功能陶瓷講義1

1、Electronic Ceramics and Their ApplicationsX.M. Chen ()Department of Materials Science & Engineering, Zhejiang University, Hangzhou 310027Tel: 87952112; E-mail: Web: 1Brief Introduction of X.M. ChenWas born in Hunan 1959B.S. Dept. Mater. Sci.& Eng., Central South University in 1981PhD Dept. Mater. Sc

2、i. & Metallurgy, The University of Tokyo in 1991Research Scientist at Yokohama R&D Labs., Furukawa Electric Co. Ltd. (Japan), 1991-1994Associate Professor, Dept. Mater. Sci. Eng., Zhejiang Univ. 1994-1996Professor, Dept. Mater. Sci. Eng., Zhejiang Univ., Since 1996Distinguished Young Scientist Found

3、ation of NSFC in 2000Professor of “Changjiang Scholar Program” 2002Member of International Advisory Board of MMA2000, MMA2002, MMA2006Chairman, MMA-2004 (Inuyama, Japan) & MMA-2008 (Hangzhou, China)Member of Executive Board, Asian Electroceramics Association (AECA). Authored or co-authored more than

4、 140 papers in pier-reviewed international journals 2Research Activities in X.M. Chens Group微波介質(zhì)陶瓷及其應(yīng)用(Microwave dielectric ceramics and their applications)中介電常數(shù)微波介質(zhì)陶瓷新體系低介電常數(shù)微波介質(zhì)陶瓷新體系疊層介質(zhì)諧振器可調(diào)諧介電薄膜鐵電與介電新材料(Ferroelectric and dielectric new materials)巨介電常數(shù)材料(Giant dielectric constant materials)非鉛鐵電與弛

5、豫鐵電陶瓷(Pb-free ferroelectric and relaxor ferroelectric ceramics)微圖案鐵電薄膜(Micro-patterned ferroelectric thin films)復(fù)相與多功能耦合陶瓷(Composite and multifunctional ceramics)磁電復(fù)相陶瓷 (Magetoelectric composite ceramics)多鐵性材料 (Multiferroic materials)磁性電介質(zhì)(Magnetic dielectrics)34功能陶瓷的基本概念與結(jié)構(gòu)陶瓷相對(duì)應(yīng)的概念，主要指具備特定的電、磁、聲、光、

6、熱等物理性能的陶瓷材料；電子陶瓷是功能陶瓷的主體；電子陶瓷：介電陶瓷(絕緣陶瓷)、鐵電陶瓷、反鐵電陶瓷、壓電陶瓷、熱釋電陶瓷、半導(dǎo)體陶瓷、電光陶瓷、磁性陶瓷等在電子、通訊、軍事、以及家電技術(shù)中有著廣泛的應(yīng)用。56789功能陶瓷的學(xué)科關(guān)系學(xué)科基礎(chǔ)：固體物理、固體化學(xué)、電磁學(xué)、材料科學(xué)基礎(chǔ)相關(guān)學(xué)科：電子、通訊、儀器儀表等無(wú)機(jī)非金屬材料功能材料功能陶瓷10功能陶瓷現(xiàn)代電子技術(shù)的三大物質(zhì)基礎(chǔ)之一半導(dǎo)體材料電介質(zhì)材料(功能陶瓷)光電子材料微電子學(xué)固體電子學(xué)光電子學(xué)電子材料111213Primary ContentsElements of Dielectrics (電介質(zhì)) and Ceramic Ins

7、ulatorsFerroelectric(鐵電), Relaxor Ferroelectric(馳豫鐵電), Antiferroelectric (反鐵電) Ceramics and Ceramic Capacitors(電容器) Microwave Dielectric Ceramics(微波介質(zhì)陶瓷)Piezoelectric(壓電) and Opto-electric CeramicsCeramic SensorsZnO Varistors(變阻器)Conducting Ceramics14Chapter 1 Elements of Dielectrics and Ceramic Ins

8、ulatorsI. Elements of Dielectrics15物質(zhì)按導(dǎo)電性能的分類(lèi)載流子長(zhǎng)程運(yùn)動(dòng)與位移傳導(dǎo)、宏觀電流導(dǎo)體：金屬、部分非金屬半導(dǎo)體：部分非金屬單質(zhì)與化合物絕緣體 （無(wú)載流子長(zhǎng)程運(yùn)動(dòng)與位移）：大部分非金屬單質(zhì)與化合物載流子短程運(yùn)動(dòng)與位移極化(Polarization)電介質(zhì)（絕緣體+半導(dǎo)體；通常為絕緣體）16電介質(zhì)的基本物理概念-極化極化-正負(fù)電荷中心偏移偶極矩(dipole moment)p=Qdx (1.1)極化強(qiáng)度PP=dp/dV=Njmj (1.2)(Nj=number of dipoles of type j; mj=average dipole moment)m

9、j= aj E (1.3)aj - polarizability of average dipole moment;E- local electric fieldP=sp (surface charge density) (1.4) 17極化機(jī)理at= as+ao+ai+ae (1.5) ae-Electronic (Atomic) Polarization; ai -Ionic Polarization;ao-Orientation (Dipolar) Polarization;as -Space Charge or Diffusional Polarization181920電位移D、電場(chǎng)

10、強(qiáng)度E與極化強(qiáng)度P的關(guān)系For case a): E=s/e0 (1.6)s - surface charge densityFor case b): E=(sT-sP)/e0 (1.7)sT total surface charge density; sP polarazation charge densitySince P= sP and sT=D (electric displacement) e0 E=P-D (1.8) D= e0 E+ P (1.9) If the dielectric is linear, P=ce e0 E, so that D= e0 E+ ce e0 E=(

11、1+ ce) e0 E (1.10) where, ce is electric susceptibility, a tensor of the second rank21介電常數(shù)(Dielectric Constant)Since D= sT, QT/A= (1+ ce) e0 U/h (1.11) QT =(1+ ce) e0 UA/h (1.12) C=QT/U= (1+ ce) e0 A/h (1.13)Since vacuum has zero susceptibility, C0=e0 A/h (1.14)If the space between the plates is fil

12、led with a dielectric of susceptibility ce, the capacitance is increased by a factor 1+ ce.Permittivity e of the dielectric is defined by e =e0(1+ ce) (1.15)Dielectric constant (relative permittivity) er = e /e0=1+ ce (1.16)22An individual atom or ion in a dielectric is not subjected directly to an

13、applied field but to a local field.The internal macroscopic field Em is the resultant of applied external field Ea and depolarizing field Edp, i.e. Ea-Edp. It is assumed that the solid can be regarded as comprising identifiable polarizable entities on the atomic scale.The local field EL (or Lorentz

14、field) differ from Em since the latter is arrived at by considering the dielectric as a continuum. EL = Em+Ep+Ed (1.17) where, Ep-the contribution from the charges at the surface of the spherical cavity (imaging for the moment that the sphere of material is removed); Ed-due to the dipoles within the

15、 boundary.Applied External Field, Internal Macroscopic Field & Local (Lorentz) Field23Clausius-Mosotti EquationEp can be shown to be P/3e0, and Ed=0 for certain crystals of high symmetry and glasses. So that, EL= Em+ P/3e0 = Ea-Edp + P/3e0 (1.18)In more general case, it is assumed that EL= Em+ gP (1

16、.19) in which g is the “internal field constant”The dipole moment p induced in the entity can be now written as p=a EL (1.20)If it is assumed that all entities are of the same type and have a density N, then P=Np=Na(Em+ gP) (1.21)Or P/e0Em =ce= Na/e0/(1-Nag) (1.22)In the particular case for which g=

17、1/3eo, we have the Clausius-Mosotti Equation (er-1)/(er+2)=Na/3e0 (1.23)24介電損耗 (Dielectric Loss)25介電損耗 (Dielectric Loss)對(duì)于理想電介質(zhì)，極化能適時(shí)響應(yīng)外電場(chǎng)變化，電位移與電場(chǎng)的相位相同(電流超前p/2) 不產(chǎn)生能量損耗；而對(duì)于實(shí)際電介質(zhì)，極化不能適時(shí)響應(yīng)外電場(chǎng)變化(滯后于電場(chǎng)d-損耗角), 而出現(xiàn)介電弛豫 介電損耗。介電損耗的數(shù)學(xué)描述 E=E0exp(iwt) (1.24) D=D0expi(wt-d) (1.25) 利用D=k*E，得 k*=ksexp(-id)=ks(co

18、nd-isind) (1.26) 其中，ks- 靜態(tài)介電常數(shù)(=D0/E0)26介電損耗 (Dielectric Loss)利用復(fù)介電常數(shù)的概念 k*=k-ik”=e*/e0=(e-ie”)/e0 (1.27) k=kscosd (1.28) k”=kssind (1.29) tand=k”/k=e”/e (1.30)tand即為介電損耗物理意義 極化過(guò)程中消耗的能量與儲(chǔ)存的能量的比值電介質(zhì)的品質(zhì)因數(shù)：Q=1/ tand27Resonance Effects In the case of atomic and ionic polarization, the electrons and ions

19、 behave, to a first approximation, as though bound to equilibrium positions by linear springs so that the restoring force is proportional to displacement, a damping factor g is included in the equation of motion. (1.31)Solving (1.31) and ignoring the transient term yields (1.32)Since ex(t) is the in

20、duced dipole moment per atom, the complex polarization P* is given by (1.33)28Resonance EffectsAnd (1.34)So that (1.35) By equating real and imaginary parts (1.36) (1.37) The above the contributions of ionic and electronic polarization, which are sensibly independent of temperature, the resonance cu

21、rves are also. 29Variation in and with frequency close to a resonance frequency w0.30Relaxation EffectsIn contrast with the electronic and ionic polarization processes, the diffusional polarization and depolarization processes are relatively slow and strongly temperature dependent.The diffusional po

22、larization Pd approaches its final static value Pds according the following equation (1.38) where, t is a relaxation time.Integrating (1.38) with initial condition Pd=0 when t=0 gives (1.39)To account for alternating applied field, Eq. (1.38) should be modified to (1.40) where, ers is the low freque

23、ncy dielectric constant.31Relaxation Effects & Debye EquationsEquation (1.40) can be integrated to give (1.41)By neglecting the transient Cexp(-t/t), we can get (1.42)The Debye Equations are obtained by separating the real and imaginary parts of Eq. (1.42) (1.43) (1.44)The relaxation frequency is w=

24、1/t323334Dielectric DispersionWith increasing frequency, dielectric constant generally decrease, and some peaks appear for dielectric loss.Origins of dielectric dispersion: Rrelaxation process (orientation and space charge polarization)Resonance process (electronic and ionic polarization)Available f

25、requencies for various polarization mechanisms:Space charge polarization: 102HzOrientation polarization: 106HzIonic polarization: 1013HzElectronic polarization: 1016Hz35Cole-Cole DistributionsCole and Cole (1942) modified equation (1.42) by including an exponent a (1.45)The distribution is obtained

26、by plotting er” as a function of er, yielding what is termed the Cole-Cole distribution.Using the circuit parameters , , , we obtain (1.46)Or (1.47)36k” or e”k or eC1/e0(C1+C2)/e0w0RC2=1Indicates high lossesRC circuitCole-Cole plotCole-Cole Plot and the RC Circuit37Physical Meaning of Cole-Cole Plot

27、The Cole-Cole plot of a material is a measure of the various relaxation times for a specific dielectric material.A very narrow distribution of relaxation times perfect dielectric. This indicates that only one primary mechanism exists for the polarization within the material;A tail in the distributio

28、n indicates a large distribution of relaxation time;A large range of relaxation times can indicate multiple polarization mechanisms but also losses due to conduction. A perfect or low loss dielectric would have a Cole-Cole plot that is nearly a semicircle;A poor or high loss dielectric would have a

29、non-bounded increasing er” with increasing er. 38Dielectric Strength (介電強(qiáng)度)Dielectric breakdown(介電擊穿): All dielectrics when placed in an electric field will lose their insulating properties if the field exceeds a certain critical value.This phenomenon is called dielectric breakdown.Dielectric streng

30、th 1.48)Dielectric breakdown mechanismsIntrinsic breakdownThermal breakdownInonization breakdownElectrochemical breakdown 39Factors Affecting Dielectric StrengthComposition: amorphous or crystalline nature, presence of mobile ions;Microstructural features: porosity, grain size, cracks, flaws, second

31、ary phases;Measurement parameters: electrode configuration, specimen thickness, temperature, time, frequency, humidity and heat transfer conditions.40Chapter 1 Elements of Dielectrics and Ceramic InsulatorsII. Ceramic Insulators41IntoductionFunction of insulator in electric circuits:Physical separat

32、ion of conductors and the regulation or prevention of current flow between them;Ancillary but important other functions are to provide mechanical support, heat dissipation and environmental protection for the conductors Advantages of ceramic insulators: Materials type used as insulators: linear diel

33、ectricsTypical elements of ceramic insulator: ceramic substrates, ceramic packages42Property Requirements to Ceramic InsulatorsDielectric constant;Dielectric loss;Dielectric strength;Resistivity (1.49)Thermal conductivity;Thermal expansion coefficient;Mechanical properties.43Property Criteria for Go

34、od Ceramic InsulatorsDielectric constant: not greater than 30;Electric resistivity: not less than 1012 W-cm;Dielectric loss (dissipation factor): not larger than 0.001;Dielectric strength: not less than 5.0kV/mmDielectric loss factor: not larger than 0.03 44Properties at 1MHz(room temperature)Materi

35、alTandDielectric constant Loss factor Dielectric strengthResistivity at 25oC(cm)Porcelain(R2OAl2O3SiO2)0.008-0.0205.0-6.50.04-0.136.1-13.01014Zircon(ZrO2SiO2)0.0018.0-9.60.008-0.00966.3-11.51014Steatite(MgOSiO2)0.008-0.00356.00.005-0.027.9-13.81014Forsterite(2MgOSiO2)0.0005-0.0015.8-6.70.003-0.0077.

36、9-11.91017Cordierite(2MgO2Al2O35SiO2)0.003-0.0054.1-5.30.012-0.0255.5-9.11017Alumina(Al2O390-99.9%)0.0003-0.0028.8-10.10.03-0.029.9-15.81016Spinel(MgOAl2O3)0.00047.50.00311.91016Mullite(3Al2O32SiO2)0.0056.2-6.80.03-0.0347.81014Magnesia(MgO)0.00018.90.00898.5-11.01014Beryllia(BeO96-99%)0.0001-0.0016.

37、00.006-0.069.5-13.81016Zirconia(ZrO2)0.0112.00.125.0109Table 1.1 Dielectric properties of Ceramic Insulators 45Table 1.1 Dielectric properties of Ceramic InsulatorsMaterialTandDielectric constant Loss factor Dielectric strengthResistivity at 25oC(cm)Thoria(ThO2)0.000313.50.0045.31010Hafnia(HfO2)0.01

38、120.12108Ceria(CeO2)0.0007150.011109Spodumene(Li2OAl2O3SiO2)0.0056.5-7.50.03-0.041011Boron nitride(BN)0.0014.20.00435.6-55.41014Silicon nitride(Si3N4)0.00016.10.000615.8-19.81013-14Pyroceram0.0017-0.0135.5-6.30.01-0.079.9-11.91012Glass-bonded mica0.0015-0.0036.4-9.20.011-0.02310.6-23.71014Mica0.0002

39、5.4-8.70.001-0.00239.5-79.11016Glass(Na2OCaOSiO2)0.0005-0.014.0-8.00.002-0.087.8-13.21012Quartz(SiO2)0.00033.8-5.40.001515-25.01014-18Pb-Al silicate0.0018.2-150.008-0.0158.9-16.01013Aluminum Nitride(AlN)0.00018.8-8.90.001151013Silicon11.946Table 1.2 Thermomechanical Properties of Ceramic Insulators

40、MaterialSpecific gravityThermal conductivity at 25oC(cal/sec-oC-cm)Thermal coefficient of expansion25-300oC(10-6/oC)Tensile strength(Mpa)MOR Transv strength(Mpa)Compress strength(Mpa)Thernal shock resistancePorcelain(R2OAl2O3SiO2)2.40.0066.04883352FairZircon(ZrO2SiO2)3.70.0124.3-4.896172524GoodSteat

41、ite(MgOSiO2)2.80.0066.9-7.8100125650ModerateForsterite(2MgOSiO2)2.80.006-0.011076140550PoorCordierite(2MgO2Al2O35SiO2)2.2-2.90.005-0.0072.2-2.465105400ExcellentAlumina(Al2O390-99.9%)3.85-3.90.06-0.078.02604453400GoodSpinel(MgOAl2O3)2.80.0186.6951031710FairMullite(3Al2O32SiO2)2.6-3.20.014.3-5.0901501

42、200FairMagnesia(MgO)3.3-3.50.04-0.00910-1390138950FairBeryllia(BeO96-99%)2.8-2.950.4-0.77-91202481600GoodZirconia(ZrO2)5.43-5.560.02-0.054.3-8.3148186940Poor47Table 1.2 Thermomechanical Properties of Ceramic InsulatorsMaterialSpecific gravityThermal conductivity at 25oC(cal/sec-oC-cm)Thermal coefficient of expansion25-300oC(10-6/oC)Tensile strength(Mpa)MOR Transv strength(Mpa)Compress strength(Mpa)Thernal shock resistanceThoria(ThO2)9.70.0335.3-9.01151311524PoorHafnia(HfO2)9.00.0046.5901101386PoorCeria(CeO2)7.00.02910.0881101386Poo