# Patent

## Title
Method of producing semiconductor porcelain composition

## Abstract

A method of producing a semiconductor disk represented by a composition formula [(Bi0.5Na0.5)x(Ba1−yRy)1−x]TiO3, in which R is at least one element of La, Dy, Eu, Gd and Y and x and y each satisfy 0≦x≦0.14, and 0.002≦y≦0.02 includes carrying out a sintering in an inert gas atmosphere with an oxygen concentration of 9 ppm to 1% and wherein a treatment at an elevated temperature in an oxidizing atmosphere after the sintering is not carried out.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of PCT International Patent Application No. PCT/JP2006/306816, filed Mar. 31, 2006, and Japanese Patent Application No. 2005-103721, filed Mar. 31, 2005, in the Japanese Intellectual Property Office, the disclosures of which are incorporated herein by reference.
TECHNICAL FIELD
The present invention relates to a method of producing a semiconductor porcelain composition for use in a PTC thermistor, a PTC heater, a PTC switch, a temperature detector or the like, which has a positive resistance temperature, has a considerably reduced resistivity at room temperature, and is capable of providing a property uniform to an inner portion of a material.
BACKGROUND ART
Conventionally, as a material showing a positive PCTR, there has been proposed a composition constituted by adding various semiconductor forming elements to BaTiO3. These compositions are provided with Curie temperature of around 120° C., and therefore, it is necessary to shift the Curie temperature in accordance with the application.
For example, although it has been proposed to shift Curie temperature by adding SrTiO3 to BaTiO3, in this case, the Curie temperature is shifted only in a negative direction and is not shifted in a positive direction. Currently, only PbTiO3 is known as an additive element for shifting Curie temperature in a positive direction. However, PbTiO3 includes an element for bringing about environmental contamination, and therefore, in recent years, a material in which PbTiO3 is not employed has been desired.
In BaTiO3 semiconductor porcelain, with an object of preventing a reduction in a resistance temperature coefficient by Pb substitution, as well as reducing a voltage dependency and promoting a productivity and a reliability, there has been proposed a method of producing a BaTiO3 semiconductor porcelain in which a composition, obtained by adding one or more kinds of any of Nb, Ta and a rare earth element to a composition in which x in Ba1-2X(BiNa)xTiO3 where a portion of Ba of BaTiO3 is substituted by Ba—Na is controlled to a range of 0<x<0.15, is sintered in nitrogen, and thereafter subjected to a heat treatment in an oxidizing atmosphere (see Patent Reference 1).
Patent Reference 1: JP-A-56-169301
In the case in which a valence control of the composition is carried out in a system in which a portion of Ba is substituted by Bi—Na, when a trivalent positive ion is added as a semiconductor forming element, the effect of semiconductor formation is reduced by the presence of monovalent Na ion, and the resistivity at room temperature is increased. Although, in Patent Reference 1, as an embodiment, there has been disclosed a composition constituted by adding 0.1 mol % of Nd2O3 to Ba1-2x(BiNa)TiO3 (0<x≦0.15) as a semiconductor element, the additive amount of Nd2O3 cannot realize semiconductor formation sufficient for PTC application.
In the above-described material, the resistance value thereof is conceived to be caused by Schottky barrier of a grain boundary. As means of controlling the Schottky barrier, oxidation/deoxidation treatment of a grain boundary has been proposed, and it is reported that a high PTC property can be achieved by a material generally subjected to oxidizing treatment in oxygen (see Nonpatent Reference 1). Further, it has been also reported that a treatment rate in the heat treatment also influences on a property (see Nonpatent Reference 2) to pose a problem that the heat treatment of the material becomes very complicated.
Nonpatent Reference 1: Titabari Kenkyukai Shiryo XVII-95-659 (1968)
Nonpatent Reference 2: J. Am. Ceram. Soc. 48, 81 (1965)
Further, according to the heat treatment, there poses a problem that, although the effect by the heat treatment can act uniformly to an inner portion of the material when the shape of the material is a comparatively small, in the case of a comparatively large shape (thick shape) applied in the application such as a PTC heater, it is difficult to provide a PTC property uniform to the inner portion of the material.
DISCLOSURE OF THE INVENTION
It is an object of the present invention to solve the above-described conventional problem and to provide a production method of providing a semiconductor porcelain composition which is capable of shifting a Curie temperature in a positive direction without using Pb and has a considerably reduced resistivity at room temperature.
Further, it is another object of the present invention to provide a method of producing a semiconductor porcelain composition which is capable of providing a property uniform to an inner portion of a material even in a material having a comparatively large and thick shape without carrying out a complicated heat treatment.
The inventors paid attention to a valence control when Ba is substituted with Bi—Na in a BaTiO3 semiconductor porcelain composition, and as a result of an intensive research of a content of an additive element for carrying out an optimum valence control, the inventors found that by substituting Ba with an R element in a specific amount, the optimum valence control can be achieved and a resistivity at room temperature can considerably be reduced.
Further, as a result of a research of a method of producing the semiconductor porcelain composition, the inventors found that, by carrying out sintering of the composition in an inert gas atmosphere with an oxygen concentration equal to or smaller than 1%, a PTC property uniform to the inner portion of the composition can be provided, and a semiconductor porcelain composition having an excellent property can be provided without carrying out a complicated control of an atmosphere, a treatment rate or the like. Thus the invention has been completed.
A method of producing a semiconductor porcelain composition according to the invention is a method of producing a semiconductor porcelain composition represented by a composition formula [(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3 in which R is at least one element of La, Dy, Eu, Gd and Y, and x and y each satisfy 0<x≦0.14 and 0.002≦y≦0.02, the method comprising carrying out a sintering in an inert gas atmosphere with an oxygen concentration equal to or smaller than 1%.
The invention also proposes a constitution according to the above-described method of producing a semiconductor porcelain composition, in which an oxygen concentration is equal to or smaller than 10 ppm, and a constitution in which an oxide of Si is contained in an amount of 3.0 mol % or smaller, and an oxide of Ca is contained in amount of 3.0 mol % or smaller.
According to the invention, there can be provided a semiconductor porcelain composition which is capable of elevating a Curie temperature thereof without using Pb which brings about an environmental contamination, and has a considerably reduced resistivity at room temperature.
According to the invention, a property uniform to the inner portion of the material can also be provided to the semiconductor porcelain composition having a comparatively large and thick shape.
According to the invention, since it is not necessary to carry out a complicated heat treatment, a semiconductor porcelain composition having an excellent property can be provided at low cost.
BEST MODE FOR CARRYING OUT THE INVENTION
One of characteristics of the invention resides in that a Curie temperature is shifted in a positive direction by substituting a portion of Ba with Bi—Na, and in that, for optimally controlling a valence disturbed by the Bi—Na substitution, a portion of Ba is substituted with a specific amount of R element (at least one element of La, Dy, Eu, Gd and Y) to give a [(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3 composition. The reason of limiting the respective compositions is described as follows.
In the [(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3 composition, R is at least one element of La, Dy, Eu, Gd and Y. In a preferable embodiment, R is La. In the composition formula, x indicates a content range of Bi+Na and a preferable range thereof is 0<x<0.14. When x is 0, the Curie temperature cannot be shifted to high temperature side, while when it exceeds 0.14, the resistivity at room temperature becomes near to 104 Ωcm and it becomes difficult to apply to a PTC heater or the like, which are not preferable.
In addition, y shows a content range of R and 0.002≦y≦0.02 is a preferable range. When y is less than 0.02, the valence control of the composition becomes insufficient and the resistivity at room temperature becomes increased. Further, when y exceeds 0.02, the resistivity at room temperature becomes increased, and therefore, it is not preferable. A preferable range of y is 0.005≦y≦0.02, and the resistivity at room temperature can further be reduced. The range 0.002≦y≦0.02 mentioned above becomes 0.2 mol % through 2.0 mol % in mol % expression.
In the [(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3 composition, it is preferable to add an oxide of Si in an amount of 3.0 mol % or smaller, and add an oxide of Ca in an amount of 4.0 mol % or smaller. Addition of the Si oxide restrains abnormal growth of crystal grain and can easily control the resistivity, and addition of the oxide of Ca can promote a sintering performance at a low temperature. In any of the oxides, when added in an amount exceeding the limit amounts, the composition does not show semiconductor formation, and therefore, it is not preferable.
Another characteristic of the invention resides in that, in the method of producing the [(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3 composition, sintering is carried out in an inert gas atmosphere with an oxygen concentration equal to or smaller than 1%. A further preferable oxygen concentration is equal to or smaller than 10 ppm. Thereby, a complicated heat treatment in an oxygen atmosphere which has been carried out conventionally becomes unnecessary and a property uniform to the inner portion of the material can be provided in the material having a comparatively large and thick shape.
When the oxygen concentration exceeds 1%, the property uniform to the inner portion of the material cannot be provided, and therefore, it is not preferable. As the inert gas, nitrogen, argon, helium, carbon dioxide gas or the like can be used. In sintering, it is preferable to use a sintering furnace having an airtight structure.
An example of the method of producing a semiconductor porcelain composition according to the invention will be explained below. With regard to a step other than a sintering step, it is not limited in the following but a publicly-known method can be adopted therefor.

    (1) Powders of BaCO3 and TiO2 as main raw materials; at least one of La2O3, Dy2O3, Eu2O3, Gd2O3 and Y2O3 as semiconductor forming elements and valence control elements; SiO2 and CaO as sinter assisting agents; and (Na2CO3.Bi2O3.TiO2) as shifters of Curie temperature are respectively prepared.
    (2) The respective powders are mixed in a wet process and then dried. At this occasion, depending on a particle size of the raw material powder, pulverization may be carried out simultaneously with mixing. As a medium in the mixing, pure water or ethanol is preferable. It is preferable that a mean particle size of a mixed powder after mixed or pulverized is 0.6 μm through 1.5 μm.
    (3) A mixed powder is calcined. It is preferable that a calcinating temperature is 900° C. through 1100° C. It is preferable that calcinating time is 2 hours through 6 hours. It is preferable that a calcinating atmosphere is in the atmosphere or in oxygen.
    (4) A calcined product after calcination is finely pulverized and then dried. It is preferable that fine pulverization is carried out in a wet process. It is preferable that a medium in the pulverization is pure water or ethanol. It is preferable that a mean particle size of a pulverized powder after fine pulverization is 0.6 μm through 1.5 μm.
    (5) The pulverized powder after fine pulverization is formed by a desired forming means. Before forming, the pulverized powder may be optionally granulated by a granulating apparatus. It is preferable that a formed product density after forming is 2 through 3 g/cm3.
    (6) The formed product is sintered. With regard to a sintering atmosphere, as descried above, when the inert gas is, for example, nitrogen, sintering is carried out in an atmosphere containing 99% or more of nitrogen, with an oxygen concentration of 1% or less, preferably 10 ppm or less. It is preferable that a sintering temperature is 1200° C. through 1400° C. , and it is preferable that a sintering period is 2 hours through 4 hours. When the powder is granulated, it is preferable to carry out a treatment of removing a binder at 300° C. through 700° C.


By including the above-described sintering step as an indispensable step, there can be provided the semiconductor porcelain composition having [(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3 composition and being considerably reduced in the resisitvity at room temperature.


EXAMPLES
Powders of BaCO3 and TiO2 as main raw materials; La2O3, Dy2O3, Eu2O3, Gd2O3 and Y2O3 as semiconductor forming elements and valence control elements; SiO2 and CaO as sinter assisting agents; and (Na2CO3.Bi2O3.TiO2) as shifters of Curie temperature were respectively prepared. The respective powders were blended as shown in Table 1 to give a composition of [(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3, mixed in ethanol, and then dried to provide a mixed powder having a mean particle size of about 9.0 μm.
The mixed powder was calcined at 1000° C. for 4 hours in the atmosphere, the resulting calcined powder was pulverized by wet pulverization to a mean particle size of 0.9 μm, and then the resulting pulverized powder was dried. Successively, PVA was added to the dried powder, and the resulting mixture was mixed and then granulated by a granulating apparatus. The resulting granulated powder was formed by a monoaxis press apparatus to provide a formed product having a dimension of 28.5 mm×28.5 mm with a thickness of 0.7 mm through 18 mm, and a forming density of 2.5 through 3.5 g/cm3.
The formed product was subjected to binder removement at 300° C. through 700° C., thereafter, in a nitrogen atmosphere having an oxygen concentration shown in Table 1, the formed product was sintered at 1280 through 1380° C. for 4 hours in accordance with respective compositions to provide a sintered product having a dimension of 23.0 mm×23.0 mm with a thickness of 0.5 mm through 15 mm and a sintering density of 5.5 g/cm3. The resulting sintered product was processed into a plate-like shape of 10 mm×10 mm×1 mm (provided that a case of a thickness of the sintered product equal to or smaller than 1 mm was excepted) to provide a test piece.
Thermal changes of resistance values of the respective test pieces were measured by a resistance measuring instrument in a range of room temperature through 270° C. Results of the measurement are shown in Table 1. In Table 1, sample number 52 is an example using Dy as R, sample number 53 is an example using Eu as R, sample number 54 is an example using Gd as R, sample number 55 is an example using Y as R.
Further, in Table 1, comparative examples are attached with * marks at sides of sample numbers. FIG. 1 is a graph showing a thermal change of a resistivity in each case that, in [(Bi0.5Na0.5)x(Ba1-yLay)1-x]TiO3 composition, the value of y is set at 0.006, and the value of x is set at 0.02 (black circle a), 0.075 (black circle b), 0.875 (black rhombic c), 0.1 (black square d), 0.1375 (black triangle e), or 0.2 (white circle t.
As is apparent from Table 1 and FIG. 1, according to a semiconductor porcelain composition provided by the example of the invention, Curie temperature can be elevated without using Pb and a resistivity at room temperature can be considerably reduced.
Further, as is apparent from Table 1 and FIG. 1, an excellent property is provided in the range that x satisfies 0<x≦0.14, and y satisfies of 0.002≦y≦0.02.
Further, as is apparent from Table 1, it is understood that when sintered in an atmosphere with an oxygen concentration equal to or smaller than 1%, an excellent property is achieved, and further, the excellent property is achieved even in a comparatively large material having a thickness of 15 mm. This is because the property uniform to an inner portion of the material can be provided by carrying out sintering in an inert gas atmosphere with an oxygen concentration equal to or smaller than 1%.















TABLE 1














Sintered










object
Oxygen





SiO2
CaO
ρ30
Tc
thickness
concentration


No.
x
y
(mol %)
(mol %)
(Ωcm)
(° C.)
(mm)
(ppm, %)





 1*
0
0
1
1.9
insulator
—
4.0
9 ppm


 2*
0
0.005
1
1.9
10127
110
4.0
9 ppm


 3
0.02
0.002
1
1.9
320
132
4.0
9 ppm


 4
0.02
0.005
1
1.9
288
132
4.0
9 ppm


 5
0.02
0.008
1
1.9
246
132
4.0
9 ppm


 6
0.02
0.02
1
1.9
228
134
4.0
9 ppm


 7
0.075
0.002
1
1.9
666
161
4.0
9 ppm


 8
0.075
0.005
1
1.9
545
162
4.0
9 ppm


 9
0.075
0.008
1
1.9
439
161
4.0
9 ppm


10
0.075
0.02
1
1.9
387
162
4.0
9 ppm


11
0.0875
0.002
1
1.9
2601
170
4.0
9 ppm


12
0.0875
0.005
1
1.9
2556
170
4.0
9 ppm


13
0.0875
0.008
1
1.9
2421
171
4.0
9 ppm


14
0.0875
0.02
1
1.9
2132
173
4.0
9 ppm


15
0.1
0.002
1
1.9
3109
170
4.0
9 ppm


16
0.1
0.005
1
1.9
3003
170
4.0
9 ppm


17
0.1
0.008
1
1.9
2985
171
4.0
9 ppm


18
0.1
0.02
1
1.9
2867
173
4.0
9 ppm


19
0.1375
0.002
1
1.9
5006
170
4.0
9 ppm


20
0.1375
0.005
1
1.9
4911
170
4.0
9 ppm


21
0.1375
0.008
1
1.9
4827
171
4.0
9 ppm


22
0.1375
0.02
1
1.9
4695
173
4.0
9 ppm


23*
0.2
0.002
1
1.9
8323
230
4.0
9 ppm


24*
0.2
0.005
1
1.9
8122
231
4.0
9 ppm


25*
0.2
0.008
1
1.9
7834
234
4.0
9 ppm


26*
0.2
0.02
1
1.9
7619
236
4.0
9 ppm


27
0.0875
0.002
1
1.9
1532
173
0.5
9 ppm


28
0.0875
0.002
1
1.9
2285
173
8.0
9 ppm


29
0.0875
0.002
1
1.9
2331
173
12.0
9 ppm


30
0.0875
0.002
1
1.9
2894
173
15.0
9 ppm

























Sintered







CaO


object
Oxygen





SiO2
(mol
ρ30
Tc
thickness
concentration


No.
x
y
(mol %)
%)
(Ωcm)
(° C.)
(mm)
(ppm, %)





31
0.0875
0.002
1
1.9
2761
171
4.0
100 ppm 


32
0.0875
0.002
1
1.9
2947
171
4.0
1%


33*
0.0875
0.002
1
1.9
72
156
0.5
3%


34*
0.02
0.002
1
1.9
7134
142
4.0
3%


35*
0.02
0.02
1
1.9
4309
144
4.0
3%


36*
0.075
0.002
1
1.9
10023
159
4.0
3%


37*
0.075
0.02
1
1.9
8209
159
4.0
3%


38*
0.0875
0.002
1
1.9
34297
171
4.0
3%


39*
0.0875
0.02
1
1.9
12224
170
4.0
3%


40*
0.1
0.002
1
1.9
unmeasurable
170
4.0
3%


41*
0.1
0.02
1
1.9
198563
undeterminable
4.0
3%


42*
0.1375
0.002
1
1.9
unmeasurable

4.0
3%


43*
0.1375
0.02
1
1.9
unmeasurable

4.0
3%


44*
0.2
0.002
1
1.9
unmeasurable

4.0
3%


45*
0.2
0.02
1
1.9
unmeasurable

4.0
3%


46*
0.25
0.002
1
1.9
unmeasurable

4.0
9 ppm


47*
0.0875
0.025
1
1.9
43285
160
4.0
9 ppm


48
0.0875
0.005
0
0
61
161
4.0
9 ppm


49
0.0875
0.005
0
1
102
159
4.0
9 ppm


50
0.0875
0.005
1
0
92
161
4.0
9 ppm


51
0.0875
0.005
0.5
1.9
84
160
4.0
9 ppm


52
0.0875
0.005
1
1.9
108
156
4.0
9 ppm


53
0.0875
0.005
1
1.9
62
166
4.0
9 ppm


54
0.0875
0.005
1
1.9
82
155
4.0
9 ppm


55
0.0875
0.005
1
1.9
76
161
4.0
9 ppm









INDUSTRIAL APPLICABILITY
The semiconductor porcelain composition provided by the invention is most suitable as a material for a PTC thermistor, a PTC heater, a PTC switch, a temperature detector or the like.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph showing a temperature change of a resistivity of a semiconductor porcelain composition according to the invention.

## Claims

1. A method of producing a semiconductor porcelain composition having a positive temperature coefficient of resistivity, the method comprising:
sintering a formed composition represented by the composition formula [(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3 in which R is at least one element of La, Dy, Eu, Gd and Y and x and y each satisfy 0<x≦0.14, and 0.002≦y≦0.02 in an inert gas atmosphere with an oxygen concentration of 9 ppm to 1% and wherein a treatment at an elevated temperature in an oxidizing atmosphere after the sintering is not carried out.

2. The method of producing a semiconductor porcelain composition according to claim 1, wherein said composition further comprises SiO2 and CaO, and the amount of SiO2 is 3.0 mol % or less and the amount of CaO is 4.0 mol % or less.

3. The method of claim 1, wherein the formed composition is a disk having a thickness of at least 4 mm.

4. The method of claim 1, wherein the formed composition is a disk having a thickness of 8 to 15 mm.

5. The method of claim 1, wherein R in the composition formula is at least one of Dy, Eu, Gd and Y.