Journal of Electron Spectroscopy and Related Phenomena 232 (2019) 11–15

Contents lists available at ScienceDirect

Journal of Electron Spectroscopy and

Related Phenomena
journal homepage: www.elsevier.com/locate/elspec

Critical absorbed dose of resinous adhesive material towards non- T

destructive chemical-state analysis using soft X-rays
⁎
Hiroyuki Yamanea, , Masaki Ouraa, Kei Sawadaa, Tomio Ebisua, Tetsuya Ishikawaa,
Noriko Yamazakib, Koichi Hasegawac, Kiyoka Takagid, Takaki Hatsuia
a
RIKEN SPring-8 Center, Sayo, Hyogo 679-5148, Japan
b
Research & Innovation Center, Mitsubishi Heavy Industries, Ltd., Yokohama 220-8401, Japan
c
Research & Innovation Center, Mitsubishi Heavy Industries, Ltd., Nagoya 455-8515, Japan
d
Fixed Wing Aircraft Engineering Department, Mitsubishi Heavy Industries, Ltd., Toyoyama 480-0202, Japan

A R T I C LE I N FO A B S T R A C T

Keywords: The local electronic state of the N,N,N',N'-tetraglycidyl-4,4′-diaminodiphenylmethane epoxy resin cured with
X-ray absorption spectroscopy 4,4′-diaminodiphenylsulfone (TGDDM-DDS), one of model adhesive materials, was investigated by the O K-edge
X-ray emission spectroscopy X-ray absorption spectroscopy (XAS) and X-ray emission spectroscopy (XES). The total-electron-yield XAS
Radiation damage spectra for TGDDM-DDS as a function of the X-ray dose exhibit the exponential-like decrease in the curing-
Critical absorbed dose
derived pre-edge intensity due to the radiation damage. The quantitative analysis on the pre-edge intensity with
Adhesion
respect to the X-ray dose enables the determination of the critical absorbed dose for the chemical change on
TGDDM-DDS as 3.83 ± 0.01 MGy at 300 K. By using resonant XES with the well-focused X-ray beam, we found
that (i) the charged-particle equilibrium exists for the soft X-rays in the range of at least 0.001–0.847 mm2 beam
spot and that (ii) the half of the critical absorbed dose can be regarded as the limit indicator for the non-
destructive chemical-state characterization on resinous adhesive materials and interfaces using soft X-rays.

1. Introduction plastics, so-called CFRPs, as well as the high glass-transition tempera-

Soft X-ray spectroscopies using synchrotron radiation are well-es-
tablished techniques to investigate local electronic states of various
materials, and have been applied for in-situ/operando and microscopic
measurements [1–3]. The high energy and high spatial resolutions in
soft X-ray spectroscopies require the highly-brilliant and well-focused
incident photon beam, which, however, induces the radiation damage
particularly for soft matters [4–8]. The basic principle of the radiation-
induced chemical change of materials includes energy transfer and free
radical reactions, which often causes the misinterpretation on local
electronic states. Therefore, the impact of the radiation damage on
materials is important for the precise characterization of the local
electronic states.
In the present work, we shed light on the radiation damage of the
epoxy resin induced by soft X-rays. Epoxy resins are the most common
matrix materials for structural composites such as automobiles and
aircraft [9]. N,N,N',N'-tetraglycidyl-4,4′-diaminodiphenylmethane
(TGDDM) epoxy resin cured with 4,4′-diaminodiphenylsulfone (DDS),
hereafter TGDDM-DDS (Fig. 1), is an archetypal model material due to
the high adhesiveness and elasticity with carbon fiber reinforced
ture (i.e., high heat resistance). Because the oxygen element can play a
crucial role in the chemical interaction and the resultant adhesion
strength at epoxy-based adhesive interfaces [10], the element/site-
specific O K-edge X-ray absorption spectroscopy (XAS) is one of pow-
erful techniques to understand the chemical interaction at resinous
adhesive interfaces. The present surface-sensitive total-electron-yield
(TEY) and bulk-sensitive fluorescence-yield (FY) XAS measurements on
TGDDM-DDS, 4,4′-diaminodiphenylmethane (DDM)-cured epoxy resin
(TGDDM-DDM), and their individual constituents reveal the followings;
1) The pre-edge structure in the O K-edge XAS for TGDDM-DDS is as-
cribed to the hydroxy (RCeOH) group formed by the curing and/or
to the carboxyl group by the oxidation.
2) The pre-edge intensity in the O K-edge XAS decreases exponentially
with increasing the X-ray dose.
3) From the quantitative analysis of the pre-edge intensity as a function
of the X-ray dose, the critical absorbed dose for the chemical change
in TGDDM-DDS is determined to be 3.83 ± 0.01 MGy.
Furthermore, we demonstrate the availability of the critical

⁎
Corresponding author.
E-mail address: yamane@spring8.or.jp (H. Yamane).

https://doi.org/10.1016/j.elspec.2018.12.005
Received 19 September 2018; Received in revised form 20 December 2018; Accepted 22 December 2018
Available online 26 December 2018
0368-2048/ © 2019 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/BY/4.0/).
H. Yamane et al. Journal of Electron Spectroscopy and Related Phenomena 232 (2019) 11–15

Fig. 1. Chemical structure of TGDDM, DDS, DDM, and TGDDM-DDS.

absorbed dose for the non-destructive chemical-state characterization Table 2

by using the soft X-ray emission spectroscopy (XES) with the well-fo- Peak assignment of the ATR-IR spectrum of TGDDM-DDS in Fig. 2(b).
cused high-brilliant photon beam in terms of the charged-particle Label ν / cm−1 Assignment
equilibrium.
(1) 810 Aromatic bending
(2) 1105 CeN, CeO stretch
2. Experimental (3) 1142 CeN, CeO stretch
(4) 1514 CeC stretch (aromatic)
2.1. Sample preparation (5) 1593 C]C stretch (aromatic)
(6) 1670 C]O stretch
(7) 1720 C]O stretch
The uncured TGDDM (C25H30N2O4) epoxy resin was supplied from (8) 2880 CeH stretch
Nippon Steel & Sumikin Chemical Co., LTD. The curing agents of DDS (9) 3380 OeH stretch
(C12H12N2O2S, purity > 97.0%) and DDM (C13H14N2, purity > 98.0%)
were purchased from Tokyo Chemical Industry Co., LTD. The cured
TGDDM-DDS and TGDDM-DDM samples were prepared by the fol- between the sample surface and the sample holder (ground level) just
lowing steps. (i) The DDS (DDM) powder was introduced into the by pasting the carbon tape. Because the usual carbon tape consists of
TGDDM epoxy resin kept at 140 °C with the weight ratio of TGDDM : oxygen elements, we put the aluminum foil on the carbon tape to avoid
DDS = 1.00 : 0.52 (TGDDM : DDM = 1.00 : 0.42). (ii) After stirring, the the unexpected detection of extrinsic oxygen peaks. The TEY-XAS
mixture was cured at 150 °C for 3 h and post-cured at 180 °C for 2 h. (iii) spectra can be obtained by measuring the sample surface very close to
The cured TGDDM-DDS (TGDDM-DDM) sample was naturally cooled to the conductive path, which is not, however, applicable for powder
the room temperature for the spectroscopic experiment. materials such as DDS and DDM and gel-type materials such as uncured
TGDDM. All spectra were measured at the room temperature (ca.
300 K).
2.2. Soft X-ray spectroscopies

The O K-edge soft X-ray spectroscopy measurements using syn- 3. Results and discussion
chrotron radiation were performed at the soft X-ray undulator beamline
BL17SU at SPring-8 [11–13] and the soft X-ray dipole beamline BL4B at To characterize the spectral change in XAS upon the curing reaction,
UVSOR-III [14]. The beamline energy was calibrated by measuring Au the O K-edge charging-free FY-XAS spectra were measured for TGDDM-
4f photoemission spectra of Au using the 1st- and 2nd-order lights at DDS, TGDDM-DDM, DDS (powder), DDM (powder), and uncured
SPring-8 and O K-edge XAS spectra of SrTiO3 at UVSOR-III. The photon TGDDM, as shown in Fig. 2(a). The FY-XAS spectra for TGDDM and
flux (Nph) and the photon spot size at the sample surface (S) in the TEY- DDS show a quite weak pre-edge feature at the incident photon energy
XAS, FY-XAS, and XES experiments are summarized in Table 1. Due to (hvin) of 531.9 eV and 531.2 eV, respectively. On the other hand, al-
the insulating character of the epoxy resin, the sample-charging effect is though the DDM molecule consists of no oxygen element, the FY-XAS
non-negligible in the TEY-XAS measurement. The sample-charging ef- spectrum for DDM shows a quite weak spectral feature, which might
fect in electron spectroscopies has been avoided by various methods originate from a low-level oxygen-containing contaminant in the
such as the metal-atom deposition, the flood gun, and the photo- powder. Upon the curing through a dehydrogenation reaction (TGDDM-
conductive effect. In the present work, we prepared the conductive path DDS and TGDDM-DDM), prominent XAS features appear at
hvin = 532.6 eV and 538 eV, which are absent for unreacted TGDDM,
Table 1 DDS, and DDM. Therefore, the observed XAS features at
Photon-beam flux (Nph) and photon-beam spot size (S) in the TEY-XAS, FY-XAS, hvin = 532.6 eV and 538 eV can be ascribed to curing-derived peaks in
and XES measurements.
TGDDM-DDS and TGDDM-DDM. It is of note that the O K-edge XAS
Method Beamline Nph (ph/sec) S (mm2) feature at hvin < 534 eV is in general ascribed to the 1 s → π* transition.
The observation of the XAS feature at hvin = 532.6 eV for TGDDM-DDS
TEY-XAS UVSOR-III BL4B 6.3 × 109 0.847
and TGDDM-DDM is unexpected because no π* orbitals exist in usual
FY-XAS SPring-8 BL17SU 1.2 × 1010 0.022
XES SPring-8 BL17SU 3.0 × 1011 0.001 hydroxy (RCeOH) groups. It is known that the O K-edge XAS spectra for
gas-phase alcohols, such as methanol, ethanol, 1-propanol, and tert-

12
H. Yamane et al.
Fig. 2. (a) O K-edge FY-XAS spectra, measured for TGDDM-DDS, TGDDM-DDM,
DDS (powder), DDM (powder), and TGDDM (uncured epoxy). (b) ATR-IR
spectrum of TGDDM-DDS. The assignment of peaks (1)–(9) is summarized in
Table 2.
butyl alcohol, have a sharp pre-edge feature at hvin = 533.8 eV, which
is energetically higher than the present pre-edge feature at
hvin = 532.6 eV [15–17]. On the other hand, the O K-edge XAS spec-
trum for the water-methanol mixture has the pre-edge feature at
hvin = 532 eV as the result of the local electronic interaction between
water and methanol molecules [18]. In the present system, the electron-
accepting property in TGDDM-DDS and TGDDM-DDM such as the sul-
fonyl and/or phenyl groups might induce the intra- and/or inter-mo-
lecular energetic modification of the electron-donating RCeOH group,
as one of the possible origins of the XAS feature at hvin = 532.6 eV. The
other possible origin is the formation of the carboxyl group due to the
oxidation during the curing process. To examine the chemical species at
the surface region, the attenuated-total-reflection infrared red (ATR-IR)
spectrum was measured for TGDDM-DDS as shown in Fig. 2(b). The
OeH stretching vibration, derived from the dehydrogenation reaction
upon the curing, is found around the wavenumber (v) of 3380 cm−1. In
addition to the OeH stretching vibration, the ATR-IR spectrum exhibits
the C]O stretching vibrations at v = 1670 and 1720 cm−1, which
might originate from the oxidization during the curing process. The
oxidization can induce the 1 s → π* transition at the resultant C]O site,
which in general appears at hvin = 531–533 eV in the O K-edge XAS
spectra, depending on the chemical environment [19]. Both possibi-
lities due to the OeH and C]O groups might be convoluted in the pre-
edge feature in XAS, which consists of at least two components.
Using the curing-derived pre-edge XAS feature at hvin = 532.6 eV,
we examined the photon-induced radiation damage on TGDDM-DDS
near the surface region. Fig. 3 shows the O K-edge TEY-XAS spectra for
TGDDM-DDS as a function of the photon dose time (tdose), where the
TEY-XAS spectra were measured at every 600 s. The spectral shape of
TEY-XAS corresponds well to that of FY-XAS in Fig. 2(a), except for the
relative peak intensity due to the different probing depth. The TEY-XAS
spectra show the evidence for the radiation damage; the curing-derived
feature at hvin = 532.6 eV gets weakened with increasing tdose. The
intensity plot at hvin = 532.6 ± 0.5 eV as a function of tdose indicates
the exponential-like decay, as shown in the inset of Fig. 3. The TEY-XAS
intensity (IXAS) plot is fitted by
IXAS = Iinf + C exp(−tdose/tcdose) (1)
13
Journal of Electron Spectroscopy and Related Phenomena 232 (2019) 11–15
Fig. 3. O K-edge TEY-XAS spectra, measured for TGDDM-DDS as a function of
the X-ray dose time (tdose). The first-scan XAS spectrum, indicated by the gray
dashed curve, has a different background due to the remanent sample charging,
which disappears after the second-scan XAS spectrum. Inset shows the intensity
plot of the pre-edge feature in XAS at hvin = 532.6 ± 0.5 eV, together with the
least-squares fitting curve using Eq. (1).
where Iinf, C, and tcdose are the XAS intensity at the saturated damage
region, a constant dependent on materials, and the critical dose time for
chemical change of materials, respectively. The least-squares fitting
using Eq. (1) with IXAS = 1.0 at tdose = 0 s gives Iinf = 0.853, C = 0.147,
and tcdose = 4968 s. The critical flux density per unit area on the sample
surface (Nph tcdose / S) is thus determined as 3.68 × 1013 ph/mm2. Here,
the kinetic energy released in materials (kerma, K) is expressed as the
product between the irradiated photon flux (Nph tdose) and the absorbed
energy per unit mass by one photon,
K = Nph tdose × Ep(1 − T)/(λ S ρ) (2)
where Ep, T, λ, and ρ are the energy of particles, the transmission
probability, the probing depth, and the density of materials (1.05 g/cm3
for TGDDM-DDS), respectively. If the photoelectron attenuation length
in materials (typically, nm order in the soft X-ray region) is short en-
ough with respect to the photon-beam irradiation area, the charged-
particle equilibrium would exist, and therefore the kerma can be equal
to the absorbed dose (Da), Da/K = 1. Under the assumption that the
probing depth for O K-edge TEY-XAS is equal to the inelastic mean-free
path of photoelectrons from polymers emitted by Ep = 555 eV
(λ = 2–10 nm) [2,7,20–22], the transmission probability is calculated
to be T = 0.99265 when λ = 6 nm by using a method in Ref. [23].
These parameters determine the critical absorbed dose (Dca) as
3.83 ± 0.01 MGy (see, Appendix A for details). The error in Dca
of ± 0.01, less than 0.3% for Dca, indicates the less dependence of the
critical absorbed dose on the probing depth, if the probing depth is
sufficiently shorter than the penetration depth of photons. Here, the
critical radiation dose, without considering (1 − T) in Eq. (2) as has
been used in Refs. [5–8], is comparable to that for other polymer ma-
terials such as polyethylene terephthalate (PET); 410–450 MGy for the
OCeOR bond and 600–800 MGy for the O = COR bond in PET [8]. The
critical radiation dose for the RCeOH bond in TGDDM-DDS of 520 MGy
is relatively stronger than the other oxygen single bonds.
On the other hand, to obtain the high energy resolution and the
spectral stability, the XES measurement requires the high photon flux
and the small photon spot; Nph = 3.0 × 1011 ph/sec and S = 100 μm
(horizontal) × 10 μm (vertical) at the soft x-ray emission spectrometer
of SPring-8 BL17SU [24]. If the half of the critical absorbed dose (Dca/
2 = 1.92 MGy) is sufficient for the non-destructive chemical-state
analysis, Eq. (2) gives tdose = 0.12 s for the XES measurement by con-
sidering the probing depth for XES, ca. λ = 1 μm. Because the de-
termined tdose of 0.12 s is quite short for the XES measurement at
SPring-8 BL17SU, which requires at least 20–30 min accumulation time
per 1 spectrum, the photon-irradiation spot on the sample surface must
H. Yamane et al. Journal of Electron Spectroscopy and Related Phenomena 232 (2019) 11–15

the soft X-ray beams with S = 0.001–0.847 mm2 because the radiation
damage occurs at the same kerma with different S. The radiation da-
mage can be ruled out from the spectroscopic data by considering the
half of the critical absorbed dose for the measurement.

4. Conclusion

Soft X-ray spectroscopies have not yet been commonly applied to

Fig. 4. O Kα resonant XES spectra, measured for TGDDM-DDS as a function of
the sample scan speed during the measurement at hvin = 531.6 eV.
be continuously scanned during the measurement. The appropriate
sample scan speed is faster than 0.08 mm/sec by considering the beam
spot in XES and the charged-particle equilibrium.
Fig. 4 shows the O Kα XES spectra, measured at hvin = 531.6 eV, for
TGDDM-DDS as a function of the sample scan speed during the mea-
surement. The overall spectral structure of XES for TGDDM-DDS is like
that for the methanol (H3C−OH) [18,25]. The prominent XES feature
at the emitted photon energy (hvout) of 526.0 eV is ascribed to the 1b1
orbital, and the substructures at hvout = 524.5 eV and 522.5 eV are as-
cribed to the 3a1 and 1b2 orbitals, respectively [18]. The XES spectrum
without the sample scan shows the broadened 1b1 peak, which gets
gradually sharpened for the sample-scanned XES spectra. The 3a1 peak
gets visible when the sample scan speed is faster than 0.10 mm/sec. The
peak broadening at hvout = 526.0 eV (1b1) and the peak disappearance
at hvout = 524.5 eV (3a1) can be thus ascribed to the radiation damage.
These results indicate that the charged-particle equilibrium exists for
the investigation of adhesive materials and interfaces because of the
experimental difficulties such as the strong insulating character of
materials and the radiation damage induced by highly-brilliant soft X-
rays. By considering the charging effect and the radiation damage, we
have investigated the local electronic state of the TGDDM-DDS epoxy
resin. The systematic O K-edge XAS measurements for TGDDM-DDS and
its constituents reveal the formation of the curing-derived feature,
which might be assigned to the OeH or C]O sites. The curing-derived
XAS feature shows the intensity decay with increasing the X-ray dose.
The quantitative analysis on the intensity decay in the curing-derived
XAS feature determines the critical absorbed dose for the chemical
change on TGDDM-DDS as 3.83 ± 0.01 MGy. Furthermore, we found
that the charged-particle equilibrium exists for the soft X-rays in the
range of at least 0.001–0.847 mm2 beam spot. The half of the critical
absorbed dose is thus applicable for non-destructive chemical-state
characterizations using soft X-rays for resinous adhesive materials and
interfaces.
Acknowledgements
The authors would like to thank to Dr. Yuka Ikemoto, Dr. Tomoko
Ishihara, and Dr. Hiroshi Iwayama for the assistance in the measure-
ments of ATR-IR, XES at SPring-8, and XAS at UVSOR-III, respectively.
N.Y., K.H., and K.T. of MHI, Ltd. acknowledge the financial support by
Innovative Science and Technology Initiative for Security, ATLA, Japan.

Appendix A

Determination of the critical absorbed dose

The unit conversion in Eq. (2), K = Nph tdose × Ep(1 − T)/(λ S ρ), is described as follows.
Ep (eV)(1 − T )(ph−1)
K = Nph (ph∙sec−1) tdose (sec)
λ (nm) S (mm2) ρ (g∙cm−3)

1.602 × 10−19Ep (1 − T ) (J)

= Nph tdose
λ× 10−9 (m) S × 10−6 (m2) ρ × 103 (kg∙m−3)

Ep (1 − T )
= 1.602 × 10−7Nph tdose (J∙kg−1 [=Gy])
λSρ
When the charged-particle equilibrium exists, using the experimental parameters in Fig. 3, Nph = 6.3 × 109 ph/sec, S = 0.847 mm2, and
ρ = 1.05 g/cm3, Eq. (2) is given as following.
K = Da = 1.135 × 103tdose Ep (1 − T )/λ Gy

Considering the molecular unit of TGDDM-DDS as C37H41N4O6S, the term of Ep(1 − T)/λ at Ep = 555 eV is calculated as follows using Ref. [23],
wherein we used λ as the thickness parameter.

• T = 0.99754 and E (1 − T)/λ = 0.69025, when λ = 2 nm.

p

• T = 0.99265 and E (1 − T)/λ = 0.68842, when λ = 6 nm.

p

• T = 0.98778 and E (1 − T)/λ = 0.68695, when λ = 10 nm.

p

The critical dose time tcdose = 4968 s gives the critical absorbed dose as Dca = 3.83 ± 0.01 MGy when λ = 6 ± 4 nm.

References [2] F.M.F. de Groot, J. Electron Spectrosc. Relat. Phenom. 67 (1994) 529–622.
[3] A.P. Hitchcock, J. Electron Spectrosc. Relat. Phenom. 200 (2015) 49–63.
[4] X. Zhang, C. Jacobsen, S. Lindaas, S. Williams, J. Vac. Sci. Technol. B 13 (1995)
[1] J. Stöhr, NEXAFS Spectroscopy, Springer-Verlag, 1992. 1477–1483.

14
H. Yamane et al.
[5] E.G. Rightor, A.P. Hitchcock, H. Ade, R.D. Leapman, S.G. Urquhart, A.P. Smith,
G. Mitchell, D. Fischer, H.J. Shin, T. Warwick, J. Phys. Chem. B 101 (1997)
1950–1960.
[6] T. Coffey, S.G. Urquhart, H. Ade, J. Electron Spectrosc. Relat. Phenom. 122 (2002)
65–78.
[7] J. Wang, C. Morin, L. Li, A.P. Hitchcock, A. Scholl, A. Doran, J. Electron Spectrosc.
Relat. Phenom. 170 (2009) 25–36.
[8] J. Wang, G.A. Botton, M.M. West, A.P. Hitchcock, J. Phys. Chem. B 113 (2009)
1869–1876.
[9] B. Ellis, Chemistry and Technology of Epoxy Resins, Springer, Netherlands, 1993.
[10] T. Semoto, Y. Tsuji, H. Tanaka, K. Yoshizawa, J. Phys. Chem. C 117 (2013)
24830–24835.
[11] K. Shirasawa, T. Tanaka, T. Seike, A. Hiraya, H. Kitamura, AIP Conf. Proc. 705
(2004) 203–206.
[12] H. Ohashi, Y. Senba, H. Kishimoto, T. Miura, E. Ishiguro, T. Takeuchi, M. Oura,
K. Shirasawa, T. Tanaka, M. Takeuchi, K. Takeshita, S. Goto, S. Takahashi,
H. Aoyagi, M. Sano, Y. Furukawa, T. Ohata, T. Matsushita, Y. Ishizawa,
S. Taniguchi, Y. Asano, Y. Harada, T. Tokushima, K. Horiba, H. Kitamura,
T. Ishikawa, S. Shin, AIP Conf. Proc. 879 (2007) 523–526.
[13] Y. Senba, H. Ohashi, H. Kishimoto, T. Miura, S. Goto, S. Shin, T. Shintake,
T. Ishikawa, AIP Conf. Proc. 879 (2007) 718–721.
15
Journal of Electron Spectroscopy and Related Phenomena 232 (2019) 11–15
[14] https://www.uvsor.ims.ac.jp/beamlines/4B/bl4b.html.
[15] I. Ishii, A.P. Hitchcock, J. Electron Spectrosc. Relat. Phonom. 46 (1988) 55–84.
[16] I. Ishii, R. McLaren, A.P. Hitchcock, M.B. Robin, J. Chem. Phys. 87 (1987)
4344–4360.
[17] A.P. Hitchcock, Gas Phase Core Excitation Database, (2018) http://unicorn.
mcmaster.ca/corex/cedb-title.html.
[18] J.-H. Guo, Y. Luo, A. Augustsson, S. Kashtanov, J.-E. Rubensson, D.K. Shuh,
H. Ågren, J. Nordgren, Phys. Rev. Lett. 91 (2003) 157401.
[19] S.G. Urquhart, H. Ade, J. Phys. Chem. B 106 (2002) 8531–8538.
[20] M. Abbate, J.B. Goedkoop, F.M.F. de Groot, M. Grionit, J.C. Fuggle, S. Hofmann,
H. Petersen, M. Sacchi, Surf. Interface Anal. 18 (1992) 65–69.
[21] B.H. Frazer, B. Gilbert, B.R. Sonderegger, G. De Stasio, Surf. Sci. 537 (2003)
161–167.
[22] J. Laverock, M. Gu, V. Jovic, J.W. Lu, S.A. Wolf, R.M. Qiao, W. Yang, K.E. Smith,
Nano Futures 1 (2017) 031001.
[23] X-ray Transmission of a Solid, X-ray Interactions With Matter, (2018) http://henke.
lbl.gov/optical_constants/filter2.html.
[24] T. Tokushima, Y. Harada, H. Ohashi, Y. Senba, S. Shin, Rev. Sci. Instrum. 77 (2006)
063107.
[25] A. Benkert, F. Meyer, D. Hauschild, M. Blum, W. Yang, R.G. Wilks, M. Bär,
F. Reinert, C. Heske, L. Weinhardt, J. Phys. Chem. A 120 (2016) 2260–2267.