CN114763292B - Sintering aid for buffer layer, resistor comprising buffer layer and resistor manufacturing method - Google Patents
Sintering aid for buffer layer, resistor comprising buffer layer and resistor manufacturing method Download PDFInfo
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- CN114763292B CN114763292B CN202110046650.XA CN202110046650A CN114763292B CN 114763292 B CN114763292 B CN 114763292B CN 202110046650 A CN202110046650 A CN 202110046650A CN 114763292 B CN114763292 B CN 114763292B
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- 238000005245 sintering Methods 0.000 title claims abstract description 117
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000011521 glass Substances 0.000 claims abstract description 44
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 20
- -1 boron barium zinc silicon aluminum vanadium Chemical compound 0.000 claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 60
- 229920005989 resin Polymers 0.000 claims description 54
- 239000011347 resin Substances 0.000 claims description 54
- 239000003960 organic solvent Substances 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- 239000000945 filler Substances 0.000 claims description 34
- 239000011787 zinc oxide Substances 0.000 claims description 30
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- 229910052720 vanadium Inorganic materials 0.000 claims description 22
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 11
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 239
- 239000011241 protective layer Substances 0.000 description 22
- 238000009472 formulation Methods 0.000 description 16
- 239000001856 Ethyl cellulose Substances 0.000 description 9
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 9
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 9
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 9
- 229920001249 ethyl cellulose Polymers 0.000 description 9
- 235000019325 ethyl cellulose Nutrition 0.000 description 9
- 229940116411 terpineol Drugs 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000009713 electroplating Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000007650 screen-printing Methods 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 239000002003 electrode paste Substances 0.000 description 3
- 238000013007 heat curing Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000003698 laser cutting Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
- H05K1/167—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor incorporating printed resistors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/4038—Through-connections; Vertical interconnect access [VIA] connections
- H05K3/4053—Through-connections; Vertical interconnect access [VIA] connections by thick-film techniques
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Non-Adjustable Resistors (AREA)
Abstract
The invention provides a sintering aid for a buffer layer, a resistor comprising the buffer layer and a resistor manufacturing method. The sintering aid for the buffer layer comprises a boron barium zinc silicon aluminum vanadium glass frit. The invention also provides a resistor comprising the buffer layer, and the buffer layer comprises the boron-barium-zinc-silicon-aluminum-vanadium glass frit, so that the adhesion force between the resistor layer and the substrate can be improved by means of the buffer layer clamped in the substrate and the resistor layer, and the deformation of the resistor layer can be further avoided, so that the resistor shows good instantaneous load, resistance tolerance and resistance temperature coefficient. The invention also provides a method for manufacturing the resistor, and the resistor has the advantage of improving the production cost.
Description
Technical Field
The present invention relates to a burn-up agent, and more particularly, to a burn-up agent for a wafer resistor. The invention also relates to a chip resistor and a manufacturing method thereof.
Background
Chip resistors (chip resistors) are commonly used to limit current or reduce voltage by printing thick metal film conductors on alumina ceramic substrates and coating protective layers on the outer layers. With the advancement of technology, the assembly of circuit boards is becoming more complex, and more stringent requirements are placed on the interlayer adhesion, the transient-time overload (STOL), the resistance tolerance (COV%) and the temperature coefficient of resistance of each layer in the chip resistor.
U.S. patent No. 6943662 discloses a method for directly forming a resistor layer on a substrate, but the resistor layer is easily deformed; in addition, it discloses the use of silver palladium electrode paste, which has a problem of high cost. Both U.S. patent application publication No. 20110089025 and U.S. patent No. 5680092 provide vapor deposition methods, but these methods require expensive materials and process equipment, and have the problems of complicated process steps and low throughput.
In summary, a process that combines the cost effectiveness of the production of the wafer resistor and the resistance layer is not easy to deform has yet to be developed.
Disclosure of Invention
In order to solve the above problems, the present invention provides a sintering aid for a buffer layer, comprising a first BSSiV-based glass frit comprising B 2 O 3 、BaO、ZnO、SiO 2 、Al 2 O 3 And V 2 O 5 And take B as 2 O 3 、BaO、ZnO、SiO 2 、Al 2 O 3 And V 2 O 5 Based on the total mole number of B 2 O 3 The content of (2) is 14.01mol% to 34mol%, the content of BaO is 1.5mol% to 8.44mol%, the content of ZnO is 20.06mol% to 34.6mol%, and the content of SiO 2 The content of (C) is 23mol% to 49.11mol%, al 2 O 3 Is present in an amount of 4.9 to 7.60mol%, and V 2 O 5 The content of (C) is 0.77mol% to 1.85mol%.
The first boron-barium-zinc-silicon-aluminum-vanadium glass frit can be B 2 O 3 -BaO-ZnO-SiO 2 -Al 2 O 3 -V 2 O 5 Is expressed in terms of (a).
The sintering aid for the buffer layer of the invention can improve the adhesion force of the resistance layer to the substrate by the buffer layer clamped between the substrate and the resistance layer when the buffer layer using the sintering aid for the buffer layer as a main component is applied to the resistor by containing specific components and specific content ranges of the specific components, can reduce the probability of damaging 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, further avoids the deformation of the resistance layer or reduces the risk of layer cracking caused by stress difference between different layers (such as the substrate and the resistance layer), and ensures that the resistor shows good instantaneous load, resistance tolerance and resistance temperature coefficient.
Preferably, in the first boron barium zinc silicon aluminum vanadium glass frit, B is 2 O 3 、BaO、ZnO、SiO 2 、Al 2 O 3 And V 2 O 5 Based on the total mole number of B 2 O 3 The content of (C) is 17mol% to 34mol%, the content of BaO is 1.5mol% to 7.5mol%, the content of ZnO is 22mol% to 34.6mol%, and SiO 2 The content of (C) is 23mol% to 45mol%, al 2 O 3 Is present in an amount of 4.9 to 7.2mol%, and V 2 O 5 The content of (2) is 0.9mol% to 1.85mol%.
More preferably, in the first boron barium zinc silicon aluminum vanadium glass frit, B is 2 O 3 、BaO、ZnO、SiO 2 、Al 2 O 3 And V 2 O 5 Based on the total mole number of B 2 O 3 The content of (2) is 19.88mol% to 31.39mol%, the content of BaO is 2.55mol% to 6.45mol%, the content of ZnO is 24.30mol% to 32.61mol%, and the content of SiO is 2 The content of (2) is 26.50mol% to 41.47mol%, al 2 O 3 Is present in an amount of 5.25 to 6.80mol%, and V 2 O 5 The content of (2) is 1.09mol% to 1.72mol%.
In some embodiments, the glass softening temperature (glass softening temperature, ts) of the first borobarium zinc alumino-vanadium based frit is from 586 ℃ to 739 ℃.
Preferably, the glass softening temperature of the first boron barium zinc silicon aluminum vanadium glass frit is 586 ℃ to 717 ℃, for example: 586 ℃, 590 ℃, 600 ℃, 620 ℃, 640 ℃, 660 ℃, 680 ℃, 700 ℃, 710 ℃ or 717 ℃; more preferably, the glass softening temperature of the first BSSiV glass frit is 608 ℃ to 695 ℃.
Preferably, the average particle size of the first boron barium zinc silicon aluminum vanadium glass frit is 1 to 5 microns.
The invention also provides a resistor, which comprises a composite layered structure and two side electrodes, wherein the two side electrodes are respectively arranged on two opposite side surfaces of the composite layered structure; the composite layered structure sequentially comprises a substrate, a buffer layer and a resistor layer, wherein the buffer layer is formed by a buffer layer composition, and the buffer layer composition comprises the sintering aid for the buffer layer, a filler, a first resin and a first organic solvent.
By arranging the buffer layer, the deformation amount of the printed resistor layer graph after sintering is reduced, namely, the deformation amount is less than 5%, and the adhesion force between the resistor layer and the substrate can be improved by the buffer layer clamped in the substrate and the resistor layer under the condition of reducing the glass frit addition amount of the resistor layer, so that the problem of generating larger resistance tolerance is avoided, the instant load is improved, and the productivity and the reliability of the resistor are effectively improved.
The sintering aid for the buffer layer forms a liquid phase in the sintering process, can improve the bonding strength of a contact interface between the resistance layer and the buffer layer, and regulates and controls the difference of thermal expansion and sintering shrinkage of the resistance layer and a base material.
In some embodiments, the filler comprises any one or combination of aluminum oxide, zinc oxide, silicon oxide, titanium oxide.
In some embodiments, the first resin comprises any one or a combination of ethylcellulose-based resin and acrylic-based resin. The present invention uses a first resin to make the composition for a buffer layer screen-printable.
In some embodiments, the first organic solvent comprises: any one or combination of terpineol, ether and ester. The first organic solvent of the present invention is used as a diluent.
In some aspects, the substrate is a ceramic substrate.
In some embodiments, in the composition for a buffer layer, the weight ratio of the burn-up aid for a buffer layer to the filler is 0.4:0.6 to 0.75:0.25, but is not limited thereto; preferably, the weight ratio of the sintering aid for the buffer layer to the filler is 0.45:0.55 to 0.75:0.25, e.g., 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 invention controls the difference of the thermal expansion coefficient and sintering shrinkage of the resistor layer and the base material by adjusting the weight ratio of the resistor layer and the base material, avoids the deformation of the resistor layer and the falling of the resistor layer, ensures that the composite layered structure of the resistor has good interlayer adhesive force, and shows low resistance, good resistance tolerance, resistance temperature coefficient and instant load.
In some embodiments, the sintering aid for a buffer layer is present in the composition for a buffer layer in an amount of 25.6 to 48 weight percent based on the total weight of the sintering aid for a buffer layer, the filler, the first resin, and the first organic solvent; the filler content is 16 to 38.4 weight percent; the content of the first resin is 1 to 2 weight percent; and the content of the first organic solvent is 30 to 40 weight percent.
Preferably, in the composition for a buffer layer, the sintering aid for a buffer layer is contained in an amount of 29 to 48 weight percent based on the total weight of the sintering aid for a buffer layer, the filler, the first resin and the first organic solvent, for example: 29, 31, 33, 35, 37, 39, 41, 43, 45, 47 or 48 weight percent; the filler is present in an amount of 16 to 35 weight percent, for example: 16, 18, 20, 22, 24, 26, 28, 30, 32, 34 or 35 weight percent; the content of the first resin is 1 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 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 from a resistive paste, and the resistive paste includes a metal powder, a sintering aid for the resistive layer, a second resin, and a second organic solvent.
Preferably, the second resin comprises any one or a combination of ethylcellulose-based resin and acrylic-based resin; more preferably, the second resin is the same as the first resin.
Preferably, the second organic solvent comprises: any one or combination of terpineol, ether and ester; more preferably, the second organic solvent is the same as the first organic solvent.
The sintering aid for the resistor layer comprises a second boron barium zinc silicon aluminum vanadium glass frit and can be B 2 O 3 -BaO-ZnO-SiO 2 -Al 2 O 3 -V 2 O 5 Is expressed in terms of (a).
In some embodiments, in the second boron barium zinc silicon aluminum vanadium based frit, the second boron barium zinc silicon aluminum vanadium based frit comprises B 2 O 3 、BaO、ZnO、SiO 2 、Al 2 O 3 And V 2 O 5 And take B as 2 O 3 、BaO、ZnO、SiO 2 、Al 2 O 3 And V 2 O 5 Based on the total mole number of B 2 O 3 The content of (2) is 26.70mol% to 29.1mol%, the content of BaO is 10.1mol% to 12.64mol%, the content of ZnO is 15.39mol% to 19.9mol%, and the content of SiO is 2 The content of (C) is 37.2mol% to 42.36mol%, al 2 O 3 Is 2.68mol% to 3mol%, and V 2 O 5 The content of (C) is 0.22mol% to 0.6mol%.
Preferably, in the second boron barium zinc silicon aluminum vanadium glass frit, the second boron barium zinc silicon aluminum vanadium glass frit comprises B 2 O 3 、BaO、ZnO、SiO 2 、Al 2 O 3 And V 2 O 5 And take B as 2 O 3 、BaO、ZnO、SiO 2 、Al 2 O 3 And V 2 O 5 Based on the total mole number of B 2 O 3 27mol% to 29.1mol%, baO 10.1mol% to 12.2mol%, znO 16.1mol% to 19.9mol%, siO 2 The content of Al is 37.2mol% to 41.5mol% 2 O 3 Is 2.73mol% to 3mol%, and V 2 O 5 The content of (C) is 0.28mol% to 0.6mol%.
More preferably, in the second BBaSiAlV glass frit, B is 2 O 3 、BaO、ZnO、SiO 2 、Al 2 O 3 And V 2 O 5 Based on the total mole number of B 2 O 3 27.40 to 28.79mol%, baO 10.48 to 11.92mol%, znO 16.69 to 19.26mol%, and SiO 2 The content of (2) is 37.98mol% to 40.89mol%, al 2 O 3 Is present in an amount of 2.77mol% to 2.95mol%, and V 2 O 5 The content of (C) is 0.33mol% to 0.55mol%.
In some embodiments, the glass softening temperature of the second borobarium zinc alumino-vanadium based glass frit is 565 ℃ to 690 ℃.
Preferably, the glass softening temperature of the second boron barium zinc silicon aluminum vanadium glass frit is 565 ℃ to 675 ℃, for example: 565 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, 660 ℃, 670 ℃, or 675 ℃; more preferably, the glass softening temperature of the second BSQSi-Al-V glass frit is 585 ℃ to 655 ℃. According to the invention, the shrinkage deformation and residual stress of the resistance layer in the sintering process can be reduced by adjusting the temperature difference between the sintering aid for the buffer layer and the glass softening point of the sintering aid for the resistance layer.
According to the invention, the second boron barium zinc silicon aluminum vanadium glass frit in the sintering aid for the resistance layer has a specific glass softening point range, so that the resistance layer can be further prevented from deforming and falling off, the resistance layer is ensured to have good adhesive force, and the low resistance, the good resistance tolerance, the resistance temperature coefficient and the instant load are shown.
Preferably, the second boron barium zinc silicon aluminum vanadium glass frit is powder; more preferably, the average particle size of the second BSSiV glass frit is 1 to 5 μm.
In some embodiments, the metal powder comprises copper and nickel, and the weight ratio of copper to nickel is 0.35:0.65 to 0.8:0.2. preferably, the weight ratio of copper to nickel is 0.35:0.65 to 0.65:0.35, e.g., 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 invention does not adopt silver palladium alloy resistance paste, so the production cost can be effectively reduced.
In some embodiments, the metal powder comprises copper powder and nickel powder, or a copper-nickel alloy powder.
According to the invention, the weight ratio of copper and nickel is controlled to further avoid the excessively high temperature coefficient of resistance.
In some embodiments, the metal powder is contained in the electrode paste in an amount of 67 to 79 weight percent based on the total weight of the metal powder, the sintering aid for the resistive layer, the second resin, and the second organic solvent; the sintering aid for the resistor layer is 2-6 weight percent; the content of the second resin is 1 to 3 weight percent; and the content of the second organic solvent is 17 to 25 weight percent.
Preferably, in the electrode paste, the metal powder is contained in an amount of 67 to 79 wt%, based on the total weight of the metal powder, the sintering aid for the resistive layer, the second resin and the second organic solvent, for example: 67, 70, 73, 76 or 79 weight percent; the sintering aid for the resistive layer is contained in an amount of 2.5 to 5.5 weight percent, for example: 2.5 weight percent, 3 weight percent, 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 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 to 25 weight percent, for example: 17, 19, 21, 23 or 25 weight percent.
According to the invention, the content of the sintering aid for the resistor layer is controlled, so that the resistor is prevented from rising and the resistor layer is prevented from falling off.
Preferably, the metal powder is spherical powder.
Preferably, the metal powder has an average particle size of 0.3 to 10 microns. When the particle diameter of the metal powder is in the above 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 comprises a back electrode and a front electrode; wherein the back electrode is arranged on the bottom surface of the substrate; the area of the top surface of the buffer layer is smaller than that of the top surface of the substrate, the area of the top surface of the resistor layer is smaller than that of the top surface of the buffer layer, the top surface of the substrate and the top surface of the buffer layer are provided with the front electrode, and the top surfaces of the front electrode and the top surface of the resistor layer are aligned to form a coplanar surface.
Preferably, the top surface area and the bottom surface area of each of the substrate, the buffer layer, the resistor layer, and the back electrode are the same.
In other embodiments, the resistor further includes a protective layer, and the protective layer is disposed on a top surface (i.e., an outermost surface) of the composite layered structure to protect the resistor layer, where the top surface of the composite layered structure refers to a surface formed by a top surface of the front electrode and a top surface of the resistor layer.
The invention further provides a resistor manufacturing method, which comprises the following steps: step (a): forming a buffer layer on the surface of a substrate; step (b): forming a resistor layer on the surface of the buffer layer, wherein the buffer layer is clamped between the substrate and the resistor layer to obtain a composite layered structure; step (c): a side electrode is respectively arranged on two opposite sides of the composite layered structure so as to obtain a resistor blank; step (d): sintering the resistor blank to obtain the resistor; wherein the buffer layer is formed of a buffer layer composition comprising the sintering aid for a buffer layer as described above, a filler, a first resin, and a first organic solvent.
Preferably, the buffer layer forming mode in the step (a) and the resistor layer forming mode in the step (b) are both formed by a screen printing method, and compared with the forming mode by a vapor deposition method, the screen printing method has higher production efficiency.
Preferably, each of the step (a), the step (b) and the step (c) may comprise a drying step, and the drying temperature is 100 ℃ to 150 ℃.
Preferably, each of the drying time of the step (a), the step (b) and the step (c) is 10 minutes to 15 minutes.
Preferably, the sintering temperature of step (d) is 880 ℃ to 920 ℃.
Preferably, the sintering time of step (d) is 10 minutes to 15 minutes.
Preferably, before the step (a), a back electrode may be formed on the bottom surface of the substrate. More preferably, the composite layered structure comprises the back electrode, the substrate, the buffer layer, the resistive layer and a front electrode; the top surface area of the buffer layer is smaller than the top surface area of the substrate, the top surface area of the resistive layer is smaller than the top surface area of the buffer layer, and the step (b) further includes: and forming the front electrode on the top surface of the substrate and the top surface of the buffer layer, wherein the top surface of the front electrode is aligned with the top surface of the resistor layer to form a coplanar surface.
Preferably, after sintering the resistor blank 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 external electrode layer, so as to finally obtain the resistor.
In some embodiments, the material of the protective layer comprises a material of glass. Preferably, the sintering temperature of the protective layer is 400 ℃ to 500 ℃. Preferably, the sintering time of the protective layer is 10 minutes to 15 minutes.
In some embodiments, the material of the protective layer comprises an epoxy-based material. Preferably, the heat curing temperature of the protective layer is 150 ℃ to 300 ℃. Preferably, the thermal curing time of the protective layer is 10 minutes to 30 minutes.
Preferably, the step of electroplating the electrode refers to electroplating copper, nickel and/or tin on the surfaces of the side electrode, the front electrode and the back electrode; in some embodiments, the electrode plating step may be preceded by copper plating of the surfaces of the side electrode, the front electrode, and the back electrode to form a copper outer electrode layer; then nickel electroplating is carried out on the surface of the copper external electrode layer so as to form a nickel external electrode layer; and performing tin electroplating on the surface of the nickel external electrode layer to form a tin external electrode layer, namely forming a group of external electrodes with three-layer structures by the copper external electrode layer, the nickel external electrode layer and the tin external electrode layer, and coating the external surfaces of the side electrode, the front electrode and the back electrode. The electrode of the invention is not limited by adopting noble metals such as silver, palladium and the like, thereby being beneficial to reducing the production cost.
In the present specification, the average particle diameter means the particle diameter corresponding to the cumulative particle diameter distribution percentage of 50% in the particle diameter distribution percentage statistics of the particles, that is, D 50 。
In summary, the resistor of the invention can increase the adhesion force between the resistor layer and the substrate by adding the buffer layer, and can avoid the deformation of the resistor layer, so that the resistor exhibits good instantaneous load, resistance tolerance and resistance temperature coefficient, thereby improving the production cost efficiency of the resistor, and having market competitiveness.
Drawings
Fig. 1 is a schematic cross-sectional structure of a resistor according to the present invention.
Fig. 2A and 2B are top-view photographs of the resistor.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
The following examples and comparative examples illustrate embodiments of the present invention, and those skilled in the art will readily appreciate that many modifications and variations are possible in the practice or application of the present invention without materially departing from the novel teachings and advantages of the invention.
Example 1: resistor
As shown in fig. 1, the resistor 1 comprises a composite layered structure 10, two side electrodes 20 and a protective layer 30, wherein 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 a top surface 110 of the composite layered structure 10; and the composite layered structure 10 comprises two back electrodes 120, a substrate 130, a buffer layer 140, a resistive layer 150 and two front electrodes 160; the two back 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, the area of the top surface 151 of the resistive layer 150 is smaller than the area of the top surface 141 of the buffer layer 140, 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 aligned with the top surface 151 of the resistive layer 150 to form a coplanar surface. The buffer layer 140 is formed of a buffer layer composition, and the buffer layer composition includes a sintering aid for a buffer layer, a filler, a first resin, and a first organic solvent.
Example 2: method for manufacturing resistor
1. Preparing a composite layered structure:
(1) Preparing a back electrode: printing a back electrode on the bottom surface of the aluminum oxide substrate in a screen printing mode, wherein the back electrode is made of copper, and drying the back electrode at 100-150 ℃ for 10-15 minutes.
(2) Preparing a buffer layer: the sintering aid, filler, first resin and first organic solvent for the buffer layer are mixed to prepare a composition for the buffer layer, the composition is printed on the top surface of an alumina substrate in a screen printing mode, and the composition is dried at 100-150 ℃ for 10-15 minutes to form the buffer layer.
(3) Preparing a resistor layer: mixing metal powder, sintering aid for the resistor layer, second resin and second organic solvent, preparing resistor paste, printing on the top surface of the buffer layer in a screen printing mode, and drying at 100-150 ℃ for 10-15 minutes to form the resistor layer.
(4) Preparing a front electrode: printing the front electrode on the top surface of the aluminum oxide substrate and the top surface of the buffer layer in a screen printing mode, wherein the front electrode is made of copper, so that the top surface of the front electrode is flush with the top surface of the resistor layer to form a horizontal coplanar surface, and then drying at 100-150 ℃ for 10-15 minutes.
2. Preparing a side electrode:
The two opposite sides of the composite layered structure (i.e. the sides formed by the front electrode, the substrate and the back electrode) are respectively coated with a side electrode made of copper in a rolling manner to form a resistor blank, and then are sintered together at 880-920 ℃ for 10-15 minutes.
3. Preparing a protective layer:
after the resistance layer is cut by laser to adjust the resistance value, the protective layer is printed on the coplanar surface formed by the front electrode and the resistance layer in a screen printing mode, namely the outermost surface of the composite layered structure, so that the resistance layer is prevented from being oxidized and vulcanized due to contact with external air; wherein the protective layer adopts epoxy resin, the heat curing temperature of the protective layer is 150 ℃ to 300 ℃, and the heat curing time is 10 minutes to 30 minutes.
4. Preparing an outer electrode layer: copper electroplating is performed on the surfaces of the side electrode, the front electrode and the back electrode to form a copper external electrode layer; then nickel electroplating is carried out on the surface of the copper external electrode layer so as to form a nickel external electrode layer; and performing tin electroplating on the surface of the nickel external electrode layer to form a tin external electrode layer, namely forming a group of external electrodes with three layers of structures by the copper external electrode layer, the nickel external electrode layer and the tin external electrode layer, and coating the external surfaces of the side electrode, the front electrode and the back electrode.
Test example 1: resistance efficacy comparison with sintering aid formulations for different buffer layers
Each group was made resistive in the manner described in example 2, but without a protective layer; the Ts point is measured before the process starts, the deformation of the resistive layer is observed after sintering is completed, and the remaining efficacy tests (i.e. adhesion, resistivity, COV%, TCR and STOL) are performed after the external electrode is electroplated as follows:
composition for buffer layer
The formulation of sintering aid for each group of buffer layers is shown in Table 1, and the filler is 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, the same proportions are adopted in each group: the content of 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 was 1.5 weight percent; and the content of the first organic solvent was 34.50 weight percent.
Table 1: sintering aid formula (unit: mol%) for each group of buffer layers
(II) resistance paste
The formulation of the sintering aid for each group of the resistor layers is the same, and the sintering aid for the resistor layers comprises the following components: b (B) 2 O 3 28.09mol%, 11.20mol% BaO, 17.98mol% ZnO, and SiO 2 The content of (C) is 39.43mol% of Al 2 O 3 Is 2.86mol% and V 2 O 5 The content of (C) was 0.44mol%. In the resistor paste, the same proportions of the metal powder, the resistor layer sintering aid, the second resin and the second organic solvent are used as follows: the copper content was 43.80 weight percent; the nickel content is 29.20 weight percent; the content of the sintering aid in the resistor layer is 4.00 weight percent; the content of the second resin was 2.00 weight percent; and (d)The content of the secondary organic solvent is 21.00 weight percent; wherein the second resin is the same as the first resin, and the second organic solvent is the same as the first organic solvent.
(III) sintering temperature
When the tail code of each group of labels is singular (namely N-1, N-3, N-5 and N-7, N is the number of the embodiment), the sintering temperature is 880 ℃; when the tail codes of each group of marks are double numbers (namely N-2, N-4, N-6 and N-8), the sintering temperature is 920 ℃.
(IV) efficacy test
1. Glass softening point: the Ts of the sintering aid for each buffer layer was measured using a thermo-mechanical thermal analyzer (Thermomechanical Analysis, TMA) according to ASTM E1545 specifications.
2. Resistance layer deformation amount: the calculation formula of the resistance layer deformation quantity: [ (maximum width-minimum width)/maximum width ] ×100%, i.e., (. DELTA.W/W) ×100%, when the amount of deformation of the resistive layer is greater than 5%, it will be determined that the resistive layer is significantly deformed at the time of recognition, as shown in FIG. 2A; when the deformation amount of the resistive layer is 5% or less, it is determined that the resistive layer is not deformed, for example, as shown in fig. 2B.
3. Adhesion force: tests were carried out according to the specifications of ISO 2409, wherein level 0 (ISO class 0) indicates "cut edge smooth and complete, coating film completely no peeling off"; class 1 (ISO class 1) indicates that "cut line intersections have small chips, and the flaking area is less than 5% of the total area"; class 2 (ISO class 2) means "small chips at both the edge and the intersection of the cut lines, the flaking area accounting for 5% to less than 15% of the total area"; grade 3 (ISO class 3) means that "the edge of the cut line, the small square, is partly or entirely peeled off, the peeled off area occupies 15% to less than 35%"; grade 4 (ISO class 4) indicates that "the edge of the cut line, the small square, has partly or entirely peeled off, the peeled off area occupies 35% to less than 65% of the total area"; and class 5 (ISO class 5) indicates that "the edge of the cut line, the small square, has partly or entirely peeled off, the peeled off area occupies 65% or more of the total area.
4. Resistivity: resistance measurement was carried out in accordance with the specification of IEC 60115-1/JIS C5201-1, clause 4.5.
5. Resistance tolerance (COV%): resistance standard deviation/resistance mean, with resistance tolerances greater than 3%, will affect the resistivity.
6. Temperature coefficient of resistance (Temperature Coefficient of Resistance, TCR): TCR (+ -100 ppm/. Degree.C.) measurements and calculations were performed according to the specification of IEC 60115-1, clause 4.8; wherein the test temperature is between T1 (25 ℃) and T2 (155 ℃), R2 is the measured resistance value of the T2 point, R1 is the measured resistance value of the T1 point, and the calculation formula is TCR (ppm/°c) = (R2-R1)/R1X1/(T2-T1) ×10 6 . In addition, when TCR exceeds the range of + -100 ppm/. Degree.C, resistance stability of the resistor at ambient temperature changes will be affected. Since the TCR of a commercially available resistor can exceed + -100 ppm/DEG C, whether the TCR is within + -100 ppm/DEG C is not the basis for determining whether the resistor is qualified or not.
7. Instantaneous load (STOL): STOL measurements were performed according to IEC 60115-1, specification 4.13, and rated 5 times for 5 seconds of overload.
Table 2: ts, deformation, adhesion, resistivity, COV%, TCR, and STOL test results for each resistor
As is clear from the test results in Table 2, B in the sintering aid for buffer layer of comparative examples 3-1 and 3-2 2 O 3 The content is 37.02mol%, higher than 34mol%, baO content is 0.63mol%, lower than 1.5mol%, znO content is 36.68mol%, higher than 34.6mol%, and SiO 2 The content is 19.16mol percent, less than 23mol percent, al 2 O 3 Content of 4.49mol%, less than 4.9mol%, and V 2 O 5 The content was 2.02mol% and higher than 1.85mol%, so that it had a glass softening point of only 565 ℃. Further, since the resistance layers of comparative examples 3-1 and 3-2 were excessively deformed in appearance, the subsequent test could not be performed.
B in the sintering aid for buffer layer of examples 3-1 and 3-2 2 O 3 The content is 14.01mol%, the BaO content is 8.44mol%, the ZnO content is 20.06mol%, and the SiO content is high 2 The content is 49.11mol%, al 2 O 3 At a content of 7.60mol% and V 2 O 5 The content is 0.77mol%, the glass softening point temperature is 739 ℃, and the content ratio and the softening point can prevent the resistance layer from deforming, so that the structure of the resistance layer is obviously improved.
Finally, B in the sintering aid for buffer layers of examples 3-3 to 3-8 2 O 3 The content is 17mol% to 34mol%, the BaO content is 1.5mol% to 7.5mol%, the ZnO content is 22mol% to 34.6mol%, and the SiO content is 1.5mol% 2 The content is 23mol% to 45mol%, al 2 O 3 In an amount of from 4.9mol% to 7.2mol%, and V 2 O 5 The content is 0.9mol% to 1.85mol%, and the temperature of the glass softening point is 608 ℃ to 695 ℃, so that the deformation amount of the resistance layer is lower than 5%, the resistance layer has better adhesive force (all belongs to the 0 th level), and simultaneously, the resistance layer has low resistance, good resistance tolerance, resistance temperature coefficient and instant load.
Test example 2: resistance efficacy comparison Using sintering aid to Filler weight ratio for different buffer layers
Each group was made resistive in the manner described in example 2, but without a protective layer; the Ts point is measured before the process starts, the deformation of the resistive layer is observed after sintering is completed, and the remaining efficacy tests (i.e. adhesion, resistivity, COV%, TCR and STOL) are performed after the external electrode is electroplated as follows:
composition for buffer layer
The formulation of sintering aid for buffer layer was the same as in examples 3-5 and examples 3-6: b (B) 2 O 3 The contents are 25.67mol%, baO 4.48mol%, znO 28.48mol% and SiO 2 The content of the aluminum alloy is 33.93mol percent, the aluminum alloy is 2 O 3 The content was 6.02mol% and V 2 O 5 The content was 1.40mol%, and the formulation of the composition for a buffer layer is shown in Table 3, wherein the filler is Al 2 O 3 The first resin is ethyl cellulose, the first The organic solvent is terpineol.
Table 3: composition formula (unit: weight percent) for each group of buffer layers
(II) resistor paste: same as in test example 1.
(III) sintering temperature: the sintering temperature was 920℃in examples 4 to 5, as in test example 1.
(IV) efficacy test: the test was performed in the same manner as in test example 1, and the results of each test are shown in Table 4.
Table 4: ts, deformation, adhesion, resistivity, COV%, TCR, and STOL test results for each resistor
As can be seen from Table 4, examples 3-5, 3-6, and 4-1 to 4-5 each have a deformation amount of less than 5% and good instantaneous load, resistance tolerance and temperature coefficient of resistance due to the use of the sintering aid for buffer layers of the present invention.
Further, since the weight ratio of sintering aid to filler for buffer layer of examples 3-5, 3-6, 4-1 to 4-4 was 0.45 as compared with examples 4-5: 0.55 to 0.75:0.25, and the content of the sintering aid for the buffer layer is 29 to 48 weight percent; the filler content is between 16 and 35 weight percent; the content of the first resin is between 1 weight percent and 2 weight percent; and the content of the first organic solvent is 30 to 40 weight percent, so that the adhesive force (all of class 0) can be better, and the adhesive has low resistance, good resistance tolerance, resistance temperature coefficient and instant load.
Test example 3: comparison of resistance efficacy with different filler types
Each group was made resistive in the manner described in example 2, but without a protective layer; the Ts point is measured before the process starts, the deformation of the resistive layer is observed after sintering is completed, and the remaining efficacy tests (i.e. adhesion, resistivity, COV%, TCR and STOL) are performed after the external electrode is electroplated as follows:
composition for buffer layer
The conditions were the same except that the filler types were different as shown in Table 5, and the following was noted:
the formulation of the sintering aid for each group of buffer layers was the same as in examples 3-5 and examples 3-6: b (B) 2 O 3 The contents are 25.67mol%, baO 4.48mol%, znO 28.48mol% and SiO 2 The content of the aluminum alloy is 33.93mol percent, the aluminum alloy is 2 O 3 The content was 6.02mol% and V 2 O 5 The content was 1.40mol%.
Each group of the first resins was ethylcellulose, each first organic solvent was terpineol, and the proportions of the compositions for the buffer layer were the same as examples 3 to 5 and examples 3 to 6: the content of the sintering aid for the buffer layer is 38.40 weight percent based on the total weight of the sintering aid for the buffer layer, the filler, the first resin and the first organic solvent; the content of the filler is 25.60 weight percent; the content of the first resin was 1.5 weight percent; and the content of the first organic solvent was 34.50 weight percent.
Table 5: each group of filler types
(II) resistor paste: same as in test example 1.
(III) sintering temperature: same as in test example 1.
(IV) efficacy test: the test was performed in the same manner as in test example 1, and the results of each test are shown in Table 6.
Table 6: ts, deformation, adhesion, resistivity, COV%, TCR, and STOL test results for each resistor
The fillers of examples 3-5, 3-6, 5-1 to 5-6 are respectively aluminum oxide, zinc oxide, silicon oxide and titanium oxide, the deformation of the resistance layer is lower than 5%, the adhesion is 0 grade, and the resistance tolerance, the resistance temperature coefficient and the instantaneous load are low.
Test example 4: comparison of resistance efficacy without buffer layer
In the comparative examples of the test, no buffer layer was printed, and the sintering aid for different resistance layers was used in the same weight percentage, and the other steps were the same.
The formulation of the second resistor paste is shown in Table 7, wherein the formulation of the sintering aid for the resistor layer is the same as that of test example 1, the second resin is ethylcellulose, and the second organic solvent is terpineol.
Table 7: resistor paste formulation (unit: weight percent)
(III) sintering temperature: same as in test example 1.
(IV) efficacy test: the test was performed in the same manner as in test example 1, and the results of each test are shown in Table 8.
Table 8: deformation, adhesion, resistivity, COV%, TCR, and STOL test results for each resistor
As can be seen from Table 8, when the resistance was not provided with the buffer layer (i.e., comparative example 6-1 and comparative example 6-2) and the content of the sintering aid for the resistance layer was 4 weight%, the adhesion test result was significantly worse, only the 3 rd or 4 th stage.
Furthermore, when the amounts of sintering aid for improving the resistance layer of comparative examples 6-3 and 6-4 were 6 weight percent under the same condition that the buffer layer was not provided, the adhesion of the resistance layer was improved but the resistance was increased by at least 3 times, the resistance tolerance was increased by about 2 times, and the temperature coefficient of resistance was increased by about 2 times.
Finally, when the amounts of sintering aids for the resistive layers of comparative examples 6 to 5 and 6 reached 8 weight%, the adhesion test results were good, but the resistive layers were excessively deformed, and the subsequent test was impossible.
Test example 5: resistance efficacy comparison Using sintering aid ratios for different resistance layers
Each group was made resistive in the manner described in example 2, but without a protective layer; the Ts point is measured before the process starts, the deformation of the resistive layer is observed after sintering is completed, and the remaining efficacy tests (i.e. adhesion, resistivity, COV%, TCR and STOL) are performed after the external electrode is electroplated as follows:
(one) composition for buffer layer:
the sintering aid for each group of buffer layers was the same as in examples 3-5 and examples 3-6: b (B) 2 O 3 The contents are 25.67mol%, baO 4.48mol%, znO 28.48mol% and SiO 2 The content of the aluminum alloy is 33.93mol percent, the aluminum alloy is 2 O 3 The content was 6.02mol% and V 2 O 5 The content was 1.40mol%.
In addition, the fillers are all Al 2 O 3 The first resin is ethyl cellulose, the first organic solvent is terpineol, and the buffer is providedThe proportions of the layer compositions are the same as in examples 3-5 and examples 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, the same proportions are adopted in each group: the content of sintering aid for the buffer layer is 38.40 weight percent; the filler content 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.
(II) resistor paste:
the formulation of the sintering aid for each group of resistor layers is shown in table 9. Based on the total weight of the metal powder, the resistor layer sintering aid, the second resin and the second organic solvent, the same proportion is adopted in each group: the copper content was 43.80 weight percent; the nickel content is 29.20 weight percent; the content of the sintering aid in the resistor layer is 4.00 weight percent; the content of the second resin was 2.00 weight percent; the content of the second organic solvent was 21.00 weight percent; wherein 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: sintering aid formula (unit: mol%) for each group of resistor layers
(III) sintering temperature: same as in test example 1.
(IV) efficacy test: the test was performed in the same manner as in test example 1, and the results of each test are shown in Table 10, wherein Ts is the glass softening point of the sintering aid for the resistive layer.
Table 10: ts, deformation, adhesion, resistivity, COV%, TCR, and STOL test results for each resistor
As is clear from Table 10, B in the sintering aid for buffer layers of examples 7 to 5 and examples 7 to 6 2 O 3 The content is 26.70mol%, the BaO content is 12.64mol%, the ZnO content is 15.39mol%, and the SiO is 2 The content is 42.36mol percent, al 2 O 3 The content is 2.68mol% and V 2 O 5 The content is 0.22mol%, and the glass softening point is 690 ℃, the resistance layer is not deformed, and the adhesive force can reach the 1 st level or the 2 nd level.
Further, compared with examples 7-5 and 7-6, B in the sintering aid for buffer layer of examples 3-5, 3-6, 7-1 to 7-4 2 O 3 The content of the ZnO is 27 to 29.1mol%, the content of BaO is 10.1 to 12.2mol%, the content of ZnO is 16.1 to 19.9mol%, and the content of SiO is 2 The content is 37.2mol% to 41.5mol%, al 2 O 3 In an amount of from 2.73mol% to 3mol% and V 2 O 5 The content is between 0.28mol% and 0.6mol%, so that the adhesive has better adhesive force (all belongs to class 0), and further has low resistance, good resistance tolerance, resistance temperature coefficient and instant load.
Test example 6: resistance efficacy comparison of different copper-nickel ratios of the resistance layer
Each group was made resistive in the manner described in example 2, but without a protective layer; the Ts point is measured before the process starts, the deformation of the resistive layer is observed after sintering is completed, and the remaining efficacy tests (i.e. adhesion, resistivity, COV%, TCR and STOL) are performed after the external electrode is electroplated as follows:
(one) composition for buffer layer: as in examples 3-5 and examples 3-6.
(II) resistor paste:
the formulation of the sintering aid for each set of resistive layers was the same and was the same as in examples 3-5 and examples 3-6: b (B) 2 O 3 28.09mol%, 11.20mol% BaO, 17.98mol% ZnO, and SiO 2 The content of (C) is 39.43mol% of Al 2 O 3 Is 2.86mol% and V 2 O 5 Is 0.44mMol%. The formulation of the resistor paste is shown in Table 11, wherein the second resin is ethylcellulose and the second organic solvent is terpineol.
Table 11: resistor paste formulation (unit: weight percent)
(III) sintering temperature: same as in test example 1.
(IV) efficacy test: the test was performed in the same manner as in test example 1, and the results of each test are shown in Table 12, wherein Ts is the glass softening point of the sintering aid for the resistive layer.
Table 12: ts, deformation, adhesion, resistivity, COV%, TCR, and STOL test results for each resistor
As can be seen from Table 12, the resistive layers of examples 3-5, examples 3-6, and examples 8-1 to 8-8 were all free from deformation and had appropriate adhesion.
Further, as can be seen from examples 3-5, examples 3-6, examples 8-5 to examples 8-8, when the weight ratio of copper to nickel is between 0.35:0.65 to 0.65:0.35, and the content of the metal powder is 67 to 79 weight percent based on the total weight of the metal powder, the sintering aid for the resistor layer, the second resin and the second organic solvent, and the temperature coefficient of resistance of the resistor can be obviously improved.
Test example 7: resistance efficacy comparison of sintering aid addition amounts for different resistance layers
Each group was made resistive in the manner described in example 2, but without a protective layer; the Ts point is measured before the process starts, the deformation of the resistive layer is observed after sintering is completed, and the remaining efficacy tests (i.e. adhesion, resistivity, COV%, TCR and STOL) are performed after the external electrode is electroplated as follows:
(one) composition for buffer layer: as in examples 3-5 and examples 3-6.
(II) resistor paste:
the formulation of the sintering aid for each set of resistive layers was the same and was the same as in examples 3-5 and examples 3-6: b (B) 2 O 3 28.09mol%, 11.20mol% BaO, 17.98mol% ZnO, and SiO 2 The content of (C) is 39.43mol% of Al 2 O 3 Is 2.86mol% and V 2 O 5 The content of (C) was 0.44mol%. The formulation of the resistor paste is shown in Table 13, wherein the second resin is ethylcellulose and the second organic solvent is terpineol.
Table 13: resistor paste formulation (unit: weight percent)
(III) sintering temperature: same as in test example 1.
(IV) efficacy test: the test was performed in the same manner as in test example 1, and the results of each test are shown in Table 14, wherein Ts is the glass softening point of the sintering aid for the resistive layer.
Table 14: ts, deformation, adhesion, resistivity, COV%, TCR, and STOL test results for each resistor
As is clear from Table 14, when the sintering aid for the resistive layer contained in examples 9-1 and 9-2 was 6 weight%, the resistive layer was not deformed and the adhesion could reach the 0 th order, however, the glass component in the resistive layer was increased, and the conductive property was improvedThe specific resistance is higher than 4×10 -5 Ω.cm。
The sintering aid for the resistive layer contained in examples 9 to 7 and examples 9 to 8 was 2 weight percent, and the adhesion between the resistive layer and the buffer layer was lowered (stage 1 or stage 2) due to the lower glass content in the resistive layer.
From the above, the content of the sintering aid for the resistive layer is 2.5 wt% to 5.5 wt% based on the total weight of the metal powder, the sintering aid for the resistive layer, the second resin and the second organic solvent, so that the adhesion between the resistive layer and the buffer layer can be further improved, and the resistivity can be further improved.
In summary, the buffer layer formed by adopting the sintering aid for the buffer layer with specific components and the content thereof can improve the adhesion between the buffer layer and the substrate by means of the buffer layer clamped in the substrate and the resistor layer, and further avoid deformation of the resistor layer, so that the resistor exhibits good instantaneous load, resistance tolerance and resistance temperature coefficient.
Claims (15)
1. A sintering aid for a buffer layer comprises a first BSSiSV glass frit comprising B 2 O 3 、BaO、ZnO、SiO 2 、Al 2 O 3 And V 2 O 5 And take B as 2 O 3 、BaO、ZnO、SiO 2 、Al 2 O 3 And V 2 O 5 Based on the total mole number of B 2 O 3 The content of (2) is 14.01mol% to 34mol%, the content of BaO is 1.5mol% to 8.44mol%, the content of ZnO is 20.06mol% to 34.6mol%, and the content of SiO 2 The content of (C) is 23mol% to 49.11mol%, al 2 O 3 Is present in an amount of 4.9 to 7.60mol%, and V 2 O 5 The content of (C) is 0.77mol% to 1.85mol%.
2. The resistor comprises a composite layered structure and two side electrodes, wherein the two side electrodes are respectively arranged on two opposite sides of the composite layered structure; the composite layered structure sequentially comprises a substrate, a buffer layer and a resistor layer; wherein the buffer layer is formed of a buffer layer composition comprising the sintering aid for a buffer layer according to claim 1, a filler, a first resin and a first organic solvent.
3. The resistor of claim 2 wherein the first boron barium zinc aluminum vanadium based frit has a glass softening temperature in the range of 586 ℃ to 739 ℃.
4. The resistor of claim 2, wherein the first boron barium zinc aluminum vanadium based frit has an average particle size of 1 micron to 5 microns.
5. The resistor of claim 2, wherein the filler comprises any one or combination of aluminum oxide, zinc oxide, silicon oxide, titanium oxide.
6. The resistor of claim 2 wherein the weight ratio of the buffer layer burn aid to the filler is 0.4:0.6 to 0.75:0.25.
7. The resistor of claim 2 wherein the buffer layer co-sintering agent is present in the buffer layer composition in an amount of 25.6 to 48 weight percent based on the total weight of the buffer layer co-sintering agent, the filler, the first resin, and the first organic solvent; the filler content is 16 to 38.4 weight percent; the content of the first resin is 1 to 2 weight percent; and the content of the first organic solvent is 30 to 40 weight percent.
8. The resistor of claim 2, wherein the resistor layer is formed from a resistor paste, and the resistor paste comprises a metal powder, a sintering aid for the resistor layer, a second resin, and a second organic solvent.
9. The resistor of claim 8 wherein the sintering aid for the resistive layer comprises a second boron barium zinc silicon aluminum vanadium based frit comprising B 2 O 3 、BaO、ZnO、SiO 2 、Al 2 O 3 And V 2 O 5 And take B as 2 O 3 、BaO、ZnO、SiO 2 、Al 2 O 3 And V 2 O 5 Based on the total mole number of B 2 O 3 The content of (2) is 26.70mol% to 29.1mol%, the content of BaO is 10.1mol% to 12.64mol%, the content of ZnO is 15.39mol% to 19.9mol%, and the content of SiO is 2 The content of (C) is 37.2mol% to 42.36mol%, al 2 O 3 Is 2.68mol% to 3mol%, and V 2 O 5 The content of (C) is 0.22mol% to 0.6mol%.
10. The resistor of claim 9 wherein the glass softening temperature of the second borobarium zinc alumino-vanadium based glass frit is 565 ℃ to 690 ℃.
11. The resistor of claim 8, wherein the metal powder comprises copper and nickel, and the weight ratio of copper to nickel is 0.35:0.65 to 0.8:0.2.
12. the resistor of claim 8 wherein the metal powder is present in the resistor paste in an amount of 67 to 79 weight percent based on the total weight of the metal powder, the sintering aid for the resistor layer, the second resin, and the second organic solvent; the sintering aid for the resistor layer is 2-6 weight percent; the content of the second resin is 1 to 3 weight percent; and the content of the second organic solvent is 17 to 25 weight percent.
13. The resistor of claim 8, wherein the metal powder has an average particle size of 0.3 microns to 10 microns.
14. A method of manufacturing a resistor comprising the steps of:
Step (a): forming a buffer layer on the surface of a substrate;
step (b): forming a resistor layer on the surface of the buffer layer, wherein the buffer layer is clamped between the substrate and the resistor layer to obtain a composite layered structure;
step (c): a side electrode is respectively arranged on two opposite sides of the composite layered structure so as to obtain a resistor blank; and
step (d): sintering the resistor blank to obtain the resistor;
wherein the buffer layer is formed of a buffer layer composition comprising the sintering aid for a buffer layer according to claim 1, a filler, a first resin and a first organic solvent.
15. The method of claim 14, wherein the sintering temperature in step (d) is 880 ℃ to 920 ℃ and the sintering time is 10 minutes to 15 minutes.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4859637A (en) * | 1987-12-17 | 1989-08-22 | Ferro Corporation | Lead-free U.V. absorbing glass |
| US5593722A (en) * | 1992-12-22 | 1997-01-14 | Nippondenso Co., Ltd. | Method of producing thick multi-layer substrates |
| RU2076475C1 (en) * | 1980-11-10 | 1997-03-27 | Государственное научно-производственное предприятие "Исток" | Thin-structure |
| JPH09275002A (en) * | 1996-04-05 | 1997-10-21 | Matsushita Electric Ind Co Ltd | Thick film resistor, chip resistor using the same, and method of manufacturing the same |
| JPH10335115A (en) * | 1997-05-30 | 1998-12-18 | Tdk Corp | Ceramics composite laminated component |
| JP2003257708A (en) * | 2002-03-05 | 2003-09-12 | Koa Corp | Thick film thermistor element and its manufacturing method |
| CN1742347A (en) * | 2002-11-21 | 2006-03-01 | Tdk株式会社 | Resistor paste, resistors and electronic components |
| CN102617137A (en) * | 2012-03-28 | 2012-08-01 | 厦门松元电子有限公司 | BaO-TiO2 lead-free Y5P capacitor dielectric material and preparation method for same |
| CN107995783A (en) * | 2016-10-26 | 2018-05-04 | 先丰通讯股份有限公司 | Circuit board structure and manufacturing method thereof |
| CN108417290A (en) * | 2018-02-28 | 2018-08-17 | 江苏国瓷泓源光电科技有限公司 | A kind of solar cell aluminum paste and preparation method thereof |
| CN111028975A (en) * | 2019-12-03 | 2020-04-17 | 南京汇聚新材料科技有限公司 | Low-temperature coefficient resistor paste and preparation method and application thereof |
| TWI742979B (en) * | 2020-12-31 | 2021-10-11 | 華新科技股份有限公司 | Sintering aid for buffer layer, resistance including buffer layer and resistance manufacturing method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101796658B1 (en) * | 2011-03-28 | 2017-11-13 | 삼성전자주식회사 | Conductive paste and electronic device and solar cell including an electrode formed using the conductive paste |
-
2021
- 2021-01-14 CN CN202110046650.XA patent/CN114763292B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2076475C1 (en) * | 1980-11-10 | 1997-03-27 | Государственное научно-производственное предприятие "Исток" | Thin-structure |
| US4859637A (en) * | 1987-12-17 | 1989-08-22 | Ferro Corporation | Lead-free U.V. absorbing glass |
| US5593722A (en) * | 1992-12-22 | 1997-01-14 | Nippondenso Co., Ltd. | Method of producing thick multi-layer substrates |
| JPH09275002A (en) * | 1996-04-05 | 1997-10-21 | Matsushita Electric Ind Co Ltd | Thick film resistor, chip resistor using the same, and method of manufacturing the same |
| JPH10335115A (en) * | 1997-05-30 | 1998-12-18 | Tdk Corp | Ceramics composite laminated component |
| JP2003257708A (en) * | 2002-03-05 | 2003-09-12 | Koa Corp | Thick film thermistor element and its manufacturing method |
| CN1742347A (en) * | 2002-11-21 | 2006-03-01 | Tdk株式会社 | Resistor paste, resistors and electronic components |
| CN102617137A (en) * | 2012-03-28 | 2012-08-01 | 厦门松元电子有限公司 | BaO-TiO2 lead-free Y5P capacitor dielectric material and preparation method for same |
| CN107995783A (en) * | 2016-10-26 | 2018-05-04 | 先丰通讯股份有限公司 | Circuit board structure and manufacturing method thereof |
| CN108417290A (en) * | 2018-02-28 | 2018-08-17 | 江苏国瓷泓源光电科技有限公司 | A kind of solar cell aluminum paste and preparation method thereof |
| CN111028975A (en) * | 2019-12-03 | 2020-04-17 | 南京汇聚新材料科技有限公司 | Low-temperature coefficient resistor paste and preparation method and application thereof |
| TWI742979B (en) * | 2020-12-31 | 2021-10-11 | 華新科技股份有限公司 | Sintering aid for buffer layer, resistance including buffer layer and resistance manufacturing method |
Non-Patent Citations (1)
| Title |
|---|
| A Thermocycler Using a Chip Resistor Heater and a Glass Microchip for a Portable and Rapid Microchip-Based PCR Device;Dongsun Yeom et al.;Micromachines;第13卷(第339期);全文 * |
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