JP2529030B2 - Thick film resistance composition, hybrid IC using the composition, and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a thick film hybrid IC.
The present invention relates to a thick film resistance composition suitable for a Cu conductor used for the above, a thick film hybrid IC using the composition, and a method for producing 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 stacked on the substrate.
The substrate used here refers to an insulating substrate made of SiC added with Al ₂ O ₃ , AlN, and BeO. The thick film resistor is a resistor circuit formed on a substrate by a thick film printing technique. In thick-film hybrid ICs, Ag-Pd materials are generally used for conductor circuits and R is used for resistors.
uO ₂ -glass materials have been used. But Ag
The -Pd-based material has a drawback that it has a high impedance and is apt to cause electromigration, which has been a problem in using it for a thick film hybrid IC. Therefore,
A Cu-based material, which has a lower impedance than that of an Ag-Pd-based material and does not cause electromigration, has been attracting attention as a material for a conductor circuit.

On the other hand, when the RuO ₂ -glass material is used as the resistor, there is a problem that RuO ₂ is reduced in nitrogen gas. Therefore, in a thick film hybrid IC using a Cu-based material for a conductor circuit, LaB is used as a resistance material that can be used even in a reducing atmosphere.
₆ is known (JP-A-55-30889). However, in reality, the resistance value can be covered only up to 10 kΩ / □.

The resistance value range required for a resistance material for a thick film hybrid IC is 10 Ω / □ to 1 MΩ / □. Therefore, in order to cover the above resistance value range of the thick film hybrid IC fired in a reducing atmosphere, 10
LaB ₆ -glass-based materials are used up to about Ω / □ to 1 kΩ / □, and SnO ₂ -glass-based materials are used for 10 kΩ / □ to 1 MkΩ / □.

Further, a high-performance resistive material comparable to the RuO ₂ -glass system has not yet been found, and therefore A
A RuO ₂ -glass type resistor is used in combination with the conductor circuit of g-Pd.

[0006]

A metal boride can be considered as the conductive component of the resistor combined with the Cu-based conductor circuit.

As the metal boride, the above LaB ₆ -glass system is used, but this has a TCR (temperature coefficient of resistance) instability and is a problem as a resistance material for hybrid ICs and the like.

The LaB ₆ -glass resistance material TCR
As a method of improving the above, TiO, Ti ₃ O ₅ , Ti ₂ O ₃ , NbO, C, Si and G which are non-reactive with LaB ₆
It has been proposed to incorporate substances such as e and SiC as TCR regulators (Japanese Patent Laid-Open No. 55-29199).

However, according to the study by the present inventors, this is due to the resistance value range (10 Ω / □ to 1 MΩ / □) required for the resistance material of the thick film hybrid IC, particularly in the low resistance region (10 Ω / □). It cannot be said to be sufficient to keep the TCR of a resistor of 1 kΩ / □) within a predetermined range.

It is an object of the present invention that the TCR of a resistor made of a thick film resistor composition containing a metal boride such as LaB ₆ is ±.
It is an object of the present invention to provide a thick film resistance composition which gives a resistance range of 100 ppm / ° C. or less and which is required as a thick film hybrid IC, and a thick film hybrid IC using the composition.

[0011]

As a constitution for achieving the above object, in a thick film resistance composition containing a metal boride, glass and an organic vehicle, 100 parts by weight of a mixture of the metal boride and glass are added, Metallic Co or crystalline C
O oxide is contained 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 is made of metal boride and glass, and metal Co or crystalline. It comprises a sintered body of a composition containing a Co oxide, and the sintered body contains metallic Co or crystalline Co oxide in an amount necessary to keep the temperature coefficient of resistance (TCR) within ± 100 ppm / ° C. A composition containing is used.

In the present invention, metal borides include metal borides selected from rare earth elements, group IV elements, group V elements, group VI elements and group VIII elements. Specific examples thereof include LaB ₆ , TiB ₂ , ZrB ₂ , TaB ₂ and Mo.
B, WB, FeB, NiB, HfB ₂ , NbB ₂ or the like is 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., it is 800 ° C.
Unless the glass has the above softening point, it will be reduced in the firing process. In particular, glass having a softening point of 500 to 600 ° C. has a property of being easily reduced in a reducing atmosphere. Therefore, in the present invention, for example, borosilicate glass is preferable.

The organic vehicle is preferably one that can be decomposed in a non-reducing atmosphere, for example, an organic vehicle in which an acrylic resin is dissolved in butyl carbitol acetate, ethyl cellulose or the like is preferable. The viscosity range of the organic vehicle is required due to the printing characteristics during paste printing,
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 relative to 0 cc.

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

More preferably, the addition is in the range of 0.1 to 5 parts by weight, and it is more effective in reducing the temperature coefficient of resistance (TCR).

By the way, the compounding ratio of the metal boride and the glass is determined according to the resistance value range of the intended resistor, etc.
It is preferable that the compounding amount be 95% by volume. This is because when the glass content exceeds 95% by volume, the effect of the metal boride becomes small, and when the glass content does not reach 50% by volume, it becomes difficult to form the thick film resistor.

Regarding the particle size of each powder, the average particle size of the metal boride is preferably smaller than the average particle size of the glass, the metal boride is about 0.5 to 3 μm, and the glass is 5 to 6 μm. is there. Co varies depending on the target resistance value range of the resistor, but when CoO powder is used, it may be 1 to 5 μm.

Although some glasses contain metallic Co or Co oxides, the inventors of the present invention have investigated the metallic Cos or Co oxides contained in such glasses as described later. The object of the invention cannot be achieved.

As described above, the thick film resistance composition in the present invention is composed of metal boride, glass, organic vehicle, metal cobalt or crystalline cobalt oxide, and LaB ₆ powder as metal boride, Borosilicate glass as glass and C as crystalline cobalt oxide
The most preferable is a composition in which a predetermined amount of an organic vehicle is added to a well-mixed oO powder.

Since the resistance composition of the present invention can be fired in a reducing atmosphere, a Cu-based material can be used for the conductor circuit, and a hybrid IC with low impedance and small TCR can be provided. it can.

Further, in the present invention, the hybrid I
As a substrate for forming an electronic circuit such as C, it is preferable to use a green body such as a green sheet that can be integrally fired in a reducing atmosphere with the Cu circuit and the resistor.
As an example, there is a green body made of alumina, alumina-borosilicate glass, or the like. These can be created by a known method.

[0023]

The resistance composition of the present invention is preferably used together with a Cu conductor, and a highly accurate resistor can be obtained by adding Co or a crystalline Co compound to a composition containing a metal boride and glass. 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 metal boride particles.

FIG. 1 shows the relationship between the amount of CoO added and the TCR. This figure is the result of an investigation based on the thick film resistors No. 1 to 5 in Table 2 having a sheet resistance value of around 10 Ω / □. It is apparent that the TCR decreases as the amount of CoO added increases. Generally, as a characteristic of the thick film resistor, as the area resistance value increases as shown in FIG. 2, the TCR value decreases accordingly.
Therefore, the amount of Co to be added (the amount of metallic Co or crystalline Co oxide) must be adjusted according to the value of the sheet resistance value. That is, when the area resistance value is small, the addition amount is increased, and when the area resistance value is large, the addition amount is decreased. As a result, the TCR value is ± 100 ppm
This is for keeping the temperature within / ° C.

As described above, the formation of the Co boride promotes the sintering of the metal boride to form a strong and stable resistor. As a result, the electrical contact between the metal borides is improved, and the variation in resistance value can be reduced. This is because the glass in the vicinity of the metal boride particles is provided with a semiconductor property, and the change in resistance is suppressed,
It is believed that the TCR of the resistor can be substantially reduced in order to change the TCR from positive to negative.

[0026]

【Example】

(Example 1) LaB ₆ (average particle size 1
μm) powder, borosilicate glass No. 1 whose composition is shown in Table 1
(Average particle size 5 μm) Powder and CoO (Average particle size 5 μm
m) Mix the powders well. A predetermined amount of an organic vehicle prepared by dissolving 30 g of an acrylic resin in 100 cc of butyl carbitol acetate was added to the mixture and mixed uniformly to prepare a paste of a resistance composition. The paste is La
B ₆ and glass No. 1 compounding amount is constant (volume ratio 1: 1)
And the amount of CoO added was changed (No. 1 to No. 6)
If, LaB _6, was obtained by changing within a certain range the amount of the amount and CoO of glass No.1 a (No.7~No.9) was prepared.

[0027]

[Table 1]

A resistance pattern was printed on the alumina substrate on which a Cu conductor circuit was formed in advance by using the above paste using a 325 mesh screen mask. 900 in a belt furnace in a nitrogen gas atmosphere with an oxygen concentration of 10 ppm
It was heated to ℃ and baked. Here, the reason for containing a slight amount of oxygen in the nitrogen gas atmosphere, that is, in the non-oxidizing atmosphere is to improve the solder wettability of the Cu conductor circuit.

Table 2 shows the characteristics of the resistor after firing.

[0030]

[Table 2]

As is clear from Table 2, 8.7Ω / □ ~
Thick film resistor TCR with a resistance of 29.6 kΩ / □
Can be made extremely small by adding a predetermined amount of CoO.

(Comparative Example 1) As shown in Table 1, comparison was made with respect to a resistance composition using CoO-containing glasses No. 2 to No. 4. The glass was mixed with each oxide, kept at 1500 ° C. for 1 hour, put into water and rapidly cooled, and cullet was crushed by a raider machine and then a ball mill to obtain an average particle size of 5 μm. What was made into a powder was used.

This was combined with LaB _{6 in the} ratio shown in Table 3 to prepare 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, the TCR cannot be lowered when CoO is added in the glass. This is because CoO in glass exists in an amorphous state. Therefore, CoO needs to be contained as crystals in the resistor.

However, even if a glass containing CoO is used, the same effect as in Example 1 can be obtained by 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 shown in Tables 4 and 5 and the metals Co and Co oxides. Further, the glass is the glass (No.
1) was used.

The metal boride and the glass were mixed in a volume ratio of about 1: 1. A resistor was prepared in the same manner as in Example 1 using the above resistance composition, and the 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, TCs of resistors were obtained by adding metallic Co or Co oxide.
R can be significantly reduced.

(Embodiment 3) 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 relation between the degree of separation of stereo sound and the resistance value accuracy is shown by the following equation.

[0044]

[Equation 1]

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

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

Therefore, among the resistance compositions shown in Table 2,
When a resistor was prepared using the composition corresponding to the present invention, excellent sound isolation was obtained.

It has been found that when the composition of the present invention is applied to the resistor of the resistance matrix circuit, it becomes a resistor of high precision with high sound isolation.

FIG. 3 shows a part of a circuit pattern obtained by forming the matrix circuit into a hybrid IC.
A Cu conductor can be used according to the present invention.

(Embodiment 4) This embodiment is an example in which the resistance composition of the present invention is applied to a resistor for an inner layer of a low temperature fired three-dimensional multilayer hybrid IC having Cu as a conductor circuit.

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

A through hole is provided in a green sheet made of alumina / borosilicate glass, and a Cu conductor circuit is printed. A resistor is printed on it. In this embodiment,
The resistance value after firing as the resistor is 30Ω / □ to 10 kΩ
The resistance compositions of Nos. 4, No. 7, No. 8 and No. 9 in Table 2 were used so that /. The mounted multilayer board was fired at 900 ° C. in the same manner as in Example 1.

The TCR of each resistor was within ± 100 ppm / ° C., and a highly accurate active filter could be obtained.

[0054]

As described above, the resistance composition of the present invention is
As a resistor of an integrated circuit having Cu as a conductor circuit, it can be integrally fired with a Cu conductor in a reducing atmosphere, and
There is an effect that the TCR of the obtained resistor can be controlled within ± 100 ppm / ° C. Therefore, this resistor can be provided for a high precision hybrid IC such as a matrix circuit which requires a high resistance value precision.

[Brief description of drawings]

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

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

FIG. 3 is a partial view of a circuit pattern obtained by forming a resistance matrix circuit into a hybrid IC.

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

[Explanation of symbols]

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Ogawa 4026 Kujimachi, Hitachi City, Hitachi, Ibaraki Prefecture Hitachi Research Laboratory, Hitachi Ltd. (72) Noritaka Kamimura 4026 Kujicho, Hitachi City, Ibaraki Hitachi Research Institute, Hitachi Ltd. In-house (72) Inventor Yoshishige Endo 502 Jinrachicho, Tsuchiura-shi, Ibaraki Hitachi Machinery Research Laboratory (72) Inventor Takao Kobayashi 1410 Inada, Katsuta-shi, Ibaraki Hitachi Ltd. Tokai factory (72) Invention Person Hiromi Isomae 1410 Inada, Katsuta-shi, Ibaraki, Ltd. 1410 Inada, Tokai Plant, Hitachi, Ltd. (72) Inventor Masaaki Kaminumi 1410 Inada, Katsuta, Ibaraki, Ltd. Tokai Plant, Hitachi, Ltd. (72) Inventor, Otani Man 1 Mito, Tako-cho, Katori-gun, Chiba Prefecture Hitachi Powder Sue Metallurgical Company Katori Factory 2) Inventor Katsuo Ebisawa 1 Mito, Tako-cho, Katori-gun, Chiba Hitachi Powder Suigei Metal Co., Ltd. Katori factory (56) References JP-A-54-149899 (JP, A) JP-A-2-139901 (JP, A) )

Claims (11)

(57) [Claims] 1. A thick film resistance composition containing a metal boride, glass and an organic vehicle, wherein metal Co or C is added to 100 parts by weight of the mixture of the metal boride and glass.
At least one of the oxides is 0.1 in terms of Co content.
10 to 10 parts by weight , and the average particle size of the metal boride is 0.
5 to 3 μm, the average particle diameter of the glass is 5 to 6 μm,
And the average particle size of the metal Co or Co oxide is 1 to 5
The thick film resistance composition is characterized by having a thickness of μm . 2. A mixture of the metal boride and glass comprises:
The thick film resistance composition according to claim 1, wherein the composition is 50 to 95% by volume of glass and the balance is metal boride. 3. The thick film resistance composition according to claim 1, wherein the glass is borosilicate glass. 4. A boride of 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, glass, and a mixture of the boride and the glass. to 100 parts by weight of at least one metal Co or Co oxide from 0.1 to 10 parts by weight in terms of Co content, includes an organic vehicle, wherein the boride
Has an average particle size of 0.5 to 3 μm, and the average particle size of the glass is
5 to 6 μm, and the flatness of the metal Co or Co oxide
A thick film resistance composition having an average particle size of 1 to 5 μm . 5. The mixture of the boride and the glass is
The thick film resistance composition according to claim 4, wherein the composition is 50 to 95% by volume of glass and the balance is metal boride. 6. The thick film resistance composition according to claim 4, wherein the glass is borosilicate glass. 7. The thick film resistance composition according to claim 4 , wherein the organic vehicle is butyl carbitol acetate in which an acrylic resin is dissolved. 8. A hybrid I having a Cu conductor circuit and a thick film resistor formed in contact with the conductor circuit on a substrate.
In C, the thick film resistor, with respect to 100 parts by weight of a mixture of metal boride and glass, at least one of the metals Co or Co oxide, in terms of Co amount 0.1 to 10
Including parts by weight , the average particle size of the metal boride is 0.5 to 3
μm, the average particle size of the glass is 5 to 6 μm, and
The average particle size of the metal Co or Co oxide is 1 to 5 μm
Hybrid I, which is a sintered body of the composition that
C. 9. The hybrid IC according to claim 8 , wherein the mixture of the metal boride and glass in the thick film resistor is 50 to 95% by volume of glass and the balance metal boride. . 10. The hybrid IC according to claim 8 , wherein the glass in the thick film resistor is borosilicate glass. 11. A step of forming a Cu conductor circuit on a green body made of an inorganic material, and 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. Boride, glass,
For 100 parts by weight of the mixture of boride and glass,
Included is 0.1 to 10 parts by weight of metallic Co or at least one of Co oxides and an organic vehicle in terms of Co amount.
The average particle size of the metal boride is 0.5 to 3 μm,
The average particle diameter of the glass is 5 to 6 μm, and the metal Co is
Alternatively, a step of forming a resistor composition having a Co oxide having an average particle size of 1 to 5 μm in contact with the conductor circuit to form a predetermined resistor pattern, in a reducing atmosphere, the grain body, the Cu conductor circuit, and the resistor. A method of manufacturing a hybrid IC, which comprises the step of integrally heating the body patterns and firing.