JPH03201403A - Composition for resistor manufacturing - Google Patents

Abstract

PURPOSE:To obtain the title resist manufacturing composition, having excellent temperature coefficient of resistance and withstand voltage characteristics, which can be used together with a copper conductor by a method wherein a chrome compound, a metal boride, silicon or silicon monoxide, glass frit and an organic vehicle are used as constituting components. CONSTITUTION:After resistance paste, which is used in thick-film forming technique, has been formed by kneading conductive powder, glass frit and organic vehicle into paste form, a circuit pattern is formed on an alumina substrate using a screen printing method and the like, and the desired resistor is formed by drying and calcinating the above-mentioned material. A metal boride, a chromium compound and silicon or silicon monoxide are used as constituting components of the above-mentioned conductive powder. A conductive substance, consisting of the mixture of a chromium boride and chromium, is grown in the resistor by sintering the metal boride and a chromium compound in a non- oxidizing atmosphere at 800 to 950 deg.C, and excellent resistor characteristics can be obtained. By adding silicon or silicon monoxide, the TCR and voltage withstand characteristics of the resistor can be improved.

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.
Along with noble metal (thick film) conductors such as RuO□ and Bi
Ruthenium oxide based (thick film) resistors such as 2 Ru 207 are 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 more cost-effective, and there is a need for the practical implementation of Cu systems that use base metal Cu as a conductor instead of noble metal conductors. . this is,
Cu has extremely high conductivity, does not cause migration like Ag-based materials, has excellent solderability, and is a material that can be expected to reduce costs. However, Cu conductors need to be fired in an inert atmosphere or a reducing atmosphere in order 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 oxide resistor is reduced to metal ruthenium, making it impossible to obtain a desired resistor. After forming the nium oxide resistor by firing in air,
A method of suppressing the reduction to metallic ruthenium by a binary firing method in which a Cu conductor is formed by firing in an inert atmosphere at about 600'C has also been proposed. However, this method requires
There is a problem of poor contact between the 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.
There is a need for a resistance paste that can be fired at around 900°C, where the Cu powder is in an optimal sintered state. So far, resistors that can be fired in a non-oxidizing atmosphere at around 900°C and can be used with Cu conductors include:
L a B b system, T a / T a N system, 5no
Resistance pastes such as 2 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 IOKΩ/portion area is capped to create a low resistance paste (LaB6).
type and T a / T a N type) and high resistance type (S n
It is necessary to use different resistance pastes with different conductive components (O2 type), and it is not possible to cover the wide resistance range of 101 to 106 Ω/mm like the ruthenium oxide resistor mentioned above with resistance pastes with the same type of conductive component. There is a problem. Furthermore, there is also the problem that the characteristics of the capped body near the IOKΩ/mouth, which is the most frequently used hybrid IC'''C, have not reached the level of practical use. In order to solve the above problems, metal borides, chromium compounds,
A composition for manufacturing a resistor comprising a glass frit and an organic vehicle is disclosed. The resistor obtained from this composition for producing a low antibody is useful because it can cover a wide resistance range, but the temperature coefficient of resistance is in the resistance range of IKΩ/Ω to 100Ω/Ω, which is frequently used in hybrid ICs. Further improvements in dielectric strength and withstand voltage characteristics are desired. This is to meet the demand for finer patterns and higher reliability of electrical circuits as electronic parts become lighter, thinner, shorter and smaller. In addition, as a characteristic 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=o%,
TCR=Oppm/'C, noise=<-30dB, ES
D.AR=O%, and although a value as close to the ideal value as possible is preferable, the values shown in Table 1 are desired as practical allowable values. Table 1 r Problems to be Solved by the Invention: Can be fired in a substantially non-oxidizing atmosphere, with IKΩ/mouth ~ 1
A resistor with excellent temperature coefficient of resistance and withstand voltage characteristics in the resistance range of 00KΩ/unit, and which can be used together with steel heavy conductors, has not been available in the prior art. In particular, in order to widely use Cu systems in hybrid IC circuits, improvements in the above characteristics are required.

[Means to solve the problem]

In order to solve the above problems, the present invention provides (a) a type 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; (b) one or more chromium compounds selected from chromium oxides and chromium borides; (c) silicon or silicon monoxide; (d) glass frit; and (e) an organic vehicle. component, and the amount of the chromium compound exceeds 5 mol% of the glass frit and 40% by mole of the glass frit.
and the molar ratio of the chromium compound to the metal boride is from 4 to 0.4, and the amount of silicon or silicon monoxide is less than mol% of the metal boride, chromium compound and glass frit. 02~ for the total amount of
It has been found that by setting the amount to 3% by weight, a composition for manufacturing a resistor can be obtained that is compatible with copper conductors and can be fired in a substantially non-oxidizing atmosphere. [Function] Resistance paste used in thick film technology generally consists 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 composition for manufacturing a resistor of the present invention, the constituent components of the conductive powder include a metal boride, a chromium compound, and silicon or silicon monoxide. Examples of metal borides include rare earth borides such as LaB6 and CeB1, alkaline earth borides such as BaB6.5rB6, and those listed in the periodic table IV such as T i B2 and Z r 82.
One or more metal borides selected from Group A borides, Va Group borides such as VB, NbB2, etc. can be used. These metal borides are usually pulverized using a pulverizer such as a ball mill. In particular, L a B b after pulverization may 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 electrically conductive product produced by firing the metal boride and the fine chromium compound described below in a substantially non-oxidizing atmosphere is important, and if the average diameter of the metal boride is larger than 5 μm, uniform conductivity is achieved. The main reason for this is that it becomes difficult to obtain sexual products. On the other hand, 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, but in order to make the average diameter smaller than 0.1 μm, it requires an extremely long grinding time, and
Contamination from the crusher can no longer be ignored, making it impractical. In addition, as other constituent chromium compounds, Crz
A material selected from chromium oxides and chromium borides such as Os, CrB, and CrB2 can be used. These react with the metal boride by firing at 800 to 950°C in a non-oxidizing atmosphere to form chromium boride (Cr
A conductive material made of one of B, Cr82, etc.) and chromium, or a mixture thereof is produced in the resistor. In order to uniformly deposit a conductive product in the resistor and form a stable conductive path, the amount of the chromium compound must exceed 5 mol% and not exceed 40 mol% of the glass frit. In addition, the average diameter of the chromium compound is preferably 1 μm or less, and particularly preferably 0.5 μm or less in the case of Cr2O5. If it is larger than that, a uniform conductive path will not be formed in the resistor, and the desired resistor characteristics cannot be obtained. The reaction product BaCr0+
This is because such problems occur. Also, if the chromium compound exceeds 40 mol% of the glass frit, the chromium compound may remain or the chromium compound and the glass frit may react preferentially, resulting in B a Cr 0
In some cases, reaction products such as No. 4 may be produced, making it impossible to obtain the desired resistor characteristics. Further, in the present invention, the total weight of the chromium compound and metal boride and the weight ratio of the glass frit are 5/95 to 60/40.
, preferably 10/90 to 50,150. If the above weight ratio is greater than 60/40, neither film strength nor adhesive strength with the substrate can be obtained, and conversely, if it is less than 5795, an appropriate conductive network is not formed and the desired resistance characteristics cannot be obtained. The molar ratio of chromium compound to metal boride is between 4 and 0.
．． A range of 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 chromium compounds may remain, or the BaCr0
The number of products such as + increases, the number of conductive substances that contribute to conductivity decreases, and the resistance characteristics of the resistor deteriorate. Moreover, when the above molar ratio is less than 0.4, the amount of conductive material generated by the reaction between the chromium compound and the metal boride is small, and it is only the unreacted metal boride that contributes to conductivity, which may be due to the effect of adding the chromium compound. It is not recognized, and the resistance characteristics on the high resistance side deteriorate. In the present invention, chromium borides and chromium are generated as conductive substances in the resistor through the reaction as described above, but if these chromium borides and chromium are used as constituents of the resistor paste from the beginning, Since the powder has poor wettability with glass and is likely to aggregate, it is difficult to obtain a uniform conductive path obtained by firing in a non-oxidizing atmosphere as in the present invention. Furthermore, the composition for manufacturing a resistor of the present invention is characterized by containing silicon or silicon monoxide as a constituent component. The effect of adding silicon or silicon monoxide is particularly effective for IKΩ/~100KΩ/, which is frequently used in hybrid ICs.
This improves the withstand voltage characteristics such as the temperature coefficient of resistance (TCR) and electrostatic withstand voltage characteristics (ESC) of the resistor. Silicon or silicon monoxide is 0.2 to 3% by weight based on the total amount of the metal boride, chromium compound, and glass frit described below.
, preferably in an amount of 1 to 2% by weight, because it has been found that such an addition amount significantly improves the TCR and withstand voltage characteristics of the resistor. If it is less than 0.2% by weight, the effect of adding silicon or silicon monoxide will not be sufficient, and even if it is more than 3% by weight, the effect will be more noticeable than that of adding 0.2 to 3% by weight. No improvement in characteristics is observed, and on the contrary, variations in resistance values, etc. increase. Silicon or silicon monoxide reacts with chromium compounds to produce conductive chromium borides or chromium, which contributes to improved electrical properties by making the conductive paths formed by the reaction between metal borides and chromium compounds more uniform. It is presumed that he does. 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. Bad, CaOlSrOlMg as glass frit
O1Si02, B203, ZrO2, S n O2, T
A material containing a plurality of oxides such as iO□ and A I 20 s as constituent components can be used. For example, alkaline earth oxides such as BaO have 20 to 60
Weight %, B2us 10-30 weight %, SiO2 20
It is possible to use metal oxides whose constituent components include up to 30% by weight and 10% by weight or less of tetravalent metal oxides such as SnO□ and TiO2 which can replace ZrO2 and ZrO2. Further, when chromium oxide is used as the chromium compound, part or all of the chromium oxide may be contained in the glass frit. 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 hole 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 specific, and may be one commonly used to produce resistive pastes. The organic vehicle consists of a solvent, a resin, and a small amount of additives, and the above-mentioned metal boride, chromium compound, silicon or silicon monoxide, and glass frit are uniformly dispersed and made into a paste. A predetermined circuit pattern can be formed on a substrate by screen printing the obtained resistor paste and then dried. Examples of the solvent include alcohols, esters, ethers, ketones, and the like. For example, terpineol, ethyl propionate, diethyl dibutyl ether, methyl ethyl getone, and the like 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 large or too small, a suitable resistor pattern cannot be obtained by screen printing. The vehicle volatilizes or decomposes during the drying and baking process.

【Example】

(Example 1) LaB6 (manufactured by Nippon Metal Co., Ltd., F grade) was ball milled in an ethanol solvent using a zirconia hole (5 mm diameter) to form a LaB6 with a BET average diameter of 0.6 μm.
B6 was used. CrxOs, silicon and SiO
The powder manufactured by Kojundo Kagaku Kenkyushin Co., Ltd. was similarly ground,
The BET average diameter is 0.3 μm for Cr2O and 0.7 for Si.
Powder of 0.8 μm was used for SiO. The glass frit contains 49.5% by weight of BaO and 20.5% by weight of BaO.
18.4% by weight, 26.7% by weight of SiO□, ZrO
The composition was 5.4% by weight of No. 2 and used in the form of a powder with an average diameter of about 5 μm. The vehicle used was terpineol as a solvent and ethyl cellulose as a resin, and the amount was 33% by weight of the resistance paste. LaB6, Cr2O5, S
t or SiO and vehicle were weighed and mixed in the proportions shown in Table 2. A specific example of formulation is Cr20i/LaB6-2
．． 4 (molar ratio), O and (Cr20.+Lad6)/glass = 15/85 (weight ratio), and when St is 2.6%, Cr2O3: 1290g, LaB6: 0.7
20g, glass frit: 11.390g, St:
0.348g, vehicle: 6.60g. 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 shaping the 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 ripe temperature coefficient (HTCR) were calculated using the formula. To measure electrical noise, use a noise meter (Q u a n -T
(manufactured by ach). The withstand voltage characteristics of the resistor were measured at 100 OV using an electrostatic withstand voltage characteristic (ESD) measuring device with a measuring circuit having a resistance R of IMΩ and a capacitor C of 200 PF as shown in Figure 1.
The change in resistance value before and after application of the voltage by the switch S five times at a time interval of 1 second was calculated using equation (4). The results of Example 1 are shown in Table 2. (Margins below this page) Resistance value of one sample 1 (Ω/port) (2) - (3) In formulas, R-ss knee 55℃ nickel resistance 1ia (Ω/port) R2
Resistance value (Ω/mouth) at s + 25°C R, 2,
: Resistance value at 125°C (Ω/mouth) (4) In the formula, RO: Initial resistance value (Ω/mouth) Rx: Resistance value after application (Ω/mouth) (Comparative Examples 1 to 2) Table 2 shows is outside the scope of the claims of the present invention in that the molar ratio of the chromium compound to the metal boride is not in the range of 4 to 0.4, or Comparative Example 1 prepared in the same manner as Example 1, and Si Alternatively, Comparative PA2 prepared in the same manner as Example 1 is also shown, although the amount of SiO is outside the scope of the claims of the present invention. As is clear from Table 2, Comparative Example 1 has a large Cv value and a negative TCR value that is too large for practical use. Further, in Comparative Example 2, although the characteristics other than the TCR and ESD characteristics are comparable to those of the ruthenium oxide resistor for firing in air, the TCR and ESD characteristics are slightly inferior. On the other hand, the resistor obtained from the resistor paste of the present invention exhibits good TCR and ESC characteristics. (Example 2) SrB6 was made from powder produced by Kojundo Kagaku Kenkyu Futsu Co., Ltd., and a resistance paste was produced in the same manner as in Example 1, except that it was ground to a BET average diameter of 0.4 μm, and a circuit was placed on an alumina substrate. After screen printing a pattern, the resistor obtained by firing in a nitrogen atmosphere was evaluated. The results are shown in Table 3. (Comparative Examples 3 to 4) Table 3 shows that the molar ratio of the chromium compound to the metal boride is outside the scope of the present invention in that it is not within the range of 4 to 0.4, but it is similar to Example 2. Comparative example 3 created in
Comparative Example 4 prepared in the same manner as Example 2 is also shown, although the amount of St or S10 is outside the scope of the claims of the present invention. As is clear from Table 3, Comparative Example 3 has a large CV value and a negative TCR value that is too large for practical use. Further, in Comparative Example 4, the characteristics other than the BSDvr characteristics are comparable to those of the ruthenium oxide resistor for firing in air, but the ESD characteristics are slightly inferior. On the other hand, the resistor obtained from the resistor paste of the present invention exhibits good ESC characteristics as well. <Example 3> Powder prepared with the formulation shown in Table 4 was 0.3 to 0°8 μm.
A resistor paste was produced in the same manner as in Example 1, except that it was crushed to a BET average diameter of . After screen printing a circuit pattern on an alumina substrate, the resulting resistor was evaluated by firing in a nitrogen atmosphere. The results are shown in Table 4. In addition, ZrB2. As NbB2, powder manufactured by Shin Nippon Metal Co., Ltd. was used. For Cr2O5, CrB2, and 5rB6, powders from Kojundo Kagaku Kenkyusha Co., Ltd. were used. (Comparative Examples 5 to 6) Table 4 shows that Example 3 and Table 4 are outside the scope of the claims of the present invention in that the molar ratio of the chromium compound to the metal boride is not within the range of 4 to 0.4. Comparative Example 5, which was prepared in the same manner, and Comparative Example 6, which was prepared in the same manner as Example 3, are also shown, although the amount of Sl or SiO is outside the scope of the claims of the present invention. As is clear from Table 4, Comparative Example 5 has a large cV value and a negative TCH value that is too large for practical use. Further, in Comparative Example 6, the characteristics other than the ESD characteristics are comparable to those of the ruthenium oxide resistor for firing in air, but the ESC characteristics are slightly inferior. On the other hand, the resistor obtained from the resistor paste of the present invention exhibits good ESD characteristics.

【Effect of the invention】

As described above, the composition for manufacturing a resistor according to the present invention, which comprises a chromium compound, a metal boride, silicon or silicon monoxide, a glass frit, and an organic vehicle, is fired in a substantially non-oxidizing atmosphere. The resistor obtained by
It has excellent resistance temperature coefficient and voltage resistance characteristics, and can be used with copper conductors.

[Brief explanation of drawings]

FIG. 1 is a circuit diagram of an electrostatic withstand voltage characteristic measuring device used for evaluation of the present invention.

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 chromium compounds selected from chromium oxides and chromium borides, (c) silicon or silicon monoxide, (d) glass frit, and (e) an organic vehicle, and the amount of the chromium compound is in an amount exceeding 5 mol % and not exceeding 40 mol % of the glass frit, and the molar ratio of the chromium compound to the metal boride is from 4 to 0.4, and the amount of silicon or silicon monoxide is A composition for manufacturing a resistor, characterized in that the amount is 0.2 to 3% by weight based on the total amount of the metal boride, chromium compound, and glass frit.