TW202227373A - Sintering aid for buffer layer, resistor including buffer layer, and method for manufacturing resistor including boron-barium-zinc-silicon-aluminum-vanadium based glass frits which is capable of increasing adhesion of a resistor layer to a substrate - Google Patents

Abstract

The present invention provides a sintering aid for a buffer layer, which includes boron-barium-zinc-silicon-aluminum-vanadium based glass frits. The present invention also provides a resistor including a buffer layer, because the buffer layer includes the boron-barium-zinc-silicon-aluminum-vanadium based glass frits, the resistor layer can increase its adhesion to a substrate through the buffer layer sandwiched between the substrate and the resistor layer, and the increased adhesion can further prevent the resistor layer from being deformed, so that the resistance exhibits good momentary load, resistance tolerance and resistance temperature coefficient. The present invention further provides a method for manufacturing the resistor, which has the advantage of improving the cost-effectiveness of production.

Description

Sintering aid for buffer layer, resistor including buffer layer, and method for making resistor

The present invention relates to a sintering aid, especially a sintering aid for chip resistors. The present invention also relates to a chip resistor and a manufacturing method thereof.

Chip resistors are generally used to limit current or reduce voltage, and are produced by printing metal thick film conductors on an alumina ceramic substrate and coating the outer layer with a protective layer. With the advancement of technology, the assembly of circuit boards has become more and more complicated, and there are stricter requirements for the interlayer adhesion, short-time overload (STOL), resistance tolerance (COV%) and temperature coefficient of resistance of each layer in chip resistors. Require.

US Patent No. 6943662 discloses the above-mentioned method of directly disposing the resistance layer on the substrate, but the resistance layer is easily deformed; in addition, it discloses the use of silver-palladium electrode paste, which has a problem of high cost. U.S. Patent Application Publication No. 20110089025 and U.S. Patent No. 5680092 both disclose the vapor deposition method, but the materials and process equipment required for these methods are not only expensive, but also have complex processes and low production capacity. question.

To sum up, it can be seen that a process that takes into account the cost-effectiveness of chip resistor production and the resistance to deformation of the resistance layer remains to be developed.

In order to solve the above problems, the present invention provides a sintering aid for a buffer layer, which comprises a first boron-barium-zinc-silicon-aluminum-vanadium-based glass frit, and the first boron-barium-zinc-silicon-aluminum-vanadium-based glass frit includes B ₂ O ₃ , BaO, ZnO, SiO ₂ , Al ₂ O ₃ and V ₂ O ₅ and based on the total moles of B ₂ O ₃ , BaO, ZnO, SiO ₂ , Al ₂ O ₃ and V ₂ O ₅ , B ₂ O ₃ The content of ZnO is 14.01 mol% to 34 mol%, the content of BaO is 1.5 mol% to 8.44 mol%, the content of ZnO is 20.06 mol% to 34.6 mol%, the content of SiO ₂ is 23 mol% to 49.11 mol%, the content of Al ₂ The content of O ₃ is 4.9 mol % to 7.60 mol %, and the content of V ₂ O ₅ is 0.77 mol % to 1.85 mol %.

The above-mentioned first boron-barium-zinc-silicon-aluminum-vanadium-based glass frit can be expressed in the form of B ₂ O ₃ -BaO-ZnO-SiO ₂ -Al ₂ O ₃ -V ₂ O ₅ .

The sintering aid for buffer layer of the present invention contains specific components and their respective specific content ranges, so that when the buffer layer using the buffer layer as the main component is applied to the resistor, in addition to the buffer layer sandwiched between the substrate and the resistor layer, the resistor layer can be used. It can improve the adhesion of the resistance layer to the substrate, and can reduce the probability of destroying the resistance layer and improve the production yield of the resistance layer when the resistance value of the resistance layer is corrected by laser cutting, and further avoid the deformation of the resistance layer or reduce the number of different layers. The risk of spalling due to stress differences (eg between the substrate and the resistive layer) allows the resistors to exhibit good transient loads, resistance tolerances and temperature coefficients of resistance.

Preferably, in the first boron-barium-zinc-silicon-aluminum-vanadium-based glass frit, based on the total moles of B ₂ O ₃ , BaO, ZnO, SiO ₂ , Al ₂ O ₃ and V ₂ O ₅ , B The content of ₂ O ₃ is 17 mol% to 34 mol%, the content of BaO is 1.5 mol% to 7.5 mol%, the content of ZnO is 22 mol% to 34.6 mol%, and the content of _SiO2 is 23 mol% to 45 mol% , the content of Al ₂ O ₃ is 4.9 mol % to 7.2 mol %, and the content of V ₂ O ₅ is 0.9 mol % to 1.85 mol %.

More preferably, in the first boron-barium-zinc-silicon-aluminum-vanadium-based glass frit, based on the total moles of B ₂ O ₃ , BaO, ZnO, SiO ₂ , Al ₂ O ₃ and V ₂ O ₅ , B The content of ₂ O ₃ is 19.88 mol % to 31.39 mol %, the content of BaO is 2.55 mol % to 6.45 mol %, the content of ZnO is 24.30 mol % to 32.61 mol %, and the content of SiO ₂ is 26.50 mol % to 41.47 mol % , the content of Al ₂ O ₃ is 5.25 mol % to 6.80 mol %, and the content of V ₂ O ₅ is 1.09 mol % to 1.72 mol %.

In some embodiments, the glass softening temperature (Ts) of the first boron-barium-zinc-silicon-aluminum-vanadium-based glass frit is 586°C to 739°C.

Preferably, the glass softening temperature of the first boron-barium-zinc-silicon-aluminum-vanadium-based glass frit is 586°C to 717°C, for example: 586°C, 590°C, 600°C, 620°C, 640°C, 660°C, 680°C, 700°C, 710°C or 717°C; more preferably, the glass softening temperature of the first boron-barium-zinc-silicon-aluminum-vanadium-based glass frit is 608°C to 695°C.

Preferably, the average particle size of the first boron-barium-zinc-silicon-aluminum-vanadium-based glass frit is 1 to 5 microns.

The present invention further provides a resistor, which includes a composite layered structure and two side electrodes, the two side electrodes are respectively disposed on opposite sides of the composite layered structure; and the composite layered structure sequentially includes a substrate, a buffer layer and a resistance layer, wherein the buffer layer is formed by a composition for a buffer layer, and the composition for a buffer layer comprises the above-mentioned sintering aid for a buffer layer, a filler, a first resin and a first organic solvent .

In the present invention, by providing the aforementioned buffer layer, in addition to reducing the shape deformation amount of the printed resistance layer pattern after sintering, that is, the deformation amount is less than 5%, it can also reduce the amount of glass frit added in the resistance layer. Therefore, the resistance layer can still use the buffer layer sandwiched between the substrate and the resistance layer to improve the adhesion between it and the substrate, so as to avoid the problem of large resistance tolerance, improve the instantaneous load, and effectively improve the production capacity and resistance. of reliability.

The buffer layer sintering aid of the present invention forms a liquid phase during the sintering process, which can improve the bonding strength of the contact interface between the resistance layer and the buffer layer, and regulate the difference between thermal expansion and sintering shrinkage between the resistance layer and the substrate.

In some embodiments, the filler comprises any one or a combination of aluminum oxide, zinc oxide, silicon oxide, titanium oxide.

In some embodiments, the first resin comprises any one or a combination of an ethyl cellulose-based resin and an acrylic resin. In the present invention, the first resin is used so that the composition for a buffer layer can be screen-printed.

In some embodiments, the first organic solvent comprises: any one or a combination of terpineols, ethers, esters. The organic solvent of the present invention is used as a diluent.

In some embodiments, the substrate is a ceramic substrate.

In some embodiments, in the composition for the buffer layer, the weight ratio of the sintering aid for the buffer layer to the filler is 0.4:0.6 to 0.75:0.25, but not limited thereto; preferably, the buffer layer The weight ratio of sintering aid to the filler is from 0.45:0.55 to 0.75:0.25, eg, 0.45:0.25, 0.55:0.45, 0.60:0.45, or 0.65:0.35. More preferably, the weight ratio of the sintering aid for the buffer layer to the filler is 0.50:0.50 to 0.70:0.30. The present invention controls the difference in thermal expansion coefficient and sintering shrinkage between the resistance layer and the base material by adjusting the weight ratio of the two, avoids deformation of the resistance layer and prevents the resistance layer from falling off, so as to ensure that the composite layered structure of the resistance has good interlayer adhesion , and exhibit low resistance, good resistance tolerance, temperature coefficient of resistance and transient load.

In some embodiments, in the buffer layer composition, based on the total weight of the buffer layer sintering aid, the filler, the first resin and the first organic solvent, the buffer layer sintering aid The content of the agent is 25.6 to 48 percent by weight; the content of the filler is 16 to 38.4 percent by weight; the content of the first resin is 1 to 2 percent by weight; and the content of the first organic solvent is 30 Weight percent to 40 weight percent.

Preferably, in the composition for the buffer layer, the content of the sintering aid for the buffer layer is based on the total weight of the sintering aid for the buffer layer, the filler, the first resin and the first organic solvent 29 to 48 percent by weight, for example: 29 percent by weight, 31 percent by weight, 33 percent by weight, 35 percent by weight, 37 percent by weight, 39 percent by weight, 41 percent by weight, 43 percent by weight, 45 percent by weight, 47 percent by weight Or 48 weight percent; the filler content is 16 weight percent to 35 weight percent, for example: 16 weight percent, 18 weight percent, 20 weight percent, 22 weight percent, 24 weight percent, 26 weight percent, 28 weight percent, 30 weight percent percentage, 32 weight percent, 34 weight percent or 35 weight percent; the content of the first resin is 1 weight percent to 2 weight percent, for example: 1 weight percent, 1.2 weight percent, 1.4 weight percent, 1.6 weight percent, 1.8 weight percent or 2 weight percent; and the content of the first organic solvent is 30 weight percent to 40 weight percent, for example: 30 weight percent, 32 weight percent, 34 weight percent, 36 weight percent, 38 weight percent or 40 weight percent.

In some embodiments, the resistive layer is formed of a resistive paste, and the resistive paste includes a metal powder, a sintering aid for the resistive layer, a second resin and a second solvent.

Preferably, the second resin comprises either ethyl cellulose resin and acrylic resin or a combination thereof; more preferably, the second resin is the same as the first resin.

Preferably, the second organic solvent comprises: any one or a combination of terpineols, ethers, esters; more preferably, the second organic solvent is the same as the first organic solvent.

The above-mentioned sintering aid for the resistance layer contains the second boron-barium-zinc-silicon-aluminum-vanadium-based glass frit, and can be expressed in the form of B ₂ O ₃ -BaO-ZnO-SiO ₂ -Al ₂ O ₃ -V ₂ O ₅ .

In some embodiments, in the second boron-barium-zinc-silicon-aluminum-vanadium-based glass frit, the second boron-barium-zinc-silicon-aluminum-vanadium-based glass frit comprises B ₂ O ₃ , BaO, ZnO, SiO ₂ , and Al ₂ O ₃ and V ₂ O ₅ , and based on the total moles of B ₂ O ₃ , BaO, ZnO, SiO ₂ , Al ₂ O ₃ and V ₂ O ₅ , the content of B ₂ O ₃ is 26.70 mol% to 29.1 mol%, BaO content is 10.1 mol% to 12.64 mol%, ZnO content is 15.39 mol% to 19.9 mol%, _SiO2 content is 37.2 mol% to 42.36 mol%, Al _{2 O3} content is 2.68 mol% to 3 mol %, and the content of V ₂ O ₅ is 0.22 mol % to 0.6 mol %.

Preferably, in the second boron-barium-zinc-silicon-aluminum-vanadium-based glass frit, the second boron-barium-zinc-silicon-aluminum-vanadium-based glass frit comprises B ₂ O ₃ , BaO, ZnO, SiO ₂ , Al ₂ O ₃ and V ₂ O ₅ , and based on the total moles of B ₂ O ₃ , BaO, ZnO, SiO ₂ , Al ₂ O ₃ and V ₂ O ₅ , the content of B ₂ O ₃ is 27 mol % to 29.1 mol %, The content of BaO is 10.1 mol% to 12.2 mol%, the content of ZnO is 16.1 mol% to 19.9 mol%, the content of _SiO2 is 37.2 mol% to 41.5 mol%, and the content of _Al2O3 is 2.73 mol% to ₃ mol% %, and the content of V ₂ O ₅ is 0.28 mol % to 0.6 mol %.

More preferably, in the second boron-barium-zinc-silicon-aluminum-vanadium-based glass frit, based on the total moles of B ₂ O ₃ , BaO, ZnO, SiO ₂ , Al ₂ O ₃ and V ₂ O ₅ , B The content of ₂ O ₃ is 27.40 mol % to 28.79 mol %, the content of BaO is 10.48 mol % to 11.92 mol %, the content of ZnO is 16.69 mol % to 19.26 mol %, and the content of SiO ₂ is 37.98 mol % to 40.89 mol % , the content of Al ₂ O ₃ is 2.77 mol % to 2.95 mol %, and the content of V ₂ O ₅ is 0.33 mol % to 0.55 mol %.

In some embodiments, the glass softening temperature of the second boron-barium-zinc-silicon-aluminum-vanadium-based glass frit is 565°C to 690°C.

Preferably, the glass softening temperature of the second boron-barium-zinc-silicon-aluminum-vanadium-based glass frit is 565°C to 675°C, for example: 565°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 670°C or 675°C; more preferably, the glass softening temperature of the second boron-barium-zinc-silicon-aluminum-vanadium-based glass frit is 585°C to 655°C. By adjusting the temperature difference of the glass softening point of the sintering aid for the buffer layer and the sintering aid for the resistance layer, the invention can reduce the shrinkage deformation and residual stress of the resistance layer during the sintering process.

According to the present invention, the second boron-barium-zinc-silicon-alumina-vanadium-based glass frit in the sintering aid for the resistance layer has a specific glass softening point range, which can further prevent the resistance layer from being deformed and peeled off, so as to ensure that the resistance layer has good properties. adhesion, and exhibits low resistance, good resistance tolerance, temperature coefficient of resistance, and transient loads.

Preferably, the second boron-barium-zinc-silicon-aluminum-vanadium-based glass frit is powder; more preferably, the average particle size of the second boron-barium-zinc-silicon-aluminum-vanadium-based glass frit is 1 to 5 microns.

In some embodiments, the metal powder includes copper and nickel, and the weight ratio of the copper and nickel is 0.35:0.65 to 0.8:0.2. Preferably, the weight ratio of the copper and nickel is 0.35:0.65 to 0.65:0.35, for example, 0.40:0.60, 0.45:0.55, 0.50:0.50, 0.55:0.45, or 0.60:0.40. The resistance layer of the present invention does not use silver-palladium alloy resistance paste, so the production cost can be effectively reduced.

In some embodiments, the metal powder includes copper powder and nickel powder, or copper-nickel alloy powder.

According to the present invention, controlling the weight ratio of copper and nickel can further prevent the temperature coefficient of resistance from being too high.

In some embodiments, in the electrode paste, the total weight of the metal powder, the sintering aid for the resistance layer, the second resin and the second solvent is the content of the base metal powder in the range of 67 to 79 percent by weight. The content of the sintering aid for the resistance layer is 2 to 6 percent by weight; the content of the second resin is 1 to 3 percent by weight; and the content of the second organic solvent is 17 to 25 percent by weight weight percent.

Preferably, in the electrode paste, based on the total weight of the metal powder, the sintering aid for the resistance layer, the second resin and the second solvent, the content of the metal powder is 67% to 79% by weight Percentage, for example: 67% by weight, 70% by weight, 73% by weight, 76% by weight or 79% by weight; the content of the sintering aid for the resistance layer is 2.5% by weight to 5.5% by weight, such as: 2.5% by weight, 3% by weight percentage, 3.5 weight percent, 4 weight percent, 4.5 weight percent, 5 weight percent or 5.5 weight percent; the content of the second resin is 1 weight percent to 3 weight percent, for example: 1 weight percent, 1.5 weight percent, 2 weight percent , 2.5 weight percent or 3 weight percent, and the content of the second organic solvent is 17 weight percent to 25 weight percent, for example: 17 weight percent, 19 weight percent, 21 weight percent, 23 weight percent or 25 weight percent.

According to the present invention, controlling the content of the sintering aid for the resistance layer can prevent the resistance from rising and the resistance layer from falling off.

Preferably, the metal powder is spherical powder.

Preferably, the average particle size of the metal powder is 0.3 microns to 10 microns. When the particle size of the metal powder is within the aforementioned range, the stacking density of the metal powder and the operability of screen printing can be improved.

In some embodiments, the composite layered structure further includes a back electrode and a front electrode; wherein, the back electrode is disposed on the bottom surface of the substrate; the area of the top surface of the buffer layer is smaller than the area of the top surface of the substrate area, the area of the top surface of the resistance layer is smaller than the area of the top surface of the buffer layer, and the top surface of the substrate and the top surface of the buffer layer are provided with the front electrode, and the top surface of the front electrode and the top surface of the resistance layer Cut the faces flush to form a common plane.

Preferably, the area of the top surface and the area of the bottom surface of the substrate, the buffer layer, the resistance layer and the back electrode are the same in size.

In other embodiments, the resistor further includes a protective layer, and the protective layer is disposed on the top surface (ie the outermost surface) of the composite layered structure to protect the resistor layer, and the top surface of the composite layered structure That is, it refers to the surface jointly formed by the top surface of the front electrode and the top surface of the resistive layer.

The present invention further provides a method for making a resistor, which comprises the following steps: step (a): forming a buffer layer on the surface of a substrate; step (b): forming a resistance layer on the surface of the buffer layer, wherein the buffer layer sandwiched between the substrate and the resistance layer to obtain a composite layered structure; step (c): respectively setting a side electrode on two opposite sides of the composite layered structure to obtain a resistance embryo; and step (d) ): sintering the resistor blank to obtain the resistor; wherein the buffer layer is formed from a composition for a buffer layer, and the composition for a buffer layer includes the aforementioned sintering aid for a buffer layer, a filler, a first resin and a first organic solvent.

Preferably, the method of forming the buffer layer in the step (a) and the method of forming the resistance layer in the step (b) are both formed by screen printing. The method has higher production efficiency.

Preferably, the step (a), the step (b) and the step (c) may each include a drying step, and the drying temperature is 100°C to 150°C.

Preferably, the drying time of each of the step (a), the step (b) and the step (c) is 10 minutes to 15 minutes.

Preferably, the sintering temperature in step (d) is 880°C to 920°C.

Preferably, the sintering time of the step (d) is 10 minutes to 15 minutes.

Preferably, before step (a), a back electrode may be formed on the bottom surface of the substrate. More preferably, the composite layered structure includes the back electrode, the substrate, the buffer layer, the resistance layer and a front electrode; the top surface area of the buffer layer is smaller than the top surface area of the substrate, and the top surface area of the resistance layer is The area is smaller than the top surface area of the buffer layer, and the step (b) further comprises: forming the front electrode on the top surface of the substrate and the top surface of the buffer layer, and the top surface of the front electrode and the top surface of the resistance layer Cut flush to form a common plane.

Preferably, after the resistor blank is sintered in the step (d), a protective layer is further formed on the top surface of the resistor blank or the composite layered structure, and then a sintering step and an electrode electroplating step are performed to form an outer electrode layer, Finally got this resistor.

In some embodiments, the material of the protective layer includes the material of glass. Preferably, the sintering temperature of the protective layer is 400°C to 500°C. Preferably, the sintering time of the protective layer is 10 minutes to 15 minutes.

In some embodiments, the material of the protective layer includes epoxy resin. Preferably, the thermal curing temperature of the protective layer is 150°C to 300°C. Preferably, the thermal curing time of the protective layer is 10 minutes to 30 minutes.

Preferably, the above-mentioned electrode electroplating step refers to the electroplating of copper, nickel and/or tin on the surface of the side electrode, the front electrode and the back electrode; in some embodiments, the electrode electroplating step may precede the electrode plating step. Copper plating is performed on the surface of the side electrode, the front electrode and the back electrode to form a copper outer electrode layer; then nickel plating is performed on the surface of the copper outer electrode layer to form a nickel outer electrode layer; and the surface of the nickel outer electrode layer is Carry out tin electroplating to form a tin outer electrode layer, that is, a set of three-layered outer electrodes formed by a copper outer electrode layer, a nickel outer electrode layer and a tin outer electrode layer are wrapped around the side electrode, the front electrode and the back electrode. The outer surface. The electrode of the present invention is not limited to the use of precious metals such as silver and palladium, so it is helpful to reduce the production cost.

In this specification, the average particle size refers to the particle size corresponding to the cumulative particle size distribution percentage reaching 50% in the particle size distribution percentage statistics of the particles, namely D ₅₀ .

To sum up, by adding a buffer layer to the resistor of the present invention, the resistance layer can increase the adhesion to the substrate, and can also avoid the deformation of the resistance layer, so that the resistor exhibits good instantaneous load, resistance tolerance and resistance temperature coefficient, thereby improving the resistance of the resistance. Cost-effective production, so it has market competitiveness.

Several examples and comparative examples are listed below to illustrate the embodiments of the present invention. Those skilled in the art can easily understand the advantages and effects that the present invention can achieve through the content of this specification, and proceed without departing from the spirit of the present invention. Various modifications and alterations to carry out or apply the teachings of the present invention.

Example 1: Resistance

As shown in FIG. 1 , the resistor 1 includes a composite layered structure 10 , two side electrodes 20 and a protective layer 30 . The two side electrodes 20 are respectively disposed on two opposite sides 100 of the composite layered structure 10 , and the protective layer 30 is disposed on the top surface 110 of the composite layered structure 10; and the composite layered structure 10 includes two back electrodes 120, a substrate 130, a buffer layer 140, a resistance layer 150 and two front electrodes 160; wherein, the two back surfaces The electrodes 120 are symmetrically disposed on the bottom surface 131 of the substrate 130 , the area of the top surface 141 of the buffer layer 140 is smaller than the area of the top surface 132 of the substrate 130 , and the area of the top surface 151 of the resistive layer 150 is smaller than that of the top surface of the buffer layer 140 and the top surface 132 of the substrate 130 and the top surface 141 of the buffer layer 140 are further symmetrically provided with the two front electrodes 160 , and the top surfaces 161 of the two front electrodes 160 are cut from the top surface 151 of the resistance layer 150 aligned to form a common plane. Wherein, the buffer layer 140 is formed by a composition for a buffer layer, and the composition for a buffer layer includes a sintering aid for a buffer layer, a filler, a first resin and a first organic solvent.

Example 2: Manufacturing method of resistor

1. Preparation of composite layered structure:

(1) Preparation of back electrode: The back electrode is printed on the bottom surface of the alumina substrate by screen printing, the material is copper, and dried at 100°C to 150°C for 10 to 15 minutes.

(2) Preparation of buffer layer: after mixing the sintering aid for buffer layer, filler, first resin and first organic solvent, a composition for buffer layer is made, and printed on the top surface of the alumina substrate by screen printing, After drying at 100°C to 150°C for 10 to 15 minutes, a buffer layer is formed.

(3) Preparation of the resistance layer: after mixing the metal powder, the sintering aid for the resistance layer, the second resin and the second solvent, a resistance paste is made, and it is printed on the top surface of the buffer layer by screen printing at 100° C. Dry at 150° C. for 10 minutes to 15 minutes to form a resistance layer.

(4) Preparation of front electrode: The front electrode is printed on the top surface of the alumina substrate and the top surface of the buffer layer by screen printing, and the material is copper, so that the top surface of the front electrode is flush with the top surface of the resistance layer, To form a horizontal co-planar, drying is performed at 100°C to 150°C for 10 to 15 minutes.

2. Preparation of side electrodes:

The opposite sides of the composite layered structure (that is, the sides formed by the front electrode, the substrate and the back electrode) are coated with side electrodes respectively by rolling and dipping. Co-sintering is carried out to 920°C for 10 minutes to 15 minutes.

3. Preparation of protective layer:

After the resistance layer is laser-cut to adjust the resistance value, the protective layer is screen-printed on the coplanar surface formed by the front electrode and the resistance layer, that is, the outermost surface of the composite layered structure, so as to prevent the resistance layer from contacting the outside world. Air causes oxidation and vulcanization; wherein, the protective layer is made of epoxy resin, the thermal curing temperature of the protective layer is 150°C to 300°C, and the thermal curing time is 10 minutes to 30 minutes.

4. Preparation of external electrode layer: copper electroplating is performed on the surface of the side electrode, the front electrode and the back electrode to form a copper external electrode layer; then nickel electroplating is performed on the surface of the copper external electrode layer to form a nickel external electrode and tin electroplating on the surface of the nickel outer electrode layer to form a tin outer electrode layer, that is, a set of three-layered outer electrodes formed by the copper outer electrode layer, the nickel outer electrode layer and the tin outer electrode layer are covered on the side. electrode, the front electrode and the outer surface of the back electrode.

Test Example 1: Comparison of Resistance Efficacy Using Different Buffer Layer Sintering Auxiliary Formulations

Each group was fabricated into resistors according to the method described in Example 2, but no protective layer was provided; wherein, the Ts point was measured before the start of the process, and the deformation of the resistor layer was observed after the sintering was completed. force, resistivity, COV%, TCR and STOL) are all carried out after the aforementioned electroplating of the outer electrodes, and are further explained as follows:

(1) Composition for buffer layer

The formulations of the sintering aids for each group of buffer layers are shown in Table 1. The fillers are all Al ₂ O ₃ , the first resins are all ethyl cellulose, and the first organic solvents are all terpineol. Based on the total weight of the sintering aid for the buffer layer, the filler, the first resin and the first organic solvent, each group adopts the same ratio: the content of the sintering aid for the buffer layer is 38.40 weight percent; the content of the filler is 25.60 weight percent ; The content of the first resin is 1.5 weight percent; and the content of the first organic solvent is 34.50 weight percent.

Table 1: Formulations of sintering aids for each group of buffer layers (unit: mol%) group number B ₂ O ₃ BaO ZnO _SiO2 Al ₂ O ₃ V ₂ O ₅ Example 3-1 14.01 8.44 20.06 49.11 7.60 0.77 Example 3-2 Example 3-3 19.88 6.45 24.30 41.47 6.80 1.09 Example 3-4 Example 3-5 25.67 4.48 28.48 33.93 6.02 1.40 Examples 3-6 Examples 3-7 31.39 2.55 32.61 26.50 5.25 1.72 Examples 3-8 Comparative Example 3-1 37.02 0.63 36.68 19.16 4.49 2.02 Comparative Example 3-2

(2) Resistor paste

The formulations of the sintering aids for each group of resistance layers are the same, and the sintering aids for the resistance layers include: the content of B ₂ O ₃ is 28.09 mol %, the content of BaO is 11.20 mol %, the content of ZnO is 17.98 mol %, The content of SiO ₂ was 39.43 mol %, the content of Al ₂ O ₃ was 2.86 mol %, and the content of V ₂ O ₅ was 0.44 mol %. In the resistive paste, based on the total weight of the metal powder, the resistive layer sintering aid, the second resin and the second organic solvent, the same proportions for each group are as follows: the content of copper is 43.80 weight percent; the content of nickel is 29.20 weight percent The content of the resistance layer sintering aid is 4.00% by weight; the content of the second resin is 2.00% by weight; and the content of the second organic solvent is 21.00% by weight; wherein, the second resin is the same as the first resin, and the second organic solvent The solvent is the same as the first organic solvent.

(3) Sintering temperature

When the suffix of each group of labels is odd (i.e. N-1, N-3, N-5 and N-7, N is the number of the example), the sintering temperature is 880°C; the suffix of each group of labels is an even number ( Namely N-2, N-4, N-6 and N-8), the sintering temperature is 920 ℃.

(4) Efficacy test

1. Glass softening point: According to the specification of ASTM E1545, the Ts of the sintering aid used for each buffer layer was measured by a thermomechanical thermal analyzer (Thermomechanical Analysis, TMA).

2. Resistance layer deformation: the calculation formula of resistance layer deformation: [(maximum width-minimum width)/maximum width]*100%, ie (△W/W)*100%, when the resistance layer deformation is greater than 5% When the resistance layer is determined, it will be determined that the resistance layer is obviously deformed, as shown in FIG. 2A ; when the deformation amount of the resistance layer is less than 5%, it will be determined that the resistance layer is not deformed, such as shown in FIG. 2B .

3. Adhesion: Tested according to ISO 2409, in which grade 0 (ISO class 0) means "the cutting edge is smooth and complete, and the coating film is not peeled at all"; grade 1 (ISO class 1) means "the intersection of the cutting line" There are small chips, and the peeling area is less than 5% of the total area"; Class 2 (ISO class 2) means "there are small chips at the edge and intersection of the cutting line, and the peeling area accounts for 5% to less than 15% of the total area"; Level 3 (ISO class 3) means "the edge of the cutting line and small squares are partially or completely peeled off, and the peeling area accounts for 15% to less than 35% of the total area"; level 4 (ISO class 4) means "the edge of the cutting line, Part or all of the small squares peeled off, and the peeled area accounts for 35% to less than 65% of the total area; more than 65% of the area.”

4. Resistivity: measure the resistance according to IEC 60115-1 / JIS C 5201-1 Clause 4.5.

5. Resistance tolerance (COV%): resistance standard deviation/resistance mean, resistance tolerance greater than 3% will affect the resistance yield.

6. Temperature Coefficient of Resistance (TCR): TCR (±100ppm/°C) is measured and calculated in accordance with IEC 60115-1 Clause 4.8; the test temperature is from T1 (25°C) to T2(155℃), R2 is the measured resistance value of T2 point, R1 is the measured resistance value of T1 point, the calculation formula is TCR(ppm/℃) = (R2-R1)/R1×1 / (T2-T1 )×10 ⁶ . In addition, when the TCR exceeds the range of ±100ppm/°C, the resistance stability of the resistor under ambient temperature changes will be affected. Since the TCR of commercially available power packs can exceed ±100ppm/°C, whether the TCR is within ±100ppm/°C is not the basis for the present invention to determine whether the resistance is qualified or not.

7. Short-time overload (STOL): According to the specification of Article 4.13 of IEC 60115-1, and the rated overload is 5 times for 5 seconds, STOL is measured.

Table 2: Ts, deformation, adhesion, resistivity, COV%, TCR and STOL test results of each resistor group number Ts (°C) Resistive layer deformation adhesion Resistivity (Ω.cm) COV% (%) TCR (ppm/℃) STOL (Ω) Example 3-1 739 none Level 2 2.52E-05 1.7 45 0.23 Example 3-2 none Level 1 1.23E-05 1.5 42 0.17 Example 3-3 695 none Level 0 2.51E-05 1.7 43 0.10 Example 3-4 none Level 0 1.22E-05 1.4 41 0.02 Example 3-5 652 none Level 0 2.50E-05 1.7 45 0.02 Examples 3-6 none Level 0 1.20E-05 1.3 40 0.01 Examples 3-7 608 none Level 0 2.48E-05 1.5 43 0.04 Examples 3-8 none Level 0 1.18E-05 1.2 42 0.08 Comparative Example 3-1 565 deformation Level 0 N/A N/A N/A N/A Comparative Example 3-2 deformation Level 0 N/A N/A N/A N/A

From the test results in Table 2, it can be seen that the content of B ₂ O ₃ in the sintering aid for buffer layer of Comparative Example 3-1 and Comparative Example 3-2 is 37.02 mol%, which is higher than 34 mol%, and the content of BaO is 0.63 mol% , below 1.5 mol%, ZnO content is 36.68 mol%, above 34.6 mol%, _SiO2 content is 19.16 mol%, below ₂₃ mol%, _Al2O3 content is 4.49 mol%, below 4.9 mol%, And the content of V ₂ O ₅ is 2.02 mol%, which is higher than 1.85 mol%, so its glass softening point is only 565℃. In addition, due to the problem that the external appearance of the resistance layer of Comparative Example 3-1 and Comparative Example 3-2 was deformed too much, subsequent tests could not be carried out.

The content of B ₂ O ₃ in the sintering aid for buffer layers of Examples 3-1 and 3-2 is 14.01 mol %, the content of BaO is 8.44 mol %, the content of ZnO is 20.06 mol %, and the content of SiO ₂ is 49.11 mol % %, the content of Al ₂ O ₃ is 7.60 mol%, and the content of V ₂ O ₅ is 0.77 mol%, and the glass softening point temperature is 739℃. The structure has been significantly improved.

Finally, the content of B ₂ O ₃ in the sintering aids for buffer layers of Examples 3-3 to 3-8 ranges from 17 mol % to 34 mol %, the content of BaO ranges from 1.5 mol % to 7.5 mol %, and the content of ZnO The content ranges from 22 mol% to 34.6 mol%, the _SiO2 content ranges from ₂₃ mol% to ₄₅ mol%, the _Al2O3 content ranges from 4.9 mol% to 7.2 mol%, and the _V2O5 content ranges from 0.9 mol% to 1.85 mol%, and the temperature of the glass softening point is between 608 °C and 695 °C, so that not only the deformation of the resistive layer is less than 5%, but also has better adhesion (both are in the 0th grade), while showing low resistance, good resistance tolerance, temperature coefficient of resistance and transient loads.

Test Example 2: Comparison of resistance efficacy with different weight ratios of sintering aid and filler for buffer layer

Each group was fabricated into resistors according to the method described in Example 2, but no protective layer was provided; wherein, the Ts point was measured before the start of the process, and the deformation of the resistor layer was observed after the sintering was completed. force, resistivity, COV%, TCR and STOL) are all carried out after the aforementioned electroplating of the outer electrodes, and are further explained as follows:

(1) Composition for buffer layer

The formula of the sintering aid for the buffer layer is the same as that of Example 3-5 and Example 3-6: the content of B ₂ O ₃ is all 25.67 mol%, the content of BaO is all 4.48 mol%, the content of ZnO is all 28.48 mol%, and the content of SiO ₂ The content of the buffer layer is 33.93 mol%, the content of Al ₂ O ₃ is 6.02 mol %, and the content of V ₂ O ₅ is 1.40 mol %, and the formula of the composition for the buffer layer is shown in Table 3, wherein the filler is Al ₂ O _3. The first resin is ethyl cellulose, and the first organic solvent is terpineol.

Table 3: Composition formula for each group of buffer layers (unit: weight percentage) group number Weight ratio of sintering aid to filler for buffer layer Sintering aid for buffer layer filler first resin first organic solvent Example 4-1 0.70 0.30 44.80 19.20 1.50 34.50 Example 4-2 Example 3-5 0.60 0.40 38.40 25.60 1.50 34.50 Examples 3-6 Example 4-3 0.50 0.50 32.00 32.00 1.50 34.50 Example 4-4 Example 4-5 0.40 0.60 25.60 38.40 1.50 34.50

(2) Resistor paste: same as Test Example 1.

(3) Sintering temperature: the same as in Test Example 1, except that the sintering temperature in Examples 4-5 was 920°C.

(4) Efficacy test: carry out with the test method described in Test Example 1, and each test result is recorded in Table 4.

Table 4: Ts, deformation, adhesion, resistivity, COV%, TCR and STOL test results of each resistor group number Ts (°C) Resistive layer deformation adhesion Resistivity (Ω.cm) COV% (%) TCR (ppm/℃) STOL (Ω) Example 4-1 652 none Level 0 2.42E-05 1.8 48 0.06 Example 4-2 none Level 0 1.56E-05 1.4 42 0.10 Example 3-5 652 none Level 0 2.50E-05 1.7 45 0.02 Examples 3-6 none Level 0 1.20E-05 1.3 40 0.01 Example 4-3 652 none Level 0 2.53E-05 1.8 44 0.12 Example 4-4 none Level 0 1.30E-05 1.5 42 0.05 Example 4-5 652 none Level 2 1.31E-05 1.4 42 0.30

As can be seen from Table 4, since the sintering aid for the buffer layer of the present invention is used in Examples 3-5, 3-6, and 4-1 to 4-5, the deformation of the resistance layer of each group of resistors is All are less than 5%, and have good transient load, resistance tolerance and resistance temperature coefficient.

Furthermore, compared with Example 4-5, since the weight ratio of the sintering aid for buffer layer and the filler in Example 3-5, Example 3-6, Example 4-1 to Example 4-4 is different, At 0.45:0.55 to 0.75:0.25, and the content of the sintering aid for the buffer layer is between 29 and 48 weight percent; the filler content is between 16 and 35 weight percent; the first resin is between 1 weight percent percentage to 2 weight percent; and the content of the first organic solvent is 30 to 40 weight percent, so it can have better adhesion (all belong to grade 0), and at the same time exhibit low resistance, good resistance tolerance, resistance temperature coefficient and transient load.

Test Example 3: Comparison of Resistance Efficacy Using Different Filler Types

Each group was fabricated into resistors according to the method described in Example 2, but no protective layer was provided; wherein, the Ts point was measured before the start of the process, and the deformation of the resistor layer was observed after the sintering was completed. force, resistivity, COV%, TCR and STOL) are all carried out after the aforementioned electroplating of the outer electrodes, and are further explained as follows:

(1) Composition for buffer layer

Except for the different types of fillers shown in Table 5, the other conditions are the same for each group, and the descriptions are as follows:

The formula of each group of buffer layer sintering aids is the same as that of Example 3-5 and Example 3-6: B ₂ O ₃ content is all 25.67 mol%, BaO content is all 4.48 mol%, ZnO content is all 28.48 mol%, The content of SiO ₂ is all 33.93 mol%, the content of Al ₂ O ₃ is all 6.02 mol %, and the content of V ₂ O ₅ is all 1.40 mol %.

The first resin of each group is ethyl cellulose, the first organic solvent is terpineol, and the ratio of the composition for the buffer layer is the same as that of Example 3-5 and Example 3-6: the buffer layer is used as a sintering aid Based on the total weight of the filler, the first resin and the first organic solvent, the content of the sintering aid for the buffer layer is 38.40% by weight; the content of the filler is 25.60% by weight; the content of the first resin is 1.5% by weight; The content of an organic solvent is 34.50 weight percent.

Table 5: Types of fillers in each group group number filler Example 3-5 Al ₂ O ₃ Examples 3-6 Example 5-1 ZnO Example 5-2 Example 5-3 _SiO2 Example 5-4 Example 5-5 TiO ₂ Embodiment 5-6

(2) Resistor paste: same as Test Example 1.

(3) Sintering temperature: same as Test Example 1.

(4) Efficacy test: carry out with the test method described in Test Example 1, and each test result is recorded in Table 6.

Table 6: Ts, deformation, adhesion, resistivity, COV%, TCR and STOL test results of each resistor Ts (°C) Resistive layer deformation adhesion Resistivity (Ω.cm) COV% (%) TCR (ppm/℃) STOL (Ω) Example 3-5 652 none Level 0 2.50E-05 1.7 45 0.02 Examples 3-6 none Level 0 1.20E-05 1.3 40 0.01 Example 5-1 652 none Level 0 2.53E-05 1.8 44 0.03 Example 5-2 none Level 0 1.21E-05 1.4 41 0.02 Example 5-3 652 none Level 0 2.48E-05 1.6 43 0.02 Example 5-4 none Level 0 1.22E-05 1.3 41 0.01 Example 5-5 652 none Level 0 2.49E-05 1.6 45 0.03 Embodiment 5-6 none Level 0 1.24E-05 1.3 42 0.02

The fillers of Examples 3-5, 3-6, 5-1 to 5-6 were selected from aluminum oxide, zinc oxide, silicon oxide and titanium oxide, respectively, and the deformation of the resistance layer was low. At 5%, the adhesion is all class 0, and exhibits low resistance, good resistance tolerance, temperature coefficient of resistance and transient load.

Test Example 4: Comparison of Resistor Efficiency Without Buffer Layer

(1) In the comparative examples of this test, no buffer layer was printed, and different weight percentages of sintering aids for resistance layers were used, and the rest of the steps were the same.

(2) The formulation of the resistance paste is shown in Table 7, wherein the formulation of the sintering aid for the resistance layer is the same as that of Test Example 1, the second resin is ethyl cellulose, and the second organic solvent is terpineol.

Table 7: Resistor paste formula (unit: weight percentage) group number Sintering aid for resistance layer copper nickel second resin second organic solvent Comparative Example 6-1 4.00 43.80 29.20 2.00 21.00 Comparative Example 6-2 Comparative Example 6-3 6.00 42.60 28.40 2.00 21.00 Comparative Example 6-4 Comparative Example 6-5 8.00 41.40 27.60 2.00 21.00 Comparative Example 6-6

(3) Sintering temperature: same as Test Example 1.

(4) Efficacy test: carry out with the test method described in Test Example 1, and each test result is recorded in Table 8.

Table 8: Deformation, adhesion, resistivity, COV%, TCR and STOL test results of each resistor group number Resistive layer deformation adhesion Resistivity (Ω.cm) COV% (%) TCR (ppm/℃) STOL (Ω) Comparative Example 6-1 none Level 4 2.63E-05 1.7 53 0.48 Comparative Example 6-2 none Level 3 1.30E-05 1.3 46 0.36 Comparative Example 6-3 none Level 3 9.56E-05 3.5 95 0.29 Comparative Example 6-4 none Level 2 8.74E-05 3.1 87 0.15 Comparative Example 6-5 deformation Level 0 N/A N/A N/A N/A Comparative Example 6-6 deformation Level 0 N/A N/A N/A N/A

As can be seen from Table 8, when the resistor is not provided with a buffer layer (ie, Comparative Example 6-1 and Comparative Example 6-2), and the content of the sintering aid for the resistor layer is 4 weight percent, the adhesion test results are obviously poor, only There is either level 3 or level 4.

Furthermore, under the same conditions without a buffer layer, when the content of the sintering aid for the resistance layer is increased to 6 weight percent in Comparative Examples 6-3 and 6-4, although the adhesion of the resistance layer can be improved, But it results in at least 3 times higher resistance, about 2 times higher resistance tolerance, and about 2 times higher temperature coefficient of resistance.

Finally, when the content of the sintering aid for the resistance layer in Comparative Examples 6-5 and 6-6 reaches 8 weight percent, although the adhesion test results are good, there is a problem that the appearance of the resistance layer is deformed too much, and the follow-up cannot be carried out. test.

Test Example 5: Comparison of resistance efficacy with different ratios of sintering aids for resistance layers

Each group was fabricated into resistors according to the method described in Example 2, but no protective layer was provided; wherein, the Ts point was measured before the start of the process, and the deformation of the resistor layer was observed after the sintering was completed. force, resistivity, COV%, TCR and STOL) are all carried out after the aforementioned electroplating of the outer electrodes, and are further explained as follows:

(1) Composition for buffer layer:

The sintering aids used in each group of buffer layers are the same as those in Example 3-5 and Example 3-6: the content of B ₂ O ₃ is 25.67 mol%, the content of BaO is 4.48 mol%, the content of ZnO is 28.48 mol%, and the content of SiO ₂ The contents are all 33.93 mol%, the Al ₂ O ₃ contents are all 6.02 mol %, and the V ₂ O ₅ contents are all 1.40 mol %.

In addition, the fillers are all Al ₂ O ₃ , the first resins are all ethyl cellulose, the first organic solvents are all terpineol, and the ratio of the composition for the buffer layer is the same as that of Example 3-5 and Example 3-6 : Based on the total weight of the sintering aid for the buffer layer, the filler, the first resin and the first organic solvent, each group adopts the same ratio: the content of the sintering aid for the buffer layer is 38.40 weight percent; the content of the filler is 25.60 weight percent; the content of the first resin is 1.5 weight percent; and the content of the first organic solvent is 34.50 weight percent.

(2) Resistor paste:

The formulations of the sintering aids for each group of resistance layers are shown in Table 9. Based on the total weight of metal powder, resistance layer sintering aid, second resin and second organic solvent, each group adopts the same ratio: copper content is 43.80 weight percent; nickel content is 29.20 weight percent; resistance layer sintering aid The content of the agent is 4.00% by weight; the content of the second resin is 2.00% by weight; the content of the second organic solvent is 21.00% by weight; the second resin is the same as the second resin, and the second organic solvent is the same as the first organic solvent. .

Table 9: Formulation of sintering aid for each group of resistance layers (unit: mol%) group number B ₂ O ₃ BaO ZnO _SiO2 Al ₂ O ₃ V ₂ O ₅ Example 7-1 28.79 10.48 19.26 37.98 2.95 0.55 Example 7-2 Example 3-5 28.09 11.20 17.98 39.43 2.86 0.44 Examples 3-6 Example 7-3 27.40 11.92 16.69 40.89 2.77 0.33 Example 7-4 Example 7-5 26.70 12.64 15.39 42.36 2.68 0.22 Example 7-6

(3) Sintering temperature: same as Test Example 1.

(4) Efficacy test: Carry out the same test method described in Test Example 1, and record the test results in Table 10, where Ts is the glass softening point of the sintering aid for the resistance layer.

Table 10: Ts, deformation, adhesion, resistivity, COV%, TCR and STOL test results of each resistor group number Ts (°C) Resistive layer deformation adhesion Resistivity (Ω.cm) COV% (%) TCR (ppm/℃) STOL (Ω) Example 7-1 585 none Level 0 2.60E-05 1.6 46 0.04 Example 7-2 none Level 0 2.00E-05 1.8 43 0.05 Example 3-5 620 none Level 0 2.50E-05 1.7 45 0.02 Examples 3-6 none Level 0 1.20E-05 1.3 40 0.01 Example 7-3 655 none Level 0 2.70E-05 1.7 47 0.09 Example 7-4 none Level 0 2.50E-05 1.5 42 0.06 Example 7-5 690 none Level 2 3.10E-05 1.6 49 0.40 Example 7-6 none Level 1 2.90E-05 1.4 43 0.33

It can be seen from Table 10 that the content of B ₂ O ₃ in the sintering aids for buffer layers of Examples 7-5 and 7-6 is 26.70 mol %, the content of BaO is 12.64 mol %, the content of ZnO is 15.39 mol %, and the content of SiO When the content of ₂ is 42.36 mol%, the content of Al ₂ O ₃ is 2.68 mol%, and the content of V ₂ O ₅ is 0.22 mol%, and the glass softening point is 690 ℃, the resistance layer is not deformed, and the adhesion can reach the first level or level 2.

Further, compared with Example 7-5 and Example 7-6, since the sintering aid for buffer layer in Example 3-5, Example 3-6, Example 7-1 to Example 7-4 The B ₂ O ₃ content ranges from 27 mol% to 29.1 mol %, the BaO content ranges from 10.1 mol % to 12.2 mol %, the ZnO content ranges from 16.1 mol % to 19.9 mol %, and the SiO ₂ content ranges from 37.2 mol % to 12.2 mol %. 41.5 mol%, Al ₂ O ₃ content ranging from 2.73 mol% to 3 mol%, and V ₂ O ₅ content ranging from 0.28 mol% to 0.6 mol%, so it can have better adhesion (all are grade 0) , and show low resistance, good resistance tolerance, temperature coefficient of resistance and instantaneous load.

Test Example 6: Comparison of Resistor Efficacy with Different Copper-Nickel Ratios in Resistor Layer

Each group was fabricated into resistors according to the method described in Example 2, but no protective layer was provided; wherein, the Ts point was measured before the start of the process, and the deformation of the resistor layer was observed after the sintering was completed. force, resistivity, COV%, TCR and STOL) are all carried out after the aforementioned electroplating of the outer electrodes, and are further explained as follows:

(1) Composition for buffer layer: the same as Example 3-5 and Example 3-6.

(2) Resistor paste:

The formulations of the sintering aids used in the resistance layers of each group are the same, and are the same as in Examples 3-5 and 3-6: the content of B ₂ O ₃ is 28.09 mol%, the content of BaO is 11.20 mol%, and the content of ZnO is 17.98 mol %, SiO ₂ content of 39.43 mol %, Al ₂ O ₃ content of 2.86 mol %, and V ₂ O ₅ content of 0.44 mol %. The formula of the resistance paste is shown in Table 11, wherein the second resin is ethyl cellulose, and the second organic solvent is terpineol.

Table 11: Resistor paste formula (unit: weight percentage) group number Copper/Nickel Weight Ratio Sintering aid for resistance layer copper nickel second resin second organic solvent Example 8-1 0.80 0.20 4.00 58.40 14.60 2.00 21.00 Example 8-2 Example 8-3 0.70 0.30 4.00 51.10 21.90 2.00 21.00 Example 8-4 Example 3-5 0.60 0.40 4.00 43.80 29.20 2.00 21.00 Examples 3-6 Example 8-5 0.50 0.50 4.00 36.50 36.50 2.00 21.00 Example 8-6 Example 8-7 0.40 0.60 4.00 29.20 43.80 2.00 21.00 Example 8-8

(3) Sintering temperature: same as Test Example 1.

(4) Efficacy test: The test method is the same as that described in Test Example 1, and the test results are recorded in Table 12, wherein Ts is the glass softening point of the sintering aid for the resistance layer.

Table 12: Ts, deformation, adhesion, resistivity, COV%, TCR and STOL test results for each resistor group number Ts (°C) Resistive layer deformation adhesion Resistivity (Ω.cm) COV% (%) TCR (ppm/℃) STOL (Ω) Example 8-1 620 none Level 0 9.80E-06 1.3 290 0.38 Example 8-2 none Level 0 9.50E-06 1.1 284 0.35 Example 8-3 620 none Level 0 2.20E-05 1.6 157 0.17 Example 8-4 none Level 0 1.10E-05 1.5 165 0.19 Example 3-5 620 none Level 0 2.50E-05 1.7 45 0.02 Examples 3-6 none Level 0 1.20E-05 1.3 40 0.01 Example 8-5 620 none Level 0 3.00E-05 1.7 69 0.03 Example 8-6 none Level 0 2.50E-05 1.5 66 0.02 Example 8-7 620 none Level 3 3.30E-05 1.9 92 0.05 Example 8-8 none Level 2 2.60E-05 1.6 90 0.03

It can be seen from Table 12 that the resistance layers of Examples 3-5, 3-6, and 8-1 to 8-8 are not deformed and have appropriate adhesion.

Further, it can be seen from Examples 3-5, 3-6, 8-5 to 8-8 that when the weight ratio of copper and nickel is between 0.35:0.65 and 0.65:0.35, and the metal Based on the total weight of the powder, the sintering aid for the resistance layer, the second resin and the second solvent, when the content of the metal powder is 67% to 79% by weight, the temperature coefficient of resistance of the resistor can be significantly improved.

Test Example 7: Comparison of Resistance Efficacy with Different Amounts of Sintering Auxiliary Additives for Resistive Layers

Each group was fabricated into resistors according to the method described in Example 2, but no protective layer was provided; wherein, the Ts point was measured before the start of the process, and the deformation of the resistor layer was observed after the sintering was completed. force, resistivity, COV%, TCR and STOL) are all carried out after the aforementioned electroplating of the outer electrodes, and are further explained as follows:

(1) Composition for buffer layer: same as Example 3-5 and Example 3-6.

(2) Resistor paste:

The formulations of the sintering aids used in the resistance layers of each group are the same, and are the same as those in Examples 3-5 and 3-6: the content of B ₂ O ₃ is 28.09 mol%, the content of BaO is 11.20 mol%, and the content of ZnO is 17.98 mol %, SiO ₂ content of 39.43 mol %, Al ₂ O ₃ content of 2.86 mol %, and V ₂ O ₅ content of 0.44 mol %. The formula of the resistance paste is shown in Table 13, wherein the second resin is ethyl cellulose, and the second organic solvent is terpineol.

Table 13: Resistor paste formula (unit: weight percentage) group number Sintering aid for resistance layer copper nickel second resin second organic solvent Example 9-1 6.00 42.60 28.40 2.00 21.00 Example 9-2 Example 9-3 5.00 43.20 28.80 2.00 21.00 Example 9-4 Example 3-5 4.00 43.80 29.20 2.00 21.00 Examples 3-6 Example 9-5 3.00 44.40 29.60 2.00 21.00 Example 9-6 Example 9-7 2.00 45.00 30.00 2.00 21.00 Example 9-8

(3) Sintering temperature: same as Test Example 1.

(4) Efficacy test: The test method is the same as that described in Test Example 1, and the test results are recorded in Table 14, wherein Ts is the glass softening point of the sintering aid for the resistance layer.

Table 14: Ts, deformation, adhesion, resistivity, COV%, TCR and STOL test results for each resistor group number Ts (°C) Resistive layer deformation adhesion Resistivity (Ω.cm) COV% (%) TCR (ppm/℃) STOL (Ω) Example 9-1 620 none Level 0 4.20E-05 1.3 88 0.09 Example 9-2 none Level 0 5.00E-05 1.5 95 0.12 Example 9-3 620 none Level 0 3.10E-05 15 65 0.06 Example 9-4 none Level 0 3.20E-05 1.3 71 0.07 Example 3-5 620 none Level 0 2.50E-05 1.7 45 0.02 Examples 3-6 none Level 0 1.20E-05 1.3 40 0.01 Example 9-5 620 none Level 0 2.60E-05 1.4 55 0.06 Example 9-6 none Level 0 2.00E-05 1.5 46 0.02 Example 9-7 620 none Level 2 3.20E-05 1.9 57 0.06 Example 9-8 none Level 1 2.50E-05 1.6 48 0.03

It can be seen from Table 14 that when the sintering aid for the resistance layer contained in Examples 9-1 and 9-2 is 6% by weight, the resistance layer is not deformed, and the adhesion can reach the 0th level. The glass composition is increased, resulting in a high resistivity, which exceeds 4x10 ^-5 Ω.cm.

The sintering aid for the resistance layer contained in Examples 9-7 and 9-8 is 2 weight percent, because the glass composition in the resistance layer is low, resulting in a decrease in the adhesion between the resistance layer and the buffer layer (grade 1 or level 2).

From the above, it can be seen that, based on the total weight of the metal powder, the sintering aid for the resistance layer, the second resin and the second solvent, when the content of the sintering aid for the resistance layer is between 2.5% by weight and 5.5% by weight, it can be further The adhesion between the resistance layer and the buffer layer is improved, and the resistivity can be further improved.

To sum up, in the present invention, by providing a buffer layer formed with a sintering aid for a buffer layer having a specific composition and its content, the resistance-removing layer can be raised between the substrate and the substrate by means of the buffer layer sandwiched between the substrate and the resistance layer. The excellent adhesion can further avoid the deformation of the resistance layer, so that the resistance exhibits good instantaneous load, resistance tolerance and resistance temperature coefficient.

1: Resistor 10: Composite Laminated Structure 20: Side electrodes 30: Protective layer 100: side 110: top surface 120: back electrode 130: Substrate 131: Bottom 132: top surface 140: Buffer layer 141: Top surface 150: Resistive layer 151: top surface 160: front electrode 161: top surface

FIG. 1 is a schematic cross-sectional structure diagram of a resistor of the present invention.

2A and 2B are top-view photos of the resistor.

none

1: Resistor

10: Composite Laminated Structure

20: Side electrodes

30: Protective layer

100: side

110: Top surface

120: back electrode

130: Substrate

131: Bottom

132: top surface

140: Buffer layer

141: Top surface

150: Resistive layer

151: top surface

160: front electrode

161: top surface

Claims (15)

A sintering aid for a buffer layer, comprising a first boron-barium-zinc-silicon-aluminum-vanadium-based glass frit, the first boron-barium-zinc-silicon-aluminum-vanadium-based glass frit comprising B ₂ O ₃ , BaO, ZnO, SiO ₂ , Al ₂ O ₃ and V ₂ O ₅ , and based on the total moles of B ₂ O ₃ , BaO, ZnO, SiO ₂ , Al ₂ O ₃ and V ₂ O ₅ , the content of B ₂ O ₃ ranges from 14.01 mol% to 34 mol%, BaO content is 1.5 mol% to 8.44 mol%, ZnO content is 20.06 mol% to 34.6 mol%, SiO ₂ content is 23 mol% to 49.11 mol%, Al ₂ O ₃ content is 4.9 mol% to 7.60 mol%, and the content of V ₂ O ₅ is 0.77 mol % to 1.85 mol %. A resistor comprising a composite layered structure and two side electrodes, the two side electrodes are respectively arranged on opposite sides of the composite layered structure; and the composite layered structure sequentially comprises a substrate, a buffer layer and a resistor layer; wherein, the buffer layer is formed by a composition for a buffer layer, and the composition for a buffer layer comprises the sintering aid for a buffer layer as described in claim 1, a filler, a first resin and a first Organic solvents. The resistor according to claim 2, wherein the glass softening temperature of the first boron-barium-zinc-silicon-aluminum-vanadium-based glass frit is 586°C to 739°C. The resistor according to claim 2, wherein the average particle size of the first boron-barium-zinc-silicon-aluminum-vanadium-based glass frit is 1 to 5 microns. The resistor of claim 2, wherein the filler comprises any one of aluminum oxide, zinc oxide, silicon oxide, and titanium oxide or a combination thereof. The resistor according to claim 2, wherein the weight ratio of the sintering aid for the buffer layer to the filler is 0.4:0.6 to 0.75:0.25. The resistor according to claim 2, wherein, in the buffer layer composition, the buffer layer is based on the total weight of the buffer layer sintering aid, the filler, the first resin and the first organic solvent. The content of the sintering aid for the layer is 25.6 to 48 percent by weight; the content of the filler is 16 to 38.4 percent by weight; the content of the first resin is 1 to 2 percent by weight; and the first organic solvent The content is 30 weight percent to 40 weight percent. The resistor of claim 2, wherein the resistor layer is formed of a resistor paste, and the resistor paste includes a metal powder, a sintering aid for the resistor layer, a second resin and a second solvent. The resistor according to claim 8, wherein the sintering aid for the resistance layer comprises a second boron-barium-zinc-alumina-vanadium-based glass frit, and the second boron-barium-zinc-silicon-alumina-vanadium-based glass frit comprises B ₂ O ₃ and BaO , ZnO, SiO ₂ , Al ₂ O ₃ and V ₂ O ₅ , and based on the total moles of B ₂ O ₃ , BaO, ZnO, SiO ₂ , Al ₂ O ₃ and V ₂ O ₅ , B ₂ O The content of ₃ is 26.70 mol% to 29.1 mol%, the content of BaO is 10.1 mol% to 12.64 mol%, the content of ZnO is 15.39 mol% to 19.9 mol%, the content of _SiO2 is 37.2 mol% to 42.36 mol%, the content of Al The content of ₂ O ₃ is 2.68 mol % to 3 mol %, and the content of V ₂ O ₅ is 0.22 mol % to 0.6 mol %. The resistor according to claim 9, wherein the glass softening temperature of the second boron-barium-zinc-silicon-aluminum-vanadium-based glass frit is 565°C to 690°C. The resistor of claim 8, wherein the metal powder comprises copper and nickel, and the weight ratio of copper and nickel is 0.35:0.65 to 0.8:0.2. The resistor according to claim 8, wherein, in the resistor paste, the content of the metal powder is based on the total weight of the metal powder, the sintering aid for the resistor layer, the second resin and the second solvent The content of the sintering aid for the resistance layer is 2 to 6 weight percent; the content of the second resin is 1 to 3 weight percent; and the content of the second organic solvent 17 to 25 weight percent. The resistor according to claim 8, wherein the average particle size of the metal powder is 0.3 to 10 microns. A method for making a resistor, comprising the following steps: Step (a): forming a buffer layer on the surface of a substrate; Step (b): forming a resistance layer on the surface of the buffer layer, wherein the buffer layer is sandwiched between the substrate and the resistance layer to obtain a composite layered structure; Step (c): Disposing a side electrode on two opposite sides of the composite layered structure to obtain a resistor embryo; and Step (d): sintering the resistor blank to obtain the resistor; Wherein the buffer layer is formed by a composition for a buffer layer, and the composition for a buffer layer comprises the sintering aid for a buffer layer as described in claim 1, a filler, a first resin and a first organic solvent. The production method according to claim 14, wherein the sintering temperature in step (d) is 880°C to 920°C, and the sintering time is 10 minutes to 15 minutes.

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