JPH03201401A - Resistor manufacturing composition - 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 a resistor in the electronics field, and particularly to a composition for manufacturing a resistor that is compatible with a copper conductor and can be fired in a substantially non-oxidizing atmosphere.

[Conventional technology]

Current circuit formation for microelectronic components involves
On an insulating substrate such as an alumina substrate, RuO□ or B 12 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, causes microcrash like Ag-based materials, has excellent solderability, and can be expected to reduce costs. However, since Cu conductors reduce their conductive efficiency when oxidized, they must be fired in an inert or reducing atmosphere. However, when firing a Cu conductor 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 the desired resistor. A method has also been proposed in which a ruthenium oxide resistor is formed by firing in air and then a Cu conductor is formed by firing in an inert atmosphere at about 600'C to suppress the reduction to metal ruthenium. 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 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, where the Cu powder is in a sintered state, 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:
L a B b system, T a / T a N system, SnO
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 area near the IOK
B 6 series and Ta / Ta N series) and high resistance (S
It is necessary to use different resistance pastes with different conductive components (N O2 type), and it is necessary to cover a wide resistance range of 10' to 10'Ω/mouth with resistance pastes with the same type of conductive components, like the ruthenium oxide resistor mentioned above. There are some problems that 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. In order to solve the above problems, the present inventors previously disclosed in Japanese Patent Application No. 01-30956 a composition for manufacturing a resistor comprising a metal boride, a tungsten compound, a glass frit, and an organic vehicle. did. The resistor obtained from this resistor manufacturing composition is useful as it can cover a wide resistance range, but IK, which is frequently used in hybrid ICs,
It is further desired to improve the temperature coefficient of resistance and withstand voltage characteristics in the resistance range from Ω/mm to 100 Ω/mm. 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 of the resistance value (C■)
, 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·ΔR=0%, 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. Table 1

[Problem to be solved by the invention]

Can be fired in a substantially non-oxidizing atmosphere, 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 copper conductors, has not been available with conventional technology, especially for hybrid ICs.
In order to widely use Cu systems in 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) one or more 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 of the periodic table; a metal boride, b) one or more tungsten compounds selected from tungsten oxide and tungsten boride, C) silicon or silicon monoxide, d) glass frit, and e) an organic vehicle, and the tungsten compound The amount of 5 of the glass frit
more than 40 mole %, and the molar ratio of the tungsten compound to the metal boride is from 4 to 0.4, and the amount of silicon or silicon monoxide is more than 40 mole %. , 0.2 to 3% by weight based on the total amount of the tungsten compound and glass frit, a composition for manufacturing a resistor that is compatible with copper conductors and can be fired in a substantially non-oxidizing atmosphere is obtained. I found out what I can get.

[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 composition for manufacturing a resistor of the present invention, the constituent components of the conductive powder include a metal boride, a tungsten compound, and further silicon or silicon monoxide. Examples of metal borides include rare earth borides such as LaB6 and Ce B6, alkaline earth borides such as BaB6.5r86, and periodic table I borides such as T i B 2 and Z r 82.
One or more metal borides selected from Va group borides, VB2, NbB2, and other Va group 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 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 conductive product produced by firing a metal boride and a fine tungsten 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 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;
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 tungsten compounds include WO, WO2, W2 B,
A material selected from notanxten oxide, tungsten boride, etc., such as W2Bs, can be used. These react with the metal boride by firing at 800 to 950'C in a non-oxidizing atmosphere to form tungsten boride Th.
(W2B, W2B5, etc.) and tungsten, or a conductive material consisting of a mixture thereof is generated in the resistor. In order to uniformly deposit a conductive product in the resistor and form a stable conductive path, the amount of the tungsten compound in the glass frit must exceed 5 mol% and not exceed 40 mol%. In addition, the tungsten compound has an average diameter of 1
μm or less is preferable, and in the case of W Os, ultrafine powder of 0.1 μm or less is preferable. When the amount of the tungsten compound is 5 mol% or less of the glass frit, or when the average diameter of the tungsten compound is larger than 1 μm, In either case, a uniform conductive bus is not formed in the resistor, making it impossible to obtain the desired resistor characteristics.The cause of this is the unreacted tungsten compound remaining, or the reaction product between the tungsten compound and the glass frit. This is because BaWO, etc. occur. In addition, even if the tungsten compound exceeds 40 mol% of the glass frit, the tungsten compound may remain, or the tungsten compound and the glass frit may preferentially react, producing reactive substances such as B a W 04. Therefore, it is impossible to obtain the desired resistor characteristics. Further, in the present invention, the total weight of the tungsten 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, film strength and adhesion strength with 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 tungsten compound to metal boride is
A range of 4 to 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 tungsten compound may remain, or the reaction with the glass component may cause B a W 04 These products increase, the amount of conductive material that contributes to conductivity decreases, and the resistance characteristics of the resistor deteriorate. If the above molar ratio is less than 0.4, the amount of conductive material generated by the reaction between the tungsten compound and the metal boride is small, and it is only the unreacted metal boride that contributes to conductivity, which reduces the effect of adding the tungsten compound. It is not recognized, and the resistance characteristics on the high resistance side deteriorate. In the present invention, tungsten boride and tungsten are generated as conductive substances in the resistor through the reaction as described above, but if these tungsten boride and tungsten are used as constituent components of the resistor base from the beginning, Because the conductive powder and the glass have poor wettability and tend to aggregate,
It is difficult to obtain a uniform S electric 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 important for IKΩ/LOOKΩ/, which is frequently used in hybrid ICs.
Temperature coefficient of resistance (TCR) and electrostatic voltage characteristics (
This is due to improvements in withstand voltage characteristics such as ESD). Silicon or silicon monoxide may be added in an amount of 0.2 to 3% by weight, preferably 1 to 2% by weight, based on the total amount of the metal boride, tungsten compound, and glass frit described below. This is because it has been found that by adding such an amount, the temperature coefficient of resistance and withstand voltage characteristics of the resistor can be significantly improved. If this weight% is less than 0.2% by weight, the effect of adding silicon or silicon monoxide will not be sufficient; on the contrary, even if it is more than 3% by weight, the effect will be more pronounced than that of 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 the tungsten compound to produce conductive tungsten boride, or tungsten, which improves electrical properties by making the conductive path formed by the reaction between the metal boride and the tungsten compound more uniform. It is assumed that this contributes to 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, SiO□, B203, ZrO2, SnO2, Ti
A material containing a plurality of oxides such as 0z and Al10s as constituent components can be used. For example, alkaline earth oxides such as BaO
Weight %, B20. is 10 to 30% by weight, and SiO2 is 20% by weight.
-30% by weight, tetravalent metal oxides such as SnO□, 'I''i02, which can be substituted for ZrO2 and ZrO□, or those having 10% by weight or less of metal oxides as a constituent component can be used. Furthermore, when tungsten oxide is used as the tungsten compound, part or all of the tungsten oxide may be contained in the glass frit.The glass frit can be manufactured by a normal method, Carbonates and oxides of glass frit constituents such as B a CO, MgO, etc. are mixed in the desired ratio, heated and melted, and after quenched, crushed with a ball mill etc. to an average diameter of 5 μm.
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 metal boride, tungsten compound, silicon or silicon monoxide, and glass frit are uniformly dispersed and made into a paste, and the resistor paste thus obtained is screen printed to form a predetermined circuit pattern on a substrate. Can be formed and dried. Examples of the solvent include alcohols, esters, ethers, ketones, etc. For example, terpineol, ethyl propionate, diethyl dibutyl ether, methyl ethyl ketone, etc. can be used. v! For example, cellulose resins such as ethyl cellulose and nitrocellulose, acrylic resins such as butyl methacrylate and methyl methacrylate, and the like can be used as the resin. 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 1 to 50
It is preferable to express it in 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 ball milled in an ethanol solvent using zirconia balls (5 mm diameter) to obtain LaB6 with a BET average diameter of 0.6 μm.
Ba was used. WO3 (manufactured by Tokyo Tekko Co., Ltd.) is
Ultrafine powder with an average diameter of 0.08 μm was used. Silicon and S
For iO, the powder manufactured by Kojundo Kagaku Kenkyushin Co., Ltd. was similarly ground in a ball mill, and the BET average diameter, St was 0.7 μm, and S
For iO, 08 μm powder was used. The glass frit contains 49.5% by weight of BaO and 20.5% by weight of BaO.
is 18.4% by weight, SiO2 is 26.7% by weight, Z r
It had a composition of 5.4% by weight of O2 and was 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. The vehicle is 33% by weight of the resistance paste, and L a
B s , WO 3 , S i or 5iO 1 and vehicle were mixed in Balance I in the proportions shown in Table 2. A specific example of formulation is WO37'LaB6=2.
5 (molar ratio), (WO3+LaB6)/glass=15
/85 (weight ratio) and when Si is 12%, WO
s: 1.488 g, LaB6: 0.522 g, glass frit: 11.390 g, Si: 0.161 g, vehicle: 6.60 g. This mixture was kneaded in a three-roll mill to form a paste. For 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). Also, the temperature coefficient of resistance ('l'CR> is -55°C
Measure the resistance values at 125°C and 125°C, and
) and (3) were used to calculate the cold temperature coefficient (CTCR) and hot battle temperature coefficient (HTCR). Current noise was measured using a noise meter (manufactured by Quan-Tach). The withstand voltage characteristics of the resistor were measured at 100 OV using an electrostatic withstand voltage characteristics (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. (Margin below this page) Ri = Sample i Chisel resistance 1ia (Ω/mouth) (2) ~ (3
) In the formula, R-ss: Resistance value at 55°C (Ω/mouth) R25
: Resistance value (Ω/mouth) R at 25°C, 25:12
Resistance value at 5°C (Ω/mouth) (4) In the formula, RO: Initial resistance fil (Ω/mouth) ◆・R×: Resistance value after application (Ω/mouth) (Comparative Examples 1 to 2) Second The table shows Comparative Example 1 prepared in the same manner as Example 1, although it is outside the scope of the claims of the present invention in that the molar ratio of the tungsten compound to the metal boride is not within the range of 4 to 0.4. , St or SiO is outside the scope of the claims of the present invention, but a comparison (!
II 2 is also shown. 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. Furthermore, in Comparative Example 2, the characteristics other than the ESC characteristics are comparable to those of the ruthenium oxide resistor for firing in air, but the ES-D characteristics are slightly inferior. On the other hand, the resistor obtained from the resistor paste of the present invention exhibits good ESD characteristics. (Example 2) SrB6 and WO2 were made from powders manufactured by Kojundo Kagaku Kenkyusha Co., Ltd., and these powders were used as SrB6 and WO2 as shown in Table 3.
B is 0.4 μm, W O2 is 0.3 μm.
A resistor paste was produced in the same manner as in Example 1 except that it was crushed to an ET average diameter, 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. (Comparative Examples 3 and 4) Table 3 shows that Example 2 and Comparative Example 3 prepared in the same manner, and Comparative Example 4 prepared in the same manner as Example 2, although the amount of St or S10 is outside the claimed scope of the present invention.
are also shown together. As is clear from Table 3, Comparative Example 3 has a large CV value and a negative TCH value that is too large for practical use. Further, in Comparative Example 4, although the characteristics other than the ESD characteristics are comparable to those of the ruthenium oxide resistor for firing in air, the ESD characteristics are slightly inferior. On the other hand, the resistor obtained from the resistor paste of the present invention exhibits good ESD characteristics. (Example 3) Powder prepared according to the formulation shown in Table 4 was used in an amount of 0.3 to 08 μrn.
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 in a nitrogen atmosphere. The results are shown in Table 4.
B2, NbB2 and W2B were powders manufactured by Shin Nippon Metal Co., Ltd., and WO□, CeB6 and SrB were powders manufactured by Nippon Metals Co., Ltd.
I used powder manufactured by Koujun Kagaku Kenkyushin. (Comparative Examples 5 to 6) Table 4 shows that Example 3 shows that the molar ratio of the tungsten compound to the metal boride is not in the range of 4 to 0.4, which is outside the scope of the claims of the present invention. Comparative Example 5 was prepared in the same manner as Example 3, and Comparative Example 6 was prepared in the same manner as in Example 3, although the amount of St or SiO was outside the scope of the claims of the present invention.
are also shown together. As is clear from Table 4, Comparative Example 5 has a large cV value and a negative TCR 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 comprising a tungsten compound, a metal boride, silicon or silicon monoxide, a glass frit, and an organic pickle according to the present invention is prepared in a substantially non-oxidizing atmosphere. The resistor obtained by firing with copper has excellent temperature coefficient of resistance and withstand voltage characteristics, and can be used together with copper conductors.

[Brief explanation of drawings]

FIG. 1 is a schematic explanatory 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 tungsten compounds selected from tungsten oxide and tungsten boride; (c) silicon or silicon monoxide; (d) glass frit; and (e) an organic vehicle; is more than 5 mol % and not more than 40 mol % of the glass frit, and the molar ratio of the tungsten compound to the metal boride is 4 to 4.
0.4, and the amount of silicon or silicon monoxide is 0.2 to 3% by weight based on the total amount of the metal boride, tungsten compound, and glass frit. Composition for use.