University of South Carolina Department of Chemistry CHEM 749 Spring 2012: Chemistry and Physics of Low-Dimensional Materials

Problem Set 2 Due Wednesday, February 8

Donors in InSb

The semiconductor indium antimonide (InSb) has an energy gap Eg = 0.23 eV, a dielectric constant = 18, and an electron effective mass of m = 0.015me . Using the effective mass approach, calculate e 1a. The binding energy for donor impurities 1b. The donor Bohr radius. 1c. At sufciently high densities, the typical distance between donor impurities becomes comparable to the Bohr radius: when this happens, the localized impurity levels can begin to interact and form extended band states of their own. What is the approximate density (number per cm3 ) of donor impurities at which you would reach this condition in InSb?

Density of states in various dimensions

The density of states (DOS) is dened as g(E) = ((E)/E), where (E) is the number of states, per unit volume, with energy less than E. Sketch the form of the density of states g(E) vs. E for a free-electron-like band in one dimensional, two dimensional, and three dimensional crystals, with conduction band minimum Ec .

Effective mass description of excitons: Example in GaAs

Absorption of light by a semiconductor creates excitons, excitations that are well-modeled as an electronhole pair. In class, we (will) show that, using the effective mass theorem, the Schr dinger equation for a o exciton in an innite crystal (free exciton) can be written as: h 2 2(m + m ) e h
2 R

2 h 2

2 r

q2 4
0 |r|

(r, R) = E(r, R)

(1)

where (r, R) is the combined envelope wavefunction for the electron and hole, with r = re rh describing m r +m r the relative position (separation) of the electron and hole, and R = eme +mh h describing the center-of mass position. The reduced effective mass = The Hamiltonian in the above equation can be separated into parts that depend only on r, and only on R. Accordingly, the eigenfunctions should be factorable as (r, R) = F (r)G(R), with F (r) the wavefunction for relative position, G(R) the wavefunction for the center-of-mass, and the total energy E = ECM + Erel . 3a. Write down the center-of-mass Schr dinger equation describing G(R) and ECM . What kind of eigeno states does it describe?
m m e h m +m . e h
e p

3b. Write down the difference (relative) equation Schr dinger equation describing F (r) and Erel . What o kind of eigenstates does it describe? 3c. Using your answer for b, and by analogy to our treatment of the bound states of donor impurities, nd the excitonic Bohr radius for an exciton in GaAs. Note that m = 0.063me , m = 0.53me , and e h = 12.9 in GaAs. 3d. What is its dissociation energy? 3e. Compare your answer for c with the unit cell dimension in GaAs (consult handout). Is use of the effective mass approximation justied here?

Strong and weak connement of excitons

In an innite crystal (see above), the motion of electron-hole pairs is separable into center-of-mass motion of the entire exciton, and the relative motion of the electron and hole in a hydrogen-like Coulomb potential. This leads to several regimes of quantum connement when we speak about small crystals. We will consider cadmium sulde (CdS), where Eg = 2.4 eV, m = 0.19me , m = 0.8me , and e h 5.7. This gives a Bohr radius aB,ex 2.0 nm and binding energy Ryex 60 meV for the free exciton. 4a. In the weak connement regime, the size of the crystal is large compared to the exciton Bohr radius, so that the relative motion of electron and hole are not much changed from bulk, but the center of mass motion is restricted enough to cause a detectable change from bulk: the electron and hole move around together, but obviously must stay within the crystal. For a spherical CdS nanoparticle, for what radius R will the lowest energy state for center-of-mass motion differ from the bulk by 10 meV? 4b. In the strong connement regime, the size of the crystal (in at least one of its dimensions) is signicantly smaller than the exciton Bohr radius. I will claim in lecture that for a spherical semiconductor particle under strong connement, we can describe the electron and hole independently with sphericalwell potentials, ignoring the Coulomb interaction. Calculate the energy of the lowest excited state of a spherical CdS particle with R = 1.2 nm using this approach. 4c. The Coulomb interaction is not actually absent under strong connement, but we can add it as a perturbation, essentially by computing the average Coulomb energy experienced by an electron and hole whose probability distributions are determined by the spherical-well wavefunctions above. This treatment of the Coulomb correction has been shown to be equal to 1.8q 2 /4 0 R. Compute this value for the particle in b. Is it larger or smaller than the free exciton binding energy (which is essentially the Coulomb correction to the lowest bulk excited state)?