High-Density, Nonvolatile, Flexible Multilevel Organic Memristor Using Multilayered Polymer Semiconductors.

Nonvolatile organic memristors have emerged as promising candidates for next-generation electronics, emphasizing the need for vertical device fabrication to attain a high density. Herein, we present a comprehensive investigation of high-performance organic memristors, fabricated in crossbar architecture with PTB7/Al-AlOx-nanocluster/PTB7 embedded between Al electrodes. PTB7 films were fabricated using the Unidirectional Floating Film Transfer Method, enabling independent uniform film fabrication in the Layer-by-Layer (LbL) configuration without disturbing underlying films. We examined the charge transport mechanism of our memristors using the Hubbard model highlighting the role of Al-AlOx-nanoclusters in switching-on the devices, due to the accumulation of bipolarons in the semiconducting layer. By varying the number of LbL films in the device architecture, the resistance of resistive states was systematically altered, enabling the fabrication of novel multilevel memristors. These multilevel devices exhibited excellent performance metrics, including enhanced memory density, high on-off ratio (>108), remarkable memory retention (>105 s), high endurance (87 on-off cycles), and rapid switching (∼100 ns). Furthermore, flexible memristors were fabricated, demonstrating consistent performance even under bending conditions, with a radius of 2.78 mm for >104 bending cycles. This study not only demonstrates the fundamental understanding of charge transport in organic memristors but also introduces novel device architectures with significant implications for high-density flexible applications.

The Influence of a Microstructural Conformation of Oriented Floating Films of Semiconducting Polymers on Organic Device Performance.

Extended π-conjugation with backbone-planarity-driven π-π stacking dominates charge transport in semiconducting polymers (SCPs). The roles of SCP film morphology and macromolecular conformation concerning the substrate in influencing charge transport and its impact on device performance have been a subject of extensive debate. Face-on SCPs promote out-of-plane charge transport primarily through π-π stacking, with conjugated polymeric chains assisting transport in connecting crystalline domains, whereas edge-on SCPs promote in-plane charge transport primarily through conjugation and π-π stacking. In this work, we fabricated three different types of devices, namely, organic field effect transistors, organic Schottky diodes, and organic bistable memristors, as representatives of planar and vertical devices. We demonstrate that a planar device, i.e., an organic field effect transistor, performs well in an edge-on conformation exhibiting a field-effect mobility of 0.12 cm2V-1s-1 and on/off ratio >104, whereas vertical devices, i.e., organic Schottky diodes and organic memristors, perform well in a face-on conformation, exhibiting exceptionally high on/off ratios of ~107 and 106, respectively.

Fast-Coating Process Based on Elongated Rodlike Preaggregate for Highly Oriented Thin Film of Donor-Acceptor π-Conjugated Polymer.

A fast meniscus-guided coating for ultrahighly oriented thin films of a typical donor-acceptor π-conjugated polymer, poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno[3,2-b]thiophene)](PDPP-DTT) was realized. A coating speed higher than 100 mm/s, which was regarded as a Landau-Levich regime, was applicable. The 2D order parameter (S2) of the thin films changed by selecting the solvent and adjusting the initial concentration of the solution, and the large elongated rodlike preaggregates formed particularly in chlorobenzene contributed to the high orientation in the solid film state, resulting in the highest value of S2 = 0.87. Focused on the PDPP-DTT preaggregate formation in the solution, the SAXS analysis was carried out to investigate the shape and size of the preaggregates. The mechanism of the molecular orientation was discussed by taking the preaggregates and the solution flow under the coating process into account.

Oriented Thin Films of Insoluble Polythiophene Prepared by the Friction Transfer Technique.

A thin film of unsubstituted polythiophene (PT), an insoluble conjugated polymer, with molecular chains uniaxially oriented in plane was prepared by the friction transfer method. The structure of highly oriented thin films of PT was investigated using grazing-incidence X-ray diffraction (GIXD), ultraviolet-visible (UV-vis) spectroscopy, and infrared (IR) spectroscopy. The polarized UV-vis and IR spectra and GIXD measurements showed the PT molecular chains were well aligned in parallel to the friction direction. The GIXD studies clarified that the polymer backbones were aligned with very narrow distribution, such that the half-width was about 4 degrees. The degree of orientation of the PT friction-transferred film was higher compared with those of regioregular poly(3-alkylthiophene)s. Moreover, the GIXD results show a preferred orientation where the a-axis is perpendicular to the substrate plane.

Ordered arrangement of F4TCNQ anions in three-dimensionally oriented P3HT thin films.

An ordered arrangement of electron-accepting molecular dopant, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), in three-dimensionally (3D) oriented poly(3-hexylthiophene) (P3HT) film was clarified. The 3D oriented P3HT thin films prepared by the friction-transfer technique were doped with F4TCNQ by dipping into an acetonitrile solution. The presence of F4TCNQ anions in the 3D oriented P3HT thin films was investigated by polarized ultraviolet/visible/near-infrared absorption spectroscopy, grazing incidence X-ray diffractometry, polarized Fourier transform infrared spectroscopy (FT-IR), and infrared p-polarized multiple-angle incidence resolution spectroscopy (pMAIRS). The F4TCNQ-doped 3D oriented P3HT films showed anisotropic properties in all characterizations. In particular, the anisotropic molecular vibrations from polarized FT-IR and pMAIRS have clearly revealed orientations of polymeric chains and molecular dopant molecules. Considering the results from several independent techniques indicated that F4TCNQ anions in the 3D oriented P3HT were orderly arranged in a 3D manner with respect to the 3D oriented P3HT such that their molecular long-axis parallel to the P3HT backbone, with in-plane molecular orientation. Additionally, the direction of the optical transition moment of the F4TCNQ anion was found to be parallel to the molecular short-axis.

Solvent-Assisted Friction Transfer Method for Fabricating Large-Area Thin Films of Semiconducting Polymers with Edge-On Oriented Extended Backbones.

Recent past has witnessed huge scientific efforts aiming toward enhancing in-plane charge transport by unidirectional orientation of conjugated polymer (CP) backbones adopting various techniques. However, in most of the existing methods, excess amounts of toxic halogenated solvents and preaggregation in solution are inevitable, which are the main bottlenecks toward large-scale fabrication. Solvent-assisted friction transfer (SAFT) is being reported as a novel method and improvisation over conventional friction transfer to expand its versatility. In this method, application of a small amount of the solvent (∼3 µL) during drawing not only leads to the entirely changed film morphology and molecular orientation but also addresses the existing substrate compatibility issues. Utilizing poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]-thiophene] as a representative CP under SAFT technique, films with extended backbone and edge-on orientation was successfully fabricated, which was confirmed by various characterization tools such as X-ray diffraction, polarized absorption, and polarized Raman spectroscopies. Further, anisotropic charge transport in these films was investigated by fabricating organic field-effect transistors and the role of contact resistance was also studied. Slight solvent use, compatibility with various substrates, and film fabrication with controlled orientation, and after validation of its generality on different CPs, SAFT can be expected to open new avenues in the area of printed electronics.

Investigation and Control of Charge Transport Anisotropy in Highly Oriented Friction-Transferred Polythiophene Thin Films.

Highly oriented thin films of poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT) were prepared by friction-transfer technique followed by their characterization using polarized absorption spectroscopy, angle-dependent polarized Raman spectroscopy, and X-ray diffraction (XRD) techniques. Orientation in high-molecular-weight (MW) polymers is hampered by chain folding or entanglements, which limit their macromolecular orientation. Interestingly, utilizing high-molecular-weight PBTTT (MW > 50 kDa) and friction-transfer technique, successful fabrication of highly oriented thin films with very high dichroic ratio (∼30) was demonstrated. The role of the substrate's surface energy and its impact on the field-effect mobility (µ) of the oriented thin films were comprehensively investigated. The influence of annealing the thin films as prepared on the bare and self-assembled monolayer (SAM)-treated SiO2 surfaces exhibiting differential trends of µ was systematically investigated. This was explained by partial and complete conformational transformation of macromolecules on bare and SAM-treated SiO2 surfaces, respectively, after annealing them beyond liquid crystalline phase transition temperature, as revealed by in-plane and out-of-plane XRD results. On bare SiO2, optimum µ up to 0.03 cm2 V-1 s-1 along the backbone orientation was obtained for the thin films annealed to 120 °C; whereas, it reached up to 0.36 cm2 V-1 s-1 on SAM-treated SiO2 after annealing at 200 °C. Finally, a charge transport mechanism was proposed taking evidence from the anisotropic optical and electrical characteristics of the friction-transferred PBTTT films into consideration.

P3HT Nanofibrils Thin-Film Transistors by Adsorbing Deposition in Suspension.

A novel film preparation method utilizing polymer suspension, entitled adsorbing deposition in suspensions (ADS), has been proposed. The poly(3-hexylthiophene) (P3HT) toluene solution forms P3HT nanofibrils dispersed suspension by aging. P3HT nanofibrils are highly crystallized with sharp vibronic absorption spectra. By the ADS method, only P3HT nanofibrils in suspension can be deposited on the substrate surface without any disordered fraction from the dissolved P3HT in suspension. Formed ADS film contains only the nanostructured conjugated polymer. Fabricated polymer thin-film transistor (TFT) utilizing ADS P3HT film shows good TFT performances with low off current, narrow subthreshold swing and large on/off current ratio.

Implication of Molecular Weight on Optical and Charge Transport Anisotropy in PQT-C12 Films Fabricated by Dynamic FTM.

Large area (>20 cm × 2 cm)-oriented thin films of PQT-C12 with varying molecular weight and polydispersity index (PDI) were fabricated by the ribbon-shaped floating film transfer method aiming toward their application as an active semiconductor element of organic field effect transistors (OFETs). Investigation on the influence of the molecular weight and PDI upon the extent of molecular alignment and anisotropic charge transport was systematically carried out. It has been demonstrated that high molecular weight in combination with low PDI not only leads to a very high optical anisotropy >10 but also high charge carrier anisotropy with a hole mobility of about 0.07 cm2/V·s for OFETs using parallel-oriented PQT-C12 thin films. Such a structure-property correlation is highly beneficial for the development of high performance organic electronic devices by synergistic and amicable tuning of the optoelectronic anisotropies and polymer synthetic variables.

Long-term air-stable n-channel organic thin-film transistors using 2,5-difluoro-1,4-phenylene-bis{2-[4-(trifluoromethyl)phenyl]acrylonitrile}.

A long-term air-stable n-type organic semiconductor, 2,5-difluoro-1,4-phenylene-bis{2-[4-(trifluoromethyl)phenyl]acrylonitrile}, was synthesized by a high-yield simple procedure of Knoevenagel condensation with aldehyde and acetonitrile derivatives. A fabricated organic thin-film transistor (OTFT) using this compound exhibited good n-channel OTFT properties with a high electron mobility of 0.17 cm(2) V(-1) s(-1) and an on/off current ratio of 10(6) under both vacuum and ambient air operation. After storage in ambient air for 1 year, a stored n-channel OTFT still shows good n-channel OTFT performance with little degradation in ambient air operation.

Multi-layered oriented polyfluorene films.

Multilayered oriented polyfluorene (PF) films were obtained by applying thermal treatment procedure to a multilayered PF film constructed with fluorene derivatives layer formed on top of a highly oriented friction-transferred crystalline poly(9,9-dioctylfluorene) (PF8) film. The orientations in the multilayered PF films were investigated by polarized photoluminescence (PL) spectroscopy and grazing incident X-ray diffraction (GIXD) analysis. The results of the multilayered PF film constructed with spin-coated PF8 on friction-transferred PF8 indicate that the rearrangement of the upper PF8 layer is induced from the orientation of lower PF8 layer by thermal treatment at the nematic phase temperature. Polarized green emission from the multilayered oriented PF film was demonstrated using the blend of PF8 and poly(9,9-dioctylfluorene-co-benzothiadiazol) (F8BT) as green light emitter for upper layer. By this method, the polarized emission color can be tuned using polymer blends for upper layer similar to the liquid-crystalline polymer arrangement without using different materials as an underlying layer such as the rubbed polyimide.

Crystal structure of friction-transferred poly(2,5-dioctyloxy-1,4-phenylenevinylene).

Poly(2,5-dioctyloxy-1,4-phenylenevinylene) (DOPPV) was found to form a highly oriented film by a friction-transfer technique. Structural investigation of friction-transferred DOPPV was studied by means of polarized ultraviolet-visible (UV-vis) absorption spectroscopy, polarized photoluminescence (PL) spectroscopy, and synchrotron-sourced grazing incident X-ray diffraction (GIXD) analysis. The polarized UV-vis absorption and PL spectra indicate clear axial alignment. DOPPV backbones in friction-transferred film are highly aligned along the drawing direction of the friction-transfer. Further information of the molecular arrangement in friction-transferred DOPPV film was investigated by both the out-of-plane and the in-plane GIXD analyses with synchrotron source. The DOPPV molecules in friction-transferred films were perfectly arranged three-dimensionally: the backbones aligned along the drawing direction of friction-transfer, the alkyl side chains lay in the film plane, and the planar backbones were arranged parallel to the film surface. Additionally, two neighboring DOPPV molecules along the direction of inter-backbones separation by alkyl side chains were found to be shifted with respect to one another by the mean distance of half of a monomeric repeat.

Correlation of the number of thiophene units with structural order and carrier mobility in unsubstituted even- and odd-numbered alpha-oligothiophene films.

We investigate the correlation of the number of thiophene units with the structural order and carrier mobility of the films through studies on thin-film transistors (TFTs) based on alpha-quinquethiophene (5T), alpha-sexithiophene (6T), and alpha-septithiophene (7T). The X-ray diffraction (XRD) data of the nT films deposited at low substrate temperatures present obviously different structural orders depending on the parity of the number of thiophene units. Although even-numbered nT films present well-ordered structures and large carrier mobilities, odd-numbered nT films present two different crystalline polymorphs and vastly low carrier mobilities reflecting the coexistence of two crystalline polymorphs. However, the XRD data of both even- and odd-numbered nT films deposited at high substrate temperatures indicate that the nT molecules form single well-ordered structures. Those ordered TFTs exhibit large carrier mobilities accompanying an increase in the number of thiophene units, 0.05, 0.08, and 0.13 cm2 V(-1) s(-1) for 5T, 6T, and 7T, respectively. The parity of the number of thiophene units affects the structural order intrinsically in grown thin films, and affects carrier mobilities extrinsically in their TFTs.