We have investigated the ferroelectric polarization switching properties of trialkylbenzene-1,3,5-tricarboxamide (BTA), which is a model system for a large class of novel organic ferroelectric materials. In the solid state BTAs form a liquid crystalline columnar hexagonal phase that provides long range order that was previously shown to give rise to hysteretic dipolar switching. In this work the nature of the polar switching process is investigated by a combination of dielectric relaxation spectroscopy, depth-resolved pyroelectric response measurements, and classical frequency- and time-dependent electrical switching. We show that BTAs, when brought in a homeotropically aligned hexagonal liquid crystalline phase, are truly ferroelectric. Analysis of the transient switching behavior suggests that the ferroelectric switching is limited by a highly dispersive nucleation process, giving rise to a wide distribution of switching times.
This study demonstrates how simple structural modification of a prototypical organic ferroelectric molecule can be used to tune its key ferroelectric properties. In particular, it is found that shortening the alkyl chain length of trialkylbenzene-1,3,5-tricarboxamide (BTA) from C18H37 to C6H13 causes an increase in depolarization activation energy (approximate to 1.1-1.55 eV), coercive field (approximate to 25-40 V mu m(-1)), and remnant polarization (approximate to 20-70 mC m(-2)). As the polarization enhancement far exceeds the geometrically expected factor, these observations are attributed to an increase in the intercolumnar interaction. The combination of the mentioned characteristics results in a record polarization retention time of close to three months at room temperature for capacitor devices of the material having the shortest alkyl chain. The long retention and the remnant polarization that is as high as that of P(VDF:TrFE) distinguish the BTA-C6 material from other small molecular organic ferroelectrics and make it a perspective choice for applications that require cheap, flexible, and lightweight ferroelectrics.
Funding Agencies|NWO Nano program; Vetenskapsradet; Swedish Government Strategic Research Area in Materials Science on Functional Materials at the Linkping University (Faculty Grant SFO Mat LiU) [2009 00971]
We investigate the polarization loss in the archetypical molecular organic ferroelectric trialkylbenzene-1,3,5-tricarboxamide (BTA). We prove that the polarization loss is due to thermally activated R-relaxation, which is a collective reversal of the amide dipole moments in ferroelectric domains. By applying a weak electrostatic field both the polarization loss and the R-relaxation are suppressed, leading to an enhancement of the retention time by at least several orders of magnitude. Alternative loss mechanisms are discussed and ruled out. By operating the thin-film devices slightly above the crystalline to liquid crystalline phase transition temperature the retention time of one compound becomes more than 12 hours even in absence of supportive bias, which is among the longest reported so far for organic ferroelectric materials.
The Preisach model has been a cornerstone in the fields of ferromagnetism and ferroelectricity since its inception. It describes a real, non-ideal, ferroic material as the sum of a distribution of ideal ‘hysterons’. However, the physical reality of the model in ferroelectrics has been hard to establish. Here, we experimentally determine the Preisach (hysteron) distribution for two ferroelectric systems and show how its broadening directly relates to the materials’ morphology. We connect the Preisach distribution to measured microscopic switching kinetics that underlay the macroscopic dispersive switching kinetics as commonly observed for practical ferroelectrics. The presented results reveal that the in principle mathematical construct of the Preisach model has a strong physical basis and is a powerful tool to explain polarization switching at all time scales in different types of ferroelectrics. These insights lead to guidelines for further advancement of the ferroelectric materials both for conventional and multi-bit data storage applications.
The combination of switchable dipolar side groups and the semiconducting core leads to a material showing continuous tunability from injection- to bulk-limited conductivity modulation.
We disclose a supramolecular material which combines semiconducting and dipolar functionalities. The material consists of a discotic semiconducting carbonyl-bridged triarylamine core which is surrounded by three dipolar amide groups. In thin films, the material self-organizes in a hexagonal columnar fashion through π-stacking of the molecular core and hydrogen bonding between the amide groups. Alignment by an electrical field in a simple metal/semiconductor/metal geometry induces a polar order in the interface layers near the metal contacts that can be reversibly switched, while the bulk material remains non-polarized.On suitably chosen electrodes, the presence of an interfacial polarization field leads to a modulation of the barrier for charge injection into the semiconductor. Consequently, a reversible switching is possible between a high-resistance, injection-limited off-state and a low-resistance, space-charge-limited on-state. The resulting memory diode shows switchable rectification with on/off ratios of up to two orders of magnitude. This demonstrated multifunctionality of a single material is a promising concept towards possible application in lowcost, large-area, non-volatile organic memories.
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