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guoqiusong

Òø³æ (³õÈëÎÄ̳)

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Fig. 4 shows the Raman spectra (LABRAMHR
Confocal Laser MicroRaman spectrometer,
514.5 nm, 250 mW) of the as-synthesized NiO
nanorods. It can be seen that there are four Raman
peaks at 420, 546, 712, and 1092 cm1, respectively.
Compared to the predicted data of
cubic NiO single crystal [26], we can assigned the
peaks at 420 and 546 cm1 to the first-order
transverse optical (TO) and longitudinal optical
(LO) phonon modes of NiO, respectively. The remaining
peaks at 712 and 1092 cm1 can be assigned
as combination of 2TO and 2LO,
respectively, and are all shifted down in frequency
about 68 cm1. Since k ¼ 0 phonons in the paramagnetic
(cubic) phase transform as C4 , no firstorder
Raman scattering is expected. Therefore the
observed first-order Raman peaks near the 420
(TO) and 546 cm1 (LO) must derive from paritybreaking
imperfections [26]. This conclusion is
confirmed by the enhancement of the first-order
Raman scattering in the black NiO, where the
nickel vacancy concentration is high. The combination
Raman scattering trends to vanish at the C
point but is usually strong elsewhere in the Brillouin
zone. This explains why the combination
peaks are all shifted down in frequency, since both
LO and TO branches are expected to be depressed
in frequency away from the zone center.

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