JPH04340201A - Thick film resistor composition, and hybrid ic using same and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide the title thick film resistor composition and hybrid IC using the same having the TCR of the thick film resistor fitting a Cu conductor circuit not exceeding + or -100ppm/ deg.C within the resistance range required for the thick film hybrid IC. CONSTITUTION:The title thick film resistor composition comprising thick film hybrid IC is composed of a mixture of a metallic boride and a glass containing a metallic Co or crystalline Co oxide. For example, when CoO is added to the thick film resistor composition comprising LaB6 and glass, it is evident that the TCR will fall in proportion to the decrease in the additive amount thereby enabling the TCR to be adjusted.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to thick film hybrid IC
The present invention relates to a thick film resistor composition suitable for Cu conductors used in, etc., a thick film hybrid IC using the composition, and a method for manufacturing the same.

0002

2. Description of the Related Art A thick film hybrid IC is one in which a conductor circuit, a thick film resistor, and a dielectric are formed on a substrate by printing and firing techniques, and semiconductor integrated circuit elements and the like are mounted thereon. The substrate used here refers to an insulating substrate made of SiC doped with Al2O3, AlN, BeO, or the like. Moreover, a thick film resistor is a resistor circuit formed on a substrate by thick film printing technology. Thick film hybrid IC
In general, an Ag-Pd based material is used for the conductor circuit, and a RuO2-glass based material is used for the resistor. but,
Ag-Pd-based materials have the disadvantage of high impedance and easy electromigration, which has been a problem when used in thick-film hybrid ICs. Therefore, Cu-based materials, which have lower impedance than Ag-Pd-based materials and do not cause electromigration, are attracting attention as materials for conductor circuits.However, since Cu is easily oxidized, it must be fired in a reducing atmosphere, such as nitrogen gas. Can not.

On the other hand, when the RuO2 -glass material is used as a resistor, there is a problem in that RuO2 is reduced in nitrogen gas. Therefore, C
In thick film hybrid ICs using U-based materials, L is used as a resistive material that can be used even in a reducing atmosphere.
aB6 is known (Japanese Patent Application Laid-Open No. 55-30889)
. However, this only covers resistance values up to 10kΩ/□.
The reality is that it is not possible.

The resistance value range required for a resistive material for thick film hybrid ICs is 10Ω/□ to 1MΩ/□. Therefore, in order to cover the above resistance value range of a thick film hybrid IC fired in a reducing atmosphere, 10
Ω/□ to around 1kΩ/□ with LaB6-glass material, and 10kΩ/□ to 1MkΩ/□ with SnO2-
This is handled using glass-based materials.

[0005] Furthermore, a high-performance resistance material comparable to that of RuO2-glass has not yet been found, and for this reason, a RuO2-glass resistor is used in combination with an Ag--Pd conductor circuit.

[0006]

[Problems to be Solved by the Invention] Metal borides can be considered as the conductive component of the resistor combined with the Cu-based conductor circuit.

[0007] As the metal boride, the above-mentioned LaB6 -
Glass-based materials are used, but this has unstable TCR (temperature coefficient of resistance), which is a problem as a resistance material for hybrid ICs and the like.

TCR of the above LaB6-glass-based resistance material
As a method to improve this, TiO, Ti3O5, Ti2O3, NbO, C, S
It has been proposed to incorporate substances such as i, Ge, and SiC as TCR regulators (Japanese Patent Laid-Open No. 55-29199).

However, according to the studies of the present inventors, this is due to the resistance value range (10Ω/□ to 1MΩ/□) required for the resistance material of thick film hybrid IC, especially in the low resistance region (10Ω/□). ~1 kΩ/□) is not sufficient to suppress the TCR of the resistor within a predetermined range.

[0010] The object of the present invention is to provide a resistor made of a thick film resistor composition containing a metal boride such as LaB6 with a TCR of within ±100 ppm/°C, and to provide a thick film hybrid I
The object of the present invention is to provide a thick film resistor composition that provides a resistance range required for C, and a thick film hybrid IC using the composition.

[0011]

[Means for Solving the Problems] In order to achieve the above object, in a thick film resistor composition containing a metal boride, a glass and an organic vehicle, for 100 parts by weight of the mixture of the metal boride and the glass, Metallic Co or crystalline C
o oxide in an amount of 0.1 to 10 parts by weight in terms of Co amount. Further, in a hybrid IC having a Cu conductor circuit on a substrate and a thick film resistor formed in contact with the conductor circuit, the thick film resistor may be made of metal boride, glass, metal Co, or crystalline. The sintered body is made of a sintered body of a composition containing Co oxide, and the sintered body contains metallic Co or crystalline Co oxide in an amount necessary for the temperature coefficient of resistance (TCR) to be within ±100 ppm/°C. using a composition containing

In the present invention, metal borides include rare earth elements, group IV elements, group V elements, group VI elements, and group VII elements.
There are borides of metals selected from group I elements. Specific examples include LaB6, TiB2, ZrB2, T
aB2, MoB, WB, FeB, NiB, HfB2
, NbB2, etc. are used.

The glass is not particularly limited as long as it is a non-reducing glass that does not reduce even in a reducing atmosphere, but since it undergoes a firing process at a temperature of about 900°C,
Unless the glass has a softening point higher than that, it will be reduced during the firing process. In particular, glass with a softening point of 500 to 600°C has the property of being easily reduced in a reducing atmosphere. Therefore, in the present invention, for example, borosilicate glass is preferred.

The organic vehicle is preferably one that can be decomposed in a non-reducing atmosphere, such as an organic vehicle prepared by dissolving an acrylic resin in butyl carbitol acetate, ethyl cellulose, or the like. Organic vehicles are required to have a viscosity range due to printing characteristics during paste printing, but
In the case of the present invention, butyl carbitol acetate 10
Good printing characteristics can be obtained if the amount of acrylic resin added is in the range of 25 to 35 g per 0 cc.

The amount of metallic Co or crystalline Co oxide is preferably in the range of 0.1 to 10 parts by weight in terms of Co amount, based on 100 parts by weight of the mixture of the metal boride and the glass.

More preferably, it is added in an amount of 0.1 to 5 parts by weight, which is more effective in reducing the temperature coefficient of resistance (TCR).

Incidentally, the blending ratio of the metal boride and the glass is determined depending on the resistance value range of the intended resistor, etc., but in the present invention, the glass is
It is preferable to mix it so that it becomes 95 volume%. This is because if the glass content exceeds 95 volume %, the effect of the metal boride becomes small, and if the glass content is less than 50 volume %, it becomes difficult to form a thick film resistor.

[0018] Regarding the particle size of each powder, it is preferable that the average particle size of the metal boride is smaller than the average particle size of the glass, with the metal boride being about 0.5 to 3 μm and the glass being about 5 to 6 μm. be. The thickness of Co varies depending on the resistance value range of the intended resistor, but when CoO powder is used, the thickness may be 1 to 5 μm.

[0019] Although some glasses contain metal Co or Co oxide, as described below, according to the studies of the present inventors, the metal Co or Co oxide contained in such glasses is The purpose of the invention cannot be achieved.

As described above, the thick film resistor composition of the present invention is composed of a metal boride, glass, an organic vehicle, metal cobalt, or crystalline cobalt oxide. as borosilicate glass, and crystalline cobalt oxide as C
Most preferred is a composition in which a predetermined amount of an organic vehicle is added to a well-mixed oO powder.

[0021] If the resistor composition of the present invention is used, it can be fired in a reducing atmosphere, so Cu-based materials can be used for the conductor circuit, and a hybrid IC with low impedance and small TCR can be provided. can.

[0022] Furthermore, in the present invention, hybrid I
As a substrate for forming an electronic circuit such as C, it is particularly preferable to use a green body such as a green sheet that can be fired integrally with the Cu circuit and resistor in a reducing atmosphere. An example is a green body made of alumina, alumina/borosilicate glass, etc. These can be created by well-known methods.

[0023]

[Operation] The resistance composition of the present invention is suitable for use with a Cu conductor, and a highly accurate resistor can be obtained by adding Co or a crystalline Co compound to a composition containing metal boride and glass. This is because it was included. As a result, when the composition is fired in a reducing atmosphere, Co boride is formed at the grain boundaries of the metal boride particles.

FIG. 1 shows the relationship between the amount of CoO added and TCR. This figure shows No. 2 in Table 2, which has a sheet resistance value of around 10Ω/□. These are the results of an investigation based on thick film resistors Nos. 1 to 5. It is clearly seen that the TCR decreases as the amount of CoO added increases. Generally, as shown in FIG. 2, the characteristics of a thick film resistor are such that as the sheet resistance value increases, the TCR value decreases accordingly. Therefore, the amount of Co added (the amount of metallic Co or crystalline Co oxide) must be adjusted depending on the sheet resistance value. That is, when the sheet resistance value is small, the amount added is increased, and when the sheet resistance value is large, the amount added is decreased. As a result, the TCR value was ±100pp.
This is to keep the temperature within m/℃.

[0025] As described above, the formation of the Co boride further promotes the sintering of the metal boride, thereby forming a strong and stable resistor. This also improves electrical contact between the metal borides and reduces variations in resistance. This is because semiconductor properties are imparted to the glass near the metal boride particles, suppressing changes in resistance.
This is believed to be because the TCR of the resistor can be substantially reduced in order to change the TCR from positive to negative.

[0026]

【Example】

(Example 1) LaB6 (average particle size 1 μm) powder as metal boride, borosilicate glass No. whose composition is shown in Table 1
．． 1 (average particle size 5 μm) powder and CoO (average particle size 5 μm) powder
μm) Mix the powder well. A predetermined amount of an organic vehicle prepared by dissolving 30 g of acrylic resin in 100 cc of butyl carbitol acetate was added to the mixture and mixed uniformly to prepare a paste of the resistance composition. In addition, the paste is
LaB6 and glass No. The blended amount of No. 1 was kept constant (1:1 by volume) and the amount of CoO added was changed (No. 1).
~No. 6) and LaB6, glass No. The blended amount of No. 1 and the added amount of CoO were changed within a certain range (No.
．． 7~No. 9) was prepared.

[0027]

[Table 1]

A resistor pattern was printed using the above paste on an alumina substrate on which a Cu conductor circuit was previously formed using a 325 mesh screen mask. This was heated in a belt furnace in a nitrogen gas atmosphere with an oxygen concentration of 10 ppm.
It was heated to 00°C and fired. The reason for containing a small amount of oxygen in the nitrogen gas atmosphere, that is, in the non-oxidizing atmosphere, is to improve the solderability of the Cu conductor circuit.

Table 2 shows the characteristics of the resistor after firing.

[0030]

[Table 2]

[0031] As is clear from Table 2, 8.7Ω/□~
TCR of thick film resistor with resistance value of 29.6kΩ/□
can be made extremely small by adding a predetermined amount of CoO.

(Comparative Example 1) As shown in Table 1, CoO-containing glass No. 2~No. Comparisons were made regarding resistance compositions using No. 4. The glass is made by mixing each oxide, holding it at 1500°C for 1 hour, and then putting it into water to quickly cool it.The resulting cullet is then ground in a sieve machine and then in a ball mill to form a cullet with an average particle size of 5 μm. A powdered version was used.

[0033] This was combined with LaB6 at the ratio shown in Table 3 to produce a resistor in the same manner as in Example 1. Table 3 shows the resistance characteristics of the resistor.

[0034]

[Table 3]

As is clear from Table 3, TCR cannot be lowered when CoO is added to the glass. This is because CoO in the glass exists in an amorphous state. Therefore, CoO must be contained in the resistor as a crystal.

However, even if glass containing CoO is used, the same effects as in Example 1 can be obtained by separately adding a predetermined amount of metallic Co or crystalline Co oxide as in Example 1.

(Example 2) A resistance composition was prepared using the metal borides and metal Co and Co oxides shown in Tables 4 and 5. In addition, the glass is the glass shown in Table 1 (No.
1) was used.

The metal boride and glass were mixed in a volume ratio of approximately 1:1. A resistor was prepared in the same manner as in Example 1 using the above resistance composition, and its resistance characteristics were measured. The results are shown in Tables 4 and 5.

[0039]

[Table 4]

[0040]

[Table 5]

As is clear from Tables 4 and 5, the resistor's TC
R can be significantly reduced.

(Third Embodiment) The resistors of the resistor matrix circuit required for stereo audio separation and video color reproduction are required to be highly accurate.

For example, the relationship between the degree of separation of stereo audio and the accuracy of resistance value is expressed by the following equation.

[0044]

[Math 1]

Here, S represents the degree of separation, and α represents the resistance value accuracy. The left and right separation degree of stereo sound is generally required to be 40 dB or more. If the resistance value accuracy is -1%, α=0.
99, and S is 46 dB. Therefore, the degree of separation is 4
To achieve 0 dB or more, the resistance value accuracy must be within ±1%, and the TCR must necessarily be within ±100 ppm/°C.

In a resistor matrix circuit for processing stereo sound, the accuracy of the resistance value of each resistor must be within ±1% in order to achieve the above-mentioned sound separation degree.

Therefore, among the resistance compositions shown in Table 2,
When a resistor was made using the composition according to the present invention, an excellent sound separation degree was obtained.

It has been found that when the composition of the present invention is applied to a resistor of a resistor matrix circuit, a highly accurate resistor with a high degree of audio separation can be obtained.

FIG. 3 shows a part of a circuit pattern in which the above matrix circuit is converted into a hybrid IC. Note that a Cu conductor can be used according to the present invention.

(Example 4) This example is an example in which the resistor composition of the present invention was applied to an inner layer resistor of a low-temperature-fired three-dimensional multilayer hybrid IC whose conductor circuits are made of Cu.

FIG. 4 is a partial cross-sectional view of the active filter.

Through holes are provided in a green sheet made of alumina/borosilicate glass, and a Cu conductor circuit is printed. A resistor is printed thereon. In this example,
The resistor has a resistance value of 30Ω/□~10kΩ after firing.
/□, No. in Table 2. 4, No. 7, No.
8 and no. No. 9 resistance composition was used. The mounted multilayer board was fired at 900° C. in the same manner as in Example 1.

[0053] TCR of each resistor is ±100ppm/°C
It was possible to obtain a highly accurate active filter.

[0054]

[Effects of the Invention] As described above, the resistance composition of the present invention has
It can be integrally fired with a Cu conductor in a reducing atmosphere as a resistor of an integrated circuit having Cu as a conductor circuit, and
There is an effect that the TCR of the obtained resistor can be within ±100 ppm/°C. Therefore, this resistor can be provided for use in high-precision hybrid ICs such as matrix circuits that require high resistance value accuracy.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the relationship between the amount of CoO added and TCR.

FIG. 2 is a diagram showing the relationship between sheet resistance value and TCR.

FIG. 3 is a partial diagram of a circuit pattern in which a resistance matrix circuit is converted into a hybrid IC.

FIG. 4 is a partial cross-sectional view of a three-dimensional multilayer hybrid IC.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1...Resistor, 2...Cu conductor electrode, 3...Dielectric, 4...Insulating substrate.

Claims (18)

[Claims] 1. A thick film resistor composition comprising a metal boride, glass, and an organic vehicle, wherein metal Co and Co are added to 100 parts by weight of the metal boride and glass mixture.
At least one of the oxides has a Co content of 0.1
A thick film resistor composition comprising ~10 parts by weight. 2. The mixture of metal boride and glass comprises:
2. The thick film resistor composition of claim 1, wherein the composition is 50 to 95 volume percent glass and the balance metal boride. 3. The metal boride has an average particle size of 0.5 to 0.5.
2. The thick film resistor composition according to claim 1, wherein the glass has an average particle size of 5 to 6 μm, and the Co oxide has an average particle size of 1 to 5 μm. 4. The thick film resistive composition according to claim 1, wherein said glass is borosilicate glass. [Claim 5] Rare earth elements, group IV elements, group V elements, VI
A boride of at least one element selected from the group consisting of Group elements and Group VIII elements, glass, and 100 parts by weight of a mixture of the boride and the glass, in terms of Co amount of 0.1 to A thick film resistor composition comprising 10 parts by weight of at least one of metallic Co and Co oxide and an organic vehicle. 6. The mixture of the boride and the glass comprises:
6. The thick film resistor composition of claim 5, wherein the composition is 50 to 95% by volume glass and the balance metal boride. 7. The boride has an average particle size of 0.5 to 3μ.
m, the average particle size of the glass is 5 to 6 μm, and the C
6. The thick film resistor composition according to claim 5, wherein the average particle diameter of the o oxide is 1 to 5 μm. 8. The thick film resistor composition according to claim 5, wherein said glass is borosilicate glass. 9. The thick film resistor composition according to claim 5, wherein the organic vehicle is an acrylic resin dissolved in butyl carbitol acetate. 10. A hybrid IC having a Cu conductor circuit and a thick film resistor formed in contact with the conductor circuit on a substrate, wherein the thick film resistor is made of a mixture of metal boride and glass. %, at least one of metal Co and Co oxide is 0.1 to 1 in terms of Co amount.
A hybrid IC characterized in that it is a sintered body of a composition containing 0 parts by weight. 11. The hybrid IC according to claim 10, wherein the mixture of metal boride and glass in the thick film resistor is 50 to 95 volume % glass and the balance metal boride. . 12. In the thick film resistor, the metal boride has an average grain size of 0.5 to 3 μm, the glass has an average grain size of 5 to 6 μm, and the Co oxide has an average grain size of 1 to 3 μm. 5
The hybrid IC according to claim 10, wherein the hybrid IC has a diameter of μm. 13. The hybrid IC according to claim 10, wherein the glass in the thick film resistor is borosilicate glass. 14. A hybrid IC having a Cu conductor circuit and a thick film resistor formed in contact with the conductor circuit on a substrate, wherein the thick film resistor includes a rare earth element, a group IV element, a group V element, and a thick film resistor formed in contact with the conductor circuit. A boride of at least one element selected from the group consisting of elements, group VI elements, and group VIII elements, glass, and 0.1 in terms of Co amount per 100 parts by weight of a mixture of the boride and glass. A hybrid IC characterized in that it is a sintered body of a composition containing ~10 parts by weight of at least one of metal Co and Co oxide, and an organic vehicle. 15. The hybrid IC according to claim 14, wherein the mixture of metal boride and glass in the thick film resistor is 50 to 95 volume % glass and the balance metal boride. . 16. In the thick film resistor, the metal boride has an average grain size of 0.5 to 3 μm, the glass has an average grain size of 5 to 6 μm, and the Co oxide has an average grain size of 1 to 3 μm. 5
The hybrid IC according to claim 14, wherein the hybrid IC has a diameter of μm. 17. The hybrid IC according to claim 14, wherein the glass in the thick film resistor is borosilicate glass. 18. A step of forming a Cu conductor circuit on a green body made of an inorganic material, at least one element selected from the group consisting of rare earth elements, group IV elements, group V elements, group VI elements, and group VIII elements. 0.1 to 10 parts by weight of metal C in terms of Co amount per 100 parts by weight of the boride, glass, and the mixture of the boride and glass.
a step of forming a resistor composition containing at least one of O and Co oxides and an organic vehicle into a predetermined resistor pattern in contact with the conductor circuit; A method for manufacturing a hybrid IC, comprising the step of heating and baking a circuit and a resistor pattern together.