CN111916248A - Thick-film resistor paste with electrostatic discharge resistance and low encapsulation change rate - Google Patents

Thick-film resistor paste with electrostatic discharge resistance and low encapsulation change rate Download PDF

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CN111916248A
CN111916248A CN202010795432.1A CN202010795432A CN111916248A CN 111916248 A CN111916248 A CN 111916248A CN 202010795432 A CN202010795432 A CN 202010795432A CN 111916248 A CN111916248 A CN 111916248A
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film resistor
raw material
thick
glass frit
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CN111916248B (en
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兰金鹏
陆冬梅
鹿宁
王要东
周宝荣
王妮
赵科良
马倩
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Xian Hongxing Electronic Paste Technology Co Ltd
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Xian Hongxing Electronic Paste Technology Co Ltd
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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
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • 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
    • H01B1/18—Conductive material dispersed in non-conductive inorganic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • 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
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • 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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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electromagnetism (AREA)
  • Glass Compositions (AREA)
  • Non-Adjustable Resistors (AREA)

Abstract

The invention discloses thick film resistor paste and a thick film resistor prepared from the thick film resistor paste. According to the invention, a proper amount of graphite alkyne is added into thick film resistor paste in the form of a paste additive or a proper amount of graphite alkyne is introduced in the form of a glass powder additive. The thick film resistor paste can be used for preparing a thick film resistor with stable resistance temperature change, electrostatic discharge resistance and/or small encapsulation change rate.

Description

Thick-film resistor paste with electrostatic discharge resistance and low encapsulation change rate
Technical Field
The invention belongs to the field of thick film resistor paste, and particularly relates to thick film resistor paste with electrostatic discharge resistance and low encapsulation change rate.
Background
With the wide application of electronic products, the light and small thinning become the mainstream development trend, the requirements on the performance of integrated circuits are higher and higher, and the resistance is used as an important functional component and plays a decisive role in the stable operation of the whole circuit. The current resistance paste can not meet the development requirement, so that the development of a new product with stable temperature change, electrostatic discharge resistance and small encapsulation change rate becomes a research hotspot.
The thick film resistor paste consists of a conductive phase, a glass phase, an additive and an organic vehicle. After high-temperature sintering, the organic phase is volatilized and decomposed, and finally the remaining glass powder, the conductive phase and the additive determine the final performance of the product.
After the thick film resistor paste is sintered, a glass layer exists between partial conductive phase particles, and the glass layer can break through the conductive phase particles when electrostatic discharge occurs, so that the resistance value is shifted. When the encapsulation glass slurry is sintered, the encapsulation glass slurry can penetrate into the resistor to cause resistance drift, so that the encapsulation change rate of the product is unqualified.
Disclosure of Invention
In order to solve the above problems of the thick film resistor paste, the present invention provides a thick film resistor paste, which comprises a proper amount of graphite alkyne or glass powder of which the raw material comprises a proper amount of graphite alkyne, and the thick film resistor with stable resistance temperature change, electrostatic discharge resistance and/or small encapsulation change rate can be prepared from the thick film resistor paste.
Specifically, the invention provides a thick film resistor paste which comprises a conductive phase, glass powder, graphite alkyne, an additive and an organic carrier.
In one or more embodiments, the particle size of the graphdine is less than 1 μm.
In one or more embodiments, the graphitic alkyne is present in the thick film resistor paste in an amount of 0.1 to 1 wt%, preferably 0.2 to 0.5 wt%, based on the total mass of the thick film resistor paste.
In one or more embodiments, the thick film resistor paste includes, based on the total mass of the thick film resistor paste, 15 to 20 wt% of the conductive phase, 45 to 55 wt% of the glass frit, 0.5 to 10 wt% of the additive, and 25 to 35 wt% of the organic vehicle.
In one or more embodiments, the raw materials of the glass frit include: PbO, SiO2CaO and Al2O, and optionally a compound selected from the group consisting of graphdiyne, B2O3、Na2O and/or K2One or more or all of O, and ZnO.
In one or more embodiments, the content of PbO in the glass frit raw material is 30 to 55 wt%, and SiO is220-40 wt%, CaO 10-25 wt%, Al2O3The content of (B) is 2-10 wt%.
In one or more embodiments, when present, the glass frit material has a graphdine content of 0.4 to 5 wt%, based on the total mass of the glass frit material, and B2O3Is 5-10 wt% of Na2O and K2The total content of O is 0.2-1 wt%, and the content of ZnO is 1-5 wt%.
In one or more embodiments, the glass frit comprises glass frit I and glass frit II, wherein the raw materials of the glass frit I comprise: PbO, SiO2、CaO、Al2O3、B2O3、Na2O and/or K2O, ZnO and optional graphdine, the glass powder II comprises the following raw materials: PbO, SiO2、CaO、Al2O3And optionally a graphdine.
In one or more embodiments, the glass frit I raw material has a PbO content of 33 to 38 wt% and SiO in the total mass of the glass frit I raw material227-32 wt%, CaO 18-22 wt%, Al2O3In an amount of 3-6 wt%, B2O3Is 5-10 wt% of Na2O and K2The total content of O is 0.2-1 wt%, and the content of ZnO is 1-5 wt%; preferably, when included, as describedThe content of the graphdine in the glass powder I raw material is 0.5-2 wt% based on the total mass of the glass powder I raw material.
In one or more embodiments, the glass frit II raw material has a PbO content of 45 to 55 wt% and SiO in the glass frit II raw material based on the total mass of the glass frit II raw material2The content of (A) is 25-35 wt%, the content of CaO is 14-20 wt%, and Al is2O3The content of (B) is 3-6 wt%; preferably, when present, the glass frit II raw material has a graphdine content of 1 to 5 wt% based on the total mass of the glass frit II raw material.
In one or more embodiments, the thick film resistor paste has a mass ratio of glass frit I to glass frit II of 1: 1 to 3: 1.
in one or more embodiments, the conductive phase comprises ruthenium oxide and ruthenate; preferably, in the thick-film resistor paste, the mass ratio of the ruthenium oxide to the ruthenate is 1: 3 to 1: 5; preferably, the ruthenium oxide is RuO2(ii) a Preferably, the ruthenate is Pb2Ru2O6。
In one or more embodiments, the organic vehicle includes an organic solvent, a thickener, and optionally a modifier; preferably, the content of the organic solvent in the organic carrier is 75-95 wt% and the content of the thickening agent is 5-20 wt% based on the total mass of the organic carrier; preferably, when present, the modifier is present in the organic vehicle in an amount of from 0 to 2.5 weight percent, based on the total mass of the organic vehicle; preferably, the organic solvent is terpineol; preferably, the thickener comprises cellulose and a resin.
In one or more embodiments, the additive is selected from one or more of manganese oxide, copper oxide, niobium oxide, antimony oxide, and silicates; preferably, the additives include oxides of manganese and silicates; preferably, the content of the manganese oxide in the thick-film resistor paste is 0.2-1 wt% based on the total mass of the thick-film resistor paste; preferably, the silicate content in the thick film resistor paste is 2-8 wt% based on the total mass of the thick film resistor paste; preferably, the manganese oxide is MnO2(ii) a Preference is given toThe silicate is ZrSiO4。
The invention also provides another thick-film resistor paste, which comprises a conductive phase, glass powder, an additive and an organic carrier, wherein the glass powder comprises the following raw materials: PbO, SiO2、CaO、Al2O3And a graphoyne, and optionally B2O3、Na2O and/or K2O, and ZnO.
In one or more embodiments, the particle size of the graphdine is less than 1 μm.
In one or more embodiments, the graphdine content of the glass frit raw material is 0.4 to 5 wt% based on the total mass of the glass frit raw material.
In one or more embodiments, the content of PbO in the glass frit raw material is 30 to 55 wt% and SiO is present in the glass frit raw material based on the total mass of the glass frit raw material220-40 wt%, CaO 10-25 wt%, Al2O3The content of (B) is 2-10 wt%.
In one or more embodiments, when present, B in the glass frit raw material is based on the total mass of the glass frit raw material2O3Is 5-10 wt% of Na2O and K2The total content of O is 0.2-1 wt%, and the content of ZnO is 1-5 wt%.
In one or more embodiments, the thick film resistor paste includes, based on the total mass of the thick film resistor paste, 15 to 20 wt% of the conductive phase, 45 to 55 wt% of the glass frit, 0.5 to 10 wt% of the additive, and 25 to 35 wt% of the organic vehicle.
In one or more embodiments, the glass frit comprises glass frit I and glass frit II, wherein the raw materials of the glass frit I comprise: PbO, SiO2、CaO、Al2O3、B2O3、Na2O and/or K2O, ZnO and optional graphdine, the glass powder II comprises the following raw materials: PbO, SiO2、CaO、Al2O3And optionally a graphdine.
In one or more embodiments, the starting material for at least one of the glass frits I and II includes graphdiyne.
In one or more embodiments, the starting material for one and only one of the glass frits I and II includes graphdiyne.
In one or more embodiments, the raw materials for glass frit I include graphyne and the raw materials for glass frit II do not include graphyne.
In one or more embodiments, the raw materials for glass frit II include graphyne and the raw materials for glass frit I do not include graphyne.
In one or more embodiments, the glass frit I raw material has a PbO content of 33 to 38 wt% and SiO in the total mass of the glass frit I raw material227-32 wt%, CaO 18-22 wt%, Al2O3In an amount of 3-6 wt%, B2O3Is 5-10 wt% of Na2O and K2The total content of O is 0.2-1 wt%, and the content of ZnO is 1-5 wt%; preferably, when present, the raw glass frit I has a graphdine content of 0.5 to 2 wt% based on the total mass of the raw glass frit I.
In one or more embodiments, the glass frit II raw material has a PbO content of 45 to 55 wt% and SiO in the glass frit II raw material based on the total mass of the glass frit II raw material2The content of (A) is 25-35 wt%, the content of CaO is 14-20 wt%, and Al is2O3The content of (B) is 3-6 wt%; preferably, when present, the glass frit II raw material has a graphdine content of 1 to 5 wt% based on the total mass of the glass frit II raw material.
In one or more embodiments, the thick film resistor paste has a mass ratio of glass frit I to glass frit II of 1: 1 to 3: 1.
in one or more embodiments, the conductive phase comprises ruthenium oxide and ruthenate; preferably, in the thick-film resistor paste, the mass ratio of the ruthenium oxide to the ruthenate is 1: 3 to 1: 5; preferably, the ruthenium oxide is RuO2(ii) a Preferably, the ruthenate is Pb2Ru2O6。
In one or more embodiments, the organic vehicle includes an organic solvent, a thickener, and optionally a modifier; preferably, the content of the organic solvent in the organic carrier is 75-95 wt% and the content of the thickening agent is 5-20 wt% based on the total mass of the organic carrier; preferably, when present, the modifier is present in the organic vehicle in an amount of from 0 to 2.5 weight percent, based on the total mass of the organic vehicle; preferably, the organic solvent is terpineol; preferably, the thickener comprises cellulose and a resin.
In one or more embodiments, the additive is selected from one or more of manganese oxide, copper oxide, niobium oxide, antimony oxide, and silicates; preferably, the additives include oxides of manganese and silicates; preferably, the content of the manganese oxide in the thick-film resistor paste is 0.2-1 wt% based on the total mass of the thick-film resistor paste; preferably, the silicate content in the thick film resistor paste is 2-8 wt% based on the total mass of the thick film resistor paste; preferably, the manganese oxide is MnO2(ii) a Preferably, the silicate is ZrSiO4。
The invention also provides a thick film resistor prepared from the thick film resistor paste according to any one of the embodiments herein.
The invention also provides glass powder, which comprises the following raw materials: PbO, SiO2、CaO、Al2O3And a graphoyne, and optionally B2O3、Na2O and/or K2O, and ZnO.
In one or more embodiments, the particle size of the graphdine is less than 1 μm.
In one or more embodiments, the graphdine content of the glass frit raw material is 0.4 to 5 wt% based on the total mass of the glass frit raw material.
In one or more embodiments, the content of PbO in the glass frit raw material is 30 to 55 wt% and SiO is present in the glass frit raw material based on the total mass of the glass frit raw material2Of 20-40 wt%, CaO10-25 wt% of Al2O3The content of (B) is 2-10 wt%.
In one or more embodiments, when present, B in the glass frit raw material is based on the total mass of the glass frit raw material2O3Is 5-10 wt% of Na2O and K2The total content of O is 0.2-1 wt%, and the content of ZnO is 1-5 wt%.
In one or more embodiments, the raw materials of the glass frit include: PbO, SiO2、CaO、Al2O3、B2O3、Na2O and/or K2O, ZnO and graphyne; preferably, the content of PbO in the glass powder raw material is 33-38 wt% and SiO is calculated by the total mass of the glass powder raw material227-32 wt%, CaO 18-22 wt%, Al2O3In an amount of 3-6 wt%, B2O3Is 5-10 wt% of Na2O and K2The total content of O is 0.2-1 wt%, and the content of ZnO is 1-5 wt%; preferably, the content of the graphdine in the glass frit raw material is 0.5-2 wt% based on the total mass of the glass frit raw material.
In one or more embodiments, the raw materials of the glass frit include: PbO, SiO2、CaO、Al2O3And a graphdiyne; preferably, the content of PbO in the glass powder raw material is 45-55 wt% and SiO is calculated by the total mass of the glass powder raw material2The content of (A) is 25-35 wt%, the content of CaO is 14-20 wt%, Al2O3The content of (B) is 3-6 wt%; preferably, the content of the graphdine in the glass frit raw material is 1-5 wt% based on the total mass of the glass frit raw material.
The invention also provides the use of a graphdine, a thick film resistor paste according to any of the embodiments herein, or a glass frit according to any of the embodiments herein, in the preparation of a thick film resistor or in the improvement of the resistance temperature change stability, resistance to electrostatic discharge, and/or rate of change of encapsulation of a thick film resistor.
Drawings
Fig. 1 is a schematic view of test patterns used in the examples, in which, (1) an electrode print pattern, (2) a resistance print pattern, and (3) an electrode and resistance combination pattern.
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.
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.
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.
Herein, unless otherwise specified, the ratio refers to a mass ratio, and the percentage refers to a mass percentage.
In this context, "comprising" covers the meaning of "consisting of … …", i.e. "a comprises a" covers the meaning of "a comprises a and others" and "a comprises only a", unless otherwise specified.
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.
Electronic pastes are the basic materials for making thick film components, usually pastes of solid powders and organic media mixed by rolling. It is understood that the various solid materials (e.g., metals, glasses, ceramics, oxides, salts, etc.) used in the preparation of electronic pastes are typically powders. The thick film resistor paste refers to electronic paste used for preparing a thick film resistor. Thick film resistor pastes typically include a conductive phase, glass frit, an organic vehicle, and optional additives.
The graphite alkyne has rich carbon chemical bonds, a large conjugated system, a wide surface space, excellent chemical stability and semiconductor performance, and is known as the most stable artificially synthesized diyne carbon allotrope. The invention discovers that a proper amount of graphite alkyne is introduced or directly added into thick film resistor paste in a glass powder raw material mode, and the thick film resistor with stable temperature change, electrostatic discharge resistance and/or small encapsulation change rate can be prepared from the thick film resistor paste. Herein, the stable temperature variation of the thick film resistor means that the absolute value of the positive temperature coefficient and/or the negative temperature coefficient of the thick film resistor is small.
Conducting phase
The thick-film resistor paste of the present invention uses a platinum group metal having a high resistivity (including ruthenium, rhodium, palladium, osmium, iridium, and platinum) and/or a compound thereof (e.g., an oxide, a salt, etc.) as a main component of the conductive phase, and more preferably uses one or more selected from the group consisting of metallic ruthenium, a ruthenium alloy (e.g., a rhodium ruthenium alloy, etc.), a ruthenium oxide (e.g., ruthenium dioxide, etc.), and a ruthenate (e.g., bismuth ruthenate, lead ruthenate, etc.) as a main component of the conductive phase. In this context, the main portion of the conductive phase means 80% or more, preferably 90% or more, and more preferably 95% or more of the total weight of the conductive phase. The thick-film resistor paste of the present invention is preferably a ruthenium-based thick-film resistor paste, i.e., the conductive phase of the thick-film resistor paste of the present invention preferably comprises ruthenium oxide and/or ruthenate, wherein the total mass of ruthenium oxide and ruthenate preferably represents more than 80%, such as more than 90%, more than 95%, or all of the total weight of the conductive phase. Herein, the ruthenium oxide is preferably ruthenium dioxide, and the ruthenate is preferably selected from bismuth ruthenate and lead ruthenate.
In some embodiments, the conductive phase of the thick film resistor paste of the present invention comprises ruthenium oxide and ruthenate, the total weight of ruthenium oxide and ruthenate being more than 80%, preferably more than 90%, more than 95% or all of the total weight of the conductive phase; the mass ratio of ruthenium oxide to ruthenate is preferably 1: 3 to 1: 5, more preferably 1: 4 to 1: 5; the ruthenium oxide is preferably present in an amount of from 10 to 25 wt%, for example from 15 to 20 wt%, based on the total weight of the conductive phase; the content of the ruthenate is preferably 75 to 90 wt.%, for example 80 to 85 wt.%, based on the total weight of the conductive phase.
In a preferred embodiment, the conductive phase of the thick film resistor paste of the present invention comprises RuO2And Pb2Ru2O6One or two of them, or RuO2And Pb2Ru2O6One or two of them. In these embodiments, RuO2And Pb2Ru2O6The total weight of (a) is more than 80%, preferably more than 90%, more than 95% or all of the total weight of the conductive phase; when present, RuO in the conductive phase based on the total weight of the conductive phase2The content of (B) is generally from 10 to 25% by weight, preferably from 15 to 20% by weight, for example from 18 to 19% by weight; when contained, Pb in the conductive phase based on the total weight of the conductive phase2Ru2O6The content of (B) is preferably 75 to 90 wt%, more preferably 80 to 85 wt%, for example 81 to 82 wt%. Preferably, the conductive phase of the thick film resistor paste of the present invention comprises RuO2And Pb2Ru2O6Or by RuO2And Pb2Ru2O6And (4) forming. When the conductive phase contains RuO2And Pb2Ru2O6While, RuO2And Pb2Ru2O6Is usually 1: 3 to 1: 5, preferably 1: 4 to 1: 5.
the conductive phase is preferably present in the thick film resistor paste of the present invention in an amount of 10 to 20 wt%, for example 15 to 20 wt%, 15 to 18 wt%, based on the total weight of the thick film resistor paste.
Glass powder
The glass powder in the thick film resistor paste is prepared from glass powder raw materials. The glass powder raw material used in the invention comprises one or more of the following materials: PbO, SiO2、CaO、Al2O3、B2O3、Na2O、K2O and ZnO. In some embodiments, the glass frit material comprises PbO, SiO2CaO and Al2O3Optionally also comprising B2O3、Na2O、K2One or more of O and ZnO, for example, optionally further comprises B2O3、Na2O and/or K2O, and ZnO. In these embodiments, the content of PbO in the glass frit raw material is preferably 30 to 55 wt%, for example 30 to 50 wt%, 35 to 50 wt%, based on the total weight of the glass frit raw material; SiO 22The content of (B) is preferably 20 to 40 wt%, for example 20 to 35 wt%, 25 to 32 wt%, 26 to 30 wt%; the CaO content is preferably 10-25 wt.%, for example 10-20 wt.%, 14-22 wt.%, 16-20 wt.%; al (Al)2O3The content of (B) is preferably 2 to 10% by weight, for example 3 to 10%, 3 to 6%, 4 to 5% by weight. In these embodiments, when present, B is present in the glass frit raw material based on the total weight of the glass frit raw material2O3The content of (B) is preferably 5 to 10 wt%, for example 6 to 8 wt%; when present, Na2O and K2The total content of O is preferably 0.2 to 1 wt.%, for example 0.4 to 1 wt.%, 0.4 to 0.6 wt.%; when included, the ZnO content is preferably 1 to 5% by weight, for example 1 to 4% by weight, 2 to 3% by weight. In some embodiments, the invention is over Na2O and K2Na is selected from O2O。
In the present invention, the glass frit raw material may further contain graphyne, and when contained, the content of graphyne in the glass frit raw material is preferably not more than 5 wt%, for example, 0.4 to 5 wt%, 0.4 to 3.5 wt%, 0.4 to 1.6 wt%, 0.4 to 1.1 wt%, 0.4 to 0.45 wt%, 1 to 1.1 wt%, etc., based on the total weight of the glass frit raw material. The invention discovers that the preparation of thick film resistor paste by using glass powder containing graphdiyne can improve the temperature change stability of the resistance value of the thick film resistor, improve the electrostatic discharge resistance and/or reduce the encapsulation change rate. The graphdiyne suitable for use in the present invention is preferably graphdiyne powder, preferably having a particle size of 1 μm or less.
The glass powder raw materials can be prepared into the glass powder by adopting the conventional method in the field, and the glass powder raw materials are generally uniformly mixed, smelted at high temperature (for example, 1200-1500 ℃), cooled (for example, water cooled) and then ball-milled to obtain the glass powder; preferably, the glass frit is sieved to obtain a glass frit of a suitable particle size. In the present invention, the temperature for melting the glass frit raw material is preferably 1300-1400 ℃. In the present invention, the particle diameter of the glass frit is preferably in the range of 0.5 to 2.5. mu.m, for example, in the range of 1 to 2 μm. In the invention, the particle size of the glass powder is intensively distributed between 1 and 2 mu m by a ball milling process, so that the tailing phenomenon can not occur, and if the requirement can not be met, the glass powder can be sieved.
The thick-film resistor paste of the present invention may include one or more glass frits, and for example, may include two or more glass frits. In the present invention, when the thick film resistor paste includes a plurality of glass frits, the content of graphdine in the glass frit raw materials is preferably 0.4 to 5 wt%, for example, 0.4 to 3.5 wt%, 0.4 to 1.6 wt%, 0.4 to 1.1 wt%, 0.4 to 0.45 wt%, 1 to 1.1 wt%, etc., based on the total weight of all glass frit raw materials. Preferably, the thick-film resistor paste of the present invention contains both glass frit I and glass frit II. In some embodiments, the thick film resistor pastes of the present invention comprise only two glass frits, glass frit I and glass frit II.
In the present invention, the raw material of the glass frit I contains PbO and SiO2、CaO、Al2O3、B2O3、Na2O and/or K2O, ZnO and optionally graphyne, or from PbO, SiO2、CaO、Al2O3、B2O3、Na2O and/or K2O, ZnO and optionally graphyne. The content of PbO in the glass frit I raw material is preferably 33 to 38 wt%, for example 34 to 36 wt%, based on the total weight of the glass frit I raw material, and SiO2Preferably 27-32 wt%, e.g. 28-31 wt%, CaO preferably 18-22 wt%, e.g. 19-21 wt%, Al2O3Preferably in an amount of 3-6 wt.%, e.g. 4-6 wt.%, B2O3Preferably in an amount of 5-10 wt.%, e.g., 6-8 wt.%, Na2O and K2The total content of O is preferably from 0.2 to 1% by weight, for example from 0.4 to 0.6% by weight, and the content of ZnO is preferably from 1 to 5% by weight, for example from 2 to 3% by weight. When contained, the content of graphdine in the glass frit I raw material is preferably 0.5 to 2 wt%, for example, 0.6 to 1.8 wt%, 0.6 to 1.6 wt%, 0.625 to 1.56 wt%, 0.5 to 0.8 wt%, 0.5 to 0.7 wt%, 1.4 to 1.8 wt%, 1.5 to 1.6 wt%, etc., based on the total weight of the glass frit I raw material. The invention discovers that the preparation of a thick film resistor using glass powder I whose raw materials include graphdiyneThe paste can improve the resistance temperature change stability of the thick film resistor, improve the electrostatic discharge resistance and/or reduce the encapsulation change rate.
In the present invention, the raw material of the glass frit II contains PbO and SiO2、CaO、Al2O3And optionally graphatidyne, or from PbO, SiO2、CaO、Al2O3And optionally a graphdine. The content of PbO in the glass frit raw material II is preferably 45 to 55 wt%, for example 48 to 52 wt%, based on the total weight of the glass frit raw material II, and SiO2Preferably in an amount of 25-35 wt.%, e.g., 26-31 wt.%, preferably in an amount of 14-20 wt.%, e.g., 15-18 wt.%, CaO, Al2O3The content of (B) is preferably 3 to 6 wt%, for example 3 to 5 wt%. When contained, the content of graphdine in the glass frit raw material II is preferably 0.5 to 5% by weight, for example, 1 to 5% by weight, 1.2 to 3.5% by weight, 1.25 to 3.125% by weight, 1 to 1.5% by weight, 1.2 to 1.3% by weight, 2.5 to 3.5% by weight, 3 to 3.2% by weight, etc., based on the total weight of the glass frit raw material II. The invention discovers that the preparation of thick film resistor paste by using glass powder II of which the raw materials comprise graphdine can improve the resistance temperature change stability of the thick film resistor, improve the electrostatic discharge resistance and/or reduce the encapsulation change rate.
In the thick-film resistor paste of the present invention, the content of the glass frit is preferably 40 to 60 wt%, for example 45 to 55 wt%, 45 to 50 wt%, based on the total weight of the thick-film resistor paste. When the thick-film resistor paste comprises glass powder I and glass powder II, the ratio of the glass powder I to the glass powder II is preferably 1: 1 to 3: 1, e.g. 1.5: 1 to 2.5: 1. 1.8: 1 to 2.2: 1. 2: about 1.
Graphtylene
The invention discovers that the addition of the graphdine to the thick film resistor paste can improve the resistance temperature change stability of the thick film resistor, improve the electrostatic discharge resistance and/or reduce the encapsulation change rate, particularly improve the electrostatic discharge resistance and reduce the encapsulation change rate. Thus, in a preferred embodiment, the thick-film resistor paste of the present invention comprises a graphdine; the content of the graphdine in the thick film resistor paste is preferably 0.1 to 1 wt%, for example, 0.1 to 0.6 wt%, 0.1 to 0.3 wt%, 0.4 to 0.6 wt%, 0.2 to 0.5 wt%, etc., based on the total weight of the thick film resistor paste. Herein, unless otherwise specified, the inclusion of a graphdine in a thick film resistor paste means that the graphdine is directly mixed with the other components of the paste (e.g., conductive phase, glass frit, organic vehicle, and additives) when the paste is prepared.
Additive agent
Thick film resistor pastes also typically contain additives. Herein, the additive means well known to those skilled in the art, and generally means a material for adjusting the resistive properties of the thick film, in addition to the conductive phase and the glass frit, including a material for controlling a temperature coefficient, maintaining a pattern, improving temperature sensitivity, enhancing weather resistance, etc., and may be, for example, one or more selected from the group consisting of metal oxides, non-metal oxides, metal nitrides, and silicates. Additives suitable for use in the present invention may be those commonly used in thick film resistor pastes, particularly ruthenium-based thick film resistor pastes, and include manganese oxides, copper oxides, niobium oxides, antimony oxides, silicates (e.g., zirconium silicate), and the like. Herein, the additive does not include graphdiyne. In some embodiments, the additives in the thick-film resistor paste of the present invention include or consist of metal oxides and silicates. The metal oxide suitable for use as an additive in the present invention is preferably manganese oxide, more preferably MnO2. The silicate suitable as an additive according to the invention is preferably ZrSiO4。
Herein, unless otherwise specified, the additive refers to a slurry additive. It will be understood by those skilled in the art that a paste additive is distinguished from a glass frit additive, by which is meant a material that is mixed directly with the other components of the paste (e.g., the conductive phase, the glass frit, and the organic vehicle) when the paste is prepared, and by which is meant a material that is used as a raw material for the glass frit to prepare the glass frit.
The thick-film resistor paste of the present invention preferably contains an additive. The additive suitable for the present invention is preferably one or more, preferably two or more, selected from the group consisting of manganese oxide, copper oxide, niobium oxide, antimony oxide and silicate, more preferably comprising or consisting of manganese oxide and silicate, wherein the manganese oxide is preferably MnO2The silicate is preferably ZrSiO4. The total content of additives in the thick-film resistor paste according to the invention is preferably 0.5 to 10 wt.%, for example 2 to 8 wt.%, 5 to 6 wt.%, based on the total weight of the thick-film resistor paste. When included, manganese oxide (e.g., MnO) in the thick film resistor paste based on the total weight of the thick film resistor paste2) The content of (B) is preferably 0.2 to 1 wt%, for example 0.4 to 0.6 wt%. When included, the silicate (e.g., ZrSiO) is present in the thick film resistor paste based on the total weight of the thick film resistor paste4) The content of (B) is preferably 2 to 8 wt%, for example 4 to 6 wt%.
Organic vehicle
The organic vehicle in the thick film resistor paste typically includes an organic solvent, a thickener, and optionally a modifier. The organic vehicle is preferably present in the thick film resistor paste of the present invention in an amount of from 20 to 40 wt%, for example from 25 to 35 wt%, 28 to 32 wt%, based on the total weight of the thick film resistor paste.
The organic solvent is generally a relatively viscous organic liquid, generally contains polar groups in its molecule, and is capable of dissolving a thickener such as cellulose, and generally has a high boiling point and is not easily volatile at normal temperature. The organic solvent may be, for example, any one or a mixture of more of terpineol, butyl carbitol acetate, ethylene glycol ethyl ether acetate, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (Texanol). In some embodiments, the present invention uses terpineol as the organic solvent. The organic solvent is generally used in an amount of 75 to 95 wt%, preferably 85 to 95 wt%, based on the total weight of the organic vehicle.
Thickeners are used to impart viscosity to the slurry and may include cellulose and/or resins. The cellulose used as the thickener includes various modified celluloses. Modified celluloses include, for example, but are not limited to polyanionic celluloses, ethylcellulose, nitrocellulose, and the like. The resin used as the thickener may be, for example, an epoxy resin, an acrylic resin, a butyral resin, a maleic resin, or the like. The thickener is generally used in an amount of 5 to 20 wt%, preferably 8 to 13 wt%, based on the total weight of the organic vehicle. In some embodiments, the thickening agent comprises a cellulose, which may be, for example, a polyanionic cellulose, and a resin, preferably an epoxy resin, such as an epoxy thermoset resin. In embodiments where the thickener comprises cellulose and a resin, the cellulose is typically used in an amount of 2 to 10 wt%, such as 4 to 6 wt%, and the resin is typically used in an amount of 2 to 10 wt%, such as 3 to 5 wt%, based on the total weight of the organic carrier.
If necessary, a dispersant, a defoaming agent, a lubricant, a thixotropic agent, and other modifiers may be added to the organic vehicle. The amount of modifier is conventional in the art and is generally not more than 5 wt%, preferably not more than 2.5 wt%, of the total weight of the organic vehicle. When included, the total amount of modifier is preferably from 0.2 to 5 weight percent, e.g., from 0.5 to 2.5 weight percent, from 1 to 2 weight percent, etc., of the total weight of the organic vehicle. The modifier preferably comprises one or more or all of lecithin, polyethylene wax and lauric acid; where present, lecithin is preferably used in an amount of 0.1 to 2 wt%, e.g., 0.5 to 1 wt%, based on the total weight of the organic vehicle; when included, the polyethylene wax is preferably used in an amount of 0.1 to 1 wt%, e.g., 0.3 to 0.8 wt%, based on the total weight of the organic vehicle; when included, lauric acid is preferably used in an amount of 0.1 to 1 wt%, for example 0.3 to 0.8 wt%, based on the total weight of the organic vehicle.
In some embodiments, the organic vehicle comprises, based on the total weight of the organic vehicle: 75-95 wt%, preferably 85-95 wt% of an organic solvent, 2-10 wt%, preferably 4-6 wt% of cellulose, 2-10 wt%, preferably 3-5 wt% of a resin and 0-2.5 wt% of a modifier; wherein, the organic solvent is terpineol; the cellulose is preferably polyanionic cellulose; the resin is preferably an epoxy thermosetting resin; when included, the modifying agents preferably include lecithin, polyethylene wax, and lauric acid.
The organic vehicle can be prepared by uniformly mixing the components of the organic vehicle, and if desired, heating while mixing. In some embodiments, the organic vehicle is prepared by first mixing the cellulose, a portion of the additive (e.g., lecithin), and a portion of the organic solvent together (this mixing may be performed at 65-75 ℃), and then mixing the resulting mixture with the resin, the remaining additive (e.g., polyethylene wax and lauric acid), and the remaining organic solvent.
Thick film resistor paste
In the present invention, the thick film resistor paste is generally prepared by uniformly mixing the conductive phase, the glass powder, the organic vehicle, the optional graphite alkyne and the optional additive, and then rolling the mixture by using a three-roll mill to obtain the paste. In some embodiments, the preparation of the thick-film resistor paste of the present invention comprises:
(1) uniformly mixing a conductive phase, glass powder, an organic carrier, optional graphite alkyne and optional additives; after mixing, preferably standing for 1-2h to complete infiltration;
(2) rolling the mixture by a three-roller machine to obtain thick film resistor paste; preferably, the roll is rolled to a fineness ≦ 5 μm.
The fineness of the thick film resistor paste of the present invention is preferably ≦ 5 μm.
In the invention, the graphdiyne can be directly mixed with the conductive phase, the glass powder, the organic carrier and optional additives to prepare thick-film resistor paste (adding the graphdiyne in the form of a paste additive), or can be used as a glass powder raw material to be prepared into glass powder with other raw materials of the glass powder and then added into the thick-film resistor paste (introducing the graphdiyne in the form of the glass powder additive).
The invention discovers that the addition of the graphite alkyne in the form of a paste additive or the introduction of the graphite alkyne in the form of a glass powder additive into thick film resistor paste can improve the resistance temperature change stability of the thick film resistor, improve the electrostatic discharge resistance and/or reduce the encapsulation change rate; in particular, the incorporation of graphdiynes in the form of glass frit additives can improve the resistance of thick film resistors to electrostatic discharge and reduce the rate of change of encapsulation, especially improve resistance to electrostatic discharge; particularly, the graphite alkyne is added in the form of a slurry additive, so that the positive temperature coefficient of the thick film resistor can be reduced, the electrostatic discharge resistance is improved, and the encapsulation change rate is reduced; the addition of the graphdine in the form of a paste additive better improves the electrostatic discharge resistance of the thick film resistor and reduces the rate of change of the encapsulation than if it were introduced in the form of a glass frit additive.
In some embodiments, a thick film resistor paste includes a conductive phase, a glass frit, an organic vehicle, and optional additives, wherein the glass frit starting material includes a graphdine; the content of the graphdiyne in the glass frit raw materials is preferably 0.4 to 5 wt%, for example, 0.4 to 3.5 wt%, etc., based on the total weight of the glass frit raw materials; the glass frit content of the thick film resistor paste is preferably 40 to 60 wt%, for example 45 to 55 wt%, 45 to 50 wt%, based on the total weight of the thick film resistor paste. In embodiments where the glass frit starting material comprises a graphyne, the thick film resistor paste may or may not comprise a graphyne. In some embodiments, the glass frit starting material includes a graphyne and the thick film resistor paste does not include a graphyne.
In some embodiments, a thick film resistor paste includes a conductive phase, a glass frit, a graphdine, an organic vehicle, and optional additives; the content of the graphdine in the thick film resistor paste is preferably 0.1 to 1 wt%, for example, 0.1 to 0.6 wt%, 0.1 to 0.3 wt%, 0.4 to 0.6 wt%, 0.2 to 0.5 wt%, etc., based on the total weight of the thick film resistor paste. In embodiments where the thick film resistor paste includes a graphyne, the glass frit starting material may or may not include a graphyne. In some embodiments, the thick-film resistor paste includes a graphyne and the glass frit inclusive material does not include a graphyne.
In some embodiments, a thick film resistor paste includes a conductive phase, glass frit I, glass frit II, an organic vehicle, and optional additives, wherein the glass frit I raw material includes a graphdiyne; the content of graphdine in the glass frit I raw material is preferably 0.5 to 2 wt%, for example, 0.6 to 1.8 wt%, 0.6 to 1.6 wt%, 0.625 to 1.56 wt%, 0.5 to 0.8 wt%, 0.5 to 0.7 wt%, 1.4 to 1.8 wt%, 1.5 to 1.6 wt%, etc., based on the total weight of the glass frit I raw material; the total content of glass frit I and glass frit II in the thick-film resistor paste is preferably 40-60 wt%, for example 45-55 wt%, 45-50 wt%, based on the total weight of the thick-film resistor paste; the ratio of the amount of the glass frit I to the amount of the glass frit II is preferably 1: 1 to 3: 1, e.g. 1.5: 1 to 2.5: 1. 1.8: 1 to 2.2: 1. 2: about 1. In embodiments where the glass frit I feedstock comprises graphdine, the glass frit II feedstock may or may not comprise graphdine. In some embodiments, the glass frit I feedstock includes graphdine and the glass frit II feedstock does not include graphdine.
In some embodiments, a thick film resistor paste includes a conductive phase, glass frit I, glass frit II, an organic vehicle, and optional additives, wherein the glass frit II feedstock includes a graphdiyne; the content of graphdine in the glass frit II raw material is preferably 0.5 to 5 wt%, for example, 1 to 5 wt%, 1.2 to 3.5 wt%, 1.25 to 3.125 wt%, 1 to 1.5 wt%, 1.2 to 1.3 wt%, 2.5 to 3.5 wt%, 3 to 3.2 wt%, etc., based on the total weight of the glass frit II raw material; the total content of glass frit I and glass frit II in the thick-film resistor paste is preferably 40-60 wt%, for example 45-55 wt%, 45-50 wt%, based on the total weight of the thick-film resistor paste; the ratio of the amount of the glass frit I to the amount of the glass frit II is preferably 1: 1 to 3: 1, e.g. 1.5: 1 to 2.5: 1. 1.8: 1 to 2.2: 1. 2: about 1. In embodiments where the glass frit II feedstock comprises a graphdine, the glass frit I feedstock may or may not comprise a graphdine. In some embodiments, the glass frit II feedstock comprises graphyne and the glass frit I feedstock does not comprise graphyne.
In some embodiments, a thick film resistor paste includes a conductive phase, glass frit I, glass frit II, a graphdine, an organic vehicle, and optional additives; the content of the graphdine in the thick film resistor paste is preferably 0.1 to 1 wt%, for example, 0.1 to 0.6 wt%, 0.1 to 0.3 wt%, 0.4 to 0.6 wt%, 0.2 to 0.5 wt%, etc., based on the total weight of the thick film resistor paste; the total content of glass frit I and glass frit II in the thick-film resistor paste is preferably 40-60 wt%, for example 45-55 wt%, 45-50 wt%, based on the total weight of the thick-film resistor paste; the ratio of the amount of the glass frit I to the amount of the glass frit II is preferably 1: 1 to 3: 1, e.g. 1.5: 1 to 2.5: 1. 1.8: 1 to 2.2: 1. 2: about 1. In some embodiments, the thick-film resistor paste includes a graphyne, and the glass frit I and glass frit II raw materials do not include a graphyne.
In the present invention, the total mass of the graphyne included in the thick film resistor paste (i.e., the graphyne added as a paste additive) and the graphyne included in the glass frit raw material (including the graphyne included in the glass frit I raw material and the graphyne included in the glass frit II raw material) is preferably 0.1 to 1 wt%, such as 0.1 to 0.6 wt%, 0.1 to 0.3 wt%, 0.4 to 0.6 wt%, 0.2 to 0.5 wt%, etc., based on the total mass of the thick film resistor paste.
The preferred composition and content of the components in the thick-film resistor paste of any embodiment of the present invention may be as described previously.
Thick film resistor
In the present invention, the preparation method of the thick film resistor can be conventional in the art, for example, screen printing, leveling, drying and sintering are performed on thick film resistor paste to obtain the thick film resistor. The drying temperature can be 150 + -10 deg.C, preferably 150 + -3 deg.C, and the drying time can be 10 + -2 min, preferably 10 + -1 min. Sintering may be carried out according to a conventional thick film resistor sintering profile, for example the thick film resistor sintering profile may be: the peak temperature is 850 + -10 deg.C, preferably 850 + -1 deg.C, the duration is 10 + -2 min, preferably 10 + -1 min, the temperature rise time is 15-40min, preferably 20-30min, and the temperature decrease time is 20-50min, preferably 30-40 min. The apparatus for sintering is not particularly limited, and may be carried out, for example, using a tunnel furnace.
The thick film resistor prepared by the thick film resistor paste containing the graphite alkyne has the advantages of stable temperature change, electrostatic discharge resistance, small encapsulation change rate and the like. Accordingly, the invention also includes thick film resistors made using the thick film resistor pastes of the invention and the use of the graphite alkyne or the thick film resistor pastes of the invention in making thick film resistors or improving the resistance temperature change stability, resistance to electrostatic discharge and/or encapsulation change rate of thick film resistors.
In some embodiments, the thick film resistor of the present invention has a positive temperature coefficient (HTCR) of absolute value of less than or equal to 100ppm, preferably less than or equal to 60ppm at 25 ℃ to 125 ℃.
In some embodiments, the thick film resistors of the present invention have an absolute negative temperature coefficient (CTCR) value of 100ppm or less, preferably 60ppm or less, at 25 ℃ to-55 ℃.
In some embodiments, the thick film resistor of the present invention has an absolute value of electrostatic discharge (ESD) at 4KV, 1s, 5 times of less than or equal to 2%, preferably less than or equal to 1.6%, less than or equal to 1.2%, less than or equal to 0.5%, or less than or equal to 0.06%.
In some embodiments, the thick film resistor of the present invention has an envelope variation of less than or equal to 3% absolute, preferably less than or equal to 2.2%, less than or equal to 1%, or less than or equal to 0.15%.
The present invention is fully illustrated by the following examples, which are intended to be illustrative only and are not intended to limit the scope of the 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.
The organic vehicle used in the following examples was prepared using the following formulation and procedure:
the method comprises the following steps: mixing 83 parts by weight of terpineol, 15 parts by weight of polyanionic cellulose and 2 parts by weight of lecithin, heating in a water bath to 65-75 ℃, continuously stirring until the mixture is completely dissolved and presents a uniform state, and stopping heating; cooling at room temperature for 24h, and storing for use;
step two: uniformly mixing 35 parts by weight of the mixture prepared in the step one, 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.
The graphite alkyne powder used in the following examples is YFY 01-graphite alkyne powder of Jiangsu Xiancheng nanometer material science and technology Limited company, the particle size is 40-100nm, and the specific parameters are described in the description of the product.
The following examples used for the encapsulation paste for testing the encapsulation change rate employ the dielectric paste of the name I-5337 from the company seian macrostem & ltSUP & gt, and the specific application method and sintering parameters are described in the description of the product.
The following performance test methods were used in the following examples:
(1) resistance (R) test method: the resistance meter selects proper measuring range, two test meter pens are respectively lapped on the electrodes at two ends of the measuring resistance, and the numerical value and the unit are recorded.
(2) Positive temperature coefficient (HTCR) test method: the temperature of the test equipment is set to 25 ℃, and after the temperature is stabilized, the resistance value is measured to be R1 and recorded. The temperature of the test equipment is set to 125 ℃, and after the temperature is stabilized, the resistance value is measured to be R2 and recorded. The calculation formula is as follows:
Figure BDA0002625428550000171
(3) negative temperature coefficient (CTCR) test method: the temperature of the test equipment is set to 25 ℃, and after the temperature is stabilized, the resistance value is measured to be R3 and recorded. Setting the temperature of the testing equipment to be 55 ℃ below zero, and measuring the resistance value to be R4 after the temperature is stabilized, and recording. The calculation formula is as follows:
Figure BDA0002625428550000181
(4) electrostatic discharge (ESD) test method: the resistance (R) was measured according to the resistance (R) test method and recorded as R5. Setting parameters (voltage 4kv, time 1s and times 5) by adopting an electrostatic discharge device, checking that electrodes at two ends of the resistor are in good contact with the device, starting to operate, placing the sample wafer for 20-30min after the experiment is finished, measuring the resistance value to be R6 according to a resistance value (R) test method, and recording. The calculation formula is as follows:
Figure BDA0002625428550000182
(5) encapsulation change rate test method: the resistance (R) was measured according to the resistance (R) test method and recorded as R7. Printing the encapsulation slurry on the upper layer of the resistor, drying the sintered sample wafer, measuring the resistance value as R8 according to the resistance value (R) test method, and recording. The calculation formula is as follows:
Figure BDA0002625428550000183
example 1
This example prepared six glass frits: glass powder A1, glass powder A2, glass powder A3, glass powder B1, glass powder B2 and glass powder B3. As shown in table 1, the formulation of each glass frit is specifically:
glass powder A1: 35 parts by weight of PbO, 30 parts by weight of SiO220 parts by weight of CaO, 5 parts by weight of Al2O37 parts by weight of B2O30.5 parts by weight of Na2O, 2.5 parts by weight of ZnO;
glass powder A2: 35 parts by weight of PbO, 28.44 parts by weight of SiO220 parts by weight of CaO, 5 parts by weight of Al2O37 parts by weight of B2O30.5 parts by weight of Na2O, 2.5 parts by weight of ZnO and 1.56 parts by weight of graphite alkyne powder;
glass powder A3: 35 parts by weight of PbO, 29.375 parts by weight of SiO220 parts by weight of CaO, 5 parts by weight of Al2O37 parts by weight of B2O3, 0.5 weight part of Na2O, 2.5 parts by weight of ZnO and 0.625 parts by weight of graphite alkyne powder;
glass powder B1: 50 parts by weight of PbO, 30 parts by weight of SiO216 parts by weight of CaO, 4 parts by weight of Al2O3；
Glass powder B2: 50 parts by weight of PbO, 26.875 parts by weight of SiO216 parts by weight of CaO, 4 parts by weight of Al2O33.125 parts by weight of graphite alkyne powder;
glass powder B3: 50 parts by weight of PbO, 28.75 parts by weight of SiO216 parts by weight of CaO, 4 parts by weight of Al2O3And 1.25 parts by weight of graphite alkyne powder.
Mixing the raw materials of the glass powder according to a certain proportion, smelting at 1350 ℃, cooling by water, ball-milling, sieving to make the particle size of the glass powder be distributed in 1-2 μm, and storing for later use.
Table 1: glass powder formula (unit: parts by weight)
Figure BDA0002625428550000191
Note: in Table 1, "- -" indicates no addition.
Example 2
This example prepares paste 1 and measures the film thickness, resistance, positive temperature coefficient, negative temperature coefficient, electrostatic discharge and encapsulation variation rate of thick film resistors made from paste 1.
The preparation of slurry 1 was as follows:
the first step is as follows: weighing RuO2 3g、Pb2Ru2O613.3g, glass powder A132 g, glass powder B116 g, ZrSiO4 5g、MnO20.5g of graphite alkyne powder, 0.5g of organic carrier and 29.7g of organic carrier;
the second step is that: uniformly stirring the solid powder and the organic carrier in the step one by using a glass rod, and standing for more than 1h to finish infiltration;
the third step: rolling the mixture on a three-roller mill to ensure that the fineness is less than or equal to 5 mu m to obtain slurry 1.
And (3) performing screen printing on the paste 1, leveling, drying at 150 ℃ for 10min, and sintering by adopting a tunnel furnace according to a thick film resistor sintering curve with the peak temperature of 850 ℃, the duration of 10min, the heating time of 25min and the cooling time of 35min to obtain the thick film resistor. The thick film resistor was tested for film thickness, resistance, ESD, TCR, and encapsulation. The composition of paste 1 and the results of the performance test of the thick film resistor made from paste 1 are shown in table 2, and the printed sintering test pattern is shown in fig. 1.
Example 3
In this example, paste 2 was prepared and the film thickness, resistance, positive temperature coefficient, negative temperature coefficient, electrostatic discharge and encapsulation change rate of thick film resistors made from paste 2 were measured.
Slurry 2 was prepared as follows:
the first step is as follows: weighing RuO2 3g、Pb2Ru2O613.3g, glass powder A132 g, glass powder B116 g, ZrSiO4 5g、MnO20.5g of graphite alkyne powder, 0.2g of organic carrier and 30g of organic carrier;
the second step is that: uniformly stirring the solid powder and the organic carrier in the step one by using a glass rod, and standing for more than 1h to finish infiltration;
the third step: rolling the mixture on a three-roller mill to ensure that the fineness is less than or equal to 5 mu m to obtain slurry 2.
And (3) performing screen printing on the paste 2, leveling, drying at 150 ℃ for 10min, and sintering by adopting a tunnel furnace according to a thick film resistor sintering curve with the peak temperature of 850 ℃, the duration of 10min, the heating time of 25min and the cooling time of 35min to obtain the thick film resistor. The thick film resistor was tested for film thickness, resistance, ESD, TCR, and encapsulation. The composition of paste 2 and the results of the performance tests of the thick film resistors made from paste 2 are shown in table 2, and the printed sintering test pattern is shown in fig. 1.
Example 4
In this example, paste 3 was prepared and the film thickness, resistance, positive temperature coefficient, negative temperature coefficient, electrostatic discharge and encapsulation change rate of thick film resistors made from paste 3 were measured.
Slurry 3 was prepared as follows:
the first step is as follows: weighing RuO2 3g、Pb2Ru2O613.3g, glass powder A232 g, glass powder B116 g, ZrSiO4 5g、MnO20.5g of organic carrier and 30.2g of organic carrier;
the second step is that: uniformly stirring the solid powder and the organic carrier in the step one by using a glass rod, and standing for more than 1h to finish infiltration;
the third step: rolling the mixture on a three-roller mill to ensure that the fineness is less than or equal to 5 mu m to obtain slurry 3.
And (3) performing screen printing on the paste 3, leveling, drying at 150 ℃ for 10min, and sintering by adopting a tunnel furnace according to a thick film resistor sintering curve with the peak temperature of 850 ℃, the duration of 10min, the heating time of 25min and the cooling time of 35min to obtain the thick film resistor. The thick film resistor was tested for film thickness, resistance, ESD, TCR, and encapsulation. The composition of paste 3 and the results of the performance tests of the thick film resistors made from paste 3 are shown in table 2. The printed sintering test pattern is shown in figure 1.
Example 5
This example prepares paste 4 and measures the film thickness, resistance, positive temperature coefficient, negative temperature coefficient, electrostatic discharge and encapsulation variation rate of thick film resistors made from paste 4.
The preparation of slurry 4 was as follows:
the first step is as follows: weighing RuO2 3g、Pb2Ru2O613.3g, glass powder A332 g, glass powder B116 g, ZrSiO4 5g、MnO20.5g of organic carrier and 30.2g of organic carrier;
the second step is that: uniformly stirring the solid powder and the organic carrier in the step one by using a glass rod, and standing for more than 1h to finish infiltration;
the third step: rolling the mixture on a three-roller mill to ensure that the fineness is less than or equal to 5 mu m to obtain slurry 4.
And (3) performing screen printing on the paste 4, leveling, drying at 150 ℃ for 10min, and sintering by adopting a tunnel furnace according to a thick film resistor sintering curve with the peak temperature of 850 ℃, the duration of 10min, the heating time of 25min and the cooling time of 35min to obtain the thick film resistor. The thick film resistor was tested for film thickness, resistance, ESD, TCR, and encapsulation. The composition of paste 4 and the results of the performance tests of the thick film resistors made from paste 4 are shown in table 2, and the printed sintering test pattern is shown in fig. 1.
Example 6
This example prepared paste 5 and measured the film thickness, resistance, positive temperature coefficient, negative temperature coefficient, electrostatic discharge and encapsulation change rate of thick film resistors made from paste 5.
The preparation of slurry 5 was as follows:
the first step is as follows: weighing RuO2 3g、Pb2Ru2O613.3g, glass powder A132 g, glass powder B216 g, ZrSiO4 5g、MnO20.5g of organic carrier and 30.2g of organic carrier;
the second step is that: uniformly stirring the solid powder and the organic carrier in the step one by using a glass rod, and standing for more than 1h to finish infiltration;
the third step: rolling the mixture on a three-roller mill to ensure that the fineness is less than or equal to 5 mu m to obtain slurry 5.
And (3) performing screen printing on the paste 5, leveling, drying at 150 ℃ for 10min, and sintering by adopting a tunnel furnace according to a thick film resistor sintering curve with the peak temperature of 850 ℃, the duration of 10min, the heating time of 25min and the cooling time of 35min to obtain the thick film resistor. The thick film resistor was tested for film thickness, resistance, ESD, TCR, and encapsulation. The composition of paste 5 and the results of the performance test of the thick film resistor made from paste 5 are shown in table 2, and the printed sintering test pattern is shown in fig. 1.
Example 7
This example prepared paste 6 and measured the film thickness, resistance, positive temperature coefficient, negative temperature coefficient, electrostatic discharge and encapsulation change rate of thick film resistors made from paste 6.
The preparation of the slurry 6 was as follows:
the first step is as follows: weighing RuO2 3g、Pb2Ru2O613.3g, glass powder A132 g, glass powder B316 g, ZrSiO4 5g、MnO20.5g of organic carrier and 30.2g of organic carrier;
the second step is that: uniformly stirring the solid powder and the organic carrier in the step one by using a glass rod, and standing for more than 1h to finish infiltration;
the third step: rolling the mixture on a three-roller mill to ensure that the fineness is less than or equal to 5 mu m to obtain slurry 6.
And (3) performing screen printing on the paste 6, leveling, drying at 150 ℃ for 10min, and sintering by adopting a tunnel furnace according to a thick film resistor sintering curve with the peak temperature of 850 ℃, the duration of 10min, the heating time of 25min and the cooling time of 35min to obtain the thick film resistor. The thick film resistor was tested for film thickness, resistance, ESD, TCR, and encapsulation. The composition of paste 6 and the results of the performance test of the thick film resistor made from paste 6 are shown in table 2, and the printed sintering test pattern is shown in fig. 1.
Example 8
This example prepared paste 7 and measured the film thickness, resistance, positive temperature coefficient, negative temperature coefficient, electrostatic discharge and encapsulation change rate of thick film resistors made from paste 7.
The preparation of the slurry 7 was as follows:
the first step is as follows: weighing RuO2 3g、Pb2Ru2O613.3g, glass powder A132 g, glass powder B116 g, ZrSiO4 5g、MnO20.5g of organic carrier and 30.2g of organic carrier;
the second step is that: uniformly stirring the solid powder and the organic carrier in the step one by using a glass rod, and standing for more than 1h to finish infiltration;
the third step: rolling the mixture on a three-roll mill to ensure that the fineness is less than or equal to 5 mu m to obtain slurry 7.
And (3) performing screen printing on the paste 7, leveling, drying at 150 ℃ for 10min, and sintering by adopting a tunnel furnace according to a thick film resistor sintering curve with the peak temperature of 850 ℃, the duration of 10min, the heating time of 25min and the cooling time of 35min to obtain the thick film resistor. The thick film resistor was tested for film thickness, resistance, ESD, TCR, and encapsulation. The composition of paste 7 and the results of the performance test of the thick film resistor made from paste 7 are shown in table 2, and the printed sintering test pattern is shown in fig. 1.
Table 2: compositions of pastes 1-7 and Performance test results for Thick film resistors made from pastes 1-7
Figure BDA0002625428550000231
Figure BDA0002625428550000241

Claims (10)

1. A thick film resistor paste, comprising a conductive phase, glass powder, graphite alkyne, an additive, and an organic vehicle;
preferably, the particle size of the graphdiyne is less than 1 μm;
preferably, the content of the graphdine in the thick-film resistor paste is 0.1-1 wt%, preferably 0.2-0.5 wt%, based on the total mass of the thick-film resistor paste.
2. A thick-film resistor paste comprising a conductive phase, a glass frit, an additive and an organic vehicle, wherein the glass frit comprises the following raw materials: PbO, SiO2、CaO、Al2O3And a graphoyne, and optionally B2O3、Na2O and/or K2One or more of O, and ZnO;
preferably, the particle size of the graphdiyne is less than 1 μm;
preferably, the content of the graphdine in the glass powder raw material is 0.4-5 wt% based on the total mass of the glass powder raw material;
preferably, the content of PbO in the glass powder raw material is 30-55 wt% and SiO is calculated by the total mass of the glass powder raw material220-40 wt%, CaO 10-25 wt%, Al2O3The content of (B) is 2-10 wt%;
preferably, when contained, B in the glass frit raw material is B based on the total mass of the glass frit raw material2O3Is 5-10 wt% of Na2O and K2The total content of O is 0.2-1 wt%, and the content of ZnO is 1-5 wt%.
3. The thick-film resistor paste of claim 1 or 2 wherein the conductive phase is present in an amount of 15 to 20 wt%, the glass frit is present in an amount of 45 to 55 wt%, the additive is present in an amount of 0.5 to 10 wt%, and the organic vehicle is present in an amount of 25 to 35 wt%, based on the total mass of the thick-film resistor paste.
4. The thick-film resistor paste of claim 1 wherein the glass frit comprises: PbO, SiO2CaO and Al2O, and optionally a compound selected from the group consisting of graphdiyne, B2O3、Na2O and/or K2One or more or all of O, and ZnO;
preferably, the content of PbO in the glass powder raw material is 30-55 wt% and SiO is calculated by the total mass of the glass powder raw material220-40 wt%, CaO 10-25 wt%, Al2O3The content of (B) is 2-10 wt%;
preferably, when present, the raw glass powder has a graphdine content of 0.4 to 5 wt%, based on the total mass of the raw glass powder, and B2O3Is 5-10 wt% of Na2O and K2The total content of O is 0.2-1 wt%, and the content of ZnO is 1-5 wt%.
5. The thick-film resistor paste of claim 1 or 2 wherein the glass frit comprises glass frit I and glass frit II, wherein the glass frit I comprises the following raw materials: PbO, SiO2、CaO、Al2O3、B2O3、Na2O and/or K2O, ZnO and optional graphdine, the glass powder II comprises the following raw materials: PbO, SiO2、CaO、Al2O3And optionally a graphdine;
preferably, the content of PbO in the glass powder I raw material is 33-38 wt%, based on the total mass of the glass powder I raw material, and SiO is227-32 wt%, CaO 18-22 wt%, Al2O3In an amount of 3-6 wt%, B2O3Is 5-10 wt% of Na2O and K2The total content of O is 0.2-1 wt%, and the content of ZnO is 1-5 wt%; preferably, when present, the content of graphdine in the glass frit I raw material is 0.5 to 2 wt% based on the total mass of the glass frit I raw material;
preferably, the content of PbO in the glass powder II raw material is 45-55 wt% and SiO is calculated by the total mass of the glass powder II raw material2The content of (A) is 25-35 wt%, the content of CaO is 14-20 wt%, and Al is2O3The content of (B) is 3-6 wt%; preferably, when present, the content of graphdine in the glass frit II raw material is 1 to 5 wt% based on the total mass of the glass frit II raw material;
preferably, in the thick film resistor paste, the mass ratio of the glass powder I to the glass powder II is 1: 1 to 3: 1.
6. the thick-film resistor paste of claim 1 or 2 wherein the thick-film resistor paste has one or more of the following characteristics:
(1) the conductive phase comprises ruthenium oxide and ruthenate; preferably, in the thick-film resistor paste, the mass ratio of the ruthenium oxide to the ruthenate is 1: 3 to 1: 5; preferably, the ruthenium oxide is RuO2(ii) a Preferably, the ruthenate is Pb2Ru2O6；
(2) The organic carrier comprises an organic solvent, a thickener and optionally a modifier; preferably, the content of the organic solvent in the organic carrier is 75-95 wt% and the content of the thickening agent is 5-20 wt% based on the total mass of the organic carrier; preferably, when present, the modifier is present in the organic vehicle in an amount of from 0 to 2.5 weight percent, based on the total mass of the organic vehicle; preferably, the organic solvent is terpineol; preferably, the thickener comprises cellulose and a resin;
(3) the additive is selected from one or more of manganese oxide, copper oxide, niobium oxide, antimony oxide and silicate; preferably, the additives include oxides of manganese and silicates; preferably, the content of the manganese oxide in the thick-film resistor paste is 0.2-1 wt% based on the total mass of the thick-film resistor paste; preferably, the silicate content in the thick film resistor paste is 2-8 wt% based on the total mass of the thick film resistor paste; preferably, the manganese oxide is MnO2(ii) a Preferably, the silicate is ZrSiO4。
7. A thick film resistor prepared from the thick film resistor paste of any one of claims 1-6.
8. The glass powder is characterized by comprising the following raw materials: PbO, SiO2、CaO、Al2O3And a graphoyne, and optionally B2O3、Na2O and/or K2One or more of O, and ZnO;
preferably, the particle size of the graphdiyne is less than 1 μm;
preferably, the content of the graphdine in the glass powder raw material is 0.4-5 wt% based on the total mass of the glass powder raw material;
preferably, the content of PbO in the glass powder raw material is 30-55 wt% and SiO is calculated by the total mass of the glass powder raw material220-40 wt%, CaO 10-25 wt%, Al2O3The content of (B) is 2-10 wt%;
preferably, when contained, B in the glass frit raw material is B based on the total mass of the glass frit raw material2O3Is 5-10 wt% of Na2O and K2The total content of O is 0.2-1 wt%, and the content of ZnO is 1-5 wt%.
9. The glass frit according to claim 8, wherein,
the glass powder comprises the following raw materials: PbO, SiO2、CaO、Al2O3、B2O3、Na2O and/or K2O, ZnO and graphyne; preferably, the content of PbO in the glass powder raw material is 33-38 wt% and SiO is calculated by the total mass of the glass powder raw material227-32 wt%, CaO 18-22 wt%, Al2O3In an amount of 3-6 wt%, B2O3Is 5-10 wt% of Na2O and K2The total content of O is 0.2-1 wt%, and the content of ZnO is 1-5 wt%; preferably, the content of the graphdine in the glass powder raw material is 0.5-2 wt% based on the total mass of the glass powder raw material; or
The glass powder comprises the following raw materials: PbO, SiO2、CaO、Al2O3And a graphdiyne; preferably, the content of PbO in the glass powder raw material is 45-55 wt% and SiO is calculated by the total mass of the glass powder raw material2The content of (A) is 25-35 wt%, the content of CaO is 14-20 wt%, Al2O3The content of (B) is 3-6 wt%; preferably, the content of the graphdine in the glass frit raw material is 1-5 wt% based on the total mass of the glass frit raw material.
10. Use of a graphdiyne, a thick-film resistor paste according to any one of claims 1-6, or a glass frit according to claim 8 or 9 in the preparation of a thick-film resistor or in improving the resistance temperature change stability, resistance to electrostatic discharge, and/or rate of change of encapsulation of a thick-film resistor.
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CN113643869A (en) * 2021-10-12 2021-11-12 西安宏星电子浆料科技股份有限公司 High-stability resistor paste for thick-film resistor
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