JPH0766884B2 - Resistor manufacturing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a glaze resistance material, which can be fired in a non-oxidizing atmosphere such as a neutral atmosphere or a reducing atmosphere, and a base metal electrode, particularly a copper thick film hybrid integrated circuit ( HIC) on the board,
The present invention relates to a method for manufacturing 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 -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 e
t al "Nitrogen-Fireale 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 was difficult to make the particle diameter 1 μm or less, and a nonuniform electric field distribution was formed inside the formed glaze resistor, and the resistance value change due to the surge voltage was remarkable.

In view of the above problems, the present invention, in the boride-glass-based glaze resistance material, does not include the boride in the resistor paste, in the firing step in a non-oxidizing atmosphere, contained in the borosilicate glass It is possible to form glaze resistors by reducing oxides and boron oxides using silicon or silicon monoxide to obtain minute borides.
A sheet resistance of 10 kΩ / □ or more, low TCR, and a wide range of 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, surge resistance can be improved.

Means for Solving the Problems In order to solve the above problems, in the method for producing a resistor of the present invention, in the firing step in a non-oxidizing atmosphere, the oxide and boron oxide contained in the borosilicate glass are High-performance glaze resistors can be formed by reducing silicon and silicon monoxide to obtain minute boride.

Action The present invention, as shown in the above-described manufacturing method, in the firing step in a non-oxidizing atmosphere, in order to reduce the oxide and boron oxide contained in the borosilicate glass using silicon or silicon monoxide, Generally, powders of borides belonging to hard metals are not obtained by mechanical pulverization, but obtained by reducing and substituting silicon or silicon monoxide, which is easy to pulverize. Resistance 10kΩ
A sheet resistance of low TCR and a high range of / □ or more can be simultaneously fired, and a paste that can be blended can be prepared.

Furthermore, since a boride having a fine grain size can be formed, surge resistance can be improved.

Example A resistance composition 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 (10-23mo1%), 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 1.
%, 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-resistant powder was obtained by weighing and dissolving isobutyl methacrylate in terpineol so that the isobutyl methacrylate would be 10% by weight. 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 temperature 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 oxide and boron oxide contained in the borosilicate glass are reduced by using silicon in a firing step in a non-oxidizing atmosphere to form a minute boride. By obtaining it, it is possible to form a high-performance glaze resistor with a sheet resistance of 10 kΩ / □ or more, low TCR, and excellent surge resistance.

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 form a glaze resistance powder, and a glaze resistance paste was obtained by mixing and kneading in the same manner as in [Example 1].

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], similar to [Example 1], in the firing step in the non-oxidizing atmosphere,
By reducing the above oxides and boron oxides contained in borosilicate glass with silicon to obtain minute borides, a sheet resistance of 10 kΩ / □ or more, low TCR, and high performance with excellent surge resistance It is possible to form a glaze resistor.

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 pulverizing 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 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], since the boride powder constituting the boride-glass-based glaze resistance material is prepared in advance and mechanically pulverized, the particle size may be 1 μm or less. It is difficult, and even if the boride powder is obtained by crushing as in [Comparative Example], it is difficult to prevent impurities from entering.

Therefore, an uneven electric field distribution is formed inside the formed glaze resistor, and the resistance value changes significantly due to the 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, 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, a minute boride which does not affect the various characteristics of the resistor is generated. 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, iso-butyl metaacrylate was used as the organic polymer, but any substance capable of depolymerizing and subliming and scattering at low temperature may be used, for example, polytetrafluoroethylene or poly-α-methylstyrene, Poly-methyl methacrylate may be used as a simple substance, a mixture, or a copolymer.

EFFECTS OF THE INVENTION As described above, the present invention, in the boride-glass-based glaze resistance material, does not include boride in the resistor paste, but is included in the borosilicate glass in the firing step in a non-oxidizing atmosphere. A glaze resistor can be formed by reducing oxides and boron oxide with silicon or silicon monoxide to obtain minute borides, with sheet resistance of 10 kΩ / □ or higher, low TCR, and high range. A sheet resistor 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 (5)

[Claims] 1. A glass containing at least one oxide which is reducible by a precursor of silicon, silicon monoxide, or a higher oxidation state of silicon monoxide, and a higher oxidation state of silicon, silicon monoxide, or silicon monoxide. At least one of the precursors, a step of kneading a vehicle containing a thermally decomposable polymer to form a resistance paste, a step of applying the resistance paste onto an inorganic material, a step of drying the applied resistance paste, A method of manufacturing a resistor, comprising the step of firing the applied resistance paste in a non-oxidizing atmosphere. 2. An oxide which is reducible by a higher oxidation state precursor of silicon, silicon monoxide or silicon monoxide,
Zircon oxide, vanadium oxide, tantalum oxide, niobium oxide, chromium oxide, tungsten oxide, molybdenum oxide, manganese oxide, lanthanum oxide, composed of at least one of titanium oxide, the glass containing the oxide, from borosilicate glass The method for producing a resistor according to claim (1), characterized in that the method is constructed. 3. An oxide and boron oxide which are reducible by silicon, silicon monoxide, and a higher oxidation state precursor of silicon monoxide contained in borosilicate glass during a firing step in a non-oxidizing atmosphere. And reducing the metal with silicon, silicon monoxide or a higher oxidation state precursor of silicon monoxide to form a boride with the metal forming the oxide and boron. A method for manufacturing a resistor according to the item. 4. The method for producing a resistor according to claim 1, wherein the oxidation concentration in the high temperature holding portion in the non-oxidizing atmosphere firing step is 10 ppm or less. 5. The method for producing a resistor according to claim 1, wherein the temperature of the high temperature holding portion in the non-oxidizing atmosphere firing step is 850 to 975 ° C.