Real-Time Observation of Temperature-Induced Surface Nanofaceting in M-Plane α-Al2O3.

The spontaneous crystal surface reconstruction of M-plane α-Al2O3 is employed for nanopatterning and nanofabrication in various fields of research including, among others, magnetism, superconductivity, and optoelectronics. In this reconstruction process the crystalline surface transforms from a planar morphology to one with a nanoscale ripple patterning. However, the high sample temperature required to induce surface reconstruction made in situ studies of the process seem unfeasible. The kinetics of ripple pattern formation therefore remained uncertain, and thus production of templates for nanofabrication could not advance beyond a trial-and-error stage. We present an approach combining in situ real-time grazing incidence small-angle X-ray scattering experiments (GISAXS) with model-based analysis and with ex situ atomic force microscopy (AFM) to observe this morphological transition in great detail. Our approach provides time-resolved information about all relevant morphological parameters required to trace the surface topography on the nanometer scale during reconstruction, i.e., the time dependence of the pattern wavelength, the ripple length, width, and height, and thus their facet angles. It offers a comprehensive picture of this process exemplified by a M-plane α-Al2O3 surface annealed at 1325 °C for 930 min. Fitting the model parameters to the experimental GISAXS data revealed a Johnson-Mehl-Avrami-Kolmogorov type of behavior for the pattern wavelength and a predominantly linear time dependence of the other parameters. In this case the reconstruction resulted in a crystalline surface fully patterned with asymmetric ripple-shaped nanostructures of 75 nm periodicity, 15 nm in height, and 630 nm in length. By elucidating the time dependence of these morphological parameters, this study shows a powerful way to significantly advance the predictability of annealing outcome and thus to efficiently customize nanopatterned α-Al2O3 templates for improved nanofabrication routines.

Evolution of the magnetic hyperfine field profiles in an ion-irradiated Fe60Al40 film measured by nuclear resonant reflectivity.

Nuclear resonant reflectivity (NRR) from an Fe60Al40 film was measured using synchrotron radiation at several grazing angles near the critical angle of total external reflection. Using laterally resolved measurements after irradiation with 20 keV Ne+ ions of gradually varying fluence of 0-3.0 × 1014 ions cm-2, the progressive creation of the ferromagnetic A2 phase with increasing ion fluence was confirmed. The observed depth selectivity of the method has been explained by application of the standing wave approach. From the time spectra of the nuclear resonant scattering in several reflection directions the depth profiles for different hyperfine fields were extracted. The results show that the highest magnetic hyperfine fields (∼18-23 T) are initially created in the central part of the film and partially at the bottom interface with the SiO2 substrate. The evolution of the ferromagnetic onset, commencing at a fixed depth within the film and propagating towards the interfaces, has been directly observed. At higher fluence (3.0 × 1014 ions cm-2) the depth distribution of the ferromagnetic fractions became more homogeneous across the film depth, in accordance with previous results.

Novel Tunnel Magnetoresistive Sensor Functionalities via Oblique-Incidence Deposition.

Controlling the magnetic properties of ultrathin films remains one of the main challenges to the further development of tunnel magnetoresistive (TMR) device applications. The magnetic response in such devices is mainly governed by extending the primary TMR trilayer with the use of suitable contact materials. The transfer of magnetic anisotropy to ferromagnetic electrodes consisting of CoFeB layers results in a field-dependent TMR response, which is determined by the magnetic properties of the CoFeB as well as the contact materials. We flexibly apply oblique-incidence deposition (OID) to introduce arbitrary intrinsic in-plane anisotropy profiles into the magnetic layers. The OID-induced anisotropy shapes the magnetic response and eliminates the requirement of additional magnetic contact materials. Functional control is achieved via an adjustable shape anisotropy that is selectively tailored for the ultrathin CoFeB layers. This approach circumvents previous limitations on TMR devices and allows for the design of new sensing functionalities, which can be precisely customized to a specific application, even in the high field regime. The resulting sensors maintain the typical TMR signal strength as well as a superb thermal stability of the tunnel junction, revealing a striking advantage in functional TMR design using anisotropic interfacial roughness.

Advanced X-ray polarimeter design for nuclear resonant scattering.

This work presents the improvements in the design and testing of polarimeters based on channel-cut crystals for nuclear resonant scattering experiments at the 14.4 keV resonance of 57Fe. By using four asymmetric reflections at asymmetry angles of α1 = -28°, α2 = 28°, α3 = -28° and α4 = 28°, the degree of polarization purity could be improved to 2.2 × 10-9. For users, an advanced polarimeter without beam offset is now available at beamline P01 of the storage ring PETRA III.

Coherent control of collective nuclear quantum states via transient magnons.

Ultrafast and precise control of quantum systems at x-ray energies involves photons with oscillation periods below 1 as. Coherent dynamic control of quantum systems at these energies is one of the major challenges in hard x-ray quantum optics. Here, we demonstrate that the phase of a quantum system embedded in a solid can be coherently controlled via a quasi-particle with subattosecond accuracy. In particular, we tune the quantum phase of a collectively excited nuclear state via transient magnons with a precision of 1 zs and a timing stability below 50 ys. These small temporal shifts are monitored interferometrically via quantum beats between different hyperfine-split levels. The experiment demonstrates zeptosecond interferometry and shows that transient quasi-particles enable accurate control of quantum systems embedded in condensed matter environments.

Incoherent Nuclear Resonant Scattering from a Standing Spin Wave.

We introduce a method to study the spatial profiles of standing spin waves in ferromagnetic microstructures. The method relies on Nuclear Resonant Scattering of 57Fe using a microfocused beam of synchrotron radiation, the transverse coherence length of which is smaller than the length scale of lateral variations in the magnetization dynamics. Using this experimental method, the nuclear resonant scattering signal due to a confined spin wave is determined on the basis of an incoherent superposition model. From the fits of the Nuclear Resonant Scattering time spectra, the precessional amplitude profile across the stripe predicted by an analytical model is reconstructed. Our results pave the way for studying non-homogeneous dynamic spin configurations in microstructured magnetic systems using nuclear resonant scattering of synchrotron light.

Nuclear Resonant Surface Diffraction of Synchrotron Radiation.

Nuclear resonant x-ray diffraction in grazing incidence geometry is used to determine the lateral magnetic configuration in a one-dimensional lattice of ferromagnetic nanostripes. During magnetic reversal, strong nuclear superstructure diffraction peaks appear in addition to the electronic ones due to an antiferromagnetic order in the nanostripe lattice. We show that the analysis of the angular distribution together with the time dependence of the resonantly diffracted x rays reveals surface spin structures with very high sensitivity. This scattering technique provides unique access to laterally correlated spin configurations in magnetically ordered nanostructures and, in perspective, also to their dynamics.

A luminescent Pt2Fe spin crossover complex.

A heterotrinuclear [Pt2Fe] spin crossover (SCO) complex was developed and synthesized employing a ditopic bridging bpp-alkynyl ligand L and alkynyl coordinated PtII terpy units: [FeII(L-PtII)2]2(BF4)2 (1). We identified two different types of crystals of 1 which differ in their molecular packing and the number of co-crystallized solvent molecules: 1H (1·3.5CH2Cl2 in P1[combining macron]) and 1L (1·10CH2Cl2 in C2/c); while 1L shows a reversible SCO with a transition temperature of 268 K, the analogous compound 1H does not show any SCO and remains blocked in the HS state. The temperature-dependent magnetic properties of 1H and 1L were complementarily studied by Mössbauer spectroscopy. It has been shown that 1L performs thermal spin crossover and that 1L can be excited to a LIESST state. The vibrational properties of 1 were investigated by experimental nuclear resonance vibrational spectroscopy. The experimentally determined partial density of vibrational states (pDOS) was compared to a DFT-based simulation of the pDOS. The vibrational modes of the different components were assigned and visualized. In addition, the photophysical properties of 1 and L-Pt were investigated in the solid state and in solution. The ultrafast transient absorption spectroscopy of 1 in solution was carried out to study the PL quenching channel via energy transfer from photoexcited PtII terpy units to the FeII-moiety.

Uniform metal nanostructures with long-range order via three-step hierarchical self-assembly.

Large-scale nanopatterning is a major issue in nanoscience and nanotechnology, but conventional top-down approaches are challenging because of instrumentation and process complexity while often lacking the desired spatial resolution. We present a hierarchical bottom-up nanopatterning routine using exclusively self-assembly processes: By combining crystal surface reconstruction, microphase separation of copolymers, and selective metal diffusion, we produce monodisperse metal nanostructures in highly regular arrays covering areas of square centimeters. In situ grazing incidence small-angle x-ray scattering during Fe nanostructure formation evidences an outstanding structural order in the self-assembling system and hints at the possibility of sculpting nanostructures using external process parameters. Thus, we demonstrate that bottom-up nanopatterning is a competitive alternative to top-down routines, achieving comparable pattern regularity, feature size, and patterned areas with considerably reduced effort. Intriguing assets of the proposed fabrication approach include the option for in situ investigations during pattern formation, the possibility of customizing the nanostructure morphology, the capacity to pattern arbitrarily large areas with ultrahigh structure densities unachievable by top-down approaches, and the potential to address the nanostructures individually. Numerous applications of self-assembled nanostructure patterns can be envisioned, for example, in high-density magnetic data storage, in functional nanostructured materials for photonics or catalysis, or in surface plasmon resonance-based sensing.

Influence of higher harmonics of the undulator in X-ray polarimetry and crystal monochromator design.

The spectrum of the undulator radiation of beamline P01 at Petra III has been measured after passing a multiple reflection channel-cut polarimeter. Odd and even harmonics up to the 15th order, as well as Compton peaks which were produced by the high harmonics in the spectrum, could been measured. These additional contributions can have a tremendous influence on the performance of the polarimeter and have to be taken into account for further polarimeter designs.

Isoprenoid Biosynthesis in Pathogenic Bacteria: Nuclear Resonance Vibrational Spectroscopy Provides Insight into the Unusual [4Fe-4S] Cluster of the E.†coli LytB/IspH Protein.

The LytB/IspH protein catalyzes the last step of the methylerythritol phosphate (MEP) pathway which is used for the biosynthesis of essential terpenoids in most pathogenic bacteria. Therefore, the MEP pathway is a target for the development of new antimicrobial agents as it is essential for microorganisms, yet absent in humans. Substrate-free LytB has a special [4Fe-4S](2+) cluster with a yet unsolved structure. This motivated us to use synchrotron-based nuclear resonance vibrational spectroscopy (NRVS) in combination with quantum chemical-molecular mechanical (QM/MM) calculations to gain more insight into the structure of substrate-free LytB. The apical iron atom of the [4Fe-4S](2+) is clearly linked to three water molecules. We additionally present NRVS data of LytB bound to its natural substrate, (E)-4-hydroxy-3-methylbut-2-en-1-yl diphosphate (HMBPP) and to the inhibitors (E)-4-amino-3-methylbut-2-en-1-yl diphosphate and (E)-4-mercapto-3-methylbut-2-en-1-yl diphosphate.

Spin precession mapping at ferromagnetic resonance via nuclear resonant scattering of synchrotron radiation.

We probe the spin dynamics in a thin magnetic film at ferromagnetic resonance by nuclear resonant scattering of synchrotron radiation at the 14.4 keV resonance of ^{57}Fe. The precession of the magnetization leads to an apparent reduction of the magnetic hyperfine field acting at the ^{57}Fe nuclei. The spin dynamics is described in a stochastic relaxation model adapted to the ferromagnetic resonance theory by Smit and Beljers to model the decay of the excited nuclear state. From the fits of the measured data, the shape of the precession cone of the spins is determined. Our results open a new perspective to determine magnetization dynamics in layered structures with very high depth resolution by employing ultrathin isotopic probe layers.

Vacuum-assisted generation and control of atomic coherences at x-ray energies.

The control of light-matter interaction at the quantum level usually requires coherent laser fields. But already an exchange of virtual photons with the electromagnetic vacuum field alone can lead to quantum coherences, which subsequently suppress spontaneous emission. We demonstrate such spontaneously generated coherences (SGC) in a large ensemble of nuclei operating in the x-ray regime, resonantly coupled to a common cavity environment. The observed SGC originates from two fundamentally different mechanisms related to cooperative emission and magnetically controlled anisotropy of the cavity vacuum. This approach opens new perspectives for quantum control, quantum state engineering and simulation of quantum many-body physics in an essentially decoherence-free setting.

From atoms to layers: in situ gold cluster growth kinetics during sputter deposition.

The adjustment of size-dependent catalytic, electrical and optical properties of gold cluster assemblies is a very significant issue in modern applied nanotechnology. We present a real-time investigation of the growth kinetics of gold nanostructures from small nuclei to a complete gold layer during magnetron sputter deposition with high time resolution by means of in situ microbeam grazing incidence small-angle X-ray scattering (µGISAXS). We specify the four-stage growth including their thresholds with sub-monolayer resolution and identify phase transitions monitored in Yoneda intensity as a material-specific characteristic. An innovative and flexible geometrical model enables the extraction of morphological real space parameters, such as cluster size and shape, correlation distance, layer porosity and surface coverage, directly from reciprocal space scattering data. This approach enables a large variety of future investigations of the influence of different process parameters on the thin metal film morphology. Furthermore, our study allows for deducing the wetting behavior of gold cluster films on solid substrates and provides a better understanding of the growth kinetics in general, which is essential for optimization of manufacturing parameters, saving energy and resources.

Cobalt nanoparticles growth on a block copolymer thin film: a time-resolved GISAXS study.

Cobalt sputter deposition on a nanostructured polystyrene-block-poly(ethylene oxide), P(S-b-EO), template is followed in real time with grazing incidence small-angle X-ray scattering (GISAXS). The polymer template consists of highly oriented parallel crystalline poly(ethylene oxide) (PEO) domains that are sandwiched between two polystyrene (PS) domains. In-situ GISAXS shows that cobalt atoms selectively decorate the PS domains of the microphase-separated polymer film and then aggregate to form surface metal nanopatterns. The polymer template is acting as a directing agent where cobalt metal nanowires are formed. At high metal load, the characteristic selectivity of the template is lost, and a uniform metal layer forms on the polymer surface. During the early stage of cobalt metal deposition, a highly asymmetric nanoparticles agglomeration is dominating structure formation. The cobalt nanoparticles mobility in combination with the high tendency of the nanoparticles to coalescence and to form immobile large-sized particles at the PS domains are discussed as mechanisms of structure formation.

A new highly automated sputter equipment for in situ investigation of deposition processes with synchrotron radiation.

HASE (Highly Automated Sputter Equipment) is a new mobile setup developed to investigate deposition processes with synchrotron radiation. HASE is based on an ultra-high vacuum sputter deposition chamber equipped with an in-vacuum sample pick-and-place robot. This enables a fast and reliable sample change without breaking the vacuum conditions and helps to save valuable measurement time, which is required for experiments at synchrotron sources like PETRA III at DESY. An advantageous arrangement of several sputter guns, mounted on a rotative flange, gives the possibility to sputter under different deposition angles or to sputter different materials on the same substrate. The chamber is also equipped with a modular sample stage, which allows for the integration of different sample environments, such as a sample heating and cooling device. The design of HASE is unique in the flexibility. The combination of several different sputtering methods like standard deposition, glancing angle deposition, and high pressure sputter deposition combined with heating and cooling possibilities of the sample, the large exit windows, and the degree of automation facilitate many different grazing incidence X-ray scattering experiments, such as grazing incidence small and wide angle X-ray scattering, in one setup. In this paper we describe in detail the design and the performance of the new equipment and present the installation of the HASE apparatus at the Micro and Nano focus X-ray Scattering beamline (MiNaXS) at PETRA III. Furthermore, we describe the measurement options and present some selected results. The HASE setup has been successfully commissioned and is now available for users.

Electromagnetically induced transparency with resonant nuclei in a cavity.

The manipulation of light-matter interactions by quantum control of atomic levels has had a profound impact on optical sciences. Such manipulation has many applications, including nonlinear optics at the few-photon level, slow light, lasing without inversion and optical quantum information processing. The critical underlying technique is electromagnetically induced transparency, in which quantum interference between transitions in multilevel atoms renders an opaque medium transparent near an atomic resonance. With the advent of high-brilliance, accelerator-driven light sources such as storage rings or X-ray lasers, it has become attractive to extend the techniques of optical quantum control to the X-ray regime. Here we demonstrate electromagnetically induced transparency in the regime of hard X-rays, using the 14.4-kiloelectronvolt nuclear resonance of the Mössbauer isotope iron-57 (a two-level system). We exploit cooperative emission from ensembles of the nuclei, which are embedded in a low-finesse cavity and excited by synchrotron radiation. The spatial modulation of the photonic density of states in a cavity mode leads to the coexistence of superradiant and subradiant states of nuclei, respectively located at an antinode and a node of the cavity field. This scheme causes the nuclei to behave as effective three-level systems, with two degenerate levels in the excited state (one of which can be considered metastable). The radiative coupling of the nuclear ensembles by the cavity field establishes the atomic coherence necessary for the cancellation of resonant absorption. Because this technique does not require atomic systems with a metastable level, electromagnetically induced transparency and its applications can be transferred to the regime of nuclear resonances, establishing the field of nuclear quantum optics.

Growth and morphology of sputtered aluminum thin films on P3HT surfaces.

Growth and morphology of an aluminum (Al) contact on a poly(3-hexylthiophene) (P3HT) thin film are investigated with X-ray methods and related to the interactions at the Al:P3HT interface. Grazing incidence small-angle scattering (GISAXS) is applied in situ during Al sputter deposition to monitor the growth of the layer. A growth mode is found, in which the polymer surface is wetted and rapidly covered with a continuous layer. This growth type results in a homogeneous film without voids and is explained by the strong chemical interaction between Al and P3HT, which suppresses the formation of three-dimensional cluster structures. A corresponding three stage growth model (surface bonding, agglomeration, and layer growth) is derived. X-ray reflectivity shows the penetration of Al atoms into the P3HT film during deposition and the presence of a 2 nm thick intermixing layer at the Al:P3HT interface.

Time-resolved ultrathin cobalt film growth on a colloidal polymer template.

Cobalt (Co) sputter deposition onto a colloidal polymer template is investigated using grazing incidence small-angle X-ray scattering (GISAXS), scanning electron microscopy (SEM), and atomic force microscopy (AFM). SEM and AFM data picture the sample topography, GISAXS the surface and near-surface film structure. A two-phase model is proposed to describe the time evolution of the Co growth. The presence of the colloidal template results in the correlated deposition of an ultrathin Co film on the sample surface and thus in the creation of Co capped polystyrene (PS) colloids. Well below the percolation threshold, the radial growth is restricted and only height growth is observed.