Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/002—Details
  • H01G4/018—Dielectrics
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  • H01G4/08—Inorganic dielectrics
  • H01G4/12—Ceramic dielectrics
  • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
  • H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
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  • H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
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  • H01C7/112—ZnO type

Definitions

• Dielectric ceramic composition preparation method of dielectric ceramic composition and electronic component
• the present invention relates to a dielectric ceramic composition, a method of preparing a dielectric ceramic composition, and an electronic component. Background technique
• Ceramic capacitors which are an example of electronic components, are used in various electronic instruments, and in recent years, there has been an increasing demand for high performance.
• a ceramic capacitor identified by a safety standard is likely to be subjected to a peak voltage due to a snubber circuit for a switching power supply. Therefore, in order to protect the circuit, it is most important not to cause the ceramic capacitor to be broken down, i.e., to improve the dielectric breakdown electric field (ACVB) of the dielectric ceramic composition.
• ACVB dielectric breakdown electric field
• a dielectric ceramic composition having a relatively high AC breakdown electric field is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2003-104774. However, even if it is high, it is only about 5kV/mm. Summary of the invention
• the present invention has been made in view of such circumstances, and an object thereof is to provide a dielectric shield ceramic composition having a high AC breakdown electric field, a high dielectric constant, and a low dielectric loss, and a method for preparing a dielectric shield ceramic composition. Further, it is an object of the invention to provide an electronic component having a dielectric layer composed of such a dielectric ceramic composition.
• the present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that the above object can be attained by setting the composition of the dielectric ceramic composition to a specific component and setting the ratio thereof to a predetermined range, thereby completing the present invention.
• y in the above composition formula is 0 y 0.08, and the total of x and y in the above composition formula is 0.975 ⁇ x + y ⁇ 1.010,
• the content of the zinc oxide is from 2 parts by weight to 12 parts by weight based on 100 parts by weight of the above main component.
• an AC breakdown electric field and a dielectric having a high dielectric constant and a low dielectric loss can be provided.
• the head of the present invention ⁇ ⁇ ⁇ ⁇ ; p; ⁇ ,
• y in the above composition formula is 0 y ⁇ 0.08, and the total of X and y in the above composition formula is 0.975 ⁇ x + y ⁇ 1.010,
• the content of the zinc oxide is from 1.6 parts by weight to 12 parts by weight, based on 100 parts by weight of the above main component.
• the preparation method has the following steps:
• the electronic component according to the embodiment of the present invention is not particularly limited, and examples thereof include a single-plate type ceramic capacitor and a laminated ceramic capacitor.
• Fig. 1(A) is a front view of a ceramic capacitor according to an embodiment of the present invention
• Fig. 1(B) is a side cross-sectional view showing a ceramic capacitor according to an embodiment of the present invention.
• Fig. 2 is a view showing the influence of the timing of adding zinc oxide and the content of zinc oxide on the alternating breakdown electric field in the preparation method of the dielectric shield ceramic composition according to the embodiment of the present invention. detailed description
• a ceramic capacitor 2 As shown in FIG. 1 (A:) and FIG. 1 (B), a ceramic capacitor 2 according to an embodiment of the present invention is formed with a dielectric layer 10, a pair of terminal electrodes 12, 14 formed on a surface opposite thereto, and The lead terminals 6, 8 respectively connected to the terminal electrodes 12, 14 are covered by the protective resin 4.
• the shape of the ceramic capacitor 2 can be appropriately determined depending on the purpose and application, but it is preferable that the dielectric layer 10 is formed into a disk-shaped disk-shaped capacitor. Further, the size thereof may be appropriately determined depending on the purpose and use, but usually the diameter is about 5 to 20 mm, preferably about 5 to 15 mm.
• the dielectric layer 10 is composed of the dielectric ceramic composition according to the embodiment of the present invention.
• the dielectric ceramic composition according to the embodiment of the present invention has a main component represented by a composition formula of (Ba x Ca y )Ti 0 3 and zinc oxide, and y in the above composition formula is 0 y 0.08, and in the above composition formula The total of X and y is 0.975 x + y 1.010.
• X in the above composition formula represents the ratio of Ba, and X is 0.915 X 1.005, preferably 0.930 ⁇ x 1.000.
• the dielectric constant tends to increase.
• y in the above composition formula represents the ratio of Ca, which is 0 y 0.08, preferably 0 y 0.07.
• Ca is an arbitrary component, and the AC breakdown electric field can be improved even when Ca is not contained.
• the total of the ratio of X to y in the above composition formula i.e., the ratio of Ba to Ca, is preferably 0.975 ⁇ x + y ⁇ 1.010, and more preferably 0.980 x + y ⁇ 1.005.
• the amount of x and y is in this range, there is a tendency that the sinterability, the alternating breakdown electric field, and the dielectric constant are improved.
• the content of zinc oxide is from 1.6 parts by weight to 12 parts by weight, preferably from 2 parts by weight to 12 parts by weight, more preferably 2.3, based on 100 parts by weight of the main component.
• the parts by weight are 10 parts by weight, and more preferably 4 parts by weight to 10 parts by weight.
• the content of zirconia, iron oxide or nickel oxide is preferably less than 1.0 part by weight, more preferably from 0 part by weight to 0.5 part by weight, per 100 parts by weight of the main component. More preferably, it is 0 weight part. If the content of zirconia, iron oxide or nickel oxide exceeds this range, the alternating breakdown electric field tends to decrease. Further, if the content of the nickel oxide exceeds this range, not only the alternating breakdown electric field but also the dielectric loss tends to increase.
• the thickness of the dielectric layer 10 is not particularly limited, and may be appropriately determined depending on the use, etc., but is preferably 0.3 to 2 mm. By making the thickness of the dielectric layer 10 within this range, it can be suitably used for medium and high pressure applications.
• terminal electrodes 12, 14 are made of a conductive material.
• Examples of the conductive material used for the terminal electrodes 12 and 14 include Cu, a Cu alloy, Ag, an Ag alloy, and an In-Ga alloy.
• a dielectric ceramic composition powder in which the dielectric layer 10 shown in Fig. 1 is formed after firing is prepared.
• Raw materials of the main components and raw materials of the respective components are prepared.
• the raw material of the main component include various oxides of Ba, Ca, and Ti, and/or a raw material for forming an oxide by firing, or a composite oxide thereof.
• BaC0 3 , CaC0 3 , Ti0 2 or the like can be used.
• various compounds which form an oxide or a titanium compound after firing such as a hydroxide can also be used. At this time, it is also possible to appropriately change the content to match the number of elements of the metal element.
• the raw material of the main component can be produced by a solid phase method or a liquid phase method such as hydrothermal synthesis or oxalate method, but it is preferably prepared by a solid phase method from the viewpoint of production cost.
• the raw materials of the respective subcomponents are not particularly limited, and various compounds such as carbonates, nitrates, and hydrogens may be formed from the oxides or composite oxides of the above-mentioned respective subcomponents or by firing to form these oxides or composite oxides.
• An oxide, an organometallic compound or the like is appropriately selected and used.
• the raw material of the main component or the raw material of the main component is blended with the raw material of the subcomponent, and wet-mixed using a ball mill or the like using a zirconia ball or the like. When the subcomponent is blended at this time, each subcomponent may be blended, or only a part of the subcomponent may be blended, and the remaining subcomponent may be added after calcination to form the composition of the dielectric ceramic composition.
• the obtained mixture is granulated and molded, and the obtained molded product is calcined in an air atmosphere, whereby a calcined powder can be obtained.
• the calcination conditions for example, the calcination temperature may preferably be 1100 to 1300 ° C, more preferably 1150 to 1250 ° C, and the calcination time may preferably be 0.5 to 4 hours.
• the raw material of the main component and the raw material of the auxiliary component may be separately calcined and then mixed to form a dielectric ceramic composition powder.
• the obtained calcined powder was coarsely pulverized.
• the subcomponent is added to form the composition of the dielectric ceramic composition together with the raw material of the subcomponent added before calcination.
• the calcined powder or the calcined powder and the raw material of the subcomponent are wet-pulverized by a ball mill or the like, and further mixed and dried to obtain a dielectric ceramic composition powder.
• a ball mill or the like wet-pulverized by a ball mill or the like, and further mixed and dried to obtain a dielectric ceramic composition powder.
• the obtained dielectric ceramic composition powder is preferably 1200 to 1400 ° C, more preferably 1250 to 1350 ° C, and preferably the firing atmosphere is air.
• the terminal electrodes are printed on the main surface of the sintered body of the obtained dielectric ceramic composition, and are baked as necessary to form terminal electrodes 12 and 14. Then, the terminal electrodes 12 and 14 are joined to the lead terminals 6 and 8 by soldering or the like, and finally the element body is covered with the protective resin 4, whereby the single-plate type ceramic capacitor shown in Fig. 1 (A) and Fig. 1 (B) is obtained. .
• the ceramic capacitor of the present invention thus produced is mounted on a printed circuit board or the like by lead terminals 6, 8 and used for various electronic instruments and the like.
• the electronic component according to the present invention is a single-plate type ceramic capacitor in which the dielectric layer is a single layer.
• the electronic component according to the present invention is not limited to a single-plate type; A laminated ceramic capacitor manufactured by a method or a sheet method. , 'Example
• BaC0 3 , CaC0 3 and Ti0 2 were separately prepared. Then, the prepared raw materials were weighed to form the compositions shown in the samples 1 to 31 and 3a of Table 1, and wet-mixed by using a pure water as a solvent and a ball mill using an oxidized sphere.
• the obtained green body was fired in the air at 1,250 to 1,350 ° C for 2 hours to obtain a disk-shaped sintered body. Further, an Ag electrode was applied to both surfaces of the main surface of the obtained sintered body, and further subjected to a heat treatment at 650 ° C for 20 minutes in the air to obtain a sample of the disk-shaped ceramic capacitor shown in Fig. 1 . .
• the dielectric layer 10 of the obtained capacitor sample had a thickness of about 1 mm and the burn-in electrode had a diameter of 12 mm. Further, for each of the obtained capacitor samples, the alternating breakdown electric field, dielectric constant, and dielectric loss were evaluated by the following methods. The evaluation results are shown in Table 1.
• AC breakdown voltage was measured as follows: For the capacitor sample, an alternating electric field was applied slowly at both ends of the capacitor at 100 V/s, and the electric field value at the time of leakage current of 100 mA was measured, and this was taken as an alternating current breakdown electric field.
• the AC breakdown electric field is high, and in the present embodiment, 6.0 kV/mm or more is good.
• the dielectric constant ⁇ was calculated as follows: For a capacitor sample, a digital LCR meter (4274A, manufactured by Agilent Technologies, Inc.) at a reference temperature of 20 ° C at a frequency of 1 kHz and an input signal level (measured voltage) of 1.0 rmrms The electrostatic capacity was measured, and the dielectric constant ⁇ (no unit) was calculated from the electrostatic capacity.
• the dielectric constant is high, and in the present embodiment, 2000 or more is good.
• the dielectric loss tanS is measured for a capacitor sample at a reference temperature of 2 (TC, using a digital LCR meter (4274A, manufactured by Agilent Technologies) at a frequency of 1 kHz and an input signal level (measured voltage) of 1.0 rmrms.
• the dielectric loss is preferably small, and 3% or less in the present embodiment is good.
• the calcined powder of the main component raw material is coarsely pulverized by a crusher and sieved, and then weighed to form a composition shown in the samples 41a to 43a of Table 2.
• the amount of ZnO was added to the calcined powder, and the firing temperature of the molded body was 1250 ° C. Otherwise, each capacitor sample was obtained in the same manner as the samples 1 to 9, and the alternating breakdown electric field, dielectric constant, and dielectric constant were applied. The electrical loss was evaluated. Namely, in the samples 41a to 43a, ZnO was added after the calcination of the main component raw material in the same manner as the samples 1 to 9. The AC breakdown electric field is measured on four samples and averaged. The composition and evaluation results of each sample are shown in Table 2. Table 2
• the calcined powder of the main component raw material is roughly pulverized by a crusher and sieved to form a composition of the samples shown in Table 3, ls ⁇ 6s, lsa. Add ZnO, Bi 2 0 3 , Zr0 2 , Fe 2 0 3 or NiO, and obtain the capacitor samples in the same manner as samples 1 to 9, respectively, for the AC breakdown electric field, dielectric constant and dielectric loss. Conduct an evaluation. The composition and evaluation results of each sample are shown in Table 3.
• each of the capacitor samples was obtained in the same manner as the samples 41 to 43 except that ZnO, Nb 2 O 5 or CuO weighed in the amount of the composition shown in the samples 6sa and 6sb of Table 3 was calcined together with the main component raw materials. , respectively, the AC breakdown electric field, dielectric constant and dielectric loss were evaluated. The composition and evaluation results of each sample are shown in Table 3. Sample 7s ⁇ 13s
• the content of zinc oxide is from 1.6 parts by weight to 12. parts by weight (samples 3 to 8, 3a, 4a, 42, 43, 42a) , 43a)
• the alternating breakdown electric field is increased, and when the content of zinc oxide is 2 parts by weight to 12 parts by weight, the alternating current is applied. The electric field is further increased.
• the electrical constant is lowered.

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• 2010
  • 2010-03-31 WO PCT/CN2010/000415 patent/WO2011120196A1/zh active Application Filing
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