Organic Field-effect Transistor Memory Devices Research Articles

Graphdiyne particles as nano-floating gates for high-performance nonvolatile organic field-effect transistor memory

Graphdiyne particles (GDYP), newcomers of carbon family, were employed as nano-floating gates in organic field-effect transistor (OFET) memories. The charge-trapping layer was prepared by blending GDYP into a polystyrene (PS) matrix. The effect of GDYP doping ratio on memory performances was investigated, and the OFET memory with the optimal doping concentration of the GDYP (0.3 mg/mL) exhibits ambipolar memory behavior with a wide memory window as large as 86 V, excellent retention time over 104 s with a high ON/OFF current ratio of 7.5 × 105. This work demonstrates that graphdiyne is a promising charge-trapping material for high-performance nonvolatile OFET memory devices.

Ambipolar charge-trapping in self-assembled nanostructures of a supramolecular miktoarm star-shaped copolymer with a zinc phthalocyanine core

Supramolecular miktoarm star-shaped copolymers with a zinc phthalocyanine core exhibit phase-separated nanostructures that enhance ambipolar charge-trapping capabilities in the organic field-effect transistor memory devices.

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.

Organic Field-Effect Transistor Memory Device Based on an Integrated Carbon Quantum Dots/Polyvinyl Pyrrolidone Hybrid Nanolayer

In this work, we present a pentacene-based organic field-effect transistor memory (OFETM) device, which employs one-step microwave-assisted hydrothermal carbon quantum dots (CQDs) embedded in a polyvinyl pyrrolidone (PVP) matrix, to form an integrated hybrid nanolayer as the charge trapping layer. The as-prepared CQDs are quasi-spherical amorphous C, with sizes ranging from 5 to 20 nm, with a number of oxygen-containing groups and likely some graphite-like domains that produce CQDs with excellent electron-withdrawing characteristics. The incorporation of CQDs into PVP dielectric materials results in a bidirectional storage property. By optimizing the concentration of CQDs embedded into the PVP matrix, the OFETM shows excellent memory characteristics with a large memory window of 8.41 V under a programming/erasing (P/E) voltage of ± 60 V and a retention time of up to 104 s.

Enhancing performance of nonvolatile transistor memories via electron‐accepting composition in triphenylamine‐based random copolymers

ABSTRACTWith the rapid advances in organic memory, organic field‐effect transistor (OFET) memory has been recognition of the value over the past few years. Although the functional polymer with the Donor‐Acceptor (D‐A) structure has been widely investigated, little research has been carried out to clarify the relationships among D‐A structure of the polymer, capability of charge‐transfer, and memory performance. Here, we report the nonvolatile memory characteristics of pentacene‐based OFET memory using random copolyimides, poly[4,4′‐diaminotriphenylamine‐hexafluoroisopropylidenediphthalimide‐co‐4‐(N,N‐bis(p‐aminophenyl)amino)‐4′‐nitroazobenzene‐hexafluoroisopropylidenediphthalimide) (PI(TPA‐6FDA‐DACx)), with feeding ratios of DAC to TPA set as x (where x = 0,10, 30,50,70,100). The OFET memory performance based on the molar ratio of DAC to TPA equal to 30:70 represents the best results with the proper charge mobility, on/off current ratio, and memory window. Intriguingly, the memory performance can be enhanced by introducing more D‐A monomer in polymer electrets, yet the concomitant inferior growth of pentacene decreases the charge mobility, attributed to the intrinsically destructive arrangement of polymer backbone. Our conclusion points out the importance of polymer arrangement and capability of charge‐transfer to the OFET performance and memory characteristics. The comparable results can also be applied for advanced OFET memory devices. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1113–1121

Pentafluorosulfanylated polymers as electrets in nonvolatile organic field-effect transistor memory devices

Styrenic polymer electrets with pentafluorosulfanylated sidechains demonstrate their charge-storage capabilities in organic nonvolatile memory devices.

Linkage effects of triphenylamine-based aromatic polymer electrets on electrical memory performance

Here, we use polyimide (PI), polyether (PE) and polyester (PET) with diphenyl sulfonyl (S) moieties combined with triphenylamine (TPA) units to obtain three polymer electrets, TPA-PIS, TPA-PES, and TPA-PETS, respectively. The pentacene-based organic field effect transistor (OFET) memories with the charge-trapping polymer electrets layer were examined. The variation in linkages in the polymer backbone noticeably influences the energy structures and molecular polarity, and thus their memory properties were systematically characterized and compared. Volatile memory characteristics can be observed for all three polymer electrets-based memories. Among these, the TPA-PIS and TPA-PETS electret OFET memory devices exhibit ambipolar trapping behavior capable of storing holes and electrons, with a memory window (MW) of 32.4 ± 1.2 V and 21.7 ± 1.0 V, respectively, and a memory ratio of 104∼106. Importantly, programming/erasing switching endurance for at least 100 cycles is achieved, allowing for tri-state memory storage. However, hole-only unipolar trapping of OFETs memory with the TPA-PES electret presents relatively slower charge detrapping phenomena and longer retention time ability due to the higher molecular dipole moment. Our comparative study demonstrates the important role of the linkage effect in aromatic polymers for developing polymer electret-based OFET memories.

Solution-Processed Wide-Bandgap Organic Semiconductor Nanostructures Arrays for Nonvolatile Organic Field-Effect Transistor Memory.

In this paper, the development of organic field-effect transistor (OFET) memory device based on isolated and ordered nanostructures (NSs) arrays of wide-bandgap (WBG) small-molecule organic semiconductor material [2-(9-(4-(octyloxy)phenyl)-9H-fluoren-2-yl)thiophene]3 (WG3 ) is reported. The WG3 NSs are prepared from phase separation by spin-coating blend solutions of WG3 /trimethylolpropane (TMP), and then introduced as charge storage elements for nonvolatile OFET memory devices. Compared to the OFET memory device with smooth WG3 film, the device based on WG3 NSs arrays exhibits significant improvements in memory performance including larger memory window (≈45 V), faster switching speed (≈1 s), stable retention capability (>104 s), and reliable switching properties. A quantitative study of the WG3 NSs morphology reveals that enhanced memory performance is attributed to the improved charge trapping/charge-exciton annihilation efficiency induced by increased contact area between the WG3 NSs and pentacene layer. This versatile solution-processing approach to preparing WG3 NSs arrays as charge trapping sites allows for fabrication of high-performance nonvolatile OFET memory devices, which could be applicable to a wide range of WBG organic semiconductor materials.

High-Performance Nonvolatile Organic Field-Effect Transistor Memory Based on Organic Semiconductor Heterostructures of Pentacene/P13/Pentacene as Both Charge Transport and Trapping Layers.

Nonvolatile organic field‐effect transistor (OFET) memory devices based on pentacene/N,N′‐ditridecylperylene‐3,4,9,10‐tetracarboxylic diimide (P13)/pentacene trilayer organic heterostructures have been proposed. The discontinuous n‐type P13 embedded in p‐type pentacene layers can not only provide electrons in the semiconductor layer that facilitates electron trapping process; it also works as charge trapping sites, which is attributed to the quantum well‐like pentacene/P13/pentacene organic heterostructures. The synergistic effects of charge trapping in the discontinuous P13 and the charge‐trapping property of the poly(4‐vinylphenol) (PVP) layer remarkably improve the memory performance. In addition, the trilayer organic heterostructures have also been successfully applied to multilevel and flexible nonvolatile memory devices. The results provide a novel design strategy to achieve high‐performance nonvolatile OFET memory devices and allow potential applications for different combinations of various organic semiconductor materials in OFET memory.

Fluorinated p-n type copolyfluorene as polymer electret for stable nonvolatile organic transistor memory device

In this study, a kind of fluorinated copolyfluorene, named poly[(4-(octyloxy)-9,9-diphenylfluorene-2,7-diyl)-alt-(2,3,5,6-tetrafluoro-1,4-phenylene)] (PODPF-TFP), is synthesized by facile palladium-based direct aromatization. Compared to the non-fluorinated counterpart, poly[(4-(octyloxy)-9,9-diphenylfluorene-2,7-diyl)-alt-(p-phenylene)] (PODPF-P), deeper HOMO/LUMO energy level combined with steric hindrance effect endow PODPF-TFP with excellent spectra and morphology stability. Finally, organic field-effect transistor (OFET) memory devices are fabricated with PODPF-P/PODPFTFP as the dielectric layers, and they both exhibit flash type storage characteristic. Owing to the electronegativity of fluorine atom, the device based on PODPF-TFP exhibits larger memory window and more stable I on/I off ratio during a retention time of 104 s as well as a better aging stability. The present study suggests that fluorinated p-n copolyfluorene electrets could enhance the capabilities of charge trapping and storage, which are promising for OFET memory devices.

Crosslinkable high dielectric constant polymer dielectrics for low voltage organic field‐effect transistor memory devices

ABSTRACTIn this study, we successfully synthesized water/methanol soluble random copolymers with a high dielectric constant, poly(n‐(hydroxymethyl) acrylamide‐co‐5‐(9‐(5‐(diethylamino)pentyl)−2‐(4‐vinylphenyl)−9H‐fluorene(P(NMA‐co‐F6NSt)), which contained chemical crosslinkable segment (NMA) and hole trapping building block (F6NSt). The feeding molar ratios of two monomers (NMA:F6NSt) were set as 100:0, 95:5, 80:20, and 67:33 for the copolymers of P1, P2, P3, and P4, respectively. The crosslinked P(NMA‐co‐F6NSt) thin film could serve as both dielectric and charge storage layers in organic field‐effect transistor (OFET) memory device and exhibited high k (i.e., 4.91–6.47) characteristics, leading to a low voltage operation and a small power consumption. Devices based on the P1‐P4 dielectrics showed excellent insulating properties and good charge storage performance under a low operating voltage in a range of ±5V because of tightly network structures and well‐dispersed trapping cites. In particular, P3‐based memory device exhibited a large memory window of 4.13 V with stable data retention stability over 104 s, a large on/off ratio of 104, and good endurance characteristics as high as 200 cycles. The above results suggested that a high‐performance OFET memory device could be facilely achieved using the novel crosslinkable high‐k copolymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3224–3236

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.

Phthalocyanine‐Cored Star‐Shaped Polystyrene for Nano Floating Gate in Nonvolatile Organic Transistor Memory Device

A novel non‐volatile organic memory device is developed based on an organic field effect transistor (OFET) with a dielectric layer of a four‐armed, star‐shaped polymer featuring a copper phthalocyanine (CuPc) core. The CuPc core unit of the star‐shaped polystyrene (CuPc‐PS4) self‐assembles to form aggregates via π–π interactions, which are isolated and dispersed in the polymer thin film. The OFET memory device employing CuPc‐PS4 shows significant hole‐trapping characteristics with a high memory ON/OFF current ratio of 107, long retention ability of over 104 s, and good endurance of more than 100 cycles, which is attributed to a flash‐type memory. The novel polymer design with CuPc core assemblies inside the polymer matrix is a promising candidate for nano floating gates in non‐volatile OFET memory.

Random styrenic copolymers with pendant pyrene moieties: Synthesis and applications in organic field‐effect transistor memory

ABSTRACTThree random copolymers comprised pendant styrene and 4‐(1‐pyrenyl)‐styrene (PyS) moieties in different molar ratios (21.4:1 (P1), 3.9:1 (P2), and 1.4:1 (P3)) were synthesized and employed as charge storage polymeric electret for nonvolatile organic field‐effect transistor (OFET) memory application. The impact of varying the molar ratio in side‐chain electron‐donating pyrene moieties on the thermal, optical, photophysical, electrochemical, and electrical properties of the resulting pendant copolymers was evaluated to establish structure–property relationship. The OFET memory with P3 electret layer exhibits a largest memory window of 41.8 V, long retention time of 104 s with memory ratio of 105, and stable reversibility of at least 100 cycles due to enhanced field‐induced holes trapping ability from higher PyS composition ratio. Therefore, polymer electret with pendant functional moieties shows potential for use as trapping layer in OFET memory devices. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 910–917

Transistor memory devices with large memory windows, using multi-stacking of densely packed, hydrophobic charge trapping metal nanoparticle array

Organic field-effect transistor (OFET) memories have rapidly evolved from low-cost and flexible electronics with relatively low-memory capacities to memory devices that require high-capacity memory such as smart memory cards or solid-state hard drives. Here, we report the high-capacity OFET memories based on the multilayer stacking of densely packed hydrophobic metal NP layers in place of the traditional transistor memory systems based on a single charge trapping layer. We demonstrated that the memory performances of devices could be significantly enhanced by controlling the adsorption isotherm behavior, multilayer stacking structure and hydrophobicity of the metal NPs. For this study, tetraoctylammonium (TOA)-stabilized Au nanoparticles (TOA-AuNPs) were consecutively layer-by-layer (LbL) assembled with an amine-functionalized poly(amidoamine) dendrimer (PAD). The formed (PAD/TOA-AuNP)n films were used as a multilayer stacked charge trapping layer at the interface between the tunneling dielectric layer and the SiO2 gate dielectric layer. For a single AuNP layer (i.e. PAD/TOA-AuNP)1) with a number density of 1.82 × 1012 cm−2, the memory window of the OFET memory device was measured to be approximately 97 V. The multilayer stacked OFET memory devices prepared with four AuNP layers exhibited excellent programmable memory properties (i.e. a large memory window (ΔVth) exceeding 145 V, a fast switching speed (1 μs), a high program/erase (P/E) current ratio (greater than 106) and good electrical reliability) during writing and erasing over a relatively short time scale under an operation voltage of 100 V applied at the gate.

Semi-conjugated acceptor-based polyimides as electrets for nonvolatile transistor memory devices

We report new polyimides as electrets for pentacene-based organic field-effect transistor (OFET) memory devices, consisting of different electron-accepting dianhydride moieties (PI(BPDA-DAP), PI(PMDA-DAP), and PI(ODPA-DAP)), and varied aliphatic spacer lengths (PI(PMDA-DAH) and PI(PMDA-DAD)). The effects of the molecular structures on the charge mobility and OFET memory characteristics were systematically investigated in terms of the related frontier energy levels and morphologies. All the devices showed bistable nonvolatile memory characteristics but with a distinct charge storage behavior. The OFET memory devices using the PI(BPDA-DAP) electret exhibited a larger memory window of 81 V compared to those of PI(PMDA-DAP) and PI(ODPA-DAP), mainly attributed to its low-lying LUMO energy level that results from its more extended conjugation. Both the high retention time (around 104 s for the ON/OFF states) and steady write-read-erase-read (WRER) cycles suggested good stability and read/write properties of the studied devices. As the aliphatic spacer length increased from PI(PMDA-DAP) to PI(PMDA-DAH) and PI(PMDA-DAD), the memory characteristics changed from flash to WORM (write once read many times) behaviour. Furthermore, the memory window was reduced with the increased aliphatic spacer length, due to the reduced density of the conjugated electron-trapping sites. This study demonstrated that the electrical characteristics and charge mobility of transistor memory devices can be effectively modulated through the extent of conjugation of the electron accepting moiety and spacer length in polymer electrets.

Nonvolatile organic field-effect transistor memory devices using polymer electrets with different thiophene chain lengths

We report the synthesis of poly(5-hexyl-2-vinylthiophene) (PVT) and poly(5-hexyl-5′′-vinyl-2,2′:5,2′′-terthiophene) (PVTT) as charge storage electrets for nonvolatile organic field effect transistor (OFET) memory devices of n-type semiconducting N,N′-bis(2-phenylethyl)perylene-3,4,9,10-bis(dicarboximide) (BPE-PTCDI). The effects of the conjugated thiophene chain length on the morphology, OFET mobility and memory characteristics are explored and compared to those of the styrene or fluorene side chain. The mobility of the OFET memory device using PVTT as an electret is significantly smaller compared with that of PVT because its large torsional angle hinders the molecular packing of BPE-PTCDI. However, the OFET memory device using the PVTT electret has the largest hysteresis window of 81 V, compared to PVT, polystyrene (PS), and poly(styrene) para-substituted with fluorene (PSt-Fl). The highest HOMO energy level of PVTT facilitates the charge transfer from BPE-PTCDI and leads to the largest memory window. The backbone non-coplanarity prevents the back transfer of the charge for the nonvolatile memory characteristics. The device shows excellent nonvolatile behavior for bistable switching and the write–read–erase–read (WRER) cycles are operated over 100 cycles. The shifted threshold voltages of the OFET memory devices using PVTT are stable over 104 s, and the ON and OFF states could maintain 104 s with the Ion/Ioff current ratios of 103. This study suggests that the pendent conjugation length and the backbone coplanarity of polymer electrets significantly affect the charge mobility and electrical characteristics of OFET memory devices.

Organic Field‐Effect Transistor Memory Devices Using Discrete Ferritin Nanoparticle‐Based Gate Dielectrics

Organic field-effect transistor (OFET) memory devices made using highly stable iron-storage protein nanoparticle (NP) multilayers and pentacene semiconductor materials are introduced. These transistor memory devices have nonvolatile memory properties that cause reversible shifts in the threshold voltage (Vth ) as a result of charge trapping and detrapping in the protein NP (i.e., the ferritin NP with a ferrihydrite phosphate core) gate dielectric layers rather than the metallic NP layers employed in conventional OFET memory devices. The protein NP-based OFET memory devices exhibit good programmable memory properties, namely, large memory window ΔVth (greater than 20 V), a fast switching speed (10 μs), high ON/OFF current ratio (above 10(4)), and good electrical reliability. The memory performance of the devices is significantly enhanced by molecular-level manipulation of the protein NP layers, and various biomaterials with heme Fe(III) /Fe(II) redox couples similar to a ferrihydrite phosphate core are also employed as charge storage dielectrics. Furthermore, when these protein NP multilayers are deposited onto poly(ethylene naphthalate) substrates coated with an indium tin oxide gate electrode and a 50-nm-thick high-k Al2 O3 gate dielectric layer, the approach is effectively extended to flexible protein transistor memory devices that have good electrical performance within a range of low operating voltages (<10 V) and reliable mechanical bending stability.

A nanostructured micellar diblock copolymer layer affects the memory characteristics and packing of pentacene molecules in non-volatile organic field-effect transistor memory devices

Organic field-effect transistor (OFET) memory devices incorporating the copolymer polystyrene-block-poly(4-vinylpyridine) (PS56k-b-P4VP8k) layer, which features a thickness-dependent micellar nanostructure (P4VP-core, PS-shell), as a charge trapping layer can exhibit tunable memory windows for p-channel applications. For instance, the memory window increased substantially from 7.8 V for the device incorporating a 60 nm thick PS56k-b-P4VP8k layer to 21 V for the device incorporating a 27 nm thick layer, an increase of more than 2.5 times. Using simultaneous synchrotron grazing-incidence small-angle X-ray scattering and wide-angle X-ray scattering to probe the nanostructured micellar PS56k-b-P4VP8k layer and the pentacene layer positioned directly on the top of the copolymer layers, respectively, we were able to elucidate the structural characteristics of the bilayer and to correlate their effects with the memory performances of devices with similar architectures. For the PS56k-b-P4VP8k layers, we found that the inter-micelle distance and their lateral arrangements depended on the layer thickness: the thickness of the PS shells in the lateral direction decreased upon increasing the layer thickness, as did the memory window for the OFET device that incorporated the PS56k-b-P4VP8k layers, showing a strong dependence of the threshold voltage shifts (i.e., memory window) on the distance between the micelles. Additionally, for the molecular packing of the pentacene layer positioned on the copolymer layer, we found that the PS56k-b-P4VP8k layers affected not only the orientation of the pentacene molecules but also their grain sizes, thereby affecting the hole mobility of the memory devices. These results suggest that tuning the micellar nanostructure of the block copolymer thin film that was used as a trapping layer can be a simple and effective way for optimizing the memory window and affecting the hole mobility of OFET memory devices.

Non-volatile organic field-effect transistor memory comprising sequestered metal nanoparticles in a diblock copolymer film

In this study, we fabricated p-channel-type non-volatile organic field-effect transistor (OFET) memory devices featuring an asymmetric PS-b-P4VP diblock copolymer layer incorporating high- and low-work-function metal nanoparticles (NPs) in the hydrophilic and hydrophobic blocks, respectively. We chose the highly asymmetric diblock copolymer PS56k-b-P4VP8k as the polymer electret to create the memory windows, and used the different work functions of the ex situ-synthesized metal NPs to tune the memory window for either p- or n-channel applications. The transfer curves of non-volatile OFET memory devices incorporating an asymmetric PS56k-b-P4VP8k layer embedded with high-work-function Pt NPs (5.65 eV) in the P4VP block exhibited a positive threshold voltage shift and a large memory window (ca. 27 V). In contrast, the transfer curves of the corresponding non-volatile OFET memory devices featuring embedded low-work-function (4.26 eV) Ag NPs exhibited a negative threshold voltage shift and a smaller memory window (ca. 19 V). This approach provides a versatile way to fabricate p- or possibly n-channel-type non-volatile organic field-effect transistor (OFET) memory devices with the same processing procedure.