Acoustic/optical phonon modes

Fig. 44. Schematic representation of the influence of different charge relaxation rates of IV rare-earth ions on the frequencies of the optical phonon modes (e.g., (dj and at ) and on the q=0 longitudinal acoustic-phonon modes, represented by the bulk modulus Cg (see text). For the stable n - and (n -1- l) -valent rare-earth compounds we show generalized reference lines. Four typical cases are shown with the representative samples given at the bottom.

Table 1.7 Acoustic and optical phonon modes in a crystal with wurtzite symmetry where s represents the number of atoms in the basis.

The number of phonon modes are limited and have been described as "phonon branches" where two types are present, "optical " and "acoustical". (These names arose due to the original methods used to study them in solids). 

Bulk silicon is a semiconductor with an indirect band structure, as schematically shown in Fig. 7.12 c. The top of the VB is located at the center of the Brillouin zone, while the CB has six minima at the equivalent (100) directions. The only allowed optical transition is a vertical transition of a photon with a subsequent electron-phonon scattering process which is needed to conserve the crystal momentum, as indicated by arrows in Fig. 7.12 c. The relevant phonon modes include transverse optical phonons (TO 56 meV), longitudinal optical phonons (LO 53.5 meV) and transverse acoustic phonons (TA 18.7 meV). At very low temperature a splitting (2.5 meV) of the main free exciton line in TO and LO replicas can be observed [Kol5]. 

An interesting aspect of many structural phase transitions is the coupling of the primary order parameter to a secondary order parameter. In transitions of molecular crystals, the order parameter is coupled with reorientational or libration modes. In Jahn-Teller as well as ferroelastic transitions, an optical phonon or an electronic excitation is coupled with strain (acoustic phonon). In antiferrodistortive transitions, a zone-boundary phonon (primary order parameter) can induce spontaneous polarization (secondary order parameter). Magnetic resonance and vibrational spectroscopic methods provide valuable information on static as well as dynamic processes occurring during a transition (Owens et ai, 1979 Iqbal Owens, 1984 Rao, 1993). Complementary information is provided by diffraction methods. 

We did not differentiate between the various modes of vibration (longitudinal, transversal, acoustical, optical) for the sake of simplicity. The vibrational states in a crystal are called phonons. Figure 5-2 illustrates the collective, correlated transversal vibrational motion of a linear elastic chain of particles. 

Although no quantum confinement should occur in the electronic energy level structure of lanthanides in nanoparticles because of the localized 4f electronic states, the optical spectrum and luminescence dynamics of an impurity ion in dielectric nanoparticles can be significantly modified through electron-phonon interaction. Confinement effects on electron-phonon interaction are primarily due to the effect that the phonon density of states (PDOS) in a nanocrystal is discrete and therefore the low-energy acoustic phonon modes are cut off. As a consequence of the PDOS modification, luminescence dynamics of optical centers in nanoparticles, particularly, the nonradiative relaxation of ions from the electronically excited states, are expected to behave differently from that in bulk materials. 

The optical spectral region consists of internal vibrations (discussed in Section 1.13) and lattice vibrations (external). The fundamental modes of vibration that show infrared and/or Raman activities are located in the center Brillouin zone where k = 0, and for a diatomic linear lattice, are the longwave limit. The lattice (external) modes are weak in energy and are found at lower frequencies (far infrared region). These modes are further classified as translations and rotations (or librations), and occur in ionic or molecular crystals. Acoustical and optical modes are often termed phonon modes because they involve wave motions in a crystal lattice chain (as demonstrated in Fig. l-38b) that are quantized in energy. 

Higher-energy optical phonons may explain the exciton relaxation well above the exciton-band bottom (to > co0 + 50cm-1) for instance, the 140-cm 1 Bg lattice mode dominates the a-polarized exciton relaxation. However, acoustical and lower-energy (around 50 cm 1) optical phonons, according to our model, account by themselves for the observed broadening at temperatures below 77 K. 

Indium nitride has twelve phonon modes at the zone centre (symmetry group Cev), three acoustic and nine optical with the acoustic branches essentially zero at k = 0. The infrared active modes are Ei(LO), Ei(TO), Ai(LO) and Ai(TO). A transverse optical mode has been identified at 478 cm 1 (59.3 meV) by reflectance [6] and 460 cm 1 (57.1 meV) by transmission [24], In both reports the location of a longitudinal optical mode is inferred from the Brout sum rule, giving respective values of 694 cm 1 (86.1 meV) and 719 cm 1 (89.2 meV). Raman scattering of single crystalline wurtzite InN reveals Ai(LO) and E22 peaks at 596 cm 1 and at 495 cm 1 respectively [25],... 

The dispersion relationships of lattice waves may be simply described within the first Brillouin zone of the crystal. When all unit cells are in phase, the wavelength of the lattice vibration tends to infinity and k approaches zero. Such zero-phonon modes are present at the center of the Brillouin zone. The variation in phonon frequency as reciprocal k) space is traversed is what is meant by dispersion, and each set of vibrational modes related by dispersion is a branch. For each unit cell, three modes correspond to translation of all the atoms in the same direction. A lattice wave resulting from such displacements is similar to propagation of a sound wave hence these are acoustic branches (Fig. 2.28). The remaining 3N-3 branches involve relative displacements of atoms within each cell and are known as optical branches, since only vibrations of this type may interact with light. 

Wurtzite ZnO structure with four atoms in the unit cell has a total of 12 phonon modes (one longitudinal acoustic (LA), two transverse acoustic (TA), three longitudinal optical (LO), and six transverse optical (TO) branches). The optical phonons at the r point of the Brillouin zone in their irreducible representation belong to Ai and Ei branches that are both Raman and infrared active, the two nonpolar 2 branches are only Raman active, and the Bi branches are inactive (silent modes). Furthermore, the Ai and Ei modes are each spht into LO and TO components with different frequencies. For the Ai and Ei mode lattice vibrations, the atoms move parallel and perpendicular to the c-axis, respectively. On the other hand, 2 modes are due to the vibration of only the Zn sublattice ( 2-low) or O sublattice ( 2-high). The expected Raman peaks for bulk ZnO are at 101 cm ( 2-low), 380 cm (Ai-TO), 407 cm ( i-TO), 437 cm ( 2-high), and 583 cm ( j-LO). 

The spectra obtained for ice Ih, LDA and HDA, using the TFXA spectrometer at 10K [53] is shown in Fig. 11. Ice Ih is the most common and readily obtainable phase of ice which has now been well studied [14,15,48,49]. Its spectrum has a very simple structure, the translational modes below 40 meV are well separated from the librational modes (or hindered rotations) in the energy region between 65-125 meV (very few system shows similar behaviour and this is due to the large mass difference between O and H). The observed acoustic phonon peak is at 7 meV. The two sharp peaks at 28 and 37 meV are the optic-phonon bands and have an unusual triangular-shape. In contrast, only a single feature appears in the IR spectrum, at 27 meV, and the Raman spectrum has an additional shoulder at 36 meV (see Fig. 10). 

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