JP2800268B2 - Voltage-dependent nonlinear resistor porcelain composition and method for manufacturing varistor - Google Patents

Description

The present invention relates to an electric device, an abnormal high voltage generated in an electronic device,
The present invention relates to a voltage-dependent nonlinear resistor porcelain composition having capacitor characteristics and varistor characteristics for protecting semiconductors and circuits of equipment from noise, static electricity, and the like, and a method for manufacturing a varistor.

2. Description of the Related Art Conventionally, SiC varistors having a voltage-dependent nonlinear resistance characteristic for absorbing abnormally high voltage, eliminating noise, eliminating sparks, and preventing static electricity in various electric and electronic devices, and ZnO.
System varistors are used. The voltage-current characteristics of such a varistor can be approximately expressed by the following equation.

I = (V / C) ^α where I is current, V is voltage, C is a varistor-specific constant, and α is voltage-current nonlinear exponent.

Α of the SiC varistor is about 2 to 7, and α of the ZnO varistor.
There are as many as 50. Such varistors have excellent performance in absorbing relatively high voltages, but because of their low dielectric constant and small inherent capacitance, they are almost incapable of absorbing relatively low voltages below the varistor voltage. No effect is exhibited, and the dielectric loss tan δ is as large as 5 to 10%.

On the other hand, a semiconductor capacitor having an apparent dielectric constant of about 5 × 10 ⁴ and a tan δ of about 1% is used for removing these low-voltage noises and the like. However, when a voltage or current exceeding a certain limit is applied to such a semiconductor capacitor due to a surge or the like, the capacitance is reduced or destroyed, so that the function as a capacitor is not achieved.

Therefore, recently, a device having SrTiO ₃ as a main component and having both a varistor characteristic and a capacitor characteristic has been developed, and is used for protecting semiconductor elements such as ICN and LSI in electronic devices such as computers.

Problems to be Solved by the Invention An element having both the functions of a varistor and a capacitor containing SrTiO ₃ as a main component as described above has a dielectric constant as large as about 10 times as large as that of a ZnO-based varistor, but has a small α and surge resistance, When the varistor voltage is lowered, the characteristics and the deterioration are liable to occur.

Therefore, an object of the present invention is to provide a voltage-dependent nonlinear resistor ceramic composition having a large dielectric constant, a low varistor voltage, a large α and a large surge withstand voltage, and a method for manufacturing a varistor.

Means for Solving the Problems In order to solve the above problems, the present invention provides Sr _1-x Ca _x
TiO ₃ (0.001 ≦ X ≦ 0.300) (hereinafter referred to as “first component”)
_{0.000~99.998mol%, Nb 2 O 5,} Ta 2 O 5, WO 3, Dy 2 O 3, Y 2 O 3, La 2 O
₃ , at least one of CeO ₂ , Sm ₂ O ₃ , Pr ₆ O ₁₁ , and Nd ₂ O ₃ (hereinafter, referred to as a second component) is 0.001 to 5.000 mol%, Al ₂ O ₃ ,
Sb ₂ O ₃ , BaO, BeO, PbO, B ₂ O ₃ , Cr ₂ O ₃ , Fe ₂ O ₃ , CdO, K ₂ O, CaO, Co ₂
O ₃ , CuO, Cu ₂ O, Li ₂ O, LiF, MgO, MnO ₂ , MoO ₃ , Na ₂ O, NaF, NiO, Rh
₂ O ₃ , SeO ₂ , Ag ₂ O, SiO ₂ , SiC, SrO, Tl ₂ O ₃ , ThO ₂ , TiO ₂ , V ₂ O ₅ , Bi
100 parts by weight of a main component containing 0.001 to 5.000 mol% of at least one or more of ₂ O ₃ , ZnO, ZrO ₂ , and SnO ₂ (hereinafter, referred to as a third component), and 60.000 to 32.500 mol% of BaTiO ₃ , SiO ₂ 40.
An additive (hereinafter referred to as a fourth component) obtained by calcining a mixture consisting of 000 to 67.500 mol% at 1200 to 1300 ° C. or higher.
An object of the present invention is to solve the problem by obtaining a voltage-dependent nonlinear resistor porcelain composition of 000 parts by weight.

Further, a method for manufacturing a varistor in which the composition is fired at 1100 ° C. or higher, or after firing the composition at 1100 ° C. or higher, firing at 1200 ° C. or higher in a reducing atmosphere, and then 900 to 900 ° C. in an oxidizing atmosphere. It proposes a method for manufacturing a varistor that is fired at 1300 ° C.

Action In the above invention, the first component is a main component, and Sr
By substituting a part of Sr of TiO ₃ with Ca, the high-resistance layer formed at the grain boundary becomes strong against surge. The second component is a metal oxide mainly promoting the conversion of the first component into a semiconductor.
The third component contributes to the improvement of the dielectric constant, α, and the surge withstand amount, and the fourth component is effective for lowering the varistor voltage and improving the dielectric constant. In particular, the fourth component has a melting point
Since it is relatively low at 1230 to 1250 ° C., it becomes a liquid phase when fired at a temperature around the melting point, and promotes the reaction of other components and the growth of particles. Therefore, the third component is easily segregated in the grain boundary portion, the grain boundary is easily increased, and the varistor function and the capacitor function are improved. Also,
Since the grain growth is promoted, the varistor voltage is lowered, and the uniformity of the grain size is improved, so that the stability of the characteristics is improved, and in particular, the surge withstand capability is improved.

Examples Hereinafter, the present invention will be described specifically with reference to examples.

First, BaTiO ₃ and SiO ₂ are weighed at various composition ratios as shown in Table 1 below, and mixed for 20 hours by a ball mill or the like. Next, after drying, firing is performed at various temperatures as shown in Table 1 below, and the powder is again ground by a ball mill or the like for 20 hours, and then dried to obtain a fourth component. Next, the first component, the second component, the third component, and the fourth component are weighed so as to have the composition ratios shown in Table 1 below, mixed with a ball mill or the like for 24 hours, dried, and dried with polyvinyl alcohol or the like. After adding 10 wt% of an organic binder and granulating, it is molded into a 10φ × 1 ^t (mm) disc at a pressing pressure of 1 (t / cm ² ),
Hr firing and debinding. Next, as shown in Table 1, 4Hr firing (first firing) at various temperatures was performed, and then 4Hr firing was performed at various temperatures in a reducing atmosphere, for example, N ₂ : H ₂ = 9: 1 gas. Firing (second firing). Thereafter, 3Hr firing (third firing) is performed in an oxidizing atmosphere while changing the temperature variously.

A conductive paste such as Ag is applied by screen printing or the like so as to leave an outer periphery on both planes of the sintered body 1 shown in FIGS. 1 and 2 thus obtained, and is baked at 600 ° C. for 5 minutes. Form a few. Next, lead wires are attached with solder or the like, and a resin such as epoxy is coated. The characteristics of the device thus obtained are shown in Table 2 below.

The apparent permittivity is calculated from the capacitance at 1 KHz. Α is 1 / Log (V ₁₀ mA / V ₁ mA) (However, V ₁ mA and V ₁₀ mA are 1 mA and 10 mA. This is the voltage applied to both ends of the device when a current is applied.) The surge withstand capability is evaluated based on the maximum pulse current value when the rate of change of V ₁ mA after application of the pulse current is within ± 10%.

Further, the range of X of the first component, Sr _1-x Ca _x TiO ₃ , is defined as follows: when X is smaller than 0.001, no effect is exhibited, and when X exceeds 0.300, lattice defects are less likely to occur, so that semiconductors are not used. Is not promoted, and Ca precipitates as a single phase at the grain boundary, resulting in a non-uniform structure and an excessively high V ₁ mA, deteriorating the characteristics. Further, if the second component is less than 0.001 mol%, no effect is exhibited, and if it exceeds 5.000 mol%, the segregation at the grain boundaries is suppressed, the increase in the resistance of the grain boundaries is suppressed, and the second phase is formed at the grain boundaries. It will deteriorate. If the content of the third component is less than 0.001 mol%, no effect is exhibited. If the content exceeds 5.000 mol%, the second phase is segregated at the grain boundary to form a second phase, so that the characteristics are deteriorated.
And the fourth component is in the phase diagram of the BaTiO ₃ and SiO ₂ component system.
BaTiO ₃ 60.000-32.500mol%, SiO ₂ 400.000-67.500mol%
Are in the region having the lowest melting point, and outside the range, the melting point is high. When the amount of the fourth component is less than 0.001 part by weight, no effect is exhibited.
If the amount exceeds 000 parts by weight, the resistance of the grain boundary increases, but the width of the grain boundary increases, so that the capacitance decreases and V ₁ mA increases, which is weak against surge. The reason why the firing temperature of the fourth component is specified is that the temperature at which the low-melting fourth component is synthesized is 1200 ° C. or higher. And the reason for defining the temperature of the first firing is that the melting point of the fourth component is
Since the temperature is 1230 to 1250 ° C, when sintering at a temperature of 1100 ° C or more, the fourth component is in a state close to a liquid phase and sintering is promoted. This is because there is no effect. The reason why the temperature for the second firing is specified is that if the temperature is lower than 1200 ° C., the sintered body after the first firing is not sufficiently reduced, and both the varistor characteristics and the capacitor characteristics deteriorate. Furthermore, the temperature of the third firing was specified by 900
If the temperature is lower than ℃, the resistance of the grain boundaries cannot be sufficiently increased, so that V ₁ mA
Is too low, and the varistor characteristics deteriorate.
If the temperature exceeds 00 ° C., the capacitance becomes too small and the capacitor characteristics deteriorate. It was also confirmed that the same effect was obtained regardless of whether the atmosphere for the first firing was an oxidizing atmosphere or a reducing atmosphere.

In addition, as the second component, two or more kinds may be used in combination in an addition amount within the above range. Also, the third
As components, Sb ₂ O ₃ , Ba in addition to the components listed in the above Examples
O, BeO, B ₂ O ₃ , CaO, LiF, Na ₂ O, NaF, Rh ₂ O ₃ , SiO ₂ , SrO, ThO ₂ , Ti
O ₂ , V ₂ O ₅ , Bi ₂ O ₃ , ZnO, SnO ₂ can be used, and the second
As in the case of the components, two or more types may be combined and used in an addition amount within the above-mentioned range. Furthermore, although only a part of the combination of these additives is shown in the above examples, it was confirmed that the same effect can be obtained with other combinations.

Effects of the Invention As described above, according to the present invention, the particle diameter is large, the varistor voltage is low, the dielectric constants ε and α are large,
Since the variation in the particle diameter is small, the surge current flows uniformly through the element, and the grain boundary is effectively increased in resistance by Ca, so that the effect of increasing the surge resistance is obtained.

[Brief description of the drawings]

FIG. 1 is a top view showing the device according to the present invention, and FIG. 2 is a cross-sectional view showing the device according to the present invention. 1 ... Sintered body, 2,3 ... Electrode.

Claims (3)

(57) [Claims] (1) Sr _1-x Ca _x TiO ₃ (0.001 ≦ X ≦ 0.300) is converted to 90.0%
_{00~99.998mol%, Nb 2 O 5,} Ta 2 O 5, WO 3, Dy 2 O 3, Y 2 O 3, La 2 O 3, C
eO ₂ , Sm ₂ O ₃ , Pr ₆ O ₁₁ , Nd ₂ O ₃
0.001 to 5.000 mol%, Al ₂ O ₃ , Sb ₂ O ₃ , BaO, BeO, PbO, B ₂ O ₃ , Cr ₂
O ₃ , Fe ₂ O ₃ , CdO, K ₂ O, CaO, Co ₂ O ₃ , CuO, Cu ₂ O, Li ₂ O, LiF, MgO, M
nO ₂ , MoO ₃ , Na ₂ O, NaF, NiO, Rh ₂ O ₃ , SeO ₂ , Ag ₂ O, SiO ₂ , SiC, Sr
O, Tl ₂ O ₃ , ThO ₂ , TiO ₂ , V ₂ O ₅ , Bi ₂ O ₃ , ZnO, ZrO ₂ , SnO ₂ 100% by weight of a main component containing 0.001 to 5.000 mol% of at least one kind or more. Part and BaTiO ₃ 60.000-32.500mol%, SiO ₂ 4
A voltage-dependent nonlinear resistor porcelain composition comprising 0.001 to 10.000 parts by weight of an additive obtained by firing a mixture of 0.000 to 67.500 mol% at 1200 ° C. or higher. 2. The method according to claim 1, wherein Sr _1-x Ca _x TiO ₃ (0.001 ≦ X ≦ 0.300) is converted to 90.0%.
_{00~99.998mol%, Nb 2 O 5,} Ta 2 O 5, WO 3, Dy 2 O 3, Y 2 O 3, La 2 O 3, C
eO ₂ , Sm ₂ O ₃ , Pr ₆ O ₁₁ , Nd ₂ O ₃
0.001 to 5.000 mol%, Al ₂ O ₃ , Sb ₂ O ₃ , BaO, BeO, PbO, B ₂ O ₃ , Cr ₂
O ₃ , Fe ₂ O ₃ , CdO, K ₂ O, CaO, Co ₂ O ₃ , CuO, Cu ₂ O, Li ₂ O, LiF, MgO, M
nO ₂ , MoO ₃ , Na ₂ O, NaF, NiO, Rh ₂ O ₃ , SeO ₂ , Ag ₂ O, SiO ₂ , SiC, Sr
O, Tl ₂ O ₃ , ThO ₂ , TiO ₂ , V ₂ O ₅ , Bi ₂ O ₃ , ZnO, ZrO ₂ , SnO ₂ 100% by weight of a main component containing 0.001 to 5.000 mol% of at least one kind or more. Part and BaTiO ₃ 60.000-32.500mol%, SiO ₂ 4
A method for producing a varistor, characterized in that a composition comprising 0.001 to 10.000 parts by weight of an additive obtained by firing a mixture of 0.000 to 67.500 mol% at 1200 ° C or higher is fired at 1100 ° C or higher. (3) Sr _1-x Ca _x TiO ₃ (0.001 ≦ X ≦ 0.300) is converted to 90.0%.
_{00~99.998mol%, Nb 2 O 5,} Ta 2 O 5, WO 3, Dy 2 O 3, Y 2 O 3, La 2 O 3, C
eO ₂ , Sm ₂ O ₃ , Pr ₆ O ₁₁ , Nd ₂ O ₃
0.001 to 5.000 mol%, Al ₂ O ₃ , Sb ₂ O ₃ , BaO, BeO, PbO, B ₂ O ₃ , Cr ₂
O ₃ , Fe ₂ O ₃ , CdO, K ₂ O, CaO, Co ₂ O ₃ , CuO, Cu ₂ O, Li ₂ O, LiF, MgO, M
nO ₂ , MoO ₃ , Na ₂ O, NaF, NiO, Rh ₂ O ₃ , SeO ₂ , Ag ₂ O, SiO ₂ , SiC, Sr
O, Tl ₂ O ₃ , ThO ₂ , TiO ₂ , V ₂ O ₅ , Bi ₂ O ₃ , ZnO, ZrO ₂ , SnO ₂ 100% by weight of a main component containing 0.001 to 5.000 mol% of at least one kind or more. Part and BaTiO ₃ 60.000-32.500mol%, SiO ₂ 4
After baking a composition consisting of 0.001 to 10.000 parts by weight of an additive obtained by baking a mixture consisting of 0.000 to 67.500 mol% at 1200 ° C. or more at 1100 ° C. or more, baking at 1200 ° C. or more in a reducing atmosphere, A method for producing a varistor, characterized in that the varistor is fired at 900 to 1300 ° C. in an oxidizing atmosphere.