JPH04279003A - Paste for forming resistor film - Google Patents

Abstract

PURPOSE:To provide paste for forming a uniform resistor film which is less in the fluctuation of resistance value. CONSTITUTION:This paste for forming resistor films is prepared by using a solution containing at least one kind of metallic organic compound selected out of metallic organic compounds and nonmetallic organic compounds and the viscosity of the paste is adjusted to 3,000-30,000cp. The paste contains the organic compound of at least one element selected out of Ru, Ir, Rh, Pt, Pd, and Os and the organic compound of at least one metal or nonmetallic element selected out of Si, Bi, Sn, Al, B, Ti, Zr, Ca, and Ba.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is applied to the formation of resistor films used in hybrid ICs and various electronic devices by applying the film by screen printing or the like and baking it to form a metal film on a substrate such as alumina or glass. The present invention relates to a resistor film forming paste that can be screen printed to freely form the shape of a resistor film made of an oxide.

0002

[Prior Art] Conventionally, as a method for forming a metal oxide film on a resistor used in hybrid ICs and various electronic devices, a resin solution is mixed as a binder into a mixture of metal and/or metal oxide powder and glass. Two methods are well known: a thick film method in which a paste is screen printed on a substrate and then baked to form a film, and a thin film method in which a resistor forming material is sputtered.

In the former thick film method, the film forming equipment is inexpensive and the productivity is high, but there are problems in that the uniformity of the formed film is poor and the resistance value varies widely. On the other hand, the thin film method can produce a uniform thin film, but has the problems of expensive equipment and low productivity.

[0004] In addition, various techniques have been proposed in the past for manufacturing thin resistor films using the above-mentioned thick film technology, which requires inexpensive manufacturing equipment.
tallo Organic Depositio
n) A law is proposed. MOD method refers to metal and/or
Alternatively, instead of a mixture of metal oxide and glass, a paste is prepared using a solution of a metal organic compound, and a thin film is formed in the same manner as the thick film method (Japanese Unexamined Patent Application Publication No. 60-1979).
-102701, JP 60-102702, JP 62-292453, JP 1-152074,
JP-A-2-39953, JP-A-2-33901, JP-A-2-33902).

[0005] In the above-mentioned method of forming a thin film using a thick film method using a solution of a metal-organic compound, there are problems in terms of viscosity suitability and storage stability when preparing a paste suitable for screen printing and the like. Therefore, an appropriate viscosity agent is required to produce a paste with excellent viscosity suitability and storage stability. For example, in pastes for conductive films, cellulose compounds such as ethyl cellulose are known as viscosity agents to adjust the viscosity (Japanese Patent Laid-Open No. 56-5
No. 354, JP-A-57-27505, JP-A-58-1
No. 9813). In addition, there are examples of resistor films using asphalt as a viscous agent, but other glass powders of metal-organic compound solutions are added to maintain film formability (Japanese Patent Application Laid-Open No. 1983-1993).
-30094).

[0006]

[Problems to be Solved by the Invention] Ethyl cellulose, etc., as a viscosity agent for a paste suitable for screen printing, etc., used in the method of forming a thin film using a thick film method using a solution of a metal-organic compound, is a metal-organic compound. In some cases, the compatibility was poor and the film formability was poor. In addition, examples of resistor film pastes that use asphalt as a viscous agent maintain film-forming properties by adding glass powder to a solution of a metal organic compound, resulting in poor uniformity of the resulting resistor film. There was variation in the resistance value of the resistor film.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and to provide a resistor film forming paste for forming a uniform resistor film with small variations in resistance value.

[0008]

[Means for Solving the Problems] In order to achieve the above object, the present invention employs the following configuration. That is, in a paste for forming a resistor film using a solution containing at least one metal organic compound among a metal organic compound and a non-metal organic compound, the paste has a weight of 3,000 to 30,000 c.
Resistor film paste with a viscosity of p, or ruthenium (Ru), iridium (Ir), rhodium (Rh), platinum (Pt), palladium (Pd), osmium (Os)
at least one metal organic compound and silicon (S
i), bismuth (Bi), lead (Pb), tin (Sn),
Aluminum (Al), boron (B), titanium (Ti)
, zirconium (Zr), calcium (Ca), and barium (Ba). A resistor film obtained by screen printing and firing, or
an electronic component using the resistor film obtained by the manufacturing method;
It is.

The metal organic compound solution used in the present invention is a carboxylate of at least one metal selected from Ru, Ir, Rh, Pt, Pd, and Os, a diketone type chelate compound, an alkoxide compound, and a mercaptide compound. etc. are used. In addition, as the solvent for the paste, it is desirable to use a solvent that dissolves each metal organic compound and has a high boiling point, such as terpineol, benzyl acetate, isophorone, butyl carbitol acetate, benzyl alcohol, etc., used alone or in combination. . Also,
Other metal or non-metal organic compounds to be added include Si, Bi, Pb, Sn, Al, B, Ti, Zr,
At least one carboxylate salt selected from Ca and Ba, a diketone type chelate compound, an alkoxide compound, a mercaptide compound, etc. are used.

Further, as the metal organic compound solution, commercially available metal resinates or nonmetal resinates may be used. Asphalt is desirable as the viscosity agent, but other viscosity agents include cellulose compounds such as ethyl cellulose and nitrocellulose, or
General-purpose polymers such as polyethylene, polystyrene, polycarbonate, etc. can be used. Furthermore, even when no viscosity agent is used, it is necessary to keep the viscosity of the paste in the range of 3,000 to 30,000 cp in order to achieve the object of the present invention. As the solvent for dissolving the viscosity agent, high boiling point solvents such as terpineol, benzyl acetate, and isophorone are desirable, and they are used alone or in combination.

[0011] Furthermore, with the aim of improving the printability and coating properties of the paste, it is also possible to add antifoaming agents, leveling agents, and other additives. A method for producing a resistor film is to print a paste prepared from a solution containing at least the metal-organic compound on a substrate by screen printing or the like, and after drying, to heat the paste at a temperature higher than the thermal decomposition temperature of the organic metal, non-metal compound, or additive. It is something that is fired. In the present invention, the viscosity is measured using a RHEOMAT115 cone-plate viscometer, and the specified viscosity range is a value at a rotational speed of 10 s-1.

0012

[Function] The viscosity range of the paste for resistor film formation can be increased from 3,000 to 3,000 by adding a viscosity agent or by concentrating the paste solution.
The paste is adjusted to within a range of 0,000 cp, and this paste is printed and applied onto a substrate and fired. Since the viscosity of the paste is adjusted, a film with good surface properties and small variations in film thickness can be obtained in screen printing or the like. As a result, variations in the resistance value of the resistor film after firing are also reduced.

[0013]

[Examples] Specific examples will be described below. Examples 1 to 5 First, the following metal resinates and nonmetal resinates were used as metal organic compounds and nonmetal organic compounds.

Ir resinate (A-1123: manufactured by NE Chemcat) [Metal content:
6.0%] 21.
12g Bi resinate (#8365: manufactured by NE Chemcat) [Metal content: 20.0%]
6.89g Si resinate (#28FC: manufactured by NE Chemcat) [Metal content: 9.3%]
After mixing 2.00 g (calculated from the metal content in the resinate, the elemental composition ratio is Ir/Bi/Si = 1/1/1), the weight was reduced to 60% in a dryer at 100 ° C. Concentrate until reduced to . Concentrated Ir, Bi,
After adding 12.0 g of an asphalt solution as a viscosity agent (described later) to 18 g of a mixed solution containing Si and stirring and mixing,
Further, it is concentrated or diluted with α-terpineol and adjusted to a predetermined viscosity to obtain a screen printing paste having a viscosity as shown in Table 1.

The paste thus obtained was screen printed (printing machine: Model 8115, manufactured by Presco Corporation) on a 1-inch square alumina substrate (GS-6, manufactured by Kyocera Corporation).
After coating, dry at 70°C for 30 minutes. Thereafter, as a result of baking at 800° C. for 15 minutes, a resistor film was obtained. The sheet resistance value was determined by the average value of five points and the resistance value variation value. Table 3 shows the sheet resistance value, resistance value variation value, and resistance value max/min (ratio of difference in resistance value to the average value of max (min) value). Here, resistance value variation refers to the standard deviation of resistance values divided by the average resistance value. The solution of asphalt as the viscosity agent is prepared as follows.

Asphalt (fine powder: Tokyo Kasei Co., Ltd.)
(manufactured by Tokyo Kasei Co., Ltd.) 150g α-terpineol (manufactured by Tokyo Kasei Co., Ltd.) 600
2,2,4-trimethyl-
25 g of pentane-1,3-diol-monobutyl ester (manufactured by Chisso Corporation) was added to prepare an asphalt solution.

(Table 1) Viscosity adjustment Viscosity (cp) Example 1 Addition of 4% α-terpineol
4,000 〃 2 1%
Concentration 8,000
〃3 3% concentrated
10,300 〃
4 4% concentrated
12,500 〃 5
8% concentrated
21,900

Comparative Examples 1 to 3 Pastes were prepared in the same manner as in Examples 1 to 5. The only difference from Examples 1 to 5 is the viscosity range when adjusting the viscosity as shown in Table 2. The paste thus obtained was applied onto a 1-inch square alumina substrate (GS-6, manufactured by Kyocera Corporation) by screen printing in the same manner as in Examples 1 to 5, and then dried at 70°C for 30 minutes. ,800℃
As a result of baking for 15 minutes, a resistor film was obtained. Table 3 shows the sheet resistance values and the resistance variation values.

(Table 2)
Viscosity adjustment Viscosity (cp) Comparative example 1 1
1.5% concentrated 39,2
30 〃 2
13% concentrated 176,
710 3 11% α-terpineol added 1,530

0020
As shown in Table 3, as the viscosity increases, the resistance value variation and resistance value max/min tend to increase. Furthermore, as the viscosity decreases, the resistance value max/min tends to increase. Examples 1 to 5 and Comparative Example 1 to
The relationship between the viscosity and resistance value variation of No. 3 is summarized in Figure 1. The viscosity range suitable as a resistor is 3,000 to 30,000.
It is cp.

(Table 3) Average resistance value Resistance value variation Resistance value max/min
(Ω/□)
(%) (%) Example 1 1,630 4.2
+4.1/-7.4 〃 2
864 3.2
+3.4/-5.5 3
743 1.9
+3.8/-5.4 4
713 2.5
+2.5/-4.7 〃 5
815 4.2 +
4.3/-7.9 Comparative example 1 1,232
6.8 +7.5/-1
2.1 〃 2 1,019
11.9 +20.3/-13.2
〃 3 728 6
．． 4 +9.6/-7.5

002
2] Examples 6 to 8/Comparative Examples 4 and 5 To 18 g of a liquid mixture containing metal organic compounds and non-metal organic compounds of Ir, Bi, and Si concentrated in the same manner as in Examples 1 to 5, the viscosity agent Dehysol R ( Anionic vegetable oil derivative manufactured by San Nopco) 1.
Add 00g of butyl carbitol acetate (
BCA) and adjusted to a predetermined viscosity to obtain a screen printing paste with a viscosity as shown in Table 4. Using the thus obtained paste, resistor films were produced in the same manner as in Examples 1 to 5. The sheet resistance value of the resistor film is 5
The average value of the points and the value of resistance value dispersion were determined. Table 5 shows the sheet resistance value, the resistance value variation value, and the resistance value max/min.

[0023]

[Table 4]

(Table 5) Average resistance value Resistance value variation Resistance value max/min
(Ω/□)
(%) (%)
Example 6 287 3.
9 +6.2/-4.6
〃 7 252 4.2
+6.5/-5.7
8 266 4.3
+8.6/-2.4 Comparative example 4
340 6.9
+9.2/-7.6 〃 5
324 13.2 +1
2.9/-19.0

Examples 9 to 11/Comparative Example 6 Ir, Bi, and S concentrated in the same manner as in Examples 1 to 5
18 g of the mixed solution containing the metal organic compound and non-metal organic compound of i was further mixed with butyl carbitol acetate (B
CA) and adjusted to a predetermined viscosity to obtain a screen printing paste with a viscosity as shown in Table 6. Using the paste thus obtained, in the same manner as in Examples 1 to 5,
A resistor film was fabricated. The sheet resistance value of the resistor film is 5
The average value of the points and the value of resistance value dispersion were determined. The sheet resistance value, resistance value variation, and resistance value max/min are shown in Table 6.
It was shown to.

[0026]

[Table 6]

Examples 12 and 13/Comparative Examples 7 and 8 A solution containing a metal organic compound and a non-metal organic compound was prepared as follows.

Rh resinate (#8826: manufactured by NE Chemcat) 5.2g Si resinate (#28
FC: manufactured by NE Chemcat) 17.6g
Mix 7.2 g of Pb resinate (#207-1: manufactured by NE Chemcat) (calculated from the metal content in the resinate, R
h/Si/Pb=1:1:1), and then concentrated in drying at 100° C. until the weight decreases to 60%. 12. Add the asphalt solution of the viscosity agent shown in Examples 1 to 5 to 18 g of a concentrated mixed solution containing metal organic compounds and non-metal organic compounds of Rh, Si, and Pb.
After adding 0 g and stirring and mixing, the mixture is further concentrated or diluted with α-terpineol and adjusted to a predetermined viscosity to obtain a screen printing paste having a viscosity as shown in Table 7. Using the thus obtained paste, resistor films were produced in the same manner as in Examples 1 to 5. Sheet resistance value of resistor film, resistance value variation value, resistance value max/min
I asked for Table 7 shows the sheet resistance value, the resistance value variation value, and the resistance value max/min.

[0029]

[Table 7]

In the above embodiment, an example was explained in which screen printing was used as the method of applying the resistor paste.
The present invention is not limited to this, but the resistor paste is coated on the entire surface of the substrate by a coating method used for forming a thick film, such as spin coating, roll coating, or dip coating, and then etched after baking. A resistor having a desired shape may be formed by using the same method. Alternatively, a direct drawing method such as an inkjet method may be used.

[0031]

Effects of the Invention When a resistor film paste having a viscosity within the viscosity range of the present invention is applied onto a substrate, a film with good surface properties and small variations in film thickness can be obtained. As a result, variations in the resistance value of the resistor film after firing are also reduced. In this way, the resulting resistor film has stable performance and is suitable for hybrid ICs.
It can be used for various electronic parts.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the relationship between the viscosity and resistance value variation of a resistor film paste according to an example of the present invention.

Claims (4)

[Claims] Claim 1. A paste for forming a resistor film using a solution containing at least one metal organic compound among a metal organic compound and a non-metal organic compound, wherein the paste has a viscosity of 3,000 to 30,000 cp. A paste for forming a resistor film, characterized by the following. Claim 2: Ruthenium (Ru), iridium (I
r), rhodium (Rh), platinum (Pt), palladium (
Pd), at least one metal organic compound of osmium (Os), and silicon (Si), bismuth (Bi),
Lead (Pb), tin (Sn), aluminum (Al), boron (B), titanium (Ti), zirconium (Zr),
2. The paste for forming a resistor film according to claim 1, containing at least one metal or nonmetallic organic compound selected from calcium (Ca) and barium (Ba). 3. A resistor film, characterized in that it is formed by printing and applying the paste for forming a resistor film according to claim 1 or 2 onto a substrate, and then baking the paste. 4. An electronic component using the resistor film according to claim 3.