In common photovoltaic devices, the part of the incident energy above the absorption threshold quickly ends up as heat, which limits their maximum achievable efficiency far below the thermodynamic limit for solar energy conversion. Conversely, if the excess kinetic energy of the photogenerated carriers could be converted into additional free energy, it would be possible to approach the thermodynamic limit. This is the principle of hot carrier devices. Unfortunately, such a device operation in conditions relevant for utilisation has never been evidenced. Here we show that the quantitative thermodynamic study of the hot carrier population, with luminance measurements, allows us to discuss the hot carrier contribution to the solar cell performance. We demonstrate that voltage and current can be enhanced in a semiconductor heterostructure due to the presence of the hot carrier population in a single InGaAsP quantum well at room temperature. These experimental results substantiate the potential of increasing photovoltaic performances in the hot carrier regime.