KR0145125B1 - Dielectric ceramic compositions - Google Patents
Dielectric ceramic compositionsInfo
- Publication number
- KR0145125B1 KR0145125B1 KR1019950052734A KR19950052734A KR0145125B1 KR 0145125 B1 KR0145125 B1 KR 0145125B1 KR 1019950052734 A KR1019950052734 A KR 1019950052734A KR 19950052734 A KR19950052734 A KR 19950052734A KR 0145125 B1 KR0145125 B1 KR 0145125B1
- Authority
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- South Korea
- Prior art keywords
- dielectric
- dielectric constant
- breakdown voltage
- multilayer ceramic
- composition
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 239000000919 ceramic Substances 0.000 title claims abstract description 13
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 abstract description 14
- 239000003985 ceramic capacitor Substances 0.000 abstract description 13
- 238000009413 insulation Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 3
- 230000010485 coping Effects 0.000 abstract 1
- 239000003989 dielectric material Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- 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
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3229—Cerium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
- C04B2235/3248—Zirconates or hafnates, e.g. zircon
- C04B2235/3249—Zirconates or hafnates, e.g. zircon containing also titanium oxide or titanates, e.g. lead zirconate titanate (PZT)
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
- C04B2235/3267—MnO2
Landscapes
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
본 발명은 미국 EIA에서 정한 Y5V 규격특성을 만족시키는 동시에 높은 유전율을 갖고, 절연저항과 절연 파괴 전압이 높고, 결정립의 입경이 작고 치밀한 소결상태를 나타내는 적층 세라믹 콘덴서 제조용 유전체 조성물에 관한 것이다.The present invention relates to a dielectric composition for producing a multilayer ceramic capacitor that satisfies the Y5V standard characteristics defined by the US EIA, has a high dielectric constant, high insulation resistance, high breakdown voltage, small grain size, and dense sintered state.
최근의 제품의 소형화와 고용량화에 대응하기 위하여 정전 용량을 높히기 위해서 높은 유전율을 갖는 유전체의 사용과 유전체 두께를 얇게하고, 고신뢰성의 적층 세라믹 콘덴서를 제조하기 위해서 소결후 유전체의 결정립이 미세하고 치밀하며 높은 절연 저항과 높은 절연 파괴 전압을 갖는 유전체의 개발이 필수적이다.In order to cope with the recent miniaturization and high capacity, the use of a dielectric having a high dielectric constant to increase the capacitance and the thickness of the dielectric is made thin. Development of dielectrics with high insulation resistance and high dielectric breakdown voltage is essential.
본 발명의 세라믹 유전체 조성물을 적층 세라믹 콘덴서에 이용하면 유전체 층의 두께를 얇게할 수 있어 원가 절감의 효과가 클뿐 아니라, 소형화 및 고용량화에 대응할 수 있는 고신뢰성의 제품을 생산할 수 있다.When the ceramic dielectric composition of the present invention is used in a multilayer ceramic capacitor, the thickness of the dielectric layer can be reduced, so that the cost reduction effect is large, and a high reliability product capable of coping with miniaturization and high capacity can be produced.
Description
제1도는 적층 세라믹 콘덴서의 개략도이다.1 is a schematic diagram of a multilayer ceramic capacitor.
제2도는 EIA의 적층 세라믹 콘덴서에 대한 Y5V 온도 특성규격을 나타내는 유전율의 온도 특성 범위와 본 발명의 실시예 3에 따른 유전율의 온도 특성을 도시한 도면.2 is a diagram showing the temperature characteristic range of the dielectric constant showing the Y5V temperature characteristic specification for the multilayer ceramic capacitor of EIA and the temperature characteristic of the dielectric constant according to the third embodiment of the present invention.
*도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings
1:유전체 2:내부전극1: Dielectric 2: Internal electrode
3:외부전극 A:Y5V 규격에서 정한 유전율의 온도특성 범위3: External electrode A: Temperature characteristic range of dielectric constant specified in Y5V standard
B:실시예 3에 따른 조성물의 유전율의 온도특성(temperature characteristics; T.C)B: Temperature characteristics (T.C) of the dielectric constant of the composition according to Example 3
본 발명은 민생용 및 산업용 전자 기기 등에 사용되는 대표적인 부품의 하나인 적층 세라믹 콘덴서 제조용 유전체 조성물에 관한 것으로, 특히 미국 EIA(Electronic Industrial Association)에서 정한 Y5V 규격특성(-30℃∼+85℃의 온도 범위에서 25℃에서의 유전율을 기준으로하여 온도 변화에 따른 유전율의 변화율이 +22%∼-82% 이내)을 만족시키는 동시에 11,000∼14,000 정도의 높은 유전율과 절연 저항이 1013Ωcm 이상이고, 절연 파괴 전압이 14KV/mm 이상이며, 결정립의 입경이 작고 치밀한 소결 상태를 나타내는 세라믹 유전체 조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dielectric composition for manufacturing multilayer ceramic capacitors, which is one of typical components used in consumer electronics and industrial electronic devices, and in particular, Y5V specification characteristics (-30 ° C. to + 85 ° C. temperature) defined by the US Electronic Industrial Association (EIA). Range of dielectric constant at 25 ° C based on the dielectric constant at 25 ℃ within + 22% to -82%), and has a high dielectric constant of about 11,000 to 14,000 and insulation resistance of 10 13 Ωcm or more. It relates to a ceramic dielectric composition having a breakdown voltage of 14 KV / mm or more and having a small grain size and a dense sintered state.
여기에서 유전체(Dielectric Substance)란 정전기장을 가할 때 전기분극(電氣分極)은 생기나 직류전류는 생기지 않는 물질을 말한다.Here, dielectric substance refers to a substance in which electric polarization occurs but no direct current occurs when an electrostatic field is applied.
최근 적층 세라믹 콘덴서는 각종 전자 기기의 소형, 경량화의 추세에 따라 표면 실장이 가능하고 부품 자체의 소형화와 단위 체적당 높은 정전용량을 나타내는 특성에 기인하여, 캠코더, 하드디스크 드라이브 등의 각종 전자 제품의 수동 소자로 광범위하게 사용되고 있으며, 앞으로도 그 이용 범위는 더욱 확대될 것으로 기대되고 있다. 표면실장이란 기판의 면과 부품의 면을 면과 면의 대응 방식으로 접속하는 방법을 말한다.Recently, multilayer ceramic capacitors can be surface-mounted according to the trend of miniaturization and weight reduction of various electronic devices, and due to the miniaturization of components and high capacitance per unit volume, the use of various electronic products such as camcorders and hard disk drives It is widely used as a passive device, and its use is expected to expand further. Surface mounting means the method of connecting the surface of a board | substrate and the surface of a component to the surface-to-surface corresponding method.
이와 같은 적층 세라믹 콘덴서의 내부 구조는 제1도에 나타나 있듯이 세라믹 유전체(1)의 내부에 교차적으로 내부 전극(2)이 형성되고, 그 내부 전극(2)의 일단이 외부로 노출된 세라믹 유전체(1)의 양 측면에 외부 전극(3)이 형성되도록 이루어진다.As shown in FIG. 1, the internal structure of the multilayer ceramic capacitor has a ceramic dielectric in which an internal electrode 2 is alternately formed inside the ceramic dielectric 1, and one end of the internal electrode 2 is exposed to the outside. The external electrodes 3 are formed on both side surfaces of (1).
이러한 내부 구조에 있어서 적층 세라믹 콘덴서의 사용에 있어서 중요한 선택 기준이 되는 정전 용량(electrostatic capacitance)은 유전체의 고유값인 유전율(Dielectric Constant), 내부 전극의 유효한 대향 면적과 적층수에 비례하고, 유전체의 두께에는 반비례하게 된다. 정전 용량은 콘덴서에서 전하를 축적할 수 있는 능력을 나타내며 단위는 파라드(farad, F)이다.The electrostatic capacitance, which is an important selection criterion in the use of multilayer ceramic capacitors in this internal structure, is proportional to the dielectric constant, the intrinsic value of the dielectric, the effective opposing area of the internal electrode, and the number of stacked layers. It is inversely proportional to the thickness. Capacitance refers to the ability to accumulate charge in a capacitor and is in units of farad (F).
따라서 최근의 제품의 소형화와 고용량화에 대응하기 위하여 규정된 크기의 적층 세라믹 콘덴서에 있어서 단위 체적당 정전 용량을 높히기 위해서는 높은 유전율을 갖는 유전체의 사용과 유전체 두께를 얇게 할 필요성이 대두되고 있다.Therefore, in order to increase the capacitance per unit volume in the multilayer ceramic capacitor of a prescribed size in order to cope with the recent miniaturization and high capacity of the product, the use of a dielectric having a high dielectric constant and the thickness of the dielectric is increasing.
특히 고신뢰성의 적층 세라믹 콘덴서를 제조하기 위해서는 소결 후 유전체의 결정립이 미세하고 치밀하여 높은 절연 저항과 높은 절연 파괴 전압을 갖게 되는 유전체의 사용이 필수 불가결한 요소가 된다.In particular, in order to manufacture a highly reliable multilayer ceramic capacitor, it is essential to use a dielectric having fine dielectric density after sintering to have high insulation resistance and high dielectric breakdown voltage.
그러나 종래의 세라믹 유전체 조성물은 BaTiO3를 주성분으로 하여 CaZrO3, CaSnO3등이 첨가된 조성물을 사용하였으나 이러한 조성물은 비교적 높은 유전율을 갖는 반면에 결정립의 입경이 10∼20㎛ 정도로 크게 되어 절연 파괴 전압이 낮아지는 단점이 있으며 이로 인하여 고신뢰성의 제품을 제조하기 어려웠다.Conventional ceramic dielectric compositions, however, were composed of BaTiO 3 containing CaZrO 3 , CaSnO 3, etc. as the main component. However, these compositions have relatively high dielectric constants while the grain size of the grains is increased to about 10 to 20 μm, resulting in dielectric breakdown voltage. This has the disadvantage of being lowered, which makes it difficult to manufacture high reliability products.
또한 일본 공고특허 소 60-51202호, 소 59-86101호, 소 60-51205호에서는 상술한 조성물의 단점인 절연 파괴 전압을 향상시키기 위하여 BaTiO3에 Sm2O3, CeC2, Dy2O3를 첨가하여 결정립의 입경을 2∼3㎛ 정도로 작게 함으로서 절연 파괴 전압을 향상시켰으나 절연 저항이 5×1012Ωcm 이하를 나타내어 고신뢰성의 적층 세라믹 콘덴서의 제조에 있어서는 곤란한 점이 있었다. 한편 대한민국 특허공보 제94-5088호, 제94-6426호에서는 BaTiO3에 CeO2및 Nd2O3등과 같은 희토류 금속 산화물과 TiO2등을 첨가하여 결정립의 입경을 2∼3㎛ 정도로 작게 하고 절연 저항도 1013Ωcm 이상이며 절연 파괴 전압도 14KV/mm 이상으로 향상된 유전체 자기 조성물을 제공하였으나 유전율이 10,000 이하로 낮아 소형화와 고용량화에 부응할 수 있는 적층 세라믹 콘덴서의 제조에는 미흡한 점이 있었다.In addition, Japanese Patent Publication Nos. 60-51202, 59-86101, and 60-51205 disclose Sm 2 O 3 , CeC 2 , Dy 2 O 3 in BaTiO 3 to improve the dielectric breakdown voltage, which is a disadvantage of the above-mentioned composition. The dielectric breakdown voltage was improved by adding the crystal grains to a size of about 2 to 3 탆, but the insulation resistance was 5 × 10 12 Pa or less, which was difficult in manufacturing a highly reliable multilayer ceramic capacitor. The Republic of Korea Patent Application No. 94-5088, 1 - No. 94-6426 and in the isolated small extent by the addition of rare earth metal oxides and TiO 2, etc., such as CeO 2 and Nd 2 O 3 in BaTiO 3 2~3㎛ the particle diameter of crystal grain Although the dielectric ceramic composition has been improved to have a resistance of 10 13 Ωcm or more and an insulation breakdown voltage of 14 KV / mm or more, it has been insufficient in the manufacture of a multilayer ceramic capacitor capable of meeting miniaturization and high capacity due to its low dielectric constant of 10,000 or less.
본 발명의 목적은 이러한 문제점들을 해결하여 결정립의 입경이 작고 치밀한 소결 상태를 나타내면서, 높은 절연 저항과 높은 절연 파괴 전압을 갖는 동시에 11,000∼14,000 정도의 고유전율을 나타낼 수 있는 Y5V 온도 특성의 고유전율 세라믹 유전체 조성물을 제공하는데 있다.The object of the present invention is to solve these problems, and the Y5V temperature characteristics of the high-k dielectric ceramic, which can exhibit a high dielectric resistance of about 11,000 to 14,000 while having a high grain resistance and a high dielectric breakdown voltage while exhibiting a small grain size and compact sintered state It is to provide a dielectric composition.
이러한 목적을 달성하기 위하여 본 발명에서는 95.90∼96.10중량%의 BaTiO3를 주성분으로 하고 여기에 0.49∼2.25중량%의 La2O3, 0.75∼1.95중량%의 CeO2, 0.60∼1.17중량%의 ZrO2, 0.25∼1.30중량%의 TiO2및 0.10∼0.25중량%의MnO2를 첨가하여 세라믹 유전체 조성물을 구성하였다.In order to achieve this object, in the present invention, 95.90 to 96.10% by weight of BaTiO 3 is the main component, and 0.49 to 2.25% by weight of La 2 O 3 , 0.75 to 1.95% by weight of CeO 2 , and 0.60 to 1.17% by weight of ZrO. 2 , 0.25-1.30 weight% TiO 2 and 0.10-0.25 weight% MnO 2 were added to form a ceramic dielectric composition.
본 발명의 상기 유전체 조성물 구성에 있어서 La2O3와ZrO2는 BaTiO3의 Ba 격자에 치환되어 약 125℃에 위치하게 되는 BaTiO3의 큐리온도(Curie Temperature)를 상온으로 이동시키는 이동제(shifter)로서의 역활과 큐리 온도에서의 유전율을 향상시키며, ZrO2및 TiO2와 함께 소결 과정중에서 액상을 형성하여 1300℃에서 소결을 가능하게 해주며, 결정립의 성장을 억제하는 효과를 나타낸다.Transfer agent (shifter) for moving the Curie temperature (Curie Temperature) of BaTiO 3 La 2 O 3 and ZrO 2 may be substituted for Ba lattice of BaTiO 3 which is located at about 125 ℃ in the dielectric composition structure of the present invention to ambient temperature It improves its role as dielectric constant at Curie temperature, and forms a liquid phase during the sintering process with ZrO 2 and TiO 2 to enable sintering at 1300 ° C and to suppress grain growth.
ZrO와 TiO2는 이동제로서의 역활과 온도에 따른 유전율의 편차를 작게 하는데 효과적인 작용을 하며, 또한 결정립의 성장을 억제하여 결정립을 작고 균일하게 성장시키게 한다.ZrO and TiO 2 play an effective role in reducing the variation of the dielectric constant according to the role of the transfer agent and the temperature, and also suppress the growth of grains, thereby making the grains grow small and uniform.
MnO2형태로 첨가되는 Mn은 다양한 원자가를 갖을 수 있기 때문에 주성분인 BaTiO3와 BaTiO3와반응하는 각 첨가물들의 전체적인 원자가를 보상하여 중성화 작용을 함으로서 유전 손실을 낮추고 절연 저항을 증가시키는 역할을 수행하게 된다.Since Mn added in the form of MnO 2 can have various valences, it neutralizes the overall valence of each additive reacting with the main components BaTiO 3 and BaTiO 3 to lower the dielectric loss and increase the insulation resistance. do.
이상의 각 첨가물들의 조성물 범위에 있어서 La2O3와CeO2는 상기 범위 이하에서는 소결성이 나빠져서 치밀한 소결체를 얻기 어려우며, 그 이상에서는 유전율은 증가하나 온도 특성을 규격치보다 벗어나게 한다.In the composition range of each of the above additives, La 2 O 3 and CeO 2 have a poor sinterability under the above range, making it difficult to obtain a compact sintered body, and above that, the dielectric constant increases, but the temperature characteristic is out of the standard value.
ZrO2와 TiO2는 상기 범위 이하에서는 소결성 저하로 인한 유전율의 감소가 크게 되고, 상기 범위 이상에서는 정상적인 결정립 외에 2차상으로 존재하게 되는 침상 형태의 결정립을 형성하고 또한 큰 기공을 형성하여 절연 저항과 절연 파괴 전압을 감소시키는 경향을 나타내게 한다.The ZrO 2 and TiO 2 have a decrease in dielectric constant due to a decrease in sinterability at the range below the above range, and at the above range, needle-shaped grains exist in the secondary phase in addition to the normal grains, and also form large pores. It tends to reduce the dielectric breakdown voltage.
또한 MnO2는 0.15중량% 이하에서는 손실값이 높아지며, 0.25중량% 이상에서는 유전율과 절연 저항을 상대적으로 감소시킨다.In addition, MnO 2 has a high loss value at 0.15% by weight or less, and a relatively low dielectric constant and insulation resistance at 0.25% by weight or more.
이상 상술한 본 발명에 따른 유전체 자기 조성물은 결정립의 입경이 작고 치밀한 소결 상태를 나타내고, 유전율이 11,000∼14,000 정도로 매우 높으며 절연 저항이 1013Ωcm 이상이고 절연 파괴 전압이 14KV/mm 이상인 동시에 Y5V 온도 특성 규격을 만족하게 된다.The dielectric ceramic composition according to the present invention described above has a small grain size and a dense sintered state, a very high dielectric constant of about 11,000 to 14,000, an insulation resistance of 10 13 Ωcm or more, an insulation breakdown voltage of 14 KV / mm or more, and a Y5V temperature characteristic. The specification is satisfied.
따라서 본 발명의 세라믹 유전체 조성물을 적층 세라믹 콘덴서의 제조에 이용하면 유전체 층의 두께를 얇게 할 수 있어 원가 절감의 효과가 지대할 뿐만 아니라, 소형화 및 고용량화에 대응할 수 있는 고신뢰성의 제품 생산이 가능해지는 효과를 나타낼 수 있다.Therefore, when the ceramic dielectric composition of the present invention is used in the manufacture of a multilayer ceramic capacitor, the thickness of the dielectric layer can be reduced, resulting in a cost reduction effect and a high reliability product that can cope with miniaturization and high capacity. Can be effective.
이하 실시예 및 비교예를 통하여 본 발명의 제조방법 및 그 효과에 대하여 구체적으로 설명한다. 그러나 본 실시예 만으로 본 발명을 한정하는 것은 아니다.Hereinafter, the production method and effects of the present invention will be described in detail through Examples and Comparative Examples. However, the present invention is not limited only to this embodiment.
[실시예 1∼6]EXAMPLES 1-6
출발원료로 BaTiO3, La2O3,CeO2, ZrO2, TiO2및 MnO2를 표 1에 기재된 조성물이 되도록 평량한 뒤, 불순물의 혼입을 방지하기 위하여 나일론 재질의 포트에서 지르코니아 볼을 이용하여 탈 이온수와 함께 볼 밀링 방법으로 약 12시간 동안 습식, 혼합하여 분말상 혼합물을 제조한다.BaTiO 3 , La 2 O 3 , CeO 2 , ZrO 2 , TiO 2 and MnO 2 were weighed to the compositions shown in Table 1 as starting materials, and then zirconia balls were used in a nylon port to prevent the incorporation of impurities. Wet and mixed with deionized water by a ball milling method for about 12 hours to prepare a powdery mixture.
균일하게 혼합된 상기 유전체 분말을 120℃ 정도에서 건조한 후, 여기에 폴리비닐알콜 5% 수용액을 유전체 분말에 대하여 약 5중량% 정도 첨가하여 조립화한 다음 일축 가압 성형기를 이용하여 직경 10mm의 원판형 성형체를 제작한다. 이때 성형체 시편의 두께는 1.0∼1.2mm 정도가 되게 하고 성형 밀도는 약 3.6g/cm3가 되게 한다.The uniformly mixed dielectric powder was dried at about 120 ° C., and then 5% by weight of a polyvinyl alcohol aqueous solution was added to the dielectric powder, and then granulated. A molded article is produced. In this case, the thickness of the molded product specimen is about 1.0 to 1.2 mm and the molding density is about 3.6 g / cm 3 .
성형된 시편은 안정화된 지르코니아 세터에 올려놓고 1300∼1320℃ 온도 범위에서 약 2시간 동안 공기분위기의 전기로에서 소결을 행한다.The molded specimen is placed on a stabilized zirconia setter and sintered in an electric furnace in an air atmosphere for about 2 hours in the temperature range of 1300 to 1320 ° C.
소결된 시편의 양면을 인쇄 도포 방법으로 은 전극을 7mm 직경의 원형으로 도포, 건조한 후 800℃에서 10분 동안 열처리하게 되면 전기적 특성을 측정할 수 있는 최종 시편이 만들어지게 된다.Both surfaces of the sintered specimens were printed and coated with a silver electrode in a 7 mm diameter circle, dried, and then heat treated at 800 ° C. for 10 minutes to produce a final specimen capable of measuring electrical properties.
전기적 특성의 측정에 있어서 유전율과 유전 손실은 미국 휴렛 팩커드사의 용량계(모델명:HP 4278A Capacitance Meter)를 이용하여 25℃, 1KHz, 0.5V의 측정 조건으로 측정하고, 유전율의 온도 특성은 상기 용량계와 -30∼+85℃까지 온도 조절이 가능한 항온조를 조합하여 측정하였으며, 절연 저항은 휴렛 팩커드사의 고저항 측정기(모델명:HP 4339A High Resistance Meter)를 이용하여 100V의 직류 전압을 1분 동안 인가한 후 측정하였다. 또한 절연 파괴 자체 제작한 절연 파괴 전압 측정기를 이용하여 공기중에서 측정시 발생하는 공기중으로 전류가 흐르는 것(over flash)을 방지하기 위하여 절연유 속에서 측정을 실시하였다.In the measurement of electrical properties, dielectric constant and dielectric loss were measured under a measurement condition of 25 ° C., 1KHz, and 0.5V using a Hewlett-Packard Co., Ltd. capacity meter (HP 4278A Capacitance Meter) of the United States. And a thermostat with temperature control from -30 to + 85 ℃ were measured. The insulation resistance was measured by applying a 100V DC voltage for 1 minute using Hewlett Packard's high resistance meter (Model: HP 4339A High Resistance Meter). It was measured after. In addition, the dielectric breakdown voltage measuring device manufactured by the dielectric breakdown was measured in the insulating oil in order to prevent the current from flowing into the air generated during the measurement in the air.
이상과 같은 방법으로 측정한 전기적 특성의 결과치를 표 2에 나타내었다.Table 2 shows the results of the electrical characteristics measured by the above method.
[비교예 1∼4][Comparative Examples 1 to 4]
BaTiO3, La2O3,CeO2, ZrO2, TiO2및 MnO2를 표 1에 기재된 것과 같이 본 발명의 범주를 벗어난 양으로 혼합, 제조한 것을 제외하고는 실시예 1∼6에 기재된 것과 동일한 방법으로 시편을 제작하였으며, 또한 동일한 방법으로 전기적 특성을 측정하여 그 결과치를 표 2에 나타내었다.BaTiO 3 , La 2 O 3 , CeO 2 , ZrO 2 , TiO 2 and MnO 2 were mixed and prepared in amounts outside the scope of the present invention as shown in Table 1, except that Specimens were prepared in the same manner, and the electrical properties were measured in the same manner and the results are shown in Table 2.
상술한 실시예 및 비교예로부터 알 수 있듯이 본 발명의 세라믹 유전체 조성물은 결정립의 입경이 2∼3㎛로 작고 치밀한 소결 상태를 나타내고 있으며, 유전율은 11,000∼14,000 정도로 높고, 유전 손실은 0.8% 이하이며, 절연 저항은 1013Ωcm 이상이고 절연 파괴 전압은 14KV/mm 이상인 동시에 Y5V 온도 특성을 만족하고 있었다.As can be seen from the examples and comparative examples described above, the ceramic dielectric composition of the present invention exhibits a compact and compact sintered state with a grain size of 2 to 3 µm, a dielectric constant of about 11,000 to 14,000, and a dielectric loss of 0.8% or less. The insulation resistance was 10 13 Ωcm or more, the dielectric breakdown voltage was 14 KV / mm or more, and the Y5V temperature characteristics were satisfied.
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