The emission directly after the excitation is spectrally very broad, yet still centered in the vicinity of the strongest exciton resonance.  As the carrier distribution relaxes and cools, the width of the PL peak decreases and the emission energy shifts to match the ground state of the exciton (such as an electron) for ideal samples without disorder. The PL spectrum  approaches its quasi-steady-state shape defined by the distribution of electrons and holes. Increasing the excitation density will change the emission spectra. They are dominated by the excitonic ground state for low densities. Additional peaks from higher subband transitions appear as the carrier density or lattice temperature are increased as these states get more and more populated. Also, the width of the main PL peak increases significantly with rising excitation due to excitation-induced dephasing and the emission peak experiences a small shift in energy due to the Coulomb-renormalization and phase-filling.
In general, both exciton populations and plasma, uncorrelated electrons and holes, can act as sources for photoluminescence as described in the semiconductor-luminescence equations. Both yield very similar spectral features  which are difficult to distinguish; their emission dynamics, however, vary significantly. The decay of excitons yields a single-exponential decay function since the probability of their radiative recombination does not depend on the carrier density. The probability of spontaneous emission for uncorrelated electrons and holes, is approximately proportional to the product of electron and hole populations eventually leading to a non-single-exponential decay described by a hyperbolic function.