Article

Cite This: J. Phys. Chem. C XXXX, XXX, XXX−XXX pubs.acs.org/JPCC

Band Gap Width Control by Cu Intercalation Into ZrSe2

A. S. Shkvarin,*,† A. I. Merentsov,‡ Yu. M. Yarmoshenko,† M. S. Postnikov,†,‡ E. G. Shkvarina,†
A. A. Titov,† I. Pis,§ S. Nappini,∥ F. Bondino,∥ and A. N. Titov†,‡
†
Institute of Metal Physics, Russian Academy of Sciences-Ural Division, 620137 Yekaterinburg, Russia
‡
Ural Federal University, 620089 Yekaterinburg, Russia
§
Elettra-Sincrotrone Trieste S.C.p.A, S.S. 14, km 163.5, 34149 Basovizza, Trieste, Italy
∥
IOM-CNR, Laboratorio TASC, S.S. 14-km 163.5, 34149 Basovizza, Trieste, Italy
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ABSTRACT: The CuxZrSe2 intercalation single crystals have been synthesized and
studied in a concentration range of x = 0−0.3, in which the semiconductor-metal
Downloaded via URAL FEDERAL UNIV on December 28, 2018 at 11:11:20 (UTC).

transition was observed. The evolution of the electronic structure of CuxZrSe2 as a

function of the copper content has been studied experimentally using the XPS and
XAS methods. The obtained results indicate the gradual shift of the Fermi level with
increasing copper content, which does not allow the metal−insulator transition to be
associated with charge transfer to the conduction band. This transition is associated
with the formation of the covalent bond between copper and the nearest selenium
atoms and of the p−d hybridized states inside the Zr 4d/Se 4p band gap. First-
principle calculations were performed in order to obtain a theoretical description of
the density of states near the Fermi level and confirm this conclusion.

■ INTRODUCTION
Quasi-two-dimensional transition metal dichalcogenides MCh2
(M = Ti, V, Zr, Nb, Mo, Hf, W; Ch = S, Se, Te) have been a
subject of considerable interest for a long time.1−4 The crystal
structure of these materials allows us to consider them as a
two-dimensional object similar to graphene5,6 with interesting
properties depending on the type of metal and chalcogen.
These materials exhibit quantum effects, such as a state with a
charge density wave and superconductivity.7−9 From a
practical point of view, they are considered as cathode
materials for lithium batteries10−13 and new materials with
applications in electronic devices,14,15 such as transistors with
high electron mobility.16 The crystal structure of these
materials allows intercalating various atoms and even
molecules into the MCh2 host lattice. As a result, the
electronic structure and physical properties of the starting
material change in a wide range. The limited space available for
intercalation allows generating nanodimensional inclusions,17
arrange intercalated atoms, or create quasi-one-dimensional
chains.18−21 Intercalation compounds based on MCh2 exhibit a
number of intriguing properties, for example, superconductiv-
ity22 and thermoelectricity.23−25 In addition, the practical use
of these materials as solar cells26,27 and in electronic
devices23,28−30 is also supposed.
These applications require the ability to control the
electronic structure of the material, particularly the width of
the band gap. Usually, this is achieved by chalcogen
substitution (e.g. ref 31 and later works32−34). At the same
time, intercalation, as another method of doping, is in general
not considered as a way to control the gap width. It is
considered that intercalation only leads to charge transfer to
the conduction band of the host material, which almost does
not affect the electronic structure of the MCh2. It was shown
that the intercalation of transition metals leads to the
formation of impurity states near the Fermi level.35−40
However, these results were obtained for materials based on
TiCh2, Ch = S, Se, and Te. The latter two materials do not
have a gap at the Fermi level. The electronic structure of the
intercalation compounds based on TiS2 is much less studied.
Moreover, this material is always contaminated with excess
titanium, which can also form impurity states. Therefore, it is
not so easy to distinguish states that arise at the intercalation
process.
Unlike the studied MCh2, ZrSe2 exhibits a rather wide gap
∼1 eV and the tendency to self- intercalation for this material
is not so significant. Therefore, the impurity states formed by
intercalated atoms are believed to be well distinguishable in
this case. Copper was chosen as the atom-intercalant, since in
the intercalation compounds based on TiCh2 copper atoms
can occupy sites that are octahedrally and tetrahedrally
coordinated by chalcogen in the interlayer space.41,42 Figure
1 shows a fragment of the CuxZrSe2 crystal structure, in which
the octahedral and tetrahedral sites are available for the
intercalation. Differences in the chemical bonding of copper in
these sites are likely to be expected. Occupation of one of these
sites should lead to the formation of impurity states in the Zr
4d/Se 4p band gap.
Received: August 24, 2018
Revised: December 6, 2018
Published: December 7, 2018

© XXXX American Chemical Society A DOI: 10.1021/acs.jpcc.8b08255

J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C Article

Resource Centre “Physical Methods of Surface Investigation”

Figure 1. Fragment of the CuxZrSe2 crystal structure: tetrahedral (left
panel) and octahedral (right panel) coordination of the Cu atoms by
Se atoms are shown.
(RC PMSI) of the Saint Petersburg State University Research
Park. All measurements were performed at room temperature
(25 °C).
First-principles calculations (“Uran” supercomputer of IMM
UB RAS) were performed to obtain a theoretical description of
the density of states of the studied materials near the Fermi
level. The calculations were performed using the full potential
linearized augmented plane wave (FP-LAPW) approach and
the ELK software package.47 Integration over the Brillouin
zone was carried out using a 10 × 10 × 5 grid of special k
points. Experimentally determined parameters of the crystal
structure were used in these calculations.

Muhammad et al.43 have concluded that the intercalation of

copper in ZrSe2 leads to a transition from the semiconductor
to the metallic state as a result of charge transfer from the
copper atoms to the conduction band of the host lattice.
However, the samples used in this work contain excess of the
zirconium atoms as it follows from the Zr 3d XPS (X-ray
Photoelectron Spectroscopy). This does not allow distinguish-
ing the influence of copper on the semiconductor-metal
transition. In the present work we prepared single crystals of
CuxZrSe2 with x = 0.1, 0.2 and 0.3, carefully controlling the
absence of superstoichiometric zirconium. Using these crystals,
we studied influence of copper on the electronic structure of
CuxZrSe2 in the concentration region in which the semi-
conductor−metal transition was observed.43
■ XPS
The spectra of the core levels provide information about the
charge state of the atom, as well as about the change in the
charge state in dependence of the amount of intercalated
copper. The core level spectra are sensitive to the appearance
of additional phases48 or nonequivalent crystallographic
positions.18,49 Figure 2 (upper panel) shows the spectra of
the Se 3d and Zr 3p, 3d for CuxZrSe2. It is seen that the
binding energy values of these levels increase equally as the
concentration of intercalated copper atoms increases (Figure 2,
lower panel).

■ EXPERIMENT
CuxZrSe2 compounds were prepared using solid state reaction
method from the metallic disperse copper and preliminary
prepared ZrSe2 powder. The synthesis technique for ZrSe2 was
described in detail previously.44 The copper intercalation into
ZrSe2 was carried out at room temperature and was described
in detail in ref 41. Single crystals were grown in quartz ampules
by the gas-transport reaction technique with I2 as a carrier
gas45 using prepared CuxZrSe2 as started material. The content
of excess zirconium is determined by the synthesis temper-
ature, which is discussed in ref 45. Our synthesis conditions
and all of the subsequent heat treatments, including the single
crystals growth, allow the content of excess titanium not to
exceed 1 mol %. This is achieved by introducing an excess
selenium into the volume of the ampule and by the use of
special thick-walled ampules that withstand a pressure of up to
25 atm.
The X-ray spectroscopy measurements were performed at
the CNR BACH beamline at the Elettra synchrotron in
Trieste, Italy.46 All of the samples were cleaved in situ in a
vacuum chamber at a pressure lower than 1 × 10−9 Torr. The
purity of the surface was confirmed by the absence of oxygen
and carbon peaks in the survey spectra. The valence band (VB)
and core level spectra were obtained using a photon energy of
540 eV and a total energy resolution of 0.15 eV. The VB
spectra obtained at a photon energy of Eexc = 330 eV had a
total energy resolution of 0.17 eV. Photoemission binding
energies were calibrated by means of Fermi level measured on
a gold reference. Zr M2,3 XAS were acquired in total electron
yield mode with an energy resolution of ∼0.08 eV and Figure 2. In the upper panel: Se 3d core levels (left part), Zr 3d core
calibrated using the corresponding absorption spectra of the levels (central part), and Zr 3p core levels (right part) for CuxZrSe2 (x
pure metal. The ZrSe2 VB spectra were calibrated using the = 0, 0.1, 0.2, and 0.3). In the lower panel: shifts of the energy
data previously obtained with the charge compensation at the positions of the maxima relative to pristine ZrSe2.

B DOI: 10.1021/acs.jpcc.8b08255
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C Article

Figure 3. Zr M3 XAS (left panel) and scheme (right panel) for changing the energy position of the spectra of core levels and absorption spectra in
dependence of the copper concentration.

Figure 4. In the left panel: VB spectra for CuxZrSe2. In the right panel: the Fermi edge fragment of the VB spectra obtained at Eexc = 330 eV for
CuxZrSe2 (the intensity is normalized to the main maximum).

The graph shown in the lower panel of Figure 2 clearly can be explained using the scheme shown in Figure 3, right
shows that the shifts of the core levels with the change in the panel.
copper concentration are the same. The reason for the equal shift of all of the XPS peaks is the

■ XAS
Absorption spectra provide information about the valence state
of an atom, and they are sensitive to changes in the local
environment. The Zr M2.3 experimental absorption spectra for
the CuxZrSe2 (x = 0, 0.1, 0.2, 0.3) studied samples are shown
in Figure 3, left panel. The shape of the Zr M2,3 absorption
spectra does not change with the increasing copper
concentration, which indicates a slight change in the local
environment of the zirconium atoms. The absence of a shift in
the absorption spectra, in contrast to the core levels spectra,
C DOI: 10.1021/acs.jpcc.8b08255
formation of a band of hybridized states and the corresponding
shift of the Fermi level toward the original semiconductor gap
in ZrSe2. Only this condition provides the unaltered photon
energy in the Zr M2.3 absorption spectrum (Zr 3p → Zr 4d
transition) with changing Cu concentration. In this case, this
energy will change with respect to the Fermi level as it is
shown in Figure 3, right panel. At the same time, the increase
of the copper concentration leads to the blurring of the VB
spectrum due to the additional copper states and, therefore, to
the decrease of the band gap.
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
Valence band. The spectra of the valence band provide
information about the state of the valence electrons that are
responsible for the chemical bonds in the material and the
electronic structure near the Fermi level
The VB spectra exhibit the same energy shift as the core
levels spectra. Even at x = 0.1, the shape of the VB spectrum
changes significantly (Figure 4, left panel). This behavior
distinguishes the CuxZrSe2 compounds from the CuxTiSe2
ones, for which the VB spectra remains just about unchanged
up to high copper concentrations.48 The change in the shape
of the spectrum can be explained by the significant
contribution to the valence band50 of the copper states,
which occupy an energy range from 0 to 6 eV for CuxTiSe2.
The right panel of Figure 4 shows an enlarged view of the
valence band for CuxZrSe2 obtained at lower excitation energy
Eexc = 330 eV in order to obtain a higher contribution of Cu
and Zr states. Despite the low peak/background ratio in the
valence band, we succeed to distinguish a low intensity peak
just below the Fermi level for Cu0.2ZrSe2 and Cu0.3ZrSe2. The
intensity of this band increases with copper concentration. The
R peak (right panel, Figure 4) can be associated with the filling
of the Zr 4d-derived conduction band. This confirms the
electrons transfer into the conduction band with increasing
copper concentration to x = 0.3. However, this peak is absent
at lower copper content, which suggests that the transfer of
copper electrons into the conduction band does not occur.
Since the valence band is filled, the only way is the charge
transfer to the hybridized states located inside the Zr 4d/Se 4p
band gap. The identical dependence of the binding energy of
the core levels and valence states on the copper content
indicates that these effects are caused by a Fermi level shift. In
the copper concentration region of x < 0.3, the Fermi level
should be below the bottom of the conduction band. Because
there is a band gap below the conduction band in ZrSe2, the
described hybridized states arise as a result of the copper
intercalation.
■ CALCULATIONS
In order to determine the spatial and energy distribution of
atomic contributions to the valence band, the band structure
and density of states (DOS) calculations were performed. The
calculations were performed for ZrSe2 and Cu0.125ZrSe2. To
simulate the intercalation of the cooper, a supercell containing
eight ZrSe2 formula units (2 × 2 × 2) was used. Introduction
of one copper atom to the interlayer space provided the
Cu0.125ZrSe2 chemical composition. The space group of the
supercell was P3̅m1 (164) as that of the host lattice. A
fragment of modeled crystal structure is shown in Figure 5.
The minimal distance between Cu atoms is equal to 7.53 Å,
which makes the interaction between copper atoms insignif-
icant. The lattice parameters and the “z” coordinates of the
selenium and cooper atoms (which occupy only tetrahedral
sites, see Figure 5) were obtained from the Rietveld refinement
of the diffraction pattern for the corresponding polycrystalline
sample. The results of the crystal structure refinements will be
published in a separate article.
The CuxZrSe2 band structure is shown in Figure 6. The
partial and total DOS for Cu0.125ZrSe2 are shown in Figure 7.
Because the contribution from the Cu states is small, it is much
easier to see it in the partial DOS (Figure 7). The total DOS
was calculated taking into account the photoionization cross-
section51 for the excitation energy Eexc = 540 eV and the
chemical composition of the compound.
D DOI: 10.1021/acs.jpcc.8b08255
Article
Figure 5. Fragment of modeled crystal structure. The tetrahedral
coordination of the Cu atom with Se atoms is indicated with black
lines.
The increase in the copper concentration leads to the shift of
the Fermi level toward the conduction band. The electronic
states of the copper and selenium atoms are uniformly
distributed, which causes a general broadening of the valence
band spectra of the intercalation compounds with copper (see
Figure 4) compared to the initial ZrSe2. Good agreement
between experimental and calculated valence band shape
(Figure 7) confirms the accuracy of the theoretical model. It
can be seen (Figure 6) that there is a direct gap at the Γ point
of the Brillouin zone for the original ZrSe2, which gives rise to
an additional interest in this material. An increase in the
number of electronic states of zirconium at the Fermi level and
in its vicinity is clearly visible in the band structure. These
states are observed in the VB spectra obtained at low excitation
energy.
■ DISCUSSION
Muhammad et al.43 found that semiconductor-to-metal
transition in CuxZrSe2 occurs by means of the filling of the
Zr 4d-derived conduction band. Because of this filling electrons
appear at the M-point of the Brillouin zone this means the
indirect Se 4p/Zr 4d band gap is in the ZrSe2 electronic
structure. However, these results are ambiguous because Zr 3d
XPS indicates the presence of the excess zirconium in the
studied samples.43 Because Zr is quadrivalent, the excess Zr
atoms may provide at least comparable or even higher
concentration of the electrons provided by the copper
intercalation. The excess of zirconium in our samples is less
than the sensitivity of the spectral techniques. Therefore, our
results indicate the effect of copper intercalation, which is not
complicated by the impurities. This allowed us to establish that
the semiconductor-to-metal transition mechanism differs from
that discovered by Muhammad et al.43 The gradual upshift of
the Fermi level with copper concentration contradicts the
assumption that the electrons transfer into the conduction
band at copper intercalation into ZrSe2 is the semiconductor-
metal transition mechanism. We believe that the copper
intercalation leads to the formation of additional states inside
the Zr 4d/Se 4p band gap. An increase in the copper
concentration leads to a broadening of this hybridized states
band and to a decrease in the effective gap width. When copper
concentration reaches x = 0.2, the hybridized band and the
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
Figure 6. Band structure for ZrSe2 (left panel) and Cu0.125ZrSe2 (right panel). The main contributions are from Zr 4d states (orange) and Se 4p
states (green). Circle diameter is proportional to the contribution of the corresponding atom states into the zone.
Figure 7. In the upper panel: experimentally obtained VB spectrum,
calculated total DOS for Cu0.125ZrSe2 and the total DOS after
Gaussian broadening. In the lower panel: Zr, Se, and Cu 3d partial
DOS (from top to bottom) for Cu0.125ZrSe2.
conduction band overlap, providing a transition to the metallic
state. Therefore, the intercalation of copper into ZrSe2 allows
one to control the width of the band gap. The absence of an
excess zirconium makes it possible to determine that the Se
E DOI: 10.1021/acs.jpcc.8b08255
Article
4p/Zr 4d band gap in ZrSe2 is a direct one. This is indicated by
the calculation data (Figure 6). Of course, the spectral data,
which are shown in the current study, are not enough for an
unambiguous conclusion, and additional optical experiments
are required. However, our data indicate that ZrSe2 and its
intercalation compounds may be promising as materials for
optical applications.
■ CONCLUSION
The theoretical and experimental study of the electronic
structure of ZrSe2 intercalated with copper was performed.
Band structure calculations indicate that the initial ZrSe2 is a
semiconductor with a direct gap. Intercalation of copper atoms
leads to a semiconductor−metal transition due to the decrease
of the Zr 4d/Se 4p band gap. The possibility of gradual change
in the width of the direct gap and control of the metal−
semiconductor transition makes intercalated ZrSe2 a promising
material for the future electronic devices.
■ AUTHOR INFORMATION
Corresponding Author
*(A.S.S.) E-mail: shkvarin@imp.uran.ru.
ORCID
A. S. Shkvarin: 0000-0002-3774-5669
I. Pis: 0000-0002-5222-9291
S. Nappini: 0000-0002-4944-5487
F. Bondino: 0000-0001-6505-9319
A. N. Titov: 0000-0003-3636-2604
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The research was performed within the state assignment of
FASO of Russia (theme “Electron” No. AAAA-A18-
118020190098-5 and theme “Spin” No. AAAA-A18-
118020290104-2). The research was supported by the Ministry
of Education and Science of Russia (Project No. 3.6545.2017/
7.8). Authors are grateful for synchrotron Elettra for support of
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
experimental Project No’s. 20160215 and 20160193. The work
was performed using “Uran” supercomputer of IMM UB RAS.
■
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G DOI: 10.1021/acs.jpcc.8b08255
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