There has been a resurgence of complex oxides of late owing to their ferroelectric and ferromagnetic properties. Although these properties had been recognized decades ago, the renewed interest stems from modern deposition techniques that can produce high quality materials and attractive proposed device concepts. In addition to their use on their own, the interest is building on the use of these materials in a stack also. Ferroelectrics are dielectric materials that have spontaneous polarization in certain temperature range and show nonlinear polarization–electric field dependence called a hysteresis loop. The outstanding properties of the ferroelectrics are due to non-centro-symmetric crystal structure resulting from slight distortion of the cubic perovskite structure. The ferroelectric materials are ferroelastic also in that a change in shape results in a change in the electric polarization (thus electric field) developed in the crystal and vice versa. Therefore they can be used to transform acoustic wav...

Processing, Structure, Properties, and Applications of PZT Thin Films

Fabricating complex transition metal oxides with a tunable bandgap without compromising their intriguing physical properties is a longstanding challenge. Here we examine the layered ferroelectric bismuth titanate and demonstrate that, by site-specific substitution with the Mott insulator lanthanum cobaltite, its bandgap can be narrowed by as much as 1 eV, while remaining strongly ferroelectric. We find that when a specific site in the host material is preferentially substituted, a split-off state responsible for the bandgap reduction is created just below the conduction band of bismuth titanate. This provides a route for controlling the bandgap in complex oxides for use in emerging oxide optoelectronic and energy applications.

/pdf/wide-bandgap-tunability-in-complex-transition-metal-oxides-48iyvpkvza.pdf

Wide bandgap tunability in complex transition metal oxides by site-specific substitution.

Photovoltaic properties of the metal-ferroelectric-metal structures, having SrRuO3 metal oxide electrodes and Pb(Zr,Ti)O3 (PZT) as ferroelectric layer, are investigated by the short-circuit photocurrent (SC-PHC) in the 200–800nm wavelength domain. The band-gap dependence on the Zr content was determined from the spectral distribution of the SC-PHC signal. It was found that the band-gap value increases linearly with the Zr content, from about 3.9eV to about 4.4eV. It is shown that the sign and the magnitude of the signal depend on the internal bias and on the spontaneous polarization direction and value. The photocurrent describes a hysteresis loop similar to that of the ferroelectric polarization and can be used as a nondestructive readout of the nonvolatile memories based on PZT films. The existence of a significant SC-PHC signal at wavelengths corresponding to subgap energies is attributed to the presence of charged, deep levels in the forbidden band. It is also shown that the epitaxial PZT films have t...

Short-circuit photocurrent in epitaxial lead zirconate-titanate thin films

We use a combination of conventional density functional theory (DFT) and post-DFT methods, which include the local density approximation plus Hubbard $U$ ($\text{LDA}+U$), PBE0, and self-consistent $\mathit{GW}$, to study the electronic properties of Ni-substituted PbTiO${}_{3}$ (Ni-PTO) solid solutions. We find that LDA calculations yield unreasonable band structures, especially for Ni-PTO solid solutions that contain an uninterrupted NiO${}_{2}$ layer. Accurate treatment of localized states in transition-metal oxides such as Ni-PTO requires post-DFT methods. $B$-site Ni/Ti cation ordering is also investigated. The $B$-site cation arrangement alters the bonding between Ni and O, and therefore strongly affects the band gap (${E}_{g}$) of Ni-PTO. We predict that Ni-PTO solid solutions should have a direct band gap in the visible light energy range, with polarization similar to the parent PbTiO${}_{3}$. This combination of properties makes Ni-PTO solid solutions promising candidate materials for solar energy conversion devices.

https://link.aps.org/accepted/10.1103/PhysRevB.83.205115

Post density functional theoretical studies of highly polar semiconductive Pb(Ti 1 − x Ni x )O 3 − x solid solutions: Effects of cation arrangement on band gap

Instead of conventional semiconductor photoelectrodes, herein, we focus on BiFeO3 ferroelectric photoelectrodes to break the limits imposed by common semiconductors. As a result of their prominent ferroelectric properties, the photoelectrodes are able to tune the transfer of photo-excited charges generated either in BiFeO3 or the surface modifiers by manipulating the poling conditions of the ferroelectric domains. At 0 V vs Ag/AgCl, the photocurrent could be switched from 0 μA cm−2 to 10 μA cm−2 and the open-circuit potential changes from 33 mV to 440 mV, when the poling bias of pretreatment is manipulated from −8 V to +8 V. Additionally, the pronounced photocurrent from charge injection of the excited surface modifiers could be quenched by switching the poling bias from +8 V to −8 V.

Switchable charge-transfer in the photoelectrochemical energy-conversion process of ferroelectric BiFeO₃ photoelectrodes.

We measure pseudodielectric functions in the visible-deep ultraviolet spectral range of Pb(ZrxTi1−x)O3 (x=0.2,0.56,0.82) (PZT), Pb0.98Nb0.04(Zr0.2Ti0.8)0.96O3, Pb0.91La0.09(Zr0.65Ti0.35)0.98O3, and Pb0.85La0.15Ti0.96O3 films grown on platinized silicon substrates using a sol-gel method and on (0001) sapphire using a radio-frequency sputtering method. Using a parametric optical constant model, we estimate the dielectric functions (ϵ) of the perovskite oxide thin films. Taking the second derivative of the fitted layer dielectric functions and using the standard critical-point model, we determine the parameters of the critical points. In the second derivative spectra, the lowest band-gap energy peak near 4eV is fitted as a double peak for annealed PZTs due to the perovskite phase. As-grown PZTs have mainly pyrochlore phase and the lowest band-gap peak is fitted as a single peak. We also examine the effect of dopants La and Nb, which substitute at Pb and Zr (Ti) sites, respectively. We found three band gaps E...

/pdf/dielectric-functions-and-electronic-band-structure-of-lead-2dg45b4cpc.pdf

Dielectric functions and electronic band structure of lead zirconate titanate thin films

Submitted for the MAR06 Meeting of The American Physical Society Visable-Deep UV Dielectric Functions and Electronic Band Structure of Lead Zirconate Titanate Thin Films HOSUN LEE, T.D. KANG, Kyung Hee Univ., Y.S. KANG, S.-J. CHO, H. MORKOC, Virginia Commonwealth Univ., J. LI, S.-H. WEI, NREL, P.G. SNYDER, Univ. of Nebraska, Lincoln — We measure pseudodielectric functions in the visible-deep ultraviolet spectral range of Pb(ZrxTi1−x)O3 (x=0.2, 0.56, 0.82) (PZT), Pb0.98Nb0.04(Zr0.2Ti0.8)0.96O3,Pb0.91La0.09(Zr0.65Ti0.35)0.98O3, andPb0.85La0.15Ti0.96O3 films. Using a parametric optical constant model, we estimate the dielectric functions (ε) of the perovskite oxide thin films. Taking the second derivative of the fitted layer dielectric functions and using the standard critical point model, we determine the parameters of the critical points. In the second derivative spectra, the lowest band gap energy peak near 4 eV is fitted as a double peak for annealed PZTs due to perovskite phase. As-grown PZTs have mainly pyrochlore phase and the lowest band gap peak is fitted as a single peak. We also examine the effect of dopants La and Nb, which substitute at Pb and Zr (Ti) sites, respectively. We found three band gaps Ea (∼3.9eV), Eb (∼4.5 eV)and Ec (∼6.5eV) in the orderof increasing energy. The Ea and Eb band gap energies were not sensitive to Zr composition. We discuss the change of critical point (CP) parameters for PZTs in comparison to the band structure calculations based on local-densityapproximation. The near-constancy of the lowest band gap energy independent of Zr composition is consistent with the band calculations. Hosun Lee Kyung Hee University Date submitted: 01 Nov 2005 Electronic form version 1.4

http://absimage.aps.org/image/MAR06/MWS_MAR06-2005-000071.pdf

P. G. Snyder

Papers

Dielectric functions and electronic band structure of lead zirconate titanate thin films

Visable-Deep UV Dielectric Functions and Electronic Band Structure of Lead Zirconate Titanate Thin Films