JPH02265210A - Composition for manufacture of resistor - 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 chromium compound. A total amount of the chromium compound of one or more kinds selected from a chromium oxide and a chromium boride and of the chromium oxide in a glass frit is adjusted in such a way that it exceeds 5mol% but does not exceed 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 chromium compound and the chromium 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 chromium boride and chromium 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 an injection method used to produce a low antibody of electronic component WF. The present invention relates to a composition for manufacturing a resistor which is compatible with other materials and which can be fired in a substantially non-oxidizing atmosphere.

[Prior art] Current circuit formation for microelectronic components involves
On an insulating substrate such as an alumina substrate, RuO2 or B12R is used together with a noble metal (thick film) conductor such as Au or Ag/Pd.
A rudenium oxide (thick film) resistor such as U207 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 lower in cost, and the practical use of Cu systems that use base metal Cu as a conductor instead of noble metal conductors has been growing. It has been demanded. This is because Cu has extremely high conductivity, does not cause migration unlike Ag-based materials, and is also solderable, making it possible to reduce costs.

However, C11 conductors need to be fired in an inert or reducing atmosphere because oxidation reduces their conductive efficiency. Cul! If the P-body is fired in an inert or reducing atmosphere with a rudenium oxide-based low antibody as described in INF, the ruthenium oxide-based resistor will be reduced to metal ruthenium, making it difficult to obtain a single desired resistor.・I can't.

A method has been proposed to suppress the reduction to metal ruthenium using a binary firing method in which a Cu conductor is formed by firing an acid-f hirthenium-based resistor in air 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, to take advantage of the rf conductivity of the CIJ conductor, a 600'
The firing temperature of about C is low, and the firing temperature is about F6.
It can be fired as close as 900"C to a stable sintered state (requires anti-basis).

As resistors that can be fired in a non-oxidizing atmosphere at around 900°C and can be used with Cu conductors, resistance pastes such as LaB6 series, Ta/Ta N series, and 5n02 series have been proposed so far. , some of which are being considered for practical use. However, it has not been possible to obtain the flat characteristics of the ruthenium oxide resistor fired in air.

Furthermore, these resistance pastes for firing in a non-oxidizing atmosphere have low resistance (L, a
B e series, Ta / Ta N series) and high and low piles (
It is necessary to use resistance paces 1- with different conductive components depending on the type of conductive component (Sn02 series), and to achieve a wide resistance range of 10 to IO6Ω/mouth like the ruthenyl oxide resistor mentioned above, it is necessary to use resistance paces 1-1- with conductive components of the same type. There are problems that cannot be covered. Furthermore, there is also the problem that the characteristics of a resistor of around 10 KΩ/mouth 1·j, which is frequently used in hybrid ICs, have not reached a practical level.

Wood XI Patent No. 11,420.338 uses metal borides as conductive components, and V, N b,
5 moles (,17
The glass containing alkaline earth borate 11 is shown below. There is. Shigashi, ヰ, ν Kaikai 62
-1.22101, this resistor has a significant resistance 6a (') (J-e
-1" 77I, machining instability h'rm+!!
2A,! : I'm here.

In JP-A-62-122101, fine particles of metal hole boride represented by LaB6 are used as conductive powder, and Ta2
A resistor containing crystalline glass in which 30 to 5 mol% of 05 is dissolved is shown in Figure 1. In this resistor, Tit205 in the crystalline glass changes to TaD2 and CaTa011 by the metal hole boride,
Although it contributes to stabilizing the resistance characteristics, Ca
It is assumed that Ta011 is not formed. Furthermore, Ta20
The amount of reducing metal oxides other than Ta205 should be 2 mol% or less, preferably 1 mol% or less based on Karasu.
2O3, Mn05NiO, Fe01■205, Na01
ZnO, Ni20, CdO, PbO1B i203, W
O3, Nb205, MoO3, etc. are listed. The reason why reducing oxides other than 'l'a205 are controlled in this way is because of their presence, the conductive components LaB6 and 'l'
This is expected to be because control of T'aB2 or the reaction product CaTa011 becomes difficult, and as a result, it becomes difficult to control the electrical characteristics.

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. , talent? It is difficult to manufacture a resistor with a resistance range higher than around 10Ω/1.

[Problem to be solved by the invention 1 Resistor bases 1~ that can be used with Cu conductors and fired in a substantially non-oxidizing atmosphere are still in the development stage]
No comparable rudenium oxide resistor paste for firing in air has been obtained.

Furthermore, the metal-hole boride-based resistance 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 low-antibody base for firing in air. In particular, it is difficult to use metal-hole boride-based resistive pastes 1 to 1 in a higher resistance range than around IOKΩ/I, and there remains great anxiety in practical use.

[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) chromium oxides and chromium borides; (c) one or more chromium compounds selected from the group consisting of Va group borides and Va group borides; A glass frit containing chromium oxide (1) to (d) an organic vehicle as constituent components, wherein the chromium compound and the chromium oxide in the glass frit exceed 5 mol% of the glass frit in total, but 3
not exceeding 0 mol % and with respect to said metal boride,
The molar ratio is 5 to 0,125, and it is suitable for 1 part copper as a conductor. .

[Function] The resistance paste used in thick film technology has -a, conductive powder,
After kneading the above constituents with a Miki roll mill etc. to form paste 1 using glass frill ~ and an organic vehicle as constituent components, a circuit pattern is formed on an alumina substrate by a screen printing method etc., followed by drying and baking. one desired resistor.

In the composition for manufacturing a resistor of the present invention, the constituent components of the conductive powder are a metal boride and a chromide.

Examples of metal borides include rare earth borides such as LaB6 and CeB6, alkali borides such as BaB6.5r86, and periodic table IV a borides such as 'f'iB2 and ZrB2.
One or more metal borides selected from Va group borides such as Va group borides, VB2, NbB2, etc. 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 set to 5 μn1 or less is that in the present invention, the metal boride and the fine romanization = tV, which will be described later, are substantially The conductive product produced by firing in a non-oxidizing atmosphere is important, and if the average diameter of the metal boride is larger than 5 μm, it will be difficult to obtain a uniform conductive product. On the other hand, the reason why the average diameter is set to 0.171 μIn or more is that metal borides are preferably as small as 0.1μIn, but to make the average diameter smaller than 0.1μIn requires a very long grinding time, and There is no contamination from the crusher (this is because it becomes invisible and is impractical).Secondly, as a chromium compound, chromium oxides such as Cr2O3, CrB, CrB2, chromium borides 'I't+, etc. are selected. These can be reacted with the metal borides by calcination at 800-950'C in a non-oxidizing atmosphere to form chromium borides (Cr B, Cr B2, etc.).
and chromium, or a mixture thereof, is produced in the resistor.

In order to uniformly precipitate these conductors in the low antibody and form a stable conductive path, the average diameter of the chromium compound must be 1.
/ll11 or less, Cr2O3 should be less than 0.5 μIn, and the average diameter of the chromium compound should be l
If it is larger than Lrn, non-uniform reaction with the metal boride will occur, making it difficult to form a completely conductive bus in the resistor, making it impossible to obtain the desired low antibody properties.

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

This is because excellent resistor properties can be obtained by using chromium oxide as a component of the glass frit, specifically chromium oxide! [The total amount of one or more chromium compounds extracted from glass and chromium borides and chromium oxide in the glass frit exceeds 5 mol% of the glass frit, but does not exceed 30 mol%.] This is based on the discovery that superior low-antibody properties can be obtained by adjusting 1Jrl.

Even if chromium oxide is not present in the glass flint constituents, one or more chromium compounds selected from chromium oxides or chromium borides react with metal borides to form a uniform conductive bus in the low antibody. do,
It is possible to make resistor compositions that can be fired in a substantially non-oxidizing atmosphere. However, by using chromium oxide as a component of the glass frit, it is possible to
The low antibody characteristics (especially TCR and noise) in the above high resistance region are significantly improved.

Note that when chromium oxide is used as the chromium compound, part or all of the chromium oxide is contained in the glass frit and does not disintegrate.

The glass frit used in the present invention is 5, Cr2
03, BaO5Cab, SrO, MgO1Si02
, B203, ZrO2, TiO2, and Al2O3 as constituent components. Among these, it is especially necessary to necessarily contain chromium oxide. For example, Cr2O3 is 0.1-15 mol%, alkaline earth oxide such as BaO is 10-40 mol%, F'1203 is 15-35 mol%, 5i02 is 25 mol%.
~50 mol%, and Z r 02 and IQ = r t
It is possible to use metal oxides containing 10 mol% or less of tetravalent metal oxides, such as tg S n02 and T i 02, as a constituent component.

l; Chromium oxide and chromium boride as described in I! I
> One or more chromium compounds selected from J and a part of the chromium oxide in Glass Furi 1~ exceeds 5 mol% but not 30 mol% of Glass Fri 1~ in h total, It is necessary to make adjustments. If the total content of chromium compounds and chromium oxides 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 occurs, making it difficult to form a uniform conductive bus in the resistor, making it impossible to obtain the desired low antibody properties.

In addition, chromium compounds and chromic acid 1 in glass frit
In the case of hydrogen, the molar ratio of i1 to the metal boride is required to be in the range of 5 to 0,525, preferably in the range of 2 to 0, and if this molar ratio exceeds 5, unreacted chromium compounds If a large amount remains, or by reaction with glass components, products such as BaCrO4 will increase, and the amount of conductive material that contributes to conductivity will decrease, resulting in poor resistance characteristics of the resistor.

On the other hand, if the molar ratio is less than 0.25, the amount of conductive material generated by the reaction between the chromium compound and the metal boride is small, and it is mainly the unreacted metal boride that contributes to conductivity, and the chromium compound addition No effect was observed, and the resistance characteristics in the high resistance region deteriorated.

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. this is,
This is because the total weight of the chromium compound and metal boride affects the function of the glass frit. Glass frit exhibits softness, flow, and heat resistance during firing in a substantially non-oxidizing atmosphere.
Helps form a conductive network in the resistor during sintering,
Guide@,! ) The role of resistance adjustment by IIJ and glass amount,
It plays the role of adhering the substrate and the low antibody, and also plays a role in improving the film strength. If the above weight ratio is larger than 60/40, film strength and adhesive strength with the substrate cannot 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 conventional method, by mixing constituent carbonates and oxides such as BaCO3 and MgO in the desired ratio, heating and melting, quenching, and then pulverizing with a ball mill or the like. It is preferable that the diameter is adjusted to about 5 μm.

In the present invention, chromium boride and chromium are generated as conductive powder in the resistor through the reaction as described above, but if these chromium boride and chromium powder are used as constituent components of the resistor paste from the beginning, the conductive powder and glass free
- Since the wettability 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 resistive pastes. , the above-mentioned metal boride, chromium compound, and glass frit are uniformly dispersed to form a paste, and the resistor paste thus obtained is formed into a predetermined circuit pattern on a substrate using a screen mark 71, and then dried. Examples of the solvent 1 include alcohols, esters, ethers, ketones, etc., such as terpineol, ethyl gropionate, diethyl dibutyl ether, methyl ethyl ketone, etc. You can use it. Examples of the resin include cellulose resins such as ethyl cellulose and 21-herocellulose, and butyl methacrylate-1.
Acrylic resins 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. lot fat component in vehicle usually 1-5
It is better to set the number of nests to 0%.

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, an appropriate resistor pattern cannot be obtained on the screen mark Wj.The vehicle evaporates or decomposes and disappears during the drying and baking process.

[Example] Hidomegoyu LaB6 (manufactured by Nippon Metal Co., Ltd., F grade) was mixed with dirnicoapol (5++unφ) in an ethanol solvent.
Ball milled to a BET average diameter of 0.8 μt.
n LaBf3 was used. Cr203 (manufactured by Kojundo Kagaku 6-no-1 Kyusho Co., Ltd.) was crushed in the same way and had an average diameter of 0.3
Not Ill powder was used.

The glass frits 1~ used had the composition (mol %) shown in Table 1 and were in the form of a powder with an average particle size of about 5)t m.

Table 1 Glass Frit No. (1) No. (2)
N013) B ao 28.1 27.0
25.8S i 02 38.0 37.2
34.8B203 27.3 26.3
25.4Zr02 4.1 4.1 4
, ICr203 2.5 5.5 9.8
The vehicle used was terpineol as a solvent and ethyl cellulose as a resin.

LaB
6, Cr203, glass frit 1~ and vehicle were mixed in the proportions shown in Table 2, and base 1 was mixed using a Miki roll mill.
~. A Cu electrode was previously formed on this base 1~ according to the normal 171fi method, and a pattern with a film thickness of 40μIn was formed on an alumina substrate, and after leveling for 30 minutes, it was dried at 120°C for 10 minutes [2. A low antibody was formed by firing in an atmosphere of Bell 1 to a conveyor furnace.

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: [1 = Trial number 4 Ri - Resistance value of trial 11 (Ω/mouth) Temperature 1 series of resistance ('r CR) is -55℃, 25℃
, 125℃, and calculate the cold temperature coefficient (C'I' CR) and the hot temperature 1 series (C'I'CR) using the following formula.
H"r' CR) was calculated.

(Lllllu / 'U) Where: R: Resistance value at -55°C (Ω/mm) E: Resistance value at 25'C (Ω/mm) R: Resistance value at 125°C (Ω/mm) / mouth) Current noise can be measured using a noise meter (Q IJ a rr
It was measured using "RackItl:".

The adhesion speed of the K anti-film is determined by the adhesive tape
Evaluation was made from the l1T state. The results are shown in Table 2.

Table 2 shows that the total amount of chromium compounds and chromium oxides in Karasu Friso L is less than 5 mol% or more than 30 mol%, or that the amount of chromium compounds and chromium oxides in glass Although it is outside the scope of the claims of the present invention in that the total amount of chromium oxide in the frit is not within the range of 5 to 0.25 in molar ratio to metal boride, Comparative Example 1 (prepared in the same manner) ) I: J-indicated with h
ing.

As is clear from Table 2, Comparative Example 1 has a large CV value, a negative TCR value that is too large, or a low membrane strength, making it a low antibody that cannot withstand practical use. The resistor obtained from -Resistance base 1 of Rikiki's invention shows good resistor characteristics.

DIλ 'I' i B2 and NbB2 were made from powders manufactured by Shin Nippon Metal Co., Ltd., and Cr203, CeB6, CrB2 and 5rB6 were made from powders made by Kojundo Kagaku Kenkyusha Co., Ltd.
A resistance paste was produced in the same manner as in Example 1, except that these powders were ground to a BET average diameter of 0.3 to 0.8 μm using a ball mill in the same manner as in Example 1, and alumina After a circuit pattern was screen-printed on the substrate, the resistor obtained by firing in a nitrogen atmosphere was evaluated. The results are shown in Table 3.

Table 3 shows that the total amount of chromium compounds and chromium oxides in the glass frit is 5 mol% or less or 30 mol% or more of the glass frit, or that the chromium compound and the chromium oxide in the glass frit are Although it is outside the scope of the claims of the present invention in that the total amount of chromium oxide and the metal boride is not within the range of 5 to 0.25 in terms of molar ratio, Example 2
Comparative Example 2 produced in the same manner as (* is shown on the (dry) line).

As is clear from Table 3, Comparative Example 2 has a large CV value and a negative TCR value, or has a weak membrane strength and is a low antibody that cannot be put to practical use. - The low antibody obtained from the civilian anti-paste of Rikiki's invention shows good resistor properties.

[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 ~IO6Ω/Ω 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) chromium oxide and chromium borides; (c) a glass frit containing chromium oxide; and (d) an organic vehicle; the amount of the chromium compound and the chromium oxide in the glass frit is Manufacturing a resistor, characterized in that the total amount of the glass frit is more than 5 mol % but not more than 30 mol %, and the molar ratio to the metal boride is 5 to 0.25. Composition for use.