Ronggang Cai

Nanoscale Design of Multifunctional Organic Layers for Low-Power High-Density Memory Devices

We demonstrate the design of a multifunctional organic layer by the rational combination of nanosized regions of two functional polymers. Instead of relying on a spontaneous and random phase separation process or on the tedious synthesis of block copolymers, the method involves the nanomolding of a first component, followed by the filling of the resulting open spaces by a second component. We apply this methodology to fabricate organic nonvolatile memory diodes of high density. These are built by first creating a regular array of ferroelectric nanodots by nanoimprint lithography, followed by the filling of the trenches separating the ferroelectric nanodots with a semiconducting polymer. The modulation of the current in the semiconductor by the polarization state of the ferroelectric material is demonstrated both at the scale of a single semiconductor channel and in a microscopic device measuring about 80,000 channels in parallel, for voltages below ca. 2 V. The fabrication process, which combines synergetically orthogonal functional properties with a fine control over their spatial distribution, is thus demonstrated to be efficient over large areas.

Photocrosslinking of ferroelectric polymers and its application in three-dimensional memory arrays

An I-line photolithography process for ferroelectric polymers is developed. It is based on photocrosslinking using a bisazide photoinitiator. Patterned layers were realized down to 1-2 µm resolution. Crosslinking yields a close-to-insoluble ferroelectric polymer network that counter intuitively has similar ferroelectric properties as a noncrosslinked film. The negative process is used to stack ferroelectric films on top of each other to make three-dimensional cross-bar arrays of nonvolatile ferroelectric capacitor memories.

An organic ferroelectric field effect transistor with poly(vinylidene fluoride-co-trifluoroethylene) nanostripes as gate dielectric

We demonstrate the fabrication of an organic Ferroelectric Field Effect Transistor (FeFET) incorporating a ferroelectric gate dielectric made of nanostripes obtained by nanoimprinting poly(vinylidene fluoride-co-trifluoroethylene) over a layer of semiconducting poly(triarylamine). The imprinting process results in a decreased switching voltage for the ferroelectric, by a factor of ca. 1.5, resulting in a decreased operating voltage compared to a reference FeFET with a continuous ferroelectric layer. The transistor consists of a large number of nanostripe-gated transistors placed in parallel, which also offers interesting possibilities for a strong size reduction of organic FeFETs.

Multiferroic Nanopatterned Hybrid Material with Room-Temperature Magnetic Switching of the Electric Polarization.

A nanopatterned hybrid layer is designed, wherein the electric polarization can be flipped at room temperature by a magnetic field aided by an electrical field. This is achieved by embedding ferromagnetic nanopillars in a continuous organic ferroelectric layer, and amplifying the magnetostriction-generated stress gradients by scaling down the supracrystalline cell of the material.

Local Maps of the Polarization and Depolarization in Organic Ferroelectric Field-Effect Transistors

We study the local ferroelectric polarization and depolarization of poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) in p-type ferroelectric field-effect transistors (FeFETs). Piezoresponse force microscopy (PFM) is used to obtain local maps of the polarization on model metal-semiconductor-ferroelectric stacks, and on FeFETs stripped from their top-gate electrode; transfer curves are measured on complete FeFETs. The influence of the semiconductor layer thickness and of the polarity and amplitude of the poling voltage are investigated. In accumulation, the stable “on” state consists of a uniform upward-polarized ferroelectric layer, with compensation holes accumulating at the ferroelectric/semiconducting interface. In depletion, the stable “off” state consists of a depolarized region in the center of the transistor channel, surrounded by partially downward-polarized regions over the source and drain electrodes and neighboring regions. The partial depolarization of these regions is due to the incomplete screening of polarization charges by the charges of the remote electrodes. Therefore, thinner semiconducting layers provide higher downward polarizations, which result in a more depleted transistor channel and a higher charge injection barrier between the electrodes and the semiconductor, leading to lower threshold voltages and higher on/off current values at zero gate bias. Clues for optimization of the devices are finally provided.

Organic ferroelectric/semiconducting nanowire hybrid layer for memory storage

Ferroelectric materials are important components of sensors, actuators and non-volatile memories. However, possible device configurations are limited due to the need to provide screening charges to ferroelectric interfaces to avoid depolarization. Here we show that, by alternating ferroelectric and semiconducting nanowires over an insulating substrate, the ferroelectric dipole moment can be stabilized by injected free charge carriers accumulating laterally in the neighboring semiconducting nanowires. This lateral electrostatic coupling between ferroelectric and semiconducting nanowires offers new opportunities to design new device architectures. As an example, we demonstrate the fabrication of an elementary non-volatile memory device in a transistor-like configuration, of which the source-drain current exhibits a typical hysteretic behavior with respect to the poling voltage. The potential for size reduction intrinsic to the nanostructured hybrid layer offers opportunities for the development of strongly miniaturized ferroelectric and piezoelectric devices.

Environmentally Friendly Super-Water-Repellent Fabrics Prepared from Water-Based Suspensions

We report on a facile, versatile, and environmentally friendly method to prepare superhydrophobic fabrics by a simple dip-coating method in water-based suspensions and emulsions. All the materials used are fluorine-free and commercially available at a large scale. The method can be easily integrated into standard textile industrial processes and has a strong potential for the mass production of environmentally friendly superwater-repellent fabrics. The produced fabrics show good resistance to machine washing and acidic or alkaline treatments. In addition, it is shown that superhydrophobicity can be quantitatively predicted based on the combination of the roughness of the fabric and of the fiber coating.

Room-Temperature Magnetic Switching of the Electric Polarization in Ferroelectric Nanopillars

Magnetoelectric layers with a strong coupling between ferroelectricity and ferromagnetism offer attractive opportunities for the design of new device architectures such as dual-channel memory and multiresponsive sensors and actuators. However, materials in which a magnetic field can switch an electric polarization are extremely rare, work most often only at very low temperatures, and/or comprise complex materials difficult to integrate. Here, we show that magnetostriction and flexoelectricity can be harnessed to strongly couple electric polarization and magnetism in a regularly nanopatterned magnetic metal/ferroelectric polymer layer, to the point that full reversal of the electric polarization can occur at room temperature by the sole application of a magnetic field. Experiments supported by finite element simulations demonstrate that magnetostriction produces large strain gradients at the base of the ferroelectric nanopillars in the magnetoelectric hybrid layer, translating by flexoelectricity into equivalent electric fields larger than the coercive field of the ferroelectric polymer. Our study shows that flexoelectricity can be advantageously used to create a very strong magnetoelectric coupling in a nanopatterned hybrid layer.

Local polarization switching in stressed ferroelectric polymers

Ferroelectric polymers are used in flexible organic ferroelectric memories, ferroelectric polarization enhanced organic solar cells, and organic multiferroics. Therefore, understanding their polarization switching mechanism under bending is important for the operation of such devices. Here, we study locally by piezoresponse force microscopy (PFM) polarization switching in bent thin films of the ferroelectric polymer poly(vinylidene fluoride-ran-trifluoroethylene). In bent samples, higher probability of domain nucleation, faster domain wall propagation, and lower coercive field are consistently observed by PFM. We ascribe these observations to a decrease of the domain wall pinning energy, resulting from the mechanical energy stored in the sample due to bending in the presence of the compression gradient generated below the PFM tip.

Field-effect memory transistors based on arrays of nanowires of a ferroelectric polymer

Ferroelectric poly(vinylidene fluoride-co-trifluoroethylene), P(VDF-TrFE), is increasingly used in organic non-volatile memory devices, e.g., in ferroelectric field effect transistors (FeFETs). Here, we report on FeFETs integrating nanoimprinted arrays of P(VDF-TrFE) nanowires. Two previously-unreported architectures are tested, the first one consisting of stacked P(VDF-TrFE) nanowires placed over a continuous semiconducting polymer film; the second one consisting of a nanostriped blend layer wherein the semiconducting and ferroelectric components alternate regularly. The devices exhibit significant reversible memory effects, with operating voltages reduced compared to their continuous film equivalent, and with different possible geometries of the channels of free charge carriers accumulating in the semiconductor.