Solution-processed flexible nonvolatile organic field-effect transistor memory using polymer electret

Flexible organic field-effect-transistor (OFET) memory is one of the promising candidates for next-generation wearable nonvolatile data storage due to its low price, solution-processability, light-weight, mechanically flexibility, and tunable energy level via molecular tailoring. In this paper, we report flexible nonvolatile OFET memory devices fabricated with solution-processed polystyrene-brush electret and organic semiconductor blends of p-channel 6, 13-bis-(triisopropylsilylethynyl)pentacene (TIPS-PEN) and n-channel poly-{[N,N′-bis(2- octyldodecyl)-naphthalene-1,4,5,8-bis-(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)} (P-(NDI2OD-2T); N2200). Fabricated flexible OFET memory devices exhibited high memory window (30 V) and ON/OFF current ratio (memory ratio) over 10³. Furthermore, we obtained reliable memory ratio (~10³) over retention time of 10⁸ s, 100 times of repeated programming/erasing cycles, and 1000 times of bending tests at a radius of 3 mm.     

Synergistic effect in organic field-effect transistor nonvolatile memory utilizing bimetal nanoparticles as nano-floating-gate

A solution-processed bimetal nano-floating-gate, with a combination of stabilized Ag and Pt nanoparticles, is utilized to achieve high-performance organic field-effect transistor nonvolatile memories. The device based on the Ag–Pt nano-floating-gate shows the synergistic superiority in memory performance compared with the corresponding Ag-only and Pt-only devices. The Ag and Pt nanoparticles are found to prefer hole and electron trapping, respectively. Upon the blending of the Ag and Pt nanoparticles, both hole and electron trapping are significantly enhanced and thus realize a large memory window. The dipole enhancement induced local work function change for both Ag and Pt is proposed to be responsible for the synergistic effect, and this physical picture is supported by the electronic structure results. It is concluded that using a hybrid nano-floating-gate is a promising strategy to optimize the device performance of organic field-effect transistor nonvolatile memories.     

The effect of porous structure of PMMA tunneling dielectric layer on the performance of nonvolatile floating-gate organic field-effect transistor memory devices

In this paper, we used the low and high density porous structure of polymethylmethacrylate (PMMA) film as tunneling dielectric layer in the floating-gate organic field-effect transistor (OFET) memory devices. Compared to the thin/thick nonporous structure of PMMA tunneling layer, the porous structure of PMMA tunneling layer had positive impacts on the device performance of the floating-gate OFET memory devices. Moreover, it was found that the memory performance was also increased as pore density of PMMA film increased. The atomic force microscopy (AFM) results of both porous structure of PMMA film and pentacene film on porous structure of PMMA film revealed that high density porous structure of PMMA tunneling layer can produce larger tunneling area and more electron transfer paths between pentacene film and PMMA film, which resulted in high electron capture and release efficiency of the floating-gate OFET memory devices with porous structure of PMMA tunneling layer. In addition, our porous structure of PMMA tunneling layer as well as nonporous PMMA film has high electrical insulating property due to their semi-hollow structure film, which is favourable to maintain stable retention property. Eventually, the floating-gate OFET memory devices with high density porous structure of PMMA tunneling layer showed good nonvolatile memory properties with a large memory window of about 43 V, a high ON/OFF current ratio of about 10⁴, and stable endurance and retention properties. Our results provided a new strategy to achieve the high performance floating-gate OFET memory devices.     

High-response organic thin-film memory transistors based on dipole-functional polymer electret layers

A molecular design for the electret material of n-operating organic field-effect transistor-based (OFET) memories is introduced. A large memory window and high operating speed were achieved while the polar groups are connected to the polymer chain of polyimide, which plays the role of electret of a transistor memory device. The phase variation of electrical force microscopy images showed that polarization field induces charge trapping states on the surface of electret layer and accumulates charged carriers within the conducting channel of OFET to achieve high-performance memory and transistor simultaneously. An extra-large memory window was also obtained by introducing photo-induced charge transfer effect.     

Morphology control of tunneling dielectric towards high-performance organic field-effect transistor nonvolatile memory

We report high-performance organic field-effect transistor nonvolatile memory based on nano-floating-gate, which shows a large memory window of about 70 V, high ON/OFF ratio of reading current over 10⁵ after 1 week storage, high field-effect mobility of 0.6 cm²/V s, and good programming/erasing/reading endurance. The devices incorporate Au nanoparticles and polystyrene layer on top to form the nano-floating-gate, and we demonstrate that the morphology control of the tunneling dielectric is critically significant to improve the memory performance. The optimized tunneling dielectric morphology is favorable to the efficient charge tunneling, reliable charge storage and high-quality organic film growth.     

Organic nonvolatile memory transistors based on fullerene and an electron-trapping polymer

We report for the first time organic n-type nonvolatile memory transistors based on a fullerene (C₆₀) semiconductor and an electron-trapping polymer, poly(perfluoroalkenyl vinyl ether) (CYTOP). The transistors with a Si++/SiO₂/CYTOP/C₆₀/Al structure show good n-type transistor performance with a threshold voltage (V_th) of 2.8 V and an electron mobility of 0.4 cm² V⁻¹ s⁻¹. Applying gate voltages of 50 or −45 V for about 0.1 s to the devices induces the reversible shifts in their transfer characteristics, which results in a large memory window (ΔV_th) of 10 V. A memory on/off ratio of 10⁵ at a small reading voltage below 5 V and a retention time greater than 10⁵ s are achieved. The memory effect in the transistor is ascribed to electrons trapped at the CYTOP/SiO₂ interface. Because of the use of high-electron-mobility C₆₀, the switching voltages of our memory transistors become significantly lower than those of conventional memory transistors based on pentacene.     

Floating-gate nanofibrous electret arrays for high performance nonvolatile organic transistor memory devices

Nanofibrous electret arrays based organic field-effect floating-gate transistor memory was firstly developed by electrospinning. The nanofiber arrays are composed of a novel porphyrin molecule of [5,15-bis[4-(pyridyl)ethynyl]-10,20-diphenyl]-21H,23H-porphyrin (DPP) as charge-trapping elements and polystyrene (PS) as the tunneling layer. The floating-gate transistor memory based on electrospinning nanofibrous electret arrays exhibited a reliable controllable threshold voltage shift and effective charge-trapping ability which was obviously superior to the counterparts fabricated with widely employed spin-coating technique. The result shows that electrospinning can be used as an effective artificial strategy to produce predesigned microstructure for the electrets, optimize the electrical memory characteristics, and may be applied in future nonwoven electronic memory devices.     

Low-voltage programmable/erasable high performance flexible organic transistor nonvolatile memory based on a tetratetracontane passivated ferroelectric terpolymer

Future flexible electronic systems require memory devices combining low power consumption and mechanical bendability. However, high programming/erasing (P/E) voltages, which are universally required to switch the storage states in previously reported ferroelectric organic field-effect transistor (Fe-OFET) nonvolatile memories (NVMs), severely prevent their practical applications. In this work, we develop a novel route to achieve a low-voltage programmable/erasable flexible Fe-OFET NVM. Ferroelectric terpolymer poly(vinylidene-fluoride-trifluoroethylene-chlorotrifluoroethylene) [P(VDF-TrFE-CTFE)], rather than the conventional ferroelectric copolymer poly(vinylidene-fluoride-trifluoroethylene) [P(VDF-TrFE)], is used as the gate dielectric. The low coercive field of P(VDF-TrFE-CTFE) is the main contribution to the low-voltage operation in the Fe-OFET NVM, even with a relative thick ferroelectric gate dielectric layer. By depositing a long-chain alkane molecule Tetratetracontane (TTC) as the passivation layer on the surface of P(VDF-TrFE-CTFE) film, the layer-by-layer growth mode of semiconductor pentacene is obtained, which results in a large crystalline grain and good interface morphology at the channel/dielectric. Therefore, the mobility of Fe-OFET NVMs is greatly improved. As a result, a high performance flexible Fe-OFET NVM is achieved, with a low P/E voltage of ±15 V, high mobility up to 0.5 cm² V⁻¹ s⁻¹, reliable P/E endurance property over 1000 cycles, stable data storage retention capability over 6000 s, and excellent mechanical bending durability without visible degradation after 2000 repetitive tensile bending cycles at a small curvature radius of 4.0 mm.     

High-k polymer dielectrics with different cross-linked networks for nonvolatile transistor memory device

Nonvolatile OFET memory devices using different pPFPA/bPEI cross-linked polymers as the dielectric layer are fabricated. The influence of bPEI content on the electrical property and memory performance of devices are systematically investigated. The results demonstrate that the introduction of bPEI into pPFPA can significantly enhance the capacitance and dielectric constant of the pPFPA/bPEI cross-linked polymer dielectrics, but it also causes a slight increase in the leakage current density. Besides, the excess bPEI induces more morphology defects of the semiconductor film, leading to an apparent decrement in charge mobility. Transistors with the 119:250 pPFPA/bPEI dielectric layer exhibit the highest on/off current ratio (~10⁷ at V_g = − 20V) and a relatively low hole mobility of 0.38 cm² V⁻¹s⁻¹. Moreover, the corresponding memory devices show good reliability in information record with a data retention time over 10⁵ s, indicating that an appropriate amount of bPEI is crucial for improving the stability of the memory devices.     

Flexible nonvolatile organic ferroelectric memory transistors fabricated on polydimethylsiloxane elastomer

The flexible organic ferroelectric nonvolatile memory thin film transistors (OFMTs) were fabricated on polydimethylsiloxane (PDMS) elastomer substrates, in which an organic ferroelectric poly(vinylidene-trifluoroethylene) and an organic semiconducting poly(9,9-dioctylfluorene-co-bithiophene) layers were used as gate insulator and active channel, respectively. The carrier mobility, on/off ratio, and subthreshold swing of the OFMTs fabricated on PDMS showed 5 × 10⁻² cm² V⁻¹ s⁻¹, 7.5 × 10³, and 2.5 V/decade, respectively. These obtained values did not markedly change when the substrate was bent with a radius of curvature of 0.6 cm. The memory on/off ratio was initially obtained to be 1.5 × 10³ and maintained to be 20 even after a lapse of 2000 s. The fabricated OFMTs exhibited sufficiently encouraging device characteristics even on the PDMS elastomer to realize mechanically stretchable nonvolatile memory devices.     

Contactless charge carrier mobility measurement in organic field-effect transistors

With the increasing performance of organic semiconductors, contact resistances become an almost fundamental problem, obstructing the accurate measurement of charge carrier mobilities. Here, a generally applicable method is presented to determine the true charge carrier mobility in an organic field-effect transistor (OFET). The method uses two additional finger-shaped gates that capacitively generate and probe an alternating current in the OFET channel. The time lag between drive and probe can directly be related to the mobility, as is shown experimentally and numerically. As the scheme does not require the injection or uptake of charges it is fundamentally insensitive to contact resistances. Particularly for ambipolar materials the true mobilities are found to be substantially larger than determined by conventional (direct current) schemes.     

Alternating dithienobenzoxadiazole-based conjugated polymers for field-effect transistors and polymer solar cells

Three new alternating copolymers derived from dithienobenzoxadizole (DTfBO) and different thiophene-based π-spacers, including terthiophene, quarterthiophene, and dithienyl flanked thienothiophene, were successfully synthesized. The DTfBO-based polymers possess optical band-gaps in the range of 1.84–1.89 eV and exhibit relatively deep HOMO levels between −5.36 eV and −5.50 eV. Due to strong interchain aggregation, DTfBO-based polymers could not be well dissolved in chlorobenzene at room temperature, but they could be processed with hot chlorobenzene solutions of ∼100 °C. Evolutions of UV absorption spectra of polymer solutions during heating process could differentiate their different aggregation ability, among which a repeating unit based on a DTfBO and a terthiophene could supply the strongest inter-chain interaction. Notably, the three DTfBO-based polymers displayed high field-effect hole mobilities between 0.21 and 0.54 cm²/(V s). In polymer solar cells (PSCs) with the three polymers as the donors, high open-circuit voltages between 0.87 and 0.93 V could be realized. For active layer thickness of 80 nm, the PSCs displayed power conversion efficiency (PCE) between 2.85% and 5.07%. A very high fill factor of 75.4% was achieved for the polymer comprising dithienyl flanked thienothiophene. With thicker ative layers of 250 nm, the three DTfBO-based polymers exhibited comparable PCEs of ∼5.61% due to obviously increased short-circuit currents. Our results suggest that DTfBO, a big coplanar heterocycle, is a promising building block to construct high mobility conjugated polymers for efficient thick-film PSCs.     

Controllable threshold voltage of a pentacene field-effect transistor based on a double-dielectric structure

The authors report controllable threshold voltage (V_th) in a pentacene field-effect transistor based on a double-dielectric structure of poly(perfluoroalkenyl vinyl ether) (CYTOP) and SiO₂. When a positive switching voltage is applied to the gate electrode of the transistor, electrons traverse through the pentacene and CYTOP layers and subsequently trapped at the CYTOP/SiO₂ interface. The trapped electrons induce accumulation of additional holes in the pentacene conducting channel, resulting in a large V_th shift from ?4.4 to +4.6 V. By applying a negative switching voltage, the trapped electrons are removed from the CYTOP/SiO₂ interface, resulting in V_th returning to an initial value. The V_th shift caused by this floating gate-like effect is reversible and very time-stable allowing the transistor to be applicable to a nonvolatile memory that has excellent retention stability of stored data.     

Organic nonvolatile memory devices utilizing intrinsic charge-trapping phenomena in an n-type polymer semiconductor

Charge trapping is an undesirable phenomenon and a common challenge in the operation of n-channel organic field-effect transistors. Herein, we exploit charge trapping in an n-type semiconducting poly (naphthalene diimide-alt-biselenophene) (PNDIBS) as the key operational mechanism to develop high performance, nonvolatile, electronic memory devices. The PNDIBS-based field-effect transistor memory devices were programmed at 60 V and they showed excellent charge-trapping and de-trapping characteristics, which could be cycled more than 200 times with a current ratio of 10³ between the two binary states. Programmed data could be retained for 10³ s with a memory window of 28 V. This is a record performance for n-channel organic transistor with inherent charge-trapping capability without using external charge trapping agents. However, the memory device performance was greatly reduced, as expected, when the n-type polymer semiconductor was end-capped with phenyl groups to reduce the trap density. These results show that the trap density of n-type semiconducting polymers could be engineered to control the inherent charge-trapping capability and device performance for developing high-performance low-cost memory devices.     

Using d-limonene as the non-aromatic and non-chlorinated solvent for the fabrications of high performance polymer light-emitting diodes and field-effect transistors

Aiming to environment protection, green solvents are crucial for commercialization of solution-processed optoelectronic devices. In this work, d-limonene, a natural product, was introduced as the non-aromatic and non-chlorinated solvent for processing of polymer light-emitting diodes (PLEDs) and organic field effect transistors (OFETs). It was found that d-limonene could be a good solvent for a blue-emitting polyfluorene-based random copolymer for PLEDs and an alternating copolymer FBT-Th₄(1,4) with high hole mobility (μ_h) for OFETs. In comparisons to routine solvent-casted films of the two conjugated polymers, the resulting d-limonene-deposited films could show comparable film qualities, based on UV–vis absorption spectra and observations by atomic force microscopy (AFM). With d-limonene as the processing solvent, efficient blue PLEDs with CIE coordinates of (0.16, 0.16), maximum external quantum efficiency of 3.57%, and luminous efficiency of 3.66 cd/A, and OFETs with outstanding μ_h of 1.06 cm² (V s)⁻¹ were demonstrated. Our results suggest that d-limonene would be a promising non-aromatic and non-chlorinated solvent for solution processing of conjugated polymers and molecules for optoelectronic device applications.     

Improving mobility and electrochemical stability of a water-gated polymer field-effect transistor

Water-gated organic transistors have attracted considerable attention in the field of biosensors, thanks to their capability of operating in the aqueous environment typical of biological systems at very low voltages (∼1 V). Some examples have been recently reported in the literature, employing different organic materials as the active semiconducting layer, ranging from small molecules to single crystals. Here we report on water-gated polymer-based organic-field effect devices using poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (pBTTT) as the active layer. Very promising electronic performances, in terms of mobility and operating voltages are obtained; notably, the charge carrier mobility is in the order of 0.08 cm²/V s, which is of the same order of magnitude of values reported for single-crystal based water-gated devices, and consistent with values reported for solid-state polymer dielectric transistors. Moreover, the pBTTT-based device shows improved electrochemical stability, as compared to previously reported polymer based water-gated devices. Importantly, good functioning of the device is demonstrated also when water is replaced by physiological-like solutions. Critical to the transistors operation, besides the good transport properties of the active material, is the key-role played by alkyl side chains and ordered morphology of the polymer at the interface with the liquid environment, which we highlight here for the first time. Our contribution overall provides a useful step towards the development of bio-organic sensors, with enhanced properties in terms of sensitivity and stability, and for a successful exploitation of organic based field effect transistors in biotic/abiotic interfaces.     

Effect of electron-donating unit on crystallinity and charge transport in organic field-effect transistors with thienoisoindigo-based small molecules

We report the effect of an electron-donating unit on solid-state crystal orientation and charge transport in organic field-effect transistors (OFETs) with thienoisoindigo (TIIG)-based small molecules. End-capping of different electron-donor moieties [benzene (Bz), naphthalene (Np), and benzofuran (Bf)] onto TIIG (giving TIIG-Bz, TIIG-Np, and TIIG-Bf) is resulted in different electronic energy levels, solid-state morphologies and performance in OFETs. The 80 °C post-annealed TIIG-Np OFETs show the best device performance with a best hole mobility of 0.019 cm² V⁻¹ s⁻¹ and threshold voltage of −8.6 ± 0.9 V using top gate/bottom contact geometry and a CYTOP gate dielectric. We further investigated the morphological microstructure of the TIIG-based small molecules by using grazing incidence wide angle X-ray scattering, atomic force microscopy and a polarized optical microscope. The electronic transport levels of the TIIG-based small molecules in thin-film states were investigated using ultraviolet photoelectron spectroscopy to examine the charge injection properties of the gold electrode.     

High mobility multibit nonvolatile memory elements based organic field effect transistors with large hysteresis

High mobility multibit nonvolatile memory elements based on organic field effect transistors with a thin layer of polyquinoline (PQ) were reported. The devices show a high mobility of 1.5 cm² V⁻¹ s⁻¹ in the saturation region which is among the best reported for nonvolatile organic memory transistors. The multibit nonvolatile memory elements can be operated at voltage less than 100 V with good stability under continuous operation condition and show long retention time. The different initial scanning positive gate voltages to −100 V result in several ON states, while the scanning gate voltage from −100 V to positive voltage leads to same OFF state. The charge trapping model of electrons into the PQ layer was used to explain the origin of the memory properties.     

Characterization of PI:PCBM organic nonvolatile resistive memory devices under thermal stress

In this study, we fabricated nonvolatile organic memory devices using a mixture of polyimide (PI) and 6-phenyl-C61 butyric acid methyl ester (PCBM) (denoted as PI:PCBM) as an active memory material with Al/PI:PCBM/Al structure. Upon increasing the temperature from room temperature to 470 K, we demonstrated the good nonvolatile memory properties of our devices in terms of the distribution of ON and OFF state currents, the threshold voltage from OFF state to ON state transition, the retention, and the endurance. Our organic memory devices exhibited an excellent ON/OFF ratio (I_ON/I_OFF > 10³) through more than 200 ON/OFF switching cycles and maintained ON/OFF states for longer than 10⁴ s without showing any serious degradation under measurement temperatures up to 470 K. We also confirmed the structural robustness under thermal stress through transmission electron microscopy cross-sectional images of the active layer after a retention test at 470 K for 10⁴ s. This study demonstrates that the operation of PI:PCBM organic memory devices could be controlled at high temperatures and that the structure of our memory devices was maintained during thermal stress. These results may enable the use of nonvolatile organic memory devices in high temperature environments.     

Charge trapping in organic transistor memories: On the role of electrons and holes

In this work, we study charge trapping in organic transistor memories with a polymeric insulator as gate dielectric. We found that the mechanism of charge trapping is tunneling from the semiconductor channel into the gate dielectric. Depending on the semiconductor and its processing, charge trapping can result in large bi-directional threshold voltage shifts, in case the semiconductor is ambipolar, or in shifts in only one direction (unipolar semiconductor). These results indicate that optimal memory performance requires charge carriers of both polarities, because the most efficient method to lower the programming field is by overwriting a trapped charge by an injected charge of opposite polarity.