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Journal of Alloys and Compounds 655 (2016) 208e214

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Journal of Alloys and Compounds


journal homepage: http://www.elsevier.com/locate/jalcom

Investigation on structures, band gaps, and electronic structures of


lead free La2NiMnO6 double perovskite materials for potential
application of solar cell
Chunfeng Lan, Shuai Zhao, Tingting Xu, Jie Ma, Shuzi Hayase, Tingli Ma*
Graduate School of Life Science and Systems Engineering, Kyushu Institute of Technology, Wakamatsu, Kitakyushu, 808e0196, Japan

a r t i c l e i n f o a b s t r a c t

Article history: Lead free double perovskites La2NiMnO6 were first studied for potential application on solar cells. The
Received 9 July 2015 rhombohedral and the monoclinic La2NiMnO6, with B-site of Ni3þ/Mn3þ, were respectively formed under
Received in revised form different synthesizing conditions. The experimental results show that the monoclinic La2NiMnO6 sample
16 September 2015
has a band gap of 1.4 eV and valence band of 5.8 eV, on the other hand, the respective values for
Accepted 20 September 2015
rhombohedral sample are 1.2 eV and 5.7 eV. The density function theory calculation demonstrates that
Available online 25 September 2015
the calculated band gap for the monoclinic La2NiMnO6 is larger than that for the rhombohedral one.
However, the electronic structures for these La2NiMnO6 are found very similar to each other. Our
Keywords:
La2NiMnO6
combined experimental and theoretical studies indicate that, from the aspects of band gaps and energy
Band gap levels, double perovskite La2NiMnO6 of monoclinic phase could be a better candidate than that of
Electronic structures rhombohedral phase for light harvesting.
Light harvesting © 2015 Elsevier B.V. All rights reserved.

1. Introduction from A-site of methylammonium organic group. Another concern is


the pollution from the B-site of lead ion, as we all know, lead is a
Hybrid organiceinorganic perovskite solar cells (PSCs) have heavy metal and it may be detrimentally harmful to our environ-
experienced a rapid development since perovskite material was ment and health [4,5]. Therefore, environmental friendly and stable
first applied to replace organic dyes in solar cells in 2009 [1]. PSC perovskite materials are eagerly desired to overcome these short-
has achieved an extraordinary high power conversion efficiency of falls. Previous reports suggested that multiferroic inorganic
20.1% to date, becoming a promising alternative of traditional sili- perovskite semiconductors might be alternatives for solar cell
con solar cells [1e3]. The excellent light to electricity conversion application [5].
efficiency of hybrid perovskite solar cells can be attributed to the The multiferroic inorganic perovskites, such as BiFeO3,
proper band gap of perovskite materials, which usually has a band [KNbO3]1x[BaNi1/2Nb1/2O3d]x and Bi2CrFeO6, are expected to be
gap of 1.5 eV for a typical methylammonium lead iodide potential alternatives for lead halide perovskite for solar cell ap-
(CH3NH3PbI3), large absorption coefficient, high carrier mobility, plications [6e10]. With BiFeO3, its band gap is too wide to absorb
and long electronehole diffusion length up to 175 mm [3], as well as visible lights [9]. With [KNbO3]1x [BaNi1/2Nb1/2O3d]x, although its
bipolar carrier transport ability [4,5]. Although the lead halide io- band gap is narrow, it is too difficult to prepare high quality thin
dide materials have demonstrated many merits in current PSCs, films [10]. With Bi2CrFeO6 it was reported to have an experimental
there are several serious problems that may hinder the wide range band gap of 1.6e1.9 eV, thus it may be suitable for light harvesting.
application of the lead halide based hybrid perovskite solar cells. Except from the view of band gap, the ITO/Bi2CrFeO6/Nb-doped
One problem is the instability of the perovskite materials and the SrTiO3 structured solar cell was also fabricated by R. Nechache et al.,
resulting poor long-term stability of solar cells. This may result and it has obtained a high power conversion efficiency of 8.1%.
However, the disadvantage is that Bi2CrFeO6 perovskites need to be
prepared by physical vapor deposition (usually pulse laser depo-
sition), and the experimental conditions to deposit them are quite
* Corresponding author.
E-mail address: tinglima@life.kyutech.ac.jp (T. Ma). complicated [11]. Therefore, it may be hard to achieve higher

http://dx.doi.org/10.1016/j.jallcom.2015.09.187
0925-8388/© 2015 Elsevier B.V. All rights reserved.
C. Lan et al. / Journal of Alloys and Compounds 655 (2016) 208e214 209

2. Experimental procedure

All the chemicals were purchased from commercial available


sources. They were used as received. The citric acid/ethylene glycol
solution with stoichiometric lanthanum acetate (99.9%, Alfa Aesar,
Russia), nickel acetate (98.0%, Wako Pure Chemical Industries,. Ltd,
Japan) and manganese acetate (99.0%, Wako Pure Chemical In-
dustries,. Ltd, Japan) was prepared as the precursor. The solution
was heated to get a dry-gel at 120  C. After being pyrolized at
400  C for 5 h, the powder was ground and heated in the tube
furnace under different conditions. The sample synthesized in the
air at 600  C for 10 h, with a heating rate 5  C/min, was labeled as
LNM600. Another sample rapidly annealed in oxygen atmosphere
in a tube furnace, at 900  C for 10 h, was labeled as LNM900.
The X-ray diffracting (XRD) diagram was recorded from 15 to
80 at a scanning step of 0.01 /s using a X-ray diffractometer
(Rigaku Co., Ltd, Tokyo, Japan) with Cu Ka radiation (l ¼ 1.54056 Å).
The S-5200 Ultra-High Resolution (S5200, Hitachi, Japan) with
energy dispersive X-ray spectroscopy (EDX) was used to charac-
Fig. 1. XRD patterns of the sample LNM600 and the sample LNM900. terize the microstructure and chemical composition. The X-ray
photoelectron spectroscopy (XPS) (AXIS-HS, KRATOS Co. Ltd.,
Japan) was applied to determine the valence state of Ni and Mn
performance solar cells and not suitable for mass production pro-
elements. A UVeVISeNIR Spectrophotometer, with an integrator
cess [12,13].
(V-670, JASSCO Co., Ltd, USA), was applied to determine the optical
Recently, double perovskite La2NiMnO6 with a band gap of
properties of the products by diffuse reflectance spectra, and the
1.5 eV was reported by Kitamura et al. [14]. Especially, compared
band gaps were calculated using Tauc Plot. An ionization energy
with Bi2CrFeO6 and [KNbO3]1x[BaNi1/2Nb1/2O3d]x, La2NiMnO6
measuring device (KV205-HK, Bunkoukeiki Co., Ltd, Japan) was
double perovskites can be synthesized by a chemical method,
used to determine the valence band through photoelectron yield
which is much easier than the methods to prepare the double pe-
spectroscopy (PYS).
rovskites mentioned above [15]. Dass and Sun et al. reported the
different crystal structures of La2NiMnO6 were formed at different
synthesis conditions, they found that these crystal structures 3. Theoretical calculations
strongly influenced the physical properties of La2NiMnO6, such as
dielectric properties and magnetic properties [15,16]. However, so All calculations were performed using Quantum ESPRESSO
far there is a lack of study on electronic properties of different simulation package based on the density functional theory, using
structured La2NiMnO6, such as B-site and phase effects on band planeewave basis sets [17,18]. The generalized gradient approxi-
gaps, electronic structures and so on, which would be key factors mation (GGA) with the PerdeweBurkeeErnzerhof (PBE) functional
for solar cell application. had been considered for the exchangeecorrelation effects [19]. The
In this work, the La2NiMnO6 materials were synthesized by the electroneion interactions were described by projector augmented
Pechini method [16], and their crystal structures were investigated wave (PAW) and the cutoffs of planeewave basis sets were set to
by X-Ray diffraction and X-ray photoelectron spectroscopy. In order 40 Ry. The 4  4  4 MonkhorstePack kemesh was used for the
to further explore the potential application of La2NiMnO6 double self-consistent calculations to determine the groundestate con-
perovskite on solar cells, we carried out the investigation of band figurations and a denser grid was used for the density of states
gaps and electronic structures with combined experimental and (DOS) calculations. The lattice vectors and atomic positions were
theoretical methods. The results revealed that monoclinic fully relaxed before electronic and optical properties calculations.
La2NiMnO6 perovskite can be a better candidate than the rhom- The DFT calculation seriously underestimates the band gap with
bohedral one for light harvesting. respect to the transition metal oxides because the strong on-site

Fig. 2. FE-SEM images of the La2NiMnO6 powders: a) LNM600; b) LNM900.


210 C. Lan et al. / Journal of Alloys and Compounds 655 (2016) 208e214

Coulomb interactions between localized electrons were ignored in


this case. An effective method to offset this underestimation was
GGA þ U method, which adds an orbitaledependent term to
describe the exchange and correlation potentials. In our study, we
used the Ueff ¼ 3 eV for Ni 3d and Mn 3d orbitals suggested in
Ref. [20].

4. Results and discussion

4.1. Structural characterization

The sample LNM600 synthesized at 600  C was dark black, and


the sample LNM900 synthesized at 900  C was gray black, which is
similar to the result reported by Dass [16]. The Powder XRD pat-
terns of the two samples are presented in Fig. 1. For the XRD pattern
of LNM600, it shows a rhombohedral phase of La2NiMnO6 (PDF 01-
072-8297) with the space group R-3. For the XRD pattern of
LNM900, the slight location difference of peaks at around 32 and
the existence of (111) at 25.65 suggest that the crystallization
might be monoclinic with the space group P 21/n (PDF 01-072-
7793) or orthorhombic phase with the space group Pbnm (PDF 01-
075-2899). Regarding the phase of LNM900, the previous reports
demonstrated that the monoclinic La2NiMnO6 was B-site ordered,
whereas the orthorhombic La2NiMnO6 was disordered [15,16]. The
temperature to form disordered La2NiMnO6 was lower than that to
form ordered, however, high temperature annealing and rapid
annealing rate could overcome the nucleation of disordered
perovskite and favor the synthesis of ordered double perovskites
[15]. Therefore, combined our XRD results with previous reports, it
is suggested that the crystal structure of LNM900 is B-site ordered
monoclinic with the space group P 21/n. Moreover, a small amount
of impurity was also observed in LNM900, which is attributed to
existence of LaMn2O5 (PDF 00-052-1095).
Fig. 2 shows the SEM images of sample LNM600 and LNM900. It
can be seen that homogeneous nanoparticles have been formed in
both LNM600 and LNM900. The particle size of LNM600 is probably
50 nm and that of LNM900 is 500 nm. The increased synthesizing Fig. 4. XPS patterns of the samples LNM600 and LNM900: a) Ni 2p / 3d XPS spec-
temperature attributes to the larger particle size. The particles ag- trum b) Mn 2p / 3d XPS spectrum.
gregation is also observed in LNM900 because higher annealing
temperature increased particle size. Further energy dispersive X-
ray spectroscopy (EDS) results from the sample LNM900, as shown Fig. 4(a) and (b) show the XPS results of LNM600 and LNM900 to
in Fig. 3, confirmed the existence of La, Mn and Ni elements. The evaluate the valence states of Ni and Mn elements. The peaks at
stoichiometric ratio of Mn and Ni in the prepared products is around 870 eV (Ni 2p1/2)were very weak to distinguish Ni2þ from
approximately 1:1. Ni3þ in X-ray absorbing spectrum results [14], even it can be seen

Fig. 3. EDX pattern from the sample LNM900.


C. Lan et al. / Journal of Alloys and Compounds 655 (2016) 208e214 211

ligands [14,15]. The split structures of peaks from 640 eV to 645 eV


which were considered as a symbol of the Mn4þ state, are neither
found in LNM600 nor LNM900. In contrast the structures are quite
similar to that of Mn state in LaMnO3 as reported [23]. Conse-
quently, it can be concluded the Mn3þ state is likely dominant in
our products. At the same time, in order to maintain a neutral
charge it can be deduced that the nickel must mainly be in the Ni3þ
formal oxidation-state both in LNM600 and LNM900 [21]. To sum
up, the XRD and XPS results suggested the product LNM600 is
rhombohedral with the B-site of Ni3þ/Mn3þ and LNM900 is
monoclinic with the B-site of Ni3þ/Mn3þ.

4.2. UVevis optical absorption properties and electronic structure

Fig. 5 shows the diffusion reflectance UVevisible spectra results


of the La2NiMnO6 powders. The sample LNM600 has light ab-
sorption near infrared range, and the band gap of LNM600 deter-
mined from the Tauc plot is approximately 1.2 eV. While for the
sample LNM900, the band gap deduced is approximately 1.4 eV,
Fig. 5. Diffusion reflectance UVevis spectrums of LNM600 and LNM900 after K-M which is very close to that of the La2NiMnO6 film as reported by
conversion and Taul Plot treatment. Kitamura [14]. Compared with the single perovksite LaMnO3 whose
experimental band gap of 1.7 eV and theoretical band gap of 2.0 eV
[22], it can be seen that both LNM600 and LNM900 show much
lower band gaps. This phenomenon can be attributed to the higher
octahedrons distortion of La2NiMnO6 crystalline after the intro-
duction of Ni3þ into the B-site [21]. The band gap difference of
0.2 eV between LNM600 and LNM900 might result from a larger
crystal distortion of R-3 phase, which might lead to higher local
energy [16]. The detailed contributions of Ni and Mn to the band
gap were discussed in the following calculation.
To understand the energy level of La2NiMnO6, photoelectron
yield spectroscopy was applied to investigate the valence band of
the samples. The PYS results show that the experimental valence
Fig. 6. Energy band diagrams of LNM600, LNM900 and related materials reported. (* bands of LNM600 and LNM900 are 5.7 eV and 5.8 eV, respec-
referred to Ref. [6]). tively. It can be seen that the valence band of rhombohedral
LNM600 is very close to that of monoclinic LNM900. As we dis-
cussed above, the valence states of B-site of sample LNM600 and
that the characteristic peaks of La and Ni are close to each other.
LNM900 are almost the same, thus the small difference of VB might
Therefore, it is very difficult to directly evaluate the valence state of
come from the crystal structures of the samples. For La2NiMnO6
Ni in our work. Fortunately, the sharp structures from 640 eV to
with B-site of Ni2þ/Mn4þ, it is reported the maximum valence band
645 eV, Mn 2p3/2, can be reliable benchmarks of the appearance of
was thought to be a state derived from Mn 3d [14]. However, to date
Mn state because they are hardly smeared by other elements
there is no report on this for La2NiMnO6 with B-site of Ni3þ/Mn3þ,
[14,21]. The shape of the peaks in this area strongly depends on the
in our work we will try to explore it in following calculations. Based
multiplet structure given by the Mn 3de3d and 2p-3d C and ex-
on the band gaps and valence states, an energy diagram is shown in
change interactions, as well as the hybridization with the O 2p
Fig. 6. It can be seen that the conduction bands of LNM600 and
LNM900 are higher than that of ITO and SrRuO3 thin films. The
energy level difference from monoclinic LNM900 to that of SrRuO3
Table 1
is 0.8 eV, whereas the difference of 0.7 eV is found for that of
Parameters for crystal structures of La2NiMnO6 with two different phases.
rhombohedral LNM600 to SrRuO3. Considering that SrRuO3 is a
P 21/n Re3 suitable electron conductor [24], the photon-excited electron in
Exp.a Cal. Exp.a Cal. La2NiMnO6 could be injected into SrRuO3 layer and form a Schottky
a 5.467 5.436 5.475 5.359 junction. Regarding Bi2CrFeO6 mentioned above, the simple ITO/
b 5.51 5.411 Bi2CrFeO6/SrRuO3 layer-structured Schottky solar cells achieved a
c 7.751 7.653 60.67 61.48 high power conversion efficiency, even though there were many
Distance (NieO) defects in Bi2CrFeO6 [6]. Therefore, from the aspects of the band gap
xey 2.011 2.019 2.008 2.013
1.976 2.017
and energy level matching, it is anticipated that La2NiMnO6 could
z 2.016 2.02 function as the same as Bi2CrFeO6 to fabricate a lead free perovksite
Distance (MneO) solar cell. Furthermore, the monoclinic LNM900 would be a better
xey 1.983 1.889 1.927 1.887 candidate than the rhombohedral LNM600 for light harvesting
1.889 1.89
from the aspect of energy level matching. Future work of fabri-
z 1.908 1.889
Angle (NieOeMn) cating the monoclinic La2NiMnO6 related solar devices with ITO
xey 168.92 157.55 162.79 158.64 and SrRuO3 materials are in progress.
157.21 158.09 In order to explain the phase effects on electronic properties of
Z 161.85 156.37 La2NiMnO6 perovskites, DFT calculation was introduced to calculate
a
Ref. [26]. the band gaps and electronic structures of La2NiMnO6. The
212 C. Lan et al. / Journal of Alloys and Compounds 655 (2016) 208e214

Fig. 7. Projected density of states of La2NiMnO6 with the space group P 21/n and Re3.

5 5
(a) (b)
4 4

3 3

2 2
Energy (eV)

1 1

0 0

−1 −1

−2 −2

−3 −3
Γ Y C Γ B E A Γ Y C Γ B E A

5 5
(c) (d)
4 4

3 3

2 2
Energy (eV)

1 1

0 0

−1 −1

−2 −2

−3 −3
Γ A H K Γ M L Γ A H K Γ M L

Fig. 8. Band structures of La2NiMnO6, (a) majority spin of P 21/n state; (b) minority spin of P 21/n state; (c) majority spin of Re3 state; (d) minority spin of Re3 state.
C. Lan et al. / Journal of Alloys and Compounds 655 (2016) 208e214 213

geometrical structures of two different phases of La2NiMnO6 were from the hybridization between Mn 3d and O 2p orbitals. In this
optimized using BroydeneFletchereGoldfarbeShanno algorithm case, compared with single perovskite LaMnO3, the narrowed band
as listed in Table 1. Based on the crystal structures and valence gap of double perovskite La2NiMnO6 mainly comes from the in-
states discussed above, Fig. 7 shows the geometrical structures of crease of valence band [22]. Nonetheless, it is worthwhile noting
two different phases of La2NiMnO6 optimized under PBE-GGA level that at the top of the valance band and the bottom of the conduc-
[25]. It can be found that the calculated lattice parameters of tion band in the minorityespin configuration, there exists the hy-
ferromagnetic state in both P 21/n and Re3 phases agree well with bridization between not only Ni 3d, but also Mn 3d orbitals with O
the measured results [26]. More specifically, in the octahedron, the 2p orbitals. Thus, from the aspects of experimental and theoretical
distance of central atom Ni with the corner atom O is slightly longer results, the B-site substitution in single perovskites is actually a
than that of Mn with the O atoms, implying higher distortion of useful method to tune the band gap and electronic structures of
crystal structure when Mn was half-replaced by Ni in LaMnO3. At inorganic perovskites, and their crystal structures can influence
the same time, we notice that the optimized angle of NieOeMn in their optical properties.
monoclinic La2NiMnO6 is larger than that of the rhombohedral,
implying a smaller distortion of crystal structure in P 21/n 5. Conclusion
La2NiMnO6, which might be an explanation for its larger band gap.
The band structures and density of states of La2NiMnO6 were Homogenous La2NiMnO6 double perovskites with monoclinic
calculated based on the optimized crystal structures above. The phase and rhombohedral phase were prepared by the Pechini
theoretical band structures near the Fermi energy level along the Method under different synthesizing conditions. XPS analysis in-
high symmetry k-points are depicted in Fig. 8 for P 21/n and R-3 dicates that Ni3þ and Mn3þ dominate in our products. Diffusion
phases respectively. According to our calculated results, the general reflectance UVeVis spectrum reveals that the monoclinic
shapes of the band structures at the conduction band minimum La2NiMnO6 is with a band gap of 1.4 eV and the rhombohedral
(CBM) and valence band maximum (VBM) are similar for the P 21/n La2NiMnO6 is with a band gap of 1.2 eV from Tauc plot. PYS results
and Re3 phases of La2NiMnO6. The band gap of P 21/n La2NiMnO6 is show that the valence band of monoclinic and rhombohedral
1.133 eV, whereas the band gap of Re3 La2NiMnO6 is slightly La2NiMnO6 are 5.8 eV and 5.7 eV, respectively. Further results of
smaller to 1.109 eV. These calculated band gaps are corresponding density function theory calculation demonstrate that the band gap
to, but a little lower than the experimental results that we gained of monoclinic La2NiMnO6 is 1.133 eV and that of rhombohedral
above. La2NiMnO6 perovskites is 1.109 eV. The small difference of band
The total density and partial density of the states of these double gaps can result from the larger distortion of B-site in rhombohedral
perovskites were calculated in order to further understand the phase than in monoclinic phase. Regarding the electronic struc-
electronic structures, which are shown in Fig. 9. We can see that the tures calculated, the top of valence band of these La2NiMnO6 is
valence band maximum is mainly attributed to the interaction of Ni mainly attributed to the interaction of Ni 3d orbitals and O 2p or-
3d orbitals as well as O 2p orbitals in both P 21/n and Re3 phases of bitals, whereas the bottom of the conduction band primarily comes
La2NiMnO6. Consequently, compared with single perovskite from the hybridization between Mn 3d and O 2p orbitals. The en-
LaMnO3, with a valence band derived from O 2p orbitals, the ergy band diagram drawn from experimental data indicates that
valence bands of double perovskites La2NiMnO6 have increased. monoclinic La2NiMnO6 would be a better candidate for light har-
Meanwhile, the bottom of the conduction band primarily comes vesting than rhombohedral La2NiMnO6.

10

P 21/n
DOS (states/eV)

total La 5d Ni 3d
Mn 3d O 2p
−10
−4 −2 0 2 4
Energy (eV)

10
R -3
DOS (states/eV)

−10
−4 −2 0 2 4
Energy (eV)

Fig. 9. Electronic structures of La2NiMnO6, (up): P 21/n; (down): Re3.


214 C. Lan et al. / Journal of Alloys and Compounds 655 (2016) 208e214

Acknowledgment Jonathan E. Spanier, Andrew M. Rappe, Nature 503 (2013) 509e512.


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