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Kalinin, Sergei V,Kim, Yunseok,Fong, Dillon D,Morozovska, Anna N IOP 2018 Reports on progress in physics Vol.81 No.3
<P>For over 70 years, ferroelectric materials have been one of the central research topics for condensed matter physics and material science, an interest driven both by fundamental science and applications. However, ferroelectric surfaces, the key component of ferroelectric films and nanostructures, still present a significant theoretical and even conceptual challenge. Indeed, stability of ferroelectric phase <I>per se</I> necessitates screening of polarization charge. At surfaces, this can lead to coupling between ferroelectric and semiconducting properties of material, or with surface (electro) chemistry, going well beyond classical models applicable for ferroelectric interfaces. In this review, we summarize recent studies of surface-screening phenomena in ferroelectrics. We provide a brief overview of the historical understanding of the physics of ferroelectric surfaces, and existing theoretical models that both introduce screening mechanisms and explore the relationship between screening and relevant aspects of ferroelectric functionalities starting from phase stability itself. Given that the majority of ferroelectrics exist in multiple-domain states, we focus on local studies of screening phenomena using scanning probe microscopy techniques. We discuss recent studies of static and dynamic phenomena on ferroelectric surfaces, as well as phenomena observed under lateral transport, light, chemical, and pressure stimuli. We also note that the need for ionic screening renders polarization switching a coupled physical–electrochemical process and discuss the non-trivial phenomena such as chaotic behavior during domain switching that stem from this.</P>
Morozovska, Anna N.,Eliseev, Eugene A.,Genenko, Yuri A.,Vorotiahin, Ivan S.,Silibin, Maxim V.,Cao, Ye,Kim, Yunseok,Glinchuk, Maya D.,Kalinin, Sergei V. American Physical Society 2016 Physical Review B Vol.94 No.17
<P>We explore the role of flexoelectric effect in functional properties of nanoscale ferroelectric films with mixed electronic-ionic conductivity. Using a coupled Ginzburg-Landau model, we calculate spontaneous polarization, effective piezoresponse, elastic strain and compliance, carrier concentration, and piezoconductance as a function of thickness and applied pressure. In the absence of flexoelectric coupling, the studied physical quantities manifest well-explored size-induced phase transitions, including transition to paraelectric phase below critical thickness. Similarly, in the absence of external pressure flexoelectric coupling affects properties of these films only weakly. However, the combined effect of flexoelectric coupling and external pressure induces polarizations at the film surfaces, which cause the electric built-in field that destroys the thickness-induced phase transition to paraelectric phase and induces the electretlike state with irreversible spontaneous polarization below critical thickness. Interestingly, the built-in field leads to noticeable increase of the average strain and elastic compliance in this thickness range. We further illustrate that the changes of the electron concentration by several orders of magnitude under positive or negative pressures can lead to the occurrence of high-or low-conductivity states, i.e., the nonvolatile piezoresistive switching, in which the swing can be controlled by the film thickness and flexoelectric coupling. The obtained theoretical results can be of fundamental interest for ferroic systems, and can provide a theoretical model for explanation of a set of recent experimental results on resistive switching and transient polar states in these systems.</P>
Chang, Hye Jung,Kalinin, Sergei V.,Morozovska, Anna N.,Huijben, Mark,Chu, Ying‐,Hao,Yu, Pu,Ramesh, Ramamoorthy,Eliseev, Evgeny A.,Svechnikov, George S.,Pennycook, Stephen J.,Borisevich, Albina Y WILEY‐VCH Verlag 2011 Advanced Materials Vol.23 No.21
<P><B>Direct atomic displacement mapping at ferroelectric interfaces</B> by aberration corrected scanning transmission electron microscopy(STEM) (a‐STEM image, b‐corresponding displacement profile) is combined with Landau‐Ginsburg‐Devonshire theory to obtain the complete interface electrostatics in real space, including separate estimates for the polarization and intrinsic interface charge contributions. </P>
Boronated Porphyrins and Chlorins as Potential Anticancer Drugs
Ol'shevskaya, Valentina A.,Zaytsev, Andrey V.,Savchenko, Arina N.,Shtil, Alexander A.,Cheong, Chan-Seong,Kalinin, Valery N. Korean Chemical Society 2007 Bulletin of the Korean Chemical Society Vol.28 No.11
Analyzed are recent advances in design of novel boronared conjugates of synthetic and natural porphyrins and chlorins. These compounds showed high efficacy as cytotoxic agents for tumor cells in culture and as phototoxins in photodynamic therapy of tumor xenografts. Thus, boronated porphyrins and chlorins emerge as promising class of anticancer agents with potentially multiple advantages: the chemotherapeutic drugs alone and photo- and radiosensitizers in binary treatments.
Boronated Porphyrins and Chlorins as Potential Anticancer Drugs
Valentina A. Ol'shevskaya,Andrey V. Zaytsev,Arina N. Savchenko,Alexander A. Shtil,정찬성,Valery N. Kalinin* 대한화학회 2007 Bulletin of the Korean Chemical Society Vol.28 No.11
Analyzed are recent advances in design of novel boronared conjugates of synthetic and natural porphyrins and chlorins. These compounds showed high efficacy as cytotoxic agents for tumor cells in culture and as phototoxins in photodynamic therapy of tumor xenografts. Thus, boronated porphyrins and chlorins emerge as promising class of anticancer agents with potentially multiple advantages: the chemotherapeutic drugs alone and photo- and radiosensitizers in binary treatments.
Interplay of Octahedral Tilts and Polar Order in BiFeO<sub>3</sub> Films
Kim, Young‐,Min,Kumar, Amit,Hatt, Alison,Morozovska, Anna N.,Tselev, Alexander,Biegalski, Michael D.,Ivanov, Ilya,Eliseev, Eugene A.,Pennycook, Stephen J.,Rondinelli, James M.,Kalinin, Sergei V. WILEY‐VCH Verlag 2013 ADVANCED MATERIALS Vol.25 No.17
<P><B>Heterointerface stabilization of a distinct nonpolar BiFeO<SUB>3</SUB> phase</B> occurs simultaneously with changes in octahedral tilts. The resulting phase arises via suppression of polarization by a structural order parameter and can thus be identified as anti‐ferroelectric (Fe displacements – bottom panel). The phase is metastable and can be switched into a polar ferroelectric state (top panel) under an applied electric bias.</P>
Electric modulation of conduction in multiferroic Ca-doped BiFeO<sub>3</sub> films
Yang, C.-H.,Seidel, J.,Kim, S. Y.,Rossen, P. B.,Yu, P.,Gajek, M.,Chu, Y. H.,Martin, L. W.,Holcomb, M. B.,He, Q.,Maksymovych, P.,Balke, N.,Kalinin, S. V.,Baddorf, A. P.,Basu, S. R.,Scullin, M. L.,Rames Nature Publishing Group 2009 Nature materials Vol.8 No.6
Many interesting materials phenomena such as the emergence of high-Tc superconductivity in the cuprates and colossal magnetoresistance in the manganites arise out of a doping-driven competition between energetically similar ground states. Doped multiferroics present a tantalizing evolution of this generic concept of phase competition. Here, we present the observation of an electronic conductor–insulator transition by control of band-filling in the model antiferromagnetic ferroelectric BiFeO<SUB>3</SUB> through Ca doping. Application of electric field enables us to control and manipulate this electronic transition to the extent that a p–n junction can be created, erased and inverted in this material. A ‘dome-like’ feature in the doping dependence of the ferroelectric transition is observed around a Ca concentration of ∼1/8, where a new pseudo-tetragonal phase appears and the electric modulation of conduction is optimized. Possible mechanisms for the observed effects are discussed on the basis of the interplay of ionic and electronic conduction. This observation opens the door to merging magnetoelectrics and magnetoelectronics at room temperature by combining electronic conduction with electric and magnetic degrees of freedom already present in the multiferroic BiFeO<SUB>3</SUB>.