JPH0482161B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a thick film resistor composition, a thick film resistor, and a thick film hybrid IC used in a thick film hybrid IC or the like. [Prior Art] Conventionally, RuO ₂ -based materials have been generally used as materials for resistors used in thick-film hybrid ICs and the like because they can be fired in air. Therefore, conductive circuits have been made of Ag--Pd materials that are free from oxidation even when fired in air. However, Ag-Pd-based materials have a relatively high resistance value, which has been an obstacle to achieving low impedance in thick-film hybrid ICs. On the other hand, copper-based circuit conductors have the advantage of lower impedance than Ag-Pd-based circuit conductors, but since copper is easily oxidized, it cannot be fired unless in a non-oxidizing atmosphere, such as nitrogen gas. In addition, if the above RuO _2- based material is used as a resistance material, it will not react in nitrogen gas.
There is a problem that RuO ₂ cannot be used because it is reduced. Therefore, baset (Japanese Patent Publication No. 51721/1983), which is a hexaboride such as LaB ₆ to which glass powder and an organic vehicle are added, is known as a resistor material for thick film hybrid ICs having copper-based conductor circuits. However, these methods have a problem in that stable low-intensity antibodies with a sheet resistance value of several kΩ/□ or more cannot be obtained. Tin oxide (SnO ₂ ) is also known as a resistor material that can be fired in a non-oxidizing atmosphere, but contrary to the above-mentioned hexaboride, a stable material with a sheet resistance value of several tens of kΩ/□ or less can be obtained. There was a problem that there was no. [Problems to be solved by the invention] The LaB ₆ series resistor paste has a resistance value of several
Since it is not actually possible to obtain more than kΩ/□,
The anti-antibody coating was lengthened, and anti-chip anti-antibodies were also used. Therefore, there were problems in that the degree of integration as a hybrid IC could not be increased, and the manufacturing process became complicated due to the attachment of chip resistors and the like. Therefore, using each of the above-mentioned low antibody materials, it is impossible to obtain several kΩ/□ to several
In order to obtain a resistance value within the range of 10kΩ/□,
We tried blending tin oxide (SnO ₂ ) and LaB ₆ , but the resistance value was unstable and varied, probably because the two undergo a chemical reaction during the firing process, making it impossible to obtain a very practical resistor. I couldn't do it. The purpose of the present invention is to achieve a firing method that can be fired in a non-oxidizing atmosphere and that is frequently used.
Thick film resistor compositions, thick film resistors, and thick film hybrids that can cover a resistance value range of 10 kΩ/□ and obtain resistors with stable resistance values.
The goal is to provide IC. [Means for Solving the Problems] The thick film resistor composition of the present invention comprises: (a) 10 to 90 parts by weight of a boride of a rare earth element in the periodic table and 90 to 10 parts by weight of a nitride of a group A element; parts by weight of glass and an effective amount of 20 to 80 parts by weight of glass and organic vehicle. (b) A thick-film low antibody which is a sintered body containing a boride of a rare earth element and a nitride of a group A element of the periodic table and an effective amount of glass. (c) A thick film having, on a ceramic substrate, a thick film resistor containing a boride of a rare earth element of the periodic table, a nitride of a group A element, and an effective amount of glass, and a thick film circuit made of a copper conductor. Hybrid IC. (d) A thick film resistor containing a boride of a rare earth element in the periodic table, a nitride of a group A element, and an effective amount of glass, a thick film circuit made of a copper conductor, and protecting them on a ceramic substrate. A thick film hybrid IC having a covering layer that Note that as the boride component increases, the resistance value of the resistor after firing tends to decrease, while as the nitride component increases, the resistance value tends to increase. It can be arbitrarily selected within the above range depending on the value. The above rare earths and group a elements include Sc, Y,
There are lanthanoids, Ti, Zr, and Hf. Furthermore, a combination in which the boride component is lanthanum boride and the nitride component is TiN is particularly preferred. The above-mentioned conductive material is used in powder form, and the powder preferably has an average particle size in the range of 0.1 to 2 μm. In addition to the above, conventionally known materials can be used as the glass as the binder and the organic vehicle during molding. As the glass, powdered borosilicate glass, such as aluminum calcium borosilicate glass, aluminum zinc borosilicate glass, and aluminum barium borosilicate glass, is used in a ratio of 20 to 20% of the conductive material component. It is preferable to use it in a range of 80% by weight. It is best to mix it according to the resistance value of the resistor. In addition, as organic vehicles, thermally decomposable resins,
For example, terpineol, methacrylic acid resin,
Use a solution dissolved in a solvent such as butyl carbitol acetate. The thick film resistor composition described above is formed by coating on a ceramic substrate, for example, by a method such as screen printing. Then, after preliminary drying, it is fired in a non-oxidizing atmosphere to obtain a thick film hybrid IC. The firing temperature varies depending on the resistance base to be blended, but is generally 850 to 950°C. [Function] When the above-mentioned blend of lanthanum boride and tin oxide is used, a reaction such as LaB ₆ + SnO ₂ → Sn + LaO ₂ + B ₂ O ₃ occurs, and a desired resistance value cannot be obtained due to the formation of metal Sn. In addition, it is thought that B ₂ O ₃ , which is unstable in water, is produced, resulting in instability and variation. In contrast, in the present invention, two or more types of conductive materials, borides of rare earth elements and nitrides of group A elements, each having a particle size of about 1 μm, are mixed with glass and fired. Therefore, during firing, borides and nitrides react, creating new
Fine particles of conductive material with a particle size of 100 angstroms are produced. Due to the formation of new conductive buses, there are more conductive buses in the resistor, for example, even if the conductive bus between boride and nitride is partially cut, the total number of paths is larger. This makes it possible to suppress variations in resistance values as resistance characteristics and the rate of change in resistance value due to heat cycles. Therefore, it exhibits very stable characteristics as a low antibody. In addition, the resistance value of the resistor after firing does not change much even when subjected to thermal shock, making it a stable thick film hybrid.
IC can be provided. [Example] The present invention will be explained below with reference to Examples. Example 1 LaB ₆ with a particle size of 2 μm or less, TiN and an average particle size of 1 μm
m of aluminum borosilicate glass powder in the proportions shown in Table 1, mixed in a crusher, and then mixed with 20% by weight methacrylic acid resin/as an organic vehicle.
About 20% by weight of butyl carbitol acetate solution was added to the powder components and kneaded at room temperature using three rolls to obtain a paste-like thick film resistor composition of the present invention. Next, as shown in FIG.
(0.8 mm x 72 mm x 55 mm), a conductor terminal 2 was formed by screen printing using a copper-based conductor paste (manufactured by DuPont: 9153), and then dried at 120°C for 10 minutes.
Firing was performed at 900°C for 10 minutes in nitrogen gas. Next, the thick film resistor composition was printed in the same manner to form a resistor 3. This was dried at 120°C for 10 minutes, then at 850, 900 and 950°C in nitrogen gas.
A resistor was created by firing. FIG. 2 shows the firing temperature dependence of the resistance value. Test samples having sheet resistance values and variation widths of resistance values as shown in Table 1 were obtained. As test samples, 90 resistor films having approximately the same resistance value were used and subjected to a test under one condition. As is clear from the table, it is stable and 28Ω/□~
A low antibody with a resistance value of 18 MΩ/□ was obtained. Here, the variation in resistance value, which indicates the stability of resistance value, was determined using the following formula. Variation in resistance value (%) = 3σ/R×100 σ (Ω) = √ {Σi (Ri−R) ² / (n−1)} In the above formula, σ = standard deviation Ri = each resistance value R = average Resistance value n=number of low antibodies measured.

【table】

[Table] Comparative Example 1 A thick film resistor composition was prepared in the same manner as in Example 1, except that the composition of the conductive material was different. After printing this on an alumina substrate, it was dried and fired to form a resistor. It was created. Table 2 shows the sheet resistance value of the obtained resistor, the variation width of the resistance value, and the results of the heat cycle test. Moreover, FIG. 3 shows the firing temperature dependence of the resistance value. Compared to Example 1, the larger the proportion of glass, the larger the range of variation in resistance value and the larger the rate of change in resistance value after heat cycling. It can also be seen that the resistance value is influenced by the firing temperature of the resistor.

[Table] Comparative Example 2 A thick film resistor composition was prepared in the same manner as in Example 1 by blending a conductive material with a particle size of 2 μm or less and an aluminum borosilicate glass powder in the proportions shown in Table 3. These were printed on an alumina substrate in the same manner as in Example 1, dried, and fired. These properties are shown in Table 3. From this comparative example, the resistance values of the obtained resistors have large variations.

[Table] [Effects of the Invention] According to the present invention, a raw film hybrid IC and a thick film resistor composition that have a small rate of change in resistance value of a resistor, are stable against heat cycles, and have an arbitrary resistance value. , a thick film resistor can be provided.

[Brief explanation of drawings]

FIG. 1 is a plan view of a test resistor used in an example of the present invention, and FIGS. 2 and 3 are graphs showing the temperature dependence of the resistor on fired body. 1... Board, 2-conductor terminal, 3... Resistor.

Claims (1)

[Claims] 1. 10 to 90 parts by weight of a boride of a rare earth element in the periodic table, 90 to 10 parts by weight of a nitride of a group A element,
A thick film resistor composition comprising an effective amount of glass and an organic vehicle in an amount of 20 to 80 parts by weight based on the above components. 2. A thick-film hypoantibody comprising a boride of a rare earth element and a nitride of a group A element of the periodic table, and is a sintered body containing an effective amount of glass. 3. On a ceramic substrate, a thick film low antibody containing a boride of a rare earth element in the periodic table, a nitride of a group A element, and an effective amount of glass, and a thick film circuit made of a copper conductor are provided. Thick film hybrid IC. 4. On a ceramic substrate, a thick film circuit consisting of a thick film low antibody containing a boride of a rare earth element in the periodic table, a nitride of a group A element, and an effective amount of glass, a copper conductor, and a coating to protect them. A thick film hybrid IC characterized by having a layer.