Professional Documents
Culture Documents
KIM, TAEYUN
Embedded Passive Applications (Under the direction of Angus I. Kingon and Jon-Paul
Maria)
To tailor the dielectric and reliability properties, ZrO2 was selected as buffer layer
between PZT and electroless Ni. Only RF magnetron sputtering process could yield
stable ZrO2 layers on electroless Ni coated Cu foil. Other processes resulted in secondary
phase formation, which supports the reaction between PZT capacitor and electroless Ni
might be dominated by phosphorous component. Incorporation of ZrO2 layers reduced
maximum capacitance density by 10 % (~ 350 nF/cm2) due to lower permittivity of ZrO2
layer. Significantly improved leakage current densities were measured for PZT thin film
capacitors on ZrO2. For PZT thin film capacitors incorporating 100 nm thick ZrO2 layer,
leakage current density of 10-8 A/cm2 was measured at 25 VDC, which is more than three
orders of magnitude lower than those directly deposited on electroless Ni coated Cu foil.
The complete set of experimental data provides validation and process conditions
for the use of PZT thin films on low cost electroless Ni coated Cu foil substrate as
embedded capacitors in high density printed circuit boards.
by
TAEYUN KIM
BIOGRAPHY
TAEYUN KIM was born on October 16, 1969 to Euijoong Kim and Jinho Yoon in South
Korea. He received his B. S. and M. S. degree from the department of ceramic engineering,
Yonsei University, Korea in 1991 and 1993, respectively. His M. S. thesis was on the
optimized YBCO superconducting powder and thick film preparation. After graduation, he
joined PDP division in Orion Electric Co. Ltd, one of the subsidiaries of Daewoo group,
Korea. He spent nearly seven years working on the development of unit processes and mass
production technologies for 42 VGA / 25 XGA grade full color plasma display panel till
October, 1999. In 1999, he got an admission from the graduate school of North Carolina
State University. He started his graduate study towards his Ph.D. degree from spring 2000 in
the department of materials science and engineering. In the meantime, he married to
Younsam Ji in June 2001 and they have one lovely daughter, Sungha (Kristin), who was born
in October 2002.
ii
ACKNOWLEDGEMENT
I would like to express my sincere gratitude to Dr. Angus I. Kingon for his continued
support, encouragement, patience and valuable advice during my graduate program. Special
thanks goes to Dr. Jon-Paul Maria for all the detailed technical advice and a lot of support in
the program. I would acknowledge my committee members, Drs. Gerd Duscher and Paul
Franzon for their suggestions on thesis. Also I acknowledge sincerely Dr. Robert Croswell
for being my committee member, providing valuable information and suggestions on this
project and passive industry. This research has been supported by Motorola Advanced
Technology Center, Schaumburg, IL, a division of Motorola Labs. I gratefully acknowledge
Dr. Aroon Tungare in Motorola Lab.
It is my pleasure to acknowledge the contribution of former group members, Charles
Parker, Dwi Wicaksana, and Dong-Joo Kim for their valuable guide on processing and
characterization skills when I was a beginner here. Actually I am indebted a lot to present
members, Brian Boyette, Brian Laughlin, Jon Ihlefeld, Dipankar Ghosh, and Sudarsan
Srinivasan. Also I cannot miss Edna Deas and Jan Jackson for administrative support.
I greatly acknowledge Dr. Alexei Gruverman and Brian Rodriguez for helping me out
from AFM measurements. And I want to thank my senior alumni and friends, Drs. Hyunmin
Shin, Yong S. Cho, Minseo Park, and Jung Won Lee, and their families for all the
immeasurable help and encouragement during on and off-campus life. Also I would like to
thank Dr. Carl. B. Wang, Kie-Jin Park, Jaehoon Lee, and Indong Kim and their families for
all the help during my graduate program in Raleigh.
I would like to express my thanks to my elder sister, who yielded a lot for me for such
a long time, and her family for their encouragement.
iii
iv
TABLE OF CONTENTS
LIST OF TABLES .................................................................................................................. ix
LIST OF FIGURES .................................................................................................................. x
1
Introduction ......................................................................................................................... 1
1.1 Introduction ................................................................................................................ 1
1.2 Research goals ............................................................................................................ 2
vi
4.4.6.2 pO2 dependent electrical properties in PZT (52/48) thin film capacitors
on electroless Ni coated Cu foils ............................................................................ 111
4.5 Thickness dependent properties.............................................................................. 114
4.5.1 Phase development and electrical properties ................................................ 114
4.5.2 Suggested interface reaction.......................................................................... 122
4.5.3 Equivalent circuit analysis ............................................................................ 124
4.6 Summary and conclusion........................................................................................ 127
4.7 References .............................................................................................................. 129
5
Ca-doped PZT (52/48) thin film capacitors on electroless Ni coated Cu foil ................ 135
5.1 Introduction............................................................................................................. 135
5.2 Ca-doped PZT (52/48) thin films on Pt/SiO2/Si substrate ...................................... 137
5.2.1 Phase development and surface microstructure............................................. 137
5.2.2 Dielectric properties ...................................................................................... 142
5.3 Ca-doped PZT (52/48) thin films on electroless Ni coated Cu foil ........................ 146
5.3.1 Phase development ....................................................................................... 146
5.3.2 Dielectric properties ...................................................................................... 150
5.3.3 Microstructure ............................................................................................... 160
5.3.4 Thickness effect............................................................................................. 162
5.3.5 Temperature dependent properties ................................................................ 165
5.3.6 pO2 dependence............................................................................................. 169
5.3.6.1 Phase development................................................................................ 169
5.3.6.2 Dielectric properties and microstructure ............................................... 177
5.3.7 Leakage current ............................................................................................. 182
5.3.7.1 Charge conduction mechanism ............................................................. 182
5.3.7.2 Charge conduction in PZT thin films on electroless Ni ........................ 185
5.4 Summary and conclusion........................................................................................ 192
5.5 References............................................................................................................... 193
vii
viii
LIST OF TABLES
Table 2.1
Table 2.2
Table 2.3
Table 2.4
Table 2.5
Table 3.1
Table 3.2
Table 3.3
Table 3.4
Table 4.1
Table 4.2
Table 4.3
Table 5.1
Table 5.2
Table 5.3
ix
LIST OF FIGURES
Figure 2.1
Figure 2.2
Figure 2.3
Figure 2.4
Figure 2.5
Crystal structures and their allowed polar axes for Pb(Zr,Ti)O3 ....................... 11
Figure 2.6
Figure 2.7
Figure 2.8
Figure 2.9
Figure 3.2
Figure 3.3
Schematics of the capacitor stack structure with base metal electrode ............. 72
Figure 4.1
XRD plot for 2-MOE based (a) and methanol based PZT (52/48) thin
film capacitors on Pt/SiO2/Si crystallized at 650 oC for 30 minutes under
O2 atmosphere ................................................................................................... 77
Figure 4.2
P-V hysteresis for 2-MOE based (a) and methanol (b) based PZT
(52/48) thin film capacitors on Pt/SiO2/Si crystallized at 650 oC for 30
minutes under O2 atmosphere............................................................................ 78
Figure 4.3
Capacitance-voltage for 2-MOE based (a) and methanol (b) based PZT
(52/48) thin film capacitors on Pt/SiO2/Si crystallized at 650 oC for 30
minutes under O2 atmosphere............................................................................ 78
Figure 4.4
Figure 4.5
Figure 4.6
Figure 4.7
Figure 4.8
X-ray diffraction plots for as-deposited (a) and 450 oC annealed (b)
electroplated Ni coated Cu foils. ....................................................................... 86
Figure 4.9
AFM image for Cu foil used for Ni coating. Scans was performed over 5
5 m range...................................................................................................... 87
Figure 4.10 AFM images for electroless Ni coated Cu foils with anneal temperature.
All scans were performed over 11 m range .................................................. 87
Figure 4.11 X-ray diffraction plots for methanol based PZT (52/48) thin film
capacitors on electroless Ni coated Cu foil with 8 % phosphorous;(a)
550 oC (b) 575 oC (c) 600 oC and (d) 650 oC..................................................... 90
Figure 4.12 X-ray diffraction plots for methanol based PZT (52/48) thin film
capacitors on electroless Ni coated Cu foil with 12 ~ 13 % phosphorous;
(a) 550 oC (b) 575 oC (c) 600 oC and (d) 650 oC ............................................... 91
Figure 4.13 Phase formation of PZT (52/48) thin film capacitors on sooth foil side.
Crystallization was done at 650 oC for 30 minutes ........................................... 92
Figure 4.14 Phase formation of PZT (52/48) thin film capacitors on rough foil side.
Crystallization was done at 650 oC for 30 minutes. .......................................... 93
Figure 4.15 Dielectric properties of methanol based PZT (52/48) thin film capacitors
on electroless Ni coated Cu foil with different phosphorous content................ 95
Figure 4.16 TEM image of PLZT capacitor deposited on electroless Ni foils ..................... 96
xi
Figure 4.17 Capacitance-voltage plots for PZT (52/48) thin film capacitors on
electroless Ni coated Cu foil crystallized between 550 and 650 oC for 30
minutes under N2 atmosphere............................................................................. 97
Figure 4.18 Capacitance-frequency plots for PZT (52/48) thin film capacitors on
electroless Ni (with 8 % phosphorous) coated Cu foil crystallized
between 550 and 650 oC for 30 minutes under N2 atmosphere ......................... 98
Figure 4.19 Leakage current densities of methanol based PZT (52/48) thin film
capacitors on electroless Ni coated Cu foil crystallized between 550 and
650 oC for 30 minutes under N2 atmosphere ................................................... 100
Figure 4.20 Log (J) vs. Log (V) for PZT (52/48) thin film capacitors on electroless
Ni coated Cu foil crystallized at 650 oC for 30 minutes under N2
atmosphere (slope of B region ~ 7.0) .............................................................. 101
Figure 4.21 Leakage current densities with voltage (a) and time (b) for PZT (52/48)
thin film capacitors on electroless Ni coated Cu foil....................................... 104
Figure 4.22 AFM images for methanol based PZT (52/48) thin film capacitors on
electroless Ni coated Cu foil (with 8 % and 12 ~ 13 % phosphorous)
crystallized for 30 minutes under N2 atmosphere. All scans were
performed over 1 1 m range....................................................................... 106
Figure 4.23 Capacitance-voltage plots for PZT (52/48) thin film capacitors on
electroless Ni with different pyrolysis histories. Crystallization was
done at 650 oC for 30 minutes under N2 atmosphere. ..................................... 107
Figure 4.24 Effects of the pyrolysis condition on the leakage current of PZT (52/48)
thin film capacitors on electroless Ni. Crystallization was done at 650
o
C for 30 minutes under N2 atmosphere . ........................................................ 108
Figure 4.25 pO2 dependence of phase developments for PZT (52/48) thin film
capacitors crystallized at 600 oC...................................................................... 112
Figure 4.26 pO2 dependence of dielectric properties for PZT (52/48) thin film
capacitors crystallized at 600 oC for 30 minutes. ............................................ 112
Figure 4.27 pO2 dependence of J-V for PZT (52/48) thin film capacitors crystallized
at 600 oC for 30 minutes .................................................................................. 113
Figure 4.28 AFM images for PZT (52/48) thin film capacitors crystallized at 600 oC
for 30 minute under different pO2 (torr). All scans were performed over
1 1 m range................................................................................................. 113
xii
Figure 4.29 X-ray diffraction plots for thickness dependence in PZT (52/48) thin
film capacitors on electroless Ni coated Cu foil (with 8 % phosphorous) ...... 116
Figure 4.30 X-ray diffraction plots for thickness dependence in PZT (52/48) thin
film capacitors on electroless Ni coated Cu foil (with 12 ~13 %
phosphorous) ................................................................................................... 116
Figure 4.31 Thickness dependent dielectric properties of PZT (52/48) thin film
capacitors on electroless Ni coated Cu foil. Crystallization was done at
600 oC for 30 minutes under N2 atmosphere ................................................... 118
Figure 4.32 (C/A)-1 with thickness relationship of PZT (52/48) thin film capacitors
in Figure 4.31................................................................................................... 119
Figure 4.33 Thickness dependent leakage current densities with voltage for PZT
(52/48) thin film capacitors on electroless Ni coated Cu foil.
Crystallization was done at 600 oC for 30 minutes under N2 atmosphere....... 120
Figure 4.34 Thickness dependent leakage current densities with V for PZT (52/48)
thin film capacitors on electroless Ni coated Cu foil. Crystallization was
done at 600 oC for 30 minutes under N2 atmosphere ...................................... 121
Figure 4.35 Leakage current densities of PZT (52/48) thin film capacitors with
thickness. Data taken at 10 VDC in Figure 4.33 .............................................. 121
Figure 4.36 Schematics of reaction sequences for PZT (52/48) thin film capacitors
on electroless Ni coated Cu foil: (a) as deposited 1st layer (b) 1st layer
pyrolysis at 450 oC (c) multiple layer pyrolysis at 450 oC (d) After final
annealing at 650 oC......................................................................................... 123
Figure 4.37 Equivalent circuit analogue for (a) capacitor with interface and (b)
contact resistance added capacitor with interface (Ri: interface
resistance, Rb: bulk resistance, Ci: interface capacitance, Cb: bulk
capacitance). .................................................................................................... 124
Figure 4.38 Comparison between measured and calculated capacitances with
frequency. Calculations were performed with different Ri. (Fixed Rb ~
105 )............................................................................................................... 125
Figure 4.39 Comparison between measured and calculated capacitances with
frequency. Calculations were performed with different Rb. (Fixed Ri ~
103 )............................................................................................................... 126
Figure 5.1
xiii
Figure 5.2
Figure 5.3
Figure 5.4
Figure 5.5
Figure 5.6
Figure 5.7
Figure 5.8
Figure 5.9
X-ray plot for the 5 mol % Ca-doped PZT thin films on electroless Ni
coated Cu foil (with 8 % phosphorous) crystallized under N2 atmosphere
for 30 minutes .................................................................................................. 148
Figure 5.10 X-ray plot for the 5 mol % Ca-doped PZT thin films on electroless Ni
coated Cu foil (with 12 ~ 13 % phosphorous) crystallized under N2
atmosphere for 30 minutes............................................................................... 148
Figure 5.11 X-ray plot for the 10 mol % Ca-doped PZT thin films on electroless Ni
coated Cu foil (with 8 % phosphorous) crystallized under N2 atmosphere
for 30 minutes .................................................................................................. 149
Figure 5.12 X-ray plot for the 10 mol % Ca-doped PZT thin films on electroless Ni
coated Cu foil (with 12 ~ 13 % phosphorous) crystallized under N2
atmosphere for 30 minutes............................................................................... 149
Figure 5.13 Capacitance-frequency plot for 5 mol % Ca-doped PZT on electroless
Ni coated Cu foil crystallized under N2 atmosphere for 30 minutes: (a) 8
% phosphorous, (b) 12 ~ 13 % phosphorous ................................................... 151
Figure 5.14 Capacitance-frequency plot for 10 mol % Ca-doped PZT on electroless
Ni coated Cu foil crystallized under N2 atmosphere for 30 minutes: (a) 8
% phosphorous, (b) 12 ~ 13 % phosphorous ................................................... 152
xiv
xv
Figure 5.26 Temperature Coefficient of Capacitance (TCC) of undoped, Ca, and Ladoped PZT thin film capacitors on electroless Ni coated Cu foil.
Crystallization was done at 650 oC for 30 minutes in N2 atmosphere ............ 168
Figure 5.27 Temperature dependence of loss tangent in undoped, Ca, and La doped
PZT thin film capacitors on electroless Ni coated Cu foil. Crystallization
was done at 650 oC for 30 minutes in N2 atmosphere ..................................... 168
Figure 5.28 X-ray plot for the 5 mol % Ca-doped PZT thin films on electroless Ni
coated Cu foil (with 8 % phosphorous) crystallized at 600 oC with pO2:
(a) 9.010-8 Torr, (b) 7.510-7 Torr, (c) 1.010-5 Torr, (d) 1.210-4 Torr,
(e) 5.510-4 Torr, (f) 7.610-4 Torr, (g) 4.010-3 Torr, (h) 1.510-1 Torr,
(i) 1.0 Torr, and (j) 10.0 Torr........................................................................... 173
Figure 5.29 X-ray plot for the 10 mol % Ca-doped PZT thin films on electroless Ni
coated Cu foil (with 12 ~ 13 % phosphorous) crystallized at 600 oC with
pO2: (a) 9.010-8 Torr, (b) 7.510-7 Torr, (c) 1.010-5 Torr, (d) 1.210-4
Torr, (e) 5.510-4 Torr, (f) 7.610-4 Torr, (g) 4.010-3 Torr, (h) 1.510-1
Torr, (i) 1.0 Torr, and (j) 10.0 Torr.................................................................. 174
Figure 5.30 Phase purity of the 5 mol % Ca-doped PZT thin films on electroless Ni
(with 8 % phosphorous) coated Cu foil. Crystallization was done at 600
o
C for 30 minutes ............................................................................................. 175
Figure 5.31 Phase purity of the 10 mol % Ca-doped PZT thin films on electroless Ni
(with 12 ~ 13 % phosphorous) coated Cu foil. Crystallization was done
at 600 oC for 30 minutes .................................................................................. 175
Figure 5.32 Suggested schematics of reactions for Ca-doped PZT thin film
capacitors on electroless Ni coated Cu foil: (a) no or minimal reaction
assumed (b) reaction at low pO2, and (c) reaction at high pO2........................ 176
Figure 5.33 Dielectric properties of 5 mol % Ca-doped PZT capacitors on electroless
Ni (with 8 % phosphorous) coated Cu foil. Crystallization was done at
600 oC. ............................................................................................................. 179
Figure 5.34 Dielectric properties of 10 mol % Ca-doped PZT capacitors on
electroless Ni (with 8 % phosphorous) coated Cu foil. Crystallization
was done at 600 oC. ......................................................................................... 179
Figure 5.35 Surface microstructure of the 5 mol % Ca-doped PZT thin film
capacitors on electroless Ni coated Cu foil (with 8 % phosphorous).
Crystallization was done at 600 oC for 30 minutes. All scans were
performed over 1 1 m range ....................................................................... 181
xvi
Figure 5.36 Surface roughness of the 5 mol % Ca-doped PZT thin film capacitors on
electroless Ni coated Cu foil (with 8 % phosphorous). Crystallization
was done at 600 oC for 30 minutes .................................................................. 182
Figure 5.37 Leakage current densities for the 5 mol % Ca-doped PZT on electroless
Ni coated Cu foil. Crystallization was done at 600 oC for 30 minutes
under different pO2. ......................................................................................... 188
Figure 5.38 Leakage current densities for the 10 mol % Ca-doped PZT on
electroless Ni coated Cu foil. Crystallization was done at 600 oC for 30
minutes under different pO2............................................................................. 189
Figure 5.39 Leakage current densities for the 5 mol % Ca-doped PZT on electroless
Ni coated Cu foil. Crystallization was done at 600 oC for 30 minutes.
Data taken at 10 VDC, step voltage of 0.5 V, duration time of 1 sec ............ 190
Figure 5.40 Leakage current densities for the 10 mol % Ca-doped PZT on
electroless Ni coated Cu foil. Crystallization was done at 600 oC for 30
minutes. Data taken at 10 VDC, step voltage of 0.5 V, duration time of 1
sec. ................................................................................................................... 190
Figure 6.1
Figure 6.2
Figure 6.3
Figure 6.4
Figure 6.5
xvii
X-ray diffraction plots for PZT (52/48) thin film capacitors on ZrO2 (50
nm) / electroless Ni coated Cu foil (with 8 % phosphorous) crystallized
under N2 atmosphere for 30 minutes at: (a) 500 oC, (b) 550 oC, (c) 575
o
C, (d) 600 oC, and (e) 650 oC, respectively .................................................... 208
Figure 6.7
X-ray diffraction plots for PZT (52/48) thin film capacitors on ZrO2
(100 nm) / electroless Ni coated Cu foil (with 8 % phosphorous)
crystallized under N2 atmosphere for 30 minutes at: (a) 500 oC, (b) 550
o
C, (c) 575 oC, (d) 600 oC, and (e) 650 oC, respectively.................................. 209
Figure 6.8
Figure 6.9
Figure 6.10 Capacitance-frequency plot for PZT (52/48) thin film capacitors on 50
nm ZrO2 / electroless Ni coated Cu foil (with 8 % phosphorous) with
crystallization temperatures. Crystallization was done for 30 minutes
under N2 flow................................................................................................... 212
Figure 6.11 Capacitance-frequency plot for PZT (52/48) thin film capacitors on 100
nm ZrO2 / electroless Ni coated Cu foil (with 8 % phosphorous) with
crystallization temperatures. Crystallization was done for 30 minutes
under N2 flow................................................................................................... 212
Figure 6.12 AFM surface microstructures for PZT (52/48) thin film capacitors on 50
nm ZrO2 crystallized for 30 minutes in N2 flow between 500 to 650 oC:
(a) 500 oC, (b) 550 oC, (c) 575 oC, (d) 600 oC, and (e) 650 oC. All scans
were performed over 2 2 m range .............................................................. 213
Figure 6.13 AFM surface microstructures for PZT (52/48) thin film capacitors on
100 nm ZrO2 crystallized for 30 minutes in N2 flow between 500 to 650
o
C: (a) 500 oC, (b) 550 oC, (c) 575 oC, (d) 600 oC, and (e) 650 oC. All
scans were performed over 2 2 m range..................................................... 214
Figure 6.14 Surface roughness (Rms) for PZT (52/48) thin film capacitors on ZrO2
buffer layers crystallized between 500 and 650 oC for 30 minutes in N2
flow: (a) for 1 1 m, (b) for 2 2 m .......................................................... 215
xviii
Figure 6.15 Leakage current densities with voltage for PZT (52/48) thin film
capacitors on ZrO2 (50nm) / electroless Ni coated Cu foil.
Crystallization was done between 500 and 650 oC.......................................... 217
Figure 6.16 Leakage current densities with voltage for PZT (52/48) thin film
capacitors on ZrO2 (100nm) / electroless Ni coated Cu foil.
Crystallization was done between 500 and 650 oC.......................................... 217
Figure 6.17 Leakage current densities with voltage for PZT (52/48) thin film
capacitors on electroless Ni coated Cu foil. Crystallization was done
between 550 and 650 oC .................................................................................. 218
Figure 6.18 Leakage current densities with time for PZT (52/48) thin film capacitors
on ZrO2 (50nm) / electroless Ni coated Cu foil. 15 VDC applied during
measurement .................................................................................................... 220
Figure 6.19 Leakage current densities with time for PZT (52/48) thin film capacitors
on ZrO2 (50nm) / electroless Ni coated Cu foil. 25 VDC applied during
measurement .................................................................................................... 220
Figure 6.20 Leakage current densities with time for PZT (52/48) thin film capacitors
on ZrO2 (100 nm) / electroless Ni coated Cu foil. 25 VDC applied
during measurement ........................................................................................ 222
Figure 6.21 Leakage current densities with time for PZT (52/48) thin film capacitors
on electroless Ni coated Cu foil. 25 VDC applied during measurement......... 222
xix
CHAPTER 1
Introduction
1.1 Introduction
As the size of electronic devices is getting smaller, and the operational speed
required by devices is getting faster, the electronic components industries are
encountering many challenges [1, 2]. One of the challenges is to have a smaller chip with
smaller size, maintaining or improving the overall performances [3]. This requirement for
miniaturization is expected to be getting more and more important in the electronics
industry during future years. Many researches are on the way to make the overall chip
size smaller and smaller, and currently, embedding the passive components capacitors,
resistors, inductors, which have been placed using the surface mount technology (SMT)
into the polymeric board [ 4 , 5 ] is receiving considerable attention. Embedding the
components can be very attractive in many ways in that it enhance the reliability by
increasing the electrical contact area, it can conserve board surface area, and reduce the
overall volumes. Also it could be quite attractive in its ability to decrease the indirect
manufacturing cost and increase the throughput in the manufacturing process.
Currently, most of the studies for embedded capacitor are concentrated on the low
temperature co-fired ceramic (LTCC) [6, 7] and ceramic/polymer composites [8, 9] for
MCM application. Both of the above approaches are commercially available in the
market, however, in the end, the technology with lower manufacturing cost, better
processing margin and the materials with higher dielectric constant, will would be
Second, the interface between high permittivity dielectric films and electroless Ni
will be studied, along with its impact on the phase formation and electrical properties.
Third, one of the isovalent dopants, Ca, will be added to the PZT (52/48)
composition and its effects on dielectric properties, reliability and microstructural
development will be studied.
1.3 References
[1] D. Liu, R. M. Kennedy, G. Korony, and S. Mak, Proceedings of Int. Conf. on High
Density Packaging and MCMs, 431 (1999).
[2] J. P. Parkerson and L. W. Schaper, Int. J. Microcircuits and Electronic Packaging, 20
(3) 297, (1997).
[3] R. C. Frye, Int. J. Microcircuits and Electronic Packaging, 19 (4) 483 (1996).
[4] T. Lenihan, L. Schaper, and G. Morcan, Int. J. of Microcircuits and Electronic
Packaging, 20 (4) 474 (1997).
[5] K. Fairchild, G. Morcan, T. Lenihan, W. Brown, L. Schaper, and S. Ang, Proceeding
of Electronic Comp. & Tech. Conf., 730 (1997).
[6] K. Delaney, J. Barrett, J. Barton, and R. Doyle, IEEE Trans. on Advanced Packaging,
(22) 1, 68 (1999).
[7] K. Niwa and Y. Takeda, Fujitsu Sci. Tech. Journal, 27 (2) 179 (1991).
[8] Y. Rao, J. Yue, and C. P. Wong, The 51th Proceedings of Electronic Comp. & Tech.
Conf., 1408 (2001).
[9] S. Ogitani, V. G. Silverstrov, P. A. Kohl, and S. A. B. Allen, Int. J. of Microcircuits
and Electronic Packaging, 23 (3) 367 (2000).
[10] R. K. Ulrich, K. Barnes, and J. Bockman, IMAPS Advanced Technology Workshop
on Passive Integration, June, 2002, ME
CHAPTER 2
Literature Review
crystals has a very large value near their Curie point, which is usually referred to as the
dielectric anomaly.[5, 6] Above the Curie point the dielectric permittivity falls off with
temperature according to the Curie-Weiss law
= 0 +
C
C
T T0 T T0
(2.1)
A (Pb)
B (Zr or Ti)
O
(a)
(b)
Figure 2.2: First-order (a) and second-order (b) ferroelectric phase transition ( is inverse
dielectric susceptibility) [4].
of PZT depend on the Zr/Ti ratio below the Curie temperature (Tc). Above Tc of PZT,
paraelectric cubic phase exists and the Zr/Ti atoms are located at the exact center of the
unit cell, regardless of the composition. The Curie temperature varies from 230 C to 490
C depending upon the Zr/Ti ratio.
Deviations from the ideal cubic perovskite structure start to occur when PZT is
cooled below the Curie point. For high Ti concentrations, the ferroelectric phase is
tetragonal. In this case, the Zr/Ti atom displaces off center and a distortion of the TiO6
octahedra occurs along one of the six (6) <00l> directions. These six directions yield six
possible domain configurations separated by either 90
or 180
direction of the Zr/Ti displacement is the tetragonal c-axis in the resulting unit cell. With
this distortion, a dipole is created since the centers of positive and negative charge no
longer coincide. This atomic displacement is the source of the spontaneous polarization.
For higher Zr concentrations, PZT is rhombohedral below the Curie temperature.
The rhombohedral distortion occurs when the Zr/Ti atom moves towards the face-center
of the oxygen octahedra (the cubic <111> direction). In this case there are eight
equivalent directions in which the Zr/Ti atom can move, with 180 o, 109
and 71
domain walls separating the possible domain orientations. Once again, the centers of
positive and negative charge are now offset, so a spontaneous polarization develops.
The most widely studied composition of PZT occurs at the boundary between the
tetragonal and rhombohedral phases. This is known as the morphotropic phase boundary
(MPB) and the composition is approximately 52 mol% of PbZrO3 and 48 mol% of
PbTiO3 at room temperature. This composition bounds the abrupt structural change
between the rhombohedral and tetragonal phases and exhibits greatly enhanced dielectric
8
and piezoelectric properties in bulk and thin film PZT [7, 8, 9]. Due to 14 possible
domain variants, a geometrically increased ease of reorientation of the polar axis is
believed to be responsible for these enhanced electrical properties [10, 11]. In Figure 2.4,
the piezoelectric coefficients measured for bulk PZT show a peak in the region of the
MPB, explaining why these compositions are technologically so interesting. At the MPB
composition, the free energy of the rhombohedral and tetragonal phases are equal and it
is probable that an electric field may easily cause switch between tetragonal and
rhombohedral domain states. There are thus effectively 14 available directions along
which polarization may be reoriented, leading to a large effective remanent polarization
for compositions near the MPB. The large remanent polarization at MPB in randomly
oriented PZT also helps to increase the peak in the piezoelectric coefficients at MPB.
Other interpretations of the origin of the peak in the properties of PZT at MPB have been
proposed [12, 13].
Good-quality single crystals of PZT with near MPB compositions are not
available due to the phase separation, therefore comparable measurements could not be
made on single-domain single crystals. Calculations using the thermodynamic
phenomenological theory have shown, however, that a peak in the piezoelectric
coefficients and dielectric permittivity should be expected at MPB in mono-domain
single crystals [14]. The important exception is the behavior of the polarization for which
theoretical calculations do not predict a peak in single crystals at MPB. The results of the
thermodynamic calculations have been recently confirmed by experimental study of the
properties of single-crystal (epitaxial) PZT thin films [15], which clearly showed a peak
in the permittivity but not in the polarization at MPB. Properties of random-oriented
9
polycrystalline PZT thin films [16] are in qualitative agreement with results obtained on
bulk ceramics.
Tc
T (C)
Cubic
Rhombohedral
(High Temp.)
Tetragonal
Rhombohedral
(Low Temp.)
PbZrO3
Mole % PbTiO3
PbTiO3
Tetragonal
Rhombohedral
Orthorhombic
Polarization along
Polarization along
Polarization along
6 equivalent <100>
8 equivalent <111>
12 equivalent<110>
Figure 2.5: Crystal structures and their allowed polar axes for Pb(Zr,Ti)O3.
11
(1.49 ) in PZT, due to the large ionic radii. Cations with smaller ionic radius like Nb5+
(0.64 ) and Ta5+ (0.68 ) are known to substitute for B-site, Zr4+ (0.72 ) or Ti4+ (0.68
). The reaction could be represented by Kroger-Vink equations.
La 2O 3 + 3TiO 2 PZT
2La Pb
+ VPb'' + 3TiTi + 9Oo
(A-site doping)
(2.2)
(B-site doping)
(2.3)
conductivity, low coercive field [19]. Also they are easy to pole and de-pole and possess
high piezoelectric coefficients [2]. Improvements in the insulation resistance by donor
doping into both A- and B-sites have been reported by many groups, and they ascribed
improved leakage characteristics to the electrical compensation of acceptor species which
thereby reduces the concentration of mobile species that contribute to electrical
conduction [20].
Acceptor doping is obtained when the valence of substituting dopant is less than
that of the lattice ions. Acceptor doping is called hard doping, and is obtained, for
example, either by replacing A site (Pb in PZT) with monovalent cations such as K+ (Asite) or by replacing B site (Zr or Ti in PZT) with acceptors such as Fe3+. Assuming that
the oxygen vacancies are doubly charged, we have the following Kroger-Vink equations:
12
+ 2TiTi + VO + 9O o
K 2O + 2TiO 2 PZT
2K Pb
(A-site doping)
(2.4)
2PbO + Fe 2O 3 PZT
2PbPb + VO + 2NbTi + 5Oo
(B-site doping)
(2.5)
The ionic compensating defects for acceptor dopants are mostly oxygen vacancies,
V0. Oxygen vacancies can move in the oxygen octahedral even at temperature below Tc,
leading to a relatively low configurational stability of the 2 FeZr-V0 defect dipole
direction. The defect dipoles will tend to align themselves in direction of the polarization
vector with domains, and this alignment will stabilize the domain structure [21, 22, 23].
Consequently, the stable domain wall structure shows high apparent coercive field [24]
and more difficult poling and de-poling of ceramics. Acceptor doping increases the dc
conductivity of PZT but the dielectric loss measured in the kHz region is lower than in
undoped ceramics. This occurs because the primary source of loss results from domainwall motion, which is reduced in hard ferroelectric ceramics [2].
13
PVD techniques require medium vacuum, usually between 10-2 and 10-6 torr, in
order to obtain a sufficient flux of atoms or ions capable of depositing onto a substrate
including. Sputtering [28, 29], evaporation [30, 31] and laser ablation [32, 33] are
examples of well-established PVD techniques. The advantages of the PVD techniques
are: (1) high purity and cleanliness, (2) potential compatibility with semiconductor
integrated circuit processing, and (3) epitaxial/single crystal film growth is possible.
However, these are offset by disadvantages such as (1) slow deposition rates, (2) difficult
stoichiometry control in multi-component systems where evaporation or sputtering rates
differ considerably, (3) high temperature post deposition annealing is often required, and
(4) high capital equipment acquisition and maintenance costs are necessary. Ion-beam
assisted evaporation and sputtering are potentially capable of increasing film uniformity
and increasing deposition rates. In general, laser ablation, a technique which is similar in
concept to flash evaporation, seems advantageous for congruent transfer of target
material, however, the ratio of ions to neutrals is quite different for the Pb, Zr, and Ti
atoms [34].
The CVD techniques are usually characterized by (1) higher deposition rates, (2)
good stoichiometry control, (3) large area, pinhole free films, and (4) lower initial
equipment costs [35, 36]. However, the limited availability, stability, and toxicity of the
precursors for the ferroelectric compositions has posed a serious, technical challenge.
Another method that has been quite extensively employed for producing
ferroelectric thin films is chemical solution deposition [37, 38, 39, 40]. Chemical solution
deposition has the advantages of precise composition and thickness control in multicomponent system [ 41 ], ease of process integration with standard semiconductor
14
In the 2-MOE based sol-gel process, alkoxides are selected as precursors, because
alkoxides provide a convenient source for inorganic network forming molecules, or
oligomers, which in most cases are soluble in common solvents. Another advantage of
using the alkoxides is the possibility to control the reaction rate by controlling hydrolysis
and condensation rates, which are the most critical processes in sol-gel technique [43].
The hydrolysis of an alkoxide, and the condensation of two M(OH) groups, or the
reaction of a M(OR) with a M(OH) group is described in the published reports [44, 45].
2-MOE is very efficiently used in the transition of transition metal alkoxides to metal
methoxyethoxide [44], which are more stable due to the inductive effects and the steric
hindrance of methoxyethoxide ligands [45].
In chelate process, the alkoxide precursors are modified by acetic acids,
acetylacetone, or amine compounds [ 46 ]. While citrate process offers advantage of
relatively simple solution synthesis over 2-MOE process, the chemistry involved in
solution preparation is quite complex due to the number of reactions that occur [47].
15
Another drawback is the solution aging, originating from the susceptibility of acetate
groups to the water molecule, resulting in the change in the precursor characteristics over
time [48]. Despite these disadvantages, thin films with better electrical properties and
microstructures have been prepared by citrate process, which suggests that the complete
homogeneity of the precursor species is not always required for high quality thin film
preparations. While most of chelate process use acetic acid or acetylacetone as stabilizing
agent, PZT thin films have been prepared using alkanolamine, and the final films were
reported to have better electrical properties and microstructural characteristics [49].
(2.4)
(examples)
Ti (OCH (CH 3 ) 2 ) 4 + 4CH 3 OCH 2 CH 2 OH Ti (OCH 2 CH 2 OCH 3 ) 4 + 4 HOCH (CH 3 ) 2
Hydrolysis Reaction
M (OR) X + H 2 O M (OR) X 1 (OH ) + ROH
(2.5)
(example)
Zr (OCH 2 CH 2 CH 3 ) 4 + H 2 O Zr (OCH 2 CH 2 OCH 3 ) 3 OH + HOCH 2 CH 2 CH 3
(2.6)
(examples)
[Pb OAc ] + [M OR ] [Pb O M ] + ROAc
+ H 2O
(2.7)
16
(example)
Pb( Ac) 2 2 x (OR) 2 x uH 2 O + vZr (OR) 4 + wTi (OR) 4 + yROH
PbZru Ti w (OR) 4( v + w) + 2 x + y ( Ac) 2 2 x y (u + y z ) H 2 O + yRAc + zH 2 O
The MOD approach consists of simply dissolving the high molecular weight
metal organic compounds in common solvents, then combining the solutions to yield the
desired final stoichiometry. The mixed solutions are deposited onto the substrate for
further heat treatment causing solvent extraction, organic removal, densification and
crystallization. Since the starting compounds are water insensitive, they do not display
the oligomerization reaction as in sol-gel process, and therefore solution synthesis is
straightforward, and allows for rapid compositional mapping of materials system [50].
However, MOD has also limitations including (1) cracking during high temperature
processing due to the large weight loss and shrinkage from the large volume fraction of
organic ligands, and (2) minimized reactivity of starting reagents resulting from inability
to tailor the properties of low reactivity starting compounds precursors. Vest et al. [51]
prepared MOD derived PZT (60/40) thin films from metal organic compounds to utilize
the advantages such as cheaper materials cost, process simplicity, and film uniformity.
They found switching characteristics from MOD derived PZT thin films were
comparable to ones from conventional sol-gel processing.
Table 2.1 shows the ratio of passive to active components used in some common
cell phones [55]. From this table, the high passive to active component ratio inside the
electronic device is evident. In addition to the need for faster operation, lower cost,
miniaturization, and improved reliability is the main driving force for the developments
of embedded passive components. Table 2.2 is the market forecast of the embedded
18
laminate and it is expected that embedded passive markets for both resistor and capacitor
market would expand more than four times in five years on the condition that the
materials supply, price reduction, and reliability issues are suitably addressed [56].
NEMI (National Electronics Manufacturing Initiatives Inc.) roadmap, another
index widely used for electronic component industry, also shows that embedded passive
based technology could significantly improve reliability and cost effectiveness (Table
2.3) [57].
Table 2.1: Passive to active ratio for cell phone components [55]
Total passives
Total ICs
Ratio
933
45
22:1
432
21
20:1
Motorola
STARTAC
Nokia 2110
Digital
2006
2
USD Million
USD Million
Embedded resistor
0.35
8.75
3.5 to 5.5
50 to 80
Embedded capacitor
2.3
10.4
11
42
19
2002
2005
R resistivity
To 100/square
To 1 M/square
To 1 M/square
$ 0.20~0.30 / in2
$ 0.20~0.30 / in2
$ 0.08~0.25 / in2
20 / in2
60 / in2
200 / in2
R tolerance (trimmed)
15 %
5%
2%
< 3 nF / in2
30 nF / in2
200 nF / in2
$ 0.05~0.30 / in2
$ 0.20 / in2
C density
C cost
LC
CC
RC
inductance (ESL, Lc) are the parasitics of real capacitor. This impedance, when plotted
with frequency, gives a graph of V shape as shown in Figures 2.7 and 2.8. The left side
of V region is the capacitive reactance portion of the impedance curve and is given as
XC =
1
2fC C
(2.8)
The right side of V region is the inductive reactance portion of the impedance curve
and is given as
X L = 2fLC
(2.9)
The frequency where these two reactances are equal and cancel each other (at the bottom
of the V) is the resonant frequency of the capacitor and is given as
f resonance =
1
2 X L C C
(2.10)
It is at this resonant frequency where the ceramic capacitors reach their minimum
impedance.
21
Of the various applications for capacitors in electronic packages, one of the most
important for both digital and analog systems is signal decoupling [59, 60]. Decoupling is
a means of overcoming physical and time constraints in the power distribution system
(PDS) of a digital circuit [ 61 ]. A decoupling capacitor is inserted in a circuit, as
22
illustrated schematically in Figure 2.9, to reduce the switching noise for circuit. This
decoupling function is getting more and important as chip level integration and chip
speed increase where the regulation of voltage supply within the chip module represents a
major challenge. This is because the inductive voltage spikes, particularly those
generated by the simultaneous current switching (di/dt), in the power distribution system
can have a frequency well above what can be supported by the conventional voltage
regulators which acts as power supplies. Consequent transient voltage noise may increase
chip-to-chip delays and, in extreme cases, collapse the power supply level [62, 63].
More specifically, in Figure 2.8, below resonance frequency, the major
component of the impedance is capacitive reactance. At resonance, it is equivalent series
resistance, and above resonance, it is inductive reactance. For decoupling application,
which will be given in the following section, the capacitor is primarily being used to
eliminate the high-speed transient noise which is above its resonance frequency. Also it is
desirable to maintain as low inductance or total impedance as possible. For a PDS, the
relations between voltage and inductance could be shown as follows.
V=L
dI
dt
(2.11)
V=LC
dI
dt
(2.12)
V=LC I
(2.13)
23
V=
1
+ I RC
C
(2.14)
Therefore one must increase the capacitance and decrease ESR in order to
decrease ripple.
In addition to sufficiently high capacitance at operating frequency, which maybe
in the GHz regime, and be physically close to the switching circuits to minimize the
effect of power connection inductance. The embedded dielectric material sandwiched
between power and the ground planes needs to be very thin, of high dielectric constant
(from low frequencies up to the GHz region), free of pinholes, with low leakage current,
and high breakdown strength. Discrete surface mount capacitors have typically been used
for this on-chip and off-chip application. However, improved signal decoupling in highspeed systems, such as multichip modules (MCMs), can be achieved with low-inductance,
thin-film capacitors that can be highly integrated into packages [64, 65, 66]
IC
Decoupling
Capacitor
Power
Supply
Figure 2.9: Schematic diagram illustrating a decoupling capacitor that acts as a local
source or sink for charge to effectively decouple the IC from the power supply.
24
Replacing bulky, discrete decoupling capacitors with thin-film capacitors that can
be integrated with ICs and MCMs generally requires the use of thin films with high
dielectric constants because decoupling capacitors typically have values of 10100 nF.
Consequently, lead zirconate titanate (PZT), barium strontium titanate (BST), and lead
manganese niobate (PMN) films are promising candidate material systems [67, 68].
(Ba,Sr)TiO3
DLC
= 10 ~ 12 [70]
Pb(Zr,Ti)O3
Ta2O5
~ 35 [72]
Pb(Mg,Nb)O3-PbTiO3
~ 3000 [73]
Table 2.4 compares the range of dielectric constants (at room temperature)
obtained for these thin film materials with the dielectric constants of some typical low
permittivity materials being developed for integrated capacitors [74]. It should be noted
that the range of dielectric constants for BST and PZT partly reflects the fact that these
materials are solid solution systems, where the permittivity is a function of the Ba/Sr and
Zr/Ti ratios, respectively. In addition, permittivity values are very sensitive to processing
conditions and overall film quality. This also contributes to the wide range of permittivity
values available in the literature.
In addition to permittivity, the properties that need to be optimized for any
capacitor application are dissipation factor, leakage current, and breakdown strength.
25
Furthermore, both the temperature and frequency dependence of these properties need to
be optimized. The higher permittivity and higher dielectric losses of PZT films compared
with BST films means that PZT films are best suited for lower frequency applications (<1
GHz) that require high capacitance, such as decoupling capacitors for digital circuits.
PZT films also have lower processing temperatures, which makes them preferable for
certain integration strategies. In comparison, the lower loss BST films are required for
higher frequency (microwave region) applications. Achieving the right combination of
properties along with a suitable processing solution dictate the best answer for a given
capacitor application.
dispersed in a polymer vehicle and formulated in the form of thick film paste [76, 77].
The photo-patterning process and dielectric constant mostly depend on the ceramic
powder loading, however due to the limitation in the upper processing temperature,
overall dielectric constant is usually not so high (~ 40). Dielectric constant depended on
the ceramic volume loading and dielectric constant of more than 110 was recently
reported by Georgia Tech [78]. Recently, DuPont presented the development of glass
powder added BaTiO3 thick film paste could realize very high dielectric constant (~
1,000) [79].
(PZT) and low temperature glass frit (PbOB2O3SiO2) for preparing thin film capacitors
on various non noble metal foils (Al, Ti, stainless steel) and showed the dependence of
electrical properties on the substrate [82]. Optimized permittivity of 64 and loss tangent
of 0.009 were measured for the capacitors on Al foil. Zou et al. showed that sol-gel lead
zirconate titanate films could be deposited on the metal foils and the dielectric properties
could be enhanced with buffer layers [83, 84]. They increased dielectric constant by a
factor of two by incorporating a LaNiO3 buffer layer and showed that more enhanced
dielectric properties might be achieved by optimized interface engineering between
capacitor film and underlying metal substrate. However, embodiments directly applicable
to embedded PWB applications (which are extremely cost competitive) has only begun
recently. Maria et al. prepared PLZT capacitors on electroless Ni on Cu foil prior to
embedding into PWB and demonstrated capacitance densities of 300 ~ 400 nF/cm2 [85].
Though other groups have demonstrated materials with higher capacitance density, this
work remains unique in its usage of materials acceptable and routinely used in todays
PWB process flows. Recently Dawdley et al. showed that a high permittivity, often
greater than 1500, could be obtained by the controlled orientation and optimized
nucleation of BST and SrTO3 deposited directly on biaxially textured nickel substrates
[86]. This work is fundamentally important in demonstrating the compatibility of the thin
film perovskite and Ni. However, the biaxially textured substrates used are not consistent
with embedding into PWBs. They are not available in large sheets and are approximately
75 m thick, which might be quite close to the limitation of embedded capacitors in
polymer circuit board.
28
same at a low temperature, about 850 ~ 875 C. There are several advantages of LTCC
compared to conventional ceramic packages. The big advantage is the possibility to use
low resistivity conductors like silver, gold, copper and alloys with palladium and
platinum instead of tungsten and molybdenum which are used in high temperature
packages. Also LTCC could be suitable for mass production because several processing
steps could be automated. One of the disadvantages of LTCC is its low thermal
conductivity (about 2.5 ~ 4 W/mK). If necessary with the help of thermal vias thermal
conductivity could be increased to 20 W/mK. An additional problem for LTCC is the
tolerance of buried resistors, which provide 3 of 30 %.
The size of the LTCC board can be reduced considerably because of the three
dimensional structure and passive components such as capacitors, inductors and resistors
can be embedded, which facilitates a high degree of integration. A schematic design of a
LTCC board is shown below [91].
(2.15)
[VO ] [VO ] + 2e
(2.16)
31
n n = p p
(2.13)
OO
where OO is oxygen ion, VO
O 2 + VO + 2 e
2
(2.17)
The electrons here remain free to conduct because donor levels are extremely shallow,
and there is negligible electron trapping. The mass action expression for this reduction
reaction is
32
[V ]n
[OO ]
= K n exp(H m / T ) p(O2 ) 1 / 2
(2.18)
Usually even the undoped material invariably contains an excess of naturally occurring
acceptor impurities. As a typical example, when trivalent acceptor oxide, A2O3, is
incorporated into MTiO3 structure, we think with charge neutrality is maintained by the
[ ]
relationship, [ATi '] = 2 VO , and when this is combined with equation (2.18), we have the
[ A']
1/ 2
exp( H n / 2T ) p(O2 ) 1 / 4
(2.19)
This pressure dependence of the conductivity is seen on the low pO2 side of the
conductivity minima in Figure 2.11. When the reduction becomes the major source of
[ ]
1/ 3
exp( H n / 3T ) p (O2 ) 1 / 6
(2.20)
This dependence of the conductivity on pO2 can be seen at the highest and lowest values
of pO2 in Figure 2.11.
33
oxygen atoms that enter the lattice require two electrons to become oxygen ions, and
these electrons are taken from the valence band. The oxidation reaction can be written as
VO + O 2 OO + 2 h
2
(2.21)
where A is an acceptor atom. The mass action expression for this oxidation reaction is
[OO ] p 2
[V ]
= K p exp( H P / T ) p (O2 )1 / 2
(2.22)
These materials are insulating at room temperature, which shows the decrease in
hole concentration (hole trapping by negatively charged acceptor). When trapping of
[ ]
concentration is given by
K p [ A']
exp( H P / 2T ) p (O2 )1 / 4
p
(2.23)
2[OO ]
This dependence of the p-type conductivity on pO2 can be seen for the pO2 region above
1/ 2
nil e + h .
H n + H p = 2 E g0
(2.24)
For the case of BaTiO3, its was shown that the good agreement was obtained with the
value of E g0 obtained from the temperature dependence of the conductivity minima [94].
The resulting defect model is summarized in the form of a Krger-Vink diagram in
Figure 2.12. This is a schematic log-log plot of the concentrations of the various defect
species as a function of the oxygen activity at constant temperature.
34
Figure 2.12: An idealized Krger-Vink diagram for an acceptor-doped perovskite for the
case of negligible hole-trapping at high temperature, and extensive hole-trapping at low
temperatures [95].
4+
35
BaTiO3
dielectrics
one
may
incorporate
acceptor-donor
mixtures,
i.e.,
36
(2.25)
[Mn ] + [W ]
2+
Ti
6 +
Ti
MnTi2+
] + [W ]
6 +
Ti
(2.26)
The interaction between donors and acceptors was found to be independent of the
special nature of the ions involved and is only determined by the ionic charge of donors
and acceptors [101]. More recently, studies on the magic dopants are found to be very
effective in improving the reliabilities of BaTiO3 capacitors. They are Y3+, Dy3+, Ho3+.
They have amphoteric character and are able to occupy either A-site or B-site in the
perovskite structure [102]. Depending on the amount of dopant, the relative ratio of B/A
varies and the donor or acceptor character prevails. The dopants act like donor-acceptor
complexes and reduce the concentration of oxygen vacancies.
37
Metal deposition processes using an aqueous solution is one of the widely used
processes due to the high solubility of most metal salts in water and also due to the good
electrical conductivity of such solutions. Usually the deposition process can be divided
into (1) electrolytic and (2) electroless plating, mostly depending on the requirements of
the final deposits.
38
Me Z + + Ze Me
(cathode)
Me Me Z + + Ze
(anode)
(2.27)
(2.28)
R n + R ( n + Z ) + Ze
(2.29)
Me Z + + Ze Me
(2.30)
39
Ni-P deposits can be prepared from both acidic and alkaline Ni-P baths. Acidic
bath could yield various electroless Ni deposits with very low residual phosphorus (1 ~ 3
%) to very high residual phosphorus (9 ~ 12 %). Deposits from acidic baths can be
identified by phosphorus content, which determines final properties of deposits. Ni-P
deposits from alkaline baths can be prepared at relatively low temperatures (~ 65 oC),
making them suitable for plating on plastics [108], compared to 85 ~ 95 oC for acid bath
operation [105]. In addition, because of the low phosphorus content deposited (3 ~ 4 %),
Ni-P deposits from alkaline baths are used in many applications where enhanced
solderability is often required, on the while, Ni-P deposits with higher phosphorous
content show better corrosion resistance [106].
Ni-B baths
Ni-B baths are usually formulated using either a borohydride (ex. sodium
borohydride, NaBH4) or amineborane (mono-[CH3NH2BH3], diethyl-[(C2H5)2NH2BH3],
dymethyl-[(CH3)2NH2BH3] or trimethylamineborane [(CH3)3NBH3]) as the chemical
reducing agent. Ni-B deposits from solutions with borohydride reducing agents are less
stable than amineborane based Ni-B deposit due to the high pH value required. Deposits
can be plated from acidic or alkaline baths. The Ni-B deposits are differentiated from NiP deposits by the following:
Low boron containing Ni-B (< 1 %) deposits from amineborane solution have high
electrical conductivity, good solderability and good bonding characteristics. Higher levels
of boron (2 ~ 3 %) in the deposit have very high hardness values as plated, and tend to
retard the formation of oxides on the surface of the deposit. Sodiumhydride baths
codeposit higher levels of boron (5 ~ 6 %), but are less stable than amineborane baths
because of the high pH values required to prevent hydrolysis and solution decomposition.
Ni 2+ + H 2 PO2 + H 2 O Ni 0 + H 2 PO3 + 2 H +
or
(2.31)
(2.32)
41
(2.33)
Therefore, in addition to the Ni, phosphorous is also formed and is included with
Ni in the deposit. Thus electroless Ni coating formed from hypophosphite are actually NiP alloys with from 3 ~ 15 % of phosphorous content.
Once the reduction reaction starts, the chain reactions take place by the adsorption
of H 2 PO2 and OH ions on the catalytically active Ni surface by the following
reactions [107].
H 2 PO2 + H 2 O H 2 PO3 + H + + H + e
(2.34)
NiOH + + 2e Ni 0 + OH
(2.35)
H 2 PO2 + 2 H + + e P + 2 H 2 O
(2.36)
The deposition process is autocatalytic; i.e., once a primary layer of nickel has
formed on the substrate, that layer and each subsequent layer become the catalyst that
causes the above reaction to continue. Thus very thick electroless Ni-P deposits can be
coated, provided that the ingredients in the plating bath are replenished in an orderly
manner. In general commercial practice, thickness range from 2.5 to 125 m are possible
with electroless plating and in some cases, 750 m deposits are not uncommon.
For electroless Ni-B deposits, the overall reactions between Ni and borohydride as
reducing agent can be written as follows;
42
(2.37)
8 BH 4 + 4 Ni 2+ + 18 H 2 O 2 Ni 2 B + 6 H 3 BO3 + 25 H 2
(In the presence of Ni ion)
(2.38)
Function
source of metal
Hypophosphite
reducing agent
ions
Example
Nickel chloride
nickel sulphate
Sodium hypophosphate
Sodium borohydride
Hydrazine
Complexants
Monocarboxylic acids
Dicarboxylic acids
Hydroxycarboxylic acids
Ammonia, alkanolamines
Accelerators
Activate hypophosphate ions and accelerate Anions of some monodeposition. Mode of action oppose and dicarboxylic acids,
stabilizers and complexants
fluorides, borates
Stabilizers
Buffers
PH regulators
Wetting agents
43
/C) [107].
44
Cu foil for use in the Cu-clad laminates used in PCB manufacturing is usually
made on a rotating drum cathode machine. In this method Cu is electrodeposited on a
rotating cylindrical drum cathode by passing an electric current from a lead (Pb) or leadantimony (Pb/Sb) anode through a Cu-containing electrolyte such as, an aqueous copper
sulfate/sulfuric acid solution, to plate copper on the surface of a rotating drum cathode
partially immersed in the electrolyte. The drum cathode typically has an outer top sheet
formed of titanium or a similar metal [113]. One side of this electrodeposited Cu foil is
formed next to the drum and is relatively smooth (shiny or glossy appearance), but the
outer surface on which Cu deposits are grown has a matte appearance with rough profile.
The thickness of the Cu foil plated on the drum cathode is determined by a
number of variable process parameters, and it is known to produce thin Cu foil and ultrathin copper foils with one-half (1/2) ounce (thickness of about 17 m) or less. However,
46
2.6 Summary
In this chapter, we have reviewed both the science and technology over a range of
topics which will come together in the study which forms the basis of this dissertation.
47
2.7 References
[1] M. Lines and A. Glass, Principles and Applications of Ferroelectrics and Related
Devices, 87 (Clarendon Press, Oxford, 1977).
[2] B. Jaffe, W. R. Cooke Jr., and H. Jaffe, Piezoelectric Ceramics (Academic Press, New
York, 1971).
[3] G. A. Smolenskii, V. A. Bokov, V. A. Isupov, N. N. Krainik, R. E. Pasynkov, and A.
I. Sokolov, Ferroelectrics and Related Materials (Gordon and Breach Science
Publishers, 1984).
[4] F. Jona and G. Shirane, Ferroelectric Crystals (Dover Publications, Inc., 1993).
[5] W. J. Merz, Phys. Rev. 76, 1221 (1949).
[6] S. Hoshino, Y. Mitsui, F. Jona, and R. Pepinsky, Phys. Rev., 107, 1255 (1957).
[7] A. J. Moulson and J. M. Herbert, Electroceramics, (Chapman & Hall, London, 1990).
[ 8 ] R. W. Schwartz, D. Dimos, S. J. Lockwood, and V. M. Torres, Integrated
Ferroelectrics, (4) 165 (1993).
[9] D. Dimos, S. J. Lockwood, R. W. Schwartz, and M. S. Rodgers, IEEE Trans. CPMTPart A (18) 174 (1995).
48
(1991).
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[26] D. L. Polla and L. F. Francis, Annual Rev. of Material Science, 28, 563 (1998).
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[36] J. Hong, H. W. Song, H. C. Lee, W. J. Lee, and K. No, J. Appl. Phys., 90 (4), 1962
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U. Boettger, and R. Waser, Sensors and Actuators, A: Physical, A97-98, 680 (2000).
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and R. Waser, Materials Research Society Symposium Proceedings, 541
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(AEPT) consortium, Jan. 30, 2003
52
53
[69] M. S. Tsai, S. C. Sun, and T.-Y. Tseng, J. Am. Ceram. Soc., 82 (2) 351 (1999).
[70] Y. Iriyama, Y. Hasegawa, and T. Ihara, J. Photopolymer Sci. Tech., 13(1), 39
(2000).
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Ferro., 2, 687 (1996).
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4(7), F13 (2001).
[73] F. Fukumaru, S. Nagakari, S. Konushi, H. Nishikawa, K. Kamigaki, and S. Nambu,
Mat. Res. Soc. Symp. Proc., (1999), 541(Ferroelectric Thin Films VII), 573 (1999).
[74] R. Kambe, R. Imai, T. Takada, M. Arakawa, and M. Kuroda, IEEE Trans. CPMTPart B (18) 23 (1995).
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Technology Workshop on Passive integration, June (2002).
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Electroceramics, 5(1), 31 (2000).
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[104] G. G. Gawrilov, Chemical Nickel Plating (Portcullis Press, Redhill, UK, 1979).
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57
CHAPTER 3
Experimental Procedure
58
[Pb(O2C2H3)23H2O]
(Aldrich
Chemical
Co.),
zirconium
propoxide
Table 3.1: Recipe for 2-methoxyethanol (2-MOE) based PZT (52/48) solution (0.4M).
Name
Chemicals
Maker
Amount
Purity
(CH3CO2)2Pb.3H2O
Aldrich
11.2 g
99 + %
Zirconium n-propoxide
Zr(OCH2CH2CH3)4
Aldrich
6.15 ml
70 wt% in 1propanol
Titanium isopropoxide
Ti[OCH(CH3)2]4
Aldrich
3.85 ml
99.999 %
2-4 Pentanedione
(Acetylacetone)
CH3COCH2COCH3
Aldrich
2.5 ml
99 + %
Formamide
HCONH2
Aldrich
2.65 ml
99.5 + %
The first step is the dissolution of appropriate amounts of lead acetate trihydrate
into the 50 ml of 2-MOE solvent at 120 oC for 20 ~ 30 minutes. Pb is added at a
composition of approximately 15 mol % more than required by stoichiometry to
compensate for the loss during the high temperature annealing. When the Pb precursor is
completely dissolved, this solution is vacuum distilled under a vacuum of 20 inch Torr at
120 ~ 130 oC until a white paste with enough moisture begins to form. This vacuum
distillation step is very important in minimizing the amount of water molecule attached to
59
the Pb acetate precursors, which affects the hydrolysis and condensation rates in the
multi-component system. During vacuum distillation, it is not desirable that powder
particles be formed, as they will tend to move toward the condenser. After distillation,
vacuum is eliminated by introducing inert gas (Ar or N2) into the flask. The flask is kept
mixing at 120 oC for another 30 minutes, and the flask is lifted out of bath, and cooled to
room temperature. In a separate flask, Zr and Ti isopropoxide are added by disposable
syringes drop by drop to 15 ml of 2-MOE, and the Zr and Ti mixture is stirred at room
temperature for 1 hour. To further stabilize the Zr and Ti precursor during solution
preparation, 2.5 ml of 2-4 pentanediol was added while Zr and Ti mixture solution is
stirring. This mixture solution was stirred for an additional 1 hour at room temperature
and the color of the solution changed slightly to light yellow, due to the modified bonding
structures in Ti and Zr propoxide.
Zr/Ti mixture solution is then added to the flask with paste-like Pb lumps. The
flask that contained Zr and Ti mixture is washed with 30 ml of 2-MOE and poured into
flask with Pb/Zr/Ti mixture. This step was repeated again so that ~ 60 ml of 2-MOE
could be introduced to the flask. This mixture is then refluxed for 3.5 hours at 120 oC for
improved homogeneity, and vacuum distilled by 20 ml to eliminate the by-products and
water molecules from reactions.
60
2 - methoxyethanol
2-methoxyethanol
Pb-Zr-Ti mixture
Reflux / distillaltion
PZT solution
Figure 3.1: A flow chart for PZT solution preparation by 2-methoxyethanol route.
After distillation, the solution is kept mixing for another 30 minutes, and cooled
to room temperature. The concentration of this solution is 0.4 M. Typically, the stock
solution is further diluted to 0.25 ~ 0.30 M to improve the wetting characteristics on the
substrate, and achieve an appropriate coating thickness. The diluted solution is stirred at
room temperature for 24 hours for complete homogenization. When the final solution
molarity is high (ex. > 0.5M), a drying control agent (formamide, ~ 4 vol%) can be
additionally added in the final dilution step to prevent the crack formation during film
deposition/drying process [4]. Final solution was filtered using 0.2 m filter paper to
minimize the incorporation of particles and dust during solution preparation.
61
62
Table 3.2: Recipe for methanol based Ca-doped PZT (5/52/48) solution preparation.
Name
Chemicals
Maker
Amount
Purity
(CH3CO2)2Pb.3H2O
Aldrich
8.202 g
99 + %
Ca acetate hydrate
(CH3CO2)2Ca.XH2O
Aldrich
0.198 g
99.9 %
Zirconium n-propoxide
Zr(OCH2CH2CH3)4
Aldrich
4.390 ml
70 wt. % solution
in 1-propanol
Titanium isopropoxide
Ti[OCH(CH3)2]4
Aldrich
2.857 ml
99.999 %
Diethanolamine
(HOCH2CH2)2NH
Aldrich
1.0 ml
98.5 %
Triethanolamine
(HOCH2CH2)3N
Aldrich
2.0 ml
98 %
Nitric Acid
HNO3
Fisher
3 ~ 6 drops
Assay 68 ~ 70 %
63
hour of stirring time. Nitric acid works as a catalyst and contribute to the formation of a
weekly bonded gel structure. In this case, the rate of hydrolysis is faster than
condensation, resulting in weakly bonded structure with less dense, linear [5] After that,
volume of the solution is measured. Typically the final volume of the solution is almost
or slightly less than 40 ml due to the evaporation of the solvents.
Based on this
measurement, the concentration of the solution is determined and used for future
dilutions. Ultimately, methanol is added to the solution for further dilution prior to
deposition. Typically, this stock solution is diluted with methanol to 0.15 ~ 0.2 M, and
mixed for 24 hours at room temperature. After dilution, this solution might be aged for
one or two days before deposition to ensure the saturated hydrolysis reaction.
More concentrated solutions are clearly preferable for more rapid processing,
however, in the case of concentrated solutions, it is more difficult to remove the higher
relative levels of organic during the pyrolysis step and compromises are often made in the
final materials structure and properties. The overall flow chart for the methanol based
undoped and Ca-doped PZT processing is shown Figure 3.2.
64
Methanol +
Chelating agent
Titanium isopropoxide
Zirconium propoxide
Lead acetate trihydrate
Calcium acetate hydrate
Nitric acid
Dilution
PZT solution
Figure 3.2: A flow chart for Ca doped PZT solution preparation by methanol route.
Different drying and pyrolysis steps were adapted for each solvent. Films from 2MOE based solution was pyrolyzed at 400 oC for 5 minutes using hot plate, while films
from methanol based solution were pyrolyzed at 450 oC for 7 minutes and partially
crystallized at 700 oC for 2 minutes, using an alumina tube furnace. The films thickness
after 6 layers of coating was in the range of 1800 ~ 2000 . For final crystallization,
samples were annealed at 650 ~ 700 oC for 15 ~ 30 minutes under flowing oxygen
atmosphere. To minimize the stability of pyrochlore phase and expedite direct perovskite
phase formation, all the samples were inserted to the temperature - preset furnace directly.
In Table 3.3, the specifications of the substrates are listed.
65
Orientation
Remarks
Pt (100nm)/SiO2 (100nm)/Si
(111)
Pt (100nm)/Ti / SiO2/Si
(111)
8 % phosphorous
12 ~ 13 % phosphorous
For the capacitor on foil, 1 oz. (~ 25 m thick) Cu foils (by Gould Co.) coated
with electroless Ni layers (by Shipley Co.) on both sides with thickness of 4 m were
used. To study the effect of phosphorous content, both electroless Ni layers with both
8 % and 12 ~ 13 % were used, respectively. The foils were cleaned under the standard
cleaning procedure using acetone and isopropyl alcohol (IPA) before capacitor
preparation. PZT coating solutions were coated using spin coater for 30 seconds at 3000
rpm. Due to the inherent absence of rigidity, foil was placed on the flat silicon piece and
fixed using sticky tape. After each spin coating, sticky tape was removed from the edges
of foil. Films then were moved to hot plate where the temperature was already kept to
250 oC. After drying at 250 oC for 5 minutes, foil was moved to 450 oC preset alumina
tube furnace and pyrolyzed for 15 minutes in an air atmosphere, to ensure complete
binder burnout. To prevent the warpage and sagging of the foil during high temperature
annealing, stainless steel frames were used in to fix the foil during 450 oC pyrolysis.
Films were coated seven times so that the total thickness would be in the range of 700 ~
800 nm. Films were crystallized between 550 and 650 oC, under varying partial oxygen
pressure.
66
67
Chemicals
Maker
Amount
Purity
Zr(OCH2CH2CH3)4
Aldrich
0.633 ml
70 wt. %
solution in 1-
CH3COCH2COCH3
Aldrich
0.3 ml
99 + %
Deionized water
H2O
0.05 ml
n-propanol
CH3 CH2CH2OH
Aldrich
27 ml
99.5 + %
Zirconium npropoxide
2, 4 Pentanedione
(Acetylacetone)
68
69
C = 0
A
t
(3.1)
70
then soldered to the test fixtures. The addition of a peltier cooler and heatsink to the
vacuum chamber system served to cool the entire chamber and further reduced the
attainable temperature from 85 K to the limit for a liquid nitrogen system, 77 K.
71
Pt top
PZT(PCZT)
Electroless Nickel
Cu
Electroless Nickel
Figure 3.3: Schematics of the capacitor stack structure with base metal electrode.
72
CuK radiation generated at 40 kV and 30 mA. The area detector enables the scattered Xrays to be collected over approximately 35o 2 and 45o simultaneously.
Atomic force microscopy (AFM) (ThermoMicroscopes, contact mode) was also
used to determine surface microstructure, roughness and grain size of the capacitor films.
Field emission scanning electron microscopy (SEM) (JEOL 6400F) was used to examine
film thickness measurement.
73
3.5 References
[1] R. W. Schwartz, Chem. Mater., 9, 2325 (1997).
[2] K. D. Budd, S. K. Dey, and D. A. Payne, Brit. Ceram. Proc., 36, 107 (1985).
[3] R. Waser, T. Schneller, S. Hoffmann-Eifert, and P. Ehrhart, Integrated Ferroelectrics,
36, 3 (2001).
[ 4 ] R. G. Polcawich, C-N. Feng, S. Kurtz, S. Perini, P. J. Moses, and S. TroilerMcKinstry, Int. J. Microcircuits and Electronic Packaging, 23, 1, 85 (2000).
[5] J. Livage, C. Sanchez, M. Henry, and S. Doeff, Solid State Ionics, 32(33), 633 (1989).
[6] H. Li., K. Liang, S. Gu, and G. Xiao, J. Mater. Sci. Lett., 20, 1301 (2001).
[7] Operation manual of the RT66A from Radiant Technology, Version 2.2 (Albuquerque,
NM).
74
CHAPTER 4
PZT (52/48) Thin Film Capacitors on Electroless Ni Coated Cu Foil
4.1 Introduction
Since the 1990s, passive components are becoming an integral part of
microelectronic device research. The number of passive components constitutes over
80 % of the components in hand-held devices. Integral passive components are expected
to be the widely used technology in the future for very high component density with
increased electrical performance, improved reliability, reduced size, weight and cost. The
integral passive components will therefore, eliminate SMT (surface mount technology)
and result in the reduction of overall part count, elimination of solder joints, improvement
of wireability and frequency due to elimination of parasitic inductance. Developing
optimized materials that satisfies electrical, reliability and processing requirements is one
of the major challenges of incorporating capacitors into a board. In this chapter, we
discuss the preparation of PZT (52/48) capacitors on electroless nickel coated copper foil
by CSD (chemical solution deposition). The electrical properties and reliability of the
capacitors are discussed in terms of the microstructure and interface reaction.
75
electrical properties, along with another advantage of perovskite phase formation at lower
temperature due to the reduced amount of chelating materials. Thin film capacitors
especially have low temperature processing requirement, in terms of the oxidation of
underlying base metal electrode. The films prepared from each route were evaluated in
terms of the phase formation, dielectric property, and microstructure while considering
the process compatibility with base metal foil.
atmosphere. In the literature, one of the mechanisms proposed for the nucleation of (111)
PZT on (111) oriented Pt substrates is the direct nucleation of PZT on Pt due to lattice
20
25
30
35
40
45
50
55
PZT (111)
PZT (101)
Intensity (a.u.)
PZT (111)
PZT (101)
Intensity (a.u.)
(b)
Pt (111)
(a)
Pt (111)
20
25
30
35
40
45
50
55
Figure 4.1: XRD plot for 2-MOE based (a) and methanol (b) based PZT (52/48) thin film
capacitors on Pt/SiO2/Si crystallized at 650 oC for 30 minutes under O2 atmosphere.
Another proposed mechanism is that a transient PbPtx alloy forms at the interface
due to reduction of Pb and reaction with Pt and (111) PZT nucleates on this cubic phase
due to the almost identical (111) lattice parameters of the two phases [3]. Brooks et al.
observed the nucleation of (111) oriented crystallites at the film/substrate interface and
subsequent growth directly by TEM. They also claimed that for the films pyrolyzed at
350 oC, transient pyrochlore phase would be formed, and it will be easily transformed
into (111) perovskite phase on (111) Pt. Alternatively for the films pyrolyzed at 420 oC, a
more stable pyrochlore phase will retard the transformation to perovskite [4].
77
200
-400
60
400
(a)
40
-200
Polarization (C/cm )
Polarization (C/cm )
-400
60
20
0
-20
-40
-60
-8 -6 -4 -2
Voltage (V)
40
-200
400
(b)
20
0
-20
-40
-60
-8 -6 -4 -2
200
Voltage (V)
Figure 4.2: P-V hysteresis for 2-MOE based (a) and methanol (b) based PZT (52/48) thin
film capacitors on Pt/SiO2/Si crystallized at 650 oC for 30 minutes under O2 atmosphere.
0.20
0.16
1200
0.12
800
0.08
400
0.04
0
-6
-4
-2
Voltage (V)
0.00
6
Dielectric constant
(a)
1600
(b)
0.16
1200
0.12
800
0.08
400
0.04
0
-6
-4
-2
Loss tangent
1600
0.20
2000
Loss tangent
Dielectric constant
2000
0.00
Voltage (V)
Figure 4.3: Capacitance-voltage for 2-MOE based (a) and methanol (b) based PZT
(52/48) thin film capacitors on Pt/SiO2/Si crystallized at 650 oC for 30 minutes under O2
atmosphere.
78
(a)
0.16
0.12
800
0.08
400
0.04
0 2
10
10
10
10
Frequency (Hz)
0.00
6
10
1600
0.20
(b)
0.16
1200
0.12
800
0.08
400
0.04
0 2
10
10
10
10
Loss tangent
1200
Dielectric constant
1600
2000
0.20
Loss tangent
Dielectric constant
2000
0.00
6
10
Frequency (Hz)
Figure 4.4: Capacitance-frequency for 2-MOE based (a) and methanol (b) based PZT
(52/48) thin film capacitors on Pt/SiO2/Si crystallized at 650 oC for 30 minutes under O2
atmosphere.
79
Ca doping study, only the methanol based process was used for preparation of Ca-doped
PZT compositions.
80
In Figure 4.5, both calculated and experimental phase diagrams of Ni-P system is
shown [7]. Ni-P alloys show different crystal structure and reaction paths depending on
the relative composition between Ni and P. The Ni-P system with Xp < 0.4 consist of
liquid, Ni (fcc), Ni3P, Ni12P5, Ni2P, Ni5P2. Though several intermediate phases have been
reported for Xp > 0.4, a reliable phase diagram has not yet been established [8]. In Table
4.1, crystallographic data for various Ni-P alloys are shown.
Space group
Structure
Lattice constant
Relative accuracy
of lattice
parameters (%)
Ni3P
I4
Fe3P (DO6 )
a = 8.954, c = 4.386
0.04
~Ni2.55P
P3 or P3
a = 6,608, c = 24.63
0.04
Ni12P5
a = 8.646, c = 5.070
0.05
Ni12P5
I4
Ni2P
P 62m
Fe2P (C22 )
NiP
Pbca
NiP
a = 5.865, c = 3.347
a = 5.859, c = 3.382
a = 6.050, b = 4.481
c = 6.890
0.04
0.04
Since the first discovery by Brenner et al. [10], various studies have been carried
out on electroless Ni deposits to investigate their microstructural properties and
crystallization behavior under the influence of deposit compositions and heat treatments.
However, many groups have reported different results regarding both these aspects [11,
12, 13, 14]. These differences are mostly believed to be from processing parameters such
81
Many studies reported the structure of as-deposited Ni-P layers and found the
dependence of crystal structure on the phosphorous content. Low phosphorous deposits
are reported to have either highly crystalline, large-grained morphology [15] or to consist
of microcrystalline Ni [16]. Medium phosphorus deposits are reported to be either fully
amorphous [15] or mixtures of microcrystalline Ni and amorphous phases [11], and highphosphorous could be fully amorphous [11], mixtures of microcrystalline Ni and
amorphous, or consist of multi-phased mixtures of Ni, amorphous Ni, NiP, Ni5P4, Ni12P5
and Ni5P2.
Crystallization behavior of electroless Ni deposits depends on both the
phosphorous content and heating condition. Electroless Ni deposits undergo from
amorphous to crystalline state at higher temperatures, and depending on the phosphorous
level, various intermediate phases could be observed. For deposits with less than 7 wt. %
phosphorous, direct transformation occurs into final stable Ni3P in a matrix of crystalline
Ni [17]. Deposits with higher phosphorous content, however, transform from amorphous
to some metastable phases such as Ni5(P,Ni)2 and Ni3(P,Ni) [17] or metastable Ni12P5
phase before transforming to Ni and the most stable Ni3P phase [18].
82
Different heating conditions also have shown significant influences on both the
microstructures and crystallization behaviors of the electroless Ni deposits. A study by
Randin et al. has indicated that the heated electroless Ni deposits consisted of Ni and
Ni3P phases only [ 19 ]. However, Keong et al. reported the sequence of phase
transformations started from amorphous phase which transformed into the mixture of
intermediate metastable phases, stable Ni3P phase, and f.c.c. nickel, and finally
transformed to mixture of stable Ni3P phase and f.c.c. nickel [20]. Results from DSC and
DTA work on deposits containing 7.4 ~ 10 wt.% phosphorous have shown that the
increase in heating rate would delay the crystallization onset temperature, regardless of
the phosphorous content [21].
For applications in the electronic materials packaging industry, the use of Ni and
other non-noble materials emerged from the high production cost and process feasibility
issues associated with noble metal or conducting oxides. Ni or Cu layers have been used
as an internal electrode, combined with Au bump contact metallurgy in the PCB industry.
These layers are routinely prepared from electroless or/and electrolytic deposition process.
Because of the economic compatibility and the relative acceptance of electroless Ni in the
PWB industry, in our study, we selected an electroless Ni coated Cu layer with 7 % and
12 ~ 13 % phosphorous content, respectively. The effect of the phosphorous on the final
properties of PZT based capacitors were studied, as this work represents the first
published reports where electroless Ni on Cu multilayers were used as substrates for
oxide films.
In Figures 4.6 and 4.7, the x-ray diffraction spectra of the as-deposited and 450 oC
heat-treated electroless Ni coated on Cu foil are shown. The presence of a broad peak
83
close to the Cu (111) peak in as-deposited deposit shows that the as-deposited coating
might be in nanocrystalline or amorphous supersaturated solution of phosphorous in a Ni
matrix. The above result is in agreement with previous studies on the structure of
electroless Ni-P deposits performed by high voltage electron microscopy [22]. Their
TEM analysis showed that low phosphorous (1 ~ 3 %) Ni deposits are crystalline, while
high phosphorous (8 ~ 14 %) deposits are amorphous. These results are in general
agreement with electroless Ni-B alloys, where the transition from a semicrystalline to
fully amorphous deposit occurs between 4.3 and 5.7 % P [ 23 ]. The threshold
phosphorous content for an electroless Ni-P deposit to be amorphous is believed to be 7 ~
Cu(200)
Cu(111)
Intensity (a.u.)
(b) 12~13% P
(a) 8% P
20
25
30
35
40
45
50
55
Figure 4.6: X-ray diffraction plots for as-deposited electroless Ni coated Cu foils; (a) with
8 % phosphorous and (b) with 12 ~ 13 % phosphorous.
84
Cu(200)
Ni(200)
Ni3P(132)
Ni(111)
Ni3P(141)
Cu(111)
Ni3P(231)
Ni12P5
Ni3P(031)
Intensity (a.u.)
(b) 12~13% P
(a) 8% P
20
25
30
35
40
45
50
55
2
Figure 4.7: X-ray diffraction plots for 450 oC-annealed electroless Ni coated Cu foils; (a)
with 8 % phosphorous and (b) with 12 ~ 13 % phosphorous.
When annealed at 450 oC, this amorphous Ni reacts with phosphorous in the
matrix to form nickel phosphide (mostly Ni3P and Ni12P5) phase, and broad peak around
2 ~ 45
disappears and the crystalline Ni (111) and Ni3P peaks appear, i.e., the
85
Ni(200)
Cu(200)
Cu(111)
NiO(003)
Intensity (a.u.)
Ni(111)
20
25
30
35
40
45
50
55
Figure 4.8: X-ray diffraction plots for as-deposited (a) and 450 oC annealed (b)
electroplated Ni coated Cu foils.
In Figures 4.9 and 4.10, the surface microstructures of Cu foil and electroless Ni
coated Cu foils are shown, respectively, as a function of air annealing temperature. The
as-deposited, electroless Ni surface has spherical grain morphologies. Also to a larger
degree, surface roughness of electroless Ni layer was dependent on the underlying Cu foil.
Other groups have reported highly non-uniform surface morphologies in electroless Ni
layers, being strongly dependent on bath condition [26]. We observed no such surface
structures in any foils used in this study.
86
Figure 4.9: AFM image for Cu foil used for Ni coating. Scans was performed over 5 5
m range.
8 % phosphorous
as-deposited
8 % phosphorous
450 oC, 15 minutes, air
8 % phosphorous
650 oC, 30 minutes, N2
12 ~ 13 % phosphorous
as-deposited
12 ~ 13 % phosphorous
450 oC for 15 minutes, air
12 ~ 13 % phosphorous
650 oC for 30 minutes, N2
Figure 4.10: AFM images for electroless Ni coated Cu foils with anneal temperature. All
scans were performed over 1 1 m range.
87
When annealed at 450 oC, surface images reveal a much finer grain structure
which is likely related to a matrix of Ni grains mixed with Ni3P second phase. This might
be related with the Ni3P phase nucleation and growth which is dominant from ~ 300 oC.
At higher temperature, coarsening of this microstructure is observed.
This changes in microstructures are in overall agreement with the report by
Grewal et al. [27] and Keyse et al. [28] who empirically observed the microstructure of
the crystalline deposit consists of a Ni3P matrix containing areas of metallic Ni, for the
phosphorous contents studied.
88
X-ray diffraction plots for PZT capacitors prepared on the electroless Ni coated
Cu foil and crystallized at different temperatures are shown in Figures 4.11 and 4.12. No
pyrochlore phases were detected in all samples. For the capacitors on foils with higher
phosphorous content, stronger peaks for Ni3P phases were observed. PZT films did not
show any trends in orientation with increases in temperature. Rather PZT films were
randomly oriented.
It is usually reported that the PZT thin films on platinized Si show preferred
orientations, depending on the processing parameter such as bottom electrode stack
structure, pyrolysis temperature and time. For the preferred orientation of PZT thin films,
the lattice mismatch between PZT thin film and bottom electrode is one of the important
parameters. Unlike PZT on Pt, lattice matching between Ni and PZT is very poor. This
lattice mismatch gets bigger for Ni3P and PZT. Moreover, Ni and Ni3P growth during
annealing is characterized by random orientation as shown in Figure 4.7.
Crystal structure
Lattice constant ()
PZT (52/48)
Tetragonal
a = 4.036, c = 4.146
a = 4.065, c = 4.110 [29]
Ni
Cubic
a = 3.5238
Ni3P
Tetragonal
a = 8.952, c = 4.388
Pt
Cubic
a = 3.9231 [30]
NiO
Rhombohedral
89
20
25
30
35
40
45
N(200)
#(200)
#(132)
#(231)
C(111)
N(111)
#(141)
P(111)/Pt(111)
#(031)
P(010/110)
P : PZT
# : Ni3P
N : Ni
C : Cu
P(100)
Intensity (a.u.)
50
55
Figure 4.11: X-ray diffraction plots for methanol based PZT (52/48) thin film capacitors
on electroless Ni coated Cu foil with 8 % phosphorous: (a) 550 oC, (b) 575 oC, (c) 600 oC,
and (d) 650 oC.
90
N(200)
#(200)
#(141)
#(231)
C(111)
N(111)
P(111)/Pt(111)
#(132)
(d)
#(031)
P(010/110)
P(100)
Intensity (a.u.)
P : PZT
# : Ni3P
N : Ni
C : Cu
(c)
(b)
(a)
20
25
30
35
40
45
50
55
Figure 4.12: X-ray diffraction plots for methanol based PZT (52/48) thin film capacitors
on electroless Ni coated Cu foil with 12 ~ 13 % phosphorous: (a) 550 oC, (b) 575 oC, (c)
600 oC, and (d) 650 oC.
To study the effect of the foil surface smoothness on the properties of capacitors,
PZT thin film capacitors were deposited on the front (shiny and smooth) and rear (rough
matte side) surfaces of electroless Ni coated Cu foils and annealed at 650 oC for 30
minutes under N2 atmosphere. The X-ray diffraction plots for the PZT (52/48) films on
electroless Ni coated Cu foils are shown in Figures 4.13 and 4.14. Well-developed
perovskite phases, together with nickel phosphide (mostly Ni3P), Ni and Cu phases were
observed on the smooth foil surface. Alternatively, when capacitors were prepared on the
rough surface side under the identical processing conditions, poor phase formation and
poor crystallization of PZT capacitors were found, and capacitors prepared on the rough
foil surface were all shorted.
91
0
20
25
30
35
40
45
Cu(200)
Cu(111)
Ni3P(231)
200
Ni3P(031)
400
PZT(101)
Intensity
600
Ni3P(141)
Ni(111)
800
50
55
Figure 4.13: Phase formation of PZT (52/48) thin film capacitors on smooth foil side.
Crystallization was done at 650 oC for 30 minutes.
92
25
30
35
40
Cu(111)
45
Cu(200)
Ni(200)
Ni3P(132)
30
0
20
Ni3P(231)
60
PZT(101)
Intensity
90
Ni3P(141)
Ni(111)
120
50
55
Figure 4.14: Phase formation of PZT (52/48) thin film capacitors on rough foil side.
Crystallization was done at 650 oC for 30 minutes.
700 oC, due to the better connectivity between grains, higher perovskite phase volume
fractions and film densification [33].
However, in this study, as the temperature increases, capacitance densities
monotonically decreased. Loss tangent does not vary much for the temperature ranges
studied, however the changes in capacitances were clear. Only 200 nF/cm2 of capacitance
density were measured for capacitors crystallized at 650 oC. The resulting capacitance
shows quite different behavior compared to the identically processed PZT capacitors on
Pt/SiO2/Si substrate. The characteristics could be summarized as follows;
(1) Capacitors show voltage independent behavior and tunability is nearly zero.
Capacitance density, together with loss tangent does not show symmetric butterfly shape
that is common to the ferroelectric thin films on Pt electrodes. This is likely an interface
or compositional effects, as supported by the decrease of capacitance density with
annealing temperature.
(2) Permittivity calculated on the basis of the measured capacitance and capacitor
dimensions are two to three times smaller than permittivities measured for PZT thin films
on ideal Pt surface.
The above suggests that the interfacial reactions between capacitor and underlying
base metal substrate might be most probable explanation. Bartic et al. measured
dependence of C-V characteristics on the crystallization temperature and time for PZT
(20/80) capacitors on platinized silicon [ 34 ]. In their study, an amorphous layer
94
dominated PZT thin films that were crystallized at 450 oC showed voltage independent
capacitance due to the incomplete perovskite phase formation and experimental plot for
(C/A)-1 vs. thickness resulted in the interfacial permittivity of 38. Similar phenomena
may be occurring in our material, especially at low crystallization temperature, but the
primary factor is chemical reaction. The evidence of chemical reaction is reported by our
research group and the cross-sectional TEM images of PLZT thin films on electroless Ni
is shown in Figure 4.16, where the interface region of ~ 20 nm thickness is identified [35,
600
0.30
on 8% P
on 12% P
500
0.25
400
0.20
300
0.15
200
0.10
100
0.05
550
575
600
625
650
Loss tangent
36].
0.00
Crystallization temperature ( C)
Figure 4.15: Dielectric properties of methanol based PZT (52/48) thin film capacitors on
electroless Ni coated Cu foil with different phosphorous content.
95
electrodeposited Cu
ion-beam sputtered Ni
a-Ni substrate
Figure 4.16: TEM image of PLZT capacitor deposited on electroless Ni foils [35, 36].
96
550 C
200
0.10
100
0.05
-4
-2
Voltage (V)
400
0.00
6
0
-6
0.15
o
0.20
o
600 C
200
0.10
100
0.05
0
-6
-4
-2
Voltage (V)
0.00
6
0.20
575 C
300
0.15
200
0.10
100
0.05
0
-6
-4
-2
Voltage (V)
400
0.00
6
0.20
o
650 C
300
0.15
200
0.10
100
0.05
0
-6
Loss tangent
0.15
Loss tangent
300
300
400
Loss tangent
0.20
Loss tangent
400
-4
-2
Voltage (V)
0.00
6
Figure 4.17: Capacitance-voltage plots for PZT (52/48) thin film capacitors on electroless
Ni coated Cu foil crystallized between 550 and 650 oC for 30 minutes under N2
atmosphere.
where Ni was used as top electrode [38]. They suggested that more oxygen
vacancies might be accumulated at the Ni/PZT interface and severe domain pinning than
at Pt/PZT interface, due to the lower work function and higher heat of formation of
oxides (for Ni: 5.15 eV, 244 10-3 J/mol, for Pt: 5.65 eV, 56 10-3 J/mol, respectively).
Similar effects may be occurring here, and will be discussed in the leakage current
section of this chapter.
97
400
550 C
o
575 C
o
600 C
o
650 C
0.20
0.16
300
0.12
200
0.08
100
0.04
0 2
10
10
10
10
10
Loss tangent
550 C
o
575 C
o
600 C
o
650 C
500
0.00
7
10
Frequency (Hz)
Figure 4.18: Capacitance-frequency plots for PZT (52/48) thin film capacitors on
electroless Ni (with 8 % phosphorous) coated Cu foil crystallized between 550 and 650
o
Leakage current mechanisms have long been the research topics for the PZT
capacitors both in theoretical and practical perspective. Usually it is suggested that the
conduction mechanisms are divided into (1) interface controlled and (2) bulk controlled
mechanisms. At higher electric field, more than one mechanism usually governs the
conduction behavior and it becomes difficult to discern the dependence. Also Schottky
emission and Poole-Frenkel mechanism have same dependence on the electrical field and
it is necessary to study the temperature dependence to verify the dominant conduction
mechanism(s).
Interface controlled
Bulk controlled
Mechanism
J vs. E relationship
Schottky emission
ln (J) vs. E2
Tunnelling
Poole-Frenkel conduction
99
10
-2
J (A/cm )
10
-4
1x10
-6
10
550 C
o
575 C
o
600 C
o
650 C
-8
10
on 8 % phosphorous
-10
10
10
15
20
25
30
35
Voltage (V)
10
-2
1x10
-4
10
-6
J (A/cm )
10
10
550 C
o
575 C
o
600 C
o
650 C
-8
on 12~13 % phosphorous
-10
10
10
15
20
25
30
35
Voltage (V)
Figure 4.19: Leakage current densities of methanol based PZT (52/48) thin film
capacitors on electroless Ni coated Cu foil crystallized between 550 and 650 oC for 30
minutes under N2 atmosphere.
100
(1) In general, leakage current scales opposite to anneal temperature. This is most
likely due to film densification with temperature.
(2) Higher phosphorous content yields higher leakage currents. Most likely,
phosphorous is diffusing into the PZT thin film and promoting a defect equilibrium
deleterious to highly insulating behavior.
10
-2
on 8 % P
on 12~13 % P
-4
J (A/cm )
1x10
10
-6
10
-8
(B)
(A)
10
-10
10
Voltage (V)
100
Figure 4.20: Log (J) vs. Log (V) for PZT (52/48) thin film capacitors on electroless Ni
coated Cu foil crystallized at 650 oC for 30 minutes under N2 atmosphere (slope of B
region ~ 7.0).
101
For more information on the conduction mechanism(s) of PZT capacitors, log J vs.
log V plots for 650 oC-crystallized capacitors is shown in Figure 4.20. From the absence
of linear relationship between log (J) vs. V, Schottky emission and Poole-Frenkel are
excluded from our consideration.
For the space charge limited conduction (SCLC), ohmic conduction occurs in
insulating film as long as the film is quasi-neutral, i.e., as long as the bulk generated
current in the film exceeds the current due to injected free carriers from the electrode.
The I V dependence in the Ohmic region is given by:
I=
qnAV
d
(4.1)
where q is the electronic charge, d is the film thickness, n is the concentration of charge
carriers, is the mobility, and A is the area of the electrodes. The slope in the lower
voltage region is not unity (1), but is close to 3.
According to the SCLC theory, as the applied voltage is increased, a strong
injection of the charge carriers in the bulk of the film takes place. For stronger injection,
the insulator traps fill up and a space charge appears. The space charge effects are
observed when the injected free carrier density exceeds the volume generated free carrier
density. Injected electrons are trapped in an insulator and form the space charge.
V2
9
J = r e 3
8
d
(4.2)
where e and d are the electron mobility and film thickness, when a single discrete trap
level exists in the band gap. However, for the general traps with a trap energy distribution
of multiple levels, the J by SCLC is
102
Vn
J =C m
d
(4.3)
where C, n, and m are arbitrary constants. In particular, Rose has shown that n has values
larger than 3 when the energy distribution of the traps in the energy gap is continuous
[40]. Although the theoretical expectation and experimental plot do not exactly match,
the conduction mechanism observed here closely follows SCLC behavior.
However, it should be kept in mind that only J vs. E does not provide sufficient
interpretation on conduction mechanism(s). Usually the precise interpretation of leakage
current behavior requires further analysis such as J vs. temperature, J vs. time, and
preferably J vs. thickness behavior. Although these further investigations are beyond the
scope of this study, it would be worthwhile to investigate more precise mechanism(s).
Figure 4.21 shows the leakage current densities for PZT thin film capacitors on
electroless Ni coated Cu foil crystallized at 650 oC for 30 minutes under N2 atmosphere.
In addition to the importance of solution preparation processing, Figure 4.21(a) also
shows the importance of the selection parameters for foil substrates. Lower leakage
current densities were measured at higher electric fields for the capacitors on the smooth
foil. Capacitors on the relatively rough surface had higher leakage currents at high field.
The most likely source of higher leakage is increased thickness variations and more
substrate asperities. Figure 4.21 (b) is the leakage current for capacitor measured with
external field of DC 5V. DC 5V was set on the basis of the information that nominal
operation voltage of bypass capacitors in the cell phone is in the range of VDC 2 ~ 3 V.
Only decrease in leakage current was observed with time during measurement, which
might be related with relaxation. Steady-state region and resistance degradation (and/or
103
breakdown) region was not observed during measurement [41]. The leakage current
approaches the stable region and breakdown was not observed after 5000 sec.
-1
10
-3
1x10
-5
10
-7
-5
1x10
(a)
(b)
-6
10
J (A/cm )
J (A/cm )
10
10
-8
10
Rms 28 nm
Rms 12 nm
-9
-7
10
10
15
Voltage (V)
20
-9
25
10
10
10
10
10
Time (sec)
Figure 4.21: Leakage current densities with voltage (a) and time (b) for PZT (52/48) thin
film capacitors on electroless Ni coated Cu foil.
AFM surface images with contact mode were taken for the capacitors annealed at
different temperatures (Figure 4.22) to study the microstructure possibilities arising with
base metal substrates. Irrespective of the phosphorous content, individual grains were not
observed at 550 oC. Grain growth was obvious from ~ 575 oC and grains with 50 ~ 60 nm
sizes were developed at 650 oC. Unlike the general surface morphology usually found in
PZT films on Pt, better connectivity was observed between the adjacent grains and the
grain boundaries between individual grains were not clear. The surface roughness of the
104
PZT films increased with temperature and was in the range of 1.0 ~ 3.0 nm. In
comparison, the surface roughness of PZT films with identical composition on
Pt/Ti/SiO2/Si substrate was around 3.0 nm [42].
The electroless Ni foil substrate is expected to produce PZT thin films with
different nucleation characteristics and ultimately different grain morphology. For PZT
thin films on Pt, larger columnar grains are nearly always observed. In this case, we see
tiny equiaxial grains, as evidenced by TEM (Figure 4.16), suggesting a more
homogeneous nucleation process. From the characteristics of the nucleation and growth
process, films that display mostly columnar in nature are dominated by only interface
nucleation. On the while when nucleation occurs through the film, polycrystalline with
equiaxed grains are typically observed [43]. The grain size of PZT (52/48) thin films
prepared by methanol based chemical solution deposition on Pt/Ti/SiO2/Si was in the
range of 80 ~ 100 nm [42]. Smaller grain size observed for PZT thin films on electroless
Ni coated Cu foil might suggest the increase in the nucleation site density at higher
temperature. Al-Shareef reported the importance of surface roughness of underlying
electrode on final grains growth in CSD PZT thin films, suggesting rough surface of Pt
tend to have higher nucleation site density than smooth RuO2 surface [ 44 ]. The
electroless Ni coated Cu foil undergoes crystal growth once amorphous phase is
crystallized, as shown in previous AFM images. One possibility for microstructure in
PZT thin films on electroless Ni might be that changes in surface roughness of electroless
Ni during high temperature crystallization could result in changes in the nucleation site
density. In addition, smaller roughness was observed for PZT capacitors with 12 ~ 13 %
phosphorous. Although there are not relevant reports regarding the effect of phosphorous
105
in PZT, this result suggests that transport in PZT may be further affected by phosphorous
additions. In a few isolated cases, tiny particles were observed for 650 oC crystallized
capacitor surfaces. These impurity particles were not always observed, and it is not sure if
these affect electrical properties of PZT capacitors.
550 oC
600 oC
575 oC
8%
550 oC
8%
8%
575 oC
12%
650 oC
650 oC
600 oC
12%
8%
12%
12%
Figure 4.22: AFM images for methanol based PZT (52/48) thin film capacitors on
electroless Ni coated Cu foil (with 8 % and 12 ~ 13 % phosphorous) crystallized for 30
minutes under N2 atmosphere. All scans were performed over 1 1 m range.
106
with final film quality. Capacitors with different pyrolysis thermal histories were
prepared from 2-MOE based solution and resulting electrical properties were studied to
demonstrate the importance of the solution chemistry on the electrical properties of the
capacitors. C-V and J-V plots for the capacitors with different thermal histories are
shown in Figures 4.23 and 4.24, respectively. Optimization in pyrolysis processing is
directly related with both the amount of the organic materials used to stabilize starting
precursors in CSD processing and following crystallization. In this 2-MOE PZT thin
films preparation, the organic materials used were 2-MOE (b.p.= 124 ~ 125 oC) and
formamide (b.p. = 210 oC), all of which has relatively lower boiling points, compared to
other solvent / stabilizer system.
0.10
0.08
150
0.06
100
0.04
50
0
-6
Loss tangent
200
0.02
-4
-2
0.00
Voltage (V)
Figure 4.23: Capacitance-voltage plots for PZT (52/48) thin film capacitors on electroless
Ni with different pyrolysis histories. Crystallization was done at 650 oC for 30 minutes
under N2 atmosphere.
107
It is speculated that the lower capacitance densities and lower loss tangent for the
capacitors pyrolyzed at 450 oC for 5 minutes might be related with a less dense
microstructure, and incomplete crystallization. These factors occur if either the organic
material is removed to quickly (at any given step of the process) or if crystallization
occurs in the presence of significant residual carbon. The effect of pyrolysis condition
was clearer in the leakage current measurements. Only for the capacitors that underwent
separate drying and pyrolysis steps measured low leakage currents up to high external
voltages.
-1
10
450 C/5min
o
450 C/15min
o
o
250 C/5min + 450 C/15min
-3
J (A/cm )
10
-5
1x10
-7
10
-9
10
10
15
20
25
30
Voltage (V)
Figure 4.24: Effects of the pyrolysis condition on the leakage current of PZT (52/48) thin
film capacitors on electroless Ni. Crystallization was done at 650 oC for 30 minutes under
N2 atmosphere.
108
interfaces in Pb(Zr0.4Ti
0.6)O3
results suggest that the fatigue is due to pinning of domain walls by oxygen vacancies
and not due to the presence of the interface layer. They based this conclusion on
measurements of the weak-field dielectric constant as a function of DC bias electric field.
At low DC bias, the permittivity of fatigued films is lower than in unfatigued films which
they interpreted to be a consequence of domain-wall pinning in the fatigued films, and
loss of the domain-wall contribution to the permittivity. At high DC electric fields, they
found that the dielectric permittivity is nearly the same in fatigued and unfatigued
samples. This is not consistent with the presence of a low dielectric permittivity surface
layer in fatigued films which would decrease the weak-signal dielectric permittivity at all
DC bias fields. It has been further suggested that creation of an oxygen-vacancy-rich
109
region at the film/metal electrode interface may lead to the formation of an n-type layer
near the interface [46,49]. The presence of this layer increases the electron injection rate
in the film during field cycling. Injected electronic carriers may get trapped at the domain
walls leading to domain-wall pinning and polarization suppression.
Another possible role of the oxygen vacancies is to stabilize the trapping of
electronic charges (and therefore to increase domain-wall pinning) through distortion of
the oxygen octahedron which is caused by the presence of an oxygen vacancy [50]. The
idea that oxygen vacancies may play an important role in the fatiguing process is
supported by the fact that Pb(Zr,Ti)O3 films with conducting oxide electrodes instead of
metal ones do not fatigue under field cycling. It has been proposed that oxide electrodes
act as sinks for oxygen vacancies and prevent their accumulation at the film/electrode
interface [49]. A smaller concentration of oxygen vacancies at the interface would reduce
injection of electronic carriers into the film, which would consequently reduce pinning of
domain walls and fatigue. Warren et al. [51] reported that annealing of films in an
oxygen-poor atmosphere may lead to polarization suppression and changes in the
hysteresis loop. Original loops in films could not be restored by electronic charge
injection but could be restored by annealing in oxygen. According to Warren et al. this
mechanism of polarization suppression is attributed to the creation of oxygen vacancies
which serve as pinning centers for domain walls in partially reduced films. It is
interesting that a similar effect on the polarization loops was observed in single crystals
of barium titanate [52]. Given the clear impact of point defects on ferroelectric properties
and the existence of large defect concentrations in leaded perovskite, the effects of pO2
were investigated for foil-based capacitors.
110
4.4.6.2 pO2 dependent electrical properties in PZT (52/48) thin film capacitors on
electroless Ni coated Cu foils
Due to the oxidation of base metals at elevated temperature, capacitors with base
metal electrodes need to be annealed in the reducing atmosphere. Therefore it is
worthwhile to investigate the pO2 dependent properties of capacitors on the base metal
electrode to determine the processing margins for the mass production stage. To make an
initial assessment of these pO2 effects, final crystallization of the capacitors were done at
600 oC, varying pO2 from 10-7 to 102 torr range.
Figure 4.25 shows the X-ray diffraction plots for the PZT capacitors processed as
a function of pO2. All the capacitors show completely random orientation. Irrespective of
pO2, pure perovskite phases were observed. Preferred orientation was not observed.
Dielectric properties of the capacitors are shown in Figure 4.26. Capacitance density of ~
350 nF/cm2 was measured at 10-3 torr pO2. As the pO2 go down to 10-6 torr, capacitance
density dropped down to almost half of the value measured at 10-3 torr pO2, and abrupt
increase in loss tangent was observed, as reported by Kwok and Desu [53]. The dielectric
properties at higher pO2 regime (> 10-2 torr) did not show any clear trends, which need to
be reviewed further.
111
N(111)
#(141)
#(231)
C(111)
N(200)
#(200)
#(132)
(f)
P(111)/Pt(111)
#(031)
P(010/110)
Intensity (a.u.)
P : PZT
# : Ni3P
N : Ni
C : Cu
(e)
(d)
(c)
(b)
(a)
25
30
35
40
45
50
55
Figure 4.25: pO2 dependence of phase developments for PZT (52/48) thin film capacitors
400
0.20
300
0.15
200
0.10
100
0.05
-6
10
-4-4
1x100
010
-2
10
10
loss tangent
0 -8
10
0.00
2
10
pO2 (Torr)
Figure 4.26: pO2 dependence of dielectric properties for PZT (52/48) thin film capacitors
crystallized at 600 oC for 30 minutes.
112
-1
10
-7
7.5X10
-5
1.0X10
-4
1.0X10
-4
7.6X10
-1
4.7X10
10.0
-3
J (A/cm )
10
-5
1x10
-7
10
-9
10
10
15
20
25
30
35
Voltage (V)
Figure 4.27: pO2 dependence of J-V for PZT (52/48) thin film capacitors crystallized at
600 oC for 30 minutes.
7.610-7
1.010-5
1.010-4
7.610-4
4.710-1
10
Figure 4.28: AFM images for PZT (52/48) thin film capacitors crystallized at 600 oC for
30 minutes under different pO2 (torr). All scans were performed over 1 1 m range.
113
Leakage current densities of the capacitors crystallized under different pO2 are
shown in Figure 4.27. Capacitors crystallized under low pO2 had a higher leakage current
densities compared to other capacitors. The PbO evaporation at elevated temperature
might be accelerated and overall PZT composition deviates from the stoichiometry. Due
to the evaporation of Pb during the crystallization, capacitor annealed at low pO2 would
leave oxygen vacancy accumulated behind. Yang et al. [54] and Du et al. [55] suggested
injected electrons induce de-ionization of the oxygen vacancy through the reaction
VO + e VO . The lower valence of VO then makes it easier to migrate by reducing the
electrostatic disturbance around it. Therefore low pO2 processed capacitors might lead to
the additional conduction path through the thin film, which lead to higher leakage current.
Surface microstructures for the capacitors with pO2 are shown in Figure 4.28.
Relatively small sized grains were observed for the capacitor processed at low pO2
(7.610-7 torr). For other capacitors, comparatively large grains were observed. The grain
morphology found at lower pO2 reflected the contribution of non-perovskite phases
developed from off-stoichiometry composition of PZT [56].
114
suggested that the formation of Pb3Ti [57] compound could promote (111) orientation in
PZT thin films. They also concluded that (100) orientation was observed when top
surface of substrate is free from Ti. Chen et al. suggested that a (111) oriented Pt5-7Pb
intermetallic phase formed during pyrolysis step provide the template for the growth of
(111) PZT [58]. Bouregba et al. used seed layer of TiOX for the growth of both PZT
(111) and PZT (100) orientation by controlling the growth characteristics of the TiOX
layer [59]. Maeder and Muralt used a buffer layer of PbTiO3 (001) orientation in order to
grow PZT (001) orientation on Pt/SiO2 /Si wafers [60]. Finally, Dawley et al. achieved
highly oriented BST thin films on Ni tape by formation of transient BaF2 related liquid
phase using fluorine in trifluoroacetic acid (TFA) [61]. However, there is no systematic
study on the Pb based thin films on electroless Ni in terms of phase formation, interfacial
reactions and their effects on the electrical properties of the capacitors. Figures 4.29 and
4.30 show the phase development of PZT thin films on electroless Ni coated Cu foil.
Thickness of the capacitors was controlled by the number of spin coated layers. About
110 nm thick films were assumed to be on the foil for every spin. X-ray diffraction plots
were taken for capacitors that underwent spin, drying and pyrolysis for each layer. After
the pyrolysis step, a mixture of perovskite and pyrochlore phases was observed. The Ni3P
phase was observed for entire thickness series and did not appear to depend on the total
dielectric thickness. For 12 ~ 13 % phosphorous foil, the relative intensity of Ni3P phase
was stronger than that for 8 %.
115
20
25
30
35
#(141)
#(132)
N(200)
#(200)
N(111)
C(111)
#(231)
P(111)
#(031)
P(010/110)
Py
P(100)
Intensity (a.u.)
P : PZT
Py : Pyro
# : Ni3P
N : Ni
C : Cu
40
45
50
55
2
Figure 4.29: X-ray diffraction plots for thickness dependence in PZT (52/48) thin film
20
25
30
35
40
45
N(200)
#(200)
#(132)
N(111)
#(141)
#(231)
C(111)
#(031)
P(111)
Py
P(010/110)
P : PZT
Py : Pyro
# : Ni3P
N : Ni
C : Cu
P(100)
Intensity (a.u.)
50
55
Figure 4.30: X-ray diffraction plots for thickness dependence in PZT (52/48) thin film
capacitors on electroless Ni coated Cu foil (with 12 ~ 13 % phosphorous).
116
Mixed perovskite and pyrochlore phases transformed to the pure perovskite phase
only after high temperature annealing. Of the models for explaining the effect of interface
on the electrical properties of ferroelectric materials, Larsen et al. [62] suggested the
blocking layer model, where they postulated the existence of the non-ferroelectric (offstoichiometric) barrier layers. The blocking layer model was investigated on the basis of
Pb(Zr0.51Ti0.49)O3 thin films deposited on Pt/SiO2/Si by OMCVD. On the basis of the
capacitance vs. voltage measurements, they calculated the inverse capacitance (1/C) vs.
thickness (d).
In this study, it is expected that the film and interfacial layer form capacitor layers
in series, the measured dielectric constant be strongly influenced by the presence of the
low dielectric constant interfacial layer, possibly resulting from Ni-O-PZT chemical
reactions.
The relationship between reciprocal capacitance and thickness is represented as follows.
d
eff
db
di
1 1 d di
+ di
+
b
i b b i
db
C
A
di
(4.4)
(4.5)
where eff is the total permittivity, b the permittivity of bilk, i the permittivity of
interface layer, d total thickness, db the bulk thickness, di the interface thickness, A the
area of the capacitor. In Figure 4.31, it is shown that capacitance densities decrease as
thickness increase, as expected. Loss tangent was in the range between 0.01 ~ 0.025. To
separate the influence of bulk and interfacial layers on the measured dielectric constant of
the film, the inverse of capacity densities, (C/A)-1, for the PZT thin films was plotted as a
117
function of the thickness in Figure 4.32. In the Figure 4.32, non-zero intercepts on the
(C/A)-1 axis were observed. The positive non-zero intercepts and the assumption of a
series capacitor model suggest the existence of a low dielectric constant interfacial layer.
From equations 5.4 and 5.5, assuming b is much bigger than i, the permittivity of the
interfacial layer and bulk dielectric layer could be calculated from the intercept on the
(C/A)-1 axis and the slope of the plot, respectively. Assuming interface thickness of 50
nm, from the intercept, i, a permittivity for the interfacial layer of ~ 30 was calculated.
And from the slope, b, permittivity of bulk, of ~ 850 was calculated. When these
permittivities are reiterated into the equation (5.5), an overall permittivity of ~ 300 is
calculated, which is a reasonable agreement from the measured results.
0.15
600
Y = 506.804 - 194.312 X
2
(C/A) (nF/cm )
500
300
0.05
200
Loss tangent
0.10
400
100
0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.00
Thickness (m)
Figure 4.31: Thickness dependent dielectric properties of PZT (52/48) thin film
capacitors on electroless Ni coated Cu foil. Crystallization was done at 600 oC for 30
minutes under N2 atmosphere.
118
0.003
0.004
-1
0.002
0.001
Y = 0.0019 + 0.0012 X
0.000
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Thickness (m)
Figure 4.32: (C/A)-1 with thickness relationship of PZT (52/48) thin film capacitors in
Figure 4.31.
Figures 4.33 and 4.34 show the leakage current behavior of capacitors crystallized
at 600 oC with different film thickness. Generally as the film thickness increases, overall
leakage current decreased, as in Figure 4.35. However, at higher fields, capacitors
showed different conduction behavior with film thickness. From the measured data, it is
possible to think of the leakage currents to be composed of four different regions.
The A section is characterized by nearly identical or decreasing currents in the
low field region. This behavior may stem from relaxation. The B to D regions show
rather different behavior depending on the film thickness. For films with thickness close
to ~ 330 nm, when ln J is plotted with V, roughly linear relationships were found, which
might suggest the dominant conduction mechanism could be Schottky emission or PooleFrenkel (Figure 4.34). Temperature dependent current measurement is required to exactly
119
figure out the predominant conduction mechanism, and was beyond the scope of this
study. For the thicker films (thickness of more than ~ 770 nm), a temporary decrease in
leakage currents was observed with increasing voltage. Chen et al. reported temporary
decrease in the leakage current in CSD PZT thick film on platinized silicon substrate [63].
They suggested that this might be due to electron trapping, which generates a negative
space charge depletion region in front of the cathode. The formation of this depletion
region subsequently lowers the effective electric field at the cathode and reduces the
leakage current. With further increase in field, the carriers are freed from the trap centers,
and SCLC is observed. The similar trends found in our PZT capacitors might suggest that
increased number of defect traps inside PZT thin films, which might be reasonable in
terms of defect nature of PZT and other defect source originating from the interface
layers.
10
-2
J (A/cm )
10
330 nm
440 nm
550 nm
660 nm
770 nm
880 nm
990 nm
1100 nm
-4
1x10
-6
10
-8
10
-10
10
10
15
20
25
30
35
Voltage (V)
Figure 4.33: Thickness dependent leakage current densities with voltage for PZT (52/48)
thin film capacitors on electroless Ni coated Cu foil. Crystallization was done at 600 oC
for 30 minutes under N2 atmosphere.
120
-1
10
330 nm
440 nm
550 nm
660 nm
770 nm
-3
J (A/cm )
10
-5
1x10
-7
10
-9
10
1/2
(V)
Figure 4.34: Thickness dependent leakage current densities with V1/2 for PZT (52/48) thin
film capacitors on electroless Ni coated Cu foil. Crystallization was done at 600 oC for 30
minutes under N2 atmosphere.
-1
1x10
-3
J (A/cm )
1x10
-5
1x10
-7
1x10
-9
1x10
-11
10
0.2
0.4
0.6
0.8
1.0
1.2
Thickness (m)
Figure 4.35: Leakage current densities of PZT (52/48) thin film capacitors with thickness.
Data taken at 10 VDC in Figure 4.33.
121
Unlike other dielectric films on the oxide or noble metal electrode, the interface
reaction between PZT dielectric film and electroless Ni has been hardly touched by
researchers. In the previous study on PLZT thin films on electroless Ni, they analyzed the
interface with TEM-EDS and they suggested the interface composed of mostly reacted
PLZT and possibly poorly crystallized NiOX [36].
Another possibility is to consider the role of phosphorous in the thermal
processing. Celi et al. reported the reaction between PZT powder and a phosphate
ester at around 800 oC resulted in the following reaction [64].
Pb(Zr0.53Ti0.47)O3 + xP2O5 yPb3(PO4)2 + (x-y)Pb4(P2O9) +
(4.6)
Pb1-4x+y(Zr0.53-4x+yTi0.47)O3-12X+3y + (4x-y)(ZrO2)
122
permittivity) phase formation from phosphorous diffusion into the bulk of PZT thin film
capacitors, considering voltage independent, reduced permittivity capacitance densities.
As discussed in the following chapter, the PZT amorphous layer and the adjacent
phosphor is highly reactive, and it is difficult to completely rule out the possibility of
reaction between them during pyrolysis at lower temperature.
(a)
(b)
(c)
(d)
Figure 4.36: Schematics of reaction sequences for PZT (52/48) thin film capacitors on
electroless Ni coated Cu foil: (a) as deposited 1st layer, (b) 1st layer pyrolysis at 450 oC,
(c) multiple layer pyrolysis at 450 oC, and (d) After final annealing at 650 oC.
123
Several groups have proposed an equivalent circuit model to analyze the effect of
interface in ferroelectric ceramics and thin films [65, 66, 67] The properties of interface
films are usually different than those in the bulk region. A capacitor with interface layer
can be expressed using one of the following analogue equivalent circuits in Figure 4.37.
Ri
Rb
Ci
Cb
(a)
Ra
Ri
Rb
Ci
Cb
(b)
Figure 4.37: Equivalent circuit analogue for (a) capacitor with interface and (b) contact
resistance added capacitor with interface (Ri: interface resistance, Rb: bulk resistance, Ci:
interface capacitance, Cb: bulk capacitance)
The total impedance for each model can be expressed in the following equations.
Rb
Ri
+
1 + jC b Rb 1 + jC i Ri
(4.7)
Rb
Ri
+
+ Ra
1 + jC b R b 1 + jC i R i
(4.8)
Z total =
Ztotal =
The total capacitance for both models can be expressed in the following equation.
1
C measured
2C b R b 2
2C i R i 2
+
1 + 2C b 2R b 2 1 + 2C i 2R i 2
(4.9)
124
On the basis of the equations above, measured capacitance was plotted with
frequency and compared with calculation results based on both models in Figure 4.38.
The value of Rb was fitted using the capacitance-voltage data for PZT thin film capacitors
on foil and Pt/SiO2/Si. The procedures was then to calculate the possible range of
interface resistance values (Ri) that would be consistent with the measured capacitancefrequency data.
Figure 4.38 shows that higher Ri showed closer matching with measured data. In
other words, we deduce that the interface layer is insulating, not semiconducting or
conducting. Additional modification by adding resistance (Ra of 0.1 ~ 10 K) to the
interface-capacitor model (Figure 4.37 (b)) did not impact this calculation, as shown in
Figure 4.39.
-10
Capacitance (F)
8.0x10
-10
6.0x10
-10
4.0x10
measured
Ri : 1 ohm
3
Ri : 10 ohm
5
Ri : 10 ohm
7
Ri : 10 ohm
9
Ri : 10 ohm
Rb : 110K ohm
-10
2.0x10
0.0
2
3
4
5
6
7
8
9
10
10 10 10 10 10 10 10 10 10
Frequency (Hz)
Figure 4.38: Comparison between measured and calculated capacitances with frequency.
125
Capacitance (F)
1.0x10
-9
8.0x10
-10
6.0x10
-10
4.0x10
-10
2.0x10
-10
measured
Rb = 1 ohm
3
Rb = 10 ohm
5
Rb = 10 ohm
7
Rb = 10 ohm
8
Rb = 10 ohm
Ri : 1K ohm (Fixed)
0.0
2
3
4
5
6
7
8
9
10
11
10 10 10 10 10 10 10 10 10 10
Frequency (Hz)
Figure 4.39: Comparison between measured and calculated capacitances with frequency.
Calculations were performed with different Rb. (Fixed Ri ~ 103 )
126
127
emission was measured for thinner films, however, for thicker films, traps in the PZT
film seem to dominate, and conduction was more close to space charge limited.
Controlled pO2 crystallization results generally suggested that low pO2 was not
favorable in terms of electrical properties of PZT capacitors.
From the electrical properties of PZT capacitors on electroless Ni, it was found
that Pb-based high permittivity thin films had a potential to be used in embedded passive
application. In the next two chapters, property modulation by doping and reliability
improvement, which is crucial to the practical device operation, would be described.
128
4.7 References
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DaSalla, J. Mater. Res., 12 (2) 444 (1997).
[2] S. Hirano, T. Yugo, K. Kikuta, Y. Araki, M. Saito, and S. Ogasahara, J. Am. Ceram.
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[3] S. Chen and I. Chen, IMF Proc., August (1993)
[4] K. G. Brooks, I. M. Reaney, R. Klissurska, Y. Huang, L. Bursill, and N. Setter, J.
Mater. Res., 9 (10) 2540 (1994)
[5] K.-H. Hur, J.-J. Jeong, and D.N. Lee, J. Mater. Sci., 25, 2573 (1990).
[6] E. Larsson, Arkiv Kemi, 23, 335 (1965).
[7] J-H. Shim, H-J Chung, and D. N. Lee, J. Alloys and Compounds, 282, 175 (1999).
[8] K.J. Lee, P. Nash, and P. Nash (Ed.), Phase Diagrams of Binary Nickel Alloys, ASM,
Materials Park, OH, 1991, p. 235.
[9] R. J. Keyse and C. Hammond, Materials Science and Technology, 3, 963 (1987).
[10] A. Brenner and G. E. Riddell, J. Research Natl. Bur. Standards 37(No.1), 31-4,
(Research Paper No. 1725) (1946).
[11] N. M. Martyak, Chemistry of Materials, 6, 1667 (1994).
[12] P. S. Kumar and P. K. Nair, J. Mater. Proc. Tech., 56, 511 (1996).
129
130
[38] W. Liu, J. Ko, and W. Zhu, Materials Letters, 49, 122 (2001).
[39] J. G. Simmons, Handbook of Thin Film Technology, (Ed. L. I. Maissel and R. Glang,
McGraw Hill, New York, 1970).
[40] A. Rose, Phys. Rev., 97, 1538 (1955).
[41] X. Chen, A. I. Kingon, L. Mantese, and O. Auciello, K. Y. Hsieh, Integrated
Ferroelectrics, 3, 355 (1993).
[42] D. J. Kim, Ph. D. Thesis, North Carolina State University (2001).
[43] R. W. Schwartz, Chemistry of Materials, 9, 11, 2325 (1997).
[44] H. M. Al-Shareef, Ph. D. Thesis, North Carolina State University (1994).
[45] H. M. Duiker, P. D. Beale, J. F. Scott, C. A. Paz de Araujo, B. M. Melnick, J. D.
Cuchiaro, and L. D. McMillan, J. Appl. Phys., 68, 5783 (1990).
[46] J. F. Scott, C. A. Paz de Araujo, B. M. Melnick, L. D. McMillan, and R. Zuleeg, J.
Appl. Phys., 70, 382 (1991).
[47] I. K. Yoo and S. B. Desu, Phys. Status Solidi, A 133, 565 (1992).
[48] T. Mihara, H. Watanabe, and C. A. Paz de Araujo, Japan. J. Appl. Phys., 33, 5281
(1994).
[ 49 ] H. N. Al-Shareef, D. Dimos, W. L. Warren, and B. A. Tuttle, Integrated
Ferroelectrics, 15, 53 (1997).
132
[50] W. L. Warren, B. A. Tuttle, and D. Dimos, Appl. Phys. Lett., 67, 1426 (1995).
[51] W. L. Warren, D. Dimos, B. A. Tuttle, G. E. Pike, R. W. Schwartz, P. J. Clews, and
D. C. McIntyre, J. Appl. Phys., 77, 6695 (1995).
[52] J. R. Anderson, G. W. Brady, W. J. Merz, and J. P. Remeika, J. Appl. Phys., 26,
1387 (1955).
[53] C. K. Kwok and S. B. Desu, Mat. Res. Soc. Proc., 243, 393 (1992).
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[55] X. Du and I.-W. Chen, J. Appl. Phys., 83 (12) 7789 (1998).
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559 (1995).
[57] T. Tani, Z. Xu, and D. A. Payne, Mat. Res. Symp. Proc., 310, 269 (1993).
[58] S.-Y. Chen and I.-W. Chen, J. Am. Ceram. Soc., 77, 2332 (1994).
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133
134
CHAPTER 5
Ca-doped PZT (52/48) Thin Film Capacitors on Electroless Ni Coated
Cu Foil
5.1 Introduction
In recent years there is an increasing interest in lead titanate (PbTiO3), along with
compositional modifications at Pb and Ti sites by Ca, Sr, La, and Zr, respectively, due to
their potential applications such as infrared sensors, electro-optic devices, and
ferroelectric memories [1, 2, 3]. Of these dopants, use of Ca in perovskite ferroelectric
materials was mostly aimed at the enhancement of piezoelectric and pyroelectric
properties. It is known that small cations like Ca2+ could be used as an A-site dopant for
PbTiO3 composition to lower the Curie temperature (Tc), which is advantageous in
obtaining high pyroelectric coefficient p = dPs / dT [ 4 ]. Among these materials,
(Pb,Ca)TiO3 (PCT) has recently attracted much attention for use in pyroelectric devices
and ferroelectric memories, particularly as nonvolatile ferroelectric random access
memories (NVFRAMs) due to the promise of high speed, radiation hardness, high
remanent polarization, high dielectric constant, and low power consumption. Substitution
of Pb for Ca will introduce shrinkage of the lattice in the c-axis direction of the tetragonal
phase in the perovskite structure of PbTiO3.
Pure PbTiO3 has a large tetragonal distortion at room temperature, c/a ~ 1.064,
which will introduce a stress in the material upon the cooling through the phase transition,
producing cracking in the material [5]. One of the dopants such as Ca substitution
135
reduces the tetragonality (c/a), reducing the strain of pure PbTiO3 thin films and inhibits
cracking. Wang et al. [6] showed that sol-gel deposited PCT films exhibited a low
tetragonal distortion and hindered the grain growth in the microstructure, both by means
of the increase of the Ca content. Recent investigation of optical properties performed by
Tang et al. [7] has shown that crystalline Ca modified lead titanate (PbTiO3) thin films
with different Ca contents from 0 to 40 %, prepared by the sol-gel process, presented a
shift of the absorption edge toward a lower energy value, with the increase of Ca. Pontes
et al. [8] reported the increased room temperature dielectric constant of the thin films
with increasing Ca contents, and they explained this improvement in terms of transition
from tetragonal to pseudocubic phase that takes place near room temperature as a result
of the Ca substitution, and correspondingly the decrease of the Curie temperature (Tc).
An additional benefit of Ca is in its ability to act as an acceptor in many
perovskite lattices. The acceptor behavior is useful for minimizing electrical conductivity
by ionically compensating for charge carriers induced by oxygen deficiency (for instance,
resulting from low pO2 firing), Consequently it is of particular interest to this work where
a reduction-resultant composition is needed for compatibility with base metal foil
substrates. In addition, the Ca addition would lower Tc to near room temperature and
yield a dielectric with a manageable temperature coefficient of capacitance. Also, cheaper
materials cost for Ca source than other dopant would be attractive in terms of practical
application.
In this chapter, we prepared 5 and 10 mol % Ca-doped PZT (52/48) capacitors on
electroless Ni (with 8 % and 12 ~ 13 % phosphorous, respectively) coated Cu foil by
chemical solution deposition process, and resulting electrical properties and reliabilities
136
of the capacitors were discussed in terms of doping, microstructure and interface reaction.
Capacitors with identical compositions (5 and 10 mol % Ca-doped PZT) were prepared
on Pt/SiO2/Si substrate to make a comparative study with those on electroless Ni coated
Cu foil.
occurring at the film-substrate interface. Grain growth from these nuclei proceeds toward
the surface of the film through the consumption of an intermediate fluorite (or
pyrochlore) phase. Speck et al. have shown that for perovskite materials that transform
via an intermediate metastable phase, for example, PZT via a fluorite phase, the
crystallization driving force is reduced by the formation of this metastable phase,
resulting in films that display only heterogeneous nucleation at the film-substrate
PZT(200)
Pt(111)
PZT(111)
PZT(101)
Intensity (a.u.)
PZT(100)
interface [11].
Ca 10%
Ca 7.5%
Ca 5%
Ca 2.5%
Ca 0%
20
25
30
35
40
45
50
55
Figure 5.1: X-ray diffraction for Ca-doped PZT thin films on Pt/SiO2/Si crystallized at
700 oC for 15 minutes under O2 atmosphere.
On the while, BaTiO3 thin films are typically polycrystalline in nature, and shows
random orientation [12]. This suggests that homogeneous nucleation within the bulk of
the film has occurred in addition to nucleation at the interface. It is not clear at this point,
138
however, one possibility for the random orientation observed for high Ca doping (10
mol %) might be from homogeneous nucleation, as similar to BaTiO3 thin films.
Figure 5.2 shows the lattice parameter changes in Ca-doped PZT (52/48)
composition crystallized at 700 oC for 15 minutes. The a-axis lattice parameters were
calculated from (100) and (200) peaks and c - axis lattice parameters were calculated
from (111) and (211) peaks. According to the calculation, an a-axis lattice for undoped
PZT (52/48) thin film is ~ 4.07 and c-axis lattice is ~ 4.09 , which is close to the
values (a = 4.055 , c = 4.07 ) obtained from Klee et al.[13]
4.20
1.010
4.15
1.005
4.10
1.000
4.05
0.995
c/a ratio
c/a
a-axis
c-axis
4.00
Ca doping (mol%)
10
0.990
Figure 5.2: Lattice parameter variations for Ca-doped PZT thin films on Pt/SiO2/Si
crystallized at 700 oC for 15 minutes under O2 atmosphere.
As the Ca doping increases, a-axis and c-axis lattice decreased, and tetragonality
ratio (c/a) also converged to unity. The reduced lattice parameter and cell volume with Ca
addition might be explained on the basis of the differences in the ionic radii. Ionic radii of
139
Pb2+ and Ca2+ are 1.18 and 0.99 , respectively. When the site occupancy is primarily
preferred for smaller sized, same valency ion, it would be reasonable to think that Ca2+
ion would initially substitute for A-site Pb ion, considering the B-site ionic radii (Zr 4+ ~
0.86 , Ti4+ ~ 0.60 ).
For additional information on the Ca doping on PZT thin films, AFM images
taken for the surface microstructures of PZT thin films with different amount of Ca
doping are shown in Figure 5.3. Average surface roughness variations with Ca doping are
shown in Figure 5.4. Surface roughness did not change significantly up to 7.5 mol %, but,
increased rather abruptly for 10 mol % Ca doping. From the surface roughness trend, the
increased amount of Ca, in the form of the CaTiO3 might have adversely contributed to
the homogeneity and densification behavior of the thin film. Therefore, it is probable
grain growth for 10 mol % Ca doping might have affected the orientation.
140
(b) Ca 5 %
(a) Ca 2.5 %
(d) Ca 10 %
(c) Ca 7.5 %
Figure 5.3: AFM images for Ca-doped PZT thin films on Pt/SiO2/Si crystallized at 700
o
C for 15 minutes under O2 atmosphere. All scans were performed over 2 2 m range.
RMS (nm)
4
3
2
1
0
2.5
5.0
7.5
10.0
Ca doping (%)
Figure 5.4: Surface roughness changes with Ca doping in PZT (52/48) thin films on
Pt/SiO2/Si crystallized at 700 oC for 15 minutes under O2 atmosphere.
141
142
and strong acceptor doping, thus domain and strongly aged properties. Microstructural
and phase development effects may also be influential factors.
It has been suggested in (Pb,Ca)TiO3 thin films that Ca goes into A-site, resulting
the reduced c/a ratio with Ca doping. This is comparatively small amount when compared
with (Pb,Ca)TiO3 thin films, where the amount of Ca doping for ferroelectric-paraelectric
transition was suggested to be around 40 mol % [8].
Polarization (C/cm )
60
40
20
Ca 0%
Ca 2.5%
Ca 5.0%
Ca 7.5%
Ca 10 %
0
-20
-40
-60
-10
-5
Voltage (V)
10
Figure 5.5: P-E hysteresis of Ca-doped PZT thin films on Pt/SiO2/Si crystallized at 700
o
143
Dielectric constant
1200
1000
0%
2.5 %
5.0 %
7.5 %
10.0 %
800
600
400
200
0
-6
-4
-2
Voltage (V)
Figure 5.6: Voltage dependence of dielectric constant of Ca-doped PZT thin films on
Pt/SiO2/Si crystallized at 700 oC for 15 minutes under O2 atmosphere.
0%
2.5 %
5.0 %
7.5 %
10.0 %
Loss tangent
0.06
0.04
0.02
0.00
-6
-4
-2
Voltage (V)
Figure 5.7: Voltage dependence of loss tangent of Ca-doped PZT thin films on Pt/SiO2/Si
crystallized at 700 oC for 15 minutes under O2 atmosphere.
144
0.25
800
0.20
600
0.15
0%
2.5 %
5%
7.5 %
10 %
400
0.10
200
0 2
10
Loss tangent
Dielectric constant
1000
0.05
10
10
10
Frequency (Hz)
0.00
6
10
Of the limited reports on Ca-doped PZT systems, Cerqueira et al. [14] reported
the enhancement of the dielectric and piezoelectric properties in the bulk PZT ceramics
(52/48) composition with CaO doping. Maximum Ca doping amount was 1.5 mol %, and
they suggested through the Ab-initio purtubated ion calculation that the addition of CaO
decreased lattice energy for both tetragonal and rhombohedral phases. Another research
group in Ramtron studied the effect of Ca-doped PZT thin films prepared by RFmagnetron sputtering for potential application in ferroelectric memory [ 15 ]. They
observed larger grain size (0.5 ~ 1.5 m), longer ferroelectric switching time (> 700 ns)
and more square hysteresis with Ca-doped PZT thin films, however they did not clearly
explain the results in terms of the relations between Ca doping effect and corresponding
electrical properties and microstructures. The effect of Ca doping on the ferroelectric
145
properties might be closely associated with the changes in lattice parameter. Ca addition
leads to the reduced a and c axis lattice parameter thus the c/a ratio would approach unity,
which would change the unit cell from tetragonal to pseudo-cubic. Consequently, a
slanted hysteresis loop would be expected, but this is clearly not observed in the literature.
Our results suggest that B-site occupancy and strong acceptor behavior is a more likely
possibility to explain these effects.
146
Table 5.1: X-ray diffraction information for representative compounds including Ca, Zr,
Ti.
CaZrO3 (# 20-0254)
CaTiO3 (# 39-01450)
Ca2Zr5Ti2O16 (# 15-0121)
30.972 (100)
29.807 (100)
54.937 (40)
25.849 (40)
35.137 (60)
49.757 (25)
147
#(200)
#(132)
N(200)
#(141) N(111)
#(231)
C(111)
#(031)
650 C
P(111)
P(010/110)
P(100)
600 C
o
575 C
550 C
Py
Intensity (a.u.)
P : PCZT
Py : Pyro
# : Ni3P
N : Ni
C : Cu
25
30
20
35
40
45
50
55
Figure 5.9: X-ray plot for the 5 mol % Ca-doped PZT thin films on electroless Ni coated
N(200)
#(200)
#(132)
#(231)
C(111)
N(111)
#(141)
P(111)
650 C
#(031)
P(010/110)
P : PCZT
Py : Pyro
# : Ni3P
N : Ni
C : Cu
P(100)
575 C
550 C
25
30
20
Py
600 C
Py
Intensity (a.u.)
35
40
45
50
55
Figure 5.10: X-ray plot for the 5 mol % Ca-doped PZT thin films on electroless Ni coated
Cu foil (with 12 ~ 13 % phosphorous) crystallized under N2 atmosphere for 30 minutes.
148
N(200)
#(200)
#(132)
#(141)
#(231)
C(111)
N(111)
650 C
#(031)
P(111)
P(010/110)
P(100)
Intensity (a.u.)
P : PCZT
Py : Pyro
# : Ni3P
N : Ni
C : Cu
Py
Py
600 C
575 C
550 C
20
25
30
35
40
45
50
55
Figure 5.11: X-ray plot for the 10 mol % Ca-doped PZT thin films on electroless Ni
Py
Py
550 C
25
30
600 C
575 C
20
35
40
45
N(200)
#(200)
#(132)
#(231)
C(111)
N(111)
#(141)
P(010/110)
650 C
Py
P(100)
Intensity (a.u.)
P : PCZT
Py : Pyro
# : Ni3P
N : Ni
C : Cu
#(031)
P(111)
50
55
Figure 5.12: X-ray plot for the 10 mol % Ca-doped PZT thin films on electroless Ni
coated Cu foil (with 12 ~ 13 % phosphorous) crystallized under N2 atmosphere for 30
minutes.
149
150
expect higher loss tangent levels from the inhomogeneous phase assemblage and the
potential for associated microstructural defects.
Capacitance-voltage plot for these capacitor are shown in Figures 5.15 and 5.16,
respectively. Capacitance-voltage measurement is very useful in characterizing the basic
properties of ferroelectric thin films. The measurement is made by applying
simultaneously on a sample a DC field that changes as a step-like function and an AC
oscillator voltage of comparatively high frequency (1 KHz or above) and small amplitude.
0.25
500
0.20
0.15
300
0.10
200
0.05
100
0 2
10
10
10
10
10
0.25
o
550 C
o
575 C
o
600 C
o
650 C
0.00
7
10
Frequency (Hz)
500
400
0.15
300
0.10
200
0.05
100
0 2
10
(b)
0.20
Loss tangent
400
600
2
(a)
550 C
o
575 C
o
600 C
o
650 C
Loss tangent
600
10
10
10
10
0.00
7
10
Frequency (Hz)
Figure 5.13: Capacitance-frequency plot for 5 mol % Ca-doped PZT thin films on
electroless Ni coated Cu foil crystallized under N2 atmosphere for 30 minutes: (a) with
8 % phosphorous, (b) with 12 ~ 13 % phosphorous.
151
0.30
0.20
300
0.15
200
0.10
100
0.05
0 2
10
10
10
10
10
0.00
7
10
500
400
0.25
0.20
300
0.15
200
0.10
100
0.05
0 2
10
10
(b)
10
10
10
Loss tangent
400
0.30
o
550 C
o
575 C
o
600 C
o
650 C
500
600
(a)
0.25
550 C
o
575 C
o
600 C
o
650 C
Loss tangent
600
0.00
7
10
Frequency (Hz)
Frequency (Hz)
Figure 5.14: Capacitance-frequency plot for 10 mol % Ca-doped PZT thin films on
electroless Ni coated Cu foil crystallized under N2 atmosphere for 30 minutes: (a) with
8 % phosphorous, (b) with 12 ~ 13 % phosphorous.
400
0.20
0.15
200
0.10
100
0.05
0
-6
-4
-2
0.00
6
500
0.25
o
550 C
o
575 C
o
600 C
o
650 C
400
300
0.20
0.15
200
0.10
100
0.05
0
-6
Voltage (V)
-4
-2
(b)
Loss tangent
300
(a)
0.25
500
Loss tangent
550 C
o
575 C
o
600 C
o
650 C
0.00
6
Voltage (V)
Figure 5.15: Capacitance-voltage plot for 5 mol % Ca-doped PZT thin films on
electroless Ni coated Cu foil crystallized under N2 atmosphere for 30 minutes: (a) with
8 % and (b) with 12 ~ 13 % phosphorous, respectively.
152
0.15
200
0.10
100
0.05
0
-6
-4
-2
0.00
500
0.25
550 C
o
575 C
o
600 C
o
650 C
400
0.20
300
0.15
200
0.10
100
0.05
0
-6
Voltage (V)
-4
-2
(b)
Loss tangent
300
(a)
0.20
400
0.25
550 C
o
575 C
o
600 C
o
650 C
Loss tangent
500
0.00
Voltage (V)
Figure 5.16: Capacitance-voltage plot for 10 mol % Ca-doped PZT thin films on
electroless Ni coated Cu foil crystallized under N2 atmosphere for 30 minutes: (a) with
8 % and (b) with 12 ~ 13 % phosphorous, respectively.
discrete jumps in permittivity at Ec. In real materials, this sharp shape is not observed
due to the physical and chemical inhomogeneities which smear coercive field over a
distribution of intensities.
The absence of butterfly shape for all the capacitors measured, along with lower
capacitance density and lower loss tangent, as already shown in undoped PZT thin films
on electroless Ni appears to originate from a low permittivity layer, and possibly from
phosphorous diffusing into the PZT. It seems that the Ca addition does not drastically
change the shape of capacitance and loss tangent, and it is speculated that the effect on CV behavior of the interfacial reaction predominates over other parameters like Ca doping.
For this purpose, the effect of another well-known donor dopant, La, was
separately investigated. 10 mol % of La-doped PZT (PLZT, 10/52/48) solution was
prepared by methanol based sol-gel process, and thin films were spin-coated by chemical
solution deposition on both Pt/SiO2/Si and electroless Ni (with 8% phosphorous),
respectively. Films were crystallized at 600 oC for 30 minutes in air and N2 flow,
respectively. In Figure 5.17, capacitance-voltage plots for PLZT thin films on both
Pt/SiO2/Si and electroless Ni (with 8 % phosphorous) are shown. When the substrate was
changed from Pt/SiO2/Si to electroless Ni coated Cu foil, peak dielectric constant of more
than 1000 drastically dropped to around 220. At the same time, tunability of more than
50 % reduced to almost 0 %. This would be another example that the specific dopant
effects would not be a critical parameter on electroless Ni coated Cu foil system.
In Figures 5.18 and 5.19, capacitance density and loss tangent of the capacitors
are shown with Ca doping level and crystallization temperature for a foil with different
phosphorous content. Regardless of phosphorous content, overall tendency showed the
154
peak of capacitance and loss tangent at 575 ~ 600 oC. At higher temperature, regardless
of the amount of Ca doping and phosphorous content, both capacitance and loss tangent
went down to ~ 200 nF/cm2 and ~ 0.01 respectively. The highest capacitance densities
observed at around 575 oC might be associated with the compromise between the
crystallization of perovskite phase and an interface reaction that dilutes the ferroelectric
properties. As suggested in the previous chapter, a likely parameters resulting in a
decrease in dielectric properties relates to phosphorous diffused into the capacitors. For
10 mol % Ca-doped PZT composition, lower capacitance densities than undoped, 5
mol % Ca-doped PZT, were measured for all temperature regime supporting this
conclusion. Actually, capacitance densities did not vary much (on 8 % phosphorous) or
gradually increased (on 12 ~ 13 % phosphorous) with crystallization temperature, which
is qualitatively in agreement with X-ray diffraction plot for same samples.
In our study Ca was chosen not only for technical reasons, but for intellectual
property reasons. A Ca-modified composition is much easier to protect legally than Lamodified compositions which are much more common. In addition, La sources,
specifically, alkoxide source, are more expensive than Ca source. Given those factors and
the goal of technology commercialization, Ca was chosen as the favored composition.
155
on Pt/SiO2/Si
on e-Ni/Cu
0.25
1200
0.20
900
0.15
600
0.10
300
0.05
0
-6
-4
-2
Loss tangent
Dielectric constant
1500
0.00
Voltage (V)
Figure 5.17: Substrate effect on the dielectric properties of PLZT (10/52/48) thin films
0.25
500
Ca 0%
Ca 5%
Ca 10%
400
0.20
300
0.15
200
0.10
100
0.05
550
575
600
625
650
Loss tangent
0.00
Crystallization temperature ( C)
Figure 5.18: Dielectric properties of Ca-doped PZT thin films on electroless Ni (with 8 %
phosphorous) coated Cu foil.
156
Ca 0%
Ca 5%
Ca 10%
400
0.20
300
0.15
200
0.10
100
0.05
550
575
600
625
650
Loss tangent
0.25
500
0.00
Crystallization temperature ( C)
Figure 5.19: Dielectric properties of Ca-doped PZT thin films on electroless Ni (with 12
~ 13 % phosphorous) coated Cu foil.
Leakage current densities in PZT thin films could be correlated with various
parameters such as doping [16], oxide electrode [17], and pyrochlore phase formation
[18] etc. Figures 5.20 and 5.21 show the leakage current densities for the Ca-doped PZT
capacitors crystallized at different temperatures. Only for the capacitors crystallized at
650 oC, lower leakage current densities were measured. For the capacitors crystallized at
600 oC or below, higher leakage currents were measured even at below 10 VDC.
Another observation in Figures 5.20 and 5.21 is phosphorous level affects the
leakage current densities of the capacitors on electroless Ni coated Cu foil. Capacitors on
high phosphorous level (12 ~ 13 %) showed higher current densities, compared to those
on low phosphorous (8 %) foil for identical doping and processing conditions, which
suggests the phosphorous affects electrical properties of capacitors.
157
1x10
-4
10
-6
o
10
10
10
(a)
PZT(52/48)
on 8% P Ni/Cu
10
-2
J (A/cm )
550 C
o
575 C
o
600 C
o
650 C
-8
10
1x10
-4
10
-6
10
-8
30min
30min
30min
30min
-10
10
15
20
25
-2
J (A/cm )
10
10
30
550 C
o
575 C
o
600 C
o
650 C
30min
30min
30min
30min
-10
10
Voltage (V)
10
10
Voltage (V)
10
(c)
PCZT(5/52/48)
on 8% P Ni/Cu
-2
10
-2
1x10
-4
-6
10
10
-6
10
-8
J (A/cm )
J (A/cm )
1x10
10
10
550 C
o
575 C
o
600 C
o
650 C
-8
-10
10
15
20
30min
30min
30min
30min
25
10
30
550 C
o
575 C
o
600 C
o
650 C
30min
30min
30min
30min
-10
10
Voltage (V)
Voltage (V)
10
-6
10
10
550 C
o
575 C
o
600 C
o
650 C
-8
-10
10
15
20
Voltage (V)
30min
30min
30min
30min
25
30
(f)
PCZT(10/52/48)
on 8% P Ni/Cu
10
10
-2
1x10
-4
10
-6
10
-8
J (A/cm )
1x10
-4
J (A/cm )
-2
10
(e)
PCZT(10/52/48)
on 8% P Ni/Cu
10
(d)
PCZT(5/52/48)
on 8% P Ni/Cu
o
-4
(b)
PZT(52/48)
on 8% P Ni/Cu
10
550 C
o
575 C
o
600 C
o
650 C
30min
30min
30min
30min
-10
10
Voltage (V)
Figure 5.20: Leakage current densities for Ca-doped PZT thin film capacitors on
electroless Ni coated Cu foil (with 8 % phosphorous): (a), (b) undoped, (c), (d) 5 mol %,
and (e), (f) 10 mol %.
158
1x10
-4
10
-6
o
10
10
10
(a)
PZT(52/48)
on 12~13% P Ni/Cu
10
-2
J (A/cm )
550 C
o
575 C
o
600 C
o
650 C
-8
10
1x10
-4
10
-6
10
-8
30min
30min
30min
30min
-10
10
15
20
25
-2
J (A/cm )
10
10
30
550 C
o
575 C
o
600 C
o
650 C
10
-4
10
-6
1x10
10
10
10
(c)
PCZT(5/52/48)
on 12~13% P Ni/Cu
550 C
o
575 C
o
600 C
o
650 C
-8
-10
10
15
20
10
1x10
-4
10
-6
10
-8
30min
30min
30min
30min
25
10
30
-2
J (A/cm )
10
J (A/cm )
Voltage (V)
-2
550 C
o
575 C
o
600 C
o
650 C
10
10
-6
o
10
10
10
(e)
PCZT(10/52/48)
on 12~13% P Ni/Cu
-4
Voltage (V)
550 C
o
575 C
o
600 C
o
650 C
-8
-10
10
15
20
Voltage (V)
30min
30min
30min
30min
25
30
10
-2
1x10
-4
10
-6
10
-8
J (A/cm )
1x10
J (A/cm )
-2
30min
30min
30min
30min
-10
10
(d)
PCZT(5/52/48)
on 12~13% P Ni/Cu
Voltage (V)
10
30min
30min
30min
30min
-10
Voltage (V)
10
(b)
PZT(52/48)
on 12~13% P Ni/Cu
10
(f)
PCZT(10/52/48)
on 12~13% P Ni/Cu
o
550 C 30min
o
575 C 30min
o
600 C 30min
o
650 C 30min
-10
10
Voltage (V)
Figure 5.21: Leakage current densities for Ca-doped PZT thin film capacitors on
electroless Ni coated Cu foil (with 12 ~ 13 % phosphorous): (a), (b) undoped, (c), (d) 5
mol %, and (e), (f) 10 mol %.
159
5.3.3 Microstructure
In case of the PZT thin films, surface morphologies are affected by many
processing parameters such as the deposition method, the starting precursor (for CSD
process), annealing conditions [19], and growth surface [20, 21]. In this section we
address these issues and the effect that they impart on Ca-doped PZT thin films prepared
on electroless Ni growth surfaces. The initial step in this process was to evaluate
microstructure. Figures 5.22 and 5.23 show AFM images for PZT thin films with 5 and
10 mol % Ca doping as a function of final crystallization temperature. For capacitors on
8 % phosphorous Ni, no significant grain growth was observed at 550 oC. An initial
morphology was observed at 575 oC with surface features between 200 and 300 nm in
lateral dimension.
Surface microstructure was relatively porous up to 575 oC. Microstructural
densification began from 600 oC. Crystallization at higher temperature reduced the
surface feature sizes, and grains with ~ 100 nm dimensions were observed after 650 oC
crystallization anneal. As suggested in chapter 4, it is expected that electroless Ni could
affect nucleation and growth of PZT thin films in a different way. The reduced grain size
with crystallization temperature found in Ca-doped PZT thin film is opposite to undoped
PZT thin films on electroless Ni where grain growth is observed with crystallization
temperature. It is not clear at this moment, however one possibility for grain growth
observed for Ca-doped PZT thin films compared to undoped composition might be from
the transient phases containing Ca.
160
550 oC
600 oC
575 oC
5%
10%
5%
5%
5%
600 oC
575 oC
550 oC
650 oC
10%
650 oC
10%
10%
Figure 5.22: AFM images for Ca-doped PZT thin film capacitors on electroless Ni coated
Cu foil (with 8 % phosphorous) crystallized for 30 minutes under N2. All scans were
performed over 1 1 m range.
600 oC
575 oC
550 oC
5%
10%
600 oC
10%
5%
5%
5%
575 oC
550 oC
650 oC
650 oC
10%
10%
Figure 5.23: AFM images for Ca-doped PZT thin film capacitors on electroless Ni coated
Cu foil (with 12 ~ 13 % phosphorous) crystallized for 30 minute under N2. All scans were
performed over 1 1 m range.
161
162
0.20
(a)
0.15
300
200
0.10
0.7 m
0.8 m
0.9 m
1.0 m
1.1 m
100
0
2
10
10
Loss tangent
400
0.05
10
10
10
0.00
7
10
Frequency (Hz)
0.20
(b)
300
0.15
200
0.10
100
0.05
0
0.6
0.7
0.8
0.9
1.0
1.1
Loss tangent
400
0.00
1.2
Figure 5.24: Dielectric properties of 5 mol % Ca-doped PZT thin film capacitors on
electroless Ni coated Cu foil (with 8 % phosphorous) crystallized at 600 oC under N2
atmosphere: (a) capacitance-frequency plot and (b) data measured at 10 kHz for each plot.
163
(a)
~ 0.7 m
~ 0.8 m
~ 0.9 m
~ 1.0 m
~ 1.1 m
300
0.20
0.15
200
0.10
100
0.05
0
2
10
10
10
10
Loss tangent
400
0.00
7
10
10
Frequency (Hz)
0.20
(b)
300
0.15
200
0.10
100
0.05
0
0.6
0.7
0.8
0.9
1.0
1.1
Loss tangent
400
0.00
1.2
Figure 5.25: Dielectric properties of 5 mol % Ca-doped PZT thin film capacitors on
electroless Ni coated Cu foil (with 8 % phosphorous) crystallized at 650 oC under N2
atmosphere: (a) capacitance-frequency plot and (b) data measured at 10 kHz at each plot.
164
165
X7R
Z5U
Y5V
Capacitance
tolerance (%)
10
20
-20, +80
Temperature
coefficient
30 ppm/oC
(-55 ~ 125 oC)
Operating
temperature range
-55 ~ 125 oC
15 %
+22, -56 %
o
(-55 ~ 125 C) (-55 ~ 125 oC)
-55 ~ 125 oC
-25 ~ 85 oC
+ 22, -82 %
(-30 ~ 125 oC)
-25 ~ 85 oC
166
maximum peak would be found around room temperature, and the discrepancy might be
caused by incomplete incorporation of La into the perovskite lattice, resulting from the
partial inhomogeniety during precursor solution preparation.
In general, the Ca doping will reduce the ferroelectric distortion, and a reduction
in both the maximum permittivity and the transition temperature are expected. This,
coupled with the diffuse nature of thin film ferroelectrics, supplies the desired reduced
temperature dependence needed for capacitor application. Furthermore, the likelihood of
non-uniform Ca incorporation raises the possibility of core-shell behavior which further
smears the dielectric anomaly.
Figure 5.27 is the variation of loss tangent with temperature. The capacitors were
crystallized at 650 oC for 30 minutes under N2 flow. Undoped PZT composition had
higher loss tangent compared to Ca and La-doped composition. Capacitors annealed
under reducing atmosphere undergo the loss of oxygen and lead and the concentration of
both vacancies increase. This results in higher loss for undoped composition. For Ladoped PZT, the addition of La ion into A-site compensate for a lead vacancy and helps to
minimize oxygen loss and minimize conductivity and loss tangent. The effect of Ca
doping on PZT under reducing atmosphere is not clearly known. It is speculated that Ca
ion might substitute for B-site Ti/Zr ions. In this case, Ca may act as a strong acceptor
and couple with vacant oxygen to form a very hard and low loss material.
167
20
15
0% Ca
10
10% Ca
5% Ca
5
15% La
0
-5
300
350
400
450
500
550
600
Temperature (K)
Figure 5.26: Temperature Coefficient of Capacitance (TCC) of undoped, Ca, and Ladoped PZT thin film capacitors on electroless Ni coated Cu foil. Crystallization was done
at 650 oC for 30 minutes in N2 atmosphere.
Loss tangent
10
-1
10
0% Ca
-2
10
5.0% Ca
15.0% La
10.0% Ca
-3
10
300
350
400
450
500
550
600
Temperature (K)
Figure 5.27: Temperature dependence of loss tangent in undoped, Ca, and La-doped PZT
thin film capacitors on electroless Ni coated Cu foil. Crystallization was done at 650 oC
for 30 minutes in N2 atmosphere.
168
169
170
higher pO2 values, the amount of Pb loss was significantly reduced. This nonstoichiometry could result in retarded or incomplete perovskite formation.
One of the studies on the instability of Ca compound was performed by Xu et al
[30]. They investigated the phase development in Ca(ZrXTi1-X)O3 system from solidreaction and sol-gel route using high temperature XRD and EXAFS. In their study, they
found the phase formation in Ca(ZrXTi1-X)O3 depend on the route used. Moreover, they
reported that the Ca(ZrXTi1-X)O3 (x = 0 ~ 1.0) xerogel from homogeneous sol-gel route
still have unreacted CaO, along with fluorite and perovskite phase after 600 oC annealing,
and they suggested that the Ca ion is unlikely incorporated into the polymer structure into
the backbone of the network. As such, the possibility that Ca incorporation influenced
phase formation in high pO2 conditions where transport would be slower cannot be
completely discounted.
The formation mechanism of non-perovskite phase in this study is not clear at this
moment. However, from the phase instability of Ca containing phase, one possibility
might be the mixed effects of both facilitated pyrochlore phase formation in high and low
O2, which were also observed in PZT system [31, 32] and other competing oxidation of
underlying Ni based electrode.
It is known that the phase purity and orientation is closely related with
ferroelectric / dielectric properties in PZT thin films. Several groups tried to quantify the
orientation of PZT thin films by using X-ray diffraction to correlate the orientation of thin
films and their ferroelectric properties [ 33 , 34 , 35 ]. Brooks et al. [34] calculated
orientation of PZT thin films using relative intensity ratio among I(100), I(110), I(111).
171
In the study by Chen et al. [35], intensities from each peak were normalized by the
corresponding intensities obtained for randomly oriented powder samples as follows.
(5.1)
where I represents the intensity of a particular reflection for the film, I* its
counterpart for the powdered sample. In this way, the influence of the different scattering
functions of different reflections is removed from the texture presented.
Generally, normalized peak intensities for PZT thin films do not quantitatively
represent the volume fraction. This results from the nearly unavoidable observation of
oriented textures in PZT thin films. This results primarily from predominant interface
nucleation, and epitaxial relationships to the underlying substrates. Fox presented a
method for calculating the volume fraction of <100>, <111> and randomly oriented
crystallites composing a PZT thin films [33]. Diffracted intensities were corrected using
absorption factor, and intensities due to oriented crystallites were calculated after the
corrections for geometrical differences in the diffraction probabilities of a textured and
randomly oriented films.
Ca-doped PZT films in our study have completely random orientation, and
therefore does not require the Lorentz and multiplicity correction. Also, the diffracted
intensity modification by absorption factor correction is not necessary. Therefore it might
be reasonable to assume that the intensities of perovskite phase directly reflect the
volume fraction of perovskite phase in X-ray diffraction plot. Volume of perovskite
phase was quantitatively calculated using the following relation and the results are shown
in Figures 5.30 and 5.31, respectively.
172
20
Py
Py
(g)
Py
(f)
(e)
(d)
(c)
Py
(b)
Py
(a)
Py
25
30
40
#(141) N(111)
Pt (111)
#(231)
C(111)
P(111)
35
45
N(200)
#(200)
#(132)
(j)
(i)
(h)
#(031)
P(010/110)
Intensity (a.u.)
P(100)
P : PCZT
Py : Pyro
# : Ni3P
N : Ni
C : Cu
50
55
Figure 5.28: X-ray plot for the 5 mol % Ca-doped PZT thin films on electroless Ni coated
Cu foil (with 8 % phosphorous) crystallized at 600 oC with pO2: (a) 9.010-8 Torr, (b)
7.510-7 Torr, (c) 1.010-5 Torr, (d) 1.210-4 Torr, (e) 5.510-4 Torr, (f) 7.610-4 Torr, (g)
4.010-3 Torr, (h) 1.510-1 Torr, (i) 1.0 Torr, and (j) 10.0 Torr.
173
#(200)
N(111)
#(141)
#(141)
N(200)
#(132)
Py
#(031)
P(111)
Pt (111)
#(231)
C(111)
(j)
(i)
(h)
(g)
P(010/110)
P(100)
Intensity (a.u.)
P : PCZT
Py : Pyro
# : Ni3P
N : Ni
C : Cu
Py
Py
Py
(f)
(e)
(d)
(c)
(b)
(a)
20
25
Py
Py
Py
Py
30
35
40
45
50
55
2
Figure 5.29: X-ray plot for the 10 mol % Ca-doped PZT thin films on electroless Ni
coated Cu foil (with 12 ~ 13 % phosphorous) crystallized at 600 oC with pO2: (a) 9.0108
Torr, (b) 7.510-7 Torr, (c) 1.010-5 Torr, (d) 1.210-4 Torr, (e) 5.510-4 Torr, (f)
7.610-4 Torr, (g) 4.010-3 Torr, (h) 1.510-1 Torr, (i) 1.0 Torr, and (j) 10.0 Torr.
174
120
100
80
60
40
20
0
-8
10
-6
10
-4
-4
1x10
10
-2
10
10
10
pO2 (torr)
Figure 5.30: Phase purity of the 5 mol % Ca-doped PZT thin films on electroless Ni (with
120
100
80
60
40
20
0
-8
10
-6
10
-4
-4
1x10
10
-2
10
10
10
pO2 (torr)
Figure 5.31: Phase purity of the 10 mol % Ca-doped PZT thin films on electroless Ni
(with 12 ~ 13 % phosphorous) coated Cu foil. Crystallization was done at 650 oC for 30
minutes.
175
(a)
(b)
(c)
Figure 5.32: Suggested schematics of reactions for Ca-doped PZT thin film capacitors on
electroless Ni coated Cu foil: (a) no or minimal reaction assumed (b) reaction at low pO2,
and (c) reaction at high pO2.
176
(5.2)
where (100), (110) and (111) intensities were used for intensity calculation of perovskite
phase and the peak at 2 30 was used for intensity calculation of pyrochlore phase.
For both 5 and 10 mol % Ca-doped PZT composition, pure perovskite phases
were found only around 5.5 ~ 7.610-4 torr pO2, which is much narrower than undoped
PZT thin film capacitors on electroless Ni coated Cu foil. From the observations and
several assumptions, the possible reactions are suggested in Figure 5.32.
177
178
0.100
300
0.075
200
0.050
100
0.025
0
-8
10
10
-6
-4
10 -4
1x10
10
-2
10
Loss tangent
400
0.000
2
10
pO2 (torr)
400
0.100
300
0.075
200
0.050
100
0.025
(with 8 % phosphorous) coated Cu foil. Crystallization was done at 600 oC for 30 minutes.
10
-6
-4
10 -4
1x10
10
-2
10
Loss tangent
0
-8
10
0.000
2
10
pO2 (torr)
179
180
9.010-8 torr
7.510-7 torr
1.010-5 torr
1.210-4 torr
5.510-4 torr
7.610-4 torr
4.010-3 torr
1.510-1 torr
1 torr
10 torr
Figure 5.35: Surface microstructure of the 5 mol % Ca-doped PZT thin film capacitors on
electroless Ni coated Cu foil (with 8 % phosphorous). Crystallization was done at 600 oC
for 30 minutes. All scans were performed over 1 1 m range.
181
Rms (nm)
5
4
3
2
1
0 -8
10
-6
10
-4
-4
1x10
10
-2
10
10
10
pO2 (torr)
Figure 5.36: Surface roughness of the 5 mol % Ca-doped PZT thin film capacitors on
electroless Ni coated Cu foil (with 8 % phosphorous). Crystallization was done at 600 oC
for 30 minutes.
J E
(5.3)
J = A T exp
kT
(5.4)
183
Poole-Frenkel is from the field assisted thermal ionization current, and has the
same temperature and field dependence for leakage current density as Schottky.
Qualitatively, the effect of Poole-Frenkel is easily separated from Schottky by making
top and bottom electrodes of different metals and measuring the asymmetry in leakage
currents with positive and negative polarity. Poole-Frenkel is symmetric with respect to
polarity under these conditions.
E 1 / 2 Q
J = A0 E exp
kT
(5.5)
where A0 and are constants and Q is the depth of the trap potential well.
Space charge limited conduction (SCLC) is usually observed when the conduction
by other mechanisms reaches a certain threshold level, such that current is not longer
limited by other conduction mechanisms. Currents become limited by the injected space
charge in the ferroelectric films [42]. That is, as the applied voltage is increased, a strong
injection of the charge carriers in the bulk of the film takes place. As the injection is
getting stronger, the insulation traps fill up and a space charge appears. At higher voltage
regime, as shown in eq. (4.3), we have,
J =C
Vn
dm
(5.6)
GBLC is usually observed in the highly heterogeneous system, and shows varistor
type I-V characteristics. Waser and Klee reported [43] fully depleted grains and Schottky
barriers by highly resistive grain boundaries in the ultrafine-grained SrTiO3 and BaTiO3.
They reported the influence of the electrode interfaces is outweighed by the large number
of grain boundaries between the electrodes. The most distinguishable characteristic of
184
GBLC (varistor type) is that it shows non-linearity relationship in J-E dependence [44].
In the intermediate field region, the slope of ln J vs. ln E decreses from nearly 1 to nearly
0 as the field increases. This is contrary to the commonly observed phenomenon and Hu
et al. explained the increase in the resistivity of the film in the intermediate field region is
associated with the change in the height of grain boundary barriers induced by the field
dependence of the film dielectric constant as follows [44].
b = e 2 nb2 / 2 0N
(5.7)
where nb is the grain boundary trap density, 0 is the permittivity of free space, k is the
effective dielectric constant of the near-grain boundary region, and N is the dopant
concentration. On the while, in the SCLC theory, the system is assumed to be
homogeneous, and all imperfections inside are mingled together in terms of traps. It
should be noted that the SCLC mechanism does not have anything to do with whether the
contact is depletion or accumulation type. SCLC is thought to occur when the injecting
electron density per given time is larger than the density of electrons passing across from
the cathode to anode.
185
and Nb doped PZT thin films prepared by sol-gel method on Pt/SiO2/Si. Kundu et al. [47]
found different leakage current behavior with film thickness in RF sputtered PZT thin
films. They observed the grain boundary limited current (GBLC) behavior for thicker
films and space charge limited current (SCLC) in thinner films and explained this SCLC
behavior in terms of the dominance in deep traps.
Figures 5.37 and 5.38 shows leakage current densities as a function of voltage for
5 and 10 mol % Ca-doped PZT capacitors crystallized under different pO2. The leakage
current densities did not manifest distinct trends with the partial oxygen pressures. The
leakage did not show linearity between ln J and V1/2, which means the Schottky and
Poole-Frenkel conduction may not contribute to the charge conduction. Rather, the
leakage current densities seem to follow Ohmic conduction at low field and SCLC at
higher field. Table 5.3 is the slope of log J vs. log V for 5 mol % Ca-doled PZT
capacitors crystallized under different pO2. For all capacitors, a slope of greater than 4.0
was measured at high field (> 10 VDC), which suggests that the energy distribution of
traps could be continuous [48].
Figures 5.40 and 5.41 show leakage current densities measured at 10 VDC. A
consistent trend between pO2 and DC leakage is not apparent from these measurements.
186
Table 5.3: Slope of log J vs. log V for 5 mol % Ca-doped PZT capacitors on electroless
Ni coated Cu foil (with 8 % phosphorous).
pO2
Slope
Range (V)
9.0 10 -8
5.5081
13 ~ 35
0.9919
7.5 10 -7
4.6296
13 ~ 35
0.9864
1.0 10
-5
5.8007
11 ~ 35
0.9995
1.2 10
-4
5.8778
11 ~ 35
0.9940
5.5 10 -4
4.1823
10 ~ 35
0.9808
7.6 10 -4
4.6023
11 ~ 35
0.9995
4.0 10 -3
5.0651
11 ~ 35
0.9878
1.15 10 -2
4.6708
11 ~ 35
0.9954
5.0444
11 ~ 35
0.9893
10
5.6762
11 ~ 35
0.9407
187
-1
10
-8
-3
J (A/cm )
10
-5
9.0X10
-7
7.5X10
-5
1.0X10
-4
1.2X10
-4
5.5X10
1x10
-7
10
-9
10
10
Voltage (V)
-1
10
-3
J (A/cm )
10
-4
7.6X10
-3
4.0X10
-2
1.15X10
1
10
-5
1x10
-7
10
-9
10
10
Voltage (V)
Figure 5.37: Leakage current densities for the 5 mol % Ca-doped PZT on electroless Ni
coated Cu foil. Crystallization was done at 600 oC for 30 minutes under different pO2.
188
10
-1
-8
-3
1x10
-5
10
-7
10
-9
J (A/cm )
10
9.0X10
-7
7.5X10
-5
1.0X10
-4
1.2X10
-4
5.5X10
10
Voltage (V)
10
-1
-4
-3
1x10
-5
10
-7
10
-9
J (A/cm )
10
7.6X10
-3
4.0X10
-1
1.15X10
1
10
10
Voltage (V)
Figure 5.38: Leakage current densities for the 10 mol % Ca-doped PZT on electroless Ni
coated Cu foil. Crystallization was done at 600 oC for 30 minutes under different pO2.
189
-1
10
-3
1x10
-5
10
-7
10
-9
J (A/cm )
10
10
-8
10
-6
-4 -4
1x10
10
-2
10
10
10
pO2 (torr)
Figure 5.39: Leakage current densities for the 5 mol % Ca-doped PZT on electroless Ni
coated Cu foil. Crystallization was done at 600 oC for 30 minutes. Data taken at 10 VDC,
step voltage of 0.5 V, duration time of 1 sec.
-1
10
-3
1x10
-5
10
-7
10
-9
J (A/cm )
10
10
-8
10
-6
-4
1x10
10
-4
10
-2
10
10
pO2 (torr)
Figure 5.40: Leakage current densities for the 10 mol % Ca-doped PZT on electroless Ni
coated Cu foil. Crystallization was done at 600 oC for 30 minutes. Data taken at 10 VDC,
step voltage of 0.5 V, duration time of 1 sec.
190
From these leakage measurements, we hypothesize that in all cases some degree of
interface between foil and PZT is present. The similarity in leakage suggests that the
interface characterization do not change significantly with changing pO2. Consequently,
we interpret that pO2 modification alone cannot be used to modulate interface formation.
pO2 control dramatically impacts phase formation, primarily, we believe through PbO
control.
191
192
5.5 References
[1] J. Mendiola, M. L. Calzada, P. Ramos, M. J. Martin, and F. A. Rueda, Thin Solid
Films, 315, 195 (1998).
[2] S. J. Kang, D. H. Chang, and Y. S. Yoon, Thin Solid Films, 373, 53 (2000).
[3] M. Es-Souni, M. Abed, A. Piorra, S. Malinowski, and V. Zaporojtchenko, Thin Solid
Films 389, 99 (2001).
[ 4 ] M. Kohlkin, A. Seifert, B. Willing, K. Brooks, and P. Muralt, Integrated
Ferroelectrics, 17, 359 (1997).
[5] S. Y. Chu and C. Z. Chen, Sensors and Actuators A, 89, 210 (2001).
[6] C. C. M. Wang, Y. T. Huang, Y. C. Chen, M. S. Lee, and M. C. Kao, Jap. J. Appl.
Phys., Part 1, 39, 3579 (2000).
[7] H. Li, X. Tang, Q. Li, Y. Liu, Z. Tang, Z. Y. Zhang, and D. Mo, Solid State Commun.,
114, 347 (2000).
[8] F. M. Pontes, D. S. L. Pontes, E. R. Leite and E. Longo, E. M. S. Santos, S.
Mergulhao, A. Chiquito, P. S. Pizani, F. Lanciotti, Jr., T. M. Boschi, and J. A. Varela,
J. Appl. Phys., 91(10), 6650 (2002).
[9] D. J. Wouters, G. Willems, E.-U. Lee, and H. E. Mae, Integrated Ferroelectrics 15,
79 (1997).
[10] G. R. Fox, Mat. Res. Symp. Proc. 541, 529 (1998).
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[23] B. Yang, T. K. Song, S. Aggarwal, and R. Ramesh, Appl. Phys. Lett., 71 (24) 3578
(1997).
[24] D. J. Wouters, G. J. Willems, and H. E. Maes, Microelectronic Engineering, 29, 249
(1995).
[25] R. W. Schwartz, J. A. Voigt, B. A. Tuttle, D. A. Payne, T. L. Reichert, and R. S.
DaSalla, J. Mater. Res., 12 (2) 444 (1997).
[26] F. Lecarpentier, M. Daglish, and T. Kemmitt, J. Aust. Ceram. Soc., 37, 1, 9 (2001).
[27] M. A. Subramanian, G. Aravamudan, and G. V. S. Rao, Prog. Solid State Chem., 15,
55 (1983).
[28] B. A Tuttle, R. W. Schwartz, D. H. Doughty, and J. A. Voigt, Mater. Res. Soc. Symp.
Proc., 200, 159 (1990).
[29] A. D. Polli, F. F. Lange, and C. G. Levi, J. Am. Ceram. Soc., 83 (4) 873 (2000).
[30] J. Xu, A. P. Wilkinson, and S. Pattanaik, Chem. Mater.,12, 3321 (2000).
[31] L.A. Bursill and K. G. Brooks, J. Appl. Phys., 75 (9) 4501 (1994).
[32] A. P. Wilkinson, J. S. Speck, and A. K. Cheetham, Chem. Mater., 6, 750 (1994).
[33] G. R. Fox, Mat. Res. Soc. Proc., 541, 529 (1999).
[34] K. G. Brooks, I. M. Reaney, R. Klissurska, Y. Huang, L. Bursill, and N. Setter, J.
Mater. Res., 9 (10) 2540 (1994).
195
[35] S.-Y. Chen and I-W Chen, J. Am. Ceram. Soc., 77 (9) 2337 (1994).
[36] M. A. McCormick, E. B. Slamovich, P. Metcalf, and M. McElfresh, Mat. Res. Soc.
Symp. Proc., 688 (Ferroelectric Thin Films X), 113 (2002).
[37] D. F. K. Hennings, J. Euro. Ceram. Soc., 21, 1637 (2001).
[38] H. F. Cheng, M. H. Yeh, K. S. Liu, and I. N. Lin, Integrated Ferroelectrics, 10 (14), 81 (1995).
[39] E. M. Griswold, L. Weaver, M. Sayer, F. Czerwinski, and J. Szpunar, Micron, 26 (6)
559 (1995).
[40] C. A. Paz de Araujo, L. D. McMillan, B. M. Melnick, J. D. Cuchiro, and J. F. Scott,
Ferroelectrics, 104, 241 (1990)
[41] J. J. ODwyer, The theory of electrical conduction and breakdown in solid dielectrics,
(Clarendon Press, Oxford, U.K., 1973).
[42] J. F. Scott, Ferroelectric Memories, Springer (2000).
[43] R. Waser and M. Klee, Integrated Ferroelectrics, 2, 257 (1992).
[44] H. Hu and S. B. Krupanidhi, J. Mater. Res., 9 (6) 1484 (1994).
[45] J. F. Scott, C. A. Paz de Araujo, B. M. Melnick, L. D. McMillan, and R. Zuleeg, J.
Appl. Phys., 70, 382 (1991).
196
197
CHAPTER 6
ZrO2 Buffer Layers
6.1 Introduction
Many efforts have been devoted to buffer layers between substrate and
ferroelectric thin / thick films. Buffer layers were introduced in the ferroelectric thin films
mostly to minimize the interface reactions and corresponding deterioration in
ferroelectric properties, to control of nucleation and growth rate in the ferroelectric thin
films, and to control film orientations to achieve better properties and microstructures.
Materials widely used for buffer layer application for modification in PZT thin film
properties include multilayer oxide electrode, perovskite materials PbTiO3 [1, 2], TiO2 [3,
4], ZrO2 [5, 6] Al2O3 [7], and LaNiO3 [8,9].
Especially in the capacitor films with base metal electrode, better electrical
properties were reported for the capacitors with optimized buffer layers due to the
enhanced chemical reactions between capacitors and (bottom) electrodes or enhanced
orientations. Dawly and Clem introduced TFA (trifluoroacetic acid) to control the
orientation of BST nucleation on (00l) oriented nickel tape to obtain high permittivity
BST and SrTiO3 thin films [ 10 ]. The university of Toronto group reported the
improvements in dielectric properties and ferroelectric properties of PZT thin films by
introducing LaNiO3 thin layers on top of the base metal electrodes [9].
In this study, controlled oxygen partial pressures were used in an attempt to
control interface formation between electroless Ni and PZT thin film. This method did
198
not provide for enhanced capacitance density, so investigations of buffer layers were
attempted. Unlike previous investigation, the economic constraints of embedded passives
did not allow for expensive buffers to be incorporated. Consequently a cheaper solution
involving an oxide buffer layer application was investigated. For this purpose, ZrO2
buffer layers were selected. ZrO2 layers were prepared on electroless Ni coated Cu foil by
chemical solution deposition, DC and RF sputtering process, respectively. The effect of
ZrO2 layer processing on the phase formation and corresponding electrical properties
were investigated. Especially, emphasis was given to the reliabilities of PZT thin films on
electroless Ni coated Cu foil. Reliability effects are of particular concern since a defective
interface leads to difficulties in the time dependent electrical properties of thin film
devices.
layer might indicate that easy achievement of (111) orientation on standard Pt/Ti
substrate due to TiO2 formation by Ti diffusion through Pt. Lee et al. [4] also obtained
improved ferroelectric properties of CSD derived PZT thin films on TiO2/Pt/Ti/SiO2/Pt
substrate and they explained TiO2 buffer layer minimized the formation of Pb3Pt
interfacial layer.
Xu et al. fabricated 1 m PZT thick thin films on ZrO2/Pt passivated silicon
substrate [5]. They reported that the dielectric constant of more than 1000 and remanent
polarization of more than 20 C/cm2 and they reported ZrO2 passivated PZT thick films
have comparable properties with those on Pt electrode. Alternatively, Bao et al. reported
that the incorporation of ZrO2 worsened the properties of PZT thin films due to the
difficulties of nucleation on ZrO2 with PbO [6]. Kim et al. used Al2O3 layer as diffusion
barrier between Pt and Si to minimize the interfacial reaction and reduced processing
temperature of PZT thin films as low as 550 oC [7]. However, most of the improved
ferroelectric properties might be ascribed to the PbTiO3 layer between Pt and PZT thin
films. LaNiO3 layers are recently investigated due to potentially improved fatigue
properties in PZT thin films [8]. Zou et al. also shown the use of LaNiO3 buffer layer
could contribute to the minimization of interface reaction and correspondingly improved
dielectric properties in PZT thin films on various metal foils [9].
Conducting barriers are advantageous in that they do not affect dielectric
properties of capacitors. However, it is relatively difficult to prepare conducting barrier
layers by simple, cost effective process such as chemical solution deposition or metal
organic decomposition. On the while, insulating layers could be relatively easily prepared
by simple process, and thermally and chemically more stable. However, when low
200
permittivity buffer layers are sandwiched between capacitor and bottom electrode, series
connected capacitor structure could reduce the total capacitance.
Among these buffer layers, ZrO2 is known to have excellent properties, such as
high mechanical strength, chemical durability, alkali resistance, and refractoriness. [11,
12, 13] Thin film ZrO2 is widely studied as a buffer layer [14] for ferroelectric thin films
and other functional thin films with Si devices. In bulk form, monoclinic ZrO2 (m-ZrO2)
is stable up to 1170 oC, when it transforms to the tetragonal (t-ZrO2), which remains
stable up to 2370 oC. From 2370 oC to melting point (2680 oC), cubic (c-ZrO2) form is
stable [15 ]. In the case of sol-gel derived thin film, ZrO2 starts to transform from
amorphous to t-ZrO2 around 600 oC [16] and as the annealing temperature goes up, the
tetragonal phase transforms to m-ZrO2.
Intensity (a.u.)
(c)
Ni (200)
Zr5P3
Cu (111)
ZrP (103)
ZrP (105)
Ni (111)
Ni P (031) / Zr5P3
3
(d)
(b)
(a)
25
30
35
40
45
50
55
60
Figure 6.1: X-ray diffraction plots for CSD derived ZrO2 layers on electroless Ni coated
Cu foil (with 8 % phosphorous) with different annealing conditions: (a) 450 oC, 5
minutes (10 minute scan), (b) 550 oC, 5 minutes (10 minute scan), (c) 650 oC, 5 minutes
(10 minute scan), and (d) 650 oC, 5 minutes (60 minute scan).
202
which suggest the significant reactivity of phosphorous with other metal compound with
amorphous structure.
This is further supported by Figure 6.2 where identical Zr containing solutions are
deposited on electroless Ni with higher phosphorous content (12 ~ 13 %). Unlike on
electroless Ni with 8 % phosphorous, Zr-P peaks are not observed on electroless Ni with
12 ~ 13 % phosphorous after annealing step. This might imply that the reactivity of
phosphorous is enough to consume other adjacent, amorphous layer prior to full- scale
crystallization. It is expected that the lower phosphorous content in electroless Ni might
stabilize ZrO2 layer prepared by chemical solution deposition. However, due to the
difficulties in phase instability of ZrO2 layers, CSD derived ZrO2 layers were excluded
Ni3P(141)
Ni3P(231)
(c)
Ni3P(031)
Intensity (a.u.)
(b)
(a)
25
30
35
40
45
50
55
60
Figure 6.2: X-ray diffraction plots for CSD derived ZrO2 layers on electroless Ni coated
Cu foil (with 12 ~ 13 % phosphorous) with different annealing conditions: (a) 450 oC, 5
minutes (10 minute scan), (b) 550 oC, 5 minutes (10 minute scan), and (c) 650 oC, 5
minutes (10 minute scan).
203
To have more stability in phase formation, another thin film deposition process,
DC magnetron sputtering, was used to deposit Zr metal layer directly on electroless Ni
coated Cu foil using Zr metal target. Final thickness of Zr thin film was in the range of 20
nm. After deposition, Zr films were post-annealed at different temperatures, ranging from
450 to 550 oC in the air atmosphere for transformation from metal Zr into ZrO2. The X-
Ni (200)
Cu (200)
Ni (111)
Ni3P (141)
Ni3P (231)
ZrPX
Ni3P(031)
Intensity (a.u.)
Cu (111)
ray diffraction plots for these annealed samples are shown in Figure 6.3.
(c)
(b)
(a)
25
30
35
40
45
50
55
60
Figure 6.3: X-ray diffraction plots for DC sputtered Zr layers on electroless Ni coated Cu
foil (with 8 % phosphorous) with different annealing conditions: (a) 450 oC, 15 minutes,
(b) 500 oC, 10 minutes, and (c) 550 oC, 10 minutes.
As in Figure 6.1 and 6.2, ZrO2 phase was not detected for all samples. Strong NiP, Zr-P peaks together with Ni and Cu peaks were observed. As annealing temperature
increases, it is seen that the intensity of peak corresponding to 2 ~ 37.7 also increases.
This could be from ZrPx phase (JCPDS 19-1494) and this could be one of the supporting
204
phase was not found by X-ray diffraction, as shown in Figure 6.5. This result suggests the
importance of selecting deposition process which would minimize the reaction between
adjacent layers. Therefore, all the capacitor preparations for evaluating electrical
properties were performed on RF sputter deposited ZrO2 layers. To investigate the effect
of the buffer layer thickness on the electrical properties of capacitors, 50 nm and 100 nm
N (200)
# (141)
# (031)
# (231)
m : m-ZrO2
# : Ni3P
N : Ni
C : Cu
Intensity (a.u.)
(c)
(b)
(a)
20
25
30
35
40
45
50
55
Figure 6.4: X-ray diffraction plots for as-deposited ZrO2 thin films deposited by RF
magnetron sputtering on electroless Ni coated Cu foil (with 8 % phosphorous): (a) 50 nm
ZrO2 (b) 100 nm ZrO2, and (c) 100 nm ZrO2 on pre-annealed (at 450 oC for 15 minutes)
electroless Ni coated Cu foil.
206
(c)
# (141)
N (200)
# (231)
# (031)
Intensity (a.u.)
m : m-ZrO2
# : Ni3P
N : Ni
C : Cu
(b)
(a)
20
25
30
35
40
45
50
55
Figure 6.5: X-ray diffraction plots for post-annealed ZrO2 thin films deposited by RF
magnetron sputtering on electroless Ni coated Cu foil (with 8 % phosphorous). Postanneal was done at 450 oC for 15 minutes: (a) 50 nm ZrO2 (b) 100 nm ZrO2, and (c) 100
nm ZrO2 on pre-annealed (450 oC for 15 minutes) electroless Ni coated Cu foil.
Figure 6.6 and 6.7 show the phase development of the PZT (52/48) thin films on
the ZrO2 / electroless Ni coated Cu foil with crystallization temperatures. Irrespective of
the ZrO2 thin film thickness, all the samples show the development of the perovskite
phases starting from 550 oC. For 500 oC-crystallized samples, pyrochlore phases were
observed. This might be from the incomplete PZT phase formation at lower
crystallization temperature, when compared with other CSD derived PZT thin films [19].
One interesting point is that the intensity of (111) orientation was a lot higher than other
perovskite peak for 500 oC-crystallized PZT thin films.
207
N(200)
#(200)
#(132)
N(111)
#(141)
#(231)
C(111)
P(111)
P(010/110)
#(031)
(e)
P(100)
(d)
(c)
(b)
20
(a)
Py
Intensity (a.u.)
P : PZT
Py : Pyro
# : Ni3P
N : Ni
C : Cu
m : m-ZrO2
25
30
35
40
45
50
55
Figure 6.6: X-ray diffraction plots for PZT (52/48) thin film capacitors on ZrO2 (50 nm) /
electroless Ni coated Cu foil (with 8 % phosphorous) crystallized under N2 atmosphere
for 30 minutes at: (a) 500 oC, (b) 550 oC, (c) 575 oC, (d) 600 oC, and (e) 650 oC,
respectively.
208
N(200)
#(200)
#(132)
N(111)
#(141)
#(231)
C(111)
#(031)
P(111)
P(010/110)
(e)
P(100)
(d)
(c)
(b)
(a)
20
25
Py
Intensity (a.u.)
P : PZT
Py : Pyro
# : Ni3P
N : Ni
C : Cu
m : m-ZrO2
30
35
40
45
50
55
Figure 6.7: X-ray diffraction plots for PZT (52/48) thin film capacitors on ZrO2 (100 nm)
/ electroless Ni coated Cu foil (with 8 % phosphorous) crystallized under N2 atmosphere
for 30 minutes at: (a) 500 oC, (b) 550 oC, (c) 575 oC, (d) 600 oC, and (e) 650 oC,
respectively.
209
0.25
400
0.20
300
0.15
200
0.10
100
0.05
500
550
575
600
625
650
Loss tangent
0.00
Crystallization temperature ( C)
Figure 6.8: Dielectric properties of PZT (52/48) thin film capacitors on electroless Ni
coated Cu foil with crystallization temperature. No buffer layers are used.
0.25
50 nm ZrO2
100 nm ZrO2
2
400
0.20
300
0.15
200
0.10
100
0.05
500
550
600
650
Loss tangent
500
0.00
Crystallization temperature ( C)
Figure 6.9: Effect of ZrO2 buffer layers on the dielectric properties of PZT (52/48) thin
film capacitors with crystallization temperature.
210
When ZrO2 layer is sandwiched between PZT and electroless Ni, capacitive
densities of approximately 10 % smaller capacitive densities were measured at each
temperature. Loss tangent increased with temperatures up to 650 oC, compared with PZT
thin film capacitor that did not have ZrO2 buffer layers. The thickness of ZrO2 buffer
layer also affected capacitance densities of PZT thin films. PZT thin films combined with
thicker (100 nm) ZrO2 buffer layer resulted in decreased capacitance densities. The lower
capacitance densities might be from the lower permittivity characteristics of ZrO2. ZrO2
has a permittivity of 25 [23]. It is generally known that when low permittivity and high
permittivity films are series connected, the total capacitance is dependent on the thickness
of low permittivity layer [24, 25]. Therefore, optimizing the minimum thickness of low
permittivity layer would be favorable in terms of dielectric properties.
Low capacitance densities measured at 500 oC could be linked with insufficient
perovskite phase development of PZT, which is supported by the X-ray diffraction plots
for the capacitors.
211
650 C
o
600 C
O
o
575 C
O
o
550 C
O
o
500 C
500
400
0.30
0.25
300
0.20
200
0.15
100
0.10
0.05
-100
2
10
10
10
10
10
Loss tangent
0.00
7
10
Frequency (Hz)
Figure 6.10: Capacitance-frequency plot for PZT (52/48) thin film capacitors on 50 nm
ZrO2 / electroless Ni coated Cu foil (with 8 % phosphorous) with crystallization
500
650 C
o
O
600 C
o
O
575 C
o
O
550 C
o
O
500 C
400
300
0.30
0.25
0.20
200
0.15
100
0.10
0.05
-100
2
10
10
10
10
10
Loss tangent
0.00
7
10
Frequency (Hz)
Figure 6.11: Capacitance-frequency plot for PZT (52/48) thin film capacitors on 100 nm
ZrO2 / electroless Ni coated Cu foil (with 8 % phosphorous) with crystallization
temperatures. Crystallization was done for 30 minutes under N2 flow.
212
(a)
(b)
(c)
rms 1.3 nm
rms 2.5 nm
rms 2.8 nm
(d)
(e)
rms 2.6 nm
rms 4.9 nm
Figure 6.12: AFM surface microstructures for the PZT (52/48) thin film capacitors on 50
nm ZrO2 crystallized for 30 minutes in N2 flow between 500 and 650 oC: (a) 500 oC, (b)
550 oC, (c) 575 oC, (d) 600 oC, and (e) 650 oC. All scans were performed over 2 2 m
range.
213
For PZT thin films with 50 nm thick ZrO2 layer, grain growth did not actively
begin up to 600 oC. At 650 oC, grains with 80 ~ 90 nm were developed. Similar
microstructures were observed for PZT thin films on 100 nm ZrO2 layer, as shown in
Figure 6.13. When compared with PZT thin films on electroless Ni, surface
microstructures seemed to be very similar, and almost similar surface roughness were
measured for PZT thin films with ZrO2 layers (Figure 6.14). The similarity of
microstructure and surface roughness might suggest that all the key reactions are rather
restricted to the interface region. For more detailed information, direct interfacial analysis
techniques such as cross sectional TEM, would be further necessary.
(a)
(b)
(c)
rms 1.1 nm
rms 3.0 nm
rms 2.0 nm
(d)
(e)
rms 2.3 nm
rms 3.6 nm
Figure 6.13: AFM surface microstructures for the PZT (52/48) thin film capacitors on
100 nm ZrO2 crystallized for 30 minutes in N2 flow between 500 and 650 oC: (a) 500 oC,
(b) 550 oC, (c) 575 oC, (d) 600 oC, and (e) 650 oC. All scans were performed over 2 2
m range.
214
Rms (nm)
(a)
No ZrO2
50 nm ZrO2
100 nm ZrO2
3
2
1
0
Temperature ( C)
Rms (nm)
(b)
No ZrO2
50 nm ZrO2
100 nm ZrO2
3
2
1
0
Temperature ( C)
Figure 6.14: Surface roughness (rms) for PZT (52/48) thin film capacitors on ZrO2 buffer
layers crystallized between 500 and 650 oC for 30 minutes in N2 flow: (a) for 1 1 m,
(b) for 2 2 m.
6.5 Reliability
One of the requirements of ferroelectric thin films for memory application is
improved leakage current behavior. One of the fast approaches for this objective is to
215
sandwich buffer layer between capacitor and bottom electrode. The buffer layer should
be chemically and thermally stable, therefore oxide layers are widely adapted for this
application. Lee et al. [4] reported improved leakage characteristics in PZT thin films on
Pt/Ti/SiO2/Si, by using sputter deposited TiO2 buffer layers. They explained TiO2 buffer
layer acts as a barrier for Pb-Pt reaction, as well as for oxygen diffusion. Jung et al. [26]
measured improved leakage current by adapting used 20 nm thick ZrO2 layer underneath
SrBi2Ta2O9 thin films on platinized silicon.
In Figures 6.15 and 6.16, leakage current is plotted with voltage for the PZT thin
film capacitors on 50 and 100 nm thick ZrO2 layers, respectively. Leakage current
densities for PZT thin films deposited directly on electroless Ni is given in Figure 6.17
for comparison purposes. It is clear from the J vs. V plots that the leakage current
drastically reduced for PZT capacitors on ZrO2 buffer layers. For capacitors with 100 nm
ZrO2 layer, reduced leakage current densities more than three to four orders of magnitude
were measured at 20 VDC, when compared with PZT capacitors on electroless Ni. Also
as we expected, lower leakage current densities were measured for PZT capacitors on
thicker (100 nm) ZrO2 layer, than those on thinner (50 nm) ZrO2 layer.
Another important implication is that leakage current densities plot might be able
to support the assumption made in the previous chapters, that is, the role of materials
(possibly phosphorous) diffusion from bottom electrode and corresponding interface
reaction. It is seen from the plots that leakage current densities of PZT capacitors directly
deposited on electroless Ni decrease with increase in crystallization temperature. On the
while, leakage current densities of PZT capacitors on ZrO2 buffer layers increased with
proportional to crystallization temperature.
216
-1
10
-3
1x10
-5
10
-7
10
-9
500 C
o
550 C
o
575 C
o
600 C
o
650 C
J (A/cm )
10
10
15
20
25
30
Voltage (V)
Figure 6.15: Leakage current densities with voltage for PZT (52/48) thin film capacitors
on ZrO2 (50nm) / electroless Ni coated Cu foil. Crystallization was done between 500
and 650 oC.
-1
10
-3
1x10
-5
10
-7
10
-9
500 C
o
550 C
o
575 C
o
600 C
o
650 C
J (A/cm )
10
10
15
20
25
30
Voltage (V)
Figure 6.16: Leakage current densities with voltage for the PZT (52/48) thin film
capacitors on ZrO2 (100nm) / electroless Ni coated Cu foil. Crystallization was done
between 500 and 650 oC.
217
-1
10
-3
1x10
-5
10
-7
10
-9
550 C
o
575 C
o
600 C
o
650 C
J (A/cm )
10
10
15
20
25
30
Voltage (V)
Figure 6.17: Leakage current densities with voltage for PZT (52/48) thin film capacitors
on electroless Ni coated Cu foil. Crystallization was done between 550 and 650 oC.
Usually it is expected that the microstructures of the ceramics is getting denser
with crystallization temperature. For CSD derived PZT thin films, electrical properties
such as leakage current depends on annealing temperature and time [27], as in Figure
6.17 where leakage current densities for PZT capacitors deposited directly on electroless
Ni coated Cu foil are shown.
The increase in leakage current densities with crystallization temperatures for
PZT thin film capacitors on ZrO2 buffer layers might suggest that density of conducting
paths might increase possibly from more active interface reaction. This observation could
support the suggestion that the assumption we made in previous chapters that the activity
of phosphorous from the bottom electrode could be increased with temperature enough to
significantly diffuse into PZT thin films. Although we observed the increase in the
218
leakage current densities with temperatures for PZT capacitors on ZrO2 buffer layers, the
current value is still three to four orders lower than PZT capacitors on electroless Ni. And
we could infer the magnitude of interface reaction would be significantly reduced.
Capacitors for decoupling and/or bypass application are operated at around 3 ~ 5
VDC. However, it is more reasonable to evaluate a capacitor at a higher voltage to ensure
reliability characteristics. For evaluation of the effect of ZrO2 layer underneath PZT
capacitor, + 15 and + 25 VDC were selected, respectively, and applied to top Pt electrode.
Figure 6.18 and 6.19 show the effect of the applied external voltage on the
leakage current densities plots with time for 50 nm ZrO2 layer incorporated PZT
capacitors. As shown in leakage current densities with voltage plot, 500 oC - crystallized
capacitors showed lowest leakage currents. Leakage currents of 107 A/cm2 were
measured up to 2000 seconds. As the temperature increased up to 650 oC, leakage current
densities increased abruptly. Also leakage current densities were dependent on the
applied external voltage. Leakage current densities measured at applied external voltage
of 25 VDC induced higher leakage current densities for every capacitor than those
measured at 15 VDC. This might be due to the increased carrier concentrations.
219
10
10
-2
1x10
-4
10
-6
10
-8
J (A/cm )
10
650 C
o
600 C
o
575 C
o
550 C
o
500 C
-10
10
100
1000
Time (sec)
Figure 6.18: Leakage current densities with time for PZT (52/48) thin film capacitors on
ZrO2 (50nm) / electroless Ni coated Cu foil. 15 VDC applied during measurement.
10
10
-2
1x10
-4
10
-6
10
-8
J (A/cm )
10
650 C
o
600 C
o
575 C
o
550 C
o
500 C
-10
10
100
1000
Time (sec)
Figure 6.19: Leakage current densities with time for PZT (52/48) thin film capacitors on
ZrO2 (50nm) / electroless Ni coated Cu foil. 25 VDC applied during measurement.
220
More drastic changes in leakage current densities were observed for PZT
capacitors with 100 nm thick ZrO2 layer (Figure 6.20). Regardless of crystallization
temperature, for all the capacitors crystallized between 500 and 650 oC, leakage current
densities with the order of 10-7 A/cm2 were measured even after one hour. Especially for
capacitors crystallized up to 575 oC, 10-8 A/cm2 of current densities were measured.
Assuming the leakage current dependence on the thickness of buffer layer, this might
suggest that the thicker buffer layer would be more effective than thinner ones in
minimizing the reactions between bottom electrode and capacitor layers. Also this might
support that the interface reactions originates from the elements from electroless Ni,
rather than from PZT layers. Depending on the application of the capacitor, it seems to
be possible to modify processing parameters such as buffer layer thickness and
crystallization temperature, and attain the specific dielectric and/or reliability
requirements.
221
10
0
o
-2
1x10
-4
10
-6
10
-8
J (A/cm )
10
10
650 C
o
600 C
o
575 C
o
550 C
o
500 C
-10
10
100
1000
Time (sec)
Figure 6.20: Leakage current densities with time for PZT (52/48) on ZrO2 (100 nm) with
crystallization temperature. 25 VDC applied during measurement.
10
10
-2
1x10
-4
10
-6
10
-8
J (A/cm )
10
650 C
o
600 C
o
575 C
o
550 C
-10
10
100
1000
Time (sec)
Figure 6.21: Leakage current densities with time for PZT (52/48) thin film capacitors on
electroless Ni coated Cu foil. 25 VDC applied during measurement.
222
223
6.7 References
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Thin Films VIII), 499, (2000).
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Agostino, N. Xanthopoulos, H. J. Mathieu, L. Patthey, and E. L. Bullock, J. Appl.
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[6] D. Bao, N. Mizutani, X. Yao, and L. Zhang, Key Engineering Materials, 214 215
(Asian Ceramic Science for Electronics I), 111 (2002).
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224
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[18] M. W. Mahoney and P. J. Dynes, Scripta Metallurgica, 19, 539 (1985).
[19] N. Tohge, S. Takahashi, and T. Minami, J. Am. Ceram. Soc., 74 (1) 67 (1991).
[20] Y. Matsuo and H. Sasaki, J. Am. Ceram. Soc., 48 (6) 289 (1965).
[21] D. L. Hankey and J. V. Biggers, J. Am. Ceram. Soc., 64 (12) C-172 (1981).
[22] B. V. Hiremath, A. I. Kingon, and J. V. Biggers, J. Am. Ceram. Soc., 66 (11) 790
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[23] G. D. Wilk, R. M. Wallace, and J. M. Anthony, J. Appl. Phys., 89, 10, 5243 (2001).
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225
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226
CHAPTER 7
Conclusion and Future Work
7.1 Conclusion
Undoped and Ca-doped PZT (52/48) thin film capacitors were prepared on base
metal foil electrode by chemical solution deposition for potential embedded passive
applications. The effects of processing parameters on the phase evolution,
microstructures, dielectric properties, and reliability were investigated.
227
constant reduced to more than half of the identical capacitors processed on Pt/SiO2/Si ,
and capacitance further reduced with higher crystallization temperature up to 650 oC. It
was suggested that these behavior might be from the interface between capacitor and
underlying electroless Ni layer.
Using two-layer capacitor model, it was suggested low permittivity interface layer
(with permittivity of ~30) exists, and a lot of traps exist near the PZT capacitor / Ni
interface. Dielectric properties of the capacitors were mostly dependent on the
crystallization temperature. Almost 350 nF/cm2 of capacitance densities and 0.02 ~ 0.03
of loss tangent were routinely measured for capacitors crystallized at 575 ~ 600 oC.
Leakage current showed dependence on film thickness and crystallization temperature.
For thinner films, conduction mechanism close to Schottky emission was measured,
however, for thicker films, traps in the PZT film seem to dominate, and conduction was
more close to space charge limited.
Interface reaction between PZT thin film and electroless Ni was suggested to be
responsible for electrical properties observed. The interfacial layer might be composed of
unreacted oxide, phosphate, phosphides, combined possibly with phosphorous diffused
from electroless Ni into PZT.
228
and reduced dielectric constant and remanent polarization was observed. Possibilities
include reduced tetragonality, acceptor doping, and inhomogeneous microstructure.
For Ca-doped PZT (52/48) thin film capacitors prepared on electroless Ni coated
Cu foil, phase stability was influenced by Ca doping and phosphorous content. Dielectric
properties showed dependence on the crystallization temperature and phosphorous
content, which was similar to undoped PZT composition. For 5 mol % Ca-doped PZT
thin film capacitors, improvement of capacitance density (~ 400 nF/cm2) was achieved by
more than 30 %, compared to undoped PZT composition. Ca doping also reduced the
temperature coefficient of capacitance (TCC) less than 10 %, all of which were found to
satisfy the requirement for embedded passive capacitors. Leakage current density was not
affected significantly by Ca doping.
230
Third, more detailed analysis would be necessary for interface between PZT
based thin film capacitor and underlying electroless Ni. Quantitative analysis and crystal
structure study for interface region might provide more insight into the interface
engineering for other similar materials system.
Fourth, lower temperature buffer layer processing should be developed for
improved interface characteristics such as better reliability required in embedded passive
application.
231