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.

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.

Negative differential resistance by molecular resonant tunneling between neutral tribenzosubporphine anchored to a Au(111) surface and tribenzosubporphine cation adsorbed on to a tungsten tip.

Tribenzosubporphyrins are boron(III)-chelated triangular bowl-shaped ring-contracted porphyrins that possess a 14π-aromatic circuit. Their flat molecular shapes and discrete molecular orbital diagrams make them ideal for observation by scanning tunneling microscopy (STM). Expanding their applications toward single molecule-based devices requires a fundamental knowledge of single molecular conductance between tribenzosubporphines and the STM metal tip. We utilized a tungsten (W) STM tip to investigate the electronic properties of B-(5-mercaptopentoxy)tribenzosubporphine 1 at the single molecular level. B-(5-mercaptopentoxy)-tribenzosubporphine 1 was anchored to the Au(111) surface via reaction with 1-heptanethiol linkers that were preorganized as a self-assembled monolayer (C7S SAM) on the Au(111) substrate. This arrangement ensured that 1 was electronically decoupled from the metal surface. Differential conductance (dI/dV - V) measurements with the bare W tip exhibited a broad gap region of low conductance and three distinct responses at 2.4,-1.3, and -2.1 V. Bias-voltage-dependent STM imaging of 1 at 65 K displayed a triangle shape at -2.1 < V < -1.3 V and a circle shape at V < -2.1 V, reflecting its HOMO and HOMO-1, respectively. In addition, different conductance behaviors were reproducibly observed, which has been ascribed to the adsorption of a tribenzosubporphine-cation on the W tip. When using a W tip doped with preadsorbed tribenzosubporphine-cation, negative differential resistance (NDR) phenomena were clearly observed in a reproducible manner with a peak-to-valley ratio of 2.6, a value confirmed by spatial mapping conductance measurements. Collectively, the observed NDR phenomena have been attributed to effective molecular resonant tunneling between a neutral tribenzosubporphine anchored to the metal surface and a tribenzosubporphine cation adsorbed on a W tip.

Ideal discrete energy levels in synthesized Au nanoparticles for chemically assembled single-electron transistors.

Ideal discrete energy levels in synthesized Au nanoparticles (6.2 ± 0.8 nm) for a chemically assembled single-electron transistor (SET) are demonstrated at 300 mK. The spatial structure of the double-gate SET is determined by two gate and drain voltages dependence of the stability diagram, and electron transport to the Coulomb box of a single, nearby Coulomb island of Au nanoparticles is detected by the SET. The SET exhibits discrete energy levels, and the excited energy level spacing of the Coulomb island is evaluated as 0.73 meV, which well corresponds to the expected theoretical value. The discrete energy levels show magnetic field evolution with the Zeeman effect and dependence on the odd-even electron number of a single Au nanoparticle.

Robust nanogap electrodes by self-terminating electroless gold plating.

Robust nanogap electrodes for nanodevices with a separation of 3.0 ± 1.7 nm were simultaneously mass-produced at a yield of 90% by a combination of electron beam lithography (EBL) and electroless gold plating (EGP). Nanogap electrodes demonstrated their robustness as they maintained their structure unchanged up to temperatures of 170 °C, during the isotropic oxygen plasma ashing removal of the amorphous carbon overlayer resulting from scanning electron microscopy observations, therefore maintaining their surface reactivity for EGP and formation of a self-assembled monolayer. A gold layer grows over the electrode surface during EGP, narrowing the separation between the electrodes; growth stops around 3 nm due to a self-termination phenomenon. This is the main factor in the high yield and reproducibility of the EGP process because it prevents contact between the electrodes. A 90% yield is achieved by also controlling the etching and physisorption of gold clusters, which is accomplished by reduction of triiodide ions and heat treatment of the EGP solution, respectively. A mixed self-assembled monolayer of octanethiol and decanedithiol can be formed at the surface of the nanogap electrodes after the oxygen plasma treatment, and decanethiol-protected Au nanoparticles were chemisorbed between the self-terminated nanogap electrodes via decanedithiol. Chemically assembled single-electron transistors based on the nanogap electrodes exhibit ideal, stable, and reproducible Coulomb diamonds.

Coulomb blockade behaviors in individual Au nanoparticles as observed through noncontact atomic force spectroscopy at room temperature.

Coulomb blockade behaviors in individual Au nanoparticles of 2 nm core diameter in double-barrier structures have been studied by means of noncontact atomic force spectroscopy (NC-AFS) at room temperature. The Au nanoparticles with a 1-decanethiol ligand were chemisorbed by 1,10-decanedithiol molecules of a mixed 1-octanethiol/1,10-decanedithiol self-assembled monolayer coated on a Au(111) surface; these particles were observed through NC-AFS. NC-AFS measurements of the cantilever frequency shift-sample voltage (Δf-V(S)) curves were sequentially conducted on three Au nanoparticles under the same experimental conditions; the Δf-V(S) curves were found to deviate from the parabolic (Δf(N)) curve in the cases where no extra charge existed on the Au core. The experimental Δf(CB)(=Δf-Δf(N)) and Δf(CB)/V curves agree well with the theoretical curves obtained using a golden-rule calculation and the same parabolic parameters. All the results, through NC-AFS, suggest Coulomb blockade behaviors in the Au nanoparticles at room temperature.

Single electron on a nanodot in a double-barrier tunneling structure observed by noncontact atomic-force spectroscopy.

A single electron has been observed on a nanodot in a double-barrier tunneling structure by noncontact atomic-force microscopy at fixed separation. Frequency shift-voltage dependence of an Au-coated cantilever/vacuum/1-decanethiol protected Au nanodot/1-octanethiol self-assembled monolayer/Au substrate structure deviates from the theoretical parabolic curve, which is attributed to the change in the number of quantized electrons on the Au nanodot caused by the Coulomb blockade phenomena.