Well-Defined Block Copolymers with Triphenylamine and Isocyanate Moieties Synthesized via Living Anionic Polymerization for Polymer-Based Resistive Memory Applications: Effect of Morphological Structures on Nonvolatile Memory Performances

The anionic block copolymerization of 4,4′-vinylphenyl-<i>N</i>,<i>N</i>-bis­(4-<i>tert</i>-butylphenyl)­benzenamine (<b>A</b>) with <i>n</i>-hexyl isocyanate (<b>B</b>) was performed using potassium naphthalenide (K-Naph) in THF at −78 and −98 °C in the presence of sodium tetraphenylborate (NaBPh₄) to afford the well-defined block copolymers for investigating the effect of morphological structures on electrical memory performances. The well-defined functional block copolymers (P<b>BAB</b>) with different block ratios had predictable molecular weights (<i>M</i>_n = 17 700–79 100 g/mol) and narrow molecular weight distributions (<i>M</i>_w/<i>M</i>_n = 1.14–1.19). It was observed from transmission electron microscopy (TEM) that the block copolymers showed different morphological structures depending on block ratios. Although all memory devices fabricated from the resulting block copolymers with different block compositions equally exhibited nonvolatile resistive switching characteristics, which are governed by the trap-controlled space-charge-limited current (SCLC) conduction mechanism and filament formation, it was found that electrical memory performances of each device varied depending on morphological structures of the block copolymer films

Correlational Effects of the Molecular-Tilt Configuration and the Intermolecular van der Waals Interaction on the Charge Transport in the Molecular Junction

Molecular conformation, intermolecular interaction, and electrode–molecule contacts greatly affect charge transport in molecular junctions and interfacial properties of organic devices by controlling the molecular orbital alignment. Here, we statistically investigated the charge transport in molecular junctions containing self-assembled oligophenylene molecules sandwiched between an Au probe tip and graphene according to various tip-loading forces (<i>F</i>_L) that can control the molecular-tilt configuration and the van der Waals (vdW) interactions. In particular, the molecular junctions exhibited two distinct transport regimes according to the <i>F</i>_L dependence (i.e., <i>F</i>_L-dependent and <i>F</i>_L-independent tunneling regimes). In addition, the charge-injection tunneling barriers at the junction interfaces are differently changed when the <i>F</i>_L ≤ 20 nN. These features are associated to the correlation effects between the asymmetry-coupling factor (η), the molecular-tilt angle (θ), and the repulsive intermolecular vdW force (<i>F</i>_vdW) on the molecular-tunneling barriers. A more-comprehensive understanding of these charge transport properties was thoroughly developed based on the density functional theory calculations in consideration of the molecular-tilt configuration and the repulsive vdW force between molecules

Electrical Properties of Synthesized Large-Area MoS₂ Field-Effect Transistors Fabricated with Inkjet-Printed Contacts

We report the electrical properties of synthesized large-area monolayer molybdenum disulfide (MoS₂) field-effect transistors (FETs) with low-cost inkjet-printed Ag electrodes. The monolayer MoS₂ film was grown by a chemical vapor deposition (CVD) method, and the top-contact Ag source/drain electrodes (S/D) were deposited onto the films using a low-cost drop-on-demand inkjet-printing process without any masks and surface treatments. The electrical characteristics of FETs were comparable to those fabricated by conventional deposition methods such as photo- or electron beam lithography. The contact properties between the S/D and the semiconductor layer were also evaluated using the Y-function method and an analysis of the output characteristic at the low drain voltage regimes. Furthermore, the electrical instability under positive gate-bias stress was studied to investigate the charge-trapping mechanism of the FETs. CVD-grown large-area monolayer MoS₂ FETs with inkjet-printed contacts may represent an attractive approach for realizing large-area and low-cost thin-film electronics

1/<i>f</i> Noise Scaling Analysis in Unipolar-Type Organic Nanocomposite Resistive Memory

We studied noise characteristics of a nanocomposite of polyimide (PI) and phenyl-C61-butyric acid methyl ester (PCBM) (denoted as PI:PCBM), a composite for the organic nonvolatile resistive memory material. The current fluctuations were investigated over a bias range that covers various intermediate resistive states and negative differential resistance (NDR) in organic nanocomposite unipolar resistive memory devices. From the analysis of the 1/<i>f</i>^γ type noises, scaling behavior between the relative noise power spectral density <i>S̃</i> and resistance <i>R</i> was observed, indicating a percolating behavior. Considering a linear rate equation of the charge trapping–detrapping at traps, the percolation behavior and NDR could be understood by the modulation of the conductive phase fraction φ with an external bias. This study can enhance the understanding of the NDR phenomena in organic nanocomposite unipolar resistive memory devices in terms of the current path formation and the memory switching

Irradiation Effects of High-Energy Proton Beams on MoS₂ Field Effect Transistors

We investigated the effect of irradiation on molybdenum disulfide (MoS₂) field effect transistors with 10 MeV high-energy proton beams. The electrical characteristics of the devices were measured before and after proton irradiation with fluence conditions of 10¹², 10¹³, and 10¹⁴ cm^–2. For a low proton beam fluence condition of 10¹² cm^–2, the electrical properties of the devices were nearly unchanged in response to proton irradiation. In contrast, for proton beam fluence conditions of 10¹³ or 10¹⁴ cm^–2, the current level and conductance of the devices significantly decreased following proton irradiation. The electrical changes originated from proton-irradiation-induced traps, including positive oxide-charge traps in the SiO₂ layer and trap states at the interface between the MoS₂ channel and the SiO₂ layer. Our study will enhance the understanding of the influence of high-energy particles on MoS₂-based nanoelectronic devices

Flexible Multilevel Resistive Memory with Controlled Charge Trap B- and N-Doped Carbon Nanotubes

B- and N-doped carbon nanotubes (CNTs) with controlled workfunctions were successfully employed as charge trap materials for solution processable, mechanically flexible, multilevel switching resistive memory. B- and N-doping systematically controlled the charge trap level and dispersibility of CNTs in polystyrene matrix. Consequently, doped CNT device demonstrated greatly enhanced nonvolatile memory performance (ON–OFF ratio >10², endurance cycle >10², retention time >10⁵) compared to undoped CNT device. More significantly, the device employing both B- and N-doped CNTs with different charge trap levels exhibited multilevel resistive switching with a discrete and stable intermediate state. Charge trapping materials with different energy levels offer a novel design scheme for solution processable multilevel memory

Transparent Large-Area MoS₂ Phototransistors with Inkjet-Printed Components on Flexible Platforms

Two-dimensional (2D) transition-metal dichalcogenides (TMDCs) have gained considerable attention as an emerging semiconductor due to their promising atomically thin film characteristics with good field-effect mobility and a tunable band gap energy. However, their electronic applications have been generally realized with conventional inorganic electrodes and dielectrics implemented using conventional photolithography or transferring processes that are not compatible with large-area and flexible device applications. To facilitate the advantages of 2D TMDCs in practical applications, strategies for realizing flexible and transparent 2D electronics using low-temperature, large-area, and low-cost processes should be developed. Motivated by this challenge, we report fully printed transparent chemical vapor deposition (CVD)-synthesized monolayer molybdenum disulfide (MoS₂) phototransistor arrays on flexible polymer substrates. All the electronic components, including dielectric and electrodes, were directly deposited with mechanically tolerable organic materials by inkjet-printing technology onto transferred monolayer MoS₂, and their annealing temperature of <180 °C allows the direct fabrication on commercial flexible substrates without additional assisted-structures. By integrating the soft organic components with ultrathin MoS₂, the fully printed MoS₂ phototransistors exhibit excellent transparency and mechanically stable operation

Electric Stress-Induced Threshold Voltage Instability of Multilayer MoS₂ Field Effect Transistors

We investigated the gate bias stress effects of multilayered MoS₂ field effect transistors (FETs) with a back-gated configuration. The electrical stability of the MoS₂ FETs can be significantly influenced by the electrical stress type, relative sweep rate, and stress time in an ambient environment. Specifically, when a positive gate bias stress was applied to the MoS₂ FET, the current of the device decreased and its threshold shifted in the positive gate bias direction. In contrast, with a negative gate bias stress, the current of the device increased and the threshold shifted in the negative gate bias direction. The gate bias stress effects were enhanced when a gate bias was applied for a longer time or when a slower sweep rate was used. These phenomena can be explained by the charge trapping due to the adsorption or desorption of oxygen and/or water on the MoS₂ surface with a positive or negative gate bias, respectively, under an ambient environment. This study will be helpful in understanding the electrical-stress-induced instability of the MoS₂-based electronic devices and will also give insight into the design of desirable devices for electronics applications

Graphene/Pentacene Barristor with Ion-Gel Gate Dielectric: Flexible Ambipolar Transistor with High Mobility and On/Off Ratio

High-quality channel layer is required for next-generation flexible electronic devices. Graphene is a good candidate due to its high carrier mobility and unique ambipolar transport characteristics but typically shows a low on/off ratio caused by gapless band structure. Popularly investigated organic semiconductors, such as pentacene, suffer from poor carrier mobility. Here, we propose a graphene/pentacene channel layer with high-k ion-gel gate dielectric. The graphene/pentacene device shows both high on/off ratio and carrier mobility as well as excellent mechanical flexibility. Most importantly, it reveals ambipolar behaviors and related negative differential resistance, which are controlled by external bias. Therefore, our graphene/pentacene barristor with ion-gel gate dielectric can offer various flexible device applications with high performances

Interface-Engineered Charge-Transport Properties in Benzenedithiol Molecular Electronic Junctions via Chemically p‑Doped Graphene Electrodes

In this study, we fabricated and characterized vertical molecular junctions consisting of self-assembled monolayers of benzenedithiol (BDT) with a p-doped multilayer graphene electrode. The p-type doping of a graphene film was performed by treating pristine graphene (work function of ∼4.40 eV) with trifluoromethanesulfonic (TFMS) acid, producing a significantly increased work function (∼5.23 eV). The p-doped graphene–electrode molecular junctions statistically showed an order of magnitude higher current density and a lower charge injection barrier height than those of the pristine graphene–electrode molecular junctions, as a result of interface engineering. This enhancement is due to the increased work function of the TFMS-treated p-doped graphene electrode in the highest occupied molecular orbital-mediated tunneling molecular junctions. The validity of these results was proven by a theoretical analysis based on a coherent transport model that considers asymmetric couplings at the electrode–molecule interfaces