Original Article
Large energy storage density, low energy loss and highly stable (Pb0.97La0.02)(Zr0.66Sn0.23Ti0.11)O3 antiferroelectric thin-film capacitors

https://doi.org/10.1016/j.jeurceramsoc.2018.03.004Get rights and content

Abstract

In this work, high performance (Pb0.97La0.02)(Zr0.66Sn0.23Ti0.11)O3 polycrystalline antiferroelectric thin-film was successfully fabricated on (La0.7Sr0.3)MnO3/Al2O3(0001) substrate via a cost-effectively chemical solution method. A large recoverable energy storage density (Wre) of 46.3 J/cm3 and high efficiency (η) of 84% were realized simultaneously under an electric field of 4 MV/cm by taking full advantage of the linear dielectric response after the electric field induced antiferroelectric-ferroelectric transition. Moreover, the PLZST thin-film displayed high temperature stability. With increasing temperature from 300 K to 380 K, the Wre decreased only 1.3%. The film also exhibited good fatigue endurance up to 1 × 105 cycling under an electric field of 2.2 MV/cm. Our work underlines the importance of the interface quality between the film and the substrate and the important role of linear dielectric answer after saturation in the improvement of the energy storage density and efficiency of antiferroelectric materials.

Introduction

In recent years, the demand for dielectric capacitors with low loss, high energy-storage density, high stability and fast discharge speed is increasing for power electronic devices due to the rapid development of electronic industry [[1], [2], [3]]. A high energy loss causes not only a waste of energy but also a heating problem which will lead to a performance deterioration of the electronics. For energy storage, it is well known that antiferroelectric (AFE) is a very good candidate in comparison to linear dielectric (LD) and ferroelectric (FE) materials. AFE materials possess higher energy storage density due to their high saturated polarization and small remnant polarization [[4], [5], [6], [7]]. However, the efficiency of typical AFE materials is quite low, which is limited by a large difference △E between EFA and EAF with △E = EAF – EFA, where EAF and EFA are the forward and backward threshold fields, respectively. So it is of practical significance to fabricate AFE materials with both high Wre and η. But this is still a problem hanging on. For example, Hu et al. [8] reported a high Wre of 61 J/cm3 in Pb0.96La0.04Zr0.98Ti0.02O3 film, but the η of the film was just 33% at 4.3 MV/cm. On the contrary, Kang et al. [9] reported a relatively higher η (78.9%) of PLZST film, but the Wre of the film was just 13 J/cm3.

The recoverable energy storage density of AFE materials can be calculated by Wre=PrPmaxEdP (E = applied electric field and P = polarization). As shown in Fig. 1, Wre is released when the electric field reduces from Emax to zero, represented by the green area (W1, caused by the linear dielectric response) and the yellow area (W2, caused by the phase transition between FE and AFE phase after electric field removal). The electric energy loss density Wloss is represented by the red area and η is defined by η=Wre/Wre+Wloss. High Wre and high η can be obtained simultaneously by increasing W1 and W2. Many approaches have been used to improve Wre and η simultaneously by enlarging W2, such as enlarging the transition electric field EFA [[10], [11], [12], [13], [14]]. Besides these, enlarging W1 can also improve Wre and η simultaneously, this possibility was not envisaged to now. From Fig. 1 it is also clear that by enhancing the breakdown electric field W1 can be enlarged. But AFE films are usually deposited on metallic bottom electrode (like Pt) and so the breakdown voltage is low. The main reason is the existence of a dead layer, which possesses a low εr, at the interface between the film and the bottom electrode by diffusion. To suppress this effect, many researches have revealed that the use of oxide bottom electrodes [15,16] is a good way.

In this work the ABO3-type metallic oxide (La0.7Sr0.3)MnO3 (LSMO), which possess a good lattice match with (Pb0.97La0.02)(Zr0.66Sn0.23Ti0.11)O3 (PLZST) [12], has been used as a bottom electrode. PLZST thin film was successfully fabricated on LSMO/Al2O3(0001) substrate via a chemical solution method. And in our work, we demonstrate that through tuning the interface quality between the film and the substrate and taking full advantage of the linear response after the AFE-FE phase transition, both high energy storage density and high efficiency of AFE materials can be achieved.

Section snippets

Experimental procedure

Both the (Pb0.97La0.02)(Zr0.66Sn0.23Ti0.11)O3 thin-film and (La0.7Sr0.3)MnO3 bottom electrode were prepared via chemical solution deposition methods. The detailed deposition process of LSMO can be found elsewhere [17]. The PLZST precursor solution was prepared by dissolving stoichiometric amounts of lead acetate trihydrate, lanthanum acetate, zirconium propoxide, tin acetate and titanium isopropoxide into glacial acetic acid and deionized water co-solvents. Lactic acid (HL) functioned as

Results and discussion

Fig. 2(a) gives the indexed XRD pattern of PLZST thin-film deposited on LSMO/Al2O3(0001) substrate. The PLZST thin-film features a pure perovskite phase with a pseudocubic structure due to the applying of PbO capping layer [18]. The XRD pattern also reveals that the thin-film is polycrystalline and randomly oriented. The SEM images inset in Fig. 2(a) displays that the PLZST thin-film possesses a dense and uniform microstructure with no micro crack. Moreover the PLZST thin-film presents a

Conclusions

In summary, a high quality PLZST thin film was fabricated on LSMO/Al2O3(0001) substrate by a modified sol-gel method. A high energy storage density of 46.3 J/cm3 together with a high energy storage efficiency of 84% was obtained at room temperature, benefiting mainly from the linear dielectric response and the use of oxide electrodes. Moreover the thin-film also exhibited excellent temperature stability and high fatigue endurance. The recoverable energy storage density decreased from 23.5 to

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. U1530156 and 11774366), International Partnership Program of Chinese Academy of Sciences (Grant No. GJHZ1821), Chinese Academy of Sciences President’s International Fellowship Initiative (Grant No. 2017VEA0002), and Shanghai Sailing Program (No. 17YF1429700).

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