The effect of tungsten trioxide thin films at ferroelectric-electrode boundaries on fatigue behaviour

A conventional thin film capacitor heterostructure, consisting of sol-gel deposited lead zirconium titanate (PZT) layers with sputtered platinum top and bottom electrodes, was subjected to fatiguing pulses at a variety of frequencies. The fatigue characteristics were compared to those of a similarly processed capacitor in which a ~20nm tungsten trioxide layer had been deposited, using pulsed laser deposition, between the ferroelectric and upper electrode. The expectation was that, because of its ability to accommodate considerable oxygen non-stoichiometry, tungsten trioxide (WO3) might act as an efficient sink for any oxygen vacancies flushed to the electrode-ferroelectric boundary layer during repetitive switching, and hence would improve the fatigue characteristics of the thin film capacitor. However, it was found that, in general, the addition of tungsten trioxide actually increases the rate of fatigue. It appears that any potential benefit from the WO3, in terms of absorbing oxygen vacancies, is far outweighed by it causing dramatically increased charge injection in the system.

The Effect of Antinotches on Domain Wall Mobility in Single Crystal Ferroelectric Nanowires

Changes in domain wall mobility, caused by the presence of antinotches in single crystal BaTiO3 nanowires, have been investigated. While antinotches appeared to cause a slight broadening in the distribution of switching events, observed as a function of applied electric field (inferred from capacitance-voltage measurements), the effect was often subtle. Greater clarity of information was obtained from Rayleigh analysis of the capacitance variation with ac field amplitude. Here the magnitude of the domain wall mobility parameter (R) associated with irreversible wall movements was found to be reduced by the presence of antinotches - an effect which became more noticeable on heating toward the Curie temperature. The reduction in this domain wall mobility was contrasted with the noticeable enhancement found previously in ferroelectric wires with notches. Finite element modeling of the electric field, developed in the nanowires during switching, revealed regions of increased and decreased local field at the center of the notch and antinotch structures, respectively; the absolute magnitude of field enhancement in the notch centers was considerably greater than the field reduction in the center of the antinotches and this was commensurate with the manner in, and degree to, which domain wall mobility appeared to be affected. We therefore conclude that the main mechanism by which morphology alters the irreversible component of the domain wall mobility in ferroelectric wire structures is via the manner in which morphological variations alter the spatial distribution of the electric field.

Stability of 71 degrees stripe domains in epitaxial BiFeO3 films upon repeated electrical switching

The 71 degrees stripe domain patterns of epitaxial BiFeO3 thin films are frequently being explored to achieve new functional properties, dissimilar from the BiFeO3 bulk properties. We show that in-plane switching and out-of-plane switching of these domains behave very differently. In the in-plane configuration the domains are very stable, whereas in the out-of-plane configuration the domains change their size and patterns, depending on the applied switching voltage frequency.

Piezoresponse force microscopy of ferroelectric relaxors

Nesta tese, ferroeléctricos relaxor (I dont know uf the order is correct) de base Pb das familias (Pb,La)(Zr,Ti)O3 (PLZT), Pb(Mg1/3,Nb2/3)O3-PbTiO3 (PMN-PT), Pb(Zn1/3,Nb2/3)O3-PbTiO3 (PZN-PT) foram investigados e analisados. As propriedades ferroeléctricas e dieléctricas das amostras foram estudadas por métodos convencionais de macro e localmente por microscopia de força piezoeléctrica (PFM). Nos cerâmicos PLZT 9.75/65/35 o contraste da PFM à escala nanometrica _ foi investigado em função do tamanho e orientação dos grãos. Apurou-se que a intensidade do sinal piezoeléctrico das nanoestruturas diminui com o aumento da temperatura e desaparece a 490 K (La mol. 8%) e 420 K (9,5%). Os ciclos de histerese locais foram obtidos em função da temperatura. A evolução dos parâmetros macroscópicos e locais com a temperatura de superfície sugere um forte efeito de superfície nas transições de fase ferroeléctricas do material investigado. A rugosidade da parede de domínio é determinada por PFM para a estrutura de domínio natural existente neste ferroeléctrico policristalino. Além disso, os domínios ferroeléctricos artificiais foram criados pela aplicação de pulsos eléctricos à ponta do condutor PFM e o tamanho de domínio in-plane foi medido em função da duração do pulso. Todas estas experiências levaram à conclusão de que a parede de domínio em relaxors do tipo PZT é quase uma interface unidimensional. O mecanismo de contraste na superfície de relaxors do tipo PLZT é medido por PFMAs estruturas de domínio versus evolução da profundidade foram estudadas em cristais PZN-4,5%PT, com diferentes orientações através da PFM. Padrões de domínio irregulares com tamanhos típicos de 20-100 nm foram observados nas superfícies com orientação <001> das amostras unpoled?. Pelo contrário, os cortes de cristal <111> exibem domínios regulares de tamanho mícron normal, com os limites do domínio orientados ao longo dos planos cristalográficos permitidos. A existência de nanodomínios em cristais com orientação <001> está provisoriamente (wrong Word) atribuída à natureza relaxor de PZN-PT, onde pequenos grupos polares podem formar-se em coindições de zero-field-cooling (ZFC). Estes nanodomínios são considerados como os núcleos do estado de polarização oposta e podem ser responsáveis pelo menor campo coercitivo para este corte de cristal em particular. No entanto, a histerese local piezoelétrica realizada pelo PFM à escala nanométrica indica uma mudança de comportamento de PZN-PT semelhante para ambas as orientações cristalográficas investigadas. A evolução das estruturas de domínio com polimento abaixo da superfície do cristal foi investigada. O domínio de ramificações e os efeitos de polarização de triagem após o polimento e as medições de temperatura têm sido estudados pela PFM e pela análise SEM. Além disso, verificou-se que a intensidade do sinal piezoeléctrico a partir das estruturas de nanodomínio diminui com o aumento da temperatura, acabando por desaparecer aos 430 K (orientaçáo <111>) e 470 K (orientação <100>). Esta diferença de temperatura nas transições de fase local em cristais de diferentes orientações é explicada pelo forte efeito de superfície na transição da fase ferroelétrica em relaxors.A comutação da polarização em relaxor ergódico e nas fases ferroeléctricas do sistema PMN-PT foram realizadas pela combinação de três métodos, Microscopia de Força Piezoeléctrica, medição de um único ponto de relaxamento eletromecânico e por ultimo mapeamento de espectroscopia de tensão. A dependência do comportamento do relaxamento na amplitude e tempo da tensão de pulso foi encontrada para seguir um comportamento logarítmico universal com uma inclinação quase constante. Este comportamento é indicativo da progressiva população dos estados de relaxamento lento, ao contrário de uma relaxação linear na presença de uma ampla distribuição do tempo de relaxamento. O papel do comportamento de relaxamento, da não-linearidade ferroeléctrica e da heterogeneidade espacial do campo na ponta da sonda de AFM sobre o comportamento do ciclo de histerese é analisada em detalhe. Os ciclos de histerese para ergódica PMN- 10%PT são mostrados como cineticamente limitados, enquanto que no PMN, com maior teor de PT, são observados verdadeiros ciclos de histerese ferroeléctrica com viés de baixa nucleação.

Ferroelectric : CNTs structures fabrication for advanced functional nano devices

This work is about the combination of functional ferroelectric oxides with Multiwall Carbon Nanotubes for microelectronic applications, as for example potential 3 Dimensional (3D) Non Volatile Ferroelectric Random Access Memories (NVFeRAM). Miniaturized electronics are ubiquitous now. The drive to downsize electronics has been spurred by needs of more performance into smaller packages at lower costs. But the trend of electronics miniaturization challenges board assembly materials, processes, and reliability. Semiconductor device and integrated circuit technology, coupled with its associated electronic packaging, forms the backbone of high-performance miniaturized electronic systems. However, as size decreases and functionalization increases in the modern electronics further size reduction is getting difficult; below a size limit the signal reliability and device performance deteriorate. Hence miniaturization of siliconbased electronics has limitations. On this background the Road Map for Semiconductor Industry (ITRS) suggests since 2011 alternative technologies, designated as More than Moore; being one of them based on carbon (carbon nanotubes (CNTs) and graphene) [1]. CNTs with their unique performance and three dimensionality at the nano-scale have been regarded as promising elements for miniaturized electronics [2]. CNTs are tubular in geometry and possess a unique set of properties, including ballistic electron transportation and a huge current caring capacity, which make them of great interest for future microelectronics [2]. Indeed CNTs might have a key role in the miniaturization of Non Volatile Ferroelectric Random Access Memories (NVFeRAM). Moving from a traditional two dimensional (2D) design (as is the case of thin films) to a 3D structure (based on a tridimensional arrangement of unidimensional structures) will result in the high reliability and sensing of the signals due to the large contribution from the bottom electrode. One way to achieve this 3D design is by using CNTs. Ferroelectrics (FE) are spontaneously polarized and can have high dielectric constants and interesting pyroelectric, piezoelectric, and electrooptic properties, being a key application of FE electronic memories. However, combining CNTs with FE functional oxides is challenging. It starts with materials compatibility, since crystallization temperature of FE and oxidation temperature of CNTs may overlap. In this case low temperature processing of FE is fundamental. Within this context in this work a systematic study on the fabrication of CNTs - FE structures using low cost low temperature methods was carried out. The FE under study are comprised of lead zirconate titanate (Pb1-xZrxTiO3, PZT), barium titanate (BaTiO3, BT) and bismuth ferrite (BiFeO3, BFO). The various aspects related to the fabrication, such as effect on thermal stability of MWCNTs, FE phase formation in presence of MWCNTs and interfaces between the CNTs/FE are addressed in this work. The ferroelectric response locally measured by Piezoresponse Force Microscopy (PFM) clearly evidenced that even at low processing temperatures FE on CNTs retain its ferroelectric nature. The work started by verifying the thermal decomposition behavior under different conditions of the multiwall CNTs (MWCNTs) used in this work. It was verified that purified MWCNTs are stable up to 420 ºC in air, as no weight loss occurs under non isothermal conditions, but morphology changes were observed for isothermal conditions at 400 ºC by Raman spectroscopy and Transmission Electron Microscopy (TEM). In oxygen-rich atmosphere MWCNTs started to oxidized at 200 ºC. However in argon-rich one and under a high heating rate MWCNTs remain stable up to 1300 ºC with a minimum sublimation. The activation energy for the decomposition of MWCNTs in air was calculated to lie between 80 and 108 kJ/mol. These results are relevant for the fabrication of MWCNTs – FE structures. Indeed we demonstrate that PZT can be deposited by sol gel at low temperatures on MWCNTs. And particularly interesting we prove that MWCNTs decrease the temperature and time for formation of PZT by ~100 ºC commensurate with a decrease in activation energy from 68±15 kJ/mol to 27±2 kJ/mol. As a consequence, monophasic PZT was obtained at 575 ºC for MWCNTs - PZT whereas for pure PZT traces of pyrochlore were still present at 650 ºC, where PZT phase formed due to homogeneous nucleation. The piezoelectric nature of MWCNTs - PZT synthesised at 500 ºC for 1 h was proved by PFM. In the continuation of this work we developed a low cost methodology of coating MWCNTs using a hybrid sol-gel / hydrothermal method. In this case the FE used as a proof of concept was BT. BT is a well-known lead free perovskite used in many microelectronic applications. However, synthesis by solid state reaction is typically performed around 1100 to 1300 ºC what jeopardizes the combination with MWCNTs. We also illustrate the ineffectiveness of conventional hydrothermal synthesis in this process due the formation of carbonates, namely BaCO3. The grown MWCNTs - BT structures are ferroelectric and exhibit an electromechanical response (15 pm/V). These results have broad implications since this strategy can also be extended to other compounds of materials with high crystallization temperatures. In addition the coverage of MWCNTs with FE can be optimized, in this case with non covalent functionalization of the tubes, namely with sodium dodecyl sulfate (SDS). MWCNTs were used as templates to grow, in this case single phase multiferroic BFO nanorods. This work shows that the use of nitric solvent results in severe damages of the MWCNTs layers that results in the early oxidation of the tubes during the annealing treatment. It was also observed that the use of nitric solvent results in the partial filling of MWCNTs with BFO due to the low surface tension (<119 mN/m) of the nitric solution. The opening of the caps and filling of the tubes occurs simultaneously during the refluxing step. Furthermore we verified that MWCNTs have a critical role in the fabrication of monophasic BFO; i.e. the oxidation of CNTs during the annealing process causes an oxygen deficient atmosphere that restrains the formation of Bi2O3 and monophasic BFO can be obtained. The morphology of the obtained BFO nano structures indicates that MWCNTs act as template to grow 1D structure of BFO. Magnetic measurements on these BFO nanostructures revealed a week ferromagnetic hysteresis loop with a coercive field of 956 Oe at 5 K. We also exploited the possible use of vertically-aligned multiwall carbon nanotubes (VA-MWCNTs) as bottom electrodes for microelectronics, for example for memory applications. As a proof of concept BiFeO3 (BFO) films were in-situ deposited on the surface of VA-MWCNTs by RF (Radio Frequency) magnetron sputtering. For in situ deposition temperature of 400 ºC and deposition time up to 2 h, BFO films cover the VA-MWCNTs and no damage occurs either in the film or MWCNTs. In spite of the macroscopic lossy polarization behaviour, the ferroelectric nature, domain structure and switching of these conformal BFO films was verified by PFM. A week ferromagnetic ordering loop was proved for BFO films on VA-MWCNTs having a coercive field of 700 Oe. Our systematic work is a significant step forward in the development of 3D memory cells; it clearly demonstrates that CNTs can be combined with FE oxides and can be used, for example, as the next 3D generation of FERAMs, not excluding however other different applications in microelectronics.

Material Characterisation and Electro-Optical Studies of a Ferroelectric Liquid Crystal

Department of Electronics, Cochin University of Science and Technology

Enhanced ferroelectric properties of La-substituted BiFeO3 thin films on LaSrCoO3/Pt/TiO2/SiO2/Si (100) substrates prepared by the soft chemical method

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Ferroelectric and dielectric behaviour of Bi0.92La0.08FeO3 multiferroic thin films prepared by soft chemistry route

Bi0.92La0.08FeO3 (BLFO) thin films were grown on platine substrates by the soft chemical route. Ferroelectric and dielectric behaviors of BLFO films deposited by spin-coating technique and annealed at 773 K for 2 h in air atmosphere were explained. BLFO thin films obtained presents a rhombohedral structure. The BLFO films present dielectric and ferroelectric behaviors with dielectric permittivity and dielectric loss of approximately 81 and 0.0144 at 1 kHz. The Au/BLFO/Pt capacitor shows a hysteresis loop with remnant polarization of 20.6 mu C/cm(2) and coercive field of 53.88 kV/cm. The polarization switching and the fatigue behavior of the BLFO films were significantly enhanced.

Ferroelectric and dielectric properties of lanthanum-modified bismuth titanate thin films obtained by the polymeric precursor method

Lanthanum-modified bismuth titanate, Bi4-xLaxTi3O12 (BLT), thin films with a La concentration of 0.75 was grown on Pt/Ti/SiO2/Si substrates by using the polymeric precursor solution and spin-coating method. The scanning electron microscopy (SEM) showed rounded grains, which is not typical for these system. The BLT films showed well-saturated polarization-electric field curve which 2P(r) = 41.4 muC/cm(2) and V-c = 0.99 V. The capacitance dependence on the voltage is strongly nonlinear, confirming the ferroelectric properties of the film resulting from the domains switching. These properties make BLT a promising material for FERAM applications.

Ferroelectric properties and leakage current characteristics of Bi3.25La0.75Ti3O12 thin films prepared by the polymeric precursor method

The ferroelectric properties and leakage current mechanisms of preferred oriented Bi3.25La0.75Ti3O12 (BLT) thin films deposited on La0.5Sr0.5CoO3 by the polymeric precursor method were investigated. These films showed excellent ferroelectric properties in terms of large remnant polarization (2P(r)) of 47.6 mu C/cm(2) and (2E(c)) of 55 kV/cm, fatigue-free characteristics up to 10(10) switching cycles, and a current density of 0.7 mu A/cm(2) at 10 kV/cm. X-ray diffraction and scanning electron microscope investigations indicate that the deposited films exhibit a dense, well-crystallized microstructure having random orientations and with a rather smooth surface morphology. The improved ferroelectric and leakage current characteristics can be ascribed to the platelike grains of the BLT films, which make the domain walls easier to be switched under external field.

Ferroelectric characteristics of BiFeO3 thin films prepared via a simple chemical solution deposition

BiFeO3 (BFO) thin films were fabricated on Pt(111)/Ti/SiO2/Si substrates by using a polymeric precursor solution under appropriate crystallization conditions. The capacitance dependence on voltage is strongly nonlinear, confirming the ferroelectric properties of the films resulting from the domain switching. The leakage current density increases with annealing temperature. The polarization electric field curves could be obtained in BFO films annealed at 500 degrees C, free of secondary phases. X-ray photoelectron spectroscopy spectra of films annealed at 500 degrees C indicated that the oxidation state of Fe was purely 3+, demonstrating that our films possess stable chemical configurations. (c) 2007 American Institute of Physics.

Influence of temperature on the dielectric and ferroelectric properties of bismuth titanate thin films obtained by the polymeric precursor method

The (1 1 7) and (0 0 1 0)-oriented Bi4Ti3O12 thin films were fabricated on Pt/Ti/SiO2/Si substrates by using a polymeric precursor solution under appropriate crystallization conditions. Atomic force microscopy and scanning electron microscopy showed relatively large grains, which is typical for this system. The capacitance dependence on voltage is strongly non-linear, confirming the ferroelectric properties of the films resulting from the domain switching. The (1 1 7)-oriented films exhibited a higher remanent polarization (23.7 μ C cm(-2)) than the (0 0 1 0)-oriented films (11.8 μ C cm(-2)). Fatigue tests revealed that the temperature of thermal treatment and degree of orientation affect the performance of the device. © 2005 Elsevier B.V. All rights reserved.

On the equivalence of the mechanisms governing switching and hysteresis phenomena

The nucleation and growth model, which is usually applied to switching phenomena, is adapted for explaining surface potential measurements on the P(VDF-TrFE) (polyvinylidene fluoride-trifluoroethylene) copolymer obtained in a constant current corona triode. It is shown that the growth is one-dimensional and that the nucleation rate is unimportant, probably because surface potential measurements take much longer than the switching ones. The surface potential data can therefore be accounted for by a growth model in which the velocity of growth varies exponentially with the electric field. Since hysteresis loops can be obtained from surface potential measurements, it is suggested that similar mechanisms can be used when treating switching and hysteresis phenomena, provided that account is taken of the difference in the time scale of the measurements.

The use of pulsed electric acoustic technique for measuring the polarization reversal in ferroelectric ceramic samples

The pulsed electric acoustic technique, PEA, has been usually applied to probe space charge profiles in polymers. Preliminary PEA results using a ferroelectric ceramic are presented. If the reverse applied electric field i of the order of the coercive field the switching polarization process occurs in a period larger than hundreds of seconds. Such a slow process allows one to use the PEA setup to follow the polarization switching dynamics and determine the electric field profile. The PEA signal obtained in the lead zirconate-titanate doped with niobium ceramic, PZTN, indicates that the polarization distribution and field are not uniform during the switching period. We were also able to observe that the acoustic wave velocity and attenuation depends on the stage of the polarization switching, which agrees with results obtained using the ultrasonic method.

Surface potentials of corona-charged ferroelectric P(VDF-TrFE) copolymer samples

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)