We have synthesized a new thermally and dimensionally stable polyimide, poly(4,4'-amino(4-hydroxyphenyl)diphenylene hexafluoroisopropylidenediphthalimide) (6F-HTPA PI). 6F-HTPA PI is soluble in organic solvents and is thus easily processed with conventional solution coating techniques to produce good quality nanoscale thin films. Devices fabricated with nanoscale thin PI films with thicknesses less than 77 nm exhibit excellent unipolar write-once-read-many-times (WORM) memory behavior with a high ON/OFF current ratio of up to 10(6), a long retention time and low power consumption, less than +/-3.0 V. Furthermore, these WORM characteristics were found to persist even at high temperatures up to 150 degrees C. The WORM memory behavior was found to be governed by trap-limited space-charge limited conduction and local filament formation. The conduction processes are dominated by hole injection. Thus the hydroxytriphenylamine moieties of the PI polymer might play a key role as hole trapping sites in the observed WORM memory behavior. The properties of 6F-HTPA PI make it a promising material for high-density and very stable programmable permanent data storage devices with low power consumption.

This study reports the synthesis and properties (in particular, the electrical switching characteristics) of a new high-performance polyimide (PI), poly(3,3'-di(4-(diphenylamino)benzylidenyliminoethoxy)-4,4'-biphenylene hexafluoroisopropylidenediphthalimide) (6F-HAB-TPAIE PI). This PI polymer bears diphenylaminobenzylidenylimine moieties as side groups and is dimensionally stable up to 280 degrees C and thermally stable up to 440 degrees C. In devices fabricated with the PI polymer as an active memory layer, the active PI polymer was found to operate at less than +/-2 V in electrically bistable unipolar and bipolar switching modes by controlling the compliance current. The PI polymer layer exhibits repeatable writing-reading-erasing capability with high reliability in ambient air conditions as well as at high temperatures up to 130 degrees C. This PI polymer also exhibits a high ON/OFF current ratio up to 10(9). The observed nonvolatile memory behaviors are due to Schottky emission and local filament formation. This study has demonstrated that this thermally, dimensionally stable PI polymer is a promising material for mass production at low cost for high-performance, programmable, nonvolatile memory devices that can be operated with low power consumption in unipolar and bipolar switching modes.

A high temperature polyimide bearing anthracene moieties, poly(3,3'-di(9-anthracenemethoxy)-4,4'-biphenylene hexafluoroisopropylidenediphthalimide) (6F-HAB-AM PI) was synthesized. The polymer exhibits excellent thermal stability up to around 410 °C. This polymer is amorphous but orients preferentially in the plane of nanoscale thin films. In device fabrications of its nanoscale thin films with metal top and bottom electrodes, no diffusion of the metal atoms or ions between the polymer and electrodes was found; however, the aluminum bottom electrode had somewhat undergone oxide layer (about 1.2 nm thick) formation at the surface during the post polymer layer formation process, which was confirmed to have no significant influence on the device performance. The polymer thin film exhibited excellent unipolar and bipolar switching behaviors over a very small voltage range, less than ±2 V. Further, the PI films show repeatable writing, reading, and erasing ability with long reliability and high ON/OFF current ratio (up to 10(7)) in air ambient conditions as well as even at temperatures up to 200 °C.

This paper reports for the first time the programmable digital memory characteristics of the nanoscale thin films of a fully π-conjugated polymer, poly(diethyl dipropargylmalonate) (pDEDPM) in the absence of doping. This π-conjugated polymer was found to exhibit good solubility in organic solvents and to be easily processed to form nanoscale thin films through the use of conventional solution spin-, roll-, or dip-coating and subsequent drying. Films of the π-conjugated polymer with top and bottom metal electrodes exhibit excellent dynamic random access memory (DRAM) characteristics or write-once-read-many-times (WORM) memory behavior without polarity, depending on the film thickness. All the PI films are initially present in the OFF-state. Films with a thickness of 30 nm were found to exhibit very stable WORM memory characteristics without polarity and an ON/OFF current ratio of 10 6 , whereas films with a thickness of 62-120 nm were found to exhibit excellent DRAM characteristics without polarity and an ON/OFF current ratio as high as 10 8 . These memory characteristics are governed by trap-limited space-charge limited conduction and heterogeneously local filament formation. In these polymer films, both the ester units and the conjugated double bonds of the polymer backbone can act as charge trapping sites. The excellent bistable switching properties and processibility of this π-conjugated polymer mean that it is a promising material for the low-cost mass production of high density and very stable digital nonvolatile WORM memory and volatile DRAM devices.

A novel polymer, poly(2-(N -carbazolyl)ethyl methacrylate) end-capped with fullerene (PCzMA-C(60) ), has been synthesized via living anionic polymerization. Electrically programmable flash memory devices were easily fabricated with this polymer by using solution coating and metal deposition. This polymer was found in these devices to exhibit bipolar and unipolar switching behaviors with a high ON/OFF current ratio, a long retention time, high reliability, and low power consumption. The excellent properties and easy processability of this polymer open up the possibility of the mass production of high performance nonvolatile memory devices at low cost.

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3-Miktoarm star terpolymer architecture provides a window of opportunity in the design of complex "three-colored" patterns at the nanometer scale. Here, the directed self-assembly (DSA) of 3-miktoarm star terpolymer (poly(1,1-dimethyl silacyclobutane)-arm-polystyrene-arm-poly(d,l-lactide acid)) (PDMSB-arm-PS-arm-PLA, noted hereafter 3 μ-DSL) into a hierarchical lamellar morphology is described. Excellent orientational order has been achieved by templating the asymmetric hierarchical lamellar morphology with topographical substrates. Increasing the PLA volume fraction leads to the formation of a hexagonal [6.6.6] Archimedean tiling which coexists with a metastable square symmetry [4.8.8] tiling stabilized by the step between terraces. Stability of the [6.6.6] tiling over the [4.8.8] one is also demonstrated with GISAXS measurements.

Poly[bis(9H-carbazole-9-ethyl)dipropargylmalonate] (PCzDPM) is a novel pi-conjugated polymer bearing carbazole moieties that has been synthesized by polymerization of bis(9H-carbazole-9-ethyl)dipropargylmalonate with the aid of molybdenum chloride solution as the catalyst. This polymer is thermally stable up to 255 degrees C under a nitrogen atmosphere and 230 degrees C in air ambient; its glass-transition temperature is 147 or 128 degrees C, depending on the polymer chain conformation (helical or planar structure). The charge-transport characteristics of PCzDPM in nanometer-scaled thin films were studied as a function of temperature and film thickness. PCzDPM films with a thickness of 15-30 nm were found to exhibit very stable dynamic random access memory (DRAM) characteristics without polarity. Furthermore, the polymer films retain DRAM characteristics up to 180 degrees C. The ON-state current is dominated by Ohmic conduction, and the OFF-state current appears to undergo a transition from Ohmic to space-charge-limited conduction with a shallow-trap distribution. The ON/OFF switching of the devices is mainly governed by filament formation. The filament formation mechanism for the switching process is supported by the metallic properties of the PCzDPM film, which result in the temperature dependence of the ON-state current. In addition, the structure of this pi-conjugated polymer was found to vary with its thermal history; this change in structure can affect filament formation in the polymer film.