Synchrotron Radiation in Materials Science E-Book
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- Herausgeber: Wiley-VCH Verlag GmbH & Co. KGaA
- Kategorie: Fachliteratur
- Sprache: Englisch
Meeting the long-felt need for in-depth information on one of the most advanced material characterization methods, a top team of editors and authors from highly prestigious facilities and institutions covers a range of synchrotron techniques that have proven useful for materials research.
Following an introduction to synchrotron radiation and its sources, the second part goes on to describe the various techniques that benefit from this especially bright light, including X-ray absorption, diffraction, scattering, imaging, and lithography. The thrid and final part provides an overview of the applications of synchrotron radiation in materials science.
bridging the gap between specialists in synchrotron research and material scientists, this is a unique and indispensable resource for academic and industrial researchers alike.
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Table of Contents
Cover
Title Page
Copyright
Preface
About the Editors
Chapter 1: Synchrotron Light Sources
1.1 Introduction
1.2 Synchrotron Radiation Generation
1.3 Light Source Storage Ring and Its Beam Dynamics
1.4 Low-Emittance Lattice for Light Source Storage Ring
1.5 Status of Storage Ring Light Sources
References
Chapter 2: Beamlines for Materials Science
2.1 Introduction
2.2 Radiation Properties of Different Sources
2.3 SR Beamline as an Optical System
2.4 Structure of Typical X-ray Beamlines
2.5 Radiation Safety and Interlock System
2.6 Beamline X-ray Optics
2.7 X-ray Beamlines for Next Generation SRs
2.8 Concluding Remarks
References
Chapter 3: Synchrotron Radiation Experimental Techniques
3.1 X-ray Diffraction
3.2 XAFS Technique
3.3 Small-Angle X-ray Scattering Technique
3.4 Imaging Technique
3.5 Soft X-ray Methodology
References
Chapter 4: Photon-In Photon-Out Spectroscopic Techniques for Materials Analysis: Some Recent Developments
4.1 Introduction
4.2 Photon-In Photon-Out Soft X-ray Techniques
4.3 Prospects
Acknowledgments
References
Chapter 5: Quantitative Femtosecond Charge Transfer Dynamics at Organic/Electrode Interfaces Studied by Core-Hole Clock Spectroscopy
5.1 Introduction
5.2 Basic Principles of Core-Hole Clock Spectroscopy
5.3 Energetic Condition for Probing Dynamic Charge Transfer
5.4 Experimental Realization
5.5 Charge Transfer Dynamics at Organic/Electrode Interfaces
5.6 Conclusions and Outlook
Acknowledgments
References
Chapter 6: Experimental Study of Ferroelectric Materials by Coherent X-ray Scattering
6.1 Introduction
6.2 Soft X-ray Speckle
6.3 Temporal Intensity Correlation
6.4 Concluding Remarks
References
Chapter 7: Probing Organic Solar Cells with Grazing Incidence Scattering Techniques
7.1 Introduction
7.2 Grazing Incidence Small Angle X-ray Scattering (GISAXS)
7.3 Grazing Incidence Wide Angle X-ray Scattering (GIWAXS)
7.4 Probing the Active Layer Morphology with GIWAXS
7.5 Probing the Active Layer Morphology with GISAXS
7.6 Summary
Acknowledgments
References
Chapter 8: Investigating Strain in Silicon-on-Insulator Nanostructures by Coherent X-ray Diffraction
8.1 Introduction
8.2 Coherence
8.3 Coherent X-ray Diffraction Imaging (CDI)
8.4 Strain Distribution in Silicon-on-Insulator (SOI) Structures
8.5 Conclusion
Acknowledgements
References
Chapter 9: Synchrotron Soft X-ray Absorption Spectroscopy Study of Carbon and Silicon Nanostructures for Energy Applications
9.1 Introduction
9.2 Carbon Nanostructures in Energy Applications
9.3 Si Nanostructures in Energy Applications
9.4 Conclusions and Prospective
Acknowledgments
References
Chapter 10: Synchrotron-Radiation-Based Soft X-ray Electron Spectroscopies Applied to Structural and Chemical Characterization of Isolated Species, from Molecules to Nano-objects
10.1 Introduction
10.2 Relevant Information in Photoelectron Spectra
10.3 Photoionization Cross Sections: A Structural Probe for Simple Molecules
10.4 Imaging Molecular Potentials
10.5 Photoelectron Spectroscopy-Based Structural Investigations of Clusters
10.6 Soft X-ray Spectroscopy Applied to Even Larger Systems: Physical Properties of Isolated Nanoparticles
10.7 Conclusion
References
Chapter 11: X-ray Imaging for Nondestructive Analysis of Material Microstructures
11.1 Introduction
11.2 Methodology Development
11.3 Applications in Material Science
References
Chapter 12: Exploring Actinide Materials through Synchrotron Radiation Techniques
12.1 Introduction
12.2 The Redox and Coordination Chemistry of Actinide
12.3 Challenges for Actinide Measurements at SR Facilities
12.4 Determination of Actinide Speciation by XAFS
12.5 Applications of XANES in Actinide Characterization
12.6 Actinide Computational Chemistry Associated with EXAFS and XANES Results
12.7 Applications of SR-Based XRD in Actinide Material
12.8 Applications of SR-Based X-ray Scattering (XRS) in Actinide Material
12.9 Synchrotron Radiation X-ray Fluorescence (SR-XRF) for Elemental Distribution and Quantitative Analysis of Actinide Materials
12.10 Scanning Transmission X-ray Microscopy for Actinide Imaging
12.11 Summary
Acknowledgments
Abbreviations
References
Chapter 13: Techniques and Demonstrations of Synchrotron-Based In situ Soft X-ray Spectroscopy for Studying Energy Materials
13.1 Introduction
13.2 Ambient Pressure Photoelectron Spectroscopy
13.3 Soft X-ray Absorption, Nonresonant X-ray Emission Spectroscopy, and Resonant Inelastic Soft X-ray Scattering
13.4 Conclusions and Future Outlook
References
Chapter 14: Synchrotron-Based Bioimaging in Cells and In vivo
14.1 Introduction
14.2 Overview of Synchrotron-Based X-ray Microscopy
14.3 Synchrotron-Based Bioimaging in Cells
14.4 Synchrotron-Based Bioimaging
In vivo
14.5 Summary
References
Chapter 15: Study on the Toxicology of Nanomaterials by Synchrotron Radiation Techniques*
15.1 Introduction
15.2 Characterization of Nanomaterials
15.3
In vitro
and
In vivo
Behaviors of Nanomaterials
15.4 Toxicological Effects of Nanomaterials in Ecosystems
15.5 Conclusions
Acknowledgments
References
Chapter 16: Synchrotron Radiation X-ray Imaging in Biomedical Research
16.1 History of Synchrotron Radiation Imaging
16.2 Principle of Synchrotron Radiation Imaging
16.3 Advantage of SR X-ray Imaging
16.4 SR X-ray Absorption-Contrast Imaging
16.5 Phase-Contrast Imaging
16.6 Development of SR Molecular Imaging
16.7 Microbeam Radiation Therapy (MRT)
16.8 The Safety of SR Imaging
16.9 Prospects
Abbreviations
References
Chapter 17: Integrative SAXS-Driven Computational Modeling of Biomolecular Complexes
17.1 Introduction
17.2 Theoretical SAXS Computing for Protein, RNA/DNA, and Their Complexes
17.3 Computational Generation of Candidate Conformations for SAXS Data Interpretation
17.4 Structural Determination from Experimental SAXS Data
17.5 Examples of SAXS Applications and Integration with Other Biophysical Techniques
17.6 Conclusions and Perspectives
Acknowledgments
References
Chapter 18: Applications of Synchrotron-Based Spectroscopic Techniques in Studying Nucleic Acids and Nucleic-Acid-Based Nanomaterials
18.1 Introduction
18.2 Synchrotron-Based Spectroscopic Techniques in the Characterization of Nucleic Acids
18.3 SAXS for Studying Electrostatics of Nucleic Acids
18.4 SAXS in Studying Conformations of Nucleic Acids
18.5 Time-Resolved Synchrotron X-ray Footprinting in Studying the Folding of Nucleic Acid Structures
18.6 Synchrotron-Based Methods in Studying DNA-Functionalized Nanomaterials
18.7 Synchrotron Radiation for Studying DNA–Lipid Interaction
18.8 Summary and Outlook
Acknowledgments
References
Chapter 19: X-ray Microscopy for Nanoscale 3D Imaging of Biological Cells and Tissues
19.1 Introduction
19.2 Intermediate-Energy X-ray Microscope
19.3 Discussions and Conclusion
Acknowledgments
References
Chapter 20: Synchrotron-Based X-ray Microscopy for Nanoscale Bioimaging
20.1 Introduction
20.2 Synchrotron-Based Nanoscale Bioimaging in Cells
20.3 Synchrotron-Based Nanoscale Bioimaging in Animals
20.4 Synchrotron-Based Nanoscale Bioimaging in Plants
20.5 Summary
References
Index
End User License Agreement
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Guide
Cover
Table of Contents
Preface
Begin Reading
List of Illustrations
Chapter 1: Synchrotron Light Sources
Figure 1.1 Synchrotron radiation from bending magnets, wigglers, and undulators [3].
Figure 1.2 Synchrotron radiation from bending magnet.
Figure 1.3 Synchrotron radiation from undulator.
Figure 1.4 The SSRF accelerator complex (150 MeV Linac, full energy booster, and 3.5 GeV storage ring).
Figure 1.5 The output radiation flux (a) and brightness (b) of the SSRF storage ring (at the electron energy of 3.5 GeV and beam current of 300 mA).
Figure 1.6 The photon beam cross-section of APS today and APS upgrade [16].
Figure 1.7 Typical types of magnetic lattice cells of light source storage rings (a) DBA, (b) TBA, (c) QBA, (d) MBA.
Figure 1.8 The SSRF storage ring lattice cell and dynamic aperture.
Figure 1.9 The MAX-IV storage ring lattice cell and dynamic aperture [19].
Figure 1.10 The ESRF-EBS HMBA storage ring lattice cell.
Chapter 2: Beamlines for Materials Science
Figure 2.1 Typical X-ray beamline structure (BL01B1 of the SPring-8).
Figure 2.2 Front end of BL19LXU at SPring-8.
Figure 2.3 Radiation spectrum of undulator.
Figure 2.4 An example of beamline optics and beam transport.
Figure 2.6 Support for a 1 m mirror in a bending magnet beamline; vertical deflection, indirect water cooling, and meridional bending.
Figure 2.5 Pumping unit for bending magnet X-ray beamlines.
Figure 2.7 Schematics of a radiation shielding hutch at SPring-8.
Figure 2.8 A channel-cut monochromator.
Figure 2.9 Fixed-exit double crystal monochromator.
Figure 2.10 Computer linked fixed-exit DCM.
Figure 2.11 Schematics of the mechanical-linked fixed-exit DCM.
Figure 2.12 Combined computer/mechanical-linked fixed-exit DCM.
Figure 2.13 Adjustable inclined double-crystal geometry for covering wider energy range [7]. (Reproduced with permission of American Institute of Physics.)
Figure 2.14 Two-dimensional focusing of an X-ray beam using a Kirkpatric–Baez mirror system.
Figure 2.15 An example of a compound refractive lens (CRL) for X-rays.
Figure 2.16 Comparison of brilliances for SPring-8 (black dashed curve) and SPring-8-II (red solid curves). Undulator parameters for SPring-8: period
λ
u
= 32 mm, number of periods
N
= 141 and total length
L
u
= 4.5 m, undulator parameters for SPring-8-II:
λ
u
= 23 mm,
N
= 156 and
L
u
= 3.6 m, maximum
K
value is 2.3.
Figure 2.17 Typical beam profiles at 30 m distance from the source, estimated for (a) SPring-8 and (b) SPring-8-II. The rectangles show typical aperture sizes of the pre-slits to the first optics. The maximum heat loads through the apertures at a stored beam current of 100 mA are: (a) 340 W for a slit size of 1.1 (H) mm × 0.6 (V) mm and (b) 200 W for 1.0 (H) mm × 0.8 (V) mm.
Chapter 3: Synchrotron Radiation Experimental Techniques
Figure 3.1 (a) The relationship between individual compound's PD peak intensity and its percentage in cement; (b) LaB6 standard diffraction pattern obtained at BL14B beamline at SSRF using Mythen1K detector using spinning capillary mode. The X-ray energy is 18 keV.
Figure 3.2 (a) One-dimensional Si microstrip linear detector developed at Paul Scherer Institute; (b)
In situ
X-ray diffraction patterns obtained using Mythen1K detector during electrochemical cycling of LiNi
0.5
Mn
0.5
O
4
vs Li battery. The X-ray energy is 18 keV.
Figure 3.3 Schematic illustration of the CTR.
Figure 3.4 Schematic illustration of the XSW.
Figure 3.5 Differential-aperture X-ray (structural) microscopy depth-profiling method. Schematic view of a white microbeam penetrating a sample and scattering into a CCD area detector.
Figure 3.6 Log–log plot of the (semiempirical) X-ray absorption cross-section of platinum (
Z
= 78) vs X-ray energy. The
K
,
L
1
,
L
2
,
L
3
, and
M
-edges are shown; fine structure is not shown.
Figure 3.7 Experimental
K
-edge XAFS spectrum
μ
(
E
)
x
of MnO (a) and KMnO
4
(b) at
T
= 80 K.
Figure 3.8 Different parts of a full spectrum.
Figure 3.9 XAFS occurs because the photo-electron can scatter from a neighboring atom. The scattered photo-electron can return to the absorbing atom, modulating the amplitude of the photo-electron wave-function at the absorbing atom. This in turn modulates the absorption coefficient
μ
(
E
), causing the EXAFS.
Figure 3.10 (a–c) Transmission XAFS experiment, fluorescence XAFS experiment, electron yield/conversion electron yield XAFS experiment.
Figure 3.11 X-ray fluorescence spectra from an Fe-rich mineral (an olivine), showing the Fe
K
α
and
K
β
emission lines, and the elastically (and nearly-elastically) scattered peaks. At lower energies, Ca, Ti, and V peaks can be seen.
Figure 3.12 The effect of a “
Z
− 1” filter on a measured fluorescence spectra. A filter of Mn placed between sample and detector will absorb most of the scatter peak, while transmitting most of the Fe
K
α
emission. For samples dominated by the scatter peak, such a filter can dramatically improve the signal-to-noise level.
Figure 3.13 The practical use of “
Z
− 1” filter for energy discrimination of a fluorescence spectra. The filter placed between sample and detector will absorb most of the scatter peak. But it can itself re-radiate. Since the filter's emission will also be isotropic, a set of metal Soller slits pointing at the sample will preferentially absorb the emission from the filter.
Figure 3.14 Atomic structural analysis of N-WS
2
layers. (a) A typical HADDF-STEM image of N-WS
2
shows clear atomic patterns in N-WS
2
. The bottom intensity profiles along the red lines exhibit the location of W and S atoms. The marked position and bonds of W atoms reveal an obvious zigzag chain superlattice. (b) The optimized WS
2
structure in zigzag-chain phase on the basis of first-principles calculation. (c and d) Synchrotron-radiation-based EXAFS spectra show the W
L
3
-edge oscillation functions
k
3
χ
(
k
) and the corresponding FT analysis. It clearly confirms the distorted W−W bonds in the N-WS
2
, agreeing with its zigzag chain superlattices.
Figure 3.15 Time-dependent (a)
kχ
(
k
) and (b) Fourier-transformed
k
2
χ
(
k
) EXAFS spectra during the dodecanethiol adsorption process on Au nanoparticles. Panels (c) and (d) are the TEM images of Au nanoparticles before and after 5 h of addition of dodecanethiol, respectively. (e) Bond lengths of surface Au−Au (solid squares) and Au−S (solid circles) at different adsorption times. (f) Time-dependent XANES spectra of reaction solution. The inset shows the magnified plot of the white line region.
Figure 3.16 (a) Total pair distribution function,
G
(
r
), (b) structure factor,
S
(
q
), (c) Cu
K
-edge, and (d) Zr
K
-edge EXAFS spectra. The solid and dashed lines denote experimental and simulation data, respectively. (e) The left is a representative ideal icosahedron, the center is one of its tetrahedron components, and the right is a perspective to show the tetrahedron and its embedded atomic parts. The blue and green balls stand for the shell and center atoms of the icosahedron, respectively.
Figure 3.17 Fe
K
-edge XANES spectra of (a) the as-prepared (Sc
0.9
Fe
0.1
)F
3
and reference compounds, and of (b) SFF-1, SFF-2, SFF-3, FeF
2
, and FeF
3
. (c) Fourier transform of the Fe
K
-edge EXAFS
k
3
χ
(
k
) functions for the calculated (dotted) and the three experimental samples of (Sc
0.9
Fe
0.1
)F
3
(three solid lines). For clarity, the intense calculated data is multiplied by 0.5. (d) Fourier transform (FT) of the Fe
K
-edge EXAFS
k
3
χ
(
k
) function for (Sc
0.9
Fe
0.1
)F
3
, and the Sc
K
-edge EXAFS
k
3
χ
(
k
) function for the pure ScF
3
. The inset displays their normalized EXAFS
k
3
χ
(
k
) functions.
Figure 3.18 Charge compensation mechanism upon Na deintercalation/intercalation in O3-Na
0.9
[Cu
0.22
Fe
0.30
Mn
0.48
]O
2
. (a)
Ex situ
XANES spectra at Cu
K
-edge collected at different charge/discharge states, and (b) the magnified region indicated by the rectangle in (a). (c)
Ex situ
XANES spectra at Fe
K
-edge collected at different charge/discharge states, and (d)
Ex situ
XANES spectra at Mn
K
-edge collected at different charge/discharge states.
Figure 3.19 Wave vectors of the incoming and outgoing radiation. The difference between two wave vectors must be dealt with by using vector algorithm (inset).
Figure 3.20 Angular pattern of scattering intensity at a point
r
by a uniform ellipsoid with a ratio
ν
of the long axis to the short axis. In this case, the wave vector
S
0
of incoming photons is in the same direction as the X-axis and the outgoing photons scatter at a direction shown graphically here.
Figure 3.21 Scattered intensity from a uniform sphere of a radius
R
(a) and of an ellipsoid (b) in the vacuum.
Figure 3.22 Scattering radiation of a multibody system. A form factor comes into being in the sum of individual form factors for two arbitrary particles located at
r
j
and
r
k
. The scattering intensity will include a product term of two individual form factors accordingly.
Figure 3.23 A size distribution deforms the profile of scattering intensity even for a system composed of sphere particles. The
q
values vary at the first point of zero intensity by an equation of
qR
= 4.493.
Figure 3.24 A typical experimental set-up for SAXS (a) and for GISAXS (b). A detector at
L
behind a sample will record the dependence of scattering radiation on
l
, a distance from the original point. A beamstop must be applied to block the transmitted X-ray beam in order to protect the detector from any damage.
Figure 3.25 Profiles of scattering intensity as a function of scattering vector
q
in samples with successive
ϕ
s of 0.38, 1.06, 1.51, and 2.12% (successively numbered by 1–4). The triangular, diamond, and heart signals denote the first-, the second- and the third-order scattering peaks in order. Inset: the correlation of
d
(001)
spacing and 1/
ϕ
; the red dots are experimental values and the blue line is the fitting function in the linear region (
ϕ
≥ 0.5%). Panel (b) gives variation of the interlayer spacing
d
with salt concentration at
ϕ
= 1.0 %.
Figure 3.26 Solution-phase synchrotron SAXS profile of the solution of Com-Tetra in water. The right inset is a model of one adamantane-shaped unit and the 3D supramolecular organic framework (1
n
· CB
2
n
, Com-Tetra). The left inset is a two-dimensional synchrotron X-ray scattering profile of Com-Tetra of the solid sample.
Figure 3.27 2D-GIWAXS patterns of (a) BDPPV-C1, (b) BDPPV-C2, (c) BDPPV-C3, (d) BDPPV-C4, (e) BDPPV-C5, and (f) BDPPV-C6 films prepared by spin coating their DCB solutions (3 mg mL
−1
) and annealed at 180 °C for 30 min. Each inset denotes correspondingly the tapping-mode AFM height images. The scope of the AFM images is 5 mm.
Figure 3.28 GISAXS patterns acquired for six polymer films with offset vertically for clarity. The arrows indicate the first-order diffuse Bragg sheet.
Figure 3.29 (a) TEM image, (b) cryo-electron tomography image, and (c) cartoon of Ag-pyramids; (d) TEM image, (e) cryo-tomography image, and (f) cartoon of Ag-pyramids in the presence of PSA (30 nM). (g) Dynamic light scattering and (h) SAXS spectra of Ag-pyramids in the absence/presence of PSA (30 nM).
Figure 3.30 (a) Experimental and simulated GISAXS patterns of the Ia3d phase of 1/8. Spots of different colors belong to different reflection groups (see legend). Simulated spots within a group are generated by permutation of {hkl} indices while keeping one of the {211} planes horizontal. Solid circles, observed; open circles, hidden below horizon. (b) Model of the infinite networks in an unit cell intersected by horizontal (211) planes.
Figure 3.31 Integral scatter distribution reconstructed by FBP [(a)–(c)] and OSEM [(d)–(f)].
Figure 3.32 Flow chart of quantitative assessment of a micro-CT image.
Figure 3.33 (a) Schematics of STXM with a divergent beam downstream of the exit slit. The FZP produces a diffraction-limited focus, the OSA selects only the first-order focus, and the detector measures intensity of the photons transmitted from the sample [121]. (b) Stage stacks inside the vacuum chamber, showing the modules and stages.
Figure 3.34 (a) Stack analysis on a stack-scanned image at energies around Fe
L
edges of γ-FeOOH nanosheets (yellow area) and nanoparticles (blue area) on reduced graphene oxide (rGO) . (b) The Fe
L
-edge absorption obtained by stack analysis showing the valance of Fe
3+
in the nanosheets [124]. (Reproduced with permission of Royal Society of Chemistry.)
Figure 3.35 Grating-based interferometry: two beam scheme (a), four beam scheme (b). 1D line patterns and 2D dot patterns are fabricated respectively.
Figure 3.36 SEM images of patterned dot arrays and line-space structures with different half pitch(HP) values in HSQ resist. (a) HSQ dot array with HP = 11 nm. (b) HSQ line-space structures with HP = 7 nm.
Figure 3.37 The schematic layout of the SSRF-XIL beamline.
Figure 3.38 (a) SEM images of the XIL patterns on the MG resist [132], (b) left: Raman spectra of different concentration Rh6G on Au nanodisk arrays [133]: (i)10
−5
M, (ii) 10
−6
M, (iii) 10
−7
M of R6G, respectively, right: SERS map (40.0 × 40.0 µm
2
), (c) Au nanodisk arrays fabricated by XIL.
Figure 3.39 Working principle: angle-resolved photoemission spectroscopy (ARPES) shown in (a), (b). [136]. (Reproduced with permission of Springer.)
Figure 3.40 In (a) demonstrated is the ARPES experimental station at Dreamline beamline at SSRF and (b) the energy resolution (17.2 meV @ 867 eV) of the beamline as measured via the step-width of Au Fermi level cooled at 13 K.
Figure 3.41 Relationship of bulk Weyl nodes and surface Fermi arcs [139]. (Reproduced with permission of Nature Publishing Group.)
Figure 3.42 Schematic diagram of an X-PEEM instrument with synchrotron radiation as its light source. (1) electron gun, (2)–(4) focusing electromagnetic lens, (5) electron beam separator, (6) transfer lens, (7) field electromagnetic lens, (8) intermediate electromagnetic lens, (9) projection lens 1, (10) retarding lens, (11) imaging lens 1, (12) electron energy analyzer, (13) imaging lens 2, (14) accelerating lens, (15) and (16) projection lens 2 and 3, (17) MCP and scintillator screen, (18) objective lens, (19) samples, (20) illumination aperture, (21) selected area aperture, (22) contrast aperture, (23) slit of electron energy analyzer.
Figure 3.43 (a) The PEEM experimental station at BL09U at SSRF and (b) the spatial resolution (16 nm @ 200 eV) of the beamline as measured via the step-width of Pb island grown on Si(111) surface measured at BL09U SSRF.
Figure 3.44 X-PEEM images and local spectra from the antiferromagnetic and ferromagnetic layers for 1.2 nm Co on LaFeO
3
/SrTiO
3
(001). (a) Fe
L
-edge XMLD image; (b) Co
L
-edge XMCD image. The respective spectra were recorded in the indicated areas and illustrate the origin of the intensity contrast in the X-PEEM images [144]. (Reproduced with permission of Nature Publishing Group.)
Figure 3.45 (a) Direct RIXS process. The incoming X-ray excites an electron from a deep-lying core level into the empty valence. The empty core state is subsequently filled by an electron from the occupied states under the emission of an X-ray. This RIXS process creates a valence excitation with momentum
k
′ −
k
and energy
ω
k
−
ω
k
′
. (b) Elementary excitations in condensed matter systems that can be measured by RIXS. The indicated energy scales are the ones relevant for transition metal-oxides.
Chapter 4: Photon-In Photon-Out Spectroscopic Techniques for Materials Analysis: Some Recent Developments
Figure 4.1 Schematic showing the excitation of an atom (blue circle) of element A in a solid containing atoms of element A and B (orange circle) with incident photon energy,
E
i
≥ threshold energy of an absorption edge of A and the emission of corresponding fluorescence X-ray with energy
E
f
at a give angle of incidence,
α
and an angle of emission,
β
;
z
is the depth axis.
l
α
= z/sin
α
and
l
β
=
z
/sin
β
is the attenuation length of the incident photon and the fluorescent X-ray, respectively. The same process takes place at atoms of B if
E
i
is greater than the threshold of B. The PFY and inverse partial florescence yield techniques discussed here are intimately related to these processes.
Figure 4.2 Schematics showing the excitation of an atom A in a solid with incident photon energy,
E
i
≥ threshold energy of an absorption edge of A, and the emission of corresponding Auger electrons with energy
E
Auger
at a given angle of incidence
α
and an angle of emission
β
, respectively;
z
is the depth axis.
l
α
=
z
/sinα and
l
β
=
z
/sin
β
is the attenuation length of the incident photon and the Auger electrons, respectively. The circled region, magnified on the right shows energy transfer from the Auger electron to the optical channel via inelastic scattering as the electron is thermalized in the solid. The length of the thermalization track can be understood in terms of the kinetic-energy-dependent escape depth (1/
e
attenuation) of the electrons shown in the universal curve.
Figure 4.3 (a) 2D display of excitation energy across the Fe
L
3,2
-edge (
y
axis) versus fluorescence X-ray energy (
x
-axis) from O and Fe detected with a silicon drift detector (SDD). The fluorescence X-ray energy (in pixels) of O
K
α
(∼525 eV) and Fe
L
α
1,2
, (∼705 eV) are marked with a vertical dotted line (intensity color coded). The Fe
L
3,2
-edge XANES (white trace) is also shown. (b): XANES recorded with TEY, FLY (Fe
L
α
), and IPFY (O
K
α
).
Figure 4.4 (a) 2D XANES-XEOL map across N and O
K
-edges with TEY overlaid (blue), black line denotes the window where optical-XANES were collected. (b) XEOL cuts taken across N and O
K-
edge at selected excitation. (c) Wavelength selected PLY (red) versus TEY across N and O
K
-edge. (d) 2D XANES-XEOL across Zn and Ga
L
3,2
-edge with TEY overlaid (blue). (e) XEOL cuts taken across Zn and Ga
L
3,2
edges. (f) Wavelength selected PLY (red) versus TEY across Zn and Ga
L
3,2
-edges [23]. (Reproduced with permission of John Wiley & Sons.)
Figure 4.5 (a) Five nanoseconds streak image of XEOL (340–640 nm) from GZNO excited at 550 eV. (b) XEOL decay lifetime taken from blue (400 nm) and red (550 nm) windows of the streak image, respectively. (c) Fast and slow XEOL taken from 0.5–0.6 ns and 1.45–1.55 ns time windows, respectively. (d) XEOL of GZNO recorded using ungated, 0.5–0.6 ns, 1.45–1.55 ns, and 0.5–5.0 ns time windows with maximum intensity normalized to unity.
Chapter 5: Quantitative Femtosecond Charge Transfer Dynamics at Organic/Electrode Interfaces Studied by Core-Hole Clock Spectroscopy
Figure 5.1 Schematic overview of different photoexcitation and decay processes. Direct photoemission from valence state (a) and core level (b). Resonant excitation of a core level electron to the LUMOs (c) and the subsequent competitive core-hole decay processes of spectator decay (resonant Auger) (d), participator decay(resonant photoemission) (e) and charge transfer of excited electron to substrate conduction band (f). Normal Auger decay process (g) follows either (f) or (b) process.
Figure 5.2 Schematic diagrams of the relative alignment between the
E
F
of the metal substrate and the LUMOs of organic molecules in the ground states (a) and in their excited states (b), and between LUMOs and CB edge of semiconductor substrate in their excited states (c).
E
F
and
E
vac
represents the Fermi level and vacuum level, respectively. BE is the binding energy of core level referred to
E
F
. Δ
E
in (b) and (c) represents the relative position of LUMOs relative to
E
F
and CB edge, respectively. (d) VB and re-scaled C
K
-edge NEXAFS spectra for 1 ML PTCDA on metal (Au) and semiconductor (TiO
2
), respectively. The relative BE of NEXAFS was referenced to the C 1s (perylene core) core level BE of PTCDA. VB spectra were measured using photon energy of 60 eV. The
E
F
of Au is marked by dashed line, and the CB edge and VB edge of TiO
2
relative to
E
F
are drawn as a guide.
Figure 5.3 Schematic view of an organic vacuum deposition system (a). Preparation of SAMs in solution and the subsequently assembled closely packed molecular layer on a substrate (b).
Figure 5.4 RPES contour plots for monolayer (a) and multilayer (b) PTCDA on Au(111). The bottom spectra in panel (a) and (b) are corresponding VB spectra measured with photon energy of 60 eV and the spectra on the left side is their respective NEXAFS spectra. (c) Integrated RPES and the corresponding C
K
-edge NEXAFS spectra for the monolayer and multilayer PTCDA molecules on Au(111). The backgrounds are marked by the dashed lines. (d) An illustration of interfacial charge transfer for PTCDA molecule physisorbed on Au(111) with lying down configuration. The charge transfer times from both C
perylene
and C
anhydride
sites are indicated.
Figure 5.5 RPES contour plots for multilayer (a), tilted (b), and flat phase (c) BDA on Au(111). The white dashed line in each panel indicates the high BE cutoff of integration window. (d) and (e) Show the integrated RPES spectra for each film at C and N
K
-edge, respectively. The intensity is normalized to the maximum intensity of RPES spectra for multilayer. (f) Calculated LUMO and LUMO+1 orbital of BDA and an illustration of charge transfer from BDA molecule to Au(111) with both lying down or tilted configuration.
Figure 5.6 Schematic illustration of the orbital geometries for
c
(4 × 2)S/Ru(0001) system (a) and Au−S−(CH
2
)
2
−CN SAMs on Au (b). In panel (a), out-of-plane excitation (S 2s → ) and in-plane excitation (S 2s → ) are achieved separately when synchrotron radiation is polarized either perpendicular or parallel to the surface, respectively. In panel (b). The electrons from an inner shell can be selectively excited into the two symmetry-split π* orbitals of and associated with the terminal nitrile moieties (−CN) using well-defined polarized X-rays. The corresponding charge transfer times are indicated.
Figure 5.7 Schematic interfacial structure of N3 molecule on ultrathin Al
10
O
13
(three atomic layers) formed on AlNi(110) (a). Schematic of the relative alignment between the LUMOs of core-excited N3 molecules and the
E
F
of the metal substrate (b). RPES contour plots for multilayer and monolayer N3 molecule on Al
10
O
13
/AlNi(110). (d) Integrated RPES and the corresponding N
K
-edge NEXAFS spectra. The integration windows from 0 to 9 eV are indicated by solid lines in (c).
Figure 5.8 Molecular structure of an N3 dye (a). Schematic illustration of the operation principle and relevant energy diagrams (bottom) of a DSSC (b). Adsorption geometry of bi-isonicotinic acid on TiO
2
(110) via covalent O−Ti bond through deprotonation of carboxylic acid groups (c).
Figure 5.9 RPES contour plots for sub-monolayer (a) and monolayer (b) PTCDA on rutile TiO
2
(110) 1 × 1 surface. The bottom spectra of each panel are corresponding VB spectra measured with photon energy of 60 eV and the spectra on the left side are their respective NEXAFS spectra. (c) Integrated RPES and the corresponding C
K
-edge NEXAFS spectra for the sub-monolayer, monolayer, and multilayer PTCDA molecules on rutile TiO
2
(110). The inset spectra show the integrated RPES at C
anhydride
1s → LUMO and C
anhydride
1s → LUMO+1∼LUMO+3 resonances after removing the linear background marked by the dashed blue lines. (d) An illustration of interfacial charge transfer for PTCDA molecule on TiO
2
(110) with slightly tilted and tilted configuration.
Figure 5.10 A schematic of the SAM designs for charge transfer dynamics investigations using the CHC technique (a). The charge transfer pathway is well defined: electrons from N inner-shell in the well-defined tail group are photo-excited to unoccupied orbitals, and subsequently transferred to the substrate though the molecular backbone and across the headgroup-substrate (S−Au) anchor. The molecular structures of nitrile-substituted SAM precursors studied by RAES (b).
Figure 5.11 SAM precursors (a) and N
K
-edge NEXAFS spectrum for NC-OPE1 on Au (b). The inset in (b) shows the calculated molecular orbitals for corresponding resonances. The RAES spectra at and resonant energies fitted by a linear combination of normal Auger spectrum (red curve) and resonant spectrum (blue line) for NC-OPE1 (c), NC-PT1 (d), and NC-BP0 (e), respectively. The background photoelectron signals in the same KE range probed with pre-edge excitation photon energy are subtracted from all RAES spectra.
Figure 5.12 RPES contour plots for multilayer (a) and monolayer (b) of 44PCP on Au(111). A schematic of charge transfer time estimated by RPES is shown in (c). The corresponding results for 22PCP are shown in (d)–(f).
Chapter 6: Experimental Study of Ferroelectric Materials by Coherent X-ray Scattering
Figure 6.1 (A
)
X-ray speckles experiment set-up, the reflection scheme for speckles measurement by means of table-top plasma-based soft X-ray laser source. X-ray pulse came from an Ag slab target pumped by a 10 J, picoseconds glass laser. The grazing angle into the BaTiO
3
single crystal was 10°. The coordinates,
x
and
q
, are in the horizontal direction. The temperature of the BaTiO
3
can be controlled from room temperature to 500 K. (B
)
Single-shot speckle patterns measured by a reflectance set-up as panel (A) shows speckles patterns from
a/c-
domain structures, where, (a) is the direct probing beam pattern, (b) is the diffraction patterns via the
a/c-
domain region at room temperature 24 °C; (c)–(h) corresponds to the diffraction pattern from the same region of the sample at temperature 106, 118, 119, 120, 121, and 130 °C, respectively.
Figure 6.2 Speckles patterns induced by polarization clusters, where, (a) and (b) are the instantaneous speckles patterns at 123.5 °C with and without undergoing an external electric field (2 kV cm
−1
normal to the BaTiO
3
surface), and (c) shows their quantitative vertical intensity distribution. The apparently broadened shape in vertical direction indicates the existence of clusters.
Figure 6.3 (a) Autocorrelation function (b) temperature dependence of cluster size
σ
, cluster distance
d
, and polarization density.
Figure 6.4 Principle of the active-type intensity correlation method.
Figure 6.5 Time correlation of intensity as a function of delay between double pulse.
Chapter 7: Probing Organic Solar Cells with Grazing Incidence Scattering Techniques
Figure 7.1 Schematic picture of the experimental setup used in GISAXS or GIWAXS. The detection of diffuse scattering is done with a 2D detector. The sample surface is placed nearly horizontally, inclined by an incident angle
α
i
. The exit angle is denoted
α
f
and the out-of-plane angle
ψ
. The color coding visualizes differences in the scattered intensity. Typical sample-detector distances for GIWAXS and GISAXS are given.
Figure 7.2 Sketch of film crystallinity and corresponding 2D GIWAXS data in case of (a) vertical lamellar stacking, (b) crystallites with vertical and horizontal orientation, (c) oriented domains, and (d) full rotational disorder of crystallites. The GISAXS signal is blocked by a beam stop (black box).
Figure 7.3 2D GIWAXS image of an as-cast P3HT thin film with indication of the most prominent Bragg reflections in the sample plane and out-of the sample plane. The red boxes indicate the region where the peak integration takes place.
Figure 7.4 GIWAXS data of neat PCPDTBT films cast from chlorobenzene. (a) As obtained from the experiment. The overlay demonstrates the geometry of radial and azimuthal binning. (b) The data from (a) in sector plot form with the positions of the two different alkyl chain stacking peaks highlighted (i.e., Alkyl 1 and Alkyl 2). Sector plots obtained from films obtained from chlorobenzene and (c) 3% DIO, and (d) 3% ODT.
Figure 7.5 (a) Schematic of the semicrystalline structure of regioregular P3HT.
a
,
b
, and
c
represent the crystal lattice constants;
d
c
and
d
a
are the thicknesses of the crystal and amorphous lamellae, respectively;
L
p
=
d
c
+
d
a
is the long period. Note that P3HT with molecular weights of 11.7 kg mol
−1
forms fully chain-extended crystals without any chain folds. (b) Combined SAXS and WAXS scattering pattern of a pure bulk P3HT sample. The reflections resulting from the semicrystalline structures in part (a) are indicated.
Figure 7.6 Schematic representation of the three phases coexisting in a P3HT:PCBM film on a solid support: Crystalline P3HT regions are surrounded by a dotted (yellow) line and increase via thermal annealing. In addition, a pure PCBM and a mixed P3HT:PCBM phase are present.
Figure 7.7 (a) Reduced 1D GIWAXS profiles of pristine P3HT, P3HT/PC
60
BM, and P3HT/PC
70
BM films. (b) Schematics of molecular-level structures for pristine and intercalated P3HT (the locally intercalated fullerene between the slightly disordered side chains) and structures of P3HT-crystal/PC
x
BM domains in P3HT/PC
x
BM films.
Figure 7.8 2-D GIWAXS images of as-cast thin films, top to bottom: P3HT, 3 : 1 P3HT-PCBM blend, 1 : 1 P3HT-PCBM blend, 1 : 3 P3HT-PCBM blend, and PCBM. The images on the left are spin cast from 2 mg mL
−1
in chloroform, and the images in the right are spin cast from 2 mg mL
−1
in chlorobenzene.
Figure 7.9 (A) Normalized crystallization and aggregation peak intensities as a function of the spinning time during the spin coating of P3HT:PCBM (62.5 wt% : 37.5 wt%). The inset indicates the time range where crystallization and phase separation occur. The onset of film formation
t
onset
and its duration Δ
t
formation
are defined in the green inset. (B) Thickness versus time of the solution during the spin coating process of the pure solvent and the P3HT:PCBM solution.
Figure 7.10 Two-dimensional GIWAXS patterns of the active layer. The weight ratio of
p
-DTS(FBTTH
2
)
2
is indicated in each image. (a) PTB7-Th:PC
71
BM (1 : 1.1), (b) PTB7-Th:
p
-DTS(FBTTH
2
)
2
:PC
71
BM (0.95 : 0.05 : 1.1), (c) PTB7-Th:
p
-DTS(FBTTH
2
)
2
:PC
71
BM (0.90 : 0.1 : 1.1), (d) PTB7-Th:
p
-DTS(FBTTH
2
)
2
:PC
71
BM (0.85 : 0.15 : 1.1), (e)
p
-DTS(FBTTH
2
)
2
:PC
71
BM (1 : 1.1), and (f) PTB7-Th:
p
-DTS(FBTTH
2
)
2
(0.85 : 0.15). The out-of-plane (g) and in-plane (h) cuts of the corresponding 2D GIWAXS patterns. (010) diffraction peak is enlarged in the inset profile. (i) FWHM of the (010) peak (black symbols) and the correlation length of the π–π stacking (red symbols).
Figure 7.11 (a) Selected GISAXS profiles measured for the P3HT/PCBM film (
c
= 1.0) during the heating process to 150 °C and the subsequent isothermal annealing within 60 s. The data are fitted (solid curves) using polydisperse spheres with the Schultz size distributions shown in (b).
Figure 7.12 Double-logarithmic plot of horizontal cuts taken at the critical angle of PCBM from 2d GISAXS measurements from as-spun (circles, lower four curves) and annealed (triangles, upper four curves) P3HT:PCBM films made from four different solvents. Curves from bottom to top refer to P3HT:PCBM films made from chloroform, toluene, cholorbenzen, and xylene solutions for each case. The dashed line indicates the resolution limit for GISAXS. All curves are shifted along the
y
-axis for clarity.
Figure 7.13 Black-and-white schematic morphology of annealed P3HT:PCBM films made from chloroform (CF), toluene, chlorobenzene (CB), and xylene solutions reconstructed from AFM, X-ray reflectivity, and GISAXS investigations. Black areas correspond to pure PCBM phases and white to pure P3HT phases. Characteristic lengths are indicated.
Figure 7.14 Data of GISAXS measurement at RT: (a) Mapping of horizontal line cuts of the GISAXS data plotted against time showing the structure evolution of the prominent shoulder at
q
x
,
y
≈ 0.25–0.3 nm
−1
. (b) Binned data of the horizontal line cuts (black dots) from 0 to 60 s in steps of 10 s along with the respective modeled data (solid red lines), as well as the unbinned data for the final film (top). The data are shifted along the intensity axis for clarity. The evolution of the prominent shoulder is highlighted by red arrows.
Figure 7.15 GI-RSoXS reciprocal space analysis of the hexagonally structured polymer–polymer interface. Scattering patterns originating from the imprinted P(NDI2OD-T2) film without capping layer (a), with solution-coated PS homopolymer on top (b) and with solution-coated P3HT on top (c). The logarithmic scale of the scattering intensity is in arbitrary units. Red represents low intensity, and blue represents high intensity. A horizontal cut summary of the three different architectures with the corresponding Miller indices is given in (d). The (10) and (11) scattering planes originating from the 2D AAO honeycomb master mold structure are highlighted in (e). A period of 103.7 nm is calculated from the (10) scattering plane (inset of e).
Chapter 8: Investigating Strain in Silicon-on-Insulator Nanostructures by Coherent X-ray Diffraction
Figure 8.1 Schematic views of (a) a lens-based imaging system and (b) a lens-less imaging system where the active area of the detector is highlighted in blue. For lens-less imaging, the maximum spatial frequency collected in the diffraction pattern in principle determines the reconstruction resolution.
Figure 8.2 Sketch of three different imaging regions in lens-less imaging system defined as a function of the Fresnel distance , where
a
is the sample size and
λ
is the wavelength.
Figure 8.3 Process flow for a typical phase retrieval algorithm.
Figure 8.4 Experimental configuration for (a) plane wave forward scattering CDI, in which a coherent beam illuminates the whole sample; and (b) Fresnel CDI in which a coherent phase-curved beam generated with Fresnel zone plate illuminates either a whole sample or part of a sample.
Figure 8.5 (a) Schematic view of a hexagonal-shaped crystal, where the dots correspond to lattice points (left); and the corresponding diffraction pattern in reciprocal space (right). Also shown here are the incoming (
k
i
) and outgoing (
k
f
) wave-vectors sketched according to the Ewald construction. As the crystal is rotated the diffraction patterns are collected by the detector (shown as a straight line perpendicular to the
k
f
direction). (b) A crystal with the same size and shape as the one in (a), but with an edge dislocation inside the crystal (left) and the corresponding diffraction pattern in reciprocal space (right). (c) Typical experimental setup for Bragg CDI.
Figure 8.6 Biaxial tensile strain effects on the conduction and valence bands of silicon (100). (a) In the conduction band, the sixfold degeneracy is lifted and electrons become repopulated into the lower energy ∆
2
sub-band, which causes the average effective mass to decrease and inter-band scattering to reduce, thereby increasing the electron mobility; (b) in the valence band, the hole mobility enhancement is mainly due to the reduction of the phonon scattering caused by the lifting of the twofold degeneracy and lowering of the spin-off band.
Figure 8.7 Schematic presentation of the process flow for the fabrication of an sSOI wafer. (a) Growth of the relaxed SiGe substrate; (b) growth of the biaxially tensile strained Si on the SiGe substrate; (c) hydrogen ion implantation into the grown heterostructure; (d) bonding of the hydrogen implanted heterostructure to a SiO
2
/Si substrate; (e) thermal annealing induced layer exfoliation around the hydrogen implantation depth; (f) strained Si layer directly on SiO
2
/Si obtained after the removal of the residual SiGe with selective etch.
Figure 8.8 Schematic presentation of the process flow for patterning square strained silicon structures on an sSOI substrate, using E-beam lithography.
Figure 8.9 (a) High resolution TEM image of the edge profile of the strained-silicon-on-insulator structure after RIE etch; inset is the zoomed in view; (b) AFM image of a 20 nm thick strained Si structure and (c) the height profile across the center of the structure.
Figure 8.10 Schematic drawing of experimental geometry. The detector was positioned 1.5 m from the sample, with in-plane angle
δ
= 21.3
°
, out-of-plane angle
γ
= 14.6°, Bragg angle 2
θ
= 25.3° for Si (−111) diffraction.
Figure 8.11 (a) The 2D diffraction frame collected at the center position of the rocking curve; (b) the 3D diffraction pattern obtained by stacking the collected 2D frames together, projected in the direction perpendicular to the sSOI thickness axis.
Figure 8.12 The reconstructed amplitude (a), phase (b), and a cross-section plot of the phase variation along the
x
direction (black square), with the COMSOL-simulated displacement (red dashed line) (c).
Figure 8.13 Schematic side view of the modeling system (a) and the simulated in-plane displacement in the
x
direction (b).
Figure 8.14 Diffraction pattern (central frame of the (−111) reflection) for an array of 11 sSOI wires (a); and the reconstructed phase map with the amplitude (translucent white) superimposed (b). scale bar = 300 nm.
Chapter 9: Synchrotron Soft X-ray Absorption Spectroscopy Study of Carbon and Silicon Nanostructures for Energy Applications
Figure 9.1 TEY of carbon
K
-edge XANES of CNTs and CNx (NCNTs).
Figure 9.2 Comparison of C
K
-edge XANES spectra of GO, GRA-200 (graphene treated at 200 °C), GRA-300, GRA-400, GRA-500, and GRA-600. The inset shows the TEM image of GRA-500.
Figure 9.3 C
K
-edge XANES of N-rmGO (blue curve) and Co
3
O
4
/N-rmGO hybrid (red curve). Inset shows O
K
-edge XANES of Co
3
O
4
(black curve) and Co
3
O
4
/N-rmGO hybrid (red curve).
Figure 9.4 STXM chemical maps of partially charged LMFP–C for visualizing the Fe valance distribution: (a) Fe
2+
and (b) Fe
3+
; (c) the color composite map of Fe
2+
and Fe
3+
(blue: Fe
2+
, red: Fe
3+
). The selected Fe
2+
and Fe
3+
regions are highlighted by the rectangular and circular box, respectively; (d) C
K
-edge XANES from the selected areas as displayed in (c).
Figure 9.5 (a) Representative pattern of GO immobilizing S. (b) C
K
-edge XAS spectra of GO and GO–S nanocomposites after heat treatment.
Figure 9.6 (a) TEM image and (b) STXM map (at the C
K
-edge) of CNTs, (c) C
K
-edge XANES spectra of tubes 1–5 labeled in panel (b), and (d) normalized XANES spectra of tubes 1–5 in panel (c).
Figure 9.7 (a) TEM image of CNTs, (b) magnified TEM image of some part of the CNT labeled as a circle in (a), (c)–(e) STXM chemical maps and XANES spectra of CNTs: (c) Fe map, (d) color composite mapping (green: CNTs, red: coating) at the C
K
-edge, and (e) C
K
-edge XANES spectra of CNTs (green) and coating (red) from the corresponding regions in (d).
Figure 9.8 (A) Si
K
-edge XANES of a core/shell Si/SiO
2
NW recorded in TEY, FLY, PLY, and wavelength-selected PLY; vertical line marks the resonance position of the white line of Si and SiO
2
. (B) XEOL excited with photon energy varying from below to above the Si
K
-edge and at the white line resonance corresponding to the Si core and the SiO
2
shell (b inset); the TEY is also shown (a inset).
Figure 9.9 (a) XES excited with photon energy above the
L
3,2
-edge. Several XES spectra are shown: XES of interest are “SiNW (as-prepared)” (Si/SiO
2
core/shell), SiNW (HF) with oxide shell removed, clean Si(100) wafer and porous silicon, PS; the smooth curves (red and blue) trace the XES data points to guide the eye. (b) XPS valence band of the same sample of SiNW (as prepared and HF treated samples as well as the references (Si(100) and PS). The smooth curves are drawn to guide the eye.
Figure 9.10 (a) and (b): Si
K
-edge XANES recorded in TEY and FLY, respectively, for LDNW and HDNW at each stage of oxidation and for porous silicon (PS); the vertical line marks the position of the WL of Si and SiO
2
. (c): XEOL excited at 1900 eV. The number after the dashed line denotes the temperature in °C at which the oxidation was carried out for 2 h. The sample labeled SiO
2
is in fact LDNW oxidized at 1000 °C for 6 hours whence element Si signal is no longer detectable at both TEY and FLY of the Si
K
-edge XANES.
Figure 9.11 Si
K
-edge XAFS of nanoparticle-chain nanowires (∼10 nm) with a series of chemical treatments: (A) TEY and (B) FLY. Curves a, b, and c correspond to the as-prepared, the HF-etched, and the AgNO
3
(1 × 10
−4
M)-treated SiNWs, respectively.
Figure 9.12 Ag
L
3,2
-edge XANES (TEY) of Ag/SiNWs (∼10 nm) compared with that of Ag metal.
Figure 9.13 (a) Normalized FLY Si
K
-edge XANES spectra for HSQ thermally processed between 500 and 1100 °C for 1 h in 5% H
2
/95% Ar. FLY spectra are also included for SiO
2
and elemental Si standards for comparison. The absorption maxima for Si and SiO
2
, 1841 and 1848 eV, respectively are noted for reference. Spectra have been shifted vertically for clarity. (b): (A) Schematic of the thermal degradation of HSQ to form oxide-embedded Si-NCs. (B) and (C) HSQ has a theoretical silicon-to-oxygen ratio of 1 : 1.5, and a Si
K
-edge absorption maximum at 1845 eV, an energy between that of the products, elemental Si (1841 eV) and SiO
2
(1848 eV).
Figure 9.14 (a)
L
3,2
absorption spectra for bulk Si and NC-Si deposited on oxidized Ge with an average diameter of 1.6 nm. (b) Photoemission spectra for the valence band of bulk Si and the NC-Si with average diameter of 1.6 nm. The VB spectra were referenced to the Si 2p core level.
Figure 9.15 (a) All solid-state “naked battery” designed by Alamgir's group for
in situ
studies, (b) the schematic of its composite structure, (c) the spectroscopic cell assembly, and (d) spectra acquired
in situ
from O
K
-edge (right) using this cell.
Figure 9.16 (A) Comparison between CoPt and Co NPs in one bar of He or H
2
at elevated temperatures. Co is completely reduced to metal at 38 °C in the CoPt NPs, while Co in pure Co NPs is only partially reduced at 250 °C (a). Soft X-ray scan penetrate in and out through the 100 nm silicon nitride membrane window (b). (B) (a)The gas inlet and outlet, cooling and heating; (b) sample mounting; and (c) the assembly. (C) O
K
-edge for reduced 4, 10, and 15 nm cobalt nanoparticles after exposure to 1 : 1 CO/He at RT and 250 °C (a). Co
L
-edge for 4 and 15 nm nanoparticles under the same conditions as for the O
K
-edge (b).
Chapter 10: Synchrotron-Radiation-Based Soft X-ray Electron Spectroscopies Applied to Structural and Chemical Characterization of Isolated Species, from Molecules to Nano-objects
Figure 10.1 From atoms to nanoparticles. SR-based soft X-ray spectroscopy provides a wealth of information on gas-phase systems of various levels of complexity, including, for example, (from left to right): electronic structure of isolated
atoms
and their photoionization dynamics; ro-vibronic structure and multidimensional potential energy surfaces of
molecules
, their X-ray-induced fragmentation pathways and structure (bond lengths and angles) being encoded into the relative partial cross sections and molecular frame angular distributions (MFPADs); elemental composition and structural properties of
clusters and nanoparticles
encoded into their photoionization cross sections, binding energy shifts, surface-to-bulk intensity ratios, and (photoelectron) extended X-ray absorption fine structure ((P)EXAFS signal); elemental and structural analysis of
nanoparticles and agglomerates of nanoparticles
such as their core–shell structures, surface segregation, crystal structure, bond lengths, and surface chemistry (e.g. growth of an oxidation shell).
Figure 10.2 Typical setup of a third generation synchrotron soft X-ray beamline.
Figure 10.3 Schematic representation of the EPICEA coincidence spectrometer permanently installed at the PLEIADES beamline.
Figure 10.4 The rotational envelope of a selected vibrational substate of the 5 photoline consists of a narrow Cl contribution (blue solid line) and a broad pedestal related to the H contribution (black solid line). The Cl contribution is formed by the P and R rotational branches related to the angular momentum transfer from the X-ray photon to the molecule (emission takes place close to the center of gravity (CG)), while the broad H band is mainly due to the angular momentum transfer from the fast photoelectron ejected from the hydrogen site far from the CG.
Figure 10.5 (a) C 1s photoelectron spectrum of trichloroethane. (b) The intensity ratio between the chlorinated carbon and the methyl carbon (diamonds are experimental data points, solid curve is a simulation) oscillates as a function of the energy of the ionizing radiation and thus as a function of the outgoing photoelectron. The schematic picture of the trichloroethane shows that if the photoelectron is emitted from a chlorinated carbon (black), the chlorine atoms (green) and neighboring carbon atom serve as sources for backscattered waves with which the original outgoing photoelectron wave interferes. It results into minima and maxima in the relative cross section corresponding to destructive and constructive interference. Since the hydrogens (white) are weaker scatterers compared to chlorines, the amplitude of the oscillations is smaller if chlorines are substituted by hydrogens.
Figure 10.6 Comparison between two B 1s BF photoelectron spectra recorded with photon energies 275 and 303 eV (black circles and gray diamonds, respectively). The spectra have been normalized to the highest vibrational peak, = 2, in order to visualize the intensity redistribution between vibrational substates at these two photon energies. The inset shows the origin of the intensity redistribution – the intramolecular electron diffraction. The central boron atom is ionized after absorption of an X-ray photon, leading, in a simplified picture, to the light-colored spherical wave. This photoelectron wave is subsequently diffracted by the neighboring fluorine atoms, creating secondary spherical waves such as the one plotted in darker color around one of the fluorine atoms. The combination of the light and dark waves leads to interferences carrying structural information about the neutral ground-state BF molecule and the core-ionized BF molecular ion [43]. (Reproduced with permission of American Institute of Physics.)
Figure 10.7 (a) An example of the valence photoionization of N molecule, where from the interference pattern encoded to the vibrationally resolved relative cross sections a bond length of the molecule can be extracted, as an analog for the distance of the slits in the Young's double-slit experiment. (b) In the photoelectron spectrum of ethene, the
gerade
and
ungerade
C 2s – derived molecular orbitals can be resolved and the relative photoionization cross sections show also an enhanced interference pattern, due to the antiphase oscillations of the
gerade
and
ungerade
states. When the
gerade
and
ungerade
states cannot be resolved, as in the case of C 1s photoionization, the interference pattern is smeared out.
Figure 10.8 Illustration of the PEC mapping in the framework of the high-resolution RPE spectroscopy. (a) The seven lowest stationary vibrational wave functions in the core-excited state. (b) Comparison between the reconstructed molecular potentials of the 1 and 1 final ionic states (solid lines) based on the ultrahigh-resolution RPE data and
ab initio
calculated potentials (open circles). The uncertainty in the reconstructed PECs is represented by the thickness of the lines. The right turning point of the core-excited wave packet at = 6 is shown by the dashed line. (c) The experimental RPE spectra are presented in relation to the reconstructed PECs.
Figure 10.9 X-ray photoelectron spectra of Argon clusters created by adiabatic expansion with three different conditions leading to different means sizes (uppermost panel), (middle panel), and (lowest panel). Diamonds are experimental data points and solid lines are fitted Voigt curves whose asymmetric shape models the postcollision interaction. The spin–orbit split doublet is further divided into three components: atom, surface, and bulk. Owing to the lack of polarizable neighbors, photoelectrons from the isolated atom have higher binding energy than the corresponding cluster components. Correspondingly, photoelectrons emitted from a surface atom of a cluster have higher binding energy than the ones emitted from bulk atoms.
Figure 10.10 (a) The Rb 3d X-ray photoelectron spectrum of small RbCl clusters shows clearly different features corresponding to the corner (A), edge (B), and face (C) ionized atoms, and they are located at lower binding energies compared to the monomer peak. The binding energy shift from the monomer RbCl is larger the more neighbors the ionized site has. (b) Cl 2p photoelectron spectrum of clusters shows only one cluster component that lies at higher binding energies compared to the monomer peaks. Solid and lined peaks show the 3d and 3d components, respectively. The main peaks come from the uncondensed monomer RbCl.
Figure 10.11 Schematic of the experimental setup installed at the PLEIADES beamline to study gas-phase nanoparticles.
Figure 10.12 (a) Si 2p XPS spectrum obtained on air-oxidized freestanding Si nanocrystals at the PLEIADES beamline,
from Sublemontier et al
. [83]. (b) Schematic drawing of a heterojunction third generation solar cell comprising doped silicon quantum dots in a SiO matrix.
Figure 10.13 (a) Br 3d and Na 2s XPS spectra obtained on sea-salt nanoaerosols at the PLEIADES beamline. (b) Schematic drawing of bromide surface segregation in solid mixed sea-salt aerosols obtained from droplets.
Figure 10.14 O 1s XPS spectra obtained on freestanding TiO nanoparticles at the PLEIADES beamline (SOLEIL synchrotron radiation facility) directly after annealing of the nanopowder (red spectrum) and during
in situ
hydration by hot water evaporation (blue spectrum).
Chapter 11: X-ray Imaging for Nondestructive Analysis of Material Microstructures
Figure 11.1 Distribution of user research field at BL13W1.
Figure 11.2 Statistics of users' publications.
Figure 11.3 Reconstructed results of the wire sample and the respective histograms; the labels indicate the peak for each material.
Figure 11.4 Retrieving error versus
Z
2
, with
Z
1
being set to (a) 50 cm, (b) 100 cm, (c) 120 cm, and (d) 150 cm.
Figure 11.5 Reconstructions and histograms of electron density distribution of samples by direct (a) and PAD-based (b) PPCT at 60 keV.
Figure 11.6 A cross section of DCM-predicted structures. Images (a) and (b) are zinc and zinc oxide distribution maps, respectively; (c) is the compositional volume fraction along the lines in (a) and (b). Dashed line means zinc and solid line represents zinc oxide. Image (d) is a 3D compositional image of corroded zinc sample, in which red is zinc, green is zinc oxide, and yellow means mixture of both.
Figure 11.7 The setup with air bearing rotation stage and the sCOMS detector for dynamic quantitative X-ray microtomography.
Figure 11.8 Sample of bell cricket (region inside the red square was observed during the experiment) and the volume of the air sac as a function of time.
Figure 11.9 Graphical construction of 2D PPFFT and its inversion (a) and schematic layout of the iterative EST algorithm (b).
Figure 11.10 A comparison between the reconstruction results of FBP and EST.2.3.
Figure 11.11 The result of 3DXRD. Images (a) and (b) are center-of-mass position of far-field data along
z
- and
x
-axes; (c) reconstruction by Laguerre tessellation algorithm; (d) and (e) are center-of-mass position of combination of far-field and near-field along
z
- and
x
-axes; (f) reconstruction by grain sweeper algorithm; (g) orientation color coding given by the inverse pole figure.
Figure 11.12 (a) Tomographic slices of reconstructed scatter distributions and (b) reconstructed SAXS pattern at different locations.
Figure 11.13 Dendrite growth morphology in Sn–12 wt% Bi alloy sample: (a) without DC; (b) with DC (7 A cm
−2
); (c) with DC (32 A cm
−2
).
Figure 11.14 Growth morphology of primary α-Al grains during continuous cooling of ZA27: (a) without TiB
2
and (b) with 1.1% TiB
2
.
Figure 11.15
In situ
radiographs showing the diffusion behavior around the interface during the melting of Al/Cu bimetal: (a)
t
= 985 s,
T
= 863 K; (b)
t
= 1076 s,
T
= 893 K. The blue curve shows the gray level of each pixel along the red vertical line.
Figure 11.16 Structure evolution in solidifying Al–10 wt% Bi immiscible alloy with the cooling rate of 0.7 K s
−1
(A), and the behaviors of group bubbles and Bi droplets (B).
Figure 11.17 (A) (a) X-ray imaged cavitation bubbles in Al–10 wt% Cu alloy melt and (b) light intensity distribution (shown by gray level of a red curve and a green fitting one) along the centerline of an X-ray imaged cavitation bubble, where the upper dark area is the sonotrode, and the circular gray zone in the center is a cavitation bubble. (B) Size distribution of cavitation bubbles statistically obtained from X-ray image series. Red bars indicate well-fitted truncated Gaussian distributed bubbles while green bars are not.
Figure 11.18 Three-dimensional X-ray microtomography images of Al–20 wt% Bi alloys showing the size and spatial distribution of Bi-rich particles in Al matrix: (a) reference sample without grain refiners and (b) with 1 wt% Al–3Ti.
Figure 11.19 Tridimensional reconstruction of cross-section images by micro-CT at 4 and 12 weeks after production of a cavity defect in the rabbit femur.
Figure 11.20 Reconstructed slices of PS/PE (70 : 30) foams with different SEBS content: 0 wt% (a), 2 wt% (b), 5 wt% (c), and 10 wt% (d).
Figure 11.21 X-ray phase-contrast radiology images of hydrogen evolution reaction on PdP (273 nm) and NiP (314 nm) films for reaction time of 60 s, respectively.
Figure 11.22 Total and partial pair-correlation functions of liquid Ag
74
Ge
26
alloy at different temperatures.
Figure 11.23 3D structure images of SiC–Al in microwave sintering.
Figure 11.24 SR-CT 3D images of Sample 1 with 15% SCFs (untreated) under (a) 0 MPa load, (b) 40 MPa load, and (c) at sample failure. Sample 2 with 15% SCFs (oxidation treatment) under (d) 0 MPa load, (e) 40 MPa load, and (f) at sample failure.
Figure 11.25 Embedded fractal clusters: (a) section through composite containing SrCrO
4
