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Dielectric properties of ceramics Polarization mechanisms After application of an electric field, the center of gravity of positive and negative charges does not correspond anymore f Electronic polarization: deformation of the electronic shell. Electronic Atomic or ionic polarization: displacement of negative and positive ions in relation to one another Ionic Dipolar Orientation Space charge or diffusional Dipolar and orientation polarization •Alignement of dipolar molecules in a liquid •Spontaneous alignement of dipoles in a polar solid (ferroelectricity) •Ion jump polarization occurs when two or more lattice positions are available for a ion or lattice defect •Reorientation of dipolar defects Space charge polarization occurs when charges accumulate at interfaces: composite materials, insulating surface skin, electrode polarization effects Polarization, capacitance and dielectric constant h A p p Dipoles and surface charges in a polarized dielectric Dipole moment Qd Polarization P N (dipole moment per unit volume) Dielectric displacement D E P (0 is the vacuum permittivity) 0 Surface charge density T 0E P For a linear dielectric P e 0 E Capacitance Permittivity C T 1 e 0 E (e is the electric susceptibility) QT T A T A A A A 1 e 0 ; C r 0 U U Eh h h h 0 1 e Relative permittivity (or dielectric constant) r 1 e 0 Polarization, capacitance and dielectric constant Polarizability () E Clausius-Mosotti relationship More generally r 1 (induced dipole moment per unit field) r 1 N i i r 2 3 0 N 1 N i 0 i i i N i i i 1 than is the local field constant i “Polarization catastroph” If Electronic polarizabilities are rather independent of crystal environment and high frequency dielectric constant can be predicted r The local field produced by polarization can increase more rapidly than the restoring force thus stabilizing the polarization further possibility of spontaneous polarization (ferroelectric instability) e ion dip sc P N r 1 P 0 E0 for a linear dielectric Dielectric losses IC: 90° in advance of U Current Angular frequency =2f = 2/T Il: in phase with U Voltage Ideal capacitor: 90° phase difference between I and U, no dissipation Real capacitor: <90° phase difference between I and U. Ic: charging current (capacitative component) Il: loss current, dissipative comp., power loss 1 1 2 P U I tan U 0 C tan Power dissipated per unit time W 0 c 2 2 Dissipated power density PW 1 2 E 0 0 r tan V 2 PW 1 2 E 0 ac V 2 Dielectric or ac conductivity ac 0 r tan tan: “dissipation factor” or “loss tangent” rtan: “loss factor” By analogy with dc current PW E 2 V Complex permittivity The behaviour of ac circuits can be conveniently analysed using complex quantities exp( i ) cos i sin i 1 90° in advance Real part Imaginary part Im Complex sinusoidal voltage U U 0 exp it Re Vacuum capacitor U iU 0 exp it iU I Q UC0 iCoU Capacitor with a lossy dielectric r* r' i r'' Ic I i r' C0U r''C0U I C i 0 r' E Il r'' tan ' r r'' r' tan I l 0 r'' E ac E By analogy with Ohm’s law: I =U/R or J = E "loss factor" Resonance effects in dielectrics E Charged particle in a harmonic potential well Equation of motion mx mx m02 qE E0 exp( it ) 0: natural vibration frequency : damping factor Q: charge m: mass E: local field This behaviour is generally observed for the electronic and ionic polarization processes, where the charges/dipoles move around the equilibrium positions and final polarization is almost instantaneously achieved. Resonant frequencies are of the order of 1013 and 1015 s-1, respectively, and fall in the optical range. Relaxation effects in dielectrics – migration & orientation polarization Dipolar and space charge polarization is generally accompanied by the diffusional movement of charge and dipoles over several atomic distances and surmounting energy barriers of different high. These polarization processes are relatively slow and strongly temperature dependent (thermally activated). If the transient polarization is described by a simple exponential function, the dipolar relaxation is described by the Debye equation. Debye relaxation Reorientation of dipolar defects (defects pairs) CaCl2 KCl CaK 2ClCl VK' CaK VK' (CaK VK' ) x Fe2O3 2 BaO BaTiO 3 2 Ba Ba 2 FeTi' 5OO VO FeTi FeTi' VO FeTi' VO VO Electrostatic potential in a glass or defective oxide dP Pf P dt ' ' r* r' , r , s r , 1 i ' ' r' r' , r , s 2 r ,2 1 ' ' r'' r , s 2 r ,2 1 ' ' ac 2 r , s 2 r ,2 1 1 r Relaxation time ’r ’r,s Debye relaxation ’r, ’’r Frequency dispersion region ½(’r,s- ’r,) ’’r << r: ions follow the field low losses (’r,s- ’r,)/ =1 Maximum loss occurs when the field frequency is equal to the jump frequency , =1 >> r: ions do not jump low losses Ea 0 exp k BT Ea takes values typical of ionic conduction processes (0.7 eV), giving a loss peak in the range 103 – 106 Hz. Relaxation effects in dielectrics – migration polarization Debye relaxation holds when the transient polarization is described by a simple exponential with a single relaxation time. In most materials, including single crystals, a distribution of relaxation times exists and permittivity dispersion is observed over a wider frequency range. This is related to variations of the ionic environment and thermal fluctuations with distance and existence of lattice defects. The extreme case is represented by glasses and amorphous materials. r' r'' 100 r' , s r' , Dielectric relaxation is better described by the equation (Cole&Cole) * r ' r , r' , s r' , 1 i which takes into account that the the motion of ions responsible for relaxation can be of cooperative type. = 0.2-0.3 for glasses. = 1: Debye Dielectric dispersion in silicate glasses Relaxation effects in dielectrics – effect of temperature and frequency Electronic and ionic polarization resonance occurs at f>1010 Hz which is above the limit of normal uses. The effect of temperature is small. Contribution from ion and defect migration as well as dc conductivity determine a sharp rise of permittivity with increasing temperature and decreasing frequency. Increasing concentration of charge carriers in turn leads to space charge effects. Dielectric constant of single crystal Al2O3 Dielectric constant of soda-lime silica glass Relaxation effects in dielectrics - Space charge polarization Polycrystalline and polyphase ceramics exhibit interface or space charge polarization (also called Maxwell-Wagner polarization) arising from different conductivity of the various phases. The most important occurrence of this phenomenon is in semiconducting ceramic oxides with resistive (oxidized) grain boundaries (magnetic ferrites, titanates, niobates) , in which the low frequency permittivity can be several orders of magnitude higher than the high frequency dielectric constant and is dominated by the contribution of grain boundaries. (1) (2) d1 d2 Brick-wall model If x = d1/d2 << 1, 1 >> 2 and ’r,1= ’r,2 2 r' r' 2 ' 0 r' 2 0 x1 1 x12 22 ' ' r0 r2 2 x1 2 1 2 x1 2 Special relationships involving permittivity RF & MW IR UV-Vis P N E0 r' 1 P 0 E0 At optical frequencies, electronic polarization is the main contribution to permittivity. If n is the index of refraction r' , n 2 BaTiO3 single crystal For ferroelectric materials in the paraelectric regime (T > TC) r' C T T0 C: Curie constant T0: Curie-Weiss temperature TC =120°C Properties and applications of dielectric ceramics of commercial interest Dielectric losses ac tan 2f r' 0 For alumina ceramics, = 10-12 ohm cm, ’r = 10, tan = 2x10-4 at 1 kHz MW region Properties of ceramics with low permittivity and low losses Typical properties of dielectric ceramics Material Applications Steatite Porcelain insulators Cordierite Applications requiring good thermal shock resistance. Supports for high-power wire-wound resistors. Alumina Best compromise of dielectric losses, high mechanical strength, high thermal conductivity. Reliable metal-ceramic joining technoloy (MolyMn) available. Beryllia Good properties, very high thermal conductivity, expensive and difficult processing. Insulating parts in high-power electromagnetic energy generation (klynstrons and magnetotrons). AlN High thermal conductivity and TEC close to that of silicon. Substrate for power electronic circuits and chips. Glass & glass-ceramics Cheap material and easy processing. Low thermal conductivity Properties of ceramics with low permittivity and low losses Typical properties of alumina ceramics Spark plugs Microstructure of alumina ceramics 99.9% Al2O3 96% Al2O3 Tan of 99.9% alumina ceramics Insulating parts in high-power electromagnetic generation. Windows for high-power microwave generators. Substrates for electronic circuits. Cheap packaging. Electronic substrates and chip packaging Power electronic substrates The role of the substrate in power electronics is to provide the interconnections to form an electric circuit (like a printed circuit board), and to cool the components. Compared to materials and techniques used in lower power microelectronics, these substrates must carry higher currents and provide a higher voltage isolation (up to several thousand volts). They also must operate over a wide temperature range (up to 150 or 200°C). Direct bonded copper (DBC) substrates are commonly used in power modules, because of their very good thermal conductivity. They are composed of a ceramic tile (commonly alumina) with a sheet of copper bonded to one or both sides by a high-temperature oxidation process. The top copper layer can be preformed prior to firing or chemically etched using printed circuit board technology to form an electrical circuit, while the bottom copper layer is usually kept plain. The substrate is attached to a heat spreader by soldering the bottom copper layer to it. Ceramic materials used in DBC include Al2O3, AlN and BeO. Dual in-line package (DIP) Ceramic (EPROM) Plastic Ceramic (Intel 8080) Pin grid array packaging (PGA) Celeron (top) Pentium (bottom) Socket PGA (AMD)