JPH01295401A - Resistor - Google Patents

Abstract

PURPOSE:To improve a surge resistance characteristic, by providing at least one of silicon, silicon monoxide and a precursor of silicon monoxide in a high- order oxide state; a boride; and glass. CONSTITUTION:Oxide and boron oxide which are incorporated in borosilicate glass are constituted with the following materials: a minute boride in the order of several hundred Angstrom , which is obtained by reduction in a firing step in a non- oxidizing atmosphere by using silicon, silicon monoxide or a precursor of silicon monoxide in a high-order oxide state; and glass. Therefore, a sheet resistor characterized by a sheet resistance of 10kOMEGA/square or more, low TCR and high range can be formed. A paste that can be blended can be formed. In this way, surge resistance characteristics can be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention applies to glazed resistors, which are fired in a neutral atmosphere or a non-oxidizing atmosphere in a reducing atmosphere, and which are applied to base metal electrodes, especially copper thick film hybrid integrated circuits ( HIC) on the board, etc.
This invention relates to a resistor configured with copper electrodes.

Conventional technology Conventionally, as a resistance material provided on an alumina substrate on which electrodes are formed, RuO2-glass is used as a resistance material.
Two-grained resistors are widely used in practical use.

This glazed resistor is made by baking an electrode made of silver or silver and palladium on a sintered alumina substrate in the air, and then applying a paste of Ru02-glass dispersed in a vehicle consisting of a resin binder and a solvent to the alumina substrate. 700-900° in air.
It is formed by firing at a temperature of C. Regarding these thick film technologies, please refer to "Thick film technology" by Planner and Phillips.
"Circuit" London Butterworth (Planer)
.

Ph1llips 'Th1ck Film C1rc
uits J, LONDON BUTTERAORT
IIS).

On the other hand, when considering forming a Rub2-glass-based glaze resistor in air on a base metal electrode other than a noble metal such as a silver-palladium electrode, for example on W, Mo, or Cu, an oxidation phenomenon of the electrode material occurs. The formation of glazed resistors on the electrodes is not possible.

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

However, due to its nature, when the RuO□-based glaze resistance material is fired in a reducing atmosphere, the reaction of RuO2+H2→Ru+H20 easily occurs, and the properties as a resistor cannot be obtained.

On the other hand, due to the nature of boride, boride-glass-based glaze resistor materials do not undergo chemical changes regardless of whether the atmosphere is a reducing atmosphere or a neutral atmosphere. It can also be fired in a neutral atmosphere.

A technique for forming a resistor using this boride is described in Donafler's ``Nitrogen Firepull Resistor'' Proceedings Op. 1987 ECC (
Donahue et al'Nttrogen
-Fireale Re5istor, I Proce
eding of 1987Electronic C
Components Conference).

Problems to be Solved by the Invention However, since the boride powder that constitutes the resistance material of the boride-glass glaze resistor is synthesized in advance and created by mechanical crushing, it is difficult to reduce the particle size to lum or less. For example, when adjusting the particle size by grinding titanium boride (mill grinder, wet carbide ball),
Looking only at particle crushing, if strong crushing is performed, it is possible to reduce the total particle size to 1 μm or less. However, T r
In the case of 82, there is a large amount of impurities mixed in due to pulverization, and the particle size is 0.
．． In some cases, as much as 35% of cemented carbide balls were mixed in when crushed to 79 μm. Furthermore, in the case of TiB, oxidation due to crushing is also large, reaching nearly 6%. As described above, particle size adjustment by grinding boride has many problems.

On the other hand, it is preferable to use the conductive particles used in glazed resistor materials in the form of as fine a powder as possible from the viewpoint of load characteristics. However, for the reasons mentioned above, it is difficult to obtain borides with a particle size of sub-micron order or less using normal grinding methods.
It's impossible. In order to use boride, whose particle size is difficult to control, as conductive particles in a thick film glaze resistor that requires minute conductive particles, it is necessary to avoid mechanical particle size control.

In view of the above-mentioned problems, the present invention provides a boride-glass glazed resistor in which the boride is not contained in the resistor paste, but is contained in the borosilicate glass in a firing process in a non-oxidizing atmosphere. This is a glaze resistor formed by reducing oxide and boron oxide using silicon, silicon monoxide, or a higher oxidation state precursor of -silicon oxide to obtain a minute human-order boride.

Means for Solving the Problems In order to solve the above-mentioned problems, the resistor of the present invention converts the oxides and boron oxide contained in borosilicate glass into silicon or silicon monoxide through a firing process in a non-oxidizing atmosphere. It is a resistor containing minute human-order boride, and has a low TCR with a sheet resistance of 10 and 07 or more.
1 and a wide range of sheet resistors can be fired simultaneously, and blendable pastes can be created.

Furthermore, since it is made of boride having a microscopic particle size on the order of a human being, it is a glaze resistor with excellent anti-surge characteristics.

As described above, the present invention provides a boride-glass glaze resistor in which boride powder, which belongs to hard metals used in boat fishing, is not obtained by mechanical crushing, but is contained in borosilicate glass. It is obtained by reducing the above-mentioned oxide and boron oxide using silicon, silicon monoxide, or a higher oxidation state precursor of -silicon oxide in a firing process in a non-oxidizing atmosphere. This is a resistor made of an order of magnitude of boride and glass.

The resistor obtained in the above process has a sheet resistance of 10.
Low TCR1 and high range sheet resistors can be formed at the same time and blendable pastes can be created.

Furthermore, since the resistor is made of boride having a microparticle size, load characteristics can be improved.

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

[Example 11 Silicon powder is obtained by coarsely pulverizing high-purity silicon powder,
Indolium stabilized zirconium (YT) in ethanol
Z) Ball milling was performed using a ball until the average particle size was approximately 0.4 μm.

Glass frit is Ba0 (10-23mo 1%), C
a0 (3-6), Mg0 (7-9), B203 (40-
55), 5in2 (6-25), Al, 03 (1-
In this example, zirconium oxide was mixed with the oxide consisting of 9) or carbonate thereof and zirconium oxide as the oxide forming the boride, and after dissolving this mixed powder at 1400'C, the melt was soaked in cold water. It was obtained by cooling, vitrifying, and crushing in a ball mill. In addition, in this [Example 1], zirconium oxide was used as the boride-forming oxide in 5.8.7.
Three glass powders A, B, and C containing 9° and 10.9 wt% were used.

These powders were mixed to form a glaze resistance powder.

The silicon/(silicon+glass) ratio at this time was 0.02 to 0.1 by weight. A vehicle for kneading this glaze-resistant powder was obtained by weighing and dissolving iso-butyl methacrylate in terpineol to a weight ratio of 10%. The vehicle to glaze resistant powder ratio was 0.4 cc/g of glaze resistant powder.

This glazed resistor paste was screen printed onto an alumina substrate with Cu electrodes using a 325 mesh stainless steel screen. Thereafter, it was dried at 120° C. for 10 minutes, and then fired in a thick film firing furnace where the atmosphere can be controlled. The firing furnace conditions are a bell-shaped temperature profile of 920°.
The total firing time was 60 minutes with CIO minutes maintained. The atmosphere at this time was a nitrogen atmosphere, and the oxygen concentration was 10 ppn+ or less, which is a range that does not oxidize the copper electrode.

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

(Margin below) Temperature coefficient of resistance (TCR) is the change in resistance value at 125°C with respect to the resistance value at room temperature (25'C), pp.
m/”C. Short-term overload test is 125 mW/”C.
A humidity test was performed by applying 2.5 times the voltage equivalent to the power of n+n+2 and evaluating the rate of change in resistance with respect to the initial value.
Evaluation was made by the rate of change in resistance with respect to the initial value after being left in an atmosphere at a temperature of 60° C. and a relative humidity of 95% for 1000 hours. In the surge resistance test, a 20009F capacitor was charged by applying a voltage of 500 µm, and then discharged into a resistor, and expressed as a rate of change with respect to the initial resistance value. In addition, a schematic cross-sectional view of the resistor before and after firing the resistor is shown in Fig. 1(a).
). In addition, the particle size of the boride was measured from the X-ray diffraction pattern and was found to be 140 people.

As described above, according to the wood [Example 1], the boride of the boride-glass resistor of the present invention is mixed with the oxide contained in the borosilicate glass in the firing process in a non-oxidizing atmosphere. Since boron is obtained by reducing boron with silicon, microscopic boride on the order of several hundred particles is obtained, and a high-performance glaze resistor with excellent surge resistance is constructed.

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

[Example 2] Silicon monoxide powder was obtained by coarsely pulverizing a silicon monoxide reagent and then ball-milling it in ethanol using zirconium balls until the average particle size was about 0.5 μm.

A glass lift was obtained in the same manner as in [Example 1].

These powders were mixed to obtain a glaze resistance powder, and 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 with a Cu electrode using a 325 mesh stainless steel screen in the same manner as [Example 1], and then
After drying at 0° C. for 10 minutes, it was fired in a membrane firing furnace where the atmosphere could be controlled in the same manner as in Example 1.

Table 2 shows the resistance characteristics of the glaze resistor thus obtained.

(Margins below) As mentioned above, in this [Example 2], [Example 1]
], the boride of the boride-glass resistor of the present invention is reduced by using silicon to reduce the oxide and boron oxide contained in the borosilicate glass in a firing process in a non-oxidizing atmosphere. As a result, fine borides are obtained, and a high-performance glaze resistor with excellent anti-surge properties is constructed.

In order to clarify the effects of the present invention, [Comparative Example]
shows.

[Comparative Example] Zirconium boride was synthesized as the boride used in [Example 1] and [Example 2] in argon gas, and this synthesized powder was prepared in ethanol using a WC ball to reduce the average particle size to 0. .5
A boride powder was obtained by grinding with a pole mill to a particle size of μm.

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]
A resistor paste was obtained by kneading with a vehicle in the same manner as above.

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

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

(Left below) As shown in the [Comparative Example] above, in boride-glass glaze resistors formed by pre-synthesizing and mechanically pulverizing boride powder, the boride particles are large and sub- Only μm particles can be obtained, and an uneven electric field distribution occurs inside the formed glazed resistor, resulting in significant changes in resistance due to surge voltage.

In addition, it is generally very difficult to grind boride, which belongs to hard metals, and even if boride powder with a particle size of 1 μm or less as shown in [Comparative Example] is obtained, it is difficult to prevent contamination with impurities. This impurity causes non-uniform electric field distribution, which promotes changes in resistance due to surge voltage.

In addition, in the zircon boride formed in this comparative example,
It contained 5 wt% of WC.

On the other hand, in the case of pulverizing silicon and silicon monoxide, there was only contamination on the order of several tens of ppm.

In this example, zirconium oxide was contained in the glass, but vanadium oxide, chromium oxide, and tungsten oxide each form a boride and show similar results as oxides for forming the boride. Preferably, zircon oxide, tantalum oxide, titanium oxide, molybdenum oxide,
Good results were obtained in which niobium oxide satisfies temperature resistance and other properties.

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

In addition, in the examples, 0.5 μm silicon powder and -silicon oxide powder were used, but the average particle size was 1 μm.
If it is below, fine borides can be obtained without affecting the resistance properties of the resistor, and good results can be obtained.

Although silicon powder and silicon monoxide powder were used in the examples, they only need to function as a reducing agent, and a higher oxidation state precursor of silicon monoxide, such as Si203,
Similar effects can be obtained with 305. It is also possible to use a mixture of these silicon powders, silicon monoxide powders, and higher oxidation state precursors of silicon monoxide.

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

In the examples, polybutyl methacrylate was used as the organic polymer, but any polymer may be used as long as it depolymerizes at low temperatures and sublimates and scatters, for example, polytetrafluoroethylene, poly-α-methylstyrene, poly-
Methyl methacrylate may be used alone, as a mixture, or as a copolymer.

Effects of the Invention As described above, the present invention provides a boride-glass glazed resistor that does not contain boride in the resistor paste.
A glaze resistor formed by reducing the oxides and boron oxide contained in borosilicate glass using silicon or silicon monoxide in a firing process in a non-oxidizing atmosphere to obtain minute borides. be.

Therefore, this glaze resistor has a sheet resistance of 10
With 7 or more holes, low TCR1 and high range sheet resistors can be fired simultaneously, and a blendable paste can be created.

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

Furthermore, since the powder that requires the pulverization process is a brittle material such as silicon or silicon monoxide, there is an effect that the contamination of impurities during the pulverization process can be minimized.

[Brief explanation of the drawing]

FIG. 1(aL) (b) is a schematic cross-sectional view of a resistor in an embodiment of the present invention (a) before firing and (b) after firing. 1...Substrate, 2... ...Glass particles, 3.
...Silicon particles, 4...Boride particles. Agent's name: Patent attorney Toshio Nakao Baka 1 Famous Confectionery! figure

Claims (5)

[Claims] (1) A resistor comprising at least one of silicon, silicon monoxide, and a higher oxidation state precursor of silicon monoxide, a boride, and glass. (2) A claim characterized in that the boride consists of titanium boride, zirconium boride, vanadium boride, niobium boride, tantalum boride, chromium boride, molybdenum boride, tungsten boride, and manganese boride. The resistor described in item (1). (3) Boride is ZrB_2, TaB_2, NbB_2
, TiB_2. , TiB_2. (4) The resistor according to claim (1), wherein the average grain size of the boride is 500 Å or less. (5) The resistor according to claim (1), wherein the average particle size of silicon, silicon monoxide, and a higher oxidation state precursor of silicon monoxide is 1 μm or less.