AVS2016 Session SA+AS+BI+MI-TuA: Synchrotron and XFEL Advances for Biological Systems (2:20-3:40 pm)/Synchrotron Radiation at the Frontiers of Device Technology (4:20-6:20 pm)

X-ray linear dichroism was first shown in natural biominerals by Metzler et al. [1]. Based on this effect, we developed Polarization-dependent Imaging Contrast (PIC)-mapping, which displayed non-quantitative crystal orientation at the nanoscale as gray levels in ratios of images acquired at different linear polarizations [2]. A later development provided grayscale, semi-quantitative PIC-maps by acquiring stacks of 19 images as the linear polarization was rotated in 5° intervals from 0° to 90° [3-7]. The latest development uses the same stacks of images to fully, quantitatively display crystal orientations in colors, including hue and brightness, which represent in-plane and off-plane crystallographic c-axis orientation angles [8-10].

Using PIC-mapping in these 3 subsequent modes, we discovered several biomineral formation mechanisms in nacre [11,7], sea urchin teeth [12-14], ascidian spicules [10], corals, eggshells, modern and fossil sea shell ultrastructure [15].

1. RA Metzler et al., Phys. Rev. Lett. 98, (2007). DOI: http://dx.doi.org/10.1103/PhysRevLett.98.268102

2. RA Metzler et al., Phys Rev B 77, 064110-1, (2008). DOI: http://dx.doi.org/10.1103/PhysRevB.77.064110

3. PUPA Gilbert et al., Proc Natl Acad Sci USA 108, (2011). DOI: 10.1073/pnas.1107917108

4. PUPA Gilbert, J Electr Spectrosc Rel Phenom, special issue on Photoelectron microscopy, Time-resolved pump-probe PES 185, (2012). DOI: http://dx.doi.org/10.1016/j.elspec.2012.06.001

5. IC Olson et al., J Am Chem Soc 134, (2012. JOURNAL COVER). DOI: dx.doi.org/10.1021/ja210808s

6. IC Olson et al., J Struct Biol 183, (2013). DOI: 10.1016/j.jsb.2013.06.006

7. IC Olson et al., J Struct Biol 184, (2013. JOURNAL COVER). DOI: 10.1016/j.jsb.2013.10.002

8. RT DeVol et al., J Phys Chem B 118, (2014). DOI: 10.1021/jp503700g

9. RT DeVol et al., J Am Chem Soc 137, (2015). DOI: 10.1021/jacs.5b07931

10. B Pokroy et al., Chem Mater 27, (2015. JOURNAL COVER.). DOI: 10.1021/acs.chemmater.5b01542

11. PUPA Gilbert et al., J Am Chem Soc 130, 17519, (2008). DOI: 10.1021/ja8065495

12. CE Killian et al., J Am Chem Soc 131, (2009). DOI: 10.1021/ja907063z

13. YR Ma et al., Procs Natl Acad Sci USA 106, (2009). DOI: 10.1073/pnas.0810300106

14. CE Killian et al., Adv Funct Mater 21, (2011). DOI: 10.1002/adfm.201001546

15. PUPA Gilbert et al., in preparation, (2016).

Synchrotron infrared beamlines use the diffraction-limited beam properties to enable a variety of cutting edge science - how can we go further?

By combining scattering-scanning near-field optical microscopy (s-SNOM) with mid-infrared synchrotron radiation, synchrotron infrared nano-spectroscopy (SINS) enables molecular and phonon vibrational spectroscopic imaging, with rapid spectral acquisition, spanning the full mid-infrared (500-5000 cm^-1) region with nanoscale spatial resolution. This highly powerful combination provides access to a qualitatively new form of nano-chemometric analysis with the investigation of nanoscale, mesoscale, and surface phenomena that were previously impossible to study with IR techniques. We have installed a SINS end-station at Beamline 5.4 at the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory, making the s-SNOM technique widely available to non-experts, such that it can be broadly applied to biological, surface chemistry, materials, or environmental science problems. We demonstrate the performance of synchrotron infrared nano-spectroscopy (SINS) on semiconductor, biomineral and protein nanostructures, providing vibrational chemical imaging with sub-zeptomole sensitivity.

The spatial field localization at the tip apex can also result in a large near-field momentum sufficient to optically excite phonon polaritons (PhPs), which are quasiparticles resulting from the strong coupling of photons with optical phonons. Here, we use SINS to image the PhP spectral response in thin hexagonal boron nitride (hBN) crystals. The large spectral bandwidth of the synchrotron source enables the simultaneous measurement of both the out-of-plane (780 cm-1) and in-plane (1370 cm-1) hBN phonon modes. In contrast to the strong and dispersive in-plane mode, the out-of-plane mode PhP response is weak. Measurements of the PhP wavelength reveal a proportional dependence on sample thickness for thin hBN flakes [2].

This talk will present the novel SINS instrumentation and a variety of scientific examples. Future directions, both technical and scientific, will be discussed.

*With Hans A Bechtel, Markus B. Raschke, Z. Shi, F. Wang, R.W. Johns, D.J. Miliron, E.A. Muller, R.L. Olmon

[1] H.A. Bechtel et al., Proceedings of the National Academy of Sciences of the USA, 111(20), 7191–7196 (2014)

[2] Z. Shi, H.A. Bechtel, S. Berweger, Y. Sun, B. Zeng, C. Jin, H. Chang, M.C. Martin, M.B. Raschke, and F. Wang, ACS Photonics 2 (7), 790-796 (2015).

Serial crystallography at XFEL’s has shown great promise in recent years for solving crystal structures of proteins, which produce only micron sized crystals. Liquid jets have been very successful for delivery of microcrystals to the X-ray beam. The commonly used liquid injection system will be discussed. High sample consumption has motivated the development of an injector, which uses high viscosity media like Lipidic Cubic Phase (LCP). G-protein coupled receptors are an important group of membrane proteins which are often crystallized in LCP. The injector generations a microscopic stream of LCP with adjustable speed for sample delivery to the X-ray beam¹. Some important GPCR structures could be solved with this device at the LCLS². In addition, new media with similar viscosity to LCP have been developed which enable delivery of soluble or membrane proteins into the X-ray beam with low sample consumption³. The high viscosity injection method has also been shown to facilitate serial diffraction experiments with microcrystals at synchrotron microfocus beamlines. This talk will highlight these developments and discuss the possibilities.

¹ Weierstall, U., James, D., Wang, C., White, T. A., Wang, D., Liu, W., et al. (2014). Lipidic cubic phase injector facilitates membrane protein serial femtosecond crystallography. Nature Communications, 5. http://doi.org/10.1038/ncomms4309

² Kang, Y., Zhou, X. E., Gao, X., He, Y., Liu, W., Ishchenko, A., et al. (2015). Crystal structure of rhodopsin bound to arrestin by femtosecond X-ray laser. Nature, 523(7562), 561–567. http://doi.org/10.1038/nature14656

³ Conrad, C. E., Basu, S., James, D., Wang, D., Schaffer, A., Zatsepin, N. A., et al. (2015). A novel inert crystal delivery medium for serial femtosecond crystallography. IUCrJ, 2(4), 421–430.

Electric-field control of charge carrier density has attracted much attention since it is remarkably simple for modulating physical properties of condensed matters and for exploring new functionalities with a transistor configuration. Owing to the limitation of dielectric breakdown in most solid dielectrics, the maximum carrier density accumulated in conventional field-effect transistors (FETs) is quite low (<< 10¹³ cm^-2) and thus seriously limits the tunability of electronic states of solids, for example, not sufficient enough to induce insulator-to-superconductor transition. While the electric-double-layer transistor (EDLT) with ionic liquids (ILs, or ionic gel) as gate dielectrics have been proved to be able to effectively attain a high carrier density up to levels of around 10¹⁵ cm^-2 and to realize a large local electric field up to 50 MV/cm at liquid/solid interfaces. For example, electric-double-layer transistors have been demonstrated for an electric-field control of emergent interfacial quantum phenomena and the electronics phase transitions in condense matters, such as insulator-superconductivity and paramagnetism-ferromagnetism transitions. However, the mechanistic/spectropic understanding of the local electronic structures at such highly charged IL/oxide EDL interfaces and also further modification under gate-bias remain elucidated and challenging.

In this talk, we conducted synchrotron radiation based X-ray absorption spectroscopy (XAS) and Auger electron spectroscopy (AES) combined with in situ electrical measurements to directly characterize the evolution of the electronic structure at a representative IL/La_0.7Sr_0.3MnO₃ (LSMO) thin film interface. We find a significant valence reduction localized to the topmost LSMO layer after interface formation, and that the gate-bias predominantly modulates this surface reduced Mn species effectively converting these top layers into an insulator. We expect the synchrotron radiation based photon science probing techniques will directly shed light on the understanding of interfacial electronic phase control under the electric field.

(This work was done in collaboration with Bongju Kim, Jun-Sik Lee, Yasuyuki Hikita adn Harold Y. Hwang. This work was supported by the Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under contract DE-AC02-76SF00515.)

We study the structural and electronic properties of strongly correlated complex-oxide thin films and interfaces using Hard X-ray Photoelectron Spectroscopy (HAXPES), Electron Energy Loss Spectroscopy (EELS) and Grazing Incidence X-ray diffraction (GIXRD) at the BM25-SpLine beamline (Branch B) at the ESRF. Strongly correlated complex-oxide exhibit a wide variety of interesting physical properties which originate from mutual coupling among spin, charge and lattice degrees of freedom. Usually, the interface drives the magnetic and electric response of the heterostructure. The chemical, mechanical, electric and magnetic properties of such devices are often intimately related to the structure, composition profile and morphology of their surface and internal interfaces. Several mechanisms are present at these interfaces as crystallographic space group modification, presence of oxygen vacancies, dislocations due to lattice strain, deviation from stoichiometry, phase segregation. In general all these phenomena modify the intrinsic properties of the materials used at the heterostructure, offering a unique way to produce artificial correlated materials with tailored properties. The growth of these materials in thin film form opens possibilities for magneto-electronic and spintronic devices applications. The results shown here are focused on the study of the influence of buried interfaces on the electric and magnetic properties of CMR and multiferroics systems. We will show the experimental methodologies at SpLine based on synchrotron radiation techniques to gain quantitative knowledge on the crystallographic and electronic properties at the interface between different complex oxides. There are few techniques able to provide an accurate insight of what is happening at these buried interfaces which in general are buried by several tens of nanometres in the material. The simultaneous combination of hard and soft X-ray photoelectron spectroscopy, electron energy loss spectroscopy with surface/interface X-ray diffraction gives unique capabilities in this respect. Here we will present a series of example to show how the interface properties can change the magnetic-conductivity properties.

The use of InGaAs as a high carrier mobility CMOS-channel material requires a proper electrical passivation of its interface with the gate dielectric. One of the passivation schemes investigated involves the use of Sulphur. In this work, high-k stacks on Sulphur passivated InGaAs substrates involving both Al2O3 and HfO2 are investigated. A major question related to the use of Sulphur relates to the chemical states at the interfaces. XPS is traditionally an important technique for interface analysis but faces several challenges in its application to the above mentioned stacks. First, due to the large number of elements involved, numerous peak interferences are present limiting the choice of useful photoemission peaks. Second, relevant stacks have total thicknesses of the order of 4 nm, which lead to very low intensities , certainly for minority elements like Sulfur. In this work, we discuss the impact of the H₂S passivation temperature as well as the use of TMA pre-pulses in the growth of Al₂O₃. We show that the Sulphur bind to In but that no As-S or Ga-S bonds could be detected. The use of a TMA pre-pulse after surface passivation leads to a reduction of the amount of Sulphur present at the interface and likely increases the amount of In-O bonds. Higher temperature H₂S passivation leads to a reduction of the amount of Sulphur at the surface.

We also observe that the presence/absence of S at the interface, as well as the presence of the Al₂O₃ buffer, which has a major impact on the relative peak position in the spectra between the substrate and the overlayer. This will be compared with the electrical characteristics of the stacks.

Finally, we show that using the Sessa software, full quantification of the stack can be obtained under the condition that all instrumental parameters are correctly taken into account.