JPH02265211A - Composition for resistor manufacturing - Google Patents

Abstract

PURPOSE:To be adaptable to a copper conductor and to execute a baking operation in a substantially nonoxidizing atmosphere by a method wherein, after a conductive powder, a glass frit and an organic vehicle have been kneaded as constituents to form a paste, a circuit pattern is formed on an alumina board and this assembly is dried and baked. CONSTITUTION:Constituents of a conductive powder are composed of a metal boride and a molybdenum compound. A total amount of the molybdenum compound of one or more kinds selected from a molybdenum oxide and a molybdenum boride and of the molybdenum oxide in a glass frit is adjusted in such a way that it exceeds 5mol% but does not exceeds 30mol% of the glass frit; as a result, an excellent resistor characteristic is obtained. In addition, it is required that a total amount of the molybdenum oxide and the molybdenum oxide in the glass frit is within a range of 5 to 0.25 in terms of a molar ratio to the metal boride; the molybdenum boride and molybdenum are produced, by a reaction, as the conductive powder in a resistor. Thereby, it is possible to execute a baking operation in a substantially nonoxidizing atmosphere; the powder can be used together with a copper conductor.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to compositions used for manufacturing resistors in the field of electronics, and in particular to compositions which are compatible with i1 conductors and which are in a substantially non-oxidizing atmosphere. The present invention relates to a composition for manufacturing a resistor that can be fired in a medium.

[Prior art] Current circuit formation for microelectronic components involves
On an insulating substrate such as an alumina substrate, RuO2 or B i2 Ru is used together with a noble metal (thick film) conductor such as Au or Ag/Pd.
A ruthenium oxide (thick film) resistor such as 207 is baked in air and used.

On the other hand, in recent years, there has been a strong demand for microelectronic components to be smaller, faster, more accurate, and to reduce costs, and there is a need for practical use of Cu systems that use base metal Cu as a conductor instead of noble metal conductors. . this is,
This is because Cu has extremely high conductivity, does not cause migration unlike Ag-based materials, has excellent solderability, and can be expected to reduce costs.

However, Cu conductors need to be fired in an inert or reducing atmosphere because oxidation reduces their conductive efficiency. When a Cu conductor is fired in an inert or reducing atmosphere together with a ruthenium oxide-based resistor as described above, the ruthenium oxide group is reduced to ruthenium metal or ruthenium, making it impossible to obtain the desired resistor.

A method of suppressing reduction to metallic ruthenium has also been proposed using a binary firing method in which a ruthenium oxide-based resistor is formed by firing in air and then a Cu conductor is formed by firing in an inert atmosphere at about 600°C.

However, this method has the problem of poor contact between the Cu conductor and the ruthenium oxide resistor. Furthermore, in order to take advantage of the crushed conductivity of the Cu conductor, the firing temperature of about 600"C is too low, and a resistance paste that can be fired at around 900"C, which is the optimum sintering state for Ca conductors, is needed. requested.

So far, resistors that can be fired in a non-oxidizing atmosphere at around 900°C and can be used with Cu conductors include:
Resistance pastes such as LaBe-based, Ta/TaN-based, and 5n02-based have been proposed, and some are being considered for practical use. However, it has not been possible to obtain excellent characteristics such as the above-mentioned ruthenium oxide resistor fired in air.

Furthermore, in these resistance pastes for firing in a non-oxidizing atmosphere, a low resistance paste (LaB6
type and T a / T a N type) and high resistance type (Sn02
It is necessary to use resistor pastes with different conductive components depending on the type of resistor, such as the ruthenyl oxide resistor mentioned above.
There is a problem in that a wide resistance range of 0 to 106 Ω/hole cannot be covered with a resistive paste having the same type of conductive component.

Furthermore, there is also the problem that the characteristics of the resistor near the IOKΩ/port which is most frequently used in the hybrid IC "'C" have not reached a practical level.

US Pat. No. 4,420,338 uses metal borides as conductive components, and V, Nb, and Ta as glass frits.
, and an alkaline earth borate glass containing 5 mol% or less of a reducing metal oxide such as W.

A resistor including a resistor is disclosed. The reducing metal oxide in this glass frit is added to improve TCR (temperature coefficient of electrical resistance) characteristics. However, JP-A-62-1
As pointed out in No. 22101, this resistor has a significant decrease in resistance value upon re-firing, and processing instability is a problem.

In JP-A-62-122101, fine particles of metal hole boride represented by LaB6 are used as conductive powder, and Ta2
A resistor is disclosed that includes crystalline glass in which 30 to 5 mol% of 05 is dissolved in a glass frit. In this resistor, Ta205 in the crystalline glass changes to T a B 2 or CaTa011 by the metal hole boride, which contributes to stabilizing the resistance characteristics, but at 5 mol% or less, CaTa0
It is said that 11 or more will not form. Furthermore, it is stated that the amount of reducing metal oxides other than Ta205 should be 2 mol % or less, preferably 1 mol % or less of the glass. Here, T
As reducing oxides other than a205, Cr203, M
nO, Ni01FeO5■205, Na01ZnO5K
20, Cd05PbO1B i203, WO3, Nb
205, MoO3, etc. In this way Ta2
Reducing oxides other than 05 are limited because their presence makes it difficult to control the conductive components LaB6 and TaB2 or the reaction product CaTa011, and as a result, it becomes difficult to control the electrical properties. It is expected that

However, even if reducing oxides are controlled in this way, the electrical characteristics of the resistor disclosed in JP-A-62-122101 are currently inferior to the ruthenium oxide resistor fired in air. In particular, it is difficult to manufacture a resistance range higher than around 10 to 07 mouths.

[Problem to be solved by the invention] Resistance pastes that can be used with Cu conductors and can be fired in a substantially non-oxidizing atmosphere are still in the development stage, and ruthenium oxide-based resistor pastes for firing in air are still in development. Nothing comparable has been found.

Furthermore, the metal hydroboride resistance paste proposed above, which can be fired in a non-oxidizing atmosphere at around 900°C, does not have the same resistor properties as the ruthenium oxide resistor paste, which can be fired in air. In particular, it is difficult to use a metal water boride resistance paste in the range from the vicinity of the IOKΩ/portion to the paper resistance range, and there remains great anxiety in practical use.

[Means for Solving the Problems] In order to solve the above-mentioned problems, in the present invention, (a) rare earth borides, alkaline earth borides, borides of group II a of the periodic table, and borides of group Va of the periodic table. (b) one or more molybdenum compounds selected from the group consisting of molybdenum oxides and molybdenum borides; (c) a glass frit containing molybdenum oxide; and (d) ) the molybdenum compound and the amount of molybdenum oxide in the glass frit together exceed 5 mol % but not more than 30 mol % of the glass frit; and The molar ratio is 5 to 0.25,
A composition for making a resistor has been found that is compatible with copper conductors and can be fired in a substantially non-oxidizing atmosphere.

[Function j] Resistance pastes used in thick film technology are generally made of conductive powder,
With glass frit and organic vehicle as constituent components,
After kneading the above components into a paste using a three-roll mill or the like, a circuit pattern is formed on an alumina substrate using a screen printing method or the like, followed by drying and firing to form a desired resistor.

In the resistor manufacturing composition of the present invention, the conductive powder consists of a metal boride and a molybdenum compound.

Examples of metal borides include rare earth borides such as LaB6 and CeB6, alkaline earth borides such as BaB6.5r86, borides of group a of the periodic table such as TiB2-Zr82, and borides of group Va such as VB2 and NbB2. One or more metal borides selected from compounds can be used. These metal borides are usually pulverized using a pulverizer such as a ball mill.

In particular, the average diameter of LaB6 after pulverization must be 5 to 0.1 μm, preferably 2 to 0.1 μm.The reason why the average diameter is 5 μm or less is that in the present invention, An important conductive product is produced by firing a boride and a fine molybdenum compound (described below) in a substantially non-oxidizing atmosphere, and the average diameter of the metal boride is 5 μm.
If it is larger than m, it will be difficult to obtain a uniform conductive product. On the contrary, the reason why the average diameter is set to 0.1 μm or more is that the finer the metal boride is, the more preferable it is;
In order to make the average diameter smaller than μm, it requires an extremely long grinding time, and contamination #J from the grinder cannot be ignored, making it impractical.

Next, as molybdenum compounds, MoO2, MoO3
, MoB, Mo82, and other molybdenum oxides and molybdenum borides can be used. These react with the metal boride by firing at 800 to 950°C in a non-oxidizing atmosphere to form molybdenum boride (MoB, M).

2B5, etc.), molybdenum, or a mixture thereof, is produced in the resistor.

In order to uniformly deposit these conductors in the resistor and form a stable conductive path, the average diameter of the molybdenum compound must be 1 μm or less, and in particular, MoO2 must have a diameter of 0.1 μm or less.
Ultrafine powder of μm or less is preferable.

If the average diameter of the molybdenum compound is larger than 1 μm,
A non-uniform reaction occurs with the metal boride, making it difficult to form a uniform conductive path in the resistor, making it impossible to obtain desired resistor characteristics.

Furthermore, in the present invention, molybdenum oxide is included as a component of the glass frit.

This is because superior resistor characteristics can be obtained by using molybdenum oxide as a component of the glass frit.
Specifically, the total amount of one or more molybdenum compounds selected from molybdenum oxide and molybdenum boride and molybdenum oxide in the glass frit exceeds 5 mol% but exceeds 30 mol% of the glass frit. This is based on the discovery that excellent resistor characteristics can be obtained by adjusting the resistance so that it does not occur.

Even if molybdenum oxide is not present in the constituent components of the glass frit, one or more molybdenum compounds selected from molybdenum oxide or molybdenum boride react with the metal boride to create a uniform conductive path in the resistor. It is possible to create resistor compositions that can be formed and fired in a substantially non-oxidizing atmosphere. However, by using molybdenum oxide as a component of the glass frit, the resistor characteristics (particularly TCR and noise) in the high resistance region of 97 or higher are significantly improved.

Note that when molybdenum oxide is used as the molybdenum compound, part or all of the molybdenum oxide may be contained in the glass frit.

As the glass frit used in the present invention, MoO3
, Bad, Cab, SrO, MgO5Si02, B2
03, ZrO2, TiO2, Al2O3, etc. can be used. Among these, it is especially necessary to necessarily contain molybdenum oxide.

For example, MoO3 is 0.1 to 15 mol%, alkaline earth oxide such as BaO is 10 to 40 mol%, B203 or 1
5 to 35 mol%, 25 to 50 mol% of 5i02, and 10 mol% or less of tetravalent metal oxides such as 5n02 and TiO2, which can be substituted for ZrO2, are used as constituent components. can.

As mentioned above, the total amount of one or more molybdenum compounds selected from molybdenum oxide and molybdenum boride and the molybdenum oxide in the glass frit exceeds 5 mol% of the glass frit, but exceeds 30 mol%. It is necessary to make adjustments so that it does not occur. If the total amount of molybdenum compound and molybdenum oxide in the glass frit is less than 5 mol% or more than 30 mol% of the glass frit, a non-uniform reaction with the metal boride may occur, resulting in uniform conductivity in the resistor. It becomes difficult to form a path, and desired resistor characteristics cannot be obtained.

Furthermore, the total amount of molybdenum compound and molybdenum oxide in the glass frit must be in the range of 5 to 0.25, preferably in the range of 2 to 0.3, as a molar ratio to the metal boride. If it exceeds 5, a large amount of unreacted molybdenum compounds may remain, or due to reaction with glass components,
For example, the amount of products such as BaMo 04 increases, and the amount of conductive material that contributes to conductivity decreases, resulting in poor resistance characteristics of the resistor. On the other hand, if the above molar ratio is less than 0°25, the amount of conductive material generated by the reaction between the molybdenum compound and the metal boride is small, and it is mainly the unreacted metal boride that contributes to conductivity, and the addition of the molybdenum compound No effect was observed, and the resistance characteristics in the high resistance region deteriorated.

Further, in the present invention, the total weight of the molybdenum compound and metal boride and the weight ratio of the glass frit are 5/95 to 60/
40, preferably 10/90 to 50,150. This is because the total weight of the molybdenum compound and metal boride affects the function of the glass frit. Glass frit softens upon firing in a substantially non-oxidizing atmosphere,
During flow and sintering, it helps form a conductive network in the resistor, plays the role of adjusting resistance by the amount of conductive material and glass, bonding the substrate and resistor, and improving film strength. . When the above weight ratio is greater than 60/40,
Film strength and adhesion strength with the substrate cannot be obtained, and if it is less than 5/95, an appropriate conductive network will not be formed, and desired resistance characteristics will not be obtained.

Glass frit can be manufactured by a normal method, and it is sufficient to mix carbonates and oxides of constituent components such as BaCO3 and MgO in the desired ratio, heat and melt, rapidly cool, and then crush with a ball mill etc. It is preferable that the diameter is adjusted to about 5 μm.

In the present invention, molybdenum boride and molybdenum are generated as conductive powder in the resistor through the reaction as described above, but if these molybdenum boride and molybdenum powder are used as constituent components of the resistor paste from the beginning, Since the wettability between the conductive powder and the glass frit is poor and the conductive powder tends to aggregate, it is difficult to obtain a uniform conductive path obtained by firing in a non-oxidizing atmosphere as in the present invention.

The organic vehicle used in the present invention does not need to be a specific one, and may be one commonly used for manufacturing a resistance paste. Metal borides, molybdenum compounds, and glass frit can be uniformly dispersed into a paste, and the resistive paste thus obtained can be screen printed to form a predetermined circuit pattern on a substrate, and then dried. Examples of the solvent 1 include alcohols, esters, ethers, ketones, etc., such as terpineol, ethyl globionate, diethyl dibutyl ether, methyl ethyl getone, etc. I can use it. v
! As the J resin, for example, cellulose resins such as ethyl cellulose and nitrocellulose, acrylic resins such as butyl methacrylate and methyl methacrylate, etc. can be used. As additives, lecithin, stearic acid, etc. can be used for purposes such as adjusting the viscosity M of the paste. The resin component in the vehicle is usually preferably 1 to 50% by weight.

Incidentally, the organic vehicle accounts for 20 to 20% of the entire composition for producing a resistor.
The amount of the vehicle is 40% by weight, and if the amount of the vehicle is too much or too little, a suitable resistor pattern cannot be obtained by screen printing.The vehicle evaporates or decomposes and disappears during the drying and baking process.

[Example] E1 League LaB6 (manufactured by Shin Nippon Metal Co., Ltd., F grade) was ball milled in an ethanol solvent using a Zirnicore ball (5 degrees φ) to obtain a ball with a BET average diameter of 0°8 μm. La
B6 was used. Mo03 (manufactured by Kojundo Kagaku Kenkyukaku Co., Ltd.) was similarly pulverized and used as a powder with an average diameter of 0.3 μm.

The composition of the glass frit used is not shown in Table 1 (mol%
) and was in the form of a powder with an average particle size of about 5 μm.

Glass frit aO r02 No, (1) NO, (2)28.
2 26.9 37.9 36.9 27.4 27.0 4.0 3.9 NO, (3) 26.0 34.5 25.8 3.7 The vehicle is terpineol as a solvent, ('!1 #3
A material made of ethyl cellulose was used as the material.

The vehicle was 33% by weight of the resistor paste and LaB6
, MoO3, glass frit, and vehicle were mixed in the proportions shown in Table 2 and made into a paste using a three-roll mill.

This paste is pre-coated with carbon dioxide according to the usual thick film method.
A film with a thickness of 40 μm was formed on the alumina substrate on which the u-electrode was formed.
After forming a pattern and leveling for 30 minutes, heat at 120°C.
The resistor was dried for 10 minutes and fired in a belt conveyor furnace in a nitrogen atmosphere to form a resistor. Firing was carried out at a maximum temperature of 900° C. for 10 minutes for a total firing time of 1 hour.

The coefficient of variation (CV) of the resistance value was calculated using the formula shown below.

Where: n = Number of samples Ri = Sample paper resistance value (Ω/mouth) Temperature coefficient of resistance (TCR) is -55”C225°C1
Measure each resistance value at 125°C and calculate the cold temperature coefficient (CTCR) and hot temperature coefficient (HTCR) using the following formula.
was calculated.

Where: R-knee resistance value at 55°C (Ω/mouth) R: 2
Resistance at 5° C. (ti (Ω/mouth) R: Resistance value at 125′C (Ω/mouth) Current noise was measured using a noise meter (manufactured by Quan-Tach).

The adhesion speed of the resistive film was evaluated by the adhesion tear test, including the peeling state, and the results are shown in Table 2.

Table 2 shows that the total amount of molybdenum compounds and molybdenum oxides in the glass frit is 5 mol% of the glass frit.
or less or more than 30 mol%, or the total amount of molybdenum compound and molybdenum oxide in the glass frit is 5 to 0.25 in molar ratio to metal boride.
Although it is outside the scope of the claims of the present invention in that it is not within the scope of , Comparative Example 1 (marked with *) prepared in the same manner is also shown.

As is clear from Table 2, Comparative Example 1 has a large CV value, a negative TCH value that is too large, or a low film strength, making it a resistor that cannot be put to practical use. -6 The resistor obtained from the resistor paste of the present invention exhibits good resistor characteristics.

Inukamiguchi 1 TiB2 and NbB2 were powders manufactured by Shinnihon fL Genus Co., Ltd., and MoO3, CeB6, MoB, and 5rB6 were powders manufactured by Kojundo Kagaku Kenkyusha Co., Ltd., and these powders were used in the experiment with ρ11. Similarly, using a ball mill, 0.3~
A resistor paste was produced in the same manner as in Example 1, except that it was ground to an average BET diameter of 0.8 μm, and after screen printing a circuit pattern on an alumina substrate, a resistor was obtained by firing in a nitrogen atmosphere. was evaluated. The results are shown in Table 3.

Table 3 shows that the total amount of molybdenum compounds and molybdenum oxides in the glass frit is 5 mol% of the glass frit.
The total amount of the molybdenum compound and the molybdenum oxide in the glass frit is 5 to 0.25 in terms of molar ratio to the metal boride.
Although it is outside the scope of the claims of the present invention in that it is not within the scope of
+su) is also shown at the same time.

As is clear from Table 3, in Comparative Example 2, the CV@ was large, the TCR value was too large, or the film strength was too low to be suitable for practical use. - The resistor obtained from the resistor paste of Rikiki's invention shows good resistor properties.

[Effects of the Invention] As described above, the composition for producing a low antibody according to the present invention can be fired in a substantially non-oxidizing atmosphere, and
Can cover a wide resistance range of 106Ω/mouth,
Can be used with copper conductors.

Patent applicant: Sumitomo Metal Mining Co., Ltd.

Claims (1)

[Claims] (a) one or more metal borides selected from the group consisting of rare earth borides, alkaline earth borides, borides of group IVa of the periodic table, and borides of group Va; (b) molybdenum oxide and molybdenum The constituent components are one or more molybdenum compounds selected from borides, (c) a glass frit containing molybdenum oxide, and (d) an organic vehicle, and the amount of the molybdenum compound and the molybdenum oxide in the glass frit is , in total, the glass frit exceeds 5 mol % but does not exceed 30 mol %, and has a molar ratio of 5 to 0.25 with respect to the metal boride. Composition for manufacturing.