David Attwood University of California, Berkeley Cheiron School September 27, 2014 SPring-8
Photon energy • See smaller features • Write smaller patterns • Elemental and chemical sensitivity ћω · λ = hc = 1239.842 eV nm n = 1 − δ + iβ δ, β << 1
Kirkpatrick-Baez (KB) mirror pair Synchrotron • Crossed cylinders at glancing incidence • Photon in / photon out, low noise background • Femtogram and part per billion (ppb) sensitivity • Micron focus (1988),  now ~25 nm (Yamauchi, Mimura and colleagues, Osaka U./SPring-8) and R. Holm, Miles Lab) FluoresMicroprobe August2014.ai J.H. Underwood and A.C. Thompson, NIM A266, 296 & 318 (1988).
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H. Mimura et al., Nature Physics, 6, 122 (2009) Courtesy of K. Yamauchi and H. Mimura, Osaka University. CheironSchool_Sept2014_Lec3.ppt 6
Focusing mirror with phase error In-situ phase compensation Focusing mirror with phase error H. Mimura et al., Nature Physics, 6, 122 (2009) 7 XRM2010, 16th, Aug, 2010
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Courtesy of Marine Cotte (ESRF, Grenoble, France)
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1st production of glass objects Egypt (1500 B.C.), opaque, colored, nanoscale calcium antimonate Courtesy of Marine Cotte (ESRF, Grenoble, France) 11
Double crystal monochrometor (8-45 keV) Visible light CCD Visible light monochromatic x-rays Rotation stage (1500 projections, at 20 keV, 0.74 μm pixel size,10 min.) Tomographic reconstruction of a 500 million year old fossilized embryo from Southern China P. Donoghue, S. Bengtson, M. Stampanoni et al., Nature 442, (2006) Courtesy of Marco Stampanoni, Swiss Light Source. 12
Markelia hunanensis relative of modern roundworms and arthropods SRXTM, 17.5 keV, 15 μm resolution Tomcat Beamline, Swiss Light Source P. Donoghue, S. Bengtson, M. Stampanoni et al., Nature 442, (2006) PAUL SCHERRER INSTITUR Courtesy of Marco Stampanoni, Swiss Light Source. 13 Courtesy of Marco Stampanoni, Swiss Light Source. 14
SRXTM, 25 keV, 15 µm resolution Tomcat Beamline, Swiss Light Source M. Stampanoni, T. Krucker et al., Adv. Neur. Res. (2008) PAUL SCHERRER INSTITUT Courtesy of Marco Stampanoni, Swiss Light Source. 15
• Spatial resolution: 10 nm • Spectral resolution: 5,000 • Shortest exposure time: 1 sec. • Bending magnet radiation • Higher radiation dose • Flexible sample environment (wet, cryo, labeled magnetic fields, electric fields, cement, …) • Least radiation dose • Spatial resolution: 10 nm • Spectral resolution: 5,000 • Requires undulator, spatially coherent radiation • Long exposure time • Flexible sample environment
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Courtesy of Anne Sakdinawat, UC Berkeley
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Spiral zone plate for phase contrast Courtesy of Anne Sakdinawat, Chang Chang, Weilun Chao and Erik Anderson (LBNL & UCB.)
59 nm thick Gd²5Fe75 layer Courtesy of  A. Sakdinawat, C. Chang and P. Fischer.
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20 Nature LETTERS

than 15 nm
Weilun Chao ¹ ،² , Bruce D. Harteneck¹, J. Alexander Liddle¹, Erik H. Anderson¹ & David T. Attwood¹ ،² Analytical tools that have spatial resolution at the nanometre scales are indispensable for the life and physical sciences. It is that these tools also permit elemental and chemical id on a scale of 10 nm or less, with large penetration depths of techniques¹ - ⁷ in X-ray imaging are currently by that may provide these combined capabilities. Here achievement of sub-15-nm spatial resolution microscope—and a clear path to below 10 nm technique for zone plate fabrication. The ne spectral range from a photon energy of 250 eV length) to 1.8 keV (~0.7 nm), so that prima resonances of elements such as C, N, O, Al, Ti, Fe, probed. This X-ray microscopy technique is there a wide range of studies; biological imaging in the studies of wet environmental samples 's . nanostructures with both elemental and spin-orbit set studies that require viewing through thin window. substrates (such as buried electronic devices in a and three-dimensional imaging of cryogenically fixed cellsバッThe microscope XM-1 at the Advanced Light Sour similar to that pioneered by the Göttingen/BESSY references therein). A 'micro' zone plate (MZP) p image to an X-ray-sensitive CCD (charge-coupled device), typically in one or a few seconds, often with several hundred in The field of view is typically 10 μ m, corresponding to a of 2,500. The condenser zone plate (CZP), with a cen- two purposes in that it provides partially coherent illumination 2 , and, in combination with a pinhole, ture of the MZP, and k , is an illumination de nification. NAMZB = N/2ArMYB where Arsra allest) zone width of the MZP 50 . For the illumination 21,22 used here, k 1 ** 0.4 and thus the t to dimensional scalar diffraction code, which an unambiguous spatial reso we describe the use of an overlay nanofabrication us to fabricate zone plates with finer outer = 15 nm, and to achieve a spatial resolution This technique overcomes nanofabrication limits roadening in high feature density pattern : results from electron scattering within the recording medium sist), leading to a loss of image contrast and thus resolvability for λ = 1.52 nm (815 eV) Δr = 15 nm N = 500 D = 30 μm f = 300 μm σ = 0.38 0.8 Δr = 12 nm Figure 4 | Soft X-ray images of a 15.1 nm half-period test object , as te to project a full field image onto a CXI rmed with zone plates having outer zone widths of 25 nm and 15 nm. Cr/Si test pattern (Cr L 3 @ 574 eV) (2000 X 2000, 104 ph/pixel)  i14_Lec3.ppt 21
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and directed onto sample windows W. Meyer-Ilse, G. Denbeaux, L. Johnson, A. Pearson (CXRO-LBNL)
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Cryo x-ray microscopy of 3T3 fibroblast cells C. Larabell, D. Yager, D. Hamamoto, M. Bissell, T. Shin (LBNL Life Sciences Division) W. Meyer-Ilse, G. Denbeaux, L. Johnson, A. Pearson (CXRO-LBNL) 24 Bending magnet radiation used with a soft x-ray microscope to form a high resolution image of a whole, hydrated mouse epithelial cell hw = 520 eV 32 µm x 32 µm Ag enhanced Au labeling of the microtubule network, color coded blue. Cell nucleus and nucleoli, moderately absorbing, coded orange. Less absorbing aqueous regions coded black. W. Meyer-Ilse et al. J. Microsc. 201, 395 (2001) 25
Nanotomography of Cryogenic Fixed Cells Soft X-Ray Nanotomography of a Yeast Cell λ = 2.4 nm Courtesy of  C. Larabell (UCSF & LBNL) and M. LeGros (LBNL)
Nanotomography of Cryogenic Fixed Cells Soft X-Ray Nanotomography of a Yeast Cell f = 650 μm σ = 0.64 Resolution = 60 nm λ = 2.4 nm Courtesy of  C. Larabell (UCSF & LBNL) and M. LeGros (LBNL) III)
C. Larabell and M. LeGros, Molec. Bio. Cell 15, 957 (2004) Depth of field = = 2 μm
Each projection image
Reconstructed image Courtesy of Anne Sakdinawat (LBNL & UCB.)
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28 Nanoscale 3-D biotomography Mother daughter yeast cells just before separation 2-D slice from 3-D Tomogram. Images every 2°, 180° data set, several minutes. Δr = 45 nm Color coding identifies subcellular components by their x-ray absorption coefficients Courtesy of Carolyn Larabell, UCSF/LBNL.
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Biotomography at 60 nm resolution Courtesy of  C. Larabell (UCSF & LBNL) • Cryofixation • 2° angular intervals • Depth of focus limits resolution • New XM-2 dedicated to biological applications, will become major facility worldwide to draw biologists to this evolving capability
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517 eV (2.4 nm) Δr = 25 nm, 1° intervals, ±60° 29 nm nuclear double membrane. Courtesy of Gerd Schneider, BESSYII and James McNally, NIH. CheironSchool_Sept2014_Lec3.ppt 31
517 eV (2.4 nm) Δr = 25 nm, 1° intervals, ±60° 29 nm nuclear double membrane. Courtesy of Gerd Schneider, BESSYII and James McNally, NIH. 32
2D slice from 3D data set Courtesy of Gerd Schneider, BESSYII and James McNally, NIH.
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In collaboration with: C. Bittencourt, U. Antwerp, Belgium P. Guttmann et al., Nature Photonics (Dec. 2011). Courtesy of Professor Paulo Monteiro, CEE, UC Berkeley Generates 1.5 billion ton of CO₂ Responsible for 7% CO₂ production in the world 1.5 billion ton of cement Environmental Consequences of Portland cement Problem! period
Calcium-Silicate-Hydrate (C-S-H): critical to cement strength and durability. Orth C 3 A Orth C 3 A + 1% CaCl 2 Orth C³A + accelerator C: carbon Ca: calcium A: alumina (Al₂O₃) S: silica (SiO₂) 520 eV, 40 nm - spatial resolution
Zone plate focusing lens | S N e S N N Scanning Soft X-Ray Microscope ALS beamline 11.0.2 395 eV; λ/Δλ = 6000 240 × 240 pixels 1.2 µm × 1.2 µm 2 ms dwell time
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Protein (gray), Ca, K RESULTS •Ni, Fe, Mn, Ca, K, O, C elemental map, (there was no sign of Cr.) •Different oxidation states for Fe and Ni Different oxidation states (minerals) found for Fe & Ni Tohru Araki, Adam Hitchcock (McMaster University) Tolek Tyliszczak, LBNL Sample from: John Lawrence, George Swerhone (NWRI- Saskatoon), Gary Leppard (NWRI-CCIW)
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M.K. Gilles, R. Planques, S.R. Leone LBNL Samples from B. Hinsberg, F. Huele IBM Almaden Exposure to UV light results in loss of carbonyl peak Map chemical spectra taken of pure samples onto a sample containing both components Courtesy of Mary Gilles, LBNL
• Shorter wavelengths, potentially better spatial resolution and greater depth-of-field. • Less absorption (β); phase shift (δ) dominates, higher efficiency. • Thicker structures required (e.g., zones), higher aspect ratios pose nanofabrication challenges. • Contrast of nanoscale samples minimal; will require good statistics, uniform background, dose mitigation. Ultra high aspect ratio nanofabrication of high efficiency, high resolution x-ray zone plates for the 50 eV-30 keV regime 43
+1 OAM No OAM -1 OAM X-rays with various amounts of orbital angular momentum can be produced using a spiral zone plate structure.  These spiral zone plate structures can also be used in place of the objective zone plate in an x-ray microscope for phase contrast imaging. Specialized x-ray diffractive optical elements enable
Spiral zone plate for producing x-rays with charge 50 orbital angular momentum Uniformly redundant array for x-ray parallel holography, alignment, and other applications Zone plate for x-ray differential interference contrast microscopy 45
“Lensless” coherent diffraction imaging (CDI) is being aggressively pursued.
Start:  Combine measured diffraction intensity pattern with random phases Inverse Fourier transform to real space CohDiffracImagSchem_Diagr_Oct09.ai
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S. Eisebitt, J. Lüning, W.F. Schlotter, M. Lörgen, O. Hellwig, W. Eberhardt & J. Stöhr / Nature , 16 Dec 2004 LenslessImagingF1.ai
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