JPH0738324B2 - 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 (Pianer, Phillips "Thick
Film Circuits ", LONDON BUTTERWORTHS).

On the other hand, when considering forming 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-Fireable Resistor" Proceeding of 198
7 Electronic Conponents Conference).

Problems to be Solved by the Invention However, since the boride powder that constitutes the resistance material of the boride-glass-based glaze resistor is prepared by synthesizing in advance and performing mechanical pulverization, the particle size is set to 1 μm or less. Difficult to do. For example, in the case of adjusting the particle size by crushing titanium boride powder (crusher: attritor, super hard ball wet type), if only crushing is performed, if powerful crushing is performed, almost all particles will be 1
It is also possible to set the thickness to μm or less. However, in the case of TiB ₂ , there is a large amount of impurities mixed by crushing, and in some cases, 35% of carbide balls were mixed when crushed to a particle size of 0.79 μm. Furthermore, in the case of TiB ₂ , oxidation due to grinding is also large,
It reaches close to 6%. As described above, there are many problems in adjusting the particle size by grinding the boride.

On the other hand, the conductive particles used for the glaze resistor material are preferably used in the finest powder state as much as possible from the viewpoint of load characteristics. For example, a particle size on the order of several hundred Å is desirable, such as RuO ₂ powder used for a ruthenium oxide-based resistance material. However, for the reasons described above, obtaining a boride on the order of sub-micron order or less is not possible with a usual pulverization method.
It is impossible. Since the boride whose particle size is difficult to adjust is used as the conductive particles of the thick film glaze resistor which requires fine conductive particles, it is necessary to avoid mechanical particle size adjustment.

In view of the above problems, the present invention, in the boride-glass-based glaze resistor, does not include the boride in the resistor paste, in the firing step in a non-oxidizing atmosphere, TiO contained in the borosilicate glass ₂ , ZrO ₂ , V ₂ O ₅ , Nb ₂ O ₅ , Ta ₂
At least one oxide of O ₅ , Cr ₂ O ₃ , MoO ₃ , WO ₃ , and MnO ₂ and boron oxide are reduced by using silicon, silicon monoxide, or a higher oxidation state precursor of silicon monoxide,
It is a glaze resistor formed by obtaining minute Å-order boride.

Means for Solving the Problems In order to solve the above problems, the resistor of the present invention is a firing step in a non-oxidizing atmosphere, and the oxide and boron oxide contained in borosilicate glass are silicon or silicon monoxide. Is a resistor containing a small amount of Å-order boride, and 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 fine grain size of Å order is formed, it is a glaze resistor with 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. It is a product obtained by reducing oxide and boron oxide using silicon, silicon monoxide, or a higher oxidation state precursor of silicon monoxide in a firing process in a non-oxidizing atmosphere. This is a resistor composed of a minute boride and 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.

Furthermore, since the resistor is made of boride having a minute grain size, the load characteristics 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 roughly crushing high-purity silicon powder,
Yttrium-stabilized zirconium (YT
Z) Ball milling was performed using balls to an average particle size of about 0.4 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 zirconium oxide are mixed in the present embodiment as the oxide forming the boride, and the mixed powder is mixed at 1400 ° C.
After being melted in (1), the melt was quenched in cold water to vitrify and ball-milled to obtain. In addition, this [Example 1]
Then, 5.8 zirconium oxide is used as the boride-forming oxide,
Three glass powders of A, B and C containing 7.9 and 10.9 wt% were used.

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 ~ 0.1. 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 is 1 g of glaze resistance powder.
It was about 0.4cc.

This glaze resistor paste was 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. At this time, the atmosphere was a nitrogen atmosphere, and the oxygen concentration was 10 ppm or less, which was a range in which the copper electrode was not oxidized.

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 equivalent to 125 mW / mm ² of electric power is applied, and the resistance change rate against the initial value is evaluated. 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. A schematic sectional view of the resistor before and after firing is shown in FIG.
It shows in (b). The particle size of the boride was measured from the X-ray diffraction pattern and found to be 140Å.

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 using silicon, minute borides of the order of several hundred Å are obtained, and high-performance glaze resistors with excellent surge resistance are constructed.

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

[Example 2] 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 form a glaze resistance powder, which was 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 a Cu electrode using a 325 mesh stainless screen in the same manner as in [Example 1], 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 a borosilicate glass in a firing step in a non-oxidizing atmosphere. Since the oxide and boron oxide contained therein are reduced by using silicon, a fine boride is obtained, and a high-performance glaze resistor having excellent surge resistance is constructed. .

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

[Comparative Example] Zirconium boride as a boride used in [Example 1] and [Example 2] was synthesized in argon gas, and this synthetic powder was used in WC balls in ethanol to have an average particle size of about 0.5. μm
It was pulverized with a ball mill to obtain a boride powder.

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 with glass, [Example 1]
In the same manner as the above, kneading was performed with the vehicle 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 type glaze resistor formed by previously synthesizing boride powder and mechanically pulverizing the boride particles, the boride particles are large and only sub-μm particles are obtained. In addition, a non-uniform electric field distribution is formed inside the formed glaze resistor, and the resistance value changes significantly due to the surge voltage.

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

In the zircon boride formed in this comparative example,
5 wt% WC was mixed.

On the other hand, for grinding silicon and silicon monoxide,
There was only ppm order of pollution.

In this example, zirconium oxide was contained in the glass, but as the oxide for forming boride, vanadium oxide, chromium oxide, tungsten oxide, and manganese oxide form boride, and the same results are obtained. Although shown, preferably, zircon oxide, tantalum oxide, titanium oxide, molybdenum oxide, and niobium oxide obtained favorable results satisfying the humidity resistance.

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, in the examples, 0.5 μm silicon powder and silicon monoxide powder were used, but if the average particle size is 1 μm or less, the fine boride will not affect the various characteristics of the resistor. Is obtained and 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 higher-order oxidation state precursors of silicon monoxide, such as Si ₂ O ₃ and Si ₃ O _5, are also used. The same effect 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 any substance may be used as long as it can be depolymerized at low temperature and sublimate and scatter, for example, polytetrafluoroethylene, poly-α-methylstyrene, poly-
Methyl methacrylate may be used alone, mixed, or copolymerized.

EFFECTS OF THE INVENTION As described above, the present invention is a boride-glass-based glaze resistor, which does not include boride in the resistor paste,
A glaze resistor formed by obtaining a minute boride by reducing the oxide and boron oxide contained in borosilicate glass with silicon or silicon monoxide in a firing step in a non-oxidizing atmosphere. is there.

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 requires 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]

1A and 1B are schematic cross-sectional views 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 (1)

[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, tantalum boride, or boride having an average particle diameter of 500 Å or less. A resistor made of at least one of niobium and glass.