JP2833658B2 - Resistor composition and electronic component using the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a resistor composition and electronic components such as a resistor, a heater, and a thick film circuit board using the resistor composition.

[Conventional technology and its problems]

As a circuit board used for a hybrid integrated circuit, a thick film circuit board in which a conductor and a resistor are formed on a ceramic substrate by screen printing and firing is widely used.
As a conductor material, a material using a noble metal material such as silver, palladium, and gold is frequently used. On the other hand, as the resistor material, ruthenium oxide (RuO ₂ ) and lead oxide (PbO)
A composition with a system glass frit has been used. However, the conductor material is expensive and migration is likely to occur, making integration difficult. Therefore, practical use of copper (Cu), which is a conductor material that is inexpensive and hardly causes migration, is being studied.

In order to form a conductor using Cu as a material, Cu must be fired in a non-oxidizing atmosphere such as a green gas because Cu is easily oxidized. However, in a non-oxidizing atmosphere, RuO ₂ used for the resistor material is reduced to Ru. For this reason, when Cu is used as the conductor material, a conventional resistance material cannot be used, and it is necessary to use a resistance material that can be fired even in a non-oxidizing atmosphere. As such a resistance material, a silicide-glass system comprising a conductor component of a metal silicide such as MoSi ₂ , TaSi ₂ , Mg ₂ Si and a glass material such as BaO, B ₂ O ₃ , SiO ₂ , CaO, MgO, etc. Has been proposed (see Japanese Patent Publication No. 60-55961). This resistance material exhibits stable resistance characteristics even when fired in a non-oxidizing atmosphere because the glass component is composed of an oxide that is very thermodynamically stable.

However, this resistance material does not have sufficient wettability between the metal silicide and the glass component. Therefore, it is difficult to uniformly disperse the silicide in the glass component. As a result, although the resistance value originally decreases as the ratio of the metal silicide increases, the resistance value may increase as the ratio of the metal silicide increases.

As a means for solving such a problem, a configuration in which a conductor component of a metal silicide is coated in advance with a glass frit is already known (for example, see Japanese Patent Publication No. 59-23442). In this configuration, the conductor component has good compatibility between the glass frit coated on the surface thereof and the glass component, and therefore is easily dispersed uniformly in the glass component. However, such a configuration requires time and effort to coat the conductor component with glass frit. Therefore, there is a problem that the resistor composition is expensive.

An object of the first invention is to provide an inexpensive resistor composition that can be fired in a non-oxidizing atmosphere and that can obtain a stable resistance value.

An object of the second invention is to provide an electronic component using the resistor composition according to the first invention.

[Means for solving the problem]

The resistor composition according to the first invention has, as a starting material,
A conductive fine powder made of a compound of at least one metal of Ta, Ti, and Mo, silicon and oxygen, and an inorganic binder made of non-reducing glass are used.

The conductive fine powder used in the present invention is composed of an oxide of a metal silicide of at least one metal element (M) of Ta, Ti, and Mo, silicon (Si), and oxygen (O). Such a compound (hereinafter referred to as a metal compound) is represented by the general formula MxSiyO
Expressed by z. In the equation, x, y, and z are values larger than 0, respectively, and x + y + z = 1. Further, two or more kinds of the metal compounds may be used as a mixture.

The metal compound may be either crystalline or amorphous. Whether the metal compound is crystalline or amorphous depends on the magnitude of the partial molar ratio z of oxygen contained in the compound. That is, the metal compound having a small value of z is crystalline, which is considered to be due to the interstitial solid solution in which the oxygen element has penetrated the metal silicide. On the other hand, a metal compound having a large value of z loses crystallinity and exists as an indefinite trait. It is known that the difference between a crystalline metal compound and an amorphous metal compound lies in its conductivity (specific resistance). According to the study of the inventor, for example, it shows a hexagonal structure
Ta _0.30 Si _0.60 O _0.10 has a specific resistance of about 40 μΩcm.
On the other hand, the specific resistance Ta _0.30 Si _0.10 O _0.60 has a specific resistance of 93
0 μΩcm. Therefore, when producing a resistor having a large resistance value, it is desirable to use a metal compound having an indefinite character.

Next, a method for producing the metal compound used in the present invention will be described.

(1) A method for producing a crystalline metal compound.

The crystalline metal compound can be produced by introducing and oxidizing oxygen in the production process of the metal silicide. The metal silicide is generally mixed in a ratio of a metal fine powder and a silicon fine powder, and the mixture is fired in a vacuum or in a non-oxidizing atmosphere at a temperature of about 800 to 1400 ° C. to be compounded. Can be produced by pulverizing the obtained compound into a fine powder. Note that there are three methods for adding oxygen: a method in which oxygen is contained in the metal and silicon as raw materials in advance, a method in which a small amount of oxygen is doped during firing, and a method in which oxygen is adsorbed during grinding. . When oxygen is added, care must be taken so that the metal compound to be produced does not contain an oxide or silicon oxide of the raw material metal.

(2) A method for producing a metal compound having an indeterminate trait.

The amorphous metal compound can be produced by melting or evaporating a metal as a raw material or silicon, mixing the mixture, quenching the mixture, and pulverizing the mixture into a fine powder. As a method of adding oxygen, there are three methods: a method of supplying the raw material at the time of melting, a method of doping oxygen into the atmosphere at the time of quenching, and a method of adsorbing oxygen during pulverization.

The particle diameter of the metal compound used in the present invention is preferably several μm or less, and more preferably in the submicron region. When the particle diameter of the metal compound is large, it is difficult to uniformly disperse the metal compound.

The metal compound used in the present invention comprises an oxide of a metal silicide as described above. That is, an oxygen atom is introduced into the metal silicide, and an electron cloud is formed in the metal compound by oxygen ions. For this reason, the metal compound of the present invention is less likely to be repelled by electron clouds due to oxygen ions of the metal oxide constituting the non-reducing glass described later. As a result, the familiarity between the metal compound and the non-reducing glass described below is improved.

The binder used in the present invention is a non-reducing glass. Since the present invention uses non-reducing glass, it can be used for a circuit board using a base metal material that is easily oxidized such as copper (Cu) and nickel (Ni) as a conductor.

As the non-reducing glass used in the present invention, a non-reducing glass having a composition composed of a metal oxide stable to the above-mentioned metal compound is used. As such a metal oxide, one having a standard Gibbs free energy of formation of -78 Kcal / mol or less at 900 ° C. per one metal-oxygen bond in the molecule is desirable. Examples of such metal oxides include CaO, MgO,
BaO, ZrO ₂ , Al ₂ O ₃ , TiO ₂ , SiO ₂ , B ₂ O, and rare earth oxides such as Sc, La, and Ce can be given.

The non-reducing glass used in the present invention is a borosilicate glass that can be obtained by mixing the metal oxides at an arbitrary ratio centering on B ₂ O ₃ and SiO ₂ among the metal oxides. It is. Table 1 shows specific examples of the non-reducing glass used in the present invention.

Such a non-reducing glass can be obtained by mixing predetermined components and heating and melting.

The resistor composition of the present invention comprises the conductive fine powder (MxSiyO
It can be obtained by mixing z) with the inorganic binder component. The resistance of the resistor to be manufactured by the resistor composition of the present invention can be adjusted by the mixing ratio of the conductive fine powder and the inorganic binder. That is, when the resistance value is reduced, the ratio of the inorganic binder is reduced, and when the resistance value is increased, the ratio of the binder is increased.

Resistor composition of the present invention is a resin component such as ethyl cellulose, acrylic resin or ethylene-vinyl acetate copolymer,
It is used by dispersing it in an organic vehicle comprising a solvent such as α-terpineol or 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and forming a paste. Then, the paste can be printed by a known means such as screen printing, for example, on a ceramic substrate in a predetermined pattern, and then fired to obtain a resistor.

The resistor composition of the present invention can be used for a chip resistor, a heater, a film thickness hybrid integrated circuit, and the like.

******** The electronic component according to the second invention is provided on a heat-resistant insulating substrate and provided at both ends of the resistor portion made of the resistor composition of the first invention and both ends of the resistor portion. Electrodes.

FIG. 1 shows a resistor as an example of the present invention. FIG. 1 shows a longitudinal sectional view of the resistor.

The resistor 1 mainly includes a ceramic base 2, a resistor 3, and an electrode 4. The electrode 4 is provided from the edge of the upper surface of the ceramic base 2 to the edge of the lower surface of the drawing through the side surface. The electrode 4 is made of a nonmetallic conductor such as Cu or Ni. A plating layer 5 is provided on the upper surface of the electrode 4 so as to cover the electrode 4.

The resistor 3 is made of a sintered product of the resistor composition of the first invention, and is provided on the upper surface of the ceramic base 2 in a substantially flat shape so as to be connected to the electrodes 4. On the resistor 3, an overcoat glass 6 for protecting the resistor 3 is provided.
Are formed.

The resistor 1 is used, for example, disposed on a circuit board as described later. At this time, in the resistor 1, a portion of the plating layer 5 on the lower surface of the ceramic substrate 2 in the drawing is fixed on the circuit board by means such as soldering.

Such a resistor 1 can be manufactured as follows.

First, a ceramic base 2 is prepared, and an electrode 4
To form The electrode 4 can be obtained by dispersing Cu or the like in an organic vehicle to form a paste, printing this paste by a known method, and firing the paste.

On the other hand, a paste in which the resistor composition according to the first invention is dispersed in an organic vehicle is prepared. Then, the paste is printed and fired by a known method (for example, screen printing) so that the electrodes 4 are connected to each other on the upper surface of the ceramic base 2. At this time, the organic vehicle is volatilized and removed. On the other hand, the resistor composition is fired on the ceramic substrate 2. Thus, the resistor 3 for connecting the electrodes 4 is formed on the ceramic base 2.

After that, when the overcoat glass is formed on the resistor 3 and the plating layer 5 is formed on the electrode 4, the resistor 1 is obtained.

Next, a circuit board as an example of the present invention is shown in FIG. FIG. 2 is a partial longitudinal sectional view of the circuit board.

The circuit board 11 has a three-layer structure in which three ceramic substrates 11a, 11b, and 11c are stacked. However, each layer is sintered and integrated. A predetermined conductor wiring 12 is formed between and on the surfaces of the ceramic bases 11a, 11b, 11c. The conductor wiring 12 can be formed by dispersing Cu or Ni base metal powder in an organic vehicle to form a paste, and printing or filling the paste followed by firing. The resistor 13 is formed in a substantially flat shape on the surface of the circuit board 11 so as to be connected to the conductor wiring 12. The resistor 13 is
The resistor composition according to the first invention is dispersed in an organic vehicle to form a paste,
After printing this paste, it can be comprised by baking. Note that the surface of the resistor 13 is covered with an overcoat glass 14.

The circuit board 11 includes another predetermined electronic component as a conductor wiring 12
Used by mounting on top. The electronic components are arranged at predetermined positions (for example, portions A and B in FIG. 3) and are fixed by means such as soldering so as to be connected to the conductor wiring 12.

〔Example〕

First, three types of glasses A, B, and C were prepared as the non-reducing glasses at the composition ratios shown in Table 1.

Examples 1 to 6 and Comparative Examples 1 and 2 As conductive fine powder, a metal compound having a composition shown in Table 2 was mixed with glass A, B, and C at a ratio shown in Table 2 to form a resistor composition. It was created.

The obtained resistor composition was mixed with ethyl cellulose and 2,2,4-
A paste was prepared by dispersing in an organic vehicle consisting of trimethyl-1,3-pentanediol monoisobutyrate. This paste is screen-printed on a ceramic substrate of 96% alumina (trade name: A476, manufactured by Kyocera Co., Ltd.), dried at 120 ° C., and then heated to a peak temperature of 900 in a nitrogen atmosphere.
A resistor was manufactured by firing at a temperature of ℃. At this time, in order to measure the resistance value of the resistor, a Cu thick film conductor was previously formed on the ceramic substrate.

The resistance value, the temperature characteristic and the third
The harmonic distortion was measured. The measuring method is as follows.

Resistance value The resistance value was standardized by the following equation.

Resistance value (Ω / □) = (Measured resistance value (Ω / □) × Resistor film thickness (μm) / 15μm) Temperature characteristics High-temperature temperature characteristics (HTCR) and low-temperature temperature characteristics (CTCR)
It measured according to the following formula.

It should be noted that HTCR and CTCR indicate that the closer to 0, the better the temperature characteristics.

Third harmonic distortion In Table 2, Examples 1 and 4 to 12 use crystalline conductive fine powder, and Examples 2 and 3 use amorphous conductive fine powder.

Example 1 and Comparative Example 1 and Example 10 and Comparative Example 2 each use the same inorganic binder in the same amount. In Examples 1 and 10, it can be seen that the resistance value and the temperature characteristic also approach 0. Therefore, it is found that it is useful to use the metal compound of the example as the conductive fine powder of the starting material.

In addition, it can be seen that the resistance and the temperature characteristics of the crystalline (Examples 1, 4 to 12) and amorphous powders (Examples 2, 3) are relatively stable.

In addition, when the molar ratio of the metal to silicon in the metal compound is 1: 2 (Examples 5 to 12), the temperature characteristics can be relatively small (within ± 350 ppm / ° C.), although it is related to the glass composition. .

Furthermore, if a crystalline material is used as the conductive fine powder, the molar ratio of the metal to silicon in the conductive fine powder is set to 1: 2, and the weight of the glass is appropriately controlled, the harmonic distortion can be reduced. Can be improved to -90 dB or less.

〔The invention's effect〕

In the first invention, non-reducing glass is used as a binder. For this reason, the resistor composition of the first invention is
It is possible to fire in a non-oxidizing atmosphere. Also,
Since the conductive fine powder used in the first invention is an oxide of a metal silicide, it is well compatible with a binder.
For this reason, in the first aspect, an inexpensive resistor having a stable resistance value can be obtained.

In the second aspect, since the resistor composition according to the first aspect is used, an electronic component exhibiting a stable resistance value can be obtained.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of a resistor as an example of the second invention,
FIG. 2 is a partial longitudinal sectional view of a circuit board as an example of the second invention. 3 ... resistor, 4 ... electrode, 11 ... circuit board, 11A, 11B,
11C: ceramic base, 12: conductor wiring, 13: resistor.

Claims (2)

(57) [Claims] 1. A resistor composition using, as a starting material, a conductive fine powder composed of a compound of at least one metal of Ta, Ti, and Mo, silicon and oxygen, and an inorganic binder composed of non-reducing glass. Stuff. 2. A conductive fine powder comprising a compound of at least one kind of metal of Ta, Ti, and Mo, silicon and oxygen, formed on a heat-resistant insulating substrate, and non-reducing glass. An electronic component comprising: a resistor portion made of a resistor composition using an inorganic binder; and electrodes provided at both ends of the resistor portion.