JPS6175502A - Resistance material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a resistive material for forming a thick film resistor or the like by firing in a non-oxidizing atmosphere. By using this resistance material, it is possible to simultaneously form a thick film resistor and a base metal wiring conductor on a common ceramic substrate.

BACKGROUND OF THE INVENTION Recently, multilayer ceramic substrates have been used to miniaturize electronic circuit devices. In order to reduce the cost of this type of multilayer ceramic substrate, attempts have been made to form wiring conductors from base metals such as nickel.

Problems to be Solved by the Invention As mentioned above, in order to form a base metal wiring conductor, an unfired ceramic sheet (green sheet) coated with a conductive paste must be fired in a non-oxidizing atmosphere. However, a resistor material that can be fired in a non-oxidizing atmosphere at the same time as the conductor paste and obtain practical characteristics has not yet been developed. In conventional multilayer ceramic substrates,
It was necessary to provide an IIM conductor between each ceramic layer, and provide receiving elements such as resistors, active elements such as transistors, and wiring conductors for these on the substrate surface.

As a result, although the wiring pattern in the ceramic layer is rough and aluminum, the wiring pattern and circuit elements are densely arranged on the surface of the ceramic substrate, which limits the miniaturization of electronic circuit devices. The above-mentioned problems and similar problems would be solved if a resistive material was available that could be fired in a non-oxidizing atmosphere.

Therefore, it is an object of the present invention to provide a resistive material that can be fired in a non-oxidizing atmosphere.

Means for Solving the Problems To achieve the above object, the resistance material of the present invention comprises molybdenum carbide 39.0~so, ox weight parts at least one of calcium fluoride, strontium fluoride, and barium fluoride. The loincloth consists of 1.0 to 51.0 parts by weight of metal fluoride and 10.0 to 60.0 parts by weight of glass.

Function: Make a resistor paste using the resistor material with the above composition.
By printing on this 7"L Hiceramic raw sheet and firing it in a non-oxidizing atmosphere, a thick layer resistor with practically usable characteristics can be obtained. Therefore.

A base metal thick film resistor can be formed simultaneously with the formation of a thick film conductor using a base metal conductor paste such as nickel.

Example 1 Next, a resistive material and a material according to an example of the present invention
(!-) The method for forming the multilayer ceramic circuit board using the original method will be described below.

Ichizu, silicon dioxide [5jot] 78-0 parts by weight, zinc oxide (ZnOJ5-5 parts by weight, zirconium oxide (Zr
O,]12.0'71 (part i, calcium carbonate (Ca
CO, ) 3.0 parts by weight, and aluminum oxide (A1
10j) Mix 1.5 parts by weight in an aluminium crucible,
The mixture was melted at 1400° C. for 30 minutes, poured into water, and rapidly cooled.

This glass is crushed to about 50 μm in an alumina mortar,
Further, this was placed in a polyethylene bot mill together with ethanol, and ground with alumina balls for 150 hours to obtain powdered glass having a particle size of 10 Itm or less.

Next, the above glass, MnC, and CaF were weighed in the proportions shown in Table 1, and mixed in a ball mill. Next, this mixture was heat-treated at 1200° C. for 1 hour in an argon gas atmosphere. Then, this was placed in a polyethylene bot mill with ethanol and ground for 24 hours with an alumina ball.
A powder of a resistive material having a size of less than m was obtained. The composition of this powder (resistance composition) is substantially the same as the composition of the initial raw material.Thereafter, 100 parts by weight of the powder of the above-mentioned resistance material, organic' was dissolved in 90 parts by weight of butylcarpitol) and 25 parts by weight were kneaded in a three-roll mill to obtain a resistor paste with approximately 800 voids.

- 10,000, a porcelain raw material for printing the above resistor paste was prepared by the following method. AI, 0. 5ON parts of powder,
Sin, 20 parts by weight of powder, SrO powder, parts by weight of Song powder, L
i. A ceramic raw material powder consisting of 1 part of O powder and 4 parts by weight of MgO powder, a binder consisting of an aqueous solution of acrylic acid ester polymer, glycerin, a carboxylic acid salt, and water are placed in a ball mill and mixed. A slip was prepared, and after degassing, a long raw sheet with a thickness of 200 μm was prepared using a doctor blade method. Then, from this raw sheet, 9 mm x 9 mm
Two types of raw sheet pieces of 6 mm x 9 mm were cut out.

Next, as shown in FIG. 1, a conductive paste made by kneading nickel LNi powder and an organic binder in a ratio of 3=1 was printed on the former raw sheet piece fil using a 200-mesh screen. By drying at 125° C. for 10 minutes, a Ni conductor film (2) as shown in FIG. 1 was formed.

Next, by screen printing in the same manner as the resistor paste (resistor paste) Y conductive paste according to the present invention and drying, a resistor film +31 'l? Formed.

Next, the other raw sheet piece (4) of the size shown by the chain line was stacked on top of the pile of raw sheet pieces, and heated at 100°C and weighed 150 kg.
/cm'', heat-treated at 500℃ in an oxidizing atmosphere to blow off the organic binder, and
12 in a reducing atmosphere of 10 liters (1.5% by volume)
After firing at 00°C for 2 hours, a porcelain layer (1
aN4a), a thick film conductor (2a) and a thick film resistor (3
A multilayer ceramic circuit board for hybrid integrated circuits with aJ was completed. The thickness of the part of the resistor [3aJ that is not covered by the conductor (2a)] is 3 mm+X3 mm, and the film thickness is 18 μm.

Next, the sheet resistance of this resistor (3aJ) at 25°C was measured using the bridge method, and the temperature coefficient of resistance was measured in the temperature range from 25°C to 125°C, and the results shown in Table 1 were obtained. .

It is clear from the above that a thick film resistor can be obtained by applying the resistor paste Z of this example to a raw porcelain sheet and firing it in a reducing atmosphere. Therefore, s N+ #
? It can be fired at the same time as base gold oval paste. Therefore, it is possible to provide a thick film resistor as well as a thick film conductor made of paste such as N1 in the ceramic layer, and the cost and size of the hybrid multiplication circuit can be reduced.

Also, as is clear from Table 1 (, Glass 10.0-60.01 Kamebe.

λ4oC39,0~80. Omltt club.

CaF, 1.0~51-07Jf Depending on the composition of ft, sheet resistance 500300~182300
It is possible to obtain a thick film resistance of 0 Ω/mm. Therefore, by appropriately selecting the m-acid ratio, any resistance value can be obtained.

In addition, the temperature coefficient of resistance is -1950 to -759ppm 7℃
, it is possible to provide a practical resistance.

Example 2 In order to confirm that the same effects as in Example 1 could be obtained even if the composition of the glass was changed, glass powder was prepared as follows: 75.0 parts by weight of silicon dioxide (Sift),
Parts by weight of diboron trioxide (BtOmJ t a-o, 10.0 parts by weight of calcium carbonate (CaCO), and 2.0 parts by weight of aluminum oxide (Al2O2) were mixed and powdered in the same manner as in Example 1. A shaped glass was obtained.

Next, this glass was mixed with MoC, CaF, and Y in the ratio shown in Table 2 to obtain a resistor composition powder in the same manner as in Example 1. to form a multilayer porcelain circuit board with the same structure.

When the electrical characteristics of Example 1 and lhJ were measured, the results shown in Table 2 were obtained.

As is clear from Example 2, there is no significant difference in resistance characteristics even if the composition of the glass is changed.

In other words, the glass used in the present invention is not necessarily limited to one specified composition.
S io, -ZnO-ZrO, -Ca in Example 1
O-AI, 03 thread glass, Slow Bt of Example 2
All Og-CaOAltOi glasses have a working point (I
The glass has a temperature of 900 to 1200°C. The glass of the resistor composition of the present invention is not limited to the glasses having the compositions of Examples 1 and 2 (900 to 12
Metal oxides (PbO1SnO, B
i, O, etc.)! Includes rx y・4 f) te, fi)
tt c) It has been confirmed that any composition may be used.Example 3 In order to confirm that the same effect as in Example 1 can be obtained even if the metal fluoride is changed, the composition of the metal fluoride was changed. SrF2'r
: Prepared glass with the same composition as in Example 1, MoC, and Sr.
F2 and F2 were weighed in the proportions shown in Table 3, and using this, the heat treatment temperature in an argon gas atmosphere was set to 900°C.
A resistor composition was formed in the same manner as in Example 1. Thereafter, in the same manner as in Example 1, a resistor paste y was prepared, and a multilayer ceramic circuit board was also prepared, and its electrical characteristics were measured, and the results shown in Table 3 were obtained.

As is clear from Table 3, even when using SrF, almost the same effects as in the case of CaF* can be obtained.

Example 4 Mo, C% as molybdenum carbide Sr as metal fluoride
In order to confirm that the same effect as in Example 1 can be obtained even when F*'l is used, laths, MO, C, SrF, and N having the same composition as in Example 1 were weighed in the proportions shown in Table 4. The ME resistor powder was prepared in the same manner as in Example 1, except that the heat treatment temperature in an argon gas atmosphere was 1100°C.
Using this, a resistor paste was made in the same manner as in Example 1, and a multilayer ceramic substrate 7 was also made, and its electrical characteristics were measured.The results shown in Table 4 were obtained.

Example 5 In order to confirm that the same effect as in Example 1 can be obtained even when using molybdenum carbide (MntC) and multiple types of metal fluorides, glass, Mo
2C, CaFhBaF, 'f7 were weighed in the proportions shown in Table 5, and a resistor composition powder was prepared in the same manner as in Example 1, except that the heat treatment temperature in argon gas was 1100°C.
Using this, a paste was made in the same manner as in Example 1, and a multilayer ceramic circuit board was also made, and the electrical characteristics were measured, and the results shown in Table 5 were obtained. As is clear from this result (even if multiple types of metal fluorides are used, the total amount is 1 to 51N).
If the amount is within the range of four parts, the same effects as in the case of one type can be obtained.

Variant The invention is not limited to the embodiments described above.

For example, the following modifications are possible.

[al] It has been confirmed that the same effects as in Example 1 can be obtained when the type of metal fluoride is 3 types, and when the molybdenum carbide is a combination of MnC, Mo, and C.

(bl) It has been confirmed that it is desirable to set the firing temperature of the mixture of glass, molybdenum carbide, and metal fluoride in the range of 900 to 1200°C.
It may be carried out in an inert atmosphere other than argon gas, in vacuum, in a neutral atmosphere, or in a reducing atmosphere.

[cl The organic binder for making the resistor pastera may be one obtained by dissolving a resin such as ethyl cellulose in a high boiling point solvent such as turpentine oil or butyl carpitol acetate. The amount of this binder is preferably about 15 to 35 parts by weight.

The atmosphere in which the resistor is fired together with the raw fdl sheet may be a neutral atmosphere.

[el] It is desirable that the raw sheet, resistor, and conductor be fired in a non-oxidizing atmosphere at a temperature in the range of 1050 to 1250°C. 7j Oh, before this firing, 400-6
It is desirable to decompose the organic VlJ by heat treatment in an oxidizing atmosphere at 00°C.

Effects of the Invention As is clear from the above description, the resistance material according to the present invention can be fired in a non-oxidizing atmosphere, and therefore can be fired together with a conductive paste made of base metal such as nickel. Therefore, the present invention contributes to miniaturization and cost reduction of electronic circuit devices.

[Brief explanation of drawings]

FIG. 1 is a plan view showing a green sheet and patterns of conductors and resistors when producing a multilayer ceramic circuit board according to an embodiment of the present invention, and FIG. 2 is a portion corresponding to the line ■-■ in FIG. 1. FIG. 3 is a cross-sectional view showing the multilayer ceramic circuit board after firing. II+...raw sheet piece, [2+...conductor film, (3)
...Resistor film, (4)...Raw sheet piece.

Claims (1)

[Scope of Claims] Molybdenum carbide 39.0 to 80.0 parts by weight, at least one metal fluoride selected from calcium fluoride, strontium fluoride, and barium fluoride 1.0 to 51.0 parts by weight, A resistance material comprising 10.0 to 60.0 parts by weight of glass. (2) The molybdenum carbide is monomolybdenum carbide (M
2. The resistance material according to claim 1, which is at least one of molybdenum monocarbide (Mo_2C). (3) The resistance material according to claim 1 or 2, wherein the glass has a working point in the range of 900 to 1200°C.