JPH02265208A - Composition for manufacture of resistor - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

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

[Prior art] Current circuit formation for microelectronic components involves
Au or Ag/P on an insulating substrate such as an alumina substrate.
RuO2 and Bi2 along with noble metal (thick film) conductors such as
A ruthenium oxide (thick film) resistor such as Ru2O7 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 C has extremely high conductivity, does not cause migration like 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. On the other hand, when firing a Cu conductor together with a ruthenium oxide resistor as described above in an inert or reducing atmosphere,
The ruthenium oxide-based resistor is reduced to metal 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 excellent conductivity of Cu conductors, a resistance paste that can be fired at around 900°C, where the Ca powder is in an optimal sintered state, is required, since the firing temperature of about 600°C is too low. has been done.

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 LaB6 series, Ta/TaN series, and Sn02 series 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 bases for firing in a non-oxidizing atmosphere, a low resistance base (LaBe
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 by a resistive paste having the same type of conductive component.

Furthermore, hybrid IC'''cR is also frequently used]
, OKΩ/There is also a problem that the characteristics of the resistor near the mouth have not reached a practical level.

U.S. Pat. No. 4,420,338 uses metal borides as conductive components and V, N b , T as glass frits.
Discloses a resistor containing an alkaline earth M borate glass containing 5 moles or less of reducing metal oxides such as a, and W. The reducing metal oxide in this glass frit is added to improve the TCR (temperature I7I number of electrical resistance) characteristics. Shigashi, Japanese Unexamined Patent Publication No. 62-122101
As pointed out in , this resistor has a significant drop in resistance value during re-firing, and processing instability is a problem.

In JP-A No. 62-122101, a resistor containing crystalline glass in which 30 to 5 mol% of Ta205 was dissolved in a glass frit was developed using f6t 4111 particles of a metal hydroboride represented by LaB6 as a conductive powder. has been done. In this low antibody, Ta205 in the crystalline glass is changed to T a B 2 or CaTa011 by the metal hydroboride and contributes to stabilizing the resistance characteristics, or CaTa0N is not formed at 5 mol % or less. Furthermore, T
The amount of reducing metal oxides other than a205 should be 2 mol % or less, preferably 1 mol % or less of the glass. Here, as a reducing oxide other than Ta205, Cr
203, Mn01Nip, Fed, V205, Na0
2Zn, O, 20, CdO, PbO1B i 203
, WO3, Nb205, MoO3, etc.

The reason why reducible oxides other than Ta205 are limited in this way is that their presence limits the conductive components LaB6 and T.
aB2. Alternatively, it is predicted that it becomes difficult to control the reaction product CaTa011, and as a result, it becomes difficult to control the electrical characteristics.

However, even if the reducing oxide is controlled in this way, the electrical characteristics of the resistor of the special FM 1986-122101 are
At present, it is inferior to the air-fired ruthenium oxide resistor, and it is particularly difficult to manufacture one with a resistance range higher than around 10 to 07.

[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.

In addition, the metal-hole boride-based resistance paste that can be fired in a non-oxidizing atmosphere at around 900°C, which has been proposed many times above, does not have the same resistance characteristics as the ruthenium oxide-based resistor paste that can be fired in air. In particular, it is difficult to use metal-hole boride-based resistance pastes in a higher resistance range than around IOKΩ/Ω, and there remains great concern in practical terms.

[Means for Solving the Problems] In order to solve the above problems, in the present invention, (a) rare earth boride, alkaline earth boride, periodic table IV a
(b) one or more tungsten compounds selected from tungsten oxide and tungsten boride; (c) tungsten oxide; and (d) an organic vehicle, the amount of the tungsten compound and the tungsten oxide in the glass frit, in total, exceeds 5 mol% but 30 mol% of the glass frit. and the molar ratio to the metal boride is 5 to 0.2.
5, is compatible with jT+1 conductors, and can be fired in a substantially non-oxidizing atmosphere.

[Function] Resistor bases 1 to 1 used in thick film technology generally consist of conductive powder, glass frit, and organic vehicle, and after mixing the components into a paste using a three-roll mill or the like, screen printing is performed. A circuit pattern is formed on the alumina substrate using a method such as the above, and is dried and fired to form a desired resistor.

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

Examples of metal borides include rare earth borides such as L, aB6, and CeB6, alkaline earth borides such as BaB6.5r86, borides of group IV a of the periodic table such as TiB2 and Zr82, VB2, NbB2, etc.<17) One or more metal borides selected from Group Va borides 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 is 5 to 0°1 μm.
The reason why the average diameter is preferably 5 μm or less is that the metal boride and the fine tungsten compound described below are substantially free from the metal boride and the fine tungsten compound described below. It is important to note that the conductive products produced by firing in an oxidizing atmosphere are important; if the average diameter of the metal boride is larger than 5 μm, it will be difficult to obtain uniform conductivity. . Conversely, the average diameter is 0.1 μm
The reason for the above is that the metal boride is 1.6t h'fJ
However, in order to obtain an average diameter smaller than 0.1 μm, an extremely long grinding time is required, and contamination from the grinding U (U) cannot be ignored, making it impractical.

Next, as tungsten compounds, WO3, WO2
, W2 B, W285, etc., tungsten boride, etc. can be used. These react with the metal boride by firing at 800 to 950°C in a non-oxidizing atmosphere to form a conductive material consisting of either tungsten boride DJ (W2B, W2B5, etc.) or tungsten, or a mixture thereof. Generates in resistor.

In order to uniformly deposit these conductors in the resistor and form a stable conductive path, the average diameter of the tungsten compound must be 1 μm or less, and in particular, WO3 must have a diameter of 0.1 μm or less.
Ultrafine powder of μm or less is preferable. If the average diameter of the tungsten compound is larger than 1 μm, a non-uniform reaction with the metal boride will occur, making it difficult to form a uniform conductive path in the resistor, making it impossible to obtain the desired low antibody characteristics. .

Furthermore, in the present invention, tungsten oxide is included as a constituent of the glass frit.

This means that excellent resistor properties can be obtained by using tungsten oxide as a constituent of the glass frit, and specifically, tungsten compounds of one or more selected from tungsten compounds and tungsten borides and glass. The total amount of tungsten oxide in the frit exceeds 5 mol% of Karas Frit 1 to 30 mol%
This is based on the discovery that excellent resistor characteristics can be obtained by adjusting the resistance so as not to exceed .

Even if tungsten oxide is not present in the constituent components of Glass Flip 1~, one or more tungsten compounds selected from tungsten oxide or tungsten boride react with the metal boride to create a uniform conductive path in the resistor. It is possible to form a resistor composition which can be fired in a substantially non-oxidizing atmosphere. However, by using tungsten oxide as a component of the glass flip 1, a high LIJ of more than lkΩ/- can be achieved.
The resistor characteristics (especially TCR and noise) in the t region are greatly improved.

Incidentally, when tungsten oxide is used as the tungsten compound, a part or all of the tungsten oxide is contained in the glass frit, so it is not removed.

As the glass frit used in the present invention, WO3=
Bad, Cab, SrO, MgO, S j02.82
03, ZrO2, TiO2, Al2O3, etc., may be used. Among these, in particular, it is necessary to have at least one W O3.
Is WO3 necessary?6 For example, 0.1 to 15 moles of WO3? 5,
Alkaline earth oxide such as BaO or 10 to 40 mol%
[3203 or 15-35 mol%, 5i02 or 25-50
mol%, and 5n02, which can replace ZrO2, Ti
A metal acid containing 10 mol % or less of a 71-valent metal oxide such as O2 (such as one containing arsenic as a constituent) can be used.

As mentioned above, the combination of one or more tungsten compounds selected from tungsten oxide and tungsten boride and tungsten oxide in the glass frit is more than 5 mol% or 30 mol% of the glass flint. It is necessary to make adjustments so that it does not exceed. If the total amount of tungsten compound and tungsten 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 hubus, and it is only possible to obtain desired resistor characteristics.

Furthermore, the total amount of the tungsten compound and the tungsten oxide in the glass frit must be in the range of 5 to 0.25, preferably in the range of 2 to 0.3, in molar ratio to the metal boride. If this molar ratio exceeds 5, a large amount of unreacted tungsten compounds will remain, or products such as B a W 04 will increase due to reaction with glass components, and the amount of conductive material that contributes to electrical conductivity will decrease. , the resistance characteristics of the resistor become worse. 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 tungsten compound and the metal boride is small, and it is mainly the unreacted metal boride that contributes to conductivity, and the addition of the tungsten compound This effect is not recognized, and the resistance characteristics in the high resistance region deteriorate.

Further, in the present invention, the ratio of the total weight of the tungsten compound and metal boride to the glass frit is 5/95 to 60.
/40, preferably 10/90 to 50,150. This is because the combined weight of the tungsten compound and metal boride affects the functionality of the glass frit. The glass frit helps form a conductive network in the resistor during softening, flow, and sintering during firing in a substantially non-oxidizing atmosphere, and the conductor and glass frit play a role in adjusting resistance.
It plays the role of bonding the substrate and the resistor and the role of improving film strength. If the above weight ratio is larger than 60/40, only the film strength and the adhesive strength with the substrate can be obtained, and 5/95
If it is smaller, 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, tungsten boride and tungsten are generated as conductive powder in the resistor through the reaction as described above, but if these tungsten boride and tungsten 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 have to be specific and can be one commonly used to make resistive pastes. The organic vehicle consists of a solvent, a resin, and a small amount of additives, and the above-mentioned metal boride, tungsten compound, and glass frit are uniformly dispersed into a paste, and the resulting resistance paste is screen printed. It is preferable if a predetermined circuit pattern can be formed on the substrate using the method and then dried. Further, examples of the solvent include alcohols, esters, ethers, ketones, etc., and for example, terpineol, ethyl propionate, diethyl dibutyl ether, methyl ethyl getone, etc. can be used. Examples of the resin include cellulose resins such as ethyl cellulose and nitrocellulose, butyl methacrylate,
Acrylic resin such as methyl methacrylate can be used. As additives, lecithin, stearic acid, and the like can be used for purposes such as adjusting the mucous membranes 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] Example 1 LaB6 (manufactured by Shin Nippon Metal Co., Ltd., F grade) was ball milled in an ethanol solvent using a Zirnicore ball (5 mmφ) to obtain LaB6 with a BET average diameter of 0, 3 μm. used. WO3 (manufactured by Tokyo Tekko Co., Ltd.) is
Ultrafine powder with an average diameter of 0.03 μm was used.

The glass frit used had the composition 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 i 02 r02 O3 1 table NO, (1) NO, (2) 27
゜8 27.0 38.5 37゜3 26.8 26゜0 4, 4 4.2 2.5 5.5 NO, (3) 25.7 35.5 24.8 4.0 9.9 Vehicle used ethyl cellulose as terpineol as 7-container formulation 1.

When the vehicle is 331t% of the resistance paste, L a
R6-WO3, 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 applied to an alumina substrate with a film thickness of 4 mm using the normal N film method, with a Cu electrode formed in advance.
After forming a 0 μm pattern and leveling for 30 minutes,
It was dried at 20° C. for 10 minutes and fired in a belt conveyor furnace in a nitrogen atmosphere to form a resistor. The maximum temperature for firing is 90
The temperature was maintained at 0°C for 10 minutes, resulting in 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 R1 - Resistance value of sample i (Ω/mouth) Temperature coefficient of resistance (TCR) is -55°C, 25°C,
125"C, and calculate the cold temperature coefficient (CT(,R) and hot temperature coefficient (HTC) using the following formula.
R) was calculated.

Where: R Knee 5 Resistance value at 5℃ (Ω/mouth)
R: Resistance value at 25°C (Ω2/' mouth) R
: Resistance value (Ω/mouth) at 125”C Ef A noise is:
It was measured using a noise meter (manufactured by Quan-Tach).

The adhesion speed of the resistive film was determined by the adhesive tape test.
Evaluate from the J^1 state. The results are shown in Table 2.

L Mosquito Hemostasis Table 2 states that the total amount of the tungsten compound and tungsten oxide in the glass frit is 5 mol% or less or 30 mol% or more of the glass frit, or that the tungsten compound and the tungsten oxide in the glass frit are The total amount of tungsten oxide is 5 to 5 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 range of 0.25, Comparative Example I (marked with *) was produced in the same manner.
It is also shown together.

As is clear from Table 2, Comparative Example I has a large CV value, a negative TCR value, or a low film strength, making it a resistor that cannot be put to practical use. -Low antibodies obtained from the resistance paste of the old invention. , showing good resistor characteristics.

TiB2, Nl, B2, and W2 BS were powders manufactured by Shin Nippon Metal Co., Ltd., and WO2, Ce BS, and 5rB
6 is made from powders manufactured by Kojundo Kagaku Kenkyusha Co., Ltd., and these powders are milled using a ball mill in the same manner as in Example 1.
A resistive paste was produced in the same manner as in Example 1, except that it was ground to an average B E "r' diameter of ~0.8 μm, and after screen-printing a circuit pattern on an alumina substrate,
The resistor obtained by firing in a nitrogen atmosphere was evaluated. The results are shown in Table 3.

Koho ■Yu Table 3 states that the total amount of the tungsten compound and tungsten oxide in the glass frit is 5 mol% or less or 30 mol% or more of the glass frit, or that the tungsten compound and the tungsten oxide in the glass frit are The total amount of tungsten oxide is 5 to 5 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 range of 0.25, Comparative Example 2 (produced in the same manner as Example 2)
*marked) are also shown together.

As is clear from Table 3, Comparative Example 2 has a large CV value, a negative TCH value that is too large, or a resistor whose film strength is too weak to withstand practical use. -6 The resistor obtained from the resistor paste of the present invention exhibits good resistor characteristics.

[Effects of the Invention] As described above, the composition for manufacturing a resistor according to the present invention can be fired in a substantially non-oxidizing atmosphere, and has a
It can cover a wide resistance range of ~106 ohms/mouth and 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) tungsten oxide and tungsten The constituent components are one or more tungsten compounds selected from borides, (c) a glass frit containing tungsten oxide, and (d) an organic vehicle, and the amount of the tungsten compound and the tungsten oxide in the glass frit is , in total, more than 5 mole % but not more than 30 mole % of the glass frit, and in a molar ratio relative to the metal boride,
A composition for manufacturing a resistor, characterized in that it has a value of 0.25.