In-situ observation of graphene growth on Ni(111)

Graphene growth of mono-, bi- and tri-layers on Ni(111) through surface segregation was observed in situ by low energy electron microscopy. The carbon segregation was controlled by adjusting substrate temperature from 1200 K to 1050 K. After the completion of the first layer at 1125 K, the second layer grew at the interface between the first-layer and the substrate at 1050 K. The third layer also started to grow at the same temperature, 1050 K. All the layers exhibited a 1 × 1 atomic structure. The edges of the first-layer islands were straight lines, reflecting the hexagonal atomic structure. On the other hand, the shapes of the second-layer islands were dendritic. The edges of the third-layer islands were again straight lines similar to those of the first-layer islands. The phenomena presumably originate from the changes of interfacial-bond strength of the graphene to Ni substrate depending on the graphene thickness. No nucleation site of graphene layers was directly observed. All the layers expanded out of the field of view and covered the surface. The number of nucleation sites is extremely small on Ni(111) surface. This finding might open the way to grow the high quality, single-domain graphene crystals.     

SEM/EDS study of metal-assisted oxide desorption

Strongly-enhanced desorption of a thick (100 nm) silicon oxide layer by the pre-sputtering of a thin germanium surface film was observed under high-temperature vacuum annealing conditions. High-resolution SEM imaging reveals that germanium nanoislands are first formed on the sample surface, and that these then act as nucleation centres for the formation of voids in the oxide, leading to a rapid desorption of the silicon oxide layer. EDS analysis of the silicon surface after oxide decomposition shows that the introduced germanium impurities are fully consumed in this desorption process.     

A theoretical study of Zn adsorption and desorption on a Pd(111) substrate

The adsorption and structure of Zn on a Pd(111) surface has been investigated using density functional theory (DFT). It could be shown that Zn prefers adsorption sites with a maximum amount of Pd neighbours on the Pd(111) surface. Zn does form a stable PdZn surface alloy on Pd(111) which shows a (2 × 1) structure. The surface energy of this surface alloy decreases with increasing numbers of PdZn layers. Furthermore the adsorption of Zn on the PdZn surface alloy was investigated. The electronic structure of the Zn layers approaches the bulk Zn state only after a thickness of 4 additional Zn layers. A clear charge transfer between Pd and Zn has been found and the electronic structure of the Zn suggests an anisotropic binding of the Zn, with higher binding energy within a Zn layer and lower binding energy between two Zn layers. This is also reflected in the different desorption energies of different Zn layers found in experiments.     

Influence of water on the surface structure of 1-hexyl-3-methylimidazolium chloride

The molecular surface structure of an ionic liquid (IL) with and without the presence of water was studied with the surface sensitive technique neutral impact collision ion scattering spectroscopy (NICISS). The IL chosen is 1-hexyl-3-methylimidazolium chloride, which is known to be hydrophilic. Binary mixtures were investigated within the water mole fraction range 0.43 ≤ χ_water ≤ 0.71 at 283 K. During approximately 3 h exposition time in vacuum, we have observed a very low water loss rate from sample. The NICISS measurements suggest that admixture of water to [HMIm]Cl leads to a layered surface structure. Three layers were identified (layer 1 — cations, layer 2 — cations and water, layer 3 — cations, water, and anions). While the first layer is unaffected by water, the thickness of the second layer depends on the water concentration. The thickness of layer 2 is relatively constant for water concentrations χ_water ≤ 0.61, but increases for water contents χ_water ≥ 0.68. The concentration range 0.61 ≤ χ_water ≤ 0.68 seems to play a key role in water network formation.     

Photo-curable epoxy functionalized cyclotetrasiloxane as a gate dielectric for organic thin film transistors

We synthesized a new photo-curable organic/inorganic hybrid material, cyclotetrasiloxane (CTS) derivative containing cyclohexene-1,2-epoxide functional groups (CTS-EPOXY), and its characteristics are compared with a prototypical organic gate insulator of poly(4-vinylphenol) (PVP) in the organic thin film transistors (OTFTs) using pentacene as an active p-type organic semiconductor. Compared with PVP, CTS-EPOXY shows better insulating characteristics and surface smoothness. A metal/insulator/metal (MIM) device with the 300-nm-thick CTS-EPOXY film shows more than two orders of magnitude lower current (less than 40 nA/cm² over the voltage range up to 60 V) compared with PVP. In addition, the pentacene TFT with CTS-EPOXY as a gate dielectric layer shows slightly higher field-effect mobility of μ_FET = 0.20 cm²/V s compared to that with PVP.     

Graphene-based nitrogen dioxide gas sensors

In this study, we demonstrated that graphene could selectively absorb/desorb NO_x molecules at room temperature. Chemical doping with NO₂ molecules changed the conductivity of the graphene layers, which was quantified by monitoring the current–voltage characteristics at various NO₂ gas concentrations. The adsorption rate was found to be more rapid than the desorption rate, which can be attributed to the reaction occurred on the surface of the graphene layer. The sensitivity was 9% when an ambient of 100 ppm NO₂ was used. Graphene-based gas sensors showed fast response, good reversibility, selectivity and high sensitivity. Optimization of the sensor design and integration with UV-LEDs and Silicon microelectronics will open the door for the development of nano-sized gas sensors that are extremely sensitive.     

Graphene domain boundaries on Pt(111) as nucleation sites for Pt nanocluster formation

The growth of Pt nanoclusters on a graphene layer on Pt(111) was studied with ultra high vacuum scanning tunneling microscopy. Different periodicities in the moiré patterns of the graphene layer are observed corresponding to different orientations with respect to the Pt(111) lattice. Various graphene orientations are possible because of a relatively weak graphene–Pt interaction. Following Pt deposition onto the graphene-covered surface, small Pt nanoclusters are observed to preferentially form along the moiré domain boundaries. The weak interaction of graphene with Pt(111) leads to a weak corrugation in the superlattice compared to other transition metals, such as Ru, but it is found even this weak corrugation is sufficient to serve as a template for the formation of mono-dispersed one-dimensional Pt nanocluster chains. These Pt nanoclusters are relatively stable and only undergo agglomeration at annealing temperatures above 600 K.     

Memory effect of pentacene field-effect transistors with embedded monolayer of semiconductor colloidal nano-dots

We demonstrate memory effect of pentacene-based field-effect transistors (FETs) in which CdSe/ZnS colloidal nano-dots (NDs) are embedded. The colloidal NDs were dispersed in chloroform, and spread over a water surface to form monolayer of NDs. Then, they were transferred onto a 30-nm-thick poly(methyl methacrylate) (PMMA) surface by horizontal lifting method, and a 30-nm-thick pentacene film was deposited as an active layer to fabricate FETs. The threshold voltage (V_th) was shifted by ∼10 V after a writing voltage of 70–100 V was applied to the gate electrode of the memory-FETs. On the other hand, such a large shift of V_th was not observed for reference pentacene-FETs without NDs. We consider that the large shift of V_th is due to electrons trapped in the NDs at the interface of pentacene and PMMA layers.     

Studies of Li intercalation of hydrogenated graphene on SiC(0001)

The effects of Li deposition on hydrogenated bilayer graphene on SiC(0001) samples, i.e. on quasi-freestanding bilayer graphene samples, are studied using low energy electron microscopy, micro-low-energy electron diffraction and photoelectron spectroscopy. After deposition, some Li atoms form islands on the surface creating defects that are observed to disappear after annealing. Some other Li atoms are found to penetrate through the bilayer graphene sample and into the interface where H already resides. This is revealed by the existence of shifted components, related to H–SiC and Li–SiC bonding, in recorded core level spectra. The Dirac point is found to exhibit a rigid shift to about 1.25 eV below the Fermi level, indicating strong electron doping of the graphene by the deposited Li. After annealing the sample at 300–400 °C formation of LiH at the interface is suggested from the observed change of the dipole layer at the interface. Annealing at 600 °C or higher removes both Li and H from the sample and a monolayer graphene sample is re-established. The Li thus promotes the removal of H from the interface at a considerably lower temperature than after pure H intercalation.     

Surface reactions of TiCl4 and Al(CH3)3 on GaAs(100) during the first half-cycle of atomic layer deposition

GaAs(100) was exposed to pulses of trimethylaluminum (TMA, Al(CH₃)₃) and titanium tetrachloride (TiCl₄) to mimic the first half-cycle of atomic layer deposition (ALD). Both precursors removed the 9.0 ± 1.6 Å-thick mixed oxide consisting primarily of As₂O₃ with a small Ga₂O component that was left on the surface after aqueous HF treatment and vacuum annealing. In its place, TMA deposited an Al₂O₃ layer, but TiCl₄ exposure left Cl atoms adsorbed to an elemental As layer. This suggests that oxygen was removed by the formation of a volatile oxychloride species. A small TiO₂ coverage of approximately 0.04 monolayer remained on the surface for deposition temperatures of 89 °C to 135 °C, but no TiO₂ was present from 170 °C to 230 °C. The adsorbed Cl layer chemically passivated the surface at these temperatures and blocked TiO₂ deposition even after 50 full ALD cycles of TiCl₄ and water vapor. The Cl and As layers desorbed simultaneously at higher temperature producing peaks in the temperature programmed desorption spectrum in the range 237–297 °C. This allowed TiO₂ deposition at 300 °C in single TiCl₄ pulse experiments. On the native oxide-covered surface where there was a higher proportional Ga oxide composition, TiCl₄ exposure deposited TiO₂.     

Decomposition of alkanethiols adsorbed on Au (1 1 1) at low temperature

The adsorption and desorption of butanethiol (CH₃(CH₂)₃SH: C4), hexanethiol (CH₃(CH₂)₅SH: C6) and octanethiol (CH₃(CH₂)₇SH: C8) on Au (1 1 1) under vacuum condition have been studied by temperature programmed desorption (TPD). Desorptions of thiolate radical species were observed for C6 and C8. Connecting the desorption temperatures of parent thiols from the first layer and that of hydrogen, we were able to find a condition for thiolate radicals to be desorbed from the surface.     

Synthesis of epitaxial graphene on rhodium from 3-pentanone

The synthesis of high quality single layer graphene on rhodium, g/Rh(111), is reported. The graphene layers are grown at 1060 K by low pressure chemical vapor deposition (CVD) using 3-pentanone as a precursor molecule. The presented growth technique shows an easy high quality production method for epitaxial graphene monolayers. The chemical composition and structural properties of such self-assembled monolayers were characterized by X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED). Scanning Tunneling Microscopy (STM) confirms the formation of a 3 nm super cell and a unique surface morphology which establishes the potential of g/Rh(111) as a template for molecules.     

The influence of substrate temperature on growth of para-sexiphenyl thin films on Ir{111} supported graphene studied by LEEM

The growth of para-sexiphenyl (6P) thin films as a function of substrate temperature on Ir{111} supported graphene flakes has been studied in real-time with Low Energy Electron Microscopy (LEEM). Micro Low Energy Electron Diffraction (μLEED) has been used to determine the structure of the different 6P features formed on the surface. We observe the nucleation and growth of a wetting layer consisting of lying molecules in the initial stages of growth. Graphene defects – wrinkles – are found to be preferential sites for the nucleation of the wetting layer and of the 6P needles that grow on top of the wetting layer in the later stages of deposition. The molecular structure of the wetting layer and needles is found to be similar. As a result, only a limited number of growth directions are observed for the needles. In contrast, on the bare Ir{111} surface 6P molecules assume an upright orientation. The formation of ramified islands is observed on the bare Ir{111} surface at 320 K and 352 K, whereas at 405 K the formation of a continuous layer of upright standing molecules growing in a step flow like manner is observed.     

Low intensity-ultrasonic irradiation for highly efficient,eco-friendly and fast synthesis of graphene oxide

High quality graphene oxide (GO) with low layer number (less than five layers) and large inter-layer space was produced via a new and efficient method using environmentally friendly, fast and economic ultrasonic radiation. The ultrasonic method neither generated any toxic gas nor required any NaNO₃, which have been the main drawbacks of the Hummers methods. The major obstacles of the recently reported improved Hummers method for GO synthesis, such as high reaction temperature (50 °C) and long reaction time (12 h), were successfully solved using a low intensity-ultrasonic bath for 45 min at 30 °C, which significantly reduced the reaction time and energy consumption for GO synthesis. Furthermore, ultrasonic GO exhibited higher surface area, higher crystallinity and higher oxidation efficiency with many hydrophilic groups, fewer sheets with higher spaces between them, a higher sp³/sp² ratio, and more uniform size distribution than classically prepared GO. Therefore, the new ultrasonic method could be applicable for the sustainable and large-scale production of GO. The production yield of the ultrasonic-assisted GO was 1.25-fold greater than the GO synthesized with the improved Hummers method. Furthermore, the required production cost based on total energy consumption for ultrasonic GO was only 6.5% of that for classical GO.     

Growth protocols and characterization of epitaxial graphene on SiC elaborated in a graphite enclosure

The epitaxial growth of graphene by the sublimation of Si-terminated silicon carbide (SiC) is studied inside a graphite enclosure in a radio-frequency furnace by comparing different in situ processes involving hydrogen etching or not and different growth conditions. For the growth under vacuum, even with the surface preparation of hydrogen etching, the morphology of the synthesized graphene is found full of voids and defects in the form of a multilayer graphene film. For the growth under Ar, the hydrogen etching plays a vital role to improve the graphene quality in terms of surface roughness, the number of graphene layers and the domain size. For the graphene samples grown with the proposed protocol, the original combination of micro-probe Raman spectroscopy and simultaneous optical transmission and reflection measurements reveals a detailed spatially resolved image of the graphene domains with monolayer domain size of ~5×5 µm² on about 2/3 of the total sample surface. The magnetotransport data yield charge-carrier mobilities up to 2900 cm²/Vs as found for high quality graphene on the Si-face of SiC. The observed magnetoquantum oscillations in the magnetoresistance confirm the expected behavior of single-layer graphene.     

Study of the microstructure and mechanical properties of white clam shell

The microstructure and mechanical properties of white clam shell were investigated, respectively. It can be divided into horny layer, prismatic layer and nacreous layer. Crossed-lamellar structure was the microstructural characteristic. The extension direction of lamellae in prismatic layer was different from that in nacreous layer, which formed an angle on the interface between prismatic layer and nacreous layer. The phase component of three layers was CaCO₃ with crystallization morphology of aragonite, which confirmed the crossed-lamellar structural characteristic. White calm shell exhibited perfect mechanical properties. The microhardness values of three layers were 273 HV, 240 HV and 300 HV, respectively. The average values of flexure and compression strength were 110.2 MPa and 80.1 MPa, respectively. The macroscopical cracks crossed the lamellae and finally terminated within the length range of about 80 μm. It was the microstructure characteristics, the angle on the interface between prismatic and nacreous layer and the hardness diversity among the different layers that enhanced mechanical properties of white calm shell.     

Hydrogen adsorption on palladium and palladium hydride at 1 bar

The dissociative sticking probability for H₂ on Pd films supported on sputtered Highly Ordered Pyrolytic Graphite (HOPG) has been derived from measurements of the rate of the H–D exchange reaction at 1 bar. The sticking probability for H₂, S, is higher on Pd hydride than on Pd (a factor of 1.4 at 140 °C), but the apparent desorption energy derived from S is the same on Pd and Pd hydride within the uncertainty of the experiment. Density Functional Theory (DFT) calculations for the (1 1 1) surfaces of Pd and Pd hydride show that, at a surface H coverage of a full mono layer, H binds less strongly to Pd hydride than to Pd. The activation barrier for desorption at a H coverage of one mono layer is slightly lower on Pd hydride, whereas the activation energy for adsorption is similar on Pd and Pd hydride. It is concluded that the higher sticking probability on Pd hydride is most likely caused by a slightly lower equilibrium coverage of H, which is a consequence of the lower heat of adsorption for H on Pd hydride.     

Concept of infrared photodetector based on graphene–graphene nanoribbon structure

We study the mechanisms of photoconductivity in graphene layer–graphene nanoribbon–graphene layer (GL–GNR–GL) structures with the i-type gapless GL layers as sensitive elements and I-type GNRs as barrier elements. The effects of both an increase in the electron and hole densities under infrared illumination and the electron and hole heating and cooling in GLs are considered. The device model for a GL–GNR–GL photodiode is developed. Using this model, the dark current, photocurrent, and responsivity are calculated as functions of the structure parameters, temperature, and the photon energy. The transition from heating of the electron–hole plasma in GLs to its cooling by changing the incident photon energy can result in the change of the photoconductivity sign from positive to negative. It is demonstrated that GL–GNR–GL photodiodes can be used in effective infrared and terahertz detectors operating at room temperature. The change in the photoconductivity sign can be used for the discrimination of the incident radiation with the wavelength 2–3 μm and 8–12 μm.     

The thermodynamic and kinetic properties of hydrogen dimers on graphene

The thermodynamic and kinetic properties of hydrogen adatoms on graphene are important to the materials and devices based on hydrogenated graphene. Hydrogen dimers on graphene with coverages varying from 0.040 to 0.111 ML (1.0 ML = 3.8 × 10¹⁵cm^? 2) were considered in this report. The thermodynamic and kinetic properties of H, D and T dimers were studied by ab initio simulations. The vibrational zero-point energy corrections were found to be not negligible in kinetics, varying from 0.038 (0.028, 0.017) to 0.257 (0.187, 0.157) eV for H (D, T) dimers. The isotope effect exhibits as that the kinetic mobility of a hydrogen dimer decreases with increasing the hydrogen mass. The simulated thermal desorption spectra with the heating rate α = 1.0 K/s were quite close to experimental measurements. The effect of the interaction between hydrogen dimers on their thermodynamic and kinetic properties was analyzed in detail.     

Stage structure in cesium doped pentacene

We have prepared the cesium doped pentacene film and have investigated the electrical properties, in order to investigate a new molecular conductive film based on pentacene. It was found that cesium is doped in the pentacene film and that electrical resistivity decreases drastically below 10 Ω cm. Moreover, in the doping process, we found the step-wise decrease of electrical resistivity. It is deduced from this result that the cesium doped pentacene forms stage structures. In addition, we have carried out the measurements of the X-ray diffraction pattern in the cesium doped pentacene film. It was found from these results that the cesium doped pentacene becomes a highly orientated intercalated conductive film. Furthermore, in the cesium doped pentacene we have observed the shift of (00l) diffraction peak to low diffraction angle. This result indicates that by doping of pentacene the c-axis lattice constant which is the length of the interval between the (001) planes becomes 1.59 nm in the stage-1 structure of the cesium doped pentacene.