High Volumetric Energy Density Supercapacitor of Additive-Free Quantum Dot Hierarchical Nanopore Structure.

The high surface-area-to-volume ratio of colloidal quantum dots (QDs) positions them as promising materials for high-performance supercapacitor electrodes. However, the challenge lies in achieving a highly accessible surface area, while maintaining good electrical conductivity. An efficient supercapacitor demands a dense yet highly porous structure that facilitates efficient ion-surface interactions and supports fast charge mobility. Here we demonstrate the successful development of additive-free ultrahigh energy density electric double-layer capacitors based on quantum dot hierarchical nanopore (QDHN) structures. Lead sulfide QDs are assembled into QDHN structures that strike a balance between electrical conductivity and efficient ion diffusion by employing meticulous control over inter-QD distances without any additives. Using ionic liquid as the electrolyte, the high-voltage ultrathin-film microsupercapacitors achieve a remarkable combination of volumetric energy density (95.6 mWh cm-3) and power density (13.5 W cm-3). This achievement is attributed to the intrinsic capability of QDHN structures to accumulate charge carriers efficiently. These findings introduce innovative concepts for leveraging colloidal nanomaterials in the advancement of high-performance energy storage devices.

Blue organic light-emitting diode with a turn-on voltage of 1.47 V.

Among the three primary colors, blue emission in organic light-emitting diodes (OLEDs) are highly important but very difficult to develop. OLEDs have already been commercialized; however, blue OLEDs have the problem of requiring a high applied voltage due to the high-energy of blue emission. Herein, an ultralow voltage turn-on at 1.47 V for blue emission with a peak wavelength at 462 nm (2.68 eV) is demonstrated in an OLED device with a typical blue-fluorescent emitter that is widely utilized in a commercial display. This OLED reaches 100 cd/m2, which is equivalent to the luminance of a typical commercial display, at 1.97 V. Blue emission from the OLED is achieved by the selective excitation of the low-energy triplet states at a low applied voltage by using the charge transfer (CT) state as a precursor and triplet-triplet annihilation, which forms one emissive singlet from two triplet excitons.

Bottom Contact 100 nm Channel-Length α-In2 Se3 In-Plane Ferroelectric Memory.

Owing to the emerging trend of non-volatile memory and data-centric computing, the demand for more functional materials and efficient device architecture at the nanoscale is becoming stringent. To date, 2D ferroelectrics are cultivated as channel materials in field-effect transistors for their retentive and switchable dipoles and flexibility to be compacted into diverse structures and integration for intensive production. This study demonstrates the in-plane (IP) ferroelectric memory effect of a 100 nm channel-length 2D ferroelectric semiconductor α-In2 Se3 stamped onto nanogap electrodes on Si/SiO2 under a lateral electric field. As α-In2 Se3 forms the bottom contact of the nanogap electrodes, a large memory window of 13 V at drain voltage between ±6.5 V and the on/off ratio reaching 103 can be explained by controlled IP polarization. Furthermore, the memory effect is modulated by the bottom gate voltage of the Si substrate due to the intercorrelation between IP and out-of-plane (OOP) polarization. The non-volatile memory characteristics including stable retention lasting 17 h, and endurance over 1200 cycles suggest a wide range of memory applications utilizing the lateral bottom contact structure.

Nanostructure-induced L10-ordering of twinned single-crystals in CoPt ferromagnetic nanowires.

L10-ordered ferromagnetic nanowires with large coercivity are essential for realizing next-generation spintronic devices. Ferromagnetic nanowires have been commonly fabricated by first L10-ordering of initially disordered ferromagnetic films by annealing and then etching them into nanowire structures using lithography. If the L10-ordered nanowires can be fabricated using only lithography and subsequent annealing, the etching process can be omitted, which leads to an improvement in the fabrication process for spintronic devices. However, when nanowires are subjected to annealing, they easily transform into droplets, which is well-known as Plateau-Rayleigh instability. Here, we propose a concept of "nanostructure-induced L10-ordering" of twinned single-crystals in CoPt ferromagnetic nanowires with a 30 nm scale ultrafine linewidth on Si/SiO2 substrates. The driving forces for nanostructure-induced L10-ordering during annealing are atomic surface diffusion and extremely large internal stress at ultrasmall 10 nm scale curvature radii of the nanowires. (Co/Pt)6 multilayer nanowires are fabricated by a lift-off process combining electron-beam lithography and electron-beam evaporation, followed by annealing. Cross-sectional scanning transmission electron microscope images and nano-beam electron diffraction patterns clearly indicate nanostructure-induced L10-ordering of twinned single-crystals in the CoPt ferromagnetic nanowires, which exhibit a large coercivity of 10 kOe for perpendicular, longitudinal, and transversal directions of the nanowires. Two-dimensional grazing incidence X-ray diffraction shows superlattice peaks with Debye-Scherrer ring shapes, which also supports the nanostructure-induced L10-ordering. The fabrication method for nanostructure-induced L10-ordered CoPt ferromagnetic nanowires with twinned single-crystals on Si/SiO2 substrates would be significant for future silicon-technology-compatible spintronic applications.

Thermodynamic Picture of Phase Segregation during the Formation of Bicontinuous Concentric Lamellar (bcl) Silica.

The thermodynamic picture describing the formation mechanism of bicontinuous concentric lamellar (bcl) nanostructured silica particles, bcl silica, was investigated thoroughly. A series of classical kinetics of bcl silica by varying the synthesis time were employed to observe the morphological evolution of bcl silica. The formation mechanism of bcl silica is proposed as the hydrolysis and condensation reactions in the reverse micelle, followed by the phase segregation process. The images of the whole part and the cross-section of bcl silica reveal that bcl silica can be obtained just 30 min after the synthesis starts. The particle morphology evolves from bicontinuous lamellar (bl) morphology, with the absence of the dense part in the center of the particle, to bicontinuous concentric lamellar (bcl) morphology. The theoretical part of this study is focused on the phase segregation process of the mixture. This process is divided thermodynamically into several reversible processes based on the reduced Helmholtz free energy state function. The type of the lamellar orientation (i.e., parallel or perpendicular orientation) changed as the stacked lamellae changed in thickness and was followed by the decrease in the free energy. It was merely shown that the segregation of the thin slab of the lamellar polysiloxane stack favors the perpendicular orientation. In contrast, the thick slab of the lamellar polysiloxane stack yields a complex lamellar structure consisting of perpendicular and parallel orientations. A lamellar polymer confined between two planar substrates can experience a topological transformation into a sphere due to an unfavorable environment, i.e., high surface tension. After the topological transformation, lamellae with a perpendicular orientation form bicontinuous lamellae, whereas the complex lamellar structure transforms into a bicontinuous concentric lamellar morphology.

Towards single electron transistor-based photon detection with microplasma-enabled graphene quantum dots.

Single-electron transistors (SETs) represent a new generation of electronic devices with high charge sensitivity, high switching speed, and low power consumption. Here a simple and controlled fabrication of graphene quantum dot (GQD)-based SETs for photon detectors has been demonstrated. The plasma-synthesized GQDs exhibit stable photoluminescence and are successfully used as the Coulomb islands between heteroepitaxial spherical-gold/platinum (HS-Au/Pt) nanogap electrodes. The as-fabricated GQD-SETs enable photon detection with 410 nm excitation owing to the ability of GQDs to generate photoluminescence emission.

Suppression Mechanisms of the Solid-Electrolyte Interface Formation at the Triple-Phase Interfaces in Thin-Film Li-Ion Batteries.

Side reactions of the charge/discharge in Li-ion batteries (LIBs) generate a solid-electrolyte interface (SEI) onto an electrode surface, resulting in the degradation of the lifetime of a cell. The suppression of SEI formations has attracted much attention for achieving longer cyclable LIBs. Our research group has previously reported that few SEI were observed at triple-phase interfaces (TPIs) consisting of BaTiO3, LiCoO2, and electrolyte interfaces in LIBs with excellent cyclability and ultrahigh-speed chargeability. An investigation on the suppression mechanisms of SEI formations at TPIs should yield important information on understanding the undesirable side reactions. Therefore, we have explored the suppression mechanisms of SEI formations by preparing epitaxial thin films and evaluating the surface of the samples after the electrochemical treatment. The results of X-ray photoelectron spectroscopy and scanning electron microscopy with energy-dispersive X-ray analysis measurements suggested that the decomposition of LiPF6 was suppressed at TPIs, implying that the generation of PF5 via the decomposition of LiPF6 contributed to SEI formation.

Revealing the Real Size of a Porphyrin Molecule with Quantum Confinement Probing via Temperature-Dependent Photoluminescence Spectroscopy.

The confinement energy of electrons in an aromatic molecule was studied by indirect and direct methods, namely, temperature-dependent photoluminescence (TDPL) spectroscopy and scanning tunneling microscopy (STM). We observed a decrease in the tetraphenylporphyrin (H2TPP) PL intensity with increasing temperature. The increase in temperature provides kinetic energy for the electrons to overcome the confinement energy barrier, making recombination via nonradiative pathways more favorable. The results of fitting the integrated TDPL intensity with a modified Arrhenius equation suggest two confinement energy values. We propose that these energy values are related to the size of the delocalized electron cloud along the plane and thickness of the H2TPP ring. These values quantitatively express an abstract form of the size of the aromatic ring system. These results are in good agreement with the topography images of single H2TPP molecules and monolayer H2TPP obtained by a direct probing method using STM. These results are also supported by the porphyrin ring orientation relative to the excited crystal face during the TDPL measurements.

Enhancement of Ultrahigh Rate Chargeability by Interfacial Nanodot BaTiO3 Treatment on LiCoO2 Cathode Thin Film Batteries.

Nanodot BaTiO3 supported LiCoO2 cathode thin films can dramatically improve high-rate chargeability and cyclability. The prepared BaTiO3 nanodot is <3 nm in height and 35 nm in diameter, and its coverage is <5%. Supported by high dielectric constant materials on the surface of cathode materials, Li ion (Li+) can intercalate through robust Li paths around the triple-phase interface consisting of the dielectric, cathode, and electrolyte. The current concentration around the triple-phase interface is observed by the finite element method and is in good agreement with the experimental data. The interfacial resistance between the cathode and electrolyte with nanodot BaTiO3 is smaller than that without nanodot BaTiO3. The decomposition of the organic solvent electrolyte can prevent the fabrication of a solid electrolyte interface around the triple-phase interface. Li+ paths may be created at non solid electrolyte interface covered regions by the strong current concentration originating from high dielectric constant materials on the cathode. Robust Li+ paths lead to excellent chargeability and cyclability.

Coherent Resonant Electron Tunneling at 9 and 300 K through a 4.5 nm Long, Rigid, Planar Organic Molecular Wire.

Organic molecular wires that operate stably at ambient temperatures are a necessary first step toward practical and useful molecular-scale electronic devices, which have thus far been hampered by many factors, including the structural and electron configurational instability of organic molecules. We report here that a single disulfanyl carbon-bridged oligo(phenylenevinylene) (COPV6) molecule embedded between thermally stable electroless Au-plated electrodes of a 4 nm nanogap undergoes coherent resonant tunneling at both 9 and 300 K and functions even after storage in air at room temperature. Such enormous stability is ascribed to the unique structural characteristics of COPV6, that is, rigidity, planarity, thermal stability, resistivity against oxidation and reduction, and an organic insulating sheath that protects the π-system. When sandwiched between the gaps without pinning, this molecule behaves as a Coulomb island with sequential single-electron tunneling at 9 K that disappears at 300 K while maintaining a stable electron flow.

Quantum Chemical Studies on Electron-Accepting Overcrowded Ethylene with a Polarizable Skeleton.

We report the quantum chemical studies on the neutral and radical anion forms of an electron-accepting overcrowded ethylene (OCE1) featuring a highly polarizable skeleton based on the density functional theory (DFT) approach using the M06-2X hybrid functional. Calculated results indicate that OCE1 (bis{4H,8H-4-(dicyanomethylene)benzo[1,2-c:4,5-c']bis[1,2,5]thiadiazol-8-ylidene}) shows conformational behaviors and energetics similar to those of bianthrone (OCE2), a typical thermochromic overcrowded ethylene. Neutral OCE1 and its radical anion have antifolded (afOCE1) and twisted (tOCE1) isomers on their potential energy surfaces. The calculated isomerization barrier heights of OCE1 and its radical anion are considerably low, indicating that its conformation is susceptible to interactions with surrounding molecules. While two afOCE1 molecules can form a simple π-stacked dimer, tOCE1 tends to be converted to afOCE1 when the two tOCE1 molecules come close together, indicating the instability of tOCE1 in the homogeneous OCE1 solid state. The thermochromic behavior difference between OCE1 and OCE2 in solution is closely associated with the considerably small energy difference between the afOCE1 and the tOCE1 as compared with OCE2. The properties of OCE1 are also compared with other typical electron-accepting overcrowded ethylenes in terms of electronic structure, energetics, and conformational behaviors.

Three-input gate logic circuits on chemically assembled single-electron transistors with organic and inorganic hybrid passivation layers.

Single-electron transistors (SETs) are sub-10-nm scale electronic devices based on conductive Coulomb islands sandwiched between double-barrier tunneling barriers. Chemically assembled SETs with alkanethiol-protected Au nanoparticles show highly stable Coulomb diamonds and two-input logic operations. The combination of bottom-up and top-down processes used to form the passivation layer is vital for realizing multi-gate chemically assembled SET circuits, as this combination enables us to connect conventional complementary metal oxide semiconductor (CMOS) technologies via planar processes. Here, three-input gate exclusive-OR (XOR) logic operations are demonstrated in passivated chemically assembled SETs. The passivation layer is a hybrid bilayer of self-assembled monolayers (SAMs) and pulsed laser deposited (PLD) aluminum oxide (AlO[Formula: see text]), and top-gate electrodes were prepared on the hybrid passivation layers. Top and two-side-gated SETs showed clear Coulomb oscillation and diamonds for each of the three available gates, and three-input gate XOR logic operation was clearly demonstrated. These results show the potential of chemically assembled SETs to work as logic devices with multi-gate inputs using organic and inorganic hybrid passivation layers.

Molecular floating-gate single-electron transistor.

We investigated reversible switching behaviors of a molecular floating-gate single-electron transistor (MFG-SET). The device consists of a gold nanoparticle-based SET and a few tetra-tert-butyl copper phthalocyanine (ttbCuPc) molecules; each nanoparticle (NP) functions as a Coulomb island. The ttbCuPc molecules function as photoreactive floating gates, which reversibly change the potential of the Coulomb island depending on the charge states induced in the ttbCuPc molecules by light irradiation or by externally applied voltages. We found that single-electron charging of ttbCuPc leads to a potential shift in the Coulomb island by more than half of its charging energy. The first induced device state was sufficiently stable; the retention time was more than a few hours without application of an external voltage. Moreover, the device exhibited an additional state when irradiated with 700 nm light, corresponding to doubly charged ttbCuPc. The life time of this additional state was several seconds, which is much shorter than that of the first induced state. These results clearly demonstrate an alternative method utilizing the unique functionality of the single molecule in nanoelectronics devices, and the potential application of MFG-SETs for investigating molecular charging phenomena.

Proving Scalability of an Organic Semiconductor To Print a TFT-Active Matrix Using a Roll-to-Roll Gravure.

Organic semiconductor-based thin-film transistors' (TFTs) charge-carrier mobility has been enhanced up to 25 cm2/V s through the improvement of fabrication methods and greater understanding of the microstructure charge-transport mechanism. To expand the practical feasibility of organic semiconductor-based TFTs, their electrical properties should be easily accessed from the fully printed devices through a scalable printing method, such as a roll-to-roll (R2R) gravure. In this study, four commercially available organic semiconductors were separately formulated into gravure inks. They were then employed in the R2R gravure system (silver ink for printing gate and drain-source electrodes and BaTiO3 ink for printing dielectric layers) for printing 20 × 20 TFT-active matrix with the resolution of 10 pixels per inch on poly(ethylene terephthalate) (PET) foils to attain electrical properties of organic semiconductors a practical printing method. Electrical characteristics (mobility, on-off current ratio, threshold voltage, and transconductance) of the R2R gravure-printed 20 × 20 TFT-active matrices fabricated with organic semiconducting ink were analyzed statistically, and the results showed more than 98% device yield and 50 % electrical variations in the R2R gravure TFT-active matrices along the PET web.

Polymerization of a divalent/tetravalent metal-storing atom-mimicking dendrimer.

The phenylazomethine dendrimer (DPA) has a layer-by-layer electron density gradient that is an analog of the Bohr atom (atom mimicry). In combination with electron pair mimicry, the polymerization of this atom-mimicking dendrimer was achieved. The valency of the mimicked atom was controlled by changing the chemical structure of the dendrimer. By mimicking a divalent atom, a one-dimensional (1D) polymer was obtained, and by using a planar tetravalent atom mimic, a 2D polymer was obtained. These poly(dendrimer) polymers could store Lewis acids (SnCl2) in their unoccupied orbitals, thus indicating that these poly(dendrimer) polymers consist of a series of nanocontainers.

Rhombic Coulomb diamonds in a single-electron transistor based on an Au nanoparticle chemically anchored at both ends.

Rhombic Coulomb diamonds are clearly observed in a chemically anchored Au nanoparticle single-electron transistor. The stability diagrams show stable Coulomb blockade phenomena and agree with the theoretical curve calculated using the orthodox model. The resistances and capacitances of the double-barrier tunneling junctions between the source electrode and the Au core (R1 and C1, respectively), and those between the Au core and the drain electrode (R2 and C2, respectively), are evaluated as 4.5 MΩ, 1.4 aF, 4.8 MΩ, and 1.3 aF, respectively. This is determined by fitting the theoretical curve against the experimental Coulomb staircases. Two-methylene-group short octanedithiols (C8S2) in a C8S2/hexanethiol (C6S) mixed self-assembled monolayer is concluded to chemically anchor the core of the Au nanoparticle at both ends between the electroless-Au-plated nanogap electrodes even when the Au nanoparticle is protected by decanethiol (C10S). This is because the R1 value is identical to that of R2 and corresponds to the tunneling resistances of the octanedithiol chemically bonded with the Au core and the Au electrodes. The dependence of the Coulomb diamond shapes on the tunneling resistance ratio (R1/R2) is also discussed, especially in the case of the rhombic Coulomb diamonds. Rhombic Coulomb diamonds result from chemical anchoring of the core of the Au nanoparticle at both ends between the electroless-Au-plated nanogap electrodes.

Ripple-Free Graphene Sheets on Alkanethiol Self-Assembled Monolayers Provided from Unzipped Multi-Walled Carbon Nanotubes.

Octanethiol (C8S, CH3(CH2)7SH) self-assembled monolayers/Au(111) were utilized as an inert surface to provide ripple-free graphene oxide layers provided from chemically unzipped multi-walled carbon nanotubes (MWCNTs). The resulting graphene oxide monolayers were characterized with atomic resolution by UHV-STM. The honeycomb structure for the graphene monolayer and "three-for-six" triangular pattern for the multi-layer graphene sheets on C8S SAMs were clearly observed without ripples by the high-resolution UHV-STM. These results provide new insight into the preparation of ripple-free graphene monolayers.

Scalability of carbon-nanotube-based thin film transistors for flexible electronic devices manufactured using an all roll-to-roll gravure printing system.

To demonstrate that roll-to-roll (R2R) gravure printing is a suitable advanced manufacturing method for flexible thin film transistor (TFT)-based electronic circuits, three different nanomaterial-based inks (silver nanoparticles, BaTiO3 nanoparticles and single-walled carbon nanotubes (SWNTs)) were selected and optimized to enable the realization of fully printed SWNT-based TFTs (SWNT-TFTs) on 150-m-long rolls of 0.25-m-wide poly(ethylene terephthalate) (PET). SWNT-TFTs with 5 different channel lengths, namely, 30, 80, 130, 180, and 230 µm, were fabricated using a printing speed of 8 m/min. These SWNT-TFTs were characterized, and the obtained electrical parameters were related to major mechanical factors such as web tension, registration accuracy, impression roll pressure and printing speed to determine whether these mechanical factors were the sources of the observed device-to-device variations. By utilizing the electrical parameters from the SWNT-TFTs, a Monte Carlo simulation for a 1-bit adder circuit, as a reference, was conducted to demonstrate that functional circuits with reasonable complexity can indeed be manufactured using R2R gravure printing. The simulation results suggest that circuits with complexity, similar to the full adder circuit, can be printed with a 76% circuit yield if threshold voltage (Vth) variations of less than 30% can be maintained.

Radio-frequency capacitance spectroscopy of metallic nanoparticles.

Recent years have seen great progress in our understanding of the electronic properties of nanomaterials in which at least one dimension measures less than 100 nm. However, contacting true nanometer scale materials such as individual molecules or nanoparticles remains a challenge as even state-of-the-art nanofabrication techniques such as electron-beam lithography have a resolution of a few nm at best. Here we present a fabrication and measurement technique that allows high sensitivity and high bandwidth readout of discrete quantum states of metallic nanoparticles which does not require nm resolution or precision. This is achieved by coupling the nanoparticles to resonant electrical circuits and measurement of the phase of a reflected radio-frequency signal. This requires only a single tunnel contact to the nanoparticles thus simplifying device fabrication and improving yield and reliability. The technique is demonstrated by measurements on 2.7 nm thiol coated gold nanoparticles which are shown to be in excellent quantitative agreement with theory.

Control of charging energy in chemically assembled nanoparticle single-electron transistors.

We show the control of a charging energy in chemically assembled nanoparticle single-electron transistors (SETs) by altering the core diameter of Au nanoparticles. The charging energy is a fundamental parameter that decides the operating temperature of SETs. Practical application of SETs requires us to regulate the value of the charging energy by tuning the diameter of quantum dots. In this study, we used 3.0, 5.0 and 6.2 nm diameter synthesized Au nanoparticles as a quantum dot in the SETs. The total capacitances and charging energy of the SETs were evaluated from the rhombic Coulomb diamonds attributed to a single Coulomb island. The capacitance and charging energy matched with a concentric sphere model much better than with a simple sphere model. The operating temperatures of the SETs suggested that a charging energy 2.2 times greater than the thermal energy was required for stable operation, in theory. These results will help us to select an appropriate core diameter for the Au nanoparticles in practical SETs.