摘要
低介电常数、高品质因数微波介质陶瓷材料的合成及研究是近年来的研究热点,本文制备了Sm_2SiO_5陶瓷,Sm_4(SiO_4)_3陶瓷,Nd_2SiO_5陶瓷,Al_2O_3-TiO_2陶瓷,MgTiO_3-CaTiO_3陶瓷和(Zn,Mg)TiO_3-TiO_2陶瓷,并用XRD、SEM、EDS和TG-DTA等多种分析测试手段及开腔谐振测试方法,研究了这些低介陶瓷的相组成、致密度和微观结构等对材料介电性能的影响,探索介电性能的演变规律,并将(Zn,Mg)TiO_3-TiO_2复合陶瓷用于制备多层片式陶瓷电容器(MLCC)。
1.研究以非化学计量比效应合成新型的单相Sm_2SiO_5低介电常数微波陶瓷。当Sm_2O_3/SiO_2摩尔比为1:1.05,在1350℃烧结4h,可得到纯的单斜Sm_2SiO_5相。随着温度的升高,可以得到少量的六方Sm_4(SiO_4)_3相,并且随着温度的升高,Sm_2SiO_5陶瓷样品的相对密度随之增加。Sm_2SiO_5陶瓷在1500℃下烧结后,有优良的介电性能:εr=8.5,Q×f=64878.71GHz和τf=-37.64ppm/℃。Sm_2SiO_5陶瓷材料有着较宽的烧成温度范围和小的负温度系数,因此可以作为优良的介电材料用于毫米波通讯装置中。
2.研究以非化学计量比效应合成新型的单相Sm_4(SiO_4)_3低介高频微波陶瓷。发现Sm_2O_3-xSiO_2(1.425≤x≤1.6)在1350-1600℃下烧结四个小时,均能得到纯六方Sm_4(SiO_4)_3相。当x=1.5时,样品的介电性能: εr=9.03,Q×f=17470.76GHz (12.40GHz)和τf=-24.4ppm/℃。Sm_4(SiO_4)_3陶瓷材料有着很宽的烧成温度范围和较小的负温度系数。
3.研究以非化学计量比效应合成新型的单相Nd_2SiO_5低介电常数微波陶瓷。当Nd2O_3/SiO_2摩尔比为1:1.05,在1450℃下烧结时,第二相六方Nd_4Si_3O_(12)相消失,纯单斜Nd_2SiO_5相出现。随着烧温的升高,Nd_2SiO_5陶瓷的相对密度升高。Nd_2SiO_5陶瓷在1500℃下烧结,介电性能: εr=7.94,Q×f=38800GHz, τf=-53ppm/℃。高自谐振频率导致低的介电常数和低的Q×f值。Nd_2SiO_5陶瓷有较宽的烧成温度范围,它们有潜力应用在微波被动元器件中。
4.使用新颖的水基溶胶凝胶法合成0.9Al_2O_3-0.1TiO_2包覆性纳米颗粒,用二(2-羟基丙酸)二氢氧化二铵合钛(TALH)为钛盐水基前驱体,与传统的钛醇盐sol-gel法相比,不需要乙醇做溶剂体系。本文对其制备条件进行了优化。α-Al_2O_3和金红石相晶粒生长指数(n)各为2.5和4,晶粒生长活化能分别为100kJ/mol和107kJ/mol。沿着晶界扩散后形成的缝合线,纳米层通过高温自组装途径生长,其微波介电性能:εr=10.4, Q×f=18000GHz, τf=-10.8ppm/℃(在1300℃烧结)和εr=13, Q×f=32000GHz, τf=45ppm/℃(又在1100℃下退火10h)。
5.采用固相法合成MgTiO_3-CaTiO_3复合陶瓷,加入CaTiO_3用来调节MgTiO_3过负的频率温度系数,加入3ZnO-B_2O_3可以促进体系的烧结。
(a) MgTiO_3-CaTiO_3陶瓷随着CaTiO_3掺入量的增加,体系的介电常数和温度系数随之增加,品质因数随之下降,样品的介电性能与微观结构和晶相转变有着密不可分的联系。0.97MgTiO_3-0.03CaTiO_3在1300℃下具有优良的微波介电性能: εr=18.23, Q×f=76529GHz (7.37GHz)和τf=-34.68ppm/°C。
(b)适量的ZB掺杂0.97MgTiO_3-0.03CaTiO_3,在降低烧温的同时,并没有明显恶化体系的介电性能。0.97MgTiO_3-0.03CaTiO_3+2wt.%ZB在1225℃下具有优良的微波介电性能: εr=17.96, Q×f=79346GHz (7.47GHz)和τf=-34.93ppm/°C。
6.采用固相法合成(Zn,Mg)TiO_3-TiO_2复合陶瓷,加入TiO_2用来稳定(Zn, Mg)TiO_3六方相和调节谐振频率温度系数,加入3ZnO-B_2O_3可以促进体系的烧结,体系遵循液相烧结机理,烧结过程中有明显的晶界运动。SEM和EDS显示,在烧结过程中,游离的(Zn, Mg)TiO_3颗粒会在晶界上产生偏析甚至脱溶出来分凝在晶界上。SnO_2因为能阻止晶界扩张而被用做晶粒细化剂。样品的介电性能与微观结构和晶相转变有着密不可分的联系,我们发现(Zn, Mg)TiO_3-0.25TiO_2+1.0wt.%3ZnO-B2O_3+0.1wt.%SnO_2(ZMTZBS,1000°C)呈现优良的介电性能: εr=27.7, Q×f=65494GHz (6.07GHz)和τf=-8.88ppm/°C。
7.用介电性能优良的ZMTZBS陶瓷粉料成功制造了具有良好电性能的多层片式陶瓷电容器。我们发现:随着电容量增加,电容器的自谐振频率和等效串联电阻相应减少,而品质因数随着频率或电容量增加而减少。
Preparation of microwave ceramic materials with low dielectric constant and highquality factor has become a research focus in recent years. In this paper, Sm_2SiO_5ceramics,Sm_4(SiO_4)_3ceramics, Nd_2SiO_5ceramics, Al_2O_3-TiO_2ceramics, MgTiO_3-CaTiO_3ceramicsand (Zn, Mg)TiO_3-TiO_2ceramics were synthesized. The phase composition, density andcrystal microstructure of ceramic materials with low dielectric constant were analyzed byXRD, SEM, EDS, TG-DTA and so on. Microwave dielectric properties were tested byHakki-Coleman opened resonator method. The relationship between microstructure andmicrowave dielectric properties was also investigated. The evolution of dielectric propertieswas discussed.(Zn,Mg)TiO_3-TiO_2composite ceramics were applied to manufacturemultilayer ceramic capacitors (MLCC).
1. Sm_2SiO_5ceramics were synthesized by solid phase method. The pure monoclinicSm_2SiO_5phase could be obtained when Sm_2O_3/SiO_2=1:1.05at1350℃. The hexagonalSm_4(SiO_4)_3second phase occurred as temperature increased. The densification of Sm_2SiO_5ceramics increased with increasing temperature. The Sm_2SiO_5ceramics sintered at1500℃exhibited microwave dielectric properties: a dielectric constant (εr) of8.5, a quality factor Q×fof64878.71GHz and a temperature coefficient of resonant frequency (τf) of-37.64ppm/℃.Sm_2SiO_5ceramics had a wide temperature region and small negative τfvalue. They arepromising candidate materials for millimeter-wave devices.
2. Sm_4(SiO_4)_3ceramics were synthesized by solid phase method. The pure hexagonalSm_4(SiO_4)_3phase could be obtained when Sm_2O_3/SiO_2=1:1.425-1.6at1350℃-1600℃for4h. when Sm_2O_3/SiO_2=1:1.5at1550℃, Sm_4(SiO_4)_3ceramics exhibited microwave dielectricproperties: a dielectric constant (εr) of9.03, a quality factor Q×f of17470.76GHz (12.40GHz)and a temperature coefficient of resonant frequency (τf) of-24.4ppm/℃. Sm_4(SiO_4)_3ceramics had a wide temperature region and small negative τfvalue.
3. Nd_2SiO_5ceramics were synthesized by solid phase method. The hexagonal Nd_4Si_3O_(12)second phase disappeared and the pure monoclinic Nd_2SiO_5phase could be obtained when themolar ratio of Nd2O_3/SiO_2was1:1.05at1450℃. The relative density of Nd_2SiO_5ceramicsincreased with increasing temperature. The Nd_2SiO_5ceramics sintered at1500℃exhibitedmicrowave dielectric properties: a dielectric constant (εr) of7.94, a quality factor (Q×f) of38800GHz and a temperature coefficient of resonant frequency (τf) of-53ppm/℃. Highresonant frequency led to a low dielectric constant and low Q×f value. Nd_2SiO_5ceramics had a wide temperature region. They are promising candidate materials for microwave passivecomponents.4. The0.9Al_2O_3-0.1TiO_2nano-particles were synthesized by novel water-based sol-gelmethod. Compared with the traditional sol-gel method using titanium alcohol salt, this methoddid not need ethanol solvent system using TALH as titanium salt water-based precursor body.The preparation condition of0.9Al_2O_3-0.1TiO_2nano-particles was optimized. The graingrowth exponent (n) values were2.5and4for α-Al_2O_3and rutile, respectively. The activationenergies of grain growth were estimated to be100and107kJ/mol for α-Al_2O_3and rutile.Along suture line emerging after grain boundary diffusion, the nano-sheets of Al_2O_3-TiO_2grew through high temperature self-assembly way. The microwave dielectric behaviors of0.9Al_2O_3-0.1TiO_2ceramics were εr=10.4, Q×f=18000GHz, τf=-10.8ppm/℃(as preparedat1300℃), and εr=13, Q×f=32000GHz, τf=45ppm/℃(post-annealed at1100℃for10h).5. MgTiO_3-CaTiO_3composite ceramics have been prepared via the solid-phase synthesismethod. CaTiO_3was employed to tone negative temperature coefficient of resonant frequency(τf) of MgTiO_3,3ZnO-B2O_3was effective to promote sintering.(a) With the content of CaTiO_3increasing, dielectric constant and temperature coefficientof MgTiO_3-CaTiO_3ceramics increased, and quality factor reduced. The dielectric propertiesdepended on microstructure and grain phase transition closely. Microwave dielectricbehaviors of0.97MgTiO_3-0.03CaTiO_3ceramics were: εr=18.23, Q×f=76529GHz (7.37GHz), τf=-34.68ppm/°C (at1300℃).(b) Right amount of ZB doping0.97MgTiO_3-0.03CaTiO_3, led to the decrease in thesintering temperature, and the dielectric properties had no significant deterioration.Microwave dielectric behaviors of0.97MgTiO_3-0.03CaTiO_3+2wt.%ZB ceramics were: εr=17.96, Q×f=79346GHz (7.47GHz), τf=-34.93ppm/°C (at1225℃).6.(Zn, Mg)TiO_3-xTiO_2composite ceramics were prepared via solid-phase synthesismethod. TiO_2was employed to tone temperature coefficient of resonant frequency (τf) andstabilized hexagonal (Zn, Mg)TiO_3phase.3ZnO-B_2O_3was effective to promote sintering. Themovement of grain boundary was obvious because of the liquid phase sintering. SEM andEDS showed that segregation and precipitation of dissociative (Zn, Mg)TiO_3grains occurredat grain boundary during sintering. SnO_2was used as inhibitor to prevent the grain boundaryfrom moving. The dielectric behaviors of specimen strongly depended on structural transitionand microstructure. We found that1.0wt.%3ZnO-B_2O_3doped (Zn, Mg)TiO_3-0.25TiO_2ceramics with0.1wt.%SnO_2additive displayed excellent dielectric properties (at1000°C): εr =27.7, Q×f=65494GHz (at6.07GHz) and τf=-8.88ppm/°C.
7. The above-mentioned material was applied successfully to make multilayer ceramiccapacitors (MLCC), which exhibited excellent electrical properties. The self-resonancefrequency (SRF) and equivalent series resistance (ESR) of capacitor decreased withcapacitance increasing, and the quality factor (Q) of capacitor reduced as frequency orcapacity increased.
引文
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