JPH0334401A - Resistor paste - Google Patents

Abstract

PURPOSE:To improve cutting characteristics of a resistor by constituting practically inorganic component of glass powder and one of ZrB2, LaB6, TaN, TiN, TaSi2, MoSi2, Mo2C, and WC, and containing a specified weight percent of Fe2O3+CoO+Cr2O3+MnO+CuO+NiO+V2O5 in the glass powder. CONSTITUTION:Resistor paste composed of conductive material powder and metal oxide for staining is manufactured. Any kind of glass can be used, but SiO2-B2O3 based glass is easy to be baked at a low temperature, and therefore desirable. The oxide component for staining must be a material having laser absorption property in the vicinity of laser wavelength (near infrared (vicinity of 1mum)). Practically, Fe2O3, CoO, Cr2O3, MnO, CuO, NiO and V2O5 are individually or mutually used, and 0.05-20wt.% of them mush effectively be contained in the glass. As the conducting material, the following can be used; ZrB2, LaB6, TaN, TiN, TaSi2, MoSi2, Mo2C, and WC. Such composition is excellent in laser trimming property, and resistor property after trimming, and has characteristics sufficiently applicable to resistor paste for thick film circuit.

Description

[Detailed description of the invention]

The present invention relates to a resistor paste.

[Conventional technology 1] In conventional thick film circuits, copper (Cu) conductors are formed as electrodes on a ceramic substrate, a resistor paste is printed between them, and the paste is fired in a nitrogen atmosphere (N2) at a temperature of about 850 to 1000°C. . Next, laser trimming is performed to adjust the resistance value, but at that time the laser trimming is not done sufficiently, so when the laser power is increased so that the thick resistor film can be cut, the resistor When the resistor is cut, the underlying substrate is also cut and dug by the laser, and the resistor is difficult to cut by the laser. There were more than 0 problems with cracks occurring at the cut ends. [Problems to be Solved by the Invention 1] The purpose of the present invention is to solve the above-mentioned drawbacks of the prior art, and to provide a new resistor paste that has not been known in the past. This is the purpose. [Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems, and the inorganic components are substantially glass powder, ZrB*, and LaB.
5. TaN, TiN, Ta5ks, MoSix, Moa
The glass powder is made of one of F and IC.
e*Os◆CoO◆Cr*Os +MnO+CuO+N
The present invention provides a resistance paste characterized by containing 0.05 to 20% by weight of iO+V-Os. SUMMARY OF THE INVENTION An object of the present invention is to produce a resistor paste with good dozer-trimming properties, which is made of a glass powder containing a conductive material powder and a metal oxide for dyeing. Any type of glass can be used in the present invention, but 5iOa
-Glass such as Ba53 is preferable because it is easy to sinter at low temperatures. An example of a glass powder according to the present invention is a glass powder having an inorganic component of substantially % by weight of Stow 8 to 60% A1.01.
0~30% MgOO~40% Ca00~40% SrOO~60% Ban O~60% MgO+CaO+SrO◆BaOto~60%LiaO
+NaaO+, 0+Cs1Oo~to%pbo
o~lO% Zn00~40% Ties◆ZrO* 0~10% egos
It consists of 5 to 40%, and these will be explained in order. In such a composition, SiO□ is a glass network former, and if it is less than 8%, the softening point becomes too low, the heat resistance decreases, and deformation is likely to occur during re-firing, which is not preferable. On the other hand, if SiO This is not suitable as it will result in poor stability. Desirably, it is in the range of 15 to 55%. Although Alas is not essential, its addition is effective in improving moisture resistance. If it exceeds 30%, the softening temperature of the glass will become high and the sinterability will deteriorate, making it unsuitable. It is preferably 28% or less. MgO+CaO◆SrO+BaO is added for the purpose of improving solubility during glass powder production and adjusting the coefficient of thermal expansion. If it is less than 10%, the above-mentioned solubility will not be improved sufficiently and devitrification will easily occur during glass production.
If it exceeds 0%, the coefficient of thermal expansion becomes too large, and neither is suitable. It is preferably in the range of 15 to 55%. Also, Mg in the above MgO+CaO+SrO+BaO
If each of O and CaO is 40% or more, the coefficient of thermal expansion becomes too large, which is inappropriate. Desirable range is 0-35
%. If S in the above MgO+CaO+SrO+BaO is 60% or more, the coefficient of thermal expansion becomes too large and is inappropriate.The desirable range is 0 to 55%.Li*0◆NatO+*0◆Cs* Although 0% is not essential, the melting properties of the glass can be improved by adding it.If it exceeds 10%, the coefficient of thermal expansion becomes too large and the matching with the substrate becomes poor, resulting in a thick film after firing. It is not appropriate as there is a high possibility that
It is as follows. Although PbO is not essential, it is effective as a flux component for glass. If it exceeds 10%, the resistance value becomes too high and is not suitable. It is preferably 5% or less. Although ZnO is not essential, it can be added up to 40% to improve the solubility of the glass, with a desirable range of 35% or less. Although ZrO□+TiO□ is not essential, adding it can improve the moisture resistance reliability of the resistor. t
The S content can be 10%, but is preferably 7% or less. B20. is used as a flux component, but if it is less than 5%, the softening point will be high, resulting in insufficient sintering and too many pores in the sintered layer. Moreover, if it exceeds 40%, the water resistance of the glass decreases and is not suitable. Desirably, it is in the range of 7 to 38%. The dyeing metal oxide component in the glass needs to be a substance that has laser absorption characteristics in the vicinity of the laser wavelength (near infrared (near 1 μm)). , Coo. Crabs, MnO, Cub, Nip, VgOa
substantially 0.05~ in the above glass by using alone or in combination
It is necessary to contain 20% by weight of Cr.
xOs, NiOs. Fe1Os, MnO, CoO are preferable, CraO
s, NiO are particularly preferable, and the above-mentioned Fetos etc. need to have these exemplified substances as the main components, but can be used even if they contain other substances. As the conductive material, ZrBa, LaBa, TaN, T
iN, TaSix. Mo5ia, MOxC, and WC can be used. The composition of the resistor paste of the present invention is one in which each powder is mixed in the above-mentioned proportions.Hereinafter, a method for producing the resistor paste of the present invention and an example of manufacturing a thick film circuit using the same will be explained. . An organic vehicle consisting of an organic binder and a solvent is added to the composition of the resistor paste of the present invention and kneaded to form a paste. The organic binder is ethyl cellulose, acrylic resin, ethylene-vinyl acetate copolymer resin, polymethylstyrene resin, and the solvent is a
-Terpineol, butyl carpitol acetate, butyl carpitol, 2,2,4-trimethylpentanedi-1,3-monoisobutyrate, diethylene glycol di-n-butyl ether, etc. can usually be used. Furthermore, a surfactant may be added as a dispersant. Next, in order to create a conductor on a solidified alumina substrate after firing or a ceramic substrate such as glass ceramics, Cu paste is printed on a predetermined circuit, and after drying, it is heated at 850 to 1000°C in a nitrogen atmosphere with an oxygen concentration of 20 ppm or less.
Bake for 5-20 minutes. The desirable range of this firing condition is 880~950℃, 7~
It is 15 minutes. Next, the resistor paste of the present invention is printed on a predetermined location where a resistor is to be provided, dried, and fired in the nitrogen atmosphere at 850 to 1000°C for 5 to 20 minutes. The desirable range of this firing condition is 880 to 950
°C for 7 to 15 minutes. In the case of bulk firing of multilayer ceramic substrates, green sheets of ceramics such as those for ceramic substrates printed with the above Cu paste and the resistor paste of the present invention are laminated after thermocompression bonding, and heated at 850-1000°C in the above nitrogen atmosphere for several times. Minutes~
Batch firing and creating multilayer boards in a few hours. Further, during glass melting, 0 to 5% of nitrates, arsenous acid, antimony oxide, sulfates, fluorides, chlorides, etc. can be added as clarifying agents and melting accelerators. Example Each raw material was mixed to have the target composition, placed in a platinum crucible, heated and stirred at 1350 to 1500°C for 2 to 3 hours, and then ground into water or flakes, and further pulverized. A glass powder having the composition shown in Table 1 was produced by pulverizing the glass powder with an average particle size of 0.5 to 6 μm using a device.
The thickness was adjusted to 1 to 5 μm. Next, these glass powders and conductive material powders were mixed in the proportions listed in Table 1,
Eight compositions according to the invention were obtained. Next, an organic vehicle consisting of ethyl cellulose as an organic binder and a-terpineol as a solvent was added and kneaded to prepare a paste with a viscosity of 30x lO'cps.
The u-paste was screen printed into a predetermined circuit, dried, and fired at 900° C. for 10 minutes in a nitrogen atmosphere. Next, the above resistor paste was screen printed on predetermined portions of the resistor using a 200 mesh screen, dried, and baked in N at 900° C. for 10 minutes. The fired film thickness was about 15 μm. Thus, the circuit was created. The resistance values of the circuit elements were measured, and then laser trimming was performed on them. These results are listed in Table-1. Table -
1 shows the resistance value after full cut laser trimming. As is clear from Table 1, the composition according to the present invention has excellent laser trimming properties and resistance properties after trimming, and has properties that allow it to be used satisfactorily as a resistor paste for thick film circuits. As comparative examples, compositions other than those according to the present invention were also evaluated in the same manner and are listed in Table 2. Table 1 shows the absorption rate measured at the wavelength of laser light (approximately 1 μm). For measurement, the reflection spectrum is measured and (l
-Reflectance) x tGo (%). [Function/Effect] In the present invention, a resistor with increased near-infrared absorption (wavelength around 1 μm) has the effect of improving cutting characteristics to increase laser absorption.

Claims (1)

[Claims] 1) Inorganic components are essentially glass powder, ZrB_2, La
B_6, TaN, TiN, TaSI_2, MoSi_2
, Mo_2C, and WC, and the glass powder is Fe_2O_3+CoO+Cr_2O_3+M
nO+CuO+NiO+V_2O_5 from 0.05 to 20
A resistance paste characterized by containing % by weight.