Effect of Bond Dispersion on Raman Spectra Shift in II-VI Semiconductor Nanocrystals

To understand Raman spectra shifts of nanocrystals, the top-down phonon confinement approach and the bottom-up quantum chemical approach were developed. The former is suitable for large-sized nanocrystals, and the latter is suitable for clusters containing fewer atoms. Here, we find that a simpler chemical bond model based on the bond dispersion feature can demonstrate Raman spectra shift either in normal size II-VI semiconductor nanocrystals or in atomically precise clusters. According to the bond dispersion model, the Raman spectral line of the II-VI semiconductor nanocrystal (A^IIB^VI) is expressed as the sum of the Lorentz subpeaks of the A^{II( i)}B^{VI( j)} bonds with different coordinates i and j. The calculated Raman lines of CdSe, CdS, CdTe, ZnS, and ZnSe nanocrystals are in agreement with the measured Raman spectral lines. The origin of the red shift and asymmetric broadening of the peak position of nanocrystals may be revealed as well. Results provide insight into how different bonds contribute to different vibrational spectra.