TW200935460A - Semiconductor ceramic composition and method for producing the same - Google Patents

Abstract

This invention provides a semiconductor ceramic composition and a method of producing the same in which a part of Ba in BaTiO3 is substituted with Bi-Na, so as to inhibit the evaporation of Bi during calcinations, and to prevent compositional shift of Bi-Na, which inhibits the formation of out-phases, reduces the resistivity at room temperature and inhibits fluctuation of Curie temperature. The Ba (TiM) O3 calcined powder (where M is a semiconductive element) and (BiNa) TiO3 calcined powders are prepared separately. The Ba(TiM)O3 calcined powder is calcined at a higher temperature, and the (BiNa)TiO3 calcined powder is calcined at a lower temperature, each being calcined at its corresponding optimum temperature respectively, so as to inhibit the evaporation of Bi and prevent compositional shift of Bi-Na and thus inhibit the formation of out-phases. The calined powders are mixed, formed, and sintered to obtain a semiconductor ceramic composition having a reduced resistivity at room temperature and a suppressed fluctuation of Curie temperature.

Description

200935460 IX. Description of the Invention: [Technical Field] The present invention relates to a semiconductor porcelain composition using a PTC thermistor, a PTC heater, a PTC switch, a temperature detector, etc., and having a positive resistance temperature, and a manufacturing thereof method. [Prior Art] As a material which exhibits a PTCR characteristic (proportional resistance temperature coefficient: p〇sitive ❹ ^mperatUre C〇efficient 〇f Resistivity), a composition in which various semiconductor elements are added to BaTi〇3 is proposed. The Curie temperature of these compositions is at 120. (: Left and right. In addition, the composition must be offset by the use of the composition. For example, it is proposed to add the SrTi〇3 in BaTi〇3 to offset the Curie temperature, but in this case, Curie The temperature is only shifted in the negative direction, in the positive direction: there is no offset. At present, it is known that the additive element that shifts the Curie temperature in the positive direction is only PbTi〇3 but 疋' because pbTi〇4 can cause environmental pollution. The bismuth element, in recent years, is eager to not use PbTi〇3 materials. For BaTiM semiconductors, it prevents the temperature coefficient of resistance caused by the replacement of pb and reduces the dependence on the battery, and improves the reliability and reliability. For the purpose of T, it is proposed that PbTiG3 is not used, but some of the brake knives in -BaTi〇3 are replaced by B-sub-Na.

In the Ba Bu 2x(BiNa)xTi〇3 structure, the force face ^ is added to any one of the Nb, Ta or rare earth elements in the composition in the range of χ<χ$0·15= After the sintering of the nitrogen towel, the BaTi〇3-based semiconductor ceramics of the oxidation process is also used in the manufacturing method (patent offer) of the f (four) U. 97104571 5 200935460 Patent Document 1: Japanese Patent Laid-Open Publication No. SHO 56-_1693 No. 1 [Draft of the Invention] ° (Problems to be Solved by the Invention) Patent Document 1 + 'In the implementation of the shots*, there will be a starting material • BaC〇 3, TiO" Bi2〇3, Na2〇3, pb0 and other constituents of the composition _ ϋ ^. Before satin burning, mixing, and satin burning, forming, firing, heat treatment. But 'BaTi〇3 Partially Ba uses Bi to replace the electroformed mash: If, as in the patent literature, all the elements constituting the composition are mixed before calcination, in the (four) burning step, Bi will volatize and cause Βϋ composition to deviate. Therefore, the generation of heterogeneous phases is promoted, and problems such as an increase in resistivity at room temperature and a change in Curie temperature are caused. In order to suppress the volatilization of Bi, calcination may be considered at a lower temperature, but

Although the diffusion of Bi is suppressed, there is a problem that the complete solid solution cannot be formed: the method obtains the desired characteristics. The object of the present invention is to provide a semiconductor ceramic composition which can shift the Curie temperature in the normal direction without using pb, and which can greatly reduce the electrical resistivity at room temperature, and a method for producing the same. Further, an object of the present invention is to provide a semiconductor porcelain composition in which a portion (6) of BaTi〇3 is substituted with Bi-Na, suppressing the V-dispersion in the calcination step, and preventing the compositional deviation of Bi-Na. In the case, the formation of a heterogeneous phase is suppressed, and the resistivity at room temperature is further lowered, and the semiconductor ceramic composition in which the Curie temperature fluctuation is suppressed and the method for producing the same can be suppressed. (Means for Solving the Problem) In order to achieve the above object, the inventors found that 97104571 6 200935460, when fabricating a semiconductor ceramic composition in which a portion Ba of BaTi〇3 is substituted with Bi_Na, is prepared by separately preparing Ba. (TiM) 〇3 calcined powder (M-based semiconductor element) and (BiNa)Ti〇3 calcined powder, and Ba(TiM)〇3 calcined powder is based on higher temperature, and (BiNa)Ti〇3 calcined powder At a lower temperature, the calcination is carried out according to the respective optimum temperatures, thereby suppressing the Bi-dispersion of Ba(TiM)〇3烺-burning powder, preventing Bi_Na composition variation, suppressing heterogeneous formation, and mixing the calcined powders. And forming and sintering, a semiconductor ceramic composition having a low resistivity to a temperature and suppressing a change in the Curie temperature can be obtained. The manufacturing method of the semiconductor porcelain composition of the present month is a method for preparing a semiconductor device composition in which t〇3 = partial Ba is replaced by Bi-Na, and includes: preparing ga(TiM)〇3 calcined powder ( a step of preparing a (Bi-based semiconductor element); a step of preparing a calcined powder of (BiNa) Ti〇3 calcined powder and (10) a) a Ti0 side-fired powder; and a step of forming and sintering the calcined powder. Further, the present invention is directed to the production method of the above configuration, and is proposed as follows: In the step of preparing Ba (TiM) 04 powder, the calcination temperature is 9 generations.

In the middle of the step, the calcination temperature is 70 (TC in the step of preparing (BiNa) Ti〇3 calcined powder ~ 950 ° C; the calcined powder is mixed in the Ba (TiM) 〇 3 calcined powder and (BiNa) Ti 〇 3 step Let the 'mixed system be dry-type; in the step of preparing the calcined powder of Ba(TiM)〇3 calcined powder, or in two steps, or prepare (BiNa)Ti〇3烺 before calcination, add Si oxide 97104571 200935460 3. 0 mol% or less, Ca carbonate or Ca oxide 4. 0 mol% or less; in the step of mixing Ba(TiM)〇3 calcined powder with (BiNa)Ti〇3 calcined powder, Addition of Si oxide of 3.0% or less, Ca carbonate or Ca oxide of 4.0% by mole or less; at least one of the semiconductor elements lanthanides Nb and Sb, and the composition of the semiconductor porcelain composition is dependent on [ (Order) 5^1_3[][141_1]〇3 indicates that the 7 series satisfies 0 <x$ 〇. 3, 〇<y$〇. 〇〇5 ; and the ratio of Bi to Na in the composition The semiconductor porcelain composition of the present invention is a Ba (TiM) 〇3 calcined powder (M-based semiconductor element, and is Nb, Sb). At least one) and (BiNa a semiconductor ceramic composition obtained by forming and sintering a mixed calcined powder of Ti〇3 calcined powder, wherein the composition formula is [(BiNa)xBai χ] [Tii means 'x, y satisfies 0 < x^〇.3, 0<y^ 0.005, the ratio of Bi to Na satisfies the relationship of Bi/Na=0.78~1. (Effect of the invention) 〇 According to the present invention, Pb which does not cause environmental pollution can be provided, and Curie can be provided. According to the present invention, the temperature rises and the electrical resistivity at room temperature is greatly reduced. - The cow can provide a Bi-voke condition capable of suppressing the calcination step + to prevent the compositional deviation of Bi-Na. The difference of Na: = is 'and can make the resistivity at room temperature more lower' and can inhibit the variation of the state of the semiconductor ceramic composition. 'Dishes】In the present invention, the Ba(TiM) Q3 gun is prepared. Burning powder (M-based semiconductor element) 97104571 8 200935460 The first step is to mix the main raw material, 3, Ti〇2, with the semiconductor element Nb2〇5 or Sb2〇3 to form a mixed raw material powder. Execution. Calcination. The calcination temperature is preferably set at _. (b) 3 Saki range The calcination time is preferably set to 0.5 hours or more. If the calcination temperature is not fully satisfied, C or - calcination time is less than 0.5 hours, and it cannot be completely formed as _3, which is not reversed and should be mixed with the environment and the medium. The moisture produces a reaction that leads to a component deviation and is therefore best avoided. Further, since the temperature of the calcination is over 1300 Torr, a sintered body is formed in the sinter-burning powder, which hinders the solid solution between the (BiNa)Ti〇3 calcined powder which is mixed with the sinter, and thus is preferably avoided. In the present invention, a step of preparing (BlNa) Ti〇3 calcined powder is carried out by first mixing Na2C〇3, Bi2〇3, and Ti〇2 of the raw material powder to prepare a mixed raw material powder, and performing calcination. The calcination temperature is preferably set at 7 〇 (rc~95 (rCi circumference), and the firing time is preferably set at 0.5 hour to 1 hour. If the calcination temperature is less than 7 〇〇C or the calcination time is less than 〇·5 hours The unreacted Ν& 〇 will react with the moisture of the environment or the solvent in the wet mixing, resulting in composition enthalpy deviation, characteristic variation, etc., and thus preferably avoided. In addition, if the calcination temperature exceeds 9501: or calcination time If it exceeds 1 hour, it will promote Bi volatilization, cause composition deviation, and promote heterogeneous formation, so it is best to avoid it. In addition, the preferred calcination temperature in the step of preparing the above Ba(TiM)〇3 calcined powder (900.〇1300) 〇, and the preferred calcination temperature in the step of preparing (BiNa) Ti〇3 satin powder (7〇〇t~950. 〇, preferably in combination with the use, etc., the optimum temperature is appropriately selected. For example (β i Na The calcination temperature of T i 〇 3 is preferably carried out at a lower temperature in order to sufficiently carry out the reaction while suppressing the dispersion of Bi, and the calcination temperature of (BiNa)Ti〇3 is further reduced to 97104571. 9 200935460 degrees is best set to The calcination temperature of Ba(TiM)〇3. The steps of preparing Ba(TiM)〇3 and preparing the (BiNa)Ti〇3 calcined powder, respectively, are the main features of the present invention, whereby Bi θ of (BiNa)Ti〇3 in the satin burning step is prevented—Bi-Na composition is prevented from deviating 俾, and heterogeneous phase generation is suppressed, and the resistivity of the temperature of the medium is further reduced and the semiconductor ceramic composition is suppressed from changing in the Curie temperature. In the step of preparing the calcined powder, the raw material powder may be mixed, and the powder may be pulverized in accordance with the particle size of the raw material powder. In addition, the mixing and pulverizing may be carried out by wet mixing, pulverization or blending using pure water or ethanol. In any of the methods such as pulverization, it is preferable to carry out dry mixing and pulverization to further prevent composition variation. In the above, BaC〇3, NaAOs, Ti (h, etc.) are exemplified as the raw material powder, but other Ba compounds are used. The compound or the like does not impair the effects of the present invention. As described above, after preparing Ba(TiM)〇3烺-burning powder and (BiNa)Ti〇3 satin-fired powder separately, each satin-fired powder is prepared and quantified. Mixing It can adopt wet mixing or dry mixing using pure water or ethanol; the method 'prefers to dry mixing, because it can prevent the composition deviation. In addition, it can also be combined with the particle size of the smoldering powder. The pulverization or the simultaneous mixing and pulverization is carried out. The average particle size of the mixed calcined powder after mixing and pulverization is preferably from 0.6/zm to 1.5/zin. The above steps and/or preparation for preparing Ba(TiM) 〇3 calcined powder ( In the step of calcining the B'TiG3 powder or the step of mixing the calcined powders, if the Si oxide is 3.0 mol% or less, and the oxide or the carbonate is 4.0% by mass or less, the Si oxide suppresses the crystal grains. The abnormality is 97104571 200935460 long, and the resistivity can be easily controlled, and the CaA compound or the c acid salt can improve the sinterability at a low temperature and can control the reducing property, which is a preferable condition. If any of the above-mentioned limited amounts is added, the composition cannot be semiconductorized, and thus it is preferable to avoid it. The addition is preferably carried out before mixing in each step. The mixed calcined powder obtained by the step of mixing Ba(TiM)〇3 calcined powder with (BiNa)Ti〇3 calcined powder is shaped and sintered. You can get: ❹ Invented semiconductor porcelain composition. An example of a preferred step after the calcining powder mixing step is exemplified below, but it is not limited thereto, and any known method can be employed. The mixed calcined powder obtained by the step of mixing Ba(TiM)〇3 satin powder and (BiNa)Ti〇3烺 powder is formed by a desired forming means. Before the forming, the pulverized powder may be granulated by a granulator as needed. The density of the formed body after molding is preferably 2 to 3 g/cm3. The sintering system can be in the atmosphere or in a reducing environment, or in an inert gas atmosphere of low oxygen concentration, and at a sintering temperature of 1200 ° C to 1400. (: The sintering time is carried out under conditions of 2 hours to 6 hours, and 'the sintering step shown below is also a preferred example. In addition, when granulation is performed before forming, it is preferable to use 3 0 before sintering. Debonding treatment is carried out at 0 °C to 7 0 °C. - The sintering step is carried out at a temperature of 1290 ° C to 135 (TC, oxygen concentration less than 1% in the environment, (1) sintering time less than 4 hours Implementation, or (2) according to the satisfaction formula: Δ T2 25t (t = sintering time (hr), Δ T = cooling rate after sintering (°C / hr)) sintering time, followed by cooling according to the above formula Speed is performed after sintering. 97104571 200935460 Any of the above sintering steps, that is, shortening the sintering time or prolonging the sintering = quenching by the appropriate quenching speed according to the sintering time, can be performed by using BaTiCh-based materials, In the atmosphere where heat is applied, etc., the semiconductor material composition that maintains a low room temperature specific resistance and raises the temperature coefficient of resistance in a high temperature region (above the Curie temperature) is used in the above sintering step. The so-called "oxygen concentration is not full U ring t" means a vacuum or an inert gas atmosphere in which the oxygen concentration is less than U. The preferred gas environment towel is preferably carried out, for example, in a nitrogen or argon atmosphere. In addition, the environment after cooling is also the most In the above sintering step, when the method of the above (1) is carried out, the sintering conditions for sintering can be arbitrarily selected. On the other hand, when the method of the above & The cooling rate Δ valence is determined according to the length of the sintering time t. For example, when the sintering time is U hr, the cooling rate is set to 25xl=25°C/hr or more, and when the sintering time t is 4 hours, In other cases, the cooling rate ΔΤ is set to 25x4=10 (rc/hr or more. That is, ♦ the case where the two junction time t increases) is matched with the sintering time, and the cooling rate is accelerated. This method is the case where the sintering time t increases. Effective, but two • Sintering time t is short (for example, less than 4 hours) is still applicable.

- The composition of the semiconductor device to be used in the present invention is to replace B part B with BtNa, as described above, and to divide (4) the melon forging powder (the step of M-system semiconductorization phantom = (BiNa) Ti〇3 The step of calcining the powder, and the same as the 'heart 1 butt, the maiden, shape, and sintering can be obtained. Dan,, Gongcheng 97104571 12 200935460 Partial BaTi (h composition substituted with Bi-Na) By adding a semiconductor element and performing valence control, it becomes a semiconductor device composition. In the present invention, a 'semiconductor element is added to BaT i 〇 3 to become Ba(TiM) 〇3 烺 burnt powder ( M system semiconductor element), the composition formula of the semiconductor semiconductor composition obtained is expressed by [(BiNa)xBai-x] [Tii-yMy ] 〇3, and X, y satisfies 0 < xS0.3, 〇 < Y$〇.〇〇5. [(BiNa)xBai-x][Tii-yMy]〇3 In the composition, x is the range of the composition of (BiNa), and 00<χ$0·3 is the preferred range. For 〇, the Curie temperature cannot be shifted toward the high temperature side. On the other hand, if it exceeds 0 3, the room temperature resistivity will be close to 104 Ωαη, which is difficult to apply to PTC heaters, etc. Therefore, it is best to avoid. In addition, at least N of Nb and Sb are preferably Nb ^, where y is the range of ingredients, and 0 yg 〇〇〇 5 is preferred. Right y is 0. 'The valence control cannot be performed, and the composition cannot be semiconductorized. 反之 On the other hand, if it exceeds 0.005, the room temperature resistivity exceeds 1〇3〇cm, so it is best to avoid it. In addition, the above G<(8) Emol%% The expression is 0 0.5 mol% (excluding 〇). The above [(BiNahBahHTn-yMy;^ composition, in order to perform valence control] is to replace Ti with M element, but in this case, π The addition (addition amount G < y money (10) 5) is for the purpose of controlling the atomic price of the tetravalent element, and it can be divided into several parts. The sword has a small amount of atomic price control and can reduce the composition of the obtained semiconductor valve. The internal strain of the object is such that the composition of t, rLNl)xBai_x][Ti,_ is ]03, Bi * Na is set to ι:ι, that is, the composition formula is preferably [(Bi〇5Na〇5)" Ai x][TiiyMy]〇3. 97104571 13 200935460 === It is also recorded that if all the elements constituting the composition are scattered, the two-heart = T burnt step In the case of Bi-swings, it promotes the generation of heterogeneous phases, which leads to an increase in the electric rate of the chamber's dish, which causes a problem of fluctuations in the Curie temperature. ❹ Resistivity in the second temperature of the Curie temperature, and can suppress X changes. When the right Bi/Na exceeds 1, Bi which acts on (BiNa)Ti〇3 will remain in the material, which causes a heterogeneous phase to be easily formed during sintering, resulting in an increase in resistivity at room temperature, and conversely, it is easy in the sintering stage. Heterogeneous is generated, resulting in a resistivity at room temperature: and thus is best avoided. According to the above-mentioned Austrian; iL ancient, soil ^. table & method, the composition formula can be obtained according to [(BiNaXJBahnTibMy^w is at least one of Nb, Sb), and X, y meets 〇 <U〇 .3, 〇 <0〇〇〇5, and the ratio of Bi to Μ satisfies the relationship of Bi/Na=0.78~l, and the semiconductor device and composition have no effect on unused Environmental pollution (4)

In the case of Pb, the Curie temperature can be increased and the electrical resistivity at room temperature can be greatly reduced. [Examples] [Example 1] Raw material powders such as BaC〇3 and Ti〇2 as main raw materials and Nb2〇s as a semiconductor element were prepared and formulated in the form of BaCTio.mNbuWO3, and were carried out in pure water. mixing. The obtained mixed raw material powder 97104571 14 200935460 was calcined at 1000 ° C for 4 hours to prepare a calcined powder of 〇 3 . The raw material powders of Na2C〇3, Bi2〇3, and Ti〇2 are prepared, and are mixed in the form of (BiuNao.OTiO3) and mixed in ethanol. The obtained mixed raw material powder is immersed in the atmosphere. c~9〇〇.〇4 hours of satin burning to obtain (BiNa)Ti〇3 calcined powder. The obtained (Bi°.5Na°.5) Ti〇3 calcined powder in 600t~90 (TC The X-ray diffraction pattern of each calcination temperature is as shown in Fig. 1. The Ba(TiNb)〇3 calcined powder and the calcined (BiNa) Ti〇3 calcined powder according to 80 (rc) are used as the molar ratio. In the way of 73:7, it is possible to add Si〇2 (〇.4 mol%) and CaC〇3 (1 4 mol/〇) as a sintering aid, and mix and pulverize with a ball mill using pure water as a medium. Until the center particle diameter of the mixed calcined powder is 〇Am, and then dried. PVA is added to the pulverized powder of the shai mixed calcined powder and mixed, and then granulated by a granulator. The granules are formed by a uniaxial pressing device, and then the above-mentioned formed body is subjected to a bismuth (the rc is subjected to a debonding adhesive agent in the atmosphere, depending on the sintering temperature 13 〇 (rc ~ 138{rc) is sintered for 4 hours to obtain a sintered body. The obtained sintered body is processed into a plate shape of 1 〇mmx 1 〇mmxl to prepare a test piece, and after forming an ohmic electrode, each will be formed. The test piece was measured by a resistance measuring device - the temperature change of the specific resistance value was performed in the range of room temperature to 270 ° C. The measurement results are shown in Table 1. In addition, the composition analysis of Bi and Na was performed, and Bi / Na was determined. The results are shown in Table 1. In addition, sample No. 5 in Table 1 is an example in which dry mixing is carried out in the atmosphere in the step of preparing (BiNa)Ti〇3烺-fired powder, and the rest belongs to ethanol. Example of mixing. 97104571 15 200935460 In addition, the "*" mark next to the sample No. refers to a comparative example. [Comparative Example 1] BaCCh and T i 〇2 as main raw materials; Nb2〇5 as a semiconductor element; As a Curie temperature shifting agent, Na2C〇3, Bi2〇3, Ti〇2, and all the elements constituting the composition were initially formulated, and Si〇2 (0.9 mol%) as a sintering aid was added. ), CaC〇3 (1.9 mol%), and then mixed in ethanol. The raw material powder is calcined in the atmosphere at 2 to 1200 ° C for 4 hours to obtain a calcined powder. The obtained [(81.. also .5)" 8b 31][1^卜1]〇3 ( Fork = 0.06, 7 = 0.005) 烺 粉 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Pva was added to the calcined powder, and after mixing, granulation was carried out by means of a granulation apparatus. The obtained granulated powder was molded by a uniaxial pressing apparatus, and the above-mentioned formed body was subjected to debonding agent according to 5 〇〇〇c, and then sintered in the atmosphere at a sintering temperature of 〇32 〇t for 4 hours to obtain a sintered body. The obtained sintered body is processed into a plate shape of 1 〇mmxl 〇mmxlmin to prepare a test piece. After forming an ohmic electrode, each test piece is subjected to a specific resistance by using a resistance measuring device to a temperature of 270 C. The temperature change of the value is determined. / The results are shown in Table 1 in the sample N〇. In addition, the implementation of βi and

The composition of Na was analyzed and the ratio of Bi/Na was determined. The results are shown in the sample N〇. 6 of Table j. 1 and 2, the (BiNa)Ti〇3 calcined powder of Example 1 completely became a single phase at 70 (TC). On the other hand, in the comparative example, the structure was 97104571 16 200935460. All of the elements are initially formulated. In this case, if it is less than 900 c or more, it is impossible to obtain a calcined powder. Further, as seen from Table i, the semiconductor valve of the present invention of the embodiment is composed. The Curie temperature can be raised, and the resistivity at room temperature can be greatly reduced. Steps and preparation for preparing Ba(TiNb)〇3 calcined powder by means of a knife (B_i〇3 calcined powder step) It can suppress Bi volatilization and has a high Bi/Natb even after sintering, so that generation of heterophase can be suppressed, and the resistivity to the temperature can be further lowered, and the variation of the Curie temperature can be suppressed. The semiconductor porcelain composition of the comparative example can achieve a rise in Curie temperature but a low temperature coefficient of yttrium resistance. Moreover, in the calcination step and the sintering step, since a large amount of Bi is volatilized, the Bi/Na ratio after sintering is 0. 77 or less. In addition, in all of the examples, the temperature coefficient of resistance Calculate according to the following formula: TCR=(InRi-InRc)xl〇〇/(T1-T〇) R1 is the maximum specific resistance, R r T ~1 I .T- Electric I Kc is the specific resistance under 1C, Τι It is the temperature of Ri, and the temperature of ❾Tc is the Curie temperature.

Bi/Na ratio -iiL) ι〇30 (Ω cm) Tc (°C) Temperature coefficient of resistance (%/°〇199 138 149 22. 6 84 158 19. 9 _i94__ 72 155 19. 5 -Λ91_ 96 161 17.8 - Α97_ 81 157 20. 3 73 160 16. 9 [Table 1]

The descriptions of the specific embodiments are described in detail, and various changes can be made without departing from the spirit and scope of the present invention. 97104571 17 200935460 The amendments can be understood by those skilled in the art. This application is based on the Japanese Patent Application (Japanese Patent Application No. 2006-298304) filed on Nov. 1, 2006, the content of which is hereby incorporated by reference in The semiconductor porcelain composition is suitable for materials such as pTC thermistors, PTC heaters, PTC switches, temperature detectors, and the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an X-ray diffraction pattern of a semiconductor ceramic composition of the present invention at each calcination temperature. Fig. 2 is a ray diffraction pattern of the semiconductor ceramic composition of the comparative example at each calcination temperature. 97104571

Claims (1)

200935460 X. Patent application scope: 1 . A method for manufacturing a semiconductor porcelain composition, which is used for manufacturing a semiconductor porcelain composition in which a part of Ba of BaTi〇3 is replaced by Bi_Na, and is characterized by comprising: preparing Ba (TiM) 〇3 calcined powder (M system semiconducting, body element) step; preparation of (BiNa)Ti (h calcined powder step; mixing .Ba(TiM)〇3 calcined powder with (BiNa)Ti〇3 calcined powder And a step of forming and sintering the mixed calcined powder. The method for producing a semiconductor ceramic composition according to claim 1, wherein in the step of preparing Ba(TiM)〇3烺 calcined powder The satin-sintering temperature is 900 ° C to 1300 ° C. 3. The method for producing a semiconductor ceramic composition according to claim 1, wherein the calcining temperature is in the step of preparing (BiNa)Ti〇3 calcined powder 700 ° C ~ 950 ° C. 4. The method for manufacturing a semiconductor porcelain composition according to claim 1, wherein the Ba (TiM) 〇 3 calcined powder and the (BiNa) Ti 〇 3 calcined powder In the mixing step, the mixing system is implemented in a dry manner. The method for producing a semiconductor ceramic composition according to item 1 of the first aspect, wherein the step of preparing Ba(TiM)〇3 calcined powder, or the step of preparing 1 (BiNa)Ti〇3 satin powder, or the two steps In the method of manufacturing a semiconductor ceramic composition according to claim 1, wherein the Si emulsion is 3.0 mol% or less, and the Ca carbonate or the Ca oxide is 40% or less. In the step of mixing Ba (TiM) 〇 3 calcined powder with (BiNa) Ti 〇 3 烺 烺 powder, 'addition of Si oxide 3.0 mol% or less, Ca broken 97104571 200935460 acid salt or Ca 氡 4 4. 〇 The molar composition is less than or equal to 7. The manufacturing method of the semiconductor ceramic composition of the first aspect of the patent application, wherein at least one of the semiconductor elements lanthanides Nb and Sb, the composition of the semiconductor porcelain composition is [[BiNa] )xBai-x] [Tii-yMy]〇3 means that x and y are satisfied by 〇< 〇. 3, 〇< 〇. 〇〇5. 8_The semiconductor ceramic composition of claim 7 The manufacturing method, wherein the ratio of Bi to Na satisfies the relationship of Bi/Na=〇.78~丨. 9. A semiconductor porcelain Composition ❹ -...You will be a semiconductor made of sinter calcined powder (M-based semiconductor element and at least one of Nb and Sb) and (_Ti〇3 calcined powder mixed calcined powder for forming and sintering) The composition of the porcelain is composed of [(BiNa)xBai_x][Til_yMy]〇3, X and y satisfy 〇<x^0.3, 0 <y$ 0.005, and the ratio of Bi to Ν& satisfies Bi/Na= The relationship of 0.78~1. 97104571 20