Multidimensional Characterization of Single-Molecule Dynamics in a Plasmonic Nanocavity.

Nanoscale manipulation and characterization of individual molecules is necessary to understand the intricacies of molecular structure, which governs phenomena such as reaction mechanisms, catalysis, local effective temperatures, surface interactions, and charge transport. Here we utilize Raman enhancement between two nanostructured electrodes in combination with direct charge transport measurements to allow for simultaneous characterization of the electrical, optical, and mechanical properties of a single molecule. This multi-dimensional information yields repeatable, self-consistent, verification of single-molecule resolution, and allows for detailed analysis of structural and configurational changes of the molecule in situ. These experimental results are supported by a machine-learning based statistical analysis of the spectral information and calculations to provide insight into the correlation between structural changes in a single-molecule and its charge-transport properties.

Intrinsic Optoelectronic Characteristics of MoS2 Phototransistors via a Fully Transparent van der Waals Heterostructure.

In the past decade, intensive studies on monolayer MoS2-based phototransistors have been carried out to achieve further enhanced optoelectronic characteristics. However, the intrinsic optoelectronic characteristics of monolayer MoS2 have still not been explored until now because of unintended interferences, such as multiple reflections of incident light originating from commonly used opaque substrates. This leads to overestimated photoresponsive characteristics inevitably due to the enhanced photogating and photoconductive effects. Here, we reveal the intrinsic photoresponsive characteristics of monolayer MoS2, including its internal responsivity and quantum efficiency, in fully transparent monolayer MoS2 phototransistors employing a van der Waals heterostructure. Interestingly, as opposed to the previous reports, the internal photoresponsive characteristics do not significantly depend on the wavelength of the incident light as long as the electron-hole pairs are generated in the same k-space. This study provides a deeper understanding of the photoresponsive characteristics of MoS2 and lays the foundation for two-dimensional materials-based transparent phototransistors.

Unidirectional Real-Time Photoswitching of Diarylethene Molecular Monolayer Junctions with Multilayer Graphene Electrodes.

We fabricate and characterize vertical molecular junctions consisting of self-assembled monolayers of diarylethene (DAE) contacted by a multilayer graphene (MLG) electrode on the top and gold on the bottom. The DAE molecular junctions show two stable electrical states, a closed state (high conductance) or an open state (low conductance), which are created upon illumination with UV or visible light, respectively. For the Au-DAE-MLG junction structure, we observe that the current levels between the two conductance states are separated by 2 orders of magnitude. However, in a real-time measurement, we observe only unidirectional switching behavior from the open to the closed state.

Highly uniform monolayer graphene synthesis via a facile pretreatment of copper catalyst substrates using an ammonium persulfate solution.

The demand for large-area, high-quality synthesis of graphene with chemical vapor deposition (CVD) has increased for the realization of next-generation transparent and flexible optoelectronic applications. In conventional CVD processes, various synthesis parameters can strongly affect the quality of the resultant graphene. In particular, surface engineering of a copper catalyst substrate is one of the most promising pathways for achieving high-quality graphene with excellent reproducibility. For this purpose, simple wet chemical etching of a catalyst substrate without toxic fume byproducts or metal ion residues is desired. Here, we suggest a facile method for preparing a pretreated copper catalyst substrate for highly uniform, large-area CVD graphene growth. This pretreatment method involves a wet copper etchant, ammonium persulfate (APS) solution, and gentle ultrasonication (100 W), which do not produce unwanted or toxic fume byproducts during their reaction. Moreover, this approach does not leave metal ion residue on the cleaned copper substrates that serves as residual nucleation sites and leads to multilayer graphene growth. To evaluate the quality of the synthesized monolayer graphene on the cleaned copper catalyst substrates, we used various characterization techniques, such as Raman spectroscopy and sheet resistance, optical transmittance, and FET characterization.

Highly Reliable Superhydrophobic Protection for Organic Field-Effect Transistors by Fluoroalkylsilane-Coated TiO2 Nanoparticles.

One of the long-standing problems in the field of organic electronics is their instability in an open environment, especially their poor water resistance. For the reliable operation of organic devices, introducing an effective protection layer using organo-compatible materials and processes is highly desirable. Here, we report a facile method for the depositing of an organo-compatible superhydrophobic protection layer on organic semiconductors under ambient conditions. The protection layer exhibiting excellent water-repellent and self-cleaning properties was deposited onto organic semiconductors directly using a dip-coating process in a highly fluorinated solution with fluoroalkylsilane-coated titanium dioxide (TiO2) nanoparticles. The proposed protection layer did not damage the underlying organic semiconductors and had good resistance against mechanical-, thermal-, light-stress-, and water-based threats. The protected organic field-effect transistors exhibited more-reliable electrical properties, even when exposed to strong solvents, due to its superhydrophobicity. This study provides a practical solution with which to enhance the reliability of environmentally sensitive organic semiconductor devices in the natural environment.

Electrical modulation of a photonic crystal band-edge laser with a graphene monolayer.

The electrical control of photonic crystal (PhC) lasers has been an attractive but challenging issue. Laser operation by electrical injection is of key importance for the viability and applicability of the PhC lasers. Another key factor is the electrical modulation of the laser output. The Fermi level of a graphene monolayer can be controlled by electrical gating, which adjusts its optical absorption. In this study, a graphene monolayer sheet is integrated on top of a two-dimensional PhC structure composed of InGaAsP multiple-quantum-wells (MQWs) in order to demonstrate the electrical modulation of a high-power (microwatt-scale) PhC band-edge laser. The introduced dielectric spacer layer presets the delicate balance between the optical gain from the MQWs and optical loss at the graphene monolayer. The proposed device is covered by an ion-gel film, which enables a low-voltage laser modulation at |Vg|≤1 V. The modulation is extensively investigated experimentally, and the obtained results are confirmed by performing numerical simulations.

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.

High-Yield Functional Molecular Electronic Devices.

An ultimate goal of molecular electronics, which seeks to incorporate molecular components into electronic circuit units, is to generate functional molecular electronic devices using individual or ensemble molecules to fulfill the increasing technical demands of the miniaturization of traditional silicon-based electronics. This review article presents a summary of recent efforts to pursue this ultimate aim, covering the development of reliable device platforms for high-yield ensemble molecular junctions and their utilization in functional molecular electronic devices, in which distinctive electronic functionalities are observed due to the functional molecules. In addition, other aspects pertaining to the practical application of molecular devices such as manufacturing compatibility with existing complementary metal-oxide-semiconductor technology, their integration, and flexible device applications are also discussed. These advances may contribute to a deeper understanding of charge transport characteristics through functional molecular junctions and provide a desirable roadmap for future practical molecular electronics applications.

Gate-dependent asymmetric transport characteristics in pentacene barristors with graphene electrodes.

We investigated the electrical characteristics and the charge transport mechanism of pentacene vertical hetero-structures with graphene electrodes. The devices are composed of vertical stacks of silicon, silicon dioxide, graphene, pentacene, and gold. These vertical heterojunctions exhibited distinct transport characteristics depending on the applied bias direction, which originates from different electrode contacts (graphene and gold contacts) to the pentacene layer. These asymmetric contacts cause a current rectification and current modulation induced by the gate field-dependent bias direction. We observed a change in the charge injection barrier during variable-temperature current-voltage characterization, and we also observed that two distinct charge transport channels (thermionic emission and Poole-Frenkel effect) worked in the junctions, which was dependent on the bias magnitude.

Origin of multi-level switching and telegraphic noise in organic nanocomposite memory devices.

The origin of negative differential resistance (NDR) and its derivative intermediate resistive states (IRSs) of nanocomposite memory systems have not been clearly analyzed for the past decade. To address this issue, we investigate the current fluctuations of organic nanocomposite memory devices with NDR and the IRSs under various temperature conditions. The 1/f noise scaling behaviors at various temperature conditions in the IRSs and telegraphic noise in NDR indicate the localized current pathways in the organic nanocomposite layers for each IRS. The clearly observed telegraphic noise with a long characteristic time in NDR at low temperature indicates that the localized current pathways for the IRSs are attributed to trapping/de-trapping at the deep trap levels in NDR. This study will be useful for the development and tuning of multi-bit storable organic nanocomposite memory device systems.

Integration of Flexible and Microscale Organic Nonvolatile Resistive Memory Devices Using Orthogonal Photolithography.

We present the integration of flexible and microscale organic nonvolatile resistive memory devices fabricated in a cross-bar array structure on plastic substrates. This microscale integration was made via orthogonal photolithography method using fluorinated photoresist and solvents and was achieved without causing damage to the underlying organic memory materials. Our flexible microscale organic devices exhibited high ON/OFF ratio (I(ON/I(OFF) > 10(4)) under bending conditions. In addition, the ON and OFF states of our flexible and microscale memory devices were maintained for 10,000 seconds without any serious degradation.

Tailoring the electrical properties of MoS2 field effect transistors by depositing Au nanoparticles and alkanethiol molecules.

We fabricated and characterized MoS2 field effect transistors. First, we measured the electrical properties of MoS2 field effect transistors (FETs) that were made with mechanically exfoliated MoS2 flakes. Then, we deposited Au nanoparticles on the MoS2 channel and measured the electrical properties. We observed whether the source-drain current increased or decreased after the Au particles were deposited. The deposited Au particles either formed an extra current path and increased the current or behaved as charge-withdrawing sites and decreased the current. Next, we deposited alkanethiol molecules on the Au particles to reduce the work function of the Au. Alkanethiol molecules are known to form a self-assembled monolayer on the Au surface, and the electric dipole moment of the molecules causes the work function of the Au to decrease. Au particles can capture electrons from the MoS2 channel due to their high work function. However, the decreased work function of the Au particles subjected to alkanethiol treatment could cause captured electrons to be released from the Au particles to MoS2. Therefore, the current increased after alkanethiol treatment. This study may provide useful methods to utilize surface treatments with particles and molecules to tailor the electrical properties of MoS2-based FETs.

Electrical characterization of benzenedithiolate molecular electronic devices with graphene electrodes on rigid and flexible substrates.

We investigated the electrical characteristics of molecular electronic devices consisting of benzenedithiolate self-assembled monolayers and a graphene electrode. We used the multilayer graphene electrode as a protective interlayer to prevent filamentary path formation during the evaporation of the top electrode in the vertical metal-molecule-metal junction structure. The devices were fabricated both on a rigid SiO2/Si substrate and on a flexible poly(ethylene terephthalate) substrate. Using these devices, we investigated the basic charge transport characteristics of benzenedithiolate molecular junctions in length- and temperature-dependent analyses. Additionally, the reliability of the electrical characteristics of the flexible benzenedithiolate molecular devices was investigated under various mechanical bending conditions, such as different bending radii, repeated bending cycles, and a retention test under bending. We also observed the inelastic electron tunneling spectra of our fabricated graphene-electrode molecular devices. Based on the results, we verified that benzenedithiolate molecules participate in charge transport, serving as an active tunneling barrier in solid-state graphene-electrode molecular junctions.

Statistical investigation of the length-dependent deviations in the electrical characteristics of molecular electronic junctions fabricated using the direct metal transfer method.

We fabricated and analyzed the electrical transport characteristics of vertical type alkanethiolate molecular junctions using the high-yield fabrication method that we previously reported. The electrical characteristics of the molecular electronic junctions were statistically collected and investigated in terms of current density and transport parameters based on the Simmons tunneling model, and we determined representative current-voltage characteristics of the molecular junctions. In particular, we examined the statistical variations in the length-dependent electrical characteristics, especially the Gaussian standard deviation σ of the current density histogram. From the results, we found that the magnitude of the σ value can be dependent on the individual molecular length due to specific microscopic structures in the molecular junctions. The probable origin of the molecular length-dependent deviation of the electrical characteristics is discussed.

Statistical Analysis of Electrical Properties of Octanemonothiol versus Octanedithol in PEDOT:PSS-Electrode Molecular Junctions.

We fabricated a large number of octanemonothiol (C8) and octanedithol (DC8) molecular electronic devices with PEDOT: PSS (3,4-ethylenedioxythiophene) interlayer and performed a statistical analysis on the electronic properties of these devices. From the analysis, we obtained the Gaussian plot of histograms of Log10 (current density (J)) and several statistical estimates such as arithmetic mean, median, Gaussian mean, arithmetic standard deviation, adjusted absolute median deviation, and Gaussian standard deviation. We determined the current density-voltage (J-V) characteristics from the statistically representative data for C8 and DC8 devices and found that the conductivity of C8 is higher than that of DC8 by a factor of ~10. The difference of the conductivity of C8 and DC8 devices is attributed to the difference of the contact properties between the C8 and DC8 PEDOT:PSS-interlayer molecular junctions.

Electrical and Optical Characterization of MoS2 with Sulfur Vacancy Passivation by Treatment with Alkanethiol Molecules.

We investigated the physical properties of molybdenum disulfide (MoS2) atomic crystals with a sulfur vacancy passivation after treatment with alkanethiol molecules including their electrical, Raman, and photoluminescence (PL) characteristics. MoS2, one of the transition metal dichalcogenide materials, is a promising two-dimensional semiconductor material with good physical properties. It is known that sulfur vacancies exist in MoS2, resulting in the n-type behavior of MoS2. The sulfur vacancies on the MoS2 surface tend to form covalent bonds with sulfur-containing groups. In this study, we deposited alkanethiol molecules on MoS2 field effect transistors (FETs) and then characterized the electrical properties of the devices before and after the alkanethiol treatment. We observed that the electrical characteristics of MoS2 FETs dramatically changed after the alkanethiol treatment. We also observed that the Raman and PL spectra of MoS2 films changed after the alkanethiol treatment. These effects are attributed to the thiol (-SH) end groups in alkanethiols bonding at sulfur vacancy sites, thus altering the physical properties of the MoS2. This study will help us better understand the electrical and optical properties of MoS2 and suggest a way of tailoring the properties of MoS2 by passivating a sulfur vacancy with thiol molecules.

1/f 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/f(γ) type noises, scaling behavior between the relative noise power spectral density S̃ and resistance R 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.

A new approach for high-yield metal-molecule-metal junctions by direct metal transfer method.

The realization of high-yield, stable molecular junctions has been a long-standing challenge in the field of molecular electronics research, and it is an essential prerequisite for characterizing and understanding the charge transport properties of molecular junctions prior to their device applications. Here, we introduce a new approach for obtaining high-yield, vertically structured metal-molecule-metal junctions in which the top metal electrodes are formed on alkanethiolate self-assembled monolayers by a direct metal transfer method without the use of any additional protecting interlayers in the junctions. The fabricated alkanethiolate molecular devices exhibited considerably improved device yields (∼70%) in comparison to the typical low device yields (less than a few %) of molecular junctions in which the top metal electrodes are fabricated using the conventional evaporation method. We compared our method with other molecular device fabrication methods in terms of charge transport parameters. This study suggests a potential new device platform for realizing robust, high-yield molecular junctions and investigating the electronic properties of devices.