Glancing angle soft x-ray reflectivity

(SXR) and total electron yield (TEY)

characterization of ZrO2 thin film near O K-
edge
Cite as: AIP Conference Proceedings 2054, 040004 (2019); https://doi.org/10.1063/1.5084605
Published Online: 16 January 2019

Mangalika Sinha, Amol Singh, R. K. Gupta, and Mohammed H. Modi

AIP Conference Proceedings 2054, 040004 (2019); https://doi.org/10.1063/1.5084605 2054, 040004

© 2019 Author(s).
 Glancing angle Soft X-ray reflectivity (SXR) and total
electron yield (TEY) characterization of ZrO2 thin film near
O K-edge

Mangalika Sinha1, 2 a), Amol Singh3, R.K. Gupta1, Mohammed H. Modi1, 2 b)

1
Soft x-ray Application Lab, Raja Ramanna Centre for Advanced Technology, Indore 452 013 India.
2
Homi Bhabha National Institute, Anushakti Nagar, Mumbai 400094, India.
3
National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan.
a)
Corresponding authors: mangalika@rrcat.gov.in b) modimh@rrcat.gov.in

Abstract: In the present study, we have analyzed the soft X-ray total electron yield and the reflection spectra of 300
Å ZrO2 thin film deposited by electron beam evaporation technique at various glancing angles near the O-K absorption
edge region. The optical constants delta (δ) and beta (β) of the ZrO2 thin film is obtained by Kramers-Krönig analysis of
the reflection spectrum measured at a glancing angle of 3°. The fine features appearing in the beta (β) spectrum matches
well with the total electron yield spectrum measured at 3°.

INTRODUCTION

In recent years, the increasing use of synchrotron beamlines for cutting edge research poses a demand of high
throughput optics, which can withstand the high brilliant radiation and the heat load coming from the insertion
devices in advanced synchrotron radiation sources. This essentially requires to find a new class of materials
satisfying the above criterion for their use as an optical element. The lack of information on optical properties for
new class of materials in the x-ray region makes the task further challenging in finding a suitable material for the x-
ray optics. The optical response of a material in the x-ray region can be known in terms of its complex refractive
index which can be expressed as n=1-δ+iβ, where δ & β are referred as the optical constants. For compound
materials, the optical constants can be expressed in terms of weighted average density of the constituents material
under consideration along with the atomic scattering factors (real part f1 and imaginary part f2) [1,2].
Several techniques can be employed for the evaluation of the optical constants in the x-ray region such as
reflectivity, transmission and absorption measurements and so on, each having certain advantages & disadvantages
both. Transmission measurements require preparation of free standing ultrathin films which is not an easy task. In
case of absorption measurements, it is difficult to extract information about the absolute value of the absorption co-
efficient. The most common method to extract the absolute value of absorption co-efficient from the x-ray
absorption measurements is to scale it with respect to the available Henke tabulated values on both higher and lower
energy sides of the absorption edge [3]. X-ray reflectivity is a powerful tool for the evaluation of optical constants as
it provides complete information about the structural parameters such as thickness, roughness along with the optical
parameters δ & β. These measurements can be performed in both angle-dependent and energy-dependent modes. In
case of angle-dependent x-ray reflectivity measurements, optical constants at discrete photon energies are evaluated.
The energy-dependent reflectivity measurements give a continuous spectrum of the optical constants over a given

Proceedings of the 13th International Conference on Synchrotron Radiation Instrumentation – SRI2018

AIP Conf. Proc. 2054, 040004-1–040004-5; https://doi.org/10.1063/1.5084605
Published by AIP Publishing. 978-0-7354-1782-3/$30.00

040004-1
energy range from phase reconstruction method [4-7]. The continuous spectrum of the optical constants also reveals
a lot of information about the electronic structure of the material [8].
It is well known that zirconium dioxide (ZrO2) is a promising material for the capping layer to protect and extend
the life of thin film & multilayer optics [9] as it exhibits high thermal and mechanical stability and owes high
dielectric constants. ZrO2 is also used to fabricate Fresnel's zone plate for soft x-ray microscopy applications in
water window region [10]. More over multilayer Laue lenses are developed using ZrO2 /Ti combination for focusing
of submicron EUV radiation [11]. However, to simulate the performance of ZrO2 thin film or multilayer mirror, it is
pre-requisite to characterize the optical properties and the factors affecting it in the energy region of interest. In
literature, Henke's database provides the standard optical constants of various elements and compound materials.
However, in case of compound materials the weighted density average of the atomic scattering factors of constituent
elements are calculated for the estimation of optical constants. This method is quite satisfactory for the energy
region away from the absorption edge, although, near the edge modifications of wave functions of the electrons due
to the formation of chemical bonds become significant and thus this approximation fails. Therefore, experimental
evaluation of the optical constants is necessary for the correct evaluation of performances of the thin films or
multilayer mirrors. Previously, Singh et al. evaluated the in-depth chemical composition [12] and optical constants
[13] of ZrO2 thin film in the 55-150 Å wavelength region covering the Zr M4,5 edge by angle-dependent reflectivity
measurements. They found that above Zr M4,5 edge i.e, in the 70-150 Å region, the δ values are 19-24% lower than
Henke tabulated values and the β values by 1-8%; whereas below the edge region, the δ values are lower by 3-21%
while the β values are higher by 3-20%.

In the present work, simultaneous glancing angle total electron yield (TEY) and soft X-ray reflectivity (SXR)
measurements of ZrO2 thin film of 300 Å are carried out near O-K absorption edge. X-ray absorption measurements
in total electron yield mode are carried out in conjunction with soft X-ray reflectivity measurements to distinguish
different features appearing in the reflection spectrum originating from the electronic structure and associated
transitions. Continuous spectrum of the optical constants is obtained from the Kramers-Kronig (KK) analysis of the
energy dependent SXR measured at a glancing angle of 3° near the O-K absorption edge. The beta spectrum as
obtained from SXR measurements matches well with the measured TEY spectra in terms of energy position and
relative strength.

EXPERIMENTAL

Sample Preparation

A 300 Å thick ZrO2 film has been deposited on a silicon (Si) substrate by using the electron beam evaporation
technique. Prior to this deposition, the substrates were cleaned ultrasonically with acetone. The deposition was
carried out at a pressure better than 2e-6 Torr with a typical deposition rate of 0.3 Å/s. The thickness of the sample
was monitored using a quartz crystal.

Characterization

SXR and TEY measurements were carried out at the soft X-ray reflectivity beamline (BL-03) of Indus-2
synchrotron radiation source. The measurements were carried out in the energy range of 500-600 eV covering the O
K absorption edge region. The beamline uses a varied line spacing plane grating monochromator (VLS-PGM).
Three gratings of different line densities are used to provide monochromatic photons in the energy range of 100-
1600 eV with high flux and spectral resolution ranging from 1000-6000. The experimental station (reflectometer) is
maintained at a high vacuum of 5.2e-8 Torr. A differential pumping system is installed to isolate the high vacuum
reflectometer with the ultra-high vacuum section of the beamline. A θ-2θ goniometer and a linear translation stage
are used for performing various scans and sample alignment purposes. The goniometer is set in vertical reflection

040004-2
geometry. The reflected beam is recorded using a soft X-ray silicon photodiode detector (International Radiation
Detector Inc, USA) which has 100 % internal quantum efficiency. The detector signal is measured in terms of
current using a Keithley electrometer (6514). The TEY signal is recorded directly from the sample using a Keithley
electrometer.

RESULTS & DISCUSSIONS

Figure 1(a) shows the TEY and 1(b) shows the energy-dependent SXR spectra measured at glancing angles of
2°, 3°,4°, 5° near the O-K absorption edge. The prime features appearing are marked as A, B, C & D respectively.
In case of lower glancing angle, the yield signal is quite lower owing to high reflection below the critical angle
region. Moreover, at lower glancing angle the electron escape depth becomes comparable to the X-ray penetration
depth resulting in the distortion of the TEY spectrum with respect to the absorption spectrum. With the increment in
glancing angle of the incidence photon, the shape of the total electron yield spectra changes.
0
10
2 deg
3 deg
A B
4 deg D
C
5 deg
TEY (arb. unit)

Reflectivity
-1
10

2 deg
3 deg
4 deg
5 deg
-2
510 520 530 540 550 560 10
510 520 530 540 550 560
Energy (eV) Energy (eV)
(a) (b)
FIGURE 1. (a) Total electron yield (TEY) spectra of ZrO2 thin film measured at different glancing angles of 2°, 3°,4°& 5°
near the vicinity of the O K- absorption edge region. Curves are vertically shifted for the sake of clarity. (b) Energy-dependent
soft X-ray reflectivity (SXR) spectra measured simultaneously along with the TEY spectra.

In the energy range of 530–540 eV, the fine features appearing in the TEY spectrum originated from the
transitions from O 1s states to O 2p final states, which are hybridized with the Zr 4d states, splitted by the crystal
field effects. The two peaks in this region, located at the energy position of 531 and 533.6 eV can be attributed to the
corresponding 4d states of eg and t2g symmetry [14]. From the yield spectra, the crystal field splitting is found to be
2.6 eV. However, the crystal field splitting of cubic, tetragonal and monoclinic phases of zirconium dioxide is
found to be 3.5, 3.0 and 2.9 eV respectively[15]. Thus, the lower value of splitting indicates that the film is mostly
amorphous in nature. This fact is confirmed from the Grazing Incidence X-ray Diffraction (GIXRD) measurement,
carried out at an angle of 0.8° with Cu K-α (1.54 Å) source as shown in Figure 2. It is observed that the peak
positions as well as the crystal field splitting energy are almost same for the TEY spectra of various glancing angles.
However, difference in the intensity ratio of the t2g to eg peak is observed with changing glancing angle. Ideally the
intensity ratio of t2g to eg peak should be 3:2, however, in most cases the experimental value deviates from the
standard one. From the XPS measurements, to be reported elsewhere [16], it is confirmed that the film surface
consists of mixed oxidation states of Zr, i.e; Zr4+ and Zr3+. As one proceed towards higher glancing angles, increase
in X-ray penetration depth leads to probing of the principal layer where the contribution of Zr3+ decreases. Above
540 eV the features appearing in the TEY spectra are due to oxygen 2p states mixed with Zr 5s states, which are
pushed up in energy due to the larger oxygen 2p–metal 5sp interactions. These features are not understood well
because of its complex nature.

040004-3
 Intensity (arb units)
10 20 30 40 50 60 70 80
2theta (deg.)

FIGURE 2. Grazing Incidence X-ray Diffraction spectrum of 300 Å ZrO2 thin film measured at an incidence angle of 0.8°.

To obtain the optical constants (δ & β) from the energy-dependent soft x-ray reflectivity data, KK relations are
used. Using KK relations, the phase of the reflected electric field is evaluated from the obtained experimental
spectrum measured at a glancing angle of 3° and simultaneously the optical constants are calculated as shown in
Figure 3. The phase spectrum I (E) obtained by KK analysis of the complex reflection coefficient contains an error
of rS which is included in our analysis [17]. Moreover, the KK relations accurately calculate the phase only when
the reflectivity spectrum is obtained over a large energy range effectively from zero to infinity. Practically it is not
possible to obtain either the absorption or the reflection data from zero to infinity frequency/energy range and
therefore different interpolation/ extrapolation techniques are used. In the present case, the reflectivity values
obtained from the theoretical calculations are used to increase the data range beyond the experimental measurement
region using the optical constants from the CXRO database [18].

The features appearing in the β spectrum obtained using the KK relations matches well with that of the TEY
spectrum in terms of the energy position and relative strengths. The difference of these two spectra lies in the fact
that the β spectrum provides the absolute value of the absorption co-efficient whereas in TEY spectrum, the yield
signal is in arbitrary units. We have also ensured the values of the obtained optical constants using KK relations.
Using the structural parameters as obtained from the analysis of grazing incidence x-ray reflectivity (GIXRR) data
(not shown here) and the optical constants, we have simulated the soft x-ray reflectivity spectrum for a glancing
angle of 3° and compared with the experimental one. The one-to-one correspondence between the calculated and the
experimental reflectivity spectra inferred the validity of the obtained optical constants.

510 520 530 540 550 560 u10

-3
-3
u10 3.0
1.8

1.6 2.5

1.4
Delta(G)
Beta E

2.0

1.2

1.5
1.0

0.8
1.0

510 520 530 540 550 560

Energy(eV)

FIGURE 3. Optical constants (δ & β) profile obtained from the KK analysis of the energy dependent soft X-ray reflectivity
(SXR) data measured at a glancing angle of 3° near the vicinity of the O K- absorption edge.

040004-4
 CONCLUSIONS

In this study, simultaneous glancing angle SXR and TEY measurements of 300 Å ZrO2 thin film is carried out
near the O K- absorption edge region. The optical constants (δ & β) of the ZrO2 thin film are evaluated from the
energy-dependent reflectivity spectrum measured at a glancing angle of 3°. The reflectivity spectrum calculated
using the structural parameters as obtained from the analysis of GIXRR data and the optical constants derived using
KK relations matches well with the experimental data, assuring the validity of the measured optical constants values.
The effect of the crystal field splitting i.e; the appearance of the e g and the t2g peaks at an energy position of 531 eV
& 533.6 eV respectively is evident from the absorption spectra. The obtained β spectrum corroborates well with the
total electron yield (TEY) spectrum of ZrO2 thin film obtained at a glancing angle of 3°.

ACKNOWLEDGMENTS

MS acknowledges Homi Bhabha National Institute (HBNI) for the financial support. Dr. Haranath Ghosh and
Dr. Tapas Ganguli are acknowledged for useful discussions and support.

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