JP2933136B2 - Method of manufacturing resistor and method of manufacturing thermal head - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for manufacturing a resistor used in a hybrid IC or various electronic devices and a method for manufacturing a thermal head.

[Conventional technology]

Conventionally, as a method of manufacturing a resistor used in an electronic device such as a hybrid IC or a thermal head, a thick film method in which a thick film resistor paste is applied on a substrate and baked to form a resistor, and sputtering is used. Thin-film systems are known.

In the former, for example, a thick film resistor paste in which a powder mixture of ruthenium oxide and glass frit is dispersed in an organic vehicle in which a solvent and a resin are mixed is screen-printed on a substrate and fired to form a resistor.

The latter applies vacuum technology.For example, a thin film of a hardly soluble metal such as tantalum is deposited on a substrate by sputtering, and a pattern is formed by photolithography to form a thin-film resistor. Used as a resistor for the head.

[Problems to be solved by the invention]

However, in the conventional thick film method using a thick film resistor paste, although the equipment for forming the resistor is inexpensive and has high productivity, the thickness of the formed resistor is as thick as about 10 μm or more,
Since the thick film paste is a non-uniform mixture of glass frit and ruthenium oxide powder, there is a problem that the strength with respect to the electric field is weak, that is, when the voltage is changed, the resistance value suddenly changes at a certain value or more.

Furthermore, it is difficult to control the resistance value of the formed resistor only by the composition ratio of glass powder and ruthenium oxide, and the resistance value greatly varies depending on the difference in the particle size of the glass powder and ruthenium oxide and the firing temperature. However, even if the composition ratio and the average particle size are the same, there is a problem that the resistance value differs depending on the lot.

In the latter thin film method, a uniform thin film resistor can be obtained,
There are problems that the equipment is expensive and the productivity is low, and that if heat treatment is not performed after deposition, the strength against electric power is weak.

Accordingly, an object of the present invention is to solve the above-mentioned problems by obtaining a uniform thin-film resistor by a thick-film method and further providing a resistor element using the resistor.

[Means and actions for solving the problem]

In order to achieve the above object, the present invention includes an organic ligand complex of Mo and an organic ligand complex of Si, and further includes an organic ligand complex of at least one metal selected from Pb or Bi. A resistor paste is applied to a substrate and then fired to form a resistor, and the Mo included in the resistor after firing of the resistor paste is formed.
Wherein the ratio (Mo / M) of the sum of the number of atoms of the other metal (M) to the number of atoms of the other metal (M) is 1 to 3.

The resulting resistor is an atomic-level mixture of molybdenum oxide (MoOx; x is usually 2), which is a conductive oxide, and oxides of other metals, which are insulating oxides. is there. By the presence of at least one of lead and bismuth, it is possible to suppress the precipitation of crystals such as Mo and Si during the firing of the resistor thin film and to homogenize it.

Further, the ratio of molybdenum oxide and the oxide of another metal can be changed by the mixing ratio of the resistance paste, whereby the resistance value can be adjusted.

The present invention further provides a thermal head using the above resistor.

〔Example〕

 An embodiment of the present invention will be described.

(1) Example 1 As a metal organic substance solution, for example, the following number of metal resinate (trade name) manufactured by Engelhard Co. is used.

Mo; # 8605 Si; # 28-FC Pb; # 207-A Bi; # 8365 The atomic ratio after firing the above solution is a predetermined value, for example, Mo: S
i: Bi = 1: 0.5: 0.5 The mixture is mixed at a ratio such that α-terpineol and a resin ethyl cellulose are used to adjust the viscosity to 8,000 to 20,000 cps to obtain a resistance paste of the present invention.

This resistance paste is printed and coated on a glazed alumina substrate coated with glass on alumina by a 150-400 mesh stainless screen, dried at 120 ° C, and fired at a peak temperature of 750 ° C for 10 minutes in an infrared belt firing furnace. To form a resistor film on the substrate.

The film thickness of the formed resistor film is 0.1 to 0.4 μm, and the sheet resistance is 230 to 270 Ω / □ when converted to a film thickness of 0.2 μm.

Note that, in the above embodiment, the case where the atomic ratio after sintering of Mo, Si, and Bi is Mo: Si: Bi = 1: 0.5: 0.5 is described, but the present invention is not limited to this. The ratio of the number of atoms to the metal M is preferably Mo / M = 1 to 3. For example, Mo: Si: Pb = 1: 0.5: 0.
With the resistor paste having the composition of 5, a resistor having a sheet resistance of 210 Ω / □ was obtained.

Further, in the above embodiment, an example was described in which a metal resinate manufactured by Engelhard Co. was used as each metal organic substance solution.However, the present invention is not limited to this. β-
Various metal organic substances can be used as long as they form stable complexes with organic substances such as diketones and mercaptans and the metal organic substances are soluble in organic solvents, for example, α-terpineol, butyl carbitol acetate and the like.

For example, as a complex of Mo, β-diketone complex such as (RCOCHCOR ') ₂ MoO ₂ , and as a complex of Bi, as a complex of Bi (OOCC ₇ H ₁₅ ) ₃ Si, a complex of Si (OOCC ₇ H ₁₅ ) ₄ Pb Examples of the complex include a complex of Pb (OOCC ₇ H ₁₅ ) ₂ Al and a carboxylic acid complex such as Al (OOCC ₇ H ₁₅ ) ₃ .

The resistor I formed in the above embodiment at a ratio of Mo: Si: Bi = 1: 0.5: 0.5 and the conventional ruthenium oxide thick film resistor II
FIG. 1 shows the results of an SST (Step Stress Test) strength test for the samples. The sizes of the resistors I and II used in this test were 105 μm × 150 μm, and the film thickness of the resistor I was 0.20 μm.
μm, resistor II is 15 μm, and the resistance value is 375Ω for resistor I,
Resistor II is 480Ω.

As is clear from FIG. 1, the resistor I according to the present invention has a small change in the resistance value, and hardly changes particularly up to 1 W which is usually used, and has high reliability.

In the resistor of the present invention, the firing condition is performed at a peak temperature of 600 ° C. or higher because the formation of the resistor film is difficult at 600 ° C. or lower.

This is also evident from the thermogravimetric analysis of the resistance paste, as shown in FIG. That is, according to FIG. 2, the decrease in weight until the calcination temperature was 200 ° C. was due to the volatilization of the solvent (arrow A), and the decrease in weight at about 300 to 500 ° C. Caused by burning (arrow B)
it is conceivable that. The gradual weight loss from 500 to 600 ° C. is due to the burning of the decomposed carbon residue. At about 600 ° C. or higher, it is considered that the organic components are completely removed, and each metal element is completely turned into an oxide to form a resistor film (arrow C).

In the case of calcination in air, a decrease in weight is observed at 750 ° C. or higher, which is thought to be due to the elimination reaction of oxygen from MoO ₂ . Therefore, 600-750 ° C for firing in air
Is desirable. Above 30% oxygen, the above weight loss does not occur.

Note that when Al oxide is contained, the sheet resistance can be increased.

(2) Second Embodiment In the first embodiment, an example in which the obtained resistor is used as a resistance element for a thermal head will be described.

FIG. 3 is an explanatory view of the configuration of the thermal head resistance element. FIG. 3 (a) is a plan view, and FIG. 3 (b) is a cross-sectional view along the XY line.

In FIG. 3, 1 is a common electrode, 2 is a counter electrode, 3 is a resistor element, 4 is an alumina substrate, 5 is an underglaze layer, and 6 is an overglaze layer.

As shown in FIG. 3, on a glazed alumina substrate composed of an alumina substrate 4 on which an underglaze layer 5 is formed,
The resistor element 3 is directly formed. This resistor element 3
Is manufactured from the resistor film formed in Example 1,
The common electrode 1 and the counter electrode 2 extend from the end of the resistor element to the glazed alumina substrate from each element.

 This thermal head is manufactured as follows.

First, a resistor film as the resistor element 3 for heat generation is formed on a glazed alumina substrate by the method described in the first embodiment.

Next, a resist pattern of the resistor is obtained by applying, exposing, and developing a resist. Subsequently, the resistor is etched using a mixed aqueous solution of hydrofluoric acid and nitric acid as an etching solution to obtain a resistor pattern having a desired density (6 to 16 dots / mm).

Next, an organic gold paste D27 manufactured by Noritake Co., Ltd. is printed on the entire surface of the resistor and baked to form a gold film, which is photolithographically etched to form a conductor pattern connected to the resistor.

Further, a glass paste LS201 manufactured by Tanaka Matsusei Co., Ltd. is printed as a protective film and then fired to form an overglaze layer 6 (not shown in FIG. 3A), thereby completing a thermal head resistance element.

〔The invention's effect〕

In the present invention, since the precipitation of molybdenum or silicon during firing can be suppressed by the presence of at least one of lead and bismuth, it is formed with inexpensive equipment similar to a conventional thick film resistor using a glass frit. Nevertheless, it can be formed as a homogeneous and thin film.

The control of the resistance value can be substantially determined by the composition ratio of each metal and the sintering conditions, and there is no need to consider the influence of other parameters such as variation among lots.

Further, it is possible to obtain a highly reliable resistor that has a small variation in resistance value due to the amount of electric power as compared with a conventional thick film resistor.

In this way, it has both the advantages of a thick-film resistor and the advantages of a thin-film resistor, and also has a high power handling strength. Use these resistors for sublimation-type thermal heads for thermal recording, etc. Is obtained.

Since the resistor is formed using an organic ligand complex, not only is the resistor film uniform, but it can also withstand extremely thin film resistors sintered and formed at the atomic and molecular levels. Fine etching can be performed, and a high-resolution resistor element having a desired shape such as a fine line can be formed at low cost.

In addition, by using a high-resolution resistor element using a resistor having a very thin film thickness, the image quality of the thermal head can be improved at low cost.

[Brief description of the drawings]

FIG. 1 is a diagram showing the results of SST strength tests of the resistor of the present invention and a conventional resistor, FIG. 2 is a thermogravimetric analysis diagram of a resistor paste, and FIG. FIG. 2 is an explanatory diagram of a main part configuration of a used thermal head. 1 ... common electrode, 2 ... counter electrode, 3 ... resistor element, 4 ... alumina substrate, 5 ... underglaze layer, 6 ... overglaze layer.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Yoshiyuki Shiratsuke 2274 Hongo, Ebina-shi, Kanagawa Fuji Xerox Co., Ltd. Ebina Works (56) References JP-A-62-252102 (JP, A) JP-A Sho 58-165301 (JP, A) JP-A-51-89192 (JP, A) JP-B-49-20911 (JP, B2)

Claims (4)

(57) [Claims] 1. A resistive paste containing an organic ligand complex of Mo and an organic ligand complex of Si and further containing an organic ligand complex of at least one metal selected from Pb or Bi is applied to a substrate. Then, the resistor is fired to form a resistor, and the ratio (Mo / M) of the sum of the number of atoms of Mo and the number of atoms of another metal (M) contained in the resistor after firing of the resistor paste. Is 1-3
A method for manufacturing a resistor, characterized in that: 2. A method of manufacturing a thermal head including a plurality of heating elements formed of resistors, wherein the resistors include an organic ligand complex of Mo and an organic ligand complex of Si, and further include Pb or Bi. A resistive paste containing an organic ligand complex of at least one metal selected from the following is applied to a substrate, and then fired to form a resistor, and the resistor included in the fired resistor of the resistor paste The ratio of the number of atoms of Mo to the number of atoms of another metal (M) (Mo / M) is 1 to
3. A method for manufacturing a thermal head, wherein 3. The method for manufacturing a resistor according to claim 1, wherein said resistor paste is fired in air or an oxidizing atmosphere at a peak temperature of 600 ° C. or higher. 4. A method for manufacturing a thermal head according to claim 2, wherein said resistance paste is fired in air or an oxidizing atmosphere at a peak temperature of 600 ° C. or more.