You are on page 1of 46

Chap. 5.

Dielectrics and Insulators -1/92-

Chapter 5. Dielectrics and insulators

1. Review of dielectric physics

2. Capacitive applications

3. Principal ceramic types and applications


- Low-K dielectrics
- Mid-K
Mid dielectrics
- Hi-K dielectrics

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -2/92-

Part I Capacitive Applications

5.1 Introduction
* Contents
Reliability of dielectric materials: dielectric strength
Electrical parameters of a capacitor
Non-ceramic capacitors
Ceramic capacitors; disc-type, tubular type, MLCC, high
power capacitors…

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -3/92-

5.2 Dielectric strength

Definition; the electric field just sufficient to initiate breakdown


of the dielectric
3 kinds; Intrinsic, thermal, discharge BD

Test conditions
- Sample geometry; Fig. 5.1
- Immersing in an insulating liquid to avoid the risk of ‘flash-
over’ across the specimen surface
- Should be specified AC or DC, the rate of voltage increase,
freq., waveforms etc.

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -4/92-

5.2.2 BD mechanisms

(a) Intrinsic BD
Avalanche BD; the kinetic E. of electrons in conduction band
increases with the field enough to ionize constituent ions
Typically the order of 1MV/cm
(b) Thermal BD
Joule heating increases the specimen temperature and leads to
an increase in conductivity and to dielectric loss
1/2
  
 
U   b
 d 
 
  'tan
5.2)
e.g., the effect
of T on BDV for a typical
aluminous porcelain (Fig.
Chap. 5. Dielectrics and Insulators -5/92-

The effect of T on BDV for a typical aluminous porcelain

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -6/92-

5.2.2 BD mechanisms

(c) Discharge BD
• BD can be initiated at pores, analogous with the mechanical
strength
• BDV decreases with specimen size, because a decrease in
size reduces the probability of occurrence of a critical defect
at a given stress (Fig. 5.3)
• E field concentration on cavity
• 1) spherical pores
 r
cE  E

rc

• 2) disc-shaped cavity
3
Ec  E
2
• The larger the pore is the more
•likely
AC BDVs
it is are to
to lead lower
BD. than
those for DC.

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -7/92-

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -8/92-

5.2.2 BD mechanisms

(c) Long-term effect


• The prolonged application of electric stress at a level well
below that causing breakdown in the normal rapid tests
results in a deterioration in resistivity that may lead to BD.
• Possibilities
- Effect of weather and atmosphere
- Electrochemical reactions

5.3 Thermal shock resistance (TSR)

A useful
A sefguide
l g to
ideTSR is 
to TSR isc/LY/
High thermal conductivity
High mechanical strength
LowLthermal
th expansion
l coefficient
i ffi i t
Low Young’s modulus

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -9/92-

5.4 Capacitors

5.4.1. Capacitor characteristics


• Volume efficiency
• DC resistance
• Equivalent parallel and series resistance
• Resonant frequency
• Breakdown and degradation

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -10/92-

5.4.1. Capacitor characteristics


• Volume efficiency

C   A
 hr 2 o  C  r o
V h

Working voltage
U w  EEb h

The maximumpermissible power density


CU 2   E 2
2Vw  r 2o b
2
Chap. 5. Dielectrics and Insulators -11/92-

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -12/92-

5.4.1. Capacitor characteristics


• DC resistance

h
RL  
A
Discharg
e thru
its own o  
resistanc  τ
e
L o r
A h
h
Q(t)  Q
t
exp  

where τ
R C
h ε oε r A
ρ
ε ε ρ
Chap. 5. Dielectrics and Insulators -13/92-

5.4.1. Capacitor characteristics

• Equivalent parallel resistance 1


R Ctanδ
p

• Equivalent series resistance s tanδ


r  C

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -14/92-

The impedance of a capacitor

High frequency equivalent circuit


- rel; resistance of the lead
- L; inductance of the lead

1
Z  rel  jL  C*

 1 
 rel  j L  ' ' '' 
C o (  r  j  r
 )
 (1 j tan ) 
  j L
rel  

'
C (1 tan  ) 
2

 tan2   1
  1
tan  
Z  rel   j  L  ' ' 
C '
  C 

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -15/92-

The rs and impedance of a capacitor

The series resistance


tan 
r r  
s el
C '
The impedance
2 1/ 2
Z  rs 2 L  1 '  
 C 

    

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -16/92-

5.4 Capacitors

Breakdown and degradation


• Recommended working voltages are usually about a factor
of 5 below the min BDV
• The breakdown field of a dielectric is generally well below
its dielectric strength since it is largely governed by the
concentration of flaws and the design of the electrode
structure.
• The effects of moisture must be protected by encapsulation
in polymers or by enclosure in sealed metal cans.
• Acceleration test
By tests at hi T and using an Arrhenius plots
 We can estimate the probability of failure under normal
working conditions.

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -17/92-

5.4.2. Non-ceramic Capacitors

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -18/92-

5.4.3 Ceramic Capacitors

(a) Class of a dielectric


A. Class I dielectrics
Low- and medium
factors less ceramics
permittivity than 0.003
with dissipation
r=15-500, TC r= +100~-2000/MK

B. Class II dielectrics
Dissipation factors usually less than 0.03
HighHigh
TC rpermittivity
>2000/MK ceramics
based on ferroelectrics
r=2000~20000

Low working
C. Class voltage < 25V
III dielectrics
High permittivity ceramics
based on semiconductors
Large capacitance as big as
Chap. 5. Dielectrics and Insulators -19/92-

(b) Form and fabrication

A. Disc type formed by dry pressing

B. Tube type formed by extrusion

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -20/92-

(c) Multilayer Ceramic Capacitors (MLCC)

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -21/92-

(c) Multilayer Ceramic Capacitors (MLCC)

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -22/92-

D. High-voltage and high-power capacitors

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -23/92-

Additional Notes for MLCC

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -24/92-

Cross-section of MLCC

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -25/92-

Fabrication process for MLCC

계속
Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -26/92-

Fabrication process for MLCC


(Continued)

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -27/92-

Fabrication Equipments for MLCC

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -28/92-

Tape Casting Machine

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -29/92-

Doctor Blade

특히 테이프의 두께를 직접 좌우하는 닥터 블레이드의 높이는 정밀


하게 고정되어야 하는데 , 전자 세라믹스용 테이프를 성형하기
위해 서는 그 오차가 적어도 0.00125 mm (0.05mils) 이 되어야
한다 . 또 테이프의 두께를 간접적으로 좌우하는 바탕 테이프의
진행속도는 microprocessor controlled digital drive 를 써서
일정하게 유지되어 야 한다 .
Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -30/92-

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -31/92-

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -32/92-

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators MLCC Trends -33/92-

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators MLCC Trends -34/92-

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators MLCC Trends -35/92-

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators MLCC Trends -36/92-

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -37/92-

Part II Principal Ceramic Types and Applications

5.5
5 5 Low
L K ceramic dielectrics
i di l t i andd IInsulators
l t

Low K < 15
Widely used for insulation
Mechanical properties may be more important than dielectric properties
except substrates
Low cost

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -38/92-

5.5.1. Electrical Porcelains

(a) Clay-based ceramics

Main application: electrical porcelains for transmitting power


Composition: clays + fluxes + filler
Clays;
C aluminosilicates such kaolinite, orthoclase…
Fluxes; glass former with low m.p.
Fillers; quartz or bauxite

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -39/92-

5.5.1. Electrical Porcelains

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -40/92-

5.5.1. Electrical Porcelains

(b) Talc-based ceramics

Ternary phases in Al2O3-MgO-SiO2


Talc=steatite= 3MgO.4SiO2.H2O

Cordierite: good TSR and high R


Steatite: Low loss for high f applications

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -41/92-

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -42/92-

5.5. . Alumina

Preparation; ‘Bayer process’ using buaxite(Al2O3.2H2O)


- Al2O3 that is stable 0K~m.p.(2050oC) is called as corundum or sapphire
9 on the Mohs scale of hardness, next hardest to diamond at 10
Various grades of alumina ceramics are used
With increasing purity, cost increases while the material properties are improved

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -43/92-

The electrical resistance of Alumina

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -44/92-

The dielectric properties of Alumina

(//
r (//c-axis) =9.39
r (c-axis) =11.58
r (average) = 10.12

As T  defects & charge carriers


become more active
 r & oss 
At high f  dielectric ects
relaxation eff

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -45/92-

The Applications of Alumina


- Spark plugs
- Klystrons and magnetrons ; radar transmitter, microwave ovens
transmitter microwave ovens,
e-gun in electron microscopes
- Thick film substrates & IC packaging

Beryllia (BeO)
- High thermal conductivity; 5-10 times greater than alumina
 substrates for high power devices
- More expensive
- Toxic when they are abraded or heated in humid atm.

Aluminum nitride (AlN)


- High thermal conductivity and thermal expansion match to Si
- Formed by the reaction of Al powder with nitrogen

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -46/92-

5.5.5. Glasses

- can be extruded as thin ribbons down to 25um


- Higher dielectric strength of 50MV/mS than general ceramics
with 10MV/m
- Low dielectric constants (4-15) and low thermal conductivity
- Low loss and extremely stable with high Pb silicate glass
containing K but no Na
- Useful for LTCC

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -47/92-

Low-TCC low-loss capacitors

- Main
M i application:
li ti high
hi h ffreq. resonance circuit filter))
i it ( LC filt
; Low TCC & loss(tan)

CC  TC  L
TCC
r 1 
TC   (  3L )
3  T

(Table 5.6)

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -48/92-

Low-TCC low-loss capacitors

- Impurities may increase tan over 0.005


---> not practical to adjust TC by adding loss-inducing
constituents
- TC can be adjusted by mixing two components
e.g.) BaTiO3 + TiOO2 (Fig. 5.31)

(Table 5.6)

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -49/92-

Microwave Dielectrics
- Applications: M/W (500MHz~30GHz) communications systems
e.g.) Mobile & satelliete comm. & broadcasting
- Requirements for DR ceramics
1. High r for small size (30~150)
2. Low TCfr (< 30 ppm/oC)
3. High Q for low power loss and freq. selectivity

(Fig 5.32)

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -50/92-

Important parameters for M/W dielectrics

c c (Fig 5.32)
fo  
1/ 2 
D
1/ 2

d r r

11
TC  ( 2 TC  L )
f

fo (Fig (Fig
.33)5 33)
Q  tan 
f r

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -51/92-

M/W ceramic materials

(Table5.7)

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -52/92-

Hakki-Coleman Meathod

Measurement of M/W characteristics of


dielectrics

Oven

Cu plate C
Coaxial
i l

Antenna
N t k DR
Network
Analyzer

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -53/92-

Microwave communication
& Microwave dielectrics

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -54/92-

Microwave communications
Wireless Home Gateway
(IAD+AP)

PSTN
Internet XDSL
Cable

WLAN(IEEE802.11a
)

Bluetooth

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -55/92-

Microwave systems

Notebook PC
connected wireless
data
d t MModem
d T Terminal
i l
PDA
Voice H
i

Terminal Smart Phone g


h
-
s Video Phone
p
e
e
d

d
a
Chap. 5. Dielectrics and Insulators Microwave systems t
a
-56/92-

Only
Voice & Low speed data

voice & video

Prof. J.S.LEE, Univ. of Ulsan

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators Automotive telematics -57/92-

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators Wireless Markets -58/92-

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators High Frequency Components -59/92-

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -60/92-

Microwave Dielectrcs

Material r Qxf (GHz) Material r Qxf (GHz)

MgTiO3-CaTiO3 21 56,000 Ba(Sn,Mg,Ta)O3 25


200,000

Ba(Zr,Zn,Ta)O3 30 100,000 Ba(Mg(Sb,Ta))O3 25 300,000


4
Ba(Sn,Mg,Ta)O
Ba(Zr,Zn,Ta)O33 -
(Zr,Sn)TiO 38 60,000 27 150,000
3
NdPbO-Bi
Nd - 22O3-BaO-
2O3-TiO
100 2,500 Ba((Co,Zn)Nb)O 34 100,000

(1990, Murata) (1998, Murata)

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -61/92-

Microwave Dielectrcs

BMT(Ba,Mg,Ta) 산화물계

Al2O3 Ba(Mg(Sb,Ta))O3
MgTiO3
Ba(Zn Ta
1/3 )O
2/3 3

100000 (Sr,Ba)
MgTiO3-CaTiO3 (Mg1/3Nb2/3)O3
(Zr,Sn)TiO
Ba(Mg1/3Ta2/3)O3
(Q×f)

CaTiO - 4
1/3 2/3 3 3 1/2 1/2 3
La(Zn Ti )O

10000 BiNbO4
BaO BiNbO
-
L 3
n
2

O
3

-
5
T
ε r i
O
2

Chap. 5. Dielectrics and Insulators (Ba,Pb)O-L2nO3-5TiO2 -62/92-


(Pb,Ca)ZrO

Dielectric
SrZrO
resonator/Filter/Duplexer
CaTiO
3
3

1000
10 100

Prof. J.S.LEE, Univ. of Ulsan

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators Ceramic Duplexer -63/92-

Duplexer Concept Review

Dielectric
Ceramic

■ 등가회로

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators Ceramic Duplexer -64/92-

Monoblock Duplexer (Motorola Type)

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -65/92-

Ceramic Duplexer & Filter

Monoblock 형 듀플렉서 개별 공진자형 필터와 듀플렉서

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators Ceramic Patch Antenna -66/92-

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators Embedded PIFA Antenna -67/92-

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators Integration Technology -68/92-

Size: Smaller space → lower the cost


Mother Board of Cellular Phone

70% area
reduction
EP with SMD

L C R Tr L C R Tr
All SMD

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -69/92-

LTCC (Low-Temperature Cofired Ceramics)

A Paradigm Shift
# of Passives: 200
Assumptions:
Comp. Value: 20pF/20nH
Comp Size: 3 mm Sq
Q Value: 30 - 100
# Layers: 8
Area: 25 X 25 mm
Approx. Cost: $3.60
Cost Savings: >$4.00*

* Doesn’t anticipate cost

savings from repartitioning of

functions
between IC’s and integrated
substrates

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators Ceramic RF LTCC Modu-7l0e/92-

LTCC=Low-Temperature Cofired Ceramics

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -71/92-

LTCC RF Module
RF ICs
Surface Acoustic Wave (SAW) Filter

Digital and Analog I/O

Discrete Devices
(transistors, diodes)

Multilayer Ceramic
With Buried Circuitry
RF Feedthrough (i.e.., resonators, filters, PLL IC
capacitors...) itit ))

Baseband Processor IC

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -72/92-

LTCC ceramics
기판재료 도체재료 소결조건 굽힘강도 (k 열팽창계수 유전특성 절연저항 열전도율 (W/ 밀도 (g/
온도 (℃) 분위기 g/cm2) (10-4/℃) (Ω cm) m K) cm2)
εr DF

Leadborosillicate Glass-Alumina Au, Ag/Pd 850∼900 Air 3500 4.2 7.8 0.003 > 1014 0.01 3.10
System

Borosillicate Glass-Alumina Cu 950∼1050 비산화 1960 4.0 5.6 0.002 > 1016 0.01
System

Borosillicate Glass-Cordierite Ag, Ag/Pd, Air 1500 7.9 5.0 > 1013 2.40
System Au, Cu 중성

Borosillicate Glass-Quartz Au, Ag, Cu 900 Air 1600 3.2 4.4 0.002 > 1014 2.24
Glass-Cordierite System 중성

(Al2O3-CaZrO3)-Glass System Au, Ag, 850 Air 2100 7.9 8.0 > 1012 > 2.89
Ag/Pd

Borosillicate Glass-Alumina 처리 Cu 900 중성 4.1 8.9 > 1014


지르코니아 System

BaSnB2O6 Au, Ag/Pd 950 Air 2100 5.4 8.5 > 1015 0.013 4.3

Al2O3-CaO-SiO2-MgO-B2O3 Cu 950 중성 2500 4.8 7.0 > 1014 0.02 2.7

결정화 Glass(Cordierite) Au, Cu 950 Air 1700 2.5∼3.0 5.6 0.001 > 1013 0.006 2.56
중성

결정화 Glass(β-Spondumene) Au, Ag/Pd, 850∼1050 Air


2000∼400 2.5∼8.3 6.0
Cu 중성
0

Borosillicate Glass-Alumina- Au, Ag/Pd 850∼900 Air


2300 5.9 7.4 > 1014
0.01 3.0
Forsterite System

Borosillicate Glass-Al2O3- Ag/Pd 830 Air


2000 5.5 7.0 > 1013
Chap. 5. Dielectrics and Insulators -73/92-

Classification of Common Thick Film Conductor

Low fire ( < 1100℃) High Fire ( >


1100℃)
Reducing Oxidizing Reducing
Oxidizing
Ag bearing Non Ag
Mo:Mn
bearing
Mo Pd
Cu Ag Au:Pt
W Pt
Ag:Pd Au:Pd
Ni
Pg:Pt Au

Chap. 5. Dielectrics and Insulators -74/92-

Comparison of LTCC technologies Prof. J.S.LEE, Univ. of Ulsan

Thin Film

Cost
Thick Film LTCC & Photo
Thick Film
Polymer

Performance

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators -75/92-

10 years later? SOP (System On Package)

SOP Goal
100

System-Level Packaging Efficiency


90
80

Packaging To D ate
60

30 CSP

DIP QFP
10
O
pp
ort
un
ity

GOALS:
TTodayoday •Performance
ToTommoorrrrooww
10
0
%

70

Chap. 5. Dielectrics and Insulators -76/92-

On
-
Ch
ip

50

40

M
C
M Prof. J.S.LEE, Univ. of Ulsan
Chap. 5. Dielectrics and Insulators -77/92-

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -78/92-

High Permittivity Ceramics


(Class II dielectrics)

- High r (>1,000)
- Suitable for chip
capacitors
- Classification: EIA code
- Materials
o BaTiO3 based ceramics
o Pb-compound relaxors

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators High Permittivity Ceramic-s79/92-

* Classification of Class II dielectrics

Fig 5.38

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators High Permittivity Ceramic-s80/92-

(Modified BaTiO3 ceramics)

* Principal effects determining dielectric properties

1. AO/BO2 ratio
2. Substituents: A-site or B-site
3. Grain size
4. Applied electric field
5. Aging
6. Secondary phases

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators High Permittivity Ceramic-s81/92-

(Modified BaTiO3 ceramics)

1. AO/BO2 ratio
1 AO/BO
- BT has little solubility of BaO or TiO2
- Intermediate phases in BaO-TiO2 system
; B2T, BT, B6T17, B4T13, B2T9, BT4
- Excess TiO2
; eutectic BT- B6T17 system (Te=1320oC) Fig. 5.39
----> liq. Phase sintering
----> large g.s. (5-50m)
- Excess BaO
; eutectic B2T -BT system (Te=1563oC)
---> sol. Phase sintering
---> small g.s. (1-5 m)

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators High Permittivity Ceramic-s82/92-

(Modified BaTiO3 ceramics)

2.
2 IIsovalent
l Substituents
S b i

- Ba-site isovalent substituent


. Ionic radius=1.3-1.6Å
. Sr, Pb (100%) and Ca
(within 20 m/o)
Ti Fig. 5.40
- Ti-site isovalent substituent
. Ionic radius=0.6-0.75Å
. Zr, Hf(100%) and Sn
Eff t 10 T
(within m/o)
- Effects on Tc (see Fig.
5.40)
Chap. 5. Dielectrics and Insulators High Permittivity Ceramic-s83/92-

(Modified BaTiO3 ceramics)

3. Aliovalent Substituents
i) Donor doping
- Trivalent ions with r21 radii
of 1.1-1.33Å)
Bi L
. Bi, La
. Lower resistivity @ low
conc. (<0.5m/o)
ii) Acceptor doping Å
- Trivalent ions with r6 radii
of 0.6-0.7Å)
. Cr, Ga, Mn, Fe, Co
. Lower Tc @ low conc.
(<2m/o)
. Increase resistivity
. Higher aging rate and degradation
due to the formation O-site vacancies
. Fe2O3 (<3m/o): flat r-T
. 0.5 m/o MnO2: lower tan

Chap. 5. Dielectrics and Insulators High Permittivity Ceramic-s84/92-


Prof. J.S.LEE, Univ. of Ulsan

(Modified BaTiO3 ceramics)

3. Effect of grain size on r

- r decrease with g.s. below ~1 m


; g.s.  domain size  Fig. 2.48
 unrelieved stress 
 tetragonality  

 r

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators High Permittivity Ceramic-s85/92-

(Modified BaTiO3
ceramics)

5. Effect of applied electric field on r


A E fi ld i
- As E field increases,

1) domain wall movement  


Fig. 5.41
 polarization   r 
2) hysteresis loop 
 power loss  tan 

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators High Permittivity Ceramic-s86/92-

(Modified BaTiO3 ceramics)

5. Aging of
5 Aging of capacitors
capacitors
- 2-5% per decade range
Fig. 2.48
:not so significant for capacitors
but important for piezoelectrics

6. Heterogeneous (multiphase)
dielectrics
Fig. 2.48
- Mixed phases give more flat r-T
curve than a single phase
e.g.) X7R dielectrics
e g ) X7R dielectrics
. Bi4Ti3O12-BaTiO3
. CdBi2Nb2O9-BaTiO3

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators High Permittivity Ceramic-s87/92-

(Other perovskite-type structures)


Relaxor dielectrics

- Pronounced change in r-f @ near Tc


e.g.) SBT, BBT
Substitution of Bi into Sr or Ba-site
 resistance, degradation rate g Fig. 5.44

- Very small microdomains combine to


form larger unit when E field is applied.
 freq. dependence of Tc

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators High Permittivity Ceramic-s88/92-

(Other perovskite-type
structures)
Pb-based relaxor dielectrics
Chemical formula of complex perovskites
;- Chemical
Pb(Ba Bb Bc Bd Be Bf )O3
formula of
complex
perovskites
e.g.) PMN;
+1 Pb(Mg
+2 1/3+3 Nb2/3+5
+4 )O+6
3
PFWN; Pb(Fe0.55+2 W0.1
a+b+c+d+e+f=1 Nb0.35 )O3
PLZT: (Pb0.85La0.1
a+2b+3c+4d+5e+6f=4 )(Zr0.2 Ti0.8 )O3
+2 +5
+
6

Needs to control Pb
Chap. 5. Dielectrics and Insulators High Permittivity Ceramic-s89/92-

(Other perovskite-type
structures)
Pb-based relaxor dielectrics

Fig. 5.45
Fig.
.46
5 Fig. 5.47

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators High Permittivity Ceramic-s90/92-

(Other perovskite-type structures)

MLCC with base metal electrodes * Oxidation condition of


Ni-electrode
- Problems of Ag-Pd electrodes Ni 
1
O ( g )  NiO
2
2
1. Too expensive Pd
1/ 2
KP
O2

2. Electromigration of Ag  o1573
G RTln K RTRT
1573  RT ln ln
p O2 1/ 2

 100 kJmol 1

 Low cost base metal electrodes P 1/ 2


exp(
2G 1573
)
o

O2 
RT
 requires reducing atm during sintering  2.5 10 7 bar (10  2 Pa)
 cause to O-deficiency in BaTiO3
 lower the electrical res. of BaTiO3

 Solution #1
Acceptor doping; Mn ions into Ti-sites
 give rise to O-vacancies
i i t O
 high resistance under reduction atm
but low resistance to degration

Prof. J.S.LEE, Univ. of Ulsan


Chap. 5. Dielectrics and Insulators High Permittivity Ceramic-s91/92-

(Other perovskite-type structures)


MLCC with base metal electrodes

 Solution #2
= Substitution of Ca for Ba or A/B>1 Fig. 5.48

e.g.) (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3

 CaTi+2 ions act as acceptors

Fig. 5.49

Prof. J.S.LEE, Univ. of Ulsan

Chap. 5. Dielectrics and Insulators -92/92-

(Other perovskite-type
structures)
Barrier- layer
capacitors(Class III)
Fig. 5.50
* Characteristic of ABO3
- Sintering in reducing atm.
 semiconducting
i l ti
- Sintering in oxidizing
atm.
 insulating
Fig. 5.51
* Types
- Surface reoxidized
dielectrics
- Internal-barrier-
layer capacitors

You might also like