In single junction solar cells a large part of the incident energy ends up as heat which limits their maximum achievable efficiency. Thus the achievement of maximum power conversion efficiencies relies on complex multijunction devices. Here we show the possibility to harvest the available solar energy using hot carrier devices and evidence a positive contribution of the hot carrier effect on photovoltaic performances. We investigated a semiconductor heterostructure based on a single InGaAsP quantum well using quantitative optoelectrical characterization, especially luminance measurements. The quantitative thermodynamic study of the hot carrier population allows us to discuss the hot carrier contribution to the solar cell performance. We demonstrate that voltage and current are enhanced due to the presence of the hot carrier population in the quantum well. These experimental results substantiate the potential of increasing photovoltaic performances in the hot carrier regime. Moreover, by developing a suitable analytic theoretical framework, we show how to obtain separate (hot) temperatures of electrons and holes from photoluminescence spectra analysis. The individual thermalization coefficients of each carrier type are also discussed. The method developed in this article paves the way towards the design of new energy harvesting devices and to the development of advanced characterization tools. Finaly, to increase the PV performance enhancement and reduce the concentration factor, an optimize design is investigated.