  Zero-mode waveguides (ZMWs) are confining light into attoliter volumes,
enabling single molecule fluorescence experiments at physiological micromolar
concentrations. Among the fluorescence spectroscopy techniques that can be
enhanced by ZMWs, F\"{o}rster resonance energy transfer (FRET) is one of the
most widely used in life sciences. Combining zero-mode waveguides with FRET
provides new opportunities to investigate biochemical structures or follow
interaction dynamics at micromolar concentration with single molecule
resolution. However, prior to any quantitative FRET analysis on biological
samples, it is crucial to establish first the influence of the ZMW on the FRET
process. Here, we quantify the FRET rates and efficiencies between individual
donor-acceptor fluorophore pairs diffusing in aluminum zero-mode waveguides.
Aluminum ZMWs are important structures thanks to their commercial availability
and the large literature describing their use for single molecule fluorescence
spectroscopy. We also compare the results between ZMWs milled in gold and
aluminum, and find that while gold has a stronger influence on the decay rates,
the lower losses of aluminum in the green spectral region provide larger
fluorescence brightness enhancement factors. For both aluminum and gold ZMWs,
we observe that the FRET rate scales linearly with the isolated donor decay
rate and the local density of optical states (LDOS). Detailed information about
FRET in ZMWs unlocks their application as new devices for enhanced single
molecule FRET at physiological concentrations.
