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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.
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
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)