JPH0558244B2 - - Google Patents

Description

[Detailed Description of the Invention] Industrial Application Field The present invention relates to a method for manufacturing a thick-film positive temperature coefficient semiconductor element that does not require a glass frit, and is a surface heating element used for heat insulation and heating of equipment. be.

Conventional structure and problems Elements made of BaTiO ₃ -based semiconductors have switching characteristics in which the resistance value increases rapidly above a certain temperature and self-heating characteristics after switching, and have fast temperature rise characteristics and self-temperature control functions. It is widely used because it does not require an external control circuit.

Conventional positive temperature coefficient thermistor heating elements have been obtained by press-molding BaTiO ₃ semiconductor powder and then firing it, but it is said to be difficult to obtain a practical thick film positive temperature coefficient thermistor heating element. Ta.

Conventionally, the following methods are known for processing BaTiO ₃ -based semiconductors into a film.

After being formed into a disk shape, it is fired and polished into thin pieces.

A thin film is formed on the substrate by vacuum evaporation.

Conductive additives and glass frit are added to BaTiO ₃ -based semiconductor powder to form a paste, which is then screen printed onto a substrate and then fired.

However, in the above method, it is extremely difficult to polish the BaTiO ₃ -based semiconductor into a film because the crystal grain size of the BaTiO 3 -based semiconductor is large and brittle. Furthermore, the above method is cumbersome to operate, and it is difficult to obtain a large amount of power suitable for the heating element. Furthermore, the above-mentioned method tends to increase sheet resistance and is difficult to control, is not suitable for heating elements, and requires preparing and firing the glass frit in advance, which is troublesome and depends on the material of the glass frit. teeth
Deteriorates the switching characteristics and self-heating characteristics of BaTiO _3- diameter semiconductors. Adding glass frit makes it vulnerable to thermal shock due to the difference in heat resistance and coefficient of thermal expansion between BaTiO ₃ -based semiconductors and glass frit, which impedes heat conduction. Furthermore, it is difficult to uniformly mix the conductive additive and the glass frit, which is one of the causes of variations in properties.

Purpose of the Invention Therefore, the present invention solves the manufacturing complexity that was a drawback of the prior art, and achieves excellent thermal shock resistance, thermal conductivity, and uniform characteristics by forming a thick film without using glass frit. It is an object of the present invention to provide a method for easily manufacturing a thick film type positive characteristic semiconductor element having the following characteristics.

Structure of the Invention The method for manufacturing a thick film type positive characteristic semiconductor element of the present invention includes adding Cr ₃ Si, Cr ₃ Si ₂ , Cr ₅ to BaTiO ₃ based semiconductor powder.
Add 1.0 to 60.0% by weight of at least one type of powder among Si ₃ , CrSi, and CrSi ₂ and make a paste-like mixture, apply it on a substrate to form a thick film, and then sinter it to create a thick film with positive characteristics. The purpose is to obtain semiconductor devices.

In the conventional method of using conductive additives and glass frits, conductive additives are required to electrically connect BaTiO ₃ -based semiconductor powders to each other, and glass frits are required to physically connect BaTiO ₃ -based powders to each other. It was hot.

However, according to the present invention, Cr ₃ is used as a conductive additive and a glass frit.
It is characterized in that at least one of Si, Cr ₃ Si ₂ , Cr ₅ Si ₃ , CrSi, and CrSi ₂ is used.

These Cr ₃ Si, Cr ₃ Si ₂ , Cr ₅ Si ₃ , CrSi, CrSi ₂
is a conductor at room temperature, and when the temperature reaches 1000 to 1100°C or higher, a portion of it decomposes and SiO ₂ is precipitated on the particle surface, but the inside of the particle remains intact and decomposition is prevented by the SiO ₂ film on the surface. Therefore, BaTiO ₃ -based semiconductor powder and Cr ₃ Si, Cr ₃ Si ₂ , Cr ₅ Si ₃ , CrSi,
When CrSi ₂ powder is mixed and fired, Cr ₃ Si, Cr ₃
SiO ₂ precipitated on the surface of Si 2 , Cr ₅ Si _{3 ,} CrSi, CrSi ₂
plays the same role as glass frit and the inside of the particle plays the role of a conductive additive, so Cr ₃ Si, Cr ₃ Si ₂ ,
By simply adding Cr ₅ Si ₃ , CrSi, and CrSi _{2 ,} a thick film type positive characteristic semiconductor device that does not require glass frit can be obtained.

Furthermore, by adding a conductive metal, the thermal conductivity becomes better than that of a glass top frit which has poor thermal conductivity, and the thermal shock resistance is also improved.

DESCRIPTION OF EMBODIMENTS Examples of the present invention will be specifically explained below with reference to FIG.

Example 1 1.0 mol % of Nb ₂ O ₅ is added to BaTiO ₃ and fired at 1300°C, followed by pulverization to obtain BaTiO ₃ -based semiconductor powder. Based on the total weight of the BaTiO ₃ -based semiconductor powder
4.0% by weight of Cr ₃ Si ₂ powder is added and mixed uniformly, and α-terpineol is further added to form paste mixture 1.

On the other hand, on a substrate 2 made of Al ₂ O ₃ etc., a pair of electrodes 3 made of a conductive material such as Ag,
4, and apply the paste mixture 1 by screen printing or the like so that a portion of the electrodes 3 and 4 remain on the electrodes 3 and 4, and then heat the mixture from room temperature to
The temperature was raised to 1350°C at a heating rate of 10°C/min, held for 1 hour, and then allowed to cool in the furnace. In this way, a thick film type positive characteristic semiconductor device was obtained.

Example 2 In the same manner as in Example 1, 3.0 mol% of BaTiO ₃ was added.
After adding Nb ₂ O ₅ and firing at 1250℃, it was crushed.
Obtain BaTiO ₃ based semiconductor powder. CrSi powder in an amount of 19.5% by weight based on the total weight is added to the BaTiO ₃ -based semiconductor powder and mixed uniformly, and α-terpineol is further added to form paste mixture 1. Next, as in Example 1, the electrodes 3 and 4 are provided on the substrate 2 in advance, and the paste mixture 1 is applied by screen printing or the like so that a portion of the electrodes 3 and 4 remains. After increasing the temperature from 10℃/min to 1300℃ and holding it for 30 minutes,
Allow to cool in the furnace. In this way, a thick film semiconductor device was obtained.

The sheet resistance at room temperature of the thick film semiconductor device thus obtained was 5.1KΩ/cm ² in Example 1 and 2.8KΩ/cm ² in Example 2, and the relationship between temperature and resistance value for each is as follows: It was as shown in Figure 2. In FIG. 2, A shows the characteristics of the device obtained in Example 1, and B shows the characteristics in Example 2.

Here, instead of Cr ₃ Si and CrSi, Cr ₃ Si ₂ , Cr ₅ Si ₃ ,
Even when CrSi ₂ was used, the same effect as in the above example could be obtained, and there was no problem even if they were added at the same time.

Effects of the Invention As described above, according to the production method of the present invention, Cr ₃
Powders such as Si ₂ and CrSi play both the roles of conventional conductive additives and glass frits, and are sufficiently effective for electrical and physical connections, allowing thick film positive temperature semiconductor devices to be fabricated without glass frits. This will be obtained.

In addition, instead of glass frit, which has poor thermal conductivity, Cr ₃ Si ₂ , which is a conductive metal with good thermal conductivity, is used.
By using CrSi or the like, heat conduction is improved and thermal shock resistance is also improved. Furthermore, since it can be manufactured by screen printing or the like, the work is easy and mass production is possible.

In the present invention, any BaTiO ₃ -based semiconductor powder may be used as long as it is made into a semiconductor by adding various additives to BaTiO ₃ . Also, Cr ₃ Si ₂ ,
The amount of powder such as CrSi added is 1 to 1 to the total weight.
The reason for specifying 60% by weight is that if it is less than 1% by weight, the sheet resistance becomes too large and is not suitable for a heating element.
It is also impossible to physically fix _BaTiO3 powders together;
If it exceeds 60% by weight, the area resistance becomes small,
This is because the self-control characteristic (PTC characteristic) becomes small, making it unsuitable for a heating element. Furthermore, although an organic solvent (α-terpineol in the example) was used to make the BaTiO ₃ -based semiconductor powder and the Cr ₃ Si ₂ and CrSi powders into a paste, any solvent may be used as long as it can be made into a paste.

As described above, according to the present invention, it is possible to easily manufacture a thick film type positive characteristic semiconductor device that does not require a glass frit, and its practical effects are great.

[Brief explanation of the drawing]

FIG. 1 is a partially cutaway perspective view showing a thick film positive temperature coefficient semiconductor device obtained by the method of the present invention, and FIG. 2 is a diagram showing the relationship between temperature and resistance value of the device according to an embodiment of the present invention. 1...Paste mixture, 2...Substrate, 3, 4
……electrode.

Claims (1)

[Claims] 1 Cr ₃ Si, Cr ₃ Si ₂ , Cr ₅ in BaTiO ₃ based semiconductor powder
A thick film characterized by adding 1.0 to 60.0% by weight of at least one type of powder among Si ₃ , CrSi, and CrSi ₂ and making a paste-like mixture and coating it on a substrate to form a thick film, followed by firing. A method for manufacturing a type positive characteristic semiconductor device.