The temperature and carrier-density dependent excitonic relaxation in bulk ZnO is studied by means of time-resolved photoluminescence. A rate-equation model is used to analyze the population dynamics and the transitions between different exciton states. Intra-excitonic (n ¼ 1) to (n ¼ 2) relaxation is clearly identified at low excitation densities and lattice temperatures with a characteristic time constant of 6 6 0.5 ps. V C 2011 American Institute of Physics.[doi:10.1063/1.3668102] Over the last decades, ZnO has attracted much interest in the scientific community mainly due to its potential application for optoelectronic devices in the ultraviolet (UV) spectral regime. In addition, properties associated with the large exciton binding energy of 60 meV and the strong electron-phonon coupling are of fundamental interest. Recently, high quality ZnO samples have become available due to improved growth methods.2-6 These advances allow for accurate studies of the electro-optical properties of the material and are important steps towards the realization of ZnO-based technology. Significant research effort has been directed towards the growth and applications of quantum well structures, 7,8 ternary ZnO-based compounds, [9][10][11][12] electron-phonon interaction, 13 and exciton-polaritons.14 Even steady-state investigations of the excited excitonic states have become possible. 15,16 In this letter, we study the dynamics of the intraexcitonic processes by means of ultrafast emission spectroscopy with sub-picosecond time resolution. We apply a rateequation model to analyze the various relaxation channels and to investigate the influence of temperature and excitation density.All time-resolved photoluminescence (PL) measurements are performed using a streak-camera setup 12 yielding spectral and time resolutions of 0.15 nm and 500 fs, respectively; a pulsed 100 fs-Ti:sapphire laser is used as an excitation source. The investigated sample is a 300 nm thick c-plane ZnO layer grown by plasma-assisted molecular beam epitaxy.11 The emission signal is collected normally to the sample surface in reflection geometry. Structural analysis by high resolution x-ray diffraction was carried out and the lattice parameters were extracted from reciprocal space maps recorded at the asymmetric (20.5) reflex. The c-lattice parameter was determined to (5.2046 6 0.001) and the a-lattice parameter to (3.2515 6 0.001). Comparison to data reported in literature reveals that the present ZnO layer can be considered as unstrained. transition is attributed to the luminescence of the free B-excitons. Also, an additional, distinct emission peak is found at 3.423 eV. In a simplified picture, the excitonic level scheme resembles the energy structure of a hydrogen atom.1 In this case, the energy of an excited states is proportional to E b n 2 , where E b is the binding energy and n is the quantum number of the corresponding state. Thus, the energy of the first excited state with (n ¼ 2) is 1/4 E b and the separation between the (n ¼ 1) and (n ¼ 2) states eq...