JPH0738323B2 - Resistor - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a glaze resistor, which is fired in a non-oxidizing atmosphere such as a neutral atmosphere or a reducing atmosphere to obtain a base metal electrode, particularly a copper thick film hybrid integrated circuit ( HIC) on a substrate or the like, and a resistor configured with a copper electrode.

_2. Description of the Related Art Conventionally, a RuO ₂ glaze resistor composed of RuO ₂ -glass has been widely put into practical use as a resistance material provided on an alumina substrate on which electrodes are formed.

In this glaze resistor, an electrode made of silver or silver and palladium on a sintered alumina substrate is baked in air, and then a paste of RuO ₂ and glass dispersed in a vehicle made of a resin binder and a solvent is used as an alumina substrate. It is formed by printing so as to be connected to the above electrode and firing in air at a temperature of 700 to 900 ° C. About these thick film technologies, Planer, Phillips "Sick Film Circuit"
London Butterworth (Planer, Phillips "Thick Film Circuits", LONDON
BUTTER WORTHS).

On the other hand, when considering formation of a RuO ₂ -glass-based glaze resistor in air on a base metal electrode other than a noble metal such as a silver-palladium electrode, for example, W, Mo, Cu, an oxidation phenomenon of the electrode material occurs. It is impossible to form a glaze resistor on the electrodes.

Therefore, in order to form the glaze resistor using the base metal electrode, it is necessary to fire the glaze resistor in a reducing atmosphere or a neutral atmosphere.

However, when the RuO ₂ -based glaze resistance material is fired in a reducing atmosphere due to its nature, the reaction of RuO ₂ + H ₂ → Ru + H ₂ O easily occurs, and the characteristics as a resistor cannot be obtained.

On the other hand, the boride-glass type glaze resistance material does not undergo a chemical change regardless of the reducing atmosphere or the neutral atmosphere due to the nature of boride. Therefore, the boride-glass type glaze resistor can be fired in a reducing atmosphere or a neutral atmosphere.

As a technique for forming a resistor using this boride, "Nitogen Fireable Register" Proceeding of 1987 ECC (Donahue et al.
al "Nitrogen-Firea-ble Resistor" Proceeding of 19
87 Electronic Conponents Conference).

Problems to be Solved by the Invention However, even in the case of boride-glass-based glaze resistance material, making a sheet resistance of 10 kΩ / □ or more shows a large negative temperature coefficient of resistance (TCR) (-300 ppm / ° C or less). Therefore, it is very difficult, and in the case of forming a high resistance, particularly 100 kΩ / □ or more, a conductor material such as tin oxide is currently used. For this reason, 10kΩ / □ resistor paste and 1
Paste blending with a 00kΩ / □ resistor paste is not possible, and simultaneous firing of boride-glass based resistance material and tin oxide-glass based resistance material is difficult due to mutual reaction. there were.

Also, since the resistor is a circuit component, it must have good surge resistance, but the boride powder that constitutes the boride-glass-based glaze resistance material is synthesized beforehand and mechanically crushed to create it. Therefore, it is difficult to reduce the grain size to 1 μm or less, and a non-uniform electric field distribution can be formed inside the formed glaze resistor, resulting in a remarkable change in resistance value due to surge voltage.

In view of the above problems, the present invention, in a boride-glass type glaze resistor, does not include boride in the resistor paste, but is contained in borosilicate glass in a firing step in a non-oxidizing atmosphere. A glaze resistor formed by reducing the oxide and boron oxide using silicon, silicon monoxide, or a higher oxidation state precursor of silicon monoxide to obtain a fine boride.

Means for Solving the Problems In order to solve the above-mentioned problems, the resistor of the present invention is a firing process in a non-oxidizing atmosphere. This is a resistor that has obtained a minute boride by reduction using silicon oxide. It has a sheet resistance of 10 kΩ / □ or more, low TCR, and a wide range of sheet resistors can be co-fired, and a paste that can be blended. Can be created.

Furthermore, since a boride having a minute grain size is formed, the glaze resistor has excellent surge resistance.

Action As described above, the present invention, in the boride-glass-based glaze resistor, is not a product obtained by mechanically pulverizing a boride powder that generally belongs to a hard metal, but is contained in a borosilicate glass. The oxide and boron oxide are obtained by reducing silicon, silicon monoxide, or a higher oxidation state precursor of silicon monoxide in a firing step in a non-oxidizing atmosphere, and the minute boride And a resistor made of glass.

The resistor obtained in the above process has a sheet resistance of 10 kΩ / □
With the above, low TCR and high range sheet resistors can be formed at the same time, and a blendable paste can be prepared.

Further, since the resistor is formed of boride having a minute grain size, surge resistance can be improved.

Example A resistor according to an example of the present invention will be described below.

[Example 1] Silicon powder was obtained by coarsely crushing high-purity silicon powder,
Zirconium balls were used for ball milling in ethanol until the average particle size was about 0.5 μm.

Glass frit is BaO (10-23mol%), CaO (3-
6), MgO (7~9), B 2 O 3 (40~55), SiO 2 (6~2
5), an oxide of Al ₂ O ₃ (7 to 9), or a carbonate thereof, and the oxide forming boride is 1 to 10 mol.
%, Mix and weigh this mixed powder at 1400 ℃
After being melted in (1), the melt was quenched in cold water to vitrify and ball-milled to obtain.

These powders were mixed to obtain a glaze resistance powder. The silicon / (silicon + glass) ratio at this time is 0.02 by weight.
It was ~ 0.4.

A vehicle for kneading the glaze resistance powder was obtained by weighing and dissolving iso-butyl methacrylate in terpineol so that the weight ratio was 10%. The ratio of this vehicle to the glaze resistance powder was 0.4 cc per 1 g of the glaze resistance powder.

This glaze resistor paste was screen-printed on an alumina substrate having a Cu electrode using a 325 mesh stainless screen. After that, it was dried at 120 ° C. for 10 minutes and then fired in a thick film firing furnace capable of controlling the atmosphere. The firing furnace conditions were a bell-shaped temperature profile and a total firing time of 60 minutes at 920 ° C for 10 minutes. The atmosphere at this time is a nitrogen atmosphere, and the oxygen concentration is within the range where the copper electrode is not oxidized.
It was performed at 10 ppm or less.

Table 1 shows various resistance characteristics of the glaze resistor thus obtained.

The temperature coefficient of resistance (TCR) represents the amount of change in the resistance value at 125 ° C relative to the resistance value at room temperature (25 ° C) in ppm / ° C. In the short-time overload test, 2.5 times the voltage corresponding to the power of 125 mW / mm ² was applied, and the resistance change rate against the initial value was used for evaluation. Evaluation was made by the rate of change in resistance with respect to the initial value after standing for a time. Anti-surge test is 500V with 2000pF capacitor
After being charged by applying the voltage of, this was discharged into a resistor and expressed by the rate of change with respect to the initial value of resistance. In addition, FIG. 1 (a) is a schematic sectional view of the resistor before and after firing.
It shows in (b).

As described above, according to the present [Example 1], the boride of the boride-glass resistor of the present invention is oxidized with the oxide contained in the borosilicate glass in the firing step in a non-oxidizing atmosphere. Since boron and boron are obtained by reduction with silicon, a minute boride is obtained, and the sheet resistance is 10 kΩ /
□ Above, a high-performance glaze resistor with low TCR and excellent surge resistance is constructed.

Next, a second embodiment of the present invention using silicon monoxide will be described.

Example 2 A silicon monoxide powder was obtained by roughly crushing a silicon monoxide reagent and then ball-milling it in ethanol using zirconium balls until the average particle size became about 0.5 μm.

The glass frit was obtained in the same manner as in [Example 1].

These powders were mixed to give a glaze resistance powder, which was then mixed and kneaded in the same manner as in [Example 1] to obtain a glaze resistance paste.

This glaze resistor paste was screen-printed on an alumina substrate having Cu electrodes in the same manner as in [Example 1] using a 325 mesh stainless screen, and then 120 ° C.
After being dried for 10 minutes in the same manner, it was baked in a thick film baking furnace whose atmosphere can be controlled in the same manner as in [Example 1].

The resistance characteristics of the glaze resistor thus obtained are shown in Table 2.

As described above, also in the present [Example 2], as in the case of [Example 1], the boride of the boride-glass resistor of the present invention is treated with borosilicate glass in a firing step in a non-oxidizing atmosphere. Since the oxide and boron oxide contained in the product are reduced by using silicon, a minute boride is obtained, which has a sheet resistance of 10 kΩ / □ or more, a low TCR, and excellent surge resistance. A high performance glaze resistor is constructed.

In order to clarify the effect of the present invention, the following [Comparative Example]
Indicates.

[Comparative example]

The borides used in [Example 1] and [Example 2] were synthesized in an argon gas, and the synthetic powder was ball-milled in ethanol using WC balls until the average particle size became about 0.5 μm. A boride powder was obtained.

The glass was obtained by melting and crushing a known non-reducing glass in the same manner as in [Example 1].

After mixing these boride powders and glass, they were kneaded with a vehicle in the same manner as in [Example 1] to obtain a resistor paste.

This resistor paste was printed, dried and fired in the same manner as in [Example 1] to form a resistor and evaluated.

Various resistance characteristics at this time are shown in Table 3.

As shown in the above [Comparative Example], in the boride-glass-based glaze resistor formed by previously synthesizing boride powder and mechanically pulverizing the boride particles, since the boride particles are large, the inside of the formed glaze resistor is A non-uniform electric field distribution is generated, and the resistance value changes significantly due to surge voltage.

Further, it is generally very difficult to grind boride which belongs to a hard metal, and even if a boride powder having a grain size of 1 μm or less as shown in [Comparative Example] is obtained, it is difficult to prevent impurities from mixing in. This impurity causes a non-uniform electric field distribution, which promotes a change in resistance value due to a surge voltage.

In the examples, firing was performed in a nitrogen atmosphere, but it is sufficient if the firing is a non-oxidizing atmosphere, and firing is also possible in a reducing atmosphere containing less than 7% hydrogen.

Further, although 0.5 μm silicon powder and silicon monoxide powder were used in the examples, if the average particle size is 1 μm or less, minute borides will be formed without affecting various characteristics of the resistor. Good results are obtained.

Although silicon powder and silicon monoxide powder were used in the examples, these may be used as long as they function as a reducing agent, and the same applies to higher-order oxidation state precursors of silicon monoxide, such as Si ₂ O ₃ and Si ₃ O _5. The effect of can be obtained. It is also possible to mix and use the silicon powder, the silicon monoxide powder, and the higher oxidation state precursor of silicon monoxide.

Furthermore, these silicon powder, silicon monoxide powder,
The higher oxidation state precursor of silicon monoxide does not need to be crystallized, and the same effect can be obtained even in the amorphous state.

In the examples, polybutyl metaacrylate was used as the organic polymer, but it may be anything as long as it undergoes depolymerization at low temperature and sublimates and scatters, for example, polytetrafluoroethylene, poly-α-methylstyrene, poly-
Methyl methacrylate may be used alone, mixed, or copolymerized.

EFFECTS OF THE INVENTION As described above, in the present invention, in the boride-glass-based glaze resistor, the resistor paste does not contain boride, but the oxidation contained in the borosilicate glass in the firing step in a non-oxidizing atmosphere. It is a glaze resistor formed by reducing a substance and boron oxide with silicon or silicon monoxide to obtain a fine boride.

Therefore, this glaze resistor has a sheet resistance of 10 kΩ /
□ Above, low TCR and high range sheet resistors can be fired at the same time, and a blendable paste can be prepared.

Furthermore, since a boride having a fine grain size can be formed, an effect of improving surge resistance can be obtained.

Furthermore, since the powder that needs the crushing step is a brittle material such as silicon or silicon monoxide, it is possible to minimize the mixing of impurities in the crushing step.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of a resistor according to an embodiment of the present invention, before (a) firing and (b) firing. 1 ... Substrate, 2 ... Glass particles, 3 ... Silicon particles,
4 ... boride particles.

Claims (2)

[Claims] 1. At least one of silicon, silicon monoxide, and a higher oxidation state precursor of silicon monoxide having an average particle diameter of 1 μm or less, and titanium boride having an average particle diameter of 1 μm or less,
At least one of tantalum boride and niobium boride, and Ti
A resistor comprising a glass containing at least one of oxides of O ₂ , Nb ₂ O ₅ and Ta ₂ O ₅ . 2. 1 to 10 mol of oxides of TiO ₂ , Nb ₂ O ₅ and Ta ₂ O ₅
%, The resistor according to claim (1).