JPH02288301A - Resistor and manufacture thereof and thermal head - 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 Field of the Invention The present invention relates to a resistor, which is an electronic component material, and a method for manufacturing the same, and particularly relates to a thermal head with excellent printing quality.

2. Prior Art A resistor, which is a conventional electronic component material, is made of Ta-5L, which is obtained by a vacuum thin film forming process such as vapor deposition or sputtering.
There are two types: the so-called thin-film type, and the thick-film type, which is a printed and fired film made of glass frit and ruthenium oxide powder. The thin film type is generally uniform but has a drawback in durability (pulse resistance), and the thick film type has excellent durability but lacks uniformity.

Here, a resistor used in a thermal head used in a printing device such as a thermal transfer printer or a thermal printing printer will be explained in detail by way of example. FIG. 1 shows a sectional view of a general configuration of a thermal head. On the alumina substrate 1 provided with the glaze layer 2, a heat generating resistor 5, a common electrode 3 and individual electrodes 4 for energizing the heat generating resistor 5 are provided, and a wear-resistant material is provided to cover the heat generating resistor 5. It is configured by providing a layer 6.

The thin film type is generally an electrode (0r-Cu, etc.) obtained by a vacuum thin film forming process such as vapor deposition or sputtering.
, resistor (Ta-51 etc.) 5, wear-resistant layer (SIC etc.) 6
For thick film type, electrode (Au etc.) 3.4, resistor (Ru
02, etc.) 5, and a wear-resistant layer (h' 5, etc.) 6 are formed by printing and baking pastes.

The two types of thermal heads mentioned above each have advantages and disadvantages. In other words, in a thin-film thermal head, the resistor shape (area, thickness, etc.) is uniform between each card and the heat capacity is uniform, so heat is evenly transferred to the paper during printing. . Furthermore, the resistance values of each resistor are uniform up to a certain level, and overall, the thermal head has excellent printing quality. Furthermore, since the thickness of the resistor layer is thin (1000-5000 A), the heat capacity is small, and the time constants for the rise and fall of the resistor temperature when pulse application is on and off are excellent, and the printing heat generation efficiency is high.

However, there are many problems that need to be solved in terms of productivity and cost reduction, such as equipment costs for thin film processes and batch production. There is also room for improvement in durability (pulse resistance).

On the other hand, thick-film thermal heads have many advantages, such as low equipment costs because they use a printing and firing method, easy continuous production, and excellent durability (pulse resistance).
Since the resistor layer is formed by printing and firing a paste consisting of a mixture of metal oxide powder such as ruthenium oxide powder and glass frit, it is difficult to obtain uniform dispersion of the metal oxide layer in the resistor layer. , it is difficult to reduce variations in resistance values between dots. In a thick-film thermal head, it is possible to reduce this variation in resistance value to ±1% or less by using an overload trimming method.

However, when focusing on the microscopic current path within a single dot, non-uniformity of trimming remains as an issue that needs improvement. These disadvantages are largely due to the large heat capacity of the thick film resistor layer, resulting in a large time constant during heat-generating printing, poor printing thermal efficiency, and poor printing quality. .

Problems to be Solved by the Invention The present invention aims to improve the uniformity and durability (pulse resistance characteristics) of a resistor used as an electronic component, and furthermore, it aims to improve the uniformity and durability (pulse resistance characteristics) of a resistor used as an electronic component. This relates to improving print quality.

A means for solving the problem consists in using a metal organic compound as a starting material and a metal silicide layer obtained by decomposing it as a resistor.

Effects According to the present invention, a resistor layer having good adhesion to a substrate and excellent durability (pulse resistance) can be obtained by a paste printing decomposition firing method.

Further, a thermal head using this as a heating element has excellent printing on/off time constants and printing quality.

Example Specific embodiments of the present invention will be shown below according to the drawings.

(Example-1) As shown in Fig. 1, a gold organic compound paste was printed and fired on a glazed alumina substrate 1 with a thickness of 0.8 mm, and a common electrode 3 and individual electrodes 4 were formed by photolithography.
After forming, tantalum fatty acid salt (liquid with 7 carbon atoms), which is the main component of the resistor, and silicon fatty acid salt (Ta:
5i=1:1.2 ratio) and a film-forming aid uniformly dispersed in the ink and baked in an inert atmosphere to form a heating resistor 5 with a thickness of about 0°3 μm. ,
Patterned using photoetching technology. Finally, a wear-resistant layer (approximately 5 μm) 8 of SiC was formed on this. It was confirmed from the electron beam diffraction pattern that the fired resistor film contained tantalum silicide.

The film-forming aids include rhodium (0.1-5%), bismuth (0.05-1%), vanadium (0.05-2%).
) was added, dissolved in an organic solvent of butyl acetate, and mixed uniformly with the vehicle. By adding the film-forming aid, the resistor layer after firing was a uniform film with little occurrence of cut-off, and had high adhesion to the substrate 1.

In addition to the above-mentioned compounds, organic compounds of boron, lead, and antimony were also used as film-forming aids, and similar effects were confirmed. Also,
A mixture of 2.3 types was preferable to addition of a single substance. The effect of this film-forming aid is thought to be to suppress the grain growth of the resistive material during firing and to improve the bonding strength with the substrate 1.

(Example 2) In the same manner as in Example 1, an electrode layer 3.4 was formed on the 0.8+ nm thick glazed alumina substrate 1 by printing and firing a gold organic compound paste and photolithography.
The main components of the resistor are titanium fatty acid salt (liquid with 7 carbon atoms) and silicon fatty acid salt (Ti:5i=1:1.
2) and a film-forming aid is printed and baked in an inert atmosphere to a thickness of approximately 0.2 mm.
Five layers of heating resistors with a thickness of 3 μm were formed and patterned using photoetching technology. Finally, a wear-resistant layer (approximately 5 μm) 8 of SiC was formed on this.

The following table shows the characteristics of the thermal heads according to Examples 1 and 2. Comparative Example 1 in the table is a typical conventional thick film type head, which uses a printed and fired thick film (10 μm) of ruthenium oxide powder and borosilicate glass frit for the resistor, and other configurations and materials. is the same as Example-1. Comparative Example 2 is a Ta5I resistor fabricated by a thin film process.
This is a thermal head using a film (0.1 μm).

Further, the resistance value dispersion in the table shows the value obtained by dividing the standard deviation of each dot resistance value by the average resistance value. Durability is 0.5W
/dot, 1/4 duty, 32m5/cyc
The number of pulses in which the resistance value changes up to ±5% when energized under the driving conditions of le is shown.

As shown in the table, the heads of Examples 1 and 2 can obtain a much thinner resistor layer than the conventional head using glass frit with a binder (comparative example), and have a resistance value of It was found that the resistance was uniform with little variation.Furthermore, compared to the conventional thin film head (Comparative Example-2),
It was found that it has excellent durability.

(Example-3) Similar to Example 1, the main components of the resistor are tungsten, molybdenum, niobium fatty acid salts (liquid with 7 carbon atoms), silicon fatty acid salts, and film-forming aids. A similar effect was confirmed when using a resistor printed with ink and fired in an inert atmosphere.

As for the combination of resistor components, a uniform and highly durable resistor was obtained even when using a three-component system or a four-component system of tantalum, titanium, tungsten, molybdenum, niobium, and silicon.

(Example 4) The organometallic compounds used in Examples 1 to 3 were mainly lower fatty acid salts having up to 20 carbon atoms, but other compounds include alkoxides, mercaptides, and polycyclic organometallic compounds. , other resinates, and rosinates alone or in mixtures thereof as starting materials, similar resistor films were obtained.

If the atmosphere during firing has a high oxygen concentration, the metal itself will be oxidized during firing of the resistor film, making it impossible to obtain the desired resistance. Furthermore, in an atmosphere where the oxygen concentration is completely reduced to zero, during firing, the decomposed organic compounds do not completely gasify and remain in the electrode as carbon, making it impossible to obtain the desired resistor. Ta. Therefore, as a result of firing using an inert nitrogen gas atmosphere with controlled oxygen concentration, the oxygen concentration was 11,000 pp or less, 10 pp.
I) Conditions of m or higher were preferred.

In addition to the screen printing method, a roll coater method, a spinner method, and an offset printing method may be used to apply the ink onto the substrate, but the method is not particularly limited. Also,
The wear-resistant layer may also be formed using a thick film technique in addition to the embodiments described above.

In addition, in Examples 1 to 4, the resistor has been described using a thermal head as an example, but the present invention is not limited to a thermal head, and can be used as a resistor in a wide range of circuit boards, electronic components, etc. It is effective.

Effects of the Invention As described above, according to the present invention, since glass frit is not used as a binder as in the conventional case, a resistor layer having a very thin and uniform thickness and excellent durability can be printed and fired. can be obtained by law. Therefore, high-quality resistors with high reliability can be continuously produced at low cost.

In particular, when used as a resistor in a thermal head, the heat capacity of the resistor layer is equivalent to that produced by a thin film process, so the thermal head exhibits excellent characteristics in terms of ON/OFF time constants and print quality during printing. You will get the head.

[Brief explanation of the drawing]

The figure shows a cross-sectional view of a typical configuration of a thermal head. 191. Alumina substrate, 333. common electrode, 4. ,,individual electrode,5. , , heating resistor, 8. ,, wear-resistant layer.

Claims (6)

[Claims] (1) A resistor characterized by containing a metal silicide obtained by a decomposition reaction using an organic compound of a metal as a starting material. (2) The resistor according to claim 1, wherein the metal organic compound mainly consists of at least one organometallic compound of tantalum, titanium, tungsten, molybdenum, and niobium and an organometallic compound of silicon. 3. The resistor according to claim 1, wherein at least one organic compound selected from the group consisting of rhodium, boron, bismuth, vanadium, lead, and antimony is added as a film-forming aid to the metal organic compound. (4) A claim characterized in that the organometallic compound is a single substance or a mixture of a salt of a lower fatty acid having up to 20 carbon atoms, an alkoxide, a mercaptide, a polycyclic organometallic compound, and other resinates and rhosinates. The resistor according to item 2 or 3. (5) After coating the ink containing an organometallic compound on the substrate, the oxygen concentration is 1000 ppm or less, 10 ppm
The method for manufacturing a resistor according to claim 1, characterized in that the firing is performed in the above inert atmosphere. (6) In a thick film type thermal head in which a heating resistor and a group of electrodes for energizing the resistor are provided on a substrate, and a wear-resistant layer is formed to partially cover the resistor and the electrode group. . A thermal head characterized in that the resistor according to claim 1 is used as the heating resistor.