JPS6412084B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention uses strontium titanate (SrTiO ₃ )
Or bismuth oxide (Bi ₂ O ₃ ) _, copper oxide (Cu _{2 O} ) _, manganese oxide (MnO ₂ ), A dielectric is created in the grain boundary region by thermally diffusing a diffusing agent mainly consisting of boron (B ₂ O ₃ ), lithium oxide (Li ₂ O), lanthanum oxide (La ₂ O ₃ ), and titanium oxide (TiO ₂ ). The present invention relates to a composition of a capacitor material obtained by providing a body layer, that is, a grain boundary dielectric layer type semiconductor ceramic. A composition of a grain boundary dielectric layer type semiconductor porcelain as a capacitor material, a composition of the semiconductor porcelain, and a grain boundary diffusion agent for increasing the resistance of the grain boundary region of the semiconductor porcelain and providing a dielectric layer at the grain boundary. It consists of both a composition and a composition. The various characteristics of the capacitor are determined by the selection of these two. The composition of the semiconductor ceramic according to the present invention is mainly composed of strontium titanate (SrTiO ₃ ) or strontium calcium titanate (Sr _1-x Ca _x TiO ₃ ) solid solution containing neodymium oxide (Nd ₂ O ₃ ). be. BACKGROUND ART Grain boundary layer type semiconductor ceramic dielectric materials in which rare earth oxides such as niobium oxide (Nb ₂ O ₅ ) and dysprosium oxide (Dy ₂ O ₃ ) are added to strontium titanate (SrTiO ₃ ) have been known. Regarding the formation of these grain boundary layers, examples include the use of a diffusing agent consisting of Bi ₂ O ₃ , PbO, and B ₂ O ₃ , or the use of a diffusion agent consisting of Bi ₂ O ₃ and Cu ₂ O and
Examples are known in which a diffusing agent containing MnO ₂ is used. In other cases, there are many cases in which one type of oxide is generally diffused. The present invention combines Nd ₂ O ₃ in SrTiO ₃ or Sr _1-x Ca _x TiO ₃
Bi ₂ O ₃ , Cu ₂ O,
This is a grain boundary layer type semiconductor ceramic dielectric material obtained by diffusing a composition consisting of MnO ₂ , B ₂ O ₃ , Li ₂ O, La ₂ O ₃ , and TiO ₂ . Therefore, this is a porcelain composition that is substantially different from that of the conventional example described above. In practice, grain boundary dielectric layer type semiconductor ceramic capacitor elements are classified into the following three types of standards from the viewpoint of the rate of change of capacitance with temperature. i.e. YR standard,
YB standard and YA standard. Capacitors whose capacitance temperature change rate is within ±15% in the temperature range of +85°C to -25°C based on the capacitance at 20°C are YR standard, and capacitors whose capacitance temperature change rate is within ±10% are YB standard. YA standard capacitors have a temperature change rate within ±5%. Capacitor elements of any standard have a large apparent permittivity ε _a , a large DC breakdown voltage V _b , and a large dielectric loss.
It is desirable that tanδ is small. However, in the YR standard, each characteristic required in practice is ε _a of 35,000 or more.
V _b is 500V/mm or more, tanδ is 0.01 or less, and YB
According to the standard, ε _a is 20000 or more, V _b is 700V/mm or more,
tan δ is 0.01 or less, and according to the YA standard, ε _a is 5000 or more, V _b is 700 V/mm or more, and tan δ is 0.01 or less. The grain boundary dielectric layer type semiconductor ceramic capacitor according to the present invention satisfies each of these practically required characteristics. In particular, the semiconductor ceramic composition recommended for YR standard has an SrO content of 50.23 to 49.00.
Mol%, _TiO2 component is _49.72 ~50.00mol%, _Nd2O3
It is a composition consisting of 0.05 to 1.0 mol% of the components, or a composition having these as the main components and containing 0.2 parts by mole or less of the SiO ₂ component per 100 parts by mole of the main component. In addition, the semiconductor ceramic composition recommended for YB standard has a SrO component of 50.23 to 34.00 mol%, CaO
component is 15 mol% or less, and contains SrO component and CaO
The content of the TiO components is within the range of 50.23 to 48.80 mol%, and the TiO ₂ component is 49.72 to 50.20 mol%, and
This is a composition containing 0.05 to 1.0 mol % of the Nd ₂ O ₃ component, or a composition containing 0.5 mol parts or less of the SiO ₂ component based on 100 mol parts of the main component. Furthermore, as a YA standard semiconductor porcelain composition,
SrO component is 35.23-26.40 mol%, CaO component is 15-26.40 mol%
22.6 mol%, and the content of SrO component and CaO component is within the range of 50.23 to 49.47 mol%, and TiO ₂
component is 49.72-50.23 mol%, and Nd ₂ O ₃ component is
A composition consisting of 0.05 to 1.0 mol %, or a composition having these as main components and containing 2 mole parts or less of the SiO ₂ component per 100 mole parts of the main component is desirable. In the semiconductor ceramic composition of any of the above standards, the range of the Nd ₂ O ₃ component amount according to the present invention is 0.05 to 1.0.
It is mole%. Nd ₂ O ₃ is SrTiO ₃ composed of SrO component and TiO ₂ component, or SrO component,
A necessary component for converting a (Sr _1-x Ca _x ) TiO ₃ solid solution consisting of a CaO component and a TiO ₂ component into a semiconductor based on the principle of valence control, and its Nd ₂ O ₃
The component amount is 0.05 mol% (SrTiO ₃ or Sr _1-x Ca _x
If the content is less than 0.1 mol% (relative to TiO ₃ ), there is no effect on semiconductor formation, while if the amount of the component is 1.0 mol%
(approximately for SrTiO ₃ or Sr _1-x Ca _x TiO ₃
2.0 mol%) exceeds SrTiO ₃ porcelain or Sr _1-x
This is undesirable because the grain growth of Ca _x TiO ₃ porcelain is suppressed and at the same time the resistivity of semiconductor porcelain increases.
In addition, in SrTiO ₃ , which is the main component of semiconductor porcelain,
Replacing the SrO component with CaO component has the effect of reducing the rate of change in capacitance with temperature as the amount of CaO component increases, but on the other hand, the sintered grain size generally tends to become smaller, and the amount of CaO component increases to 22.6 mol. % (almost
Sr _0.55 Ca _0.45 TiO ₃ corresponding to the composition), the sintered grain size of the porcelain becomes 5 μm or less, making it impossible to secure the minimum apparent dielectric constant (ε _a ) of 5000 required for practical use, which is not desirable. In addition, the SrO component and
Even if the content with CaO component exceeds 50.23 mol%,
Even if the _TiO2 component is less than 49.72 mol%, the sintered grain size of the semiconductor porcelain becomes small, and the apparent permittivity (ε _a ) decreases to 5000.
cannot be secured. Furthermore, even if the total amount of SrO component and CaO component is less than 48.80 mol%, the TiO ₂ component is still 50.23 mol%.
%, the sintered grain size of the semiconductor porcelain similarly becomes smaller, and ε _a =5000 cannot be ensured. this is
SrO component, CaO component added in excess of a certain limit to SrTiO ₃ or Sr _1-x Ca _x TiO ₃ , or
If TiO ₂ components are mixed, SrTiO ₃ particles and
This is because grain growth of Sr _1-x Ca _x TiO ₃ particles is suppressed. Next, the effect of containing _two SiO components promotes the sintering of SrTiO ₃ or Sr _1-x Ca _x TiO ₃ -based semiconductor porcelain (as a result, the main firing temperature can be lowered), and the dielectric loss (tan δ ) is to be made slightly smaller. However, the content of the _two SiO components is SrO,
If it exceeds 2 mol parts per 100 mol parts of the main component consisting of 3 to 4 components of CaO, TiO ₂ and Nd ₂ O ₃ ,
It is undesirable because it has a large grain growth suppressing effect, and an average grain size of 5 μm or more cannot be obtained (that is, a property with a dielectric constant (ε _a ) of 5000 or more cannot be obtained). Next, the composition of the grain boundary diffusing agent in the present invention is
93.5-8.5 mol% Bi ₂ O ₃ component, 4.5-45 mol%
_Cu2O component, 0.5-4 mol% _MnO2 component, 1-8.5
B ₂ O ₃ component of mol%, La ₂ O ₃ component of 17 mol% or less and TiO ₂ , Li ₂ O component of 20 mol% of 17 mol% or less
It is characterized by being a five-component to seven-component mixture composed of the following compositions. As a result of research related to the present invention, when the Bi ₂ O ₃ component increases in the grain boundary diffusion component after thermal diffusion, ε _a increases, but V _b decreases, and the capacitance temperature change rate (85℃ to -25℃) becomes larger. Conversely, as the Cu ₂ O component increases, the capacitance temperature change rate decreases, V _b increases, but ε _a decreases. Even if the Bi ₂ O ₃ component exceeds 93.5 mol%,
Or even if the Cu ₂ O component is less than 4.5 mol%,
This is undesirable because it is not possible to obtain characteristics with V _b of 500 V/mm or more, which is the minimum value required for practical use. Also Bi ₂ O ₃
Even if the component is less than 8.5 mol% or Cu ₂ O
Even if the component exceeds 45 mol %, it is not desirable because the property of ε _a of 5000 or more cannot be obtained (even if semiconductor porcelain with a relatively large average grain size of about 20 μm is used). Next, when MnO ₂ is added as a diffusing agent component, V _b
This has the effect of increasing the value of , but on the other hand, ε _a tends to decrease slightly and tan δ increases.
If the amount of MnO ₂ component exceeds 4 mol %, the property of tan δ of 0.01 or less cannot be obtained, so it is desirable that the amount of MnO ₂ contained is 4 mol % or less. In addition,
When the amount of MnO ₂ is less than 0.5 mol %, there is almost no effect of increasing V _b . Furthermore, when B ₂ O ₃ is added as a diffusing agent component, it has the effect of reducing tan δ, but on the other hand, it tends to reduce V _b . B ₂ O ₃
If the content exceeds 8.5 mol%, it will not be possible to obtain a property with V _b of 500 V/mm or more, so the amount of B ₂ O ₃ component contained should be
The content is preferably 8.5 mol% or less. In addition,
When the amount of B ₂ O ₃ is less than 1 mol %, there is almost no effect of reducing tan δ. Next, the La ₂ O ₃ component, which is one of the characteristics of the diffusing agent according to the present invention, has the effect of reducing the capacitance temperature change rate of the capacitor element. However, when the amount of La ₂ O ₃ component increases, ε _a decreases significantly, and V _b also tends to decrease. When the amount of La ₂ O ₃ component exceeds 17 mol%
YR standard ε _a 35000 or more, V _b 500V/mm or more characteristics,
Otherwise, it is not desirable because it does not satisfy the YB standard characteristics of ε _a 20000 or more and V _b 700V/mm or more. do not have,
When the amount of La ₂ O ₃ component is less than 0.5 mol %, there is almost no effect of reducing the rate of change in capacity with temperature. Next, when the TiO ₂ component is added in the presence of the La ₂ O ₃ component, the effect of further reducing the capacitance temperature change rate is observed. However, if the content of TiO ₂ component exceeds 17 mol%, both ε _a and V _b decrease, so TiO ₂
Addition of more than 17 mol% of the component is unnecessary. As described above, the grain boundary dielectric layer type semiconductor ceramic composition according to the present invention satisfies the characteristics of the YR standard, YB standard, and YA standard required for practical capacitor elements. When the capacitance temperature change rate is within ±15%, ε _a is 40000
~60000, V _b is 600 ~ 1300V/mm, tanδ is 0.003 ~
0.005, YB standard, that is, capacitance temperature change rate is ±10%
Within ε _a is 20000 to 35000, V _b is 1000 to 2000V/
mm, tan δ is 0.003 to 0.005, and YA standard, that is, the capacitance temperature change rate is within ±5%, ε _a is 7000 to 7000.
20000, V _b is 2000 to 4000V/mm, tanδ is 0.003 to
It provides excellent capacitor characteristics of 0.005. The details of the present invention will be explained below by giving examples. Example 1 Commercially available industrial raw materials SrCO ₃ powder (purity 97.5% or higher), CaCO ₃ powder (purity 98% or higher), TiO ₂ (anatase type, purity 98.5% or higher), and Nd ₂ O ₃ powder (purity 98% or higher) (above), were blended to the composition ratio of the semiconductor ceramic composition shown in Table 1, and after wet mixing, drying, and pre-firing at a temperature of 1200℃, the average
After grinding to 2.5 μm powder, add and mix polyvinyl alcohol aqueous solution as a binder, size the powder into 32 mesh passes, and make the sized powder 15 mm in diameter and thickness.
Formed into a 0.5mm disc shape with a pressure of approximately 1 ton/ ^cm2 ,
These molded bodies were heat-treated at 1000°C in air, and then fired for 4 hours at 1390°C in a mixed gas flow of 95% N ₂ - 5% H ₂ to give a diameter of about 12.5 mm and a thickness. A disk-shaped semiconductor porcelain with a diameter of about 0.4 mm was obtained. The fractured surfaces of these semiconductor ceramics were polished and etched, observed under a microscope, and the average grain size was measured. Table 1 shows the results. Note that the average grain size of the sintered body did not change even if the main firing temperature was changed within the range of 1380°C to 1400°C.

【table】

【table】

[Table] *marked is comparative sample. Specific resistance (In
-Ga electrode) are all except Sample 1 and Sample 32.
It was in the range of 0.2 to 0.5 Ωcm. However, sample 1
Comparative sample 32 showed a high resistivity of 5.1 Ωcm and 6.7 Ωcm, indicating that valence-controlled semiconductor formation was insufficient. On the other hand, a comparative sample in which the amount of Nd ₂ O ₃ component exceeded 1.0 mol%
No. 14, No. 27, and No. 37 had grain growth suppressed and the average grain size was small, less than 5 μm. In addition, Sample 2 with an SrO component amount exceeding 50.23 mol%, Sample 13 with a total amount of SrO component and Cao component of less than 49.00 mol%, and Sample 26 with a TiO ₂ component amount of 49.72 mol%.
Samples 2, 5 and 18 with less than mol% TiO, samples 10, 13 and 23 with _TiO2 component amount exceeding 50.20 mol%
and No. 26, grain growth was suppressed and the average grain size was small, less than 5 μm. Further, a sample in which the amount of CaO component exceeds 22.6 mol % is also undesirable because the sintered grain size becomes less than 5 μm.
Sample 2, 5, 10, 13, 14, 18, 23,
All samples other than Sample No. 26, No. 27, No. 32, No. 37, and No. 39 had an average particle size of 5 μm or more. Next, among the samples shown in Table 1, the average particle size is 12μ
For samples with a particle diameter of more than m, apply a paste-like diffusing agent to the semiconductor porcelain and heat treat it at a temperature of 1150°C for 2 hours, and for samples shown in Table 1 with an average particle size of 12 μm or less. applied a paste-like diffusing agent to the semiconductor porcelain and subjected each to a heat treatment at a temperature of 1000°C for 2 hours to form a dielectric layer at the grain boundaries. The composition of the diffusing agent at this time was 67.6 mol% Bi ₂ O ₃ ,
12.0 mol% _{Cu2O ,} 2.4 mol% _MnO2 , 6.0 mol% _B2O3 , _4.0 mol% _La2O3 , and 8.0 mol%
There were six components consisting of _TiO2 . All of the raw material powders used for this diffusing agent were commercially available special grade reagents. Coating amount is per semiconductor porcelain element (250mg)
It was 1.9 mg. Furthermore, during thermal diffusion, care was taken to prevent the applied diffusion component from evaporating or diffusing out of the sample. Ag electrodes were baked on both sides of the disc-shaped element of the grain-boundary dielectric layer semiconductor porcelain obtained in this way to form a capacitor element, and ε _a (1 KHz), tan δ (1 KHz), and V _b were measured. These results are shown in Table 2.

【table】

[Table] Comparative samples marked with * Samples 101, 116, and 132 had tan δ exceeding 0.01, so they lacked practical value and were excluded from the scope of the present invention. In addition, samples 102, 105, 110, and
113, 114, 118, 123, 126, 127,
Samples No. 132, No. 137, and No. 139 had an ε _a of less than 5000 and lacked practical value as large-capacity capacitors, and were therefore excluded from the scope of the present invention. Among the samples of the present invention shown in Table 2, sample 104
107, 108, 111, 115, 117, 120,
Both 124 and 128 have ε _a of 35000 or more and tan δ
It has practical characteristics such as V b of 0.01 or less, V _b of 500 V/mm or more, and capacitance temperature change rate of within ±15% (YR standard). In addition, samples 121, 129, 130, and 131 have ε _a of 20000 or more, tan δ of 0.01 or less, and V _b of 700 V/mm.
Above, the capacitance temperature change rate is within ±10% (YB standard)
It has practical characteristics. In addition, sample 103,
106, 109, 112, 119, 122, 125,
133, 134, 135, 136, and 138 all have ε _a of 5000 or more, tan δ of 0.01 or less, and V _b of 700V/
mm or more, and has practical characteristics with a capacitance temperature change rate of within ±5% (YA standard). Example 2 Commercially available reagent special grade Bi ₂ O ₃ , Cu ₂ O, MnO ₂ , B ₂ O ₃ ,
Li ₂ O, La ₂ O ₃ , and TiO ₂ powders were blended to the composition ratio of the dispersant composition shown in Table 3, dry mixed, and an appropriate amount of pine tar, turpentine oil, etc. was added and mixed. A paste-like diffusing agent was prepared. This paste-like diffusing agent was applied to a semiconductor ceramic element (average particle size: 20 μm) of Sample 8 shown in Table 1 of Example 1. The amount of the diffusing agent applied was 1.9 mg per element (250 mg) in terms of oxide powder. The semiconductor ceramic element coated with this paste-like diffusing agent was heat-treated at a temperature of 1150° C. for 2 hours. In this thermal diffusion treatment, care was taken to ensure that the applied diffusion component was not lost to the outside of the sample due to evaporation, melting, or diffusion to the outside of the sample. On both sides of the disk-shaped element of the grain boundary dielectric layer type semiconductor porcelain obtained in this way,
The Ag electrode is baked to form a capacitor element, and ε _a (1K
Hz), tanδ (1KHz), V _b and capacitance temperature change rate (with reference to 20°C in the temperature range of +85°C to -25°C)
was measured. These results are shown in Table 3.

【table】

[Table] *marked is comparative sample Sample 1111, Sample 1116, Sample 1121, Sample 1126, Sample 1127,
1128, 1135, 1139, 1143, and 1148
Other samples according to the present invention have ε _a of 35000 or more,
Practical characteristics of YR standard with tan δ 0.01 or less, V _b 500 V/mm or more, and capacitance change rate within ±15%, or ε _a 20000 or more, tan δ 0.01 or less, and V _b 700 V/mm.
As described above, the capacitance change rate satisfies one of the practical characteristics of the YB standard, which is within ±10%. Example 3 A paste-like diffusing agent having the composition of the diffusing agent composition shown in Table 4 was prepared in the same manner as in Example 2. This paste-like diffusing agent was applied to a semiconductor ceramic element of Sample 36 (average particle size: 8.5 μm) shown in Table 1 of Example 1. The amount of the diffusing agent applied was 1.9 mg per element (250 mg) in terms of oxide powder. The semiconductor ceramic element coated with this paste-like diffusing agent was heat-treated at a temperature of 1000° C. for 2 hours. At this time, as in Example 2, care was taken to prevent the diffused components from escaping to the outside of the sample. Ag electrodes were added to the disk-shaped element of the grain boundary dielectric layer type semiconductor porcelain obtained in this way,
Each characteristic was measured in the same manner as in Example 2. These results are shown in Table 4.

[Table] Comparison samples are marked with *. Samples according to the present invention other than Samples 1149, 1150, 1155, 1159, and 1161 have an _{ε a} of 5000 or more and a tan δ of
It has practical characteristics of YA standard: 0.01 or less, V _b of 700V/mm or more, and capacitance temperature change rate within ±5%. Example 4 Using the commercially available industrial raw materials shown in Example 1 and the commercially available reagent grade SiO ₂ powder, they were mixed to have the composition ratio of the semiconductor ceramic composition shown in Table 5, and the same procedure as in Example 1 was carried out. Mixing, drying, calcining, crushing, sizing,
and molding. After heat-treating these molded bodies at 1000℃ in air, 95%N ₂ -5
1390℃~1330℃ in mixed gas stream of % _H2
The final firing was carried out for 4 hours at a constant temperature in the range of 1.5 to 2.5 mm to obtain a disk-shaped semiconductor porcelain with a diameter of about 12.5 mm and a thickness of about 0.4 mm. Table 5 shows the results of measuring the average grain size of these semiconductor ceramic sintered bodies in the same manner as in Example 1.

[Table] *marked is comparative sample
The amount of SiO ₂ components is the main components (SrO, CaO, TiO ₂ ,
In samples 2022 and 2031, in which the amount of 3 to 4 components consisting of Nb ₂ O ₅ exceeded 2 mol parts per 100 mol parts, the average grain size of the semiconductor porcelain sintered body was less than 5 μm due to the grain growth suppressing effect of SiO ₂ It was hot. Next, the sintering promoting effect of SiO ₂ is clear from the comparison of samples 2013, 2014, and 2015. In other words, the main firing temperature is
Even when the temperature is lowered from 1390℃ to 1350℃, the average particle size hardly changes. A similar effect was obtained for samples 2017, 2018, and 2019 containing 1 mol part of SiO ₂ or samples containing 1 mole of SiO ₂ .
This is also evident in samples 2026 and 2027, which contained 0.5 mole part. Next, among the samples shown in Table 5, the average particle size is 12 μm.
For samples exceeding 1,150°C, the same paste-like diffusing agent as in Example 1 (the diffusing agent composition is also the same as in Example 1) was applied to the semiconductor porcelain, and the sample was heated at a temperature of 1150°C.
For the samples shown in Table 5 with an average particle size of 12 μm or less, the same paste-like diffusing agent as in Example 1 was applied to the semiconductor porcelain, and the sample was heated at a temperature of 1000°C for 2 hours. A dielectric layer was formed at the grain boundaries by performing heat treatment. The coating amount and other diffusion treatment conditions were also the same as in Example 1. Ag electrodes were applied to the disk-shaped element of the grain boundary dielectric layer type semiconductor ceramic thus obtained, and each characteristic was measured in the same manner as in Example 1. These results are shown in Table 5. Samples according to the present invention other than samples 2022 and 2031 have ε _{a of} 35000 or more, tan δ of 0.01 or less, and V _b
Practical characteristics of YR standard of 500V/mm or more, capacitance change rate within ±15% (sample 2011, 2012, 2013,
2014, 2015, 2023, 2024), or ε _a
Practical characteristics of _YB standard (sample
2016, 2025, 2026, 2027), or ε _a
5000 or more, tan δ 0.01 or less, V _b 700V/mm or more, capacity change rate within ±5% (sample
2017, 2018, 2019, 2020, 2021,
2028, 2029, 2030). In addition, in the above examples, a highly purified reagent of neodymium oxide (Nd ₂ O ₃ ) was used, but with low-purity industrial raw materials, Nd ₂ O ₃ 60% by weight or more and Pr ₆ O ₁₁ 40% by weight. Hereinafter, even if a composition containing 5% by weight or less of La ₂ O ₃ Sm ₂ O ₃ CeO ₂ was used, there was almost no significant effect.

Claims (1)

[Claims] 1. Strontium oxide (SrO) component is 50.23~
48.80 mol%, titanium oxide (TiO ₂ ) component is 49.72 ~
50.20 mol%, as well as neodymium oxide (Nd ₂ O ₃ )
Semiconductor porcelain with a composition ratio of 0.05 to 1.0 mol%, or a total amount of strontium oxide (SrO) and calcium oxide (CaO) of 50.23 to 48.80
The calcium oxide (CaO) component is 22.60 mol% or less, the titanium oxide (TiO ₂ ) component is 49.72 to 50.20 mol%, and the neodymium oxide (Nd ₂ O ₃ ) component is 0.05 to 1.0 mol%. The grain boundaries of semiconductor porcelain have a composition ratio of 93.5 to 8.5 mol% bismuth oxide (Bi ₂ O ₃ ) and copper oxide (Cu ₂ O).
The component is 4.5 to 45 mol%, the manganese oxide (MnO ₂ ) component is 0.5 to 4 mol %, and boron oxide (B ₂ O ₃ ).
A composition with a composition ratio of 1.0 to 8.0 mol%, or a composition containing 93.5 to 8.5 mol% of bismuth oxide (Bi ₂ O ₃ ) component, 4.5 to 45 mol% of copper oxide (Cu ₂ O) component, and manganese oxide ( MnO ₂ ) component is 0.5 to 4 mol %, boron oxide (B ₂ O ₃ ) component is 1 to 8.5 mol %, lithium oxide (Li ₂ O) component is 20.0 mol % or less, lanthanum oxide (La ₂ O ₃ ) component A grain boundary dielectric layer type semiconductor, characterized in that a dielectric layer is formed by diffusing a composition having a composition ratio of 17.0 mol % or less and a titanium oxide (TiO ₂ ) component of 17 mol % or less. Porcelain composition. 2 Strontium oxide (SrO) component is 50.23~
48.80 mol%, titanium oxide (TiO ₂ ) component is 49.72 ~
50.20 mol%, as well as neodymium oxide (Nd ₂ O ₃ )
Semiconductor porcelain containing silicon oxide (SiO ₂ ) component in an amount not exceeding 2 mole parts per 100 parts of a composition containing 0.05 to 1.0 mole %, or strontium oxide (SrO) component and calcium oxide (CaO) 50.23 to 48.80 mol%, the calcium oxide (CaO) component is 22.60 mol% or less, the titanium oxide (TiO ₂ ) component is 49.72 to 50.20 mol%, and neodymium oxide (Nd ₂ O ₃ ). Bisman oxide (Bi ₂ O ₃ ) is added to the grain boundaries of semiconductor porcelain, which contains silicon oxide (SiO ₂ ) in an amount not exceeding 2 mol parts per 100 mol % of a composition containing 0.05 to 1.0 mol %.
Ingredients are 93.5-8.5 mol%, copper oxide (Cu ₂ O) component
4.5 to 45 mol%, manganese oxide (MnO ₂ ) component
A composition with a composition ratio of 0.5 _to 4 mol% and a boron oxide ( _B2O3 ) component of 1.0 to 8.5 mol%, or a composition with a composition ratio of 93.5 to 8.5 mol% of a bismuth oxide ( _Bi2O3 ) component and a boron oxide ( _B2O3 ) component of 93.5 to 8.5 mol%. Cu ₂ O) component: 4.5 to 45 mol%, manganese oxide (MnO ₂ ) component: 0.5 to 4 mol%, boron oxide (B ₂ O ₃ ) component: 1 to 8.5 mol%, lithium oxide (Li ₂ O) component A dielectric layer is formed by diffusing a composition having a composition ratio of 20.0 mol% or less, a lanthanum oxide (La ₂ O ₃ ) component of 17.0 mol% or less, and a titanium oxide (TiO ₂ ) component of 17 mol% or less. A grain boundary dielectric layer type semiconductor ceramic composition characterized by comprising: