JP2001006904A - Voltage nonlinear resistor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a voltage nonlinear resistor wherein V1 mA/t is high and at least 400 V/mm, uniformity of voltage distribution in an element is excellent, and surge endurance is large. SOLUTION: In this resistor, ZnO is made as main component, and, as atomic percentage of each metal element, at least one kind of rare earth element of 0.08-5.0 atm.% as the total amount, Co of 0.1-10.0 atm.%, Ca of 0.01-1.0 atm.%, at least one kind out of K, Cs, Rb of 0.01-1.0 atm.% as the total amount, Cr of 0.01-1.0 atm.%, at least one kind out of Al, Ga, In of 1×10-4-5×10-2 atm.% as the total amount, Bi of 0.7-1.1 atm.%, and material wherein Sb is added in a range of Sb/Bi=0.8-1.2 as an adding ratio to Bi are added as subcomponent. For another way, Si and/or Mn of 0.1-1.0 atm.% are added further to material wherein B of 5×10-4-1×10-1 atm.% is added as atomic percentage of metal element to the above subcomponent. Then baking is performed. The figure shows relations of loadings of Si and Mn to surge endurance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a voltage non-linear resistor,
More specifically, the present invention relates to a voltage non-linear resistor mainly composed of zinc oxide (ZnO 2) used as an overvoltage protection element.

[0002]

2. Description of the Related Art A voltage non-linear resistor mainly composed of zinc oxide (ZnO) has characteristics such as a low limiting voltage and a large voltage non-linear index. Therefore, it is widely used as an arrester element for the purpose of protection against overvoltage of a device constituted by a device having a small overcurrent capability such as a semiconductor device or protection of a power device.

[0003] In this connection, zinc oxide (ZnO) is a main component, and at least one rare earth element as a subcomponent is 0.08 to 5.0 atomic% in total, and cobalt (Co) is 0.1 to 0.1 atomic%.
10.0 at%, calcium (Ca) 0.01-5.0 at%, potassium (K), cesium (Cs), rubidium (Rb) at least one of 0.01-1.0 at% in total, chromium (Cr) 0.01-1.0 Atomic%, at least one of aluminum (Al), gallium (Ga), and indium (In) in a total amount of 1 × 10 ^{−4 to} 5 × 10 ⁻² atomic%, and bismuth (Bi) of 0.1%.
An excellent voltage non-linear resistor can be manufactured by adding 7 to 1.1 atomic% and antimony (Sb) in an addition ratio of Bi to Sb / Bi = 0.8 to 1.2 and firing. Further, boron (B) is further added to the above composition in an amount of 5 × 10 ^-4 to 1 × 10 ^-1 atomic%.
It is also proposed in Japanese Patent Application No. 10-66760 that an excellent voltage non-linear resistor can be produced by adding and firing.

[0004] The addition of a small amount of B has the effect of changing the grain size distribution of the ZnO resistor after firing, reducing the grain size at the periphery, smoothing the stress distribution, and increasing the surge withstand capability of the ZnO resistor.

[0005]

However, such a voltage non-linear resistor also has the following problems. The voltage non-linear resistor is fired at a temperature of about 1100 to 1400 ° C. for several hours. Usually, V1 mA / t is set to a desired value by using a simple method of adjusting the firing temperature. V1mA / t
Is V1mA per unit thickness, and V1mA is the resistance current 1m
This is the voltage when A flows. V1mA / t is the firing temperature
When the temperature is lowered by 1 ° C., the voltage increases by 1 to 2 V / mm, so that the desired value can be easily set.

[0006] From this, it is difficult to operate at a high voltage.
In order to obtain a non-linear resistor having a large voltage of V1mA, it is generally considered that the firing temperature is lowered, the grain growth of ZnO is suppressed, and V1mA / t is increased. Forming a molded body using the raw material powder having the composition described in Japanese Patent Application No. 10-66760,
The voltage non-linear resistor was fired, and the characteristics of the voltage non-linear resistor were examined. Figure 7 shows V1mA / t and 2 ms of a conventional voltage nonlinear resistor.
It is a graph which shows the relationship with surge withstand. As can be seen from the graph, the voltage non-linear resistor fired at low temperature has V1 mA
/ t can be increased to 400 V / mm, but the surge withstand capability is about 200 J / cm ³ , and V1mA / t is about 1/3 of about 600 J / cm ³ obtained with the 200 V / mm element. , And it was not possible to obtain an element having excellent surge withstand capability.

This is considered to be due to the fact that when fired at a low temperature, the sintering of zinc oxide did not proceed sufficiently, and the diffusion of the added element became insufficient, and the particle size distribution in the device became non-uniform. As a result, when V1mA / t is as high as 400 V / mm, the surge withstand capability decreases even if the composition has excellent surge withstand capability when V1mA / t is 200 V / mm. In other words, it is considered that the sintering of zinc oxide does not proceed unless firing at a certain high temperature, the distribution of the added element in the device becomes nonuniform, and the characteristics of the device vary within the device, thus deteriorating the characteristics. Therefore, in order to obtain a device with a large V1mA / t and excellent surge withstand capability, V1
firing at low temperature to increase mA / t, particle size distribution,
Inconsistent baking conditions such as baking at a certain high temperature in order to make the characteristics in the device uniform are required. For this reason, in the prior art, it was difficult to obtain an element having an excellent surge resistance with an element having a large V1 mA / t.

The present invention has been made in view of the above points, and has a high V1mA / t of 400 V / mm or more, a uniform voltage distribution in the device, and a large voltage non-linear resistor having a large surge withstand capability. Is to provide.

[0009]

[MEANS FOR SOLVING THE PROBLEMS] To achieve the object,
ZnO as the main component, and as a sub-component, at least one rare earth element in total in the atomic ratio of metal elements
0.08-5.0 atomic%, Co 0.1-10.0 atomic%, Ca 0.01-
1.0 atomic%, at least one of K, Cs, and Rb in total
0.01-1.0 atomic%, Cr 0.01-1.0 atomic%, Al, Ga, In
At least one of them is 1 × 10 ^{-4 to} 5 × 10 ^-2 atoms in total
%, Bi is 0.7 to 1.1 atomic%, and Sb is Sb in an addition ratio with Bi.
/Bi=0.8 to 1.2, and further add Mn to 0.1 to 1.0
Atomic% is added and fired. Further, B is further added to the subcomponent in an atomic ratio of a metal element of 5 × 10 ⁻⁴ to 1 × 10
^It is better to add ^-1 atomic% and bake.

[0010] ZnO as a main component, and as a sub-component,
In each case, the atomic ratio of the metal elements is 0.08 to 5.0 atomic% in total of at least one rare earth element, and 0.1 to 10.0 atomic% of Co.
, Ca is 0.01 to 1.0 atomic%, K, Cs, and Rb are at least one of 0.01 to 1.0 atomic% in total, and Cr is 0.01 to 1.0 atomic%.
%, At least one of Al, Ga, and In in a total amount of 1 × 10 ^-4
~ 5 × 10 ^-2 atomic%, Bi 0.7 to 1.1 atomic% and Sb Bi
Sb / Bi = 0.8 to 1.2 in the addition ratio of
i is added in the range of 0.1 to 1.0 atomic% and fired. Further, it is preferable that B is added to the subcomponent in an atomic ratio of 5 × 10 ⁻⁴ to 1 × 10 ⁻¹ atomic% in terms of a metal element, followed by firing.

[0011] ZnO as a main component, and as a sub-component,
In each case, the atomic ratio of the metal elements is 0.08 to 5.0 atomic% in total of at least one rare earth element, and 0.1 to 10.0 atomic% of Co.
, Ca is 0.01 to 1.0 atomic%, K, Cs, and Rb are at least one of 0.01 to 1.0 atomic% in total, and Cr is 0.01 to 1.0 atomic%.
%, At least one of Al, Ga, and In in a total amount of 1 × 10 ^-4
~ 5 × 10 ^-2 atomic%, Bi 0.7 to 1.1 atomic% and Sb Bi
Sb / Bi = 0.8 to 1.2 in the addition ratio of
i is added at 0.1 to 1.0 at% and Mn is added at 0.1 to 1.0 at%, followed by firing. Further, it is preferable that B is added to the subcomponent in an atomic ratio of 5 × 10 ⁻⁴ to 1 × 10 ⁻¹ atomic% in terms of a metal element, followed by firing. The rare earth element is preferably Pr.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION A voltage non-linear resistor having zinc oxide as a main component and the above-mentioned subcomponent (metal element) added thereto includes zinc oxide powder (ZnO 2), oxide powder of the above metal element and It is manufactured by mixing a binder, pressing and sintering. In addition to metal oxides, compounds that can become oxides during the firing process, such as carbonates, hydroxides, fluorides and their solutions, can be used as the additional components. Can be turned into an oxide. Example 1 In a zinc oxide (ZnO 2) powder, praseodymium oxide (Pr ₆ O ₁₁ ) was 0.5 atom%, cobalt oxide (Co ₃ O ₄ ) was 5.0 atom%, and calcium carbonate (CaCO ₂ ) was an atomic ratio of all metal elements.
₃ ) 0.3 atom%, potassium carbonate (K ₂ CO ₃ ) 0.1 atom
%, Chromium oxide (Cr ₂ O ₃ ) 0.1 atomic%, aluminum oxide (Al ₂ O ₃ ) 0.005 atomic%, bismuth oxide (Bi
₂ O ₃ ) and antimony oxide (Sb ₂ O ₃ ) powder at 1.0 atomic%
After adding a binder to each of the compositions of Examples in which manganese oxide (MnO ₂ ) was added in the range of 0.1 atomic% to 0.1 atomic%, and then mixed well, the mixture was added to the mixture (the above is referred to as a basic composition). Press-formed into a disk shape of 1050-13
It was fired in the air at 00 ° C. for 2 hours to obtain a sintered body. For comparison, a sintered body was similarly obtained using the basic composition.

After polishing the obtained sintered body to a thickness of 1 mm,
As an element for measuring electrical characteristics (mainly surge withstand capability), electrodes with a diameter of 11 mm are provided on both end faces, and as an element for measuring voltage distribution, an electrode with a diameter of 11 mm is provided on one end face and on the other end face. 37 spot electrodes of 1 mm square were provided with a center electrode spacing of 2 mm. These electrodes were formed by baking Ag.

First, the surge resistance was measured as an electrical characteristic. Surge withstand was calculated from the maximum current value without penetrating and creeping breakdowns by flowing a 2ms-wide square wave current in 10A steps while increasing it. The calculation formula is as follows.

[0015]

[Equation 1] Surge tolerance [J / cm ³ ] = Maximum current [A] × V50A [V] ×
0.002 [s] / volume of element [cm ³ ] However, V50A has a surge withstand voltage, which is a voltage between electrodes when a current of 50 A flows, is about 200 J / cm ³ in a conventional element.

FIG. 1 is a graph showing the dependency of the surge resistance of the voltage nonlinear resistor according to the present invention on the amount of added Mn. For these samples, V1mA / t was adjusted to 350 to 400 V / m by adjusting the firing temperature.
set to m. From FIG. 1, it can be seen that those having a surge withstand capability of 600 J / cm ³ or more have a Mn addition amount in the range of 0.1 to 1.0 atomic%.

Next, a voltage (V10 μA) between the electrodes when a current of 10 μA was applied to each spot was measured, and a voltage distribution in the end face of the element was obtained. FIG. 2 shows that the amount of added Mn according to the present invention is
6 is a graph showing a voltage distribution in an end face of a voltage non-linear resistor element of 0.5 at%. FIG. 8 is a graph showing a voltage distribution in an end face of a conventional (composition) voltage nonlinear resistor element.
The voltage distribution shows the deviation from the average of V10μA of all spots as a percentage. As is clear from this, the in-plane voltage distribution of the voltage non-linear resistor according to the present invention has a substantially flat distribution, indicating that the voltage non-linear resistor has much better uniformity than the conventional voltage non-linear resistor. Example 2 B was further added to the composition of Example 1 above at 5 × 10 ^-4 to 1 × 10 ^-1.
Atomic% was added and baked to produce a voltage non-linear resistor as a prototype, and its electrical characteristics were evaluated. As a result, the uniformity of the in-plane voltage distribution was improved as compared with Example 1, and the surge withstand capability was accordingly reduced. Slightly improved. In addition, the difference-tolerance against impulse surge current of 8 / 20μs was improved by about 10%.

In Examples 1 and 2, only one example (basic composition) of the sub-components was shown, but cobalt (Co) was 0.1 to 10.0 at% and calcium (Ca) was 0.01 to 0.01%.
1.0 at%, potassium (K), cesium (Cs), rubidium (Rb) at least one of 0.01 to 1.0 at% in total, chromium (Cr) 0.01 to 1.0 at%, aluminum (Al), gallium (Ga) ), At least one of indium (In) is added in a total amount of 1 × 10 ^{−4 to} 5 × 10 ^{−2 at} %, bismuth (Bi) is added at 0.7 to 1.1 at%, and antimony (Sb) is added to bismuth (Bi). The same effect as in Examples 1 and 2 was confirmed by adding Sb / Bi in a ratio of 0.8 to 1.2 in a ratio and further adding manganese (Mn) in a range of 0.1 to 1.0 atomic% as a result of another experiment. Although only Pr is shown as a rare earth element, a rare earth element other than Pr may be used in the range of 0.08 to 5.0 atomic%. It should be noted that addition of a rare earth element, typically of Pr, has good high-limit voltage and steep-wave response in a large current range. In addition, it has features such as large capacitance due to large relative permittivity, simplification of the shield ring for voltage sharing correction and the need for a capacitor, etc., even if the above-mentioned new additives coexist. Is not lost. In addition, K may be Cs or Rb, or K, Cs, or Rb, and Al may be Ga, In, or Al, Ga, or In.
Separate experiments confirmed that the same effects as described above, which is the main feature of the present invention, can be obtained even in such a composition system. Example 3 Zinc oxide (ZnO 2) powder was mixed with praseodymium oxide (Pr ₆ O ₁₁ ).
0.5 at%, cobalt oxide (Co ₃ O ₄ ) at 5.0 at%,
0.3 at% of calcium carbonate (CaCO ₃ ), 0.1 at% of potassium carbonate (K ₂ CO ₃ ), 0.1 of chromium oxide (Cr ₂ O ₃ )
Atomic%, aluminum oxide (Al ₂ O ₃ ) 0.005 atomic%,
Bismuth oxide (Bi ₂ O ₃ ) and antimony oxide (Sb ₂ O ₃ ) were each added to 1.0 atomic% (basic composition) and silicon oxide (Si
O ₂ ) is added in an amount equivalent to 0.1 to 1.0 atomic%, a binder is added and mixed well, and then pressed into a disc having a diameter of 15.85 mm, V1mA / t is about 400 (V / mm) The sintering temperature was adjusted so that sintering was performed, and sintering was performed in air for 2 hours to obtain a sintered body. The obtained sintered body was formed into a device in the same manner as in Example 1, electrodes were attached, and the in-plane voltage distribution and surge withstand capability of the device were measured.

FIG. 3 is a graph showing the dependency of the surge resistance of the voltage nonlinear resistor according to the present invention on the amount of Si added. From Fig. 3, it is clear that the surge withstand capability is obtained when the Si addition amount is 0.1 to 1.0 atomic%.
It turns out that it becomes 550 [J / cm ³ ] or more. Also, the amount of Si added is 0.
The surge withstand capability of less than 1 at.% And more than 1.0 at.% Was about 300 J / cm ³ at the conventional level or at most.

FIG. 4 is a graph showing an in-plane voltage distribution of the voltage non-linear resistor element according to the present invention to which 0.5 atomic% of Si is added. It can be seen that the uniformity of the in-plane distribution is improved as compared with the conventional element (FIG. 8). Example 4 B was added to the composition of Example 3 above in an amount of 5 × 10 ^-4 to 1 × 10 ^-1.
Atomic% was added and baked to produce a voltage non-linear resistor as a prototype, and its electrical characteristics were evaluated. The surge withstand voltage was slightly improved compared to Example 3, and the uniformity of the in-plane voltage distribution was the same as in Example 3. Was confirmed.

In Examples 3 and 4, only one example (basic composition) of the sub-component composition was shown. However, cobalt (Co) was 0.1 to 10.0 atomic% and calcium (Ca) was 0.01 to 0.01 atomic%.
1.0 at%, potassium (K), cesium (Cs), rubidium (Rb) at least one of 0.01 to 1.0 at% in total, chromium (Cr) 0.01 to 1.0 at%, aluminum (Al), gallium (Ga) ), At least one of indium (In) is added in a total amount of 1 × 10 ^{−4 to} 5 × 10 ^{−2 at} %, bismuth (Bi) is added at 0.7 to 1.1 at%, and antimony (Sb) is added to bismuth (Bi). The same effect as in Examples 1 and 2 was confirmed by adding Sb / Bi in a ratio of 0.8 to 1.2 in a ratio and further adding manganese (Mn) in a range of 0.1 to 1.0 atomic% as a result of another experiment. Although only Pr is shown as a rare earth element, a rare earth element other than Pr may be used in the range of 0.08 to 5.0 atomic%. It should be noted that addition of a rare earth element, typically of Pr, has good high-limit voltage and steep-wave response in a large current range. In addition, it has features such as large capacitance due to large relative permittivity, simplification of the shield ring for voltage sharing correction and the need for a capacitor, etc., even if the above-mentioned new additives coexist. Is not lost. In addition, K may be Cs or Rb, or K, Cs, or Rb, and Al may be Ga, In, or Al, Ga, or In.
Separate experiments confirmed that the same effects as described above, which is the main feature of the present invention, can be obtained even in such a composition system. Example 5 Zinc oxide (ZnO 2) powder was mixed with praseodymium oxide (Pr ₆ O ₁₁ ).
0.5 at%, cobalt oxide (Co ₃ O ₄ ) at 5.0 at%,
0.3 at% of calcium carbonate (CaCO ₃ ), 0.1 at% of potassium carbonate (K ₂ CO ₃ ), 0.1 of chromium oxide (Cr ₂ O ₃ )
Atomic%, aluminum oxide (Al ₂ O ₃ ) 0.005 atomic%,
Bismuth oxide (Bi ₂ O ₃ ) and antimony oxide (Sb ₂ O ₃ ) powder were added at 1.0 atomic% to the basic composition, and silicon oxide (SiO ₂ ) and manganese oxide (MnO ₂ ) were added at 0.1% each.
After adding the binder and mixing well, the mixture was pressed into a disc with a diameter of 15.85 mm and fired in air at 1050-1300 ° C for 2 hours to obtain a sintered body. I got The obtained sintered body was formed into a device in the same manner as in Example 1, electrodes were attached, and the in-plane voltage distribution and surge withstand capability of the device were measured.

FIG. 5 is a graph showing the dependency of the surge withstand capacity of the voltage nonlinear resistor element of the embodiment according to the present invention on the addition amount of Si and Mn. In the sample of FIG. 5, V1 mA / t was set at 350 to 400 V / mm by adjusting the firing temperature. Surge resistance is, in the conventional device 200 J / cm ³ or so, also the Si
When Mn is added alone, it is about 600 to 650 J / cm ³ . On the other hand, from FIG. 5, it can be seen from FIGS. 5A and 5B that when the surge withstand capability is 650 J / cm ³ or more, which is larger than the case where Si and Mn are individually added (see Examples 1 and 3), the Si addition amount is 0.1 to 0.1%. 1.0 atomic% and the amount of Mn added is 0.1 to 1.0 atomic
It turns out that it is in the range of%.

FIG. 6 shows Si and Mn according to the present invention, respectively.
5 is a graph showing a voltage distribution in a direction of an end face of a voltage non-linear resistance element to which 0.5 atomic% is added. FIG. 6 shows that the in-plane voltage distribution of the voltage non-linear resistor according to the present invention has a substantially flat distribution, and that the voltage non-linear resistor has much better uniformity than the conventional voltage non-linear resistor (FIG. 8). I understand. Example 6 B was further added to the composition of Example 5 above at 5 × 10 ^-4 to 1 × 10 ^-1.
Atomic% was added and baked to produce a voltage non-linear resistor and its electrical characteristics were evaluated. The surge withstand voltage was slightly improved compared to Example 5, and the uniformity of the in-plane voltage distribution was the same as in Example 5. Was confirmed.

In Examples 5 and 6, only one example (basic composition) of the sub-components was shown, but 0.1 to 10.0 atomic% of cobalt (Co) and 0.01 to 10.0 atomic% of calcium (Ca) were used.
1.0 at%, potassium (K), cesium (Cs), rubidium (Rb) at least one of 0.01 to 1.0 at% in total, chromium (Cr) 0.01 to 1.0 at%, aluminum (Al), gallium (Ga) ), At least one of indium (In) is added in a total amount of 1 × 10 ^{−4 to} 5 × 10 ^{−2 at} %, bismuth (Bi) is added at 0.7 to 1.1 at%, and antimony (Sb) is added to bismuth (Bi). The same effect as in Examples 1 and 2 was confirmed by adding Sb / Bi in a ratio of 0.8 to 1.2 in a ratio and further adding manganese (Mn) in a range of 0.1 to 1.0 atomic% as a result of another experiment. Although only Pr is shown as a rare earth element, a rare earth element other than Pr may be used in the range of 0.08 to 5.0 atomic%. It should be noted that addition of a rare earth element, typically of Pr, has good high-limit voltage and steep-wave response in a large current range. In addition, it has features such as large capacitance due to large relative permittivity, simplification of the shield ring for voltage sharing correction and the need for a capacitor, etc., even if the above-mentioned new additives coexist. Is not lost. In addition, K may be Cs or Rb, or K, Cs, or Rb, and Al may be Ga, In, or Al, Ga, or In.
Separate experiments confirmed that the same effects as described above, which is the main feature of the present invention, can be obtained even in such a composition system.

[0025]

According to the present invention, ZnO is used as a main component, and as a sub-component, at least one rare earth element in a total amount of 0.08 to 5.0 at.
0.1 to 10.0 at.%, Ca 0.01 to 1.0 at.%, K, Cs, R
at least one of b is 0.01 to 1.0 atomic% in total, Cr
0.01 to 1.0 at%, at least one of Al, Ga, and In at a total amount of 1 × 10 ^{−4 to} 5 × 10 ^{−2 at} %, Bi at 0.7 to 1.1 at%, and Sb at an addition ratio of Bi to Sb. /Bi=0.8 to 1.2, or the above-mentioned sub-components further added with B in an atomic ratio of 5 × 10 ⁻⁴ to 1 × 10 ^-1 atomic%, and further added Si or / and / or Since Mn was added at 0.1 to 1.0 atomic% and calcined, the voltage nonlinear resistor was
V1mA / t was as high as 400V / mm, and the uniformity of the in-plane distribution was improved. In particular, the voltage non-linear resistor fired with simultaneous addition of Si and Mn has higher surge withstand characteristics and higher reliability than the case where each of Si and Mn is added alone.

[Brief description of the drawings]

FIG. 1 shows the surge withstand capability of a voltage nonlinear resistor according to the present invention.
Graph showing Mn addition amount dependency

FIG. 2 is a graph showing a voltage distribution in an end face of a voltage nonlinear resistor element having an addition amount of Mn of 0.5 at% according to the present invention.

FIG. 3 shows the surge withstand capability of the voltage non-linear resistor according to the present invention.
Graph showing dependency of Si addition amount

FIG. 4 is a graph showing an in-plane voltage distribution of a voltage non-linear resistance element to which 0.5 atomic% of Si is added according to the present invention.

FIG. 5 is a graph showing the dependency of the surge withstand capacity of the voltage non-linear resistor element according to the embodiment of the present invention on the addition amounts of Si and Mn.

FIG. 6 shows that each of Si and Mn according to the present invention is 0.5 atomic%.
4 is a graph showing the voltage distribution in the direction of the end face of the added voltage nonlinear resistor element;

FIG. 7 is a graph showing the relationship between V1 mA / t of a conventional voltage non-linear resistor and a surge tolerance of 2 ms.

FIG. 8 is a graph showing a voltage distribution in an end face of a conventional (composition) voltage nonlinear resistor element.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tokuhisa Nagata 1-1-1, Tanabe-Nitta, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Inside Fuji Electric Co., Ltd. (72) Inventor Akiki Tanaka 1, Tanabe-Nitta, Kawasaki-ku, Kawasaki-shi, Kanagawa No. 1 Inside Fuji Electric Co., Ltd. (72) Inventor Kazuo Mukai No. 1-1 Tanabe Nitta, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture F-term inside Fuji Electric Co., Ltd. 5E034 CA09 CB01 CC07 DA03 DE07

Claims (7)

[Claims] 1. Zinc oxide (ZnO 2) as a main component, and as sub-components, at least one rare earth element in a total amount of 0.08 to 5.0 at% and cobalt (Co) in an atomic ratio of a metal element. 0.1-10.0 atomic%, calcium (Ca) 0.01-
1.0 at%, potassium (K), cesium (Cs), rubidium (Rb) at least one of 0.01 to 1.0 at% in total, chromium (Cr) at 0.01 to 1.0 at%, aluminum (Al), gallium (Ga) ), At least one of indium (In) is added in a total amount of 1 × 10 ^{−4 to} 5 × 10 ⁻² atomic%, bismuth (Bi) is added in an amount of 0.7 to 1.1 atomic%, and antimony (Sb) is added to bismuth (Bi). A non-linear voltage resistor characterized by being added in a ratio of Sb / Bi = 0.8 to 1.2 in a ratio, and further added with 0.1 to 1.0 at% of manganese (Mn) and fired. 2. The method according to claim 1, wherein boron (B) is further added to said subcomponent in an atomic ratio of 5 × 10 ^-4 to 1 × 10 ^-1 atomic% of a metal element and fired. 2. The voltage non-linear resistor according to 1. 3. Zinc oxide (ZnO 2) as a main component, and as an auxiliary component, at least one rare earth element in a total amount of 0.08 to 5.0 at% and cobalt (Co) in an atomic ratio of a metal element. 0.1-10.0 atomic%, calcium (Ca) 0.01-
1.0 at%, potassium (K), cesium (Cs), rubidium (Rb) at least one of 0.01 to 1.0 at% in total, chromium (Cr) at 0.01 to 1.0 at%, aluminum (Al), gallium (Ga) ), At least one of indium (In) is added in a total amount of 1 × 10 ^{−4 to} 5 × 10 ⁻² atomic%, bismuth (Bi) is added in an amount of 0.7 to 1.1 atomic%, and antimony (Sb) is added to bismuth (Bi). A non-linear voltage resistor characterized in that Sb / Bi is added in a ratio of 0.8 to 1.2 in a ratio, and silicon (Si) is further added in a range of 0.1 to 1.0 at% and fired. 4. The method according to claim 3, wherein boron (B) is further added to said auxiliary component in an atomic ratio of 5 × 10 ^-4 to 1 × 10 ^-1 atomic% in a metal element, followed by firing. 2. The voltage non-linear resistor according to 1. 5. A zinc oxide (ZnO 2) as a main component, and as a sub-component, at least one rare earth element in a total amount of 0.08 to 5.0 at% and cobalt (Co) in an atomic ratio of a metal element. 0.1-10.0 atomic%, calcium (Ca) 0.01-
1.0 at%, potassium (K), cesium (Cs), rubidium (Rb) at least one of 0.01 to 1.0 at% in total, chromium (Cr) at 0.01 to 1.0 at%, aluminum (Al), gallium (Ga) ), At least one of indium (In) is added in a total amount of 1 × 10 ^{−4 to} 5 × 10 ⁻² atomic%, bismuth (Bi) is added in an amount of 0.7 to 1.1 atomic%, and antimony (Sb) is added to bismuth (Bi). A voltage non-voltage characterized by being added in a ratio of Sb / Bi = 0.8 to 1.2 in a ratio, and further adding 0.1 to 1.0 atomic% of silicon (Si) and 0.1 to 1.0 atomic% of manganese (Mn) and firing. Linear resistor. 6. The method according to claim 3, wherein boron (B) is further added to the subcomponent in an atomic ratio of 5 × 10 ^-4 to 1 × 10 ^-1 atomic% of a metal element, followed by firing. 2. The voltage non-linear resistor according to 1. 7. The voltage non-linear resistor according to claim 1, wherein said rare earth element is praseodymium (Pr).