Ferroelectric polymers are a kind of promising materials for low-cost flexible memories. However, the relatively high thermal annealing temperature restricts the selection of some flexible polymer substrates. Here we report an alternative method to obtain ferroelectric poly(vinylidenefluoride-co-trifluoroethylene) (P(VDF-TrFE)) thin films under low process temperatures. Spin-coated P(VDF-TrFE) thin films were solvent vapor processed at 30 °C for varied times. Structural analyses indicated that solvent vapor annealing induced crystallization to form a ferroelectric β phase, and electrical measurements from both macroscopic ferroelectric switching and microscopic vertical piezoresponse force microscopy further proved the films enduring solvent vapor annealing for suitable short times possessed good ferroelectric and piezoelectric properties. To illuminate the application of solvent vapor annealing on ferroelectric devices, we further fabricated ferroelectric capacitor memory devices with a structure of Al/P(VDF-TrFE)/Al2O3/p-Si/Al where the ferroelectric layer was solvent vapor annealed. Ferroelectric capacitors showed obvious bistable operation and comparable ON/OFF ratio and retention performance. Our work makes it possible to structure ferroelectric devices on flexible substrates that require low process temperatures.

Organic semiconducting/ferroelectric blend films attracted much attention due to their electrical bistability and rectification properties and thereof the potential in resistive memory devices. During film deposition from the blend solution, spinodal decomposition induced phase separation, resulting in discrete semiconducting phase whose electrical property could be modulated by the continuous ferroelectric phase. However, blend films processed by common spin coating method showed extremely rough surfaces, even comparable to the film thickness, which caused large electrical leakage and thus compromised the resistive switching performance. To improve film roughness and thus increase the productivity of these resistive devices, we developed temperature controlled spin coating technique to carefully adjust the phase separation process. Here we reported our experimental results from the blend films of ferroelectric poly(vinylidene fluoride-trifluoroethylene (P(VDF-TrFE)) and semiconducting poly(3-hexylthiophene) (P3HT). We conducted a series of experiments at various deposition temperatures ranging from 20 to 90 °C. The resulting films were characterized by AFM, SEM, and VPFM to determine their structure and roughness. Film roughness first decreased and then increased with the increase of deposition temperature. Electrical performance was also characterized and obviously improved insulating property was obtained from the films deposited between 50 and 70 °C. By temperature control during film deposition, it is convenient to efficiently fabricate ferroelectric/semiconducting blend films with good electrical bistability.

Zong-Yuan(浮宗元) a) , Zhang Jian-Chi(张剑驰) b , Hu Jing-Hang(胡静航) a) , Jiang Yu-Long(蒋玉龙) b) † , Ding Shi-Jin(丁士进) b) ‡ , and Zhu Guo-Dong(朱国栋) a) §

Polarization fatigue is a kind of phenomenon usually observed in most ferroelectric films, which severely degrades the electrical performance of ferroelectric devices. How to restore those degraded polarization as well as how to improve fatigue endurance has been attracting much attention. Here, we report the observation of ultraviolet (UV) irradiation induced polarization restoration in ferroelectric polymer films. Large numbers of experiments indicate that the simultaneous application of UV irradiation and DC bias voltage will result in polarization restoration, which is dependent on both electrical polarity of DC bias and the UV intensity. Repeated fatigue and restoration measurements are also conducted. Based on fatigue mechanism in ferroelectric polymer films, UV-induced restoration is discussed.

Organic semiconducting/ferroelectric blend films attracted much attention due to their electrical bistability and rectification properties and thereof the potential in resistive memory devices. Blend films were usually deposited from solution, during which phase separation occurred, resulting in discrete semiconducting phase whose electrical property was modulated by surrounding ferroelectric phase. However, phase separation resulted in rough surface and thus large leakage current. To further improve electrical properties of such blend films, poly(methyl metacrylate) (PMMA) was introduced as additive into P3HT/P(VDF-TrFE) semiconducting/ferroelectric blend films in this work. It indicated that small amount of PMMA addition could effectively enhance the electrical stability to both large electrical stress and electrical fatigue and further improve retention performance. Overmuch PMMA addition tended to result in the loss of resistive switching property. A model on the configuration of three components was also put forward to well understand our experimental observations.