Standing Wave Technique Research Articles

TiO2 as diffusion barrier at Co/Alq3 interface studied by x-ray standing wave technique

Nano-scale diffusion at the interfaces in organic spin valve thin films plays a vital role in controlling the performance of magneto-electronic devices. In the present work, it is shown that a thin layer of titanium dioxide at the interface of Co/Alq3 can act as a good diffusion barrier. The buried interfaces of Co/Alq3/Co organic spin valve thin film has been studied using x-ray standing waves technique. A planar waveguide is formed with Alq3 layer forming the cavity and Co layers as the walls of the waveguide. Precise information about diffusion of Co into Alq3 is obtained through excitation of the waveguide modes. It is found that the top Co layer diffuses deep into the Alq3 resulting in incorporation of 3.1% Co in the Alq3 layer. Insertion of a 1.7 nm thick barrier layer of TiO2 at Co/Alq3 interface results in a drastic reduction in the diffusion of Co into Alq3 to a value of only 0.4%. This suggests a better performance of organic spin valve with diffusion barrier of TiO2.

Widefield standing wave microscopy of red blood cell membrane morphology with high temporal resolution.

We report the first demonstration of widefield standing wave (SW) microscopy of fluorescently labelled red blood cells at high speeds that allow for the rapid imaging of membrane deformations. Using existing and custom MATLAB functions, we also present a method to generate 2D and 3D reconstructions of the SW data for improved visualization of the cell. We compare our technique with standard widefield epifluorescence imaging and show that the SW technique not only reveals more topographical information about the specimen but does so without increasing toxicity or the rate of photobleaching and could make this a powerful technique for the diagnosis or study of red blood cell morphology and biomechanical characteristics.

Orientation-Dependent Work-Function Modification Using Substituted Pyrene-Based Acceptors.

The adsorption of molecular acceptors is a viable method for tuning the work function of metal electrodes. This, in turn, enables adjusting charge injection barriers between the electrode and organic semiconductors. Here, we demonstrate the potential of pyrene-tetraone (PyT) and its derivatives dibromopyrene-tetraone (Br-PyT) and dinitropyrene-tetraone (NO2-PyT) for modifying the electronic properties of Au(111) and Ag(111) surfaces. The systems are investigated by complementary theoretical and experimental approaches, including photoelectron spectroscopy, the X-ray standing wave technique, and density functional theory simulations. For some of the investigated interfaces the trends expected for Fermi-level pinning are observed, i.e., an increase of the metal work function along with increasing molecular electron affinity and the same work function for Au and Ag with monolayer acceptor coverage. Substantial deviations are, however, found for Br-PyT/Ag(111) and NO2-PyT/Ag(111), where in the latter case an adsorption-induced work function increase of as much as 1.6 eV is observed. This behavior is explained as arising from a face-on to edge-on reorientation of molecules in the monolayer. Our calculations show that for an edge-on orientation much larger work-function changes can be expected despite the prevalence of Fermi-level pinning. This is primarily ascribed to a change of the electron affinity of the adsorbate layer that results from a change of the molecular orientation. This work provides a comprehensive understanding of how changing the molecular electron affinity as well as the adsorbate structure impacts the electronic properties of electrodes.

Non-dipolar effects in photoelectron-based normal incidence X-ray standing wave experiments

The normal incidence X-ray standing waves technique is one of the most well-established methods for investigating the geometric structure at interfaces and surfaces. It is able to measure vertical positions and distances of individual atomic species with very high precision (typically <0.02Å). These data not only yield valuable structural information, but also represent an excellent benchmark for density functional theory and ab initio calculations. Non-dipolar effects are well known to strongly affect the result, in particular when light elements are involved. A correction mechanism for these effects is established, but in its commonly-used form it is based on one essential restriction, namely the assumption of perfect normal incidence of the X-rays with respect to the relevant lattice planes of the crystal. Here, we show that small deviations from normal incidence, as they are unavoidable in typical experimental setups, lead to significant systematic errors in the NIXSW results. The magnitude of this effect depends on the specific conditions in a non-linear way and may reach up to 5%, corresponding to several tenths of an Ångström in the adsorption height. We present a straightforward way of accounting for this effect, and demonstrate that recording the photoelectron yield in an angular-resolved mode is indispensable, since the correction parameters strongly depend on the electron take-off angle.

Adsorption heights and bonding strength of organic molecules on a Pb-Ag surface alloy

The understanding of the fundamental geometric and electronic properties of metal-organic hybrid interfaces is a key issue on the way to improving the performance of organic electronic and spintronic devices. Here, we studied the adsorption heights of copper-II-phthalocyanine (CuPc) and 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) on a ${\mathrm{Pb}}_{1}{\mathrm{Ag}}_{2}$ surface alloy on Ag(111) using the normal-incidence x-ray standing waves technique. We find a significantly larger adsorption height of both molecules on the Pb-Ag surface alloy compared to the bare Ag(111) surface which is caused by the larger size of Pb. This increased adsorption height suppresses the partial chemical interaction of both molecules with Ag surface atoms. Instead, CuPc and PTCDA molecules bond only to the Pb atoms with different interaction strength ranging from a van der Waals--like interaction for CuPc to a weak chemical interaction with additional local bonds for PTCDA. The different adsorption heights for CuPc and PTCDA on ${\mathrm{Pb}}_{1}{\mathrm{Ag}}_{2}$ are the result of local site-specific molecule-surface bonds mediated by functional molecular groups and the different charge donating and accepting character of CuPc and PTCDA.

Structural and Electronic Properties of Nitrogen-Doped Graphene.

We investigate the structural and electronic properties of nitrogen-doped epitaxial monolayer graphene and quasifreestanding monolayer graphene on 6H-SiC(0001) by the normal incidence x-ray standing wave technique and by angle-resolved photoelectron spectroscopy supported by density functional theory simulations. With the location of various nitrogen species uniquely identified, we observe that for the same doping procedure, the graphene support, consisting of substrate and interface, strongly influences the structural as well as the electronic properties of the resulting doped graphene layer. Compared to epitaxial graphene, quasifreestanding graphene is found to contain fewer nitrogen dopants. However, this lack of dopants is compensated by the proximity of nitrogen atoms at the interface that yield a similar number of charge carriers in graphene.

Approaching truly freestanding graphene: the structure of hydrogen-intercalated graphene on 6H-SiC(0001).

We measure the adsorption height of hydrogen-intercalated quasifreestanding monolayer graphene on the (0001) face of 6H silicon carbide by the normal incidence x-ray standing wave technique. A density functional calculation for the full (6√3×6√3)-R30° unit cell, based on a van der Waals corrected exchange correlation functional, finds a purely physisorptive adsorption height in excellent agreement with experiments, a very low buckling of the graphene layer, a very homogeneous electron density at the interface, and the lowest known adsorption energy per atom for graphene on any substrate. A structural comparison to other graphenes suggests that hydrogen-intercalated graphene on 6H-SiC(0001) approaches ideal graphene.

Pentacene on Ag(111): Correlation of Bonding Distance with Intermolecular Interaction and Order

We report coverage and temperature dependent bonding distances of vacuum-sublimed pentacene (PEN) submonolayers on Ag(111) obtained by the X-ray standing wave technique. The average vertical bonding distance of 2.98 Å at room temperature for 0.50 monolayer (ML) coverage increases to 3.12 Å for 0.75 ML due to competing intermolecular and adsorbate-substrate interactions. In contrast, decreasing the temperature from 295 to 145 K does not impact the bonding distance despite the concomitant transition from a "liquidlike" to an ordered molecular arrangement. In combination with X-ray photoelectron spectroscopy results, we could identify "soft chemisorption" with a subtle balance of molecule-molecule and substrate-molecule interactions as being responsible for this special adsorption behavior. Thus our study sheds light not only on the interface between PEN and Ag(111), but also on fundamental adsorption processes of organic adsorbates on metals in the context of chemi- and physisorption.

Hard x-ray photoemission spectroscopy on the trilayer system MgO/Au/Fe using standing-wave excitation

The trilayer system MgO/Au monolayer/Fe was investigated by hard x-ray photoemission experiments in combination with the standing-wave technique. The insertion of the Au layer into the Fe/MgO tunnel junction provides an additional handle to influence the properties of the interface. The recently explored method of standing-wave excited hard x-ray photoemission was used to investigate both the structural properties and chemical states of the interfacial layers in one experiment. The results show that the Au monolayer does not grow as a closed layer, but intermixes strongly with the Fe below. This behaviour results in a very sharp interface between the Au/Fe and the MgO layer on top. However, the XPS spectra show no hint for a formation of FeO at the interface.

Bessel standing wave technique for optical induction of complex refractive lattice structures in photorefractive materials

A novel counter-propagating Bessel beam technique is suggested and realized for optical formation of complex two-dimensional (2D) refractive lattice structures in photorefractive materials. The 2D complex lattices optically induced by the suggested method are a combination of annular and planar gratings with refractive index modulation in the radial direction in the transverse plane and the in axial direction along the optical beam propagation. The recording of the lattices is performed by 532 nm and 633 nm laser beams. The counter-propagating beam geometry builds up the Bessel standing wave with periodic annular structure in each anti-node. The refractive lattices are recorded in Z- and Y-cut 2 mm thick photorefractive lithium niobate crystals singly doped by Fe and doubly doped by Fe and Cu. The readout of recorded lattices is performed by Gaussian red and green probe laser beams. The direct observation of recorded lattices by optical phase microscope is also performed. The formed photonic structures have a period of 10 ± 1 m in the radial direction and a half-wavelength standing wave period of 266 nm or 316.5 nm in the axial direction. The diffraction efficiency of the photonic lattices reaches up to 25%.

Ascertaining the nanocluster formation within an ion-irradiated Pt/Ni/C multi-trilayer with X-ray absorption spectroscopy

In this work nanoclusters formed in a Pt/Ni/C multi-trilayer by the ion-irradiated method of synthesis are characterized. In particular, an attempt to understand the role of interfaces in the synthesis is made. With this objective, ion-irradiation-induced structural changes in a Pt/Ni/C multi-trilayer using X-ray absorption spectroscopy (at the Ni K-edge) in conjunction with the X-ray standing-wave technique are investigated. The XANES analysis identifies chemical binding at pristine Ni/C and Ni/Pt interfaces, in contrast with physical adsorption at the Pt/C interface. The chemical nature of the interfaces determines their relative stability with respect to irradiation and controls the extent of metallic diffusion. The most interesting structural change, upon irradiation, is the disruption of the Pt/C interface and subsequent migration of Pt atoms towards pre-diffused Ni atoms within the C layer, leading to the formation of Ni-centered Ni-Pt bimetallic nanoclusters (with Ni:Pt = 60:40). These clusters are highly disordered beyond their nearest neighbor and find wide-scale applications as, for example, magnetic devices etc. The implications of these findings on the design goals are discussed.

Fe diffusion in amorphous Si studied using x-ray standing wave technique

Diffusion of Fe impurity in amorphous Si at the intermediate concentration range of 25 at.% Fe has been studied. A combination of x-ray standing wave technique and secondary ion mass spectrometry provides unambiguous determination of the concentration profiles of the constituent species with sub-nanometer depth resolution. X-ray standing waves are generated using total external reflection from an underlying W layer. It is found that up to 573 K, Fe diffusivity is less than 10−23m2/s. This is in stark contrast to isolated Fe impurity diffusion in Si or to the interdiffusion at Fe/Si interface, which are orders of magnitude higher. An interesting phenomenon is observed, when a Pt buffer layer is used instead of W for generating standing waves: With thermal annealing, as the Pt atoms move into Si layer and cross the marker layer containing Fe atoms, Fe atoms also move along. This results in an upwards shift of the concentration profile of Fe.

Graphene on Ir(111): Physisorption with Chemical Modulation

The nonlocal van der Waals density functional approach is applied to calculate the binding of graphene to Ir(111). The precise agreement of the calculated mean height h = 3.41 Å of the C atoms with their mean height h = (3.38±0.04) Å as measured by the x-ray standing wave technique provides a benchmark for the applicability of the nonlocal functional. We find bonding of graphene to Ir(111) to be due to the van der Waals interaction with an antibonding average contribution from chemical interaction. Despite its globally repulsive character, in certain areas of the large graphene moiré unit cell charge accumulation between Ir substrate and graphene C atoms is observed, signaling a weak covalent bond formation.

Hard x-ray photoemission using standing-wave excitation applied to the MgO/Fe interface

Many applications in electronics and spintronics rely on interfaces, which are buried a few nanometers deep and thus are hardly accessible in real devices except for invasive techniques. Here, we report on hard x-ray photoemission spectroscopy combined with the x-ray standing-wave technique as a noninvasive method to access buried interfaces with a depth resolution of a few \AA{} and enhanced interface sensitivity. Within these experiments, the film thicknesses and also the thicknesses of the intermixing layers are determined. We extend the data analysis scheme previously developed for soft x-rays to the hard x-ray regime and apply the method to buried epitaxial Fe/MgO interfaces, which play a crucial role in magnetic tunnel junctions and their applications. It was found that there was no detectable intermixing or reaction of the Fe and MgO layers at the interface.

Orientational Ordering of Nonplanar Phthalocyanines on Cu(111): Strength and Orientation of the Electric Dipole Moment

In order to investigate the orientational ordering of molecular dipoles and the associated electronic properties, we studied the adsorption of chlorogallium phthalocyanine molecules (GaClPc, Pc=C32N8H16(-2) on Cu(111) by using the x-ray standing wave technique, photoelectron spectroscopy, and quantum mechanical calculations. We find that for submonolayer coverages on Cu(111) the majority of GaClPc molecules adsorb in a Cl-down configuration by forming a covalent bond to the substrate. For bilayer coverages the x-ray standing wave data indicate a coexistence of the Cl-down and Cl-up configurations on the substrate. The structural details established for both cases and supplementary calculations of the adsorbate system allow us to analyze the observed change of the work function.

Standing wave measurements in tubes.

speed measurements have been made using a standing wave technique for possible inclusion in Project Listen Up! In a previous paper [S. A. Cheyne and W. C. McDermott, Sound speed measurements in air using a variable sound source and tubes, J. Acoust. Soc. Am. 125, 2625 (2009)], sound speed measurements in tubes were made using traditional standing wave techniques. A low‐cost variable frequency sound source was constructed and used to produce the sound waves. Resonances in the source itself made it difficult to make reliable measurements. Also, it was difficult to detect the tube resonances by simply listening to the resonances with one's ear. In this work, we have improved the quality of the apparatus to make it easier to generate and detect tube resonances.

Fourier transform imaging of impurities in the unit cells of crystals: Mn in GaAs

The lattice sites of Mn in ferromagnetic (Ga,Mn)As thin films were imaged using the x-ray standing wave technique. The model-free images, obtained straightforwardly by Fourier inversion, disclose immediately that the Mn mostly substitutes the Ga with a small fraction residing on minority sites. The images further reveal variations in the Mn concentrations of the different sites upon post-growth treatments. Subsequent model refinement based on the directly reconstructed images resolves with high precision the complete Mn site distributions. It is found that post-growth annealing increases the fraction of substitutional Mn at the expense of interstitial Mn whereas hydrogenation has little influence on the Mn site distribution. Our study offers an element-specific high-resolution imaging approach for accurately determining the detailed site distributions of dilute concentrations of atoms in crystals.

Valence band photoelectron emission of analyzed with X-ray standing waves

Abstract The X-ray standing wave technique is used for a site specific analysis of the valence band of SrTiO 3 . The determined partial photoelectron yields reveal the hybridization of metal and oxygen derived states. Fitting ab initio calculated density of states to the data yields solid state photoelectric cross sections, which are much larger than for corresponding atomic states for Ti 4 s and Sr 5 s . Valence band features are significantly broader than predicted by single particle band structure calculations in particular for oxygen derived states. This can, at least in part, be explained by correlation effects.

Ab Initio Calculation of the Dispersion Interaction between a Polyaromatic Molecule and a Noble Metal Substrate: PTCDA on Ag(110)

The geometry of PTCDA adsorbed on a (110)-oriented silver crystal is optimized on a finite metal cluster used as a rigid substrate. In a comparison between second-order Moller−Plesset perturbation theory (MP2) and density functional theory (DFT), we find pronounced differences; MP2 gives a nearly flat adsorbate, in agreement with the geometries deduced from X-ray standing wave studies on similar substrates, whereas the lack of dispersion interactions in DFT results in a strongly bent geometry. In MP2, the van-der-Waals attraction counterbalances the overlap repulsion, resulting in an average height of the PTCDA adsorbate above the topmost substrate layer of 2.68 A for C atoms, comparing favorably with recent measurements based on X-ray standing wave techniques. The carboxylic oxygens interact more strongly with the substrate than the anhydride groups, so that we predict a height difference of 0.13 A between both types of oxygen atoms.

X-ray standing waves and hard X-ray photoelectron spectroscopy at the insertion device beamline ID32

Investigations on the geometrical structure, chemical composition and electronic properties of surfaces and interfaces are performed on beamline ID32 at the ESRF. It is a high resolution beamline covering the photon energy range 1.4–30 keV optimized for X-ray standing wave, surface X-ray diffraction, and hard X-ray photoelectron spectroscopy experiments. Fresnel zone plates and compound refractive lens systems are used to focus the monochromatic beam. After outlining the principles of X-ray standing wave measurements the unique features of the ID32 beamline are described. Future developments are discussed and finally some selected examples illustrating the advantages of combining the X-ray standing wave technique with hard X-ray photoelectron spectroscopy are presented.