you can always tra capacitance voltage measurement if your sample is not very resisitive, in that case, you can get the charge carrier density but you will not know if it is due to electrons or holes.
You can also do steady-state or time-resolved photoconductivity measurements (contact or contactless, like microwave). However, (as above) you won't be able to determine directly a sign of carriers involved in a transport. Modeling can help.