Self-polarization effect on large photovoltaic response in lead free ferroelectric 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 epitaxial film
06 Dec 2018-Applied Physics Letters (AIP Publishing LLC AIP Publishing)-Vol. 113, Iss: 23, pp 233902
TL;DR: In this article, an epitaxial lead free ferroelectric 0.5Ba(Zr0.2Ti0.8)O3-0.3) thin film is fabricated on a (001)Nb:SrTiO3 single crystalline substrate by the pulsed laser deposition method.
Abstract: An epitaxial lead free ferroelectric 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 (BZT-BCT) thin film is fabricated on a (001)Nb:SrTiO3 single crystalline substrate by the pulsed laser deposition method. The 2.3% lattice mismatch between the BZT-BCT and substrate suggests that the film is grown under a compressively strained state by leaving a large strain gradient near the interface. Polarization versus electric field measurement reveals that the film exhibits a ferroelectric hysteresis character with a large imprint effect indicating the existence of an internal electric field. The origin of the internal electric field is correlated with the strain gradient induced flexoelectric effect and the interfacial built-in field. Consequently, the resultant internal electric field could lead to a self-polarized non-switchable layer at the interface. The evidence for the envisaged self-polarization effect is indeed shown by the piezo force microscopic measurements. Importantly, photovoltaic studies performed on the film display an open circuit voltage of 1.1 V, which is higher than the values reported for many ferroelectric films. The observed photovoltaic response is correlated with the depolarization field and the self-polarization effect. The demonstrated large photo-response illustrates the application potential of the BZT-BCT system in photovoltaic devices.
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References
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TL;DR: The use of a solid hole conductor dramatically improved the device stability compared to (CH3NH3)PbI3 -sensitized liquid junction cells.
Abstract: We report on solid-state mesoscopic heterojunction solar cells employing nanoparticles (NPs) of methyl ammonium lead iodide (CH3NH3)PbI3 as light harvesters. The perovskite NPs were produced by reaction of methylammonium iodide with PbI2 and deposited onto a submicron-thick mesoscopic TiO2 film, whose pores were infiltrated with the hole-conductor spiro-MeOTAD. Illumination with standard AM-1.5 sunlight generated large photocurrents (JSC) exceeding 17 mA/cm2, an open circuit photovoltage (VOC) of 0.888 V and a fill factor (FF) of 0.62 yielding a power conversion efficiency (PCE) of 9.7%, the highest reported to date for such cells. Femto second laser studies combined with photo-induced absorption measurements showed charge separation to proceed via hole injection from the excited (CH3NH3)PbI3 NPs into the spiro-MeOTAD followed by electron transfer to the mesoscopic TiO2 film. The use of a solid hole conductor dramatically improved the device stability compared to (CH3NH3)PbI3 -sensitized liquid junction cells.
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TL;DR: It is predicted that the single-crystal form of the MPB composition of the present system may reach a giant d(33) = 1500-2000 pC/N, which may provide a new recipe for designing highly piezoelectric materials (both Pb-free and P b-containing) by searching MPBs starting from a TCP.
Abstract: We report a non-Pb piezoelectric ceramic system Ba(Ti(0.8)Zr(0.2))O(3)-(Ba(0.7)Ca(0.3))TiO(3) which shows a surprisingly high piezoelectric coefficient of d(33) approximately 620 pC/N at optimal composition. Its phase diagram shows a morphotropic phase boundary (MPB) starting from a tricritical triple point of a cubic paraelectric phase (C), ferroelectric rhombohedral (R), and tetragonal (T) phases. The high piezoelectricity of the MPB compositions stems from the composition proximity of the MPB to the tricritical triple point, which leads to a nearly vanishing polarization anisotropy and thus facilitates polarization rotation between 001T and 111R states. We predict that the single-crystal form of the MPB composition of the present system may reach a giant d(33) = 1500-2000 pC/N. Our work may provide a new recipe for designing highly piezoelectric materials (both Pb-free and Pb-containing) by searching MPBs starting from a TCP.
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TL;DR: In this paper, the authors show that lanthanum-substituted bismuth titanate (SBT) thin films provide a promising alternative for FRAM applications, since they are fatigue-free on metal electrodes, they can be deposited at temperatures of ∼650°C and their values of Pr are larger than those of the SBT films.
Abstract: Non-volatile memory devices are so named because they retain information when power is interrupted; thus they are important computer components. In this context, there has been considerable recent interest1,2 in developing non-volatile memories that use ferroelectric thin films—‘ferroelectric random access memories’, or FRAMs—in which information is stored in the polarization state of the ferroelectric material. To realize a practical FRAM, the thin films should satisfy the following criteria: compatibility with existing dynamic random access memory technologies, large remnant polarization (Pr) and reliable polarization-cycling characteristics. Early work focused on lead zirconate titanate (PZT) but, when films of this material were grown on metal electrodes, they generally suffered from a reduction of Pr (‘fatigue’) with polarity switching. Strontium bismuth tantalate (SBT) and related oxides have been proposed to overcome the fatigue problem3, but such materials have other shortcomings, such as a high deposition temperature. Here we show that lanthanum-substituted bismuth titanate thin films provide a promising alternative for FRAM applications. The films are fatigue-free on metal electrodes, they can be deposited at temperatures of ∼650 °C and their values of Pr are larger than those of the SBT films.
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TL;DR: The review ends with the current status of RRAMs in terms of stability, scalability and switching speed, which are three important aspects of integration onto semiconductors.
Abstract: The resistance switching behaviour of several materials has recently attracted considerable attention for its application in non-volatile memory (NVM) devices, popularly described as resistive random access memories (RRAMs). RRAM is a type of NVM that uses a material(s) that changes the resistance when a voltage is applied. Resistive switching phenomena have been observed in many oxides: (i) binary transition metal oxides (TMOs), e.g. TiO(2), Cr(2)O(3), FeO(x) and NiO; (ii) perovskite-type complex TMOs that are variously functional, paraelectric, ferroelectric, multiferroic and magnetic, e.g. (Ba,Sr)TiO(3), Pb(Zr(x) Ti(1-x))O(3), BiFeO(3) and Pr(x)Ca(1-x)MnO(3); (iii) large band gap high-k dielectrics, e.g. Al(2)O(3) and Gd(2)O(3); (iv) graphene oxides. In the non-oxide category, higher chalcogenides are front runners, e.g. In(2)Se(3) and In(2)Te(3). Hence, the number of materials showing this technologically interesting behaviour for information storage is enormous. Resistive switching in these materials can form the basis for the next generation of NVM, i.e. RRAM, when current semiconductor memory technology reaches its limit in terms of density. RRAMs may be the high-density and low-cost NVMs of the future. A review on this topic is of importance to focus concentration on the most promising materials to accelerate application into the semiconductor industry. This review is a small effort to realize the ambitious goal of RRAMs. Its basic focus is on resistive switching in various materials with particular emphasis on binary TMOs. It also addresses the current understanding of resistive switching behaviour. Moreover, a brief comparison between RRAMs and memristors is included. The review ends with the current status of RRAMs in terms of stability, scalability and switching speed, which are three important aspects of integration onto semiconductors.
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