Photo-switching Operation of MoS2 Field Effect Transistor by Photoisomerization of Azobenzene in Solution Delivered on a Microfluidic Platform.

Combining the photoisomerization of molecules with an electrical device is important for developing optoelectronic devices. Field effect transistors (FETs) with atomically thin channels are suitable for this purpose because the FET properties respond to chemical changes in molecules. Since the photoisomerization wavelength of the switching molecules can be tuned, complex logic operations can be realized if a specific molecule is delivered to the target FET of an integrated circuit. However, conventional techniques for transferring molecules, such as drop casting and sublimation, cannot efficiently realize this goal. In this study, we fabricated a MoS2 FET device combined with a microfluidic platform, wherein the MoS2 channel was in contact with the flow of an azobenzene solution in isopropyl alcohol as the solvent. UV radiation (365 nm) and thermal relaxation realize the cycle of trans- and cis-azobenzene states and the switching of the substantial FET properties. This study demonstrated the feasibility of using the solution for optical switching of the MoS2-FET, which can realize quick phase changes in the molecule and the delivery of the molecule to the target FET by a microfluidic platform. .

Spatially Resolving Electron Spin Resonance of π-Radical in Single-molecule Magnet.

The spintronic properties of magnetic molecules have attracted significant scientific attention. Special emphasis has been placed on the qubit for quantum information processing. The single-molecule magnet bis(phthalocyaninato (Pc)) Tb(III) (TbPc2) is one of the best examined cases in which the delocalized π-radical electron spin of the Pc ligand plays the key role in reading and intermediating the localized Tb spin qubits. We utilized the electron spin resonance (ESR) technique implemented on a scanning tunneling microscope (STM) and use it to measure local the ESR of a single TbPc2 molecule decoupled from the Cu(100) substrate by a two-monolayer NaCl film to identify the π-radical spin. We detected the ESR signal at the ligand positions under the resonance condition expected for an S = 1/2 spin. The results reveal that the π-radical electron is delocalized within the ligands and exhibits intramolecular coupling susceptible to the chemical environment.

Control of the Magnetic Interaction between Single-Molecule Magnet TbPc2 and Superconductor NbSe2 Surface by an Intercalated Co Atom.

We demonstrate that an intercalated Co atom in superconductor NbSe2 could control the magnetic interaction between the adsorbed magnetic molecule of TbPc2 and the NbSe2 substrate. An intercalated Co atom enhances the magnetic interaction between the NbSe2 and the TbPc2 spin to cause Kondo resonance at the TbPc2 position, a spin-singlet state formed by the itinerary electron. By applying a surface-normal magnetic field, we change the molecule's spin direction from the initial one directed to the Co atom to the surface normal. The change appears as a split Kondo resonance at the TbPc2, one of which is enhanced at the Tb site, which disappears when the outer magnetic field normal to the surface is applied and never appears, even if we return B to 0 T. The phenomenon suggests that the intercalated magnetic atoms can control the magnetic interaction between a magnetic molecule and the superconductor NbSe2.

A microfluidic approach for the detection of uric acid through electrical measurement using an atomically thin MoS2 field-effect transistor.

There is a demand for biosensors working under in vivo conditions, which requires significant device size and endurance miniaturization in solution environments. We demonstrated the detection of uric acid (UA) molecules, a marker of diseases like gout, whose continuous monitoring is required in medical diagnosis. We used a field effect transistor (FET) composed of an atomically thin transition metal dichalcogenide (TMD) channel. The sensor detection was carried out in a solution environment, for which we protected the electrodes of the source and drain from the solution. A microfluidic channel controls the solution flow that can realize evaporation-free conditions and provide an accurate concentration and precise measurement. We detected a systematic change of the drain current with the concentration of the UA in isopropyl alcohol (IPA) solvent with a detection limit of 60 nM. The sensor behavior is reversible, and the drain current returns to its original value when the channel is washed with pure solvent. The results demonstrate the feasibility of applying the MoS2-FET device to UA detection in solution, suggesting its possible use in the solution environment.

In situ study of sensor behavior of MoS2 field effect transistor for methyl orange molecule in ultra high vacuum condition.

We investigate the sensor behavior of the MoS2 field effect transistor (FET) device with the deposition of methyl orange (MO) molecule which is widely used as a chemical probe. The channel of the FET is made of the single layer of MoS2 which makes it highly sensitive to the molecule adsorption, but at the same time the behavior depends much on the surface conditions of the MoS2 channel. In order to make the channel-surface conditions more defined, we prepare an in situ experimental system in which the molecule deposition and the surface- and electrical-characterization of the MoS2 FET are executed in a single ultra-high vacuum chamber. This system makes it possible to examine the change of the FET properties with precise control of the molecule coverage in the sub-monolayer region without the effect of the atmosphere. We detected the shift of the I d-V g curve of the MoS2-FET device with the increase of the molecule coverage (θ) of the MO molecule, which is quantitatively analyzed by plotting the threshold voltage (V th) of the I d-V g curve as a function of θ. The V th shifts towards the negative direction and the initial change with θ can be expressed with an exponential function of θ, which can be accounted for with the Langmuir type adsorption of the molecule for the first layer and the charge transfer from the molecule to the substrate. The V th versus θ curve shows a kink at a certain θ, which is conserved as the starting of the second layer growth. We detected the adsorption of MO far less than monolayer and the phase change from the first layer to the second layer growth, which is realized by the benefit of the in situ UHV experimental condition.

Chemistry of the photoisomerization and thermal reset of nitro-spiropyran and merocyanine molecules on the channel of the MoS2 field effect transistor.

We have explored the chemical reaction of the photoisomerization and thermal reaction of the photochromic spiropyran (SP) 1',3'-Dihydro-1',3',3' trimethyl-6-nitrospiro[2H-1 benzopyran-2,2'-(2H)-indole] molecule deposited on the atomic thin channel of a MoS2 field-effect transistor (FET) through the analysis of the FET property. With four monolayers of SP molecules on the channel, we observed a clear shift of the threshold voltage in the drain-current vs gate-voltage plot with UV-light injection on the molecule, which was due to the change of the SP molecule to merocyanine (MC). A complete reset from MC to SP molecule was achieved by thermal annealing, while the injection of green light could revert the FET property to the original condition. In the process of change from MC to SP, two types of decay rates were confirmed. The quick- and slow-decay components corresponded to the molecules attached directly to the substrate and those in the upper layer, respectively. The activation energies for the conversion of MC to SP molecules were estimated as 71 kJ/mol and 90 kJ/mol for the former and latter, respectively. Combined with DFT calculations, we concluded that the Id-Vg shift with photoisomerization from SP to MC is due to the upper layer molecules and the dipole moment in the surface normal direction. Based on the estimated activation energy of 90 kJ/mol for the reset process, we calculated the conversion rate in a controllable temperature range. From these values, we consider that the chemical state of MC can be maintained and switched in a designated time period, which demonstrates the possibility of this system in logical operation applications.

Microfluidic tank assisted nicotine sensing property of field effect transistor composed of an atomically thin MoS2 channel.

We investigated the sensor behavior of a field effect transistor, the channel of which is made of atomically thin MoS2 layers, focusing on the interaction of the MoS2 channel with the solution containing target molecules. For this purpose, we made a newly designed device in which the mask covered the electrodes of the source and the drain in order to make the solution contact only with the channel. In addition, a micro-fluid tank was fabricated above the channel as a solution reservoir. We examined the FET properties of this device for the sensing of the nicotine molecule for the development of a detection system for this molecule in the human body under in vivo conditions. We detected the sensor behavior both for the drop-cast process and for the condition where the channel contacts with the solution. The drain-current vs. gate-voltage variation of the MoS2-FET with the attachment of the nicotine molecule was clearly observed for both cases. For the latter case, the threshold voltage shifted in the negative gate-voltage direction with the increase of the concentration of the nicotine in the solution. This can be explained by the electron transfer from the molecule to the MoS2 channel, which was further confirmed by analyzing the X-ray photoemission spectroscopy and Raman spectroscopy together with the DFT calculation. The sensor can detect the variation of the nicotine concentration in the IPA solution by detecting the Vth change of the MoS2-FET.

Spatially Resolved Magnetic Anisotropy of Cobalt Nanostructures on the Au(111) Surface.

Understanding the origin of perpendicular magnetic anisotropy in surface-supported nanoclusters is crucial for fundamental research as well as data storage applications. Here, we investigate the perpendicular magnetic anisotropy energy (MAE) of bilayer cobalt islands on Au(111) substrate using spin-polarized scanning tunneling microscopy at 4.6 K and first-principles theoretical calculations. Au(111) substrate serves as an excellent model system to study the effect of nucleation site and stacking sequence on MAE. Our measurements reveal that the MAE of bilayer islands depends strongly on the crystallographic stacking of the two Co layers and nucleation of the third layer. Moreover, the MAE of Co atoms on Au(111) is enhanced by a factor of 1.75 as compared to that reported on Cu(111). Our first-principles calculations attribute this enhancement to the large spin-orbit coupling of the Au atoms. Our results highlight the strong impact of nanometer-scale structural changes in Co islands on MAE and emphasize the importance of spatially resolved measurements for the magnetic characterization of surface-supported nanostructures.

The Frontier of Molecular Spintronics Based on Multiple-Decker Phthalocyaninato Tb(III) Single-Molecule Magnets.

Ever since the first example of a double-decker complex (SnPc2) was discovered in 1936, MPc2 complexes with π systems and chemical and physical stabilities have been used as components in molecular electronic devices. More recently, in 2003, TbPc2 complexes were shown to be single-molecule magnets (SMMs), and researchers have utilized their quantum tunneling of the magnetization (QTM) and magnetic relaxation behavior in spintronic devices. Herein, recent developments in Ln(III)-Pc-based multiple-decker SMMs on surfaces for molecular spintronic devices are presented. In this account, we discuss how dinuclear Tb(III)-Pc multiple-decker complexes can be used to elucidate the relationship between magnetic dipole interactions and SMM properties, because these complexes contain two TbPc2 units in one molecule and their intramolecular Tb(III)-Tb(III) distances can be controlled by changing the number of stacks. Next, we focus on the switching of the Kondo signal of Tb(III)-Pc-based multiple-decker SMMs that are adsorbed onto surfaces, their characterization using STM and STS, and the relationship between the molecular structure, the electronic structure, and the Kondo resonance of Tb(III)-Pc multiple-decker complexes.

Epitaxial growth of CeO2(111) film on Ru(0001): scanning tunneling microscopy (STM) and x-ray photoemission spectroscopy (XPS) study.

We formed an epitaxial film of CeO2(111) by sublimating Ce atoms on Ru(0001) surface kept at elevated temperature in an oxygen ambient. X-ray photoemission spectroscopy measurement revealed a decrease of Ce(4+)/Ce(3+) ratio in a small temperature window of the growth temperature between 1070 and 1096 K, which corresponds to the reduction of the CeO2(111). Scanning tunneling microscope image showed that a film with a wide terrace and a sharp step edge was obtained when the film was grown at the temperatures close to the reduction temperature, and the terrace width observed on the sample grown at 1060 K was more than twice of that grown at 1040 K. On the surface grown above the reduction temperature, the surface with a wide terrace and a sharp step was confirmed, but small dots were also seen in the terrace part, which are considerably Ce atoms adsorbed at the oxygen vacancies on the reduced surface. This experiment demonstrated that it is required to use the substrate temperature close to the reduction temperature to obtain CeO2(111) with wide terrace width and sharp step edges.

First observation of a Kondo resonance for a stable neutral pure organic radical, 1,3,5-triphenyl-6-oxoverdazyl, adsorbed on the Au(111) surface.

We investigated spin states of stable neutral pure-organic radical molecules of 1,3,5-triphenyl-6-oxoverdazyl (TOV) and 1,3,5-triphenyl-6-thioxoverdazly (TTV) adsorbed on an Au(111) surface, which appears as a Kondo resonance because of spin-electron interaction. By using scanning tunneling spectroscopy (STS), a clear Kondo resonance was detected for the TOV molecule. However, no Kondo resonance was detected for TOV molecules with protrusions in the occupied state image and for TTV molecules. Spin-resolved DFT calculations showed that an unpaired π electron was delocalized over the adsorbed TOV molecule, which was the origin of the Kondo resonance. For the TOV molecules with protrusions, we proposed a model in which an additional H atom was attached to the TOV molecule. Calculations showed that, upon transfer of an electron to the verdazyl ring, the unpaired π electron disappeared, accounting for the absence of a Kondo resonance in the STS spectra. The absence of a Kondo resonance for the TTV molecule can be explained in a similar manner. In other words, electron transfer to the verdazyl ring occurs because of Au-S bond formation.

Spin doping of individual molecules by using single-atom manipulation.

Being able to control the spin of magnetic molecules at the single-molecule level will make it possible to develop new spin-based nanotechnologies. Gate-field effects and electron and photon excitations have been used to achieve spin switching in molecules. Here, we show that atomic doping of molecules can be used to change the molecular spin. Furthermore, a scanning tunneling microscope was used to place or remove the atomic dopant on the molecule, allowing us to change the molecular spin in a controlled way. Bis(phthalocyaninato)yttrium (YPc(2)) molecules deposited on an Au (111) surface keep their spin-1/2 magnetic moment due to the small molecule-substrate interaction. However, when Cs atoms were carefully placed onto YPc(2) molecules, the spin of the molecule vanished as shown by our conductance measurements and corroborated by the results of density functional theory calculations.

Enhanced photocatalytic activity of Cu and Ni-doped ZnO nanostructures: A comparative study of methyl orange dye degradation in aqueous solution.

Heterogeneous photocatalysis has been considered one of the most effective and efficient techniques to remove organic contaminants from wastewater. The present work was designed to examine the photocatalytic performance of metal (Cu and Ni) doped ZnO nanocomposites in methyl orange (MO) dye degradation under UV light illumination. The wurtzite hexagonal structure was observed for both undoped/doped ZnO and a crystalline size ranging between 8.84 ± 0.71 to 12.91 ± 0.84 nm by X-ray diffraction (XRD) analysis. The scanning electron microscope (SEM) and energy dispersive X-ray (EDX) revealed the irregular spherical shape with particle diameter (34.43 ± 6.03 to 26.43 ± 4.14 nm) and ensured the purity of the individual elemental composition respectively. The chemical bonds (O-H group) and binding energy (1021.8 eV) were identified by Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) results respectively. The bandgap energy was decreased from 3.44 to 3.16 eV when Ni dopant was added to the ZnO lattice. The comparative photocatalytic activity was observed in undoped and doped nanocomposites and found to be 76.31%, 81.95%, 89.30%, and 83.39% for ZnO, Cu/ZnO, Ni/ZnO, and Cu/Ni/ZnO photocatalysts, respectively, for a particular dose (0.210 g) and dye concentration (10 mg L-1) after 180 min illumination of UV light. The photocatalytic performance was increased up to 94.40% with the increase of pH (12.0) whereas reduced (35.12%) with an increase in initial dye concentration (40 mg L-1) using Ni/ZnO nanocomposite. The Ni/ZnO nanocomposite showed excellent reusability and was found 81% after four consecutive cycles. The best-fitted reaction kinetics was followed by pseudo-first-order and found reaction rate constant (0.0117 min-1) using Ni/ZnO nanocomposite. The enhanced photodegradation efficiency was observed due to decreases in bandgap energy and the crystalline size of the photocatalyst. Therefore, Ni/ZnO nanocomposite could be used as an emerging photocatalyst to degrade bio-persistent organic dye compounds from textile wastewater.

Observation of Yu-Shiba-Rusinov States and Inelastic Tunneling Spectroscopy for Intramolecule Magnetic Exchange Interaction Energy of Terbium Phthalocyanine (TbPc) Species Adsorbed on Superconductor NbSe2.

We investigated the spin properties of the terbium phthalocyanine (TbPc) species adsorbed on the superconductor NbSe2 surface using scanning tunneling microscopy and spectroscopy. TbPc2 is a molecule in a class of single-molecule magnets (SMMs), and the use of superconductor electrodes attracts attention for the application to the devices using the spin degree of freedom. TbPc is a building block of TbPc2 and can reveal the spin component's behavior. In the experiment, TbPc species were placed on the surface of the superconductor NbSe2. We measured Yu-Shiba-Rusinov (YSR) states caused by the interaction between the superconducting state and magnetic impurity and inelastic tunneling spectroscopy (IETS) for the spin excitation, below 1 K. We also measured the Kondo state formed by the magnetic singlet formation. We detected the radical spin at the ligand position of the TbPc by the presence of the Kondo peak and demonstrated that the radical spin forms the YSR feature. In addition, the exchange interaction energy (Eex) between the spins of the radical ligand (Pc) and the center 4f metal atom (Tb3+) is determined by using the IETS technique. Eex is a critical parameter that determines the blocking temperature, below which the sample behaves as an SMM. IETS results show that the statistical distribution of Eex has peaked at 1.3, 1.6, and 1.9 meV. The energy range is comparable to the recent theoretical calculation result. In addition, we show that the energy variation is correlated with the bonding configuration of TbPc.

Observation of a Yu-Shiba-Rusinov state originating from the magnetic moment in a curved monolayer island of 1T-phase NbSe2 .

We report the finding of a 1T phase island of NbSe2 on a cleaved surface and its magnetic properties. Tunneling spectroscopy at 400 mK shows robust peaks in the superconducting gap, which we assign to the Yu-Shiba-Rusinov (YSR) state originating from the magnetic moment placed in the superconducting state. The YSR peak appears on a specific position of an island of the 1T phase, not on the surrounding 2H phase area, and shows an anisotropic decay behavior. In addition, we found a close relationship between the enhancement of the YSR peak and the local curvature of the film. We assign the origin of the magnetic moment to the curvature of the 1T phase island, which can form a magnetic moment through a rotation of the wave function by a robust spin-orbit coupling, as indicated by a recent theoretical study.

Site selective inelastic electron tunneling spectroscopy probed by isotope labeling.

We study inelastic scattering in alkanethiol self-assembled monolayers using isotope labeling and unambiguously determine which molecular vibrations are active in the inelastic electron tunneling spectroscopy. The selective deuteration of the molecule also allows us to show that the different parts of the molecule contribute approximately equally to inelastic signal. Our first principles calculations confirm the experimental results and provide insights on electron transport through molecules.

Sensor behavior of MoS2 field-effect transistor with light injection toward chemical recognition.

The application of field-effect transistor (FET) devices with atomically thin channels as sensors has attracted significant attention, where the adsorption of atoms/molecules on the channels can be detected by the change in the properties of FET. Thus, to further enhance the chemical sensitivity of FETs, we developed a method to distinguish the chemical properties of adsorbates from the electric behavior of FET devices. Herein, we explored the variation in the FET properties of an MoS2-FET upon visible light injection and the effect of molecule adsorption for chemical recognition. By injecting light, the drain current (I d) increased from the light-off state, which is defined as (ΔI d)ph. We examined this effect using CuPc molecules deposited on the channel. The (ΔI d)ph vs. wavelength continuous spectrum in the visible region showed a peak at the energy for the excitation from the highest occupied orbital (HOMO) to the molecule-induced state (MIS). The energy position and the intensity of this feature showed a sensitive variation with the adsorption of the CuPc molecule and are in good agreement with previously reported photo-absorption spectroscopy data, indicating that this technique can be employed for chemical recognition.

Inelastic tunneling spectroscopy of alkanethiol molecules: high-resolution spectroscopy and theoretical simulations.

We investigate inelastic electron tunneling spectroscopy (IETS) for alkanethiol self-assembled monolayers (SAM) with a scanning tunneling microscope and compare it to first-principles calculations. Using a combination of partial deuteration of the molecule and high-resolution measurements, we identify and differentiate between methyl (CH3) and methylene (CH2) groups and their symmetric and asymmetric C-H stretch modes. The calculations agree quantitatively with the measured IETS in producing the weight of the symmetric and asymmetric C-H stretch modes while the methylene stretch mode is largely underestimated. We further show that inelastic intermolecular scattering is important in the SAM by plotting the theoretical current densities.

Metal-free phthalocyanine (H2Pc) molecule adsorbed on the Au(111) surface: formation of a wide domain along a single lattice direction.

Using low-temperature scanning tunneling microscopy (STM), we observed the bonding configuration of the metal-free phthalocyanine (H2Pc) molecule adsorbed on the Au(111) surface. A local lattice formation started from a quasi-square lattice aligned to the close-packed directions of the Au(111) surface. Although we expected the lattice alignment to be equally distributed along the three crystallographically equivalent directions, the domain aligned normal to the ridge of the herringbone structure was missing in the STM images. We attribute this effect to the uniaxial contraction of the reconstructed Au(111) surface that can account for the formation of a large lattice domain along a single crystallographical direction.

Enhanced magnetic spin-spin interactions observed between porphyrazine derivatives on Au(111).

Magnetic molecules are of interest for application in spintronic and quantum-information processing devices. Therein, control of the interaction between the spins of neighboring molecules is the critical issue. Substitution of outer moieties of the molecule can tune the molecule-molecule interaction. Here we show a novel spin behavior for a magnetic molecule of vanadyl tetrakis (thiadiazole) porphyrazine (abbreviated as VOTTDPz) adsorbed on Au(111), which is modified from vanadyl phthalocyanine (VOPc) by replacing the inert phthalocyanine ligand with a reactive thiadiazole moiety. The magnetic properties of the molecules are examined by observing the Kondo resonance caused by the screening of an isolated spin by conduction electrons using scanning tunneling spectroscopy. The Kondo features are detected at the molecule whose shape and intensity show site-dependent variation, revealing complex spin-spin interactions due to the enhanced interaction between molecules, originating from the functionalization of the ligand with a more reactive moiety.