprises conductive powder, glass powder and an organic carrier, wherein the conductive powder comprises a copper sulfide ruthenium oxide composite material, and the chip resistor paste comprises 10wt% -30 wt% of the conductive powder, 30wt% -50 wt% of the glass powder and 20wt% -50 wt% of the organic carrier based on the total weight of the chip resistor paste. The invention adopts ruthenium oxide-copper sulfide to replace ruthenium oxide, effectively reduces the dosage of the conductive phase and greatly reduces the cost of the slurry.
Description
Technical Field
The invention belongs to the technical field of resistance paste, and particularly relates to low-cost chip resistance paste.
Background
As electronic products go deep into the aspects of daily life of people, the electronic market continues to keep a high-speed growth situation. With the miniaturization, thinning and miniaturization of electronic products, components such as resistors, capacitors, inductors and the like, which are basic components of the electronic products, are continuously developed in the direction of miniaturization, chip type, low cost, integration and intellectualization.
The chip resistor paste is a core raw material of a chip resistor and consists of a conductive phase, a glass phase, an additive and an organic carrier. The low-resistance section (0.1-10 omega) conductive phase of the chip resistance slurry is mainly silver powder, palladium powder and the like, the medium-resistance section (100-10 k omega) conductive phase is mainly ruthenium oxide, and the high-resistance section (100-10M omega) conductive phase is mainly lead ruthenate and the like. The noble or rare metals contained in the conductive phase largely determine the cost of the chip resistor product.
Therefore, there is a need in the art for a low cost chip resistor paste that can save the amount of precious or rare metals.
Disclosure of Invention
Aiming at the problems, the invention develops low-cost chip resistor paste. The invention finds that the copper sulfide ruthenium oxide composite material is used for replacing ruthenium oxide serving as a conductive phase of a middle resistance section, so that the using amount of the conductive phase can be effectively reduced, and the resistance performance is maintained to be basically unchanged, thereby reducing the production cost and creating profits for enterprises.
Specifically, the invention provides a chip resistor paste which comprises conductive powder, glass powder and an organic carrier, wherein the conductive powder comprises a copper sulfide ruthenium oxide composite material, and the chip resistor paste comprises 10wt% -30 wt% of the conductive powder, 30wt% -50 wt% of the glass powder and 20wt% -50 wt% of the organic carrier based on the total weight of the chip resistor paste.
In one or more embodiments, the glass powder comprises the following components in a mass ratio of (2-4): 1, wherein the raw materials of the glass powder A comprise 25-35 wt% of PbO, 20-40 wt% of SiO2, 10-25 wt% of CaO, 5-10 wt% of Al2O3, 5-10 wt% of B2O3, 1.5-2.5 wt% of ZnO and 0.2-0.5 wt% of Na2O and/or K2O, and the raw materials of the glass powder B comprise 30-50 wt% of PbO, 20-40 wt% of SiO2, 10-20 wt% of CaO and 2-10 wt% of Al2O 3.
In one or more embodiments, the glass frit a and the glass frit B are prepared using the following method: the preparation method comprises the steps of uniformly mixing raw materials of the glass powder, smelting at 1200-1500 ℃, cooling, and performing ball milling to obtain the glass powder.
In one or more embodiments, the copper sulfide ruthenium oxide composite has a mass ratio of copper sulfide to ruthenium oxide of (1-3): 5.
in one or more embodiments, the copper sulfide ruthenium oxide composite is prepared using the following method: dispersing copper sulfide in a ruthenium trichloride aqueous solution, reacting for 8-12 h at 150-200 ℃, filtering, washing and drying to obtain the copper sulfide ruthenium oxide composite material.
In one or more embodiments, the conductive powder is a copper sulfide ruthenium oxide composite, or consists of a copper sulfide ruthenium oxide composite and ruthenium oxide.
In one or more embodiments, the chip resistor paste further includes an additive, and the additive is included in the chip resistor paste in an amount of 0.1wt% to 20wt% based on the total weight of the chip resistor paste.
In one or more embodiments, the additive includes niobium pentoxide and manganese oxide.
The invention also provides a chip resistor which is prepared by adopting the chip resistor paste in any embodiment of the invention.
The invention also provides a circuit board, which comprises the chip resistor in any embodiment of the invention.
Drawings
Fig. 1 is a sheet-type resistance print pattern used in the test example. In FIG. 1, 1 is a test pattern of 1 mm. times.1 mm.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, 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 belongs.
Herein, the sum of the percentages of all the components of the composition is equal to 100%.
Unless otherwise specified herein, "comprise," include, "" contain, "and the like, encompass the meanings of" consisting essentially of … … "and" consisting of … …, "i.e.," a comprises a "encompasses the meanings of" a comprises a and others, "" a consists essentially of "and" a consists of a. Herein, unless otherwise specified, "consisting essentially of … …" is understood to mean "consisting of … …% or more, preferably 90% or more, more preferably 95% or more".
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
The chip resistor slurry is a paste formed by rolling and mixing solid powder and an organic carrier, and is a base material for manufacturing chip resistors. The components of the chip resistor paste generally include a conductive phase, a glass binder phase, and an organic vehicle, and optionally or preferably may further include additives. The invention finds that the copper sulfide ruthenium oxide composite material can be used as a conductive phase of the medium-resistance segment sheet type resistance slurry to replace or partially replace ruthenium oxide, can effectively reduce the using amount of the conductive phase, simultaneously maintains the resistance performance basically unchanged, and saves the cost of using rare metal ruthenium.
Conducting phase
The conductive phase of the chip resistor paste comprises one or more conductive powders. The conductive powder is mainly used for regulating and controlling the resistance value of the chip resistor. The chip resistor paste of the present invention may include various conductive powders commonly used in chip resistor pastes, including, but not limited to, platinum group metal powders, powders of platinum group metal compounds (e.g., platinum group metal oxides, platinum group metal salts, etc.), and the like.
The content of the conductive powder in the chip resistor paste is 10wt% to 30wt%, for example, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 18wt%, 20wt%, 23wt%, 25wt%, based on the total mass of the chip resistor paste.
The chip resistor paste has high requirements on a conductive phase, and mainly requires that the conductive phase, glass powder and an inorganic additive can complete good chemical and physical changes at a sintering temperature of about 850 ℃, so that the resistor meets the requirements on resistance, positive temperature coefficient, negative temperature coefficient, electrostatic discharge and encapsulation change rate. The complex chemical and physical changes of the glass powder and the additive during high-temperature sintering at about 850 ℃ can cause the performance of the copper sulfide ruthenium oxide composite material to change. In the prior art, the application of copper sulfide or copper sulfide ruthenium oxide composite material as a conductive phase of sheet resistance paste does not exist. The invention unexpectedly finds that the copper sulfide ruthenium oxide composite material can be used as a conductive phase of the medium-resistance segment chip resistor slurry, can complete good chemical and physical changes with glass powder and inorganic additives at a sintering temperature of about 850 ℃, so that the resistor meets the requirements of resistance, positive temperature coefficient, negative temperature coefficient, electrostatic discharge and encapsulation change rate, the consumption of the conductive phase can be effectively reduced, and the cost of using rare metal ruthenium is saved.
The chip resistance paste is characterized in that the contained conductive powder comprises a copper sulfide ruthenium oxide composite material. The copper sulfide ruthenium oxide composite material can be prepared by a hydrothermal method. In some embodiments, the copper sulfide ruthenium oxide composite is prepared using the following method: dispersing copper sulfide in a ruthenium trichloride aqueous solution, reacting for 8-12 h at 150-200 ℃, filtering, washing and drying to obtain the copper sulfide ruthenium oxide composite material. Copper sulfide can be dispersed in a ruthenium trichloride aqueous solution by adding the copper sulfide into the ruthenium trichloride aqueous solution and stirring for 0.5-1 h. The concentration of the ruthenium trichloride aqueous solution can be 10-20 mg/ml. The washing may include water washing and alcohol washing. The drying can be carried out at 150-200 ℃ for 20-30 h. In the reaction process, ruthenium trichloride is converted into ruthenium oxide, so the mass ratio of copper sulfide to ruthenium oxide in the copper sulfide-ruthenium oxide composite material is determined by the feeding ratio of copper sulfide to ruthenium trichloride. The copper sulfide used for preparing the copper sulfide ruthenium oxide composite material can be prepared by adopting the following method: dissolving copper chloride in a solvent, adding thiourea, stirring for 0.5-1 h, reacting for 8-12 h at 150-200 ℃, filtering, washing and drying to obtain the copper sulfide. The copper chloride may be hydrated copper chloride. The solvent may be ethylene glycol. The amount of copper chloride used may be 20 to 100g, for example 20 to 30g, per 1000ml of solvent. The thiourea may be present in an amount of 1.5 times or more, for example, 1.5 to 2.5 times the mass of the copper chloride. The washing may include water washing and alcohol washing. The drying can be carried out at 150-200 ℃ for 20-30 h. The copper sulfide prepared by the method is nano copper sulfide.
In the present invention, the mass ratio of copper sulfide to ruthenium oxide in the copper sulfide-ruthenium oxide composite is preferably 1:5 to 3:5, and controlling the mass ratio of copper sulfide to ruthenium oxide within this range is advantageous for the copper sulfide-ruthenium oxide composite to exert the function of maintaining the sheet resistance as a conductive phase while effectively reducing the content of the conductive phase.
In some embodiments, the chip resistor paste of the present invention contains conductive powder including only copper sulfide ruthenium oxide composite. In these embodiments, the content of the conductive powder in the chip resistance paste of the present invention is preferably 10wt% to 20wt%, for example 12wt% to 16wt%, 13wt% to 15wt%, 14wt%, based on the total mass of the chip resistance paste. Compared with the method of using ruthenium oxide as the conductive powder, the method of using the copper sulfide ruthenium oxide composite material as the conductive powder can greatly reduce the content of the conductive powder.
In some embodiments, the conductive powder contained in the chip resistor paste of the present invention includes other conductive powders known to be used in chip resistor pastes, such as platinum group metal powders, powders of platinum group metal compounds (e.g., platinum group metal oxides, platinum group metal salts, etc.), and the like, in addition to the copper sulfide ruthenium oxide composite material. In these embodiments, the mass fraction of the copper sulfide ruthenium oxide composite material in the sheet resistor paste of the present invention in the conductive powder is preferably 50% or more, for example, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more, so as to effectively reduce the content of the conductive powder in the sheet resistor paste.
In some embodiments, the chip resistor paste of the present invention includes a conductive powder including a copper sulfide ruthenium oxide composite and ruthenium oxide. In these embodiments, in the sheet resistor paste of the present invention, the mass fraction of the sum of the copper sulfide ruthenium oxide composite material and the ruthenium oxide in the conductive powder is preferably 50% or more, for example, 60% or more, 70% or more, 80% or more, 90% or more, 95% or more, and 100% or more, and the ratio of the mass of the copper sulfide ruthenium oxide composite material to the mass of the ruthenium oxide is preferably not less than 1, for example, not less than 2, not less than 5, and not less than 10. For example, the conductive powder contained in the chip resistor paste of the present invention may be composed of a copper sulfide ruthenium oxide composite material and ruthenium oxide, wherein the mass ratio of the copper sulfide ruthenium oxide composite material to the ruthenium oxide may be greater than or equal to 1, greater than or equal to 2, greater than or equal to 5, or greater than or equal to 10.
The chip resistor paste is preferably a middle-resistance segment chip resistor paste. In the embodiment where the chip resistor paste is a middle-resistance chip resistor paste, the conductive powder contained in the chip resistor paste of the present invention is mainly a copper sulfide ruthenium oxide composite material or a copper sulfide ruthenium oxide composite material and ruthenium oxide, i.e., the mass fraction of the copper sulfide ruthenium oxide composite material in the conductive powder is more than 80%, such as more than 90%, more than 95%, or 100%, or the mass fraction of the sum of the copper sulfide ruthenium oxide composite material and ruthenium oxide in the conductive powder is more than 80%, such as more than 90%, more than 95%, or 100%.
In the present invention, the particle diameter of the conductive powder (e.g., ruthenium oxide, copper sulfide, ruthenium oxide composite) is preferably distributed between 1 to 2 μm.
Glass binder phase
The glass binder phase of the chip resistor paste includes one or more glass frits. The glass powder is generally prepared from raw materials of the glass powder by processes of melting, quenching, ball milling and the like, for example, the raw materials of the glass powder can be uniformly mixed, and the obtained mixture is placed in a melting furnace for melting to obtain glass liquid; quenching the molten glass, for example, water quenching, to obtain glass;and ball milling the glass into glass powder. The raw material of the glass powder in the sheet type resistance paste can comprise one or more selected from the following materials: PbO, Pb3O4、B2O3、CaO、SiO2、BaO、Al2O3、Na2O、K2O and ZnO. The temperature of the melting may be 1200 ℃ to 1500 ℃, for example 1350 ± 50 ℃.
Two or more kinds of glass frit may be used as the glass binder phase of the chip resistor paste. In some embodiments, the glass bonding phase in the chip resistor paste of the present invention comprises glass powder A and glass powder B, wherein the glass powder A is Pb-Si-Ca-Al-B-Zn bulk glass powder, and the glass powder B is Pb-Si-Ca-Al bulk glass powder. The mass ratio of glass frit a to glass frit B may be between 2:1 and 4:1, for example 3: 1. The glass powder A and the glass powder B have matched high and low softening points, the glass powder with the high softening point forms a framework to keep the shape during sintering, and the glass powder with the low softening point plays roles in infiltration and filling. The total mass of the glass powder a and the glass powder B may account for more than 80%, for example, more than 90%, more than 95%, 100% of the total mass of the glass binder phase in the sheet resistance paste.
In the present invention, the Pb-Si-Ca-Al-B-Zn glass powder is a glass powder containing positive valence elements mainly Pb, Si, Ca, Al, B and Zn. The total mass of Pb, Si, Ca, Al, B and Zn is usually 80% or more, for example, 90% or more, 95% or more, 98% or more, or 99% or more of the total mass of positive valence elements in the Pb-Si-Ca-Al-B-Zn glass powder. The Pb-Si-Ca-Al-B-Zn bulk glass powder may further contain a small amount of Na and/or K. Herein, containing Na and/or K means containing one or both of Na and K. In some embodiments, the raw material of the glass frit A used in the present invention comprises 25wt% to 35wt% of PbO, 20wt% to 40wt% of SiO210 to 25 weight percent of CaO, 5 to 10 weight percent of Al2O35 to 10 weight percent of B2O31.5 to 2.5 weight percent of ZnO and 0.2 to 0.5 weight percent of Na2O and/or K2O, for example, the raw material of the glass frit A may include 35wt% of PbO, 30wt% of SiO220wt% of CaO, 5wt% of Al2O37wt% of B2O32.5% by weight of ZnO and0.5wt% of Na2And O. Herein, including Na2O and/or K2O means including Na2O and K2One or both of O. Na (Na)2O and/or K2The mass fraction of O is defined as when only Na is included2O or K2When it is O, Na2O or K2The mass fraction of O, or when Na is included2O and K2O，Na2O and K2Total mass fraction of O.
In the present invention, the Pb-Si-Ca-Al system glass powder means a glass powder containing positive valence elements mainly of Pb, Si, Ca and Al. The total mass of Pb, Si, Ca and Al is usually 80% or more, for example, 90% or more, 95% or more, 98% or more, 99% or more and 100% or more of the total mass of positive valence elements in the Pb-Si-Ca-Al-B-Zn bulk glass powder. In some embodiments, the raw material of the glass frit B used in the present invention comprises 30wt% to 50wt% of PbO, 20wt% to 40wt% of SiO210 to 20 weight percent of CaO and 2 to 10 weight percent of Al2O3For example, the raw material of the glass frit B may include 50wt% of PbO, 30wt% of SiO216wt% CaO and 4wt% Al2O3。
In the present invention, the particle size of the glass frit (e.g., glass frit A and glass frit B) is preferably distributed between 1 to 2 μm.
The content of the glass binder phase in the chip resistor paste of the present invention is 30wt% to 50wt%, for example, 35wt%, 36wt%, 40wt%, 45wt%, based on the total mass of the chip resistor paste.
Organic vehicle
The organic vehicle in the chip resistor paste generally includes a resin, a solvent, and an organic additive.
The resin is used to make the chip resistor paste have a certain viscosity. The amount of resin used is generally from 8wt% to 20wt%, for example 9wt%, 9.25wt%, 9.5wt%, 10wt%, 15wt% of the total weight of the organic vehicle. The resin suitable for the present invention may be one or more selected from cellulose and thermosetting resins. Examples of thermosetting resins include epoxy thermosetting resins. The cellulose may be a modified cellulose. Examples of the modified cellulose include polyanionic cellulose. In some embodiments, the resin used in the present invention comprises a polyanionic cellulose and an epoxy thermoset resin in a mass ratio of 1:1 to 2:1, for example 1:1 to 3:2, 5:4 to 5.5:4, 5.25: 4. The total mass of the polyanionic cellulose and the epoxy thermosetting resin may account for more than 80%, for example more than 90%, more than 95%, 100% of the total mass of the resin.
The solvent is generally a relatively viscous liquid organic substance, and the molecule of the solvent generally contains polar groups, so that the solvent can dissolve the resin, and generally has a high boiling point and is not easy to volatilize at normal temperature. The amount of solvent used is generally from 80wt% to 90wt%, e.g., 85wt%, 88wt%, 89wt%, 89.05wt%, 89.1wt%, 89.5wt%, based on the total weight of the organic vehicle. The solvent suitable for the present invention may be one or more selected from the group consisting of ester solvents, alcohol solvents and ether solvents. Examples of the alcohol solvent include terpineol. In some embodiments, the solvent used in the present invention comprises terpineol. The terpineol may be present in an amount of 80% by weight or more, for example 90% by weight or more, 95% by weight or more, 100% by weight or more, based on the total weight of the solvent.
Organic additives such as a dispersant, a defoaming agent, a lubricant, and a thixotropic agent may be added to the organic vehicle as needed. The total amount of organic additives used is generally not more than 5% by weight of the total weight of the organic vehicle. When included, the total amount of organic additives is preferably from 1wt% to 5wt%, e.g., 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 2wt%, 2.5wt%, based on the total weight of the organic vehicle. In some embodiments, the organic additive used in the present invention comprises lecithin, polyethylene wax and lauric acid, and the mass ratio of the lecithin to the polyethylene wax to the lauric acid may be 1 (0.5-1) to (0.5-1), for example 0.7:0.5: 0.5. Lecithin acts as a dispersing agent. The polyethylene wax acts as a thixotropic agent. Lauric acid acts as a lubricant. The total mass of lecithin, polyethylene wax and lauric acid may be more than 80%, for example more than 90%, more than 95%, 100% of the total mass of the organic additive.
In some embodiments, the organic vehicle in the sheet resistor paste of the present invention comprises 80wt% to 90wt% of a solvent, 8wt% to 15wt% of a resin, and 1wt% to 5wt% of an organic additive, based on the total weight of the organic vehicle, wherein the solvent comprises terpineol, the resin comprises polyanionic cellulose and epoxy thermosetting resin, and the organic additive comprises lecithin, polyethylene wax, and lauric acid.
The organic vehicle can be prepared by uniformly mixing the components of the organic vehicle, and if necessary, heating (for example, heating to 65-75 ℃ for mixing) can be performed during mixing. In some embodiments, the organic vehicle is prepared by first mixing a portion of the organic additive (e.g., lecithin), a portion of the resin (e.g., polyanionic cellulose), and a portion of the organic solvent (e.g., a portion of terpineol) to form a mixture; the resulting mixture is then mixed uniformly with the remaining resin (e.g., epoxy thermoset resin), the remaining additives (e.g., polyethylene wax, lauric acid), and the remaining solvent (e.g., the remaining terpineol) to obtain the organic vehicle.
The organic vehicle is contained in the chip resistor paste of the present invention in an amount of 20wt% to 50wt%, for example, 30wt%, 35wt%, 40wt%, 45wt%, 47wt%, 48wt%, 49wt%, based on the total mass of the chip resistor paste.
Additive agent
The chip resistance paste of the present invention may contain additives commonly used in the art for chip resistance pastes. The additives in the chip resistance paste refer to materials for adjusting resistance properties other than the conductive phase and the glass binder phase, including materials for controlling resistance, temperature coefficient, pattern retention, adjusting sintering characteristics, improving temperature sensitivity, enhancing weather resistance, and the like. Unlike the organic additives in the organic vehicle, the additives are typically inorganic and may be, for example, one or more selected from elemental metals, metal oxides, non-metal oxides, metal nitrides, metal fluorides, and silicates.
When additives are contained, the total content of the additives in the chip resistance paste of the present invention may be 0.1wt% to 2wt%, for example, 0.2wt%, 0.5wt%, 0.8wt%, 1wt%, 1.2wt%, 1.5wt%, based on the total mass of the chip resistance paste.
Additives suitable for use in the thick film resistor paste of the present invention may include those selected from the group consisting of elemental copper, copper-containing compounds, elemental manganese, manganese-containing compounds, elemental tantalum, tantalum-containing compounds, niobium pentoxide (Nb)2O5) And antimony trioxide (Sb)2O3) One or more ofAnd (4) seed preparation. In some embodiments, the additives in the chip resistor paste of the present invention include manganese oxide and niobium pentoxide. The content of manganese oxide in the sheet resistance paste of the present invention may be 0.05wt% to 1wt%, for example, 0.1wt%, 0.2wt%, 0.5wt%, based on the total mass of the sheet resistance paste.
In some embodiments, the additives in the chip resistor paste of the present invention include manganese oxide and niobium pentoxide. The total mass of manganese oxide and niobium pentoxide may be more than 80%, for example more than 90%, more than 95%, 100% of the total mass of the additive.
Chip resistor paste, chip resistor and circuit board
The chip resistor paste can be prepared by the following method: uniformly mixing the conductive powder, the glass powder, the organic carrier and the additive, and rolling by using a three-roll mill to obtain the slurry. Preferably, the conductive powder, the glass frit, the organic vehicle and the additive are uniformly mixed and then left for a period of time (for example, more than 1 hour) to complete the impregnation. Preferably, the roller is rolled to the fineness of less than or equal to 5 mu m. The composition and content of the components in the sheet resistance paste may be as described in any of the embodiments herein.
The chip resistance paste provided by the invention contains the copper sulfide ruthenium oxide composite material as the conductive phase, so that the dosage of the conductive phase can be effectively reduced on the premise of keeping the performance basically unchanged, and the cost of the chip resistance paste is remarkably reduced.
In some embodiments, the chip resistor paste of the present invention comprises or consists of 10wt% to 30wt% of a conductive powder, 30wt% to 50wt% of a glass frit, 20wt% to 50wt% of an organic vehicle, and optionally 0.1wt% to 2wt% of an additive, wherein the conductive powder comprises a copper sulfide ruthenium oxide composite, the glass frit preferably comprises glass frit a and glass frit B described herein, and the additive preferably comprises manganese oxide and niobium pentoxide.
The invention comprises a chip resistor prepared from the chip resistor paste. In the invention, the sheet film resistor can be prepared by screen printing, leveling, drying and sintering the sheet resistor paste. The drying temperature may be 150 + -10 deg.C. The drying time may be 10 to 11 min. The peak temperature of sintering may be 850 + -20 deg.C, such as 850 + -10 deg.C, 850 + -5 deg.C, 850 + -1 deg.C. The duration at peak temperature may be 10 ± 0.5 min. The temperature rise time can be 20-25 min. The cooling time can be 30-35 min. The apparatus for sintering may be a mesh belt sintering furnace.
The chip resistor prepared by the chip resistor paste has the following temperature coefficient performance, electrostatic discharge resistance and encapsulation change rate which meet the requirements: absolute values of a positive temperature coefficient of 25 ℃ to 125 ℃ and a negative temperature coefficient of 25 ℃ to-55 ℃ are less than 100 ppm/DEG C, and a static discharge coefficient and an encapsulation change rate are within +/-5%.
The invention includes a circuit board comprising the chip resistor of the invention. The circuit board comprises a substrate and a chip resistor formed on the substrate. The chip resistor is formed by sintering the chip resistor slurry.
The present invention is described in detail below with reference to specific examples, which do not limit the scope of the present invention. The scope of the present invention is defined only by the appended claims, and any omissions, substitutions, and changes in the form of the embodiments disclosed herein that may be made by those skilled in the art are intended to be included within the scope of the present invention.
The following examples use instrumentation conventional in the art. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. In the following examples, various starting materials were used, unless otherwise specified, in conventional commercial products, the specifications of which are those commonly used in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
Preparation example 1: preparation of copper sulfide ruthenium oxide composite material
(1) Dissolving 25g of hydrated copper chloride in 1000ml of ethylene glycol, adding 45g of thiourea, stirring for 0.8h, carrying out hydrothermal reaction for 10h at 160 ℃, carrying out suction filtration, water washing, alcohol washing, and drying for 24h at 180 ℃ to obtain a copper sulfide nano material;
(2) and (2) adding the copper sulfide nano material prepared in the step (1) into a ruthenium trichloride aqueous solution with the concentration of 15mg/ml, stirring for 0.8h, carrying out hydrothermal reaction for 10h at 170 ℃, carrying out suction filtration, washing with water, washing with alcohol, and drying for 24h at 180 ℃ to obtain the copper sulfide ruthenium oxide composite material.
Three copper sulfide ruthenium oxide composite materials with the mass ratios of copper sulfide to ruthenium oxide of 1:5, 2: 5 and 3:5 are prepared by adjusting the ratio of copper sulfide to ruthenium trichloride in the step (2), and the composite materials are crushed and sieved to ensure that the particle size is distributed at 1-2 mu m and are used as the conductive phase of the slurry in the embodiment.
Preparation example 2: preparation of glass powder A
The glass powder A comprises the following raw materials in percentage by mass: 35% PbO, 30% SiO2、20%CaO、5%Al2O3、7%B2O3、0.5%Na2O and 2.5% ZnO. Uniformly mixing the raw materials of the glass powder A, smelting at 1350 ℃, performing water cooling, performing ball milling, and sieving to ensure that the particle size is intensively distributed in 1-2 mu m.
Preparation example 3: preparation of glass frit B
The glass powder B comprises the following raw materials in percentage by mass: 50% PbO, 30% SiO216% CaO and 4% Al2O3. And uniformly mixing the raw materials of the glass powder B, smelting at 1350 ℃, cooling by water, performing ball milling, and sieving to intensively distribute the particle size of the glass powder B to 1-2 mu m.
Preparation example 4: preparation of organic vehicle
The organic vehicle used in the examples and comparative examples was prepared using the following formulation and procedure:
(1) mixing 83 parts by weight of terpineol, 15 parts by weight of polyanionic cellulose and 2 parts by weight of lecithin, heating to 70 ℃ in a water bath, continuously stirring until the mixture is completely dissolved and presents a uniform state, stopping heating, cooling at room temperature for 24 hours, and storing for use;
(2) uniformly mixing 35 parts by weight of the mixture prepared in the step (1), 60 parts by weight of terpineol, 4 parts by weight of epoxy thermosetting resin, 0.5 part by weight of polyethylene wax and 0.5 part by weight of lauric acid to obtain the organic carrier.
Example 1
(1) Taking 14g of copper sulfide ruthenium oxide composite material (the mass ratio of copper sulfide to ruthenium oxide is 1: 5), 36g of glass powder (the mass ratio of glass powder A to glass powder B is 3: 1), 0.1g of manganese oxide and 0.9g of niobium pentoxide;
(2) adding 49g of organic carrier into the powder obtained in the step (1), uniformly stirring by using a glass rod, and standing for more than 1h to complete infiltration;
(3) rolling with a three-roll mill to make the fineness less than or equal to 5 μm to obtain slurry.
And (3) screen printing is carried out on the slurry, leveling is carried out, drying is carried out for 10min at 150 ℃, and sintering is carried out by adopting mesh belt type sintering according to a resistance sintering curve with the peak temperature of 850 ℃ and the duration of 10min, the temperature rise time of 25min and the temperature drop time of 35min, so as to obtain the chip resistor.
Example 2
(1) Taking 14g of copper sulfide ruthenium oxide composite material (the mass ratio of copper sulfide to ruthenium oxide is 2: 5), 36g of glass powder (the mass ratio of the glass powder A to the glass powder B is 3: 1), 0.1g of manganese oxide and 0.9g of niobium pentoxide;
(2) adding 49g of organic carrier into the powder obtained in the step (1), uniformly stirring by using a glass rod, and standing for more than 1h to complete infiltration;
(3) rolling with a three-roll mill to make the fineness less than or equal to 5 μm to obtain slurry.
And (3) screen printing is carried out on the slurry, leveling is carried out, drying is carried out for 10min at 150 ℃, and sintering is carried out by adopting mesh belt type sintering according to a resistance sintering curve with the peak temperature of 850 ℃ and the duration of 10min, the temperature rise time of 25min and the temperature drop time of 35min, so as to obtain the chip resistor.
Example 3
(1) Taking 14g of copper sulfide ruthenium oxide composite material (the mass ratio of copper sulfide to ruthenium oxide is 3: 5), 36g of glass powder (the mass ratio of the glass powder A to the glass powder B is 3: 1), 0.1g of manganese oxide and 0.9g of niobium pentoxide;
(2) adding 49g of organic carrier into the powder obtained in the step (1), uniformly stirring by using a glass rod, and standing for more than 1h to complete infiltration;
(3) rolling with a three-roll mill to make the fineness less than or equal to 5 μm to obtain slurry.
And (3) screen printing is carried out on the slurry, leveling is carried out, drying is carried out for 10min at 150 ℃, and sintering is carried out by adopting mesh belt type sintering according to a resistance sintering curve with the peak temperature of 850 ℃ and the duration of 10min, the temperature rise time of 25min and the temperature drop time of 35min, so as to obtain the chip resistor.
Example 4
(1) Taking 13g of copper sulfide ruthenium oxide composite material (the mass ratio of copper sulfide to ruthenium oxide is 1: 5), 36g of glass powder (the mass ratio of glass powder A to glass powder B is 3: 1), 0.1g of manganese oxide and 0.9g of niobium pentoxide;
(2) adding 50g of organic carrier into the powder obtained in the step (1), uniformly stirring by using a glass rod, and standing for more than 1h to complete infiltration;
(3) rolling with a three-roll mill to make the fineness less than or equal to 5 μm to obtain slurry.
And (3) screen printing is carried out on the slurry, leveling is carried out, drying is carried out for 10min at 150 ℃, and sintering is carried out by adopting mesh belt type sintering according to a resistance sintering curve with the peak temperature of 850 ℃ and the duration of 10min, the temperature rise time of 25min and the temperature drop time of 35min, so as to obtain the chip resistor.
Example 5
(1) Taking 15g of copper sulfide ruthenium oxide composite material (the mass ratio of copper sulfide to ruthenium oxide is 3: 5), 36g of glass powder (the mass ratio of the glass powder A to the glass powder B is 3: 1), 0.1g of manganese oxide and 0.9g of niobium pentoxide;
(2) adding 48g of organic carrier into the powder obtained in the step (1), uniformly stirring by using a glass rod, and standing for more than 1h to complete infiltration;
(3) rolling with a three-roll mill to make the fineness less than or equal to 5 μm to obtain slurry.
And (3) screen printing is carried out on the slurry, leveling is carried out, drying is carried out for 10min at 150 ℃, and sintering is carried out by adopting mesh belt type sintering according to a resistance sintering curve with the peak temperature of 850 ℃ and the duration of 10min, the temperature rise time of 25min and the temperature drop time of 35min, so as to obtain the chip resistor.
Comparative example 1
(1) 23g of ruthenium oxide (with the particle size of 1-2 mu m), 36g of glass powder, 0.1g of manganese oxide and 0.9g of niobium pentoxide are taken;
(2) adding 40g of organic carrier into the powder obtained in the step (1), uniformly stirring by using a glass rod, and standing for more than 1h to complete infiltration;
(3) rolling with a three-roll mill to make the fineness less than or equal to 5 μm to obtain slurry.
And (3) screen printing is carried out on the slurry, leveling is carried out, drying is carried out for 10min at 150 ℃, and sintering is carried out by adopting mesh belt type sintering according to a resistance sintering curve with the peak temperature of 850 ℃ and the duration of 10min, the temperature rise time of 25min and the temperature drop time of 35min, so as to obtain the chip resistor.
The slurry formulations of examples 1-5 and comparative example 1 are shown in table 1.
Table 1: slurry formulations of examples 1 to 5 and comparative example 1 (unit: parts by weight)
Test example
The sheet resistors of examples 1 to 5 and comparative example 1 were subjected to film thickness, resistance, electrostatic discharge (ESD), Temperature Coefficient (TCR), and envelope variation rate tests, and three samples were measured for each group, and the test pattern was the 1mm × 1mm pattern shown in fig. 1, and the specific test method was as follows, and the test results are shown in table 2.
1. Resistance (R) test method: selecting a resistance meter with a proper measuring range, and respectively lapping two test meter pens on electrodes at two ends of the measured resistance to record numerical values and units.
2. Positive temperature coefficient (HTCR) test method: setting the temperature of the test equipment to 25 ℃, and measuring the resistance value to beR1And recording. Setting the temperature of the test equipment to 125 ℃, and measuring the resistance value to beR2And recording. Positive temperature coefficient X(HTCR)The calculation formula is as follows:
3. negative temperature coefficient(CTCR) test method: setting the temperature of the test equipment to 25 ℃, and measuring the resistance value to beR3And recording. Setting the temperature of the test equipment to-55 ℃, and measuring the resistance value to beR4And recording. Negative temperature coefficient X(CTCR)The calculation formula is as follows:
4. electrostatic discharge (ESD) test method: according to the resistance (R) test method, the resistance is determined to beR5And recording. Adopting an electrostatic discharge device, setting parameters: the voltage is 3kV, the time is 1s, the times are 5, the electrodes at two ends of the resistor are checked to be in good contact with the equipment, the operation is started, the sample wafer is placed for 20-30 min after the experiment is finished, and the resistance value is measured according to the resistance value (R) testing methodR6And recording. Electrostatic discharge coefficient X(ESD)The calculation formula is as follows:
5. encapsulation change rate test method: according to the resistance (R) test method, the resistance is determined to beR7，And recorded. Printing an encapsulation slurry on the upper layer of the resistor (the dielectric slurry is I-5311 by Xian Hongxing electronic slurry science and technology Co., Ltd., and the specific use method and sintering parameters are described in the product description), drying the sintered sample wafer, and measuring the resistance value according to the resistance value (R) test methodR8And recording. Envelope rate of change X(envelope)The calculation formula is as follows:
table 2: performance test data
As can be seen from table 2, the copper sulfide ruthenium oxide composite material is used to replace ruthenium oxide, so that the content of the conductive phase can be significantly reduced, and the film thickness, the resistance value, the positive temperature coefficient, the negative temperature coefficient, the electrostatic discharge and the encapsulation change rate have no significant change, and meet the requirements. The use amount of the ruthenium oxide is greatly reduced, so that the cost of the slurry is greatly reduced, and considerable profits are created for enterprises.
Claims (10)
1. The chip resistor paste is characterized by comprising conductive powder, glass powder and an organic carrier, wherein the conductive powder comprises a copper sulfide ruthenium oxide composite material, and the chip resistor paste contains 10wt% -30 wt% of the conductive powder, 30wt% -50 wt% of the glass powder and 20wt% -50 wt% of the organic carrier, based on the total weight of the chip resistor paste.
2. The chip resistance paste according to claim 1, wherein the glass powder comprises the following components in a mass ratio of (2-4): 1, wherein the raw materials of the glass powder A comprise 25-35 wt% of PbO and 20-40 wt% of SiO210 to 25 weight percent of CaO, 5 to 10 weight percent of Al2O35 to 10 weight percent of B2O31.5 to 2.5 weight percent of ZnO and 0.2 to 0.5 weight percent of Na2O and/or K2O, the raw materials of the glass powder B comprise 30 to 50 weight percent of PbO and 20 to 40 weight percent of SiO210 to 20 weight percent of CaO and 2 to 10 weight percent of Al2O3。
3. The chip resistor paste according to claim 2, wherein the glass frit A and the glass frit B are prepared by the following method: the preparation method comprises the steps of uniformly mixing raw materials of the glass powder, smelting at 1200-1500 ℃, cooling, and performing ball milling to obtain the glass powder.
4. The chip resistance paste according to claim 1, wherein the copper sulfide ruthenium oxide composite material has a mass ratio of copper sulfide to ruthenium oxide of (1-3): 5.
5. the chip resistor paste of claim 1 wherein the copper sulfide ruthenium oxide composite is prepared by: dispersing copper sulfide in a ruthenium trichloride aqueous solution, reacting for 8-12 h at 150-200 ℃, filtering, washing and drying to obtain the copper sulfide ruthenium oxide composite material.
6. The chip resistor paste as claimed in claim 1, wherein the conductive powder is a copper sulfide ruthenium oxide composite material, or is composed of a copper sulfide ruthenium oxide composite material and ruthenium oxide.
7. The chip resistor paste according to claim 1, wherein the chip resistor paste further comprises an additive, and the additive is contained in the chip resistor paste in an amount of 0.1wt% to 20wt% based on the total weight of the chip resistor paste.
8. The chip resistor paste as claimed in claim 7, wherein the additives include niobium pentoxide and manganese oxide.
9. A chip resistor, characterized in that the chip resistor is prepared by using the chip resistor paste as claimed in any one of claims 1-8.
10. A circuit board comprising the chip resistor of claim 9.
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