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C: Energy Conversion and Storage; Energy and Charge Transport

Energy Storage Performance and Electric Breakdown Field of Thin Relaxor Ferroelectric PLZT Films using Microstructure and Growth Orientation Control Minh Nguyen, Evert P. Houwman, and Guus Rijnders J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.8b04251 • Publication Date (Web): 19 Jun 2018 Downloaded from http://pubs.acs.org on June 20, 2018

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The Journal of Physical Chemistry

Energy Storage Performance and Electric Breakdown Field of Thin Relaxor Ferroelectric PLZT Films using Microstructure and Growth Orientation Control

Minh D. Nguyen,*,†,‡,§ Evert P. Houwman,§ and Guus Rijnders§

†

Division of Computational Mechatronics, Institute for Computational Science, Ton Duc

Thang University, Ho Chi Minh City, Vietnam ‡

Faculty of Electrical & Electronics Engineering, Ton Duc Thang University, Ho Chi Minh

City, Vietnam §

MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500AE

Enschede, The Netherlands

1 ACS Paragon Plus Environment

The Journal of Physical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ABSTRACT. Thin relaxor-ferroelectric Pb0.9La0.1(Zr0.52Ti0.48)O3 (PLZT) films were deposited on Si substrates using Ca2Nb3O10 (CNOns) and Ti0.87O2 (TiOns) nanosheets as the growth template layer and SrRuO3 (SRO) as the base electrode layer, using pulsed laser deposition. XRD and cross-sectional SEM results show that the structure of the PLZT layers changes from very dense with (001)-orientation to columnar with (110)-orientation for CNOns and TiOns, respectively. The recoverable energy-storage density (Ureco) is nearly proportional to the critical electric breakdown field (EBD), which increases with PLZT film thickness. A very high Ureco value of 58.4 J cm-3 and energy-storage efficiency (η) of 81.2% were obtained at an EBD of 3400 kV cm-1 for the 1000-nm-thick PLZT film on CNOns/Si, significantly higher than for the film on TiOns/Si (Ureco = 44.0 J cm-3 and η = 59.6% for EBD =2800 kV cm-1). This excellent energy storage performance in the PLZT/SRO/CNOns/Si is due to the dense film structure and nearly hysteresis-free relaxor behavior. These results are important for improving the performance of relaxor-ferroelectric thin films for high-power capacitor applications.


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INTRODUCTION Dielectric capacitors are currently receiving much attention for pulse-power applications because of their fast charge–discharge rates and high power capabilities.1-3 The energy storage capability of a dielectric capacitor is often described by the energy density, i.e. the amount of stored energy per unit weight or volume. In general, the volumetric energy storage density (Ustore) can be expressed as:

=

(1)

= +

(2)

where D is the electric displacement induced on the dielectric material under an applied electric field E. P is the polarization of the dielectric and the vacuum dielectric constant. For linear dielectrics, Eq. (2) can be written as: = + = ( the relative dielectric constant of the dielectric) and Eq. (1) can be simplified to:

= =

(3)

Next to the linear dielectrics (DE), there are three other types of dielectrics that can be used for energy storage applications: ferroelectrics (FE), relaxor ferroelectrics (RFE) and antiferroelectrics (AFE). Figure S1 shows typical polarization hysteresis (P-E) loops and the corresponding energy storage characteristics of these materials. The

energy

storage

density

in

ferroelectrics,

relaxor

ferroelectrics

and

antiferroelectrics can be determined by integrating the area under the P–E hysteresis loops (as in Figure S1b–f). The energy stored per unit volume (Ustore = yellow + green area in the graph), recoverable energy-storage density (Ureco = yellow area), energy-loss density (Uloss = green area) and energy-storage efficiency (η) can be calculated as:

=


(4)


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=

(5)

= −

(6)

%! = 100 × ⁄

(7)

where Pr-, Pr+ and Ps are the negative remanent polarization, positive remanent polarization and saturation polarization, i.e. the polarization at the highest applied electrical field Emax (Figure S2), respectively. Emax must be equal to or less than the critical electric breakdown field (EBD), just below the electric field where the capacitor is broken completely. In practice, the dielectric already starts to show increased leakage currents at much lower field strengths, for example around 50% of EBD. Although linear dielectrics (Figure S1a) often possess a high breakdown field and very low energy loss (thus a high energy-storage efficiency η ≈ 100%), their much lower εr value (and therefore much lower energy storage density, as shown in Eq. (3)) makes them unsuitable for high energy-storage applications. Ferroelectrics often have a large saturation polarization (Figure S1b), but also show a small recoverable energy-storage density and low energy-storage efficiency due to their large remanent polarization. Relaxor ferroelectrics and antiferroelectrics with high Ps and low Pr values are therefore more suitable for high energy-storage applications (Figure S1c,d). However, the presence of the doublehysteresis P–E loop characteristic of a typical AFE (Figure S1d), representing a sharp phase switching between the FE and the AFE phases, reduces the energy-storage efficiency due to the larger energy loss. For these reasons, relaxor ferroelectrics with a slim hysteresis loop and low remanent polarization (Figure S1c) are considered to be the most promising candidates for high energy-storage applications. From Eq. (5) it is seen that a high Ureco value can be obtained for a low Pr+ and large Ps, thus for a large Emax value, a high electric breakdown field is required. Previous studies showed that the RFE poly(vinylidene fluoride) (PVDF)-based polymers had a high Ureco value 4 ACS Paragon Plus Environment

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of about 27 J cm-3 owing to their very high EBD value up to 8000 kV cm-1.4-6 However, their potential application in energy storage is limited due to the low maximum allowable working temperature (less than 100 oC). Lead-free RFE thin films for energy storage have also been investigated. Zhang et al. obtained Ureco = 27 J cm-3 for EBD of 1894 kV cm-1 in RFE Mndoped ((Na0.5Bi0.5)TiO3)0.7-(SrTiO3)0.3 sol-gel films.7 An even larger Ureco = 51 J cm-3 at EBD = 3600 kV cm-1 for RFE Mn-doped BiFeO3-SrTiO3 pulsed laser deposited films was reported by Pan et al.8 However, partial rounding of the P-E loops near Emax, which might be caused by the presence of free carriers and leakage currents, was observed in these films, resulting in a significant reduction of energy-storage efficiency when a high electric field is applied. Another particularly interesting thin-film RFE is the La-doped Pb(Zr,Ti)O3 system. Hao et al. showed a large Ureco = 28.7 J cm-3 (η ≈ 58%) at EBD = 2177 kV cm-1 for 1-µm-thick sol-gel Pb0.91La0.09(Ti0.65Zr0.35)O3 films on Pt/Ti/SiO2/Si.9 Tong et al. reported a high Ureco of about 22 J cm-3 (η ≈ 77%) at &'( = 1600 kV cm-1 for 3-µm-thick Pb0.92La0.08(Zr0.52Ti0.48)O3 films deposited on LaNiO3/Ni using the sol-gel method.10 Recently, we reported on the energy-storage performance and the EBD values of 500-nm-thick Pb0.9La0.1(Ti0.52Zr0.48)O3 (PLZT) thin films deposited using the pulsed laser deposition (PLD) method, as a function of the film growth mechanism and microstructure.11 The results showed that the epitaxial (001)oriented PLZT films with a dense structure on SrRuO3/SrTiO3/Si (STO/Si) and a SrRuO3 top electrode, have a high Ureco of 40.2 J cm-3 (η = 83.8%) at the high EBD = 2500 kV cm-1. In contrast, the polycrystalline PLZT film with a columnar structure PLD-deposited on Pt/Ti/SiO2/Si (Pt/Si) showed a much lower Ureco = 20.2 J cm-3 (η = 79.6%), because of the much lower EBD (1700 kV cm-1). These results indicate that good energy-storage performance and a high electric breakdown field can be achieved in PLD PLZT films with a high crystalline quality and a dense structure. Moreover, excellent fatigue-free operation (tested up to 1010 cycles) and a high thermal stability (up to 200 oC) were also observed in these 5 ACS Paragon Plus Environment


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epitaxial films. The conductive oxide SRO electrodes prevent the degradation of the interfaces between the PLZT layer and the electrodes, which is known to be the main cause of fatigue in PLZT and Pb(Zr,Ti)O3 (PZT) capacitor structures in general. The highly textured PLD PLZT films grown on SrRuO3/Ca2Nb3O10-nanosheet/Si (SRO/CNOns/Si substrates), reported in the same study, exhibited a lower Ureco (28.4 J cm-3 at EBD = 2000 kV cm-1) value as compared to the above-discussed epitaxial PLZT films (Ureco = 40.2 J cm-3 at EBD = 2500 kV cm-1). However, the fatigue and thermal stability properties were very similar to those of the epitaxial films. The PLZT films on CNOns/Si are therefore promising for industrial applications due to the possibility of large-scale and low-cost production.11 Here we report on a study of the energy-storage performance and electric breakdown field of high-quality textured RFE Pb0.9La0.1(Zr0.52Ti0.48)O3 (PLZT) thin films in the thickness range 300–1000 nm, deposited on SrRuO3/Ca2Nb3O10-nanosheet/Si and SrRuO3/Ti0.87O2nanosheet/Si (SRO/TiOns/Si) using PLD. Highly textured (001)-oriented PLZT films with dense structure were grown on CNOns/Si, while highly textured (110)-oriented films with a columnar structure were obtained on TiOns/Si. The ferroelectric properties, energy-storage performance and electric breakdown field were investigated as a function of film thickness and crystalline orientation. The main result of this study is that for the same applied electric field, the Ureco value is nearly independent of the film thickness and crystalline orientation. However, EBD is enhanced for the films with a dense structure and for larger film thicknesses, resulting in a higher Ureco value.

METHODS Nanosheet Deposition. Ca2Nb3O10 (CNOns) and Ti0.87O2 (TiOns) nanosheets were deposited on

Si

substrates

by

the

exfoliation

of

layered

protonated

calcium

niobate

(HCa2Nb3O10•1.5H2O), and layered protonated titanate (H1.07Ti1.73O4•H2O), respectively, 6 ACS Paragon Plus Environment

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using the Langmuir–Blodgett deposition method (Figure S3a).12 The nanosheet thicknesses were about 2.7 and 0.7 nm, respectively, for the CNOns and TiOns monolayers.12 Pulsed Laser Deposition. Thin relaxor-ferroelectric Pb0.9La0.1(Zr0.52Ti0.48)O3 (PLZT) films were grown on 100-nm-thick SrRuO3 (SRO) electrodes deposited on CNOns/Si and TiOns/Si substrates using the pulsed laser deposition (PLD) method with a KrF excimer laser source (Lambda Physik, 248 nm wavelength). The steps of the fabrication procedure of the RFE capacitor structures are shown schematically in Figure S3a,b. The deposition conditions of the PLZT films were: laser repetition frequency 10 Hz, substrate temperature 600 °C, energy density 2.5 J cm-2 and O2 pressure 0.1 mbar. The deposition conditions were 4 Hz, 600 oC, 2.5 J cm-2 and 0.13 mbar O2 for the SRO electrodes. All layers were deposited successively without breaking the vacuum. After deposition, the films were cooled down to room temperature in a 1 bar oxygen atmosphere and at a ramp rate of 8 oC minute-1. Fabrication of Thin-Film Capacitors. The capacitor structures (size: 100×100 µm2) were patterned by a standard photolithography process and structured by argon-ion beam etching of the SRO top-electrodes (Figure S3c) and wet-chemical etching (HF-HCl solution) of the PLZT films (Figure S3d). Analysis and Characterization. The crystallographic properties of the thin films were analyzed by X-ray θ-2θ scans (XRD) and omega scans using a PANalytical Xray diffractometer

(PANalytical,

Almelo,

The

Netherlands)

with

Cu-Kα radiation

(wavelength: 1.5405 Å). Cross-sectional high-resolution scanning electron microscopy (HRSEM: Zeiss-1550, Carl Zeiss Microscopy GmbH, Jena, Germany) was performed to investigate the microstructure and thickness of the as-grown thin films. The polarization-electric field (P-E) hysteresis loop, switching current (IS-E) and leakage current density (J-E) measurements were performed with the dynamic hysteresis measurement (DHM) and breakdown measurement (BDM) features in the ferroelectric 7 ACS Paragon Plus Environment


module of the aixACCT TF-2000 Analyzer (aixACCT Systems GmbH, Aachen, Germany). A Keithley 4200 Semiconductor Characterization System (Tektronix, Beaverton-Oregon, United States) was used for the capacitance measurement. The capacitance–electric ﬁeld (C-E) curves were measured up to a dc electric field of ±200 kV cm-1 and with a 1 kHz frequency ac electric field of 2 kV cm-1. The corresponding dielectric constants (e33-E) were calculated from the C-E curves. All measurements were performed at room temperature.

RESULTS AND DISCUSSION The crystallinity of the PLZT thin films on SRO/CNOns/Si and SRO/TiOns/Si substrates was investigated by X-ray θ-2θ scans. Figure 1a,b show that the PLZT thin films grown on CNOns/Si are predominantly (001)-oriented with a small fraction of (110)orientation, whereas preferentially (110)-oriented growth and a minor (001)-oriented fraction are found in the films on TiOns/Si. Clearly all the thin films have crystallized in a pure perovskite phase and no evidence of secondary phase formation, such as the pyrochlore phase, is apparent. This is similar to ferroelectric Pb(Zr0.52Ti0.48)O3 (PZT) thin films on the same type of substrates.12 Thus it is demonstrated that, by changing the type of nanosheet, the crystalline orientation of the PLZT thin films can be controlled and follows the orientation of the SRO bottom electrodes. This is explained by the lattice matching between the nanosheets and the SRO layers. The pseudo-cube (pc) on cube (c) fit of the SRO layer on CNOns is in the [001]pc direction (apc = 3.93 Å for SRO, ac = 3.86 Å for CNOns and the lattice mismatch is +1.8%), while the TiOns (with in-plane lattice parameters a = 3.76 Å and b = 2.97 Å) promote the growth of the SRO layer in the [110]pc direction.13 The crystalline quality of the thin films was further determined from the rocking curves (or omega scans) of the PLZT(002) and PLZT(110) reflection peaks, as shown in Figure 1c,d. The full-width at half maximum (FWHM) values of the rocking curves of the 8 ACS Paragon Plus Environment

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PLZT(002) and PLZT(110) peaks are in the range of 0.21–0.29o and 2.2–3.1o, respectively, for (001)- and (110)-oriented PLZT films (see Table 1). The width of the rocking curves is a measure of the range over which the lattice structure in the different grains tilts with respect to the film normal14 and is therefore an indication of the crystalline homogeneity of a film. The difference in FWHM means that the PLZT thin films grown on CNOns/Si exhibit a high crystalline quality in comparison to those on TiOns/Si. With increasing film thickness, the FWHM value of the rocking curve only slightly increases, indicating that the average growth orientation in the grains hardly changes with increasing (columnar) grain length.

1000 nm 40

50

1.0

(c)

0.5 0.0

-1.0

PLZT(002) 1000 nm

-0.5

300 nm 0.0

0.5

1.0

SRO(002)

PLZT(002)

PLZT(111)

SRO(110)

600 nm

20

Normalized intensity

30

2-Theta (degree)

300 nm

Si(002)

600 nm

20

PLZT(001)

Log(intensity) (a.u.)

SRO(002)

PLZT(002)

PLZT(110) Si(002)

SRO(001)

PLZT(001)

Log(intensity) (a.u.)

300 nm

PLZT(110)

(b)

(a)

Normalized intensity

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


30

1000 nm 40

50

2-Theta (degree)

(d)

1.0

PLZT(110)

1000 nm 0.5

300 nm 0.0

-4

-2

0

2

4

Omega (degree)

Omega (degree)

Figure 1. XRD patterns of PLZT thin films grown on SRO buffered (a) CNOns/Si and (b) TiOns/Si substrates. (c) and (d) Corresponding rocking curves of the PLZT(002) reflection peaks in Figure 1a and PLZT(110) reflection peaks in Figure 1b, respectively.

The film microstructure was investigated by cross-sectional SEM as shown in Figure 2. The (001)-oriented PLZT films show a very dense structure (Figure 2a-c), whereas, by



using TiOns as a growth template layer, columnar microstructures are obtained in the (110)oriented films (Figure 2d-f).

Figure 2. Cross-sectional SEM images of PLZT thin films with thicknesses of 300, 600 and 1000 nm grown on (a-c) CNOns/Si and (d-f) TiOns/Si substrates.

-30

-500

0

E (kV/cm) (c) CNOns/Si

500

3

Ustore

η (%)

90 85

400

600

-30

800

1000

-500

0

500

1000

75

95

16 90

14

85 Ustore

12

80

Ureco

10 200

(1)

0

95

14

(2)

E (kV/cm) (d) TiOns/Si

16

12

30

-60 -1000

1000

(3)

300 nm (1) 600 nm (2) 1000 nm (3)

10 200

η (%)

2

0

-60 -1000

3

60

Ustore & Ureco (J/cm )

2

P (µC/cm )

30

(b) TiOns/Si

(3) (2) (1)

300 nm (1) 600 nm (2) 1000 nm (3)

P (µC/cm )

(a) CNOns/Si 60

Ustore & Ureco (J/cm )

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 10 of 27

80

Ureco

400

600

800

1000

75

Thickness (nm)

Thickness (nm)

Figure 3. P–E hysteresis loops of PLZT films with thickness of 300, 600 and 1000 nm grown on (a) CNOns/Si and (b) TiOns/Si substrates. (c,d) stored energy per unit volume (Ustore), recoverable energystorage density (Ureco) and energy-storage efficiency (η) of these PLZT thin films. The measurements were performed at & =1000 kV cm-1 and 1 kHz frequency.


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The polarization hysteresis (P-E) loops of the films on CNOns/Si and TiOns/Si with different thicknesses, measured to a maximum electric field of ±1000 kV cm-1 and at 1 kHz frequency, are shown in Figure 3a,b. The energy-storage properties were calculated from these loops (Figure 3c,d). The Ps(Emax) value slightly increases for increasing film thickness (Table 1) and the loop rotates counter-clockwise, while the remanent polarization is almost unchanged (Figure S4a,b). No significant difference is observed for thin films with different growth orientations. These results imply that the recoverable energy-storage density (Ureco) values are very similar for both (001)- and (110)-oriented PLZT thin films, irrespective of the film thickness. The energy-storage efficiency is somewhat higher in the (001)-oriented films, but for both types η is nearly independent of thickness (Figure 3c,d and Table 1). The somewhat lower efficiency for the (110) films is due to the slightly larger broadening of the

P-E loops, thus higher energy loss, as can be seen in Figure S5. The thickness and orientation dependences of ferroelectric properties in PZT films are very different from those of the RFE PLZT films. (001)-oriented PZT films have a larger remanent polarization than (110)-oriented PZT films because the spontaneous polarization is along the [001] crystallographic direction.12,15 In the FE PZT films the Pr value increases significantly with increasing thickness, due to the reduction of substrate constraints and tensile stress, as well as the decrease in the effect of an interfacial ‘dead’ layer.16,17 Brown et al. studied the influence of film thickness on the ferroelectric and energystorage properties of RFE Pb0.92La0.08(Zr0.52Ti0.48)O3 (PL8ZT). They found that both the Ps and Pr+ values increase with film thickness, but Ps more than Pr+, resulting in a higher Ureco value for the thicker films.18 However, the thinner films showed much higher η values (about 77% for 250 nm film) compared to the thicker films (34% for 1000 nm film) under the same applied electric field (160 kV cm-1), because the P-E loops open up as the film thickness 11 ACS Paragon Plus Environment


increases, because the dielectric behavior changes from nearly linear dielectric-like to that of nonlinear hysteretic relaxor ferroelectrics.18 In our films the P-E loops and Ureco values are almost independent of film thickness and crystalline orientation, reflecting nearly hysteresisfree RFE behavior. However, in the next section we show that in our PLZT films there is a small AFE-like contribution present at low fields. Switching current, IS (µΑ)

(a) CNOns/Si 20 10 0 -10 -20

2000

-200

-100

0

100

10 0

-20

200

E (kV/cm)

(c) CNOns/Si

1000nm 600nm

1500

300nm

1000 500

(b) TiOns/Si 20

-10

300nm 600nm 1000nm

Dielectric constant, e33

Dielectric constant, e33 Switching current, I (µΑ) S

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 27

-200

-100

0

E (kV/cm)

100

200

2000

300nm 600nm

1000nm

-200

-100

0

E (kV/cm)

100

200

(d) TiOns/Si 1000nm

1500

600nm 300nm

1000 500

-200

-100

0

E (kV/cm)

100

200

Figure 4. (a,b) Switching current-electric field and (c,d) dielectric constant-electric field (e33-E) curves, of PLZT thin films on CNOns/Si and TiOns/Si substrates. The measurements were performed at ±200 kV cm-1 and 1 kHz frequency.

Figure S6 shows an IS-E measurement of a typical PbZrO3 film with the four switching peaks typical of an antiferroelectric (AFE) material. Although Figure 3a,b show the slim P-E hysteresis loops for both the (001) and (110)-oriented PLZT thin films, indicating the RFE nature of the bulk of the films, the IS-E curves (Figure 4a,b) also show a multiple switching behavior (at low field) typical of AFE-like behavior. Similar double peaks are observed in the dielectric constant-electric field (e33-E) curves (Figure 4c,d). The peak 12 ACS Paragon Plus Environment

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positions in the IS-E and e33-E curves are also almost independent of the crystalline orientation and film thickness. The switching currents in the CNOns/Si and TiOns/Si capacitors are of the same order of magnitude, suggesting that the amount of the film that shows AFE-like behavior is approximately the same for all films. This in turn likely suggests that the AFE region is present at an interface and is not a present in the bulk of the film. The AFE switching current contribution is also reflected in the small kinks and bumps in the low field part of the P-E loops (Figure S4a,b). The dielectric constant increases with film thickness. Such behavior was reported previously and attributed to the change of the relative thickness fraction of a dead-layer (at the film/electrode layer)19,20 and/or the enhancement of 180o-domain wall motion (extrinsic contribution) with increasing film thickness.21,22

Figure 5. P–E hysteresis loops of 1000-nm-thick PLZT thin films grown on (a) CNOns/Si and (b) TiOns/Si substrates, measured until their critical EBD values (3400 and 2800 kV cm-1, respectively, for the films on CNOns/Si and TiOns/Si). Optical images of broken PLZT film capacitors on (c) CNOns/Si measured at 3500 kV cm-1 and (d) TiOns/Si measured at 2900 kV cm-1. The top-electrode size of all measured PLZT film capacitors is 100×100 µm2.



In order to determine the electric breakdown field, the P-E loops were measured from a low maximum electric field (such as 200 kV cm-1) up to the electric field where the capacitors failed. Figure 5a,b show the P-E loops of typical 1000-nm-thick PLZT thin films grown on CNOns/Si and TiOns/Si substrates, measured up to their EBD values. The PLZT films on CNOns/Si devices have a significantly higher electric breakdown field (typically EBD = 3400 kV cm-1) than those on TiOns/Si (EBD = 2800 kV cm-1). Figure 5c,d show capacitors after breakdown. The P-E loops of PLZT films on TiOns/Si show more hysteresis than the loop of the device on CNOns/Si (Figure S7), causing a lower efficiency. On the other hand, even the Ureco values in the films on CNOns/Si and TiOns/Si are almost unchanged at the same applied electric field due to the discharge curves coinciding with each other; however, the required energy consumption during the charging process is lower with higher energy efficiency in the films on CNOns/Si.

(a)

(b) BD complete

CNOns/Si TiOns/Si 2

Breakdown field (kV/cm)

0.010

J (A/cm )

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 27

0.005

BD start

0.000 0

1000

2000

3000

4000

E (kV/cm)

CNOns/Si

3600

TiOns/Si

3000 2400 1800

BD-start BD-complete BD-complete (from J-E) (from J-E) (from P-E)

Figure 6. (a) Leakage current density (J) versus applied electric field (E) and (b) variation of the starting point of breakdown process (BD-start, J-E) and completely broken point (BD-complete, J-E) from J-E measurements, and completely broken point (BD-complete, P-E) from P-E measurements, of 1000-nm-thick PLZT films on CNOns/Si and TiOns/Si.

Commonly, the measured P-E hysteresis loop contains contributions arising from leakage currents and possibly free charge carriers, in addition to the switched charge 14 ACS Paragon Plus Environment

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density.23 Figure 6a shows that below breakdown the leakage current increases exponentially with increasing field, starting at about half EBD. The higher leakage current density (J) in PLZT thin films on TiOns/Si in Figure 6a is an artefact, because it is scaled to the top electrode area, whereas one can see from Figure 5d that the leakage current spreads out far beyond the electrode boundary, whereas for the device on CNOns/Si there is only leakage below the top electrode. This suggests that in the latter case only leakage currents perpendicular to the film plane arise, whereas in the TiOns/Si device there is also a large lateral spread of the currents, likely along the conductive planes between the columnar grains (Figure 7b), which is consistent with partial rounding of the P-E loops near Emax. The main reasons for this phenomenon are leakage currents and free carriers. Figure 6a shows the leakage current density plotted as a function of the electric field (J-E) of 1000-nm-thick PLZT films on CNOns/Si and TiOns/Si. The change of breakdown field in the J-E and P-E measurements of film capacitors is shown in Figure 6b. In the J-E measurements, the starting points (local breakdown/breakdown spot) of the breakdown process (BD-start, J-E) are 2624 and 2085 kV cm-1, respectively, for the thin films on CNOns/Si and TiOns/Si. The completely broken values in the J-E measurements (3280 and 2624 kV cm-1, respectively, for the thin films on CNOns/Si and TiOns/Si) are smaller than the corresponding values obtained from the P-E measurements (3500 and 2900 kV cm-1), but show the same trend. The difference between these values may be related to the condition of the measurements. In the J-E measurements, the dc electric fields are continuously applied to the capacitors from the low electric field until the electric field where the capacitors are fully broken, whereas the P-E loops are measured from the low ac-applied electric field to the ac-applied electric field where the capacitors are broken but with a discontinuous process. The appearance of the breakdown spots as the results of local discharge may explain the lower completely broken values obtained from the J-E measurements. The visible degradation of the SRO top electrode 15 ACS Paragon Plus Environment


(or SRO/PLZT/SRO capacitor) of the columnar structure PLZT film, with 1000-nm thickness for example, during the J-E measurement process is shown in Figure S8a. In this process, the top electrode begins to break at the applied electric field of about 2085 kV cm-1 (Figure S8b). With increasing applied electric field, more and more breakdown spots appear on the top electrode (Figure S8c) and this process is finished when the top electrode is broken completely (Figure S8d). The breakdown spot on the top electrode in Figure S8b (blue-box line) is zoomed-in and observed by SEM, as shown in Figure S8b1. The zoomed-in image of the red-box line in Figure S8b1 is shown in Figure S8b2. It indicates that the PLZT film is melted and even the melted liquid-like form is flowed outward from the breakdown spot.

Figure 7. Energy selective Backscattered (EsB) cross-sectional images of 600-nm-thick PLZT films grown on (a) CNOns/Si and (b) TiOns/Si substrates.

Moreover, it appears that the breakdown is related to the microstructure of the PLZT thin films. The current is more and less uniformly distributed in the dense structure (Figure 7a) and columnar structure (Figure 7b), respectively. It is assumed that the current concentrates around weak points (defects) in the films. Lee et al. also indicated that the leakage current through grain boundaries is much higher than that through bulk PZT film.24 The increase of the grain boundary density leads to a decrease of the electric breakdown field. The Energy selective Backscattered (EsB) image in Figure 7b shows that gaps along the boundary of columnar grains (arrow direction) are observed in PLZT film grown on TiOns/Si. 16 ACS Paragon Plus Environment

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It is possible that the accumulation of defects at the grain/columnar boundaries produces the high leakage current density and the reduced electric breakdown field in the columnarstructure PLZT film grown on TiOns/Si. Figure 8 illustrates the recoverable energy-storage density (Ureco) and energy efficiency (η) calculated from the P-E loops of PLZT films on CNOns/Si and TiOns/Si as a function of the applied electric field, measured until a critical electric breakdown field, EBD (just below the electric field where the capacitor is broken completely). As expected, Ureco of all samples increases linearly with increasing electric field (Figure 8a,b). Further, it is found that the increase of Ureco with film thickness is mainly due to the increase in the breakdown field. Table 1 shows the change in Ureco and also EBD values with increase of the film thickness. The EBD and thus Ureco values in the PLZT films on CNOns/Si are higher than those in the films on TiOns/Si with the same thickness. The maximum Ureco values at their corresponding EBD values are 58.4 J cm-3 (EBD = 3400 kV cm-1) and 44.0 J cm-3 (EBD = 2800 kV cm-1) for the 1000-nm-thick PLZT films grown on CNOns/Si and TiOns/Si, respectively. The energy-storage efficiency (η) values are relatively stable in the dense-structure PLZT thin films (η ≈ 90.2– 91.4%) in the range of electric field below 1500 kV cm-1 and then slightly decrease with increasing electric field (until their EBD values), as shown in Figure 8c. The η values in the columnar-structure PLZT thin films are also quite stable in the range of electric field below 700 kV cm-1 but with lower values (η ≈ 88.0– 89.4%), as shown in Figure 8d. However, as the applied electric field increases, a significant decrease in η values is observed in the columnar-structure PLZT thin films, due to the partial broadening or rounding of P-E loops near the saturation field (as shown in Figure 5b). The main reasons for this phenomenon are the high mobility of the free-charge carriers (such as defects and oxygen vacancies) along the columnar boundaries. 17 ACS Paragon Plus Environment


60

Ureco (J/cm )

(a) CNOns/Si 3

3

Ureco (J/cm )

60 40

300 nm 600 nm 1000 nm

20 0

0

1000

2000

40

300 nm 600 nm 1000 nm

20 0

3000

(b) TiOns/Si

0

1000

E (kV/cm) 100

2000

3000

E (kV/cm) 100

(c) CNOns/Si

(d) TiOns/Si 90

η (%)

90

η (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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80 70

300 nm 600 nm 1000 nm

60 0

80 70

300 nm 600 nm 1000 nm

60

1000

2000

3000

0

1000

E (kV/cm)

2000

3000

E (kV/cm)

Figure 8. Electric field dependence of recoverable energy-storage density (Ureco) and energy-storage efficiency (η) of the PLZT thin films on (a) CNOns/Si and TiOns/Si substrates. Table 1. Structure, orientation, electric breakdown field and energy storage performance of PLZT thin films grown on CNOns/Si and TiOns/Si substrates. PLZT on

Thickness (nm)

Orient/

FWHM

Ps (µC cm-2)

Ureco (J cm-3)

η (%) at

EBD (kV

Ureco (J

η (%)

Struct.

o

at 1000 kV

at 1000 kV

1000 kV

cm-1)

cm-3) at

at EBD

cm-1

cm-1

cm-1

()

EBD

CNOn

300

(001)/

0.21

50.0

13.5

91.9

2000

287

86.9

s/Si

600

Dense

0.26

52.8

13.7

91.4

2600

40.8

84.3

0.29

54.3

13.8

90.4

3400

58.4

81.2

1000 TiOns /Si

300

(110)/

2.2

49.7

13.2

87.2

1700

23.8

80.5

600

Column

2.7

52.2

13.4

86.8

2300

35.2

71.4

3.1

53.1

13.5

84.3

2800

44.0

59.6

1000

As mentioned above, the highest recoverable energy-storage density (Ureco) of 58.4 J cm-3 (η = 81.2%) is obtained at the electric breakdown field (EBD) of 3400 kV cm-1 for the 1000-nm-thick PLZT film with the dense structure. For comparison, the Ureco and EBD values of some representative ferroelectric (FE),2,25,26 antiferroelectric (AFE)1,27-30 and relaxorferroelectric (RFE) thin films7,9,31-33 are plotted in Figure 9. It shows that the higher Ureco 18 ACS Paragon Plus Environment

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values are mostly obtained in the films with the larger EBD values (Figure 9, region III). However, the AFE films measured at large applied electric field exhibit quite low energystorage efficiency (η) due to the presence of a typical ‘square’ double P-E loop, representing a shape phase transition from FE to AFE and vice versa.27,30 Meanwhile, the films with opposite double-heterojunction ferroelectric-insulator25 or multilayer26 structure exhibit high

η values (≈81.3%) even at large EBD values. In this study, the combination of a slim P-E loop, due to the coexistence of relaxor-ferroelectric and antiferroelectric-like behaviors, and a high electric breakdown field of 3400 kV cm-1 in the 1000-nm-thick PLZT on CNOns/Si devices results in an excellent energy-storage performance (Ureco = 58.4 J cm-3) combined with a high efficiency (η = 81.2%). 70

REF Pb0.9La0.1(Zr0.52Ti0.48)O3 [this study]

(III)

(II)

AFE Pb0.97Y0.02[(Zr0.6Sn0.4)0.925Ti0.075]O3 [1]

60

RFE 0.8Pb(Mg1/3Nb2/3)O3-0.2PbTiO3 [31] RFE BaTiO3/Ba0.3Sr0.7TiO3 superlattices [32] FE 6mol.% BiFeO3-doped (K0.5Na0.5)(Mn0.005Nb0.995)O3 [2]

50

3

Ureco (J/cm )

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


FE Pb(Zr0.52Ti0.48)O3/Al2O3/ Pb(Zr0.52Ti0.48)O3 [25] AFE (Pb0.97La0.02)(Zr0.7Sn0.25Ti0.05)O3 [27]

40

RFE 1mol.% Mn-doped 0.7(Na0.5Bi0.5)TiO3-0.3SrTiO3 [7] AFE Pb0.94La0.04(Zr0.98Ti0.02)O3 [30]

30

AFE Pb0.97La0.02(Zr0.98Ti0.02)O3 [28] AFE Pb0.82La0.12Zr0.85Ti0.15O3 [29]

20

RFE Pb0.91La0.09(Ti0.65Zr0.35)O3 [9]

10 0

RFE Textured Pb0.8Ba0.2ZrO3 [33]

(IV)

(I)

FE Ba0.7Ca0.3TiO3/BaZr0.2Ti0.8O3 multilayers [26]

Solid symbols: η >= 80%

0

1000 2000 3000 4000 5000 6000 Half-solid symbols: 50% < η < 80% Open symbols: η =< 50%

EBD (kV/cm)

Figure 9. Comparison of electric breakdown field (EBD) and recoverable energy-storage density (Ureco) for some representative thin films.

CONCLUSIONS In summary, RFE PLZT thin films with different thicknesses were deposited on conductive-oxide SRO buffered CNOns/Si and TiOns/Si using pulsed laser deposition. It was found that the crystalline orientation and microstructure depend strongly on the buffer layer. 19 ACS Paragon Plus Environment


The PLZT thin films can be tuned from (001)-orientation with dense structure to (110)orientation with columnar structure by using the CNOns and TiOns as the seed layer, respectively. One interesting thing here is that the Ps – Pr+ and then Ureco values, measured at the same applied electric field, are almost unchanged with film thickness, crystalline orientation and also microstructure. Meanwhile, the films with dense structure have low energy-loss density due to the slimmer P-E loops, which favor achieving high energy-storage efficiency. Moreover, at the same thickness, the films with dense structure have a higher EBD and the EBD values are enhanced as the thickness increases. As a result, the great Ureco value of 58.4 J cm-3, high η value of 81.2% and large EBD value of 3400 kV cm-1 are obtained in the 1000-nm-thick RFE PLZT film with dense structure, which is promising for high-power capacitor applications.

ASSOCIATED CONTENT

Supporting Information. Schematic illustration of polarization hysteresis loops of linear dielectrics, ferroelectrics, relaxor ferroelectrics and antiferroelectrics; Schematic illustration of a polarization (P-E) hysteresis loop; Schematic of the fabrication of thin films and capacitors; Zoon-in view, in the range of -100 to +100 kV cm-1, of the P-E loops of PLZT films with various thicknesses; Comparison of the P-E loops of 1000-nm-thick PLZT films on CNOns/Si and TiOns/Si, measured at 1000 kV cm-1; Switching current–electric field of antiferroelectric PbZrO3 thin film; Comparison of the P-E loops of 1000-nm-thick PLZT films on CNOns/Si and TiOns/Si, measured at 2800 kV cm-1; Leakage current density– electric field, microscope and SEM images of breakdown spot of columnar structure PLZT film. This material is available free of charge via the Internet at http://pubs.acs.org.


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AUTHOR INFORMATION

Corresponding Author *E-mail: [email protected]

Author Contributions The manuscript was written through contribution of all authors. All authors discussed the results, commented on the manuscript and gave their approval to the final version of the manuscript.

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS This research was ﬁnancially supported by the MESA+ Institute for Nanotechnology, University of Twente, The Netherlands. The authors thank Mr. Phu Le and Prof. Johan E. ten Elshof for the nanosheet deposition, and Mr. Mark Smithers for performing the HRSEM experiment.

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