M. Vondráček

Facile fabrication of tin-doped hematite photoelectrodes – effect of doping on magnetic properties and performance for light-induced water splitting

We present a new, easily scalable method for the deposition of nanocrystalline hematite photoelectrodes based on the spin-coating of a mixed solution containing tin(II) and iron(III) chlorides followed by thermal treatment. Our facile approach does not require any additional film-forming organic species and allows simple control of the photoelectrochemical performance of the electrode by adjusting the degree of tin doping. When annealed at 650 °C a strong increase in the water oxidation photocurrent is observed with increasing tin concentration. The maximum performance (0.45 mA cm−2 at 1.43 V vs. RHE) was found at the highest possible tin loading (20 : 100, Sn : Fe). The contrasting performance of electrodes annealed at 650 °C and 800 °C suggests different activation processes for dopant diffusion and activation. The doping of tin into the crystal structure of hematite thin films is directly evidenced by X-ray photoelectron spectroscopy and indirectly by changes in the intrinsic magnetic parameters (Morin temperature, Neel temperature) of the hematite films. The magnetization measurements thus represent a potential technique to quantify doping amounts in hematite.

Self-Assembled Carbon Nanotubes on Gold: Polarization-Modulated Infrared Reflection−Absorption Spectroscopy, High-Resolution X-ray Photoemission Spectroscopy, and Near-Edge X-ray Absorption Fine Structure Spectroscopy Study

Recently we reported noncovalent functionalization of nanotubes in an aqueous medium with ionic liquid-based surfactants, 1-dodecyl-3-methylimidazolium bromide (1) and 1-(12-mercaptododecyl)-3-methylimidazolium bromide (2), resulting in positively charged single-wall carbon nanotube (SWNT)-1,2 composites. Thiolation of SWNTs with 2 provides their self-assembly on gold as well as templating gold nanoparticles on SWNT sidewalls via a covalent -S-Au bond. In this investigation, we studied the electronic structure, intermolecular interactions, and packing within noncovalently thiolated SWNTs and also nanotube alignment in the bulk of SWNT-2 dried droplets and self-assembled submonolayers (SAMs) on gold by high-resolution X-ray photoemission spectroscopy (HRXPS), C K-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS). HRXPS data confirmed the noncovalent nature of interactions within the nanocomposite of thiolated nanotubes. In PM-IRRAS spectra of SWNT SAMs on gold, the IR-active vibrational SWNT modes have been observed and identified. According to PM-IRRAS data, the hydrocarbon chains of 2 are oriented with less tilt angle to the bare gold normal in a SAM deposited from an SWNT-2 dispersion than those of 1 deposited from an SWNT-1 dispersion on the mercaptoethanesulfonic acid-primed gold. For both the dried SWNT-2 bulk and the SWNT-2 SAM on gold, the C K-edge NEXAFS spectra revealed the presence of CH-pi interactions between hydrocarbon chains of 2 and the pi electronic nanotube structure due to the highly resolved vibronic fine structure of carbon 1s --> R*/sigma*C-H series of states in the alkyl chain of 2. For the SWNT-2 bulk, the observed splitting and upshift of the SWNT pi* orbitals in the NEXAFS spectrum indicated the presence of pi-pi interactions. In the NEXAFS spectrum of the SWNT-2 SAM on gold, the upshifted values of the photon energy for R*/sigma*C-H transitions indicated close contact of 2 with nanotubes and with a gold surface. The angle-dependent NEXAFS for the SWNT-2 bulk showed that most of the molecules of 2 are aligned along the nanotubes, which are self-organized with orientation parallel to the substrate plane, whereas the NEXAFS for the SWNT-2 SAM revealed a more normal orientation of functionality 2 on gold compared with that in the SWNT-2 bulk.

Electronic and Chemical Properties of Donor, Acceptor Centers in Graphene

Chemical doping is one of the most suitable ways of tuning the electronic properties of graphene and a promising candidate for a band gap opening. In this work we report a reliable and tunable method for preparation of high-quality boron and nitrogen co-doped graphene on silicon carbide substrate. We combine experimental (dAFM, STM, XPS, NEXAFS) and theoretical (total energy DFT and simulated STM) studies to analyze the structural, chemical, and electronic properties of the single-atom substitutional dopants in graphene. We show that chemical identification of boron and nitrogen substitutional defects can be achieved in the STM channel due to the quantum interference effect, arising due to the specific electronic structure of nitrogen dopant sites. Chemical reactivity of single boron and nitrogen dopants is analyzed using force-distance spectroscopy by means of dAFM.

Nickel: The time-reversal symmetry conserving partner of iron on a chalcogenide topological insulator

We report on the quenching of single Ni adatom moments on Te-terminated Bi2Te2Se and Bi2Te3 topological insulator surfaces. The effect becomes manifested as a missing X-ray magnetic circular dichroism for resonant L3,2 transitions into partially filled Ni 3d states of occupancy nd = 9.2. On the basis of a comparative study of Ni and Fe using scanning tunneling microscopy and ab initio calculations we are able to relate the element specific moment formation to a local Stoner criterion. While Fe adatoms form large spin moments of ms = 2.54μB with out-of-plane anisotropy due to a sufficiently large density of states at the Fermi energy, Ni remains well below an effective Stoner threshold for local moment formation. With the Fermi level remaining in the bulk band gap after adatom deposition, non-magnetic Ni and preferentially out-of-plane oriented magnetic Fe with similar structural properties on Bi2Te2Se surfaces constitute a perfect platform to study off-on effects of time-reversal symmetry breaking on topological surface states.

Simple device for the growth of micrometer-sized monocrystalline single-layer graphene on SiC(0001)

The thermal decomposition of SiC wafers has proven to be a reliable method to obtain epitaxial graphene. However, the sublimation of Si induced by annealing of SiC substrates is notoriously difficult to control. To tackle the problem, the authors developed a fairly simple apparatus for the growth of micrometer-scale homogeneous single- and bilayer graphene in Ar atmosphere. The device is a furnace based on a considerably improved version of a directly heated element, and can achieve the desired sample quality reproducibly and efficiently. The authors characterize the samples prepared using this device by atomic force microscopy, low energy electron diffraction, Raman spectroscopy, scanning tunneling microscopy, x-ray photoemission spectroscopy, and near-edge x-ray absorption spectroscopy.

Surface analysis of the Heusler Ni49.7Mn29.1Ga21.2 Alloy: The composition, phase transition, and twinned microstructure of martensite

Surface analysis was used to study the dynamics of the martensitic transformation on macro- and mesoscopic scales. The chemical state, morphology, and magnetic and surface structure were monitored at particular stages of the phase transition. At room temperature, the martensitic phase of the Ni49.7Mn29.1Ga21.2 (100) single crystal exhibited macroscopic a/c twinning and a corresponding magnetic domain structure characterized by magnetization vector in and out of the surface plane. Induced by radiation heating, the transformation from martensite to austenite takes place separately at the surface and in the bulk. Its dynamics depend on the history of the sample treatment which affects the crystallographic orientation of twins and minor changes of the surface stoichiometry. The interfaces (twin planes) between twin variants in the martensitic phase were noticeable also in the austenitic phase, thanks to the shape memory effect of this material.

Enhanced absorption of TiO2 nanotubes by N-doping and CdS quantum dots sensitization: insight into the structure

Anodization of titanium film sputtered on fluorine doped tin oxide (FTO) glass was performed to obtain highly ordered ∼2 μm long and ∼60 nm wide TiO2 nanotubes. The titania films were annealed in ammonia atmosphere to enable the doping with N. The annealing did not affect the nanotubular morphology and the porosity remained open which is a very important requirement for further deposition of CdS quantum dots. The analysis done by transmission electron microscopy (TEM) has shown that the N-doped nanotubes have a smaller interplanar distance as compared to the undoped ones, whose interplanar distance corresponded to anatase phase. This difference was attributed to the N doping and the Sn migration from the substrate, as demonstrated by energy dispersive spectroscopy (EDS) combined with electron energy loss spectroscopy (EELS). The near edge X-ray absorption fine structure (NEXAFS) analysis clearly demonstrated that also the doped TiO2 film has anatase phase. Regarding the chemical composition of the studied samples, the X-ray photoelectron spectroscopy (XPS) and synchrotron radiation photoelectron spectroscopy (SRPES) analyses have shown that N is incorporated both interstitially and substitutionally in the TiO2 lattice, with a decreased contribution of the interstitial after ionic sputtering. The shift of the valence band maximum (VBM) position for the doped TiO2 vs. the undoped TiO2 proved the narrowing of the band gap. The CdS/TiO2 films show bigger VBM shifting that can be attributed to CdS deposit. Comparing the absorption spectra of the bare undoped and doped TiO2 samples, it was noticed that the doping causes a red shift from 397 to 465 nm. Furthermore, the CdS deposition additionally enhances the absorption in the visible range (575 nm for undoped TiO2/CdS and 560 nm for doped TiO2/CdS films).

Nanofaceting as a stamp for periodic graphene charge carrier modulations

The exceptional electronic properties of monatomic thin graphene sheets triggered numerous original transport concepts, pushing quantum physics into the realm of device technology for electronics, optoelectronics and thermoelectrics. At the conceptual pivot point is the particular two-dimensional massless Dirac fermion character of graphene charge carriers and its volitional modification by intrinsic or extrinsic means. Here, interfaces between different electronic and structural graphene modifications promise exciting physics and functionality, in particular when fabricated with atomic precision. In this study we show that quasiperiodic modulations of doping levels can be imprinted down to the nanoscale in monolayer graphene sheets. Vicinal copper surfaces allow to alternate graphene carrier densities by several 1013 carriers per cm2 along a specific copper high-symmetry direction. The process is triggered by a self-assembled copper faceting process during high-temperature graphene chemical vapor deposition, which defines interfaces between different graphene doping levels at the atomic level.

Electronic structure origin of conductivity and oxygen reduction activity changes in low-level Cr-substituted (La,Sr)MnO3

The electronic structure of the (La(0.8)Sr(0.2))(0.98)Mn(1-x)Cr(x)O3 model series (x = 0, 0.05, or 0.1) was measured using soft X-ray synchrotron radiation at room and elevated temperature. O K-edge near-edge X-ray absorption fine structure (NEXAFS) spectra showed that low-level chromium substitution of (La,Sr)MnO3 resulted in lowered hybridisation between O 2p orbitals and M 3d and M 4sp valance orbitals. Mn L3-edge resonant photoemission spectroscopy measurements indicated lowered Mn 3d-O 2p hybridisation with chromium substitution. Deconvolution of O K-edge NEXAFS spectra took into account the effects of exchange and crystal field splitting and included a novel approach whereby the pre-peak region was described using the nominally filled t(2g) ↑ state. 10% chromium substitution resulted in a 0.17 eV lowering in the energy of the t(2g) ↑ state, which appears to provide an explanation for the 0.15 eV rise in activation energy for the oxygen reduction reaction, while decreased overlap between hybrid O 2p-Mn 3d states was in qualitative agreement with lowered electronic conductivity. An orbital-level understanding of the thermodynamically predicted solid oxide fuel cell cathode poisoning mechanism involving low-level chromium substitution on the B-site of (La,Sr)MnO3 is presented.

Photoemission from Al(100): experiment and one-step theory

Experimental and theoretical study of angle resolved photoemission from the Al(100) surface is presented. Photoelectron spectra are calculated with an ab initio one-step theory of photoemission within the augmented plane wave formalism and are found to be in excellent agreement with the experiment. The lifetime of the (100) surface state and the photon energy dependence of the intensity of photoemission from the surface state are determined. The treatment of inelastic scattering by the optical potential within the one-step theory perfectly describes the surface sensitivity of the photoemission from Al(100) for energies up to 100 eV.