Fabrication of doped Pb(Zr,Ti)O3 capacitors

(100)

(200)

(310)
(210)
(110)

(211)

(311)
Pt
Si

Si

Si
PZT
on Pt substrates with different orientations Pt
Si

R. Tamano, T. Amano, Y. Takada, N. Okamoto, T. Saito✉,

PYZT
T. Yoshimura, N. Fujimura, K. Higuchi and A. Kitajima

intensity , a.u.
The effects of crystallographic orientation on the ferroelectric proper- PNZT

ties of Pb(Zr,Ti)O3 (PZT) thin films grown on (111) and (100)-oriented

Pt substrates are investigated. The effects of doping PZT with species PLZT
X (forming PXZT) thin films (Pb:X:Zr:Ti, 113:3:30:70; X = La, Nb, or
Y) using chemical solution deposition were studied. The crystallinity
of all PXZT films was almost identical. The remnant polarisation of PZT
20 30 40 50 60 70 80
the un-doped, La-, Nb-, and Y-doped PZT capacitors with Pt(111) 2q , deg
bottom electrodes were 133.4, 64.7, 60.2, and 98.4 µC/cm2, respect- a
ively. In ferroelectric capacitors with Pt(100) bottom electrodes, the

(100)

(200)

(310)
(210)
(110)

(211)
MgO
remnant polarisations were 185.6, 148.1, 103.1, and 135.7 µC/cm2, PZT

Pt

Pt
Pt
respectively. The remnant polarisation was larger with Pt(100) than MgO

with Pt(111). The initial remnant polarisation of the un-doped PZT

capacitors was larger than that of PXZT.

intensity , a.u.
Introduction: Ferroelectric random access memory (FeRAM) is an
especially promising technology for non-volatile memory, and has
attracted considerable attention because of the high-speed operation,
large number of rewrite cycles, low power consumption, and good
tamper resistance. Applications include integrated circuit (IC) cards,
IC tags, and smart meters [1, 2]. The decrease in the remnant polaris- 20 30 40 50 60 70 80
ation caused by repeated functioning (i.e. fatigue), as well as by a redu- 2q , deg
b
cing atmosphere, is a significant drawback for highly integrated and
reliable FeRAM applications. Doping of Pb(Zr,Ti)O3 (PZT) has been
Fig. 1 XRD patterns of doped-PZT films formed on
investigated as a strategy to improve the reliability of PZT devices;
a Pt(111)
for example, substitution of La, Nd, or Nb into the site of host atoms b Pt(100)
(Pb, Zr, and Ti). The addition of donor species also reduces the concen-
tration of intrinsic oxygen vacancies created due to PbO evaporation
during sintering of PZT thin films [3–5]. La3+ is often used as a PZT PLZT

dopant in PZT since PLZT films possess attractive dielectric and electro-
optic properties. The inclusion of La3+ in a solid solution of PZT results
primarily in A-site vacancies, as well as a reduced concentration of
oxygen vacancies [6, 7]. Solid solubility of these dopants is usually
quite high in the host lattice. For example, Ca2+ can be included with PNZT PYZT
concentrations of up to 8 at.%, and Sr2+ at up to 10 at.%; these elements
substitute for Pb2+ in PZT (53/47) and increase the dielectric constant
from 544 to 888 and 1127, respectively [8]. Furthermore, the ferroelec-
tricity varies depending on the crystallinity and orientation of the 500 nm
ferroelectric film. a
In this Letter, we investigated the influence of orientation of the
PZT PLZT
substrate by using (111) and (100) highly oriented Pt substrates, and
investigated doping of PZT films with La, Nb, or Y using a chemical
solution deposition (CSD). We then characterised the electrical proper-
ties of the resulting films.

PNZT PYZT
Experimental: Highly (111)-oriented Pt (Pt/Ti/SiO2/Si) and highly
(100)-oriented Pt was deposited onto MgO(100) layers that were
formed by sputtering. Doped PZT thin films (Pb:La, Nb, or Y:Zr:Ti =
113:3:30:70), as well as un-doped-PZT thin film, were prepared using
500 nm
CSD. A solution was spin-coated onto the Pt substrate to form capacitor
structures. Details of the fabrication process have been reported b
previously [9–11].
Fig. 2 Surface morphology of doped-PZT films formed on
The ferroelectric properties of PZT capacitors that were 200 µm in
diameter and featured Pt top electrodes were characterised by applying a Pt(111)
b Pt(100)
15 V (giving a field of 500 kV/cm) at room temperature to measure
polarisation–voltage (P–V) hysteresis loops. X-ray diffraction (XRD)
Figs. 2a and b show FE-SEM images of the ferroelectric films depos-
and field-emission scanning electron microscopy (FE-SEM) were used
ited on Pt(111) and Pt(100) substrates. A rosette structure can be observed
to investigate the crystal structure and morphology [12, 13].
if a pyrochlore phase exists [14]; however, rosette structures were not
observed, and no pyrochlore peaks were detected at the surface of the
Results and discussion: Fig. 1 shows XRD patterns of ferroelectric PXZT films, suggesting that the films in the work contained no pyrochlore
films formed using Pt(111) and Pt(100) substrates. The films were poly- phases. Sun et al. [15] reported that addition of more than 2 mol% of
crystalline regardless of the orientation of lower substrate, and exhibited dopant Nb ions inhibits grain growth due to the accumulation of ions at
primal (100) and (110), as well as weak (210), (211), (310), and (311) grain boundaries. We found a similar trend for dopant species Y, La,
peaks. Pyrochlore (222), (400), (440), and (622) phase around and Nb. Regardless of the lower electrode, the grain size was almost
2θ = 29°, 34°, 49°, and 59°, respectively, were observed with CSD equal to the thickness of the PZT, PLZT, or PYZT film.
PZT [14–16]. Only the perovskite phase (ferroelectric phase) was con- Figs. 3a and b show P–V hysteresis loops of ferroelectric capacitors
firmed, and pyrochlore phase was not found in any of the ferroelectric formed using Pt(111) and Pt(100) lower electrodes, respectively. The
films. In addition, there were no consistent variations in the crystal struc- remnant polarisation of the un-doped, La-, Nb-, and Y-doped PZT capaci-
ture due to doping. tors with Pt(111) bottom electrodes were 2Pr = 133.4, 64.7, 60.2, and

ELECTRONICS LETTERS 4th August 2016 Vol. 52 No. 16 pp. 1399–1401

98.4 µC/cm2, respectively. The PZT films exhibited the largest remnant R. Tamano, T. Amano, Y. Takada, N. Okamoto and T. Saito
polarisation and the smallest coercive fields yet reported. The Y-doped (Department of Chemical Engineering, Osaka Prefecture University,
PZT films on Pt(111) exhibited rectangular hysteresis loops, similar to Sakai, Osaka 599-8531, Japan)
those of PZT. The La- and Nb-doped PZT capacitors exhibited hysteresis ✉ E-mail: [email protected]
loops that shifted toward negative voltages, as has been reported previously
[16, 17]. The remnant polarisations of un-doped, La-, Nb-, and Y-doped T. Yoshimura and N. Fujimura (Department of Physics and Electronics,
PZT capacitors with Pt(100) bottom electrodes were 2Pr = 185.6, 148.1, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan)
103.1, and 135.7 µC/cm2, respectively. Compared with the capacitors K. Higuchi and A. Kitajima (Institute of Scientific and Industrial
formed on Pt(111), the ferroelectricity improved remarkably. When the Research, Osaka University, Ibaraki, Osaka 567-0047, Japan)
film orientation and spontaneous polarisation vector are in the same direc-
tion, the ferroelectricity may be expected to improve [18]. The remnant
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PYZT
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and Y, as well as un-doped PZT thin films. Two types of Pt substrates (9B), pp. 5342–5345
were used: highly (111) or (100) oriented. We obtained ferroelectric 14 Bhaskar, A., Chang, T.H., Chang, H.Y., and Cheng, S.Y.: ‘Pb
films that exhibited only the perovskite phase. The remnant polarisation (Zr0.53Ti0.47)O3 thin films with different thicknesses obtained at low
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Acknowledgments: The (111)-oriented Pt-sputtered substrates were 16 Fujii, T., Hishinuma, Y., Mita, T., and Arakawa, T.: ‘Preparation of Nb
supplied by Fujitsu Semiconductor Ltd. This work was supported in doped PZT film by RF sputtering’, Solid State Commun., 2009, 149,
part by the Nanotechnology Open Facilities at Osaka University, and (41–42), pp. 1799–1802
the Cooperative Research Program of ‘Network Joint Research Center 17 Gruveman, A., Rodriguez, B.J., Kingon, A.I., Nemanich, R.J.,
for Materials and Devices’. Tagantsev, A.K., Cross, J.S., and Tsukada, M.: ‘Mechanical stress
effect on imprint behavior of integrated ferroelectric capacitors’, Appl.
Phys. Lett., 2003, 83, (4), p. 728–730
© The Institution of Engineering and Technology 2016 18 Yamazoe, S., Sakurai, H., Fukada, M., Adachi, H., and Wada, T.: ‘The
Submitted: 1 June 2016 E-first: 5 July 2016 effect of SrTiO3 substrate orientation on the surface morphology and
doi: 10.1049/el.2016.1949 ferroelectric properties of pulsed laser deposited NaNbO3 films‘,
One or more of the Figures in this Letter are available in colour online. Appl. Phys. Lett., 2009, 95, (6), 062906, doi: 10.1063/1.3205103

ELECTRONICS LETTERS 4th August 2016 Vol. 52 No. 16 pp. 1399–1401