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1 软 X 射线谱学显微技术及其应用进展 Latest of Soft X-ray Spectromicroscopy and its Applications Lijuan Zhang 中国科学院上海应用物理研究所 Zhanglijuan@sinap.ac.cnac cn -SSRF

2 Outline Introduction of synchrotron Radiation STXM beamline 2D STXM Spectromicroscopy NEXAFS/TEY and examples. Dual energy contrast imaging and examples. 3D STXM spectro-tomography Experimental, data acquisition and analysis Example: Macrophage ( 巨噬细胞 ) STXM developments (CDI, XEOL, XRF) Conclusions 2

3 What is synchrotron radiation? i Synchrotron radiation is electromagnetic radiation emitted when charged particles are radially accelerated (move on a curved path).

4 Generated by charged particles of matter spiraling through the cosmos 6000 light years away. Crab nebula In 1947, radiation was first observed on First light was observed and recorded 70MeV electron synchrotron in GE on 1054 AD (Song Dynasty). Schenectady, called synchrotron radiation.

5 A synchrotron radiation beamline / bend magnet/wiggler Optics cabin Control room Experiments cabin

6 Synchrotron radiation

7 Synchrotron is an powerful tool to study microscopic i world.

8 Science and dart Nautilus Pompiplius

9 Beamlines 9 in operation 6 under construction 16 phase II The SSRF Complex Storage Ring 3.5GeV, C=432m Booster 3.5GeV,C=180m Electron Linac 150MeV Synchrotron radiation Beam was observed at very first run.

10 Operated beamlines Beamlines Energy Goals Macromolecular Crystallography Beamline (BL17U1) Small Angle X-ray Scattering Beamline ( BL16B1) Hard X-ray Microfocusing Beamline( BL15U1) 5-18keV 5-20keV keV 高性能通用蛋白质晶体结构测定高分子和纳米体系的结构分析复杂体系微区成分及化学态分析 XRD Beamline(BL14B1) 4-22keV 材料凝聚态等领域的结构分析 XAFS Beamline (BL14W1) X-ray Medical Imaging Beamline(13W1 ) Soft X-ray Spectromicroscopy Beamline (BL08U1A) Soft X-ray Interference Lithography beamline(bl08u1b) Dreamline (BL09U) keV(focus) keV(non focus 催化环境等的原子电子结构 ) keV 无损高分辨动态三维成像 eV 2000 纳米高空间分辨元素成像吸收 eV 大面积周期性纳米结构制备 eV 用高能量分辨率研究凝聚态能带精细结构 ( 量子材料 : 强关联拓扑和超导等 )

11 Soft X-ray Spectromicroscopy beamline (BL08U1A)

12 Soft X-ray Microscopies STXM TXM X-PEEM SPEM 12

13 Comparison with Other Techniques Ch hemical Inf formation Conte ent High Low NMR IR OM RM XPS EDS FM STXM X-PEEM NSOM STEM-EELS SEM TEM STM AFM 100 mm 1 mm 10 nm 1 Å Technique Spatial Resolution Speciation Capability NMR > 1 µm excellent IR > 1 µm excellent Raman ~ 0.3 µm excellent Optical ~ 0.5 µm needs chromophores Scanning probe nm variable TOF-SIMS ~ 1 µm excellent (S)TEM - EELS < 10 nm good (but radiation Soft X-ray damage!) spectromicroscopy 5 ~ 30 nm excellent Spatial Resolution Excellent t combination of spatial resolution and chemical speciation Quantitative chemical analysis Multiple environments - wet, magnetic fields, cryo, surfaces etc. Much lower radiation damage than TEM-EELS 13

14 What could we do? Abilities Imaging, providing quantitative maps of elemental distributions ib i at high h spatial resolution, 30nm. High energy resolution absorption spectra (XANES) The research fields: Environmental science; Biological science; Medical science; Nanomaterials; Physics; BL08U

15 Electron binding energy (ev) The photon energy covers the K edges of C, N, O, F, Na, Mg, Al, Si, and L edges of Cl, K, Ca, Fe, Cu, Zn. 250 ev < E < 2000 ev Kedge H L 2,3 edge He Li Be M 4,5 edge B C N O F Ne Na Mg Al Si P S Cl Ar K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe Cs Ba Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn Fr Ra Lr Rf Db Sg Bh Hs Mt Ds Rg Uub Uut Uuq Uuh La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No

16 The Beamline Layout Side view 4-D slit Collimating mirror PGM Plane grating G M3 STXM Zone plate Detector EPU ( 0.2mrad 0.1mrad ) Acceptance angles M1 M2 Plane mirror Toroidal mirror Exit slit Specimen Zone plate 1.5 o Detector Top view Exit slit Specimen 1.5 o End station Monochromatic light 0 20m 30m 32m 34m 42m 44m BL08U

17 Schematic STXM principle p Zone Plate OSA Sample PMT 50nm nanoprobe To block the direct beam from reaching the focal plane. Computer OSA: Order sorting aperture; PMT: Photomultiplier tube BL08U

$5%) (~ 10%) 2 2 f rn ( f m: diffraction order n: number of zones λ: X-ray wavelength mn ) 2 2 For m = 1, and f >> nλ D Focal$

18 STXM Principle (~ 25%) 200um (< 2.5%) (~ 10%) 2 2 f rn ( f m: diffraction order n: number of zones λ: X-ray wavelength mn ) 2 2 For m = 1, and f >> nλ D Focal Length : f Detector Position : L r n S f D Resolution rn Maximum A0 Distance: A0 OSA D f 18

19 Mechanical layout in end station Stage stacks and components in chamber Microscope vacuum chamber Focusing optics module

Sample holders Wet samples: The thickness

20 How to prepare your sample? Dry samples: The size of particles is smaller than 10 m, better than 2 m. Substrates: Si 3 N 4 window Copper nets Sample holders Wet samples: The thickness of less than 2 m is required. two silicon nitride windows BL08U1A

21 In situ condition electric field: magnetic field:3000 Gauss for spectra, 300 Gauss for imaging. high/low temperature: up to 150 o C, nitrogen temperature BL08U1A

22 Main experimental techniques NEXAFS or XANES, Total electron yield method (TEY):to measure X-ray Absorption in a large sample area. Energy stacking method:to measure chemical composition and its spatial distribution, corresponding XANES of element. Dual-energy contrast imaging:to quantitatively measure 2D spatial distribution of elements. Nano-3D-CT: It combined STXM and computed tomography technique to develop the Nano-CT technique, which obtains both 3D elemental mapping and chemical information. X-ray magnetic circular dichroism in X-ray absorption (XMCD) and X-ray magnetic linear dichroism in X-ray absorption (XLCD): To study the magnetic properties of sample using X-ray linear polarization states or circularly polarized states. Scanning Coherent Diffractive Imaging, or Ptychography: it can obtain the image with high resolution (better than 10nm). Soft X-ray Excited Optical Luminance (SXEOL): can be combined with total electron yield (TEY- NEXAFS) to investigate charge transfer properties for nano-sized samples. Soft X-ray Fluorescence.

23 (1) Near Edge X-ray Absorption Fine Structure (NEXAFS or XANES) σ* Vacuum 2π* LUMO: 1π* Continuum σ* Optica al Density per nm thic ckness σ* * σ* C-H HOMO Quasi-bound or Multiple scattering state Polystyrene C1s * n Energy C 1s X-rays Photon Energy (ev) 2 P E 2 2 if ( ) 4 e x ( E) f e p i ( E) 2 f F ( E) m c ph 23

NEXAFS /TEY sample X-ray e- e- current Thin-Layer Fe 2 TiO 5 on Hematite for Efficient Solar Water

Total Yield Field Synchrotron-based soft X-ray absorption spectroscopy analyses clearly revealed

25 NEXAFS /TEY sample X-ray e- e- current Thin-Layer Fe 2 TiO 5 on Hematite for Efficient Solar Water Oxidation Hematite( 赤铁矿 ) is a good photocatalyst for solar water oxidation because of its favorable optical band gap ( ev), low cost, abundance, and chemical stability in oxidative environment. Total Yield Field Synchrotron-based soft X-ray absorption spectroscopy analyses clearly revealed the existence of an Fe 2 TiO 5 structure on hematite forming a heterojunction, which reduced the photogenerated hole accumulation and ACS Nano. 2015, 9, then improved the performance.

NEXAFS /TEY Electric-field control of tri-state phase transformation with a selective dual-ion switch XAS analysis

It will help to understand the phase transition and corresponding physical properties. Nature, 2017, 546, 124-128.

5 and then to SrCoO 3 δ suggests an increase in valence states.

26 NEXAFS /TEY Electric-field control of tri-state phase transformation with a selective dual-ion switch XAS analysis provides the direct evidence about the change of electron states after ions insertion. It will help to understand the phase transition and corresponding physical properties. Nature, 2017, 546, Soft X-ray absorption spectra of cobalt L-edges (a) and oxygen K-edges (b) for SrCoO3 δ, SrCoO2.5 and phase A (HSrCoO2.5). The shift in the peak positions of the cobalt L- edge (towards higher-energy states) from phase A to SrCoO 2.5 and then to SrCoO 3 δ suggests an increase in valence states. The oxygen K-edge results show distinct differences between phase A and the other two phases, namely the total suppression of hybridization between the 2p orbital of oxygen and the 3d orbital of cobalt, and the appearance of spectral features that represent hydroxyl bonds. Pu Yu Group, Tinghua University

27 (2) Stack analysis Raw Data (Transmission) Nitrogen-Doped Carbon Nanotube (N-CNT) Image Stack FT Alignment, Normalized to I 0 Treated Data (Absorbance, OD) Movie Clip Image Stack I 0 I0 OD A -lnt ln( ) l I Quantitative Color Composite Map Stack Fit with Linear Reference Spectra 1.0 Extract XANES Spectroscopy N 1s nm e Absorbance Energy (ev) 27 J. Zhou et al. J. Phys. Chem. Lett. 1 (2010) 1709.

(2) Stack analysis Biotransformation of Ceria Nanoparticles in

environmental and biological conditions.

4 while in the shoots as CeO 2 and cerium carboxylates.

cucumber roots, which might attributed to the enhanced

28 (2) Stack analysis Biotransformation of Ceria Nanoparticles in Cucumber Plants CeO 2 nanoparticles (NPs) are stable under environmental and biological conditions. NEXAFS showed that Ce presented in the roots as CeO 2 and CePO 4 while in the shoots as CeO 2 and cerium carboxylates. Some CeO 2 NPs were transformed to CePO 4 on the surface of cucumber roots, which might attributed to the enhanced dissolution of NPs at the nano-bio interface. Peng Zhang, Renzhong Tai et al., ACS Nano, 2012, 6 (11):

(3) Dual-energy contrast imaging The influence of

migration of adsorbed arsenic Dual-energy contrast

of this element by analyzing the two images of STXM

Dual energy analysis of As-TiO2-SRB after cultured

Based on STXM technique it was studied tdidon the

release and migration of arsenic under the

29 (3) Dual-energy contrast imaging The influence of Sulfate reducing bacteria on the release and migration of adsorbed arsenic Dual-energy contrast imaging: To obtain the two dimensional distribution of this element by analyzing the two images of STXM before and on edge. Dual energy analysis of As-TiO2-SRB after cultured 4days. Based on STXM technique it was studied tdidon the valence change of adsorbed d arsenic on nano TiO2 surfaces in molecular level. Those results provided a strong support for the release and migration of arsenic under the involving of microorganisms and a theoretical basis for the evaluation of safety of adsorbed arsenic. Ting Luo et al. Environmental Science & Technology, 2013, 47,

(3) Dual-energy contrast imaging The endohedral metallofullerenol, Gd@C82(OH)22, serves as a

toxicity. on Norm malized absorpti Gd 2 O 3 TEY slit2=100*100 1193.7eV 1198.

Gd@C82(OH)22 nanoparticles in the macrophages based on the X ray absorption signals from Gd atoms

They found that the uptake of Gd@C82(OH)22 is dependent on the exposure time and the major location

30 (3) Dual-energy contrast imaging The endohedral metallofullerenol, serves as a potential nanomedicine that can efficiently inhibit the growth and invasion of tumors with low toxicity. on Norm malized absorpti Gd 2 O 3 TEY slit2=100* eV eV Photon energy (ev) Using STXM technique to image the intracellular Gd@C82(OH)22 nanoparticles in the macrophages based on the X ray absorption signals from Gd atoms with as high as 30 nm spatial resolution. They found that the uptake of Gd@C82(OH)22 is dependent on the exposure time and the major location is in the cytoplasm rather than the nuclei. These results provided key and direct evidences about how Gd@C82(OH)22 takes part in the immunological modulation during tumor therapy. Small, 2014, 10 (12),

31 Imaging in liquid Interfacial nanobubbles investigated by STXM X-ray Number of bubbles m) Based diameters ( m SF6+Urea SF6+Carbon Ne+cyclodextrin Based diameters of bubbles Now the scientists t pay more and more attentions ti on the existence mechanism of interfacial nanoubbles due to their potential influence on the biological, environmental fields and device designing. g It is the first time to obtain the STXM images of nanobubbles and found that the bubbles smaller than 2.5um are very stable compared with large ones. This results was consistent to AFM results obtained before. Lijuan Zhang et al. J. Synchrotron Rad , STXM group

32 (4)3D X-ray Tomography X-ray computed tomography (CT) is the construction of a 3D image from 2D projections taken at different orientations. Hard X-ray Tomography Medical CT Synchrotron CT by CLS BMIT Beamline Phase Contrast Tomography S. Mayo et al. J. Phys. Conf. 186 (2009) Soft X-ray Tomography [1] [1] BESSY, [2] ALS cryo-txm [2] [1] First STXM Tomography at NSLS [2] NSLS cryo-stxm ALS STXM Spectro-Tomography [1] D. Weiß et al. Ultramicroscopy 84 (2000) 185. [2] C.A. Larabell et al. Mol. Biol. Cell 15 (2004) 957. [1] W.S. Haddad et al. Science 266 (1994) [2] Y. Wang et al. J. Microscopy 197 (2000) 80. G.A. Johansson et al. J. Sync. Rad. 14 (2007)

33 3D STXM Spectro-Tomography Setup Glass Capillary Tomography TEM Grid and Wet Cell Tomography 100 m Glass Capillary 2 m 1 mm 0 o 360 o rotation Rotation wobble: < 300 μm Used for O 1s edge and above. Sample holder -70 o +70 o rotation Luxel TM Wet Cell Rotation wobble: < 200 μm Used for C 1s edges and above. 33

34 3D STXM Spectro-Tomography Element distribution+ 3D structure 3D image Macrophage of uptaking metallofullerenol 82 (OH) 22 ) nanoparticles. Ab bsorption A B Distribution of Gd in 3D structure Energy (ev) A : before Gd L edge;b : on the Gd L edge Cooperation with Prof. Huaidong Jiang and Prof. Chunying Chen

(5) X-ray Magnetic Circular Dichroism (XMCD) Magnetoelectric t coupling induced d by interfacial orbital reconstruction XA S XMCD Mn L -edge XMLD difference in absorption intensities for the in-

The burning requirement for high-density memory integration advances the development of newly-structured spintronic devices, which have reduced stray fields and are insensitive to magnetic field

35 (5) X-ray Magnetic Circular Dichroism (XMCD) Magnetoelectric t coupling induced d by interfacial orbital reconstruction XA S XMCD Mn L -edge XMLD difference in absorption intensities for the in- plane and out-of-plane of linear polarization vectors E :a)6 nm IrMn at H, b) 6 nm IrMn at + H, c) 10 nm IrMn at H, and d) 10 nm IrMn at + H. The burning requirement for high-density memory integration advances the development of newly-structured spintronic devices, which have reduced stray fields and are insensitive to magnetic field perturbations. This could be visualized in magnetic tunnel junctions incorporating antiferromagnetic (AFM), instead of ferromagnetic electrodes. Here they report room-temperature AFM-controlled tunneling anisotropic magnetoresistance in a novel perpendicular junction where IrMn AFM stay immediately at both sides of AlO x tunnel barrier as the functional layers. Bi-stable resistance states governed by the relative arrangement of uncompensated antiferromagnetic IrMn moments are obtained here, rather than the traditional spin-valve signal observed in ferromagnet-based tunnel junctions. Significant technical support was provided by Beamline BL08U1A in Shanghai Synchrotron Radiation Facility (SSRF) for XAS/XLD measurements. The elemental specific XMLD Mn L-edge x-ray results provide crucial evidence to confirm the twisted IrMn moments in the [Pt/Co]/IrMn coupling layer. The experimental observation of room-temperature tunneling magnetoresistance controlled directly by AFM is practically significant that might pave the way for the new-generation memories based on AFM spintronics. Advanced Functional Materials 2015, 25(6),

Magnetic Imaging Schematic figure of the experimental setup.

transmitting x- ray intensity at each point is detected by PMT

The specimen is rotated by 20 in order to measure the in-plane

Comparison between experimental and simulated vortex

(A) (B)(C)STXM( ) images of magnetic vortex state for permalloy

Micromagnetic simulations of the magnetic vortex statefor

36 Magnetic Imaging Schematic figure of the experimental setup. The income X- ray beam is focused on the specimen, and the transmitting x- ray intensity at each point is detected by PMT detector. The specimen is rotated by 20 in order to measure the in-plane magnetization components. Comparison between experimental and simulated vortex magnetization. (A) (B)(C)STXM( ) images of magnetic vortex state for permalloy circle, square and triangle geometries; (D) (E) (F) Micromagnetic simulations of the magnetic vortex statefor circular, square and triangle geometries. The color and the arrows in D-F indicate the direction of the in-plane magnetization component;(g)(h)(i) profiles along the red circular in (A) (B)(C)(red hollow circle) and (D) (E) (F) (blue solid square dots).

$diffraction imaging A$ $diffraction imaging (CDI)$ STXM-Ptychography Sample

37 (6) Soft X-ray coherent diffraction imaging A schematic figure of coherent diffraction imaging (CDI) STXM-Ptychography Sample in-focus or out-of-focus CCD detector Reciprocal-space images Wavelength limited spatial resolution (~ 2nm) Large computation in data process Scanning CDI is based on the overlap correlation, in which the sample size is unlimited, and the reconstruction converges faster and more stable.

$(6) Soft X-ray coherent diffraction imaging$ imaging ZP,OSA and sample PMT CCD in vacuum

STXM (left), and the noise-proof mask covering

10nm! Softwares to construction Constructed

38 (6) Soft X-ray coherent diffraction imaging Lower-dose, higher resolution ptychography imaging ZP,OSA and sample PMT CCD in vacuum epie Ppie Pcpie NLO MX Scanning CDI platform in STXM (left), and the noise-proof mask covering CCD. The spatial resolution can be better than 10nm! Softwares to construction Constructed results of stardard sample Zijuan Xu will report more details!

39 (7) X-ray excited optical luminescence (XEOL) XEOL XEOL monitors the optical luminescence (UV-visible-Near IR) emitted by a sample at selected excitation photon energies in soft x-ray range, often across the absorption edge of interest. Huaina Yu will report more details. 2D XEOL-TEY PLY and TEY of Nano ZnO at O K edge

40 (8) Soft X-ray Fluorescence 1. X-ray fluorescence (XRF) of the element is obtained by soft X-ray excitation. Elemental components can be analyzed qualitatively and quantitatively by their characteristic peak. 2. Bulk information can be obtained by the NEXAFS with PFY mode. The new developed PFY mode will be the supplement of current TEY mode. 3. NEXAFS by PFY mode can be extended to in-situ cell study, including the solid-liquid interface. Figure 1. ()St (a) Structuret of Fluorescence measurement system, (b) holder of the SDD detector inside vacuum chamber, (c) configuration of SDD detector, sample, and incident soft X-ray window. Figure 2 (a) XRF of TiO 2 nanotubes under different wavelength of excited soft X-ray. (b) NEXAFS of TiO 2 nanotubes obtained by both TEY and PFY mode. Zhenhua Chen will report more details.

41 Summary and Future Work STXM is capable to image the nano scaled structure, quantitative distributions of chemical components, molecular orientation, as well as obtains the spatially-resolved NEXAFS spectroscopy. STXM instrumentation developments have demonstrated powerful capabilities, STXM-Ptychography and 3D STXM- Tomography, XEOL, XRF. In situ condition ( temperature, Magnetic field, in situ reaction..) are optimized or developing. 41

42 Acknowledgements STXM beamline stuff STXM developments: CDI: Zijian Xu; Haigang Liu 3D CT: Xiangzhi Zhang XEOL: Huaina Yu XRF: Zhenhua Chen Cooperation CLS: Jian Wang ALS: Tolek Tyliszczak; Jinghua Guo McMaster University: A.P. Hitchcock PAL: HyunJoon Shin 42

5 questions, 3 points each, 15 points total possible. 26 Fe Cu Ni Co Pd Ag Ru 101.

Physical Chemistry II Lab CHEM 4644 spring 2017 final exam KEY 5 questions, 3 points each, 15 points total possible h = 6.626 10-34 J s c = 3.00 10 8 m/s 1 GHz = 10 9 s -1. B= h 8π 2 I ν= 1 2 π k μ 6 P