Chemical Physics Letters 739 (2020) 136998

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Chemical Physics Letters

journal homepage: www.elsevier.com/locate/cplett

Research paper

Crystal structure and optical absorption properties of Er and Yb doped T

InTaO4 and InTaO4-yNy as photocatalysts under visible light
Juan Cruz-Puertoa, Cristina Ramirez-Carrilloa, Jorge Puga-Lechugaa, Pablo de la Morab,
Gustavo Tavizona,
⁎

a
Facultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, Ciudad de México 04510, Mexico
b
Facultad de Ciencias, Universidad Nacional Autónoma de México, Ciudad de México 04510, Mexico

HIGHLIGHTS

• ErIn Ersubstitution
3+
at In3+
sites in the InTaO lattice expands light absorption.
• One sub-band
4
TaO shows rich absorbance spectra in the visible (400–800 nm) region.
• When Er and Ybgapreplace
1-x x 4
at about 2.9–3.05 eV, associated to the In:5p-O:2p transitions.
• The localized character ofIntheatoms new states are introduced into the gap.
• 4f electrons, does not modify the gap energy.

ARTICLE INFO ABSTRACT

Keywords: Polycrystalline samples of In1-xRExTaO4 (RE = Er and Yb) in the 0 ≤ x ≤ 0.20 range, crystallizing in the
Photocatalysis wolframite structure, were prepared by the solid-state reaction method. All samples were characterized by X-ray
Water splitting photocatalysts diffraction, and their structural parameters were obtained by Rietveld refinements. The optical response of these
Tantalate crystal structure compounds was obtained by diffuse reflectance spectroscopy in the UV–vis range to determine the effect of the
Weberite-type tantalate
Er3+ and Yb3+ cations and the N anion on the band gap value of InTaO4. Even though it was found that Er3+
Optical properties of tantalates
Tantalates electronic structure
substitution at In3+ sites in the InTaO4 lattice provides an expanded range of light absorption from 300 nm to the
visible range of the light spectrum, this is only reflected in a small drop of the optical bandgap. For the In1-
xRExTaO4 system, there are two optical band gap sets, one of them ranging from 3.94 to 4.15 eV, and the other
one, from 2.8 to 3.2 eV. In the N-doped In1-xRExTaO4 compounds, these values were practically the same for the
first set, and slightly lower for the second set, from 2.9 to 3.0 eV. A DFT-based method was used to compute the
electronic structure of the RE3+ and N-doped compounds. Based on experimental and theoretical results, the
effect of the RE and N doping on InTaO4 is discussed.

1. Introduction
Semiconductor mediated photocatalysis (SMP) represents a desir-
able synthesis alternative as compared to direct synthetic methods; this
is especially significant when the energetics of transformation implies
an “uphill” reaction (ΔG° > 0), such as the case of water splitting to
obtain hydrogen and oxygen as products. SMP received enormous at-
tention since 1972 when Fujishima and Honda achieved UV light-in-
duced water cleavage using TiO2 as photoanode in combination with Pt
as the counter electrode, immersed in an aqueous electrolytic solution
[1]. Nowadays, SMP is one of the most concurrent proposals to be
applied in mineralization of organic pollutants, disinfection of water
and air, production of renewable fuels, and organic syntheses. In such a
scenario, the achievement of semiconductor mediated photocatalytic
activity under visible light conditions has become one of the most
promising challenges to solve large-scale problems, such as those re-
lated to the pollution associated with the use of fossil fuels [2] and the
remediation of wastewater [3].
Tantalum pentoxide, Ta2O5, is a wide gap semiconductor
(4.2–4.6 eV) [4,5]. This oxide has several advantages over other pho-
tocatalysts such as TiO2; the most important of them resides in the value
of his redox potentials in an aqueous medium [6]. For Ta2O5, the lower
edge of the conduction band results more negative than the H+/H2
redox potential (0 V vs. NHE). On the other hand, the upper edge of the

⁎
Corresponding author at: Laboratorio F 214, Facultad de Química, Ciudad Universitaria, Ciudad de México C.P. 04510, Mexico.
E-mail address: gtavizon@unam.mx (G. Tavizon).

https://doi.org/10.1016/j.cplett.2019.136998
Received 23 August 2019; Received in revised form 23 November 2019; Accepted 27 November 2019
Available online 02 December 2019
0009-2614/ © 2019 Elsevier B.V. All rights reserved.
J. Cruz-Puerto, et al.
valence band is more positive than the O2/H2O redox potential (1.23 V
vs. NHE), both values at pH = 0 [7]. These conditions for semi-
conductor photocatalysts, make Ta2O5 a suitable and promising mate-
rial to obtain hydrogen and oxygen from overall water splitting [8,9].
Regarding the solubility in water, Ta2O5 is extremely insoluble in
water, and no photodegradation of this compound has been reported up
to now. The disadvantage of using Ta2O5 as photocatalyst is the λ va-
lues for excitation that should be used must be less than 295 nm. To
achieve tantalum oxide-based photocatalysts with enhanced visible-
light photocatalytic activity, partial substitution of O by N in Ta2O5 to
obtain Ta2O5-xNx and TaO1-xNx has been done [10–13]. The idea is that
N doping will introduce localized N:2p states above the valence band
that could be responsible for the redshift in the absorption spectra, and
the bandgap value diminishes due to the mixing of N:2p and O:2p states
[8]. Thus, the electron transition energy from the valence band to the
conduction band could be reduced [11]; the band gap value reported
for TaON is 2.4 eV [13]. Another relevant contribution to reducing the
band gap value of the tantalum oxide-based photocatalysts resulted
from the synthesis of In1-xNixTaO4 that crystallizes in the wolframite-
type structure [14]. Z. Zou et al. used these compounds to produce H2
and O2 from water splitting under λ > 420 nm (2.95 eV); they also
observed that the photocatalytic activity disappeared when
λ > 550 nm (2.26 eV). The bandgap values reported were 2.6 (x = 0)
and 2.3 eV (x = 0.1) [14]. J. Ye et al. synthesized the In1-xMxTaO4
(M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn) system [15] and investigated
their activity as photocatalysts in the water-splitting reaction under
visible light conditions. In their report, the photocatalytic activity of
InTaO4 was significantly enhanced when In3+ was substituted by Ni but
suppressed in most of the other 3d transition-metal substitutions. They
also found that the evolution rate of H2 for In0.8Ni0.2TaO4 (the highest)
increased by about 74% compared with the pristine tantalate, InTaO4
[15]. The expectative of introducing 3d and 4f cations is directly related
to the new electronic states they could introduce in the bandgap of the
modified oxides photocatalysts in order to diminish the gap value. In
exhaustive studies of the Ta2O5-In2O3-NiO system, A. Malingowski et al.
showed that the visible light-catalytic activity of the Ni-doped InTaO4
system cannot be associated to the intrinsic properties of In1-xNixTaO4
compounds and they reported a band gap value of 3.7–3.9 eV for In1-
xNixTaO4 [16]. As observed by them, the weak optical internal transi-
tions associated to Ni2+ are not relevant to the photocatalytic activity
of the Ni-doped InTaO4 system.
Given the broad interest in the photocatalytic activity of InTaO4, in
this work, the synthesis of In1-xErxTaO4, In1-xYbxTaO4, and the corre-
sponding N-doped compounds, for x values in the 0 ≤ x ≤ 0.20 range
are studied. The effect of cationic (Er3+ and Yb3+) and anionic (N)
doping on the crystal structure, and optical (UV–Vis-NIF) spectroscopy
properties are also presented. The photocatalytic activity of these
compounds, under visible irradiation, is also studied in the light of
electronic structure calculations computed by a density functional
theory (DFT) method; we also discuss the modification of the bandgap
values as a function of the dopant contents. Even though InTaO4,
ErTaO4, and YbTaO4 are well-known compounds [17,18], this is the
first time that solid solutions involving Er and Yb cations in indium
tantalates are studied as photocatalysts.
2. Experimental and computing details
Polycrystalline samples of the In1-xRExTaO4 (RE = Er and Yb) in the
x range of 0 ≤ x ≤ 0.20 were prepared by solid-state reaction method,
starting from Ta2O5 (99.99%), In2O3 (99.99%) and Er2O3 and Yb2O3
(99.9%), all of them from Sigma-Aldrich. These chemicals were mixed
in an agate mortar with acetone as dispersing media, then the mixture
was slowly fired up to 900 °C for 12 h, and then the temperature was
raised to 1150 °C for 7 days with several intermediate regrinds. In order
to obtain the corresponding oxynitride, the synthesized In1-xRExTaO4
(RE = Er and Yb) compounds were exposed to vapors produced by
2
Chemical Physics Letters 739 (2020) 136998
thermal ammonolysis at 800 °C in a tube furnace by 24 h. Quantitative
elemental chemical analyses of the products (nitrogen content analysis)
were performed in a Perkin Elmer 2400 Series II CHNS/O Analyzer. X-
ray diffraction measurements were performed in a Bruker D8 dif-
fractometer with Cu-Kα radiation, equipped with a linxeye detector in
step scanning mode with a step size of 0.02 every 2 s; the 2 Θ range was
10°-90°. Rietveld refinements of the X-ray diffraction data were per-
formed using the GSAS-II (v. 3676) [19] code in which the initial
structure data were taken from O. Harneit et al. [20] Spectroscopic
characterization of samples was performed in a Cary 5E spectro-
photometer in the modality of diffuse reflectance using the integrating
sphere module, under room temperature conditions. SEM images of
samples were obtained in a JEOL 7800F 30 kV field emission scanning
electron microscope; a JEOL 2010F was used for the TEM images.
Electronic structure calculations were made with WIEN2k, which is
a full potential-linearized augmented plane wave (FP-LAPW) method
based on the DFT [21]. The unit cell of InTaO4 has two formula units
(Z = 2), so it has 8 oxygen atoms; therefore, when one N replaces O, the
product is InTaO7/2N1/2. In the InTaO4 there are 2 equivalent Wyckoff
positions for O, 4 g(1), with coordinates 0.438(3), 0.102(3), 0.213(4);
and 4 g(2) with 0.902(3), 0.383(3), 0.265(3), for x, y and z, respectively
[20]. The nearest neighbors of O-4 g(1) are two Ta and one In, while
that of O-4 g(2) is two In and one Ta. For the computational study of the
oxynitrides, In1-xRExTaO4-yNy, the oxygen atom at the 4 g(1) position
was replaced by N. To study oxygen vacancies, this same O 4 g(1) was
removed without replacing it with another atom to give InTaO7/2. For
In being replaced by RE in In1-xRExTaO4, with x = 1/4, four formula
units (Z = 4) are needed, that is, the unit cell has to be doubled; this
was done in the z direction (1X1X2) to obtain In3/4RE1/4TaO4. In all
these calculations, after the atom substitutions or removal, the internal
coordinates of the atoms are relaxed in order to obtain the optimized
crystal structure.
3. Experimental results
The reaction synthesis of the In1-xRExTaO4 (RE = Er, Yb) solid so-
lution was treated by two methods, in the first one, the complex
polymeric route was used, with citric acid as a chelating agent and
ethylene glycol as the connecting agent. After getting dry powders for
each composition, the obtained black ashes were fired at 1150 °C for
72 h, X-ray diffraction of the products showed that this procedure fa-
vors the formation of ErTaO4 and YbTaO4 in M-fergusonite phase (I2/a,
space group (SG) No. 15), since a noticeable fraction of these com-
pounds appeared as products of the reaction. On the other hand, the
solid-state reaction yields a majority phase in the wolframite type
structure, and the compounds of this work were obtained by this route.
The results of Rietveld refinements showed that all compounds of the
In1-xRExTaO4 (RE = Er, Yb) solid solution in the range 0 ≤ x ≤ 0.20
crystallize in the wolframite structural type, which is monoclinic with
SG P12/c1. In this structure, In1-xRExTaO4 has two kinds of octahedra in
the unit cell, TaO6 and (In/RE)O6. The (In/RE)O6 octahedra connect to
form zigzag chains by sharing edges. These (In/RE)O6 chains are con-
nected through TaO6 octahedra to form the three-dimensional network.
InTaO4 was obtained as a pure polycrystalline phase with unit cell
parameters in excellent agreement with a previously reported com-
pound [20,22]. X-ray patterns of all compounds and the isostructural
character of the solid solutions, In1-xErxTaO4 and In1-xYbxTaO4, is
shown in Fig. 1. Graphical results of the Rietveld refinement of InTaO4
are shown in Fig. 2, in which a single polycrystalline phase with the
wolframite monoclinic structure can be seen.
Graphical results of Rietveld refinements for several compositions of
the In1-xRExTaO4 solid solution can be seen in Fig. 3. As can be noticed
in the X-ray patterns of Figs. 1 and 3, for RE compositions larger than
0.10, a new phase alien to In1-xRExTaO4 appears. To get a better fit in
the Rietveld refinements, additional phases were introduced for the
x = 0.05, 0.10, 0.15 and 0.20 compositions, these phases were ErTaO4
J. Cruz-Puerto, et al.
Fig. 1. X-ray patterns for (A) In1-xErxTaO4 and (B) In1-xYbxTaO4 for x values in the 0 ≤ x ≤ 0.20 range. As can be noticed in these plots, extra-reflections in the x‐ray
diffraction pattern of InTaO4 appear around 2 Θ ≈ 29°; these reflections are associated with RETaO4 as a secondary phase. The relative amounts of these phases were
evaluated by Rietveld refinements and are listed in Table 1.
(phase 2) in In1-xErxTaO4, and YbTaO4 (phase 2) in In1-xYbxTaO4.
Through Rietveld refinements of powders, the contributions of these
phases to the X-ray patterns were estimated, and the values are listed in
Table1, in which the cell parameters of the compounds are also shown.
As can be seen in Table 1, as the x content of RE increases, the weight
fraction of the secondary phase (ErTaO4 and YbTaO4) increases; how-
ever, the variation of cell parameters and cell volumes are indicative of
a solid solution formation in the In1-xRExTaO4 system.
Crystal cell parameters of In1-xErxTaO4 and In1-xYbxTaO4, as well as
the cell volumes, are depicted in Fig. 4. As expected from the ionic
radius value of In3+ (0.57 Å) as compared with that of Er3+ (0.89 Å)
and Yb2+(0.86 Å) [22] (all of them in octahedral coordination), the cell
parameters values of InTaO4 are the smallest and the β angle, 91.35°,
corresponds to a quasi-orthorhombic cell [20]. According to an em-
pirical packing factor (EPF) of rigid spheres (Z = 2), considering the
ionic radius of Ta5+ in an octahedral environment (0.64 Å), the EPF of
the InTaO4 is 0.664. With this EPF, the expected maximum increase in
volume for In1-xErxTaO4 and In1-xYbxTaO4 would be 0.91% and 0.74%,
respectively. Er3+ and Yb3+ ionic radii are 56% and 51% larger than
In3+, respectively [23]. The experimentally observed volumes showed
an increment of 0.1% for In1-xErxTaO4 and 0.14% for In1-xYbxTaO4. This
behavior, when a larger cation, Er3+/Yb3+, substitutes a smaller one,
as In3+, is not the regular case in solid solutions, but it has been ob-
served in other systems such as the (Y1-xLax)2(Ce1-xZrx)2O7 fluorite-
pyrochlore [24]. As can be seen in Fig. 2B, in the crystal structure of In1-
xRExTaO4 (RE = Er, Yb), there are an alternating stacking of TaO6 and
(In/RE)O6 octahedra slabs along c-axis. This arrangement can explain
why a and b-cell parameters exhibit little change with the In3+ sub-
stitution by Er3+/Yb3+ as compared with a slightly more pronounced
change in the c-cell parameter, showing this latter the cation size effect
of the substitution. Although ErTaO4 and YbTaO4 crystallize in the
same space group than InTaO4, P12/c1 (space group No. 13), they
notably differ in the β-angle value of the monoclinic unit cell; while in
InTaO4, β = 91.35(2), for the Er tantalate (ErTaO4), β = 96.28°, and
for the Yb tantalate (YbTaO4), β = 96.44°. This variation in the β value
creates an important difference between such structures, while for
InTaO4 an almost well-defined octahedral coordination for In and Ta
can be described, the O-coordination of cations look distinct for Ta, Er,
and Yb in ErTaO4 and YbTaO4. According to the reported structures for
these compounds [17,25], in ErTaO4, the Ta O-coordination looks more
like a triangular prism than a regular octahedron; for Er, the O-octa-
hedra are distorted, with the Er3+ cation out of the equatorial plane. In
YbTaO4 a fully distorted O-octahedra can be observed in both Ta and
Yb cases.
According to quantitative chemical analysis of nitrogen, the
minimum formulas of the obtained compounds correspond to
3
Chemical Physics Letters 739 (2020) 136998
InTaO3.95N0.05, In0.95Er0.05TaO3.93N0.07, In0.9Er0.1TaO3.91N0.09, In0.85
Er0.15TaO3.90N0.10, In0.80Er0.2TaO3.90N0.10, In0.95Yb0.05TaO3.89N0.11,
In0.9Yb0.1TaO3.86N0.14, In0.85Yb0.15TaO3.89N0.11, and In0.8Yb0.2TaO3.90
N0.10. As can be observed, the nitrogen amount that by the thermal
ammonolysis procedure can be incorporated into compounds is about
2.5% of the anion positions of the crystal cell. The N content in oxy-
nitride samples hardly can be increased by the ammonolysis procedure,
and the nitrogen content of samples is of the order previously reported
[10].
X-ray diffraction patterns of the oxynitride phase, formed from
ammonolysis treatment of In1-xRExTaO4 to obtain In1-xRExTaO4-yNy
(RE = Er, Yb) are not entirely distinguishable from those of the oxide
phases. In those X-ray patterns, only a slight shift toward lower values
in 2Θ can be appreciated and is associated with a larger anion N3–
(1.46 Å) compared to O2– (1.4 Å), see Fig. 5. On the other hand, the
oxynitrides hkl reflections are the same as those of the corresponding
oxides, as expected for an isostructural phase where a larger N anion
substitutes O in these compounds.
SET (TEM) images of InTaO4 and In0.9RE0.1TaO4 of Figs. 6 and 7,
show particles with varying geometrical shape and wide size distribu-
tion. For InTaO4, the statistical size distribution is 0.36 ± 0.14 μm; for
In0.9Er0.1TaO4 is 0.43 ± 0.15 μm, and for In0.9Yb0.1TaO4 is
0.47 ± 0.15 μm. The predominant morphology of all samples is of
faceted spherical particles, and few of them are elongated. Although the
solid-state synthesis route used in this work hardly leads to small par-
ticles, surprisingly, many small size particles have been found.
Fig. 8(A) and (B) show the absorbance spectra obtained by diffuse
reflectance (DR) of the In1-xErxTaO4 and In1-xYbxTaO4 samples. As
shown in this plot, the In1-xErxTaO4 system shows rich absorbance
spectra in the visible (400–800 nm) region of the electromagnetic
spectrum (EMS), as compared to that of InTaO4. On the other hand, as
compared with InTaO4, the In1-xYbxTaO4 system does not modify the
absorbance spectra in the visible region of the EMS. In In1-xRExTaO4,
the contributions to the electronic spectra result from internal 4f-4f
electronic transitions, that due to the localized character of these 4f
electrons, they are not able to absorb the momentum of the photons.
The absorption spectra bands of In1-xErxTaO4, Fig. 8, have been
previously reported and assigned to the following transitions, all of
them form the 4I15/2 ground state of Er3+ to the 4I11/2, 4I9/2, 4F9/2, 4S3/
2 4 4 4 4 2 4 2 4 2
2, ( H, G)11/2, F7/2, F5/2, F3/2, ( G, F, H)9/2, G11/2 and G9/2 ex-
3+
cited states [26]. For the samples containing Yb , In1-xYbxTaO4, they
present an absorption peak from the 2F7/2 ground state to the excited
state 2F5/2 with its respective Stark components, centered at 970 nm
[18,27]. Spectroscopy studies on semiconductor photocatalysts, parti-
cularly those determined by diffuse reflectance spectroscopy (DRS), are
essential to characterize the response of these solids to electromagnetic
J. Cruz-Puerto, et al. Chemical Physics Letters 739 (2020) 136998

Fig. 2. (A) Rietveld refinement for InTaO4. In the text of this plot appears the goodness-of-fit criteria of the refinement. The initial structure for this refinement was
taken from O. Harneit et al. [20] The number of variables simultaneously refined was 31, additionally to those of the background function (Chebyshev polynomial
expansion). (B) Crystal cell (1X2X2) of the In1-xRExTaO4 compounds crystallizing in the wolframite-type structure.

radiation. From these spectra, it is possible to obtain the threshold for
photons to be absorbed (optical band gap) and observe changes in this
value as a function of chemical composition, size of the particles, etc.
The diffuse DRS data (R) of all compounds, In1-xRExTaO4 and In1-
xRExTaO4-yNy (RE = Er, Yb), were converted to units of relative ab-
sorption (α) by a Kubelka-Munk (KM) transform,[28] α
(E) = (1 − R)2/2R. As can be seen, in Figs. 9 and 10, the characteristic
features in the visible region of the EMS have been preserved in the KM
transform of the spectra, but the most important absorption, associated
to an electronic transition from localized, valence, states toward ex-
tended, conduction, states only occurs below 420 nm in both spectra of
In1-xErxTaO4 and In1-xYbxTaO4 in Fig. 8.
As can be seen in Figs. 9 and 10, additionally to the main optical
bandgap, which appears at about 3.74–4.25 eV for all compounds, and
that should be associated to O:2p-Ta:5d [29], it also appears one sub-
bandgap at about 2.9–3.10 eV that is probably associated with the
In:5p-O:2p electronic transitions [29]. It is also known that the tail
observed in the DRS may also reflect the existence of disorder and
defects in the crystal structure, which leads to the formation of loca-
lized states present in the bandgap [30,31]. In the case of the In1-
xRExTaO4 system, the presence of these tails in the DRS represents a
reduction of about 1 eV, with respect to the reported value for the
pristine compound. It should be mentioned that InTaO4 is the one that
more notoriously exhibits such a tail. On the other hand, these im-
perfections in photocatalysts can act as charge trappings, and the pre-
sence of Urbach tails can also act with a detrimental effect on photo-
catalysis. The presence of tails in the DRS absorption spectra can
contribute significantly to the absorption of photons by reducing the
value of the optical band gap, but, on the other hand, this tail could also
be associated to the presence of charge trappings [32] that diminish the
efficiency of the photocatalytic conversion.
As depicted in Fig. 9, there is a widening of the curves that define

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J. Cruz-Puerto, et al. Chemical Physics Letters 739 (2020) 136998

Fig. 3. Graphic results of the Rietveld refinements for two compositions of In1-xErxTaO4 (A and B) and In1-xYbxTaO4 (C and (D). For A and B, two phases were
necessary for the refinement, phase 1, In1-xErxTaO4, is isostructural to InTaO4, and phase 2 to ErTaO4. In C and D, phase 1, In1-xYbxTaO4, is isostructural to InTaO4
and phase 2 to YbTaO4. As can be noticed, phase 1 is the majority in both cases. The weight fraction of the phases is listed in Table 1.

Table 1
Structural parameters of the In1-xRExTaO4 solid solution compounds.
In1-xRExTaO4

x In1-xErxTaO4 In1-xYbxTaO4

a(Å) b(Å) c(Å) β(degrees) Vol (Å3) wt % of ErTaO4 a(Å) b(Å) c(Å) β(degrees) Vol (Å3) wt % of YbTaO4

0 5.16132 5.78112 4.83235 91.382 144.14674

0.05 5.16177 5.78133 4.83309 91.3834 144.18653 2.3 5.16183 5.78123 4.83339 91.3834 144.19466 1.8
0.10 5.16104 5.7805 4.83201 91.3809 144.11338 5.5 5.16184 5.78004 4.83437 91.4027 144.19331 2.2
0.15 5.16271 5.78049 4.83621 91.4213 144.28258 11.8 5.16334 5.78105 4.83657 91.4139 144.32537 7.3
0.20 5.16087 5.77758 4.83648 91.4468 144.16499 12.0 5.16385 5.7803 4.83763 91.4307 144.35148 12.6

The numeric values for the weight percentage of phases ErTaO4 and YbTaO4 were also obtained from Rietveld refinements. The cell-volume reported for ErTaO4 and
YbTaO4 are 143.01 and 143.50 Å3, respectively.[17,25].

the main optical gap (4.8 to 4.2 eV), therefore, a diminishing in the gap
value should be expected for In1-xRExTaO4; the same situation occurs in
Fig. 10, in which the slopes of the curves remain almost constant, with a
reduction of the gap in the same energy range. On these two figures,
several observations should be remarked. (1) the main optical gap for
InTaO4 is 3.94 eV; (2) this optical gap value is one of the lowest gap
values in the series In1-xRexTaO4; (3) In In1-xErxTaO4, there is no re-
lationship between gap value and Er3+ content; (4) in In1-xYbxTaO4 for
x ≠ 0, Fig. 9 B, all the optical gap values are about 4.1 eV. On the sub-
gap values of In1-xErxTaO4, appearing in the 2.8–3.2 eV range, the
lowest values, 2.8 and 2.9 eV, appear for the higher Er3+ compositions;
in In1-xYbxTaO4, all values seem to converge at 3.15 eV. In the case of
oxynitrides, Fig. 10 A and B, the remarkable observations are; (1) the
higher value of the main optical gap corresponds to InTaO4-yNy at
4.13 eV and the lowest value, 3.74 eV, for In0.85Er0.15TaO4-yNy. (2) the
other compositions in In1-xErxTaO4-yNy show a slight reduction in the
gap, ranging from 4.0 to 4.07 eV, with no clear dependence on com-
position. (3) in the In1-xYbxTaO4-yNy series, these values increase with
Yb content, ranging from 4.07 to 4.25 eV. (4) for the sub-gap values in
the In1-xErxTaO4-yNy series, these values are from 2.9 to 3.0 eV, while
for the In1-xYbxTaO4-yNy series their values are in the 2.92–3.0 eV
range, with the lowest value for that of the higher Yb3+ content.
Summarizing, for all samples of the In1-xRExTaO4 series, the main
optical gap appears in the 3.94–4.15 eV range. In this set of compounds,

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J. Cruz-Puerto, et al. Chemical Physics Letters 739 (2020) 136998

Fig. 4. (A) Lattice parameters and (B) volume variations as a function of composition in In1-xErxTaO4 and In1-xYbxTaO4. These values result from the Rietveld
refinements, and the error bars are negligible as compared to the plotted values. In (B), the estimated cell volume was calculated through rigid spheres with ionic
radii of trivalent Er and Yb substituting In3+.

the lower value, associated to O:2p-Ta:5d [29], corresponds to InTaO4;
for RE = Er, although there is not a clear dependence on the Er com-
position, and in the case of the RE = Yb series this value is centered at
4.1 eV. In the In1-xRExTaO4 series, the optical sub-gap appears in the
2.8–3.2 eV range, and for RE = Er the minimum value appears at
2.8 eV. Again, for the RE = Yb, the series value is centered at 3.15 eV.
In the case of oxynitrides, In1-xRExTaO4-yNy, the minimum value of the
main optical gap appears for RE = Er, x = 0.15, and y = 0.10, and the
highest for InTaO4-xNy. The RE = Yb series has the main gap of about
4.25 eV. The sub-gap of the Er oxynitrides has a minimum at 2.90 eV
(x = 0.15 and y = 0.10), and for RE = Yb the sub-gap value is centered
at 3.0 eV. It is important to remark that beyond the lowest optical gap
value for InTaO4, 3.94 eV, a clear relationship between the RE = Er, Yb
content, and the main optical gap value is not observed; furthermore,
this value does not decrease with N-doping. For both series In1-xErxTaO4
and In1-xYbxTaO4, the sub-gap value consistently decreases with N-
doping.
Although most of rare earth oxides show absorption signals in the
visible range of the EMS, the incorporation of these elements and the
associated color of compounds should not be though as sufficient to
form optically active catalysts in that range of the EMS, since such
absorption bands result from 4f to 4f internal electronic transition

Fig. 5. XRD patterns of N-doped In1-xRExTaO4. In (A) InTaO4, (B) In0.95Er0.05TaO4, (C) In0.90Er0.10TaO4 and (D) In0.90Yb0.10TaO4. The XRD patterns of In1-xRExTaO4
tantalates (black) are compared against those resulting from the N-doped, In1-xRExTaO4-yNy, samples (red). The 020, 200, and 002 reflections are used to show an
enlargement of the unit cell by a small shift towards lower 2 Θ values.

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J. Cruz-Puerto, et al. Chemical Physics Letters 739 (2020) 136998

Fig. 6. SEM images of InTaO4 (A-C) show the particles exhibiting varying geometrical shapes and particle sizes, most of them are spherical and faceted. In (D), TEM
for some of the smallest particles found in the InTaO4 sample.

associated with electrons prevented to interact with visible photons, (1–1.5%) TiO2 hollow spheres [33], where the value changed from 2.98
due to the localized character of the 4f bands introduced in the gap. to 2.93 eV; or in Ce, Pr, La, Nd-doped TiO2 samples, where the bandgap
When TiO2 has been doped with rare-earth cations, the effect on the value continues to be very close to 3.0 eV [34].
bandgap values was barely appreciable, such is the case of Yb-doped As shown in Fig. 11, the band structure calculations of InTaO4 gives

Fig. 7. SEM images of In0.9Er0.1TaO4 (A and B), in which the same characteristic morphology than InTaO4 and wide distribution of sizes. SEM images (C and D) of
In0.9Yb0.1TaO4, in these particles, the faceted morphology looks clearer.

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J. Cruz-Puerto, et al. Chemical Physics Letters 739 (2020) 136998

Fig. 8. Diffuse reflectance UV–Vis spectra of (A) In1-xErxTaO4 and (B) In1-xYbxTaO4 in the 200–1250 nm range (the figures were shifted upward for visibility
purposes). As can be observed in these plots, the absorption spectra are quite different in the visible region of the EMS. In both cases, the spectrum of the pristine
compound, InTaO4, has been included (black line).

Fig. 9. Relative absorption obtained via a Kubelka-Munk transform of diffuse reflectance spectra of the compounds of the series (A) In1-xErxTaO4 and (B) In1-
xYbxTaO4. In the inset of these figures a zoom is shown in which two optical gap sets can be observed, in (A) the values of the first set range from 3.94 to 4.10 eV and
the second from 2.8 to 3.10 eV; in (B) the corresponding sets range from 3.94 to 4.15 eV, and from 3.05 to 3.2 eV, respectively.

Fig. 10. Relative absorption obtained via a Kubelka-Munk transform of diffuse reflectance spectra of the N-doped compounds of the series In1-xRExTaO4. (A) In1-
xErxTaO4-yNy and (B) In1-xYbxTaO4-yNy. In the inset of these figures, a zoom is shown in which two optical gap sets can be observed, in A) the values these gap sets
appear from 3.74 to 4.13 eV and 2.9 to 3.0 eV; in (B) these optical gap sets appear from 4.06 to 4.25 eV and from 2.92 to 3.1 eV. As can be observed, for the x = 0.15
Er oxynitride, a notable gap reduction appears at 3.74 eV (compared with 4.1 eV of In0.85Er0.15TaO4).

8
J. Cruz-Puerto, et al.
Fig. 11. Band structure calculation of InTaO4. The structure is qua-
siorthorhombic (β = 91.35°), and for this reason, the used band directions
correspond to the orthorhombic structure.
a bandgap of 3.95 eV, which is reasonably close to the experimental
optical gap (3.96 eV) [16]. As can also be seen in this figure, the top of
the valence band varies very little; therefore, there is not a critical
energy difference between the direct and indirect electronic transitions.
The density of states (DOS), Fig. 12, shows that the valence band states
mainly result from O:2p, while the conduction band is mainly formed
by Ta:5d with a small contribution from O:2p.
For the InTaO4 system, previous DFT calculations showed a
bandgap of 3.7 eV, and for the N-doped InTaO4, this value decreased by
0.3 eV [35]. On the other hand, the experimental band gap reported by
Malingowski et al. for InTaO4 is 3.96 eV [16].
When Er and Yb replace In atoms, new states are introduced in the
gap (Fig. 13); for the calculations, the unit cell was doubled in the c
direction, so there are 4 In, and one of them was replaced for a RE,
resulting in In3/4RE1/4TaO4. In the case of the RE = Er system, down
spin states are introduced in the gap, some at the beginning and some in
the middle, these states are due to the Er:4f and they are quite localized,
this is the reason why these DOS peaks are so narrow. There is a tiny
gap below these peaks; between these peaks there is a 0.9 eV gap, and
Fig. 12. (A) DOS of InTaO4, this system shows a gap of 3.8 eV. The valence band is mainly due to the oxygen atoms, while the conduction band is due to tantalum
with a smaller contribution of oxygen. (B) DOS of InTaO7/2N1/2, in this system, one oxygen of the unit cell was replaced by nitrogen. This atom incorporates a peak at
the beginning of the gap, and EF moves to the middle of this peak; therefore, the system is no longer an insulator, although not a good conductor. The bandgap
diminishes to 3.15 eV.
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Chemical Physics Letters 739 (2020) 136998
EF is in this gap; above the higher peaks there is a more significant 2 eV
gap. Now, for RE = Yb the same down spin states also appear, but all of
them are at the beginning of the gap. EF is again in the middle gap, but
this is now a tiny gap, and the system would be a semiconductor, but
due to the localized character of the Yb:4f, the system would be quite
insulating.
These RE:4f states could act as stepping stones for the electrons to
jump to an extended state of higher energy (in the conduction band). In
these extended states, the angular momentum is lost, and the bands
become wide. On the other hand, these RE:4f states do not overlap and
keep their high angular momentum. A transition from these RE:4f states
to a delocalized extended state cannot be induced by a photon, since the
photon has an angular moment of ħ, compared to √12 ħ of the RE:4f.
In the case of N replacing an O in InTaO4, there are 8 oxygen atoms
in the unit cell, therefore, for the electronic structure calculations, if N
replaces one O atom, then the result is InTaO7/2N1/2. As shown in
Fig. 12B, a peak in the DOS appears just above the valence band formed
by O:2p and N:2p states, and EF moves into this peak; therefore, the
system is “metalized”, and the bandgap is reduced to 3.15 eV.
When one O is removed to obtain InTaO7/2, a broad O-In peak ap-
pears in the gap, splitting the gap in two, with EF in the upper gap,
Fig. 14. This upper gap is reduced to 2 eV. Similar results, with cal-
culations on a 2X2X1 InTaO4 supercell, have been previously reported
by H. Chang et al. and G-L Li et al. [29,30] Although this was not done
experimentally in this work, in real systems, the formation of oxygen
vacancies is a highly probable process when high vapor pressure oxides
are involved, as is the case of In2O3 at high temperature [36]. So, at the
temperatures at which the formation of InTaO4 occurs, Schottky defects
are highly probable to be formed with oxygen vacancies involved in
such a process.
For the In3/4Yb1/4TaO4 case Fig. 13B, the system holds its semi-
conductor character, with a small gap value, and the main gap has a
value of 3.15 eV. The main contribution of the low energy states is from
4f localized states, with a little contribution from O:2p states. In this
situation, an effective diminishing of the bandgap value, resulting from
the RE = Yb doping would not be expected. In the light of the results of
electronic structure calculations, the unique system in which a dimin-
ishing of the bandgap value observed is InTaO4, via the formation of
oxygen vacancies.
4. Conclusions
By solid-state reaction, solid solutions of In1-xErxTaO4 and In1-
xYbxTaO4 crystallizing in the wolframite structure were obtained. By
J. Cruz-Puerto, et al.
Fig. 13. (A) DOS of In3/4Er1/4TaO4, in this system the unit cell is doubled, that is, it has four formula units, and one indium atom is replaced by erbium. This system is
now magnetic, and it introduces down spin peaks in the gap. EF is at the beginning of the gap, and the system remains as an insulator. There are other down spin
peaks in the gap further up in energy. (B) DOS of In3/4Yb1/4TaO4, this system is the same as the erbium doping, but instead of erbium, ytterbium is introduced. Again,
there are down spin peaks at the beginning of the gap, EF is again at the beginning of a gap, but in this case, the gap is tiny, and the system is a semiconductor.
Fig. 14. Results of DOS for oxygen vacancy-doped InTaO4 (InTaO7/2) sample in
which an oxygen atom of the wolframite crystal cell has been removed. A sub-
gap for E < EF raises and the main gap drops to ~2.0 eV. The low energy states
result from O:2p states and the conduction band is predominantly formed by
Ta:5d states.
thermal ammonolysis, the corresponding In1-xErxTaO4-yNy and In1-
3+
xYbxTaO4-yNy oxynitrides were also prepared. Although the In sub-
3+
stitution by Er introduces new electronic transitions in In1-xErxTaO4
in the visible region of the EMS, these transitions are associated with
RE:4f-4f internal transitions and such electronic transitions, due to the
localized character of the 4f electrons, do not modify the gap energy
associated with electronic transition towards extended states as that in
which electron-hole pair is formed. From experimental observations,
the effect of RE:4f electrons, introduced by Er3+ and Yb3+, or the N-
doping, do seem to play any effect in diminishing the bang gap value of
the pristine compound InTaO4. Based on electronic structure calcula-
tions, it is hypothesized that the sub-gap appearing at ~ 3.0 eV in
InTaO4 and In1-xRExTaO4, should be related to the oxygen vacancies in
the crystal structure of compounds.
CRediT authorship contribution statement
Juan Cruz-Puerto: Conceptualization, Investigation. Cristina
Ramirez-Carrillo: Conceptualization, Formal analysis. Jorge Puga-
Lechuga: Methodology, Validation. Pablo de la Mora: Investigation,
Methodology, Writing - original draft. Gustavo Tavizon: Investigation,
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Chemical Physics Letters 739 (2020) 136998
Methodology, Project administration, Visualization, Writing - original
draft, Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors would like to thank Q.I. Cecy Salcedo for X-ray dif-
fraction measurements, Dr. Samuel Tehuacanero-Cuapa (I. de Física)
for the support in SEM and TEM, and Dr. Sandra Rodil (IIM, UNAM) for
valuable discussions. We appreciate the financial support from
CONACyT (A1-S-10890) and from PAPIIT (UNAM) under projects IN-
115618 and IN-225217.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cplett.2019.136998.
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