Novel digital memory devices were fabricated with a thermally and dimensionally stable polyimide containing carbazole moieties in its side groups by using a simple and conventional solution coating process. The devices exhibit excellent unipolar ON and OFF switching behavior. With very low power consumption, the devices can be repeatedly written, read, and erased in air. The ON/OFF current ratio of the devices is high up to 1011. The high ON/OFF switching ratio and stability of the devices, as well as their repeatable writing, reading, and erasing capability with low power consumption, open up the possibility of the mass production of high performance non‐volatile memory devices at low cost.

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.

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.

We have fabricated electrically programmable memory devices with thermally and dimensionally stable poly(N-(N',N'-diphenyl-N'-1,4-phenyl)-N,N-4,4'-diphenylene hexafluoroisopropylidene-diphthalimide) (6F-2TPA PI) films and investigated their switching characteristics and reliability. 6F-2TPA PI films were found to reveal a conductivity of 1.0 x 10(-13)-1.0 x 10(-14) S cm(-1). The 6F-2TPA PI films exhibit versatile memory characteristics that depend on the film thickness. All the PI films are initially present in the OFF state. The PI films with a thickness of >15 to <100 nm exhibit excellent write-once-read-many-times (WORM) (i.e. fuse-type) memory characteristics with and without polarity depending on the thickness. The WORM memory devices are electrically stable, even in air ambient, for a very long time. The devices' ON/OFF current ratio is high, up to 10(10). Therefore, these WORM memory devices can provide an efficient, low-cost means of permanent data storage. On the other hand, the 100 nm thick PI films exhibit excellent dynamic random access memory (DRAM) characteristics with polarity. The ON/OFF current ratio of the DRAM devices is as high as 10(11). The observed electrical switching behaviors were found to be governed by trap-limited space-charge-limited conduction and local filament formation and further dependent on the differences between the highest occupied molecular orbital and the lowest unoccupied molecular orbital energy levels of the PI film and the work functions of the top and bottom electrodes as well as the PI film thickness. In summary, the excellent memory properties of 6F-2TPA PI make it a promising candidate material for the low-cost mass production of high density and very stable digital nonvolatile WORM and volatile DRAM memory devices.

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.

We synthesized two polyimides (PIs), poly(4,4‘-(9,9-fluorenyl)diphenylene cyclobutanyltetracarboximide) (CBDA-FDA) and poly(4,4‘-(9,9-fluorenyl)diphenylene pyromellitimide) (PMDA-FDA), and investigated in detail the surface morphology, molecular orientation, and nematic liquid crystal (LC) alignments of rubbed CBDA-FDA and PMDA-FDA films. The rubbed CBDA-FDA film surface was found to contain microgrooves that run parallel to the rubbing direction, but was found to induce LC alignment perpendicular to the rubbing direction. In contrast, the rubbed PMDA-FDA film surface was found to contain unusual meandering microgrooves that run perpendicular to the rubbing direction; this is the first report of such structures on a rubbed PI film. The PMDA-FDA film surface was found to induce LC alignment parallel to the rubbing direction. Even though these two PI films have quite different groove structures and LC alignment behaviors, the polymer main chains in their surfaces lie in the film plane and are preferentially oriented along the rubbing direction, and the fluorenyl side groups lie in the out-of-plane and are preferentially oriented perpendicular to the rubbing direction. These LC alignment, anchoring energy, surface morphology, and polymer segmental orientation results indicate that LC alignments on the surfaces of rubbed PI films are determined by the interplay between the directionally anisotropic interactions of the LC molecules with the oriented polymer main chain segments, the oriented fluorenyl side groups, and the microgrooves. The directionally anisotropic interactions of the LC molecules with the oriented polymer chain segments were found to be much stronger than those with the directionally developed microgrooves. We conclude that CBDA-FDA and PMDA-FDA PIs are promising alignment layer materials for the fabrication of advanced LC display devices.

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