KR20160065415A - A semiconductor ceramics composition of perovskite structure - Google Patents

Abstract

The present invention relates to a semiconductor Perovskite composition, and more particularly to a semiconductor Perovskite structure that has a suitable specific resistance at room temperature to prevent damage due to an electrostatic discharge (ESD). Accordingly, the present invention provides a semiconductor ceramic composition of a Perovskite structure in ABO_3 form, wherein the composition has a A_n(M_1-xM_nx_nO_3n+1) structure, and here, A is a metal of Group 2A, M is a metal of Group 4A or 4B.

Description

A semiconductor ceramics composition of perovskite structure having a perovskite structure.

The present invention relates to a semiconductive perovskite composition and more particularly to a perovskite perovskite composition having a specific resistivity at room temperature to prevent damages due to electrostatic discharge (ESD) ) Composition.

Recently, with the development of electronic industry, there have been increasing demands for parts with special electrical conditions. Among them, electric and electronic materials having a perovskite structure have been attracting attention in many researches and various applications until now. Semiconductive ceramics having a perovskite structure refers to a material having an electrical resistivity of about 10 ² to 10 ⁹ Ω · cm at a room temperature region and includes a thermistor, a varistor, a capacitor, an oxygen sensor, Solid electrolytes, and many other studies. Recently, semiconductive ceramics have been attracting attention in order to reduce the industrial damage caused by electrostatic discharge (ESD) by using the conductive characteristics of the perovskite structure. However, Research is minimal.

Damage caused by electrostatic discharge (ESD) is caused by explosion of electric and electronic products, inductive explosion of powders, fire in painting, and so on. The industrial damage caused by ESD is caused by the spark caused by the sudden discharge from the charged object. In order to reduce the industrial damage by this discharge effect, it is necessary to have a proper resistance value at room temperature. Proper resistivity values should have a characteristic of room temperature resistivity of 10 ⁴ to 10 ⁷ Ω · cm. Among the materials having a perovskite structure with ABO3 structure, A-site generally consists of elements such as Ba ²⁺ , Ca ²⁺ , and Sr ²⁺ , and B-stie has Ti ⁴⁺ , Zr ⁴⁺ , and Sn ⁴⁺ Elements. Both CaTiO ₃ and CaZrO ₃ are generally insulating materials. Research has been conducted to replace the transition metal in the B-site with a perovskite structure that exhibits such an insulating property so as to have a proper resistance and a semiconductive property of the material. Lisbeth Rormark, Ekaterina I. goldyreva, J. Briatico et al. Describe the conduction phenomenon caused by the O-vacancy formed by the transition metal Mn in the perovskite CaMnO ₃ composition as a conduction mechanism. However, there is no academic paper on the resistivity characteristics of Mn substitution. In addition, in the ABO ₃ structure of perovskite, the academic report based on the layered oxide crystal structure following the substitution of A-site has only reported on the permittivity and crystal structure factor.

Thus, the present invention is Ca _{n + 1} having an insulating property _{(M 0.5 Mn 0.5) n O} 3n + 1 (M = 4A, 4B -group metal) to the transition metal MnO ₂ on the B-site with the composition x = 0.3, 0.5, In another embodiment, Mn was fixed at 0.5 mol in B-site and Ca was added to the A-site at n = ∞, 1, 2, and 3, and the resulting crystal structure And resistivity at room temperature.

PCT / JP2004 / 000565 Ceramics consisting of conductive AlN (aluminum nitride) and rare earth nitrides in the grain boundary phase

W. D. Kingery, H. K. Bowen and D. R. Uhimann, "Introduction to ceramics", p.22, p.847, Jhon Wiley & Sons Inc, New Tork (1976). William D. Callister, "Materials Science and Engineering an Introuction ", pp. 402-426 (1995). R. C. Evans, " An Introduction To Crystal Chemistry ", p. 79 (1996).

In the conventional component-related technology for electrostatic removal of Japan OGIC method for reducing the peeling charge phenomenon to the surface treatment in社of the aluminum member, by the addition of additives to the Kyocera Al2O3 method for producing a conductive ceramic, MgO and SiO ₂ composite oxide A method of adding an additive, a method of adding an additive to glass, a method of adding Al ₂ O ₃ in which Cr ₂ O ₃ is dissolved in ZrO ₂ , a method of mixing particles, flakes, whiskers and fibrous semiconductor fillers with various kinds of resins .

The above-mentioned technical products have problems such as deterioration of lifetime due to peeling, insufficient effect of removing static electricity due to high surface resistance characteristics, increase in process cost due to high temperature sintering, difficulty in manufacturing due to impurities or changes in resistance depending on manufacturing process, The generation of foreign matter and the reliability problem due to weakness have been raised. Thus, there is a need for a material having an appropriate resistance value of 10 ⁴ to 10 ⁷ Ω · cm at room temperature with a stable physical property.

Accordingly, in order to prevent the damage caused by electrostatic discharge (ESD), the present invention provides a perovskite-type perovskite oxide having a resistivity at room temperature and an appropriate resistance value of 10 ⁴ to 10 ⁷ Ω · cm, ) Composition to solve the above problems.

That is, the present invention has the composition of the ABO ₃ type of perovskite (Perovskite) in the semiconductive ceramic composition of the _{structure, A n (M 1-x} Mn x) n O 3n + 1 in order to solve the above problems, A is a Group 2A metal and M is a Group 4A or Group 4B metal.

The present invention provides a perovskite perovskite composition having a proper value of resistivity at room temperature and a stable mechanical property in order to prevent damage due to electrostatic discharge (ESD).

According to the present invention as described above, it is possible to realize a semi-permanent product which is substituted for the polymer-type electrostatic shielding part. In case of Company D, we are using SEM coating on metal mold contact parts. We use PEEK + CNT system as part of D company touch screen panel (TSP) laminate equipment to prevent yellowing after UV curing of resin. Prevention. In the film processing equipment for the Y-touch screen, alumina was treated with antistatic coating to solve problems caused by static electricity. In the case of the above product structure, there is a weakness due to Nick, deterioration in lifetime due to peeling, high price for quality, consumable parts (less than 6 months), but in the case of semiconductive perovskite composition of the present invention, There is an advantage that it can be used semi-permanently since it is excellent in ease of processing, high strength and abrasion resistance.

In addition, the semiconductive perovskite composition of the present invention can be applied as a replacement for ceramic and antistatic post-treatment (anodizing) parts. In the case of ARM for transferring semiconductor wafer heat treatment equipment of T company, the problem of static electricity is solved by using SiC coating product in alumina, and the price of SiC coating product is high at 900,000 Won, and the lifetime of coating material is less than 6 months. In the panel stage of 8G Cell Cut InLine transfer equipment, which is supplied to China B company, we are producing a product after antistatic treatment on alumina. In case of antistatic treatment product, There is a disadvantage that the antistatic effect is insufficient. On the contrary, the semiconductive perovskite composition of the present invention can be produced as an integrated product when it is applied as an ARM for semiconductor wafer transfer, and can be used semi-permanently since it does not use a coating agent. It is possible to fabricate a structure having a surface resistance value, which is advantageous in that the antistatic effect is excellent.

The semiconductive perovskite composition of the present invention is also applicable as an alternative to antistatic coatings on alumina porous products. In the case of film processing equipment for Y's touch screen, antistatic coating product is used for alumina porous product. It is mounted inside the equipment jig and the yield is lowered due to the problem of flatness between the surface coating and the jig, There is a disadvantage that the life is shortened due to the development and the cost is high. On the contrary, the semiconductive perovskite composition of the present invention can be processed as an integrated product without surface resistance change as mentioned above, and can be expected to have a problem due to the peeling phenomenon and a price competitiveness.

1 is a graph showing the relative density of Ca (Zr _1-x Mn _x ) O 3 (0.3? _X ? 0.7 mol) composition.
Fig. 2 is a graph showing the x-ray diffraction analysis of a specimen sintered at 1400 deg.
FIG. 3 is a graph showing that the room temperature resistivity characteristic decreases as the addition amount (x) of Mn increases.
4 is a graph showing the relative density of a composition of Ca (Ti _1-x Mn _x ) O ₃ (0.3? _X ? 0.7 mol).
5 is a graph showing the results of X-ray diffraction analysis of a composition of Ca (Ti _1-x Mn _x ) O ₃ (0.3? X? 0.7 mol).
6 is a graph showing resistivity characteristics with addition of MnO _{2 in} the composition of Ca (Ti _1-x Mn _x ) O ₃ .
7 is a graph showing room temperature resistivity characteristics of a composition obtained by adding MnO ₂ to a B-site having a composition of Ca (Ti _1-x Mn _x ) O ₃ (M = Zr, Ti).
8 is a graph of relative density according to the composition of Ca _{n + 1} (M _0.5 Mn _0.5 ) _n O _{3n + 1} .
9 is a graph showing x-ray diffraction analysis according to the composition of Ca _{n + 1} (M _0.5 Mn _0.5 ) _n O _{3n + 1} .
10 is a graph showing room temperature resistivity at a composition of Ca _{n + 1} (M _0.5 Mn _0.5 ) _n O _{3n + 1} .
11 is a graph showing the relative density characteristics of a composition of Ca _{n + 1} (M _0.5 Mn _0.5 ) _n O _{3n + 1} .
12 is a graph showing the results of x-ray diffraction analysis of a composition of Ca _{n + 1} (M _0.5 Mn _0.5 ) _n O _{3n + 1} .
13 is a graph showing room temperature resistivity of a composition of Ca _{n + 1} (M _0.5 Mn _0.5 ) _n O _{3n + 1} .
14 is a graph showing room temperature resistivity characteristics according to n = ∞, 1, 2, 3 of the composition Ca _{n + 1} (M _0.5 Mn _0.5 ) _n O _{3n + 1} (M = Zr, Ti).

BRIEF DESCRIPTION OF THE DRAWINGS FIG.

The present invention relates to a semiconductive ceramic composition of the Perovskite structure of the ABO ₃ type, which has a composition of A _n (M _{1 -x} Mn _x ) _n O _{3n + 1} , wherein A is a Group 2A metal and M is 4A or 4B metal, which is a perovskite structure.

The Group 2A metal 'A' may be one selected from Ba ²⁺ , Ca ²⁺ and Sr ²⁺ , and Ca ²⁺ is particularly preferable.

The 'M' is preferably Ti or Zr which is a group 4A element. Any one of Sn, Ge, and Pb, which is a group 4B element, may be applied.

_X representing the molar ratio of Mn of the composition of A _n (M _{1 -x} Mn _x ) _n O _{3n + 1} is preferably 0.2 to 0.7. As described above, in the embodiment where the value of x is 0.2 to 0.7, the amount of Mn to be added is controlled to determine the ratio experimentally.

In another embodiment, the composition of A _n (M _{1 -x} Mn _x ) _n O _{3n + 1} is fixed to x = 0.5 and the ratio of (n + 1) / n can be set to 1 to 2 . The semiconductive ceramics of the perovskite structure of the present invention having the above composition ratio has a room temperature resistivity of 5.3 x 10 ³ to 2.5 x 10 ⁸ Ω · cm.

The semiconductive ceramics of the perovskite structure is preferably prepared by firing at a temperature of 1300-1420 ° C.

The semiconductive ceramics of the perovskite structure of the present invention has a bulk density of 3.75 to 40.5 g / cm 3. In this case, the semiconductive ceramics of the perovskite structure has a porosity of 0.4 to 1.6%.

Hereinafter, experimental results in the above composition ratio will be described.

First, measurement results of Ca (M _1-x Mn _x ) O ₃ (M = Zr, Ti) according to addition of MnO ₂ (0.3 ≦ _x ≦ 0.7 mol) will be described.

In Fig. 1, the relative density showing the same behavior as the shrinkage ratio was shown. The theoretical density of the complex was calculated by using CaZrO ₃ (JCPDF No. 35-0790) and Ca-MnO ₃ (JCPDF No. 76-1132) to calculate the relative density, and the theoretical density was calculated by Archimedes method Relative densities indicating the degree of densification were measured in comparison with the measured bulk density. In FIG. 2, as the addition amount x of MnO2 increases, it is confirmed that the relative density of x = 0.5 mol 95% and x = 0.7 mol 90% in the relative density of the composition of x = 0.3 mol is 98%. As the x content of the MnO ₂ added with shrinkage and relative density decreases, the property of lowering is lowered due to the result of x-ray diffraction analysis and microstructure analysis, and a mixture of CaZrO ₃ and CaMnO ₃ mixture (Compo- and the ratio of CaMnO ₃ increases as x increases. Therefore, it is considered that the shrinkage rate and the relative density are lowered by increasing the porosity distribution due to mutual interference.

FIG. 2 is a view showing an x-ray diffraction analysis of a specimen sintered at 1400 ° C. by pulverization.

It can be seen that it is formed as a compound composed of a mixture of orthorhombic CaZrO ₃ and CaMnO ₃ as shown in FIG. In the perovskite structure of ABO ₃ , the ionic radius of B-site Zr (0.85 Å) ion and Mn (0.56 Å) ion are large. It is believed that CaMnO ₃ was formed as a compound.

Also, it can be seen that the ratio of CaMnO ₃ increases as the content x of MnO ₂ added increases.

As a result of calculating the relative ratio using the intensity of 100 peaks measured by x-ray diffraction analysis, the composition of x = 0.3 mol showed a ratio of CaZrO ₃ : CaMnO ₃ = 70.42: 29.58. The composition of CaZrO ₃ : CaMnO ₃ = 55.02: 44.98 and the composition of x = 0.7 mol showed a ratio of CaZrO ₃ : CaMnO ₃ = 34.66: 66.44 in the composition of MnO ₂ addition x = 0.5 mol. As the amount of x increases, the relative intensity ratio is different from the molar ratio added. Particularly, the reason why the ratio is different in the composition of x = 0.5 and 0.7 mol is the JCPDF card No. 1. 35-0790 and shifted to the right by 2θ 31.580 ° measured at 100peak diffraction angle 2θ 31.540 ° of CaZrO ₃ .

That is, when the measured diffraction angle of 100peak is shifted to the right, the result of analysis shows that Mn (0.56 ANGSTROM) having a small ion radius is replaced with a small amount of ion sites of Zr (0.85 ANGSTROM) mol ratio and the intensity ratio of CaMnO ₃ is low.

As shown in FIG. 3, the resistivity at room temperature is lowered as the addition amount of x increases. Lisbeth Rormark, Ekaterina I. goldyreva, J. Briatico et al. Reported that Mn ions located in the B-site of the Perovs-kite structure exist in the AMnO ₃ structure as Mn ⁴⁺ and Mn ³⁺ , Oxygen vacancies are generated to maintain uniformity with oxygen (O) octahedra by double-exchange interaction, and it is explained by the composition formula of AMnO _3-σ and the electron conduction phenomenon by O-vancacy occurs The B-site Zr of BaMO3 with insulating properties or Mn substituted by Ti sites by RN Bhowmik, C. Gargori, A. Shukla, I. Burn, etc., plays a stabilizing role by suppressing the movement of the domain wall. In order to compensate for the nonuniformity, vacancy is formed at the oxygen (O) position, and the change of electrical characteristics is explained by the combination of Mn ion and O-vacancy. Therefore, the reason why the resistivity at room temperature is lowered as the addition amount x of MnO ₂ increases is that the ratio of CaMnO _3-σ having the room temperature resistivity characteristic of 10 Ω · ㎝, which is an electron conduction phenomenon, Is expected to decline.

The graphs of FIGS. 4 to 13 show the characteristics of the composition of Ca (Ti _1-x Mn _x ) O ₃ according to the addition of MnO _{2 to} which titanium is applied.

_{Ca (Ti 1-x Mn x} ) O 3 (0.3≤x≤0.7mol) exhibited a relative density of the sample fired to 1300 ~ 1425 ℃ composition in Fig. Each composition has an S-shaped curve at 1400 ° C, similar to that of M = Zr, and a reaction with a zirconia plate at 1425 ° C or higher.

The composition to which MnO ₂ was added in an amount of 0.3 and 0.5 mol was slightly lower in the composition with the addition amount x of 0.5 mol in terms of the shrinkage percentage and the relative density, but in the composition of 0.7 mol, the shrinkage and relative density were 0.3 and 0.5 mol It is confirmed that it is relatively low. As a result of the x-ray diffraction analysis, these results show that the composition of 0.3 and 0.5 mol of x is substituted with Mn in the Ti ion site of B-site, resulting in a compound having a single phase of CaTiO ₃ And 0.7mol of the composition is formed by the layer phase oxide compound having a single phase of Ca ₄ Ti ₃ O ₁₀ and the composition of 0.7mol in the relative density characteristic shows a relatively low shrinkage rate and relative density .

The addition amount of MnO ₂ of 0.3 and 0.5 mol was substituted with MnO ₂ to form a single phase phase of CaTiO _{3. However} , the addition of 0.5 mol of the composition resulted in a shrinkage of 0.3 mol and a relative density of 0.3 mol As shown above, MnO ₂ , which is slightly lower than that of one composition, can be confirmed by the microstructure analysis that a small amount of MnO ₂ , which is not substituted in the B-site of CaTiO ₃ , Could. That is, it is considered that the grain boundary becomes smaller due to the inhibition of the grain growth and the porosity is formed, thereby increasing the shrinkage ratio and the porosity.

FIG. 5 shows the results of x-ray diffraction analysis. When the addition amount x of MnO ₂ was 0.3 and 0.5 mol, the composition of CaTiO ₃ was completely displaced to the Ti site of the B-site and the monoclinic CaTiO ₃ single Phase (Single phase) (JCPDF No. 75-0437). The 100peak of monoclinic CaTiO _{3 indicated} in JCPDF was diffracted at 2θ 23.391 °, but the diffraction angle of 100peak of the composition to which 0.3mol of MnO ₂ was added was 2θ 23.340 ° and 0.5mol of x was added It was confirmed that the diffraction angle of 100peak of the composition was 2? 23.460 ° and the diffraction angle became larger gradually. From these results, it is considered that the lattice becomes smaller as the 2θ of 100peak is shifted to the right, and Mn (0.56 Å) having a small ion radius is substituted for Ti (0.64 Å). It is believed that this is caused by monoclinic (monoclinic) CaTiO ₃ in the general orthorhombic structure due to the collapse of the lattice caused by this.

In the composition containing 0.7 mol of MnO ₂ , Ca ₄ Ti ₃ O ₁₀ (JCPDF No. 78-2481) of A ₄ B ₃ O ₁₀ , which is a layered oxide structure, was produced. The layered oxide structure of Ca ₄ Ti ₃ O ₁₀ is described by Ruddlesden and Popper in the study of SrO TiO ₃ perovskite and SrO composite oxide layer oxide with double prerovskite structure of Sr ₃ Ti ₂ O ₇ , Jacob, Sapna gupta reported on the layered oxides of Ca _{n + 1} Ti _n O _{3n + 1} (n = 1, 2, 3, ∞ ...) type with CaO addition to CaTiO ₃ with orthorhombic structure Respectively.

However, in this experiment, the composition obtained by adding 0.7 mol of MnO ₂ to the B-site ion site changed into the structure of A ₄ B ₃ O ₁₀ , not the structure of A (B'B ") O ₃ . No study on the lattice structure change of layered oxides with substitution has been reported.

FIG. 6 shows the resistivity characteristics of MnO ₂ added to Ca (Ti _1-x Mn _x ) O ₃ composition. As the content of x increased, the resistivity was lowered. This is explained by the decrease of the resistivity at room temperature due to the increase of O vacancy due to the substitution of Mn as described above. However, the composition with 0.3 and 0.5 mol of Mn stabilized the resistivity characteristics from 1400 ℃, but the composition with 0.7 mol of Mn showed a steady decrease in the resistivity at room temperature. It is known that when the layered oxide structure is formed, the electrical resistance increases as compared with the general perovskite structure. However, at 0.7 mol, it is produced as a layered oxide structure, but the addition of x produced in the single phase and the addition of 0.3 and 0.5 mol Which is lower than that at room temperature. This phenomenon has been reported by H. Ueoka et al. That the resistance of these particles is much lower than that of submicron sized particles when large particles are grown in the semiconductive BaTiO3 ceramics specimen. And the specific resistance at room temperature is not stable due to the double action of O-vacancy.

FIG. 7 shows the room temperature resistivity of the composition obtained by adding MnO ₂ to the B-site of Ca (M _{1 -x} Mn _x ) O ₃ (M = Zr, Ti). It was found that the resistivity at room temperature was lowered as the addition amount x of MnO ₂ was increased in both the compositions of Zr or Ti in B-site. As described above, since the Mn ions added form O-vacancies through mutual double action, they become conductive. Therefore, it is considered that the resistivity at room temperature is lowered as the addition amount of MnO ₂ increases.

The graphs of FIGS. 8 to 10 show the measurement results of the examples according to the addition of CaO (n = ∞, 1, 2, 3) to the Ca _{n + 1} (M _0.5 Mn _0.5 ) _n O _{3n + 1} Respectively.

In the embodiment according to the addition of CaO (n = ∞, 1, 2, 3) to the composition of Ca _{n + 1} (M _0.5 Mn _0.5 ) _n O _{3n + 1} (M = Z), the structure of the perovskite structure As described for the layered oxide structure, Mn was fixed at 0.5 mol in the B-site, Ca was added to the A-site at n = ∞, 1, 2 and 3 mol to obtain Ca _{n + 1} (M _0.5 Mn _0.5 ) _n O Electrical properties and structural changes of the composition of _{3n + 1} were measured.

 As the amount of CaO added to A-site increases, the ratio of (n + 1) / n to (n + 1) / n increases as the amount of CaO added to A- The ratio of A-site to B-site is also changed, and the ratio of A-site is represented by (n + 1), and the ratio of B-site is represented by n. n + 1) / n ratio means that the ratio of CaO as A-site increases.

As can be seen from the relative density in FIG. 8, the shrinkage ratio increases as the (n + 1) / n ratio increases. However, the composition (n = 1, 2, 3) with a (n + 1) / n ratio of 1.33, 1.5, Shows that the shrinkage rate from temperature of 1325 ° C shows a high shrinkage rate, and that the shrinkage rate slightly increases even when the firing temperature is increased.

 Also, as the content of CaO increased, the relative density showed a high relative density at 1325 ° C as in the shrinkage characteristic. It is considered that the densification is caused by CaO which acts as sintering aid.

according to the CaO added to the A-site as shown in Figure 9 showing the x- ray diffraction analysis was the generation of a mixture consisting of a compound of CaZrO ₃ and CaMnO _3, Ca ₂ MnO _4. The composition with (n + 1) / n ratio of 1 is the result of x-ray diffraction analysis of the composition in which MnO ₂ was added to the preceding B-site, and it was formed as a mixture of CaZrO ₃ and CaMnO ₃ . The A-site with the addition of CaO (n + 1) / n is the ratio 1.33, 1.5, 2 composition (n = 1, 2, 3 ) has been substituted at the A-site of CaMnO ₃ compound Ca ₂ MnO ₄ layered oxide structure. In addition, as the ratio of (n + 1) / n increased with the addition of CaO, the diffraction peak of CaO doped with CaMnO ₃ could not be substituted, but the diffraction intensity was gradually increased. The results of x-ray diffraction analysis show that the shrinkage and relative density increase with increasing ratio of (n + 1) / n. .

As shown in FIG. 10, the resistivity at room temperature according to the (n + 1) / n ratio shows an increase in the resistivity at room temperature as the ratio of (n + 1) / n increases. It is considered that the conduction phenomenon due to the formation of O-vacancies due to the double interaction of Mn ₃₊ and Mn ₄₊ is reduced due to the liquid phase of CaO serving as a sintering aid in the specimen. However, the composition (n = 3) with the (n + 1) / n ratio of 1.33 exhibits stable room temperature resistivity characteristics in a wide temperature range from 1350 to 1425 ° C. As described above, a small amount of over-substituted CaO remained and was formed as a mixture of CaZrO ₃ and Ca ₂ MnO ₄ . ID Fawcett et al. Reported that Ca ₂ MnO ₄ having a layered oxide structure exhibited a low resistivity characteristic similar to that of CaMnO ₃ at room temperature, and that the resistivity characteristics due to temperature by F. Kawashima et al. It has a property is due to the report has been generated by the layered oxide structure of Ca ₂ MnO _4, and shows the specific resistance characteristic similar to the room temperature resistivity in the characteristics (n + 1) / n composition of ratio a 1 of the (n = ∞), wide And it shows that it shows stable resistivity characteristics in the sintering temperature range.

The graphs of FIG. 11 to FIG. 14 are measurement graphs of the Ca _{n + 1} (Ti _0.5 Mn _0.5 ) _n O _{3n + 1} composition with the application of titanium and CaO (n = ∞, 1, 2, 3) addition.

The relative density of CaO added to A-site (n = ∞, 1, 2, 3) is shown in FIG. (n + 1) / n ratio = 2, all compositions show a relative density of 95% or more at 1400 ° C or higher. (n + 1) / n ratio = 2 showed low shrinkage and low density. This degradation is due to a mixture of Ca ₃ (Ti _0.5 Mn _0.5 ) ₂ O ₇ , CaO and Ca ₂ MnO ₄ due to the x-ray diffraction analysis shown in Fig. 4-2-9, The relative density characteristics are considered to be lowered.

Also on the basis of the x- ray diffraction analysis shown in the grid 12 changes in accordance with the Ca added to the A-site is (n + 1) / n ratio = 1 (n = ∞) is a composition of Mn is CaTiO ₃ As in the previous experiment is completely eco-friendly composition was to create a compound having a single-phase (single phase) of the CaTiO _3, it has a composition formula of _{Ca (Ti 0.5 Mn 0.5) O} 3.

(n + 1) / n ratio = 1.33 (n = 3) of the composition is as the CaO is substituted at the _{A-site Ca 4 Ti 3 O} 10 was of a cheungsan oxide having a single phase (single phase), Ca ₄ ( Ti _0.5 Mn _0.5 ) ₃ O ₁₀ . (n + 1) / n ratio = 1.5 (n = 2) is a layered oxide having a single phase of Ca ₃ Ti ₂ O ₄ and has a composition formula of Ca ₃ (Ti _0.5 Mn _0.5 ) ₂ O ₇ . (n + 1) / n composition of ratio = 2 (n = 1) is, but attempts to manufacture a composition having a lattice structure of the Ca ₂ TiO ₄ as a substitution of CaO in the A-site, with a grid structure of A ₂ BO ₄ Ca ₂ TiO ₄ was not synthesized and results were obtained with compounds of Ca ₃ (Ti _0.5 Mn _0.5 ) ₂ O ₇ , CaO, Ca ₂ MnO ₄ . Thus, changes in the lattice structure, with the addition of CaO in the A-site is cheungsan oxide of CaO and via the phase diagram of the TiO ₂ by a mixture of CaO and _{TiO 2 Ca 3 Ti 2 O 7} , Ca 4 Ti 3 O 10 Although the structure is described, it can be understood that when CaO is added in excess, it is formed as a compound of Ca ₃ Ti ₂ O ₇ and CaO. That is, the composition (n = 1) having the ratio (n + 1) / n of ₂ is present as a mixture of Ca ₃ Ti ₂ O ₇ and CaO by the excess addition of CaO, and the added MnO ₂ is CaTiO ₃ is produced as a compound of Ca ₂ MnO ₄ due to solubilization and re-precipitation on the B-site.

13 shows that the room temperature resistivity increases as the room temperature resistivity characteristic (n + 1) / n ratio increases and that the composition (n = 1) with the (n + 1) / n ratio of 2 exhibits a low room temperature resistivity characteristic Respectively.

 The increase in the resistivity at room temperature with increasing (n + 1) / n ratio is attributed to the results of Ian D. Fawcett et al.

In the Ruddlesden-Popper report, a schematic diagram of the layered oxide structure of CaMnO ₃ , Ca ₂ MnO ₄ , Ca ₃ Mn ₂ O ₇ and Ca ₄ Mn ₃ O ₁₀ composed of A-site Ca and B-site Mn ions can be confirmed. When n = 1 in the layered oxide structure, one perovskite structure and the z-axis are separated into CaO layers. In case of n = 2, there are two perovskite structures and CaO layers, n = 3 consists of three perovskite structures and CaO layer, and when n = ∞, one perovskite structure is formed . In this lattice structure, the resistivity of the O-vacancy and the B-site Mn ions in the lattice structure is increased due to the CaO layer which performs lattice separation along the z-axis. As the perovskite structure between the CaO layers increases, And Ian D. Fawcett et al. Reported that the specific resistivity increases. Therefore, as shown in the schematic diagram of the layered oxide structure, the resistivity at room temperature increases as the (n + 1) / n ratio increases. The resistivity of the composition (n = 1) with (n + 1) / n ratio of 2 is slightly lower than that of the composition (n = 1) of (n + 1) / n ratio of 2, Ray diffraction analysis and microstructural analysis results, it was considered that the room temperature resistivity was lowered because it was formed as a mixture of Ca ₃ Ti ₂ O ₇ and Ca ₂ MnO ₄ and CaO.

FIG. 14 shows the resistivity at room temperature according to n = ∞, 1, 2 and 3 of the composition Ca _{n + 1} (M _0.5 Mn _0.5 ) _n O _{3n + 1} (M = Zr, Ti). The composition of M = Zr according to the addition of CaO is 3.0 × 10 ² to 1.3 × 10 ³ Ω · cm and the composition with M = Ti has a room temperature resistivity of 3.5 × 10 ⁵ to 2.55 × 10 ⁸ Ω · cm Respectively.

In other words, when the above measured values are summarized, MnO ₂ is added to B-site in a composition of Ca _{n + 1} (M _{1 -x} Mn _x ) _n O _{3n + 1} (M = Zr, Ti) mol, and CaO n = ∞, 1, 2 and 3 were added to the A-site. The S-curve was obtained at 1400 ° C. The structural characteristics and the room temperature resistivity of each composition were as follows. The same conclusion was obtained.

1. In the case of M = Zr in the composition of Ca (M _{1 -x} Mn _x ) O ₃ , Mn was added to B-site in the amount of 0.2 mol to 0.3 ≦ x ≦ 0.7 mol, resulting in a mixture of CaZrO ₃ and CaMnO _3-σ Generation. As the content of x increased, the bulk density decreased and the porosity increased. As the ratio of CaMnO _{3 - σ} with low room temperature resistivity increases with the addition of MnO _2, the resistivity at room temperature is 2.5 × 10 ³ Ω · · · Cm to 3.1x10? 占 ㎝ m.

2. In the case of M = Ti in the composition of Ca (M _{1 -x} Mn _x ) O ₃ , MnO ₂ was added to B-site in 0.3 mol, 0.3 mol, -site, which is a monoclinic CaTiO ₃ single phase, in which the Mn ion is substituted for the Ti ion site, and Mn having a small ion radius is substituted for the Ti site, 2 &thetas; gradually shifts to the right, and the grating becomes smaller. 0.7mol The added composition was changed to lattice structure of Ca ₄ Ti ₃ O ₁₀ which is a layered oxide structure due to the excess addition of MnO ₂ . The room temperature resistivity showed the characteristic of room temperature resistivity decreased from 1.4 × 10 ⁷ Ω · ㎝ to 5.3 × 10 ³ Ω · ㎝ as MnO ₂ addition amount increased.

3. In the composition of Ca _{n + 1} (M _0.5 Mn _0.5 ) _n O _{3n + 1} , when M = Zr, the characteristics of CaO with n = ∞, 1, 2, as n + 1) / n ratio is increased in the lattice structure of CaMnO ₃ was a layered oxide of Ca ₂ MnO ₄ was generated from a mixture of not unsubstituted is added to the compound and an excess of _{CaZrO 3, Ca 2 MnO 4 CaO} . As the ratio of (n + 1) / n increased, the resistivity at room temperature could be made to have a characteristic of 3.0 × 10 ² Ω · cm to 1.3 × 10 ³ Ω · cm. In particular, a composition having a room temperature resistivity characteristic in a wide temperature range from 1325 to 1425 ° C was obtained in the composition (n = 3) having (n + 1) / n ratio of 1.33.

4. The composition (n = ∞) with (n + 1) / n ratio of 1 for CaO added to A-site when M = Ti in the composition of Ca _{n + 1} (M _0.5 Mn _0.5 ) _n O _{3n +} (N + 1) / n ratio of 1.33 (n = 3) was produced by CaTiO ₃ single phase compound having a composition formula of Ca (Ti _0.5 Mn _0.5 ) O ₃ , .5) 4O10 with a composition of Ca4Ti3O4 single phase. In addition, a composition (n = 2) with an (n + 1) / n ratio of 1.5 was produced as a Ca ₃ Ti ₂ O ₇ single phase compound having a composition formula of Ca ₃ (Ti _0.5 Mn _0.5 ) ₂ O ₇ . (N + 1) / n ratio of 2 (n = 1), Ca ₃ Ti ₂ O ₇ , Ca ₂ MnO ₄ and excess addition CaO was added to the mixture. According to the change of the mixture and the lattice, a composition having room temperature resistivity of 3.5 × 10 ⁵ Ω · ㎝ and room temperature resistivity of 2.5 × 10 ⁸ Ω · ㎝ was obtained.

Therefore, the present invention is based on the finding that the addition of transition metal MnO ² to B-site and the addition of CaO to A-site in a composition of CaMO ³ (M = Zr, Ti) having insulating properties widely used as electric / And a room temperature resistivity, it was possible to obtain a compound or a mixture having a room temperature resistivity characteristic of 5.3 × 10 ³ Ω · cm to 2.5 × 10 ⁸ Ω · cm and to prevent a large discharge effect for the ESD shelter It is expected that it can be applied as an electronic material which can be used for a special purpose purpose.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it should be understood that various changes and modifications will be apparent to those skilled in the art. Obviously, the invention is not limited to the embodiments described above. Accordingly, the scope of protection of the present invention should be construed according to the following claims, and all technical ideas which fall within the scope of equivalence by alteration, substitution, substitution, Range. In addition, it should be clarified that some configurations of the drawings are intended to explain the configuration more clearly and are provided in an exaggerated or reduced size than the actual configuration.

Claims (7)

In a semiconductive ceramics composition of the perovskite structure of the ABO ₃ type,
_Wherein A is a Group 2A metal and M is a Group 4A or Group 4B metal having the composition A _n (M _{1 -x} M _nx ) _n O _{3n + 1} , .
The method according to claim 1,
Wherein the Group 2A metal 'A' is one selected from Ba ²⁺ , Ca ²⁺ and Sr ²⁺ .
The method according to claim 1,
Wherein the M is one selected from Ti, Zr, and Sn.
The method according to claim 1,
_Wherein x representing the molar ratio of Mn of the composition A _n (M _{1 -x} M _nx ) _n O _{3n + 1} is 0.2 to 0.7.
The method according to claim 1,
The composition of A _n (M _{1 -x} M _nx ) _n O _{3n + 1} is such that A is Ca,
Ca _{n + 1} (M _0.5 Mn _0.5 ) _n O _{3n + 1} with x = 0.5,
wherein the ratio of (n + 1) / n is from 1 to 2. < Desc / Clms Page number 23 >
The method according to claim 1,
Wherein the semiconductive ceramics of the Perovskite structure form a solid solution. ≪ RTI ID = 0.0 > [10] < / RTI >
The method according to claim 1,
Wherein the semiconductive ceramics of the perovskite structure has a room temperature resistivity of 5.3 x 10 ³ to 2.5 x 10 ⁸ Ω · cm.

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