US20040176238A1 - Nonreducing dielectric ceramic, its production method and multilayer ceramic capacitor - Google Patents

Nonreducing dielectric ceramic, its production method and multilayer ceramic capacitor Download PDF

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US20040176238A1
US20040176238A1 US10/480,198 US48019803A US2004176238A1 US 20040176238 A1 US20040176238 A1 US 20040176238A1 US 48019803 A US48019803 A US 48019803A US 2004176238 A1 US2004176238 A1 US 2004176238A1
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accessory
constituents
dielectric ceramic
cubic
principal
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Toshiyuki Ito
Harunobu Sano
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Murata Manufacturing Co Ltd
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Assigned to MURATA MANUFACTURING CO., LTD. reassignment MURATA MANUFACTURING CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SANO, HARUNOBU, ITO, TOSHIYUKI
Publication of US20040176238A1 publication Critical patent/US20040176238A1/en
Priority to US11/875,683 priority Critical patent/US7498285B2/en
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Definitions

  • the present invention relates to a strontium titanate-based nonreducing dielectric ceramic, a method for manufacturing the same, and a monolithic ceramic capacitor using the nonreducing dielectric ceramic.
  • the present invention is intended to increase the relative dielectric constant of the nonreducing dielectric ceramic and to thus enhance the reliability of the monolithic ceramic capacitor.
  • dielectric ceramic materials are reduced to semiconductors by firing under a low oxygen partial pressure in, for example, a neutral or reducing atmosphere. Accordingly, internal electrodes of a monolithic ceramic capacitor comprising such a dielectric ceramic material have to be formed of a conductive material, such as palladium and platinum, that is not oxidized by firing under a high oxygen partial pressure nor is melted at the sintering temperature of the dielectric ceramic material. This makes it difficult to reduce the price and increase the capacitance of the monolithic ceramic capacitor.
  • a conductive material such as palladium and platinum
  • a dielectric ceramic material is required which is not changed to semiconductor by firing in a neutral or reducing atmosphere with a low oxygen partial pressure and which provides excellent dielectric characteristics if these base metals are used.
  • compositions expressed by the formula (Sr 1-x Ca x )(Ti 1-y Zr y )O 3 have been proposed (for example, in Japanese Unexamined Patent Application Publication Nos. 2000-53466 and 63-224106).
  • base metals such as nickel and copper, can be used as a conductive material for the internal electrodes of monolithic ceramic capacitors.
  • the relative dielectric constant of the strontium titanate-based nonreducing dielectric ceramic disclosed in Japanese Unexamined Patent Application Publication No. 2000-53466 is as low as less than 150.
  • the relative dielectric constant of the strontium titanate-based nonreducing dielectric ceramic disclosed in Japanese Unexamined Patent Application Publication No. 2001-351828 is disadvantageously as low as less than 100.
  • an object of the present invention is to provide a strontium titanate-based nonreducing dielectric ceramic exhibiting a high relative dielectric constant of 150 or more and a high reliability for high temperature loading, and a method for manufacturing the same.
  • Another object of the present invention is to provide a monolithic ceramic capacitor comprising the nonreducing dielectric ceramic.
  • a nonreducing dielectric ceramic which comprises a SrTiO 3 -based perovskite principal crystal phase containing 55 mole percent or more of SrTiO 3 and accessory crystal phases including all the crystal phases other than the perovskite crystal phase.
  • a nonreducing dielectric ceramic which comprises a (Sr, Ca) (Ti, Zr)O 3 -based perovskite principal crystal phase containing 55 mole percent or more of SrTiO 3 and accessory crystal phases including all the crystal phases other than the perovskite crystal phase.
  • the powder CuK ⁇ X-ray diffraction pattern was actual data without smoothing obtained from a measurement with an X-ray diffractometer (Model: RU-200PL) manufactured by Rigaku Industrial Corporation.
  • the measurement was conducted with a radiation source of CuK ⁇ using a 1/2° divergent slit, a 1/2° scattering slit, a 0.15 mm receiving slit at a tube voltage of 40 kV and a tube current of 25 mA, with continuous scanning at a scanning speed of 4°/min, a scanning width of 0.02° C., and a scanning range of 200 to 60°.
  • the SrTiO 3 -base perovskite crystal phase containing 55 mole percent or more of SrTiO 3 refers to a SrTiO 3 perovskite crystal phase expressed by the general formula ABO 3 in which the strontium content in the A site is 55 mole percent or more and the titanium content in B site is 55 mole percent or more.
  • the (Sr, Ca)(Ti, Zr)O 3 -base perovskite crystal phase containing 55 mole percent or more of SrTiO 3 refers to a SrTiO 3 perovskite crystal phase expressed by the general formula ABO 3 in which the strontium content in the A site is 55 mole percent or more and the titanium content in B site is 55 mole percent or more.
  • the invention according to the first and second aspects is advantageously applied to a nonreducing dielectric ceramic having the following composition.
  • the principal constituents of the nonreducing dielectric ceramic preferably, constitute a composition expressed by the formula (Sr 1-w-x Ca w Ba x ) m (Ti 1-y-z Zr y Hf z )O 3 , where w, x, y, z, and m satisfy the expressions: 0 ⁇ w ⁇ 0.45; 0 ⁇ x ⁇ 0.05; 0 ⁇ w+x ⁇ 0.45; 0 ⁇ y+z ⁇ 0.45; and 0.95 ⁇ m ⁇ 1.05.
  • the accessory constituents contain at least one element selected from the group consisting of Mn, Ni, and Co, and the total content of these elements in terms of MnO, NiO, or CoO is in the range of 0.05 to 6.0 moles relative to 100 moles of the principal constituents.
  • the nonreducing dielectric ceramic may further contain Re being at least one element selected from the group consisting of Dy, Ho, Er, Tm, Yb, Lu, Y, and Sc, as accessory constituents.
  • the nonreducing dielectric ceramic of the present invention may have the following composition.
  • the principal constituents of the nonreducing dielectric ceramic preferably constitute a composition expressed by the formula (Sr 1-w-x Ca w Ba x ) m (Ti 1-y-z Zr y Hf z )O 3 , where w, x, y, z, and m satisfy the expressions: 0 ⁇ w ⁇ 0.45; 0 ⁇ x ⁇ 0.05; 0 ⁇ w+x ⁇ 0.45; 0 ⁇ y+z ⁇ 0.45; and 0.95 ⁇ m ⁇ 1.05.
  • the accessory constituents contain Re being at least one element selected from the group consisting of Dy, Ho, Er, Tm, Yb, Lu, Y, and Sc, and the total content of these elements is in the range of 0.05 to 5.0 moles relative to 100 moles of the principal constituent, in terms of DyO 3/2 , HoO 3/2 , ErO 3/2 , TmO 3/2 , YbO 3/2 , LuO 3/2 , YO 3/2 , or ScO 3/2 .
  • the accessory constituents further contain at least one element selected from the group consisting of Mn, Ni, and Co, and the total content of these elements in terms of MnO, NiO, or CoO is in the range of 0.05 to 6.0 moles relative to 100 moles of the principal constituents.
  • the nonreducing dielectric ceramic having any of the foregoing compositions further contains at least one of an aluminium compound and a magnesium compound as accessory constituents, and their total content is 6.0 moles or less in terms of AlO 3/2 or MgO relative to 100 moles of the principal constituents.
  • the nonreducing dielectric ceramic of the present invention may further contain a sintering agent containing at least one of Si and B.
  • the sintering agent content is 20 parts by weight or less to 100 parts by weight of all the constituents of the principal constituents and the accessory constituents.
  • the present invention is also directed to a method for manufacturing the nonreducing dielectric ceramic.
  • the method includes: the step of preparing a plurality of starting materials containing elements constituting a composition expressed by (Sr 1-w-x Ca w Ba x ) m (Ti 1-y-z Zr y Hf z )O 3 , where 0 ⁇ w ⁇ 0.45, 0 ⁇ x ⁇ 0.05, 0 ⁇ w+x ⁇ 0.45, 0 ⁇ y+z ⁇ 0.45, and 0.95 ⁇ m ⁇ 1.05; the step of mixing the starting materials; the preliminary calcination step of calcining the mixture of the starting materials; the mixing and pulverization step of mixing and pulverizing the preliminarily calcined material; the main calcination step of fully calcining the preliminarily calcined material at a temperature higher than the temperature of the preliminary calcination so as to complete the reaction, after the mixing and pulverizing step; and the step of firing the material subjected to the main calcination to be sintered.
  • a nonreducing dielectric ceramic containing 55 mole percent or more of SrTiO 3 and exhibiting a maximum peak intensity of less than 5% of accessory crystal phases being crystal phases other than the perovskite crystal phase can be produced while the accessory crystal phases are prevented from being produced.
  • the present invention is also directed to a monolithic ceramic capacitor.
  • the monolithic ceramic capacitor of the present invention includes a plurality of dielectric ceramic layers, and a plurality of internal electrodes containing a base metal as a conductive constituent.
  • the internal electrodes lie along specific interfaces between the dielectric ceramic layers. External electrodes each electrically connected to some of the internal electrodes are also provided.
  • the dielectric ceramic layers comprise the above-described nonreducing dielectric ceramic of the present invention.
  • the base metal contained in the internal electrodes may be nickel, a nickel alloy, copper, or a copper alloy.
  • the monolithic ceramic capacitor using the nonreducing dielectric ceramic of the present invention exhibits a high relative dielectric constant of 150 or more and a low third-order harmonic distortion.
  • the thickness of the dielectric ceramic layers of the monolithic ceramic capacitor can be reduced to about 5 ⁇ m. This is advantageous for reducing the size and increasing the capacitance of monolithic ceramic capacitors.
  • inexpensive base metals such as nickel and copper, can be used as the conductive material of the internal electrodes in monolithic ceramic capacitors without problems.
  • FIG. 1 is a schematic sectional view of a monolithic ceramic capacitor 1 according to an embodiment of the present invention.
  • FIG. 2 is a powder X-ray diffraction pattern of a fully calcined powder of Sample 8 according to the present invention.
  • FIG. 3 is a powder X-ray diffraction pattern of a sintered compact of Sample 8 according to the present invention.
  • FIG. 4 is a powder X-ray diffraction pattern of a sintered compact of Sample 20 outside the scope of the present invention.
  • FIG. 5 is a powder X-ray diffraction pattern of a fully calcined powder of Sample 22 outside the scope of the present invention.
  • FIG. 6 is a powder X-ray diffraction pattern of a sintered compact of Sample 22 outside the scope of the present invention.
  • FIG. 1 is a sectional view of a monolithic ceramic capacitor 1 according to an embodiment of the present invention.
  • the monolithic ceramic capacitor 1 includes a laminate 2 .
  • the laminate 2 includes a plurality of dielectric ceramic layers 3 and a plurality of internal electrodes 4 and 5 formed along specific interfaces between the dielectric ceramic layers 3 .
  • the internal electrodes 4 and 5 extend to external surfaces of the laminate 2 . Specifically, the internal electrodes 4 extending to one side surface 6 of the laminate 2 and the internal electrodes 5 extending to the other side surface 7 are alternately disposed in the laminate 2 so that two adjacent internal electrodes 4 and 5 separated by the dielectric ceramic layer 3 produce a capacitance.
  • the internal electrodes 4 and 5 contain a base metal, such as nickel, a nickel alloy, copper, or a copper alloy, as a conductive constituent.
  • external electrodes 8 and 9 are respectively provided on the external side surfaces 6 and 7 of the laminate 2 to be electrically connected to either the internal electrodes 4 or 5 .
  • the conductive material of the external electrodes 8 and 9 may be the same as that of the internal electrodes 4 and 5 , and besides, silver, palladium, a silver-palladium alloy, and the like may be used.
  • the external electrodes 8 and 9 are formed by applying and burning a conductive paste containing a powder of these metals and a glass frit.
  • the external electrodes 8 and 9 are respectively covered with first plating layers 10 and 11 formed of nickel, copper, or the like, and the first plating layers 10 and 11 are respectively covered with second plating layers 12 and 13 formed of solder, tin, or the like.
  • the dielectric ceramic layers 3 are formed of a nonreducing dielectric ceramic of the present invention.
  • the ceramic has a low Curie temperature of ⁇ 60° C. or less and does not exhibit ferroelectricity at room temperature. Therefore, the nonreducing dielectric ceramic can exhibit a low dielectric loss, a low third-order harmonic distortion rate, and a relative dielectric constant of 150 or more.
  • the maximum peak intensity ratio of the accessory crystal phases is less than 5%, the lifetime in a high temperature-loading test becomes relatively long and, thus, a high reliability can be achieved.
  • the nonreducing dielectric ceramic may further contain barium in the A site and hafnium in the B site.
  • the nonreducing dielectric ceramic typically contains principal constituents forming a composition expressed by the formula (Sr 1-w-x Ca w Ba x ) m (Ti 1-y-z Zr y Hf z )O 3 .
  • w satisfies the relationship 0 ⁇ w ⁇ 0.45. This is because a w value of more than 0.45 leads to a low relative dielectric constant.
  • x satisfies the relationship 0 ⁇ x ⁇ 0.05. This is because an x value of more than 0.05 leads to a high relative dielectric constant, but undesirably increases the dielectric loss and the third-order harmonic distortion rate. Besides, it causes accessory crystal phases to be produced to reduce the specific resistance and reliability.
  • y+z satisfies the relationship 0 ⁇ y+z ⁇ 0.45. This is because a y+z value of more than 0.45 leads to a low relative dielectric constant.
  • m satisfies the relationship 0.95 ⁇ m ⁇ 1.05.
  • An m value of 0.95 or less causes accessory crystal phases to be produced to increase the dielectric loss and reduces the lifetime in a high temperature-loading test.
  • an m value of 1.05 or more not only causes accessory phases to be produced, but also extremely degrades the sintering characteristics of the ceramic. Accordingly, it is preferable that m satisfy the relationship 0.95 ⁇ m ⁇ 1.05.
  • the nonreducing dielectric ceramic containing the above-described principal constituents contains at least one element selected from among Mn, Ni, and Co as accessory constituents. This is because at least one element of Mn, Co and Ni has the effects of increasing the sintering characteristics, specific resistance, and mean lifetime of the ceramic.
  • the total content of these element in terms of MnO, NiO, or CoO is less than 0.05 mole relative to 100 moles of the principal constituents, the above-described effects are not sufficiently achieved and, accordingly, the sintering characteristics are negatively affected to produce accessory crystal phases. Consequently, the dielectric loss is increased; the specific resistance is reduced; and the lifetime in a high temperature-loading test is extremely reduced.
  • a total content of more than 6.0 moles increases the maximum peak intensity ratio of the accessory crystal phases to reduce the specific resistance and the lifetime in a high temperature-loading test. Accordingly, it is preferable that the total content of Mn, Ni, and Co, being accessory constituents, be in the range of 0.05 to 6.0 moles relative to 100 moles of the principal constituents.
  • the nonreducing dielectric ceramic further contains Re (at least one element selected from the group consisting of Dy, Ho, Er, Tm, Yb, Lu, Y, and Sc) as accessory constituents.
  • Re acting as accessory constituents, enhances the stability of the ceramic in a sintering atmosphere, so that a base metal, such as nickel or copper, can be used as the conductive material of the internal electrodes 4 and 5 of the monolithic ceramic capacitor 1 without problems.
  • the total content of the accessory constituent Re is in the range of 0.05 to 5.0 moles relative to 100 moles of the principal constituents, in terms of DyO 3/2 , HoO 3/2 , ErO 3/2 , TmO 3/2 , YbO 3/2 , LuO 3/2 , YO 3/2 , or ScO 3/2 .
  • a Re content of more than 5.0 moles reduces the specific resistance, and a Re content of less than 0.05 mole does not sufficiently produce the effect of Re.
  • the nonreducing dielectric ceramic further contains at least one of an aluminium compound and a magnesium compound as accessory constituents, and their total content in terms of AlO 3/2 or MgO is 6.0 moles or less relative to 100 moles of the principal constituents.
  • the specific resistance and relative dielectric constant are increased; the third-order harmonic distortion rate is reduced; and the lifetime in a high temperature-loading test is increased, in comparison with a ceramic not containing these compounds.
  • the content of the aluminium and magnesium compounds is 6.0 moles or less as described above because a content of more than 6.0 moles produces accessory crystal phases and reduces the lifetime in a high temperature-loading test.
  • the nonreducing dielectric ceramic further contains a sintering agent containing at least one of Si and B.
  • the sintering agent helps the sintering temperature of the nonreducing dielectric ceramic decrease, accordingly reducing the cost for a firing step for obtaining laminate 2 of the monolithic ceramic capacitor 1 .
  • the sintering agent content is 20 parts by weight or less to 100 parts by weight of all the constituents of the principal constituents and the accessory constituents. This is because a sintering agent content of more than 20 parts by weight further increases the maximum peak intensity ratio of the accessory crystal phases and reduces the lifetime in a high temperature-loading test.
  • the nonreducing dielectric ceramic of the present invention constituting the dielectric ceramic layers 3 of the monolithic ceramic capacitor 1 is resultantly obtained through the process for manufacturing the monolithic ceramic capacitor 1 .
  • ceramic green sheets which constitute the dielectric layers 3 .
  • an organic binder, an organic solvent, and necessary additives are added to a calcined powder prepared by calcining a plurality of starting powder materials to form a slurry, and the slurry is formed into sheets.
  • a process for preparing the calcined powder contained in the ceramic green sheets will be described later.
  • a conductive paste film which will serve as the internal electrode 4 or 5 , is formed on each of the main surfaces of some of the ceramic green sheets. Then, a necessary number of the ceramic green sheets with the conductive paste film are layered, and the ceramic green sheets with no conductive paste film are laid on the top and bottom of the layered ceramic green sheets. The layered ceramic green sheets are pressed to obtain a laminate 2 in a raw state.
  • the laminate 2 in a raw state is cut into pieces, as required, and fired to be sintered in a reducing atmosphere at a predetermined temperature.
  • the foregoing calcined powder is sintered in this stage, thereby forming the dielectric ceramic layers 3 comprising the nonreducing dielectric ceramic of the present invention.
  • the external electrodes 8 and 9 are formed on the respective side surfaces 6 and 7 of the laminate 2 .
  • the external electrodes 8 and 9 are, if necessary, covered with the first plating layers 10 and 11 and the second plating layers 12 and 13 to complete the monolithic ceramic capacitor 1 .
  • the calcined powder contained in the ceramic green sheets is, preferably, prepared as follows.
  • the mixture of the starting powder materials is calcined in a preliminary calcination step (first calcination step).
  • the preliminary calcination is performed, for example, at a temperature in the range of 500 to 1000° C. for 2 hours in the air.
  • the preliminarily calcined material is mixed and pulverized in a mixing and pulverization step.
  • the mixing and pulverization step By performing the mixing and pulverization step, the dispersibility of the preliminarily calcined material is increased.
  • the preliminarily calcined material is fully calcined to complete the reaction at a temperature higher than the temperature of the preliminary calcination in a main calcination step (second calcination step).
  • the main calcination is performed, for example, at a temperature in the range of 800 to 1200° C. for 2 hours in the air.
  • the resulting material subjected to the main calcination is used as the foregoing calcined powder contained in the ceramic green sheets.
  • the uniformity of the composition is enhanced and the occurrence of heterogeneous phases is prevented.
  • the above-described accessory constituents may be added at the stage of mixing the starting powder materials, after the preliminary calcination step, or after the main calcination step.
  • the starting powder materials for the principal constituents and accessory constituents and the sintering agent may be in any form, and, for example, in a form of oxide, carbonate, hydroxide, or organometallic compounds.
  • the uncalcined powder mixture was preliminarily calcined at 750° C. for 2 hours in the air to prepare a preliminarily calcined material.
  • the preliminarily calcined material was mixed and pulverized in a wet ball mill.
  • the mean particle size of the mixed and pulverized material was as small as 0.05 to 0.2 ⁇ m, and the presence of unreacted carbonates of the raw materials was observed by X-ray diffraction.
  • Sample 16 shown in Table 1, which is of a comparative example, has the same composition as sample 11, but was subjected to only main calcination at 1100° C. for 2 hours in the air without the preliminary calcination.
  • Each fully calcined powder sample thus obtained was measured for particle size with a scanning electron microscope (SEM) to determine the mean particle size, and was subjected to powder X-ray diffraction analysis using CuK ⁇ radiation (tube voltage: 40 kV, tube current: 25 mA).
  • SEM scanning electron microscope
  • the obtained particle size, accessory crystal phases XRD maximum peak intensity ratio, and crystal system type of the fully calcined powder are shown in Table 2.
  • the ceramic green sheets were layered one on top of another to form a ceramic green sheet laminate. This laminate was pressed in the layered direction and, then, cut out to a rectangular form with a predetermined size.
  • the ceramic green sheet laminate cut out was heated at 350° C. to burn the binder, and was, subsequently, fired at a firing temperature shown in Table 2 in a reducing atmosphere of H 2 —N 2 —H 2 O gas to yield a ceramic compact.
  • the ceramic compact was pulverized in a mortar and subjected to powder X-ray diffraction with CuK ⁇ radiation (tube voltage: 40 kV, tube current: 25 mA).
  • the obtained crystal system type of the compact, and accessory crystal phases XRD peak intensity ratio of the compact are shown in Table 2.
  • a plurality of the ceramic green sheets each having the conductive paste film were layered so as to alternately arrange the sides of the respective sheets to which the conductive films extend, and ceramic green sheets with no conductive paste were disposed on the top and the bottom of the layered ceramic green sheets.
  • the resulting composite was pressed in the layered direction, and then cut out to a predetermined size to obtain a green laminate.
  • the green laminate was heated to 350° C. in an atmosphere of nitrogen to decompose the binder, and was, subsequently, fired at the firing temperature shown in Table 2 in a reducing atmosphere of H 2 —N 2 —H 2 O gas to yield a monolithic ceramic capacitor.
  • the outside dimensions of the resulting monolithic ceramic capacitor were 3.2 mm in width by 4.5 mm in length by 1.2 mm in thickness, and the dielectric ceramic layer measured 5 ⁇ m in thickness.
  • the number of effective dielectric ceramic layers was five.
  • the relative dielectric constant shown in Table 3 was derived from the capacitance of the monolithic ceramic capacitor obtained from a measurement at a frequency of 1 kHz, 1 V rms , and a temperature of 25° C.
  • TC which represents the change in capacitance with temperature, was derived from the following expression using capacitances measured at temperatures of 20° C. and 85° C. at a frequency of 1 kHz and 1 V rms .
  • C 85 and C 20 in the expression represent capacitances measured at 85° C. and 20° C., respectively.
  • the third-order harmonic distortion rate of each monolithic ceramic capacitor was measured according to the method for measuring the nonlinearity of fixed resistors, specified in the standard RC 2111 of Electronic Industries Association of Japan (EIAJ).
  • the third-order harmonic distortion rates were measured with respective alternating voltages of 50 V/mm and 200 V/mm applied at 10 kHz, using a meter CLT-1 manufactured by RE TECHNOLOGY AS.
  • the nonreducing dielectric ceramic of the present invention comprises a SrTiO 3 -based or (Sr, Ca) (Ti, Zr)O 3 -based perovskite primary crystal phase containing 55 mole percent or more of SrTiO 3 .
  • the monolithic ceramic capacitors produced from samples 1 to 15 each exhibit a high relative dielectric constant of 150 or more and a low dielectric loss of 0.05% or less, as shown in Table 3.
  • their specific resistances are as high as 10 13 ⁇ cm or more
  • their third-order harmonic distortion rates are as low as ⁇ 110 dB or less at 50 V/mm and ⁇ 100 dB or less at 200 V/mm.
  • the mean lifetimes are as long as 50 hours or more.
  • samples 1 to 15 whose SrTiO 3 content in the principal crystal phase is 55 mole percent or more, have a low Curie temperature of ⁇ 60° C. or less and no ferroelectricity at room temperature, accordingly exhibiting a dielectric loss of 0.05% or less, a low third-order harmonic distortion rate, and a relative dielectric constant of 150 or more.
  • an accessory crystal phases XRD peak intensity ratio of 5% or more reduces the mean lifetime, as in samples 16, 17, 22, 23, 24, 25, 26, and 27.
  • an accessory crystal phases XRD peak intensity ratio of 5% or more negatively affects the characteristics in a short time.
  • an accessory crystal phases XRD peak intensity ratio of less than 5% leads to a long mean lifetime, as shown in samples 1 to 15, thus resulting in a highly reliable ceramic material. It is therefore preferable that the accessory crystal phases XRD peak intensity ratio be less than 5%.
  • FIGS. 2 and 3 respectively show the X-ray diffraction patterns of the fully calcined powder (SrTiO 3 content in the principal crystal phase: 55 mol % or more, accessory crystal phases XRD peak intensity ratio: less than 1%) and the sintered compact (SrTiO 3 content in the principal constituents: 55 mol % or more, accessory crystal phases XRD peak intensity ratio: less than 1%) of sample 8 within the scope of the present invention.
  • FIG. 4 shows an X-ray diffraction pattern of the sintered compact (SrTiO 3 content in the principal constituents: less than 55 mol %) of sample 20 outside the scope of the present invention.
  • composition of the strontium titanate-based nonreducing dielectric ceramic that is, the composition expressed by the formula (Sr 1-w-x Ca w Ba x ) m (Ti 1-y-z Zr y Hf z )O 3 .
  • a Ca ratio w in the composition formula of more than 0.45 leads to a low relative dielectric constant, as in samples 18 and 27. It is therefore preferable that the Ca ratio w satisfy the relationship 0 ⁇ w ⁇ 0.45.
  • a Ba ratio x of more than 0.05 leads to a high relative dielectric constant, but undesirably increases the dielectric loss and the third-order harmonic distortion rate, as in sample 22. Furthermore, accessory crystal phases are produced, consequently reducing the specific resistance and reliability. If the Ba ratio x is further increased, the third-order harmonic distortion rate is extremely increased, as in sample 21. It is therefore preferable that the Ba ratio x satisfy the relationship 0 ⁇ x ⁇ 0.05.
  • a sum total of Zr and Hf, that is, y+z, of more than 0.45 leads to a low relative dielectric constant, as in samples 19, 20, and 27. It is therefore preferable that the Zr and Hf total ratio, y+z, satisfy the relationship 0 ⁇ y+z ⁇ 0.45.
  • an m value of 0.95 or less causes secondary crystal phases to be produced to increase the dielectric loss and reduces the lifetime, as in sample 23.
  • an m value of 1.05 or more not only causes secondary phases to be produced, but also extremely degrades the sintering characteristics of the ceramic, as in sample 24. It is therefore preferable that the m value satisfy the relationship 0.95 ⁇ m ⁇ 1.05.
  • At least one element of Mn, Co, and Ni, being the accessory constituents has the effects of increasing the sintering characteristics, specific resistance, and mean lifetime of ceramics.
  • a total content of less than 0.05 mole of the accessory constituents Mn, Co, and Ni, as in sample 25, does not produce these effects and negatively affects the sintering characteristics to cause accessory crystal phases to be produced. Consequently, the dielectric loss is increased, the specific resistance is reduced; and the mean lifetime is extremely reduced.
  • a Mn, Co, and Ni total content of more than 6.0 moles increases the accessory crystal phases XRD peak intensity ratio to reduce the specific resistance, and reduces the mean lifetime, as in sample 26. It is therefore preferable that the Mn, Co, and Ni total content be in the range of 0.05 to 6.0 moles.
  • the uncalcined powder mixture was preliminarily calcined at 800° C. for 2 hours in the air to prepare a preliminarily calcined material.
  • the preliminarily calcined material was mixed and pulverized in a wet ball mill, as in Experimental Example 1.
  • the mean particle size of the resulting preliminarily calcined powder after mixing and pulverization was as small as 0.05 to 0.2 ⁇ m.
  • Sample 48 shown in Table 4 which is of a comparative example, has the same composition as Sample 37, but was subjected to only main calcination at 1000° C. for 2 hours with no preliminary calcination.
  • the monolithic ceramic capacitors produced from these samples 28 to 47 exhibit a high relative dielectric constant of 150 or more, a low third-order harmonic distortion rate of ⁇ 110 dB or less at 50 V/mm and ⁇ 100 dB or less at 200 V/mm, and a long mean lifetime of 50 hours or more.
  • Samples 49 and 50 whose SrTiO 3 content in the principal crystal phase is less than 55 mole percent, exhibit a low relative dielectric constant of 140 or less.
  • samples 28 to 47 whose SrTiO 3 content in the principal crystal phase is 55 mole percent or more, have a low Curie temperature of ⁇ 60° C. or less and no ferroelectricity at room temperature, accordingly exhibiting a low third-order harmonic distortion rate, a relative dielectric constant of 150 or more, and a dielectric loss of 0.30% or less.
  • an accessory crystal phases XRD peak intensity ratio of 5% or more reduces the mean lifetime, as in samples 48 and 51 to 57.
  • an accessory crystal phases XRD peak intensity ratio of 5% or more negatively affects the characteristics in a short time.
  • an accessory crystal phases XRD peak intensity ratio of less than 5% leads to a long mean lifetime, as shown in samples 28 to 47, thus resulting in a highly reliable ceramic material. It is therefore preferable that the accessory crystal phases XRD peak intensity ratio be less than 5%.
  • composition of the strontium titanate-based nonreducing dielectric ceramic that is, the composition expressed by the formula (Sr 1-w-x Ca w Ba x ) m (Ti 1-y-z Zr y Hf z )O 3 .
  • a Ca ratio w in the composition formula of more than 0.45 leads to a low relative dielectric constant, as in sample 49. It is therefore preferable that the Ca ratio w satisfies the relationship 0 ⁇ w ⁇ 0.45.
  • a Ba ratio x of more than 0.05 leads to a high relative dielectric constant, but undesirably increases the third-order harmonic distortion rate, as in sample 53. Furthermore, accessory crystal phases are produced, consequently reducing the specific resistance and reliability. It is therefore preferable that the Ba ratio x satisfies the relationship 0 ⁇ x ⁇ 0.05.
  • a sum total of Zr and Hf, that is, y+z, of more than 0.45 leads to a low relative dielectric constant, as in sample 50. It is therefore preferable that the Zr and Hf total ratio, y+z, satisfy the relationship 0 ⁇ y+z ⁇ 0.45.
  • an m value of 0.95 or less causes secondary crystal phases to be produced to increase the dielectric loss and reduces the lifetime, as in sample 51.
  • an m value of 1.05 or more not only causes secondary phases to be produced, but also extremely degrades the sintering characteristics of the ceramic, as in sample 52. It is therefore preferable that the m value satisfy the relationship 0.95 ⁇ m ⁇ 1.05.
  • At least one element selected from accessory constituents 1 shown in Table 4, consisting of Dy, Ho, Er, Tm, Yb, Lu, Y, and Sc enhances the stability of the ceramic in a sintering atmosphere, so that a base metal, such as nickel, can be used as the conductive material of the internal electrodes without problems.
  • a base metal such as nickel
  • This effect is achieved when the total content of accessory constituents 1 is set at 0.05 mole or more.
  • a total content of accessory constituents 1 of more than 5.0 moles leads to a low specific resistance, as in sample 54. It is therefore preferable that the total content of accessory constituents 1 be in the range of 0.05 to 5.0 moles.
  • At least one element selected from accessory constituents 2 consisting of Mn, Co, and Ni has the effects of increasing the sintering characteristics, specific resistance, and mean lifetime of the ceramic.
  • a total content of accessory constituents 2 of less than 0.05 mole, as in sample 57 does not produce these effects.
  • a total content of accessory constituents 2 of more than 6.0 moles increases the accessory crystal phases XRD peak intensity ratio to reduce the specific resistance, and reduces the mean lifetime, as in samples 55 and 56. It is therefore preferable that the total content of accessory constituents 2 be in the range of 0.05 to 6.0 moles.
  • SrCO 3 , CaCO 3 , and TiO 2 powders with purities of 99% or more were prepared as the starting powder materials for the principal constituents.
  • Yb 2 O 3 , MnO, Al 2 O 3 , and MgCO 3 powders were prepared as the starting powder materials for the accessory constituents. These starting powder materials were each weighed out so that the principal constituents form the composition (Sr 0.6 Ca 0.4 )TiO 3 and that the mole numbers of the accessory constituents in terms of YbO 3/2 , MnO, AlO 3/2 , or MgCO 3 became the values shown in Table 7 relative to 100 moles of the principal constituents.
  • the uncalcined powder mixture was preliminarily calcined at 800° C. for 2 hours in the air to prepare a preliminarily calcined material.
  • the preliminarily calcined material was subjected to main calcination at 1100° C. for 2 hours in the air.
  • the product was pulverized to yield a fully calcined powder.
  • a ceramic compact and a monolithic ceramic capacitor were prepared from the ceramic green sheets through firing at a firing temperature shown in Table 8, in the same manner as in Experimental Example 1.
  • the resulting ceramic compact and the monolithic ceramic capacitor were examined for the accessory crystal phases XRD peak intensity ratio of the compact, the crystal system type of the compact, the relative dielectric constant, the dielectric loss, TC, log p, the mean lifetime, and the third-order harmonic distortion rate, and the results are shown in Table 8.
  • Tables 7 and 8 show that samples 58 to 65 of the present invention achieve a high relative dielectric constant of 150 or more, a low third-order harmonic distortion rate of ⁇ 110 dB or less at 50 V/mm and ⁇ 100 dB or less at 200 V/mm, and a long mean lifetime of 50 hours or more.
  • samples 59 to 65 which contain at least one of Al and Mg, exhibit a specific resistance higher than that of sample 58, which does not contain these elements.
  • an Al and Mg total content of more than 6.0 moles causes accessory crystal phases to be produced to increase their XRD peak intensity ratio to 5% or more and reduces the mean lifetime, as in sample 66.
  • the Al and Mg total content be 6.0 moles or less relative to 100 moles of the principal constituents.
  • the uncalcined powder mixture was preliminarily calcined at 800° C. for 2 hours in the air to prepare a preliminarily calcined material.
  • the preliminarily calcined material was subjected to main calcination at 1100° C. for 2 hours in the air.
  • the product was pulverized to yield a fully calcined powder.
  • a ceramic compact and a monolithic ceramic capacitor were prepared from the ceramic green sheets through firing at a firing temperature shown in Table 10, in the same manner as in Experimental Example 1.
  • Table 10 shows that samples 67 to 75 of the present invention achieve a high relative dielectric constant of 150 or more, a low third-order harmonic distortion rate of ⁇ 110 dB or less at 50 V/mm and ⁇ 100 dB or less at 200 V/mm, and a long mean lifetime of 50 hours or more.
  • samples 68 to 76 which contain a sintering agent as shown in Table 9, can be sintered at a temperature 100° C. or more lower than the sintering temperature of sample 67, which contains no sintering agent, as shown in the “sintering temperature” columns in Table 10.
  • a sintering agent content of more than 20 parts by weight to 100 parts by weight of all the principal constituents and the accessory constituents increases the accessory phases XRD peak intensity ratio to 5% or more and reduces the mean lifetime to 50 hours or less, as in sample 76.
  • the sintering agent content is 20 parts by weight or less to 100 parts by weight of all the constituents of the principal constituents and the accessory constituents.
  • the nonreducing dielectric ceramic of the present invention can advantageously be used not only for temperature compensating capacitors and low-loss capacitors, but also as microwave dielectric resonators, and, thus, has large value in industrial use.

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