@ Denali of stteoy 3 Ab, oe) = Mier F microsebes accenefblie. to ; Ayster— in ergy befeseen— E ot EtdE = P(E) volume CE th Amal. inberval fp emeitye ork OLB) 6 HE donaita 4 Atabos > whid- beat to fio number Ab CIO betes in ouwk anergy iatervet ovourd E H Pe) = qotal number > prnostedza decempibl— ft f— bho emmy EB, ton , ote) =

EU) (emeye= a 4p ome) ve ye % gmyret_.. © ek 5] ple) = ‘exemR = a bor (m7, n) ate posihiney- ——$ cog Henee no, of pevticle— porficu— bite & beh pg —y ord En d® > 2(e)-_2f 8e | BE a Y _- a, JOlE)= omy (2m. Ep 8E © T Density + shhin in 2b, 1D ard fan god: © Frr 2D box i — me > (eme) = TY one dit=- R= 1 ee LEE Te (i tev) . a(B) = ame m ra © Pr LD box, P(E)= Axe = Re +. int el)? 7 lm gL ee 2 tle gE es © In ner tr @ fulmenoioral bom, alec Et od ole)e pintChapter 3 Band Structure and Density of States at Nan y levels iit re treated as quasi-continuous states and called energy bands, as indicated by the shaded region in Fig. 3.2(a), The 2N s-states will be completely filled with 2N s-electrons, whereas ON p-states will be partially filled with 2N p-electrons As the interatomic spacing decreases further, the energy gap (E,) between the two bands (as shown in Fig. 3.2(b)) decreases as and when the interaction between the atoms becomes very large. The energy band structure then depends on the crystal structure of the materials and onic configuration of the atoms constituting the material, The Schrésdinger equation for the pand structure will become very much complicated and the solutions would lead to an approximate band structure [3] as schematically illustrated in Fig. 3.2(b). For small enough jnicratomic distances, the s-band and p-band overlap to give a total of 8N (GN p-levels + 2N s-levels) allowed levels, out of which half will be occupied by 4N (2N s-electrons + 2N p-electrons) electrons, These electrons are then could not be identified as s- or p-electrons of individuals atoms, rather they would belong to the crystal as a whole. For this reason, the abov mentioned elements (C, Si, Ge, Sn, etc.) are tetravalent in nature, At the lattice spacing, as shown in Fig, 3.2(b), the band structure would consist of completely filled yalence band with 4N valence electrons, an upper vacant band, called conduction band, seperated by an energy gap, p (Ey). known as forbidden ga — ‘Conduction band 4Nstates, 0 electrons a Valence band 4N states, 4N electrons , interatomic spacing Fig. 3.2(b) Schematic diagram of the formation of valence band and conduction band at lattice spacings (after Ref. (51). ‘Although electronic band structures are usually associated with crystalline materials, quasi- crystalline [4] and amorphous solids may also exhibit band structures. However, the periodic nature and symmetrical properties of crystalline materials make it much easier to examine the band structures of these materials theoretically. In addition, the well-defined symmetry axes of crystalline materials make it possible to determine the dispersion relationship between theith electron: T>0K - T=0Kk ito 10 e,, g pos £ £ Ee ° E - z 5 E 2aT 27 (b) (c) ‘ Fermi-Dirac function ature variations o Fig. 36 Temper fi f for which, at T = 9, ¥ roy is defined as that energy 3 , all lever . For metals, the Fermi enetzy 8 dehine ie all levels above it are empl, ag git alow it are filled W eal show i empl. conduction ba Se ene free to move into “empty” states of conduction band wi ‘hom in Fig, 3.7(a), Blectrons C4 Ya igh electrical conductivity. At T > 0, electrons h trie. fiel eading to high ¢ a ave 4 ial nen Nee ‘excited’ from below the Fermi energy to above it probability to be S Fe vae : Ee Conduction band {partially filled) E=0 4 oO Fig. 3.7(@) Band diagram of metals. Electrons are occupied up to the Fermi level at T = 0K. For insulators, the Fermi level lies at the mid-point of the large (6-10 eV) forbidden Bap as shown in Fig. 3.7(b). At T = 0, lower valence band is filled with electrons and upper conduction band is empty. leading to zero conductivity, At T > 0, most of the valence lectrons do not acquire thermal energy to be ‘excited’ from valence to conduction band, leading to poor conductivity For intrinsic semiconductors, Fermi level lies at the middle of the energy gap, E, as shown in Fig. 3.7(c). At T = 0, valence band is completely filled and conduction band is empty, leading to zero conductivity. At T > 0, electrons thermally ‘excited’ from valence to the Conduction band, leaving an empty state in the valence band, which is called the hole. Thus, with increase in temperature, the conductivity of semiconductors increases,Control voltages for plozolube Tunnelling urrent Distance contro! amplifier and scanning unit electrodes Piezoelectric tube Tunnelling. Te wltage SS 5 . Data processing ‘and display (a) (b) fig. 6.21 (a) Schematic diagram of a Scanning Tunnelling Microscope [12], and (b) STM image of a graphite surface showing highly oriented pyrolytic graphite atoms. where the symbols have the same meanings as described earlier and the exponential term provides the dominant dependence, Application of this nanophysical tunnelling is used in Scanning Tunnelling Microscope (STM), as shown in Figs. 5.21(a) and (b), to detect the surface profile of nanostructured materials. This instrument has given experimental access to the fascinating nano-scale world. This techmique offers the opportunity to image conducting and semiconducting surfaces and to perform tunnelling spectroscopy with atomic-scale spatial resolution. It is a non-optical microscopy technique which employs principles of quantum mechanical barrier tunnelling, as explained above. A sharp probe (the tip), whose end is as sharp asa single atom, moves over the surface of the material under study, and a voltage is applied between the probe and the sample surface. Depending on the voltage applied, electrons will tunnel through the potential barrier between the surface and probe, resulting in a weak electric current. The direction of the tunnelling depends on the polarity of the electric field. The magnitude of this current is exponentially dependent on the distance between the probe and the surface (cf. Eq. (5.72)) and carry the information of the surface profile of the material under test. (@) Potential box: Trapped particle in 3D: Nanodot If we consider a particle inside a 3D infinite trap (Fig, 5.22) of volume L* with impenetrable walls, then we need to consider the generalized Schrodinger equation in three dimensions as > [F)rvo-vowe =Ey() (5.73) ; where Y7 joa and F is the position vector. And the corresponding solutions ay” will be) (7 Pin 7) ) WACO ah) AE ; 7, Three-dimensional infin tential well, a Fi -dimensional infinite pol ig. 5.22 and 4 =| lot +n} +n) "| 8m? os 1, 2, yon ete, These results can also be used for boxes of unequal dimer « [ where n, = 1, 2, 3,.-.5 tC dL as dim kes win mo E, =| Sahat A “ae ae |e 2) ie en : t from the above equation that the energy is dependent on three quantum Dine, ae ee The lowest energy is Ej, and non-zero (for n, = 1, ny = 1 and n, = 1). The crerdy level coresponds to Ep, and is equivalent t0 Eyx and Eyr (for either one Of the mks as 2 and the other two as 1). Therefore, the second energy level has three States for same, aS Yous Vii and Yi12. The number of states that have the same energy is called degeneracy that energy level. Hence the second energy level is thus three-fold degenerate. Nanoparticles with a fraction of a nanometer to a few tens of nanometers size can be as the classic examples of three-dimensional confinement of carriers in a small 3p Figure 5.23(a) shows the Field Emission Scanning Electron Microscopy (FESEM) image q; Si nanoparticle (shown by the arrow). The particle diameter is around 15 nm. Figure S524) shows the High Resolution Transmission Electron Microscopy (HRTEM) image of a sing kind of Si nanoparticle of diameter around 15 nm. Highly oriented atomic planes are obsenai in different parts of the nanoparticle [13]. Carriers are confined within the 3D space of tis nanoparticle and discrete energy levels will be formed whose expressions will be similar Eq. (5.76), with a little modification due to quantum confinement effect, which will be discusei later.uUCIOI ry Quantum Mechanics for Nanoscience (a) Fig. 5.23 (a) FESEM image of a single Si nanoparticle shown the arrow, at TEM it of a 15 nm Si nanoparticle. Oriented atomic planes Ly pana eae re visible inside the nanoparticle [13]. (e) Electron trapped in 2D plane: Nanosheet ‘The abovementioned results can also be used for 2D spaces (Fig. 5.24) where carriers are confined in one-dimension, say along Z-direction to a very small thickness #, and free to move along X- and Y-directions. In nanophysics, this is the case of nanosheets where carriers are allowed to move along a two-dimensional plane. In this case, the modification of wavefunction and energy will respectively be ie 22 vine ! VAG. DE (2) sin (=) ike gio (6.77) and a aR E, =| eee * Fae oer G28) Fig. 5.24 Two-dimensional space, Particles can move along X- and Y-directions freely but confined along Z-direction by a small distance t.98 + Introduction 10 1, is called the sub and index and for = 1 the carrigp ation in a semiconduc i alle pe olectron motion ia sem con Huctor band jo 8 de ¢ 4]. Pigure Mh if electrons (and holes) [41, Figure 5.19 shows "en where the quantum number ] to be in the first sub-band, In gene by introducing the effective mass i AI}, The well is gene med by a circuls 7m picture of a 2D circular potential well The well gener ee acre array ot 28) Cu surface and the free electrons On the Cu surface le this 2D Poten anowire/rod/belt ia} Wel sion: N ers are confined in both directions (say, Y Y and dy (f Flectrons moving in one-din 5.25, in. nanowire, carti As shown in Fig. Fig. 525 One-dimensional nanowire: Particles are only allowed to move freely al one yong Y- and Z-diections by a small distance ! (assuming se nO Xt ag cross se small dimension, 1 (assuming square cross-section, 7) and allowed to move ff length of x-axis. In this case, the wavefunction and the energy will respect cite along th Yon (29.2) = (2)0(] sn TM) iksx ‘ i i (57 Tea 2,2 | tae eee em 2m (5a In nanophysi i ies i a BT carries in carbon nanotubes or similar kind of it Ses co ie a equation, although the actual bound stant eae = xpress aa - . ‘ chetgy eee ee complicated. Figure 5.26 shows different types of on