JPH027161B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a resistance material for forming a thick film resistor etc. by firing in a non-oxidizing atmosphere. By using this resistive material, it is possible to simultaneously form a thick film resistor and a base metal wiring conductor on a common ceramic substrate. 2. Description of the Related Art Recently, multilayer ceramic substrates have come into use in order 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, when forming a wiring conductor using a base metal, a conductive paste must be applied to an unfired ceramic sheet (raw sheet) and then fired in a non-oxidizing atmosphere. . However, a resistive material that can be fired in a non-oxidizing atmosphere at the same time as the conductive paste and has practical characteristics has not yet been developed. Therefore, in conventional multilayer ceramic substrates in which wiring conductors are formed from base metals, wiring conductors are provided between each ceramic layer, and passive elements such as resistors, active elements such as transistors, and their wiring conductors are formed on the surface of the substrate. had to be established. As a result, although the wiring pattern in the ceramic layer is rough, the wiring pattern and circuit elements are arranged densely on the surface of the ceramic substrate.
There has been a limit to 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. Accordingly, 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 The resistance material of the present invention to achieve the above object contains at least one of 29.0 to 75.0 parts by weight of molybdenum boride, calcium fluoride, strontium fluoride, and barium fluoride. It consists of 1.0 to 61.0 parts by weight of metal fluoride and 10.0 to 70.0 parts by weight of glass. Function A resistor paste is made using the resistor material with the above composition, and this is printed on a raw ceramic sheet.
By firing in a non-oxidizing atmosphere, a thick film resistor with practical 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 resistor material according to an example of the present invention and a method of forming a multilayer ceramic circuit board using the same will be described. First, 78.0 parts by weight of silicon dioxide (SiO ₂ ), 5.5 parts by weight of bad lead oxide (ZnO), and zirconium oxide (ZrO ₂ ).
12.0 parts by weight, 3.0 parts by weight of calcium carbonate (CaCO ₃ ), and 1.5 parts by weight of aluminum oxide (Al ₂ O ₃ ) were mixed and melted at 1400°C for 30 minutes in an alumina crucible, and this melt was poured into water. , rapidly cooled. This glass was ground to about 50 μm in an alumina mortar, then placed in a polyethylene pot mill with ethanol, and ground for 150 hours with an alumina ball to obtain powdered glass with a particle size of 10 μm or less. Next, the above glass, Mo ₂ B, and CaF ₂ were mixed into a first
They were weighed in the proportions shown in the table and mixed in a ball mill. Next, this mixture was heat-treated at 1200° C. for 1 hour in an argon gas atmosphere. This was then placed in a polyethylene pot mill with ethanol and ground for 24 hours with an alumina ball.
A powder of a resistive material having a diameter of 10 μm or less, preferably 5 μm or less was obtained. Note that the composition of this powder (resistor composition) is substantially the same as that of the initial raw material.
Thereafter, 100 parts by weight of the above resistance material powder and 25 parts by weight of an organic binder (10 parts by weight of nitrocellulose dissolved in 90 parts by weight of butyl carbitol) were kneaded in a three-roll mill to obtain a resistance of approximately 800 poise. It was made into a body paste. On the other hand, a raw porcelain sheet for printing the above resistor paste was produced by the following method. _{Al2O3 powder} 50
parts by weight, 20 parts by weight of SiO ₂ powder, 25 parts by weight of SrO powder,
Ceramic raw material powder consisting of 1 part by weight of Li ₂ 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 were placed in a ball mill and mixed. After making a slip and degassing it, the thickness was adjusted using the doctor blade method.
A long raw sheet of 200 μm was produced. and,
From this raw sheet, we made 2 pieces of 9mm x 9mm and 6mm x 9mm.
Cut out different raw sheet pieces. Next, as shown in FIG. 1, the former raw sheet piece 1
A conductive paste made by kneading nickel (Ni) powder and an organic binder at a ratio of 3:1 was printed on the top using a 200 mesh screen and dried at 125°C for 10 minutes to form the pattern shown in Figure 1. A Ni conductor film 2 was formed as shown. Next, the resistor paste according to the present invention was screen printed in the same manner as the conductive paste and dried to form a resistor film 3 as shown in FIG. Next, the other raw sheet piece 4 of the size shown by the chain line is laminated on top of the raw sheet piece 1, and heated at 100℃ and 150℃.
Kg/cm ² thermocompression bonded at 500°C in an oxidizing atmosphere.
The organic binder was blown off by heat treatment at 1200 °C in a reducing atmosphere of N ₂ (98.5 vol%) + H ₂ (1.5 vol%).
℃ for 2 hours, and as shown in Figure 2, the porcelain layer 1
a, 4a, a thick film conductor 2a and a thick film resistor 3a
We have completed a multilayer ceramic circuit board for hybrid integrated circuits. Note that the size of the portion of the resistor 3a that does not cover the conductor 2a is 3 mm x 3 mm, and the film thickness is 18 μm. Next, the sheet resistance of this resistor 3a at 25°C was measured by the bridge method, and from 25°C to 125°C.
When we measured the temperature coefficient of resistance in the temperature range of
The results shown in Table 1 were obtained.

[Table] As is clear from the above, a thick film resistor can be obtained by applying the resistor paste of this example to a raw porcelain sheet and firing it in a reducing atmosphere. Therefore, it can be fired simultaneously with a base metal paste such as Ni. Therefore, it becomes possible to receive a thick film resistor as well as a thick film conductor made of a paste such as Ni in the ceramic layer, thereby making it possible to reduce the cost and size of the hybrid integrated circuit. Furthermore, as is clear from Table 1, depending on the composition of 10.0 to 70.0 parts by weight of glass, 29.0 to 75.0 parts by weight of Mo ₂ B, and 1.0 to 61.0 parts by weight of CaF ₂ , the sheet resistance varies from 172.5 to 143080 Ω/.
A thick film resistor of □ can be obtained. Therefore, by appropriately selecting the composition ratio, any resistance value can be obtained. Furthermore, since the temperature coefficient of resistance falls within the range of -970 to +150 ppm/°C, it is possible to provide a practically usable resistance. Example 2 In order to confirm that the same effects as in Example 1 can be obtained even if the composition of the glass is changed, glass powder was prepared as follows. Silicon dioxide (SiO ₂ )
75.0 parts by weight, 13.0 parts by weight of diboron trioxide (B ₂ O ₃ ), 10.0 parts by weight of calcium carbonate (CaCO ₃ ), and 2.0 parts by weight of aluminum oxide (Al ₂ O ₃ ),
Powdered glass was obtained in the same manner as in Example 1. Next, this glass, Mo ₂ B and CaF ₂ were mixed in the ratio shown in Table 2 to obtain a powder of a resistor composition in the same manner as in Example 1. A multilayer ceramic circuit board having the same structure was formed by the method described in (1), and its electrical characteristics were measured in the same manner as in Example 1, and the results shown in Table 2 were obtained.

[Table] As is clear from Example 2, there is no significant difference in resistance characteristics even if the composition of the glass is changed. That is, the glass used in the present invention is not necessarily limited to one specified composition. Note that SiO ₂ −ZnO− in Example 1
ZrO ₂ -CaO-Al ₂ O ₃ -based glass, SiO ₂ - of Example 2
All B ₂ O ₃ -CaO-Al ₂ O ₃ type glasses have a working point (temperature at which 1×10 ⁴ noise is obtained) 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,
As long as it has a working point of 900 to 1200℃ and does not contain metal oxides (PbO, SnO ₂ , Bi ₂ O _3, etc.) that are easily metalized when fired in a cyclic atmosphere, what can be done? 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, metal fluoride SrF ₂ was prepared, and glass with the same composition as in Example 1 and Mo ₂ were prepared. B and SrF ₂ were weighed in the proportions shown in Table 3, and a resistor composition was formed using the same method as in Example 1, except that the heat treatment temperature in an argon gas atmosphere was 900°C. . After that, a resistor paste was made using the same method as in Example 1, and a multilayer ceramic circuit board was also made, and the electrical characteristics were measured.
The results shown in Table 3 were obtained.

[Table] As is clear from Table 3, even when SrF ₂ is used, almost the same effects as in the case of CaF ₂ can be obtained. Example 4 In order to confirm that the same effects as in Example 1 can be obtained even if Mo ₂ B ₅ is used as molybdenum boride and SrF ₂ is used as the metal fluoride, glass with the same composition as in Example 1, Mo ₂ O ₅ and SrF ₂ were weighed in the proportions shown in Table 4, and a resistor composition powder was prepared in the same manner as in Example 1, except that the heat treatment temperature in an argon gas atmosphere was 1000°C. A resistor paste was made using the same method as in Example 1, and a multilayer ceramic substrate was also made, and its electrical characteristics were measured, and the results shown in Table 4 were obtained.

【table】

[Table] Example 5 Implemented except that glass having the composition of Example 1, Mo ₂ B ₅ and BaF ₂ were weighed in the proportions shown in Table 5, and the heat treatment temperature in an argon gas atmosphere was 900°C. A powder of a resistor composition was prepared in the same manner as in Example 1, and using this powder, a resistor 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. The results shown in Table 5 were obtained. As is clear from this table, the same effects as in Example 1 can be obtained even if the types of molybdenum boride and metal fluoride are changed.

[Table] Example 6 Molybdenum boride is used as MoB, and metal fluoride is used as MoB.
In order to confirm that the same effects as in Example ₁ can be obtained with BaF 2, glass, MoB, and BaF ₂ having the same composition as in Example 1 were weighed in the proportions shown in Table 6, and A powder of a resistor composition was prepared by the method, and using this powder, the same method as in Example 1 was carried out.
Make a paste, then make a multilayer porcelain circuit board,
When the electrical characteristics were measured, the results shown in Table 6 were obtained.

【table】

[Table] Example 7 In order to confirm that the same effect as in Example 1 can be obtained even when molybdenum boride is used as MoB and multiple types of metal fluorides are used, glass with the same composition as in Example 1, MoB, Weigh CaF ₂ and SrF ₂ in the proportions shown in Table 7, and set the heat treatment temperature in argon gas.
A powder of a resistor composition was made in the same manner as in Example 1 except that the temperature was 1100°C, and a paste was made using this in the same manner as in Example 1. A multilayer ceramic circuit board was also made, and the electrical characteristics were determined. When measured, the results shown in Table 7 were obtained. As is clear from this result,
Even if multiple types of metal fluoride are used, the same effects as when using one type of metal fluoride can be obtained as long as the total is within the range of 1 to 61 parts by weight.

[Table] Example 8 Molybdenum boride is MoB ₂ , and metal fluoride is
In order to confirm that the same effects as in Example 1 can be obtained using SrF ₂ and BaF ₂ , glass having the same composition as in Example 1, MoB ₂ , SrF ₂ , and BaF ₂ were used in the eighth example.
Weigh the proportions shown in the table, make a powder of a resistor composition in the same manner as in Example 1, use this to make a paste in the same manner as in Example 1, and further make a multilayer ceramic circuit board. When we measured the characteristics of
The results shown in Table 8 were obtained.

[Table] Modifications The present invention is not limited to the above-described embodiments, and for example, the following modifications are possible. (a) When there are three types of metal fluorides, and molybdenum boride is used as Mo ₂ B, Mo ₂ B ₅ , MoB, MoB ₂
It has been confirmed that the same effects as in Example 1 can be obtained even when a combination of a plurality of types is used. (b) It has been confirmed that it is desirable to set the firing temperature of the mixture of glass, molybdenum boride, and metal fluoride in the range of 900 to 1200°C. Further, this firing may be performed in an inert atmosphere other than argon gas, in vacuum, in a neutral atmosphere, or in a reducing atmosphere. (c) The organic binder for making the resistor paste may be a resin such as ethyl cellulose dissolved in a high boiling point solvent such as turpentine oil or butyl carbitol acetate. Further, the amount of this binder is preferably about 15 to 35 parts by weight. (d) The atmosphere in which the resistor is fired together with the raw sheet may be a neutral atmosphere. (e) 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. In addition, before this firing, 400 ~
It is desirable to perform heat treatment in an oxidizing atmosphere at 600°C to decompose organic substances. Effects of the Invention As is clear from the above, the resistance material according to the present invention can be fired in a non-oxidizing atmosphere, so it can be fired together with a conductive paste made of a 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 the 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.
FIG. 2 is a cross-sectional view showing a multilayer ceramic circuit board after firing of a portion corresponding to a line. 1... raw sheet piece, 2... conductor film, 3... resistor film, 4... raw sheet piece.

Claims (1)

[Scope of Claims] 1. 29.0 to 75.0 parts by weight of molybdenum boride, 1.0 parts by weight of at least one metal fluoride selected from calcium fluoride, strontium fluoride, and barium fluoride.
Resistance material consisting of ~61.0 parts by weight and 10.0 to 70.0 parts by weight of glass. 2 The molybdenum boride includes molybdenum boride di(Mo ₂ B), molybdenum pentaboride (Mo ₂ B ₅ ), molybdenum boride monoboride (MoB), and molybdenum diboride (MoB ₂ ). The resistance material according to claim 1, which is at least one of the following. 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.