CN105174941B - A kind of highly reliable X8R type multilayer ceramic capacitor dielectric material and preparation method thereof - Google Patents

A kind of highly reliable X8R type multilayer ceramic capacitor dielectric material and preparation method thereof Download PDF

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CN105174941B
CN105174941B CN201510563648.4A CN201510563648A CN105174941B CN 105174941 B CN105174941 B CN 105174941B CN 201510563648 A CN201510563648 A CN 201510563648A CN 105174941 B CN105174941 B CN 105174941B
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moles
dielectric
multilayer ceramic
ceramic capacitor
temperature
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CN201510563648.4A
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CN105174941A (en
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陈世纯
张兵
司留启
张莹
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山东国瓷功能材料股份有限公司
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Abstract

The invention discloses the composition and preparation method of a kind of highly reliable X8R type multilayer ceramic capacitor dielectric material, component includes 100 moles of barium titanate calcium Ba of main component1‑XCaXTiO3(0.005 < x≤0.05), 0.1-0.6 moles of MnCO3, 0.2-2.0 moles of MgO, 1.5-5.5 moles of SiO2, 0.1-0.5 moles of Al2O3, 1.0-4.0 moles of ZrO2, 0.5-3.5 moles be selected from Y2O3、Ho2O3、Er2O3、Yb2O3、Gd2O3At least one of or several compounds, 0.01-0.5 moles be selected from WO3、MoO3、V2O5At least one of or several compounds.The multilayer ceramic capacitor of dielectric material manufacture, interior electrode use nickel or nickel alloy, and multilayer ceramic capacitor meets the X8R characteristic of U.S.'s ELA standard, and the average life span under high-temperature load, in 48h or more, multilayer ceramic capacitor reliability is excellent.

Description

A kind of highly reliable X8R type multilayer ceramic capacitor dielectric material and preparation method thereof
Technical field
The present invention relates to a kind of multiple-layer sheet ceramic capacitor dielectric material more particularly to a kind of meeting using nickel electrode The medium material for multilayer ceramic capacitors with high reliability of X8R characteristic.
Background technique
Currently, multiple-layer sheet ceramic capacitor (Multilayer Ceramic Capacitors) abbreviation MLCC, extensive Applied to blocking, coupling, bypass, frequency discrimination etc.;It is that electrode material is replaced in parallel overlap with ceramic material with multilayer Come, by one entirety of high temperature firing, reburns end external electrode processed and formed;MLCC is with small in size, insulation resistance is high, inductance Low plurality of advantages and by favor, particularly suitable for chip surface mounting technology, be greatly improved Circuit assembly density, reduce Machine volume, the feature of this protrusion make MLCC become dosage maximum, a kind of slice component with fastest developing speed in the world.
According to International Electronics Industry Association EIA (Electronic Industries Association) standard, X8R type MLCC refers on the basis of 25 DEG C of capacitance, within the temperature range from -55 DEG C to 150 DEG C, temperature coefficient of capacitance≤± 15%. In recent years, some electronic equipments to work at high temperature are greater than 125 DEG C to the operating temperature upper limit, and the especially workability upper limit is 150~200 DEG C of MLCC product, there is very big demand.In terms of high-temperature stable MLCC is mainly used in following two: first is that answering For in all kinds of Vehicular electronic control units;Electronic control unit module, the anti-lock braking system installed in such as enging cabin; These electronic equipments are used for engine control, Driving control and brake control, and security implications are great, but its working environment is disliked very much Bad, especially summer, the temperature in enging cabin can be more than 130 DEG C, and this requires electronic components must have good temperature Spend stability and high-temperature stability.Second is that it is related to the application of defence and military, aerospace and Exploration Domain, the high-power phase of specific volume Control battle array radar, armored vehicle, missile-borne/arrow carry circuit and oil exploration etc., be required to device operating temperature reach 150 DEG C with On.And the operating temperature range of X7R type MLCC is -55~125 DEG C, it is clear that it is improper, so research and development have high-temperature stability X8R type MLCC dielectric material has highly important practical significance.
Although the MLCC dielectric material proposed in many patent documents can satisfy X8R characteristic requirements, but in high-temperature load Under life time it is short;In order to improve the high-temperature load service life of dielectric material, herein by hydrothermal synthesis method synthesis of barium titanate calcium, Using barium titanate calcium as main component, lattice defect is generated after replacing Ti with the Ca of part, therefore barium titanate calcium has high antigen former Property;In order to meet X8R characteristic, modification is doped by barium titanate calcium, it is mobile to high temperature direction to make curie point, while widening residence In peak, with obtain -55~150 DEG C at a temperature of temperature coefficient of capacitance within ± 15%, meet X8R characteristic requirements.
Summary of the invention
The purpose of the present invention is to defect of the existing technology, provides and a kind of meet X8R spy using nickel electrode The medium material for multilayer ceramic capacitors with high reliability of property.
Its technical solution is: a kind of highly reliable X8R type multilayer ceramic capacitor dielectric material, molar composition ratio are as follows: 100 moles of barium titanate calcium Ba1-xCaxTiO3(0.005 < x≤0.05), 0.1-0.6 moles of MnCO3, 0.2-2.0 moles of MgO, 1.5- 5.5 moles of SiO2, 0.1-0.5 moles of Al2O3, 1.0-4.0 moles of ZrO2, 0.5-3.5 moles be selected from Y2O3、Ho2O3、Er2O3、 Yb2O3、Gd2O3At least one of or several compounds, 0.01-0.5 moles be selected from WO3、MoO3、V2O5At least one of or Several compounds.
The Ba1-xCaxTiO3It is produced using hydro-thermal method, particle size is in 200-600nm.
A kind of preparation method of highly reliable X8R type multilayer ceramic capacitor dielectric material, comprises the following steps:
(1) additive MnCO is chosen3、MgO、SiO2、Al2O3、ZrO2
(2) Y is chosen2O3、Ho2O3、Er2O3、Yb2O3、Gd2O3One of and the above compound;
(3) WO is chosen3、MoO3、V2O5At least one of or several compounds;
(4) additive powder chosen in step (1) to (3) mixed, calcined;
(5) after being mixed together by calcined powder and remaining ingredient and barium titanate calcium, disperse, dry, dielectric material is obtained.
The calcination temperature of additive powder is 500-900 DEG C after mixing.
The invention has the advantages that the temperature stability of the dielectric material is good, high reliablity;Using the high titanium of resistance to reduction Sour barium calcium is main component, introduces auxiliary element additive in formula, keeps Curie peak straight and curie point is mobile to high temperature direction, Make the temperature coefficient of capacitance of dielectric material that X8R standard be more easily satisfied;The rare earth oxide of introducing improves the anti-reduction of dielectric material Property.
Using formula and technique of the invention, the X8R type dielectric material of high reliability can be obtained.Utilize the dielectric material The multilayer ceramic capacitor of preparation is suitble to be sintered in a reducing atmosphere, and sintering temperature is at 1250~1320 DEG C.Utilize the medium material The multilayer ceramic capacitor of material preparation has 2000 or more dielectric constant, and temperature characterisitic meets the X8R characteristic of U.S.'s EIA standard; And average life span of the high-temperature load reliability in 150 DEG C of DC voltages for applying 25V/ μm is in 48h or more.
Specific embodiment
A kind of highly reliable X8R type multilayer ceramic capacitor dielectric material and preparation method thereof, the present invention use hydro-thermal method The barium titanate calcium Ba of production1-xCaxTiO3For principal component, additive diffusion rate in crystal grain is controlled, uniform lattice knot is obtained Structure, MLCC high reliablity meet X8R standard.
Additive component in the present invention improves the resistance to reduction of dielectric material, special to temperature stability and high-temperature temperature Property is advantageous.
A kind of highly reliable X8R type multilayer ceramic capacitor dielectric material barium titanate calcium Ba1-xCaxTiO3Performance be close Key, the production technology of barium titanate calcium have solid phase method, hydro-thermal method or sol-gal process.The barium titanate calcium of hydro-thermal method technique production, tool Have that grain development is complete, light, particle of reuniting is without hole, and powder does not need high-temperature calcination to handle, and avoids in sintering process and causes Crystal grain grow up, defect formed and impurity introduce.Dielectric material can be made to obtain height less without hole, defect in barium titanate calcium crystal grain Reliability.
Additive component in the present invention, plays an important role in dielectric material.MnCO3, accelerate sintering and improve exhausted Edge resistance and IR durability, 0.1-0.6 moles of additional amount (compare 100 moles of barium titanate calcium Ba1-xCaxTiO3) properly, additional amount Excessively, sufficient effect cannot be obtained, additional amount is very few, is unfavorable for the temperature coefficient of capacitor.MgO makes the temperature coefficient of capacitor It is straight, and growing up for crystal grain can be inhibited, 0.2-2.0 moles of additional amount (compares 100 moles of barium titanate calcium Ba1-xCaxTiO3) close Suitable, additional amount is excessive, can cause the degeneration of sintering characteristic, and additional amount is very few, and crystal grain cannot obviously be inhibited to grow up and straight capacitor Temperature coefficient.SiO2, sintering aid, reduce and broadening material sintering temperature, 1.5-5.5 moles of additional amount (is rubbed compared to 100 You are barium titanate calcium Ba1-xCaxTiO3) properly, additional amount is very few, causes the degeneration of sintering characteristic, and be unfavorable for capacitance temperature factor And insulation resistance, additional amount is excessive, causes burning, causes the decline of dielectric constant.Al2O3, improve sintering characteristic, insulation resistance, 0.1-0.5 moles of additional amount (compares 100 moles of barium titanate calcium Ba1-xCaxTiO3) properly, additional amount is very few, causes sintering characteristic Degeneration, additional amount is excessive, causes the decline of insulation resistance.ZrO2, improve Curie temperature and keep the temperature coefficient of capacitor straight Change, 1.0-4.0 moles of additional amount (compares 100 moles of barium titanate calcium Ba1-xCaxTiO3) properly, additional amount is very few, improved effect Insufficient, additional amount is excessive, is unfavorable for insulation resistance.Selected from Y2O3、Ho2O3、Er2O3、Yb2O3、Gd2O3At least one of or Several compounds improve the resistance to reduction that material is sintered under reducing atmosphere, improve Curie temperature and make the temperature coefficient of capacitor Straightened, improves insulation resistance and average life span, and 0.5-3.5 moles of additional amount (compares 100 moles of barium titanate calcium Ba1- xCaxTiO3) properly, additional amount is very few, is unfavorable for the resistance to reduction of sintering and the straightened of capacitance temperature factor, additional amount mistake It is more, cause the degeneration of sintering characteristic.Select WO3、MoO3、V2O5At least one of or several compounds, improving Curie temperature and makes The temperature coefficient straightened of capacitor, 0.01-0.5 moles of additional amount (compare 100 moles of barium titanate calcium Ba1-xCaxTiO3) properly, add Enter that amount is very few, cannot adequately make the temperature coefficient straightened of capacitor, additional amount is excessive, causes the decline of insulation resistance;Meet EIA X8R standard.
Firstly, preparing main component barium titanate calcium Ba using hydro-thermal method1-xCaxTiO3;Then, at least two or more mixing is auxiliary It helps additive component and is calcined at 500-900 DEG C;Then be mixed together calcined powder and remaining ingredient and barium titanate calcium, The techniques such as dispersion, dry, obtain MLCC dielectric material.
Then above-mentioned acquisition dielectric material is proportionally mixed with adhesive, solvent, slurry then is made by dispersion, Medium green compact diaphragm is made by casting machine in slurry, prints nickel or nickel alloy electrode on membrane surface by screen printer, then According to the design number of plies, electrode in lamination diaphragm and printing;Alternative stacked prints the dielectric film of interior electrode, forms green compact lamination Piece;Ceramic body is sintered into 1250-1320 DEG C of reducing atmosphere, seals up the external electrical of Cu or Cu alloy at ceramic body both ends End is burnt in pole in protective atmosphere, to obtain multilayer ceramic capacitor MLCC.
Below by the embodiment dielectric material that the present invention will be described in detail.
Firstly, the Ba prepared using hydro-thermal method1-xCaxTiO3;Then, MnCO is mixed3、MgO、SiO2、Al2O3、ZrO2, choosing From Y2O3、Ho2O3、Er2O3、Yb2O3、Gd2O3At least one of or several compounds, 0.01-0.5 moles be selected from WO3、MoO3、 V2O5At least one of or several compounds, 650 DEG C calcine;Then, according to a certain percentage by Ba1-xCaxTiO3After burning Powder and remaining additive component by the techniques such as mixing, dispersion, dry, obtain MLCC dielectric material, material mixing It is shown in Table 1.
Then, adhesive, solvent are added in the dielectric material of acquisition, according to the manufacturer of above-mentioned multilayer ceramic capacitor Method obtains multilayer ceramic capacitor.
Then, under conditions of 25 DEG C, using LC electric bridge, the appearance of multilayer ceramic capacitor is tested at 1.0KHz, 1.0V Amount, loss;Using insulation resistance instrument, in 100V, the insulation resistance of 10 seconds test multilayer ceramic capacitors;Using high-low temperature chamber, At -55 DEG C~+150 DEG C, 1.0KHz, 1.0V, the temperature characterisitic TCC of multilayer ceramic capacitor is tested;It can as high-temperature load It is tested by property, applies 25V/ μm of DC voltage at 150 DEG C of temperature, change with time to test its insulation resistance, by each examination The insulating resistance value of sample becomes being set as failure when 108 Ω or less, finds out average life time, and dielectric properties test is shown in Table 2.
Referring to table 2, the multilayer ceramic capacitor of nickel electrode X8R type MLCC dielectric material of the present invention, at -55 DEG C~+150 DEG C Temperature characterisitic meets EIAX8R standard, and dielectric constant is greater than 2000, has good insulation resistance, applies 25V/ μm at 150 DEG C DC voltage when average life span in 48h or more.
1 dielectric material component list of table
2 MLCC dielectric properties table of table
What has been described above is only a preferred embodiment of the present invention, it is noted that for those of ordinary skill in the art For, without departing from the concept of the premise of the invention, various modifications and improvements can be made, belongs to guarantor of the invention Protect range.

Claims (1)

1. a kind of highly reliable X8R type multilayer ceramic capacitor dielectric material, it is characterised in that: its molar composition ratio are as follows: 100 rub You are barium titanate calcium Ba1-XCaXTiO3, wherein 0.005 < x≤0.05,0.1-0.6 moles of MnCO3, 0.2-2.0 moles of MgO, 1.5- 5.5 moles of SiO2, 0.1-0.5 moles of Al2O3, 1.0-4.0 moles of ZrO2, 0.5-3.5 moles be selected from Y2O3、Ho2O3、Er2O3、 Yb2O3、Gd2O3At least one of or several compounds, 0.01-0.5 moles be selected from WO3、MoO3、V2O5At least one of or Several compounds;The Ba1-XCaXTiO3It is produced using hydro-thermal method, particle size is in 200-600nm;
The dielectric material is prepared by following preparation method, and preparation method includes the following steps:
(1) additive MnCO is chosen3、MgO、SiO2、Al2O3、ZrO2
(2) Y is chosen2O3、Ho2O3、Er2O3、Yb2O3、Gd2O3One of and the above compound;
(3) WO is chosen3、MoO3、V2O5At least one of or several compounds;
(4) additive powder chosen in step (1) to (3) mixed, calcined;The calcining temperature of additive powder after mixing Degree is 500-900 DEG C;
(5) after being mixed together by calcined powder and barium titanate calcium, disperse, dry, dielectric material is obtained.
CN201510563648.4A 2015-09-08 2015-09-08 A kind of highly reliable X8R type multilayer ceramic capacitor dielectric material and preparation method thereof CN105174941B (en)

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CN1819066A (en) * 2005-01-20 2006-08-16 Tdk株式会社 Electronic device, dielectric ceramic composition and the production method
CN1903787A (en) * 2005-07-28 2007-01-31 三星电机株式会社 Dielectric ceramic composition for low temperature sintering and multilayer ceramic capacitor using the same
CN101781115A (en) * 2009-01-19 2010-07-21 清华大学 X8R type multilayer ceramic capacitor dielectric material and preparation method thereof
CN103553591A (en) * 2013-10-11 2014-02-05 山东国瓷功能材料股份有限公司 Dielectric ceramic material for multilayer ceramic capacitor with high temperature insulation performance

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CN1332131A (en) * 2000-07-05 2002-01-23 三星电机株式会社 Dielectric ceramic composition, ceramic capacitor using the same and manufacture thereof
CN1819066A (en) * 2005-01-20 2006-08-16 Tdk株式会社 Electronic device, dielectric ceramic composition and the production method
CN1903787A (en) * 2005-07-28 2007-01-31 三星电机株式会社 Dielectric ceramic composition for low temperature sintering and multilayer ceramic capacitor using the same
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