X-ray Standing Wave Technique Research Articles

Atypical magnetism in Pt/MgO/FeCoB/Pt waveguide structure by exchanging the order of MgO and FeCoB layers

Interfaces in FeCoB/MgO/FeCoB magnetic tunnel junction play a vital role in controlling their magnetic and transport properties for various applications in spintronics and magnetic recording media. In this work, interface structures of a few nm thick FeCoB layers in FeCoB/MgO and MgO/FeCoB bilayers are comprehensively studied using x-ray standing waves (XSW) generated by depositing bilayers between Pt waveguide structures. High interface selectivity of nuclear resonance scattering (NRS) under the XSW technique allowed to measure structure and magnetism at the two interfaces, namely FeCoB-on-MgO and MgO-on-FeCoB, yielding an interesting result that electron density and hyperfine fields are not symmetric at both interfaces. The formation of a high-density FeCoB layer at the MgO/FeCoB (FeCoB-on-MgO) interface with an increased hyperfine field (∼34.65 T) is attributed to the increasing volume of FeCo at the interface due to boron diffusion from 57FeCoB to the MgO layer. Furthermore, it caused unusual angular-dependent magnetic properties in MgO/FeCoB bilayer, whereas FeCoB/MgO is magnetically isotropic. In contrast to the literature, where the unusual angular dependent in FeCoB based system is explained in terms of in-plane magnetic anisotropy, present findings attributed the same to the interlayer exchange coupling between bulk and interface layer within the FeCoB layer.

Interface-resolved study of magnetism in MgO/FeCoB/MgO trilayers using x-ray standing wave techniques

Interfaces in the MgO-FeCoB-MgO trilayer have been studied with grazing incident nuclear resonance scattering (GINRS) using the x-ray standing waves (XSW) technique. High depth selectivity of the present method allows one to measure magnetism and structure at the two interfaces of FeCoB, namely, FeCoB-on-MgO and MgO-on-FeCoB, independently, yielding an intriguing result that both interfaces are not symmetric. A high-density layer with an increased magnetic hyperfine field at the FeCoB-on-MgO interface suggests different growth mechanisms at the two interfaces. The azimuthal angle-dependent magneto-optic Kerr effect measurements reveal the presence of unusual uniaxial magnetic anisotropy (UMA) in the trilayer. An in-situ temperature-dependent study discovered that this UMA systematically reduces with temperature. The trilayer becomes isotropic at 450C with an order-of-magnitude increase in coercivity. The asymmetry at the interfaces is, in turn, explained by boron diffusion from the FeCoB interface layer into the nearby MgO layer. Stress-induced UMA is observed in the boron-deficient FeCoB layer, superimposed with the bulk FeCoB layer, and found to be responsible for unusual UMA. The temperature-dependent variation in the UMA and coercivity can be understood in terms of variations in the internal stresses and coupling between FeCoB bulk and the interface layer.

Vertical structure of Sb-intercalated quasifreestanding graphene on SiC(0001)

Using the normal incidence x-ray standing wave technique as well as low energy electron microscopy we have investigated the structure of quasi-freestanding monolayer graphene (QFMLG) obtained by intercalation of antimony under the $\left(6\sqrt{3}\times6\sqrt{3}\right)R30^\circ$ reconstructed graphitized 6H-SiC(0001) surface, also known as zeroth-layer graphene. We found that Sb intercalation decouples the QFMLG well from the substrate. The distance from the QFMLG to the Sb layer almost equals the expected van der Waals bonding distance of C and Sb. The Sb intercalation layer itself is mono-atomic, flat, and located much closer to the substrate, at almost the distance of a covalent Sb-Si bond length. All data is consistent with Sb located on top of the uppermost Si atoms of the SiC bulk.

Boron nitride on SiC(0001)

The promising properties of heterostructures of 2D materials call for scalable sample production via epitaxy. The authors focus on surface structures obtained in a surfactant atmosphere in which a boron nitride template layer forms on SiC(0001). Remarkably, they find that this template is a hexagonal B${}_{x}$N${}_{y}$ layer, but not high-quality hBN. Experiments with the normal-incidence x-ray standing wave technique and spot-profile analysis low-energy electron diffraction reveal the $R{0}^{\ensuremath{\circ}}$ orientation of the layer, the presence of an unexpected boron buffer layer, and the interlayer distances with sub-Angstrom precision.

Growth, domain structure, and atomic adsorption sites of hBN on the Ni(111) surface

One of the most important functionalities of the atomically thin insulator hexagonal boron nitride (hBN) is its ability to chemically and electronically decouple functional materials from highly reactive surfaces. It is therefore of utmost importance to uncover its structural properties on surfaces on an atomic and mesoscopic length scale. In this paper, we quantify the relative coverages of structurally different domains of a hBN layer on the Ni(111) surface using low-energy electron microscopy and the normal incidence x-ray standing wave technique. We find that hBN nucleates on defect sites of the Ni(111) surface and predominantly grows in two epitaxial domains that are rotated by ${60}^{\ensuremath{\circ}}$ with respect to each other. The two domains reveal identical adsorption heights, indicating a similar chemical interaction strength with the Ni(111) surface. The different azimuthal orientations of these domains originate from different adsorption sites of N and B. We demonstrate that the majority ($\ensuremath{\approx}70%$) of hBN domains exhibit a $(\mathrm{N},\mathrm{B})=(\mathrm{top},\mathrm{fcc})$ adsorption site configuration while the minority ($\ensuremath{\approx}30%$) show a $(\mathrm{N},\mathrm{B})=(\mathrm{top},\mathrm{hcp})$ configuration. Our study hence underlines the crucial role of the atomic adsorption configuration in the mesoscopic domain structures of in situ fabricated two-dimensional materials on highly reactive surfaces.

Surfactant-Mediated Epitaxial Growth of Single-Layer Graphene in an Unconventional Orientation on SiC.

We report the use of a surfactant molecule during the epitaxy of graphene on SiC(0001) that leads to the growth in an unconventional orientation, namely R0° rotation with respect to the SiC lattice. It yields a very high-quality single-layer graphene with a uniform orientation with respect to the substrate, on the wafer scale. We find an increased quality and homogeneity compared to the approach based on the use of a preoriented template to induce the unconventional orientation. Using spot profile analysis low-energy electron diffraction, angle-resolved photoelectron spectroscopy, and the normal incidence x-ray standing wave technique, we assess the crystalline quality and coverage of the graphene layer. Combined with the presence of a covalently bound graphene layer in the conventional orientation underneath, our surfactant-mediated growth offers an ideal platform to prepare epitaxial twisted bilayer graphene via intercalation.

Vertical bonding distances and interfacial band structure of PTCDA on a Sn-Ag surface alloy

Molecular materials enable a vast variety of functionalities for novel electronic and spintronic devices. The unique possibility to alter or substitute organic molecules or metallic substrates offers the opportunity to modify and optimize interfacial properties for almost any desired field of application. For this reason, we extend the successful approach to control molecular interfaces by surface alloying. We present a comprehensive characterization of the structural and electronic properties of the interface formed between the prototypical molecule PTCDA and a Sn-Ag surface alloy grown on an Ag(111) single crystal surface. We monitor the changes of adsorption height of the surface alloy atoms and electronic valence band structure upon adsorption of one layer of PTCDA using the normal incidence x-ray standing wave technique in combination with momentum-resolved photoelectron spectroscopy. We find that the vertical buckling and the surface band structure of the SnAg$_2$ surface alloy is not altered by the adsorption of one layer of PTCDA, in contrast to our recent study of PTCDA on a PbAg$_2$ surface alloy [Phys. Rev. Lett. 117, 096805 (2016)] . In addition, the vertical adsorption geometry of PTCDA and the interfacial energy level alignment indicate the absence of any chemical interaction between the molecule and the surface alloy. We attribute the different interactions at these PTCDA/surface alloy interfaces to the presence or absence of local $\sigma$-bonds between the PTCDA oxygen atoms and the surface atoms. Combining our findings with results from literature, we are able to propose an empiric rule for engineering the surface band structure of alloys by adsorption of organic molecules.

X-ray standing waves reveal lack of OH termination at hydroxylated ZnO(0001) surfaces

The vertical adsorption distances of the planar conjugated organic molecule 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) on hydroxylated ZnO(0001), determined with the x-ray standing wave technique (XSW), are at variance with adsorption geometries simulated with density functional theory for surface-structure models that consider terminating OH, whereas good agreement is found for PTCDI in direct contact with the topmost Zn layer. The consequential assignment of OH to subsurface sites is supported by additional, independent XSW and energy scanned photoelectron diffraction data and calls for a reconsideration of the prevalent surface models with important implications for the understanding of ZnO(0001) surfaces.

Heteromolecular Bilayers on a Weakly Interacting Substrate: Physisorptive Bonding and Molecular Distortions of Copper-Hexadecafluorophthalocyanine.

Heteromolecular bilayers of π-conjugated organic molecules on metals, considered as model systems for more complex thin film heterostructures, are investigated with respect to their structural and electronic properties. By exploring the influence of the organic-metal interaction strength in bilayer systems, we determine the molecular arrangement in the physisorptive regime for copper-hexadecafluorophthalocyanine (F16CuPc) on Au(111) with intermediate layers of 5,7,12,14-pentacenetetrone and perylene-3,4,9,10-tetracarboxylic diimide. Using the X-ray standing wave technique to distinguish the different molecular layers, we show that these two bilayers are ordered following their deposition sequence. Surprisingly, F16CuPc as the second layer within the heterostructures exhibits an inverted intramolecular distortion compared to its monolayer structure.

Lifting Epitaxial Graphene by Intercalation of Alkali Metals

We studied the effect of alkali metal intercalation (Cs and Li) on the geometry of graphene on Ir(111) using the X-ray standing waves technique. For both alkali metals, the increase in the mean hei...

Energy-level alignment at strongly coupled organic–metal interfaces

Energy-level alignment at organic–metal interfaces plays a crucial role for the performance of organic electronic devices. However, reliable models to predict energetics at strongly coupled interfaces are still lacking. We elucidate contact formation of 1,2,5,6,9,10-coronenehexone (COHON) to the (1 1 1)-surfaces of coinage metals by means of ultraviolet photoelectron spectroscopy, x-ray photoelectron spectroscopy, the x-ray standing wave technique, and density functional theory calculations. While for low COHON thicknesses, the work-functions of the systems vary considerably, for thicker organic films Fermi-level pinning leads to identical work functions of 5.2 eV for all COHON-covered metals irrespective of the pristine substrate work function and the interfacial interaction strength.

Surface structure determination by x-ray standing waves at a free-electron laser

We demonstrate the structural sensitivity and accuracy of the x-ray standing wave technique at a high repetition rate free-electron laser, FLASH at DESY in Hamburg, by measuring the photoelectron yield from the surface SiO2 of Mo/Si multilayers. These experiments open up the possibility to obtain unprecedented structural information of adsorbate and surface atoms with picometer spatial and femtosecond temporal resolution. This technique will substantially contribute to a fundamental understanding of chemical reactions at catalytic surfaces and the structural dynamics of superconductors.

X-ray standing wave technique with spatial resolution: In-plane characterization of surfaces and interfaces by full-field x-ray fluorescence imaging

The present paper describes a powerful extension of the x-ray standing-wave technique that combines it with the capability of full-field x-ray fluorescence imaging, so that the impurity depth profiles at all different parts of a nanolayer material can be measured in parallel. The imaging capability improves the robustness and reliability of the x-ray standing-wave technique in investigating inhomogeneous two-dimensional materials and soft interfaces. It can also visualize the three-dimensional element-specific structure at a buried interface with a depth resolution at the nanometer level.

Modifying the geometric and electronic structure of hexagonal boron nitride on Ir(111) by Cs adsorption and intercalation

Epitaxial hexagonal boron nitride on Ir(111) is significantly modified by adsorption and intercalation of alkali-metal atoms. Regarding geometry, intercalation lifts the two-dimensional layer from its substrate and reduces the characteristic corrugation imprinted by direct contact with the metal substrate. Moreover, the presence of charged species in close proximity to the hexagonal boron nitride (hBN) layer strongly shifts the electronic structure (valence bands and core levels). We used scanning tunneling microscopy, low-energy electron diffraction, x-ray photoelectron spectroscopy (XPS), and the x-ray standing wave technique to study changes in the atomic structure induced by Cs adsorption and intercalation. Depending on the preparation, the alkali-metal atoms can be found on top and underneath the hexagonal boron nitride in ordered and disordered arrangements. Adsorbed Cs does not change the morphology of hBN/Ir(111) significantly, whereas an intercalated layer of Cs decouples the two-dimensional sheet and irons out its corrugation. XPS and angle-resolved photoelectron spectroscopy reveal a shift of the electronic states to higher binding energies, which increases with increasing density of the adsorbed and intercalated Cs. In the densest phase, Cs both intercalates and adsorbs on hBN and shifts the electronic states of hexagonal boron nitride by 3.56 eV. As this shift is not sufficient to move the conduction band below the Fermi energy, the electronic band gap must be larger than 5.85 eV.

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.

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.

Photoelectron spectroscopy of transition metal oxide interfaces

In the present paper we review applications of the photoelectron spectroscopy (PES) technique to the investigation of transition metal oxide (TMO) interfaces. We summarize very briefly some of the principle, specific characteristics of TMOs. Because of the buried nature of the interfaces, the photoelectrons must penetrate certain thicknesses of material, which is easier with higher kinetic energies in the keV range. Thus, we also briefly summarize some of the hallmarks of hard X-ray photoelectron spectroscopy (HAXPES), before presenting four explicit samples of the analysis of TMO interfaces: The LaAlO3/SrTiO3 (0 0 1) interface, which had attracted attention because of the discovery of a sheet of high mobility electrons below the thin layer of LaAlO3; superlattices of the two insulators CaCuO2 and SrTiO3, which can be prepared to become superconducting at about 40 K; epitaxial films of the 90 K superconductor GdBa2Cu3O7−δ on NdGaO3; and finally the analysis of the nucleation of the 90 K superconductor YBa2Cu3O7−δ on SrTiO3 (0 0 1). The latter two cases of the investigation of the superconducting films are examples of photoelectron spectroscopy by X-ray standing wave (XSW) excitation. Because of this, the bare essential features of the XSW technique are also briefly reviewed.