JPH0378207A - Composition for resistor manufacturing - Google Patents

Abstract

PURPOSE:To improve withstand voltage characteristics by using metallic boride and manganese compound as a conductor component. CONSTITUTION:Manganese oxide or manganese boride is used as manganese compound. The amount of manganese compound exceeds 5 mole % of glass frit and does not exceed 40 mole %. Mole ratio of manganese compound to boride is made 4 to 0.4. Use of such a composition for a resistor leads to good withstand voltage characteristics which enables burning in a non-oxide atmosphere.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to compositions used for manufacturing resistors in the electronics field, and particularly to compositions for manufacturing resistors that are compatible with copper conductors and can be fired in a substantially non-oxidizing atmosphere.

[Conventional technology]

Current circuit formation for microelectronic components involves
Au or Ag/P on an insulating substrate such as an alumina substrate.
RuO□ 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 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 atmosphere or a reducing atmosphere to prevent oxidation. However,
When a Cu conductor is fired together with a ruthenium oxide resistor as described above in an inert or reducing atmosphere, the ruthenium oxide resistor is reduced to metal ruthenium, making it impossible to obtain a 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, the firing temperature of about 600°C is too low, and a resistance paste that can be fired at around 900°C, where the Cu powder is in an optimal sintered state, is required. has been done. It is possible to fire in a non-oxidizing atmosphere around 900"C, and Cu
Resistors that can be used with conductors include L a B 6 series, T a / T a N series, and 5
Resistance pastes such as n02 series have been proposed, and some are being considered for practical use. However, a resistor with excellent characteristics such as the above-mentioned ruthenium oxide resistor for firing in air has not been obtained. Furthermore, in these resistance pastes for firing in a non-oxidizing atmosphere, the area near the IOK
B 6 series and Ta / Ta N series) and high resistance (S
It is necessary to use resistance pastes with different conductive components (N O2 series), and it is not possible to cover a wide resistance range of 10 to 106 Ω/mouth with resistor pastes with the same type of conductive components, as with the ruthenium oxide resistor mentioned above. There is a problem that it cannot be done. Furthermore, there is also the problem that the characteristics of the mouthpiece near the IOKΩ/mouth, which is most frequently used in hybrid ICs, have not reached a level of practical use. U.S. Patent No. 4,420,338 discloses an alkaline earth borate glass containing metal boride as a conductive component and reducing metal oxides such as 1, Nb, Ta, and W at 5 mol% or less as a glass frit. Discloses a resistor comprising: The reducing metal oxide in this glass frit is added to improve TCR (temperature coefficient of electrical resistance) characteristics. However, as pointed out in Japanese Patent Laid-Open No. 62-122101, this resistor has a significant drop in resistance value during re-firing, and processing instability is a problem. In JP-A-62-122101, fine particles of metal hole boride represented by L a B 4 are used as conductive powder,
A resistor is disclosed that includes a glass frit containing crystalline glass in which 30 to 5 mol% of Ta20s is dissolved. In this resistor, Ta2O in the crystalline glass is converted into TaB2 and CaTaO+ by the metal hole boride.
1 and contributes to stabilizing the resistance characteristics, but it is said that Ca T a Olr is not formed at 5 mol % or less. Furthermore, it is stated that the amount of reducing metal oxides other than Ta1ls should be 2 mol % or less, preferably 1 mol % or less of the glass. Here, as reducing oxides other than T a 20 s, Cr2O5, MnO, Ni05Fed
, V2Q, , Nap, ZnO5K20. Cd01pbo
. BizOs, WO3, Nb2O5, MO03, etc. are listed. The reason why reducing oxides other than TazO5 are limited in this way is because of the presence of these reducing oxides, which are conductive components such as L a B 6 and TaB2. Alternatively, the reaction product Ca
This is expected to be because it becomes difficult to control the T a O eye, and as a result, it becomes difficult to control the electrical properties. 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. In addition, as the characteristics of the resistor, the coefficient of variation (CV) of the resistance value,
Temperature coefficient of resistance (TCR), noise, electrostatic withstand voltage characteristics (
ESD), and their ideal values are CV=1%,
TCR=Oppm/”C, Noise=<-30dB, ES
D·ΔR=O%, and a value as close to the ideal value as possible is preferable, but the values shown in Table 1 are desired as practical allowable values.

[Problem to be solved by the invention]

Resistance pastes that can be used with Cu14 bodies and can be fired in a substantially non-oxidizing atmosphere are still in the development stage, and nothing comparable to ruthenium oxide resistor pastes for firing in air has yet to be obtained. Furthermore, the metal-hole boride-based resistor paste that can be fired in a non-oxidizing atmosphere at around 900°C, as proposed above, does not have the same resistance properties 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 the range from the vicinity of IOKΩ/opening to the opening resistance range, and there remains a great deal of anxiety in practical use.

[Means to solve the problem]

In order to solve the above problems, the present invention provides: (a) one selected from the group consisting of rare earth borides, alkaline earth borides, borides of group IV a of the periodic table, and borides of group Va; The above metal borides, (b) one or more manganese compounds selected from manganese oxides and manganese porides, (c) glass frit, and (d) organic vehicle are the constituent components, and the amount of the manganese compound is as described above. In an amount exceeding 5 mole % and not exceeding 40 mole % of the glass frit, and when the molar ratio of the manganese compound to the metal boride is between 4 and 0.4, it is compatible with the copper conductor and substantially It has been found that a composition for manufacturing a resistor that can be fired in a non-oxidizing atmosphere can be obtained.

[Effect]

Resistive pastes used in thick film technology are generally made of conductive powder,
A glass frit and an organic vehicle are used as constituent components. After kneading the constituent 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, and the desired resistor is formed by drying and firing. It is said that In the resistor manufacturing composition of the present invention, the conductive powder consists of a metal boride and a manganese compound. Examples of metal borides include rare earth borides such as LaBa and CeB6, supra-alkali borides such as B a B6 and S r 86, borides of Group IVa of the periodic table such as T i B2 and Z r B2, VB2, V such as NbB2
One or more metal borides selected from group a borides can be used. These metal borides are usually pulverized using a pulverizer such as a ball mill. In particular, the L a B 6 after pulverization should have an average diameter of 5 to 0.1 μm, preferably 2 to 0.1 μm.The reason for setting the average diameter to 5 μm or less is that in the present invention, ,
The conductive product produced by firing the metal boride and the fine manganese boron compound described below in a substantially non-oxidizing atmosphere is important, 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 other hand, for buried cavities with an average diameter of 0.1 μm or more, the finer the metal boride, the better;
Achieving an average diameter smaller than μm requires extremely long grinding times, and contamination from the grinder cannot be ignored, making it impractical. In addition, other constituent manganese compounds include Mn0
A material selected from manganese oxides and manganese borides such as 1Mn0z, MnzOs, and MnB can be used. These range from 800 to 95 in a non-oxidizing atmosphere.
By firing at 0° C., it reacts with the metal boride to generate a conductive material made of manganese boride (MnB, etc.), manganese, or a mixture thereof in the resistor. In order to uniformly deposit the conductive product in the resistor and form a stable conductive path, an amount of the manganese compound or glass frit of more than 5 mol % and not more than 40 mol % is required. Further, the manganese compound preferably has an average diameter of 1 μm or less, and particularly in the case of M n 203, ultrafine powder with an average diameter of 0.5 μm or less is preferable. If the amount of the manganese compound is less than 5 mol% of the glass frit, or if the average diameter of the manganese compound is larger than 1 μm, a uniform conductive path will not be formed in the resistor, and the desired resistor characteristics will not be achieved. can't get it,
This is because unreacted manganese compounds may remain or reaction products between manganese compounds and glass frit may be produced. Also, if the manganese compound exceeds 40 mol% of the glass frit, the manganese compound may remain or the manganese compound and the glass frit may react preferentially to produce a reaction product, which may affect the prescribed resistor characteristics. can't get it. Further, in the present invention, the total weight of the manganese compound and metal boride and the weight ratio of the glass frit are 5/95 to 60/4.
0, preferably 10/90 to 50,150. If the weight ratio is greater than 60/40, film strength and adhesion strength to the substrate cannot be obtained, and conversely, if it is less than 5/95, an appropriate conductive network is not formed and desired resistance characteristics cannot be obtained. The molar ratio of the manganese compound to the metal boride is 4 to
A range of 0.4 is preferable, and a range of 2 to 0.45 is particularly preferable. If this molar ratio exceeds 4, a large amount of unreacted manganese compounds will remain, reaction products due to reaction with the glass component will increase, the number of conductors that contribute to conductivity will decrease, and the resistance characteristics of the resistor will deteriorate. If the above molar ratio is less than 0.4, the amount of conductive material generated by the reaction between the manganese compound and the metal boride is small, and it is only the unreacted metal boride that contributes to conductivity, and the effect of adding the manganese compound is reduced. It is not recognized, and the resistance characteristics on the high resistance side deteriorate. In the present invention, manganese boride and manganese are generated as conductive substances in the resistor through the reaction as described above, but if these manganese boride and manganese are used as constituent components of the resistor paste from the beginning, Since the conductive powder has poor wettability with glass and 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 glass frit helps form a conductive network in the resistor during softening, flow, and sintering during firing in a substantially non-oxidizing atmosphere. It plays the role of adhering the resistor and improving the film strength. As glass frit, BaO1Cab, SrO, Mg
O, S io2, B20s, ZrO2,5nOz,
A material containing a plurality of oxides such as TiO2 and A120s as constituent components can be used. For example, 20 to 50% by weight of alkaline earth oxide such as BaO, B20. is 10-30% by weight, 5t02 is 20-30% by weight
It is also possible to use a metal oxide having 30% by weight or less of a metal oxide as a top component, and 10% by weight or less of a tetravalent metal oxide such as SnO2 or TiO2 which can replace Z r 02 and Z r O2. Glass frit can be manufactured by a conventional method, by mixing carbonates and oxides of glass frit constituents such as B a COs and MgO in a desired ratio, heating and melting, quenching, and then pulverizing with a ball mill or the like. The average diameter is 5μ
You can use one adjusted to about m. The organic vehicle used in the present invention does not need to be a specific one, and may be one that is commonly used for manufacturing resistance pastes. The above-mentioned metal boride, manganese compound, and glass frit can be uniformly dispersed and made into a paste, and the resistor paste thus obtained can be used to form a predetermined circuit pattern on a substrate by screen printing and then dried. can. Examples of the solvent include alcohols, esters, ethers, ketones, etc. For example, terpineol, ethyl propionate, diethyl dibutyl ether, methyl ethyl getone, etc. can be used. As the 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, for example, lecithin, stearic acid, etc. can be used for purposes such as adjusting the viscosity of the paste. The resin component in the vehicle is usually preferably 1 to 50% by weight. The organic vehicle accounts for about 20-4% of the total resistor manufacturing composition.
If the amount of vehicle is too much or too little, a suitable resistor pattern cannot be obtained by screen printing, and the vehicle volatilizes or decomposes during the drying and baking process.

[Example] (Example 1) LaB6 (manufactured by Nippon Metal Co., Ltd., F grade) was mixed with zirconia balls (5IIIInφ) in an ethanol solvent.
By using a ball mill, the BET average diameter is 0.8 μm.
L a B b was used. Mn203 (manufactured by Kojundo Kagaku Kenkyukaku Co., Ltd.) was crushed in the same way and had an average diameter of 0.4 μm.
powder was used. The glass frit contains 48°1% by weight of BaO and B203.
The composition is 20%, 8IIJi%, 25.5% by weight of SiO2, and 5.7% by weight of ZrO□, and the average diameter is about 5%.
It was used in the form of a μm powder. The vehicle used was terpineol as a solvent and ethyl cellulose as a resin. The vehicle was 33% by weight of the resistance paste, LaB6,
Mn2O3 and vehicle were weighed and mixed in the proportions shown in Table 2. To give an example of a specific formulation, M n 203/L a
B6-2.0 (molar ratio), and (M n x o 3
+LaB-)/glass=30/70 (weight ratio), Mrz Os: 2.443g, LaB6:
1577 g, glass frit: 9.380 g, vehicle: 6.60 g. This mixture was kneaded in a three-roll mill to form a paste. In the case of other formulations, predetermined weights of each component were weighed and mixed and kneaded in the same manner to form a paste. These pastes were applied to a film thickness of 40 mm on an alumina substrate on which a Cu electrode had been formed in advance using a normal thick film method.
After forming a μm pattern and leveling for 30 minutes, 1
It was dried at 20° C. for 10 minutes and fired in a belt conveyor furnace in a nitrogen atmosphere to form a resistor. Maximum firing temperature is 900℃
C. for 10 minutes and a total firing time of 1 hour. The coefficient of variation (CV) of the resistance value was calculated using equation (1). In addition, the temperature coefficient of resistance (TCR) is -55℃, 25℃
, 125°C, and (2) and (
3) The cold temperature coefficient (CTCR) and the hot temperature coefficient (HTCR) were calculated using the formula. The current noise was measured using a noise meter (manufactured by Quan ach). The results of Example 1 are shown in Table 2. (Space below this page) i Resistance lit! (Ω) of sample i /port) ΣRi Rav= (2) to (3) In formulas, R knee resistance value at 55℃ (Ω/port) 55 R25+resistance value at 25℃ (Ω/port) R: resistance value at 125℃ ( Ω/mouth) 25 Table 2 Table 3 Main soil pH Mn2O3/(SrBM+TiB2) (Comparative Example 1) Table 2 shows that the molar ratio of manganese compound to metal boride was 4 to 0. Although it is outside the scope of the claims of the present invention in that it is not within the scope of Example 4, Comparative Example 1 (marked with *) prepared in the same manner as Example 1 is also shown together. As shown, Comparative Example 1 has a large Cv value and a negative TCH value, making it difficult to put into practical use.On the other hand, the resistor obtained from the resistor paste of the present invention has good resistance. (Example 2) T i B 2 and NbB2 were powders manufactured by Shin Nippon Metal Co., Ltd., and MnO, MnB, Ce B6 and 5rB6 were powders manufactured by Nippon Metal Co., Ltd.
A resistance paste was produced in the same manner as in Example 1, except that high-purity chemical research fracture powders were used as raw materials and these powders were pulverized to a BET average diameter of 0.3 to 0.8 μm according to the composition shown in Table 3. After screen printing a circuit pattern on an alumina substrate, a resistor obtained by firing in a nitrogen atmosphere was evaluated. The results are shown in Table 3. (Comparative Example 2) Table 3 shows that the molar ratio of the manganese compound to the metal boride is not within the range of 4 to 0.4, which is outside the scope of the claims of the present invention, but similar to Example 2. The prepared Comparative Example 2 (marked with *) is also shown. As is clear from Table 3, Comparative Example 2 has a large CV value and a negative TCH value that is too large for practical use. On the other hand, the resistor obtained from the resistor paste of the present invention exhibits good resistor characteristics.

【Effect of the invention】

As described above, it is possible to sinter the composition for manufacturing a resistor comprising a manganese compound, a metal boride, a glass frit, and an organic vehicle in a substantially non-oxidizing atmosphere according to the present invention. It can cover a wide resistance range of ~106 ohms/mouth and can be used with copper conductors.

Claims (1)

[Scope of 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 ) one or more manganese compounds selected from manganese oxides and manganese borides; (c) a glass frit; and (d) an organic vehicle; the amount of the manganese compound exceeds 5 mol% of the glass frit; A composition for manufacturing a resistor, characterized in that the amount does not exceed 40 mol%, and the molar ratio of the manganese compound to the metal boride is 4 to 0.4.